Unit Operations of Chemical Engineering (McCabe, 5 )
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Rodrigo RamosUnit Operations of Chemical Engineering (McCabe, 5 )
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Rodrigo RamosUNIT OPERATIONS
OF CHEMICAL ENGINEERING
McGraw-HiII Chemical Engineering Series
Editorial Advisory Board
lames J. Carberry, Professor of Chemical Engineering, University of Noire Dame
lames R. Fair, Professor of Chemical Engineering, University of Texas, Austin
William P. Schowalter, Dean, School of Engineering, University of Illinois
Matthew Tirrell, Professor of Chemical Engineering, University of Minnesota
lames Wef, Dean, School of Engineering, Princeton University
Max S. Peters, Emeritus, Professor of Chemical Engineering, University of Colorado
Building the Literature of a Profession
Fifteen prominent chemical engineers first met in New York more than 60 years
ago to plan a continuing literature for their rapidly growing profession. From
Industry came such pioneer practitioners as Leo H. Baekeland, Arthur D. Little,
Charles L. Reese, John V. N. Dorr, M. C. Whitaker, and R. S. McBride. From
the universities came such eminent educators as William H. Walker, Alfred H.
White, D. D. Jackson, J. H. James, Warren K. Lewis, and Harry A. Curtis. H. C.
Parmelee, then editor of Chemical and Metallurgical Engineering, served as
chairman and was joined subsequently by S. D. Kirkpatrick as consulting editor.
After several meetings, this committee submitted its report to the McGraw-
Hill Book Company in September 1925. In the report were detailed specifications
for a correlated series of more than a dozen texts and reference books which have
since become the McGraw-Hill Series in Chemical Engineering and which became
the cornerstone of the chemical engineering curriculum.
From this beginning there has evolved a series of texts surpassing by far the
scope and longevity envisioned by the founding Editorial Board. The McGraw-
Hill Series in Chemical Engineering stands as a unique historical record of the
development of chemical engineering education and practice. In the series one finds
the milestones of the subject's evolution: industrial chemistry, stoichiometry, unit
operations and processes, thermodynamics, kinetics, and transfer operations.
Chemical engineering is a dynamic profession, and its literature continues
to evolve. McGraw-Hill, with its editor, B. J. Clark and its consulting editors,
remains committed to a publishing policy that will serve, and indeed lead, the
needs of the chemical engineering profession during the years to come.
The Series
Bailey and Ollis: Biochemical Engineering Fundamentals
RenDett and Myers: Momentum, Heat, and Mass Transfer
Brodkey and Hershey: Transport Phenomena: A Unified Approach
Carberry: Chemical and Catalytic Reaction Engineering
Constantinides: Applied Numerical Methods with Personal Computers
Coughanowr: Process Systems Analysis and Control
de Nevers: Fluid Mechanics for Chemical Engineers
Douglas: Conceptual Design of Chemical Processes
Edgar and Himmelblau: Optimization of Chemical Processes
Gates, Katzer, and Schuit: Chemistry of Catalytic Processes
Holland: Fundamentals of Mu/ticomponent Distillation
Holland and Liapis: Computer Methods for Solving Dynamic Separation Problems
Katz and Lee: Natural Gas Engineering: Production and Storage
King: Separation Processes
Lee: Fundamentals of Microelectronics Processing
Luyben: Process Motieling, Simulation, and Control for Chemical Engineers
McCabe, Smith, and Harriott: Unit Operations of Chemical Engineering
Mickley, Sherwood, and Reed: Applied Mathematics in Chemical Engineering
Middleman and Hochberg: Process Engineering Analysis in Semiconductor Device
Fabrication
Nelson: Petroleum Refinery Engineering
Perry and Chilton (Editors): Perry -s Chemical Engineers' Handbook
Peters: Elementary Chemical Engineering
Peters and Timmerhaus: Plant Design and Economics for Chemical Engineers
Reid, Prausnitz, and Rolling: Properties of Gases and LiqUids
Smith: Chemical Engineering Kinetics
Smith and Van Ness: Introduction to Chemical Engineering Thermodynamics
Treybal: Mass Transfer Operations
Valle-Riestra: Project Evaluation in the Chemical Process Industries
Wei, Russell, and Swartzlander: The Structure of the Chemical Processing Industries
Wentz: Hazardous Waste Management
UNIT
OPERATIONS
OF CHEMICAL
ENGINEERING
Fifth Edition
Warren L. McCabe
Late R 1. Reynolds Professor in Chemical Engineering
North Carolina State University
Julian C. Smith
Emeritus Professor of Chemical Engineering
Comel! University
Peter Harriott
Fred H. Rhodes Professor of Chemical Engineering
Cornell University
McGraw-HiII, Inc.
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UNIT OPERATIONS OF CHEMICAL ENGINEERING
International Editions 1993
Exclusive rights by McGraw-Hill Book Co. - Singapore for manufacture and export. Tlus
book cannot be re-exported from the COWltry to which it is consigned by McGraw-Hill.
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Except as pernlitted under the United States Copyright Act of 1976, no part of this
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This book was set in Times Roman.
The editors were BJ. Clark and Eleanor Castellano;
the production supervisor was Louise Karam.
The cover was designed by Joseph GiIlians.
Library of Congress Cataloging-in-Publication Data
McCabe, Warren 1. (Warren Lee), (date).
Unit operations of chemical engineering / Warren 1. McCabe. Juiian C. Smitll.
Peter Harriot!. - 5th ed.
p. cm. - (McGraw-Hill chemical engineering series)
Includes index.
ISBN 0-07-044844-2
1. Chenlical processes. r. Snlith, Julian C. (Julian Cleveland), (date).
IT. Harriott, Peter. Ill. Title. IV. Series.
1P155. 7. M393 1993
660'. 2842-dc20 92-36218
When ordering this title, use ISBN 0-07-112738-0
Printed in Singapore
ABOUT THE AUTHORS
JuJian C. Smith (B.Chem., Chem.E., Cornell University) is Professor Emeritus
of Chemical Engineering at Cornell University, where he joined the faculty in 1946.
He was Director of Continuing Engineering Education at Cornell from 1965 to
1971, and Director of the School of Chemical Engineering from 1975 to 1983. He
retired from active teaching in 1986. Before joining the faculty at Cornel~ he was
employed as a chemical engineer by E.I. duPont de Nemours and Co. He has
served as a consultant on process development to Du Pont, American Cyanamid,
and many other companies, as well as government agencies. He is a member of
the American Chemical Society and a Fellow of the American Institute of Chemical
Engineers.
Peter Harriott (B. Chem.E., Cornell University, ScD., Massachusetts Institute of
Technology) is the Fred H. Rhodes Professor of Chemical Engineering at Cornell
University. Before joining the Cornell faculty in 1953, he worked as a chemical
engineer for the E.!. duPont de Nemours and Co. and the General Electric Co.
In 1966 he was awarded an NSF Senior Postdoctoral Fellowship for study at the
Institute for Catalysis in Lyon, France, and in 1988 he received a DOE fellowship
for work at the Pittsburgh Energy Technology Center. Professor Harriott is the
author of Process Control and a member of the American Chemical Society and
the American Institute of Chemical Engineers. He has been a consnltant to the
U.S. Department of Energy and several industrial firms on problems of mass
transfer, reactor design, and air pollution control.
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CONTENTS
Preface xix
Section 1 Introduction
1 Definitions and Principles 3
Unit Operations 4
Unit Systems 5
Physical Quantities 5
SI Units 5
egs Units 9
Gas Constant ID
Fps Engineering Units 11
Conversion of Units 12
Units and Equations 14
Dimensional Analysis 16
Basic Concepts 18
Equations of State of Gases 18
Symbols 20
Problems 22
References 23
Section 2 Fluid Mechanics 25
2 Fluid Statics and Its Applications 27
Symbols 39
Problems 40
References 41
ix
X CONTENTS
3 Fluid-Flow Phenomena 42
Turbulence 48
Symbols 61
Problems 62
References 62
4 Basic Equations of Fluid Flow 64
Symbols 81
Problems 82
References 82
5 Flow of Incompressible Fluids in Conduits and Thin Layers 83
Flow of Incompressible Fluids in Pipes 83
Laminar Flow in Pipes 86
Turbulent Flow in Pipes and Closed Channels 92
Flow of Liquids in Thin Layers 112
Symbols 115
Problems 117
References 119
6 Flow of Compressible Fluids 120
Processes of Compressible Flow 125
How through Variable-Area Conduits 126
Adiabatic Frictional Flow 133
Isothennal Frictional Flow 137
Symbols 139
Problems 141
References 142
7 Flow Past Immersed Bodies 143
Friction in Flow through Beds of Solids 151
Motion of Particles through Fluids 155
Fluidization 165
Symbols 177
Problems 178
References 180
8 Transportation and Metering of Fluids 181
Pipe, Fittings, and Valves 181
Fluid-moving Machinery 188
Pumps 189
Positive-Displacement Pumps 193
Centrifugal Pumps 195
Fans, Blowers, and Compressors 204
Measurement of Flowing Fluids 214
Full-Bore Meters 215
Insertion Meters 229
Symbols 231
Problems 233
References 234
9 Agitation and Mixing of Liquids 235
Agitation of Liquids 236
Circulation, Velocities, and Power Consumption in Agitated Vessels 243
Blending and Mixing 257
Suspension of Solid Particles 264
Dispersion Operations 269
Symbols 279
Problems 281
References 282
Section 3 Heat Transfer and Its Applications 285
10 Heat Transfer by Conduction 289
Steady-State Conduction 292
Unsteady-State Conduction 299
Symbols 306
Problems 307
References 308
11 Principles of Heat Flow in Fluids 309
Energy Balances 313
Rate of Heat Transfer 315
Overall Heat-Transfer Coefficient 315
Individual Heat-Transfer Coefficients 319
Effective Coefficients for Unsteady-State Heat Transfer 327
Symbols 328
Problems 329
References 329
12 Heat Transfer to Fluids without Phase Change 330
Heat Transfer by Forced Convection in Laminar Flow 333
Heat Transfer by Forced Convection in Turbulent Flow 340
Transfer by Turbulent Eddies and Analogy between Transfer
of Momentum and Heat 348
Heat Transfer in Transition Region between Larninar and Turbulent Flow 353
Transfer to Liquid Metals 355
Heating and Cooling of Fluids in Forced Convection outside Tubes 359
Natural Convection 362
Symbols 369
Problems 371
References 373
XII CONTENTS
13 Heat Transfer to Fluids with Phase Change 374
Heat Transfer from Condensing Vapors 374
Heat Transfer to Boiling Liquids 385
Symbols 394
Problems 395
References 396
14 Radiation Heat Transfer 397
Emission of Radiation 398
Absorption of Radiation by Opaque Solids 402
Radiation between Surfaces 405
Radiation to Semitransparent Materials 416
Combined Heat Transfer by Conduction-Convection and Radiation 422
Symbols 423
Problems 425
References 426
15 Heat-Exchange Equipment 427
Heat Exchangers 428
Condensers 439
Boilers and Calandrias 442
Ext.nded Surface Equipment 445
Heat Transfer in Agitated Vessels 451
Scraped-Surface Exchangers 453
Heat Transfer in Packed Beds 455
Symbols 457
Problems 459
References 461
16 Evaporation 463
Types of Evaporators 465
Performance of Tubular Evaporators 470
Evaporator Capacity 470
Evaporator Economy 476
Vapor Recompression 490
Symbols 492
Problems 492
References 494
Section 4 Mass Transfer and Its Applications
17 Equilibrium-Stage Operations 501
Principles of Stage Processes 505.
Equilibrium-Stage Calculations for Muiticomponent Systems 519
Symbols 519
Problems 519
References 520
18 Distillation 521
Flash Distillation 521
Continuous Distillation with Reflux (Rectification) 525
Material Balances in Plate Columns 529
Number of Ideal Plates; McCabe-Thiele Method 531
Enthalpy Balances for Fractionating Columns 553
Design of Sieve-Plate Columns 560
Plate Efficiency 568
Rectification in Packed. Towers 576
Batch Distillation 576
Symbols 580
Problems 582
References 587
19 Introduction to Multicornponent Distillation 588
Flash Distillation of Multicomponent Mixtures 592
Fractionation of Multicomponent Mixtures 593
Azeotropic and Extractive Distillation 609
Symbols 610
Problems 611
References 613
20 Leaching and Extraction 614
Leaching 614
Leaching Equipment 615
Principles of Continuous Countercurrent Leaching 617
Liquid Extraction 623
Extraction Equipment 624
Principles of Extraction 632
Supercritical Fluid Extraction 641
Symbols 643
Problems 644
References 646
21 Principles of Diffusion and Mass Transfer between Phases 647
Theory of Diffusion 648
Mass-Transfer Coefficients and Film Theory 658
Penetration Theory of Mass Transfer 662
Experimental Measurement of Mass-Transfer Coefficients 663
Coefficients for Mass Transfer through Known Areas 665
Mass Transfer to Pipes and Cylinders 666
Mass Transfer to Particles 670
Two-Film Theory 674
Stage Efficiencies 676
XIV CONTENTS
Symbols 681
Problems 683
References 685
22 Gas Absorption 686
Design of Packed Towers 686
Principles of Absorption 697
Rate of Absorption 701
Mass-Transfer Correlations 713
Absorption in Plate Columns 721
Absorption from Rich Gases 722
Absorption with Chemical Reaction 728
Other Separations in Packed Columns 730
Symbols 732
Problems 734
References 736
23 Humidification Operations 738
Wet-Bulb Temperature and Measurement of Humidity 747
Equipment for Humidification Operations 751
Theory and Calculation of Humidification Processes 753
Symbols 763
Problems 764
References 766
24 Drying of Solids 767
Principles of Drying 769
Phase Equilibria 774
Cross-Circulation Drying 776
Through-Circulation Drying 788
Drying of Suspended Particles 791
Drying Equipment 791
Dryers for Solids and Pastes 791
Dryers for Solutions and Slurries 801
Selection of Drying Equipment 805
Symbols 806
Problems 808
References 809
25 Adsorption 810
Adsorption Equipment 811
Equilibria; Adsorption Isotherms 814
Principles of Adsorption 818
Basic Equations for Adsorption 825
Solutions to Mass-Transfer Equations 826
Adsorber Design 832
Symbols 834
Problems 835
References 837
26 Membrane Separation Processes 838
Separation of Gases 838
Separation of Liquids 859
Dialysis 860
Membranes for Liquid-Liquid Extraction 862
Pervaporation 864
Reverse Osmosis 871
Symbols 878
Problems 879
References 881
27 Crystallization 882
Crystal Geometry 883
Principles of Crystallization 884
Equilibria and Yields 884
Nucleation 892
Crystal Growth 899
Crystallization Equipment 902
Applications of Principles to Design 909
MSMPR Crystallizer 909
Crysta11ization from Melts 918
Symbols 920
Problems 921
References 923
Section 5 Operations Involving Particulate Solids 925
28 Properties, Handling, and Mixing of Particulate Solids 927
Characterization of Solid Particles 927
Properties of Particulate Masses 936
Storage of Solids 939
Mixing of Solids 941
Types of Mixers 942
Mixers for Cohesive Solids 943
Mixers for Free-Flowing Solids 952
Symbols 957
Problems 958
References 959
29 Size Reduction 960
Principles of Comminution 961
~ ., Computer Simulation of Milling Operations 965
Size-Reduction Equipment 970
Crushers 971
Grinders 975
Ultrafine Grinders 982
Cutting Machines 986
Xl'. CONTENTS
Equipment Operation 987
Symbols 990
Problems 992
References 992
30 MechaniCal Separations 994
Screening 994
Screening Equipment 995
Filtration 1002
Cake Filters 1003
Centrifugal Filters 1011
Principles of Cake Filtration 1016
Clarifying Filters 1030
Liquid Clarification 1030
Gas Cleaning 1031
Principles of Clarification 1032
Crossftow Filtration 1033
Types of Membranes 1034
Permeate Flux for Ultrafiltration 1036
Concentration Polarization 1037
Partial Rejection of Solutes 1043
Microfiltration 1046
Separation Based on the Motion of Particles through Fluids 1047
Gravity Settling Processes 1048
Centrifugal Settling Processes 1060
Symbols 1072
Problems 1074
References 1076
Appendixes 1079
Appendix I Cgs and SI Prefixes for Multiples and Submultiples 1079
Appendix 2 Values of Gas Constant 1080
Appendix 3 Conversion Factors and Constants of Nature 1081
Appendix 4 Dimensionless Groups 1084
Appendix 5 Dimensions, Capacities, and Weights of Standard Steel Pipe 1086
Appendix 6 Condenser and Heat-Exchanger Tube Data 1088
Appendix 7 Properties of Saturated Steam and Water 1090
Appendix 8 Viscosities of Gases 1092
Appendix 9 Viscosities of Liquids 1094
Appendix 10 Thermal Conductivities of Metals 1097
Appendix 11 Thermal Conductivities of Various Solids and Insulating
Materials 1098
Appendix 12 Thermal Conductivities of Gases and Vapors 1100
Appendix 13 Thermal Conductivities of Liquids Other Than Water 1101
Appendix 14 Properties of Liquid Water 1102
Appendix,15 Specific Heats of Gases 1103
Appendix 16 Specific Heats of Liquids 1104
Appendix 17 Prandtl Numbers for Gases at I atm and 100°C 1105
Appendix 18 Prandtl Numbers for Liquids 1106
Appendix 19 Dilfusivities and Schmidt Numbers for Gases in Air at ooe
and I atm 1107
Appendix 20 Tyler Standard Screen Scale 1108
Appendix 21 K Values for Light Hydrocarbons (Low Temperatures) 1110
Appendix 22 K Values for Light Hydrocarbons (High Temperatures) 1111
Index 1113
PREFACE
This revised edition of the text on the unit operations of chemical engineering
contains much updated and new material, reflecting, in part, the broadening of
the chemical engineering profession into new areas such as food processing,
electronics, and biochemical applications. Its basic structure and general level of
treatment, however, remain unchanged from previous editions. It is a beginning
text, written for undergraduate students in the junior or senior years who have
completed the usual courses in mathematics, physics, chemistry, and an introduc-
tion to chemical engineering. An elementary knowledge of material and energy
balances and of thermodynamic principles is assumed.
Separate chapters are devoted to each of the principal operations, which are
grouped in four main sections: fluid mechanics, heat transfer, equilibrium stages
and mass transfer, and operations involving particulate solids. One-semester or
one-quarter courses may be based on any of these sections or combinations of
them.
In this edition SI units are emphasized much more than in previous editions,
but the older cgs and fps systems have not been completely eliminated. Chemical
engineers must still be able to use all three systems of units. The great majority
of the equations and correlations, it should be noted, are dimensionless and may
be used with any set of consistent units.
A new chapter on membrane separations has been added, and the order of
the chapters on multi component distillation, extraction, drying, and crystallization
has been made more logical. The discussion of particulate solids has been
shortened and two former chapters on properties and handling of solids and of
solids mixing have been combined into one. New material has been added on flow
measurement, dispersion operations, supercritical extraction, pressure-swing ad-
sorption, crystallization techniques, crossflow filtration, sedimentation, and many
other topics. The treatment of dimensional analysis has been condensed and moved
from the appendixes to Chapter 1.
xix
A.A. PKt:t'-ACE
About two-thirds of the problems at the ends of the chapters are new or
revised, with a large majority of them expressed in SI units. Nearly all the problems
can be solved with the aid of a pocket calculator, although a computer solution
may be preferred in some cases.
McGraw-Hill and the authors would like to thank Edward Cussler, Uni-
versity of Minnesota, and Robert Kabel, Pennsylvania State University, for their
helpful reviews of the manuscript.
The senior author, Or. Warren L. McCabe, died in August 1982. This book
is dedicated to his memory.
Julian C. Smith
Peter Harriott
SECTION
I
INTRODUCTION
CHAPTER
1
DEFINITIONS
AND
PRINCIPLES
Chemical engineering has to do with industrial processes in which raw materials
are changed or separated into useful products. The chemical engineer must
develop, design, and engineer both the complete process and the equipment used;
choose the proper raw materials; operate the plants efficiently, safely, and econo-
mically; and see to it that products meet the requirements set by the customers.
Chemical engineering is both an art and a science. Whenever science helps the
engineer to solve a problem, science should be used. When, as is usually the case,
science does not give a complete answer, it is necessary to use experience and
judgment. The professional stature of an engineer depends on skill in utilizing all
sources of information to reach practical solutions to processing problems.
The variety of processes and industries that call for the services of chemical
engineers is enormous. Products of concern to chemical engineers range from
commodity chemicals like sulfuric acid and chlorine to high-technology items like
polymeric lithographic supports for the electronics industry, high-strength compo-
site materials, and genetically modified biochemical agents. The processes de-
scribed in standard treatises on chemical technology and the process industries
give a good idea of the field of chemical engineering, as does the 1988 report on
the profession by the National Research Council!"t
t Superior numerals in the text correspond to the numbered references at the end of each chapter.
3
.q INTRODUCTION
Because of the variety and complexity of modern processes, it is not
practicable to cover the entire subject matter of chemical engineering under a
single head. The field is divided into convenient, but arbitrary, sectors. This text
covers that portion of chemical engineering known as the unit operations.
UNIT OPERATIONS
An economical method of organizing much of the subject matter of chemical
engineering is based on two facts: (1) although the number of individual processes
is great, each one can be broken down into a series of steps, called operations,
each of which in turn appears in process after process; (2) the individual operations
have common techniques and are based on the same scientific principles. For
example, in most processes solids and fluids must be moved; heat or other forms
of energy must be transferred from one substance to another; and tasks like drying,
size reduction, distillation, and evaporation must be performed. The unit-operation
concept is this: by studying systematically these operations themselves-opera-
tions that clearly cross industry and process lines-the treatment of all processes
is unified and simplified.
The strictly chemical aspects of processing are studied in a companion area
of chemical engineering called reaction kinetics. The unit operations are largely
used to conduct the primarily physical steps of preparing the reactants, separating
and purifying the products, recycling unconverted reactants, and controlling the
energy transfer into or out of the chemical reactor.
The unit operations are as applicable to many physical processes as to
chemical ones. For example, the process used to manufacture common salt consists
of the following sequence of the unit operations: transportation of solids and
liquids, transfer of heat, evaporation, crystallization, drying, and screening. No
chemical reaction appears in these steps. On the other hand, the cracking of
petroleum, with or without the aid of a catalyst, is a typical chemical reaction
conducted on an enormous scale. Here the unit operations-transportation of
fluids and solids, distillation, and various mechanical separations-are vital, and
the cracking reaction could not be utilized without them. The chemical steps
themselves are conducted by controlling the flow of material and energy to and
from the reaction zone.
Because the unit operations are a branch of engineering, they are based on
both science and experience. Theory and practice must combine to yield designs
for equipment that can be fabricated, assembled, operated, and maintained. A
balanced discussion of each operation requires that theory and equipment be
considered together. An objective of this book is to present such a balanced
treatment.
SCIENTIFIC FOUNDATIONS OF UNIT OPERATIONS. A number of scientific
principles and techniques are basic to the treatment of the unit operations. Some
are elementary physical and chemical laws such as the conservation of mass and
u<or"~IIIVI~" " ...... '"''''-''' ~~w _
energy, physical equilibria, kinetics, and certain properties of matter. Their general
use is described in the remainder of this chapter. Other special techniques
important in chemical engineering are considered at the proper places in the text.
UNIT SYSTEMS
The. official international system of units is the SI system (Systeme International
d'Unites). Strong efforts are underway for its universal adoption as the exclusive
system for all engineering and science, but older systems, particularly the centi-
meter-gram-second (cgs) and foot-pound-second (fps) engineering gravitational
systems, are still in use and probably will be around for some time. The chemical
engineer finds many physiochemical data given in cgs units; that many calculations
are most conveniently made in fps units; and that SI units are increasingly
encountered in science and engineering. Thus it becomes necessary to be expert
in the use of all three systems.
In the following treatment, the SI system is discussed first, and the other
systems are then derived from it. The procedure reverses the historical order, as
the SI units evolved from the cgs system. Because of the growing importance of
the SI system, it should logically be given a preference. If, in time, the other systems
are phased out, they can be ignored and the SI system then used exclusively.
Physical Quautities
Any physical quantity consists of two parts: a unit, which tells what the quantity
is and gives the standard by which it is measured, and a number, which tells how
many units are needed to make up the quantity. For example, the statement that
the distance between two points is 3 m means all this: a definite length has been
measured; to measure it, a standard length, called the meter, has been chosen as
a unit; and three i-m units, laid end to end, are needed to cover the distance. If
an integral number of units is either too few or too many to cover a given distance,
submultiples, which are fractions of the unit, are defined by dividing the unit into
fractions, so that a measurement can be made to any degree of precision in terms
of the fractional units. No physical quantity is defined until both the number and
the unit are given.
SI Units
The SI system covers the entire field of science and engineering, including
electromagnetics and illumination. For the purposes of this book, a subset of the
SI units covering chemistry, gravity, mechanics, and thermodynamics is sufficient.
The units are derivable from (1) four proportionalities of chemistry and physics;
(2) arbitrary standards for mass, length, time, temperature, and the mole; and (3)
arbitrary choices for the numerical values of two proportionality constants.
6 INTRODUCTION
BASIC EQUATIONS. The basic proportionalities, each written as an equation with
its own proportionality factor, are
d
F=k -(mu) (1.1)
1 dt
(1.2)
(1.3)
· pV
T= k 4 1I m - (1.4)
p"'O m
wheret F = force
t = time
m = mass
u = velocity
r = distance
~=work
Q, = heat
p = pressure
V = volume
T = thermodynamic absolute temperature
klo k 2 , k 3 , k4 = proportionality factors
Equation (1.1) is Newton's second law of motion, showing the proportional-
ity between the resultant of all the forces acting on a particle of mass m and the
time rate of increase in momentum of the particle in the direction of the resultant
force.
Equation (1.2) is Newton's law of gravitation, giving the force of attraction
between two particles of masses nI, and In, a distance r apart.
Equation (1.3) is one statement of the first law of thermodynamics. It affirms
the proportionality between the work performed by a closed system during a cycle
and the heat absorbed by that system during the same cycle.
Equation (1.4) shows the proportionality between the thermodynamic abso-
lute temperature and the zero-pressure limit of the pressure-volume product of a
definite mass of any gas.
Each equation states that if means are available for measuring the values of
all variables in that equation and if the numerical value of k is calculated, then
the value of k is constant and depends only on the units used for measuring the
variables in the equation.
t A list of symbols is given at the end of each chapter.
STANDARDS. By international agreement, standards are fixed arbitrarily for the
quantities mass, length, time, temperature, and the mole. These are five of the base
units of the SI system. Currently, the standards are as follows.
The standard of mass is the kilogram (kg), defined as the mass of the
international kilogram, a platinum cylinder preserved at Sevres, France.
The standard of length is the meter (m), defined' (since 1983) as the length
of the path traveled by light in vacuum during a time interval of 1/299,792,458'
of a second. t
The standard of time is the second (s), defined as 9,192,631.770* frequency
cycles of a certain quantum transition in an atom of '33Ce.
The standard of temperature is the kelvin (K), defined by assigning the value
273.16* K to the temperature of pure water at its triple point, the unique
temperature at which liquid water, ice, and steam can exist at equilibrium.
The mole (abbreviated mol) is defined" as the amount of a substance
comprising as many elementary units as there are atoms in 12* g of 12C. The
definition of the mole is equivalent to the statement that the mass of one mole of
a pure substance in grams is numerically equal to its molecular weight calculated
from the standard table of atomic weights, in which the atomic weight of carbon
is given as 12.01115. This number differs from 12* because it applies to the natural
isotopic mixture of carbon rather than to pure 12C.
EVALUATION OF CONSTANTS. From the basic standards, values of m, m" and
m, in Eqs. (1.1) and (1.2) are measured in kilograms, ,. in meters, and u in meters
per second. Constants k, and k2 are not independent but are related by eliminating
F from Eqs. (1.1) and (1.2). This gives
k, d(mu}/dt
"2 ma mb/r2
Either k, or k2 may be fixed arbitrarily. Then the other constant must be found
by experiments in which inertial forces calculated by Eq. (1.1) are compared with
gravitational forces calculated by Eq. (1.2). In the SI system, k, is fixed at unity
and k2 found experimentally. Equation (1.1) then becomes
d
F=-(mu) (1.5)
dt
The force defined by Eq. (1.5) and also used in Eq. (1.2) is called the newton
(N). From Eq. (1.5),
1 N == 1 kg_m/s 2 (1.6)
t The asterisk at the end of a number signifies that the number is exact, by definition.
lS INTRODUCTION
Constant k2 is denoted by G and called the gravitational constant. Its
recommended value is 3
G = 6.6726 X 10- 11 N_m 2jkg2 (1.7)
WORK, ENERGY, AND POWER. In the SI system both work and energy are
measured in newton-meters, a unit called the joule (1), and so
1 J '" 1 N-m = 1 kg_m 2/s 2 (1.8)
Power is measured in joules per second, a unit called the watt (W).
HEAT. The constant k3 in Eq. (1.3) may be fixed arbitrarily. In the SI system it,
like k1' is set at unity. Equation (1.3) becomes
Q, = It; (1.9)
Heat, like work, is measured in joules.
TEMPERATURE. The quantity pV/m in Eq. (1.4) may be measured in
(N/m2)(m3jkg), or Jjkg. With an arbitrarily chosen gas, this quantity can be
determined by measuring p and V of m kg of gas while it is immersed in a
thermostat. In this experiment, only constancy of temperature, not magnitude, is
needed. Values of pV/m at various pressures and at constant temperature can then
be extrapolated to zero pressure to obtain the limiting value required in Eq. (1.4)
at the temperature of the thermostat. For the special situation when the thermostat
contains water at its triple point, the limiting value is designated by (pV/m)o. For
this experiment Eq. (1.4) gives
273.16 = k4 lim (PV)
m
p .... O 0
(1.10)
For an experiment at temperature T K Eq. (1.4) can be used to eliminate k.
from Eq. (1.10), giving
T '" 273.16Iimp~o (pV/m)T (1.11)
limp~o (p V/m)o
Equation (1.11) is the definition of the Kelvin temperature scale from the experi-
mental pressure-volume properties of a real gas.
CELSIUS TEMPERATURE. In practice, temperatures are expressed on the Celsius
scale, in which the zero point is set at the ice point, defined as the equilibrium
temperature of ice and air-saturated water at a pressure of one atmosphere.
Experimentally, the ice point is found to be 0.01 K below the triple point of water,
and so it is at 273.15 K. The Celsius temperature ("C) is defined by
TOC", T K - 273.15 (1.12)
Ul:rll'llllVI'I;> AI'ILI rl<.il....... lrl.,.c.;) /
On the Celsius scale, the experimentally measured temperature of the steam
point, which is the boiling point of water at a pressure of One atmosphere, is
l00.00'C.
DECIMAL UNITS. In the SI system a single unit is defined for each quantity, but
named decimal multiples and submultiples also are recognized. They are listed in
Appendix 1. Time may be expressed in the nondecimal units: minutes (min), hours
(h), or days (d).
STANDARD GRAVITY. For certain purposes, the acceleration of free fall in the
earth's gravitational field is used. From deductions based on Eq. (1.2), this quantity,
denoted by g, is nearly constant. It varies slightly with latitude and height above
sea level. For precise calculations, an arbitrary standard gn has been set, defined by
gn '" 9.80665* m/s2 (1.13)
PRESSURE UNITS. The natural unit of pressure in the SI system is the newton
per square meter. This unit, called the pascal (Pa), is inconveniently small, and a
multiple, called the bar, also is used. It is defined by
1 bar", 1 x 105 Pa = 1 x 105 N/m2 (1.14)
A more common empirical unit for pressure, used with all systems of units,
is the standard atmosphere (atm), defined by
1 atm '" 1.01325* x 105 Pa = 1.01325 bars (1.15)
CGS Units
The older cgs system can be derived from the SI system by making certain arbitrary
decisions.
The standard for mass is the gram (g), defined byt
1 g '" 1 X 10- 3 kg (1.16)
The standard for length is the centimeter (cm), defined byt
lcm"'lxlO- 2 m (1.17)
Standards for time, temperature, and the mole are unchanged.
As in the SI system, constant kl in Eq. (1.1) is fixed at unity. The unit of
force is called the dyne (dyn), defined by
1 dyn '" 1 g-cm/s2 (1.18)
t See Appendix 1.
1: See Appendix 1.
1U INTRODUCTION
The uuit for energy and work is the erg, defined by
1 erg'" 1 dyn-cm = 1 x 10-' J (1.19)
Constant k3 in Eq. (1.3) is not unity. A unit for heat, called the calo";e (cal),
is used to convert the unit for heat to ergs. Constant l/k3 is replaced by J, which
denotes the quantity called the mechanical equivalent of heat and is measured in
joules per calorie. Equation (1.3) becomes
(1.20)
Two calories are defined 6 The thermochemical calorie (cal), used in chemistry,
is defined by
1 cal '" 4.1840' x 10' ergs = 4.1840' J (1.21)
The international steam table calorie (caI IT), used in engineering, is defined by
1 calIT '" 4.1868* x 10' ergs = 4.1868* J (1.22)
The calorie is so defined that the specific heat of water is approximately 1 calfg-dc.
The standard acceleration of free fall in cgs units is
gn'" 980.665 cm/s2 (1.23)
Gas Constant
If mass is measured in kilograms or grams, constant k, in Eq. (1.4) differs from
gas to gas. But when the concept of the mole as a mass unit is used, k, can be
replaced by the universal gas constant R, which, by Avogadro's law, is the same
for all gases. The numerical value of R depends only on the units chosen for energy,
temperature, and mass. Then Eq. (1.4) is written
. pV
hm-=R (1.24)
p-o nT
where n is the number of moles. This equation applies also to mixtures of gases
if n is the total number of moles of all the molecular species that make up the
volume V.
The accepted experimental value of R is'
R = 8.31447 JjK-mol = 8.31447 x 10' ergsjK-mol (1.25)
Values of R in other units for energy, temperature, and mass are given in
Appendix 2.
Although the mole is defined as a mass in grams, the concept of the mole is
easily extended to other mass units. Thus, the kilogram mole (kg mol) is the usual
molecular or atomic weight in kilograms, and the pound mole (lb mol) is that in
avoirdupois pounds. When the mass unit is not specified, the gram mole (g mol)
is intended. Molecular weight M is a pure number.
FPS Engineering Units
In some countries a non decimal gravitational unit system has long been used in
commerce and engineering. The system can be derived from the SI system by
making the following decisions.
The standard for mass is the avoirdupois pound (lb), defined by
lIb = 0.45359237* kg (1.26)
The standard for length is the inch (in.), defined as 2.54' cm. This is
equivalent to defining the foot (ft) as
1 ft == 2.54 x 12 x 10- 2 m = 0.3048* m (1.27)
The standard for time remains the second (s).
The thermodynamic temperature scale is called the Rankine scale, in which
temperatures are denoted by degrees Rankine and defined by
l0R == _l_K (1.28)
1.8
The ice point on the Rankine scale is 273.15 x 1.8 = 491.67°R.
The analog of the Celsius scale is the Fahrenheit scale, in which readings
are denoted by degrees Fahrenheit. It is derived from the Rankine scale by setting
its zero point exactly 32°F below the ice point on the Rankine scale, so that
roF == TOR - (491.67 - 32) = TOR - 459.67 (1.29)
The relation between the Celsius and the Fahrenheit scales is gIVen by the
exact equation
(1.30)
From this equation, temperature differences are related by
IJ. TOC = 1.8 IJ. TOF = IJ. T K (1.31)
The steam point is 212.00°F.
POUND FORCE. The fps system is characterized by a gravitational unit of force,
called the pound Jorce (lbf ). The unit is so defined that a standard gravitational
field exerts a force of one pound on a mass of one avoirdupois pound. The standard
acceleration of free fall in fps units is, to five significant figures,
9.80665 m/s2
g, = 0.3048 m/ft 32.174 ft/s2 (1.32)
The pound force is defined by
1lbf == 32.1741b-ft/s 2 (1.33)
.I.. IN I KVUU{,;I IVN
Then Eq. (1.1) gives
Fib == d(mu)/dt Ib-ft/s2 (1.34)
J 32.174
Equation (1.1) can also be written with l/g, in place of k,:
F = d(mu)fdt
(1.35)
g,
Comparison of Eqs. (1.34) and (1.35) shows that to preserve both numerical
equality and consistency of units in these equations, it is necessary to define g~
called the Newton's-law proportionality Jactor Jar the gravitational Jorce unit, by
g, == 32.174Ib-ft/s 2-lb J (1.36)
The unit for work and mechanical energy in the fps system is the Joot-pound
Jorce (ft-lbJ ). Power is measured by an empirical unit, the horsepower (hp), defined
by
1 hp == 550 ft-lb J/s (1.37)
The unit for heat is the British thermal unit (Btu), defined by the implicit
relation
1 Btuflb-OF == 1 callT/g-OC (1.38)
As in the cgs system, constant k3 in Eq. (1.3) is replaced by 1/l, where J is the
mechanical equivalent of heat, equal to 778.17 ft-lb JiBtu.
The definition of the Btu requires that the numerical value of specific heat
be the same in both systems, and in each case the specific heat of water is
approximately 1.0.
Conversion of Units
Since three unit systems are in common use, it is often necessary to convert the
magnitudes of quantities from one system to another. This is accomplished by
using conversion factors. Only the defined conversion factors for the base units
are required since conversion factors for all other units can be calculated from
them. Interconversions between the SI and cgs systems are simple. Both use the
same standards for time, temperature, and the mole, and only the decimal
conversions defined by Eqs. (1.16) and (1.17) are needed. The SI and fps systems
also use the second as the standard for time; the three conversion factors defined
for mass, length, and temperature by Eqs. (1.26), (1.27), and (1.28), respectively,
are sufficient for all conversions of units between these two systems.
Example 1.1 demonstrates how conversion factors are calculated from the
exact numbers used to set up the definitions of units in the SI and fps systems. In
conversions involving gc in fps units, the use of the exact numerical ratio
9.80665/0.3048 in place of the fps number 32.1740 is recommended to give
maximum precision in the final calculation and to take advantage of possible
cancellations of numbers during the calculation.
Example 1.1. Using only exact definitions and standards, calculate factors for
converting (a) newtons to pounds force, (b) British thermal units to IT calories, (c)
atmospheres to pounds force per square inch, and (d) horsepower to kilowatts.
Solution
(a) From Eqs. (1.6), (1.26), and (1.27),
Ilb-ft/s2
IN = I kg-m/s2 = ---~---
0.45359237 x 0.3048
From Eq. (1.32)
2 0.3048
Ilb-ft/s = - - I br
9.80665
and so
0.3048
IN = Ib
9.80665 x 0.45359237 x 0.3048 r
I
9.80665 x 0.45359237 Ibr = 0.224809 Ibr
In Appendix 3 it is shown that to convert newtons to pound force, one should
multiply by 0.224809. Clearly, to convert from pounds force to newtons, multiply by
9.80665 x 0.45359237 = 4.448222.
(b) From Eq. (1.38)
lIb PF
1 Btu = 1 caIIT - -
I g 1°C
lIb I kg 1°F
=lcalIT---
IkglglOC
From Eqs. (1.16), (1.26), and (1.31)
0.45359237 x 1000
I Btu = I caIn 251.996 callT
1.8
(c) From Eqs. (1.6), (1.14), and (1.15)
I atm = 1.01325 x 10' kg_m/s 2_m 2
From Eqs. (1.26), (1.27), and (1.36), since I ft = 12 in,
Ilb/s 2 0.3048
I atm = 1.01325 x 10' x -:--:-c:c:-'=-=
0.45359237 ft
_ _1.-:0",13_2_5-:-X_IO_'_X_O._30_4_8-:o 2
Ibr/in.
32.174 x 0.45359237 x 122
= 14.6959Ibr /in. 2
14 INTRODUCfION
(d) From Eqs. (1.33) and (1.37)
1 hp = 550 ft-1bfls = 550 x 32.174 ft'-Ib/s 3
Using Eqs. (l.26) and (l.27) gives
1 hp = 550 x 32.174 x 0.45359237 x 0.3048'
= 745.70 Jls
Substituting from Eq. (l.8) and dividing by 1000,
1 hp = 0.74570 kW
Although conversion factors may be calculated as needed, it is more efficient
to use tables of the common factors. A table for the factors used in this book is given
in Appendix 3.
Units and Equations
Although Eqs. (1.1) to (1.4) are sufficient for the description of unit systems,
they are but a small fraction of the equations needed in this book. Many
such equations contain terms that represent properties of substances, and these
are introduced as needed. All new quantities are measured in combinations of
units already defined, and all are expressible as functions of the five base units for
mass, length, time, temperature, and mole.
PRECISION OF CALCULATIONS. In the above discussion, the values of experi-
mental constants are given with the maximum number of significant digib
consistent with present estimates of the precision with which they are known, and
all digits in the values of defined constants are retained. In practice, such extreme
precision is seldom necessary, and defined and experimental constants can be
truncated to the number of digits appropriate to the problem at hand, although
the advent of the digital computer makes it possible to retain maximum precision
at small cost. The engineer should use judgment in setting a suitable level of
precision for the particular problem to be solved.
GENERAL EQUATIONS. Except for the appearance of the proportionality factors
g, and J, the equations for all three unit systems are alike. In the SI system, neither
constant appears; in the cgs system, g, is omitted and J retained; in the fps system
both constants appear. In this text, to obtain equations in a general form for all
systems, g, and J are included for use with fps units; then either g, or both g, and
J may be equated to unity when the equations are used in the cgs or SI systems.
DIMENSIONLESS EQUATIONS AND CONSISTENT UNITS. Equations derived
directly from the basic laws of the physical sciences consist of terms that either
have the sam'e units or can be written in the same units by using the definitions
of derived quantities to express complex units in terms of the five base ones.
Equations meeting this requirement are called dimensionally homogeneous equa-
tions. When such an equation is divided by anyone of its terms, all units in each
term cancel and only numerical magnitudes remain. These equations are called
dimensionless equations.
A dimensionally homogeneous equation can be used as it stands with
any set of units provided that the same units for the five base units are used
throughout. Units meeting this requirement are called consistent units. No conver-
sion factors are needed when consistent units are used.
For example, consider the usual equation for the vertical distance Z traversed
by a freely falling body during time t when the initial velocity is U o:
(1.39)
Examination of Eq. (1.39) shows that the units in each term reduce to that for
length. Dividing the equation by Z gives
uot gt 2
1= - +- (1.40)
Z 2Z
A check of each term in Eq. (1.40) shows that the units in each term cancel and
each term is dimensionless. A combination of variables for which all dimensions
cancel in this manner is called a dimensionless group. The numerical value of a
dimensionless group for given values of the quantities contained in it is in-
dependent of the units used, provided they are consistent. Both terms on the
right-hand side of Eq. (1.40) are dimensionless groups.
DIMENSIONAL EQUATIONS. Equations derived by empirical methods, in which
experimental results are correlated by empirical equations without regard to
dimensional consistency, usually are not dimensionally homogeneous and contain
terms in several different units. Equations of this type are dimensional equations,
or dimensionally nonhomogeneous equations. In these equations there is no
advantage in using consistent units, and two or more length units, e.g., inches and
feet, or two or more time units, e.g., seconds and minutes, may appear in the same
equation. For example, a formula for the rate of heat loss from a horizontal pipe
to the atmosphere by conduction and convection is
q /:;.T1.25
-
A = 0 5 0--
. (D;)O.25 (141)
.
where q = rate of heat loss, Btu/h
A = area of pipe surface, ft 2
/:;. T = excess of temperature of pipe wall over that of ambient
(surrounding atmosphere), OF
D~ = outside diameter of pipe, in.
Obviously, the units of q/A are not those of the right-hand side of Eq.
(1.41), and the equation is dimensional. Quantities substituted in Eq. (1.41)
must be expressed in the units as given, or the equation will give the wrong
10 INTRODUCTION
answer. If other units are to be nsed, the coefficient must be changed. To
express !l T in degrees Celsius, for example, the numerical coefficient must
be changed to 0.50 x 1.81.25 = 1.042 since there are 1.8 Fahrenheit degrees in 1
Celsius degree of temperature difference.
Iu this book all equations are dimensionally homogeneous unless otherwise
noted.
DIMENSIONAL ANALYSIS
Many important engineering problems cannot be solved completely by theoretical
or mathematical methods. Problems of this type are especially common in
fluid-flow, heat-flow, and diffusional operations. One method of attacking a
problem for which no mathematical equation can be derived is that of empirical
experimentation. For example, the pressure loss from friction in a long, round,
straight, smooth pipe depends on all these variables: the length and diameter of
the pipe, the flow rate of the liquid, and the density and viscosity of the liquid. If
anyone of these variables is changed, the pressure drop also changes. The empirical
method of obtaining an equation relating these factors to pressure drop requires
that the effect of each separate variable be determined in turn by systematically
varying that variable while keeping all others constant. The procedure is laborious,
and it is difficult to organize or correlate the results so obtained into a useful
relationship for calculations.
There exists a method intermediate between formal mathematical develop-
ment and a completely empirical study. 2 It is based on the fact that if a theoretical
equation does exist among the variables affecting a physical process, that equation
must be dimensionally homogeneous. Because of this requirement, it is possible
to group many factors into a smaller number of dimensionless groups of variables.
The groups themselves rather than the separate factors appear in the final
equation.
This method is called dimensional analysis, which is an algebraic treatment
of the symbols for units considered independently of magnitude. It drastically
simplifies the task of fitting experimental data to design equations; it is also useful
in checking the consistency of the units in equations, in converting units, and in
the scaleup of data obtained in model test units to predict the performance of
full-scale equipment.
A dimensional analysis cannot be made unless enough is known about
the physics of the situation to decide what variables are important in the
problem and what physical laws would be involved in a mathematical solution if
one were possible. Sometimes this condition is fairly easily met: the fundamental
differential equations of fluid flow, for example, combined with the laws of heat
conduction and diffusion, suffice to establish the dimensions and dimensionless
groups appropriate to a large number of chemical engineering problems. Dimen-
sional analysis, however, does not yield a numerical equation, and experiment is
needed to complete the solution to the problem.
DEFINITIONS AND PIUNClPL~~ .ll
Important principles in testing the dimensional consistency of an equation
are as follows:
1. The sums of the exponents relating to any given dimension (length, for
example) must be the same on both sides of the equation.
2. An exponent must itself be dimensionless-a pure number.
3. All the factors in the equation must be collectible into a set of dimensionless
groups. The groups themselves may carry exponents of any magnitude, not
necessarily whole numbers.
It is these exponents, and any numerical coefficients in the equation, that
are determined by experiment.
Example 1.2. Check the dimensional consistency of the following empirical equation
for a heat-transfer coefficient (see Chap. 12):
hi = O.023Go.8ko.67C~·33D-o.2Jl-O.47 (1.42)
where hi = heat transfer coefficient
G = mass velocity
le = thermal conductivity
cp = specific heat
D = diameter
Jl = absolute viscosity
Solution
The dimensions of the quantIties needed are designated as follows: length L;
mass M; time I; temperature T; and heat, energy, or work H. Let the phrase the
dimensions of be shown by the use of square brackets. Thus, since the dimension of
a diameter is length,
[D] = f,
Typical units of the other quantities in Eq. (1.42) are given in Chap. 12. The
corresponding dimensions, which are independent of the units chosen, are
Eh,] = Ht- 1 L- 2 1'- 1
[G] = 1i1f- 1L-2
[k] = Hf-1f,-l1'- 1
[c p ] = H1i1- 11'- 1
[Il] = 1i1L- 1i- l
Substituting these in Eq. (1.42) gives
Hi-1 L- 21'- 1 = (1i1i-1L-2)O"(Hi-1 L- 11'- 1)o.67(H1i1- 11'- 1)o·"L-o.2
X(1i1f,- l i- 1)-O.47
= Mo.aI-o.s L-1.6H-o.67I-o.67 L-o.67f-o.67 Ho.33
X M-o.33'T-o.33 £-0.2 M-o.47 !J.47Io.47 (1.43)
18 INTRODUCTION
Summing the exponents on the right-hand side of Eq. (1.43) gives
For fi: 0.67 + 0.33 =1
For t: -0.8 - 0.67 + q.47 = -I
For L: -1.6 - 0.67 - 0.2 + 0.47 = -2
ForT -0.67 - 0.33 = -I
ForM: 0.8 - 0.33 - 0.47 =0
These sums equal the exponents on the left-hand side; thus Eq. (1.42)
is dimensionally homogeneous. [Equation (1.42) is given in dimensionless form on
p. 341, Eq. (12.30).] ,
NAMED DIMENSIONLESS GROUPS. Some dimension less groups occur with
such frequency that they have been given names and special symbols. A list of the
most important ones is given in Appendix 4.
BASIC CONCEPTS
Underlying the unit operations of chemical engineering are a small number
of basic concepts, including the equations of state of gases, material balances,
and energy balances. These topics are treated extensively in introductory courses
in chemistry and chemical engineering, and because of this they are discussed only
briefly here. Illustrative problems, and answers, are included at the end of this
chapter for anyone who wishes practice in applying these concepts.
Equations of State of Gases
A pure gas consisting of n mol and held at a temperature T and pressure p
will fill a volume V. If any of the three quantities are fixed, the fourth also
is determined and only three of these quantities are independent. This can
be expressed by the functional equation
J(P, T, V, n) = 0 (1.44)
Specific forms of this relation are called equations oJ state. Many such equations
have been proposed, and several are in common use. The most satisfactory
equations of state can be written in the form
pV BeD
--=1+-+--+--+'" (1.45)
nRT V/n (V/n)2 (V/n),
This equation, known as the virial equation, is well substantiated by molecular gas
theory. Coefficients B, C, and D are called the second, third, and fourth virial
coefficients, respectively. Each is a function of temperature and is independent of
pressure. Additional coefficients may be added, but numerical values for coeffi-
cients beyond D are so little known that more than three are seldom used. The
DEFINITION:) ANU PKINLlPL~:'> J..7
virial equation also applies to mixtures of gases. Then the virial coefficients depend
on temperature and composition of the mixture. Rules are available for estimating
the values of B, C, and D for mixtures from those of the individual pure gases'
COMPRESSIBILITY FACTOR AND MOLAR DENSITY. For engineering purposes,
Eq. (1.45) often is written
z = _P- = 1 + PMB + pi,c + pK,D . (1.46)
PMRT
where z is the compressibility factor and PM the molar density, defined by
n
PM=- (1.47)
V
IDEAL-GAS LAW. Real gases under high pressure require the use of all three
virials for accuracy in calculating z from PM and T. As the density is reduced by
lowering the pressure, the numerical values of the virial terms fade out although
the values of the coefficients remain unchanged. As the effect of D beccmes
negligible, the series is truncated by dropping its term, then the term in C, and so
on, until at low pressures (about 1 or 2 atm for ordinary gases), all three virials
can be neglected. The result is the simple gas law
pV P
Z=--=--= 1 (1.48)
nRT PMRT
This equation clearly is consistent with Eq. (1.11), which contains the definition
of the absolute temperature. The limiting process indicated in Eq. (1.11) rigorously
eliminates the virial coefficients to provide a precise definition; Eq. (1.48) covers
a useful range of densities for practical calculations and is called the ideal-gas law.
PARTIAL PRESSURES. A useful quantity for dealing with the individual compo-
nents in a gas mixture is partial pressure. The partial pressure of a component in
a mixture, e.g., component A, is defined by the equation
PA '" PYA (1.49)
where PA = partial pressure of component A in mixture
YA = mole fraction of component A in mixture
P = total pressure on mixture
If all the partial pressures for a given mixture are added, the result is
PA + Pn + Pe + ... = P(y" + Yn + Ye + ...)
Since the sum of the mole fractions is unity,
PA+Pn+Pe+"'=P (1.50)
20 INTRODUCfION
All partial pressures in a given mixture add to the total pressure. This applies to
mixtures of both ideal and nonideal gases.
MATERIAL BALANCES. The law of conservation of matter states that matter
cannot be created or destroyed. This leads to the concept of mass, and the law
may be stated in the form that the mass of the materials taking part in any process
is constant. It is known now that the law is too restricted for r.latter moving at
velocities near that of light or for substances undergoing nuclear reactions. Under
these circumstances energy and mass are interconvertible, and the sum of the two
is constant, rather than only one. In most engineering, however, this transforma-
tion is too small to be detected, and in this book it is assumed that mass and
energy are independent.
Conservation of mass requires that the materials entering any process must
either accumulate or leave the process. There can be neither loss nor gain. Most
of the processes considered in this book involve neither accumulation nor
depletion, and the law of conservation of matter takes the simple form that input
equals output. The law is often applied in the form of material balances. The
process is debited with everything that enters it and is credited with everything
that leaves it. The sum of the credits must equal the sum of the debits. Material
balances must hold over the entire process or equipment and over any part of it.
They must apply to all the material that enters and leaves the process and to any
single material that passes through the process unchanged.
ENERGY BALANCES. An energy balance may be made for a process, or part of
a process, that is separated from the surroundings by an imaginary boundary. As
in a mass balance, input across the boundary must equal output plus any
accumulation; if conditions are steady and unvarying with time, input equals
output.
All forms of energy must be included in an energy balance. In most flow
processes some forms, however, such as magnetic, surface, and mechanical-stress
energies, do not change and need not be considered. The most important forms
are kinetic energy, potential energy, enthalpy, heat, and work; in electrochemical
processes electric energy must be added to the list.
SYMBOLS
In general, quantities are given in SI, cgs, and fps units; quantities given only in
either cgs or fps systems are limited to that system; quantities used in only one
equation are identified by the number of the equation.
A Area of heating surface, ft2 [Eq. (1.41)J
B Second virial coefficient, equation of state, m 3 /kg mol, cm 3 /g mol, or
ft 3f1b mol
C Third virial coefficient, equation of state, m 6 /(kg mol)2, cm 6 /(g mol)', or
ft 6 (lb mol)2
cp Specific heat, J/g_OC or Btujlb-oF
D Diameter, m or ft; also fourth virial coefficient, equation of state,
m9/(kg mol)', cm 9/(g mol)', or ft9/(lb mol)'
D; Outside diameter of pipe, in. [Eq. (1.41)]
F Force, N, dyn, or lb f
f Function of
G Mass velocity, kgfs-m 2 or Ib/h-ft 2; also gravitational constant, N_m 2jkg2,
dyn_cm 2/g 2, or ft-1b r ft 2jlb 2
g Acceleration of free fall, m/s2, cm/s 2, or ft/S2; g.. standard value, 9.80665'
m/s2, 980.665 cm/s 2, 32.1740 ft/S2
g, Proportionality factor, l/k, in Eq. (1.35), 32.1740 ft-Ibjlb rs2
El Dimension of heat, energy, or work
h, Heat transfer coefficient, W/m2_0C or Btu/h-ft'-oF
J Mechanical equivalent of heat, 4.1868 J/cal'T' 778.17 ft-Ibf/Btu
k Thermal conductivity, W/m-oC or Btu/h-ft-OF; also proportionality factor,
k, in Eq. (1.1); k2 in Eq. (1.2); k, in Eq. (1.3); k. in Eq. (1.4)
[, Dimension of length
M Molecular weight
M Dimension of mass
m Mass, kg, g, or lb; m" mb, masses of particles [Eq. (1.2)]
n Number of moles
P Total pressure on mixture
p Pressure, Pa, dyn/cm2, or Ibf /ft2; PA' partial pressure of component A;
P., partial pressure of component B; Pc, partial pressure of component C
Q Quantity of heat, J, cal, or Btu; Q" heat absorbed by system during cycle
q Rate of heat transfer, Btu/h [Eq. (1.41)]
R Gas-law constant, 8.31447 x 10' J/K-kg mol, 8.31447 x 107 ergs/K-g
mol, or 1.98588 Btu;oR-1b mol
r Distance between two mass points In, and Inb [Eq. (1.2)]
T Temperature, K, QC, OR, or OF; thermodynamic absolute temperature
[Eq. (1.11)]
f Dimension of temperature
t Time, s; t, dimension of time
u Linear velocity, m/s, cm/s, or ft/s; uo, initial velocity of falling body
V Volume, m 3 , cm 3 , or ft3
W Work, J, ergs, or ft-Ib f ; w.:, work delivered by system during cycle
y Mole fraction in gas mixture; YA. mole fraction of component A; YB, mole
fraction of component B; yc, mole fraction of component C
Z Height above datum plane, m, cm, or ft
z Compressibility factor, dimensionless
Greek letters
t.T Temperature difference, OF [Eq. (1.41)]
J1 Absolute viscosity, kg/m-s or lb/ft-s
PM Molar density, kg mol/m', g mol/cm', or lb mol/ft'
PROBLEMS
1.1. Using defined constants and conversion factors for mass, length, time, and tem-
perature, calculate. conversion factors for (a) foot-pounds force to kilowatt-hours,
(b) gallons (I gal ~ 231 in. 3) to liters (10 3 cm 3), (c) Btu per pound mole to joules per
kilogram mole.
Answers: See Appendix 3.
1.2. The Beattie-Bridgman equation, a famous equation of state for real gases, may be
written
(1.51)
where a, A o• b, B o• and c are experimental constants, and v is the molar volume, Ilg
mol. (a) Show that this equation can be put into the form of Eq. (1.46) and derive
equations for the virial coefficients B, C, and D in terms of the constants in Eq. (1.51).
(b) For air the constants are a ~ 0.01931, Ao ~ 1.3012, b ~ -0.01101, Bo ~ 0.04611,
and c x 10- 4 = 66.00, all in egs units (atmos~heres, liters, gram moles, kelvins, with
R ~ 0.08206). Calculate values of the virial coefficients for air in SI units. (c) Calculate
z for air at a temperature of 300 K and a molar volume of 0.200 m 3 /kg mol.
1.3. A mixture of 25 percent ammonia gas and 75 percent air (dry basis) is passed upward
through a vertical scrubbing tower, to the top of which water is pumped. Scrubbed
gas containing 0.5 percent ammonia leaves the top of the tower, and an aqueous
solution containing 10 percent ammonia by weight i.::aves the bottom. Both entering
and leaving gas streams are saturated with water vapor. The gas enters the tower at
37.8°C and leaves at 21.1°C. The pressure of both streams and throughout the tower
is 1.02 atm gauge. The air-ammonia mixture enters the tower at a rate of 28.32 m3/min,
measured as dry gas at 15.6°C and 1 atm. What percentage of the ammonia entering
the tower is not absorbed by the water? How many cubic meters of water per hour
are pumped to the top of the tower?
Answers: 1.5%; 2.71 m'/h
1.4. Dry gas containing 75 percent air and 25 percent ammonia vapor enters the bottom
of a cylindrical packed absorption tower that is 2 ft in diameter. Nozzles in the top of
the tower distribute water over the packing. A solution of ammonia in water is drawn
from the bottom of the column, and scrubbed gas leaves the top. The gas enters at
80°F and 760 mm Hg pressure. It leaves at 60°F and 730 mm. The leaving gas contains,
on the dry basis, 1.0 percent ammonia. (a) If the entering gas flows through the empty
bottom of the column at an average velocity (upward) of 1.5 ft/s, how many cubic feet
of entering gas are treated per hour? (b) How many pounds of ammonia are absorbed
per hour?
Allswers: (a) 16,965 ft3fh; (b) 177lb
1.5. An evaporator is fed continuously with 25 t (metric tons)/h of a solution consisting of
10 percent NaOH, 10 percent NaCI, and 80 percent H 2 0. During evaporation, water
is boiled off, and salt precipitates as crystals, which are settled and removed from the
remaining liquor. The concentrated liquor leaving the evaporator contains 50 percent
NaOH, 2 percent NaCI, and 48 percent H,O.
Calculate (a) the kilograms of water evaporated per hour, (b) the kilograms of
salt precipitated per hour, and (c) the kilograms of concentrated liquor produced per
hour.
Answers: (a) 17,600 kg/h; (b) 2400 kgfh; (c) 5000 kgfh
1.6. Air is flowing steadily through a horizontal heated tube. The air enters at 40°F and
at a velocity of 50 ft/so It leaves the tube at 140°F and 75 ft/so The average specific heat
of air is 0.24 Btu/lb-oF. How many Btu per pound of air are transferred through the
wall of the tube?
Answer: 24.1 Btu/lb
REFERENCES
1. Austin, G. T.; Shreve's Chemical Process Industries, 5th ed., McGraw-HiIl, New York, 1984.
2. Bridgman, P. W.: Dimensional Analysis, AMS Press, New York, 1978.
3. CRC Handbook of Chemistry and Physics, 69th cd., CRC Press, Boca Raton, Fla., 1988, p. F-191.
4. Halladay, D., and R. Resnick: Fundamentals of Physics, 3rd ed., Wiley, New York, 1988, p. 4.
5. Moldover, M. R., et al.: J. Res. Natl. Bur. Stand., 93{2):85 (1988).
6. Natl. Bur. Stand. Tech News Bull., 55:3 (March 1971).
7. National Research Council: Frontiers in Chemical Engineering, National Academy Press,
Washington, D.C., 1988.
8. Prausnitz, l. M., R. N. Lichtenthaler, and E. G. de Azevedo: Molecular Theory of Fluid-Phase
Equilibria, Prentice-Hall, Englewood Cliffs, N.l., 1986.
SECTION
11
FLUID
MECHANICS
T he behavior of fluids is important to process engineering generally and
constitutes one of the foundations for the study of the unit operations. An
understanding of fluids is essential, not only for accurately treating problems on
the movement of fluids through pipes, pumps, and all kinds of process equipment
but also for the study of heat flow and the many separation operations that depend
on diffusion and mass transfer.
The branch of engineering science that has to do with the behavior of
fluids-and fluids are understood to include liquids, gases, and vapors-is called
fluid mechanics. Fluid mechanics in turn is part of a larger discipline called
continuum mechanics, which also includes the study of stressed solids.
Fluid mechanics has two branches important to the study of unit operations:
fluid statics, which treats fluids in the equilibrium state of no shear stress, and fluid
dynamics, which treats fluids when portions of the fluid are in motion relative to
other parts.
The chapters of this section deal with those areas of fluid mechanics that
are important to unit operations. The choice of subject matter is but a sampling
of the huge field of fluid mechanics generally. Chapter 2 treats fluid statics and
some of its important applications. Chapter 3 discusses the important phenomena
,/ou tLUIU Mt:.LHANlL:"l
appearing in flowing fluids. Chapter 4 deals with the basic quantitative laws and
equations of fluid flow. Chapter 5 treats flow of incompressible fluids through
pipes and in thin layers, Chap. 6 is on compressible fluids in flow, and Chap. 7
describes flow past solids immersed in the flowing fluid. Chapter 8 deals with the
important engineering tasks of moving fluids through process equipment and of
measuring and controlling fluids in flow. Finally, Chap. 9 covers mixing, agitation,
and dispersion operations, which in essence are applied fluid mechanics.
CHAPTER
2
FLUID
STATICS
AND ITS
APPLICATIONS
NATURE OF FLUIDS. A fluid is a substance that does not permanently resist
distortion. An attempt to change the shape of a mass of fluid results in layers of
fluid sliding over one another until a new shape is attained. During the change
in shape, shear stresses exist, the magnitudes of which depend upon the viscosity
of the fluid and the rate of sliding, but when a final shape has been reached, all
shear stresses will have disappeared. A fluid in equilibrium is free from shear
stresses.
At a given temperature and pressure, a fluid possesses a definite density,
which in engineering practice is usually measured in kilograms per cubic meter
or pounds per cubic foot. Although the density of all fluids depends on the
temperature and pressure, the variation in density with changes in these variables
may be small or large. If the density changes only slightly with moderate changes
in temperature and pressure, the fluid is said to be incompressible; if the changes
in density are significant, the fluid is said to be compressible. Liquids are generally
considered to be incompressible and gases compressible. The terms are relative,
however, and the density of a liquid can change appreciably if pressure and
temperature are changed over wide limits. Also, gases subjected to small percentage
changes in pressure and temperature act as incompressible fluids, and density
changes under such conditions may be neglected without serious error.
27
PRESSURE CONCEPT. The basic property of a static fluid is pressure. Pressure
is familiar as a surface force exerted by a fluid against the walls of its container.
Pressure also exists at every point within a volume of fluid. A fundamental question
is: What kind of quantity is pressure? Is pressure independent of direction, or does
it vary with direction? For a static fluid, as shown by the following analysis,
pressure turns out to be independent of the orientation of any internal surface on
which the pressure is assumed to act.
Choose any point 0 in a mass of static fluid and, as shown in Fig. 2.1,
construct a cartesian system of coordinate axes with 0 as the origin. The x and
y axes are in the horizontal plane, and the z axis points vertically upward.
Construct a plane ABC cutting the x, y, and z axes at distances from the origin
of flx, fly, and flz, respectively. Planes ABC, AOC, COB, and AOB form a
tetrahedron. Let e be the angle between planes ABC and COB. This angle is less
than 90° but otherwise is chosen at random. Imagine that the tetrahedron is
isolated as a free body and consider all forces acting on it in the direction of the
z axis, either from outside the fluid or from the surrounding fluid. Three forces
I
Llzl
I
I
I
~t;:{~-----------~ - -:..;-~,-----;~
/.,8 B y
.6:.- /'
/"
I "
/
/"
FIGURE 2.1
Forces on static element of fluid,
are involved: (1) the force of gravity acting downward, (2) the pressure force on
plane COB acting upward, and (3) the vertical component of the pressure force
on plane ABC acting downward. Since the fluid is in eqnilibrium, the resultant of
these forces is zero. Also, since a flnid in equilibrium cannot snpport shear stresses,
all pressure forces are normal to the surface on which they act. Otherwise there
would be shear-force components parallel to the faces.
The area of face COB is /:J.x /:J.y/2. Let the average pressure on this face be
p,. Then the upward force on the face is p, /:J.x /:J.y/2. Let p be the average pressure
on face ABC. The area of this face is /:J.x /:J.y/(2 cos e), and the total force on the
face is p /:J.x /:J.y (2 cos e). The angle between the force vector of pressure p with
the z axis is also e, so the vertical component of this force acting downward is
P/:J.x/:J.ycose p/:J.x/:J.y
2 cos e 2
The volume of the tetrahedron is /:J.x /:J.y /:J.z/6. If the fluid density is p, the
force of gravity acting on the fluid in the tetrahedron is p /:J.x /:J.y t.z g/6g,. This
component acts downward. The force balance in the z direction becomes
p,/:J.x/:J.y p/:J.x /:J.y
2 2
Dividing by /:J.x t.y gives
p, _ E_ p /:J.z 9 = 0 (2.1)
2 2 6g,
Now, keeping angle e constant, let plane ABC move toward the origin o. As
the distance between ABC and 0 approaches zero as a limit, /:J.z approaches zero
also and the gravity term vanishes. Also, the average pressures p and p, approach
p and p" the local pressures at point 0, and Eq. (2.1) shows that p, becomes equal
to p.
Force balances parallel to the x and y axes can also be written. Each gives
an equation like Eq. (2.1) but containing no gravity term, and in the limit
px = py = p, = p
Since both point 0 and angle e were chosen at random, the pressure at any
point is independent of direction.
Fine powdery solids resemble fluids in many respects but differ considerably
in others. For one thing, a static mass of particulate solids, as shown in Chap. 28,
can support shear stresses of considerable magnitude and the pressure is /lot the
same in all directions.
HYDROSTATIC EQUILIBRIUM. In a stationary mass of a single static fluid, the
pressure is constant in any cross section parallel to the earth's surface but varies
from height to height. Consider the vertical column of fluid shown in Fig. 2.2.
Assume the cross-sectional area of the column is S. At a height Z above the base
I
I
I
r
.J-- 7'
.------
[
[
[
[
[
[
[
~PresSlJre =(p+dp)
[
z.
(] I
/::l::- --j -±dZ
! i PresstJre=p
l:~ 1t
/j
Density = jJ
t
Zbv. 1- -./ ><"'Ar.eo = S
FIGURE 2.2
Hydrostatic equilibrium.
of the column let the pressure be p and the density be p. As in the preceding
analysis, the resultant of all forces on the small volume of fluid of height dZ and
cross-sectional area S must be zero. Three vertical forces are acting on this volume:
(1) the force from pressure p acting in an upward direction, which is pS; (2) the
force from pressure p + dp acting in a downward direction, which is (p + dp)S; (3)
the force of gravity acting downward, which is (g/gJpS/dZ. Then
+ pS - (p + dp)S - -"-- pS dZ = 0 (2.2)
g,
In this equation, forces acting upward are taken as positive and those acting
downward as negative. After simplification and division by S, Eq. (2.2) becomes
9
dp +-pdZ= 0 (2.3)
g,
Equation (2.3) cannot be integrated for compressible fluids unless the variation
of density with pressure is known throughout the column of fluid. However, it is
often satisfactory for engineering calculations to consider p to be essentially
constant. The density is constant for incompressible fluids and, except for large
changes in height, is nearly so for compressible fluids. Integration of Eq. (2.3) on
the assumption that p is constant gives
-p + -Z
9
= const (2.4)
p g,
or, between the two definite heights Z, and Zb shown in Fig. 2.2,
l!!> _ ~ = i (Z, - Zb) (2.5)
ppg,
Equation (2.4) expresses mathematically the condition of hydrostatic equi-
librium.
BAROMETRIC EQUATION. For an ideal gas the density and pressure are related
by the equation
pM
P = RT (2.6)
where M = molecular weight
T = absolute temperature
Substitution from Eq. (2.6) into Eq. (2.3) gives
dp gM
-+--dZ=O (2.7)
P g,RT
Integration of Eq. (2.7) between levels a and b, on the assumption that T is
constant, gives
Ph gM
In- = ---(Zb - Z,)
p, g,RT
or
Pb = exp [_ gM(Zb - Z,)] (2.8)
p, g,RT
Equation (2.8) is known as the barometric equatioll.
Methods are available in the literature' for estimating the pressure distribu-
tion in situations, for example, a deep gas well, in which the gas is not ideal and
the temperature is not constant.
As stated on page 14, these equations are used in SI units by setting g, = 1.
HYDROSTATIC EQUILIBRIUM IN A CENTRIFUGAL FIELD. In a rotating cen-
trifuge a layer of liquid is thrown outward from the axis of rotation and is held
against the wall of the bowl by centrifugal force. The free surface of the liquid
takes the shape of a paraboloid of revolution, 2 but in industrial centrifuges the
rotational speed is so high and the centrifugal force so much greater than the force
of gravity that the liquid surface is virtually cylindrical and coaxial with the axis
of rotation. This situation is illustrated in Fig. 2.3, in which r 1 is the ~~dial distance
from the axis of rotation to the free liquid surface and r2 is the "radius of the
centrifuge bowl. The entire mass of liquid indicated in Fig. 2.3 is rotating like a
rigid body, with no sliding of one layer of liquid over another. Under these
conditions the pressure distribution in the liquid may be found from the principles
of fluid statics.
FIGURE 23
Single liquid in centrifuge bowl.
The pressure drop over any ring of rotating liquid is calculated as follows.
Consider the ring of liquid shown in Fig. 2.3 and the volume element of thickness
dr at a radius r:
2
dF= w rdm
g,
where dF = centrifugal force
dm = mass of liquid in element
w = angular velocity, rad/s
If p is the density of the liquid and b the breadth of the ring,
dm = 21Cprb dr
Eliminating dm gives
21Cpbw 2,.2 dr
dF
g,
The change in pressure over the element is the force exerted by the element of
liquid divided by the area of the ring:
2
dp= dF = w prdr
21Crb g,
The pressure drop over the entire ring is
"
I
w2pr dr
P2 - Pt =
1'[ gc
Assuming the density is constant and integrating gives
w 2 p(d - ri}
P2 - Pt (2.9)
MANOMETERS. The manometer is an important device for measuring pressure
differences. Figure 2.4 shows the simplest form of manometer. Assume that the
shaded portion of the U tube is filled with liquid A having a density PA and that
the arms of the U tube above the liquid are filled with fluid B having a density
PB' Fluid B is immiscible with liquid A and less dense than A; it is often a gas
such as air or nitrogen.
A pressure Pa is exerted in one arm of the U tube and a pressure Pb in the
other. As a result of the difference in pressure Pa - Pb, the meniscus in one branch
of the U tube is higher than in the other, and the vertical distance between the
two meniscuses Rm may be used to measure the difference in pressure. To derive
a relationship between Pa - Pb and Rm, start at the point 1, where the pressure is Pa;
then, as shown by Eq. (2.4), the pressure at point 2 is Pa + (g!g,)(Zm + Rm)PB' By the
principles of hydrostatics, this is also the pressure at point 3. The pressure at point
4 is less than that at point 3 by the amount (g!g,)RmPA' and the pressure at point
5, which is Pb, is still less by the amount (g!g,)ZmPB' These statements can be
summarized by the equation
Simplification of this equation gives
(2.10)
Note that this relationship is independent of the distance Zm and of the dimensions
of the tube provided that pressures Pa and Pb are measured in the same horizontal
plane. If fluid B is a gas, PB is usually negligible compared to PA and may be
omitted from Eq. (2.10).
pressure! I Pressure
Po }Pb
-T- 5
r-
Fluid B
DensitY!l8
4
Rm
2 _-.l_ 3
Fluid A
Density f'A
FIGURE 2.4
Simple manometer.
Pressure Pressure
Pa Pb
f t
FIGURE 2.5
" Inclined manometer.
Example 2.1. A manometer of the type shown in Fig. 2.4 is used to measure the
pressure drop across an orifice (see Fig. 8.19). Liquid A is mercury (density
13,590 kg/m') and fluid E, flowing through the orifice and filling the manometer
leads, is brine (density 1260 kg/m'). When the pressures at the taps are equal, the
level of the mercury in the manometer is 0.9 m below the orifice taps. Under operating
conditions, the gauge pressuret at the upstream tap is 0.14 bar; the pressure at the
downstream tap is 250 mm Hg below atmospheric. What is the reading of the
manometer in mi11imeters?
Solution
Call atmospheric pressure zero and note that gc = 1; then the numerical data for
substitution in Eq. (2.10) are
P. ~ 0.14 X 10' ~ 14,000 Pa
From Eq. (2.5)
Pb ~ 2,(g/g,)
~ -250/1000 x (9.80665/1) x 13,590
~ -33,318 Pa
Substituting in Eq. (2.10) gives
14,000 + 33,318 ~ Rm x 9.80665 x (13,590 - 1260)
Rm ~ 0.391 m or 391 mm
For measuring small differences in pressure, the inclined nzanometer shown
in Fig. 2.5 may be used. In this type, one leg of the manometer is inclined in such
a manner that, for a small magnitude of Rm, the meniscus in the inclined tube
must move a considerable distance along the tube. This distance is Rm divided by
the sine of a, the angle of inclination. By making a small, the magnitude of Rm is
multiplied into a long distance R" and a large reading becomes equivalent to a
l' Gauge pressure is pressure measured above the prevailing atmospheric pressure.
small pressure difference; so
(2.11)
In this type of pressure gauge, it is necessary to provide an enlargement in the
vertical leg so that the movement of the meniscus in the enlargement is negligible
within the operating range of the instrument.
CONTINUOUS GRAVITY DECANTER. A gravity decanter of the type shown in
Fig. 2.6 is used for the continuous separation of two immiscible liquids of differing
densities. The feed mixture enters at one end of the separator; the two liquids flow
slowly through the vessel, separate into two layers, and discharge through overflow
lines at the other end of the separator.
Provided the overflow lines are so large that frictional resistance to the flow
of the liquids is negligible, and provided they discharge at the same pressure as
that in the gas space above the liquid in the vessel, the performance of the decanter
can be analyzed by the principles of fluid statics.
For example, in the decanter shown in Fig. 2.6 let the density of the heavy
liquid be PA and that of the light liquid be P•. The depth of the layer of heavy
liquid is ZAl and that of the light liquid is Z •. The total depth of liquid in the
vessel ZT is fixed by the position of the overflow line for the light liquid. Heavy
liquid discharges through an overflow leg connected to the bottom of the vessel
and rising to a height Z A2 above the vessel floor. The overflow lines and the top
of the vessel are all vented to the atmosphere.
Heavy - liquid outlet
ci<~r
Feed
c: TOPVIEW
[----light - Uqu;d outl"
Vent
Light Heavy
SIDE VIEW liquid liquid
FIGURE 2.6
Continuous gravity decanter for immiscible liquids.
Since there is negligible frictional resistance to flow in the discharge lines,
the column of heavy liquid in the heavy-liquid overflow leg must balance the
somewhat greater depth of the two liquids in the vessel. A hydrostatic balance
leads to the equation
Z.P. + ZA1PA = ZAZPA (2.12)
Solving Eq. (2.12) for ZAl gives
ZAl = ZA2 - Z. -P. = ZAZ - (Z T - ZA1) -P. (2.13)
PA PA
where the total depth of liquid in the vessel is ZT = Z. + ZA1' From this
ZAl = ZAZ - ZT(P./PA) (2.14)
1 - P./PA
Equation (2.14) shows that the position of the liquid-liquid interface in the
separator depends on the ratio of the densities of the two liquids and on the
elevations of the overflow lines. It is independent of the rates of flow of the liquids.
Equation (2.14) shows that as PA approaches PD' the position of the interface
becomes very sensitive to changes in Z AZ, the height of the heavy-liquid leg. With
liquids that differ widely in density this height is not critical, but with liquids of
nearly the same density it must be set with care. Often the top of the leg is made
movable so that in service it can be adjusted to give the best separation.
The size of a decanter is established by the time required for separation,
which in turn depends on the difference between the densities of the two liquids
and on the viscosity of the continuous phase. Provided the liquids are clean and
do not form emulsions, the separation time may be estimated from the empirical
equation 1
1001'
t= (2.15)
PA - P.
where t = separation time, h
PA, P. = densities of liquids A and B, kg/m'
I' = viscosity of the continuous phase, cP
Equation (2.15) is not dimensionless, and the indicated units must be used.
Example 2.2. A horizontal cylindrical continuous decanter is to separate 1500 bbljd
(day) (9.93 m'/h) of a liquid petroleum fraction from an equal volume of wash acid.
The oil is the continuous phase and at the operating temperature has a viscosity
of l.l cP and a density of 54lb/ft' (865 kg/m'). The density of the acid is 72 lb/ft'
(1153 kg/m'). Compute (a) the size of the vessel, and (b) the height of the acid overflow
above the vessel floor.
Solution
(a) The vessel size is found from the separation time. Substitution in Eq. (2.15) gives
100 x l.l = 0.38 h
1153 - 865
FLUID STATICS AND IT!) APPLlt.:A"IIUN!) JI
or 23 min. Since 1 bbl = 42 gal, the rate of flow of each stream is
1500 x 42
- - - = 43.S gal/m in
24 x 60
The total liquid holdup is
2 x 43.S x 23 = 2014 gal
The vessel should be about 95 percent full, so its volume is 2014/0.95, or 2120,
gal (S.03 m').
The length of the tank should be about 5 times its diameter. A tank 4 ft (1.22 m)
in diameter and 22 ft (6.10 m) long would be satisfactory; with standard dished heads
on the ends, its total volume would be 2124 gal.
(b) The fraction of the tank volume occupied by the liquid will be 95 percent,
and for a horizontal cylinder this means that the liquid depth will be 90 percent of
the tank diameter. 4a Thus
Zr = 0.90 x 4 = 3.6 ft
If the interface is halfway between the vessel floor and the liquid surface, ZAl = 1.80 ft.
Solving Eq. (2.14) for ZA2, the height of the heavy-liquid overflow, gives
ZA2 = I.S0 + (3.60 - I.S0)~ = 3.15 ft (0.96 m)
Successful operation of a decanter depends on both the sedimentation and
the coalescence of the dispersed phase. Equation (2.15) gives poor results if the
liquids to be separated are not clean but contain particulates or polymeric films
that reduce the rate of coalescence. Such contaminants may also lead to the
formation of a dirty layer of uncoalesced droplets-called a "rag"-at the
liquid-liquid interface. Coalescing devices such as beds of porous solids, mem-
branes, or high-voltage fields are often necessary for a satisfactory separation 4b
With cleaner liquids the size of a decanter can often be greatly reduced by putting
in horizontal or slightly inclined pipes or flat plates, so that the heavy-phase
droplets need to fall only a short distance before reaching a layer of the heavy
liquid.
CENTRIFUGAL DECANTER. When the difference between the densities of the
two liquids is small, the force of gravity may be too weak to separate the liquids
in a reasonable time. The separation may then be accomplished in a liquid-liquid
centrifuge, shown diagrammatically in Fig. 2.7. It consists of a cylindrical metal
bowl, usually mounted vertically, that rotates about its axis at high speed. In Fig.
2.7a the bowl is at rest and contains a quantity of two immiscible liquids of differing
densities. The heavy liquid forms a layer on the floor of the bowl beneath a layer
of light liquid. If the bowl is now rotated, as in Fig. 2.7b, the heavy liquid forms
a layer, denoted as zone A in the figure, next to the inside wall of the bowl. A
layer of light liquid, denoted as zone B, forms inside the layer of heavy liquid. A
cylindrical interface of radius r, separates the two layers. Since the force of gravity
can be neglected in comparison with the much greater centrifugal force, this
interface is vertical. It is called the neutral zone.
38 FLUID MECHANICS
(a)
-"'ff"'" solIds (b)
FIGURE 2.7
Centrifugal separation, of immiscible liquids: (a) bowl at rest; (b) bowl rotating. Zone A. separation
of light liquid from heavy; zone B, separation of heavy liquid from light. (1) Heavy-liquid drawoff.
(2) Light-liquid drawoff.
In operation of the machine the feed is admitted continuously near the
bottom of the bowl. Light liquid discharges at point 2 through ports near the axis
of the bowl; heavy liquid passes under a ring, inward toward the axis of rotation,
and discharges over a dam at point 1. If there is negligible frictional resistance to
the flow of the liquids as they leave the bowl, the position of the liquid-liquid
interface is established by a hydrostatic balance and the relative "heights" (radial
distances from the axis) of the overflow ports at 1 and 2.
Assume that the heavy liquid, of density PA' overflows the dam at radius rA,
and the light liquid, of density Pa, leaves through ports at radius rB' Then if both
liquids rotate with the bowl and friction is negligible, the pressure difference in
the light liquid between ra and ri must equal that in the heavy liquid between rA
and ri' The principle is exactly the same as in a continuous gravity decanter.
Thus
Pi - Pn = Pi - PA (2.16)
where Pi = pressure at liquid-liquid interface
Pa = pressure at free surface of light liquid at ra
PA = pressure at free surface of heavy liquid at rA
From Eq. (2.9)
(j)2 Pa(r1 - r~)
Pi - PB = and
2g, 2g,
Equating these pressure drops and simplifying leads to
FLUID STATICS AND ITS APPLICATIONS 5':)
Solving for ri gives
r~ -(pBlpA)r~
(2.17)
l-PBlpA
Equation (2.17) is analogous to Eq. (2.14) for a gravity settling tauk. It shows
that ri' the radius of the neutral zone, is sensitive to the density ratio, especially
when the ratio is nearly unity. If the densities of the fluids are too nearly alike,
the neutral zone may be unstable even if the speed of rotation is sufficient to
separate the liquids quickly. The difference between PA and PB should not be less
than approximately 3 percent for stable operation.
Equation (2.17) also shows that if r. is held constant and rA' the radius of
the discharge lip for the heavier liquid, increased, the neutral zone is shifted toward
the wall of the bowl. If rA is decreased, the zone is shifted toward the axis. An
increase in rn, at constant rA' also shifts the neutral zone toward the axis, and a
decrease in rB causes a shift toward the wall. The position of the neutral zone is
important practically. In zone A, the lighter liquid is being removed from a mass
of heavier liquid, and in zone E, heavy liquid is being stripped from a mass of light
liquid. If one of the processes is more difficult than the other, more time should
be provided for the more difficult step. For example, if the separation in zone E
is more difficult than that in zone A, zone E should be large and zone A small.
This is accomplished by moving the neutral zone toward the wall by increasing
I'A or decreasing I'B' To obtain a larger time factor in zone A, the opposite
adjustments would be made. Many centrifugal separators are so constructed that
either I'A or I'D can be varied to control the position of the neutral zone.
FLOW THROUGH CONTINUOUS DECANTERS. Equations (2.14) and (2.17) for
the interfacial position in continuous decanters are based entirely on hydrostatic
balances. As long as there is negligible resistance to flow in the outlet pipes, the
position of the interface is the same regardless of the rates of flow of the liquids
and of the relative quantities of the two liquids in the feed. The rate of separation
is the most important variable, for as mentioned before, it fixes the size of a gravity
decanter and determines whether or not a high centrifugal force is needed. The
rates of motion of a dispersed phase through a continuous phase are discussed in
Chap. 7.
SYMBOLS
b Breadth, m or ft
F Force, N or lb f
g Gravitational acceleration, m/s2 or ft/s2
g, Newton's-law proportionality factor, 32.174 ft-lb/Ib r s2
M Molecular weight
III Mass, kg or lb
40 FLUID MECHANICS
P Pressure, N/m 2 or lbf/ft'; PA, at surface of heavy liquid in centrifuge; PB'
at surface of light liquid in centrifuge; Pa. at location a; Pb' at location b;
Pi, at liquid-liquid interface; Px, PY ' P:. in x, y, z directions; Pl' at free liquid
surface; P2, at wall of centrifuge bowl; p, average pressure
R Gas-law constant, 8314.47 J/kg mol-K or 1545 ft-IbfjIb mol-oR
Rm Reading of manometer, m or ft; R l , of inclined manometer
r Radial distance from axis, m or ft; rA' to heavy-liquid overflow; rn, to
light-liquid overflow; ri' to liquid-liquid interface; rI' to free-liquid surface
in centrifuge; 1'2' to wall of centrifuge bowl
S Cross-sectional area, m 2 or ft 2
T Absolute temperature, K or oR
t Separation time, h
Z Height, m or ft; ZAI' of layer of heavy liquid in decanter; ZA2' of heavy
liquid in overflow leg; ZB, of layer of light liquid in decanter; ZT, total
depth of liquid; Zoo Zb' heights at locations a and b; Zm, height of pressure
connections in manometer above measuring liquid
Greek letters
a Angle with horizontal
e Angle in tetrahedral element of fluid
J1 Viscosity of continuous phase, cP
P Density, kg/m' or lb/ft'; PA, of fluid A; PB' of fluid B
w Angular velocity, rad/s
PROBLEMS
2.1. A simple U-tube manometer is installed across an orifice meter. The manometer is
filled with mercury (specific gravity 13.6), and the liquid above the mercury is car-
bon tetrachloride (specific gravity 1.6). The manometer reads 200 mm. What is
the pressure difference over the manometer in newtons per square meter?
2.2. The temperature of the earth's atmosphere drops about 5°C for every 1000 m of
elevation above the earth's surface. If the air temperature at ground level is 15°C and the
pressure is 760 mm Hg, at what elevation is the pressure 380 mm Hg? Assume that
the air behaves as an ideal gas.
2.3. How much error would be introduced in the answer to Prob. 2.2 if the equation for
hydrostatic equilibrium [Eq. (2.5)] were used, with the density evaluated at ooe and an
arithmetic average pressure?
2.4. A continuous gravity decanter is to separate chlorobenzene, with a density of
1109 kg/m', from an aqueous wash liquid having a density of 1020 kg/m'. If the total
depth in the separator is 1 m and the interface is to be 0.6 m from the vessel fioor,
(a) what should the height of the heavy-liquid overflow leg be; (b) how much would an
error of 50 mm in this height affect the position of the interface?
2.5. What should be the volume of the separator in Prob. 2.4 to separate 1600 kgjh chlor-
obenzene from 2100 kgfh of wash liquid? The wash liquid is to be the continuous
phase; its viscosity is the same as that of water at the operating temperature of 35°C.
FLUID STATICS AND ITS APPLICATIONS 41
2.6. A centrifuge bowl 250-mm ID (internal diilmeter) is turning at 4000 r/min. It contains
a layer of chlorobenzene 50 mm thick. J£the density of the chlorobenzene is 1109 kg/m'
and the pressure at the liquid surfafce is atmospheric, what gauge pressure is exerted
on the wall of the centrifuge bO~wi?
2.7. The liquids described in Pro:o. 2.4 are to be separated in a tubular centrifuge bowl
with an inside diameter of 150 mm, rotating at 8000 r/min. The free-liquid surface
inside the bowl is 4C mm from the axis of rotatiqn. If the centrifuge bowl is to contain
equal volumeF; of the two liquids, what should be the radial distance from the rota-
tional axi; to the top of the overflow dam for heavy liquid?
REFE~ENCES
1. llarton, R. L.: Chem. Eng., 81(14):111 (1974).
2. Bird, B., W. E. Stewart, and E. N. Lightfoot: Transport Phenomena, Wiley, New York, 1959, pp.
96-98.
3. Knudsen, J. G .. and D. L. Katz: Fluid Dynamics and Heat Transfer, McGraw-HilI, New York, 1958,
pp. 69-71.
4. Perry, R. H., and D. Green (eds.): Perry's Chemical Engineers' Handbook, 6th ed., McGraw-HilI,
New York, 1984; (a) p. 6-108; (b) pp. 21-64 to 21-66.
CHAPTER
3
FLUID-FLOW
PHENOMENA
The behavior of a flowing fluid depends strongly on whether or not the fluid
is under the influence of solid boundaries. In the region where the influence of the
wall is small, the shear stress may be negligible and the fluid behavior may
approach that of an ideal fluid, one that is incompressible and has zero viscosity.
The flow of such an ideal fluid is called potential flow and is completely described
by the principles of newtonian mechanics and conservation of mass. The mathema-
tical theory of potential flow is highly developed 6 but is outside the scope of this
book. Potential flow has two important characteristics: (1) neither circulations nor
eddies can form within the stream, so that potential flow is also called irrotational
flow, and (2) friction cannot develop, so that there is no dissipation of mechanical
energy into heat.
Potential flow can exist at distances not far from a solid boundary. A
fundamental principle of fluid mechanics, originally stated by Prandtl in 1904, is
that, except for fluids moving at low velocities or possessing high viscosities, the
effect of the solid boundary on the flow is confined to a layer of the fluid
immediately adjacent to the solid wall. This layer is called the boundary layer, and
shear and shear forces are confined to this part of the fluid. Outside the boundary
layer, potential flow survives. Most technical flow processes are best studied by
considering the fluid stream as two parts, the boundary layer and the remaining
fluid. In some situations such as flow in a converging nozzle, the boundary layer
may be neglected, and in others, such as flow through pipes, the boundary layer
fills the entire channel, and there is no potential flow.
42
FLUID-FLOW PHENOMENA 4j
Within the current of an incompressible fluid under the influence of solid
boundaries, four important effects appear: (1) the coupling of velocity-gradient
and shear-stress fields, (2) the onset of turbulence, (3) the formation and growth
of boundary layers, and (4) the separation of boundary layers from contact with
the solid boundary.
In the flow of compressible fluids past solid boundaries additional effects
appear, arising from the significant density changes characteristic of compressible
fluids. These are considered in Chap. 6, on flow of compressible fluids.
THE VELOCITY FIELD. When a stream of fluid is flowing in bulk past a solid
wall, the fluid adheres to the solid at the actual interface between solid and fluid.
The adhesion is a result of the force fields at the boundary, which are also
responsible for the interfacial tension between solid and fl uid. If, therefore, the
wall is at rest in the reference frame chosen for the solid-fluid system, the velocity
of the fluid at the inte/face is zero. Since at distances away from the solid the
velocity is finite, there must be variations in velocity from point to point in the
flowing stream. Therefore, the velocity at any point is a function of the space
coordinates of that point, and a velocity field exists in the space occupied by the
fluid. The velocity at a given location may also vary with time. When the velocity
at each location is constant, the field is invariant with time and the flow is said
to be steady.
One-dimensional flow. Velocity is a vector, and in general, the velocity at a point
has three components, one for each space coordinate. In many simple situations
all velocity vectors in the field are parallel or practically so, and only one velocity
component, which may be taken as a scalar, is required. This 3itt'ation, which
obviously is much simpler than the general vector field, is called one-dimensional
flow; an pv-::mp!~ is steady flow through straight pipe. The following discussion is
based on the assumptions of steady one-dimensional flow.
LAMINAR FLOW. At low velocities fluids tend to flow without lateral mixing,
and adjacent layers slide past one another like playing cards. There are neither
cross-currents nor eddies. This regime is called laminar flow. At higher velocities
turbulence appears and eddies form, which, as discussed later, lead to lateral
mixing.
VELOCITY GRADIENT AND RATE OF bHEAR. Consider the steady one-dimen-
sional laminar flow of an incompressible fluid along a solid plane surface. Figure
3.1a shows the velocity profile for such a stream. The abscissa u is the velocity,
and the ordinate y is the distance measured perpendicular from the wall and
therefore at right angles to the direction of the velocity. At y = 0, u = 0, and u
increases with distance from the wall but at a decreasing rate. Focus attention on
the velocities on two nearby planes, plane A and plane B, a distance ,1y apart.
.... rLUIU MhCHANICS
'"
...i Ye
..J
Plane 2
''""
:2
0
0:
Ye
Plane2
CL Y
Plane2
w ~
u
z
i'-'
if)
0
0 0
0 LOCAL FLUID VELOCITY. u 0 du/dy
(a) (b)
FIGURE 3.1
Profiles of velocity and velocity gradient in layer flow: (a) velocity; (b) velocity gradient or rate of shear.
Let the velocities along the planes be UA and "B. respectively, and assume that
"n > UA' Call Llu = Un - "A' Define the velocity gradient at YA, du/dy, by
du
(3.1)
dy
The velocity gradient is clearly the reciprocal of the slope of the velocity profile
of Fig. 3.1a. The local velocity gradient is also called the shear rate, or time rate
of shear. The velocity gradient is usually a function of position in the stream and
therefore defines a field, as illustrated in Fig. 3.1h.
THE SHEAR-STRESS FIELD. Since an actual fluid resists shear, a shear force must
exist wherever there is a time rate of shear. In one-dimensional flow the shear
force acts parallel to the plane of the shear. For example, at plane C at distance
Yc from the wall, the shear force F" shown in Fig. 3.1a, acts in the direction shown
in the figure. This force is exerted by the fluid outside of plane C on the fluid
between plane C and the wall. By Newton's third law, an equal and opposite force,
- F" acts on the fluid outside of plane C from the fluid inside plane C. It is
convenient to use, not total force F" but the force per unit area of the shearing
plane, called the shear stress and denoted by r, or
F,
-r = - (3.2)
A,
where A, is the area of the plane. Since r varies with y, the shear stress also
constitutes a field. Shear forces are generated in both laminar and turbulent flow.
The shear stress arising from viscous or laminar flow is denoted by r". The effect
of turbulence is described later.
NEWTONIAN AND NON-NEWTONIAN FLUIDS. The relationships between the
shear stress and shear rate in a real fluid are part of the science of rheology. Figure
3.2 shows several examples of the rheological behavior of fluids. The curves are
plots of shear stress vs. rate of shear and apply at constant temperature and
pressure. The simplest behavior is that shown by curve A, which is a straight line
passing through the origin. Fluids following this simple linearity are called
newtonian fluids. Gases and most liquids are newtonian. The other curves shown
in Fig. 3.2 represent the rheological behavior of liquids called non-newtonian.
Some liquids, e.g., sewage sludge, do not flow at all until a threshold shear stress,
denoted by To, is attained and then flow linearly at shear stresses greater than TO'
Curve B is an example of this relation. Liquids acting this way are called Bingham
plastics. Line C represents a pseudoplastic fluid. The curve passes through the
origin, is concave downward at low shears, and becomes nearly linear at high
shears. Rubber latex is an example of such a fluid. Curve D represents a dilatant
fluid. The curve is concave upward at low shears and almost linear at high shears.
Quicksand and some sand-filled emulsions show this behavior. Pseudoplastics are
said to be shear rate thinning and dilatant fluids shear rate thickening.
Time-dependent flow. None of the curves in Fig. 3.2 depends on the history of the
fluid, and a given sample of material shows the same behavior no matter how
Bmghom plastic
vi
.. Pseudo-
plastic A
if)
w
Cl:
c-
if)
Cl:
od:
W New/onion
I
if)
o
'0
FIGURE 3.2
Shear stress vs. velocity gradient for
VELOCITY GRADIENT, du/dy newtonian and non-newtonian fluids.
TABLE 3.1
Rheological characteristics of fluids
Designation Effect of increasing shear rate Time dependent?
Pseudoplastic Thins No
Thixotropic Thins Yes
Newtonian None No
Dilatant Thickens No
Rheopectic Thickens Yes
long the shearing stress has been applied. Such is not the case for some non-
newtonian liquids, whose stress-vs.-rate-of-shear curves depend on how long the
shear has been active. Thixotropic liquids break down under continued shear and
on mixing give lower shear stress for a given shear rate; that is, their apparent
viscosity decreases with time. RiIeopectic substances behave in the reverse manner,
and the shear stress increases with time, as does the apparent viscosity. The original
structures and apparent viscosities are usually recovered on standing.
The rheological characteristics of fluids are summarized in Table 3.1.
VISCOSITY. In a newtonian fluid the shear stress is proportional to the shear rate,
and the proportionality constant is called the viscosity:
du
(3.3)
'" = Il dy
In SI units '" is measured in newtons per square meter and Il in kilograms per
meter-second or pascal-second. In the cgs system viscosity is expressed in grams
per centimeter-second, and this unit is called the poise (P). Viscosity data are
generally reported in centipoises (cP = 0.01 P = 1 mPa-s), since most fluids have
viscosities much less than 1 P.
In English units viscosity is defined using the Newton's-law conversion factor
g" and the units of Il are pounds per foot-second or pounds per foot-hour. The
defining equation is
Il du
! =-- (3.4)
" g, dy
Conversion factors among the different systems are given in Table 3.2.
TABLE 3.2
Conversion factors for viscosity
Pa-s P eP Iblft-s Ib/ft-h
I 10 1000 0.672 2420
0.1 I 100 0.0672 242
10- 3 0.01 6.72 x 10- 4 2.42
FLUID-FLOW PH ENOMENA *I
VISCOSITY AND MOMENTUM FLUX. Although Eq. (3.3) serves to define the
viscosity of a fluid, it can also be interpreted in terms of momentum flux. The
moving fluid just above plane C in Fig. 3.1 has slightly more momentum in the
x direction than the fluid just below this plane. By molecular collisions momentum
is transferred from one layer to the other, tending to speed up the slower moving
layer and to slow down the faster moving one. Thus, momentum passes across
plane C to the fluid in the layer below; this layer transfers momentum to the next
lower layer, and so on. Hence x-direction momentum is transferred in the - y
direction all the way to the wall bounding the fluid, where u = 0, and is delivered
to the wall as wall shear. Shear stress at the wall is denoted by Tw'
The units of momentum fluxt are (kg-m/s)/m2-s or kg/m-s2, the same as the
units for T, since N/m2 equals kg/m-s2. Equation (3.3) therefore states that the
momentum flux normal to the direction of flow of the fluid is proportional to the
velocity gradient, with the viscosity as the proportionality factor.
Momentum transfer is analogous to conductive heat transfer resulting from
a temperature gradient, where the proportionality factor between the heat flux
and temperature gradient is called the thermal conductivity. In laminar flow,
momentum is transferred as a result of the velocity gradient, and the viscosity
may be regarded as the conductivity of momentum transferred by this mechanism.
VISCOSITlES OF GASES AND LIQUIDS. The viscosity of a newtonian fluid
depends primarily on temperature and to a lesser degree on pressure. The viscosity
of a gas increases with temperature approximately in accordance with an equation
of the type
/1
/10 =
(T)"
273
(3.5)
where /1 = viscosity at absolute temperature T, K
/10 = viscosity at O°C (273 K)
n = constant
Viscosities of gases have been intensively studied in kinetic theory, and accurate
and elaborate tables of temperature coefficients are available. Exponent n ~ 0.65
for air; it is approximately 0.9 for carbon dioxide and simple hydrocarbons and
about 1.1 for sulfur dioxide and steam.
The viscosity of a gas is almost independent of pressure in the region of
pressures where the gas laws apply. In this region the viscosities of gases are
generally between 0.01 and 0.1 cP (see Appendix 8 for the viscosities of common
gases at 1 atm). At high pressures, gas viscosity increases with pressure, especially
in the neighborhood of the critical point.
The viscosities of liquids are generally much greater than those of gases and
cover several orders of magnitUde. Liquid viscosities decrease significantly when
t Flux is defined generally as any quantity passing through a unit area in unit time_
... 0 l'LUIU MeCHANIC::'
the temperature is raised. For example, the viscosity of water falls from 1.79 cP at
O°C to 0.28 cP at 100°C. The viscosity of a liquid increases with pressure, but the
effect is generally insignificant at pressures less than 40 atm. Data for common
liquids over a range of temperatures are given in Appendix 9.
The absolute viscosities of fluids vary over an enOrmous range ofmagnitudes,
from about 0.1 cP for liquids near their boiling point to as much as 106 P for
polymer melts. Most extremely viscous materials are non-newtonian and possess
no single viscosity independent of shear rate.
Kinematic viscosity. The ratio of the absolute viscosity to the density of a fluid,
/1/ p, is often useful. This property is called the kinematic viscosity and designated
by v. In the SI system, the unit for v is square meters per second. In the cgs system,
the kinematic viscosity is called the stoke (St), defined as 1 cm 2/s. The fps unit is
square feet per second. Conversion factors are
1 m 2/s = 104 St = 10.7639 ft2/S
For liquids, kinematic viscosities vary with temperature over a somewhat
narrower range than absolute viscosities. For gases, the kinematic viscosity
increases more rapidly with temperature than does the absolute viscosity.
RATE OF SHEAR VERSUS SHEAR STRESS FOR NON-NEWTONIAN FLUIDS.
Bingham plastics like that represented by curve B in Fig. 3.2 follow a rheological
equation of the type
du
',go = 'og, +K dy (3.6)
where K is a constant. Over some range of shear rates dilatant and pseudoplastic
fluids often follow a power law, also called the Ostwald-de Waele equation,
',go = K' (~;r (3.7)
where K' and n' are constants called the flow consistency index and the flow
behavior index, respectively. Such fluids are known as power-law fluids. For
pseudoplastics (curve C) n' < 1, and for dilatant fluids (curve D) n' > 1. Clearly
n' = 1 for newtonian fluids.
TURBULENCE
It has long been known that a fluid can flow through a pipe or conduit in two
different ways. At low flow rates the pressure drop in the fluid increases directly
with the fluid velocity; at high rates it increases much more rapidly, roughly as
the square of the velocity. The distinction between the two types of flow was first
demonstrated in a classic experiment by Osborne Reynolds, reported in 1883. A
horizontal glass tube was immersed in a glass-walled tank filled with water. A
controlled flow of water could be drawn through the tube by opening a valve.
The entrance to the tube was flared, and provision was made to introduce a fine
filament of colored water from the overhead flask into the stream at the tube
entrance. Reynolds found that, at low flow rates, the jet of colored water flowed
intact along with the mainstream and no cross mixing occurred. The behavior of
the color band showed clearly that the water was flowing in parallel straight lines
and that the flow was laminar. When the flow rate was increased, a velocity, called
the critical velocity, was reached at which the thread of color became wavy and
gradually disappeared, as the dye spread uniformly throughout the entire cross
section of the stream of water. This behavior of the colored water showed that
the water no longer flowed in laminar motion but moved erratically in the form
of crosscurrents and eddies. This type of motion is turbulent jlow.
REYNOLDS NUMBER AND TRANSITION FROM LAMINAR TO TURBULENT
FLOW. Reynolds studied the conditions under which one type of flow changes
into the other and found that the critical velocity, at which laminar flow changes
into turbulent flow, depends on four quantities: the diameter of the tube and the
viscosity, density, and average linear velocity the liquid. Furthermore, he found
that these four factors can be combined into one group and that the change in
kind of flow occurs at a definite value of the group. The grouping of variables so
found was
DVP DV
N Re = - - = - (3.8)
I' v
where D = diameter of tube
V = average velocity of liquid [Eq. (4.4)]
I' = viscosity of liquid
p = density of liquid
v = kinematic viscosity of liquid
The dimensionless group of variables defined by Eq. (3.8) is called the
Reynolds number N R ,. It is one of the named dimensionless groups listed in
Appendix 4. Its magnitude is independent of the units used, provided the units
are consistent.
Additional observations have shown that the transition from laminar to
turbulent flow actually may occur over a wide range of Reynolds numbers. In a
pipe, flow is always laminar at Reynolds numbers below 2100, but laminar flow
can persist up to Reynolds numbers of several thousand under special conditions
of well-rounded tube entrance and very quiet liquid in the tank. Under ordinary
conditions, the flow in a pipe or tube is turbulent at Reynolds numbers above
about 4000. Between 2100 and 4000 a transition region is found where the flow
may be either laminar or turbulent, depending upon conditions at the entrance
of the tube and on the distance from the entrance.
REYNOLDS NUMBER FOR NON-NEWTONIAN FLUIDS. Since non-newtonian
fluids do not have a single-valued viscosity independent of shear rate, Eq. (3.8) for
the Reynolds number cannot be used. The definition of a Reynolds number for
such fluids is somewhat arbitrary; a widely used definition for power-law fluids is
N = 2'-0' __n_ DO' il 0
, )0' _-,-P-,-_' 2
-
Rc,n (3n' + 1 K'
(3.9)
The basis of this somewhat complicated definition is discussed on page 100. The
following equation has been proposed for the critical Reynolds number at which
transition to turbulent flow begins";
N = 2100 (4n' + 2)(5n' + 3) (3.10)
Ro.o, 3(3n' + 1)'
Equation (3.10) is in accord with observations that the onset of turbulence occurs
at Reynolds numbers above 2100 with pseudoplastic fluids, for which n' < 1.
NATURE OF TURBULENCE. Because of its importance in many branches of
engineering, turbulent flow has been extensively investigated in recent years, and
a large literature has accumulated on this subject.' Refined methods of measure-
ment have been used to follow in detail the actual velocity fluctuations of the
eddies during turbulent flow, and the results of such measurements have shed
much qualitative and quantitative light on the nature of turbulence.
Turbulence may be generated in other ways than by flow through a pipe.
In general, it can result either from contact of the flowing stream with solid
boundaries or from contact between two layers of fluid moving at different
velocities. The first kind of turbulence is called wall turbulence and the second
kindfi'ee turbulence. Wall turbulence appears when the fluid flows through closed
or open channels or past solid shapes immersed in the stream. Free turbulence
appears in the flow of a jet into a mass of stagnant fluid or when a boundary
layer separates from a solid wall and flows through the bulk of the fluid. Free
turbulence is especially important in mixing, which is the subject of Chap. 9.
Turbulent flow consists of a mass of eddies of various sizes coexisting in the
flowing stream. Large eddies are continually formed. They break down into smaller
eddies, which in turn evolve still smaller ones. Finally, the smallest eddies
disappear. At a given time and in a given volume, a wide spectrum of eddy sizes
exists. The size of the largest eddy is comparable with the smallest dimension of
the turbulent stream; the diameter of the smallest eddies is 10 to 100 I'm. Smaller
eddies than this are rapidly destroyed by viscous shear. Flow within an eddy is
laminar. Since even the smallest eddies contain about 10 12 molecules, all eddies
are of macroscopic size, and turbulent flow is not a molecular phenomenon.
Any given eddy possesses a definite amount of mechanical energy, much like
that of a small spinning top. The energy of the largest eddies is supplied by the
potential energy of the bulk flow of the fluid. From an energy standpoint
turbulence is a transfer process in which large eddies, formed from the bulk flow,
I'LUIU-l'LUW t"I1I:NUMI:NA J.l
pass energy of rotation along a continuous series of smaller eddies. Mechanical
energy is not appreciably dissipated into heat during the breakup of large eddies
into smaller and smaller ones, but such energy is not available for maintaining
pressure or overcoming resistance to flow and is worthless for practical purposes.
This mechanical energy is finally converted to heat when the smallest eddies are
obliterated by viscous action.
DEVIATING VELOCITIES IN TURBULENT FLOW. A typical picture of the
variations in the instantaneous velocity at a given point in a turbulent flow field
is shown in Fig. 3.3. This velocity is really a single component of the actual velocity
vector, all three components of which vary rapidly in magnitude and direction.
Also, the instantaneous pressure at the same point fluctuates rapidly and simultan-
eously with the fluctuations of velocity. Oscillographs showing these fluctuations
provide the basic experimental data on which modern theories of turbulence are
based.
Although at first sight turbulence seems to be structureless and randomized,
studies 7 of oscillographs like that in Fig. 3.3 show that this is not quite so. The
randomness and unpredictability of the fluctuations, which are nonetheless con-
strained between definite limits, exemplify the behavior of certain mathematical
"chaotic" nonlinear functions. 3 Such functions, however, have not yet proved
useful in quantitatively characterizing turbulence. This is done by statistical
analysis of the frequency distributions.
The instantaneous local velocities at a given point can be measured by
laser-Doppler anemometers, which are capable of following the rapid oscillations.
Local velocities can be analyzed by splitting each component of the total
instantaneous velocity into two parts, one a constant part that is the time average,
or mean value, of the component in the direction of flow of the stream, and the
other, called the deviating velocity, the instantaneous fluctuation of the component
around the mean. The net velocity is that measured by ordinary flow meters, such
as a pitot tube, which are too sluggish to follow the rapid variations of the
fluctuating velocity. The split of a velocity component can be formalized by the
following method. Let the three components (in cartesian coordinates) of the
instantaneous velocity in directions x, y, and z be Uj, Vj, and Wj , respectively.
Assume also that the x is oriented in the direction of flow of the stream and that
-------+
Time
FIGURE 3.3
Velocity fluctuations in turbulent flow. The percentages are based on the constant velocity. [After
F. L. Wattendorfalld A. M. KlIethe, Physics,S, 153 (1934).]
components v, and w, are the y and z components, respectively, both perpendicular
to the direction of bulk flow. Then the equations defining the deviating velocities
are
(3.11)
where Uj , Vj , Wi = instantaneous total velocity components in x, y, and z directions,
respectively
u = constant net velocity of stream in x direction
u', v', w' = deviating velocities in x, y, and z directions, respectively
Terms v and ware omitted in Eqs. (3.11) because there is no net flow in the
directions of the y and z axes in one-dimensional flow, and so v and ware zero.
The deviating velocities ut, v', and w' all fluctuate about zero as an average.
Figure 3.3 is actually a plot oUhe deviating velocity u'; a plot of the instantaneous
velocity u" however, would be identical in appearance, since the ordinate would
everywhere be increased by the constant quantity u.
For pressure,
p,=p + p' (3.12)
where p, = variable local pressure
p = constant average pressure as measured by ordinary manometers or
pressure gauges
p' = fluctuating part of pressure due to eddies
Because of the random nature of the fluctuations, the time averages of the
fluctuating components of velocity and pressure vanish when averaged over a time
period to 0: the order of a few seconds. Therefore
-1
to
i"
0
u'dt=O -1
to
i"
0
w'dt=O
-1 I"~ v'dt=O -1 I"~ p'dt=O
to 0 to 0
The reason these averages vanish is that for every positive value of a fluctuation
there is an equal negative value, and the algebraic sum is zero.
Although the time averages of the fluctuating components themselves are
zero, this is not necessarily true of other functions or combinations of these
components. For example, the time average of the mean square of anyone of
these velocity components is not zero. This quantity for component u' is defined by
-1
to
it"
0
-
(u')' dt = (u')' (3.13)
Thus the mean square is not zero, since u' takes on a rapid series of positive
and negative values, which, when squared, always give a positive product.
Therefore (u')' is inherently positive and vanishes only when turbulence does not
exist.
FLUID-FLOW PHENOMENA 53
In laminar flow there are no eddies; the deviating velocities and pressure
fluctuations do not exist; the total velocity in the direction of flow Ui is constant
and equal to u; and Vj and Wi are both zero.
STATISTICAL NATURE OF TURBULENCE. The distribution of deviating veloci-
ties at a single point reveals that the value of the velocity is related to the frequency
of occurrence of that value and that the relationship between frequency and value
is gaussian and therefore follows the error curve characteristic of completely
random statistical quantities. This result establishes turbulence as a statistical
phenomenon, and the most successful treatments of turbulence have been based
upon its statistical naturel
By measuring u', D', and w' at different places and over varying time periods
two kinds of data are obtained: (1) the three deviating velocity components at a
single point can be measured, each as a function of time, and (2) the values of a
single deviating velocity (for example, u') can be measured at different positions
over the same time period. Figure 3.4 shows values of u' measured simultaneously
at two points separated by vertical distance y. Data taken at different values of y
show that the correspondence between the velocities at the two stations varies
from a very close relationship at very small values of y to complete independence
when y is large. This is to be expected, because when the distance between the
measurements is small with respect to the size of an eddy, it is a single eddy that
is being measured, and the deviating velocities found at the two stations are
strongly correlated. This means that when the velocity at one station changes
either in direction or in magnitude, the velocity at the other station acts in
practically the same way (or exactly the opposite way). At larger separation
distances the measurements are being made on separate eddies, and the correlation
disappears.
When the three components of the deviating velocities are measured at the
same point, in general any two of them are also found to be correlated and a
change in one is accompanied by a change in the other two.
These observations are quantified by defining correlation coefficients.2 One
such coefficient, which corresponds to the situation shown in Fig. 3.4, is defined
y
,
u2
2
•T
y
I •
u', , ...l
FIGURE 3.4
Fluctuating velocity components in measurement
z of scale of turbulence.
54 FLUID MECHANICS
as follows:
(3.14)
where u; and Uz are the values of u' at stations 1 and 2, respectively. Another
correlation coefficient that applies at a single point is defined by the equation
u'v'
(3.15)
R,." = -.j"'(u"',);r2("'v,''''!'
where u' and v' are measured at the same point at the same time.
INTENSITY AND SCALE OF TURBULENCE. Turbulent fields are characterized
by two average parameters. The first measures the intensity of the field and refers
to the speed of rotation of the eddies and the energy contained in an eddy of a
specific size. The second measures the size of the eddies, Intensity is measured by
the root-mean-square of a velocity component. It is usually expressed as a
percentage of the mean velocity or as 100 J(U')2/U. Very turbulent fields, such as
those immediately below turbulence-producing grids, may reach an intensity of 5
to 10 percent. In unobstructed flow, intensities are less and of the order of 0.5 to
2 percent. A different intensity usually is found for each component of velocity.
The scale of turbulence is based on correlation coefficients such as R",
measured as a function of the distance between stations. By determining the values
of R", as a function of y, the scale Ly of the eddy in the y direction is calculated
by the integral
(3.16)
Each direction usually gives a different value of L y , depending upon the choice of
velocity components used in the definition. For air flowing in pipes at 12 m/s, the
scale is about 10 mm, and this is a measure of the average size of the eddies in
the pipe.
ISOTROPIC TURBULENCE, Although correlation coefficients generally depend
upon the choice of component, in some situations this is not true, and the
root-mean-square components are equal for all directions at a given point. In this
situation the turbulence is said to be isotropic, and
(U')2 = (v')' = (W)2
Nearly isotropic turbulence exists when there is no velocity gradient, as at the
centerline of a pipe or beyond the outer edge of a boundary layer. Nearly isotropic
turbulence is also found downstream of a grid placed in the flow. Turbulent flow
near a boundary is anisotropic, but the anisotropy occurs mainly with the larger
FLUID-FLOW PHENOMENA 55
eddies. Small eddies, especially those near obliteration from viscous action, are
practically isotropic.
REYNOLDS STRESSES. It has long been known that shear forces much larger
than those occurring in laminar flow exist in turbulent flow wherever there is a
velocity gradient across a shear plane. The mechanism of turbulent shear depends
upon the deviating velocities in anisotropic turbulence. Turbulent shear stresses
are called Reynolds stresses. They are measured by the correlation coefficients of
the type R,.,. defined in Eq. (3.15).
To relate Reynolds stresses to correlations of deviating velocities, the
momentum principle may be used. Consider a fluid in turbulent flow moving in a
positive x direction, as shown in Fig. 3.5. Plane S is parallel to the flow. The
instantaneous velocity in the plane is u" and the mean velocity is u. Assume that
u increases with y, the positive direction measured perpendicular to the layer S,
so that the velocity gradient du/dy is positive. An eddy moving toward the wall
has a negative value of v', and its movement represents a mass flow rate p( -v')
into the fluid below plane S. The velocity of the eddy in the x direction is u" or
u + II'; if each such eddy crossing plane S is slowed down to the mean velocity u,
the rate of momentum transfer per unit area is p( -v')u'. This momentum flux,
after time averaging for all eddies, is a turbulent shear stress or Reynolds stress
given by the equation
(3.17)
EDDY VISCOSITY. By analogy with Eq. (3.4), the relationship between shear stress
and velocity gradient in a turbulent stream is used to define an eddy viscosity E,:
du
7:,gc = Ev dy (3.18)
Quantity E, is analogous to /1, the absolute viscosity. Also, in analogy with the
kinematic viscosity v the quantity BM' called the eddy diffusivity oJ momentum, is
defined as BM = E,/p.
Vi (negative sign
entering fluid below S)
Vi (positive sign
y
leaving fluid belowS) )
s
FIGURE 3.5
o~~--------~------------
u Reynolds stress.
56 FLUID MECHANICS
The total shear stress in a turbulent fluid is the sum of the viscous stress and
the turbulent stress, or
du
<go = (fl + E") dy (3.19)
d(pu)
<go = (v + BM) dY (3.20)
Although E" and BM are analogous to fl and v, respectively, in that all these
quantities are coefficients relating shear stress and velocity gradient, there is a
basic difference between the two kinds of quantities. The viscosities fl and v are true
properties of the fluid and are the macroscopic result of averaging motions and
momenta of myriads of molecules. The eddy viscosity E" and the eddy diffusivity
BM are not just properties of the fluid but depend on the fluid velocity and the
geometry of the system. They are functions of all factors that influence the detailed
patterns of turbulence and the deviating velocities, and they are especially sensitive
to location in the turbulent field and the local values of the scale and intensity of the
turbulence. Viscosities can be measured on isolated samples of fluid and presented
in tables or charts of physical properties, as in Appendixes 8 and 9. Eddy viscosities
and diffusivities are determined (with difficulty, and only by means of special
instruments) by experiments on the flow itself.
FLOW IN BOUNDARY LAYERS. A boundary layer is defined as that part of a
moving fluid in which the fluid motion is influenced by the presence of a solid
boundary. As a specific example of boundary-layer formation, consider the flow
of fluid parallel with a thin plate, as shown in Fig. 3.6. The velocity of the fluid
upstream from the leading edge of the plate is uniform across the entire fluid
stream. The velocity of the fluid at the interface between the solid and fluid is
zero. The velocity increases with distance from the plate, as shown in Fig. 3.6.
Each of these curves corresponds to a definite value of x, the distance from the
leading edge of the plate. The curves change slope rapidly near the plate; they
also show that the local velocity approaches asymptotically the velocity of the
bulk of the fluid stream.
In Fig. 3.6 the dashed line OL is so drawn that the velocity changes are
confined between this line and the trace of the wall. Because the velocity lines are
asymptotic with respect to distance from the plate, it is assumed, in order to locate
the dashed line definitely, that the line passes through all points where the velocity
is 99 percent of the bulk fluid velocity U ro ' Line OL represents an imaginary surface
that separates the fluid stream into two parts: one in which the fluid velocity is
constant and the other in which the velocity varies from zero at the wall to a
velocity substantially equal to that of the undisturbed fluid. This imaginary surface
separates the fluid that is directly affected by the plate from that in which the
local velocity is constant and equal to the initial velocity of the approach fluid.
The zone, or layer, between the dashed line and the plate constitutes the boundary
layer.
FLUID-FLOW PHENOMENA 57
./
./
z'x
c' c"
FIGURE 3.6
Prandtl boundary layer: x, distance from leading edge; U"", velocity of undisturbed stream; Z",. thickness
of boundary layer at distance x; 11, local velocity; abc, db'c', d'b"c", velocity-vs.-distance-from-walI
curves at points c, c', e"; OL, outer limit of boundary layer. (The vertical scale is greatly exaggerated.)
The formation and behavior of the boundary layer are important, not only
in the flow of fluids but also in the transfer of heat, discussed in Chap. 12, and
mass, discussed in Chap. 21.
LAMINAR AND TURBULENT FLOW IN BOUNDARY LAYERS. The fluid velocity
at the solid-fluid interface is zero, and the velocities close to the solid surface are,
of necessity, small. Flow in this part of the boundary layer very near the surface
therefore is essentially laminar. Actually it is laminar most of the time, but
occasionally eddies from the main portion of the flow or the outer region of the
boundary layer move very close to the wall, temporarily disrupting the velocity
profile. These eddies may have little effect on the average velocity profile near the
wall, but they can have a large effect on the profiles of temperature or concentra-
tion when heat or mass is being transferred to or from the wall. This effect is most
pronounced for mass transfer in liquids.
Farther away from the surface the fluid velocities, though less than the
velocity of the undisturbed fluid, may be fairly large, and flow in this part of the
boundary layer may become turbulent. Between the zone of fully developed
turbulence and the region of laminar flow is a transition, or buffer, layer of
intermediate character. Thus a turbulent boundary layer is considered to consist
of three zones: the viscous sublayer, the buffer layer, and the turbulent zone. The
existence of a completely viscous sublayer is questioned by some, since mass
transfer studies suggest that some eddies penetrate all the way through the
boundary layer and reach the wall.
:"0 FLUID MECHANICS
<f)
<f)
w
z
'"
u
I
I- Turbulent flow in
0:: boundary layer
~ Laminor flow in
:J, boundary layer
~ Onset of
g turbulence
z
::>
V
, _-'-""'e tI tJ
...·w·
~ ~
[BUffer layer.
allL__.JI_~_··-.:~.,.::t--,~,-,'==;'-"~=:-=_c:-_=-::_===-=-,===,-,£~=-:.-:=!,,,~=S:':=~",~=S_::~::!!.=~::~~=~,,~=:':.~=O-
DISTANCE FROM LEADING EDGE, x
FIGURE 3.7
D.evelopment of turbulent boundary layer on a flat plate. (The vertical scale is greatly exaggerated.)
Near the leading edge of a flat plate immersed in a fluid of uniform velocity,
the boundary layer is thin, and the flow in the boundary layer is entirely laminar.
As the layer thickens, however, at distances farther from the leading edge, a point
is reached where turbulence appears. The onset of turbulence is characterized by
a sudden rapid increase in the thickness ofthe boundary layer, as shown in Fig. 3.7.
When flow in the boundary layer is laminar, the thickness Zx of the layer
increases with XO. 5 , where x is the distance from the leading edge of the plate. 5
For a short time after turbulence appears, Zx increases with X1.5 and then, after
turbulence is fully developed, with xO ...
The initial, fully laminar part of the boundary layer may grow to a moderate
thickness of perhaps 2 mm with air or water moving at moderate velocities. Once
turbulence begins, however, the thickness of the laminar part of the boundary
layer diminishes considerably, typically to about 0.2 mm.
Transition from laminar to turbulent flow; Reynolds number. The factors that
determine the point at which turbulence appears in a laminar boundary layer are
coordinated by the dimensionless Reynolds number defined by the equation
XUOJp
NRe.x=-I'- (3.21)
where x = distance from leading edge of plate
U oo = bulk fluid velocity
p = density of fluid
I' = viscosity of fluid
With parallel flow along a plate, turbulent flow first appears at a critical Reynolds
number between about 105 and 3 x 106 • The transition occurs at the lower
Reynolds numbers when the plate is rough and the intensity of turbulence in the
approaching stream is high and at the higher values when the plate is smooth and
the intensity of turbulence in the approaching stream is low.
FLUID·FLOW PHENOMENA 59
BOUNDARY-LAYER FORMATION IN STRAIGHT TUBES. Consider a straight
thin-walled tube with fluid entering it at a uniform velocity. As shown in Fig. 3.8,
a boundary layer begins to form at the entrance to the tube, and as the fluid moves
through the first part of the channel, the layer thickens. During this stage the
boundary layer occupies only part of the cross section of the tube, and the total
stream consists of a core of fluid flowing in rodlike manner at constant velocity
and an annular boundary layer between the waIl and the core. In the boundary
layer the velocity increases from zero at the wall to the constant velocity existing
in the core. As the stream moves farther down the tube, the boundary layer
occupies an increasing portion of the cross section. Finally, at a point well
downstream from the entrance, the boundary layer reaches the center ofthe tube,
the rodlike core disappears, and the boundary layer occupies the entire cross
section of the stream. At this point the velocity distribution in the tube reaches
its final form, as shown by the last curve at the right of Fig. 3.8, and remains
unchanged during the remaining length of the tube. Such flow with an unchanging
velocity distribution is calledfully developed flow.
Transition length for laminar and turbulent flow. The length of the entrance region
of the tube necessary for the boundary layer to reach the center of the tube and
for fully developed flow to be established is called the transition length. Since the
velocity varies not only with length of tube but with radial distance from the center
of the tube, flow in the entrance region is two dimensional.
The approximate length of straight pipe necessary for completion of the final
velocity distribution is, for laminar flow,'
x,
- =0.05NR , (3.22)
D
where x, = transition length
D = diameter of pipe
Thus for a 50-mm- (2-in.-) ID pipe and a Reynolds number of 1500 the transition
length is 3.75 m (12.3 ft). If the fluid entering the pipe is turbulent and the velocity
in the tube is above the critical, the transition length is nearly independent of the
Reynolds number and is about 40 to 50 pipe diameters, with little difference
between the distribution at 25 diameters and that at greater distances from the
entrance. For a 50-mm-ID pipe, 2 to 3 m of straight pipe is sufficient when flow
I Jit1ir~ I
FIGURE 3.8
Development of boundary-layer flow in pipe.
()U FLUID MECHANICS
is all turbulent. If the fluid entering the tube IS III laminar flow and becomes
turbulent on entering the tube, a longer transition length, as large as 100 pipe
diameters, is needed.
BOUNDARY-LAYER SEPARATION AND WAKE FORMATION. In the preceding
paragraphs the growth of boundary layers has been discussed. Now consider what
happens at the far side of a submerged object, where the fluid leaves the solid
surface.
At the trailing edge of a flat plate that is parallel to the direction of flow,
the boundary layers on the two sides of the plate have grown to a maximum
thickness. For a time after the fluid leaves the plate, the layers and velocity
gradients persist. Soon, however, the gradients fade out; the boundary layers
intermingle and disappear, and the fluid once more moves with a uniform velocity.
This is shown in Fig. 3.9a.
Suppose, now, the plate is turned at right angles to the direction of flow, as
in Fig. 3.9b. A boundary layer forms as before in the fluid flowing over the
upstream face. When the fluid reaches the edge of the plate, however, its mo-
mentum prevents it from making the sharp turn around the edge and it separates
from the plate and proceeds outward into the bulk of the fluid. Behind the plate
is a backwater zOne of strongly decelerated fluid, in which large eddies, called
-----+ Direction of flow
~~~~~~~~~~~~~~~~~~~~~~~~'
" __ Varying
.,
l
i
~
3
)-
velocity
LUniform
velocity (0)
(b)
FIGURE 3.9
Flow past flat plate: (a) flow parallel with plate; (b) flow perpendicular to plate.
FLUID-FLOW PHENOMENA 61
vortices, are formed. This zone is known as the wake. The eddies in the wake are
kept in motion by the shear stresses between the wake and the separated current.
They consume considerable mechanical energy and may lead to a large pressure
loss in the fluid.
Boundary-layer separation occurs whenever the change in velocity of the
fluid, either in magnitude or direction, is too large for the fluid to adhere to the
solid surface. It is most frequently encountered when there is an abrupt change in
the flow channel, like a sudden expansion or contraction, a sharp bend, or an
obstruction around which the fluid must flow. As discussed in Chap. 5, page 110,
separation may also occur from velocity decrease in a smoothly diverging channel.
Because of the large energy losses resulting from the formation of a wake, it is
often desirable to minimize or prevent boundary-layer separation. In some cases
this can be done by suction, i.e., by drawing part of the fluid into the solid surface
at the area of potential separation. Most often, however, 'separation is minimized
by avoiding sharp changes in the cross-sectional area of the flow channel and by
streamlining any objects over which the fluid must flow. For some purposes, such
as the promotion of heat transfer or mixing in a fluid, boundary-layer separation
may be desirable.
SYMBOLS
A Area m 2 or ft2; A" of plane on which shear force acts
D Diameter, m or ft
E" Eddy viscosity, Pa-s or Ib/ft-s, P
F, Shear force, N or Ibf
g, Newton's-law proportionality factor, 32.174 ft-Ib/lb r s 2
K Constant in Eq. (3.6)
K' Flow consistency index, gjm_s 2-.' or Ib/ft-s2-.' [Eq. (3.7)]
Ly Scale of turbulence, m or ft
NRo Reynolds number, DVp/l'; N R ,." for non-newtonian fluids; N R, . "
based on distance x from leading edge of plate
n Exponent in Eq. (3.5)
n' Flow behavior index, dimensionless [Eq. (3.7)J
p Pressure N/m 2 or Ibf/ft'; p;, variable local pressure; p',
fluctuating component
Correlation coefficients defined by Eqs. (3,14) and (3.15)
Absolute temperature, K
Time, s; to, time interval for averaging
Velocity, m/s or ft/s; velocity component in x direction UA, UB, at
planes A, B; uj , instantaneous value; U a:)) bulk velocity of undis-
turbed fluid; u', deviating velocity; U'b uz, at stations 1,2
Average velocity, m/s or ft/s
v, W Velocity components in y and z directions, respectively; Vj , Wb
instantaneous values; v', w', deviating velocities
O~ FLUID MECHANICS
x Distance measured parallel with flow direction, m or ft; x"
transition length
Y Distance perpendicular to wall, m or ft; YA, Ye, at planes A, C
Zx Thickness of boundary layer, m or ft
Greek letters
Eddy diffusivity of momentum, m 2/s or ft2/S
Viscosity, absolute, Pa-s or lb/ft-s; Po, at T = 273 K
Kinematic viscosity pip, m 2/s or ft2/S
Density, kg/m 3 or Ib/ft 3
,p Shear stress, N/m 2 or Ib j /ft2; '" turbulent shear stress; '" laminar
shear stress; 'r w , stress at wall; 'r o, threshold stress for Bingham
plastic
PROBLEMS
3.1. For the following situations of steady flow, determine whether flow is laminar or
turbulent: (a) water at woe flowing at an average velocity of 2 m/s in a lOO-mm pipe;
(b) air at 2 atm pressure and 180'F flowing at 50 ft/s in a 12-in. duct; (c) oil with a
specific gravity of 0.78 and a viscosity of 20 cP flowing at 5 ft/s in a 2-in. pipe;
(d) polymer melt with a density of 900 kg/m' and a viscosity of I Pa-s flowing at
0.2 m/s in a IS-mm tube.
3.2. The thickness of the laminar boundary layer on a flat plate Zx is approximately given
by the equation Zx = 5.5(pX/UlX)p)1/2. Show that at the transition to the turbulent flow
the Reynolds number based on this thickness, instead of on x as in Eq. (3.21), is close
to the transition Reynolds number for flow in a pipe.
3.3. Use the nomograph in Appendix 8 to determine the value of n in the equation for gas
viscosity, Eq. (3.5), for carbon monoxide and for helium over the ranges 0 to 300°C
and 300 to 6OO'C.
3.4. (a) Estimate the transition length at the entrance to a IS-mm tube through which
lOO percent glycerol at 60'C is flowing at a velocity of 0.3 m/so The density of glycerol
is 1240 kg/m'. (b) Repeat part (a) for lOO percent n-propyl alcohol entering a 3-in. pipe
at 30'C and a velocity of 7 ft/so The density of n-propyl alcohol is SOlb/ft'.
3.5. (a) Estimate the ReynoIds number for flow in an automobile exhaust pipe if the 2-L
engine is operating at 3000 rpm. (b) If the catalytic converter has four times the cross
section of the exhaust pipe, how small must the channels in the converter be to get
laminar flow?
3.6. Plot the viscosity of water, hexane, and 100 percent glycerol on semilog coordinates
and discuss how nearly the viscosity follows an Arrhenius relationship (J1. = Ae- E/ R1).
REFERENCES
1. Hinze, J. 0.: Turbulence, 2nd ed., McGraw-Hill, New York, 1975.
2. Knudsen, J. G., and D. L. Katz: Fluid Dynamics and Heat Transfer, McGraw-HiII, New York, 1958,
pp. 115-120.
rI..ULU-rI..UW t'HI:'.NUMI:'.NA UJ
3_ Langford, W. F.: in P. Fischer and W. R. Smith (eds.), Chaos, Fractals and Dynamics, M. Bekker,
New York, 1985, pp. 94-95.
4. Rothfus, R. R., and R. S. Prengle: lnd. £ng. Chem., 44: 1683 (1952).
5. Schlichting, H. Boundary Layer Theory. 7th ed., McGraw-Hill, New York, 1979, p. 42.
6. Streeter, V. L., and E. B. WyIie: Fluid Mechanics, 8th ed.; McGraw-Hill, New York. 1985.
7. Wattendorf, F. L., and A. M. Kuethe: Physics, 5:153 (1934).
CHAPTER
4
BASIC
EQUATIONS
OF
FLUID
FLOW
The principles of physics most useful in the applications of fluid mechanics
are the mass-balance, or continuity, equations; the linear- and angular-
momentum-balance equations; and the mechanical-energy balance. They may be
written in differential form, showing conditions at a point within a volume element
of fluid, or in integrated form applicable to a finite volume or mass of fluid. Only
the integral equations are discussed in this chapter.
Certain simple forms of the differential equations of fluid flow are given in
later chapters. A complete treatment requires vector and tensor equations outside
the scope of this text, the best known of which are the Navier-8tokes equations
for fluids of constant density and viscosity. They underlie more advanced study
of the phenomena and are discussed in many texts dealing with applied mechanics
and transport processes. 1- 3
MASS BALANCE. In steady flow the mass balance is particularly simple. The rate
of mass entering the flow system equals that leaving, as mass can be neither
accumulated nor depleted within a flow system under steady conditions.
Streamlines and stream tubes. Discussions of fluid-flow phenomena are facilitated
by visualizing, in the stream of fluid, fluid paths called streamlines. A streamline
is an imaginary curve in a mass of flowing fluid so drawn that at every point on
64
BASIC EQUATIONS OF FLUID FLOW 65
the curve the net-velocity vector u is tangent to the streamline. No net flow takes
place across such a line. In turbulent flow eddies do cross and recross the
streamline, but as shown in Chap. 3, the net flow from such eddies in any direction
other than that of flow is zero.
A stream tube, or stream filamelIt, is a tube of small or large cross section
and of any convenient cross-sectional shape that is entirely bounded by stream-
lines. A stream tube can be visualized as an imaginary pipe in the mass of flowing
fluid through the walls of which no net flow is occurring.
The mass balance gives an important relation concerning flow through a
stream tube. Since flow cannot take place across the walls of the tube, the rate of
mass flow into the tube during a definite period of time must equal the rate of
mass flow out of the tube. Consider the stream tube shown in Fig. 4.1. Let the
fluid enter at a point where the area of the cross section of the tube is So and leave
where the area of the cross section is Sb' Let the velocities normal to the cross
sections at these points be Uo and "b' Let the corresponding densities be Po and
Pb and assume that the density at any given cross section is constant. Assume also
that the flow tube does not have a boundary layer so that the velocity is constant
across the tube. The mass of fluid entering and leaving the tube in unit time is
(4.1)
where ,n is the rate of flow in mass per unit time. From this equation it follows
for a stream tube
In = puS = const (4.2)
Equation (4.2) is called the equation of continuity. It applies either to compressible
or incompressible fluids. In the latter case, Po = Pb = p.
AVERAGE VELOCITY. If the flow through the stream tube lies wholly or in part
within a boundary layer in which shear stresses exist, the velocity u will vary from
point to point across the area So and ub will vary from point to point across area
Sb' Then it is necessary to distinguish between the local and the average velocity.
If the fluid is being heated or cooled, the density of the fluid also varies from
point to point in a single cross section. In this text density variations in a single
cross section of a stream tube are neglected, and both Po and Pb are independent
of location within the cross section.
Direction of flow
)
:]~~~~~~~~~~~~I~~~
===-
o
Density = flo Denstfy =I'b
Ve/ocity=u
Area=Sa , ( ) ve/oci!y
Area=Sb =ub )
FIGURE 4.1
Mass balance-continuity.
66 FLUID MECHANICS
The mass flow rate through a differential area in the cross section of a stream
tube is
dll! = pu dS
and the total mass flow rate through the entire cross-sectional area is
II! = pIu dS (4.3)
The integral Ss signifies that the integration covers the area S.
The average velocity j7 of the entire stream flowing through cross-sectional
area S is defined by
_ ri! q (4.4)
V= Ps=sJ,udS
Velocity j7 also equals the total volumetric flow rate of the fluid divided by
the cross-sectional area of the conduit; in fact, it is usually calculated this way. Thus
- q
V=- (4.5)
S
where q is the volumetric flow rate.
The continuity equation for flow through a finite stream tube in which the
velocity varies within the cross section is
(4.6)
For the important special case where the flow is through channels of circular cross
section
from which
p,~, = (Db)2 (4.7)
PbVb D,
where D, and Db are the diameters of the channel at the upstream and downstream
stations, respectively.
MASS VELOCITY. Equation (4.4) can be written
_ ril
Vp=-=G (4.8)
S
This equation defines the mass velocity G, calculated by dividing the mass flow
rate by the cross-sectional area of the channel. In practice, the mass velocity is
expressed in kilograms per square meter per second, pounds per square foot per
second, or pounds per square foot per hour. The advantage of using G is that it is
independent of temperature and pressure when the flow is steady (constant ril) and
BASIC EQUATIONS OF FLUID FLOW 67
the cross section is unchanged (constant 8). This fact is especially useful when
compressible fluids are considered, for both i7 and p vary with temperature and
pressure. Also, certain relationships appear later in this book in which i7 and p
are associated as their product, so that the mass velocity represents the net effect
of both variables. The mass velocity G can also be described as the mass current
density or mass flux, where flux is defined generally as any quantity passing
through a unit area in unit time. The average velocity i7, as shown by Eq. (4.5),
can be described as the volume flux of the fluid.
Example 4.1. Crude oil, specific gravity 60'F/60'F = 0.887, flows through the piping
shown in Fig. 4.2. Pipe A is 2-in. (50-mm) Schedule 40, pipe B is 3-in. (75-mm)
Schedule 40, and each of pipes C is l!-in. (38-mm) Schedule 40. An equal quantity
of liquid flows through each of the pipes C. The flow through pipe A is 30 gal/min
(6.65 m' fh). Calculate (a) the mass flow rate in each pipe, (b) the average linear velocity
in each pipe, and (c) the mass velocity in each pipe.
Solution
Dimensions and cross-sectional areas of standard pipe are given in Appendix 5.
Cross-sectional areas needed are, for 2-in. pipe, 0.0233 ft2; for 3-in. pipe, 0.0513 ft2;
and for 1~-in. pipe, 0.01414 ft'.
(a) The density of the fluid is
p = 0.887 x 62.37 = 55.3 lb/ft'
Since there are 7.48 gal in 1 ft3 (Appendix 3), the total volumetric flow rate is
30 x 60
q = - - = 240.7 ft'fh
7.48
The mass flow rate is the same for pipes A and B and is the product of the density
and the volumetric flow rate, or
In = 240.7 x 55.3 = 13,300 lbfh
The mass flow rate through each of pipes C is one-half the total or 13,300/2 =
6650lb/h (0.8379 kg/s).
(b) Use Eq. (4.4). The velocity through pipe A is
240.7
2.87 ft/s
3600 x 0.0233
A ~L'__~B__~"L'__~'?jm
~b: ~
"---:Z:-:-in-.--""-..,,, ---::-:'---"M '"
3 in. Vc
C
'fin. \
FIGURE 4.2
Piping system for Example 4.1.
68 FLUlD MECHANICS
through pipe B is
_ 240.7
VB = 3600 x 0.0513 1.30 It/s
and through each of pipes C is
_ 240.7
Vc = = 2.36 It/s
2 x 3600 x 0.01414
(c) Use Eq. (4.8). The mass velocity through pipe A is
13,300
GA = - - = 571,000 Ib/lt 2_h (744 kg/m2-s)
0.0233
through pipe B is
13,300
Gn = - - = 259,000 Ib/lt2-h (351 kg/m 2 -s)
0.0513
and through each of pipes C is
13,300
Gc = 470,000 Ib/ft 2-h (637 kg/m 2 _s)
2 x 0.01414
MACROSCOPIC MOMENTUM BALANCE. A momentum balance, similar to the
overall mass balance, can be written for the control volume shown in Fig. 4.3,
assuming that flow is steady and unidirectional in the x direction. The sum of all
forces acting on the fluid in the x direction, by the momentum principle, equals
the increase in the time rate of momentum of the flowing fluid. That is to say, the
sum offorces acting in the x direction equals the difference between the momentum
leaving with the fluid per unit time and that brought in per unit time by the fluid, or
"L.,F=-(Mb
1 . - M,)
. (4.9)
g,
---.!.
M, ~J_ _ _ _ _ _ _ _ _ _ _ _ _ _- - ,
(a) > J
x direction I
(b)
FIGURE 4.3
Momentum ba1ance.
BASIC EQUATIONS OF FLUID FLOW 69
MOMENTUM OF TOTAL STREAM; MOMENTUM CORRECTION FACTOR. The
momentum flow rate M of a fluid stream having a mass flow rate In and all moving
at a velocity u equals Inu. If u varies from point to point in the cross section of
the stream, however, the total momentum flow does not equal the product of the
mass flow rate and the average velocity, or IhY; in general it is somewhat greater
than this.
The necessary correction factor is best found from the convective momentum
flux, i.e., the momentum carried by the moving fluid through a unit cross-sectional
area of the channel in a unit time. This is the product of the linear velocity normal
to the cross section and the mass velocity (or mass flux). For a differential
cross-sectional area dS, then, the momentum flux is
dM
dS = (pu)u = pu 2 (4.10)
The momentum flux of the whole stream, for a constant-density flnid, is
M =pJs u2 dS (4.11)
S S
The momentum correction factor f! is defined by the relation
f! '" M{~ (4.12)
pV
Substituting from Eq. (4.11) gives
(4.13)
To find f! for any given flow situation, the variation of u with position in the cross
section must be known.
Fg
FIGURE 4.4
Forces acting on volume element
of stream tube, potential flow.
70 FLUID MECHANICS
Thus Eq. (4.9) may be written
"L,F = tiJ.g, (Pb Vb - Pa Va) (4.14)
In using this relation, care must be taken to identify and include in 2: F all force
components acting on the fluid in the direction of the velocity component in the
equation. Several such forces may appear: (1) pressure change in the direction of
flow; (2) shear stress at the boundary between the fluid stream and the conduit
or (if the conduit itself is considered to be part of the system) external forces acting
on the solid wall; (3) if the stream is inclined, the appropriate component of the
force of gravity. Assuming one-dimensional flow in the x direction, a typical
situation is represented by the equation
LF = PaSa - PbSb + Fw - Fg (4.15)
where Pa, Pb = inlet and outlet pressures, respectively
Sa, Sb = inlet and outlet cross sections, respectively
F w = net force of wall of channel on fluid
Fg = component offorce of gravity (written for flow in upward direction)
When flow is not unidirectional, the appropriate vector components of momentum
and force are used in applying Eqs. (4.14) and (4.15).
MOMENTUM BALANCE IN POTENTIAL FLOW; THE BERNOULLI EQUATION
WITHOUT FRICTION. An important relation, called the Bernoulli equation
without friction, can be derived by applying the momentum balance to the steady
flow of a fluid in potential flow.
Consider a volume element of a stream tube within a larger stream of fluid
in steady potential flow, as shown in Fig. 4.4. Assume that the cross section of the
tube increases continuously in the direction of flow. Also, assume that the axis
of the tube is straight and inclined upward at an angle if> from the vertical. Denote
the cross section, pressure, linear velocity, and elevation at the tube entrance by
S, P, u, and Z, respectively, and let the corresponding quantities at the exit be
S + I:;.S, P + I:;.p, u + I:;.u, and Z + I:;.Z. The axial length is I:;.L, and the constant
fluid density is p. The constant mass flow rate through the tube is m.
The rate of momentum flow at the tube entrance Ma is mu, and that at the
exit Mb is m(u + I:;.u). Equation (4.9) can therefore be written
LF = lill:;.u (4.16)
g,
The pressure forces normal to the cross section of the tube at the inlet and
outlet of the tube, with the terminology of Eq. (4.15), are
PbSb = (p + I:;.p)(S + I:;.S) (4.17)
Since the side of the tube is not parallel to the axis, the pressure at the side
possesses a component in the axial direction acting to increase momentum. Let
BASIC EQUATIONS OF FLUID FLOW 71
dA be an element of side area. Since the flow is potential, there is no shear force
and the local pressure p' is normal to the surface element. The pressure force is
p'dA. Its component in the direction of flow is p' dA sin "', where", is the angle
between the axis and the pressure vector at element dA. But dA sin", is also the
projection of area dA on the cross section at the discharge, so that the pressure
acting in the direction of flow is p' dS. Since the total projected area from the side
of the tube is exactly tJ.S, the total side force is
(4.18)
where p', the average value of the pressure surrounding the tube, has a value
between p and p + tJ.p.
The only other force acting on the flowing fluid is the component of gravity
acting along the axis. The volume of the tube may be written as S tJ.L, where S is
the average cross section, which has a value between Sand S + tJ.S. Then the mass
of fluid in the tube is Sp tJ.L. The component of the gravitational force opposite
to the direction of flow is
g -
Fg = - SptJ.L cos <p
g,
Since cos <p = tJ.Z/tJ.L,
(4.19)
Substitution from Eqs. (4.16) to (4.19) in Eq. (4.15) gives
,n A
- ,-,u =
A -, g-
,-,S{ji - p) - S tJ.p - tJ.p tJ.S - - Sp tJ.Z (4.20)
gc gc
Dividing Eq. (4.20) by pS tJ.L yields
m tJ.u
- - = ---- - --
p' - p tJ.S 1 tJ.p tJ.S tJ.p
+ --- - ---
g S tJ.z
(4.21)
g,pS tJ.L pS tJ.L p tJ.L pS tJ.L g, S tJ.L
Now find the limits of all terms in Eq. (4.21) as tJ.L --+ O. Then tJ.S --+ 0, S --+ S,
p' - p --+ 0, and the ratios of increments all become the corresponding differential
coefficients, so that, in the limit,
(4.22)
The mass flow rate is
m=upS
72 FLUID MECHANICS
Substituting in Eq. (4.22) gives
upS du _ 1 dp g dZ _ 0
---- -------
g,pS dL P dL g, dL
and
~ dp +! dZ + d(u 2 j2) = 0 (4.23)
p dL g, dL g,dL
Equation (4.23) is the point form of the Bernoulli equation without friction.
Although derived for the special situation of an expanding cross section and an
upward flow, the equation is applicable to the general case of constant or
contracting cross section and horizontal or downward flow (the sign of the
differential dZ corrects for change in direction).
When the cross section is constant, u does not change with position, the
term d(u 2 j2)jdL is zero, and Eq. (4.23) becomes identical with Eq. (2.3) for a
stationary fluid. In unidirectional potential flow at a constant velocity, then, the
magnitude of the velocity does not affect the pressure drop in the tube; the pressure
drop depends only on the rate of change of elevation. In a straight horizontal
tube, in consequence, there is no pressure drop in steady constant-velocity potential
flow.
The differential form of Eq. (4.23) is
2
dp +! dZ + 2. d(U ) = 0 (4.24)
p g, g, 2
Between two definite points in the tube, say stations a and b, Eq. (4.24) can
be integrated, since p is constant, to give
Pa gZa
-+-+-=-+-+-
u; Pb gZb u~
(4.25)
P g, 2g, p g, 2g,
Equation (4.25) is known as the Bernoulli equation without friction.
MECHANICAL-ENERGY EQUATION. The Bernoulli equation is a special form
of a mechanical-energy balance, as shown by the fact that all the terms in Eq.
(4.25) are scalar and have the dimensions of energy per unit mass. Each term
represents a mechanical-energy effect based on a unit mass of flowing fluid. Terms
(gjg,)Z and u2 j2g, are the mechanical potential and mechanical kinetic energy,
respectively, of a unit mass of fluid, and pj p represents mechanical work done by
forces, external to the stream, on the fluid in pushing it into the tube or the work
recovered from the fluid leaving the tube. For these reasons Eq. (4.25) represents
a special application of the principle of conservation of energy.
Discussion of the Bernoulli equation. Equation (4.25) also shows that in the absence
of friction, when the velocity u is reduced, either the height above datum Z or the
pressure p or both must increase. When the velocity increases, it does so only at
BASIC EQUATIONS OF FLUID FLOW 73
the expense of Z or p. If the height is changed, compensation must be found in a
change of either pressure or velocity.
The Bernoulli equation has a greater range of validity than its derivation
implies. Although in the derivation the assumption was made that the stream tube
is straight, the principle of conservation of energy permits the extension of the
equation to potential flow taking place in curved stream tubes. If the tube is curved, ,
the direction of the velocity changes and in the Bernoulli equation the scalar speed,
rather than the vector velocity, is used. In all real situations there are some friction
losses in the fluid and some variation of velocity within a cross section of the tube,
but in some cases these are small enough to be ignored. In other situations, by
the use of correction factors the equation can be modified for use in boundary-layer
flow, where velocity variations within a cross section occur and friction effects are
active. The corrections are discussed in the next sections.
To apply the Bernoulli equation to a specific problem it is essential to identify
the streamline or stream tube and to choose definite upstream and downstream
stations. Stations a and b are chosen on the basis of convenience and are usually
taken at locations where the most information about pressures, velocities, and
heights is available.
Example 4.2. Brine, specific gravity 60°F(60°F ~ 1.15, is draining from the bottom
of a large open tank through a 50-mm pipe. The drainpipe ends at a point 5 m below
the surface of the brine in the tank. Considering a streamline starting at the surface
of the brine in the tank and passing through the center of the drain line to the point
of discharge and assuming that friction along the streamline is negligible, calculate
the velocity of flow along the streamline at the point of discharge from the pipe.
Solution
To apply Eq. (4.25), choose station a at the brine surface and station b at the end of
the streamline at the point of discharge. In SI units, gc = 1, and may be omitted.
Since the pressure at both stations is atmospheric, Pa and Pb are equal, and pJ p = pJp.
u;
At the surface of the brine, Ua is negligible, and the term /2 is dropped. The datum
for measurement of heights can be taken through station b, so Zb = 0 and Za = 5 m.
Substitution in Eq. (4.25) gives
5g = tu;
and the velocity on the streamline at the discharge is
Ub ~ J 5 x 2 x 9.80665 ~ 9.90 m(s
Note that this velocity is independent of density and of pipe size.
BERNOULLI EQUATION: CORRECTION FOR EFFECTS OF SOLID BOUNDAR-
IES. Most fluid-flow problems encountered in engineering involve streams that
are influenced by solid boundaries and therefore contain boundary layers. This is
especially true in the flow of fluids through pipes and other equipment, where the
entire stream may be in boundary-layer flow.
To extend the Bernoulli equation to cover these practical situations, two
modifications are needed. The first, usually of minor importance, is a correction
74 FLUID MECHANICS
of the kinetic-energy term for the variation of local velocity 1I with position in the
boundary layer; the second, of major importance, is the correction of the equation
for the existence of fluid friction, which appears whenever a boundary layer forms.
Also, the usefulness of the corrected Bernoulli equation in solving problems
of flow of incompressible fluids is enhanced if provision is made in the equation
for the work done on the fluid by a pump.
KINETIC ENERGY OF STREAM. The term ,,2/2g, in Eq. (4.25) is the kinetic energy
of a unit mass of fluid all of which is flowing at the same velocity u. When the
velocity varies across the stream cross section, the kinetic energy is found in the
following manner. Consider the element of cross-sectional area dS. The mass flow
rate through this is pu dS. Each unit mass of fluid flowing through area dS carries
kinetic energy in amount u2 /2g" and the energy flow rate through area dS is
therefore
. u2 pu 3 dS
dE, = (pu dS) - =--
2g, 2g,
where E, represents the time rate of flow of kinetic energy. The total rate
of flow of kinetic energy through the entire cross section S is, assuming constant
density within the area S,
E, = l'-
2g,
ru
Js
3 dS (4.26)
The total rate of mass flow is given by Eqs. (4.3) and (4.8), and the kinetic
energy per pound of flowing fluid, which replaces u 2 /2g, in the Bernoulli equation,
is
E, _ (1/2g,) Ss u3 dS Ss
(1/2g,) u 3 dS
(4.27)
In - SsudS VS
Kinetic-energy correction factor. It is convenient to eliminate the integral of Eq.
(4.27) by a factor operating on y 2 /2g, to give the correct value of the kinetic
energy as calculated from Eq. (4.27). This factor, called the kinetic-energy correc-
tion factor, is denoted by a and is defined by
aY' == E, = Ss u3_dS
2g, m 2g,VS
3
Ss u dS
a = "":=- (4.28)
V3S
If a is known, the average velocity can be used to calculate the kinetic energy
from the average velocity by using ay 2 /2g, in place of u 2 /2g,. To calculate the
value of a from Eq. (4.28), the local velocity must be known as a function of
location in the cross section, so that the integral in the equation can be evaluated.
BASIC EQUATIONS OF FLUID FLOW 75
The same knowledge of velocity distribution is needed to calculate the value of
i7 by Eq. (4.4). As shown in Chap. 5, a = 2.0 for laminar flow and is about 1.05
for highly turbulent flow.
CORRECTION OF BERNOULLI EQUATION FOR FLUID FRICTION. Friction
manifests itself by the disappearance of mechanical energy. In frictional flow the
quantity
2
P u 9
-+-+-Z
P 2g, g,
is not constant along a streamline, as called for by Eq. (4.25), but always
decreases in the direction of flow, and in accordance with the principle of
conservation of energy, an amount of heat equivalent to the loss in mechanical
energy is generated. Fluid friction can be defined as any conversion of mechanical
energy into heat in a flowing stream.
For incompressible fluids, the Bernoulli equation is corrected for friction by
adding a term to the right-hand side of Eq. (4.25). Thus, after introducing the
kinetic-energy correction factors aa and ab, Eq. (4.25) becomes
-2 -2
Pa gZa "'aVa Pb gZb abVb h
-+-+--=-+-+--+
P g, 2g, p g, 2g,
f (4.29)
The units of hf and those of all other terms in Eq. (4.29) are energy per unit
mass. The term hf represents all the friction generated per unit mass of fluid (and
therefore all the conversion of mechanical energy into heat) that occurs in the fluid
between stations a and b. It differs from all other terms in Eq. (4.29) in two ways:
1. The mechanical terms represent conditions at specific locations, namely, the
inlet and outlet stations a and b, whereas hf represents the loss of mechanical
energy at all points between stations a and b.
2. Friction is not interconvertible with the mechanical-energy quantities.
The sign of hf' as defined by Eq. (4.29), is always positive. It is zero, of course,
in potential flow.
Friction appears in boundary layers because the work done by shear forces
in maintaining the velocity gradients in both laminar and turbulent flow is
eventually converted into heat by viscous action. Friction generated in unseparated
boundary layers is called skin Fiction. When boundary layers separate and form
wakes, additional energy dissipation appears within the wake and friction of this
type is calledJormJriction since it is a function of the position and shape of the solid.
In a given situation both skin friction and form friction may be active in
varying degrees. In the case of Fig. 3.9a, the friction is entirely skin friction; in
that of Fig. 3.9b, the friction is largely form friction, because of the large wake,
and skin friction is relatively unimportant. The total friction hf in Eq. (4.29)
includes both types of frictional loss.
76 FLUID MECHANICS
Example 4.3. Water with a density of 998 kglm' (62.3 Ib/ft') enters a 50-mm (1.969-
in.) pipe fitting horizontally, as shown in Fig. 4.5, at a steady velocity of 1.0 mjs
(3.28 ft/s) and a gauge pressure of lOO kN/m2 (2088.5Ibf/fe). It leaves the fitting
horizontally, at the same elevation, at an angle of 45° with the entrance direction.
The diameter at the outlet is 20 mm (0.787 in.). Assuming the fluid density is constant,
the kinetic-energy and momentum correction factors at both entrance and exit are
unity, and the friction loss in the fitting is negligible, calculate (a) the gauge pressure
at the exit of the fitting and (b) the forces in the x and y directions exerted by the
fitting on the fluid.
Solution
(a) V. ~ 1.0 m/so From Eq. (4.7),
_ _(D.)2
Vb ~ V. Db
(50)2
~ 1.0 20 ~ 6.25 m/s
P. ~ lOO kN/m2
The outlet pressure Pb is found from Eq. (4.29). Since Za = Zb and hJ may be
neglected, Eq. (4.29) becomes
Pa - Pb V~ - V;
p 2
from which
998(6.25 2 - 1.0 2)
lOO - --':-::-:-::--::---'
1000 x 2
~ lOO -18.99 = 81.01 kN/m2 (11.75Ibf/in.2)
Note that Bc is omitted when working in SI units (but B is not).
(b) The forces acting on the fluid are found by combining Eqs. (4.14) and (4.15).
For the x direction, since Fg = 0 for horizontal flow, this gives
(4.30)
FIGURE 45
Flow through reducing fitting, viewed
from the top. Example 4.3.
BASIC EQUATIONS OF FLUID FLOW 77
where Sa.x and Sb.x are the projected areas of Sa and Sb on planes normal to the
initial flow direction. (Recall that pressure p is a scalar quantity.) Since the flow enters
in the x direction, Va.x = Va and
S•. , = S. = ~ 0.050' = 0.001964 m'
From Fig. 4.5
Vb., = Vb cos e = 6.25 cos 45· = 4.42 m/s
Also
Sb x "
. = Sb sin 0 = -4 0.020' sin 45· = 0.000222 m'
From Eq. (4.6)
I;' = V.pS. = 1.0 x 998 x 0.001964 = 1.960 kg/s
Substituting in Eq. (4.30) and solving for Fw,x, assuming Pa = Pb = 1, gives
Fw.x = 1.96(4.42 - 1.0) - 100,000 x 0.001964 + 81,010 x 0.000222
= 6.7 - 196.4 + 18.0 = -171.7 N (-38.6Ib,)
Similarly for the y direction, Va,}, = 0 and Sa,}, = 0, and
Vb., = Vb sin 0 = 4.42 m/s Sb., = Sb cos 0 = 0.000222 m'
Hence
Fw,y = lil(Pb Vb.y - Pa Va,y) - PaSa,y + PbSb,y
= 1.96(4.42 - 0) - 0 + 81.01 x 0.000222 x 1000
= 8.66 + 17.98 = 26.64 N (5.991b,)
PUMP WORK IN BERNOULLl EQUATION. A pump is used in a flow system to
increase the mechanical energy of the flowing fluid, the increase being used to
maintain flow, provide kinetic energy, offset friction losses, and~sometimes~in
crease the potential energy. Assume that a pump is installed between the stations
a and b linked by Eq. (4.29). Let Wp be the work done by the pump per unit mass
of fluid. Since the Bernoulli equation is a balance of mechanical energy only,
account must be taken of friction occurring within the pump. In an actual pump
not only are all the sources of fluid friction active, but mechanical friction occurs
as well, in bearings and seals or stuffing boxes. The mechanical energy supplied
to the pump as negative shaft work must be discounted by these frictional losses
to give the net mechanical energy actually available to the flowing fluid. Let hIp
be the total friction in the pump per unit mass of fluid. Then the net work to the
78 FLUID MECHANICS
fluid is Wp - hfp' In practice, in place of hfp a pump efficiency denoted by '1 is used,
defined by the equation
or
Wp - hfp
'1 = (4.31)
Wp
The mechanical energy delivered to the fluid is, then, q Wp , where q < 1. Equation
(4.29) corrected for pump work is
P g z
(J, j72
-,,+_a+~+11W
P gZ (J, j72
=~+-b+~+hf (4.32)
p g, 2g, Ppg, 2g,
Equation (4.32) is a final working equation for problems on the flow of in compress-
ible fluids.
Example 4.4. In the equipment shown in Fig 4.6, a pump draws a solution of specific
gravity 1.84 from a storage tank through a 3-in. (75-mm) Schedule 40 steel pipe. The
efficiency of the pump is 60 percent. The velocity in the suction line is 3 ft/s (0.914 m/s).
The pump discharges through a 2-in. (50-mm) Schedule 40 pipe to an overhead tank.
The end of the discharge pipe is 50 ft (15.2 m) above the level of the solution in the
feed tank. Friction losses in the entire piping system are 10 ft-Ibf/lb (29.9 Jfkg). What
pressure must the pump develop? What is the power of the pump?
Solution
Use Eq. (4.32). Take station a at the surface of the liquid in the tank and station b
at the discharge end of the 2-in. pipe. Take the datum plane for elevations through
the station a. Since the pressure at both stations is atmospheric, Pa = Pb' The velocity
at station a is negligible because of the large diameter of the tank in comparison
with that of the pipe. For turbulent flows the kinetic-energy factor 0: can be taken
as 1.0 with negligible error. Equation (4.32) becomes
W," =-2,
g V;
+- + hf
gc 20c
2in.
T
50leel
~~J FIGURE 4.6
Flow diagram for Example 4.4.
BASIC EQUATIONS OF FLUID FLOW 79
By Appendix 5, the cross-sectional areas of the 3- and 2-in. pipes are 0.0513 and
0.0233 ft2, respectively. The velocity in the 2-in. pipe is
_ 3 x 0.0513
Vb = 0.0233 6.61 ftls
Then
g 6.6J2
0.60w" = 50 - + - - + 10 = 60.68
g, 64.34
and
60.68
Wp = - - = 101.1 ft-IbJ/lb
0.60
The pressure developed by the pump can be found by writing Eq. (4.32) over the
pump itself. Station a is in the suction connection and station b is in the pump
discharge. The difference in level between suction and discharge can be neglected, so
Z, = Zb, and Eq. (4.32) becomes
Pb- Pa
p
The pressure developed by the pump is
Pb - p, = 1.84 x 62.37 (3' - 6.61' + 60.68)
2 x 32.17
6902
= 6902lb J lft' or - - = 47.9Ibflin.' (330 kN/m')
144
The power used by the pump is the product of Wp and the mass flow rate divided
by the conversion factor, 1 hp = 550 ft-Ibfls. The mass flow rate is
rh = 0.0513 x 3 x 1.84 x 62.37 = 17.66 Ibis
and the power is
InWp 17.66 x 101.1
p = - = = 3.25 hp (2.42 kW)
550 550
ANGULAR-MOMENTUM EQUATION. Analysis of the performance of rotating
fluid-handling machinery such as pumps, turbines, and agitators is facilitated by
the use of force moments and angular momentum. The moment of a force F about
point 0 is the vector product of F and the position vector r of a point on the line
of action of the vector from O. When a force, say Fo, acts at right angles to the
80 FLUID MECHANICS
Q
Dire~tion of
1 rotation
FIGURE 4.7
Angular momentum of flowing liquid.
position vector, at a radial distance r from point 0, the moment of the force equals
the torque T, or
(4.33)
The angular momentum (also called the moment of momentwn) of an object
moving about a center of rotation is the vector product of the position vector and
the tangential momentum vector of the object (its mass times its tangential
component of velocity). Figure 4.7 shows the rotation for a situation involving
two-dimensional flow: fluid at point P is moving about a point 0 at a velocity V,
which has radial and tangential components u, and u" respectively. The angular
momentum of a mass m of fluid at point P is therefore rmu,.
Suppose that Fig. 4.7 represents part of the impeller of a centrifugal pump
or turbine through which fluid is flowing at a constant mass rate nl. It enters
at point Q near the center of rotation at a radial distance r, from point 0 and
leaves at radial distance r2. Its tangential velocities at these points are u" and U02 '
respectively. The tangential force F, on the fluid at point P is proportional to the
rate of change of angular momentum of the fluid; hence the torque is given, from
Eq. (4.33), by the relation
In
T = For2 = - (r 2u02 - r,u,,) (4.34)
g,
Equation (4.34) is the angular-momentum equation for steady two-dimen-
sional flow. It is analogous to Eq. (4.14), the momentum equation. It is assumed
in deriving Eq. (4.34) that at any given radial distance r all the fluid is moving with
the same velocity, so /3, = /32 = 1. Applications of Eq. (4.34) are given in Chaps.
8 and 9.
BASIC EQUATIONS OF FLUID FLOW 81
SYMBOLS
A Area, m' or ft'
D Diameter of circular channel, m or ft; D" at station a; Db, at station b
Ek Kinetic energy of fluid, J or ft-lbJ; E" time rate of flow of kinetic energy,
J/s or ft-lbJls
F Force, N or lbr ; F g , component of gravity force; F", net force of channel
wall on fluid; F W,X' component of F w in x direction; F w,Y' component in
y direction; F " tangential force or force component
G Mass velocity, kg/m'-s or Ib/ft'-s
g Acceleration of gravity, mls' or ft/s2
g, Newton's-law proportionality factor, 32.174 ft-Ib/lb rS'
h Friction loss, Jjkg or ft-lbJflb; hr' friction loss in conduit between stations
a and b; hJp, total friction loss in pump
L Length, m or ft
M Momentum, kg-m/s or ft-Ibis; M, time rate of flow of momentum, kg_m/s2
or ft-Ibis'; M" at station a; Mh , at station b
In Mass, kg or lb; rn, mass flow rate, kgls or Ibis
P Power, kW or hp
p Pressure, N/m' or IbJlft'; p" at station a; Ph at station b; p', normal to
surface; ji', average value of pi
q Volumetric flow rate, m'ls or ft'/s
r Radial distance, m or ft; r1 , at station 1; r" at station 2
S Cross-sectional area, m2 or fe; Su! at station a; Sb! at station b; Su,x, Sb,x!
projections of Su and Sb on planes normal to x axis; SU,y, Sb,y, projections
on planes normal to y axis; S, average value
T Torque, N-m or ft-lb J
u Velocity or velocity component in x direction, mls or ft/s; u" at station
a; Ub, at station b; UT' in radial direction; Uo, in tangential direction
V Total velocity vector, mls or ft/s; V, average velocity; V" at station a; Vh'
at station b; VX! component of average velocity in x direction; Vy ,
component in y direction
Wp Pump work per unit mass of fluid, Jig or ft-lbJflb
Z Height above datum plane, m or ft; Z., at station a; Zh, at station b
Greek letters
" Kinetic-energy correction factor defined by Eq. (4.28); "., at station a; "b,
at station b
P Momentum correction factor defined by Eq. (4.12); P., at station a; Ph' at
station b; p" at station 1; P" at station 2
~ Overall efficiency of pump, dimensionless
e Angle of discharge pipe, Fig. 4.5
P Density, kglm' or lb/ft'; P., station a; Ph, at station b
</> Angle with vertical
'" Angle between axis and pressure vector, in Fig. 4.4
82 FLUID MECHANICS
PROBLEMS
4.1. A liquid is flowing in steady flow through a 75-mm pipe. The local velocity varies
with distance from the pipe axis as shown in Table 4.1. Calculate (a) average velo-
city if, (b) kinetic-energy correction factor a, and (c) momentum correction factor p.
TABLE 4.1
Data for Prob. 4.1
Local Distance Local Distance
velocity u, from pipe velocity 11, from pipe
rnls axis, mm rnls axis, mm
1.042 0 0.919 22.50
1.033 3.75 0.864 26.25
1.019 7.50 0.809 30.00
0.996 11.25 0.699 33.75
0.978 15.00 0.507 35.625
0.955 18.75 0 37.50
4.2. (a) A water tank is 30 ft in diameter and the normal depth is 25 ft. The outlet is a 4-in.
horizontal pipe at the bottom. If this pipe is sheared off close to the tank, what is the
initial flow rate of water from the tank? (Neglect friction loss in the short stub of pipe.)
(b) How long will it take for the tank to be empty? (c) Calculate the average flow rate
and compare it with the initial flow rate.
4.3. Water at 200C is pumped at a constant rate of 9 m 3jh from a large reservoir resting
on the floor to the open top of an experimental absorption tower. The point of
discharge is 5 m above the floor, and frictional losses in the 50-mm pipe from the
reservoir to the tower amount to 2.5 Jjkg. At what height in the reservoir must the
water level be kept if the pump can develop only 0.1 kW?
4.4. Water enters a lOO-mm-ID 90" elbow, positioned in a horizontal plane at a velocity
of 6 mjs and a pressure of 70 kNjm 2 gauge. Neglecting friction, what are the magni-
tude and the direction of the force that must be applied to the elbow to keep it in
position without moving?
REFERENCES
1. Bennett, C. 0., and 1. E. Myers: Momentum, Heat, alld Mass Transfer, 3rd ed., McGraw-Hill, New
York, 1982.
2. Bird, R. 8., W. E. Stewart, and E. N. Lightfoot: Transport Phenomena, Wiley, New York, 1960.
3. Streeter, V. L., and E. B. WyJie: Fluid Mechanics, 8th ed., McGraw-Hill, New York, 1985.
CHAPTER
5
FLOW
OF
INCOMPRESSIBLE
FLUIDS
IN
CONDUITS
AND
THIN
LAYERS
Industrial processes necessarily require the flow of fluids through pipes, conduits,
aud processing equipment. Chemical engineers most often are concerned with flow
through closed pipes filled with the moving fluid. They also encounter problems
involving the flow of fluids in partially filled pipes, in layers down vertically inclined
surfaces, through beds of solids, and in agitated vessels.
This chapter is concerned with flow through closed pipes and in layers on
surfaces. Other types of flow are discussed in later chapters.
FLOW OF INCOMPRESSIBLE FLUIDS IN
PIPES
Flow in circular conduits is important not only in its own right as an engineering
operation but as an example of the quantitative relationships involving fluid flow
in general. It is therefore discussed in some detail in this chapter. This discussion
is restricted to steady flow.
84 FLUID MECHANICS
SHEAR-STRESS DISTRIBUTION IN A CYLINDRICAL TUBE. Consider the steady
flow of a viscous fluid at constant density in fully developed flow through a
horizontal tube. Visualize a disk-shaped element of fluid, concentric with the axis
of the tube, of radius l' and length dL, as shown in Fig. 5.1. Assume the element
is isolated as a free body. Let the fluid pressure on the upstream and downstream
faces of the disk be p and p + dp, respectively. Since the fluid possesses a viscosity,
a shear force opposing flow will exist on the rim of the eler.lent. Apply the
momentum equation (4.14) between the two faces of the disk. Since the flow is
fully developed, Pb = Pa, and Vb = Va, so that L F = O. The quantities for substitu-
tion in Eq. (4.15) are .
Sa = Sb = nr2 Pa = P PbSb = (nl")(p + dp)
The shear force F, acting on the rim of the element is the product of the shear
stress and the cylindrical area, or (2nl'dL)!. [Force F, equals Fw in Eq. (4.15).]
Since the channel is horizontal, F, is zero. Substituting these quantities into Eq.
(4.15) gives
L: F = nl'2p - n1'2(p + dp) - (2nl' dL)r = 0
Simplifying this equation and dividing by nI" dL gives
dp 2r
-+-=0 (5.1)
dL l'
In steady flow, either laminar or turbulent, the pressure at any given cross section
of a stream tube is constant, so that dp/dL is independent of 1'. Equation (5.1) can
be written for the entire cross section of the tube by taking t = tw and r = 1"11"
where r" is the shear stress at the wall of the conduit and 1'" is the radius of the
tube. Equation (5.1) then becomes
dp + 2rw = 0 (5.2)
dL I'll'
Subtracting Eq. (5.1) from Eq. (5.2) gives
1:"11' 1:"
(5.3)
rw r
FIGURE 5.1
Fluid element in steady flow through pipe.
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 85
t of pipe
Pipe wall
I' ,,,-----+1·1
o SHEAR STRESS, '
FIGURE 5.2
Variation of shear stress in pipe.
Also, when r = 0, , = O. The simple linear relation between, and r in Eq. (5.3) is
shown graphically in Fig. 5.2.
RELATION BETWEEN SKIN FRICTION AND WALL SHEAR. Equation (4.29) can
be written over a definite length ilL of the complete stream. In Chap. 4, /lp was
defined as Pb - p" but usually (though not always) p, > Pb and thus Pb - p, is
usually negative. The term /lp is commonly used for pressure drop, i.e., p, - Pb,
and this terminology is employed in this and subsequent chapters. Here, then,
p, = P, Pb = P - /lp, Zb - Z, = 0, and the two kinetic-energy terms cancel. Also,
the only kind of friction is skin friction between the wall and the fluid stream.
Denote this by hi" Then Eq. (4.29) becomes
E_p-Ilp +'h
P- P i'
or
IIp
-=h fs (5.4)
p
For a definite length of pipe, dp/dL in Eq. (5.2) becomes /lp/ilL. Eliminating
/lp from Eqs. (5.2) and (5.4) gives the following relation between hi, and 'wO
21"\11 41"w
hi, = --IlL = --IlL (5.5)
p rw pD
where D is the diameter of the pipe.
THE FRICTION FACTOR. Another common parameter, especially useful in the
study of turbulent flow, is the friction factor,t denoted by J and defined as the
t The friction factor f, defined by Eq. (5.6), is called the Fanning frictiolljactor. Another friction factor
common in fluid mechanics literature and called the Blasius or Darcy friction factor is 4f.
86 FLUID MECHANICS
ratio of the wall shear stress to the product of the density and the velocity head
jl2/2g,:
(5.6)
RELATIONS BETWEEN SKIN-FRICTION PARAMETERS. The four common
quantities used to measure skin friction in pipes, hIs, I1ps' 1"w, and f, are related
by the equations
(5.7)
from which
J = !lp,g,D
(5.7a)
2!l LpV 2
The subscript s is used in !lp, and hf' to call attention to the fact that in Eqs. (5.7)
and (5.7a) these quantities, when they are associated with the Fanning friction
factor, relate only to skin Fiction. If other terms in the Bernoulli equation are
present or if form friction is also active, Po - Ph differs from !lp,. If boundary-layer
separation occurs, h f is greater than hfs' The last term in Eq. (5.7), which includes
the friction factor, is written in a manner to show the relation of hfs to the velocity
head fl 2 /2g,.
The various forms in Eq. (5.7) are convenient for specific purposes, and all
are frequently encountered in the literature and in practice.
Laminar Flow in Pipes
Equations (5.1) to (5.7a) apply both to laminar and turbulent flow provided the
fluid is incompressible and the flow is steady and fully developed. Use of the
equations for more detailed calculations depends upon the mechanism of shear
and therefore also upon whether the flow is laminar or turbulent. Because the
shear-stress law for laminar flow is simple, the equations can be applied most
readily to laminar flow. The treatment is especially straightforward for a newtonian
fluid.
LAMINAR FLOW OF NEWTONIAN FLUIDS. In the discussion of general fluid-
flow relations in Chap. 4 it was shown that the key step in their derivations is
that of relating local velocity u to position in the stream tube. In circular channels,
because of symmetry about the axis of the tube, the local velocity u depends only
on the radius r. Also, the element of area dS is that of a thin ring of radius r with
width dr. The area of this elementary ring is
dS = 2nr dr (5.8)
The desired velocity-distribution relation is u as a function of r.
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 87
A direct method of obtaining the velocity distribution for newtonian fluids
is to use the definition of viscosity [Eq. (3.3)] written as
~g,
/1= - - - (5.9)
du/dl'
The negative sign in the equation accounts for the fact that in a pipe u decreases
as I' increases. Eliminating r from Eqs. (5.3) and (5.9) provides the following
ordinary differential equation relating u and 1':
du e 'Cg 'Cwg e
~= --= ---I' (5.10)
dr /1 '\1'/1
Integration of Eq. (5.10) with the boundary condition u = 0, I' = 1'" gives
f."
o
du = - :.wgc
wJ.i
f'
r",
r dr
(5.11)
The maximum value of the local velocity is denoted by urn" and is located
at the center of the pipe. The value of Urn" is found from Eq. (5.11) by substituting
o for 1', giving
'Cwgc"w
li max =-- (5.12)
2/1
Dividing Eq. (5.11) by Eq. (5.12) gives the following relationship for the ratio
of the local velocity to the maximum velocity:
U
-=1- - (1')2 (5.13)
Urnux rw
The form of Eq. (5.13) shows that in laminar flow the velocity distribution with
respect to radius is a parabola with the apex at the centerline of the pipe. The
distribution is shown as the dashed line in Fig. 5.3.
AVERAGE VELOCITY, KINETIC-ENERGY FACTOR, AND MOMENTUM COR-
RECTION FACTOR FOR LAMINAR FLOW OF NEWTONIAN FLUIDS. Exact
formulas for the average velocity P, the kinetic-energy correction factor ", and the
momentum correction factor {J are readily calculated from the defining equations
in Chap. 4 and the velocity distribution shown in Eq. (5.11).
Average velocity. Substitution of dS from Eq. (5.8), U from Eq. (5.11), and nl'~. for
S into Eq. (4.4) gives
(5.14)
88 FLUID MECHANICS
1.0
--- -- -- t--
8. 0.8
'<i
'0 0 .6
-- --- - i"--..
~ 0.4
- ........ ... "-
o
::: 0.2
Lominor flow- ,_\ ,
E
~ 0- - - r-- 1-- - -- t-- - C- - - f -
go Q2 Turblllent flow __ ~j
/
~ 0.4
~
.~ 0.6 ~
~~
'\ /
15 ~-- V
- --- --- - --
~ 0.8 -~-
1.0
o 0.10 0,20 0,30 0,40 0,50 0,60 Q.70 0,80 0,90 1.00
Fraction of maximum velocity
FIGURE 5.3
Velocity distribution in pipe, fully developed flow of newt ani an fluid, for laminar flow and for turbulent
How at N Rc = 10,000.
Comparison of Eqs, (5,12) and (5.14) shows that
Y
-=0,5 (5,15)
umax
The average velocity is precisely one-half the maximum velocity,
Kinetic-energy correction factor. The kinetic-energy factor a is calculated from Eq.
(4.29), using Eqs, (5,8) for as, (5.11) for U, and (5,14) for Y. The final result is a = 2.0.
The proper term for kinetic energy in the Bernoulli equation for laminar flow is
therefore y 2 /g"
Momentum correction factor. Again, to obtain the value of f! for laminar flow, the
defining equation (4,13) is used. The result is f! =~,
HAGEN-POISEUILLE EQUATION. For practical calculations, Eq, (5.14) is trans-
formed by eliminating 'w in favor of iJ.p, by use ofEq, (5.7) and using pipe diameter
in place of pipe radius, The result is
Y = iJ.p, g, r w "w = Ap, g))2
i'lL 2 4Jl 32 i'lL Jl
Solving for Ap, gives
32 i'lL Y Jl
Ap, = 2 (5.16)
goD
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND·
and since I!.p, = 4rwlD I!.L,
8 VI'
r =--
W gjJ
Substituting from Eq. (5.17) into Eq: (5.6) gives
J=16! =~ (5.18)
DVp N R,
Equation (5.16) is the Hagen-Poiseuille equation. One of its uses is in the
experimental measurement of viscosity, by measuring the pressure drop and
volumetric flow rate through a tube of known length and diameter. From the flow
rate V is calculated by Eq. (4.4) and I' is calculated by Eq. (5.16). In practice,
corrections for kinetic-energy and entrance effects are necessary.
LAMINAR FLOW OF NON-NEWTONIAN LIQUIDS. Because of the difference in
the relation between shear stress and velocity gradient, the shape of the velocity
profile for non-newtonian liquids differs from that of a newtonian liquid. In the
more complicated situations of non-newtonian flow the shape of the profile is
determined experimentally. For the simpler cases such as the power-law model
[Eq. (3.7)] or the Bingham model [Eq. (3.6)] the same methods used for determin-
ing the flow parameters of a newtonian fluid can be used for non-newtonian fluids
in these categories.
For fluids following the power-law model the velocity variation with radius
follows the formula
r g )1/11' r1;t 1/11' _ rl + l/n'
U = -'-'-'
( rwK'
_'c..'- - - - - (5.19)
1 + Iln'
Velocity profiles defined by Eq. (5.19) when n' = 0.5 (a pseudoplastic fluid),
n' = 1.0 (a newtonian fluid), and n' = 2.0 (a dilatant fluid) are shown in Fig. 5.4.
In all cases K' is assumed to be the same. The curve for the dilatant fluid is
narrOwer and more pointed than a true parabola; that for the pseudoplastic fluid
is blunter and flatter.
The pressure difference for the flow of a power-law fluid is found by the
methods used in deriving Eq. (5.16) for a newtonian fluid. The result is
Ilps
2K' (3n' +
= - --,-
1)"' V"' 11' + 1 ilL (5.20)
gc n rw
Equation (5.20) corresponds to Eq. (5.16) for a newtonian fluid.
The behavior of fluids following the Bingham-plastic flow model is somewhat
more complicated. The general shape of the curve of u versus r is shown in Fig,
5.5a. In the central portion of the tube there is no velocity variation with the
radius, and the velocity gradient is confined to an annular space between the
central portion and tube wall. The center portion is moving in plug flow. In this
region the shear stress that would be generated in other types of flow is too small
~Uto MECHANICS
2.8
--'"
2.6
2.4
..¥ ~
Dilatant: n' = 2
2.2
2.0
1.8 ....... '\.
Newtonfan: n' 1
"""" ~
u
1.6
i7 1.4
1.2 -
/
Pseudoplastic:
n'~O.5
~
, ~
1.0 I~
0.8 ~
0.6 ~~ r-
0.4
0.2 ~
\
00 .1 .2 .3 .4 .5 .6 .7 .8 .9 1.0 FIGURE 5.4
r Velocity profiles in the laminar flow of
rw newtonian and non~newtonian liquids.
to overcome the threshold shear To' The shear diagram is shown in Fig. S.Sb. For
the velocity variation in the annular space between the tube wall and the plug,
the following equation applies:
u = -g, (rw - r) - [Tw (1 + -:-r) - TO ] (S.21)
K 2 'w
where K is a constant. The boundary between the plug and the remaining fluid
is found by differentiating Eq. (S.21) and setting the velocity gradient equal to
zero, or more simply by reading the value from Fig. S.Sb. The result is
(S.22)
The velocity in the central core u" the speed at which the plug is moving, is
found by substituting the value of r, from Eq. (S.22) for r in Eq. (S.21) and
rearranging. This gives
(S.23)
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 91
Pipe wall
Flow It of Pipe
~rt------------------+--r----~-------
r. Plug flow in
L this region
o Velocity, u
(a)
Pipe wall
IPlug flow
t of P1i?eT__' t---------="'!-[~----Jr-----'-·I--_- . --- . - - . -
[
[
I
To------l Pi e wall
o Shear stress, r ----;.-
(b)
FIGURE 5.5
(a) Velocity profile. (b) Shear diagram for Bingham-plastic flow.
An interesting observation with some non-newtonian mixtures 7 is that at
high shear they appear to violate the zero-velocity boundary condition at the wall.
For multiphase fluids such as suspensions and fiber-filled polymers, this effect is
believed to be the result of a thin layer near the wall that is depleted of particulates
or fibers and thus has a lower viscosity than the bulk of the fluid. This gives the
appearance of a "slip" at the wall. Empirical formulas are often used in the
literature to account for such wall effects13
92 FLUID MECHANICS
Turbulent Flow in Pipes and Closed Channels
In flow of fluid through a closed channel turbulence cannot exist permanently at
the boundary between the solid and the flowing fluid. The velocity at the interface
is zero because of the adherence of the fluid to the solid, and (except very.
infrequently) velocity components normal to the wall do not exist. Within a thin
volume immediately adjacent to the wall, the velocity gradient is essentially
constant and the flow is viscous most of the time. This volume is called the viscous
sublayer. Formerly it was assumed that this sublayer had a definite thickness and
was always free from eddies, but measurements have shown velocity fluctuations
in the sublayer caused by occasional eddies from the turbulent fluid moving into
this region. Very close to the wall, eddies are infrequent, but there is no region
that is completely free of eddies. Within the viscous sublayer only viscous shear
is important, and eddy diffusion, if present at all, is minor.
The viscous sublayer occupies only a very small fraction of the total cross
section. It has no sharp upper boundary, and its thickness is difficult to define. A
transition layer exists immediately adjacent to the viscous sublayer in which both
viscous shear and shear due to eddy diffusion exist. The transition layer, which is
sometimes called a buffer layer, also is relatively thin. The bulk of the cross section
of the flowing stream is occupied by entirely turbulent flow called the turbulent
core. In the turbulent core viscous shear is negligible in comparison with that from
eddy viscosity.
VELOCITY DISTRIBUTION FOR TURBULENT FLOW. Because of the depen-
dence of important flow parameters on velocity distribution, considerable study,
both theoretical and experimental, has been devoted for determining the velocity
distribution in turbulent flow. Although the problem has not been completely
solved, useful relationships are available that may be used to calculate the
important characteristics of turbulence; and the results of theoretical calculations
check with experimental data reasonably well.
A typical velocity distribution for a newtonian fluid moving in turbulent
flow in a smooth pipe at a Reynolds number of 10,000 is shown in Fig. 5.3. The
figure also shows the velocity distribution for laminar flow at the same maximum
velocity at the center of the pipe. The curve for turbulent flow is clearly much
flatter than that for laminar flow, and the difference between the average velocity
and the maximum velocity is considerably less. At still higher Reynolds numbers
the curve for turbulent flow would be even flatter than that in Fig. 5.3.
In turbulent flow, as in laminar flow, the velocity gradient is zero at the
centerline. It is known that the eddies in the turbulent core are large but of low
intensity, and those in the transition zone are small but intense. Most of the
kinetic-energy content of the eddies lies in the buffer zone and the outer portion
of the turbulent core. At the centerline the turbulence is isotropic. In all other
areas of the turbulent-flow regime, turbulence is anisotropic; otherwise, there
would be no shear.
It is customary to express the velocity distribution in turbulent flow not as
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 93
velocity vs. distance but in terms of dimensionless parameters defined by the
following equations:
(5.24)
U
u+ : : - (5.25)
u*
+ yu*p y ~
y :: - - = - V 7: w gc p (5.26)
. J1 J1
where u* = friction velocity
u+ = velocity quotient, dimensionless
y+ = distance, dimensionless
y = distance from wall of tube
Note that y+ may be considered to be a Reynolds number based on the
friction velocity and the distance from the wall. The relationship between y, 1", and
1"", the radius of the tube, is
"w = l' + y (5.27)
Equations relating u+ to y+ are called universal velocity-distribution laws.
UNIVERSAL VELOCITY-DISTRIBUTION EQUATIONS. Since the viscous sub-
layer is very thin, I" "" I" w' and Eq. (5.10) can be written, with the substitution of -dy
for dl", as
du 'wg,
(5.28)
dy J1
Substituting u* from Eq. (5.24), u+ from Eq. (5.25), and y+ from Eq. (5.26) into
Eq. (5.28) gives
du+
-=1
dy+
Integrating, with the lower limits u+ = y+ = 0, gives, for the velocity distribution
in the laminar sublayer,
u+ = y+ (5.29)
An empirical equation for the so-called buffer layer is
u+ = 5.00 In y+ - 3.05 (5.30)
For the turbulent core a number of correlations has been proposed. An
equation proposed by Prandtl!O with empirical constants, is
u+ = 2.5 In y+ + 5.5 (5.31)
94 FLUID MECHANICS
1"V
25
20
_,V'''O~~~ 1-8uL. "Y"~ t-lbu,Jcm,
sublayer
)~
5
[;Y'
V
10 - ~Z
<0'/
5
V
1/
0
7'
3 5 10 30 50 100 300 500 1,000
y'
FIGURE 5.6
Universal velocity distribution; turbulent flow of newtonian fluid in smooth pipe.
Figure 5.6 is a semilogarithmic plot of Eqs. (5.29), (5.30), and (5.31). From
the two intersections of the three lines representing the equations the ranges
covered by the equations are as follows:
Equation (5.29), for the viscous sublayer: y+ < 5
Equation (5.30), for the buffer zone: 5 < y+ < 30
Equation (5.31), for the turbulent core: 30 < y+
LIMITATIONS OF UNIVERSAL VELOCITY·DISTRIBUTION LAWS. The univer·
sal velocity equations have a number of limitations. It is certain that the buffer
zone has no independent existence and that there is no discontinuity between the
buffer zone and the turbulent core. Also, there is doubt as to the reality of the
existence of a truly viscous sublayer. The equations do not apply well for Reynolds
numbers from the critical to approximately 10,000, and it is known that a simple
y+ ·u+ relationship is not adequate for the turbulent core near the buffer zone or
in the buffer zone itself. Finally, Eq. (5.31) calls for a finite velocity gradient at the
centerline of the pipe, although it is known that the gradient at this point must
be zero.
Much research has been devoted to improving the velocity·distribution
equations and eliminating or reducing some of their deficiencies. This work is
reported in advanced texts 3 •11 but is beyond the scope of this book.
FLOW QUANTITIES FOR TURBULENT FLOW IN SMOOTH ROUND PIPES.
With a velocity·distribution relation at hand, the important flow quantities can
be calculated by the usual methods. The quantities of interest are the average
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 95
velocity in terms of the maximum velocity at the center of the pipe; relations
linking the flow-resistance parameters 'wand f with the average velocity, the
maximum velocity, and the Reynolds number; the kinetic-energy correction factor
a; and the momentum correction factor {3.
Calculation of the flow quantities requires an integration with pipe radius
from the centerline of the pipe to the wall. Strictly, the integration should be
conducted in three parts, the first over the range y+ = 0 to y+ = 5, using Eq.
(5.29); the second from y+ = 5 to y+ = 30, using Eq. (5.30); and the third from
y+ = 30 to its value at the center of the pipe, using Eq. (5.31). Because of the
thinness of the layers covered by the first two integrations, they may be neglected,
and for approximate calculations a single integration based on Eq. (5.31) over the
entire range r = 0 to r = r" is justified, even though this predicts a finite value of
velocity at the pipe wall.
Average velocity. Equation (5.31) may be written for the centerline ofthe pipe as
u: = 2.5 In y: + 5.5 (5.32)
where u: and y: are the values of u+ and y+ at the centerline, respectively. Also,
by Eqs. (5.25) and (5.26)
+ U max
U =- (5.33)
, u*
(5.34)
where Urn., is the maximum velocity at the centerline and v = 1'/p.
Subtracting Eq. (5.32) from Eq. (5.31) yields
+
Y
u+ =u,+ +2.5In + (5.35)
y,
The average velocity ji is, from Eq. (4.4) after substituting nr~ for Sand 2nr dr
for dS,
- =2n
V - I'w urdr (5.36)
1!r~ 0
From Eq. (5.27) r = r" - y and dr = -dy. Also, when r = 0, y = r", and when
r = r", y = O. Equation (5.36) becomes, after elimination of r,
V- = 2"
2 I'w u(r" - y) dy (5.37)
"w 0
Equation (5.37) can be written in dimensionless parameters by substituting u from
Eq. (5.25), y from Eq. (5.26), and u+ from Eq. (5.35). This gives
(5.38)
96 FLUID MECHANICS
Formal integration of Eq. (5.38)t gives
jI 1
-=--=u/ -3.75 (5.39)
u* J1ji
Substituting u/ from Eq. (5.33) and u* from Eq. (5.24) into Eq. (5.39) gives
jI 1
(5.40)
urn., 1 + (3.75J1ji)
Equation (5.40) gives values that are somewhat too high because the low velocities
of the fluid in the layers near the wall, some 2 percent of the total volume flow,
are not properly taken into account.
The Reynolds number-friction factor law for smooth tubes. The equations at hand
can be used to derive an important relation between N R, and J for turbulent flow
in smooth round pipes. This equation is derived by appropriate substitutions into
Eq. (5.32). From the defining equation of y/ [Eq. (5.34)] and from the definition
of u* [Eq. (5.24)J
y,
+ = rwjl
v,,)'2
fl.. = DV 2vJ1ji = N2,,)'2fl.. = N R',,)'8fl..
R,
(5.41)
From Eq. (5.39)
+ 1
u, = J1ji + 3.75 (5.42)
Substituting u/ from Eq. (5.42) and y/ from Eq. (5.41) into Eq. (5.32) gives, after
rearrangement, the von Karman equation '
(5.43)
The kinetic-energy and momentum correction factors. Values of " and f3 for
turbulent flow are closer to unity than for laminar flow. Equations for these
correction factors are readily obtained, however, by integrating Eqs. (4.13) and
(4.28), which define them, and using the logarithmic velocity law. The equations
so found are
,,= 1 + 0.78J(15 - 15.9J7) (5.44)
f3 =1 + 3.9lf (5.45)
t Substitution of x = y+ /yt and use of standard integral tables suffices for this integration Also, for
the lower limit, x In x = 0 and x 2 1n x = 0 when x = O. From Eq. (5.24), fl/u* = 1/$2.
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 97
For turbulent flow J is of the order of 0.004 (see Fig. 5.9) and for this value
a = 1.044 and f3 = 1.016. Hence the error is usually negligible if both a and f3 are
assumed to equal unity.
The kinetic-energy correction factor may be important in applying
Bernoulli's theorem between stations when one is in laminar flow and the other in
turbulent flow. Also, factors Cl. and f3 are of some importance in certain types of
compact heat-exchange equipment, where there are many changes in size of the
fluid channel and where the tubes or heat-transfer surfaces themselves are short. 2
In most practical situations both are taken as unity in turbulent flow.
RELATIONS BETWEEN MAXIMUM VELOCITY AND AVERAGE VELOCITY. The
quantities N Ro and ratio VfUm" are useful in relating the average velocity to the
maximum velocity in the center of the tube as a function of flow conditions; for
example, an important method of measuring fluid flow is the pitot tube (page 229),
which can be used to measure urn,,, and this relationship is then used to determine
the average velocity from this single observation.
Experimentally measured values of VfUm" as a function of the Reynolds
number are shown in Fig. 5.7, which covers the range from laminar flow to
turbulent flow. For laminar flow the ratio is exactly 0.5, in accordance with Eq.
(5.15). The ratio changes rapidly from 0.5 to about 0.7, when laminar flow changes
to turbulent, and then increases gradually to 0.87 when N R, = 106
EFFECT OF ROUGHNESS. The discussion thus far has been restricted to smooth
tubes without defining smoothness. It has long been known that in turbulent flow
1. 0
0.9
o.8 l- -
f
o. 7
f
o. 6 I
I
O. 5
10' 10' 10' 10'
DVp!p
FIGURE 5.7
V/u,ym versus N Re'
98 FLUID MECHANICS
a rough pipe leads to a larger friction factor for a given Reynolds number than a
smooth pipe does. If a rough pipe is smoothed, the friction factor is reduced. When
further smoothing brings about no further reduction in friction factor for a given
Reynolds number, the tube is said to be hydraulically smooth. Equation (5.43) refers
to a hydraulically smooth tube.
Figure 5.8 shows several idealized kinds of roughness. The height of a single
unit of roughness is denoted by k and is called the roughness parameter. From
dimensional analysis, J is a function of both N R , and the relative roughness kiD,
where D is the diameter of the pipe. For a given kind of roughness, e.g., that shown
in Fig. 5.8a and b, it can be expected that a different curve of J versus N R, would
be found for each magnitude of the relative roughness and also that for other
types of roughness, such as those shown in Figs. 5.8c and d, different family of
curves of N R, versus J would be found for each type of roughness. Experiments
on artificially roughened pipe have confirmed these expectations. It has also been
found that all clean, new commercial pipes seem to have the same type of roughness
and that each material of construction has its own characteristic roughness
parameter.
Old, foul, and corroded pipe can be very rough, and the character of the
roughness differs from that of clean pipe.
Roughness has no appreciable effect on the friction factor for laminar flow
unless k is so large that the measurement of the diameter becomes uncertain.
THE FRICTION-FACTOR CHART. For design purposes, the frictional characteris-
tics of round pipe, both smooth and rough, are summarized by the friction-factor
chart (Fig. 5.9), which is a log-log plot of J versus NRo- For laminar flow Eq. (5.18)
relates the friction factor to the Reynolds number. A log-log plot of Eq. (5.18) is
a straight line with a slope of -1. This plot line is shown on Fig. 5.9 for Reynolds
numbers less than 2100.
kt~lk~l
D D
~J~l (bl (dl
FIGURE 5.8
Types of roughness.
1.0
Material k,fl
Drown tubing Smoolh
Wrought irontsteel o.o.o.()15
Galvanized iron 0.0.0.135
Cast Iron 0.0.0085
Concrete 0.0./-000/
1"'-
~
f "-
k/O
'" ... 1 1\
00
o.OOf\
III
o.. 1 0. 001
0.0006
ItM 0.0004.
~~ Smoolh o~W
0.00001
~ I,
---
1 _
,11 0005
/ 'q~ofl
0.0001
0..0.
- 105 10' 10.
N Re
FIGURE 5.9
Friction-factor chart.
100 FLUID MECHANICS
For turbulent flow the lowest line represents the friction factor for smooth
tubes and is consistent with Eq. (5.44). A much more convenient empirical equation
for this line is the relation
f = 0.046NR,o.2 (5.46)
This applies over a range of Reynolds numbers from about 50,000 to 1 X 106 •
Another equation, applicable over a range of Reynolds numbers from 3000 to
3 X 106, is
0.125
f=0.0014+~ (5.47)
N R,
The other curved lines in the turbulent-flow range represent the friction
factors for various types of commercial pipe, each of which is characterized by
a different value of k. The parameters for several common metals are given in the
figure. Clean wrought-iron or steel pipe, for example, has a k value of 1.5 x 10- 4 ft,
regardless of the diameter of the pipe. Drawn copper and brass pipe may be
considered hydraulically smooth.
Figure 5.9 is useful for calculating hf' from a known pipe size and flow rate,
but it cannot be used directly to determine the flow rate for a given pressure drop,
since NR , is not known until Y is determined. However, since f changes only
slightly with N R, for turbUlent flow, a trial-and-error solution converges quickly,
as shown in Example 5.1, page 109.
REYNOLDS NUMBERS AND FRICTION FACTOR FOR NON-NEWTONIAN
FLUIDS. Equation (5.7a), the relation ol:.friction factor to pressure drop, and Eq.
(5.20), the equation for the friction pressure loss of a power-law fluid, may be used
to calculate the friction factor for pseudoplastic fluids. If I!.p, is eliminated from
these two equations, the equation for f can be written
(5.48)
From this equation a Reynolds number NR,," for non-newtonian fluids can
be defined, on the assumption that for laminar flow
f=~ (5.49)
N Re ,1l
Combining Eqs. (5.48) and (5.49) yields
2
N -2 3 - n' )'" D"'py -"'
11 ' ---
( 3n' + 1
(5,50)
Re,/I - K'
This is the definition of the Reynolds number N R,," given in Eq. (3,9). Thi"
Reynolds number reduces to the Reynolds number for a newtonian fluid when
n' = 1, and it reproduces the linear portion of the logarithmic plot of f versus
N R" with a slope of - 1, for the laminar flow of newtonian fluids.
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 101
I" 1 1
I I I
f-+-H~++----,-'---t-+-+-H+H Non-New/onion
Friction-factor diagram
'-
I
a:
0 0.0 I -- - n'-
f-
U
it
9
8
7
-- -
?:O
l-I~
z 6
2
f-
u
5
4 rt~+H--~--~~~H+~-+~--+~-
_ --. _ -I'- <2;8
t--
t-- -- t-- 1.0
a:
lL 3 H-+++tt---t--t--t-hl-+-l:+I-::::.o...--=-_.p+-_+-H
. 0.6
(9
........ 1--.... . . r-
~
............ ............ 04
2 ~~~~----+--t-+-+~~,dt--~~_~.-+-._~+4~
z
z - - - Experimental regions .... 0.3
it - - - - EXlrOPO/OI~d refo 7 ,,~~ - 02
0.00 I
1000 10,000 100,000
MODIFIED REYNOLDS NUM8ER, N R',n
FIGURE 5.10
Friction-factor chart, power-law fluid. (After D. W. Dodge and A. B. Metzner. l )
Figure 5.10 is a friction-factor chart in which J is plotted against N •• ,n for
the flow of power-law fluids in smooth pipes.! A series of lines depending on the
magnitude of n' is needed for turbulent flow. For these lines the following equation,
analogous to Eq, (5.43), for newtonian fluids, has been suggested!:
_1--~(lnN J!-0.5"')_~ (5.51)
Jj - (n')O.75 R.,n (n') 1.2
Figure 5.10 shows that for pseudoplastic fluids (n' < 1), laminar flow persists
to higher Reynolds number than with newtonian fluids.
DRAG REDUCTION IN TURBULENT FLOW. Dilute solutions of polymers in
water or other solvents sometimes give the peculiar effect of a reduction in drag
in turbulent flow. The phenomenon was first noted by Toms!2 and has prompted
many theoretical studies and some practical applications. As shown in Fig. 5.11,
the friction factor can be significantly below the normal value for turbulent flow
with only a few parts per million of polymer in water, and at 50 to lOO ppm, the
drag reduction may be as much as 70 percent. Similar effects have been shown
for some polymers in organic solvents,
Drag reduction is found generally with dilute solutions of high-molecular-
weight linear polymers and is believed to be related to the extension of these
flexible molecules at high turbulent shear stress near the walL The extended
molecules increase the local viscosity, which damps the small eddies and leads to
increased thickness of the viscous sublayer4 With a thicker sublayer at the same
102 FLUID MECHANICS
0.0 1
0.008
t--.
--... t-.Water if}
~LJIef}t flow
0.00 6
"-
i'- ~
I"" 1 ppm
"'" ~~
0.00 4 5 ppm
"'~
f
0.00 3
0.002
. "~ 1 ppm
,.-
I~
--- P
T
~
50
0.00 1
2 X 10 3 3 4 6 8 10
, 2 3 4 6 8 10 5
FIGURE 5.11
Friction factors for turbulent flow of dilute solutions of polyethylene oxide (MW:::::: 10 6 ). [After R. W.
Patterson and F. H. Abernatlly.6]
total flow, the values of (dll/dy)" and ,ware reduced, giving lower pressure drop.
The apparent solution viscosity, as measured in laminar flow, may still be very
close to that of the solvent, with only slight departures from newtonian behavior,
but careful measurements show non-newtonian behavior, including viscoelastic
effects.
The major applications of drag reduction have been to increase the flow of
water in a line of fixed size. Only a few parts per million of polyethylene oxide, a
cheap nontoxic polymer, can double the capacity of a fire hose or a line carrying
cooling water. In a long pipeline or with repeated use, degradation of the polymer
under the high shear reduces its effectiveness.
EFFECT OF HEAT TRANSFER ON FRICTION FACTOR. The methods for calcu-
lating friction described thus far apply only where there is no transfer of heat
between the wall of the channel and the fluid. When the fluid is either heated or
cooled by a conduit wall hotter or colder than the fluid, the velocity field is
modified by the temperature gradients thus created within the fluid. The effect on
the velocity gradients is especially pronounced with liquids where viscosity is a
strong function of temperature. Quite elaborate theories have been developed for
the effect of heat transfer on the velocity distribution of gases. For ordinary
engineering practice the following simple method is empirically justified for both
gases and liquids.
1. The Reynolds number is calculated on the assumption that the fluid tempera-
ture equals the mean bulk temperature, which is defined as the arithmetic average
of the inlet and outlet temperatures.
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 103
2. The friction factor corresponding to the mean bulk temperature is divided by
a factor 1/1, which in turn is calculated from the following equations":
-,-,-)°·17 for heating (S.S2a)
For N R , > 2100: 1/1 = 1(-,-,-)0.11
I'w
(I'w for cooling (S.S2b)
-,-,-)°·3" for heating (S.S3a)
For N R , > 2100: 1/1= 1(-,-,-)0.23
fill'
(IllI' for cooling (S.S3b)
where I' = viscosity of fluid at mean bulk temperature
I'w = viscosity at temperature of wall of conduit
Equations (S.52) and (S.S3) are based on data for values of I'll'w between 0.1
and 10 and should not be used for values outside these limits.
FRICTION FACTOR IN FLOW THROUGH CHANNELS OF NONCIRCULAR
CROSS SECTION. The friction in long straight channels of constant noncircular
cross section can be estimated by using the equations for circular pipes if the
diameter in the Reynolds number and in the definition of the friction factor is
taken as an equivalent diameter, defined as four times the hydraulic radius. The
hydraulic radius is denoted by rH and in turn is defined as the ratio of the
cross-sectional area of the channel to the wetted perimeter of the channel:
(S.S4)
where S = cross-sectional area of channel
Lp = perimeter of channel in contact with fluid
Thus, for the special case of a circular tube, the hydraulic radius is
The equivalent diameter is 4rH , or simply, D.
An important special case is the annulus between two concentric pipes. Here
the hydraulic radius is
nD;/4 - nDf/4 D, - D,
rH = (S.5S)
nD, + nD, 4
104 FLUID MECHANICS
where Di and D, are the inside and outside diameters of the annulus, respectively.
The equivalent diameter of an annulus is therefore the difference of the diameters.
Also, the equivalent diameter of a square duct with a width of side b is 4(b 2 j4b) = b.
The hydraulic radius is a useful parameter for generalizing fluid-flow pheno-
mena in turbulent flow. Equation (5.7) can be so generalized by substituting 4rH
for D or 2rH for rII':
!" !!.p, !!.L y2
hj, = - ! ! . L = - = J - - (5.56)
prH P rH 2g,
4rH Yp
N Rc -
-
- J1,
- (5.57)
The simple hydraulic-radius rule does not apply to laminar flow through
noncircular sections. For laminar flow through an annulus, for example, J and
NR , are related by the equation'
16
J =-</J
N ., (5.58)
R.
where cp, is the function of DdD, shown in Fig. 5.12. The value of cp, is unity for
circular cross sections and 1.5 for parallel planes. Equations for laminar flow
through other cross sections are given in various texts.' Flow of viscous non-
newtonian liquids through channels of complex shape, as in injection molding
operations, may be analyzed by methods of numerical approximation.
1.50
v
V
V
/
1.40 /
<P.
/
1.30 /
/
/
1.24
0.01 0.1 1.0 FIGURE 5.12
0,./0. Value of <P. in Eq. (5.58).
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 105
FRICTION FROM CHANGES IN VELOCITY OR DIRECTION. Whenever the
velocity of a fluid is changed, either in direction or magnitude, by a change in the
direction or size of the conduit, friction is generated in addition to the skin friction
from flow through the straight pipe. Such friction includes form friction resulting
from vortices that develop when the normal streamlines are disturbed and when
boundary-layer separation occurs. In most situations, these effects cannot be
calculated precisely, and it is necessary to rely on empirical data. Often it is possible
to estimate friction of this kind in specific cases from a knowledge of the losses
in known arrangements.
Friction loss from sudden expansion of cross section. If the cross section of the
conduit is suddenly enlarged, the fluid stream separates from the wall and issues
as a jet into the enlarged section. The jet then expands to fill the entire cross
section of the larger conduit. The space between the expanding jet and the conduit
wall is filled with fluid in vortex motion characteristic of boundary-layer separa-
tion, and considerable friction is generated within this space. This effect is shown
in Fig. 5.13.
The friction loss hr, from a sudden expansion of cross section is proportional
to the velocity head of the fluid in the small conduit and can be written
hr, = K,-
V; (5.59)
2g,
where K, is a proportionality factor called the expanSion-loss coefficient and
Va is the average velocity in the smaller, or upstream, conduit. In this case the
calculation of K, can be made theoretically and a satisfactory result obtained. The
calculation utilizes the continuity equation (4.1), the steady-flow momentum-
balance equation (4.14), and the Bernoulli equation (4.29). Consider the control
volume defined by sections AA and BB and inner surface of the larger downstream
conduit between these sections, as shown in Fig. 5.13. Gravity forces do not appear
FIGURE 5.13
Flow at sudden enlargement of cross section.
106 FLUID MECHANICS
because the pipe is horizoutal, and wall friction is negligible because the wall is
relatively short and there is almost no velocity gradient at the wall between the
sections. The only forces, therefore, are pressure forces on sections AA and BB.
The momentum equation gives
(p,Sb-PbSb)g, = m(PbVb - P,V,) (5.60)
Since Z, = Zb, Eq. (4.29) may be written for this situation as
(5.61)
For usual flow conditions, a, = ab = 1, and p, = Pb = 1, and these correction
factors are disregarded. Also, elimination of p, - Pb between Eqs. (5.60) and (5.61)
yields, since /il/S b = PVb'
(5.62)
From Eq. (4.5), Vb = V,(S,ISb)' and Eq. (5.62) can be written
(5.63)
Comparison of Eqs. (5.59) and (5.63) shows that
(5.64)
A correction for (t and P should be made if the type of flow between the two
sections differs. For example, if the flow in the larger pipe is laminar and that in
the smaller pipe turbulent, (tb should be taken as 2 and Pb as ~ in Eqs. (5.60) and
(5.61).
Friction loss from sudden contraction of cross section. When the cross section of
the conduit is suddenly reduced, the fluid stream cannot follow around the sharp
corner and the stream breaks contact with the wall of the conduit. A jet is formed,
which flows into the stagnant fluid in the smaller section. The jet first contracts
and then expands to fill the smaller cross section, and downstream from the point
of contraction the normal velocity distribution eventually is reestablished. The
cross section of minimum area at which the jet changes from a contraction to an
expansion is called the vena contracta. The flow pattern of a sudden contraction
is shown in Fig. 5.14. Section CC is drawn at the vena contracta. Vortices appear
as shown in the figure.
The friction loss from sudden contraction is proportional to the velocity
head in the smaller conduit and can be calculated by the equation
hfe =
v1
Ke- (5.65)
2g,
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 107
Direction )
c-c Plane of vena contracto
of flow
FIGURE 5.14
Flow at sudden contraction of cross section.
where the proportionality factor K, is called the contraction-loss coefficient and
Vb is the average velocity in the smaller, or downstream, section. Experimentally,
for laminar flow, K, < 0.1, and the contraction loss hI, is negligible. For turbulent
flow, K, is given by the empirical equation
(5.66)
where S, and Sb are the cross-sectional areas of the upstream and downstream
conduits, respectively.
EFFECT OF FITTINGS AND VALVES. Fittings and valves disturb the normal
flow lines and cause friction. In short lines with many fittings, the friction loss
from the fittings may be greater than that from the straight pipe. The friction loss
hff from fittings is found from an equation similar to Eqs. (5.59) and (5.65):
(5.67)
where KI = loss factor for fitting
V, = average velocity in pipe leading to fitting
Factor K I is found by experiment and differs for each type of connection. A short
list of factors is given in Table 5.1.
Form-friction losses in the Bernoulli equation. Form-friction losses are incor-
porated in the hI term of Eq. (4.32). They are combined with the skin-friction
losses of the straight pipe to give the total friction loss. Consider, for example, the
flow of incompressible fluid through the two enlarged headers, the connecting
108 FLUID MECHANICS
TABLE 5.1
Loss coefficients for standard
threaded pipe fittingst
Fitting K/
Globe valve, wide open 10.0
Angle valve, wide open 5.0
Gate valve
Wide open 0.2
Half open 5.6
Return bend 2.2
Tee 1.8
Elbow
90° 0.9
45° 0.4
t From J. K. Vennard, in V. L. Streeler
(cd.),Ham/book of Fluid Dynamics,
McGraw~HiIl Book Company, New
York, 1961, p. 3-23.
tube, and the open globe valve shown in Fig. 5.1S. Let j7 be the average velocity
in the tube, D the diameter of the tube, and L the length of the tube. The
skin-friction loss in the straight tube is, by Eq. (S.7), 4f(LjD)(j72j2g,); the contrac-
tion loss at the entrance to the tube is, by Eq. (S.6S), K,(i72j2g,); the expansion
loss at the exit of the tube is, by Eq. (S.S9), K,(i72j2g,); and the friction loss in the
globe valve is, by Eq. (S.67), Kij72j2g,). When skin friction in the entrance and
exit headers is neglected, the total friction is
(S.68)
a b
Pressu.re = PI
Flaw. I Pressure:Pb
Pressure=po
VelocIJ'y=Vc,
I
VelocJly= Vb
-
FIGURE 5.15
Flow of incompressible fluid through typical assembly.
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS lU~
To write the Bernoulli equation for this assembly, take station a in the inlet header
and station b in the outlet header. Because there is no pump between stations a
and b, Wp = 0; also IX, and IXb can be taken as 1.0, the kinetic-energy term can be
canceled, and Eq. (4.32) becomes
(5.69)
Example 5.1. Crude oil having a specific gravity of 0.93 and a viscosity of 4 cP is
draining by gravity from the bottom of a tank. The depth of liquid above the drawoff
connection in the tank is 6 m. The line from the drawoff is 3-1n. Schedule 40 pipe.
Its length is 45 m, and it contains one ell and two gate valves. The oil discharges
into the atmosphere 9 m below the drawoff connection of the tank. What flow rate,
in cubic meters per hour, can be expected through the line?
Solution
The quantities needed are
I' = 0.004 kg/m-s L = 45 m
3.068
D = -- = 0.256 ft (Appendix 5) = 0.0779 m
12
p = 0.93 x 998 = 928 kg/rn'
For fittings, from Table 5.1,
I Kf = 0.9 + (2 x 0.2) = 1.3
From Eq. (4.29), assuming Cl b = 1 and since Pn = Pb and Va = 0,
V~
- + hf = g(2, - 2 b) = 9.80665(6 + 9) = 147.1 m 2 /s 2
2
Use Eq. (5.68). There is no final expansion loss, since the stream does not expand
upon discharge, and K" = O. From Eq. (5.66), since Sa is very large, Kc = 0.4. Hence
hf=(4f~+K,+IKf) ~~
4 x 45f ) j72 j72
= ( - - + 0.4 + 1.3 -" = (2311f + 1.7)-"
0.0779 2 2
Thus
j7~ (1 + 2311f + 1.7) = 147.1
2
147.1 x 2 294.2
2.7 + 2311f 2.7 + 2311f
110 FLUID MECHANICS
Use Fig. 5.9 to find f For this problem
0.0779 x 928 Vb
NR, = 0.004 18073Vb
k 0.3048
- = 0.00015 x - - = 0.00059
D 0.0779
Trials give the following:
f
Pb,estimated, rn!s NR~ x 10- 4 (from Fig. 5.9) Vb,':'kUI~lOd' rn!s
4.00 7.23 0.0056 4.34
4.34 7.84 0.0055 4.37
4.37 7.40 0.0055 4.37
The cross-sectional area of the pipe is 0.0513 ft' or 0.00477 m' (Appendix 5), and the
flow rate is 4.37 x 3600 x 0.00477 = 75.0 m3 /h.
PRACTICAL USE OF VELOCITY HEADS IN DESIGN. As shown by Eq. (5.69),
the friction loss in a complicated flow system is expressible as a number of velocity
heads for losses in pipes and fittings and for expansion and contraction losses.
This fact is the basis for a rapid practical method for the estimation of friction.
By setting 4J(L/D) = 1.0, it follows that a length equal'to a definite number of
pipe diameters generates a friction loss equal to one velocity head. Since, in
turbulent flow, J varies from about 0.01 to about 0.002, the number of
pipe diameters equivalent to a velocity head is from 1/(4 x 0.01) = 25 to
1/(4 x 0.002) = 125, depending upon the Reynolds number. For ordinary practice,
50 pipe diameters is assumed for this factor. Thus, if the pipe in the system of Fig.
5.15 is standard 2-in. steel (actual ID 2.07 in.) and is 100 ft long, the skin friction
is equivalent to (lOO x 12)/(2 x 50) = 12 velocity heads. In this case, the friction
from the single fitting and the expansion and contraction are negligible in
comparison with that in the pipe. In other cases, where the pipes are short and
the fittings and expansion and contraction losses numerous, the friction loss in
the pipes only may be negligible.
SEPARATION FROM VELOCITY DECREASE. Boundary-layer separation can
occur even where there is no sudden change in cross section if the cross section
is continuously enlarged. For example, consider the flow of a fluid stream through
the trumpet-shaped expander shown in Fig. 5.16. Because of the increase of cross
section in the direction of flow, the velocity of the fluid decreases, and by the
Bernoulli equation, the pressure must increase. Consider two stream filaments,
one, aG, very near the wall, and the other, bb, a short distance from the wall. The
pressure increase over a definite length of conduit is the same for both filaments,
because the pressure throughout any single cross section is uniform. The loss in
velocity head is, then, the same for both filaments. The initial velocity head of
filament aa is less than that of filament bb, however, because filament aa is nearer
FLOW OF INCOMPRESSiBLE FLUIDS IN CONDUITS AND THIN LAYERS 111
c
FIGURE 5.16
Separation of boundary layer in diverging channel.
to the wall. A point is reached, at a definite distance along the conduit, where the
velocity of filament aa becomes zero but where the velocities of filament bb and
of all other filaments farther from the wall than aa are still positive. This point is
point s in Fig. 5.16. Beyond point s the velocity at the wall changes sign, a backflow
of fluid between the wall and filament aa occurs, and the boundary layer separates
from the wall. In Fig. 5.16, several curves are drawn of velocity u vs. distance from
the wall y, and it can be seen how the velocity near the wall becomes zero at point
s and then reverses in sign. The point s is called a separation point. Line sA is
called the line of zero tangential velocity.
The vortices formed between the wall and the separated fluid stream, beyond
the separation point, cause excessive form-friction losses. Separation occurs in
both laminar and turbulent flow. In turbulent flow, the separation point is farther
along the conduit than in laminar flow. Separation can be prevented if the angle
between the wall of the conduit and the axis is made small. The maximum angle
that can be tolerated in a conical expander without separation is 7°.
MINIMIZING EXPANSION AND CONTRACTION LOSSES. A contraction loss
can be nearly eliminated by reducing the cross section gradually rather than
suddenly. For example, if the reduction in cross section shown in Fig. 5.14 is
obtained by a conical reducer or by a trumpet-shaped entrance to the smaller
pipe, the contraction coefficient K, can be reduced to approximately 0.05 for all
values of SblSo' Separation and vena-contracta formation do not occur unless the
decrease in cross section is sudden.
An expansion loss can also be minimized by substituting a conical expander
for the flanges shown in Fig. 5.13. The angle between the diverging walls of the
112 FLUID MECHANICS
cone must be less than r, however, or separation may occur. For angles of 35
or more, the loss through a conical expander can become greater than that througt
a sudden expansion for the same area ratio S,/Sb because of the excessive form
friction from the vortices caused by the separation.
FLOW OF LIQUIDS IN THIN LAYERS
COUETTE FLOW. In one form of layer flow, illustrated in Fig. 5.17, the fluid is
bounded between two very large, flat, parallel plates separated by distance B. The
lower plate is stationary, and the upper plate is moving to the right at a constant
velocity uo. For a newtonian fluid the velocity profile is linear, and the velocity
u is zero at y = 0 and equals Uo at y = B, where y is the vertical distance measured
from the lower plate. The velocity gradient is constant and equals uo/B. Consider-
ing an area A of both plates, the shear force needed to maintain the motion of the
top plate is, from Eqs. (3.3) and (3.4),
JiAuo
Fs=-- (5.70)
goB
Flow under these conditions is called eouette flow.
A nearly identical flow pattern exists in the annular space between two
concentric cylinders, one rotating and the other stationary, provided the width of
the annulus, B, is small compared to the diameters of the cylinders. A device that
makes use of this is the Couette viscometer. By measuring the torque required to
rotate one cylinder at a known speed, the viscosity Ji may be readily calculated
from Eq. (5.70).
LAYER FLOW WITH FREE SURFACE. In another form of layer flow the liquid
layer has a free surface and flows under the force of gravity over an inclined or
vertical surface. Such flow is in steady state, with fully developed velocity gradients,
and the thickness of the layer is assumed to be constant. Flow usually is laminar,
and often there is so little drag at the free liquid surface that the shear stress there
can be ignored. Under these assumptions and the further assumptions that the
Moving plate
BTI---U--¥
y Profile of fluid velocity
FIGURE 5.17
Velocities and velocity gradient in a
Stotionory plote fluid between flat plates.
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 113
Layer af
r- liquid
Liquid element
(con/ro! vo!ume) Plate
FIGURE 5.18
Forces on liquid element in layer
flow.
liquid surface is flat and free from ripples, the fluid motion can be analyzed
mathematically.
Consider a layer of a newtonian liquid flowing in steady flow at constant rate
and thickness over a flat plate as shown in Fig. 5.18. The plate is inclined at an
angle f3 with the vertical. The breadth of the layer in the direction perpendicular
to the plane of the figure is b, and the thickness of the layer in the direction
perpendicular to the plate is 15. Isolate a control volume as shown in Fig. 5.18.
The upper surface of the control volume is in contact with the atmosphere, the
two ends are planes perpendicular to the plate at a distance L apart, and the lower
surface is the plane parallel with the wall at a distance r from the upper surface
of the layer.
Since the layer is in steady flow with no acceleration, by the momentum
principle the sum of all forces on the control volume is zero. The possible forces
acting on the control volume in a direction parallel to the flow are the pressure
forces on the ends, the shear forces on the upper and lower faces, and the
component of the force of gravity in the direction of flow. Since the pressure on
the outer surface is atmospheric, the pressures on the control volume at the ends
of the volume are equal and oppositely directed. They therefore vanish. Also, by
assumption, the shear on the upper surface of the element is neglected. The two
forces remaining are therefore the shear force on the lower surface of the control
volume and the component of gravity in the direction of flow. Then
(5.71)
where Fg = gravity force
! = shear stress on lower surface of control volume
A = area of lower surface of control volume
114 FLUID MECHANICS
From this equation, noting that A = bL and Fg = prLbg/g"
g
prLb - cos f3 = ,Lb
g,
or
,g, = prg cos f3 (S.72)
Since the flow is laminar, ,g, = -I' du/dr and
du
-I' - = gpr cos f3 (S.73)
dr
Rearranging and integrating between limits gives
i"o
du = - gp cos f3
tt
f'{)
r dr
(S.74)
where 15 is the total thickness of the liquid layer. Equation (S.74) shows that in
laminar flow on a plate the velocity distribution is parabolic, as it is in a pipe.
The ratio of the maximum local velocity to the average velocity, however, is ~
instead of 2.0 as in laminar flow in a pipe.
Consider now a differential element of cross-sectional area dS, where
dS = b dr. The diflerential mass flow rate din through this element equals pub dr.
The total mass flow rate of the fluid then is
m= J: pubdr (5.75)
Substituting from Eq. (5.74) into Eq. (S.75) and integrating gives
,n 15 3 p2 g cos f3
(S.76)
-= =1
b 31'
where 1 == ,n/b and is called the liquid loading. The dimensions of 1 are kilograms
per second per meter of width or pounds per second per foot of width.
Rearrangement of Eq. (S.76) gives, for the thickness of the layer,
(5.77)
REYNOLDS NUMBER. The Reynolds number for layer flow is found by using
four times the hydraulic radius as the length parameter. The hydraulic radius,
defined by Eq. (5.54), is S/L p , where S is the cross-sectional area of the layer and
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 115
Lp is the wetted perimeter. For flow down a flat plate, S = Lpb, and the hydraulic
radius is equal to the layer thickness. The Reynolds number, by the use of Eq.
(4.8), becomes
(5.78)
For flow of a liquid down either the inside or the outside of a pipe, the layer
thickness is usually a very small fraction of the pipe diameter, so the cross-sectional
area of the layer is essentially Lpb and the Reynolds number is the same as for a
flat plate, Eq. (5.78).
The equation for thickness of a falling laminar film was first presented by
Nusselt,5 who used the result to predict heat-transfer coefficients for condensing
vapors. Measurements of film thickness on a vertical surface (cos f3 = 1) show
that Eq. (5.77) is approximately correct for N Ro "" 1000, but the thickness actually
varies with about 0.45 power of the Reynolds number, and the layers are thinner
than predicted at low N Ro and thicker than predicted above N Ro = 1000. The
deviations may be due to ripples or waves in the films, which are apparent even
at quite low Reynolds numbers.
The transition from laminar to turbulent flow is not as easily detected as in
pipe flow since the film is very thin and the ripples make it difficult to observe
turbulence in the film. A critical Reynolds number of 2100 has often been used
for layer flow, but film thickness measurements· indicate a transition at
N R, '" 1200. Above this point, the thickness increases with about the 0.6 power
of the flow rate.
Equation (5.78) also applies when the liquid fills the pipe; i.e., for a given
mass flow rate the Reynolds number is the same whether the pipe is full or the
fluid is flowing in a layer form. The last equality in Eq. (5.78) provides a convenient
method of calculating N R, from the mass rate of flow for either layer flow or
full-pipe flow.
SYMBOLS
A Area, m 2 or re
B Distance between fixed and moving plates, m or ft
b Width of square duct, m or ft; also breadth of liquid layer, m or ft
D Diameter, m or ft; Dj, inside diameter of annulus; Do, outside diameter
of annulus
F Force, N or IbJ; Fg , gravity force; F" shear force
f Fanning friction factor, dimensionless
g Gravitational acceleration, mjs' or ftjs'
g, Newton's-law proportionality factor, 32.174 ft-Ibjlb rs2
hJ Friction loss, Jjkg or ft-IbJjlb; hJ" from sndden contraction; hJ" from
sudden expansion; hJJ , in flow throngh fitting or valve; hJ" skin friction
116 FLUID MECHANICS
K Constant in Eqs. (5.21) and (5.23)
Kc Contraction-loss coefficient, dimensionless
Kc Expansion-loss coefficient, dimensionless
K[ Loss factor for fitting or valve, dimensionless
K' Flow consistency index, kg/m-s 2 -,,· or Ib/ft-s 2 -,,'
k Roughness parameter, m or ft
L Length, m or ft
Lp Wetted perimeter, m or ft
,h Mass flow rate, kg/s or Ib/s
N., Reynolds number, dimensionless; N R ,.", modified Reynolds number for
non-newtonian fluids, defined by Eq. (5.50)
11' Flow behavior index, dimensionless
P Pressure, N/m2 or Ib[/ft 2; Pa, at station a; Pb, at station b
,. Radial distance from pipe axis, m or ft; also distance from surface of
liquid layer; ,." radius of cylinder of plastic fluid in plug flow; ,.",
radius of pipe
"H Hydraulic radius of conduit, m or ft
S Cross-sectional area, m2 or ft 2 ; Sa' at station a; Sb' at station b
" Net or time-average local fluid velocity in x direction, m/s or ft/s; lI"
velocity of cylinder of plastic fluid in plug flow; "rn,,' maximum local
velocity; "0' velocity of moving plate [Eq. (5.70)J
11* Friction velocity, V/M
u+ Dimensionless velocity quotient, u/u*; uc+, at pipe axis
V Average fluid velocity in x direction; Va , Vb' at stations a and b
»;, Pump work, J/kg or ft-Ib [/Ib
y Radial distance from pipe wall, m or ft
y+ Dimensionless distance, yu*/v; y/, at pipe axis
Z Height above datum plane, m or ft; Z", at station a, Zb, at station b
Greek letters
r:J. Kinetic-energy correction factor, dimensionless; aa' at station a; ab' at
station b
P Angle with vertical; also momentum correction factor, dimensionless; p",
at station a; Pb' at station b
r Liquid loading in layer flow, kg/m-s or Ib/ft-s
IIp Pressure loss, p, - Pb; IIp,, from skin friction
o Thickness of liquid layer, m or ft
I' Absolute viscosity, P or Ib/ft-s; I'w, at temperature of pipe wall
v Kinematic viscosity, I'/p, m 2 /s or fe/s
p Density, kg/m 3 or Ib/ft 3
t Shear stress, N/m2 or Ib[/fe; t,,, at pipe wall; to, threshold stress in
plastic fluid
<p, Factor in Eq. (5.58) for laminar flow in annulus, dimensionless
'" Temperature correction factor for skin friction, dimensionless
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 117
PROBLEMS
5.1. Prove that the flow of a liquid in laminar flow between infinite parallel flat plates is
given by
where L = length of plate in direction of flow
a = distance between plates
Neglect end effects.
5.2. For flow of water in a smooth 60-mm pipe at N Re = 5 X 104 , what is the thickness of
the viscous sublayer? What fraction of the cross-sectional area of the pipe does this
represent? About what fraction of the flow is in the viscous sublayer?
5.3. A newtonian fluid is in laminar flow in a rectangular channel with a large aspect ratio.
Derive the relationship between local and maximum velocity and determine the ratio
umax/fl.
5.4. Calculate the power required per meter of width of stream to force lubricating oil
through the gap between two horizontal flat plates under the following conditions:
Distance between plates, 6 mm
Flow rate of oil per meter of width, 100 m 3 /h
Viscosity of oil, 25 cP
Density of oil, 0.88 g/cm'
Length of plates, 3 m
Assume that the plates are very wide in comparison with the distance between them
and that end effects are neglected.
5.5. A liq uid with a specific gravity of 2.6 and a viscosity of 2.0 cP flows through a smooth
pipe of unknown diameter, resulting in a pressure drop of 0.183Ibr /in. 2 for 1.73 mi.
What is the pipe diameter in inches if the mass rate of flow is 7000 Ib/h?
5.6. Water flows through an 8-in. steel pipe at an average velocity of 6 ft/so Downstream
the pipe divides into an 8-in. main and a 2-in. bypass. The equivalent length of the
bypass is 22 ft; the length of the 8-in. pipe in the bypassed section is 16 ft. Neglecting
entrance and exit losses, what fraction of the total water flow passes through the
bypass?
5.7. A steel pipe 2 ft in diameter carries water at about 15 ft/so If the pipe has a roughness
of 0.0003 ft, could the capacity be increased by inserting a smooth plastic liner that
reduces the inside diameter to 1.9 ft? Calculate the change in pressure drop for the
same flow and the change in capacity for a fixed pressure drop.
5.8. Water at 60°F is pumped from a reservoir to the top of a mountain through a
6-in. Schedule 120 pipe at an average velocity of 12 ft/so The pipe discharges into
the atmosphere at a level 3000 ft above the level in the reservoir. The pipeline
itself is 4500 ft long. If the overaIl efficiency of the pump and the motor driving
it is 70 percent and the cost of electric energy to the motor is 4 cents per kilowatt-hour,
what is the hourly energy cost for pumping this water?
5.9. A reverse-osmosis unit for purifying brackish water has about 900,000 hollow fibers
that permit the diffusion of water but reject most of the salt. The fibers are 85 J-lm in
outside diameter, 42 J-lm in inside diameter, and about 3 ft long. The average flow
through the tubes is 2000 gal of water every 24 h when the feed pressure is 400 psig.
118 FLUID MECHANICS
What is the pressure drop withi'Il: an individual fiber from the feed end to the discharge
end?
5.10. Chlorine gas leaving a reactor at 200°C and 1.5 atm with a flow of 4lb/min is to be
compressed and recycled to the reactor, where the pressure is 1.6 atm. The length of
pipe needed is about 80 ft, and the line will have six elbows and two globe valves.
Suggest a pipe size and calculate the velocity and pressure drop.
5.11. Exhaust gas from a power plant passes through a 15-by-20-ft rectangular duct at an
average velocity of 50 ft/so The total length of duct is 250 ft and there are two 90°
bends. The gas is at 180°F and about 1 atm, and the properties are similar to those
of air. Calculate the pressure drop in the duct and the power required to overcome
pressure losses.
5.12. A centrifugal pump takes brine from the bottom of a supply tank and delivers
it into the bottom of another tank. The brine level in the discharge tank is
150 ft above that in the supply tank. The line between the tanks is 600 ft of
4-in. Schedule 40 pipe. The flow rate is 400 galfmin. In the line are two gate
valves, four standard tees, and four ells. What is the energy cost for running
this pump for one 24-h day? The specific gravity of brine is 1.18; the viscosity
of brine is 1.2 cP, and the energy cost is $400 per horsepower-year on a basis
of 300 d/year. The overall efficiency of pump and motor is 60 percent.
5.13. Cooling water for a chemical plant must be pumped from a river 2500 ft from the
plant site. Preliminary design cans for a flow of 600 gal/min and 6-in. steel pipe.
Calculate the pressure drop and the annual pumping cost if power cost 3 cents per
kilowatt-hour. Would the use of an 8-in. pipe reduce the power cost enough to offset
the increased pipe cost? Use $15/ft of length for the installed cost of 6-in. pipe and
$20/ft for 8-in. pipe. Annual charges are 20 percent of the installed cost.
5.14. A fan draws air at rest and sends it through a 2oo-by-300-mm rectangular duct 45 m
long. The air enters at 15°C and 750 mm Hg absolute pressure at a rate of 0.6 m3 /s.
What is the theoretical power required?
5.15. The laminar flow of a certain aqueous polystyrene sulfonate solution can be re-
presented by the Ostwald-de Waele model with an exponent of 0.500. The solution
is contained in a tank that is a vertical cylinder. Solution flows out through a
horizontal tube attached to the bottom of the tank. (a) If the time for the height of
solution in the tank to fan from 10.00 to 9.90 m is 30.0 min, how much time wiII it
take to half-empty the tank (from a height of 10.0 m down to a height of 5.0 m)? (b)
If the tank has a diameter of 2.0 m and the pipe has a diameter of 0.050 m with a
length of 200 m, what is the flow consistency index of the solution? The solution has
a density of 1200 kg/m'.
5.16. A portion ofa fire protection system can be modeled as a smooth tube with a diameter
of 0.12 m, a length of 600 m, and a total drop in elevation of 12 m. End effects can
be neglected. How much polyethylene oxide would have to be added to water at 25°C
to increase the flow rate by a factor of 1.25? (See Fig. 5.11.)
5.17. A vertical cylindrical reactor 2.5 m in diameter and 4 m high is cooled by spraying
water on the top and allowing it to flow down the outside wall. The water flow rate
is 0.15 m3/min, and the average water temperature is 40°C. Estimate the thickness of
the layer of water.
5.1S. An absorption column packed with I-in. Raschig rings is operated at a water rate of
3500 lb/ft'-h. From published correlations, the hold up of water is about 0.06 ft' liquid
per cubic foot of packed column. Compare this with an estimate based on the
FLOW OF INCOMPRESSIBLE FLUIDS IN CONDUITS AND THIN LAYERS 119
equations for layer flow over inclined surfaces; assume half of the packing area is
wetted.
REFERENCES
1. Dodge, D. W., and A. B. Metzner: AIChE J., 5:189 (1959).
2. Kays, W. M., and A. L. London: Compact Heat Exchangers, 2nd ed., McGraw-Hill, New York,
1964.
3. Knudsen, J. G., and D. L. Katz: Fluid Dynamics and Heat Transfer, McGraw-Hill, New York,
1958, pp. 97, 101-105, 158-171.
4. Lumley, J. A.: Physics of Fluids, 20(1O):S64 (1977).
5. Nusselt, W.: VDI 2., 60:541, 569 (1916).
6. Patterson, R. W., and F. H. Abernathy: J. Fluid Mech., 51:177 (1972).
7. Pearson, J. R. A.: Mechanics of Polymer Processing, Elsevier, London and New York, 1985, pp.
191-194.
8. Perry, J. H. (cd.): Chemical Engineers' Handbook, 5th ed., McGraw-Hill, New York, 1973. p. 5-23.
9. Portalski, S.: Chem. Ellg. Sci., 18:787 (1963).
10. Prandtl, L.: VDI 2.,77:105 (1933).
11. Schlichting, H.: Boundary Layer Theory, 7th ed., McGraw-Hill, New York, 1979.
12. Toms, B. A.: Proc. Intern. Congr. Rheology, Holland, North-Holland, Amsterdam, 1949, p.II-13S.
13. Vinogradov, G. V., G. B. Froishteter, K. K. Trilisky, and E. L. Smorodinsky: Rheologica Acta,
14:765 (1975).
CHAPTER
6
FLOW
OF
COMPRESSIBLE
FLUIDS
Many important applications of fluid dynamics require that density variations be
taken into account. The complete field of compressible flnid flow has become very
large, and it covers wide ranges of pressure, temperatnre, and velocity. Chemical
engineering practice involves a relatively small area from this field. For in-
compressible flow the basic parameter is the Reynolds number, a parameter also
important in some applications of compressible flow. In compressible flow at
ordinary densities and high velocities a more basic parameter is the Mach number.
At very low densities, where the mean free path of the molecules is appreciable in
comparison with the size of the equipment or solid bodies in contact with the gas,
other factors must be considered. This type of flow is not treated in this text.
The Mach number, denoted by N M" is defined as the ratio of u, the speed
of the fluid, to a, the speed of sound in the fluid under conditions of flow,
U
N Ma =-a (6.1)
By speed of the fluid is meant the magnitude of the relative velocity between
the fluid and a solid bounding the fluid or immersed in it, whether the solid is
considered to be stationary and the fluid flowing past it or the fluid is assumed
to be stationary and the solid moving through it. The former situation is the more
170
FLOW OF COMPRESSIBLE FLUIDS 121
common in chemical engineering, and the latter is of great importance in aeronau-
tics, for the motion of missiles, rockets, and other solid bodies through the
atmosphere. By definition the Mach number is unity when the speed of fluid equals
that of sound in the same fluid at the pressure and temperature of the fluid. Flow
is called subsonic, sonic, or supersonic, according to whether the Mach number is
less than unity, at or near unity, or greater than unity, respectively. The most
interesting problems in compressible flow lie in the high-velocity range, where
Mach numbers are comparable with unity or where flow is supersonic.
Other important technical areas in fluid dynamics include chemical reactions,
electromagnetic phenomena, ionization, and phase change,l which are excluded
from this discussion.
In this chapter the following simplifying assumptions are made. Although
they may appear restrictive, many actual engineering situations may be adequately
represented by the mathematical models obtained within the limitations of the
assumptions.
1. The flow is steady.
2. The flow is one dimensional.
3. Velocity gradients within a cross section are neglected, so that Cl. = P= 1 and
j7 = u.
4. Friction is restricted to wall shear.
5. Shaft work is zero.
6. Gravitational effects are negligible, and mechanical-potential energy is
neglected.
7. The fluid is an ideal gas of constant specific heat.
The following basic relations are used:
1. The continuity equation
2. The steady-flow total-energy balance
3. The mechanical-energy balance with wall friction
4. The equation for the velocity of sound
5. The equation of state of the ideal gas
Each of these equations must be put into a suitable form.
CONTINUITY EQUATION. For differentiation, Eq. (4.2) may be written in logar-
ithmic form:
In p + In S + In u = const
Differentiating this equation gives
dp dS du
-+-+-=0 (6.2)
p S u
1.L.L FLUID MECHANICS
TOTAL-ENERGY BALANCE. Consider a fluid in steady flow through a system,
entering at station a with velocity "a and enthalpy Ha and leaving at station b
with velocity Ub and enthalpy H b• For the flow of m kilograms or pounds of
material, heat in the amount of Q joules or Btu must be added through the
boundaries of the system to the material flowing through it. Provided there is no
significant change in elevation between stations a and b and no work is done by
the system on the outside or on the system from the outside, the heat added to
the fluid is given by the equation
2
Q
_ = Bb - Ba IP__ _ua_
+ _' (6.3)
m 2gJ 2gJ
This equation written differentially is
dQ
-=dH+d (- ,,2 ) (6.4)
m 2gJ
MECHANICAL-ENERGY BALANCE. Equation (4.29) may be written over a short
length of conduit in the following differential form:
dp
p
+ d('" j72) + i
2g, g,
dZ + dh f = ° (6.5)
In the light of the assumptions, this equation is simplified by omitting the
potential-energy terms, noting that "'a = ab = 1.0, U = i7, and restricting the friction
to wall shear. Equation (6.5) then becomes
(6.6)
From Eq. (5.56)
(6.7)
Eliminating dh f, from Eqs. (6.6) and (6.7) gives the form of the mechanical-energy
equation suitable for treatment of compressible flow:
(6.8)
VELOCITY OF SOUND. The velocity of sound through a continuous material
medium, also called the acoustical velocity, is the velocity of a very small
compression-rarefaction wave moving adiabatically and frictionlessly through the
medium. Thermodynamically, the motion of a sound wave is a constant-entropy,
or isentropic, process. The magnitude of the acoustical velocity in any medium is
FLOW OF COMPRESSIBLE FLUIDS 123
shown in physics texts to be
a Jg,G:)s
= (6.9)
where the subscript S calls attention to the isentropic restraint on the process.
IDEAL-GAS EQUATIONS. Subject to assumptions 1 to 6, Eqs. (6.2) to (6.9) apply
to any fluid. In fact, they may be used for incompressible flow simply by assuming
that the density p is constant. To apply them to compressible flow, it is necessary
that the density be related to temperature and pressure. The simplest relation, and
one of considerable engineering utility, is the ideal-gas law [Eq. (1.48)], which for
the present purpose may be written in the· form
R
p=~pT (6.10)
M
where R = molar gas-law constant, in units of mechanical energy per mole per
degree absolute
M = molecular weight
The gas may either be pure or a mixture, but if it is not pure, the composition
should not change. Equation (6.10) may be written logarithmically and then
differentiated to give
dp dp dT
~=~+ (6.11)
p p T
Since the specific heat c p is assumed to be independent of temperature, the
enthalpy of the gas at temperature T is
H = Ho + ciT - To) (6.12)
where H = enthalpy per unit mass at temperature T
Ho = enthalpy at arbitrary temperature To
The differential form of Eq. (6.12) is
dH = cpdT (6.13)
Acoustical velocity and Mach number of ideal gas. For an ideal gas, an isentropic
path follows the equations
pp-' = const (6.14)
Tp-(l-l/Y) = const (6.15)
where y is the ratio of cp, the specific heat at constant pressure, to c" the specific
heat at constant volume. For an ideal gas,
c
y '" -1' = _ _"--_ (6.16)
c, cp - RIMJ
Since, by assumption, cp is independent of temperature, so are c, and y.
124 FLU1D MECHAN1CS
The quantity (dpjdp), can be calculated by differentiating the logarithmic
form of Eq. (6.14), giving
dp dp dP)
--y-=O
p p
and ( dp s = yPP
Substituting into Eq. (6.9) yields
a = l~p = l'r;R (6.17)
Equation (6.10) is used to establish the second equality in Eq. (6.17), which shows
that the acoustical velocity of an ideal gas is a function of temperature only. From
Eqs. (6.1) and (6.17) the square of the Mach number of an ideal gas is
(6.18)
THE ASTERISK CONDITION. The state of the fluid moving at its acoustic
velocity is important in some processes of compressible-fluid flow. The condition
where u = a and N", = 1 is called the asterisk condition, and the pressure,
temperature, density, and enthalpy are denoted by p*, T*, pO, and H* at this state.
STAGNATION TEMPERATURE. The stagnation temperature of a high-speed fluid
is defined as the temperature the fluid would attain were it brought to rest
adiabaiically without the development of shaft work. The relation between the
actual fluid temperature, the actual fluid velocity, and the stagnation temperature
is found by using the total-energy equation (6.3) and the enthalpy equation (6.12).
The terminal a in Eq. (6.3) and reference state 0 in Eq. (6.12) are identified with
the stagnation condition, and stagnation is denoted by subscript s. Also, terminal
bin Eq. (6.3) is chosen as the state of the flowing gas, and this subscript is dropped.
Then, since the process is adiabatic and Q = 0, Eq. (6.3) becomes
u2
H-H = - - = H - H o (6.19)
, 2gJ
Eliminating H - Ho from Eq. (6.19) by substitution from Eq. (6.12) gives, for the
stagnation temperature T"
u2
T,=T+-- (6.20)
2g,Jcp
The stagnation enthalpy H, is defined by the equation
u2
H,=H+-- (6.21)
2gJ
Equation (6.3) can be written
Q
- = Hsb - Hsa = (~b - ~a)cp (6.22)
m
FLOW OF COMPRESSIBLE FLUIDS 125
where H,. and H'b are the stagnation enthalpies at states a and b, respectively.
For an adiabatic process, Q = 0, T,. = T,b' and the stagnation temperatnre is
constant.
PROCESSES OF COMPRESSIBLE FLOW
The individual processes to be considered in this chapter are shown diagrammatic-
ally in Fig. 6.1. It is assumed that a very large supply of gas at specified temperature
and pressure and at zero velocity and Mach number is available. The origin of
the gas is called the reservoir, and the temperature and pressure of the gas in the
Convergent
section
";; Divergent section
Reservoir Receiver
"
f~
~
""
Flow
-
ThermOI '
Insulat '
~ IOn
Isen/roplC (a)
section
'".(J' Friction sec/ion
Reservoir I Receiver
Adiabatic
Flow
Thermal insulalion
(b)
Reservoir Receiver
Isen/ropic sec/ion
--+
r:.. Friclion sec/ion
Iso/hermol
low •
Healing jacket./'
(c)
FIGURE 6.1
(a) Isentropic expansion in convergent-divergent nozzle, (b) Adiabatic frictional flow, (c) Isothermal
frictional flow,
126 FLUID MECHANICS
reservoir are called reservoir conditions. The reservoir temperature is a stagnation
value, which does not necessarily apply at other points in the flow system.
From the reservoir the gas is assumed to flow, without friction loss at the
entrance, into and through a conduit. The gas leaves the conduit at definite
temperature, velocity, and pressure and goes into an exhaust receiver, in which
the pressure may be independently controlled at a constant value less than the
reserVOIr pressure.
Within the conduit anyone of the following processes may occur;
1. An isentropic expansion. In this process the cross-sectional area of the conduit
must change, and the process is described as one of variable area. Because the
process is adiabatic, the stagnation temperature does not change in the conduit.
Such a process is shown diagrammatically in Fig. 6.1a.
2. Adiabatic frictional flow through a conduit of constant crOss section. This
process is irreversible, and the entropy of the gas increases, but as shown by
Eq. (6.22), since Q = 0, the stagnation temperature is constant throughout the
conduit. This process is shown in Fig. 6.1h.
3. Isothermal frictional flow through a conduit of constant cross-sectional area,
accompanied by a flow of heat through the conduit wall sufficient to keep the
temperature constant. This process is nonadiabatic and nonisentropic; the
stagnation temperature changes during the process, since T is constant, and by
Eq. (6.20), T, changes with u. The process is shown in Fig. 6.1c.
The changes in gas temperature, density, pressure, velocity, and stagnation
temperature are predictable from the basic equations. The purpose of this section
is to demonstrate how these three processes can be treated analytically on the
basis of such equations.t
Flow through Variable-Area Conduits
A conduit suitable for isentropic flow is called a nozzle. As shown in Fig. 6.1a, a
complete nozzle consists of a convergent section and a divergent section joined
by a throat, which is a short length where the wall of the conduit is parallel with
the axis of the nozzle. For some applications, a nozzle may consist of a divergent
section only, and the throat connects directly with the receiver. The configuration
of an actual nozzle is controlled by the designer, who fixes the relation between
S, the cross-sectional area, and L, the length of the nozzle measured from the
entrance. Nozzles are designed to minimize wall friction and to suppress boundary-
layer separation. The convergent section is rounded and can be short, since
separation does not occur in a converging channel. To suppress separation in the
t A generalized treatment, including general heat transfer to and from the gas, injection of gas
into the conduit, variations in specific heat and molecular weight, chemical reactions, the drag of
internal bodies, and change of phase, is given in Re[ 3.
FLOW OF COMPRESSIBLE FLUIDS 117
divergent section, the diverging angle is made small, and this section is therefore
relatively long. The nozzle entrance is sufficiently large relative to the throat to
permit the velocity at the entrance to be taken as zero and the temperature and
pressure at the entrance to be assumed equal to those in the reservoir.
The purpose of the convergent section is to increase the velocity and decrease
the pressure of the gas. At low Mach numbers the process conforms essentially to
the usual Bernoulli relation for incompressible flow [Eq. (4.25)]. In the convergent
section flow is always subsonic, but it may become sonic at the throat. Mach
numbers greater than unity cannot be generated in a convergent nozzle. In the
divergent section, the flow may be subsonic or supersonic. The purpose of the
divergent section differs sharply in the two situations. In subsonic flow the purpose
of the section is to reduce the velocity and regain pressure, in accordance with
the Bernoulli equation. An important application of these nozzles is the measure-
ment of fluid flow, which is discussed in Chap. 8. In supersonic flow, the usual
purpose of the divergent section is to obtain Mach numbers greater than unity
for use in experimental devices such as wind tunnels.
Flow through a given nozzle is controlled by fixing the reservoir and receiver
pressures. For a given flow through a specific nozzle, a unique pressure exists at
each point along the axis of the nozzle. The relation is conveniently shown as a
plot of plpo versus L, where Po is the reservoir pressure and p the pressure at point
L. Figure 6.2 shows how the pressure ratio varies with distance and how changes
in receiver pressure at constant reservoir pressure affect the pressure distribution.
The pressures at the throat and in the receiver are denoted by P, and p"
respectively.
If p, and Po are equal, no flow occurs and the pressure distribution is
represented by the line aa'. If the receiver pressure is slightly below the reservoir
pressure, flow occurs and a pressure distribution such as that shown by line abe
1.00 a'
c
e
i
P*/Po ---------
it q
,
I
1
j
1
t
cf
_I
1
~:p
q
",I
~ "'I f
0 1 k
0 L-
FIGURE 6.2
Variation of pressure ratio with distance from nozzle inlet.
Ins FLUID MECHANICS
is established. Pressure recovery in the convergent section is shown by line bc.
The maximum velocity occurs at the throat. If the receiver pressure is further
reduced, the flow rate and the velocity throughout the nozzle increase. A limit is
attained when the velocity at the throat becomes sonic. This case is shown by line
ade, where Pt = p', Ut = a, and N M, = 1. The ratio p'/Po is called the critical
pressure ratio and is denoted by r,. Flpw is subsonic at all other points on line ade.
As the receiver pressure is decreased from that of point a' to that of point
e, the mass flow rate through the nozzle increases. The flow rate is not affected
by reduction of pressure below that corresponding to critical flow. Figure 6.3
shows how mass flow rate varies with the pressure ratio p,/Po' The flow rate attains
its maximum at point A, which is reached when the pressure ratio in the throat
is reduced to its critical value. Further reduction in pressure p, does not change
the flow rate.
The reason for this is as follows: when the velocity in the throat is sonic and
the cross-sectional area of the conduit is constant, sound waves cannot move
upstream into the throat and the gas in the throat has no way of receiving a
message from downstream. Further reduction of the receiver pressure cannot be
transmitted into the throat.
If the receiver pressure is reduced to the level shown by point f in Fig. 6.2,
the pressure distribution is represented by the continuous line adghf This line is
unique for a given gas and nozzle. Only along the path dghf is supersonic flow
possible. If the receiver pressure is reduced below that of point J, for example, to
point k, the pressure at the end of the nozzle remains at that of point f and flow
through the nozzle remains unchanged. On issuing from the nozzle into the
receiver the gas suffers a sudden pressure drop from that of point f to that of
point k. The pressure change is accompanied by wave phenomena in the receiver.
If the receiver pressure is held at a level between points e and J, pressure-
distribution curves of the type dgg'i and dhh'j are found. Sections dg and dh
to
~ Constant flow rate
A Maximum
"
.!: -------
flow rate
~
,.~
,l?
'"'"
~'"
00 1.0 FIGURE 6.3
Pressure ratio Pr/Po Mass flow rate through nozzle.
FLOW OF COMPRESSIBLE FLUIDS 129
represent isentropic supersonic flow. The sudden pressure jumps gg' and hh'
represent shock waves, where the flow changes suddenly from supersonic to
subsonic. Shocks are thermodynamically irreversible and are accompanied by an
increase in entropy in accordance with the second law of thermodynamics. Curves
g'i and h'j represent subsonic flows in which ordinary pressure recovery is taking
place.
The area below line adghJ is not accessible to any kind of adiabatic flow.
Isentropic flow is confined to the subsonic area adea'a and the single line dghJ.
The qualitative discussions of Figs. 6.2 and 6.3 apply to the flow of any
compressible fluid. Quantitative relations are most easily found for ideal-gas flow.
EQUATIONS FOR ISENTROPIC FLOW. The phenomena occurring in the flow
of ideal gas through nozzles are described by equations derivable from the basic
equations given earlier in this chapter.
Change in gas properties during flow. The density and temperature paths of the
gas through any isentropic flow are given by Eqs. (6.14) and (6.15). The constants
are evaluated from the reservoir condition. This gives
P Po
(6.23)
P' pI,
T To
--=-- (6.24)
pI-I!1' P6- 1/1'
These equations apply both to frictionless subsonic and supersonic flow, but
they must not be used across a shock front.
Velocity in nozzle. In the absence of friction, the mechanical-energy balance [Eq.
(6.6)] becomes simply
dp
P
= -d(~)
2g,
(6.25)
Eliminating P from Eq. (6.25) by substitution from Eq. (6.23) and integrating
from a lower limit based on the reservoir, where P = Po, P = Po, and u = 0, gives
r" d(~)
Jo 2g,
= - P6Po/' JPPoPd!;,
Integrating and substituting the limits yields, after rearrangement,
u2 = 2yg,po
(y - l)po
[1 _(£.)1-1/'J
Po
(6.26)
A Mach-number form of Eq. (6.26) is convenient. It is derived by substituting
u2 from Eq. (6.2) into the first equality of Eq. (6.18) and eliminating p/Po by
l:5U FLUID MECHANICS
substitution from Eq. (6.23). This gives
N~, = _ 2 Po £
y - 1 p Po
[I _(.£..),-I/'
Po
J = _ 2 [(PO)'-'
Y- 1 P
I
, _ IJ (6.27)
Solved explicitly for the pressure ratio, Eq. (6.27) becomes
P 1
(6.28)
Po {I + [(y - 1)/2JN~,}'I('-'I')
Ihe criticaL pressure ratio, denoted by r" is found from Eq. (6.28) by
substituting P* for P and 1.0 for N",:
re = p* = (_2_)1/(1-I/Y) (6.29)
Po Y+ 1
The mass velocity is found by calculating the product of u and p, using Eqs.
(6.23) and (6.26),
G = up = 2yg,poPo ( P )'
y - 1 \Po
1
' J 1_ (..£..)'
Po
11, (6.30)
EFFECT OF CROSS-SECTIONAL AREA. The relation between the change in
cross-sectional area, velocity, and Mach number is useful in correlating the various
cases of nozzle flow. Substitution of p from Eq. (6.25) into the continuity equation
(6.2) gives
du + dS _ (d P ) u du = 0 (6.31)
u S dp s g,
Subscript S is used to call attention to the fact that the flow is isentropic. From
Eq. (6.9)
(6.32)
Eliminating (dp/dp), from Eqs. (6.31) and (6.32) gives
du
u
(I _ua 2
2
) + dS
S
= 0
and, by substituting N M , from Eq. (6.1),
du 2 dS
-;;(NM , -I) = S (6.33)
Equation (6.33) shows that for subsonic flow, where N M , < I, the velocity
increases with decreasing cross section (converging conduit) and decreases with
increasing cross section (diverging conduit). This corresponds to the usual situation
of incompressible flow. Lines abc, ade, g'i, and h'j of Fig. 6.2 represent examples.
FLOW OF COMPRESSIBLE FLUIDS 131
For supersonic flow, where N Ma > 1, the velocity increases with increasing cross
section, as in the diverging section of the nozzle. This conforms to line dghf of
Fig. 6.2. The apparent anomaly of snpersonic flow is a result of the variation in
density and velocity along an isentropic path. Since the mass flow rate is the same
at all points in the nozzle, by continuity the cross-sectional area of the nozzle must
vary inversely with the mass velocity up. The velocity steadily increases with Mach
number, and the density decreases. However, at NM , = 1, the value of G goes
through a maximum. In the subsonic regime the velocity increases faster than the
density decreases, the mass velocity increases, and S decreases. In the supersonic
regime, the increase in velocity is overcome by a sharper decrease in density, the
mass velocity decreases, and S increases to accommodate the total mass flow. This
behavior of G is demonstrated by studying the first and second derivatives of Eq.
(6.30) in the usual manner for investigating maxima and minima.
Example 6.1. Air enters a convergent-divergent nozzle at a temperature of 555.6 K
(10000 R) and a pressure of 20 atm. The throat area is one-half that of the discharge
of the divergent section. (a) Assuming the Mach number in the throat is 0.8, what
are the values of the following quantities at the throat: pressure, temperature, linear
velocity, density, and mass velocity? (b) What are the values of p*, T*, u*, and G*
corresponding to reservoir conditions? (c) Assuming the nozzle is to be used
supersonically, what is the maximum Mach number at the discharge of the divergent
section? For air y = 1.4 and M = 29.
Solution
(a) The pressure at the throat is calculated from Eq. (6.28):
p, 1
c-------""7"=~1~,1~.4) = 0.656
20 {I + [(1.4 - 1)!2]0.8'j1"1
p, = 13.12 atm
From Eq. (6.10), since R = 82.056 X 10-' atm-m'/kg mol-K
20 x 29
Po = 82.056 X 10-' x 555.6 12.72 kgjm' (0.795Ib/ft')
Substituting Po/Po from Eq. (6.10) into Eq. (6.26) gives, for the velocity in the
throat,
2yg,RTo [1 _(p,)I-l/']
M(y - 1) \Po
2 x 1.4 x 82.056 x 10 'x 555.6 Jl _ 0.656 1 111.4
29(1.4 - 1)
= 1.1175 (m'-atm/kg)l/2
These units are converted to meters per second as ronows. From Appendix 2,
1 atm = 1.01325 x 10' N/m'. By definition, 1 N = 1 kg-m/s'. Hence
u, = 1.1175J1.01325 x JO' = 355.7 m/s (1167 ft/s)
132 FLUID MECHANICS
The density at the throat is, from Eq. (6.23),
p, = poGJ 1/, = 12.72 X 0.6561/1. 4 = 9.41 kg/m 3 (0.587Ib/ft 3 )
The mass velocity at the throat is
G, = U,p, = 355.7 x 9.41 = 3348 kg/m2_s (686 Ib/ft 2-s)
[The mass velocity can also be calculated directly by use of Eq. (6.30).] The
temperature at the throat is, from Eq. (6.24),
T, = ToGJ 1-1/, = 555.6 x 0.656 ' - ' /1.4 = 492.5 K (886.5'R)
(b) From Eq. (6.29)
P* ( 2 )1/(1-1/1.4)
r, =- = -- = 0.528 P* = 20 x 0.528 = 10.56 atm
Po 1.4 + 1
From Eqs. (6.24) and (6.29)
T* = 555.6(_2_) = 463 K (833.4'R)
1.4 + 1
From Eq. (6.23)
Po)' = Po
(p* P* = (P*)"'
P* Po Po
p* = 12.72 X 0.528 ' /1. 4
= 8.06 kg/m 3 (0.503 Ib/ft 3 )
From Eq. (6.30)
G* = 2 x 1.4 x 12.72 x 20 x 1.01325 X 10' 0.5281/1.4)1 _ 0.528 111.4
1.4 - 1 '
2
= 3476 kg/m _s (712 Ib/ft'-s)
G* 3476
u* = - = - - = 431 m/s (1415 ft/si
p* 8.06
(c) Since, by continuity, Get: l/S, the mass velocity at the discharge is
G, = 3",76 = 1738 kg/m'-s (356 Ib/ft 2-s)
From Eq. (6.30)
4 4
1738 = 2 x 1.4 x 12.72 x02~ x 1.01325 x 10' [1 - G J l/1 JGJ/1.
(~r)[1 -
4
GJ 1I1. J = 0.1294
This equation is solved for Pr/PO to give
1'.c = 0.0939
Po
FLOW OF COMPRESSIBLE FLUIDS 133
From Eq. (6.27) the Mach number at the discharge is
N
Ma,r
= J 2 (1
--
1.4 _ 1 0.09391 1/1.4
)
-1 =2.20
Adiabatic Frictional Flow
Flow through straight conduits of constant cross section is adiabatic when
heat transfer through the pipe wall is negligible. The process is shown dia-
grammatically in Fig. 6.lh. The typical situation is a long pipe into which
gas enters at a given pressure and temperature and flows at a rate determined
by the length and diameter of the pipe and the pressure maintained at the
outlet. In long lines and with a low exit pressure, the speed of the gas may
reach the sonic velocity. It is not possible, however, for a gas to pass through
the sonic barrier from the direction of either subsonic or supersonic flow; if
the gas enters the pipe at a Mach number greater than I, the Mach number
will decrease but will not become less than 1. If an attempt is made, by
maintaining a constant discharge pressure and lengthening the pipe, to force
the gas to change from subsonic to supersonic flow or from supersonic to
subsonic, the mass flow rate will decrease to prevent such a change. This
effect is called choking.
THE FRICTION PARAMETER. The basic quantity that measures the effect of
friction is the friction parameter fLlr ll • This arises from the integration of Eq.
(6.8). In adiabatic frictional flow, the temperature of the gas changes. The viscosity
also varies, and the Reynolds number and friction factor are not actually constant.
In gas flow, however, the effect of temperature on viscosity is small, and the effect
of Reynolds number on the friction factor f is still less. Also, unless the Mach
number is nearly unity, the temperature change is small. It is satisfactory to use
an average value for f as a constant in calculations. If necessary, f can be evaluated
at the two ends of the conduit and an arithmetic average used as a constant.
Friction factors in supersonic flow are not well established. Apparently,
they are approximately one-half those in subsonic flow for the same Reynolds
number. 2
In all the integrated equations in the next section it is assumed that
the entrance to the conduit is rounded to form an isentropic convergent nozzle.
If supersonic flow in the conduit is required, the entrance nozzle must include a
divergent section to generate a Mach number greater than 1.
EQUATIONS FOR ADIABATIC FRICTIONAL FLOW. Equation (6.8) is multiplied
by pip, giving
dp p II dll P1l2 f dL
-+--+---=0 (6.34)
ppg, 2pg, rH
134 FLUID MECHANICS
It is desired to obtain an integrated form of this equation. The most useful
integrated form is one containing the Mach number as the dependent variable
and the friction parameter as an independent variable. To accomplish this, the
density factor is eliminated from Eq. (6.34) using Eq. (6.18), and relationships
between N M" dp/p, and du/u are found from Eqs. (6.2) and (6.11). Quantity dT/T,
when it appears, is eliminated by usiug Eqs. (6.4), (6.13), and (6.18). The results are
dp = _ 1 +(y-l)N~, dN M ,
(6.35)
P 1 + [(y - 1)/2JN~, N M,
Also
(6.36)
Substitution from Eqs. (6.35) and (6.36) into Eq. (6.34) and rearrangement gives
the final differential equation
dL 2(1 - N~,) dN",
yN~,{1 + [(y - 1)/2JN~,}
(6.37)
1 rH =
Formal integration of Eq. (6.37) between an entrance station a and exit
station b gives
L. -dL=
1 JNM'," 2 )dN
2(1 - N Ma Ma
JL, rH N Mop yN~,{1 + [(y - 1)f2JN~,}
j JAL
-(Lb - La) = - -
rH rH
1 (1 1 y + 1 N~'.b{1 + [(r - 1)/2JN~,.a}) (6.38)
N~".a - N~'.b - -2- N~,.a{1 + [(y - 1)/2JN~'.b}
ln
=;;
where j is the arithmetic average value of the terminal friction factors, (fa + Ib)/2,
and AL = Lb - La.
Property equations. For calculating the changes in pressure, temperature, and
density, the following equations are useful.
I n adiabatic frictional flow the ratio of the inlet and outlet pressures
is found by direct integration of Eq. (6.35) between the limits Pa, Pb' and NM,.a'
N Ma,b to give
Pa NM,.b 1 + [(y - 1)f2JN~'.b
-=- (6.39)
Pb NM,.a 1 + [(y - 1)/2JN~,.a
The temperature ratio is calculated from Eq. (6.20), noting that Toa =
TOb ; so
(6.40)
FLOW OF COMPRESSIBLE FLUIDS 135
From the temperature form of Eq. (6.18) for the Mach nnmber of an ideal gas,
yR1'aN~la,a yR1bN~fa,b
T=
a 2MJe p
=1b+ 2MJe (6.41)
p
From Eq. (6.16)
JCpM =_Y- (6.42)
R y-l
Substituting JepMIR from Eq. (6.42) into Eq. (6.41) and solving for the temperature
ratio gives
T. 1 + [(y - 1)!2]N~'a.b
(6.43)
1b 1 + [(y - 1)/2]Ntfa.a
The density ratio is calculated from the gas equation of state (6.10) and
the pressure and temperature ratios given by Eqs. (6.39) and (6.43), respec-
tively,
f!.a. = Pa1b = N Ma .b 1 + [(y - 1)!2]N~a a
(6.44)
Pb PbT. N Ma .a 1 + [(y - 1)!2]Nt'a.b
Maximum conduit length. To ensure that the conditions of a problem do not call
for the impossible phenomenon of a crossing of the sonic barrier, an equation is
needed giving the maximum value of JLlrH consistent with a given entrance Mach
number. Such an equation is found from Eq. (6.38) by choosing the entrance to
the conduit as station a and identifying station b as the asterisk condition, where
N Ma = 1.0. Then the length Lb - La represents the maximum length of conduit
that can be used for a fixed value of N Ma .a. This length is denoted by Lma.. Equation
(6.38) then gives
JLma. = ~ (_1__ 1 _ + 1 1n 2{1 + [(y - 1)/2]N~a.a}) (6.45)
rH Y Nt".a 2 N~a.a(Y + 1)
Corresponding equations for pip', TIT', and pip' are found from Eqs. (6.39),
(6.43), and (6.44).
MASS VELOCITY. To calculate the Reynolds number for evaluating the friction
factor, the mass velocity is needed. From Eq. (6.18) and the definition of G
(puj2 G2 G2
N~fa = ~-"--'--
p2g,yTRIM p2g,yTRIM pg,YP
and
G = pN"a J9,YTR c:=
~ = N"aY pg,YP (6.46)
136 FLUID MECHANICS
Since, for constant-area flow, G is independent of length, the mass velocity
can be evaluated at any point where the gas properties are known. Normally
the conditions at the entrance to the conduit are used.
Example 6.2. Air flows from a reservoir through an isentropic nozzle into a long
straight pipe. The pressure and temperature in the reservoir are 20 atm and lOoooR
(555.6 K), respectively, and the Mach number at the entrance of the pipe is 0.05. (a)
What is the value of jLmax/rll ? (b) What are the pressure, temperature, density,
linear velocity, and mass velocity when Lb = Lmn><.? (c) What is the mass velocity
when JLm,,/rH = 400?
Solution
(a) Values for substitution in Eq. (6.45) are y = 1.4 and N", .• = 0.05. Then
JLm.. 1 (' 1 1.4 + 1 2{1 + [(1.4 - 1)/2]0.05'}) =280
--=- ---I---ln
rH 1.4 0.05' 2 (1.4 + 1)0,05 2
(b) The pressure at the end of the isentropic nozzle p. is given by Eq. (6.28):
20 20
P. = {I + [(1.4 _ 1)j2]0.05'}1.4f(1.4 1) = 1.0016'" 20 atm
The pressure, temperature, and density change in the nozzle are negligible, and
except for linear velocity, the reservoir conditions also pertain to the pipe entrance.
From Example 6.1, the density of air at 20 atm and 10000R is 0.795Ib/ft 3 . The
acoustic velocity is, from Eq. (6.17),
1545
a• = 1.4 x 32.174 x 1000-- = 1550 ft/s (472.4 m/s)
29
The velocity at the entrance of the pipe is
u. = 0.05 x 1550 = 77.5 ft/s (23.6 m/s)
When Lb = Lmllx , the gas leaves the pipe at the asterisk condition, where N Ma,b = 1.0.
From Eq. (6.43)
1000 24
-= = 1.2
T* 2{1 + [(1.4 - 1)j2]0.05')
T* = 834°R (463.3 K)
From Eq. (6.44)
0.795 2{1 + [(1.4 - 1)j2]0.05')
p* 0.05 2.4
p* = 0.0435Ib/ft' (0.697 kg/m')
From Eq. (6.39)
20 1
p* = 0.05 JU
p* = 0.913 atm
FLOW OF COMPRESSIBLE FLUIDS 137
The mass velocity through the entire pipe is
G = 0.795 x 77.5 = 0.0435u* = 61.611b/rt2 -s (300.S kgfm 2 _s)
a = u* = 1416 rt/s (431.6 m/s)
Since the exit velocity is sonic, u* can also be calculated from Eq. (6.17) using
T = T* = SWR (463.3 K):
a = u* = 1550
(c) Using Eq. (6.45) with
J:0
34
- - = 1416 ft/s (431.6 m/s)
1000
jLm..lr H = 400 gives
400 = ~ (_1_ _ I _ 1.4 + I 2{1 + [(1.4 - 1)f2]N~•.•})
ln
1.4 N~... 2 N~, .•(1.4 + I)
This equation must be solved for N MI1 •a by trial and error. The final result is
N M ••• = 0.04194. Then
c 0.04194
u. = - - 77.5 = 65.0 rt/s (19.S m/s)
0.05
G = 65.0 x 0.795 = 51.71b/ft 2 -s (252.4 kgfm 2 _s)
Isothermal Frictional Flow
The temperature of the fluid in compressible flow through a conduit of constant
cross section may be kept constant by a transfer of heat through the conduit wall.
Long, small, uninsulated pipes in contact with air transmit sufficient heat to keep
the flow nearly isothermal. Also, for small Mach numbers, the pressure pattern
for isothermal flow is nearly the same as that for adiabatic flow for the same
entrance conditions, and the simpler equations for isothermal flow may be used.
The maximum velocity attainable in isothermal flow is
a'=f}=l,~R (6.47)
The dimensions of a' are those of velocity. Comparing Eq. (6.47) with Eq. (6.17)
for the acoustic velocity shows that
a=a'JY (6.48)
Thus, for air where JY = J1.4 '" 1.2 the acoustic velocity is approximately
20 percent larger than a'. Corresponding to the true Mach number, an isothermal
Mach number may be defined:
(6.49)
The parameter Ni plays the same part in isothermal flow as the Mach number
does in adiabatic flow. An isothermal process cannot pass through the limiting
138 FLUID MECHANICS
condition where Ni = 1.0. If the flow is initially subsonic, it must remain so and
a maximum conduit length for a given inlet velocity is reached at the limiting
condition. The velocity obtainable in isothermal flow is less than that in adiabatic
flow because a' is less than a.
The basic equation for isothermal flow is simple. It is obtained by introducing
the mass velocity into the mechanical-energy balance [Eq. (6.8)] and integrating
directly.
Multiplying Eq. (6.8) by P' gives
p'u du p'u' f dL
pdp +--+ . 0 (6.50)
gc 2gcrH
Since pu = G, u du = -(G'p-') dp, and p = Mp/RT, Eq. (6.50) can be written
M G'dp G'JdL
-pdp---+ =0 (6.51)
RT g, P 2g,rH
Integrating between stations a and b gives
~ (p~ _ p~) _ G' In "-" = G'J I1L (6.52)
2RT g, Ph 2g,rH
The pressure ratio Po/Ph may be used in place of P,/Ph in Eq. (6.52).
Equation (6.52) can also be used when the temperature change over the
conduit is small. Then, in place of T, an arithmetic average temperature may be
used. For example, adiabatic flow at low Mach numbers (below about 0.3) follows
the equation closely.
Example 6.3. Air at 1.7 atm gauge and lSoC enters a horizontal 7S-mm steel pipe
that is 70 m long. The velocity at the entrance of the pipe is 60 m/so Assuming
isothermal flow, what is the pressure at the discharge end of the line?
Solution
Use Eq. (6.52). The quantities needed are
0.075
D = 0.075 m I'll = - - = 0.01875 m
4
" = 0.0174 eP (Appendix 8) = 1.74 X 10-' kgjm-s
29 2.7 273
Po = - x - x - = 3.31 kgfm'
22.4 1 288
Then
G = ]7 P = 60 x 3.31 = 198.6 kgfm'-s
198.6
N R, = 0.075 x 8.56 x 10'
1.74 x 10 '
k 0.3048
- = 0.00015 x -- = 0.00061
d 0.075
f = 0.0044 (Fig. 5.9)
Let (Po + p,)/2 = p, so
(Po - p,)' = (Po - p')(Po + p,) = 2p(po - p,)
From Eq. (6.52), omitting g,
Po - p, = R'!G'
pM
(I!1L
2rlf
+ ln~)
Pb
where Pll = 2.7 atm
M=29
!1L = 70m
R = 82.056 X 10- 3 m3 -atm/kg mol-K (Appendix 2)
T = 15 + 273 = 288 K
By trial, p is found to be 1.982 atm and p, = 1.264 atm.
Check: Since 1 atm = 101,325 N/m' = 101,325 kg/m-s' [Eqs. (1.14) and (1.15)J,
82.056 x 10- 3 x 288 X 198.6 2 (0.0044 x 70 2.7 )
p,=2.7- +In--
1.982 x 29 x 101,325 2 x 0.01875 1.264
= 1.264 atm abs or 0.264 atm gauge
The average pressure is
_ 2.7 + 1.264
p= 1.982 atm
2
HEAT TRANSFER IN ISOTHERMAL FLOW. The steady-flow energy equation
(6.22) and Eq. (6.20) for the stagnation temperature combine to give, after noting
that 7; = 1/"
Q u~-u~
(6.53)
m 2gJ
Substituting Gip for u gives the mass-velocity form of Eq. (6.53),
fL~(~_~) (6.54)
In - 2gJ pl p;
In these equations Qlm is the heat flow into the gas in joules per kilogram
or Btu per pound.
Equations (6.52) to (6.54) are used for subsonic flow only.
SYMBOLS
a Acoustical velocity in fluid, m/s or ft/s; ao , at pipe entrance
a' Maximum attainable velocity in isothermal flow in conduit, m/s or ft/s
C Specific heat, Jig_PC or Btujlb-PF; cp , at constant pressure; Co, at
constant volume
.. "tU l'LUIU M!!CHANICS
D Diameter, m or ft
f Fanning friction factor, dimensionless; fa, at station a; fb' at station b;
j, average value
G Mass velocity, kg/m 2 -s or Ib/ft2-s; G" in receiver; G" at throat; G*, value
when N M, = 1.0
9 Gravitational acceleration, m/s or ft/s
g, Newton's-law proportionality factor, 32.174 ft-Ib/lb r s2
H Enthalpy, Jig or Btu(lb; HO' at station a; H b , at station b; Ho, at reference
temperature; H s ' at stagnation; H*, value when N Ma = 1.0
hJ Friction loss, N-m/g or ft-IbJ(lb; hJ" loss from skin friction
J Mechanical equivalent of heat, 778.17 ft-IbJIBtu
k Roughness parameter, m or ft
L Length, m or ft, La' from entrance to station a; L b , to station b; L max ,
length of conduit when N rn, = 1.0 at outlet
M Molecular weight of fluid
In Mass, kg or lb
In Mass flow rate, kg/s or Ibis
Ni Mach number for isothermal flow, ula'
NMa Mach number, u/a; NMa,a' at station a; Nma,b' at station b; NMa,r' at
nozzle discharge
p Pressure, N/m 2 or Ib j /ft2; Pa, at station a; Pb. at station b; Pr' in receiver;
Pt. at throat of convergent-divergent nozzle; Po, in reservoir; p*, value
when NMa = 1.0; p, average value
Q Quantity of heat, J or Btu
R Gas-law constant, 8.314 Jig mol-K or 1545 ft-IbJllb mol-oR
" Critical pressure ratio, p* Ipo
rll Hydraulic radius of conduit, m or ft
S Cross-sectional area of conduit, m 2 or ft 2
T Temperature, K or oR; Ta. at station a; T", at station b; 7;;, stagnation
value; 7;, at nozzle throat; To. reference value; T*, value when NMa = 1.0
u Fluid velocity, m/s or ft/s; u" at station a; Ub' at station b; Ut, at throat
of convergent-divergent nozzle; u*, value when N", = 1.0
j7 Average velocity of fluid stream, m/s or ft/s
Z Height above datum plane, m or ft
Greek letters
a Kinetic-energy correction factor; aa. at station a; ab. at station b
fJ Momentum corrector factor
y Ratio of specific heats, cplc"
P Density of fluid, kg/m 3 or lb/ft'; PO' Pb, at stations a and b; p" at throat
of convergent-divergent nozzle; Po. in reservoir; p*, value when
N M , = 1.0
J1 Absolute viscosity, P or lb/ft-s
FLOW OF COMPRESSIBLE FLUIDS 141
Subscripts
a At station a
b At station b
S Isentropic flow
s Stagnation value
o Reference value, reservoir conditions
PROBLEMS
6.1. For the inlet conditions of Example 6.2, what is the maximum length of pipe that may
be used if the pipe is 2 in. in diameter? What is it for the inlet conditions of Example 6.3?
6.2. Natural gas consisting essentially of methane is to be transported through a 20Min.-ID
pipeline over fiat terrain. Each pumping station increases the pressure to
lOO Ibj/in-' abs, and the pressure drops to 25 Ibj/in.' abs at the inlet to the next
pumping station 50 mi away. What is the gas flow rate in cubic feet per hour measured
at 60°F and 30 in. Hg pressure?
6.3. A divergent-convergent nozzle has the proportions shown in Table 6.1. Air (y = 1.40,
M = 29.0) enters the nozzle from a reservoir in which the pressure is 20 atm abs and
the temperature is 550 K. Plot the pressure, the temperature, and the Mach number
vs. the length of the nozzle when (a) the flow rate is a maximum without shock and
with subsonic discharge; (b) the flow is isentropic and the discharge is supersonic.
TABLE 6.1
Data in Prob. 6.3
Length Diameter Length Diameter
Reservoir 0 00 Throat 0.30 0.25
0.025 0.875 0.40 0.28
0.050 0.700 0.50 0.35
0.075 0.575 0.60 0.45
0.100 0.500 0.70 0.56
0.150 0.375 0.80 0.68
0.200 0.300 0.90 0.84
Receiver 1.00' 1.00
6.4. A standard I-in. Schedule 40 horizontal steel pipe is used to conduct chlorine gas. The
gas enters the pipe through a rounded entrance at a pressure of 6 atm abs, a tempera-
ture of 120°C, and a velocity of 35 m/so (a) What is the maximum possible length of
the pipe? (b) What is the pressure and stagnation temperature of the gas at the end
of the pipe at maximum length? Assume adiabatic flow. For chlorine, y = 1.36, and
M = 70.91
6.5. Assuming that the flow process in Prob. 6.4 occurs isothermally, (a) what is the
maximum pipe length? (b) How much heat must be transferred to the gas when the
length equals the maximum?
142 FLUID MECHANICS
REFERENCES
1. Cambel, A. B.: in V. L. Streeter (ed.): Handbook of Fluid Dynamics, McGraw-Hill, New York, 1961,
pp. 8-5 to 8-12.
2. Cambel, A. B., and B. H. Jennings: Gas Dynamics, McGraw-Hill, New York, 1958, pp. 85-86.
3. Shapiro, A. H., and W. R. Hawthorne: J. Appl. Mech., 14:A-317 (1947).
CHAPTER
7
FLOW
PAST
IMMERSED
BODIES
The discussion in Chaps. 4 and 5 centered about the laws of fluid flow and
factors that control changes of pressure and velocity of fluids flowing past solid
boundaries and was especially concerned with flow through closed conduits.
Emphasis during the discussion was placed primarily on the fluid. In many
problems, however, the effect of the fluid on the solid is of interest. The fluid may
be at rest and the solid moving through it; the solid may be at rest and the fluid
flowing past it; or both may be moving. The sItuation where the solid is immersed
in, and surrounded by, fluid is the subject of this chapter.
It is generally immaterial which phase, solid or fluid, is assumed to be at
rest, and it is the relative velocity between the two that is important. An exception
to this is met in some situations when the fluid stream has been previously
influenced by solid walls and is in turbulent flow. The scale and intensity of
turbulence then may be important parameters in the process. In wind tunnels, for
example, where the solid shape is at rest and the stream of air is in motion,
turbulence may give different forces on the solid than if the solid were moving at
the same relative velocity through a quiescent and turbulence-free mass of air.
Objects in free fall through a continuous medium may move in spiral patterns or
rotate about their axis or both; again the forces acting on them are not the same
as when they are held stationary and the fluid is passed over them.
144 FLUID MECHANICS
DRAG. The force in the direction of flow exerted by the fluid on the solid is called
drag. By Newton's third law of motion, an equal and opposite net force is exerted
by the body on the fluid. When the wall of the body is parallel with the direction
of flow, as in the case of the thin flat plate shown in Fig. 3.9a, the only drag force
is the wall shear 'wo More generally, however, the wall of an immersed body makes
an angle with the direction of flow. Then the component of the wall shear in the
direction of flow contributes to drag. An extreme example is the drag of the flat
plate perpendicular to the flow, shown in Fig. 3.9b. Also, the fluid pressure, which
acts in a direction normal to the wall, possesses a component in the direction of
flow, and this component also contributes to the drag. The total drag on an element
of area is the sum of the two components. Figure 7.1 shows the pressure and shear
forces acting on an element of area dA inclined at an angle of 90° - a to the
direction of flow. The drag from wall shear is '" sin Cl dA, and that from pressure
is p cos Cl dA. The total drag on the body is the sum of the integrals of these
quantities, each evaluated over the entire surface of the body in contact with the
fluid.
The total integrated drag from wall shear is called wall drag, and the total
integrated drag from pressure is called form drag.
In potential flow, 'w= 0, and there is no wall drag. Also, the pressure drag
in the direction of flow is balanced by an equal force in the opposite direction,
and the integral of the form drag is zero. There is no net drag in potential flow.
The phenomena causing both wall and form drag in actual fluids are
complicated, and in general the drag cannot be predicted. For spheres and other
regular shapes at low fluid velocities, the flow patterns and drag forces can be
estimated by numerical methods 14 ; for irregular shapes and high velocities they
are most easily determined by experiment.
pcosadA
(form drag)
Direction
of flow
FIGURE 7.1
Wall drag and form drag on immersed body.
FLOW PAST IMMERSED BODIES 145
DRAG COEFFICIENTS. In treating fluid flow through conduits, a friction factor,
defined as the ratio of the shear stress to the product of the velocity head and
density, was shown to be useful. An analogous factor, called a drag coefficient, is
used for immersed solids. Consider a smooth sphere immersed in a flowing fluid
and at a distance from the solid boundary of the stream sufficient for the
approaching stream to be at a uniform velocity. Define the projected area of the
solid body as the area obtained by projecting the body on a plane perpendicular
to the direction of flow, as shown in Fig. 7.2. Denote the projected area by Ap.
For a sphere, the projected area is that of a great circle, or (n/4)D;, where Dp
is the diameter. If F D is the total drag, the average drag per unit projected area
is F D/Ap. Just as the friction factor J is defined as the ratio of 'w to the product
of the density of the fluid and the velocity head, so the drag coefficient CD is
defined as the ratio of F D/Ap to this same product, or
CD == F ~/Ap (7.1)
pU o/2g,
where Uo is the velocity of the approaching stream (by assumption 110 is constant
over the projected area).
For particles having shapes other than spherical, it is necessary to specify
the size and geometrical form of the body and its orientation with respect to the
direction of flow of the fluid. One major dimension is chosen as the characteristic
length, and other important dimensions are given as ratios to the chosen one.
Such ratios are called shape Jactors. Thus for short cylinders, the diameter is usually
chosen as the defining dimension, and the ratio of length to diameter is a shape
factor. The orientation between the particle and the stream also is specified. For
a cylinder, the angle formed by the axis of the cylinder and the direction of flow
is sufficient. Then the projected area is determinate and can be calculated. For a
cylinder so oriented that its axis is perpendicular to the flow, Ap is LDp, where L
is the length of the cylinder. For a cylinder with its axis parallel to the direction
of flow, Ap is (n/4)D;, the same as for a sphere of the same diameter.
From dimensional analysis, the drag coefficient of a smooth solid in an
incompressible fluid depends upon a Reynolds number and the necessary shape
FlUId approach velocity Uo
Projected area Ap
Fluid streamlines
FIGURE 7.2
Flow past immersed sphere.
146 FLUID MECHANICS
factors. For a given shape
CD = 4>(N Ro . p )
The Reynolds number for a particle in a fluid is defined as
_ GoDp
NRe,p = -p- (7.2)
where D p = characteristic length
Go = uoP
A different CD-versus-NRo,p relation exists for each shape and orientation, The
relation must in general be determined experimentally, although a well-sub-
stantiated theoretical equation exists for smooth spheres at low Reynolds numbers,
Drag coefficienls for compressible fluids increase with increase in the Mach
number when the latter becomes more than about 0.6. Coefficients in supersonic
flow are generally greater than in subsonic flow.
DRAG COEFFICIENTS OF TYPICAL SHAPES, In Fig, 7.3, curves of CD versus
NRo,p are shown for spheres, long cylinders, and disks, The axis of the cylinder
and the face of the disk are perpendicular to the direction of flow; these curves
apply only when this orientation is maintained. If, for example, a disk or cylinder
is moving by gravity or centrifugal force through a quiescent fluid, it will twist
and turn as it moves freely through the fluid,
From the complex nature of drag, it is not surprising that the variation of
CD with NRo,p is more complicated than that of J with N", The variations in
slope of the curves of CD versus NRo,p at different Reynolds numbers are the result
of the interplay of the various factors that control form drag and wall drag. Their
effects can be followed by discussing the case of the sphere.
For low Reynolds numbers the drag force for a sphere conforms to a
theoretical equation called Stokes' law, which may be written
pUoDp
FD = 3,,-- (7.3)
go
From Eq, (7.3), the drag coefficient predicted by Stokes' law, using Eq. (7.1), is
24
CD = - - (7.4)
NRe,p
In theory, Stokes' law is valid only when NRo,p is considerably less than
unity, Practically, as shown by the left-hand portion of the graph of Fig, 7.3, Eqs,
(7.3) and (7.4) may be used with small error for all Reynolds numbers less than 1.
At the low velocities at which the law is valid, the sphere moves through the fluid
by deforming it. The wall shear is the result of viscous forces only, and inertial
forces are negligible. The motion of the sphere affects the fluid at considerable
distances from the body, and if there is a solid wall within 20 or 30 diameters of
100,000
" 1,,\
10,000
~,,'"
<>.
~~
c..'" ~ "- 1'\
~o 1,000I
II~
,.:
1',
zw .~
"-
100I ,
~
8 "-
,
,
~
10I - - - SPHERES
... ------ DISKS
-.. - - - CYLINDERS
1.0,
- .::-1-- "
-- -- - ....- -- - -~ ---
1\
O. \
00001 0.001 0.01 0.1 ID 10 100 1,000 10,000 100,000 1,000,000
_ Dp,Pt.lo
REYNOLDS NUMBER,NRe,p-p-
FIGURE 7.3
Drag coefficients for spheres, disks, and cylinders. [By permissionjram J. H. Perty (ed.), Chemical Engineers' Handbook, 6th ed., p. 5-64. Copyright,
© 1984, McGraw~Hil/ Book Company.]
148 FLUID MECHANICS
la}
FIGURE 7.4
Flow past single sphere, showing
separation and wake formation:
(a) laminar flow in boundary
layer; (b) turbulent flow in bound-
ary layer; B, stagnation point;
C, separation point. [By permis-
sion from J. C. Hunsaker and
B. G. Riglicmire, Engineering Ap-
plication of Fluid M ecilanics,
pp. 202-203. CopyrigiJt, © 1947,
(b) McGraw-Hill Book CompaIlY.]
the sphere, Stokes' law must be corrected for the wall effect. The type of flow
treated in this law is called creeping flow. The law is especially valuable for
calculating the resistance of small particles, such as dusts or fogs, moving through
gases or liquids of low viscosity or for the motion ()f larger particles through highly
viscous liquids.
As the Reynolds number is increased to 10 or above, well beyond the range
of Stokes' law, separation occurs at a point just forward of the equatorial plane,
as shown in Fig. 7.4a, and a wake, covering the entire rear hemisphere, is formed. 7
It has been shown in Chap. 3 that a wake is characterized by a large friction loss.
It also develops a large form drag, and in fact, most form drag occurs as a result
of wakes. In a wake, the angular velocity of the vortices, and therefore their kinetic
energy of rotation, is large. The pressure in the wake is, by the Bernoulli principle,
less than that in the separated boundary layer; a suction develops in the wake,
and the component of the pressure vector acts in the direction of flow. The pressure
drag, and hence the total drag, is large, much greater than if Stokes' law still
applied.
At moderate Reynolds numbers the vortices disengage from the wake in a
regular fashion, forming in the downstream fluid a series of moving vortices known
as a "vortex street." At high Reynolds numbers, however, vortices are no longer
shed from the wake.t A stable boundary layer forms, originating at the apex,
point B in Fig. 7.4. The boundary layer grows and separates, flowing freely around
t With some "bluff bodies," such as a bar with a trapezoidal cross section, vortex streets are formed
over a wide range of Reynolds numbers (see Chap. 8).
FLOW PAST IMMERSED BODIES 149
the wake after separation. At first the boundary layer is in laminar flow, both
before and after separation. The drag coefficient is nearly constant; as shown in
Fig. 7.3, for spheres and cylinders it increases slightly with the Reynolds number.
As the Reynolds number is still further increased, transition to turbulence takes
place, first in the free boundary layer and then in the boundary layer still attached
to the fron t hemisphere of the sphere. When turbulence occurs in the latter, the
separation point moves toward the rear of the body and the wake shrinks, as
shown in Fig. 7.4b. Both friction and drag decrease, and the remarkable drop in
drag coefficient from 0.45 to 0.10 at a Reynolds number of about 300,000 is a
result of the shift in separation point when the boundary layer attached to the
sphere becomes turbulent.
The Reynolds number at which the attached boundary layer becomes
turbulent is called the critical Reynolds number for drag. The curve for spheres
shown in Fig. 7.3 applies only when the fluid approaching the sphere is non-
turbulent or when the sphere is moving through a stationary static fluid. If the
approaching fluid is turbulent, the critical Reynolds number is sensitive to the
scale of turbulence and becomes smaller as the scale increases. For example, if the
scale of turbulence, defined as 100,! (u')' /u, is 2 percent, the critical Reynolds
number is about 140,000. 9 One method of measuring the scale of turbulence is to
determine the critical Reynolds number and use a known correlation between the
two quantities.
The curve' of CD versus N R, for an infinitely long cylinder normal to the flow
is much like that for a sphere, but at low Reynolds numbers, CD does not vary
inversely with N R, because of the two-dimensional character of the flow around
the cylinder. For short cylinders, such as catalyst pellets, the drag coefficient falls
between the values for spheres and long cylinders and varies inversely with the
Reynolds number at very low Reynolds numbers. Disks do not show the drop in
drag coefficient at a critical Reynolds number, because once the separation occurs
at the edge of the disk, the separated stream does not return to the back of the
disk and the wake does not shrink when the boundary layer becomes turbulent.
Bodies that show this type of behavior are called bluff bodies. For a disk the drag
coefficient CD is approximately unity at Reynolds numbers above 2000.
The drag coefficients for irregularly shaped particles such as coal or sand
appear to be about the same as for spheres of the same nominal size at Reynolds
numbers less than 50 4 However, the curve of CD versus NR, levels out at
N R, "" 100, and the values of CD are two to three times those for spheres in the
range N R , = 500 to N R , = 3000. Similar results for isometric particles such as
cubes and tetrahedrons have been reported 20
FORM DRAG AND STREAMLINING. Form drag can be minimized by forcing
separation toward the rear of the body. This is accomplished by streamlining. The
usual method of streamlining is to so proportion the rear of the body that the
increase in pressure in the boundary layer, which is the basic cause of separation,
is sufficiently gradual to delay separation. Streamlining usually calls for a pointed
150 FLUID MECHANICS
FIGURE 75
Streamlined body: AB, streamline to stagnation point B.
rear, like that of an airfoil. A typical streamlined shape is shown in Fig. 7.5. A
perfectly streamlined body would have no wake and little or no form drag.
Stagnation point. The streamlines in the fluid flowing past the body in Fig. 7.5
show that the fluid stream in the plane of the section is split by the body into two
parts, one passing over the top of the body and the other under the bottom.
Streamline AB divides the two parts and terminates at a definite point B at the
nose of the body. This point is called a stagnation point. The velocity at a
stagnation point is zero. Equation (4.25) may be written on the assumption that
the flow is horizontal and friction along the streamline is negligible. The undis-
turbed fluid is identified with station a in Eq. (4.25) and the stagnation point with
station h. Then
Ps - Po 116
---=- (7.5)
p 2g,
where Ps = pressure on body at stagnation point
Po = pressure in undisturbed fluid
"0 = velocity of undisturbed fluid
p= density of fluid
The pressure increase p, - Po for the streamline passing through a stagnation point
is larger than that for any other streamline, because at that point the entire velocity
head of the approaching stream is converted into pressure head.
STAGNATION PRESSURE. Equation (7.5) may be used for compressible fluids at
low Mach numbers but becomes increasingly inaccurate when N M , is larger than
about 0.4. The proper pressure to use for Ps then is the isentropic stagnation
pressure, defined as the pressure of the gas when the stream is brought to rest
FLOW PAST IMMERSED BODIES 151
isentropically, and calculated from the equations of Chap. 6 as follows. From Eq.
(6.24)
(p,)'-'/' = T, (7.6)
\Po To
where Ps = stagnation pressure
T, = stagnation temperature
To = temperature of approaching stream
From Eq. (6.43), using 7;, = 7;" 'Tb = To, N M••• = 0, and N M •• b = N M•• O '
T. Y- 1
-'-= 1 + __ N 2 (7.7)
To 2 Ma,O
Combining Eqs. (7.6) and (7.7),
p, _ ( l' - 1 2 )1 / (1 -1/'1)
- - 1+--NM •• o (7.8)
Po 2
Equation (7.8) can be brought into the same form as Eq. (7.5) by subtracting unity
from both sides and expanding the right-hand side of Eq. (7.8) by the binomial
theorem. After substitution and simplification, using the relationship for N M. given
in Eq. (6.18), and multiplication by Po/Po, the result is
p, - Po = u6 (1 + N~b.O + 2 - Y N4 + ... ) (7.9)
Po 2g, 4 24 M,.O
Comparison of Eq. (7.9) with Eq. (7.5) shows that the quantity in the parentheses
is the correction factor for converting Eq. (7.5) into a form suitable for compressible
fluids in the range 0 ,,; N M. < 1.0.
FRICTION IN FLOW THROUGH
BEDS OF SOLIDS
In many technical processes, liquids or gases flow through beds of solid particles.
Important examples are filtration and the two-phase countercurrent flow of liquid
and gas through packed towers. In filtration, the bed of solids consists of small
particles that are removed from the liquid by a filter cloth or fine screen. In other
equipment, such as ion-exchange or catalytic reactors, a single fluid (liquid or gas)
flows through a bed of granular solids. Filtration is discussed in Chap. 30 and
packed towers in Chap. 22. The present treatment is restricted to the flow of a
single fluid phase through a column of stationary solid particles.
The resistance to the flow of a fluid through the voids in a bed of solids is
the resultant of the total drag of all the particles in the bed. Depending on the
Reynolds number, DpGo/l', laminar flow, turbulent flow, form drag, separation,
and wake formation occur. As in the drag of a single solid particle, there is no
sharp transition between laminar and turbulent flow like that occurring in flow
through conduits of constant cross section.
152 FLUID MECHANICS
Although progress has been reported in relating the total pressure drop
through a bed of solids to the drag of the individual particles,21 the most common
methods of correlation are based on estimates of the total drag of the fluid on the
solid boundaries of the tortuous channels through the bed particles. The actuaf
channels are irregular in shape, have a variable cross section and orientation,
and are highly interconnected. However, to calculate an equivalent channel
diameter, it is assumed that the bed has a set of uniform circular channels whose
total surface area and void volume match that of the bed. The total surface area
is the surface area per particle times the number of particles, but it is more
convenient to base the calculation on the volume fraction particles in the bed and
the surface-volume ratio for the particles. This ratio is 6/D p for a sphere, since
sp = nDJ, and vp = 1/6nD~. For other shapes or irregular particles, the equation
for surface-volume ratio includes a sphericity <1>" defined as the surface-volume
ratio for a sphere of diameter D p divided by the surface-volume ratio for the particle
whose nominal size is Dp. Thus
<1>, = (6/Dp)/(sp/vp)
or
~=_6_ (7.10)
vp <I>sDp
Values of the sphericity for several materials are given in Table 28.1. For granular
solids, <1>, ranges from 0.6 to 0.95.
The volume fraction particles in the bed is 1 - 8, where 8 is the porosity or
void fraction. If the particles are porous, the pores are generally too small to
permit any significant flow through them, so 8 is taken to be the external void
fraction of the bed and not the total porosity.
To determine the equivalent channel diameter D", the surface area for n
parallel channels of length L is set equal to the surface-volume ratio times the
particle volume, SoL (1 - 8), where So is the cross-sectional area of the bed:
6
nnD"L = SoL(1 - 8)-- (7.11)
fPsDp
The void volume in the bed is the same as the total volume of the n channels:
SoLe = imr:D~qL (7.12)
Combining Eqs. (7.11) and (7.12) gives an equation for D,,:
2 8
D" = J<I>,Dp-- (7.13)
1- 8
For the typical void fraction of 004, D" = 0.44<1>,D p , or the equivalent
diameter is roughly half the particle size.
The pressure drop depends on the average velocity in the channels V, which
is proportional to the superficial or empty-tower velocity Vo and inversely
FLOW PAST IMMERSED BODIES 153
proportional to the porosity:
- Vc,
v=-E
(7.14)
With the average velocity and channel size now expressed in terms of the
measurable parameters 170 , Dp, and E, th~ channel model can be used to predict
the form of the correlation for pressure drop. For flow at very low Reynolds
numbers, the pressure drop should vary with the first power of the velocity and
inversely with the square of the channel size, in accordance with the Hagen-
Poiseuille equation for laminar flow in straight tubes, Eq. (5.16). The equations
for V and D,. are used in Eq. (5.16), and a correction factor A, is added to account
for the fact that the channels are actually tortuous and not straight and parallel:
/!.p 3217Il
-=--= (7.15)
4 <l>2D2
~gce s p
or
/!.p 72A,Voll (1 - E)2
-= 3
(7.16)
L g/I>;D; 8
Several studies have shown that the form of Eq. (7.16) is correct, and
3
(7.17)
L gcClJ; D; 8
Equation (7.17) is called the Kozeny-Carman equation and is applicable for
flow through beds at particle Reynolds numbers up to about 1.0. There is no sharp
transition to turbulent flow at this Reynolds· number, but the frequent changes
in shape and direction of the channels in the bed lead to significant kinetic energy
losses at higher Reynolds numbers. The constant 150 corresponds to A, = 2.1,
which is a reasonable value for the tortuosity factor. For a given system, Eq. (7.17)
indicates that the flow is proportional to the pressure drop and inversely propor-
tional to the fluid viscosity. This statement is also known as Darcy's law, which
is often used to describe flow of liquids through porous media.
As the flow rate through a packed bed increases, the slope ofthe /!.p-versus-Vo
plot gradually increases, and at very high Reynolds numbers, /!.p varies with the
1.9 or 2.0 power of the superficial velocity. If the usual equation for turbulent flow
in pipes [Eq. (5.7)J is applied to the packed bed, with a correction factor ,1.2 to
account for the tortuosity, the predicted equation is
(7.18)
or
(7.19)
154 FLUID MECHANICS
An empirical correlation for pressure drop in packed beds at high Reynolds
number (NR,.p > 1000) is the Burke-Plummer equation:
IJ.p 1.75pV6 1 - 8
3
(7.20)
L g/I>sDp 8
Although this equation has the same form as Eq. (7.19), the constant 1.75 is
much higher than expected based on friction factors for pipe flow. If NR,.p is 104
and N R , based on Do. is therefore about 4000, the friction factor for smooth pipe
is f ~ 0.01 (Fig. 5.9). This means that the correction factor )'2 is 1.75/0.03 = 58,
which is much too large to explain by the tortuosity of the channels or roughness
of the particle surfaces. The main contribution to the pressure drop must be the
kinetic-energy losses caused by changes in channel cross section and flow direction.
As the fluid passes between particles, the channel becomes smaller and then larger,
and the maximum velocity is much greater than the average velocity. Since the
channel area changes rapidly, most of the kinetic energy of the fluid is lost as an
expansion loss [see Eq. (5.62)], and this loss is repeated at each layer of particles.
To emphasize the magnitude of the kinetic-energy losses, the pressure drop
from Eq. (7.20) can be divided by pV2/2g, to get the number of velocity heads.
Using the average velocity Vo/8 for V gives
IJ.p 1 - -8) -L-
2 x 1.75 ( - (7.21)
(p/2g')(Vo/8)2 8 r"P,Dp
For a typical void fraction of 0.4 and a bed of spheres, the pressure drop
corresponds to a loss of 5.25 velocity heads for each layer of particles
(2 x 1.75 x 0.6/0.4). This number is greater than 1.0, because the maximum local
velocity in the bed is probably two to three times the average velocity V.
An equation covering the entire range of flow rates can be obtained by
assuming that the viscous losses and the kinetic energy losses are additive. The
result is called the El'gun equation:
IJ.p 150Vol' (1 - 8)2 1.75pV6 1 - 8
-=--- + 3 (7.22)
3
L gc(j>;D! 8 gc(j>sD p 8
Ergun showed that Eq. (7.22) fitted data for spheres, cylinders, and crushed
solids over a wide range of flow rates.' He also varied the packing density for
some materials to verify the (1 - 8f/8 3 term for the viscous loss part of the
equation and the (1 - 8)/8 3 term for the kinetic-energy part. Note that a small
change in 8 has a very large effect on IJ.p, which makes it difficult to predict IJ.p
accurately and to reproduce experimental values after a bed is repacked.
The void fractions for spheres, cylinders, and granular packings generally
range from 0.3 to 0.6 depending on the ratio of particle size to tube size and the
method of packing. Some data by Leva and Grummer'2 for dumped packings are
given in Table 7.1. Vibrating the bed results in void fractions a few percent lower
than for dumped packing. Particles with a rough surface had void fractions a few
FLOW PAST IMMERSED BODIES 155
TABLE 7.1
Void fractions for dumped packings
DpID, £ for spheres £ for cylinders
0 0.34 0.34
0.1 0.38 0.35
0.2 0.42 0.39
0.3 0.46 0.45
0.4 0.50 0.53
0.5 0.55 0.60
percent larger than for smooth particles. With a distribution of particle sizes, the
void fractions are lower than for uniform particles.
For Raschig rings and Berl saddles, which have porosities of 0.60 to 0.75,
Eq. (7.22) predicts pressure drops lower than those found experimentally. For these
materials and other packings of high surface area and high porosity, the pressure
drop should be obtained using the packing factors in Table 22.1 or information
from the supplier.
MIXTURES OF PARTICLES. Equation (7.22) can be used for beds consisting of
a mixture of different particle sizes by using, in place of Dp, the surface-mean
diameter of the mixture 15,. This mean may be calculated from the number of
particles Ni in each size range or from the mass fraction in each size range Xi:
,
I N,D~i
D, = i=l
-,::--- (7.23)
I
i=l
N,D~i
(7.24)
Compressible fluids. When the density change of the fluid is small-and seldom
is the pressure drop large enough to change the density greatly-Eq. (7.22) may
be used by calculating the inlet and outlet values of Vc, and using the arithmetic
mean for 170 in the equation.
MOTION OF PARTICLES
THROUGH FLUIDS
Many processing steps, especially mechanical separations, involve the movement
of solid particles or liquid drops through a fluid. The fluid may be gas or liquid,
and it may be flowing or at rest. Examples are the elimination of dust and fumes
156 FLUID MECHANICS
from air or flue gas, the removal of solids from liquid wastes to allow discharge
into public drainage systems, and the recovery of acid mists from the waste gas
of an acid plant.
MECHANICS OF PARTICLE MOTION. The movement of a particle through a
fluid requires an external force acting on the particle. This force may come from
a density difference between the particle and the fluid or it may be the result of
electric or magnetic fields. In this section only gravitational or centrifugal forces,
which arise from density differences, will be considered.
Three forces act on a particle moving through a fluid: (1) the external force,
gravitational or centrifugal; (2) the buoyant force, which acts parallel with the
external force but in the opposite direction; and (3) the drag force, which appears
whenever there is relative motion between the particle and the fluid. The drag
force acts to oppose the motion and acts parallel with the direction of movement
but in the opposite direction.
In the general case, the direction of movement of the particle relative to the
fluid may not be parallel with the direction of the external and buoyant forces,
and the drag force then makes an angle with the other two. In this situation, which
is called two-dimensional motion, the drag must be resolved into components, which
complicates the treatment of particle mechanics. Equations are available for
two-dimensional motion, 1 0 but only the one-dimensional case, where the lines of
action of all forces acting on the particle are coIlinear, will be considered in this
book.
EQUATIONS FOR ONE-DIMENSIONAL MOTION OF PARTICLE THROUGH
FLUID. Consider a particle of mass m moving through a fluid under the action
of an external force Fe' Let the velocity of the particle relative to the fluid be u.
Let the buoyant force on the particle be Fb , and let the drag be FD' Then the
resultant force on the particle is Fe - Fb - F D, the acceleration of the particle is
du/dt, and by Eq. (1.35), since m is constant,
mdu
--=F,-Fb-FD (7.25)
g, dt
The external force can be expressed as a product of the mass and the acceleration
a, of the particle from this force, and
(7.26)
The buoyant force is, by Archimedes' principle, the product of the mass of the
fluid displaced by the particle and the acceleration from the external force. The
volume of the particle is m/pp, where pp is the density of the particle, and the
particle displaces this same volume of fluid. The mass of fluid displaced is (m/pp)p,
fLOW PAST IMMERSED BODIES 157
where P is the density of the fluid. The buoyant force is then
(7.27)
The drag force, is, from Eq. (7.1),
CDu~pAp
Fn =~-:=-" (7.28)
2g,
where Cn = dimensionless drag coefficient
Ap = projected area of particle measured in plane perpendicular to
direction of motion of particle
Uo = u
Substituting the forces from Eqs. (7.26) to (7.28) into Eq. (7.25) gives
(7.29)
Motion from gravitational force. If the external force is gravity, a, IS g, the
acceleration of gravity, and Eq. (7.29) becomes
dll Pp - P C nu2 pAp
-=g--- (7.30)
dt Pp 2m
Motion in a centrifugal field. A centrifugal force appears whenever the direction
of movement of a particle is changed. The acceleration from a centrifugal force
from circular motion is
(7.31)
where r = radius of path of particle
w = angular velocity, radjs
Substituting into Eq. (7.29) gives
du 2 Pp - P Cnu2 pAp
-=1"W --- (7.32)
dt Pp 2m
In this equation, u is the velocity of the particle relative to the fluid and is directed
outwardly along a radius.
TERMINAL VELOCITY. In gravitational settling, 9 is constant. Also, the drag
always increases with velocity. Equation (7.30) shows that the acceleration de-
creases with time and approaches zero. The particle quickly reaches a constant
velocity, which is the maximum attainable under the circumstances, and which is
158 FLUID MECHANICS
called the terminal velocity. The equation for the terminal velocity u, is found, for
gravitational settling, by taking du/dt = O. Then from Eq. (7.30),
2g(pp - p)m
(7.33)
ApppCDP
In motion from a centrifugal force, the velocity depends on the radius, and
the acceleration is not constant if the particle is in motion with respect to the
fluid. In many practical uses of centrifugal force, however, du/dt is small in
comparison with the other two terms in Eq. (7.32), and if du/dt is neglected, a
terminal velocity at any given radius can be defined by the equation
2r(p p - p)m
(7.34)
ApppCDP
DRAG COEFFICIENT. The quantitative use of Eqs. (7.29) to (7.34) requires that
numerical values be available for the drag coefficient CD' Figure 7.3, which shows
the drag coefficient as a function ofReynolds number, indicates such a relationship.
A portion of the curve of CD versus N Ro •p for spheres is reproduced in Fig. 7.6.
The drag curve shown in Fig. 7.6 applies, however, only under restricted condi-
tions. The particle must be a solid sphere, it must be far from other particles and
from the vessel walls so that the flow pattern around the particle is not distorted,
and it must be moving at its terminal velocity with respect to the fluid. The drag
100
!I..
~ i
~
r-Slokes'
ow
,
Newtons law
O. I
10 Id'
FIGURE 7.6
Drag coefficients for spheres.
FLOW PAST IMMERSED BODIES 159
coefficients for accelerating particles are appreciably greater than those shown in
Fig. 7.6, so a particle dropped in a still fluid takes longer to reach terminal velocity
than would be predicted using the steady-state values of CD 6 Particles injected
into a fast flowing stream also accelerate more slowly than expected, and the drag
coefficients in this case are therefore less than the normal values. However, for
most processes involving small particles or drops, the time for acceleration to the
terminal velocity is still quite small and is often ignored in analysis of the process·
Variations in particle shape can be accounted for by obtaining separate
curves of CD versus NR,.p for each shape, as shown in Fig. 7.3 for cylinders and
disks. As pointed out earlier, however, the curves for cylinders and disks in Fig.
7.3 apply only to a specified orientation of the particle. In the free motion of
nonspherical particles through a fluid the orientation is constantly changing. This
change consumes energy, increasing the effective drag on the particle, and CD is
greater than for the motion of the fluid past a stationary particle. As a result the
terminal velocity, especially with disks and other platelike particles, is less than
would be predicted from curves for a fixed orientation.
In the following treatment the particles will be assumed to be spherical, for
once the drag coefficients for free-particle motion are known, the same principles
apply to any shape.'·'o
When the particle is at sufficient distance from the boundaries of the
container and from other particles, so that its fall is not affected by them, the
process is called Jree settling. If the motion of the particle is impeded by other
particles, which will happen when the particles are near each other even though
they may not actually be colliding, the process is called hindered settling. The drag
coefficient in hindered settling is greater than in free settling.
If the particles are very small, Brownian movement appears. This is a random
motion imparted to the particle by collisions between the particle and the
molecules of the surrounding fluid. This effect becomes appreciable at a particle
size of about 2 to 3 !lm and predominates over the force of gravity with a particle
size of 0.1 !lm or less. The random movement of the particle tends to suppress the
effect of the force of gravity, so settling does not occur. Application of centrifugal
force reduces the relative effect of Brownian movement.
MOTION OF SPHERICAL PARTICLES. If the particles are spheres of diameter
Dp ,
In =
liInD3p p p (7.35)
and
A p -- 41 nD'p (7.36)
Substitution of In and Ap from Eqs. (7.35) and (7.36) into Eq. (7.33) gives the
equation for gravity settling of spheres:
(7.37)
160 FLUID MECHANICS
In the general case, the terminal velocity can be found by trial and error after
guessing NR,.p to get an initial estimate of CD' For the limiting cases of very low
or very high Reynolds numbers, equations can be used to get Ut directly.
At low Reynolds numbers, the drag coefficient varies inversely with NR,.p,
and the equations for CD' FD, and Ut are
24
CD = - - (7.38)
NRe,p
3"Jlut D p
F D = --'--'--" (7.39)
g,
gD~(pp - p)
Ut = (7.40)
18Jl
Equation (7.40) is known as Stokes' law, and it applies for particle Reynolds
numbers less than 1.0. At NR,.p = 1.0, CD = 26.5 instead of 24.0 from Eq. (7.38),
and since the terminal velocity depends on the square root of the drag coefficient,
Stokes' law is about 5 percent in error at this point. Equation (7.40) can be
modified to predict the velocity of a small sphere in a centrifugal field by
substituting I'W 2 for g.
For 1000 < NR,.p < 200,000, the drag coefficient is approximately constant,
and the equations are
CD = 0.44 (7.41)
FD = 0.055"D~u;- P (7.42)
g,
Ut = 1.75 JgDp(P; - p) (7.43)
Equation (7.43) is Newton's law and applies only for fairly large particles falling
in gases or low-viscosity fluids.
As shown by Eqs. (7.40) and (7.43), the terminal velocity Ut varies with D~
in the Stokes'-law range, whereas in the Newton's-law range it varies with D~·'.
CRITERION FOR SETTLING REGIME. To identify the range in which the motion
of the particle lies, the velocity term is eliminated from the Reynolds number by
substituting Ut from Eq. (7.40) to give, for the Stokes'-law range,
N _ Dputp _ D;gp(pp - p)
R,.p - Jl - 18Jl2 (7.44)
If Stokes' law is to apply, NR,.p must be less than 1.0. To provide a convenient
criterion K, let
_ [gP(Pp - p)J1 /3 (7.45)
K -Dp 2
Jl
FLOW PAST IMMERSED BODIES 161
Then, from Eq. (7.44), NR,.p = ftK'. Setting NR,.p equal to 1.0 and solving gives
K = 18'/' = 2.6. !fthe size of the particle is known, K can be calculated from Eq.
(7.45). If K so calculated is less than 2.6, Stokes' law applies.
Substitution for u, from Eq. (7.43) shows that for the Newton's-law range
NR,.p = 1.75 Kl.'. Setting this equal to 1000 and solving gives K = 68.9. Thus if
K is greater than 68.9 but less than 2360, Newton's law applies. When K is greater
than 2360, the drag coefficient may change abruptly with small changes in fluid
velocity. Under these conditions, as well as in the range between Stokes' law and
Newton's law (2.6 < K < 68.9), the terminal velocity is calculated from Eq. (7.37)
using a value of CD found by trial from Fig. 7.6.
Example 7.1. (a) Estimate the terminal velocity for 80-to-100-mesh particles of
limestone (pp = 2800 kg/m3) falling in water at 30'C. (b) How much higher would
the velocity be in a centrifugal separator where the acceleration is SOg?
Solution
(a) From Appendix 20,
Dp for 100 mesh = 0.147 mm
Dp for 80 mesh = 0.175 mm
Average diameter Dp = 0.161 mm
From Appendix 14, I' = 0.801 cP; p = 62.16Ib/ft 3 or 995.7 kg/m3. To find which
settling law applies, calculate criterion K [Eq. (7.45)]:
K = 0.161 x 10_3[9.80665 x 995.7(2800 - 995.7)J'/3
(0.801 x 10 3)'
=4.86
This is slightly above the Stokes'-law range. Assume NRe,p = 4.4; then from Fig. 7.6,
CD = 7.9, and from Eq. (7.37)
_ [4 x 9.80665(2800 - 995.7)0.161 x 1O- 3
u,-
J' 12
3 x 7.9 x 995.7
= 0.0220 m/s
Check:
0.161 X 10- 3 x 0.0220 x 995.7
N Re • p -----,-..,.,---co----- = 4.40
0.801 x 10 3
(b) Using a, = 50g in place of 9 in Eq. (7.45). since only the acceleration changes,
K = 4.86 X 50 1 / 3 = 17.90. This is still in the intermediate settling range. Estimate
NRe,p = 80; from Fig. 7.6, CD = 1.2 and
u, = [4 x 9.80665 x 50(2800 - 995.7)0.161 x 1O- 3 J' 12
3 x 1.2 x 995.7
= 0.40 m/s
162 FLUID MECHANICS
Check:
0.161 X 10- 3 x 0040 x 995.7
N Rc • p = = 79.8
0.801 x 10- 3
For irregular particles at this Reynolds number, CD is about 20 percent greater
than that for spheres, and CD = 1.20 x 1.2 = 1.44. The estimated value of Ut is
then 0.40 x (1.2/1.44)1/2 ~ 0.37 m/so
HINDERED SEITLING. In hindered settling, the velocity gradients around each
particle are affected by the presence of nearby particles, so the normal drag
correlations do not apply. Also, the particles in settling displace liquid, which flows
upward and makes the particle velocity relative to the fluid greater than the
absolute settling velocity. For a uniform suspension, the settling velocity u, can
be estimated from the terminal velocity for an isolated particle using the empirical
equation of Maude and Whitmore l5 :
(7.46)
Exponent n changes from about 4.6 in the Stokes' -law range to about 2.5 in
the Newton's-law region, as shown in Fig. 7.7. For very small particles, the
calculated ratio u,lu, is 0.62 for e = 0.9 and 0.095 for e = 0.6. With large particles
the corresponding ratios are u,iu, = 0.77 and 0.28; the hindered settling effect is
not as pronounced because the boundary-layer thickness is a smaller fraction of
the particle size. In any case, Eq. (7.46) should be used with caution, since the
settling velocity also depends on particle shape and size distribution. Experimental
data are needed for accurate design of a settling chamber.
If particles of a given size are falling through a suspension of much finer
solids, the terminal velocity of the larger particles should be calculated using the
density and viscosity of the fine suspension. Equation (7.46) may then be used to
estimate the settling velocity with e taken as the volume fraction of the fine
suspension, not the total void fraction. Suspensions of very fine sand in water are
--
5
4
~
--
n ......
3
i""-r-
2
0.1 10 10' 10'
FIGURE 7.7
Plot of exponent 11 versus NRc,p for Eq. (7.46).
FLOW PAST IMMERSED BODIES 163
used in separating coal from heavy minerals, and the density of the suspension is
adjusted to a value slightly greater than that of coal to make the coal particles
rise to the surface, while the mineral particles sink to the bottom.
The viscosity of a suspension is also affected by the presence of the dispersed
phase. For suspensions of free-flowing solid particles, the effective viscosity 1', may
be estimated from the relation!8
1', 1 + 0.5(1 - 8)
4
(7.47)
I' 8
Equation (7.47) applies only when 8 > 0.6 and is most accurate when 8 > 0.9.
Example 7.2. Particles of sphalerite (specific gravity 4.00) are settling under the force
of gravity in carbon tetrachloride (CCI 4) at 20'C (specific gravity 1.594). The diameter
of the sphalerite particles is 0.004 in, (0.10 mm), The volume fraction of sphalerite in
CCJ 4 is 0.20. What is the settling velocity of the sphalerite?
Solutioll
The specific gravity difference between particles and liquid is 4.00 - 1.594 = 2.406.
The density difference Pp - P is 62.37 x 2.406 ~ 150.06 Ib/ft'. The density orthe CCI4
is 62.37 x 1.594 ~ 99.42 Ib/ft'. The viscosity of CCI 4 at 20'C, from Appendix 9, is
1.03 cP. Criterion K, from Eq. (7.45), is
0.004 [32.174 x 99.42 x 150.06J I 13
K~-- ~3.34
12 (1.03 x 6.72 x 10 4)'
The settling is almost in the Stokes'-law range. The terminal velocity ofa free-settling
sphalerite particle would be, from Eq. (7.40),
32.174 x (0.004/12)' x 150.06
Ut =
18 x 1.03 x 6.72 x 10- 4
~ 0.043 ft/s
The terminal velocity in hindered settling is found from Eq. (7.46). The particle
Reynolds number is
0.004 x 0.043 x 99.42
NRC,p = = 2.06
12 x 1.03 x 6.72 x 10 4
From Fig. 7.7, 11 ~ 4.1. From Eq. (7.46), u, ~ 0.043 X 0.8 4 •1 ~ 0.017 ftjs (5.2 mm/s).
SETTLING AND RISE OF BUBBLES AND DROPS. Unlike solid particles, dis-
persed drops of liquid or bubbles of gas may change shape as they move through
a continuous phase. Form drag tends to flatten the drops, but the surface tension
opposes this force. Because of their large surface energy per unit volume, drops
or bubbles smaller than about 0.5 mm are nearly spherical and have about the
same drag coefficients and terminal velocities as solid spheres. The coefficient is
not exactly the same because skin friction tends to set up circulation patterns
inside a falling drop, and movement of the gas-liquid interface makes the total
164 FLUID MECHANICS
drag somewhat less than for a rigid sphere. However, impurities that concentrate
at the interface inhibit motion of the interface, and the lower drag coefficients are
usually noticed only in very pure systems.
Drops from one to a few millimeters in diameter, typical of falling raindrops,
are somewhat flattened in the direction of flow and fall more slowly than a sphere
of the same volume. (The familiar teardrop shape of the cartoonist is entirely
imaginary.) With further increase in size, the drops become flattened ellipsoids or
may oscillate from oblate to prolate form. The drag coefficient increases with
Reynolds number, and the terminal velocity may go through a maximum with
increasing drop size. This is shown in Fig. 7.8 for air bubbles moving relative to
turbulently flowing water. The relative velocities are said to be slightly higher than
those for quiescent liquid. Various published results, however, for single air bubbles
in water do not agree well with one another, probably because of differences in
water purity, wall effects, and measurement techniques. A stream of bubbles formed
in rapid succession at a central nozzle rises more rapidly than a single bubble,
since the bubbles cause an upward flow of liquid in the central region. A similar
effect is found for bubbles formed at a vertical electrode in an electrolysis cell.
Bubbles in a swarm distributed uniformly over the cross section of the apparatus
generally rise more slowly than single bubbles because of the hindered settling
32
28
/
24
/ '---- Air in water
i j
" 20
>-'
t-
U
gw 16
Stokes'
r
/
law
> I
w
!!!
0: 12
~! I
8
/1 Rigid sphere
r(calculated from Fig. 7-6)
4
t
if
II 4 5 6 8 10
2 3
BUBBLE DIAMETER, mm
FIGURE 7.S
Rise velocity of air bubbles in water at 70°F. [By permission, data takell!ram J. L. L. Baker alld B. T.
Chao, A/ChE J .• I1:268 (1965).J
FLOW PAST IMMERSED BODIES 165
effect. In some cases higher average velocities have been found for swarms of
bubbles in a small column, but this may have been due to occasional large bubbles
or slugs of gas rising up the center. 5 Further work on bubble and drop phenomena
is reviewed by Tavlarides et al. 23
FLUIDIZATION
When a liquid or a gas is passed at very low velocity up through a bed of solid
particles, the particles do not move, and the pressure drop is given by the Ergun
equation (7.22). If the fluid velocity is steadily increased, the pressure drop and
the drag on individual particles increase, and eventually the particles start to move
and become suspended in the fluid. The terms "fluidization" and "fluidized bed"
are used to describe the condition of fully suspended particles, since the suspension
behaves like a dense fluid. If the bed is tilted, the top surface remains horizontal
and large objects will either float or sink in the bed depending on their density
relative to the suspension. The fluidized solids can be drained from the bed through
pipes and valves just like a liquid, and this fluidity is one' of the main advantages
in the use of fluidization for handling solids.
CONDITIONS FOR FLUIDIZATION. Consider a vertical tube partly filled with
a fine granular material such as catalytic cracking catalyst as shown schematically
in Fig. 7.9. The tube is open at the top and has a porous plate at the bottom to
support the bed of catalyst and to distribute the flow uniformly over the entire
cross section. Air is admitted below the distributor plate at a low flow rate and
passes upward through the bed without causing any particle motion. If the
particles are quite small, flow in the channels between the particles will be laminar
and the pressure drop across the bed will be proportional to the superficial velocity
I- Fixed bed -t- Fluidized bed
T ;w
I
~I----:"'B!:"""""
::(1----i: A i
1.6nm"h isis I
r-t-__ f1-,P~ _ _ _ _ _ ~~!..b,!.d
Air
SUPERFICIAL VELOCITY, Vo
FIGURE 7.9
Pressure drop and bed height vs. superficial velocity for a bed of solids.
166 FLUID MECHANICS
170 [Eq. (7.17)]. As the velocity is gradually increased, the pressure drop increases,
but the particles do not move and the bed height remains the same. At a certain
velocity, the pressure drop across the bed counterbalances the force of gravity on
the particles or the weight of the bed, and any further increase in velocity causes
the particles to move. This is point A on the graph. Sometimes the bed expands
slightly with the grains still in contact, since just a slight increase in e can offset
an increase of several percent in Vc, and keep I1p constant. With a further increase
in velocity, the particles become separated enough to move about in the bed, and
true fluidization begins (point B).
Once the bed is fluidized, the pressure drop across the bed stays constant,
but the bed height continues to increase with increasing flow. The bed can be
operated at quite high velocities with very little or no loss of solids, since the
superficial velocity needed to support a bed of particles is much less than the
terminal velocity for individual particles, as will be shown later.
If the flow rate to the fluidized bed is gradually reduced, the pressure drop
remains constant, and the bed height decreases, following the line BC which was
observed for increasing velocities. However, the final bed height may be greater
than the initial value for the fixed bed, since solids dumped in a tube tend to pack
more tightly than solids slowly settling from a fluidized state. The pressure drop
at low velocities is then less than in the original fixed bed. On starting up again,
the pressure drop offsets the weight of the bed at point B, and this point, rather
than point A, should be considered to give the minimum fluidization velocity,
VOM • To measure VOM ' the bed should be fluidized vigorously, allowed to settle
with the gas turned off, and the flow rate increased gradually until the bed
starts to expand. More reproducible values of VOM can sometimes be obtained
from the intersection of the graphs of pressure drop in the fixed bed and the
fluidized bed.
MINIMUM FLUIDIZATION VELOCITY. An equation for the minimum fluidiza-
tion velocity can be obtained by setting the pressure drop across the bed equal
to the weight of the bed per unit area of cross section, allowing for the buoyant
force of the displaced fluid:
g
I1p = -(1 - e)(p - p)L (7.48)
g, P
At incipient fluidization, e is the minimum porosity eM. (If the particles themselves
are porous, e is the external void fraction of the bed.) Thus
I1p g
- = - (1 - eM)(pp - p) (7.49)
L g,
The Ergun equation for pressure drop in packed beds [Eq. (7.22)J can be
rearranged to
(7.50)
FLOW PAST IMMERSED BODIES 167
Applying Eq. (7.50) to the point of incipient fluidization gives a quadratic equation
for the minimum fluidization velocity VOM :
150"Vo,,(I-eM) l.75pV6M 1
(7.51)
<fJ;D~ e~f + <fJ,Dp df =g(pp-p)
For very small particles, only the laminar-flow term of the Ergun equation
is significant. With N Ro • p < 1, the equation for minimum fluidization velocity
becomes
v. '" g(pp - p) e1 <fJ2D2 (7.52)
OM 150fJ.. 1 - eM ' p
Many empirical equations state that VOM varies with somewhat less than the
2.0 power of the particle size and not quite inversely with the viscosity. Slight
deviations from the expected exponents occur because there is some error in
neglecting the second term of the Ergun equation and because the void fraction
eM may change with particle size. For roughly spherical particles, eM is generally
between 0.40 and 0.45, increasing slightly with decreasing particle diameter. For
irregular solids, the uncertainty in eM is probably the major error in predicting
VOM from Eq. (7.51) or (7.52).
Minimum fluidization velocities for particles in air calculated from Eq. (7.51)
are shown in Fig. 7.10. Note that the dependence on D; holds up to particles
about 300 I'm in size; in many applications of fluidization, the particles are in the
range 30 to 300 "m. However, fluidization is also used for particles larger than
1 mm, as in the fluidized-bed combustion of coal. In the limit of very large sizes,
the laminar-flow term becomes negligible, and VOM varies with the square root
of the particle size. The equation for N Ro • p > 10' is
/
V, _ [<fJ,Dp9(Pp - P)dfJ' 2
OM - l.75p (7.53)
The terminal velocity for individual particles falling in still air is also shown
in Fig. 7.10. For low Reynolds number, u, and VOM both vary with D;, (pp - p)
and 1/", so the ratio U,lVOM depends mainly on the void fraction at minimum
fluidization. From Eqs. (7.40) and (7.52),
u, gD;(pp - p) 150" 1 - eM
VOM = 18" g(pp - p)<fJ;D; e1
8.33(1 - eM)
(7.54)
For spheres, with eM '" 0.45, the terminal velocity is 50 times the minimum
fluidization velocity, so a bed that fluidizes at 10 mm/s could probably be operated
with velocities up to 400 mm/s with few particles carried out with the exit gas.
With a wide distribution of particle sizes there would be more carryover or
entrainment of the fines than of average size particles, but most of the fines can
168 FLUID MECHANICS
100
/
1/ /
/ j 1/ /
i jUt /
11 / I 1/
0
/
I, 11 lh1J 110.5 !:lp, g/ cm 3
1 1 1 I1 1
1 11 11
li 1 1 1 I1
/ 1
1. 0
/
1 1// I1
I /
1 1 11 1
/ 11 I1 11 1
1 1/
11 11 I111
O. 1
10
11 /
20
I1 1
30 40 60 80100 200 300 600 1,000 2,000 5,000
Dp,/lm
FIGURE 7.10
Minimum fluidization velocity and terminal velocity with air at 20°C and 1 atm (eM = 0.50, (1)3 =
0.8, lip ~ pp - p).
be recovered by filters or cyclone separators and returned to the bed. Some
fluidized beds are operated at velocities of 100 times YaM' with high entrainment
but nearly complete recovery of the entrained solids.
For nonspherical particles <1>, is less than 1, and Eq. (7.54) might seem to
indicate a wider range of fluidization without entrainment. However, the value of
BM is generally greater for irregular particles than for spheres, and for <1>, = 0.8
and BM = 0.5, the ratio u'/YaM is 52, about the same as that estimated for spheres.
For large particles, the terminal velocity is given by Newton's law [Eq.
(7.43)], and this can be compared with YaM from Eq. (7.53). For spheres, with
N."p greater than 10"
-'!"t = 1.75 [gDp(Pp - p)J1 2[
/
l.75p 3J112
V aM P gD/pp-p)BM
2.32
(7.55)
FLOW PAST IMMERSED BODIES 169
For BM = 0.45, uJVOM = 7.7, which is a much lower ratio than for fine particles.
This may be a slight disadvantage to the use of coarse particles in a fluidized bed,
but the optimum particle size generally depends on other factors such as grinding
cost, heat- and mass-transfer rates, and desired gas velocity.
TYPES OF FLUIDIZATION. The equations derived for minimum fluidization
velocity apply to liquids as well as to gases, but beyond VOM the appearance'
of beds fluidized with liquids or gases is often quite different. When fluidizing sand
with water, the particles move farther apart and their motion becomes more
vigorous as the velocity is increased, but the average bed density at a given velocity
is the same in all sections of the bed. This is called "particulate fluidization" and
is characterized by a large but uniform expansion of the bed at high velocities.
Beds of solids fluidized with air usually exhibit what is called aggregative or
bubbling fluidization. At superficial velocities much greater than VDM most of the
gas passes through the bed as bubbles or voids which are almost free of solids,
and only a small fraction of the gas flows in the channels between the particles.
The particles move erratically and are supported by the fluid, but in the space
between bubbles, the void fraction is about the same as at incipient fluidization.
The non uniform nature of the bed was at first attributed to aggregation of the
particles, and the term aggregative fluidization was applied; but there is no
evidence that the particles stick together, and the term bubbling fluidization is a
better description of the phenomenon. The bubbles that form behave much like
air bubbles in water or bubbles of vapor in a boiling liquid, and the term "boiling
bed" is sometimes applied to this type of fluidization. Studies that account for the
rates of heat or mass transfer or chemical reaction in a bubbling bed often refer
to the "two-phase theory of fluidization," in which the bubbles are one phase and
the dense bed of suspended particles is the second phase.
The behavior of a bubbling fluidized bed depends very strongly on the
number and size of the gas bubbles, which are often hard to predict. The average
bubble size depends on the nature and size distribution of the particles, the type
of distributor plate, the superficial velocity, and the depth of the bed. Bubbles tend
to coalesce and grow as they rise through the fluidized bed, and the maximum
stable bubble size may be several inches to a few feet in diameter. If a small
diameter column is used with a deep bed of solids, the bubbles may grow until
they fill the entire cross section. Successive bubbles then travel up the column
separated by slugs of solids. This is called "slugging" and is usually undesirable
because of pressure fluctuations in the bed, increased entrainment, and difficulties
in scaling up to larger units.
The generalization that liquids give particulate fluidization of solids while
gases give bubbling fluidization is not completely valid. The density difference is
an important parameter, and very heavy solids may exhibit bubbling fluidization
with water, while gases at high pressures may give particulate fluidization of fine
solids. Also, fine solids of moderate density, such as cracking catalysts, may exhibit
particulate fluidization for a limited range of velocities and then bubbling fluidiza-
tion at high velocities.
J/U FLUID MECHANICS
EXPANSION OF FLUIDIZED BEDS. With both types of fluidization the bed
expands as the superficial velocity increases, and since the total pressure drop
remains constant, the pressure drop per unit length decreases as e increases.
Rearranging Eq. (7.48) gives
I1p g
- = - (1 - e)(p - p) (7.56)
L gc P
Particulate fluidization. For particulate fluidization the expansion is uniform, and
the Ergun equation, which applies to the fixed bed, might be expected to hold
approximately for the slightly expanded bed. Assuming the flow between the
particles is laminar, using the first term ofEq. (7.50) leads to the following equation
for the expanded beds:
(7.57)
I - e g(pp - p)<I>;D~
Note that this equation is similar to Eq. (7.52) for the minImum fluidization
velocity, but now v.,
is the independent variable and 8 the dependent variable.
Equation (7.57) predicts that 8 3/(1 - 8) is proportional to Vo for values greater
than VOM' The expanded bed height may be obtained from 8 and the values of L
0.30
0.28
0 .26
V
L~ rs 0.24
0.22
~ r 0.20
.-----6 0.18
Vc> ~
'" 0.16 E
[9:JY /
od 0.14 -i
,"\""(\e",...'/
o. 6 0 0.12
",'"
,3 0.10
o. 4 1=€ l../ 0.08
Ix 0.06
",/ b
o. 2 '0' 0.04
In-d-D 0.02
/
o
o '"
0
2 4 6 8 10 12 14 16 18
FIGURE 7.11
Bed expansion in particulate fluidization. [By permissioll,data takenfrom R. H. Wilhelm and M. Kwallk,
Chel11. ElIg. Prog .. 44:201 (1948).]
FLOW PAST IMMERSED BODIES 171
and s at incipient fluidization, using the equation
1- EM
L=LM -- (7.58)
I-s
Data for the fluidization of small glass beads (510 f1II1) in water24 are shown
in Fig. 7.11. The first data point is for SM = 0.384 and VOM = 1.67 mm/s, and the
theoretical line is a straight line from the origin through this point. The actual
expansion is slightly less than predicted over much of the range, perhaps because
of local variations in void fraction that decrease the hydraulic resistance. Note
that the bed height increased nearly linearly with velocity, and the bed height has
about doubled at Vo = 10VOM .
For particulate fluidization of large particles, in water, the expansion of the
bed is expected to be greater than that corresponding to Eq. (7.57), since the
pressure drop depends partly on the kinetic energy of the fluid, and a greater
increase in 6 is needed to offset a given percentage increase in VD' The expansion
data can be correlated by the empirical equation proposed by Lewis, Gilliland,
and Bauer '3 :
(7.59)
Data for two sizes of glass beads 24 are plotted in Fig. 7.12, and although
the data do not fit Eq. (7.59) exactly, a straight line is aciequate for engineering
estimates of the bed expansion. Data from many investigations show that the
slopes of such plots vary from about 0.22 in the laminar region to 0.4 at high
Reynolds numbers. These slopes equal 1/111. A correlation for In given by Leva 11
is shown in Fig. 7.13. To predict the bed expansion, In is estimated using the
Reynolds number at the minimum fluidization velocity, and Eq. (7.59) is applied
directly or in ratio form. An alternate method is to determine VOM and u, and
draw a straight line on a plot such as Fig.7.12.
1. 0 op
1
0•51 L
l~ .,P
n° !S""C ru po
,.... -\Op = 5 mm
v
o. 11.0 10 10
, 10'
ito . mm/s
FIGURE 7.12
Variation of porosity with fluid velocity in a fluidized bed. [By permission, data taken from R. H.
Willlelm and M. Kwauk, Chem. Eng. Prog., 44:201 (1948).]
172 FLUID MECHANICS
m
4
--- .....
--- r--
---
3
2
0.1 10
, 10 3
FIGURE 7.13
Exponent In in correlation for bed expansion [Eq. (7.59)]. (By permissioll,jrom M. Leva, Fluidization,
p. 89. Copyright, © 1959. McGraw-HiII Book CompaIlY.)
Example 7.3. A bed of ion-exchange beads 8 ft deep is to be back washed with water
to remove dirt. The particles have a density 1.24 gjcm 3 and an average size of 1.1 mm.
'What is the minimum fluidization velocity using water at 20°C, and what velocity
is required to expand the bed by 25 percent? The beads are assumed to be spherical
(<I>, = 1) and &M is taken as 0.40.
Solutio/,
The quantities needed are
!l = 0.01 P
/;p = 0.24 g/cm 3
From Eq. (7.51),
150(0.01)VoM 0.6 1.75(1.0)(170 ,,)' 1
+ = 980(0.24)
(0.11)' 0.4' 0.11 0.4'
1162170 " + 248.6V~" = 235.2
From the quadratic formula, VOM = 0.194 cm/s or 1.94 mm/so At VOM '
_ 0.11(0.194)(1.24)
NR - 2.65
c,p 0.01
From Fig. 7.13, m", 3.9. From Eq. (7.59)
&)3.9 170
(GM =170M
For 25 percent expansion, L = 1.25L" or 1 - &= (1 - &,,)/1.25 = 0.48. From this,
&= 0.52, and 170 = 1.94(0.52/0.40),·9 = 5.40 mm/so
Bubbling fluidization. For bubbling fluidization, the expansion of the bed comes
mainly from the space occupied by gas bubbles, since the dense phase does not
expand significantly with increasing total flow. In the following derivation, the gas
FLOW PAST IMMERSED BODIES 173
flow through the dense phase is assumed to be 170 " times the fraction of the bed
occupied by the dense phase, and the rest of the gas flow is to be carried by the
bubbles. Thus,
170 = fbUb + (1 - !.)Vo" (7.60)
where fb = fraction of bed occupied by bubbles
ub = average bubble velocity
Since all of the solid is in the dense phase, the height of the expanded bed times
the fraction dense phase must equal the bed height at incipient fluidization:
L" = L(1 - fb) (7.61)
Combining Eqs. (7.60) and (7.61) gives
L
(7.62)
When Ub is much greater than 170 , the bed expands only slightly, even though Vo
may be several times 17oM .
An empirical equation for bubble velocity in a fluidized bed is 22
Ub "" 0.7 .Jiii. (7.63)
There is only a small effect of particle size or shape on the coefficient in Eq. (7.63),
and although large bubbles are mushroom-shaped rather than spherical, the
equation holds quite well with Db taken as the equivalent spherical diameter. For
Db = 100 mm, Ub is 700 mm/s, and if l70M = 10 mm/s and 170 = 100 mm/s, L/LM
would be 1.15. Doubling the velocity would increase L/L" to 1.38 if the bubble
size were constant, but the bubble size generally increases with gas velocity because
of coalescence, and the bed height often increases nearly linearly with velocity.
The expansion of the bed is usually in the range of 20 to 50 percent, even at
velocities up to 50 times 17oM , in contrast to the large expansions found in
particulate fluidization.
Some fine powders fluidized with a gas exhibit particulate fluidization over
a limited range of velocities near the minimum fluidization point. With increasing
velocity the bed expands uniformly until bubbles start to form, gradually collapses
to a minimum height as the velocity is increased past the bubble point, and then
expands again as bubble flow becomes predominant. Silica-alumina cracking
catalyst shows this anomalous behavior, and bed-expansion data for a commercial
catalyst are contrasted with those for a fine sand in Fig. 7.14. The region of
particulate fluidization is fonnd only with quite small or low-density particles. A
classification of solids based on these properties is given by Geldart. 2
APPLICATIONS OF FLUIDIZATION. Extensive use of fluidization began in the
petroleum industry with the development of fluid-bed catalytic cracking. Although
the industry now generally uses riser or transport-line reactors for catalytic
cracking, rather than fluid beds, the catalyst regeneration is still carried out in
fluid-bed reactors, which are as large as 30 ft in diameter. Fluidization is used in
11"1 FLUID MECHANICS
1.6,---,---,----,------,-----,------,
56-pm Catalyst
1.4
•
'...." 105-pm Sand
1.2
1.00 100
60 80 120
Vo. mm/s
FIGURE 7.14
Expansion of fluidized beds of sand and cracking catalyst.
other catalytic processes, such as the synthesis of acrylonitrile, and for carrying
out solid-gas reactions. There is much interest in the fluidized-bed combustion of
coal as a means of reducing boiler cost and decreasing the emission of pollutants.
Fluidized beds are also used for roasting ores, drying fine solids, and adsorption
of gases.
The chief advantages of fluidization are that the solid is vigorously agitated
by the fluid passing through the bed, and the mixing of the solids ensures that
there are practically nO temperature gradients in the bed even with quite exother-
mic or endothermic reactions. The violent motion of the solids also gives high
heat-transfer rates to the wall or to cooling tubes immersed in the bed. Because
of the fluidity of the solids it is easy to pass solids from one vessel to another.
The main disadvantage of gas-solid fluidization is the uneven contacting of
gas and solid. Most of the gas passes through the bed as bubbles and directly
contacts only a small amount of solid in a thin shell, known as the bubble cloud,
around the bubble. A small fraction of the gas passes through the dense phase,
which contains nearly all of the solid. There is some interchange of gas between
the bubbles and the dense phase by diffusion and by turbulent processes such as
bubble splitting and coalescence, but the overall conversion of a gaseous reactant is
generally much less than with uniform contacting at the same temperature, as in
an ideal plug-flow reactor. The extent of interchange between bubbles and the
dense bed, as well as the rate of axial mixing, may change with vessel diameter
because of changes in the bubble size, so scaleup of fluidized reactors is often
uncertain. Other disadvantages, which are more easily dealt with by proper design,
are erosion of vessel internals and attrition of the solids. Most fluid beds have
internal or external cyclones to recover fines, but filters or scrubbers are often
needed also.
CONTINUOUS FLUIDIZATION; SLURRY AND PNEUMATIC TRANSPORT.
When the fluid velocity through a bed of solids becomes large enough, all the
particles are entrained in the fluid and are carried along with it, to give continuous
FLOW PAS1'~MERSED BODIES 175
fluidization. Its principal application is in transporting solids from point to point
in a processing plant, although some gas-solid reactors operate in this fashion.
Hydraulic or slurry transport. Particles smaller than about 50 J1.m in diameter settle
very slowly and are readily suspended in a moving liquid. Larger particles are
harder to suspend, and when the diameter is 0.25 mm or greater, a fairly large
liquid velocity is needed to keep the particles from moving at all, especially in
horizontal pipes. The critical velocity v,:, below which particles will settle out, is
typically between 1 and 5 m/s, depending on the density difference between solids
and liquid, the particle diameter, the slurry concentration, and the size of the pipe.
Critical velocities are larger in big pipe than in small pipe. A semitheoretical
general equation for predicting v,: has been proposed by Oroskar and Turian. 17
The pressure drop in slurries of non settling particles may be found from the
equations for a homogeneous liquid, with appropriate allowance for the increased
density and apparent viscosity. For "settling slurries" there is no single satisfactory
correlation; the pressure drop in a horizontal pipe is greater than that in a
single-phase fluid of the same density and viscosity as the slurry, especially near
the critical velocity, but approaches that in the single-phase liquid as the velocity
increases. When the velocity is 3v,: or greater, the pressure drop in the slurry
and that in the equivalent single-phase liquid are equal. The velocity in a long
slurry pipeline is typically 1.5 to 2 times v,:.
Pneumatic conveying. The suspending fluid in a pneumatic conveyor is a gas,
usually air, flowing at velocities between 15 and 30 m/s (50 and 100 ft/s) in pipes
ranging from 50 to 400 mm (2 to 16 in.) in diameter. There are two principal types
of systems: negative-pressure (vacuum) systems, useful for transferring solids from
multiple intake points (railroad cars, ships' holds, etc.) to a single delivery point,
and positive-pressure systems, which are best with a single input station and one
or more points of delivery. A typical vacuum system is shown in Fig. 7.15. In
AIr oul
t Exhausler
(bJ
Oust
colleclor
7b bin
(aJ
FIGURE 7.15
Pneumatic conveying system: (a) typical multiple-inlet system; (b) nozzle detail.
11() FLUID MECHANICS
vacuum systems the mass ratio of solids to gas is usually less than 5; for such
suspensions the critical velocity, in meters per second, may be estimated from the
empirical relation 190
v= 132.4 Pp DO•• O (7.64)
, Pp + 998 p
where Dp is the diameter of the largest particle to be conveyed. In Eq. (7.64),
meter-kilogram-second units must be used.
Most pneumatic conveyors operate under positive pressure, with a blower
or compressor feeding air (or occasionally nitrogen) at 1 to 5 atm gauge pressure
into the system. The ratio of solids to gas is usually higher than in vacuum systems.
Sometimes the gas is recycled to the blower or compressor inlet in a closed system
to save a valuable gas or prevent loss of dust to the atmosphere.
The pressure drop required to pass air alone through a pneumatic conveying
system is small, but it is greatly augmented when additional energy must be
supplied to lift and move the solids. This additional energy requirement, by a
mechanical-energy balance based on Eq. (4.32), is
2
E, = r Pb - p, + V2,b - V" + !!... (Zb - Z,) ] (7.65)
[ Ps 2gc; gc;
where r = mass ratio of solids to gas
v'a = velocity of solids at inlet
V,b = velocity of solids at outlet
p, = density of solid
The energy E, is supplied by the air. It is transmitted to the solid particles
through the action of drag forces between the air and the solid. The energy E, is
a work term, and it must appear in the mechanical-energy balance for the air.
Assuming the pressure drop is a small fraction of the absolute pressure, the
air can be considered to be an incompressible fluid of constant density p, the
average density of the air between the inlet and outlet. When the change in velocity
head is neglected, when the kinetic-energy factor is assumed to be unity, and when
E, is allowed for, the Bernoulli equation (4.32) becomes, for a unit mass of air,
Pb - p, g
-_-+-(Zb- Z ,) = -E,-h[ (7.66)
p g,
where h[ is the total friction in the stream. Eliminating E, from Eqs. (7.65) and
(7.66) and solving for p, - Pb gives
(g/g,)(1 + r)(Zb - Z,) + r(V;b - V;,l/2g, + h[
(7.67)
P,-Pb= l/p+r/p,
Methods of calculating the friction loss h[ are discussed in the literature. ' •
The problem of simultaneous flow of two phases is complex, and the friction loss
can rarely be calculated with high accuracy. In many conveying systems, however,
the friction loss is small compared with the losses resulting from elevation and
FLOW PAST IMMERSED BODIES 177
acceleration of the solids, and the total pressure drop p, - Pb as given by Eq. (7.67)
is usually fairly accurate despite the uncertainty in hf' Data and nomographs for
the preliminary design of pneumatic conveyors are given in Ref. 19b; practical
design considerations are discussed by Mills.!6
SYMBOLS
A Area m 2 or fe; Ap, projected area of particle
a, Acceleration of particle from external force, m/s2 or ft/s 2
CD Drag coefficient, 2F Dgolu'f,pAp, dimensionless
D Diameter, m or ft; D,q, equivalent diameter of channels in packed bed;
Dp, diameter of spherical particle; also nominal size or characteristic
length of a particle; Dpi , average particle diameter in fraction i; D"
mean effective diameter for mixture of particles
E, Energy supplied to solids by air in a pneumatic conveyor, J/kg or
ft-Ibfflb
F Force, N or Ibf ; F D, total drag force; F b , buoyant force; F" external
force
f Fanning friction factor, dimensionless: fp, friction factor for packed bed
fb Volume fraction of fluidized bed occupied by gas bubbles
Go Mass velocity of fluid approaching particle, kg/m2_s or Ib/ft 2 -s; also
superficial mass velocity in packed bed
g Gravitational acceleration, m/s2 or ft/s2
g, Newton's-law proportionality factor, 32.174 ft-Ib/lb rs2
hf Total friction loss in fluid, J/kg or ft-Ibf/lb
K Criterion for settling, defined by Eq. (7.45), dimensionless
L Length of cylindrical particle, m or ft; also length of channels in packed
bed; also total height of packed or fluidized bed; L M , bed height at
incipient fluidization
m Mass, kg or Ib; also exponent in Eq. (7.59)
Ni Number of particles in each size range
N Ma Mach number, dimensionless; NMa,a, NMa,b' at stations a and b; NMa,o,
of approaching fluid
NR, Reynolds number, dimensionless; NR,.p, particle Reynolds number,
D p Go/I" dimensionless
n Number of channels in packed bed; also exponent in Eq. (7.46)
P Pressure, N/m2 or Ibf/fe; PO' Pb, at stations a and b; P" at stagnation
point; Po, in undisturbed fluid
I' Radius of particle path, m or ft; also mass ratio of solids to air in
pneumatic conveyor
S Cross-sectional area, m 2 or fe; So, of empty tower
sp Surface area of single particle, m 2 or fe
T Temperature, K, °C, OF, or OR; 'Fa, '1b, at stations a and b; 7;, at
stagnation point; To, of approaching stream
Time, s
178 FLUID MECHANICS
u Velocity of fluid or particle, m/s or ft/s; "b' average bubble velocity in
fluidized bed; Us, settling velocity of uniform suspension; Up terminal
velocity of particle; "0, velocity of approaching stream; It, fluctuating
component
V, Velocity of solids in pneumatic conveyor, m/s or ft/s; v'a, at inlet; V,b'
at outlet
V Volumetric average fluid velocity, m/s or ft/s; T;, critical velocity in
hydraulic transport; VD' superficial or empty-tower velocity; VDU' mini-
mum superficial velocity for fluidization
vp Volume of single particle, ft' or m'
Xi Volume fraction of particles of size i in bed of mixed particles
Z Height above datum plane, m or ft; Za, Zb, at stations a and b
Greek letters
a Angle with perpendicular to flow direction
y Ratio of specific heats, cp/cp
IJ.p Pressure drop in packed or fluidized bed
IJ.p Density difference, Pp - P
" Porosity or volume fraction of voids In bed of solids; "M, mInImum
porosity for fluidization
A, Constant in Eqs. (7.15) and (7.16)
}" Constant in Eqs. (7.18) and (7.19)
I' Absolute viscosity, cP or lb/ft-s; 1'" effective viscosity of suspension
p Density, kg/m' or lb/ft'; Pp, of particle; p" of conveyed solid; Po, of
approaching stream; p, average density of air in pneumatic conveyor
rH' Shear stress at channel boundary, N/m' or lb f/ft'
<1>, Sphericity, defined by Eq. (7.10)
'" Function
{jJ Angular velocity, rad/s
PROBLEMS
7.1. A partial oxidation is carried out by passing air with 1.2 mole percent hydrocarbon
through 40-mm tubes packed with 2 m of 3-by-3-mm cylindrical catalyst pellets. The
air enters at 350°C and 2.0 atm with a superficial velocity of 1 m/so What is the pressure
drop through the packed tubes? How much would the pressure drop be reduced by
using 4-mm pellets? Assume e = 0040.
7.2. A catalyst tower 40 ft high and 18 ft in diameter is packed with I-in.-diameter spheres.
Gas enters the top of the bed at a temperature of 450°F and leaves at the same
temperature. The pressure at the bottom of the catalyst bed is 30 Ib j /in. 2 abs. The
bed porosity is 0.40. If the gas has average properties similar to propane and the time
of contact (based on flow in the void space) between the gas and the catalyst is 8 s,
what is the inlet pressure?
73. The pressure drop for air flow through a column filled with I-in. ceramic Raschig rings
is 0.01 in. water per foot when Go = 80Ib/ftl-h and 0.9 in. water per foot when
Go = 8001b/ft 2 -h, all for a mass velocity of the liquid flowing countercurrently of
FLOW PAST IMMERSED BODIES 179
645lb/ft'-h (Ref. 18, p. 18-27). Since the change in pressure drop with liquid rate is
slight in the range of liquid mass velocities between 645 and 1980 lb/fe-h, ignore the
liquid holdup and estimate the void fraction if the rings have a wall thickness of
i in. Use this void fraction and the Ergun equation to predict the pressure drop,
and discuss the difference between predicted and experimental values.
7.4. The following data are reported for the flow of air through beds of granular activated
carbon. Compare the pressure drops with values predicted using the Ergun equation
and predict the pressure drops for both sizes at air velocities of 100 and 200 ft/min.
4 x 6 mesh, 4 x Smesh,
AP, in. H 20/ft AP, in. H 20/ft
10 0.25 0.32
40 1.40 1.80
7.5. The pressure drop through a particle bed can be used to determine the external surface
area and the average particle size. Data for a bed of crushed ore particles show
!;pIL ~ 84 (lbJ/in.')/ft for airflow at a superficial velocity of 0.015 ft/s. The measured
void fraction is 0.47, and the estimated sphericity <lls is 0.7. Calculate the average
particle size and the surface area per unit mass if the solid has a density of 4.1 gjcm 3 •
How sensitive is the answer to an error of 0.01 in 6?
7.6. A 6-in. thick demister pad for removing fine droplets of H 2 S04 from a gas stream is
made of 50-,um fibers randomly oriented in the plane perpendicular to the gas flow.
The average porosity is 0.90. Calculate the pressure drop for gas velocities of 1 and
3 ft/s at 90°C and 1 atm using the drag coefficients for individual fibers.
7.7. How long will it take for the spherical particles in Table 7.2 to settle, at their terminal
velocities under free-settling conditions, through 2 m of water at 20°C?
TABLE 7.2
Data for Prob. 7.7
Specific
Substance gravity Diameter, mm
Galena 7.5 0.25
0.025
Quartz 2.65 0.25
0.025
Coal 1.3 6
Steel 7.7 25
7.8. A cyclone separator is used to remove sand grains from an airstream at 150°C. If the
cyclone body is 0.6 m in diameter and the average tangential velocity is 16 m/s, what
is the radial velocity near the wal1 of particles 20 and 40,um in size? How much
greater are these values than the terminal velocity in gravity settling?
7.9. Urea pellets are made by spraying drops of molten urea into cold gas at the top of
a tall tower and allowing the material to solidify as it falls. Pellets 6 mm in diameter
180 FLUID MECHANICS
are to be made in a tower 25 m high containing air at 20°C. The density of urea is
1330 kg/m'. (a) What would be the terminal velocity of the pellets, assuming
free-settling conditions? (b) Would the pel1ets attain 99 percent of this velocity before
they reached the bottom of the tower?
7.10. Spherical particles 1 mm in diameter are to be fluidized with water at twice the
minimum velocity. The particles have an internal porosity of 40 percent, an average
pore diameter of 10 ,urn, and a particle density of 1.5 g/cm3 • Prove that the flow
through the internal pores is very sman compared to the flow between the particles
and that the internal porosity can be neglected in predicting the fluidization behavior.
7.11. Catalyst pellets 0.2 in. in diameter are to be fluidized with 100,000 Ib/h of air at 1 atm
and 170°F in a vertical cylindrical vessel. The density of the catalyst particles is
60 Ib/ft 3 ; their sphericity is 0.86. If the given quantity of air is just sufficient to fluidize
the solids, what is the vessel diameter?
REFERENCES
1. Ergun, S.: Chem. Eng. Prog., 48:89 (1952).
2. Geldart, D.: Powder Technology, 7:285 (1973).
3. Heiss, J. F., and J. Coull: Chem. Eng. Prog., 48:133 (1952).
4. Hottovy, J. D., and N. D. Sylvester: Ind Eng. Chem. Proc. Des. Dev., 18:433 (1979).
5. Houghton, G., A. M. McLean, and P. D. Ritchie: Chem. Eng. Sci., 7:26 (1957).
6. Hughes, R R, and E. R Gilliland: Chem. Eng. Prog., 48:497 (1952).
7. Hunsaker, J. C, and B. G. Rightmire: Engineering Applications of Fluid Mechanics, McGraw-Hill,
New York, 1947, pp. 202-203.
8. Ingebo, R. D.: NACA Tech. Note 3762 (1956).
9. Knudsen, J. G., and D. L. Katz: Fluid Mechanics and Heat Transfer, McGraw-Hill, New York,
1958, p. 317.
10. LappJe, C. E., and C. B. Shepherd: lnd Eng. Chem., 32:605 (1940).
11. Leva, M.: Fiuidizatioll, McGraw-HilI, New York, 1959.
12. Leva, M., and M. Grummer: Chem. Eng. Prog., 43:713 (1947).
13. Lewis. W. K., E. R GilIiland, and W. C Bauer: IlId ElIg. Chem., 41:1104 (1949).
14. Masiiyah, J. H., and N. Epstein: J. Fluid Meck, 44:493 (1970).
15. Maude, A. D., and R. L. Whitmore: Br. J. Appl. Phys., 9:477 (1958).
16. Mills, D.: Chem. Eng., 97(2):70 (1990).
17. Oroskar, A. R., and R. M. Turian; AIChE J., 26:550 (1980).
18. Perry,J. H.(ed.): Chemical Engin,eers' Handbook, 5th ed., McGraw-Hill, New York, 1973,p.3-247.
19. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York, 1984;
(a) p. 5-46, (b) pp. 7-17 to 7-25.
20. Pettyjohn, E. S., and E. B. Christiansen: Chem. Eng. Prog., 44:157 (1948).
21. Ran~ W. E.: Chem. Eng. Prog., 48:247 (1952).
22. Rowe, P. N.: in J. F. Davidson and D. Harrison (eels.), Fluidization, Academic, New York, 1971,
p.145.
23. Tavlarides, L. L., C A. Coulaloglou, M. A. Zeitlin, G. E. Klinzing, and B. Gal-Or: Ind. ElIg. Chem.,
62(Il):6 (1970).
24. Wilhelm, R. H., and M. Kwauk: Chem. Ellg. Prog., 44:201 (1948).
CHAPTER
8
TRANSPORTATION
AND METERING
OF FLUIDS
Preceding chapters have dealt with theoretical aspects of fluid motion. The
engineer is concerned, also, with practical problems in transporting fluids from
one place to another and in measuring their rates of flow. Such problems are the
subject of this chapter.
The first part of the chapter deals with the transportation of fluids, both
liquids and gases. Solids are sometimes handled by similar methods by suspending
them in a liquid to form a pumpable slurry or by conveying them in a high-velocity
gas stream. It is cheaper to move fluids than solids, and materials are transported
as fluids whenever possible. In the process industries, fluids are nearly always
carried in closed channels sometimes square or rectangular in cross section but
much more often circular. The second part of the chapter discusses common
methods of measuring flow rate.
PIPE, FITTINGS, AND VALVES
PIPE AND TUBING. Fluids are usually transported in pipe or tubing, which is
circular in cross section and available in widely varying sizes, wall thicknesses,
and materials of construction. There is no clear-cut distinction between the terms
pipe and tubing. Generally speaking, pipe is heavy walled, relatively large in
diameter, and comes in moderate lengths of 20 to 40 ft; tubing is thin walled and
often comes in coils several hundred feet long. Metallic pipe can be threaded;
1R1
1~2 FLUID MECHANICS
tubing usually cannot. Pipe walls are usually slightly rough; tubing has very
smooth walls. Lengths of pipe are joined by screwed, flanged, or welded fittings;
pieces of tubing are connected by compression fittings, flare fittings, or soldered
fittings. Finally, tubing is usually extruded or cold drawn, while metallic pipe is
made by welding, casting, or piercing a billet in a piercing mill.
Pipe and tubing are made from many materials, including metals and alloys,
wood, ceramics, glass, and various plastics. Polyvinyl chloride, or PVC, pipe is
extensively used for water lines. In process plants the most common material is
low-carbon steel, fabricated into what is sometimes called black-iron pipe.
Wrought-iron and cast-iron pipes are also used for a number of special purposes.
Sizes. Pipe and tubing are specified in terms of their diameter and their wall
thickness. With steel pipe the standard nominal diameters, in American practice,
range from k to 30 in. For large pipe, more than 12 in. in diameter, the nominal
diameters are the actual outside diameters; for small pipe the nominal diameter
does not correspond to any actual dimension. The nominal value is close to the
actual inside diameter for 3- to 12-in. pipe, but for very small pipe this is not true.
Regardless of wall thickness, the outside diameter of all pipe of a given nominal
size is the same to ensure interchangeability of fittings. Standard dimensions of
steel pipe are given in Appendix 5. Pipe of other materials is also made with the
same outside diameters as steel pipe to permit interchanging parts of a piping
system. These standard sizes for steel pipe, therefore, are known as IPS (iron pipe
size) or NPS (normal pipe size). Thus the designation "2-in. nickel IPS pipe" means
nickel pipe having the same outside diameter as standard 2-in. steel pipe.
The wall thickness of pipe is indicated by the schedule number, which
increases with the thickness. Ten schedule numbers, 10,20,30,40, 60, 80, 100, 120,
140, and 160, are in use, but with pipe less than 8 in. in diameter only numbers
40, 80, 120, and 160 are common. For steel pipe the actual wall thicknesses
corresponding to the various schedule numbers are given in Appendix 5; with
other alloys the wall thickness may be greater or less than that of steel pipe,
depending on the strength of the alloy. With steel at ordinary temperatures the
allowable stress is one-fourth the ultimate strength of the metal.
The size of tubing is indicated by the outside diameter. The normal value is
the actual outer diameter, to within very close tolerances. Wall thickness is
ordinarily given by the BWG (Birmingham wire gauge) number, which ranges
from 24 (very light) to 7 (very heavy). Sizes and wall thicknesses of heat-exchanger
tubing are given in Appendix 6.
Selection of pipe sizes. The optimum size of pipe for a specific situation depends
upon the relative costs of investment, power, maintenance, and stocking pipe and
fittings. In small installations rules of thumb are sufficient. For example, rep-
resentative ranges of velocity in pipes are shown in Table 8.1. The values in the
table are representative of ordinary practice, and special conditions may dictate
velocities outside the ranges. Low velocities should ordinarily be favored, especially
TRANSPORTATION AND METERING OF FLUIDS 183
TABLE S.1
Fluid velocities in pipe
Velocity range
Fluid Type of flow ftls rnls
Thin liquid Gravity flow 0.5-1 0.15-0.30
Pump inlet 1-3 0.3-0.9
Pump discharge 4-10 1.2-3
Process line 4-8 1.2-2.4
Viscous liquid Pump inlet 0.2-0.5 0.06-0.15
Pump discharge 0.5-2 0.15-1).6
Steam 30-50 9-15
Air or gas 30-100 9-30
in gravity flow from overhead tanks. The relation between pipe size. volumetric
flow rate, and velocity is shown in Appendix 5.
For large complex piping systems the cost of piping may be a substantial
fraction of the total investment. and elaborate computer methods of optimizing
pi pe sizes are justified.
JOINTS AND FITTINGS. The methods used to Jom pieces of pipe or tubing
depend in part on the properties of the material but primarily on the thickness of
the wall. Thick-walled tubular products are usually connected by screwed fittings,
by flanges, or by welding. Pieces of thin-walled tubing are joined by soldering or by
compression or flare fittings. Pipe made of brittle materials like glass or carbon
or cast iron is joined by flanges or bell-and-spigot joints.
When screwed fittings are used, the ends of the pipe are threaded externally
with a threading tool. The thread is tapered, and the few threads farthest from
the end of the pipe are imperfect, so that a tight joint is formed when the pipe is
screwed into a fitting. Tape of polytetrafluoroethylene is wrapped around the
threaded end to ensure a good seal. Threading weakens the pipe wall, and the
fittings are generally weaker than the pipe itself; when screwed fittings are used,
therefore, a higher schedule number is needed than with other types of joints.
Screwed fittings are standardized for pipe sizes up to 12 in., but because of the
difficulty of threading and handling large pipe, they are rarely used in the field
with pipe larger than 3 in.
Lengths of pipe larger than about 2 in. are usually connected by flanges or
by welding. Flanges are matching disks or rings of metal bolted together and
compressing a gasket between their faces. The flanges themselves are attached to
the pipe by screwing them on or by welding or brazing. A flange with no opening,
used to close a pipe, is called a blind flange or a blank flange. For joining pieces
of large steel pipe in process piping, especially for high-pressure service, welding
has become the standard method. Welding makes stronger joints than screwed
fittings do, and since it does not weaken the pipe wall, lighter pipe can be used
184 FLUID MECHANICS
for a given pressure. Properly made welded joints are leakproof, whereas other
types of joints are not. Environmental protection legislation considers flanged and
screwed joints to be sources of emission of volatile materials. Almost the only
disadvantage of a welded joint is that it cannot be opened without destroying it.
ALLOWANCES FOR EXPANSION. Ahnost all pipe is subjected to varying tem-
peratures, and in some high-temperature lines the temperature change is very large.
Such changes cause the pipe to expand and contract. If the pipe is rigidly fixed
to its supports, it may tear loose, bend, or even break. In large lines, therefore,
fixed supports are not used; instead the pipe rests loosely on rollers or is hung
from above by chains or rods. Provision is also made in all high-temperature lines
for taking up expansion, so that the fittings and valves are not put under strain.
This is done by bends or loops in the pipe, by packed expansion joints, by bellows,
or packless joints, and sometimes by flexible metal hose.
PREVENTION OF LEAKAGE AROUND MOVING PARTS. In many kinds of
processing equipment it is necessary to have one part move in relation to another
part without excessive leakage of a fluid around the moving member. This is true
in packed expansion joints and in valves where the stem must enter the valve body
and be free to turn without allowing the fluid in the valve to escape. It is also
necessary where the shaft of a pump or compressor enters the casing, where an
agitator shaft passes through the wall of a pressure vessel, and in other similar
places.
Common devices for minimizing leakage while permitting relative motion
are stuffing boxes and mechanical seals. Neither completely stops leakage, but if
no leakage whatever of the process fluid can be tolerated, it is possible to modify
the device to ensure that only innocuous fluids leak into or escape from the
equipment. The motion of the moving part may be reciprocating or rotational or
both together; it may be small and occasional, as in a packed expansion joint, or
virtually continuous, as in a process pump.
Stuffing boxes. A stuffing box can provide a seal around a rotating shaft and also
around a shaft that moves axially. In this it differs from mechanical seals, which
are good only with rotating members. The "box" is a chamber cut into the
stationary member surrounding the shaft or pipe, as shown in Fig. 8.la. Often a
boss is provided on the casing or vessel wall to give a deeper chamber. The annular
space between the shaft and the wall of the chamber is filled with packing,
consisting of a rope or rings of inert material containing a lubricant such as
graphite. The packing, when compressed tightly around the shaft, keeps the fluid
from passing out through the stuffing box and yet permits the shaft to turn or
move back and forth. The packing is compressed by a follower ring, or gland,
pressed into the box by a flanged cap or packing nut. The shaft must have a
smooth surface so that it does not wear away the packing; even so, the pressure
TRANSPORTATION AND METERING OF FLUIDS 185
Vacuum)
or
of
vessel
(aJ (b)
FIGURE 8.1
Stuffing boxes: (a) simple form; (b) with lantern gland.
of the packing considerably increases the force required to move the shaft. A
stuffing box, even under ideal conditions, does not completely stop fluid from
leaking out; in fact, when the box is operating properly, there should be small
leakage. Otherwise the wear on the packing and the power loss in the unlubricated
stuffing box are excessive.
When the fluid is toxic or corrosive, means must be provided to prevent it
from escaping from the equipment. This can be done by using a lantern gland (Fig.
8.1b), which may be looked upon as two stuffing boxes on the same shaft, with
two sets of packing separated by a lantern ring. The ring is H-shaped in cross
section, with holes drilled through the bar of the H in the direction perpendicular
to the axis of the shaft. The wall of the chamber of the stuffing box carries a pipe
that takes fluid to or away from the lantern ring. By applying vacuum to this pipe,
any dangerous fluid that leaks through one set of packing rings is removed to a
safe place before it can get to the second set. Or by forcing a harmless fluid such
as water under high pressure into the lantern gland, it is possible to ensure that
no dangerous fluid leaks out the exposed end of the stuffing box.
Mechanical seals. In a rotary, or mechanical, seal the sliding contact is between
a ring of graphite and a polished metal face, usually of carbon steel. A typical seal
is shown in Fig. 8.2. Fluid in the high-pressure zone is kept from leaking out
around the shaft by the stationary graphite ring held by springs against the face
of the rotating metal collar. Stationary V-cup packing of rubber or plastic is set
in the space between the body of the seal and the chamber holding it around the
shaft; this keeps fluid from leaking past the nonrotating part of the seal and yet
leaves the graphite ring free to move axially so that it can be pressed tightly against
186 FLUID MECHANICS
High-pressure
screw
<---0,"01 slop
Graphite ring
(stationary)
FIGURE 8.2
Mechanical seal.
the collar. Rqtary seals require less maintenance than stuffing boxes and have
come into wide use in equipment handling highly corrosive fluids.
VALVES. A typical processing plant contains thousands of valves of many different
sizes and shapes. Despite the variety in their design, however, all valves have a
common primary purpose: to slow down or stop the flow of a fluid. Some valves
work best in on-or-off service, fully open or fully closed. Others are designed to
throttle, to reduce the pressure and flow rate of a fluid. Still others permit flow
in one direction only or only under certain conditions of temperature and pressure.
A steam trap, which is a special form of valve, allows water and inert gas to pass
through while holding back the steam. Finally, through accessory devices, valves
can be made to contrQl the temperature, pressure, liquid level, or other properties
of a fluid at points remote from the valve itself.
In all cases, however, the valve initially stops or controls flow. This is done
by placing an obstruction in the path of the fluid, an obstruction that can be
moved ahout as desired inside the pipe with little or no leakage of the fluid from
the pipe to the outside. Where the resistance to flow introduced by an open valve
must be small, the obstruction and the opening that can be closed by it are large.
For precise control of flow rate, usually obtained at the price of a large pressure
drop, the cross-sectional area of the flow channel is greatly reduced, and a small
obstruction is set into the small opening.
Gate valves and globe valves. The two most common types of valves, gate valves
and globe valves, are illustrated in Fig. 8.3. In a gate valve the diameter of the
opening through which the fluid passes is nearly the same as that of the pipe, and
the direction offlow does not change. As a result, a wide-open gate valve introduces
only a small pressure drop. The disk is tapered and fits into a tapered seat; when
TRANSPORTATION AND METERING OF FLUIDS 187
Handwheel---.,.,G""~
Slem--~
or gland
Packing nul-~l'1llI Packing nul
(0) (b)
FIGURE 8.3
Common valves: (a) gate valve; (b) globe valve.
the valve is opened, the disk rises into the bonnet, completely out of the path of
the fluid. Gate valves are not recommended for controlling flow and are usually
left fully open or fully closed.
Globe valves (so called because in the earliest designs the valve body was
spherical) are widely used for controlling flow. The opening increases almost
linearly with stem position, and wear is evenly distributed around the disk. The
fluid passes through a restricted opening and changes direction several times, as
can be seen by visualizing the flow through the valve illustrated in Fig. 8.3b. As
a result the pressure drop in this kind of valve is large.
Plug cocks and ball valves. For temperatures below 250'C, metallic plug cocks are
useful in chemical process lines. As in a laboratory stopcock, a quarter turn of
the stem takes the valve from fully open to fully closed, and when fully open, the
channel through the plug may be as large as the inside of the pipe itself, and the
pressure drop is minimal. In a ball valve the sealing element is spherical, and the
problems of alignment and "freezing" of the element are less than with a plug
cock. In both plug cocks and ball valves the area of contact between moving
element and seat is large, and both can therefore be used in throttling service. Ball
valves find occasional applications in flow control.
Check valves. A check valve permits flow in one direction only. It is opened by
the pressure of the fluid in the desired direction; when the flow stops or tends to
reverse, the valve automatically closes by gravity or by a spring pressing against
the disk. Common types of check valves are shown in Fig. 8.4. The movable disk
is shown in solid black.
188 FLUID MECHANICS
(0) (b) (c)
FIGURE 8.4
Check valves: (a) lift check; (b) ball check; (c) swing check.
RECOMMENDED PRACTICE. In designing and installing a piping system, many
details must be given careful attention, for the successful operation of the entire
plant may turn upon a seemingly insignificant feature of the piping arrangement.
Some general principles are important enough to warrant mention. In installing
pipe, for example, the lines should be parallel and contain, as far as possible,
right-angle bends. In systems where the process lines are likely to become clogged,
provision should be made for opening the lines to permit cleaning them out.
Unions or flanged connections should be generously included, and tees or crosses
with their extra openings closed with plugs should be substituted for elbows in
critical locations. With hazardous materials, especially volatile ones, flanged or
screwed fittings should be used sparingly.
In gravity-flow systems the pipe should be oversize and contain as few bends
as possible. Fouling of the lines is particularly troublesome where flow is by
gravity, since the pressure head on the fluid cannot be increased to keep the flow
rate up if the pipe becomes restricted.
Leakage through valves should also be expected. Where complete stoppage
of flow is essential, therefore, where leakage past a valve would contaminate a
valuable product or endanger the operators of the eqnipment, a valve or check
valve is inadequate. In this situation a blind flange set between two ordinary
flanges will stop all flow; or the line can be broken at a union or pair of flanges
and the open ends capped or plugged.
Valves should be mounted vertically with their stems up, if possible. They
should be accessible and well supported without strain, with suitable allowance
for thermal expansion of the adjacent pipe. Room should be allowed for fully
opening the valve and for repacking the stuffing box.
FLUID-MOVING MACHINERY
Fluids are moved through pipe, equipment, or the ambient atmosphere by pumps,
fans, blowers, and compressors. Such devices increase the mechanical energy of
the fluid. The energy increase may be used to increase the velocity, the pressure,
or the elevation of the fluid. In the special case of liquid metals energy may be
TRANSPORTATION AND METERING OF FLUIDS 189
added by the action of rotating electromagnetic fields. Air lifts, jet pumps, and
ejectors utilize the energy of a second fluid to move a first. By far the most common
method of adding energy is by positive displacement or centrifugal action supplied
by outside forces. These methods lead to the two major classes of fluid-moving
machinery: (1) those applying direct pressure to the fluid and (2) those using torque
to generate rotation. The first group includes positive-displacement devices and
the second includes centrifugal pumps, blowers, and compressors. Also, in positive-
displacement devices, the force may be applied to the fluid either by a piston acting
in a cylinder or by rotating pressure members. The first type is called reciprocating
machines and the second is called rotary positive-displacement machines.
The terms pump, Jail, blower, and compressor do not always have precise
meanings. For example, air pump and vacuum pump designate machines for
compressing a gas. Generally, however, a pump is a device for moving a liquid;
a fan, a blower, or a compressor adds energy to a gas. Fans discharge large
volumes of gas (usually air) into open spaces or large ducts. They are low-speed
rotary machines and generate pressures of the order of a few inches of water.
Blowers are high-speed rotary devices (using either positive displacement or
centrifugal force) that develop a maximum pressure of about 2 atm. Compressors
discharge at pressures from 2 atm to thousands of atmospheres.
From the standpoint of fluid mechanics the phenomena occurring in these
devices can be classified under the usual headings of incompressible and compress-
ible flow. In pumps and fans the density of the fluid does not change appreciably,
and in discussing them, incompressible-flow theory is adequate. In blowers and
compressors the density increase is too great to justify the simplifying assumption
of constant density, and compressible-flow theory is required.
In all units certain performance requirements and operating characteristics
are important. Flow capacity-measured usually in volumetric flow per unit time
at a specified density-power requirements, and mechanical efficiency are obvious-
ly important. Reliability and ease of maintenance are also desirable. In small units,
simplicity and trouble-free operation are more important than high mechanical
efficiency with its savings of a few kilowatts of power.
Pumps
In pumps, the density of the fluid is both constant and large. Pressure differences
are usually considerable, and heavy construction is needed.
DEVELOPED HEAD. A typical pump application is shown diagrammatically in
Fig. 8.5. The pump is installed in a pipeline to provide the energy needed to draw
liquid from a reservoir and discharge a constant volumetric flow rate at the exit
of the pipeline, Zb feet above the level of the liquid. At the pump itself, the liquid
enters the suction connection at station a and leaves the discharge connection at
station b. A Bernoulli equation can be written between stations a and b. Equation
(4.32) serves for this. Since the only friction is that occurring in the pump itself
190 FLUID MECHANICS
a !w
p
b
zb'
l
t- "
l
- <==If Pump
Zo
,1'1'
J
____ 1 ___ b
-
Reservoir
P=i
FIGURE <'85
Pump flow system.
and is accounted for by the mechanical efficiency q, hI = O. Then Eq< (4.32) can
be wriften
p, gZ, abvt) gZa aa ;) V
qW = ( -+-+-- - (Pa
-+-+-- (S.l)
Ppg, 2g, p g, 2g,
The quantities in the parentheses are called total heads and are denoted by H, or
P gZ aV 2
H=-+-+- (S2)
p g, 2g,
In pumps the difference between the heights of the suction and discharge connec-
tions is usually negligible, and Za and Zb can be dropped from Eq< (S.n If
Ha is the total suction head, Hb the total discharge head, and!!.H = H, - Ha, Eq<
(S<l) can be written
W =H,-Ha !!.H
(S3)
P 'I q
POWER REQUIREMENT. The power supplied to the pump drive from an external
source is denoted by PB It is calculated from Wp by
<
. Ih!!.H
PB = mWP = -q- (S.4)
where ,n is the mass flow rate<
The power delivered to the fluid is calculated from the mass flow rate and
the head developed by the pump< It is denoted by PI and defined by
(S5)
TRANSPORTATION AND METERING OF FLUIDS 191
From Eqs. (8.4) and (8.5)
(8.6)
Equations (8.1) to (8.6) can also be used for fans by using an average density
P= (Pa + Pb)/2 for p.
SUCTION LIFT AND CAVITATION. The power calculated by Eq. (8.4) depends
on the difference in pressure between discharge and suction and is independent
of the pressure level. From energy considerations it is immaterial whether the
suction pressure is below atmospheric pressure or well above it as long as the
fluid remains liquid. However, if the suction pressure is only slightly greater than
the vapor pressure, some liquid may flash to vapor inside the pump, a process
called cavitation, which greatly reduces the pump capacity and causes severe
erosion. If the suction pressure is actually less than the vapor pressure, there will
be vaporization in the suction line, and no liquid can be drawn into the pump.
To avoid cavitation, the pressure at the pump inlet must exceed the vapor
pressure by a certain value, called the net positive suction head (NPSH). The
required value of NPSH is about 2 to 3 m (5 to 10 ft) for small centrifugal pumps,
but it increases with pump capacity, impeller speed, and discharge pressure, and
values up to 15 m (50 ft) are recommended for very large pumps' For a pump
taking suction from a reservoir, like that shown in Fig. 8.5, the available NPSH
is customarily calculated as
(8.7)
where Pa' = absolute pressure at surface of reservoir
PI) = vapor pressure
hfs = friction in suction line
The velocity head at the pump inlet aaV? /2g, could be subtracted from the result
given by Eq. (8.7) to give a more theoretically correct value of the available NPSH,
but this term is usually only about 30 to 60 cm (1 to 2 ft) and is accounted for in
the values of the minimum required net positive suction head (NPSHR) specified
by the pump manufacturers. Because of the cyclic variations in flow rate, the
velocity head (or more properly, in this case, the acceleration head) may be
important in specifying positive-displacement pumps.'
For the special situation where the liquid is practically nonvolatile (Po = 0),
the friction negligible (h f , = 0), and the pressure at station a' atmospheric, the
maximum possible suction lift can be obtained by subtracting the required NPSH
from the barometric head. For cold water, this maximum suction lift is about 34 ft
(lOA m); the maximum practical lift is about 25 ft (7.6 m).
192 FLUID MECHANICS
Example 8.1. Benzene at 100'F (37.8'C) is pumped through the system of Fig. 8.5
at the rate of 40 gal/min (9.09 m3jh). The reservoir is at atmospheric pressure. The
gauge pressure at the end of the discharge line is 50IbJ /in.' (345 kN/m'). The
discharge is 10 ft and the pump suction 4 ft above the level in the reservoir. The
discharge Hne is 1i-in. Schedule 40 pipe. The friction in the suction line is known to
be O.5lbJ /in-' (3.45 kN/m'), and that in the discharge line is 5.5lbJ /in.' (37.9 kN/m').
The mechanical efficiency of the pump is 0.60 (60 percent). The density of benzene is
541b/ft 3 (865 kg/m3), and its vapor pressure at l00'F (37.8'C) is 3.8IbJ /in.'
(26.2 kN/m'). Calculate (a) the developed head of the pump and (b) the total power
input. (c) If the pump manufacturer specifies a required NPSHR of 10 ft (3.05 m), will
the pump be suitable for this service?
Solution
(a) The pump work w" is found by using Eq. (4.32). The upstream station a' is at the
level of the liquid in the reservoir, and the downstream station b' is at the end of
the discharge Jine, as shown in Fig. 8.5. When the level in the tank is chosen as
the datum of heights and it is noted that v,;. = 0, Eq. (4.32) gives
Pb' gZb' V;,
Ilb' pQ'
w,,~ = - +- + - - + hJ --
p gc 2gc P
The exit velocity ~, is found by using data from Appendix 5. For a It-in.
Schedule 40 pipe, a velocity of 1 ftfs corresponds to a flow rate of 6.34 gal/min,
and
_ 40
v,. = - = 6.31 ft/s
6.34
With .b' = 1.0, Eq. (4.32) gives
(14.7 + 50)144 g 6.31' (5.5 + 0.5)144 14.7 x 144
W~= +-10+ + ----
p 54 g, 2 x 32.17 54 54
= 159.9 ft-lb dlb
By Eq. (8.3) w,,~ is also the developed head, and
dH = Hb - H, = 159.9 ft-lbJ/lb (477.9 J/kg)
(b) The mass flow rate is
40 x 54
m= 7.48 x 60 = 4.81Ib/s (2.18 kg/s)
The power input is, from Eq. (8.4),
4.81 x 159.9
- - - - ' - = 2.33 hp (1.74 kW)
550 x 0.60
(c) Use Eq. (8.7). p,./p = 14.7 x 144/54 = 39.2 ft-lbJ/lb. The vapor pressure
corresponds to a head of
3.8 x 144
10.1 ft-lb J/lb (30.2 Jjkg)
54
TRANSPORTATION AND METERING OF FLUIDS 193
The friction in the suction line is
0.5 x 144
hj = = 1.33 ft-Ibj/lb (3.98 J/kg)
54
The value of the available NPSH from Eq. (8.7), assuming gig, = 1, is
NPSH = 39.2 - 10.1 - 1.33 - 4 = 23.77 ft (7.25 m)
The available NPSH is considerably larger than the minimum required
value of 10 ft, so the pump should be suitable for the proposed service.
Positive-Displacement Pumps
In the first major dass of pumps a definite volume of liquid is trapped in a chamber,
which is alternately filled from the inlet and emptied at a higher pressure through
the discharge. There are two subdasses of positive-displacement pumps. In
reciprocating pumps the chamber is a stationary cylinder that contains a piston
or plunger; in rotary pumps the chamber moves from inlet to discharge and back
to the inlet.
RECIPROCATING PUMPS. Piston pumps, plunger pumps, and diaphragm pumps
are examples of reciprocating pumps. In a piston pump liquid is drawn through
an inlet check valve into the cylinder by the withdrawal of a piston and then
forced out through a discharge check valve on the return stroke. Most piston
pumps are double acting with liquid admitted alternately on each side of the piston
so that one part of the cylinder is being filled while the other is being emptied.
Often two or more cylinders are used in parallel with common suction and
discharge headers, and the configuration of the pistons is adjusted to minimize
fluctuations in the discharge rate. The piston may be motor driven through
reducing gears or a steam cylinder may be used to drive the piston rod directly.
The maximum discharge pressure for commercial piston pumps is about 50 atm.
For higher pressures plunger pumps are used. An example is shown in Fig.
8.6a. A heavy-walled cylinder of small diameter contains a dose-filling recipro-
cating plunger, which is merely an extension of the piston rod. At the limit of its
stroke the plunger fills nearly all the space in the cylinder. Plunger pumps are
single acting and usually are motor driven. They can discharge against a pressure
of 1500 atm or more.
In a diaphragm pump the reciprocating member is a flexible diaphragm of
metal, plastic, or rubber. This eliminates the need for packing or seals exposed to
the liquid being pumped, a great advantage when handling toxic or corrosive
liquids. A typical unit is shown in Fig. 8.6b. Diaphragm pumps handle small to
moderate amounts of liquid, up to about 100 gal/min, and can develop pressures
in excess of 100 atm.
The mechanical efficiency of reciprocating pumps varies from 40 to 50 per-
cent for small pumps to 70 to 90 percent for large ones. It is nearly independent
194 FLUID MECHANICS
Oul/el ball
check valves
(aJ
Suction ball
valve
Ib)
FIGURE 8.6
Positive-displacement reciprocating pumps: (a) plunger pump; (b) diaphragm pump.
of speed within normal operating limits and decreases slightly with increase in
discharge pressure because of added friction and leakage.
Volumetric efficiency. The ratio of the volume of fluid discharged to the volume
swept by the piston or plunger is called the volumetric efficiency. In positive-
displacement pumps the volumetric efficiency is nearly constant with increasing
discharge pressure, although it drops a little because of leakage. Because of the
constancy of volume flow, plunger and diaphragm pumps are widely used as
"metering pumps," injecting liquid into a process system at controlled but
adjustable volumetric rates.
TRANSPORTATION AND METERING OF FLUIDS 195
Discharge
Discharge
Inlet
Inlet
(aJ (bJ
FIGURE 8.7
Gear pumps: (a) spur-gear pump; (b) internal-gear pump.
ROTARY PUMPS. A wide variety of rotary positive-displacement pumps is avail-
able. They bear such names as gear pumps, lobe pumps, screw pumps, cam pumps,
and vane pumps. Two examples of gear pumps are shown in Fig. 8.7. Unlike
reciprocating pumps, rotary pumps contain no check valves. Close tolerances
between the moving and stationary parts minimize leakage from the discharge
space back to the suction space; they also limit the operating speed. Rotary pumps
operate best on clean, moderately viscous fluids, such as light lubricating oil.
Discharge pressures up 10 200 aim or more can be attained.
In the spur-gear pump (Fig. 8.7a) intermeshing gears rotate wilh close
clearance inside the casing. Liquid entering the suction line at the bottom of the
casing is caught in Ihe spaces between the teeth and the casing and is carried
around to the top of the casing and forced out the discharge. Liquid cannot
short-circuit back to the suction because of the close mesh of the gears in the
center of the pump.
In the internal-gear pump (Fig. 8.7b) a spur gear, or pinion, meshes with a
ring gear with internal teeth. Both gears are inside the casing. The ring gear is
coaxial with the inside of the casing, but the pinion, which is externally driven, is
mounted eccentrically with respect to the center of the casing. A stationary metal
crescent fills the space between the two gears. Liquid is carried from inlet to
discharge by both gears, in the spaces between the gear teeth and the crescent.
Centrifngal Pumps
In the second major class of pumps the mechanical energy of the liquid is increased
by centrifugal action. A simple, but very common, example of a centrifugal pump
is shown in Fig. 8.8a. The liquid enters through a suction connection concentric
196 FLUID MECHANICS
(a)
Discharge volute
Impeller
-M'--'~-.,H!~Suction channels
(b)
FIGURE 8.8
Volute centrifugal pumps: (a) single suction; (b) double suction.
with the axis of a high-speed rotary element called the impeller, which carries radial
vanes integrally cast in it. Liquid flows outward in the spaces between the vanes
and leaves the impeller at a considerably greater velocity with respect to the ground
than at the entrance to the impeller. In a properly functioning pump the space
between the vanes is completely filled with liquid flowing without cavitation. The
liquid leaving the outer periphery of the impeller is collected in a spiral casing
called the volute and leaves the pump through a tangential discharge' connection.
In the volute the velocity head of the liquid from the impeller is converted int"
pressure head. The power is applied to the fluid by the impeller and is transmitted
to the impeller by the torque of the drive shaft, which usually is driven by a
direct-connected motor at constant speed, commonly at 1750 r/min.
TRANSPORTATION AND METERING OF FLUIDS 197
Under ideal conditions of frictionless flow the mechanical efficiency of a
centrifugal pump is, of course, 100 percent, and ry = 1. An ideal pump operating
at a given speed delivers a definite discharge rate at each specific developed head.
Actual pumps, because of friction and other departures from perfection, fall
considerably short of the ideal case.
Centrifugal pumps constitute the most common type of pumping machinery
in ordinary plant practice. They come in a number of types other than the simple
volute machine shown in Fig. 8.8a. A common type uses a double-suction impeller,
which accepts liquid from both sides, as shown in Fig. 8.8b. Also, the impeller
itself may be a simple open spider, or it may be enclosed or shrouded. Handbooks,
texts on pumps, and especially the catalogs of pump manufacturers show many
types, sizes, and designs of centrifugal pumps.
CENTRIFUGAL-PUMP THEORY. The basic equations interrelating the power,
developed head, and capacity of a centrifugal pump are derived for the ideal pump
from fundamental principles of fluid dynamics. Since the performance of an actual
pump differs considerably from that of an ideal one, actual pumps are designed
by applying experimentally measured corrections to the ideal situation.
Figure 8.9 shows diagrammatically how the liquid flows through a cen-
trifugal pump. The liquid enters axially at the suction connection, station a. In
the rotating eye of the impeller, the liquid spreads out radially and enters the
(I)
FIGURE 8.9
Centrifugal pump showing BernoulIi stations.
198 FLUID MECHANICS
channels between the vanes at station 1. It flows through the impeller, leaves the
periphery of the impeller at station 2, is collected in the volute, and leaves the
pump discharge at station b.
The performance of the pump is analyzed by considering separately the three
parts of the total path: first, the flow from station a to station 1; second, the flow
through the impeller from station 1 to station 2; and third, the flow through the
volute from station 2 to station b. The heart of the pump is the impeller, and the
fluid-mechanical theory of the second section of the fluid path is considered first.
Figure 8.10 shows a single vane, one of the several in an impeller. The vectors
represent the various velocities at the stations 1 and 2 at the entrance and exit of
the vane, respectively. Consider first the vectors at station 2. By virtue of the design
of the pump the·tangent to the impeller at its terminus makes an angle P2 with
the tangent to the circle traced out by the impeller tip. Vector V 2 is the velocity
of the fluid at point 2 as seen by an observer moving with the impeller, and is
therefore a relative velocity. Two idealizations are now accepted. It is assumed,
first, that all liquid flowing across the periphery of the impeller is moving at the
same speed, so the numerical value (but not the vector direction) is V 2 at all points;
second, it is assumed that the angle between the vector V 2 and the tangent is the
actual vane angle P2' This assumption in turn is equivalent to an assumption that
there are an infinite number of vanes, of zero thickness, at an infinitesimal distance
apart. This ideal state is referred to as pelfect guidance. Point 2 at the tip of the
blades is moving at peripheral velocity U 2 with respect to the axis. Vector V2 is
the resultant velocity of the fluid stream leaving the impeller as observed from the
ground. It is called the absolute velocity of the fluid and is, by the parallelogram
law, the vector sum of relative velocity V 2 and peripheral velocity u2 • The angle
between vectors V2 and U 2 is denoted by "'2'
A comparable set of vectors applies to the entrance to the vanes at station
1, as shown in Fig. 8.lOa. in the usual design, "'1 is nearly 90", and vector VI can
be considered radial.
Figure 8.10b is the vector diagram for point 2 that shows the relations
among the various vectors in a more useful way. It also shows how the absolute-
velocity vector V2 can be resolved into components, a radial component denoted
by 1-';2 and a peripheral component denoted by Vo2 '
The power input to the impeller, and therefore the power required by the
pump, can be calculated from the angular-momentum equation for steady flow,
Eq. (4.34). To be consistent with Fig. 8.10, quantity U0 2 in Eq. (4.34) becomes v,,2,
and UOl becomes v,,1' Then
(8.S)
The momentum correction factors [the P's of Eq. (4.14)J are unity in view of the
assumption of perfect guidance. Also, in radial flow, where", = 90", v" = 0. At the
entrance, therefore, r 1 v,,1 = 0, the second telm in the parentheses of Eq. (S.8)
vanishes, and
(8.9)
TRANSPORTATION AND METERING OF FLUIDS 199
(
1+---- r2 - - - f - - + - (
(a)
"-
V2 V2 "- \V2
V,2 \
/32 a2 /32
"-
VU2
U2
u
FIGURE 8.10
(b)
Velocities at entrance and discharge of vanes in centrifugal pump: (a) vectors and vane; (b) vector
diagram at tip of vane.
200 FLUID MECHANICS
Since P = Tw, the power equation for an ideal pump is
(8.10)
where the subscript r denotes a frictionless pump.
HEAD-FLOW RELATIONS FOR AN IDEAL PUMP. From Eq. (8.5), written for
an ideal pump, P = Pf' = In I'1H, and therefore,
I'1H = r2 v,,2W (8.11)
g,
(8.12)
From Fig. 8.10b, v,,2 = U2 - V,2/tan /32' and
U (U
2 2 - V,2/tan /32)
I'1H, = -"'-"----""'---'-'''- (8.13)
g,
The volumetric flow rate q, through the pump is given by
(8.14)
where Ap is the total cross-sectional area of the channel around the periphery.
Combining Eqs. (8.13) and (8.14) gives
I'1H = U,(U2 - q,/A p tan /32) (8.15)
, g,
Since U2 , Ap, and /32 are constant, Eq. (8.15) shows that the relation between
head and volumetric flow is linear. The slope of the head-flow rate line depends
on the sign of tan /32 and therefore varies with angle /32' If /32 is less than 90·, as
is nearly always the case, the line has a negative slope. Flow in a piping system
may become unstable if the line is horizontal or has a positive slope.
HEAD-WORK RELATION IN AN IDEAL PUMP. The work done per unit mass
of liquid passing through an ideal pump, from Eqs. (8.4) and (8.10), is
Plr W
l1j,r = -.- = - r 2 l';,2 (8.16)
In gr:
A Bernoulli equation written between stations 1 and 2, assuming no friction,
neglecting Z. - Zb and assuming perfect guidance, gives
w P2 PI V~ Vi
-r2l';,2 = - - - + - - - (8.17)
g, p p 2g, 2g, •
TRANSPORTATION AND METERING OF FLUIDS 201
Also, Bernoulli equations written between stations a and 1 and band 2, respec-
tively, are
(8.18)
P2
-+-=-+--
V~ Pb a;vt (8.19)
p 2g, p 2g,
Adding Eqs. (8.17), (8.18), and (8.19) gives
Pb ab V~ Pa aaY; w
- + - - = - +-- + -r2v,,2 (8.20)
p 2g, p 2g, g,
Equation (8.20) can be written in the form
(8.21)
Equation (8.21) is in agreement with Eq. (8.3) for a frictionless or ideal pump,
where q = 1.0, I1H = I1H" and W. = w.,.
Effect of speed change. A practical problem arises when the rotational speed of a
pump is changed to predict the effect on head, capacity, and power consumed.
When speed n is increased, tip speed u2 rises proportionally; in an ideal pump
velocities V2, v,,2' and V,2 also increase directly with n. Hence
Capacity q varies with n [from Eq. (8.14)].
Head I1H varies with n2 [from Eq. (8.12)].
Power P varies with n 3 [from Eq. (8.10), since m= pq and therefore varies
with n].
ACTUAL PERFORMANCE OF CENTRIFUGAL PUMP. The developed head of
an actual pump is considerably less than that calculated from the ideal pump
relation ofEq. (8.21). Also, the efficiency is less than unity and the fluid horsepower
is greater than the ideal horsepower. Head losses and power losses will be discussed
separately.
LOSS OF HEAD; CIRCULATORY FLOW. A basic assumption in the theory of the
ideal pump was that of complete guidance, so the angle between vectors "2 and
U2 equals the vane angle /32. The guidance is not perfect in the real pump, and
the actual stream of fluid leaves at an angle considerably less than /32. The physical
reason is that the velocity in a given cross section is far from uniform. The effect
is the result of an end-to-end circulatory flow ofliquid within the impeller channels
superimposed on the net flow through the channel. Because of circulation, the
202 FLUID MECHANICS
FIGURE 8.11
Vector diagram showing effect of circu-
~---------------U2--------------~
lation in pump impeIIer.
resultant velocity V2 is smaller than the theoretical value. The vector diagram in
Fig. 8.11 shows how circulation modifies the theoretical velocities and angles. The
full lines and the primed quantities apply to the actual pump and the dotted lines
and the unprimed quantities apply to the theoretical case. The speed of the pump,
and hence U2, and the flow of fluid through the pump, proportional to V,2, are the
same in the two cases. It is clear that the angle [32 and the tangential component
V;" both decrease. By Eq. (8.21), then, the developed head is also decreased.
CHARACTERISTIC CURVES; HEAD-CAPACITY RELATION. The plots of actual
head, total power consumption, and efficiency vs. volumetric flow rate are called
the characteristic curves of a pump. Such curves are iIIustrated schematically in
Fig. 8.12. In Fig. 8.12a, the theoretical head-flow rate (often called head-capacity)
relation is a straight line, in accordance with Eq. (8.21); the actual developed head
is considerably less and drops precipitously to zero as the rate increases to a certain
value in any given pump. This is known as the zero-head flow rate; it is the
maximum flow the pump can deliver under any conditions. The rated or optimum
operating flow rate is, of course, less than this.
The difference between the theoretical and actual curves results primarily
from circulatory flow. Other contributing factors to the head loss are fluid friction
Ideal (100%)
I Total power,Po
6H p
Actual
/ "- Actual
Fluid power, P,
\
\
0 0
0 q 0 q q
{,I (hi {cl
FIGURE 8.12
Characteristic curves of a centrifugal pump: (a) head capacity; (b) power; (c) efficiency.
TRANSPORTATION AND METERING OF FLUIDS 203
in the passages and channels of the pump and shock losses from the sudden change
in direction of the liquid leaving the impeller and joining the stream of liquid
traveling circumferentially around the casing. Friction is highest at the maximum
flow rate; shock losses are a minimum at the rated operating conditions of the
pump and become greater as the flow rate is increased or decreased from the rated
value.
POWER CURVES. Typical curves of fluid power P J and total power PH versus
flow rate are shown in Fig. 8.12b. The difference between ideal and actual
performance represents the power lost in the pump; it results from fluid friction
and shock losses, both of which are conversion of mechanical energy into heat,
and by leakage, disk friction, and bearing losses. Leakage is the unavoidable
reverse flow from the impeller discharge past the wearing ring to the suction eye;
this reduces the volume of the actual discharge from the pump per unit of power
expended. Disk friction is the friction between the outer surface of the impeIler
and the liquid in the space between the impeIler and the inside of the casing.
Bearing losses constitute the power required to overcome mechanical friction in
the bearing and stuffing boxes or seals of the pump.
EFFICIENCY. As shown by Eq. (8.6), the pump efficiency is the ratio of fluid power
to the total power input. The curve in Fig. 8.12c, derived from the curves in Fig.
8.12b, shows that the efficiency rises rapidly with flow rate at low rates, reaches
a maximum in the region of the rated capacity, then falls as the flow rate
approaches the zero-head value.
MULTISTAGE CENTRIFUGAL PUMPS. The maximum head that it is practicable
to generate in a single impeller is limited by the peripheral speed reasonably
attainable. A so-called high-energy centrifugal pump can develop a head of
more than 650 ft (200 m) in a single stage, but generally when a head greater than
about lOO ft (30 m) is needed, two or more impellers can be mounted in series on
a single shaft and a multistage pump so obtained. The discharge from the first
stage provides suction for the second, the discharge from the second provides
suction for the third, and so forth. The developed heads of all stages add to give
a total head several times that of a single stage.
LEAKPROOF PUMPS. Because of environmental considerations, leakproof cen-
trifugal pumps are increasingly used for handling dangerous liquids. There are
two main types, both of which contain no seals or stuffing boxes. In canned-rotor
pumps a stainless steel canlike enclosure surrounds the motor rotor to keep the
pumped fluid away from the motor. In magnetic-drive pumps the impeller, which
carries magnets, is driven by a magnet-carrying disk on the other side of the casing
wall. Both types are less efficient than conventional pumps, but a lower efficiency
is often preferable to installing complicated mechanical seals and seal-flushing
systems.
204 FLUID MECHANICS
PUMP PRIMING. Equation (8.21) shows that the theoretical head developed hy
a centrifugal pump depends on the impeJIer speed, the radius of the impeJIer, and
the velocity of the fluid leaving the impeJIer. If these factors are constant, the
developed head is the same for fluids of all densities and is the same for liquids
and gases. The increase in pressure, however, is the product of the developed head
and the fluid density. If a pump develops, say, a head of 100 ft and is fuJI of water,
the increase in pressure is 100 x 62.3/144 = 43 Ibf /in. 2 (2.9 atm). If the pump is
full of air at ordinary density, the pressure increase is about 0.1 Ibf /in 2 (0.007 atm).
A centrifugal pump trying to operate on air, then, can neither draw liquid upward
from an initiaJIy empty suction line nor force liquid along a fuJI discharge line. A
pump with air in its casing is airbound and can accomplish nothing until the air
has been replaced by a liquid. Air can be displaced by priming the pump from an
auxiliary priming tank connected to the suction line or by drawing liquid into the
suction line by an independent source of vacuum. Also, several types of self-priming
pumps are available.
Positive-displacement pumps can compress a gas to a required discharge
pressure and are not usuaJIy subject to air binding.
Fans, Blowers, and Compressors
Machinery for compressing and moving gases is conveniently considered from the
standpoint of the range of pressure difference produced in the equipment. This
order is fans, blowers, compressors.
FANS. Large fans are usuaJIy centrifugal, operating on exactly the same principle
as centrifugal pumps. Their impeJIer blades, however, may be curved forward; this
would lead to instability in a pump, but not in a fan. Typical fan impeJIers are
shown in Fig. 8.13; they are mounted inside light sheet-metal casings. Clearances
are large and discharge heads low, from 5 to 60 in. (130 to 1500 mm) H 2 0.
Sometimes, as in ventilating fans, nearly all the added energy is converted into
velocity energy and almost none into pressure head. In any case, the gain in
velocity absorbs an appreciable fraction ofthe added energy and must be included
FIGURE 8.13
ImpelJers for centrifugal fans.
TRANSPORTATION AND METERING OF FLUIDS 205
in estimating efficiency and power. The total efficiency, where the power output
is credited with both pressure and velocity heads, is about 70 percent.
Since the change in density in a fan is small, the incompressible-flow
equations used in the discussion of centrifugal pumps are adequate. One difference
between pumps and gas equipment recognizes the effect of pressure and tempera-
ture on the density of the gas entering the machine. Gas equipment is ordinarily
rated in terms of standard cubic feet. A volume in standard cubic feet is that
measured at a specified temperature and pressure regardless of the actual tempera-
ture and pressure of the gas to the machine. Various standards are used in different
industries, but a common one is based on a pressure of30 in. Hg and a temperature
of 60'F (S20'R). This corresponds to a molal volume of 378.7 ft' fib-mol.
Example 8.2. A centrifugal fan is used to take flue gas at rest and at a pressure of
29.0 in. (737 mm) Hg and a temperature of 200'F (93.3'C) and discharge it at a
pressure of 30.1 in. (765 mm) Hg and a velocity of 150 ft/s (45.7 m/s). Calculate the
power needed to move 10,000 std ft'/min (16,990 m'jh) of gas. The efficiency of the
fan is 65 percent, and the molecular weight of the gas is 31.3.
Solution
The actual suction density is
31.3 x 29.0(460 + 60)
0.06291b/ft'
p, = 37S.7 x 30(460 + 200)
and the discharge density is
30.1 ,
Pb = 0.0629 - = 0.0653 lb/ft
29.0
The average density of the flowing gas is
p = i(O.0629 + 0.0653) = 0.06411b/ft'
The mass flow rate is
. 10,000 x 31.3
m = ---'----- 13.78 Ibis
37S.7 x 60
The developed pressure is
Pb - p, (30.1 - 29)144 x 14.7
--= = 1214 rt-lbfjlb
P 29.92 x 0.0641
The velocity head is
v: 150'
349.7 ft-lbf jlb
2g, 2 x 32.17
From Eq. (S.I), calling ". =.b = 1.0, v.. = 0, and Z. = Zb,
Wp = -1 (Pb
-- - P. v:)
+ - = 1214 + 349.7 = 2406 ft-lbf jlb
'1 P 2g, 0.65
206 FLUID MECHANICS
From Eq. (8.4)
P -mW,
- - 13.78 x 2406 603
. hp (45.0 kW)
B - 550 - 550
BLOWERS AND COMPRESSORS. When the pressure on a compressible fluid is
increased adiabatically, the temperature of the fluid also increases. The tempera-
ture rise has a number of disadvantages. Because the specific volume of the fluid
increases with temperature, the work required to compress a pound of fluid is
larger than if the compression were isothermal. Excessive temperatures lead to
problems with lubricants, stuffing boxes, and materials of construction. The fluid
may be one that cannot tolerate high temperatures without decomposing.
For the isentropic (adiabatic and frictionless) pressure change of an ideal
gas, the temperature relation is, using Eq. (6.24),
'Tb = (Pb)l-l/, (8.22)
7;, \Pa
where 7;" 'Tb = inlet and outlet absolute temperatures, respectively
Pa' Pb = corresponding inlet and outlet pressures
For a given gas, the temperature ratio increases with increase in the
compression ratio Pb/Pa' This ratio is a basic parameter in the engineering
of blowers and compressors. In blowers with a compression ratio below about 3
or 4, the adiabatic temperature rise is not large, and no special provision is made
to reduce it. In compressors, however, where the compression ratio may be as high
as 10 or more, the isentropic temperature becomes excessive. Also, since actual
compressors are not frictionless, the heat from friction is also absorbed by the gas,
and temperatures well above the isentropic temperature are attained. Compressors,
therefore, are cooled by jackets through which cold water or refrigerant is
circulated. In small cooled compressors, the exit gas temperature may approach
that at the inlet, and isothermal compression is achieved. In very small ones, air
cooling by exterual fins cast integrally with the cylinder is sufficient. In larger units,
where cooling capacity is limited, a path different from isothermal or adiabatic
compression, called polytropic compression, is followed.
POSITIVE-DISPLACEMENT BLOWER. A positive-displacement blower is shown
in Fig. 8.14. These machines operate like gear pumps except that, because of the
special design of the "teeth," the clearance is only a few thousandths of an inch.
The relative position of the impellers is maintained precisely by heavy external
gears. A single-stage blower can discharge gas at 0.4 to 1 atm gauge, a two-stage
blower at 2 atm. The blower shown in Fig. 8.14 has two lobes. Three-lobe machines
are also common.
CENTRIFUGAL BLOWERS. A single-stage centrifugal blower is shown in Fig.
8.15. In appearance it resembles a centrifugal pump, except that the casing is
narrower and the diameters of the casing and discharge scroll are relatively larger
TRANSPORTATiON AND METERING OF FLUIDS 207
Discharge
t
FIGURE 8.14
Impeller Inlet blower.
Two~lobe
than in a pump. The operating speed is high, 3600 r/min or more. The ideal power
is given by Eq. (8.10). The reason for the high speed and large impeller diameter
is that very high heads, measured in feet or meters oflow-density fluid, are needed
to generate moderate pressure ratios. Thus, the velocities appearing in a vector
diagram like Fig. 8.10 are, for a centrifugal blower, approximately tenfold those
in a centrifugal pump.
Centrifugal compressors are multistage units containing a series of impellers
on a single shaft rotating at high speeds in a massive casing. I.' Internal channels
lead from the discharge of one impeller to the inlet of the next. These machines
compress enormous volumes of air or process gas-up to 200,000 ft' /min
(340,000 m' /h) at the inlet-to an outlet pressure of 20 atm. Smaller capacity
machines discharge at pressures up to several hundred atmospheres. Interstage
cooling is needed on the high-pressure units.
Axial-flow machines handle even larger volumes of gas, up to 600,000 ft' /min
(1 x 106 m' /h), but at lower discharge pressures of 2 to 10 or 12 atm. In these
Oischarqe
scroll
Rotor
If/let
FIGURE 8.15
Single~suction centrifugal blower.
208 FLUID MECHANICS
units the rotor vanes propel the gas axially from one set of vanes directly to the
next. Interstage cooling is normally not required.
POSITIVE-DISPLACEMENT COMPRESSORS. Rotary positive-displacement com-
pressors can be used for discharge pressures to about 6 atm. Most compressors
operating at discharge pressures above 3 atm are reciprocating positive-displace-
ment machines. A simple example of a single-stage compressor is shown in Fig.
8.16. These machines operate mechanically in the same way as reciprocating
pumps, with the important differences that prevention of leakage is more difficult
and the temperature rise is important. The cylinder walls and cylinder heads are
cored for cooling jackets using water or refrigerant. Reciprocating compressors
are usually motor driven and are nearly always double acting.
When the required compression ratio is greater than can be achieved
in one cylinder, multistage compressors are used. Between each stage are coolers,
which are tubular heat exchangers cooled by water or refrigerant. Intercoolers
have sufficient heat-transfer capacity to bring the interstage gas streams to the
initial suction temperature. Often an aftercooler is used to cool the high-pressure
gas from the final stage.
EQUATIONS FOR BLOWERS AND COMPRESSORS. Because of the change in
density during compressible flow, the integral form of the BernouIIi equation is
inadequate. Equation (4.32), however, can be written differentially and used to
relate the shaft work to the differential change in pressure head. In blowers and
compressors the mechanical, kinetic, and potential energies do not change appreci-
ably, and the velocity and static-head terms can be dropped. Also, on the
assumption that the compressor is frictionless, ~ = 1.0 and hJ = O. With these
simplifications, Eq. (4.32) becomes
dW =dp
P'
P
Cooling water
jackets
I I
1::'.;-'
Piston and piston rings
tInlet
FIGURE 8.16
Reciprocating compressor.
TRANSPORTATION AND METERING OF FLUIDS 209
Integration between the suction pressure Po and the discharge pressure Pb gives
the work of compression of an ideal frictionless gas:
Wpr - JP'd p
- - (8.23)
P. P
To use Eq. (8.23), the integral must be evaluated, which requires information
on the path followed by the fluid in the machine from suction to discharge. The
procedure is the same whether the compressor is a reciprocating unit, a rotary
positive-displacement unit, or a centrifugal unit, provided only that the flow is
frictionless and that in a reciprocating machine the equation is applied over an
integral number of cycles, so there is neither accumulation nor depletion of fluid
in the cylinders; otherwise the basic assumption of steady flow, which underlies
Eq. (4.32), would not hold.
Adiabatic compression. For uncooled units, the fluid follows an isentropic path.
For ideal gases, the relation between P and P is given by Eq. (6.14), which may
be written
or
(8.24)
Substituting P from Eq. (8.24) into Eq. (8.23) and integrating gives
W = p~f' Jp' .:!L = p~fY (p'-'fY _ l-l/Y)
P' Po P. p'fy (1 _ Ify)po' Po
By multiplying the coefficient by p~ -1/y and dividing the terms in the parentheses
by the same quantity, this equation becomes
w;" = PoY [(Pb)'-'
(y - l)po \Po
/Y
- IJ (8.25)
Equation (8.25) shows the importance of the compression ratio P./Po'
Isothermal compression. When cooling during compression is complete, the tem-
perature is constant and the process is isothermal. The relation between P and p
then is, simply,
P Po
(8.26)
P Po
Eliminating p from Eqs. (8.23) and (8.26) and integrating gives
W = Po Jp> dp = Po In Pb = RT" In Pb (8.27)
P'
Pa p" P p(J p(J M p(J
210 FLUID MECHANICS
For a given compression ratio and suction condition, the work require-
ment in isothermal compression is less than that for adiabatic compression.
This is one reason why cooling is useful in compressors.
A close relation exists between the adiabatic and isothermal cases. By
comparing the integrands in the equation above, it is clear that if y = I, the
equations for adiabatic and for isothermal compression are identical.
Polytropic compression. In large compressors the path of the fluid is neither
isothermal nor adiabatic. The process may still be assumed to be frictionless,
however. It is customary to assume that the relation between pressure and
density is given by the equation
(8.28)
where n is a constant. Use of this equation in place of Eq. (8.24) obviously
yields Eq. (8.25) with the replacement of y by n.
The value of n is found empirically by measuring the density and pressure
at two points on the path of the process, e.g., at suction and discharge. The value
of n is calculated by the equation
In (Pb/Pa)
n=;-=~
In (Ph/Pa)
This equation is derived by substituting Pb for P and Pb for P III Eq. (8.28)
and taking logarithms.
Compressor efficiency. The ratio of the theoretical work (or fluid power) to
the actual work (or total power input) is, as usual, the efficiency and is denoted
by 'I. The maximum efficiency of reciprocating compressors is about 80 to
85 percent; it can be up to 90 percent for centrifugal compressors.
Power equation. The power required by an adiabatic compressor is readily
calculated from Eq. (8.25). The dimensional formula is
P = 0.0643T.,yqo
B
520(y - I)ry
[(Pb)'
\Pa
-'/' - IJ (8.29)
where P B = brake horsepower
qo = volume of gas compressed, std ft3/min
T., = inlet temperature, aR
For isothermal compression
(8.30)
TRANSPORTATION AND METERING OF FLUIDS 211
The corresponding equation for adiabatic compression, in SI units, is
P
B= 0.371T"No
(y - 1)~
[()Jb)1-1/ Y-
\Pa
IJ (S.29a)
where PB = power, kW
qo = volume of gas compressed, std m' Is, evaluated at oae and
760 mm Hg
Ya = inlet temperature, K
For isothermal compression, with SI units,
1.97T"qo I Pb
n- (S.30a)
~ Pa
Example 8.3. A three-stage reciprocating compressor is to compress 180 std ft 3 jmin
(306 m 3 jh) of methane from 14 to 900 IbJ/in.' (0.95 to 61.3 atm) abs. The inlet
temperature is 80°F (26.7°C). For the expected temperature range the average
properties of methane are
C p = 9.3 Btufib mol-'F (38.9 J/g mol-'C) y = 1.31
(a) What is the brake horsepower if the mechanical efficiency is 80 percent? (b) What
is the discharge temperature from the first stage? (c) If the temperature of the cooling
water is to rise 20°F (ll.l°C), how much water is needed in the intercoolers and
aftercooler for the compressed gas to leave each cooler at 80°F (26.7°C)? Assume
that jacket cooling is sufficient to absorb frictional heat.
Sollltion
(a) For a multistage compressor it can be shown that the total power is a minimum
if each stage does the same amount of work. By Eq. (8.25) this is equivalent to the
use of the same compression ratio in each stage. For a three-stage machine, therefore,
the compression ratio of one stage should be the cube root of the overall compression
ratio, 900/14. For one stage
~ = (900)1/3 = 4
Pa 14
The power required for each stage is, by Eq. (8.29),
P = (80
B
+ 460)(0.0643) x 1.31 x 180 (41-1/1.31 _ 1) = 24.6 hp
520(1.31 - 1)(0.80)
The total power for all stages is 3 x 24.6 = 73.8 hp (55.0 kW).
(b) From Eq. (S.22), the temperature at the exit of each stage is
7; = (80 + 460)4' -1/1.31 = 750'R = 290'F (143.3'C)
(c) Since 1 Ib mol = 378.7 std ft', the flow rate is
ISO x 60
-37-S-.7- = 2S.51b moljh (12.9 kg mOl/h)
212 FLUID MECHANICS
The heat load in each cooler is
28.5(290 - 80X9.3) = 55,660 Btu/h
The total heat load is 3 x 55,660 = 166,980 Btu/h. The cooling-water require-
ment is
166,980
- - = 83491b/h = 16.7 gal/min (3.79 m 3 /h)
20
VACUUM PUMPS. A compressor that takes suction at a pressure below atmo-
spheric and discharges against atmospheric pressure is called a vacuum pump. Any
type of blower or compressor, reciprocating, rotary, or centrifugal, can be adapted
to vacuum practice by modifying the design to accept very low density gas at the
suction and attain the large compression ratios necessary. As the absolute pressure
at the suction decreases, the volumetric efficiency drops and approaches zero at
the lowest absolute pressure attainable by the pump. Usually the mechanical
efficiency is also lower than for compressors. The required displacement increases
rapidly as the suction pressure falls, so a large machine is needed to move much
gas. The compression ratio used in vacuum pumps is higher than in compressors,
ranging up to 100 or more, with a correspondingly high adiabatic discharge
temperature. Actually, however, the compression is nearly isothermal because of
the low mass flow rate and the effective heat transfer from the relatively large area
of exposed metal.
Jet Ejectors. An important kind of vacuum pump that does not use moving parts
is the jet ejector, shown in Fig. 8.17, in which the fluid to be moved is entrained
in a high-velocity stream of a second fluid. The motive fluid and the fluid to be
moved may be the same, as when compressed air is used to move air, but usually
they are not. Industrially most use is made of steam-jet ejectors, which are valuable
Sleam
Inlel
Vapor
Inlel
FIGURE 8.17
Steam-jet ejector.
TRANSPORTATION AND METERING OF FLUIDS 213
for drawing a fairly high vacuum. As shown in Fig. 8.17, steam at about 7 atm is
admitted to a converging-diverging nozzle, from which it issues at supersonic
velocity into a diffuser cone. The air or other gas to be moved is mixed with the
steam in the first part of the diffuser, lowering the velocity to acoustic velocity
or below; in the diverging section of the diffuser the kinetic energy of the mixed
gases is converted into pressure energy, so that the mixture can be discharged
directly to the atmosphere. Often it is sent to a water-cooled condenser, particu-
larly if more than one stage is used, for otherwise each stage would have to handle
all the steam admitted to the preceding stages. As many as five stages are used in
industrial processing.
Jet ejectors require very little attention and maintenance and are especially
valuable with corrosive gases that would damage mechanical vacuum pumps. For
difficult problems the nozzles and diffusers can be made of corrosion-resistant
metal, graphite, or other inert materiaL Ejectors, particularly when multistage, use
large quantities of steam and water. They are rarely used to produce absolute
pressures below 1 mm Hg. Steam jets are no longer as popular as they once were,
because of the dramatic increase in the cost of steam. In many instances where
corrosion is not a serious consideration, they have been replaced by mechanical
vacuum pumps, which use much less energy for the same service.
COMPARISON OF DEVICES FOR MOVING FLUIDS. Positive-displacement ma-
chines, in general, handle smaller quantities of fluids at higher discharge pressures
than centrifugal machines do. Positive-displacement pumps are not subject to air
binding and are usually self-priming. In both positive-displacement pumps and
blowers the discharge rate is nearly independent of the discharge pressure, so that
these machines are extensively used for controlling and metering flow. Reciproca-
ting devices require considerable maintenance but can produce the highest
pressures. They deliver a pUlsating stream. Rotary pumps work best on fairly
viscous lubricating fluids, discharging a steady stream at moderate to high
pressures. They cannot be used with slurries. Rotary blowers usually discharge
gas at a maximum pressure of 2 atm from a single stage. The discharge line of a
positive-displacement pump cannot be closed without stalling or breaking the
pump, so that a bypass line with a pressure-relief valve is required.
Centrifugal machines, both pumps and blowers, deliver fluid at a uniform
pressure without shocks or pulsations. They run at higher speeds than positive-
displacement machines and are connected to the motor drive directly instead of
through a gearbox. The discharge line can be completely closed without damage.
Centrifugal pumps can handle a wide variety of corrosive liquids and slurries.
Centrifugal blowers and compressors are much smaller, for given capacity, than
reciprocating compressors and require less maintenance.
For producing vacuum, reciprocating machines are effective for absolute
pressures down to 10 mm Hg. Rotary vacuum pumps can lower the absolute
pressure to 0.01 mm Hg and over a wide range of low pressures are cheaper to
operate than multistage steam-jet ejectors. For very high vacuums, specialized
devices such as diffusion pumps are needed.
214 FLUID MECHANICS
MEASUREMENT OF FLOWING FLUIDS
To control industrial processes, it is essential to know the amount of material
entering and leaving the process. Because materials are transported in the form
of fluids wherever possible, it is important to measure the rate at which a fluid is
flowing through a pipe or other channel. Many different types of meters are used
industrially. Selection of a meter is based on the applicability of the instrument
to the specific problem, its installed cost and costs of operation, the range of flow
rates it can accommodate (its rangeability), and its inherent accuracy. Sometimes
a rough indication of the flow rate is all that is needed; at other times a highly
accurate measurement, usually of the mass flow rate, is required for such purposes
as controlling reactor feeds or transferring custody of the fluid from one owner
to another.
A few types of flowmeters measure the mass flow rate directly, but the
majority measure the volumetric flow rate or the average fluid velocity, from which
the volumetric flow rate can be calculated. To convert the volumetric rate to the
mass flow rate requires that the fluid density under the operating conditions be
known. Most meters operate on all the fluid in the pipe or channel and are known
as full-bore meters. Others, called insertion meters, measure the flow rate, or more
commonly the fluid velocity, at one point only. The total flow rate, however, can
often be inferred with considerable accuracy from this single-point measurement.
Detailed descriptions of commercial flowmeters, listing their advantages and
limitations, are available in the Iiterature3
Full-Bore Meters
FUll-bore meters include variable-head meters such as venturi and orifice meters
and variable-area meters such as rotameters. These will be described in some detail.
Briefer descriptions are given of other full-bore measuring devices: V-element,
magnetic, vortex shedding, turbine and positive-displacement meters, ultrasonic
meters, and mass flow devices such as Coriolis and thermal flowmeters.
VENTURI METER. A venturi meter is shown in Fig. 8.18. It is constructed from
a flanged inlet section A consisting of a short cylindrical portion and a truncated
cone; a flanged throat section B; and a flanged outlet section C consisting of a
long truncated cone. In the upstream section, at the junction of the cylindrical
and conical portions, an annular chamber D is provided, and a number of small
holes E are drilled from the inside of the tube into the annular chamber. The
annular ring and the small holes constitute a piezometer ring, which has the
function of averaging the individual pressures transmitted through the several
small holes. The average pressure is transmitted through the upstream pressure
connection F. A second piezometer ring is formed in the throat section by an
integral annular chamber G and a liner H. The liner is accurately bored and
finished to a definite diameter, as the accuracy of the meter is reduced if the throat
is not carefully machined to close tolerances. The throat pressure is transmitted
TRANSPORTATION AND METERING OF FLUIDS 215
F. I
FIGURE 8.18
Venturi meter: A, inlet section; E, throat section; C, outlet section; D, G, piezometer chambers; E,
holes to piezometer chambers; F, upstream pressure tap; H, liner; I, downstream tap.
through the pressure tap f. A manometer or a differential pressure transmitter is
connected between the taps F and f.
In the venturi meter, the velocity is increased, and the pressure decreased,
in the upstream cone. The pressure drop in the upstream cone is utilized as shown
below to measure the rate of flow through the instrument. The velocity is then
decreased, and the original pressure largely recovered, in the downstream cone.
To make the pressure recovery large, the angle of the downstream cone C is small,
so boundary-layer separation is prevented and friction minimized. Since separation
does not occur in a contracting cross section, the upstream cone can be made
shorter than the downstream cone. Although venturi meters can be applied to the
measurement of gas, they are most commonly used for liquids, especially water.
The following treatment is limited to incompressible fluids.
The basic equation for the venturi meter is obtained by writing the Bernoulli
equation for incompressible fluids between the two pressure stations at F and f.
Friction is neglected, the meter is assumed to be horizontal, and there is no pump.
If v" and V. are the average upstream and downstream velocities, respectively, and
p is the density of the fluid, Eq. (4.32) becomes
-V2 -V2 2g,(po - Pb)
(/.bb-(/.(l(l= (8.31)
p
The continuity relation (4.7) can be written, since the density is constant, as
- (Db)2_ 2- (8.32)
V. = Do V, = f3 V,
where Do = diameter of pipe
Db = diameter of throat of meter
f3 = diameter ratio Db/Do
If v" is eliminated from Eqs. (8.31) and (8.32), the result is
V. = 1 2g,(po - Pb)
(8.33)
.Jab - f3'a o P
216 FLUID MECHANICS
Venturi coefficient. Equation (8.33) applies strictly to the frictionless flow of
noncompressible fluids. To account for the small friction loss between locations
a and b, Eq. (8.33) is corrected by introducing an empirical factor C, and writing
v" = C, J2 g,(P, - Pb) (8.34)
Jl-f34 P
The small effects of the kinetic-energy factors "', and "'b are also taken into account
in the definition of C,. The coefficient C, is determined experimentally. It is called
the venturi coefficient, velocity of approach not included. The effect of the approach
velocity v., is accounted for by the term 1/~. When Db is less than !D" the
approach velocity and the term f3 can be neglected, since the resulting error is less
than 0.2 percent.
For a well-designed venturi, the constant C, is about 0.98 for pipe diameters
of 2 to 8 in. and about 0.99 for larger sizes.'
Mass and volumetric flow rates. The velocity through the venturi throat v" usually
is not the quantity desired. The flow rates of practical interest are the mass and
volumetric flow rates through the meter. The mass flow rate is calculated by
substituting Vb from Eq. (8.34) in Eq. (4.6) to give
. -
m = v"SbP =
C,Sb
;:;---;;4.
J 2g,(p, - Pb)P (8.35)
vI - f34
where In = mass flow rate
Sb = area of throat
The volumetric flow rate is obtained by dividing the mass flow rate by the density,
or
q= ~= C,Sb J2 g,(P, - Pb) (8.36)
P ~ P
where q is the volumetric flow rate.
Pressure recovery. If the flow through the venturi meter were frictionless, the
pressure of the fluid leaving the meter would be exactly equal to that of the fluid
entering the meter and the presence of the meter in the line would not cause a
permanent loss in pressure. The pressure drop in the upstream cone p, - Pb would
be completely recovered in the downstream cone. Friction cannot be completely
eliminated, of course, and a permanent loss in pressure and a corresponding loss
in power do occur. Because of the small angle of divergence in the recovery cone,
the permanent pressure loss from a venturi meter is relatively small. In a properly
designed meter, the permanent loss is about 10 percent of the venturi differential
p, - Pb, and approximately 90 percent of the differential is recovered.
TRANSPORTATION AND METERING OF FLUIDS 217
Example 8.4. A venturi meter is to be installed in a 100~mm line to measure the flow
of water. The maximum flow rate is expected to be 75 m 3 /h at 15°C. The manometer
used to measure the differential pressure is to be filled with mercury. and water is to
fill the leads above the surfaces of the mercury. The water temperature will be 15°C
throughout. (a) If the maximum manometer reading is to be 1.25 m and the venturi
coefficient is 0.98, what throat diameter, to the nearest mi1limeter, should be specified
for the venturi? (b) What will be the power to operate the meter at full load if the
pressure recovery is 90 percent of the differential pressure?
Solution
(a) Equation (8.36) is used to calculate the throat diameter. The quantities to be
substituted are
q = 75/3600 = 0.0208 m'/s
p = 62.37 x 16.018 = 999 kg/m' (Appendix 14)
C, = 0.98 g = 9.80665 m/s'
From Eq. (2.10), since g, = 1,
p, - Pb = 9.80665 x 1.25 x (13.6 - 1.0) x 999
= 154,300 N/m'
Substituting these values in Eq. (8.36) gives
0.98S b 2 x 154,300
0.0208= ~
y1- P' 999
from which
nD~
Sb = 1.208 X 10- 3
~ 4~
As a first approximation, call J1 - f34 = 1.0. Then
Db = 39.2 mm f3 = 39.2/100 = 0.392
and
~= J1 - 0.392 4
= 0.988
The effect of this term is negligible in view of the desired precision of the final
result. To the nearest millimeter, the throat diameter should be 39 mm.
(b) The permanent loss in pressure is 10 percent of the differential, or
15,430 N/m 2 . Since the maximum volumetric flow rate is 0.0208 m 3 /s, the power
required to operate the venturi at full flow is
p = 0.0208 x 15,430 = 0.32 kW
1000
ORIFICE METER. The venturi meter has certain practical disadvantages for
ordinary plant practice. It is expensive, it occupies considerable space, and its ratio
of throat diameter to pipe diameter cannot be changed. For a given meter and
218 FLUID MECHANICS
definite manometer system, the maximum measurable flow rate is fixed, so if the
flow range is changed, the throat diameter may be too large to give an accurate
reading or too small to accommodate the next maximum flow rate. The orifice
meter meets these objections to the venturi but at the price of a larger power
consumption.
A standard sharp-edged orifice is shown in Fig. 8.19. It consists of an
accurately machined and drilled plate mounted between two flanges with the hole
concentric with the pipe in which it is mounted. (Off-center or segmental openings
are also used on occasion.) The opening in the plate may be beveled on the
downstream side. Pressure taps, one above and one below the orifice plate, are
installed and are connected to a manometer or differential pressure transmitter.
The positions of the taps are arbitrary, and the coefficient of the meter will depend
upon the position of the taps. Three of the recognized methods of placing the taps
are shown in Table 8.2. Flange taps are the most common. The taps shown in
Fig. 8.19 are vena-contracta taps.
The principle of the orifice meter is identical with that of the venturi. The
reduction of the cross section of the flowing stream in passing through the orifice
increases the velocity head at the expense of the pressure head, and the reduction
in pressure between the taps is measured by the manometer. Bernoulli's equation
provides a basis for correlating the increase in velocity head with the decrease in
pressure head.
§~ 0
.-Eo
<,~
o~
E:::
_:0
0 50
~~
0,
~
u.
,
. ~
,r~
FIGURE 8.19
Orifice meter.
TRANSPORTATION AND METERING OF FLUIDS 219
TABLE 8.2
Data on orifice taps
Distance of upstream tap from upstream Distance of downstream tap from
Type of tap face of orifice downstream face
Flange 1 in. (25 mm) 1 in. (25 mm)
Vena contracta 1 pipe diameter (actual inside) 0.3-0.8 pipe diameter, depending on p
Pipe 2! times nominal pipe diameter 8 times nominal pipe diameter
One important complication appears in the orifice meter that is not found
in the venturi. Because of the sharpness of the orifice, the fluid stream separates
from the downstream side of the orifice plate and forms a free-flowing iet in the
downstream fluid. A vena contracta forms, as shown in Fig. 8.19. The iet is not
under the control of solid walls, as is the case in the venturi, and the area of the
iet varies from that of the opening in the orifice to that of the vena contracta. The
area at any given point, e.g., at the downstream tap, is not easily determinable,
and the velocity of the iet at the downstream tap is not easily related to the
diameter of the orifice. Orifice coefficients are more empirical than those for the
venturi, and the quantitative treatment of the orifice meter is modified accordingly.
Extensive and detailed design standards for orifice meters are available in
the literature. 2 They must be followed if the performance of a meter is to be
predicted accurately without calibration. For approximate or preliminary design,
however, it is satisfactory to use an equation similar to Eq. (8.34) as follows:
C, 2g,(p, - Ph)
u, (8.37)
p
where Uo = velocity through the orifice
{3 = ratio of orifice diameter to pipe diameter
P., Pb = pressures at stations a and b in Fig. 8.19
In Eq. (8.37) Co is the orifice coefficient, velocity of approach not included. It
corrects for the contraction of the fluid iet between the orifice and the vena
contracta, for friction, and for a. and ab' Coefficient C, is always determined
experimentally. It varies considerably with changes in {3 and with Reynolds number
at the orifice, N Ro ". This Reynolds number is defined by
_ D,u,p _ 4,n
N Re,o - .- (8.38)
'" nD,,"
where D, is the orifice diameter.
Equation (8.37) is useful for design because Co is almost constant and
independent of {3 provided NRO" is greater than about 30,000. Under these
conditions C, may be taken as 0.61 for both flange taps and vena-contracta taps.
220 FLUID MECHANICS
For process applications, (J should be between 0.20 and 0.75. If (J is less than 0.25,
the term ~ differs negligibly from unity, and Eq. (8.37) becomes
u, = 0.61lg,(p~ - Pb) (8.39)
The mass flow rate /h is given by
(8.40)
Substituting the following equivalent value of SO' the cross-sectional area of
the orifice, in Eq. (8.40) gives
(8.41)
and solving for (J2 gives the following equation, which can be used to calculate
(J directly,
(8.42)
Unless considerable precision is desired, Eq. (8.42) is adequate for orifice design.
A check on the value of the Reynolds number should be made, however, since the
coefficient 0.61 is not accurate when NR,., is less than about 30,000.
It is especially important that enough straight pipe be provided both above
and below the orifice to ensure a flow pattern that is normal and undisturbed by
fittings, valves, or other equipment. Otherwise the velocity distribution will not
be normal, and the orifice coefficient will be affected in an unpredictable manner.
Data are available for the minimum length of straight pipe that should be provided
upstream and downstream from the orifice to ensure normal velocity distribu-
tion. 2b Straightening vanes in the approach line may be used if the required length
of pipe is not available upstream from the orifice.
Pressure recovery. Because of the large friction losses from the eddies generated
by the reexpandingjet below the vena contracta, the pressure recovery in an orifice
meter is poor. The resulting power loss is one disadvantage of the orifice meter.
The fraction of the orifice differential that is permanently lost depends on the
value of (J, and the relationship between the fractional loss and (J is shown in Fig.
8.20. For a value of (J of 0.5, the lost head is about 73 percent of the orifice
differen tial.
The pressure difference measured by pipe taps, where the downstream tap
is eight pipe diameters below the orifice, is really a measurement of permanent
loss rather than of the orifice differential.
TRANSPORTATION AND METERING OF FLUIDS 221
1.0
:§
ee? 0.8 I-- r--..
;; .......
~
~0.6
~
'g ........
~o 0.4
.~
-.0.2
"'" I'
~
00 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
,9
FIGURE 8.20
Overall pressure loss in orifice meters. (After American Society of Mechanical Engineers. 2 )
Example 8.5. An orifice meter equipped with flange taps is to be installed to measure
the flow rate of topped crude to a cracking unit. The oil is flowing at 100'F (37.8'C)
through a 4 in. (lOO-mm) Schedule 40 pipe. An adequate run of straight horizontal
w
pipe is available for the installation. The expected maximum flow rate is 12,000 bbljd
(I bbl = 42 U.S. gal) (79.5 m'fh), measured at 60'F (15.6'C). Mercury is to be used
as a manometer fluid, and glycol (specific gravity 1.11) is to be used in the leads as
sealing liquid. The maximum reading of the meter is to be 30 in. (762 mm). The
viscosity of the oil at 100'F (37.8'C) is 5.45 cP. The specific gravity (60'F/60'F) of
the oil is 0.8927. The ratio of the density of the oil at lOO'F (37.8'C) to that at 60'F
(15.6'C) is 0.984. Calculate (a) the diameter of the orifice and (b) the power loss.
Solution
(0) Use Eq. (8.42). The values to be substituted are as follows:
Density at 60'F:
Pn = 0.8927 x 62.37 = 55.68Ib/ft'
Density at lOO'F:
P = 0.8927 x 62.37 x 0.984 = 54.79Ib/ft'
. 12,000 x 42 x 55.68
m = -::-:--::c=-=-:-:- 43.42Ib/s
24 x 3600 x 7.48
4.026
Do = - - = 0.3355 ft
12
12 ~
(9)
Po - Pb = -30 (13.6 - 1.11)62.37 - = 1948 Ibf /ft 2
Then, from Eq. (8.42),
4 x 43.42
0.3073
2
1t X 0.3355 x 0.61J2 x 32.17 x 1948 x 54.79
222 FLUID MECHANICS
from which fJ = 0.554, and D, = 0.554 x 0.3355 = 0.186 ft. The orifice diameter
is 12 x 0.186 = 2.23 in. (56.6 mm). The viscosity is
I' = 5.45 x 6.72 x 10- 4 = 0.00367Ib/ft-s
The Reynolds number is, by Eq. (8.38),
4 x 43.42
N Re 0 = 81.000
. n x 0.186 x 0.00367
The Reynolds number is sufficiently large to justify the value of 0.61 for Co.
(b) Since fJ = 0.554, the fraction of the differential pressure that is permanently
lost is. by Fig. 8.20, 68 percent of the orifice differential. The maximum power
consumption of the meter is
43.42 x 1948 x 0.68
:-:-::-:---:::-::-::---::-:-::-::=--::-:c: = 1.9 hp (1.4 kW)
0.984 x 62.37 x 0.8927 x 550
FLOW OF COMPRESSIBLE FLUIDS THROUGH VENTURIS AND ORIFICES.
The preceding discussion of fluid meters was concerned only with the flow of fluids
of constant density. When fluids are compressible, similar equations and discharge
coefficients for the various meters may be used. Equation (S.35) for venturi meters
is modified to the form
.
In =
C,YS b
~
J 2g,{Pa - Pb)Pa (S.43)
..,;1- {J'
For orifice meters Eq. (S.40) becomes
I;' = 0.61 YSaJ2g,{P, - Pb)Pa (S.44)
In Eqs. (S.43) and (8.44) Y is a dimensionless expansion factor, and Pa is
the density of the fluid under upstream conditions. For the isentropic flow
of an ideal gas through a venturi, Y can be calculated theoretically by integrating
Eq. (6.25) between stations a and b and combining the result with the definition
of Y implied in Eq. (8.43). The result is
Y= (Pb)'/'{ y(I-{J')[I-{Pb/Pa)'-l/,] }'/2
\Pa (y - 1)(1- Pb/Pa)[1 - {J'{Pb/Paf/] (8.45)
Equation (S.45) shows that Y is a function of Ph/Pa> P, and y. This equation
cannot be used for orifices because of the vena contracta. An empirical equation
in Ph/Pa> P, and y for standard sharp-edged orifices is 2
Y = 1 _ 0.41 + 0.35p4 (1 _ Pb) (8.46)
y Pa
Equations (S.45) and (8.46) must not be used when Ph/Pa is less than about
0.53, which is the critical pressure ratio at which airflow becomes sonic.
V-ELEMENT METERS. In these meters the flow is restricted by a V-shaped
indentation in the side of the pipe or by a metal wedge inserted in the pipe,
TRANSPORTATION AND METERING OF FLUIDS 223
-.~-""--~-"",-.",-.--"--.-,,--~.-.-.,,,,-
--_._"._------.._._"-_._---_.",."-- FIGURE 8.21
V-element meter.
as shown in Fig. 8.21. They are relatiyely expensive devices, but their accuracy is
high, approximately ± 0.5 percent of the measured rate, and they can measure
flow rates of hard-to-handle fluids such as liquids containing solid particles or
undissolved gases or gases carrying drops of condensate. The flow coefficient is
about 0.8; unlike that of orifice meters, it is essentially constant at low flow rates,
down to Reynolds numbers as low as 500.
AREA METERS: ROTAMETERS. In the orifice, nozzle, or venturi, the varia-
tion of flow rate through a constant area generates a variable pressure drop,
which is related to the flow rate. Another class of meters, called area meters,
consists of devices in which the pressure drop is constant, or nearly so, and
the area through which the fluid flows varies with flow rate. The area is
related, through proper calibration, to the flow rate.
The most important area meter is the rotameter, which is shown in Fig.
8.22. It consists essentially of a gradually tapered glass tube mounted vertically in
a frame with the large end up. The fluid flows upward through the tapered tube
and suspends freely a float (which actually does not float but is completely
Float - ~W t ..-- Drag force
1_ - Net gravitational
t force
t
Flow
FIGURE 8.22
Principle of a rotameter.
224 FLUID MECHANICS
submerged in the fluid). The float is the indicating element, and the greater the
flow rate, the higher the float rides in the tube. The entire fluid stream must flow
through the annular space between the float and the tube wall. The tube is marked
in divisions, and the reading of the meter is obtained from the scale reading at
the reading edge of the float, which is taken at the largest cross section of the
float. A calibration curve must be available to convert the observed scale reading
to flow rate. Rotameters can be used for either liquid- or gas-flow measurement.
The bore of a glass rotameter tube is either an accurately formed plain
conical taper or a taper with three beads, or flutes, parallel with the axis of
the tube. The tube shown in Fig. 8.22 is a tapered tube. In the first rotameters,
angled notches in the top of the float made it rotate, but the float does not
rotate in most current designs. For opaque liquids, for high temperatures or
p,essures, or for other conditions where glass is impracticable, metal tubes
are used. Metal tubes are plain tapered. Since in a metal tube the float is
invisible, means must be provided for either indicating or transmitting the
meter reading. This is accomplished by attaching a rod, called an extension,
to the top or bottom of the float and using the extension as an armature.
The extension is enclosed in a fluid-tight tube mounted on one of the fittings.
Since the inside of this tube communicates directly with the interior of the
rotameter, no stuffing box for the extension is needed. The tube is surrounded
by external induction coils. The length of the extension exposed to the coils
varies with the position of the float. This in turn changes the inductance of
the coil, and the variation of the inductance is measured electrically to operate
a control valve or to give a reading on a recorder. Also, a magnetic follower,
mounted outside the extension tube and adjacent to a vertical scale, can be
used as a visual indicator for the top edge of the extension. By such modifications
the rotameter has developed from a simpte visual indicating instrument using only
glass tubes into a versatile recording and controlling device.
Floats may be constructed of metals of various densities from lead to
aluminnm or from glass or plastic. Stainless steel floats are common. Float
shapes and proportions are also varied for different applications.
THEORY AND CALIBRATION OF ROTAMETERS. For a given flow rate, the
equilibrium position of the float in a rotameter is established by a balance
of three forces: (1) the weight of the float, (2) the buoyant force of the fluid
on the float, and (3) the drag force on the float. Force 1 acts downward, and
forces 2 and 3 act upward. For equilibrium
(8.47)
where F D = drag force
g= acceleration of gravity
g, = Newton's-law proportionality factor
vf = volume of float
Pf = density of float
P= density of fluid
TRANSPORTATiON AND METERING OF FLUIDS 225
The quantity vf can be replaced by Inf /Pf' where nIf is the mass of the float, and
Eq. (8.47) becomes
FD 9,=nIf 9(1- :J (8.48)
For a given meter operating On a certain fluid, the right-hand side of Eq.
(8.48) is constant and independent of the flow rate. Therefore F D is also constant,
and when the flow rate increases, the position of the float must change to keep
the drag force constant. The drag force F D can be expressed as a drag coefficient
times the projected area of the float and the velocity head, as in Eq. (7.1), but the
velocity head is based on the maximum velocity past the float, which occurs at
the largest diameter or metering edge of the float. Thus,
U!ax
FD = AfCDP- (8.49)
2g,
If the change in drag coefficient is small, which is usually the case for
large rotameters with low- or moderate-viscosity fluids, the maximum velocity
stays the same with increasing flow rate, and the total flow rate is proportional
to the annular area between the float and the wall:
(8.50)
where D f = float diameter
Dt = tu be diameter
For a linearly tapered tube with a diameter at the bottom about equal
to the float diameter, the area for flow is a quadratic function of the height
of the float h:
(D~ - DJ) = (D f + aW - DJ = 2D f ah + a2 h2 (8.51)
When the clearance between float and tube wall is small, the term a 2 h 2 is relatively
unimportant and the flow is almost a linear function of the height h. Therefore
rotameters tend to have a nearly linear relationship between flow and position of
the float, compared with a calibration curve for an orifice meter, for which the
flow rate is proportional to the square root of the reading. The calibration of a
rotameter, unlike that of an orifice meter, is not sensitive to the velocity distribu-
tion in the approaching stream, and neither long, straight, approaches nor
straightening vanes are necessary. Methods of constructing generalized calibration
curves are available in the literature·
TARGET METERS. In a target meter a sharp-edged disk is set at right angles to
the direction of flow, as shown in Fig. 8.23, and the drag force exerted on the disk
by the fluid is measured. The flow rate is proportional to the square root of this
force and to the fluid density. Target meters are rugged and inexpensive and can
226 FLUID MECHANICS
FIGURE 8.23
Target meter.
be used with a variety of fluids, even viscous liquids and slurries. The bar
mechanism, however, tends to clog if the solids content of the slurry is high.
VORTEX-SHEDDING METERS. In a vortex-shedding meter the "target" is a bluff
body, often trapezoidal in cross section (Fig. 8.24). This body is designed to create,
when flow is turbulent, a "vortex street" in its wake. (See Chap. 7, p. 148.) Sensors
Flow transmitter
Piezoelectric element
Side view
Pipe wall
Vortex shedder
\I
Vortices FIGURE 8.24
Horizontal section Vortex-shedding meter.
TRANSPORTATION AND METERING OF FLUIDS 227
close to the bluff body measure the pressure fluctuations and hence the frequency
of the vortex shedding, from which the volumetric flow rate may be inferred. These
meters are applicable to many types of fluids, including high-temperature gas and
steam. The minimum Reynolds number required for a linear response is fairly
high, so the flow rate of highly viscous liquids cannot be measured by this type
of instrument.
TURBINE METERS. In the turbine meter shown in Fig. 8.25 a bladed rotor is
suspended axially in the flow stream and spins at a rate proportional to the fluid
velocity. In some models the rotor blades are made of a magnetic material that
induces an alternating voltage in the signal pickoff coil. In other designs the rate
of rotation is detected by a radio-frequency pickoff, with a high-frequency carrier
signal modulated by the spinning blades. Turbine meters are exceptionally accur-
ate when used under proper conditions, but they tend to be fragile and their
maintenance costs may be high.
POSITIVE-DISPLACEMENT METERS. Many of the positive-displacement pumps
and blowers described earlier can be made to function as flowmeters, essentially
by running them backward and counting the number of times the moving
compartment is filled and emptied. Frictional losses are supplied by the pressure
drop in the fluid. Although some models indicate a rate of flow, most of these
meters measure the total volume of fluid that has passed through the unit. Nutating
disk, oscillating piston, sliding vane, and other types of positive-displacement
meters are available. They are highly accurate and applicable to clean gases and
liquids, even viscous ones; in fact, the higher the viscosity, the better the perfor-
mance. These meters cannot handle dirty liquids or slurries. They are relatively
expensive and may be costly to operate.
MAGNETIC METERS; ULTRASONIC METERS. These meters are nonintrusive;
that is, there is no obstruction placed in the fluid stream or any reduction of the
flow channel. They create no pressure drop in the fluid. The rate of flow is
measured from outside the tube.
~ To digital receiver
Signal pickoff coil
FIGURE 8.25
Turbine meter.
228 FLUID MECHANICS
In a magnetic meter the flow tube is lined with a non conducting material
with two or more metal electrodes mounted flush with the liner wall. Elec-
tromagnetic coils surrounding the tube generate a uniform magnetic field within
it. By Faraday's law of electromagnetic induction, the motion of a conducting fluid
through the magnetic field induces a voltage that is directly and linearly propor-
tional to the velocity of the flowing fluid. Commercial magnetic flowmeters can
measure the velocity of almost all liquids except hydrocarbons, which have too
small an electrical conductivity. Since the induced voltage depends on velocity
only, changes in the viscosity or density of the liquid have no effect on the meter
reading.
Ultrasonic meters are of two types: transit time and Doppler shift. In the
first type a high-frequency pressure wave is beamed at an angle across the pipe.
The velocity of the wave is found from its time of transit. When the wave is
transmitted in the direction of the flow, its velocity is increased, and vice versa.
From the change in transit time from that in a quiescent fluid the fluid velocity
can be determined. Transit-time meters are applicable to clean fluids only.
Doppler-shift meters, on the other hand, depend on reflections of the pressure
wave from suspended particles or bubbles in the stream, which are assumed to be
moving at the velocity of the stream. The pressure wave is projected into the fluid
at an angle to the direction of flow. The difference between the frequency of the
projected wave and that of the reflected wave is proportional to the fluid velocity.
Though not highly accurate, ultrasonic meters are useful in many types of
service, including measuring the flow rate of corrosive fluids.
CORIOLIS METERS. An object moving in a rotating system experiences a Coriolis
force proportional to its mass and forward velocity and to the angular velocity of
the system. This force is perpendicular to the object's direction of travel and to
the direction of the angular velocity of the system. In a Coriolis meter (Fig. 8.26)
the fluid is passed through two U-shaped curved tubes that are vibrated at their
Brace bar
/
Sensor coil
FIGURE 8.26
Typical Coriolis mass flow sensor geometry.
TRANSPORTATION AND METERING OF FLUIDS 229
natural frequency. This creates an alternating Coriolis force that produces small
elastic deformations in the tubes. From the magnitude of the deformations the
mass flow rate may be calculated.
Coriolis meters are highly accurate and directly measure the mass flow rate.
Used mostly with small pipes, they are costly to install and operate. Consequently
their applications are generally limited to difficult fluids or to situations where
their high accuracy justifies their higher cost.
THERMAL METERS. These meters also measure mass flow rate directly, by
measuring the rise in temperature of the fluid as it passes over a heating element
or the rate of heat transfer to the stream from a heated surface. From these
measurements and the specific heat and thermal conductivity of the fluid the mass
flow rate may be determined. Although generally applicable to various kinds of
fluid, thermal meters are most used to measure gas flow in small lines.
Insertion Meters
In this type of meter the sensing element, which is small compared to the size of
the flow channel, is inserted into the flow stream. A few insertion meters measure
the average flow velocity, but the majority measure the local velocity at one point
only. The positioning of the sensing element is therefore important if the total flow
rate is to be determined. The local measured velocity must bear a constant and
known relationship to the average velocity of the fluid.
The point of measurement may be at the centerline of the channel and the
average velocity found from the ratio of the average to the maximum velocity.
(See Chap. 5.) Alternatively, the sensor may be located at the "critical point" in
the channel where the local velocity equals the average velocity. In either case
precautions must be taken, usually by providing long calming sections upstream
ofthe meter, to ensure that the velocity profile is fully developed and not distorted.
PITOT TUBE. The pitot tube is a device to measure the local velocity along a
streamline. The principle of the device is shown in Fig. 8.27. The opening of the
Direct/on
of flow
A;-------,BO==~
b
-'C--W-Reod/nq
FIGURE 8.27
Principle of pitot tube.
230 FLUID MECHANICS
impact tube a is perpendicular to the flow direction. The opening of the static
tube b is parallel to the direction of flow. The two tubes are connected to the legs
of a manometer or equivalent device for measuring small pressure differences. The
static tube measures the static pressure Po since there is no velocity component
perpendicular to its opening. The impact opening includes a stagnation point B
at which the streamline AB terminates.
The pressure p" measured by the impact tube, is the stagnation pressure of
the fluid given for ideal gases by Eq. (7.8). Then Eq. (7.9) applies, where Po is the
static pressure measured by tube b. Solving Eq. (7.9) for Uo gives
2gip, - Po) ) 1/2
U
o = ( Po{1 + (N~,/4) + [(2 _ y)/24]Nt" + ... } (8.52)
Since the manometer of the pitot tube measures the pressure difference p, - Po,
Eq. (8.52) gives the local velocity of the point where the impact tube is located.
Normally, only the first Mach-number term in the equation is significant.
For incompressible fluids, the Mach-number correction factor is unity, and
Eq. (8.52) becomes simply
2glp, - Po)
IlO = (8.53)
P
The velocity measured by an ideal pitot tube would conform exactly to Eq.
(8.52). Well-designed instruments are in error by not more than 1 percent of theory,
but when precise measurements are to be made, the pitot tube should be calibrated
and an appropriate correction factor applied. This factor is used as a coefficient
before the bracketed terms in Eq. (8.52). It is nearly unity in well-designed pitot
tubes.
The disadvantages of the pitot tube are (1) that most designs do not give
the average velocity directly and (2) that its readings for gases are extremely small.
When it is used for measuring low-pressure gases, some form of multiplying gauge,
like that shown in Fig. 2.5, must also be used.
Example 8.6. Air at 200'F (93.3'C) is rorced through a long, circular flue 36 in.
(914 mm) in diameter. A pitot-tube reading is taken at the center of the flue at a
sufficient distance from flow disturbances to ensure normal velocity distribution. The
pitot reading is 0.54 in. (13.7 mm) H2 0, and the static pressure at the point of
measurement is 15.25 in. (387 mm) H 2 0. The coefficient of the pitot tube is 0.98.
Calculate the flow of air, in cubic feet per minute, measured at 60°F (15.6°C)
and a barometric pressure of 29.92 in. (760 mm) Hg.
Solution
The velocity at the center of the flue, which is that measured by the instrument, is
calculated by Eq. (8.52), using the coefficient 0.98 to correct for imperfections in the
flow pattern caused by the presence of the tube. The necessary quantities are as
follows. The absolute pressure at the instrument is
15.25
p = 29.92 +-- = 31.04 in. Hg
13.6
TRANSPORTATION AND METERING OF FLUIDS 231
The density of the air at flowing conditions is
p ~ 29 x 492 x 31.04 ~ 0.0625 Ib/ft'
359(460 + 200)(29.92)
From th~ manometer reading
0.54 2
p, - Po ~ - 62.37 ~ 2.811b j /ft
12
By Eq. (8.53), the maximum velocity, assuming N~h is negligible. is
2.81
U max = 0.98 2 x 32.174-- ~ 52.7 ft/s
0.0625
This is sufficiently low for the Mach-number correction to be negligible. To obtain
the average velocity from the maximum velocity, Fig. 5.7 is used. The Reynolds
number, based on the maximum velocity, is calculated as follows. From Appendix
8, the viscosity of air at 200°F is 0.022 cP, and
N _ (36/12)(52.7)(0.0625)
R"m" - 0.022 x 0.000672 670,000
The ratio V/u max , from Fig. 5.7, is a little greater than 0.86. Using 0.86 as an estimated
value,
v
~ 0.86 x 52.7 = 45.3 ft/s
The Reynolds number N R, is 670,000 x 0.86 = 576,000, and V/u m " is exactly 0.86 as
estimated. The volumetric flow rate is
36)' " 520 31.04
q ~ 45.3 ( - - - - - 60 = 15,704 ft'/min (7.41 m'/s)
12 4 660 29.92
OTHER INSERTION METERS. Modified forms of magnetic meters, turbine me-
ters, ultrasonic meters, thermal mass flowmeters, and other types are available as
insertion meters. They all have advantages for certain services. Insertion meters
are generally cheaper than full-bore meters and are usually the most cost-effective
method of measuring flow in large pipes.
SYMBOLS
A Area, m 2 or fe; AI' projected area of rotameter float; A p , cross-
sectional area of channels at periphery of pump impeIler
a Coefficient in Eq. (8.51)
CD Drag coefficient, dimensionless
Co Orifice coefficient, velocity of approach not included
Cp Molal specific heat at constant pressure, Jig mol-oC or Btujlb mol-of
Co Venturi coefficient, velocity of approach not included
cp Specific heat at constant pressure, J/g-OC or Btujlb-oF
Co Specific heat at constant volume, J/g-OC or Btujlb-oF
232 FLUID MECHANICS
D Diameter, m or ft; Da , of pipe; Db' of venturi throat; Df' of rota~
meter float; DO' of orifice; D" of rotameter tube
Drag force, N or IbJ
Gravitational acceleration, m/s2 or ft/s2
Newton's-law proportionality factor, 32.174 ft-Ib/lb rs2
Total head, J/kg or ft-IbJ/lb; Ha, at station a; Hb , at station b
Height of rotameter float, mm or in.
Friction loss, J/kg or ft-IbJ/lb; "J" in pump suction line
Molecular weight
In Mass, kg or Ib; In J , of rotameter float
m Mass flow rate, kg/s or Ibis
NPSH Net positive suction head; NPSHR, minimum required value
N M, Mach number, dimensionless
N R, Reynolds number in pipe, DVpl/1
NRe,ma:< Maximum local Reynolds number in pipe, Du m"pl/1
NRe,o Reynolds number at orifice, D,u,pl/1
11 Rotational speed, rls; also constant in Eq. (8.28)
P Power, W or ft-IbJls; p., power supplied to pump, kW or hp;
P J, fluid power in pump; PJ" in ideal pump
p Pressure, atm or Ibf /ft2; Pal at station a; Pa', at station a'; Pb' at
station b; Pb', at station bl; Ps, impact pressure; Pv, vapor pressure;
Po, static pressure; Pi' P2, at stations 1 and 2
q Volumetric flow rate, m 3 /s or ft 3 /s; q" through ideal pump; qo,
compressor capacity, std ft'/min
R Gas-law constant, 8.314 N-m/g mol-K or 1545 ft-IbJ/lb mol-'R
,. Radius, m or ft; r" of impelIer at suction; r" of impeller at discharge
S Cross-sectional area, m 2 or ft2; Sb' of venturi throat; So, of orifice
T Absolute temperature, K or oR; ~, at compressor inlet; Tb, at
compressor dicharge; also torque, J or ft-Ib J
U Local fluid velocity, m/s or ft/s; Um,,, maximum velocity in pipe;
u" at orifice; uo, at impact point of pitot tube; u" peripheral velo-
city at inlet of pump impeller; u2 , at impeller discharge; uo I , U02,
tangential velocity components at stations 1 and 2
v Resultant velocity, absolute, in pump impelIer, m/s or ft/s; y"2,
radial component of velocity V,; V", tangential component; v,,1., of
velocity JI;.; Yu2' of velocity V2 ; Vb at suction; V2 , at disclfarge
Average fluid velocity, m/s or ft/s; v", at station a; v"., at station d;
17" at station b; 17,., at station b'
v Flnid velocity relative to pump impelIer, m/s or ft/s; VI' at snction;
V 2 , at discharge
Volume of rotameter float, m 3 or ft3
Pump work, J/kg or ft-IbJ/lb; Wp" by ideal pump
Expansion factor, flowmeter
Height above datum plane, m or ft; Z" at station a; Zo" at station
d; Zb' at station b; Zb" at station b'
TRANSPORTATION AND METERING OF FLUIDS 233
Greek letters
a Kinetic-energy correction factor; aa, at station a; O:b, at station b;
IXb" at station b'; also angle between absolute and peripheral velo-
cities in pump impeller; 0: 1 , at suction; 0: 2 , at discharge
f3 Vane angle in pump impeller; f3i' at suction; f32, at discharge; also
ratio, diameter of orifice or venturi throat to diameter of pipe
y Ratio of specific heats, cp/c,
!J.H Head developed by pump; !J.H" in frictionless or ideal pump
'1 Overall mechanical efficiency of pump, fan, or blower
J1 Absolute viscosity, cP or Ib/ft-s
P Density, kg/m 3 or Ib/ft'; p" at station a; P., at base conditions;
Pb' at station b; Pf, of rotameter float; Po, of fluid approaching
pitot tube; p, average density (P. + Pb)j2
Q) Angular velocity, rad/s
PROBLEMS
8.1. Make a preliminary estimate of the approximate pipe size required for the following
services: (a) a transcontinental pipeline to handle 10,000 std m3 jh of natural gas at an
average pressure of 3 atm abs and an average temperature of 20°C; (b) feeding a slurry
of p-nitrophenol crystals in water to a continuous centrifugal separator at the rate
of 1 t (metric tonlfh of solids. The slurry carries 45 percent solids by weight. For
p-nitrophenol p ~ 1475 kg/m'.
8.2. It is proposed to pump 10,000 kg/h of toluene at 114°C and 1.1 atm abs pressure
from the reboiler of a distillation tower to a second distillation unit without cooling the
toluene before it enters the pump. If the friction loss in the line between the reboiler
and pump is 7 kN/m2 and the density of toluene is 866 kg/m" how far above the pump
must the liquid level in the reboiler be maintained to give a net positive suction head
of 2.5 m?
8.3. Calculate the power required to drive the pump in Prob. 8.2 if the pump is to elevate
the toluene 10 rn, the pressure in the second unit is atmospheric, and the friction loss in
the discharge line is 35 kN/m2. The velocity in the pump discharge line is 2 m/s.
8.4. Air entering at 70°F and atmospheric pressure is to be compressed to 4000 lb [/in. 2
gauge in a reciprocating compressor at the rate of 125 std fe Imin. How many
stages should be used? What is the theoretical shaft work per standard cubic foot for
frictionless adiabatic compression? What is the brake horsepower if the efficiency of
each stage is 85 percent? For air y = 1.40.
8.5. What is the discharge temperature of the air from the first stage in Prob. 8.4?
8.6. After the installation of the orifice meter of Example 8.5, the manometer reading at
a definite constant flow rate is 45 mm. Calculate the flow through the line in barrels per
day measured at 60°F.
8.7. Natural gas having a specific gravity relative to air of 0.60 and a viscosity of 0.011 cP
is flowing through a 6-in. Schedule 40 pipe in which is installed a standard sharp-
edged orifice equipped with flange taps. The gas is at 100°F and 20 Ibf /in. 2 abs at
the upstream tap. The manometer reading is 46.3 in. of water at 60°F. The ratio
of specific heats for natural gas is 1.30. The diameter of the orifice is 2.00 in. Calculate
234 FLUID MECHANICS
the rate of flow of gas through the line in cubic feet per minute based on a
pressure of 14.4lb r /in. 2 and a temperature of 60°F.
8.8. A horizontal venturi meter having a throat diameter of 20 mm is set in a 75-mm-ID
pipeline. Water at 15°C is flowing through the line. A manometer containing mer-
cury under water measures the pressure differential over the instrument. When the
manometer reading is 500 mm, what is the flow rate in gallons per minute? If
12 percent of the differential is permanently lost, what is the power consumption of
the meter?
8.9. A V-element meter is used to measure the flow of a 15 percent slurry of ion-exchange
beads in water. The slurry is carried in a 3-in. Schedule 40 pipe, and the expected
range offiows is 30 to 150 gal/min. The particle density is 1250 kgfm', and the average
particle size is 250ltm. (a) What is the expected pressure drop at maximum flow if
the V-element or wedge extends across two-thirds of the pipe diameter? (b) If the
differential pressure transmitter has an accuracy of 0.05 Ib[/in. 2, what is the accuracy
of the flow measurement at maximum and minimum flows?
8.10. The mass flow rate of flue gas in a 4-by-6-ft. rectangular duct is to be measured using
a thermal meter. The normal gas composition is 76 percent N 2 • 3 percent O 2 • 14 per-
cent CO 2 , and 7 percent H 2 0, and the average velocity is 40 ftls at duct conditions
of 300°F and 1 atm. (a) If a 5000-W heating element is centrally mounted in the duct,
what is the temperature rise after the heated gas has mixed with the rest of the gas?
What is the accuracy of the flow measurement if the upstream and downstream
temperatures can be determined to ±0.02°F? (b) If the meter is calibrated for the
normal gas composition, what is the effect of a change to 12 percent CO 2 ?
REFERENCES
1. Dwyer, J. J.: Chem. £lIg. Prog., 70(10):71 (1974).
2. Fluid Meters: Their Theory alld Applications, 6th ed., American Society of Mechanical Engineers,
New York, 1971, pp. 58-65.
3. Ginesi, D., and G. Grebe: Chem. Ellg., 94(9):102 (1987).
4. Haden, R. c.: Chem. Ellg. Prog., 70(3):69 (1974).
5. Jorissen, A. L.: Trails. ASME, 74:905 (1952).
6. Martin, J. J.: Chem. Ellg. Prog., 45:338 (1949).
7. Neerken, R. F.: Chem. Eng., 94(12):76 (1987).
8. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hil~ New York, 1984, p. 6-6.
CHAPTER
9
AGITATION
AND MIXING
OF LIQUIDS
Many processing operations depend for their success on the effective agita-
tion and mixing of fluids. Though often confused, agitation and mixing are not
synonymous. Agitation refers to the induced motion of a material in a specified
way, usually in a circulatory pattern inside some sort of container. Mixing is the
random distribution, into and through one another, of two or more initially
separate phases. A single homogeneous material, such as a tankful of cold water,
can be agitated, but it cannot be mixed until some other material (such as a
quantity of hot water or some powdered solid) is added to it.
The term mixing is applied to a variety of operations, differing widely in the
degree of homogeneity of the "mixed" material. Consider, in one case, two gases
that are brought together and thoroughly blended and, in a second case, sand,
gravel, cement, and water tumbled in a rotating drum for a long time. In both
cases the final product is said to be mixed. Yet the products are obviously not
equally homogeneous. Samples of the mixed gases--even very small samples-all
have the same composition. Small samples of the mixed concrete, on the other
hand, differ widely in composition.
This chapter deals with the agitation of liquids of low to moderate viscosity
and the mixing of liquids, liquid-gas dispersions, and liquid-solid suspensions.
Agitation and mixing of highly viscous liquids, pastes, and dry solid powders are
discussed in Chap. 28.
236 FLUID MECHANICS
AGITATION OF LIQUIDS
PURPOSES OF AGITATION. Liquids are agitated for a number of purposes,
depending on the objectives of the processing step. These purposes include
1. Suspending solid particles
2. Blending miscible liquids, e.g., methyl alcohol and water
3. Dispersing a gas through the liquid in the form of small bubbles
4. Dispersing a second liquid, immiscible with the first, to form an emulsion or
suspension of fine drops
5. Promoting heat transfer between the liquid and a coil or jacket
Often one agitator serves several purposes at the same time, as in the catalytic
hydrogenation of a liquid. In a hydrogenation vessel the hydrogen gas is dispersed
through the liquid in which solid particles of catalyst are suspended, with the heat
of reaction simultaneously removed by a cooling coil and jacket.
AGITATION EQUIPMENT. Liquids are most often agitated in some kind of tank
or vessel, usually cylindrical in form and with a vertical axis. The top of the vessel
may be open to the air; more usually it is closed. The proportions of the tank
vary widely, depending on the nature of the agitation problem. A standardized
design such as that shown in Fig. 9.1, however, is applicable in many situations.
The tank bottom is rounded, not fiat, to eliminate sharp corners or regions into
--Molor
LiqUid surface
Dip leg
Thermowell
Jackel S ~Shafl
Baffle ~}=i¥~~J~+U-Jj.-lmpeller
FIGURE 9.1
Typical agitation process vessel.
AGITATION AND MIXING OF LIQUIDS 237
which fluid currents would not penetrate. The liquid depth is approximately equal
to the diameter of the tank. An impeller is mounted on an overhung shaft, i.e., a
shaft supported from above. The shaft is driven by a motor, sometimes directly
connected to the shaft but more often connected to it through a speed-reducing
gearbox. Accessories such as inlet and outlet lines, coils, jackets, and wells for
thermometers or other temperature-measuring devices are usually included.
The impeller creates a flow pattern in system, causing the liquid to circulate
through the vessel and return eventually to the impeller. Flow patterns in agitated
vessels are discussed in detail later in this chapter.
IMPELLERS. Impeller agitators are divided into two classes: those that generate
currents parallel with the axis of the impeller shaft and those that generate currents
in a tangential or radial direction. The first are called axial:flolV impellers, the
second radial:flolV impellers.
The three main types of impellers are propellers, paddles, and turbines. Each
type includes many variations and subtypes, which will not be considered here.
Other special impellers are also useful in certain situations, but the three main
types solve perhaps 95 percent of all liquid-agitation problems.
Propellers. A propeller is an axial-flow, high-speed impeller for liquids of low
viscosity. Small propellers turn at full motor speed, either 1150 or 1750 r/min;
larger ones turn at 400 to 800 r/min. The flow currents leaving the impeller
continue through the liquid in a given direction until deflected by the floor or wall
of the vesseL The highly turbulent swirling column of liquid leaving the impeller
entrains stagnant liquid as it moves along, probably considerably more than an
equivalent column from a stationary nozzle would. The propeller blades vigorously
cut or shear the liquid. Because of the persistence of the flow currents, propeller
agitators are effective in very large vessels.
A revolving propeller traces out a helix in the fluid, and if there were no slip
between liquid and propeller, one full revolution would move the liquid long-
itudinally a fixed distance depending on the angle of inclination of the propeller
blades. The ratio of this distance to the propeller diameter is known as the pitch
of the propeller. A propeller with a pitch of 1.0 is said to have square pitch.
A typical propeller is illustrated in Fig. 9.20. Standard three-bladed marine
propellers with square pitch are most common; four-bladed, toothed, and other
designs are employed for special purposes.
Propellers rarely exceed 18 in. in diameter regardless of the size of the vesseL
In a deep tank two or more propellers may be mounted on the same shaft, usually
directing the liquid in the same direction. Sometimes two propellers work in
opposite directions, or in "push-pull," to create a zone of especially high turbulence
between them.
Paddles. For the simpler problems an effective agitator consists of a flat paddle
turning on a vertical shaft. Two-bladed and four-bladed paddles are common.
Sometimes the blades are pitched; more often they are verticaL Paddles turn at
238 FLUID MECHANICS
(a) (b) (c) (d) (e)
FIGURE 9.2
Mixing impellers: (a) three-blade marine propeller; (b) open straight-blade turbine; (c) bladed disk
turbine; (d) vertical curved-blade turbine; (e) pitched-blade turbine,
slow to moderate speeds in the center of a vessel; they push the liquid radially
and tangentially with almost no vertical motion at the impel\er unless the blades
are pitched. The currents they generate travel outward to the vessel wall and then
either upward or downward. In deep tanks several paddles are mounted one above
the other on the same shaft. In some designs the blades conform to the shape of
a dished or hemispherical vessel so that they scrape the surface or pass over it
with close clearance. A paddle of this kind is known as an anchor agitator. Anchors
are useful for preventing deposits on a heat-transfer surface, as in ajacketed process
vessel, but they are poor mixers. They nearly always operate in conjunction with
a higher speed paddle or other agitator, usually turning in the opposite direction.
Industrial paddle agitators turn at speeds between 20 and 150 r/min. The
total length of a paddle impeller is typically 50 to 80 percent of the inside diameter
of the vessel. The width of the blade is one-sixth to one-tenth its length. At very
slow speeds a paddle gives mild agitation in an unbaffled vessel; at higher speeds
baffles become necessary. Otherwise the liquid is swirled around the vessel at high
speed but with little mixing.
Turbines. Some of the many designs of turbine are shown in Fig. 9.2b, c, d, and
e. Most of them resemble multibladed paddle agitators with short blades, turning
at high speeds on a shaft mounted centrally in the vessel. The blades may be
straight or curved, pitched or vertical. The diameter of the impeller is smaller than
with paddles, ranging from 30 to 50 percent of the diameter of the vessel.
Turbines are effective over a very wide range of viscosities. In low-viscosity
liquids turbines generate strong currents that persist throughout the vessel, seeking
out and destroying stagnant pockets. Near the impeller is a zone of rapid currents,
high turbulence, and intense shear. The principal currents are radial and tangential.
The tangential components induce vortexing and swirling, which must be stopped
by baffles or by a diffuser ring if the impeller is to be most effective.
AGITATION AND MIXING OF LIQUIDS 239
FLOW PATIERNS IN AGITATED VESSELS. The type of flow in an agitated vessel
depends on the type of impeller; the characteristics of the fluid; and the size and
proportions ofthe tank, baffles, and agitator. The velocity of the fluid at any point
in the tank has three components, and the overall flow pattern in the tank depends
on the variations in these three velocity components from point to point. The first
velocity component is radial and acts in a direction perpendicular to the shaft of
the impeller. The second component is longitudinal and acts in a direction parallel
with the shaft. The third component is tangential, or rotational, and acts in a
direction tangent to a circular path around the shaft. In the usual case of a vertical
shaft, the radial and tangential components are in a horizontal plane, and the
longitudinal component is vertical. The radial and longitudinal components are
useful and provide the flow necessary for the mixing action. When the shaft is
vertical and centrally located in the tank, the tangential component is generally
disadvantageous. The tangential flow follows a circular path around the shaft and
creates a vortex in the liquid, as shown in Fig. 9.3 for a flat-bladed turbine. Exactly
the same flow pattern would be observed with a pitched-blade turbine or a
propeller. The swirling perpetuates stratification at the various levels without
accomplishing longitudinal flow between levels. If solid particles are present,
circulatory currents tend to throw the particles to the outside by centrifugal force,
from where they move downward and to the center of the tank at the bottom.
Instead of mixing, its reverse, concentration, occurs. Since, in circulatory flow, the
liquid flows with the direction of motion of the impeller blades, the relative velocity
between the blades and the liquid is reduced, and the power that can be absorbed
by the liquid is limited. In an un baffled vessel circulatory flow is induced by all
types of impellers, whether axial flow or radial flow. If the swirling is strong, the
flow pattern in the tank is virtually the same regardless of the design of the impeller.
At high impeller speeds the vortex may be so deep that it reaches the impeller,
Liquid
Level
Side Bottom
FIGURE 9.3
Swirling flow pattern with a radial-flow turbine in an unbaffled vessel. (After Ofdslme. JS)
240 FLUID MECHANICS
and gas from above the liquid is drawn down into the charge. Generally this is
undesirable.
Prevention of swirling. Circulatory flow and swirling can be prevented by any of
three methods. In small tanks, the impeller can be mounted off center, as shown
in Fig. 9.4. The shaft is moved away from the centerline of the tank, then tilted
in a plane perpendicular to the direction of the move. In larger tanks, the agitator
may be mounted in the side of the tank, with the shaft in a horizontal plane but
at an angle with a radius.
In large tanks with vertical agitators, the preferable method of reducing
swirling is to install baffles, which impede rotational flow without interfering with
radial or longitudinal flow. A simple and effective baffling is attained by installing
vertical strips perpendicular to the wall of the tank. Baffles of this type are shown
in Fig. 9.1. Except in very large tanks, four baffles are sufficient to prevent swirling
and vortex formation. Even one or two baffles, if more cannot be used, have a
strong effect on the circulation patterns. For turbines, the width of the baffle need
be no more than one-twelfth of the vessel diameter; for propellers, no more than
one-eighteenth the tank diameter is needed. 3 With side-entering, inclined, or
off-center propellers baffles are not needed.
Once the swirling is stopped, the specific flow pattern in the vessel depends
on the type of impeller. Propeller agitators usually drive the liquid down to the
bottom of the tank, where the stream spreads radially in all directions toward the
wall, flows upward along the wall, and returns to the suction of the propeller from
the top. Propellers are used when strong vertical currents are desired, e.g., when
heavy solid particles are to be kept in suspension. They are not ordinarily used
when the viscosity of the liquid is greater than about 50 P. Pitched-blade turbines
with 45° down-thrusting blades are also used to provide strong axial flow for
suspension of solids.
~.// FIGURE 9.4
Flow pattern with off-center propeller. (After Bissell
et al.3)
AGITATION AND MIXING OF LIQUIDS 241
Paddle agitators and flat-blade turbines give good radial flow in the plane
of the impeller, with the flow dividing at the wall, to form two separate circulation
patterns, as shown later in Fig. 9.11. One portion flows downward along the wall
and back to the center of the impeller from below, and the other flows upward
toward the surface and back to the impeller from above. In an unbaffled tank,
there are strong tangential flows and vortex formations at moderate stirrer speeds.
With baffles present, the vertical flows are increased, and there is more rapid
mixing of the liquid.
In a vertical cylindrical tank, the depth of the liquid should be equal to or
somewhat greater than the diameter of the tank. If greater depth is desired, two
or more impellers are mounted on the same shaft, and each impeller acts as a
separate mixer. Two circulation currents are generated for each impeller, as shown
in Fig. 9.5. The bottom impeller, either of the turbine or the propeller type, is
mounted about one impeller diameter above the bottom of the tank.
Draft tubes. The return flow to an impeller of any type approaches the impeller
from all directions, because it is not under the control of solid surfaces. The flow
to and from a propeller, for example, is essentially similar to the flow of air to
and from a fan operating in a room. In most applications of impeller mixers this
is not a limitation, but when the direction and velocity of flow to the suction of
the impeller are to be controlled, draft tubes are used, as shown in Fig. 9.6. These
devices may be useful when high shear at the impeller itself is desired, as in the
manufacture of certain emulsions, or where solid particles that tend to float on
the surface of the liquid in the tank are to be dispersed in the liquid. Draft tubes
for propellers are mounted around the impeller, and those for turbines are
Baffle Baffle
c
c FIGURE 9.S
Multiple turbines in tall tank.
242 FLUID MECHANICS
Boffle Baffle
c\,r
~lll -
Droft
tube
( \ if \
!{
1
-Boffle -
~~ uu
(0) (b)
FIGURE 9.6
Draft tubes, baffled tank: (a) turbine; (b) propeller. (Afrer Bissell et al. 3 )
mounted immediately above the impeller. This is shown in Fig. 9.6. Draft tubes
add to the fluid friction in the system, and for a given power input, they reduce
the rate of flow, so they are not used unless they are required.
"STANDARD" TURBINE DESIGN. The designer of an agitated vessel has an
unusually large number of choices to make as to type and location of the impeller,
the proportions of the vessel, the number and proportions of the baffles, and so
forth'? Each of these decisions affects the circulation rate of the liquid, the velocity
patterns, and the power consumed. As a starting point for design in ordinary
agitation problems, a turbine agitator of the type shown in Fig. 9.7 is commonly
~ J'+-
-.-L
w
g-D~T \<-L -1
-.,-
I
1
11 ·1
FIGURE 9.7
Measurements of turbine. (After Rushtoll et al. 42 )
AGITATION AND MIXING OF LIQUIDS 243
used. Typical proportions are
D. 1 H J 1
-= 1 -=~
D, 3 D, D, 12
E 1 W 1 L
-=-
D, 3 D. 5 Do 4
The number of baffles is usually 4; the number of impeller blades ranges
from 4 to 16 but is generally 6 or 8. Special situations may, of course, dictate
different proportions from those listed above; it may be advantageous, for example,
to place the agitator higher or lower in the tank, or a much deeper tank may be
needed to achieve the desired process result. The listed "standard" proportions,
nonetheless, are widely accepted and are the basis of many published correlations
of agitator performance.
CIRCULATION, VELOCITIES, AND POWER
CONSUMPTION IN AGITATED VESSELS
For a processing vessel to be effective, regardless of the nature of the agitation
problem, the volume of fluid circulated by the impeller must be sufficient to sweep
out the entire vessel in a reasonable time. Also, the velocity of the stream leaving
the impeller must be sufficient to carry the currents to the remotest parts of the
tank. In mixing and dispersion operations the circulation rate is not the only
factor, or even the most important one; turbulence in the moving stream often
governs the effectiveness of the operation. Turbulence results from properly
directed currents and large velocity gradients in the liquid. Circulation and
turbulence generation both consume energy; the relations between power input
and the design parameters of agitated vessels are discussed later. Some agitation
problems, as will be shown, call for large flows or high average velocities, while
others require high local turbulence or power dissipation. Although both flow rate
and power dissipation increase with stirrer speed, selection of the type and size of
the impeller influences the relative values of flow rate and power dissipation. In
general, large impellers moving at medium speed are used to promote flow, and
smaller impellers operating at high speed are used where internal turbulence is
required.
FLOW NUMBER. A turbine or propeller agitator is, in essence, a pump impeIler
operating without a casing and with undirected inlet and output flows. The
governing relations for turbines are similar to those for centrifugal pumps
discussed in Chap. 8."· Consider the flat-bladed turbine impeIler shown in Fig. 9.8.
The nomenclature is the same as in Fig. 8.11: U 2 is the velocity of the blade
tips; V;,2 and V;2 are the actual tangential and radial velocities of the liquid leaving
the blade tips, respectively; and V~ is the total liquid velocity at the same point.
244 FLUID MECHANICS
~'
2
r-o
FIGURE 9,8
Velocity vectors at tip of turbine impeller blade.
Assume that the tangential liquid velocity is some fraction k of the blade-tip
velocity, or
(9.1)
since Uz = nDan. The volnmetric flow rate through the impeller, from Eq, (8.14),
is
q = V;2Ap (9.2)
Here Ap is taken to be the area of the cylinder swept out by the tips of the
impeller blades, or
(9.3)
where Da = impeller diameter
W = width of blades
From the geometry of Fig, 9.8
V;2 = (U2 - V~z) tan fJ, (9.4)
Substituting for V~2 from Eq, (9.1) gives
V;2 = nDan(1 - k) tan fJ, (9.5)
Figure 9.9 shows the velocity pattern of liquid flowing radially from the
blade of a standard turbine. The velocities shown are those at the tip of the blade.
The radial velocity is a maximum in the plane of the middle of the blade and is
much smaller at the upper and lower edges, As discussed later, the velocity pattern
changes with distance from the impeller tip. The volumetric flow rate q is the total
flow leaving the impeller, as measured at the tip of the blades. From Eqs, (9.2) to
(9.4) this volumetric flow rate is therefore
q = Kn2D;nW(1 - k) tan fJ, (9.6)
AGITATION AND MIXING OF LIQUIDS 245
Impetler
FIGURE 9.9
Typical velocity profile of flow from a straight-blade turbine, showing definition of shear rate. (After
Oldslrue. JS ,,)
where K is a constant that allows for the fact that the radial velocity is not
actually constant over the width of the blade. For geometrically similar impellers
W is proportional to Da' and K, k, and fJ'z are approximately constant. Hence
q IX nD; (9.7)
The ratio of these two quantities is called the flow number N Q' which is
defined by
N =...!L
Q - llD'
(9.8)
a
Equations (9.6) to (9.8) imply that N Q is constant for each type of impeller.
For a standard flat-blade turbine, in a baffled vessel, N Q may be taken as 1.3. 21
This gives the discharge flow from the tips of the impeller and not the total flow
produced. The high-velocity stream of liquid leaving the tip of the impeller entrains
some of the slowly moving bulk liquid, which slows down the jet but increases
the total flow rate. For flat-blade turbines, the total flow, estimated from the
average circulation time for particles or dissolved tracers,21 was shown to be
qr = O.92IlD~ (~:) (9.9)
For the typical ratio D,/Da = 3, qr is 2.76IlD~, or 2.1 times the value at
the impeller (N Q = 1.3). Equation (9.9) should be used only for D,/Da ratios
between 2 and 4.
For axial-flow impellers such as pitched-blade turbines or marine propellers,
q is the discharge rate in a vertical direction as measured immediately below the
impeller. The flow number N Q may be considered constant. For the design of
baffled agitated vessels the following values are recommended:
For marine propellers 1s• (square pitch) N Q = 0.5
For a four-blade 45° turbine 1s, (W/Da = !) N Q = 0.87
246 FLUID MECHANICS
VELOCITY PATTERNS AND VELOCITY GRADIENTS. More details of the flow
patterns, the local velocities, and the total flow produced by an impeller have been
obtained by use of small velocity probes 21 or by photographic measurements of
tracer particles. 13 Some of Cutter's results 13 for a 4-in. flat-blade turbine in an
11.5-in. tank are shown in Fig. 9.10. As the fluid leaves the impeller blades, the
radial component of the fluid velocity V; at the centerline of the impeller is about
0.6 times the tip speed u2 • The radial velocity decreases with vertical distance from
the centerline, but, as shown in Fig. 9.9, the jet extends beyond the edge of the
blades because of entrainment, and integration gives a total flow of 0.75qB' where
qB is the flow that would exist if all the fluid were moving at velocity U2 across
the sides of the cylinder swept out by the blades. The entrained flow at this point
is therefore 25 percent of the flow coming directly from the blades.
As the jet travels away from the impeller, it slows down because of the
increased area for flow and because more liquid is entrained. Along the centerline
of the impeller, the velocity drops more or less linearly with radial distance, and
the product V;r is nearly constant, as was shown by other studies 2I The total
volumetric flow increases with radius to about 1.2q. because of further entrainment
and ther: drops near the vessel wall because the flow has started to divide into
the upward and downward circulation loops. The maximum flow of 1.2qB
compared to the radial discharge velocity of 0.6u 2 indicates a total flow twice
the direct impeller discharge, in agreement with the factor of 2.1 calculated using
Eq. (9.9).
The velocity gradients in an agitated vessel vary widely from one point to
another in the fluid. The gradient equals t.Vjt.y, as illustrated in Fig. 9.9. It is
quite large near the edge of the jet leaving the impeller, since the velocity is high
and the jet is relatively narrow. Based on the vertical velocity profiles at the blade
tip, the velocity gradient at this point is approximately O.9ujO.75W, where 0.9u is
~1.4
<t
oc
~ 1.2
.J I \
"-
oc 1 L
01.0
>-
>-
u
d .8 :/ q/qe 1\
>
;;j .6
r
"
<t
oc .4
[~ V V U2
//
w "-
> Tip of--i
~.J impeller I I'---
w
oc
.2
; \ FIGURE 9.10
I
2 3 4 5 6 Radial velocity V~/U2 and volumetric flow rate q/qs
RADIAL DISTANCE, INCHES in a turbine-agitated vessel. (After Cutter. I3)
AGITATION AND MIXING OF LIQUIDS 247
the resultant of the radial and tangential velocities, and 0.75W is half the width
ofthejet leaving the impeller. Since u = nllD, and W = D,/5 for a standard turbine,
this corresponds to a velocity gradient of 1911, which can serve as an estimate of
the maximum shear rate in the region near a turbine impeller. As the jet travels
away from the impeller, it slows down, and the velocity gradient at the edge of
the jet diminishes. Behind the turbine blades there are intense vortices where the
local shear rate may be as high as 50n.'"
Figure 9.11 shows the fluid currents observed with a six-bladed turbine, 6 in.
in diameter, turning at 200 r/min in a 12-in. vessel containing cold water. 32 The
plane of observation passes through the axis of the impeller shaft and immediately
in front of a radial baffle. Fluid leaves the impeller in a radial direction, separates
into longitudinal streams flowing upward or downward over the baffle, flows
inward toward the impeller shaft, and ultimately returns to the impeller intake.
At the bottom of the vessel, immediately under the shaft, the fluid moves in a
swirling motion; elsewhere the currents are primarily radial or longitudinal.
The numbers in Fig. 9.11 indicate the scalar magnitude of the fluid velocity
at various points as fractions of the velocity of the tip of the impeller blades. Under
the conditions used, the tip velocity is 4.8 ft/s (1.46 m/s). The velocity in the jet
quickly drops from the tip velocity to about 0.4 times the tip velocity near the
vessel wall. Velocities at other locations in the vessel are of the order of 0.25 times
the tip velocity, although there are two toroidal regions of almost stagnant fluid,
one above and one below the impeller, in which the velocity is only 0.10 to 0.15
times the tip velocity.
Shaft
O~OI5:::-it
02 015
04
1025 ro2
I .,,/
1
I:i\
04 0.3\
025
11/025
Vessel 04
wall . 1 ~
'02
_
\
05
FIGURE 9.11
Velocity patterns in turbine agitator. (After Morrison
et al. 32 )
248 FLUID MECHANICS
Increasing the impeller speed increases the tip velocity and the circulation
rate. It does not, however, increase the fluid velocity at a given location in the
same proportion, for a fast-moving jet entrains much more material from the bulk
of the liquid than a slower-moving jet does, and the jet velocity drops very quickly
with increasing distance from the impeller.
POWER CONSUMPTION. An important consideration in the design of an agitated
vessel is the power required to drive the impeller. When the flow in the tank is
turbulent, the power requirement can be estimated from the product of the flow
q produced by the impeller and the kinetic energy Ek per unit volume of the fluid.
These are
and
Ek = p(V~)2
2g,
Velocity V~ is slightly smaller than the tip speed U2' If the ratio V~/U2 is
denoted by a, V~ = annD, and the power requirement is
(9.10)
In dimensionless form,
Pg a'n'
--'----N (9.11)
n3D~p - 2 Q
The left-hand side of Eq. (9.11) is called the power number N p, defined by
Pg,
(9.12)
Np =""'---D'
n aP
Fora standard six-bladed turbine, N Q = 1.3, and if a is taken as 0.9, N p = 5.2.
This is in good agreement with observation, as shown later.
POWER CORRELATION. To estimate the power required to rotate a given
impeller at a given speed, empirical correlations of power (or power number) with
the other variables of the system are needed. The form of such correlations can
be found by dimensional analysis, given the important measurements of the tank
and impeller, the distance of the impeller from the tank floor, the liquid depth,
and the dimensions of the baflles if they are used. The number and arrangement
of the baflles and the number of blades in the impeller must also be fixed. The
variables that enter the analysis are the important measurements of tank and
AGITATION AND MIXING OF LIQUIDS 249
impeller, the viscosity I' and the density p of the liquid, the speed n, and because
Newton's law applies, the dimensional constant g,. Also, unless provision is made
to eliminate swirling, a vortex will appear at the surface of the liquid. Some of the
liquid must be lifted above the average, or unagitated, level of the liquid surface,
and this lift must overcome the force of gravity. Accordingly, the acceleration of
gravity 9 must be considered as a factor in the analysis.
The various linear measurements can all be converted to dimensionless
ratios, called shape factors, by dividing each of them by one of their number which
is arbitrarily chosen as a basis. The diameter of the impeller D a and that of the
tank D, are suitable choices for this base measurement, and the shape factors are
calculated by dividing each of the remaining measurements by the magnitude of
Da or D,. Let the shape factors, so defined, be denoted by S"S2,S" ... , S,. The
inipeller diameter Dais then also taken as the measure of the size of the equipment
and used as a variable in the analysis, just as the diameter of the pipe was in the
dimensional analysis of friction in pipes. Two mixers of the same geometrical
proportions throughout but of different sizes will have identical shape factors but
will differ in the magnitude of Da. Devices meeting this requirement are said to
be geometrically similar or to possess geometrical similarity.
When the shape factors are temporarily ignored and the liquid is assumed
newtonian, the power P is a function of the remaining variables, or
P = 1/I(n, Da , g" 1', g, p) (9.13)
Application of the method of dimensional analysis gives the result'2
~= 1/1 (nD~p, n2Da) (9.14)
n'D;p . I' 9
By taking account of the shape factors, Eq. (9.14) can be written
Pg, (nD~p n2Da ) (9.15)
-,-,- = 1/1 - - , - - , Si' S2" .. , Sn
n DaP I' 9
The first dimensionless group in Eq. (9.14), PgJn'D;p, is the power number
N p • The second, nD~p/J1" is a Reynolds number N Ro ; the third, n2Da/g, is the
Froude number N F ,. Equation (9.15) can therefore be written
(9.16)
SIGNIFICANCE OF DIMENSIONLESS GROUPS. 23 The three dimensionless
groups in Eq. (9.14) may be given simple interpretations. Consider the group
nD~p/J1,. Since the impeller tip speed U 2 equals nDan,
N = nD;;p = (nDalDaP oc u2 DaP (9.17)
Ro
I' I' I'
and this group is proportional to a Reynolds number calculated from the diameter
and peripheral speed of the impeller. This is the reason for the name of the group.
250 FLUID MECHANICS
The power number N p is analogous to a friction factor or a drag coefficient.
It is proportional to the ratio of the drag force acting on a unit area of the impeller
and the inertial stress, that is, the flow of momentum associated with the bulk
motion of the fluid.
The Froude number N F • is a measure of the ratio of the inertial stress to the
gravitational force per unit area acting on the fluid. It appears in fluid-dynamic
situations where there is significant wave motion on a liquid surface. It is especially
important in ship design.
Since the individual stresses are arbitrarily defined and vary strongly from
point to point in the container, their local numerical values are not significant.
The magnitudes of the dimensionless groups for the entire system, however, are
significant to the extent that they provide correlating magnitudes that yield much
simpler empirical equations than those based on Eq. (9.13). The following equa-
tions for the power number are examples of such correlations.
POWER CORRELATIONS FOR SPECIFIC IMPELLERS. The various shape
factors in Eq. (9.16) depend on the type and arrangement of the equipment. The
necessary measurements for a typical turbine-agitated vessel are shown in Fig. 9.7;
the corresponding shape factors for this mixer are S, = D.ID" S2 = EID" S, =
LID., S. = WID., S5 = JID" and S. = HID,. In addition, the number of baffles
and the number of impeller blades must be specified. If a propeller is used, the pitch
and number of blades are important.
Baffled tanks. Typical plots of N p versus N R, for baffled tanks fitted with centrally
located flat-bladed turbines with six blades are shown in Fig. 9.12. Curve A applies
Curve S, s, 50 s. s, S,
A 0.33 0.33 0.25 0.2 0.1 1.0
B 0.33 0.33 0.25 0.125 0.1 1.0
C 0.33 0.33 0.25 0.2 0.1 1.0
0 0.3: 0.33 J.25 0.25 1.
,,, A
"
10
I
c
10
1 10 0' 10' J'
FIGURE 9.12
Power number N p versus N Re for six-blade turbines. (After CJwdacekll; OldsJzue. 35 ) With the dashed
portion of curve D, the value of N p read from the figure must be multiplied by N~r'
AGITATION AND MIXING OF LIQUIDS 251
A'" PitC~ OS;O O~~ ~~O
B ~: 1 0.30 0.30 .0
10
10 - Four baffles S, ~ 0.1
B
A
0.1
1 10 10' 10' 10' 10'
FIGURE 9.13
Power number Np versus N Rc for threcMblade propellers. (After Oldshue. 35 ) With the dashed portion
of curve B, the value of N p read from thc figure must be multiplied by N';r.
to vertical blades with S4 = 0.2; curve B applies to a similar impeller with narrower
blades (S4 = 0.125). Curve C is for a pitched-bladed turbine, otherwise similar to
that corresponding to curve A. Curve D is for an unbaffled tank.
Curve A in Fig. 9.13 applies to a three-bladed propeller centrally mounted
in a baffled tank. Propellers and pitched-blade turbines draw considerably less
power than a turbine with vertical blades.
Uobaffled tanks. At low Reynolds numbers, below about 300, the power number
curves for baffled and unbaffled tanks are identical. At higher Reynolds numbers
the curves diverge, as shown by the dashed portions of curve D in Fig. 9.12 and
curve B in Fig. 9.13. In this region of Reynolds numbers, generally avoided in
practice in un baffled tanks, a vortex forms and the Froude number has an effect.
Equation (9.16) is then modified to
(9.18)
The exponent m in Eq. (9.18) is, for a given set of shape factors, empirically
related to the Reynolds number by the equation 42
(9.19)
where a and b are constants. The magnitudes of a and b for the curves of Figs.
9.12 and 9.13 are given in Table 9.1. When the dashed curves in Fig. 9.12 or 9.13
252 FLUID MECHANICS
TABLE 9.1
Constants a and b of Eq. (9.19)
Figure Line a b
9.12 D 1.0 40.0
9.13 B 1.7 18.0
are used, the power number N p read from the ordinate scale must be corrected
by multiplying it by N~, (see Example 9.2).
EFFECT OF SYSTEM GEOMETRY. The effects on N p of the shape factors
S" S" ... , S, in Eq. (9.16) are sometimes small and sometiInes very large. Some-
times two or more of the factors are interrelated; i.e., the effect of changing S"
say, may depend on the magnitude of S2 or S3. With a flat-bladed turbine
operating at high Reynolds numbers in a baffled tank, the effects of changing the
system geometry may be summarized as follows':
1. Decreasing S " the ratio of impeller diameter to tank diameter, increases N p
when the baffles are few and narrow and decreases N p when the baffles are
many and wide. Thus shape factors S, and S5 are interrelated. With four baffles
and S 5 equal to iz, as is common in industrial practice, changing S, has almost
no effect on N p.
2. The effect of changing S2, the clearance, depends on the design of the turbine.
Increasing S2 increases N p for a disk turbine of the type shown in Fig. 9.7. For
a pitChed-blade turbine increasing S210wers N p considerably, as shown in Table
9.2; for an open straight-blade turbine it lowers N p slightly.
3. With a straight-blade open turbine the effect of changing S4, the ratio of blade
width to impeller diameter, depends on the number of blades. For a six-blade
turbine N p increases directly with S.; for a four-bladed turbine N p increases
with Sl·25. With pitChed-blade turbines the effect of blade width on power
consumption is much smaller than with straight-blade turbines (see Table 9.2).
TABLE 9.2
Effect of blade width and clearance
on power consnmption of six-blade
45° turbinesll ,39
WID., (S,) Clearance. S2 KT
0.3 0.33 2.0
0.2 0.33 1.63
0.2 0.25 1-.74
0.2 0.17 1.91
AGITATION AND MIXING OF LIQUIDS 253
4. Two straight-blade turbines on the same shaft draw about 1.9 times as much
power as one turbine alone, provided the spacing between the two impelIers is
at least equal to the impelIer diameter. Two closely spaced turbines may draw
as much as 2.4 times as much power as a single turbine.
5. The shape of the tank has relatively little effect on N p. The power consumed
in a horizontal cylindrical vessel, whether baffled or unbaffled, or in a baffled
vertical tank with a square cross section is the same as in a vertical cylindrical
tank. In an unbaffled square tank the power number is about 0.75 times that
in a baffled cylindrical vessel. Circulation patterns, of course, are strongly
affected by tank shape, even though power consumption is not.
CALCULATION OF POWER CONSUMPTION. The power delivered to the liquid
is computed from Eq. (9.12) after a relationship for N p is specified. Rearranging
Eq. (9.12) gives
3
p= N p n D'p
u
(9.20)
g,
At low Reynolds numbers, the lines of N p versus N R, for both baffled and
unbaffled tanks coincide, and the slope of the line on logarithmic coordinates
is -1. Therefore
(9.21)
This leads to
2
p = K L n D3"
ur-
(9.22)
g,
The flow is laminar in this range, and density is no longer a factor. Equations
(9.21) and (9.22) can be used when N R, is less than 10.
In baffled tanks at Reynolds numbers larger than about 10,000, the power
number is independent of the Reynolds number, and viscosity is not a factor. In
this range the flow is fully turbulent and Eq. (9.16) becomes
(9.23)
from which
3
p= K T n D'p
u
(9.24)
g,
Magnitudes of the constants KT and KL for various types of impeIlers and tanks
are shown in Table 9.3.
254 FLUID MECHANICS
TABLE 9.3
Values of constants KL and KT in Eqs. (9.21) and
(9.23) for baffied tanks having four baffies at tank
wall, with width equal to 10 percent of the tank
diameter
Type of impeller KL KT
Propeller, three blades
Pitch 1.0'4.0 41 0.32
Pitch 1.5 35 55 0.87
Turbine
Six-blade disk 3s (S3 == 0.25, S4 == 0.2) 65 5.75
Six curved blades40 (S4 == 0.2) 70 4.80
Six pitched blades 39 (45°, S4 = 0.2) 1.63
Four pitched blades 35 (45°, S4 == 0.2) 44.5 1.27
Flat paddle, two blades40 (S4 = 0.2) 36.5 1.70
Anchor 35 300 0.35
Example 9.1. A flat-blade turbine with six blades is installed centrally in a vertical
tank. The tank is 6 ft (1.83 m) in diameter; the turbine is 2 ft (0.61 m) in diameter and
is positioned 2 ft (0.61 m) from the bottom of the tank. The turbine blades are 5 in.
(127 mm) wide. The tank is filled to a depth of 6 ft (1.83 m) with a solution of
50 percent caustic soda, at 150°F (65.6°C), which has a viscosity of 12 cP and a density
of 93.5lb/ft' (1498 kg/m'). The turbine is operated at 90 r/min. The tank is baffled.
What power will be required to operate the mixer?
Solution
Curve A in Fig. 9.12 applies under the conditions of this problem. The Reynolds
number is calculated. The quantities for substitution are, in consistent units,
n = ~g = 1.5 rls
p. ~ 12 x 6.72 x 10- 4 ~ 8.06 X 10-' lb/ft-s
p ~ 93.5 lb/ft' 9 ~ 32.17 ft/s2
Then
N ~ D;np ~ 22 x 1.5 x 93.5 ~ 69600
., p. 8.06xlQ' '
From curve A (Fig. 9.12), for N., ~ 69,600, Np = 5.8, and from Eq. (9.20)
5.8 x 93.5 x 1.5' x 2'
p=------
32.17
The power requirement is 1821/550 = 3.31 hp (2.47 kW).
Example 9.2. What would the power requirement be in the vessel described in
Example 9.1 if the tank were unbaffled?
AGITATION AND MIXING OF LIQUIDS 255
Solution
Curve D of Fig. 9.12 now applies. Since the dashed portion of the curve must be
used, the Froude number is a factor; its effect is calculated as follows:
n2 D 1.5 2 x 2
Ne - --" - 0.14
.,- 9 - 32.17
From Table 9.1~ the constants a and b for substitution into Eq. (9.19) are a = 1.0 and
b ~ 40.0. From Eq. (9.19),
1.0 -log 10 69,600
m ~ ~ -0.096
40.0
The power number read from Fig. 9.12, curve D, for N Ro ~ 69,600, is 1.07; the
corrected value of N p is 1.07 X 0.14- 0 . 096 ~ 1.29. Thus, from Eq. (9.20),
1.29 x 93.5 x 1.5 3 x 25
p~-------
32.17
The power requirement is 406/550 ~ 0.74 hp (0.55 kW).
It is usually not good practice to operate an unbaffied tank under these conditions
of agitation.
Example 9.3. The mixer of Example 9.1 is to be used to mix a rubber-latex compound
having a viscosity of 1200 P and a density of 70 Ib/ft 3 (1120 kg/m 3 ). What power will
be required?
Solution
The Reynolds number is now
22 X 1.5 x 70
N ~ ~ 5.2
Ro 1200 x 0.0672
This is well within the range of laminar flow. From Table 9.3, KL = 65; from Eq.
(9.21), Np ~ 65/5.2 ~ 12.5, and
12.5 x 70 x 1.5 3 X 25
P~ ~ 2938 ft-Ib I/s
32.17
The power required is 2938/550 ~ 5.34 hp (3.99 kW). This power requirement is
independent of whether or not the tank is baffled. There is no reason for baffles in
a mixer operated at low Reynolds numbers, as vortex formation does not occur under
such conditions.
Note that a 1O,OOO-fold increase in viscosity increases the power by only about
60 percent over that required by the baffled tank operating on the low-viscosity liquid.
POWER CONSUMPTION IN NON-NEWTONIAN LIQUIDS. In correlating power
data for non-newtonian liquids the power number Pg,!n 3 D:,p is defined in the
same way as for newtonian fluids. The Reynolds number is not easily defined,
since the apparent viscosity of the fluid varies with the shear rate (velocity gradient)
256 FLUID MECHANICS
and the shear rate changes considerably from one point to another in the vessel.
Successful correlations have been developed, however, with a Reynolds number
defined as in Eq. (9.17) using an average apparent viscosity /la calculated from an
average shear rate (du/dy)". The Reynolds number is then
nD;p
NRe,.n=-- (9.25)
/la
For a power-law fluid, as shown by Eq. (3.7), the average apparent viscosity
can be related to the average shear rate by the equation
,(du)"'-l (9.26)
/la = K -
dy av
Substitution in Eq. (9.25) gives
nD;p
N - -----'''--c-c- (9,27)
Ro." - K'(du/dy);;-l
For a straight-blade turbine in' pseudoplastic liquids it has been shown
that the average shear rate in the vessel is directly related to the impeller
speed, For a number of pseudoplastic liquids a satisfactory, though approximate,
relation is 8 ,17,27
dU) = 11n (9.28)
( dy av
Note that the average shear rate of 11n is slightly more than half the maximum
estimated value of 1911 (see p, 247). The volumetric average shear rate for the tank
is probably much less than lln, but the effective value for power consumption
depends heavily on shear rates in the region of the stirrer.
Combining Eqs. (9.27) and (9.28) and rearranging gives
_ n -n'Da p
2 2
N (9.29)
Re,n - l1n' 1 K'
Figure 9.14 shows the power number-Reynolds number correlation for
a six-blade turbine impeller in pseudoplastic fluids. The dashed curve is taken
from Fig, 9.12 and applies to newtonian fluids, for which N Ro = nD;p//l. The
solid curve is for pseudoplastic liquids, for which N Ro •n is given by Eqs, (9.25) and
(9.29). At Reynolds numbers below 10 and above 100 the results with pseudoplastic
liquids are the same as with newtonian liquids. In the intermediate range of
Reynolds numbers between 10 and 100, pseudoplastic liquids consume less power
than newtonian fluids. The transition from laminar to turbulent flow in pseudo-
plastic liquids is delayed until the Reynolds number reaches about 40, instead of
10 as in newtonian liquids.
The flow patterns in an agitated pseudoplastic liquid differ considerably
from those in a newtonian liquid. Near the impeller the velocity gradients
are large, and the apparent viscosity of a pseudoplastic is low. As the liquid
AGITATION AND MIXING OF LIQUIDS 257
50
Non-New/onion
- - - - New/onion
, 4 Baffles,-
r- "- -
":--...
I
2 10 iD2
urrwr 10
,
NRe=nDa 2~/ft or NRe,n""nDo2 p / PO
FIGURE 9.14
Power correlation for a six~blade turbine in non~newtonian liquidS.
travels away from the impeller, the velocity gradient decreases, and the apparent
viscosity of the liquid rises. The liquid velocity drops rapidly, decreasing the
velocity gradients further and increasing the apparent viscosity still more. Even
when there is high turbulence near the impeller, therefore, the bulk of the liquid
may be moving in slow laminar flow and consuming relatively little power. The
toroidal rings of stagnant liquid indicated in Fig. 9.11 are very strongly marked
when the agitated liquid is a pseudoplastic.
BLENDING AND MIXING
Mixing is a much more difficult operation to study and describe than agitation.
The patterns of flow of fluid velocity in an agitated vessel are complex but
reasonably definite and reproducible. The power consumption is readily measured.
The results of mixing studies, on the other hand, are seldom highly reproducible
and depend in large measure on how mixing is defined by the particular exper-
imenter. Often the criterion for good mixing is visual, as in the use of interference
phenomena to follow the blending of gases in a duct 30 or the color change of an
acid-base indicator to determine liquid-blending times. 16 •33 Other criteria that
have been used include the rate of decay of concentration or temperature 25
fluctuations, the variation in the analyses of small samples taken at random from
various parts of the mix, the rate of transfer of a solute from one liquid phase to
another, and in solid-liquid mixtures, the visually observed uniformity of the
suspension.
BLENDING OF MISCIBLE LIQUIDS. Miscible liquids are blended in relatively
small process vessels by propellers or turbine impellers, usually centrally mounted,
and in large storage and waste-treatment tanks by side-entering propellers or jet
mixers. In a process vessel all the liquid is usually well agitated and blending is
258 FLUID MECHANICS
fairly rapid. In a large storage tank the agitator may be idle much of the time and
be turned on only to blend the stratified layers of liquid that were formed as the
tank was being filled. Stratified blending is often very slow.
BLENDING IN PROCESS VESSELS. The impeller in a process vessel produces a
high-velocity stream and the liquid is well mixed in the region close to the impelIer
because of the intense turbulence. As the stream slows down while entraining other
liquid· and flowing along the wall, there is some radial mixing, as large eddies
break down to smaller ones, but there is probably little mixing in the direction of
flow. The fluid completes a circulation loop and returns to the eye of the impeller,
where vigorous mixing again occurs. Calculations based on this model show that
essentially complete mixing (99 percent) should be achieved if the contents of the
tank are circulated about five times. The mixing time can then be predicted from
the correlations for total flow produced by various impellers. For a standard
six-blade turbine
q = O.92nD; (~:) (9.30)
5V nD;H I
tT ""- = 5 (9.31)
q 4 0.92IlD~D,
or
D,)2(D,)
H = const = 4.3 (9.32)
/lt T ( D,
For a given tank and impeller or geometrically similar systems the mixing
time is predicted to vary inversely with the stirrer speed, which is confirmed by
experimental studies. 13 •31 Figure 9.15 shows the results for several systems plotted
as IltT versus N Ro ' For a turbine with Da/D, = t and D,/H = 1 the value of IltT is
36 for NR , > 10', compared with a predicted value of 39.
The mixing times are appreciably greater when the Reynolds numbers
are in the range 10 to 1000, even though the power consumption is not much
different than for the turbulent range. As shown in Fig. 9.15, the mixing time
using batHed turbines varies with about the - 1.5 power of the stirrer speed
in this region and then increases more steeply as the Reynolds number is
reduced still further. The data in Fig. 9.15 are for certain ratios of impeller
size to tank size. A general correlation given by Norwood and Metzner 33 is
shown in Fig. 9.16. Their mixing-time factor can be rearranged to show how
it differs from the prediction for the turbulent regime, Eq. (9.32):
= tT(nD~)2/'gl/6D~/2 = nt (Da)2(D,)'/2(_g_)'/6 (9.33)
J. ,
H'/2D'/2 T D, H n2D,
The Froude number in Eq. (9.33) implies some vortex effect, which may be present
at low Reynolds numbers, but it is doubtful whether this term should be included
AGITATION AND MIXING OF LIQUIDS 259
10
,
Pr6pelle~,
1
"p,~pelle~,
DalD t 3
" " "
.,
• , =!
DID 6
h
< 3 " Turbine, " 1',
""--
Turbine 1
DalDr ~ 3
'"f- 10
0
baffled
t)
"
~ 11------ 0, , --
w
r-- "
-
:--_Helix
'i="
'" 10,
;;;
~
-r- --- ~
" , 1', -- -
'" --- - ~
10
1 10 10
, 10'
REYNOLDS NUMBER, NRe '" nD;pl/J.
FIGURE 9,15
Mixing times in agitated vessels. Dashed lines are for unbaffied tanks; solid line is for an unbaffled tank.
for a baffled tank at high Reynolds numbers, When NR , > 10', j, is almost constant
at a value of 5. For Do/D, = t, D,/H = 1, and ignoring the Froude number, litT
is about 45, somewhat greater than predicted from Eq, (9.32),
Other types of impeIIers may be preferred for mixing certain liquids.
A helical ribbon agitator gives much shorter mixing times for the same power
input with very viscous liquids31 but is slower than the turbine with thin
"
"" ~
I'-..... :-....
I
10 10'
FIGURE 9,16
Correlation of blending times for miscible liquids in a turbine-agitated baffled vessel. (After Norwood
and Metzner. 33 )
260 FLUID MECHANICS
liquids. The mixing times for propellers seem high by comparison with turbines,
but of course the power consumption is more than an order of magnitude lower
at the same stirrer speed. The propeller data in Fig. 9.15 were taken from a general
correlation of Fox and Gex,'6 whose mixing-time function differs from both Eqs.
(9.32) and (9.33):
;; = tT(nZ~;:;~1/6 ntT (~:r(~r(n2~,r (9.34)
Their data were for D,/D, of 0.07 to 0.18; the extrapolation to D,/D, = i for Fig.
9.15 is somewhat uncertain.
In a pseudo plastic liquid, blending times at Reynolds numbers below
about 1000 are much longer than in newtonian liquids under the same impeller
conditions. 17 •31 In the regions of low shear, far from the impeller, the apparent
viscosity of the pseudoplastic liquid is greater than it is near the impeller. In these
remote regions turbulent eddies decay rapidly, and zones of almost stagnant liquid
are often formed. Both effects lead to poor mixing and long blending times. At
high Reynolds numbers there is little difference in the mixing characteristics of
newtonian and pseudoplastic liquidS.
When gas bubbles, liquid drops, or solid particles are dispersed in a
liquid, the blending time for the continuous phase is increased, even if the
comparison is made at the same specific power input. 15 The effect increases
with viscosity, and for viscous liquids the blending time can be up to twice
the normal value when the gas holdup is only 10 percent.
Example 9.4. An agitated vessel 6 ft (1.83 m) in diameter contains a six-blade
straight-blade turbine 2 ft (0.61 m) in diameter, set one impeller diameter above the
vessel floor, and rotating at 80 r/min. It is proposed to use this vessel for neutralizing
a dilute aqueous solution of NaOH at 70°F with a stoichiometrically equivalent
quantity of concentrated nitric acid (HN0 3 ). The final depth of liquid in the vessel
is to be 6 ft (1.83 m). Assuming that all the acid is added to the vessel at one time,
how long will it take for the neutralization to be complete?
Sollltion
Figure 9.15 is used. The quantities needed are
D, = 6 ft D, = 2 ft E = 2ft
80
n= - = 1.333 rls
60
Density of liquid: p = 62.3 lb/ft' (Appendix 14)
Viscosity of liquid: !' = 6.6 X 10- 4 lb/ft-s (Appendix 14)
The Reynolds number is
nD;p 1.333 x 2' x 62.3
N R, = - - = 503,000
!' 6.60 x 10 4
AGITATION AND MIXING OF LIQUIDS 261
From Fig. 9.15, for N., = 503,000, nIT = 36. Thus
36
IT =--=27s
1.333
STRATIFIED BLENDING IN STORAGE TANKS. For effective blending in a
large tank a side-entering propeller must be oriented precisely with regard
to both its angle with the horizontal (for top-to-bottom circulation) and, in
the horizontal plane, the angle it makes with the tangent to the tank wall
at the point of entry. For optimum results this angle has been found to be
between 80° and 83°.35 The time required for stratified blending depends on
the circulation rate but more importantly on the rate of erosion of the interface
between the stratified liquid layers. No general correlations are available for
stratified blending.
JET MIXERS. Circulation in large vessels may also be induced by one or more
jets of liquid. Sometimes jets are set in clusters at several locations in the tank.
The stream from a single jet maintains its identity for a considerable distance, as
seen in Fig. 9.17, which shows the behavior of a circular liquid jet issuing from a
nozzle and flowing at high velocity into a stagnant pool of the same liquid. The
velocity in the jet issuing from the nozzle is uniform and constant. It remains so
in a core, the area of which decreases with distance from the nozzle. The core is
surrounded by an expanding turbulent jet, in which the radial velocity decreases
with distance from the centerline of the jet. The shrinking core disappears at a
distance from the nozzle of 4.3D j, where Dj is the diameter of the nozzle. The
turbulent jet maintains its integrity well beyond the point at which the core has
disappeared, but its velocity steadily decreases. The radial decrease in velocity in
the jet is accompanied by a pressure increase in accordance with the Bernoulli
principle. Fluid flows into the jet and is absorbed, accelerated, and blended
Nominol boundary of the jet
Jet diameter
Dj
Turbulent
. - - . ---;ei - -
Constant velocity
/+" _ _co_,_e_ x _ _4c.::.3:...:cDJ'-jI _ _ _ _ _4 ••- ' - - . . . ,
e
<:from here on qe = (4.foj -/}Qo
AI e, 10101 flow=3qo
FIGURE 9.17
Flow of a submerged circular jet. (After Ruslltoll and Oldshue. 43 )
262 FLUID MECHANICS
into the augmented jet. This process is called entrainment. An equation applying
over distances larger than 4.3D
j is
q, = (4.:D j - 1) qo (9.35)
where q, = volume of liquid entrained per unit time at distance X from nozzle
qo = volume of liquid leaving jet nozzle per unit time
In addition to entrainment, strong shear stresses exist at the boundary
between the jet and the surrounding liquid. These stresses tear off eddies at
the boundary and generate considerable turbulence, which also contributes to the
mixing action.
A large flow of liquid alone does not achieve satisfactory mixing. Enough
time and space must be provided for the stream to blend thoroughly into the mass
of fluid by the mechanism of entrainment.
Correlations are available for the mixing time with a side-entering jet
in relatively small process vessels.!6
MOTIONLESS MIXERS. Gases or nonviscous liquids can often be satisfactorily
blended by passing them together through a length of open pipe or a pipe
containing orifice plates or segmented baflles. Under appropriate conditions the
pipe length may be as short as 5 to 10 pipe diameters, but 50 to 100 pipe diameters
is recommended. 2 4-
More difficult mixing tasks are accomplished by motionless mixers, commer-
cial devices in which stationary elements successively divide and recombine
portions of the fluid stream"'!O In the mixer shown in Fig. 9.18 each short helical
element divides the stream in two, gives it a 180 twist, and delivers it to the
0
succeeding element, which is set at 90 to the trailing edge of the first element.
0
The second element divides the already divided stream and twists it 180 in the
0
opposite direction. For n elements, then, there are 2n divisions and recombinations,
or over 1 million in a 20-element mixer. The pressure drop for laminar flow is
typically 4 times as large as in the same length of empty pipe. For turbulent flow
the pressure drop may be 10 to 100 times greater because of the kinetic energy
losses after each change in direction. In other commercial designs the stream is
divided 4 or more times by each element. Mixing, even of highly viscous materials,
is excellent after 6 to 20 elements. Static mixers are used for liquid blending,
gas and liquid dispersion, chemical reactions, and heat transfer. They are especially
effective in mixing low-viscosity fluids with viscous liquids or pastes.
MIXER SELECTION. There is not necessarily any direct relation between power
consumed and amount or degree of mixing. When a low-viscosity liquid is swirled
about in an unbaflled vessel, the particles may follow parallel circular paths almost
indefinitely and mix almost not at all. Little of the energy supplied is used for
mixing. If baflles are added, mixing becomes rapid; a larger fraction of the energy
is used for mixing and relatively less for circulation.
AGITATION AND MIXING OF LIQUIDS 263
i
Elements
Housing
Jacket
(optional)
FIGURE 9.18
Motionless mixer. (Chemineer, Inc.)
When the mlXlng time is critical, the best mIxer is the one that mixes
in the required time with the smallest amount of power. In many cases a
short mixing time is desirable, but not essential, and the mixing time is a
compromise arrived at by considering the energy cost for mixing and the
capital cost of the mixer. For mixing reagents in a feed tank or blending
product from different batches in a storage tank, a relatively small size mixer
might be used, even if several minutes are required for complete mixing.
264 FLUID MECHANICS
SUSPENSION OF SOLID PARTICLES
Particles of solids are suspended in liquids for many purposes, perhaps to produce
a homogeneous mixture for feeding to a processing unit, to dissolve the solids, to
catalyze a chemical reaction, or to promote growth of a crystalline product from
a supersaturated solution. Suspension of solids in an agitated vessel is somewhat
like fluidization of solids with liquids, as discussed in Chap. 7, in that the particles
are separated and kept in motion by the fluid flowing past them. However, the
fluid flow pattern created by the agitator has regions of horizontal flow as well
upward and downward flow, and to keep the solids in suspension in a tank
generally requires much higher average fluid velocities than would be needed to
fluidize the solids in a vertical column.
When solids are suspended in an agitated tank, there are several ways
to define the condition of suspension. Different processes require different degrees
of suspension, and it is important to use the appropriate definition and correlation
in a design or scaleup problem. The degrees of suspension are given below in the
order of increasing uniformity of suspension and increasing power input.
Nearly complete suspension with filleting. Most of the solid is suspended in
the liquid, with a few percent in stationary fillets of solid at the outside periphery
of the bottom or at other places in the tank. Having a small amount of solids not
in motion may be permissible in a feed tank to a processing unit, as long as the
fillets do not grow and the solids do not cake. 34 For crystallization or a chemical
reaction, the presence of fillets would be undesirable.
Complete particle motion. All the particles are either suspended or are moving
along the tank bottom. Particles moving on the bottom have a much lower
mass-transfer coefficient than suspended particles, which might affect the perfor-
mance of the unit.!9
Complete suspension or complete olf-bottom suspension. All the particles are
suspended off the tank bottom or do not stay on the bottom more than 1
or 2 s. When this condition is just reached, there will generally be concentra-
tion gradients in the suspension and there may be a region of clear liquid
near the top of the tank. The gradient in solid concentration will have little
effect on the performance of the unit as a dissolver or a chemical reactor,
and the mass-transfer coefficient will not increase very much with further increases
in stirrer speed.
Uniform suspension. At stirrer speeds considerably above those needed for com-
plete suspension, there is no longer any clear liquid near the top of the tank, and
the suspension appears uniform. However, there may still be vertical concentration
gradients, particularly if the solids have a wide size distribution, and care is needed
in getting a representative sample from the tank.
AGITATION AND MIXING OF LIQUIDS 265
Complete suspension of solids would be satisfactory for most purposes,
and the correlations developed to predict conditions for suspension have generally
used this criterion. Some of these correlations are discussed here along with
guidelines for scaleup. Keep in mind that these correlations give the minimum
agitation condition for suspension, and that requirements for dispersion of a gas
or good heat transfer to a coil or jacket may indicate higher power inputs for'
some cases.
The ease with which solids are suspended in a liquid depends on the
physical properties of the particles and the liquid and on the circulation patterns
in the tank. The terminal velocity of free-settling particles can be calculated using
the drag coefficient curve (Fig. 7.3), as shown previously. It is more difficult to
suspend particles that have a high settling velocity, but there is no simple
correlation between this velocity and a characteristic velocity in the tank, such as
the tip speed of the impeller. The limiting factor is the liquid velocity near the
bottom, where the flow is almost horizontal, and to get complete suspension, the
velocity in this region is generally many times the settling velocity. Since it is
difficult to measure or predict the velocity distribution, investigators have generally
measured the critical stirrer speed for complete suspension and developed empir-
ical equations for different agitators.
Zwietering's4 7 correlation is based on data for five types of impellers
in six tanks from 6 ·in. to 2 ft in diameter. The critical stirrer speed is given
by the dimensionless equation
!!.p)O.45
n~~·85 = Svo.lD~·2
(9 P B O. 13
(9.36)
where n, = critical stirrer speed
Do = agitator diameter
S= shape factor
v= kinematic viscosity
D p = average particle size
g = gravitational acceleration
!!.p = density difference
p = liquid density
B = 100 x weight of solid/weight of liquid
Typical values of S are given in Table 9.4. Note that for the same impeller
size ratio and clearance ratio, the critical speed is about the same for the standard
turbine and the flat paddle, and S for the propeller is slightly lower. However,
because of the large differences in the power number N p, the turbine takes about
twice as much power as the paddle and 15 to 20 times as much power as the
propeller to get complete suspension of solids. With the turbine in normal position,
slightly less than half of the flow produced by the impeller goes down at the wall
(see Fig. 9.11), and the average velocity along the bottom of the tank is relatively
low. The total flow produced by a propeller of the same size is not quite as great,
but it is all directed downward, giving higher velocities and higher shear rates
266 FLUID MECHANICS
TABLE 9.4
Shape factor S in Eq. (9.36) for critical
stirrer speed
Impellcr type DtlDa DrlE S
Six-blade turbine 2 4 4.1
Do/W ~ 5 3 4 7.5
Np = 6.2 4 4 11.5
Two-blade paddle 2 4 4.8
Do/W ~ 4 3 4 8
Np = 2.5 4 4 12.5
Three-blade propeller 3 4 6.5
N p = 0.5 4 4 8.5
4 2.5 9.5
near the bottom. If the only purpose of the stirrer is to suspend solids, a propeller
or other axial-flow impeller such as pitched-blade turbine would be chosen rather
than a radial-flow impeller. However, a standard turbine may be needed for good
gas dispersion or to get higher shear, and then correlations such as Eq. (9.36) could
be used in checking conditions needed for solid suspension.
The positive exponent for viscosity in Eq. (9.36) is questionable, since the
terminal velocity is lower in more viscous fluids, and viscosity was not varied
independently in Zwietering's tests. Other studies'·46 have shown a slight decrease
in the critical speed as the viscosity was increased. A theoretical equation for stirrer
speed by Wichterle46 predicts that the exponents for viscosity, particle size, and
density difference all change with particle size and may even change sign. His
model is based on comparing the particle terminal velocity and the product of
particle size and shear rate near the bottom of the tank. The model does not yet
account for the effect of solids concentration, and it requires independent measure-
ment of shear rates, but it should be useful in interpreting existing data and in
scaleup.
In discussing scaleup procedures, all workers report that lower stirrer speeds
are needed to suspend solids in larger tanks if geometrical similarity is maintained.
However, small differences in the exponents for D" in the equation for /l, can lead
to large differences in power requirements, since the power per unit vol ume PIV
varies with /l3 D;;. Some data for suspending sand in water using 45" pitched-
blade turbines (downward pumping) are given in Figure 9.19. Some of the points
shown are direct observations and others were calculated from the authors'
correlations for Dp = 200 I'm, D"ID, = t and EID, = ±. The solid lines show
the range of tank sizes used, and the dashed lines are extrapolations. The large
differences in PIV may be due partly to different criteria for complete suspension
or slight differences in geometry.
In the study of Rao et al.,39 /l, varied with D;;O.85, in agreement with
Zwietering, and this indicates PIV varies with D;;O.55 [the exponent equals
3 x (-0.85) + 2]. A six-blade turbine was used with WID" = 0.30, and suspension
AGlTATION AND MIXING OF LIQUIDS 267
20
0;
~
0>
0
0
0 10
"-
~
I"-
""0:
~
5
E
~
l"!
"0 I\..,
>
,.,.. Ln-- -- ' ,~
'"
~
...
-- -
~
0.
c
~
,
...
~
0
a. 'V Connolly and Winter12
O Rao 39
C- o Chudacekl1
C- D.. Buurman 6
0.5 ill ~
0.6 1.0 5 10 50
Tank diameter Of' ft
FIGURE 9.19
Power required for complete suspension of solids in agitated tanks using pitched~blade turbines.
was judged complete if particles did not stay stationary on the flat bottom for
more than 2 s. Chudacek l l used narrower turbines (WID, = 0.20) but the same
suspension criterion, and his correlation indicates that PIV increases somewhat
with D,. However, he also reported conditions for other criteria, and for 98 percent
complete suspension, PIV was 30 to 50 percent less than the values in Fig. 9.19,
and PjV decreased slightly as D, increased. The tests of Buurman et al" were
made in dished-bottom tanks using four-blade stirrers with WID, = 0.25. An
ultrasound Doppler meter was used to measure velocity near the bottom, and a
transition in the velocity marked complete suspension. These tests showed that 11,
varied with D;;2/3 and PIV was independent of D,. The more negative exponents
for D, in other studies were attributed to incorrect scaling of the stirrer blade
thickness.
The strongest dependence of PIV on D, and the highest power consumptions
were reported by Connolly and Winter,12 who recommended applying constant
torque per unit volume, which is equivalent to making nD, constant and PIV
proportional to D;; 1. However, they did not measure the minimum stirrer speed
but only showed that their criterion led to nearly uniform suspension in each tank.
The power required for uniform suspension is greater than for complete off-bottom
suspension, and the ratio is greater for small tank sizes. Buurman found nearly
homogeneous suspension at 1.211, in a 14-ft tank, but 1.9n, was needed for
comparable uniformity in the 1.5-ft tank.
268 FLUID MECHANICS
If satisfactory suspension is obtained in a small tank, whether judged by
visual observations, particle velocities, or mass transfer rates, the safe scaleup rule
is to keep geometrical similarity and constant power per unit volume. The ratios
Da/D, = t and E/D, = i are often recommended, though some prefer Da/D, = 0.4
for solids suspension. The critical speed can be reduced by decreasing the clearance,
but it may be hard to start the stirrer if it is in a layer of solids very near the bottom.
Example 9.5. An agitated vessel 6 ft (1.8 m) in diameter with a working depth of 8 ft
(2.44 m) is used to prepare a slurry of lSD-mesh fluorspar in water at 70°F. The solid
. has a specific gravity of 3.18, and the slurry is 25 percent solids by weight. The impeller
is a four-blade pitched-blade turbine 2 ft (0.61 m) in diameter set 1.5 ft above the vessel
floor. (a) What is the power required for complete suspension? (b) What is the critical
stirrer speed?
Solution
(a) Use the data of Buurman et al. in Fig. 9.19, correcting for differences in physical
properties and solids concentration. Assume the exponents of Eq. (9.36) apply and
that ne varies with D~·2 D. p0.45 BO. 13 .
Sand Fluorspar
200 104
1.59 2.18
11.1 33.3
Change in ne:
104)0.2(2.18)0."(33.3)0.13
( -200 -
1.59
-
11.1
=1.157
Change in P: (1.157)' = 1.55
From Fig. 9.19, PIV = 2.1 hpllOOO gal for sand. For fluorspar, PIV = 2.1 x 1.55 =
3.3 hp/lOOO gal:
v = in x 62 x 8 = 226.2ft'
226.2 x 7.48 = 1692 gal
1692
P = 3.3 x - = 5.58 hp (4.16 kW)
1000
(b) D, = 2 ft. From Table 9.3, for a four-blade turbine, KT = Np = 1.27
. I
Pm = slurry densIty = = 1.207 g/cm' = 75.2lb/ft'
(0.25/3.18) + 0.75
, , 5.58 x 550 x 32.17
n, = Pg,INppD, = , = 32.3
1.27 x 75.2 x 2
n, = 3.18 rls
AGITATION AND MIXING OF LIQUIDS 269
DISPERSION OPERATIONS
In suspending solids, the size and the surface area of the solid particles exposed
to the liquid are fixed, as is the total volume of suspended solids. In gas-liquid or
liquid-liquid dispersion operations, by contrast, the size of the bubbles or drops
and the total interfacial area between the dispersed and continuous phases vary
with conditions and degree of agitation. New area must constantly be created
against the force of the interfacial tension. Drops and bubbles are continually
coalescing and being redispersed. In most gas-dispersion operations, bnbbles rise
through the liquid pool and escape from the surface and must be replaced by new
ones.
In this dynamic situation the volume of the dispersed phase held up in the
liquid pool is also variable, depending on the rate of rise of the bubbles and the
volumetric feed rate. Statistical averages are used to characterize the system, since
the holdup, interfacial area, and bubble diameter vary with time and with position
in the vessel.
CHARACTERISTICS OF DISPERSED PHASE; MEAN DIAMETER. Despite these
variations, a basic relationship exists between the holdup 'I' (the volume fraction
of dispersed phase in the system), the interfacial area a per unit volume, and the
bubble or drop diameter Dp. If the total volume of the dispersion is taken as unity,
the volume of dispersed phase, by definition, is '1'. Let the number of drops or
bubbles in this volume be N. Then if all the drops or bubbles were spheres of
diameter D p' their total volume would be given by
nND 3
--p = 'I' (9.37)
6
The total surface area of the drops or bubbles in this volume would be
nND: = a (9.38)
Dividing Eq. (9.37) by Eq. (9.38) and rearranging gives
6'1'
Dp = --;; (9.39)
Actually, of course, the drops or bubbles differ in size and are not spherical.
However, for given values of 'I' and a an equivalent average diameter can be
defined by an equation similar to Eq. (9.39) as follows:
-
6'1'
D s =- (9.40)
a
Diameter D, in Eq. (9.40) is known as the volume-surface mean diameter or
the Sauter mean diameter.
GAS DISPERSION; BUBBLE BEHA VIOR. In a quiescent liquid a single bubble
issuing from a submerged circular orifice will be a sphere if the flow rate is small.
Under these conditions the bubble diameter Dp can be calculated as follows, by
270 FLUID MECHANICS
equating the net buoyant force on the bubble to the opposing drag force at the
"edge of the orifice. The net buoyant force, acting upward, is
9 reD!
Fb - Fg = - -·(PL - Pv) (9.41)
g, 6
where PL = density of liquid
Pv = density of vapor
F b = total buoyant force
Fg = force of gravity
The drag force F D is
FD = nDo(J (9.42)
where D, = orifice diameter
er = interfacial tension
When the bubble becomes large enough, the drag force is no longer strong enough
to keep the bubble attached to the edge of the orifice; at this point the opposing
forces become equal, and the bubble is detached from the orifice. The bubble
diameter can be found by combining Eqs. (9.41) and (9.42) and solving for Dp to
give
D _ [
p -
6D,erg,
g(PL - Pv)
J' /
3 (9.43)
At very low flow rates the bubbles formed are slightly smaller than predicted
by Eq. (9.43), because some of the gas stays behind when the bubble leaves. At
higher flow rates, D p is greater than predicted because of additional gas that enters
during separation of the bubble from the orifice. At still higher rates, the gas stream
appears to be a continuous jet, which actually consists of large closely spaced
irregular bubbles and disintegrates into a cloud of smaller bubbles a few inches
above the orifice. In stirred tanks or unstirred bubble columns the average bubble
size usually depends on the superficial velocity in the equipment and on the power
dissipation rather than on the orifice size of the sparger (perforated pipe).
As discussed in Chap. 7, bubbles change in shape from spherical to ellipsoidal
to lens-shaped as their diameter increases. Larger bubbles often rise in spiral paths,
at terminal velocities that are almost constant and independent of their size (see
Fig. 7.8). In clouds or swarms of bubbles there may be considerable coalescence;
the rate of rise of clouds of small bubbles is considerably less than that of single
bubbles if the bubbles are distributed uniformly over the cross section of the vessel.
A cloud of bubbles rising at one location creates an upflow of liquid, and this
chimney effect may greatly increase the bubble velocity.
GAS DISPERSION IN AGITATED VESSELS. Gas is normally fed to a processing
vessel through the open end of a submerged pipe, through a sparger, or through
a porous ceramic or metal plate. Sometimes the gas by itself provides sufficient
AGITATION AND MIXING OF LIQUIDS 271
agitation of the liquid; more commonly a motor-driven turbine impeller is used
to disperse the gas and circulate the liquid and bubbles through the vessel.
For low gas holdups ('f' < 0.15) the following dimensional equations are
available for gas dispersion in pure liquids by a six-blade turbine impeller. 7b The
average bubble diameter D; in millimeters is given by
(O"g )0.6
D; = 4.15 ' 'f'1/2 + 0.9 (9.44)
(PgolJl)0.4p~.2
The average bubble diameter does not change much with stirrer speed and is
usually in the range 2 to 5 mm. Smaller bubbles are formed in the high-shear
region near the tip of the impeller, but they coalesce rapidly, and the average size
is determined by the balance between coalescence and breakup in the rest of the
tank. Theory for turbulent breakup of drops indicates the size should vary with
the group (O"g,)0.6/(PgolJl)0.4p~.2, but the other terms in Eq. (9.44) were determined
empirically. The term 'f'1/2 reflects the importance of bubble coalescence, which
is more frequent at high gas holdups.
The interfacial area can be calculated from the average bubble size and the
holdup or from the following equation,7b where a' is in mm - L
2
a' = 1.44 (PgolJl)0.4 p2· fV,)1/2 (9.45)
(O"g,)0.6 ,,;;
where V, =superficial velocity of gas
=volumetric gas feed rate divided by the cross-sectional area of vessel
u, = bubble rise velocity in stagnant liquid
Equation (9.45) underestimates the area in mixing vessels operated at high
impeller Reynolds numbers, because additional gas is drawn into the liquid by
surface aeration. Combining Eqs. (9.40), (9.44), and (9.45) leads to the following
dimensional equation for gas holdup:
~
'f')1/2 (Pg /JI)0.'pO.2 ~)1/2
'f' = -'- + 0.216' L-'. (9.46)
u, (erg,)0.6 u,
In Eqs. (9.44) to (9.46) all quantities involving the dimension of length are in
millimeters.
The terminal velocity enters into Eqs. (9.45) and (9.46), but this velocity does
not change much with diameter for bubbles larger than 1 mm (Fig. 7.8), and a
value of 0.2 m/s can be used for gases in water or similar pure liquids. For air
bubbles in electrolyte solutions, coalescence is greatly retarded, and the average
bubble size can be much less than in pure water, with corresponding increases in
interfacial area and gas holdup.
POWER INPUT TO TURBINE DISPERSERS. The power consumed by a turbine
impeller dispersing a gas is less than that indicated by Fig. 9.12 for agitating just
liquids. The ratio of the power when gas is present to that for the liquid alone
272 FLUID MECHANICS
depends mainly on the superficial gas velocity and to some extent on the stirrer
speed, tank size, impeller diameter, and properties of the liquid 20 Some data for
dispersing air in water with standard six-blade turbines Da/D, = t are shown in
Fig. 9.20. The relative power Pg/Po drops rapidly to about 0.5 or 0.6 at a velocity
of 10 mm/s and then decreases slowly to less than 0.3 at a velocity of 90 mm/so
The work of Pharamond et al. 3' showed that relative power is almost independent
of stirrer speed in the low-velocity region where Pg/Po> 0.5. The relative power
is about 10 to 15 percent higher for D, = 1.0 m than for D, of 0.48 or 0.29 m, but
there are no data to show whether this trend continues for still larger tanks.
The study of Dickey!' covers the higher range of gas velocities, and in this
region the relative power generally decreases with increasing stirrer speed as well
as with increasing gas velocity. This work and others·· 28 •3 • show that Pg varies
with about the 2.1 to 2.9 power of the stirrer speed compared to the 3.0 power
for liquids. The exponent for stirrer speed depends on gas velocity and other
variables, and no simple correlation is available. In the region of high gas velocities,
Pg/Po also depends on the ratio of imp eller diameter to tank size. For Da/D, = 0.4
(data not shown here), the values of Pg/Po are lower by about 0.03 to 0.10 than
those for Da/D, = 0.33. The main effect of using a larger impeller is that greater
volumes of gas can be dispersed at a given stirrer speed.
Data for relative power consumption have often been presented as a function
of a dimensionless aeration number, N A< = qg/nD;, where qg is the total gas flow,
and nD; is a measure of the flow rate of liquid from the impeller. When N Ao is
increased by increasing qg, Pg/Po decreases as shown in Fig. 9.20. However, when
N Ao is increased by decreasing n, Pg/Po generally increases (high-velocity region)
1.0,.--------------------------,
Six-blade turbine
0.8 Dr/D, == ~
___ Pharamond et al.3!l
0.6 n = 1.675- 1 Dr= 1.52 m _ _ Dickey14
2.08S~?1 \ .......
~--
:~~::~S2.:4g:S:--'___==;~~~~ ~~~~1
0.4
Dr= 0.48 m 2.91 S-1
____________
n == 1.5-4.05- 1 4.14 S-1
0.2
FIGURE 9.20
Power consumption in aerated turbine-agitated vessels.
AGITATION AND MIXING OF LIQUIDS 273
or is unchanged (low-velocity region). Therefore a correlation based on just N A,
could be misleading, and it seems clearer to show the effects of the variables
separately as in Fig. 9.20. This plot can be used for systems other than air-water
if the change in physical properties is not very great. A fourfold increase in viscosity
and a 40 percent reduction in surface tension had no significant effect on PgIP0'
but the relative power was 10 to 20 percent lower with a Na 2 SO, solution, in
which the bubbles were smaller because of reduced coalescence. 2o
The decrease in power with gassing is not just an effect of the lower average
density of the gas-liquid dispersion, since the gas holdup is generally 10 percent
or less when Pg/Po is reduced to 0.5. The decrease in power is associated with the
formation of gas pockets behind the turbine blades.'s Bubbles are captured in the
centrifugal field of vortices that form behind the horizontal edges of the blades,
and coalescence leads to large cavities that interfere with normal liquid flow.
The change in power dissipation with gassing must be allowed for in the
design of large units. An agitator drive chosen to handle the torque for a gassed
system could be overloaded if the system has to operate occasionally with no gas
flow, and a dual-speed drive might be needed. Also, good performance sometimes
requires constant power dissipation per unit volume, and scaleup may lead to
different values of V, and Pg/Po.
GAS-HANDLING CAPACITY AND LOADING OF TURBINE IMPELLERS. If the
gas throughput to a turbine-agitated vessel is progressively increased, the impeller
eventually floods and can no longer disperse the gas effectively. The flooding point
is not as distinct a transition as in a packed column, and various criteria for
flooding have been proposed. One definition of flooding based on visual inspection
is when most of the bubbles rise vertically between the turbine blades rather than
being dispersed radially from the tips of the blades. 14 The critical gas velocity for
this transition, v,." was found to be proportional to the power per unit volume
dissipated by the stirrer, with a slight effect of tank size. From data for tanks 1.54
and 0.29 m in diameter and velocities up to 75 mm/s, the following dimensional
equation was obtained:
v,., = 0.114 ( ; )(~~r7 (9.47)
In Eq. (9.47), (Pg/V) is in W/m 3 , D, in m, and v,., in mm/so The effect of
D t is somewhat uncertain, since it is based only on two sizes, and for a conservative
scaleup, this factor could be ignored. Of course, conditions close to flooding may
not be optimum for mass transfer, since bubble coalescence in the regions away
from the impeller could greatly reduce the surface area.
Example 9.6. A baffled cylindrical vessel 2 m in diameter is agitated with a turbine
impe11er 0.667 m in diameter turning at 180 r/min. The vessel contains water at 20°C,
through which 100 m 3 jh of air is to be passed at atmospheric pressure. Ca1culate
(a) the power input and power input per unit volume of liquid, (b) the gas holdup,
(c) the mean bubble diameter, and (d) the interfacial area per unit volume of liquid.
274 FLUID MECHANICS
For water the interfacial tension is 72.75 dyn/cm. The rise velocity of the bubbles
may be assumed constant at 0.2 m/so
Sollltion
(a) The power input for the ungassed liquid is first calculated; it is then corrected,
by Fig. 9.20, for the effect of the gas. From the conditions of the problem
D. = 0.667 m 11 = 3 rls p = 1000 kg/m'
I' = 1 cP = I X 10-' kg/m-s qg= 100m'/h
Hence
3 X 0.667 2 X 1000 6
NR, = = 1.33 x 10
1 x 10 '
At this large Reynolds number Eq. (9.24) applies. For a flat-blade turbine, from Table
9.3, KT = 5.75. Hence, from Eq. (9.24), the power required for the ungassed liquid is
5.75 X 3' x 0.667' x 1000
Po = = 20.49 kW
1000
The cross-sectional area of the vessel is nD;/4, or 3.142 m2 ; hence the superficial gas
velocity is
_ lOO
V = 0.00884 m/s
, 3600 x 3.142
From Fig. 9.20, PglPo is about 0.60. Therefore
Pg = 0.60 x 20.49 = 12.29 kW
The depth of the liquid, assuming the "standard" design shown in Fig. 9.7, equals
DJ or 2 m. The liquid volume is therefore
V = inD;DJ = 2n = 6.28 m3
Hence the power input per unit volume is
P 12.29
-". = - - = 1.96 kW/m' (9.9 hp/lOOO gal)
V 6.28
This is not an unusually high power input for a gas-dispersing agitator. Because of
the high tip speeds required for good dispersion, the power consumption is con-
siderably greater than in simple agitation of liquids.
(b) Since the holdup will probably be low, use Eq. (9.46). For substitution in
Eq. (9.46) the following equivalences are helpful:
I dyn/cm = I g/s2
I kg/m' = 10- 6 g/mm'
I kW/m' = 10' g/mm-s'
AGITATION AND MIXING OF LIQUIDS 275
Hence from the conditions of the problem and the power calculated in part (a),
(f = 72.75 g/S2 PL = 10-' g/mm'
P
-" = 1.96 X 10' g/mm-s'
V
Substitution in Eq. (9.46) gives
0.00884
'I' = ( - - 'I'
)'/2 + 0.216 (2.32 x 10 )°.4(10-')°.2 (°.00884)'/
3
--
2
0.2 72.75°·6 0.2
Solving this as a quadratic equation gives '¥ = 0.0760.
(c) The mean bubble diameter is now found from Eq. (9.44). Substitution gives
D' = 415 72.75°·6 00760'/2 09 - 38
, . (1.96 X 10')0.4(10-')0.2 . + . - . mm
(d) From Eq. (9.40)
, 6'1' 6 x 0.0781
a == = = O.l2mm- 1
D~ 3.8
Example 9.7. Estimate the maximum gas-handling capacity of the vessel described
in Example 9.6.
Solution
Assume Pg/Po decreases to 0.25:
(0.25)(20,490)
Pg/V = = 816 W/m' (4.14 hp/1000 gal)
6.28
From Eq. (9.47),
v". = 0.114(816) (~)0.'7
1.5
= 98 mm/s or 0.098 m/s
qg = 0.098(3.142) = 0.308 m'/s or 1110 m'/h
The calculated flooding velocity is beyond the range of the data on which Eq.
(9.47) was based, so it may not be reliable. Based on ~,c = 75 mm/s, the highest
measured value, qg would be 850 m 3 /h.
DISPERSION OF LIQUIDS IN LIQUIDS. One liquid, say, benzene, may be dis-
persed in another liquid, say, water, which is immiscible with the first liquid, in
various types of equipment. In agitated vessels or pipeline dispersers, the drop
sizes are generally in the range of 0.1 to 1.0 mm, much smaller than for gas bubbles
in water. Such liquid-liquid dispersions are not stable, since the drops will settle
(or rise) and coalesce in the absence of agitation. Stable emulsions of very small
droplets can be formed in colloid mills or other devices that produce very high
shear rates.
276 FLUID MECHANICS
Many correlations for the drop size have been proposed, some based on
power per unit volume and some on impeller tip speed. A correlation for turbine
agitators, similar to Eq. (9.44) for gases, is 7.
]5 = 0224 [ (erg,)0.6 ] '£'1/2(l'd)114 (9.48)
, . (PgJV)0.4p~.2 1',
The viscosity term shows that it is difficult to disperse a viscous liquid in a
low-viscosity continuous phase; in this situation there is less shear stress at the
drop surface than with drops of low-viscosity liquid, and the viscous drop resists
deformation. This equation, however, should not be used for very low values of
I'd/I'" since it does not fit the data for the dispersion of gases in liquids. An alternate
equation proposed for the dispersion of liquids with six-blade turbines is 7,
]5 ( erg )0.6
--= = 0.06(1 + 9'1') -,---f-- (9.49)
Da n DaPe
where p, is the density of the continuous liquid phase.
The group n2D;,p,/erg, is called the Weber number Nw,. It may be written
in the following form, which shows that it is the ratio of the kinetic energy of the
fluid at the impeller tip speed to a surface-tension stress based on D.,
N _ (nD.)2
w, - p, jD (9.50)
age a
Many other definitions of the Weber number have been used in other situations.
Equations (9.48) and (9.49) predict that the average drop size varies with
n-1.2D;;0.8, or approximately with the reciprocal of the impeller tip speed, and
that better dispersion is obtained at the same power input by using a smaller
impeller rotating at high speed.
A dispersion of one liquid in another can be obtained by passing the mixture
in turbulent flow through a pipe. The largest stable drop size D m" depends on
the ratio of the disruptive forces caused by turbulent shear to the stabilizing forces
of surface tension and drop viscosity. For low-viscosity drops such as benzene or
water, the effect of viscosity is negligible, and a force balance for drops smaller
than the main eddies leads to
(9.51)
where Nw, = DpV 2/erg,
D = pipe diameter
Equation (9.51) fits the data fairly well for drops up to about Dm " ~ O.03D. For
systems where the large drops are close to the primary eddy size, an alternate
derivation 26 gives
(9.52)
AGITATION AND MIXING OF LIQUIDS 277
When it is not clear which equation applies, the equation giving the larger size
should be used. More complex correlations are available for the dispersion of very
viscous liquids. 22 ,44
Static mixers can also be used to make a liquid-liquid dispersion, and the
average drop size is much smaller than that produced in a straight pipe because
of the greater rate of energy dissipation. About 10 to 20 elements in series are
needed to reach an equilibrium dispersion, but, of course, coalescence may increase
the average size after the fluid leaves the mixer29:
15, = 0.35Nw~.6 rO.4 (9.53)
D
For a Kenics mixer with D = 1.91 cm the friction factor J was constant' at 0.416
for N R , of 12,000 to 20,000. For dispersing p-xylene in water at N R , = 20,000 and
Nw, = 574, Eq. (9.53) gives D,/D = 0.011 or 15, = 0.24 mm. The data for drop
size distribution showed that Dm " = LSD" so for this example Dm " = 0.36 mm.
For an empty pipe, the values of Dm " from Eqs. (9.51) and (9.52) are several-fold
greater.
SCALEVP OF AGITATOR DESIGN. A major problem in agitator design is to scale
up from a laboratory or pilot-plant agitator to a full-scale unit. The scaleup of
vessels for suspending solids has already been discussed. For some other problems
generalized correlations such as those shown in Figs. 9.12 to 9.16 are available
for scaleup. For many other problems adequate correlations are not available; for
these situations various methods of scaleup have been proposed, all based on
geometrical similarity between the laboratory and plant equipment. It is not
always possible, however, to have the large and small vessels geometrically similar.
Furthermore, even if geometrical similarity is obtainable, dynamic and kinematic
similarity are not, so that the results of the scaleup are not always fully predictable.
As in most engineering problems the designer must rely on judgment and
experience.
Power consumption in large vessels can be accurately predicted from curves
of N p versus N R " as shown in Figs. 9.12 and 9.13. Such curves may be available
in the published literature or they may be developed from pilot-plant studies using
small vessels of the proposed design. With low-viscosity liquids the amount of
power consumed by the impeller per unit volume of liquid has been used as a
measure of mixing effectiveness, based on the reasoning that increased amounts
of power mean higher degree of turbulence and a higher degree of turbulence
means better mixing. Studies have shown this to be at least roughly true. In a
given mixer the amount of power consumed can be directly related to the rate of
solution of a gas or the rate of certain reactions, such as oxidations, that depend
on the intimacy of contact of one phase with another. In a rough qualitative way
t
it may be said that to 1 hp per 1000 gal of thin liquid gives "mild" agitation,
2 to 3 hp per 1000 gal gives "vigorous" agitation, and 4 to 10 hp per 1000 gal
gives "intense" agitation. These figures refer to the power that is actually delivered
278 FLUID MECHANICS
to the liquid and do not include power used in driving gear-reduction units or in
turning the agitator shaft in bearings and stuffing boxes. The agitator designed in
Example 9.4 would require about H hp per 1000 gal of liquid and should
provide rather mild agitation. (Note that 5 hp per 1000 gal is equivalent to
1.0 kW/m 3 .)
The optimum ratio of impeller diameter to vessel diameter for a given power
input is an important factor in scaleup. The nature of the agitation problem
strongly influences this ratio: for some purposes the impeller should be small,
relative to the size of the vessel; for others it should be large. For dispersing a gas
in a liquid, for example, the optimum rati041 is about 0.25; for bringing two
immiscible liquids into contact, as in liquid-liquid extraction vessels, the optimum
ratio is 0.40. 36 For some blending operations the ratio should be 0.6 or even more.
In any given operation, since the power input is kept constant, the smaller the
impeller, the higher the impeller speed. In general, operations that depend on large
velocity gradients rather than on high circulation rates are best accomplished by
small, high-speed impellers, as is the case in the dispersion of gases. For operations
that depend on high circulation rates rather than steep velocity gradients, a large,
slow-moving impeller should be used.
Blending times are usually much shorter in small vessels than in large ones,
for it is often impractical to make the blending times the same in vessels of different
sizes. This is shown by the following example.
Example 9.8. A pilot-plant vessel 1 ft (305 mm) in diameter is agitated by a six-blade
turbine impeller 4 in. (102 mm) in diameter. When the impeller Reynolds number is
10\ the blending time of two miscible liquids is found to be 15 s. The power required
is 2 hp per 1000 gal (0.4 kW/m3) of liquid. (a) What power input would be required
to give the same blending time in a vessel 6 ft (1830 mm) in diameter? (b) What would
be the blending time in the 6-ft (1830-mm) vessel if the power input per unit volume
was the same as in the pilot-plant vessel?
Solution
(a) Since the Reynolds number in the pilot-plant vessel is large, the Froude number
term in Eq. (9.33) would not be expected to apply, and the correlation in Fig. 9.15
will be used in place of the more complicated relation in Fig. 9.16. From Fig. 9.15,
for Reynolds numbers of 104 and above, the mixing-time factor nty is constant, and
since time ty is assumed constant, speed n will be the same in both vessels.
In geometrically similar vessels the power input per unit volume is proportional
to PjDZ. At high Reynolds numbers, from Eq. (9.24)
For a liquid of given density this becomes
AGITATION AND MIXING OF LIQUIDS 279
where C2 is a constant. From this the ratio of power inputs per unit volume in
the two vessels is
(9.54)
Since III = 11 6 ,
The power per unit volume requited in the 6-ft vessel is then 2 x 36 = 72 hp
per 1000 gal (14.4 kW/m'). This is an impractically large amount of power to deliver
to a low-viscosity liquid in an agitated vesse1.
(b) If the power input per unit volume is to be the same in the two vessels, Eq.
(9.54) can be solved and rearranged to give
116 = (D .,)2/'
111 Da6
Since ntT is constant, n6/nl = tTl /t T6 , and
t
~ = (D~ )2/3 = 62 / 3 = 3.30
tTl Dol
The blending time in the 6-ft vessel would be 3.30 x 15 ~ 49.5 s.
Although it is impractical to achieve the same blending time in the full-scale
unit as in the pilot-plant vessel, a moderate increase in blending time in the larger
vessel reduces power requirement to a reasonable level. Such trade-offs are often
necessary in scaling up agitation equipment.
SYMBOLS
Area of cylinder swept out by tips of impeller blades, m2 or fe
Interfacial area per unit volume, m-I or ft-I; also, constant in Eq.
(9.19); a', interfacial area per unit volume calculated from Eq. (9.45),
mm- 1
B Solids concentration in suspension [Eq. (9.36)J
b Constant in Eq. (9.19)
D Diameter of pipe, m or ft; DO' diameter of impeller; Dj, diameter of
jet and nozzle; DO' orifice diameter; Dp , diameter of particles, drops,
or bubbles; Dp tank diameter; Dmax , maximum stable drop size in
dispersion
15, Volume-surface mean diameter of drops or bubbles, m or ft; 15;,
mean diameter calculated from Eq. (9.46), mm
E Height of impeller above vessel floor, m or ft
Ek Kinetic energy of fluid, J/m 3 or ft-lb flft 3
280 FLUID MECHANICS
F Force, N or lb f ; F D , drag force; F b , buoyant force; F g , gravitational
force
J Friction factor, dimensionless
J. Blending-time factor, dimensionless, defined by Eq. (9.33); J;, by
Eq. (9.34)
9 Gravitational acceleration, m/s2 or ft/S2
g, Newton's-law proportionality factor, 32.174 ft-Ibjlb rs2
H Depth of liquid in vessel, m or ft
J Width of baffles, m or ft
K Constant in Eq. (9.6)
KL,K r Constants in Eqs. (9.21) and (9.23), respectively
K' Flow consistency index of non-newtonian fluid
k Ratio of tangential liquid velocity at blade tips to blade-tip velocity
L Length of impeller blades, m or ft
m Exponent in Eq. (9.18)
N Number of drops or bubbles per unit volume
NA, Aeration number, qg/nD:
N F, Froude number, n2 D,/g
Np Power number, PgJn 3 D:;p; N p.g at gas redispersion point
NQ Flow number, q/nD:; N Q • g , at gas redispersion point
N R, Agitator Reynolds number, nD; p/,,; N R,." for non-newtonian fluid,
defined by Eq. (9.25)
Nw, Weber number, DpV2 /ug, or D:n 2 pJug,
n Rotational speed, r/s; nO' critical speed for complete solids suspension
n' Flow behavior index of non-newtonian fluid
P Power, kW or ft-Ibf/s; Pg, with gas dispersion or at gas redispersion
point; Po, power consumption in ungassed liquid
q Volumetric flow rate, m 3/s or ft 3/s; q., leaving impeller; qT, total
liquid flow rate; q" entrained in jet; qg, total gas flow rate; qo,
leaving jet nozzle
r Radial distance from impeller axis, m or ft
S Shape factor; SI = D,/D,; S2 = E/D,; S3 = L/D,; S4 = W/D,;
Ss = J/D,; S6 = H/D,; also factor in Eq. (9.36)
tT Blending time, s
U Velocity, m/s or ft/s; u" terminal velocity of particle, drop, or.
bubble; U2, velocity of impeller blade tip
v Volume, m 3 or ft3
V' Resultant velocity, absolute, in impeller, m/s or ft/s; V;, radial com-
ponent; V~2' radial component of velocity V;; V~2' tangential
component of velocity V,,; V", actual velocity at impeller blade tips
Average velocity of liquid in pipe, m/s or ft/s; v" superficial velocity
of gas in agitated vessel; v,." critical velocity at flooding
W Impeller width, m or ft
X Distance from jet nozzle, m or ft
Y Coordinate normal to flow direction
AGITATION AND MIXING OF LIQUIDS 281
Greek letters
a Ratio V'z/U 2
[32 Angle between impeller blade tips and the tangent to the circle
traced out by the impeller tip; [32, angle between the actual relative
velocity vector of the liquid and the tangent
!J.p Density difference, kg/m' or lb/ft'
!l Absolute viscosity, P or lb/ft-s; !la' apparent viscosity of non-
newtonian fluid; !l" viscosity of continuous phase in liquid-liquid
dispersion; !ld, of dispersed phase
v Kinematic viscosity, m 2/s or ft2/S
P Density, kg/m' or Ib/ft2; p" of continuous phase in liquid-liquid
dispersion; PL, of liquid in gas-liquid dispersion; Pv, of gas in gas-
liquid dispersion; Pm' of liquid-solid suspension
(J Interfacial tension, dyn/cm or lbf/ft
If' Volumetric fractional gas or liquid holdup in dispersion, dimensionless
if! Function
PROBLEMS
9.1. A tank 1.2 m in diameter and 2 m high is filled to a depth of 1.2 m with a latex
having a viscosity of 10 P and a density of 800 kg/m'. The tank is not baffled. A
three-blade 360-mm-diameter propeller is installed in the tank 360 mm from the
bottom. The pitch is 1: 1 (pitch equals diameter). The motor available develops
8 kW. Is the motor adequate to drive this agitator at a speed of 800 r/min?
9.2. What is the maximum speed at which agitator of the tank described in Prob. 9.1 may
be driven if the liquid is replaced by one having a viscosity of 1 P and the same density?
9.3. What power is required for the mixing operation of Prob. 9.1 if a propeller 360 mm
in diameter turning at 15 rls is used and if four baffles, each 120 mm wide, are
installed?
9.4. The propeller in Prob. 9.1 is replaced with a six-blade turbine 400 mm in diameter,
and the fluid to be agitated is a pseudoplastic power-law liquid having an apparent
viscosity of 15 P when the velocity gradient is 10 S-l. At what speed should the turbine
rotate to deliver 1 kW/m' of liquid? For this fluid n' ~ 0.75 and p ~ 950 kg/m'.
9.5. A mixing time of 29 s was measured for a 4.5-ft baffled tank with a 1.5-ft six-blade
turbine and a liquid depth of 4.8 ft. The turbine speed was 75 r/min, and the fluid
has a viscosity of 3 cP and a density of 65 Ib/ft3. Estimate the mixing times if an
impeller one-quarter or one-half the tank diameter were used with the speeds chosen
to give the same power per unit volume.
9.6. A pilot-plant reactor, a scale model of a production unit, is of such size that 1 g
charged to the pilot-plant reactor is equivalent to 500 g of the same material charged
to the production unit. The production unit is 2 m in diameter and 2 m deep and
contains a six-blade turbine agitator 0.6 m in diameter. The optimum agitator speed
in the pilot-plant reactor is found by experiment to be 330 r/min. (a) What are the
significant dimensions of the pilot-plant reactor? (b) If the reaction mass has the
properties of water at 70°C and the power input per unit volume is to be constant,
at what speed should the impeller turn in the large reactor? (c) At what speed should
282 ,FLUID MECHANICS
it turn if the mixing time is to be kept constant? (d) At what speed should it turn if
the Reynolds number is held constant? (e) Which basis would you recommend for
scaleup? Why?
9.7. A stirred tank reactor 3 ft in diameter with a 12-in. flat-blade turbine has been used
for a batch reaction in which the blending time of added reagents is considered critical.
Satisfactory results were obtained with a stirrer speed of 400 rjmin. The same reaction
is to be carried out in a tank 7 ft in diameter, for which a 3-ft standard turbine is
available. (a) What conditions would give the same blending time in the larger tank?
(b) What would be the percentage change in the power per unit volume? Density
p ~ 60 Ib/ft 3 ; viscosity Jl ~ 5 cP.
9.8. A six-blade disk turbine (Da = 3 Ft) is used to disperse hydrogen gas into a slurry
reactor containing methyl linoleate at 90°C and 60lbj jin. 2 gauge with 1 percent
suspended catalyst particles (15 s = 50 pm, Pp = 4 gjcm 3 ). The reactor diameter is 9 ft
and the depth is 12 ft. The gas flow rate is 1800 std ft3jmin. The oil viscosity is 1.6 cP
and the density is 0.84 g/cm 3 at 90'C. The reactor is fully baffled. (a) What agitator
speed is needed to give 5 hp/IOOO gal during the reaction? (b) What is the power
consumption with gas flow on and with gas flow off?
9.9. For the conditions of Prob. 9.8, estimate the power required for complete suspension
of the catalyst.
9.10. A 15 percent slurry of 20-to-28-mesh limestone in water is to be kept in suspension
in a 20-ft-diameter tank using a six-blade 45° turbine. (a) If DajDt = t, and WjDa = 0.2,
what stirrer speed is required? (b) Calculate the stirrer speed and power requirement
if D,/D, ~ 004.
9.11. A reaction in which the product forms a crystalline solid has been studied in a
1-ft-diameter pilot-plant reactor equipped with a 4-in. six-blade turbine with curved
blades. At stirrer speeds less than 600 rIm in, a solid deposit sometimes forms on the
bottom, and this condition must be avoided in the commercial reactor. Density of
the liquid is 701bjft 3 ; viscosity is 3 cP. (a) What is the power consumption in the
small reactor, and what is recommended for an 8000-gal reactor if geometrical
similarity is preserved? (b) How much might the required power be lowered by using
a different type of agitator or different geometry?
9.12. Gaseous ethylene (C2 H 4 ) is to be dispersed in water in a turbine-agitated vessel at
110°C and an absolute pressure of 3 atm. The vessel is 3 m in diameter with a
maximum liquid depth of 3 m. For a flow rate of 1000 m 3 jh of ethylene, measured
at process conditions, specify (a) the diameter and speed of the turbine impeller, (b)
the power drawn by the agitator, (c) the maximum volume of water allowable, and
(d) the rate at which water is vaporized by the ethylene leaving the liquid surface.
Assume that none of the ethylene dissolves in the water and that the ethylene leaving
is saturated with water.
9.13. For a flow rate of 250 m 3 jh in the vessel described in Prob. 9.121 estimate the gas
holdup, mean bubble diameter, and interfacial area per unit volume.
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AGITATION AND MIXING OF LIQUIDS 283
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SECTION
III
HEAT
TRANSFER
AND ITS
APPLICATIONS
P ractically all the operations that are carried out by the chemical engineer
involve the production or absorption of energy in the form of heat. The
laws governing the transfer of heat and the types of apparatus that have for their
main object the control of heat flow are therefore of great importance. This section
of the book deals with heat transfer and its applications in process engineering.
NATURE OF HEAT FLOW. When two objects at different temperatures are
brought into thermal contact, heat flows from the object at the higher temperature
to that at the lower temperature. The net flow is always in the direction of the
temperature decrease. The mechanisms by which the heat may flow are three:
conduction, convection, and radiation.
Conduction. If a temperature gradient exists in a continuous substance, heat
can flow unaccompanied by any observable motion of matter. Heat flow of
285
286 HEAT TRANSFER AND ITS APPLICATIONS
this kind is called conduction. In metallic solids, thermal conduction results
from the motion of unbound electrons, and there is close correspondence between
thermal conductivity and electrical conductivity. In solids that are poor conductors
of electricity and in most liquids, thermal conduction results from the transport
of momentum of individual molecules along the temperature gradient. In gases
conduction occurs by the random motion of molecules, so that heat is "diffused"
from hotter regions to colder ones. The most common example of conduction is
heat flow in opaque solids, as in the brick wall of a furnace or the metal wall of
a tube.
Convection. When a current or macroscopic particle of fluid crosses a specific
surface, such as the boundary of a control volume, it carries with it a definite
quantity of enthalpy. Such a flow of enthalpy is called a convective flow of heat
or simply convection. Since convection is a macroscopic phenomenon, it can occur
only when forces act on the particle or stream of fluid and maintain its motion
against the forces of friction. Convection is closely associated with fluid mechanics.
In fact, thermodynamically, convection is not considered as heat flow but as flux
of enthalpy. The identification of convection with heat flow is a matter of
convenience, because in practice it is difficult to separate convection from true
conduction when both are lumped together under the name convection. Examples
of convection are the transfer of enthalpy by the eddies of turbulent flow and by
the current of warm air from a household furnace flowing across a room.
Natural and forced convection. The forces used to create convection currents in
fluids are of two types. If the currents are the result of buoyancy forces generated
by differences in density and the differences in density are in turn caused by
temperature gradients in the fluid mass, the action is called natural convection.
The flow of air across a heated radiator is an example of natural convection. If the
currents are set in motion by the action of a mechanical device such as a pump
or agitator, the flow is independent of density gradients and is called forced
convection. Heat flow to a fluid pumped through a heated pipe is an example of
forced convection. The two kinds of force may be active simultaneously in the
same fluid, and natural and forced convection then occur together.
Radiation. Radiation is a term given to the transfer of energy through space by
electromagnetic waves. If radiation is passing through empty space, it is not
transformed into heat or any other form of energy nor is it diverted from its path.
If, however, matter appears in its path, the radiation will be transmitted, reflected,
or absorbed. It is only the absorbed energy that appears as heat, and this
transformation is quantitative. For example, fused quartz transmits practically all
the radiation that strikes it; a polished opaque surface or mirror will reflect most
of the radiation impinging on it; a black or matte surface will absorb most of the
radiation received by it and will transform such absorbed energy quantitatively
into heat.
AGITATION AND MIXING OF LIQUIDS 287
Monatomic and most diatomic gases are transparent to thermal radiation,
and it is quite common to find that heat is flowing through masses of such gases
both by radiation and by conduction-convection. Examples are the loss of heat
from a radiator or uninsulated steam pipe to the air of a room and heat transfer
in furnaces and other high-temperature gas-heating equipment. The two mechan-
isms are mutually independent and occur in parallel, so that one type of heat flow
can be controlled or varied independently of the other. Conduction-convection
and radiation can be studied separately and their separate effects added together
in cases where both are important. In very general terms, radiation becomes
important at high temperatures and is independent of the circumstances of the
flow of the fluid. Conduction-convection is sensitive to flow conditions and is
relatively unaffected by temperature level.
Chapter 10 deals with conduction in solids, Chaps. 11 to 13 with heat transfer
to fluids by conduction and convection, and Chap. 14 with heat transfer by
radiation. In Chaps. 15 and 16 the principles developed in the preceding chapters
are applied to the design of equipment for heating, cooling, condensing, and
evaporating.
I
I
CHAPTER
10
HEAT
TRANSFER
BY
CONDUCTION
Conduction is most easily understood by considering heat flow in homogen-
eous isotropic solids because in these there is no convection and the effect of
radiation is negligible unless the solid is translucent to electromagnetic waves.
First, the general law of conduction is discussed; second, situations of steady-state
heat conduction, where the temperature distribution within the solid does not
change with time, are treated; third, some simple cases of unsteady conduction,
where the temperature distribution does change with time, are considered.
FOURIER'S LAW. The basic relation of heat flow by conduction is the proportio-
nality between the rate of heat flow across an isothermal surface and the
temperature gradient at the surface. This generalization, which applies at any
location in a body and at any time, is called Fourier's law. 3 It can be written
dq=_k aT (10.1)
dA an
where A = area of isothermal surface
n= distance measured normally to surface
q= rate of heat flow across surface in direction normal to surface
T= temperature
k= proportionality constant
289
290 HEAT TRANSFER AND ITS APPLICATIONS
The partial derivative in Eq. (10.1) calls attention to the fact that the
temperature may vary with both location and time. The negative sign reflects the
physical fact that heat flow occurs from hot to cold and the sign of the gradient
is opposite that of the heat flow.
In using Eq. (10.1) it must be clearly understood that the area A is that of
a surface perpendicular to the flow of heat and distance n is the length of path
measured perpendicularly to area A.
Although Eq. (10.1) applies specifically across an isothermal surface, the same
equation can be used for heat flow across any surface, not necessarily isothermal,
provided the area A is the area of the surface and the length of the path is measured
normally to the surface 2a This extension of Fourier's law is vital in the study of
two- or three-dimensional flows, where heat flows along curves instead of straight
lines. In one-dimensional flow, which is the only situation considered in this text,
the normals representing the direction of heat flow are straight. One-dimensional
heat flow is analogous to one-dimensional fluid flow, and only one linear
coordinate is necessary to measure the length of the path.
An example of one-dimensional heat flow is shown in Fig. 10.1, which
represents a flat water-cooled furnace wall. Initially the wall is all at 2S a C, in
equilibrium with cooling water at the same temperature. The temperature distribu-
tion in the wall is represented by line r. At temperature equilibrium, T is
independent of both time and position. Assume now that one side of the walI is
suddenly exposed to furnace gas at 700 a C. Compared with the thermal resistance
of the wall, the resistances to heat flow between the hot gas and the wall and
between the wall and the cooling water may be considered negligible. The
Hot gas
Water
II-_-+W
FIGURE 10.1
Temperature distributions, unsteady-state heating of
furnace wall: I, at instant of exposure of waIJ to
high temperature; II. during heating at time t; Ill. at
steady state.
HEAT TRANSFER BY CONDUcrlON 291
temperature at the gas side of the wall immediately rises to 7000C; that at the
other side remains at 25°C. Heat flow begins, and after the elapse of some time,
the temperature distribution can be represented by a curve like that of curve II.
The temperature at a given distance, e.g., that at point c, is increasing; and T
depends upon both time and location. The process is called unsteady-state
conduction, and Eq. (10.1) applies at each point at each time in the slab. Finally,
if the wall is kept in contact with hot gas and cool air for a sufficiently long time,
the temperature distribution shown by line III will be obtained, and this distribu-
tion will remain unchanged with further elapse of time. Conduction under the
condition of constant temperature distribution is called steady-state conduction.
In the steady state T is a function of position only, and the rate of heat flow at
anyone point is a constant. For steady one-dimensional flow, Eq. (10.1) may be
written
q dT
-= -k- (10.2)
A dll
THERMAL CONDUCTIVITY. The proportionality constant k is a physical prop-
erty ofthe substance called the thermal conductivity. It, like the newtonian viscosity
1', is one of the so-called transport properties of the material. This terminology is
based on the analogy between Eqs. (3.4) and (10.2). In Eq. (3.4) tne quantity <g,
is a rate of momentum flow per unit area, the quantity du/dy is the velocity
gradient, and I' is the required proportionality factoL In Eq. (10.2), q/A is the rate
of heat flow per unit area, dT/dn is the temperature gradient, and k is the
proportionality factor. The minus sign is omitted in Eq. (3.4) because of convention
in choosing the direction of the force vector.
In engineering units, q is measured in watts or Btu/h and dT/dn in cC/m or
°F/ft. Then the units of k are W/m-oC or Btu/ft2-h-(OF/ft), which may be written
Btu-ft-h_oF.
Fourier's law states that k is independent of the temperature gradient but not
necessarily of temperature itself. Experiment does confirm the independence of k
for a wide range of temperature gradients, except for porous solids, where radiation
between particles, which does not follow a linear temperature law, becomes an
important part of the total heat flow. On the other hand, k is a function of
temperature, but not a strong one. For small ranges of temperature, k may be
considered constant. For larger temperature ranges, the thermal conductivity can
usually be approximated by an equation of the form
k= a + bT (10.3)
where a and b are empirical constants. Line III in Fig. 10.1 applies to a solid of
constant k, where b = 0; the line would show some curvature if k were dependent
on temperature.
Thermal conductivities of metals cover a wide range of values, from about
10 Btu/ft-h_oF (17 W/m-°C) for stainless steel to 240 Btu/ft-h_oF (415 W/m-°C) for
silver. For glass and most nonporous minerals the thermal conductivities are much
292 HEAT TRANSFER AND ITS APPLICATIONS
lower, from about 0.2 to 2 Btu/ft-h-'F (0.35 to 3.5 W/m-'C). Water has a thermal
conductivity of 0.3 to 0.4 Btu/ft-h-'F (0.5 to 0.7 W/m-'C), about three times that
of most organic liquids. Gases have the lowest conductivities; for air k is
0.014 Btu/ft-h-'F (0.024 W/m-'C) at 32'F (O'C). The thermal conductivity of gases
is nearly independent of pressure but increases with temperature because of the
increase in molecular velocity.
Solids having low k values are used as heat insulators to minimize the rate
of heat flow. Porous insulating materials such as polystyrene foam act by
entrapping air and thus eliminating convection. Their k values are about equal
to that of air itself. Data showing typical thermal conductivities are given in
Appendixes 10 to 14.
S'TEADY-STATE CONDUCTION
For the simplest case of steady-state conduction, consider a flat slab like that
shown in Fig. 10.1. Assume that k is independent of temperature and that the area
of the wall is very large in comparison with its thickness, so that heat losses from
the edges are negligible. The external surfaces are at right angles to the plane of
the illustration, and both are isothermal surfaces. The direction of heat flow is
perpendicular to the wall. Also, since in steady state there can be neither
a<:cumulation nor depletion of heat within the slab, q is constant along the path
of heat flow. If x is the distance from the hot side, Eq. (10.2) can be written
i = -k dT
A dx
or
q
dT= --dx (10.4)
kA
Since the only variables in Eq. (10.4) are x and T, direct integration gives
i=k Tl - T2 =kI!.T (10.5)
A x 2 - Xl B
where X 2 - Xl = B = thickness of slab
Tl - T2 = I!. T = temperature drop across slab
When the thermal conductivity k varies linearly with temperature, in accor-
dance with Eq. (10.3), Eq. (10.5) still can be used rigorously by taking an average
value k for k, which may be found either by using the arithmetic average of the
individual values of k for the two surface temperatures, Tl and T2, or by calculating
the arithmetic average of the temperatures and using the value of k at that
temperature.
Equation (10.5) can be written in the form
q I!.T
-= (10.6)
A R
HEAT TRANSFER BY CONDUcnON 293
where R is the thermal resistance of the solid between points 1 and 2. Equation
(10.6) is an instance of the general rate principle, which equates a rate to the ratio
of a driving force to a resistance. In heat conduction, q is the rate and AT the
driving force. The resistance R, as shown by Eq. (10.6) and using k for k to
account for a linear variation of k with temperature, is Blk. The reciprocal of
a resistance is called a conductance, which for heat conduction is klB. Both
resistance and the conductance depend upon the dimensions of the solid as well
as on the conductivity k, which is a property of the material.
Example 10.1. A layer of pulverized cork 6 in. (152 mm) thick is used as a layer of
thermal insulation in a fiat wall. The temperature the cold side of the cork is 40"F
(4.4°C), and that of the warm side is ISO°F (S2.2°C). The thermal conductivity of the
cork at 32°F (O°C) is 0.021 Btujft-h_oF (0.036 Wjm-°C), and that at 200°F (93.3°C) is
0.032 (0.055). The area of the wall is 25 ft' (2.32 m'). What is the rate of heat flow
through the wall in Btu per hour (watts)?
Solution
The arithmetic average temperature of the cork layer is (40 + IS0)/2 = 1l0°F. By
linear interpolation the thermal conductivity at 11O"F is
_ (1l0 - 32)(0.032 - 0.021)
k = 0.021 + '----:c::-:-----:co----'-
200 - 32
= 0.021 + 0.005 = 0.026 Btujft-h_oF
Also,
A = 25ft' !1T = ISO - 40 = 140°F B=h=0.5ft
Substituting in Eq. (10.5) gives
0.026 x 25 x 140
q= 0.5 IS2 Btujh (53.3 W)
CO~ RESISTANCES IN SERIES. Consider a flat wall constructed of a
seri~~S, as shown in Fig. 10.2. Let the thicknesses of the layers be BA' Bn,
/
and Bc and the average conductivities of the materials of which the layers are
made be kA , kn, and kc, respectively. Also, let the area of the compound wall, at
right angles to the plane of the illustration, be A. Let ATA , ATn, and ATc be the
temperature drops across layers A, B, and C, respectively. Assume, further, that
the layers are in excellent thermal contact, so that no temperature difference exists
across the·interfaces between the layers. Then, if AT is the total temperature drop
across the entire wall,
(10.7)
It is desired, first, to derive an equation for calculating the rate of heat flow
through the series of resistances and, second, to show how the rate can be
calculated as the ratio of the overall temperature drop AT to the overall resistance
of the wall.
294 HEAT TRANSFER AND ITS APPLICATIONS
LOTa
',\T
, LOTe
, I nGUREla2
' -_ _ _ _ _--'---_ _ _-'-_-' -....l.- Thennal resistances in series.
Equation (10.5) can be written for each layer, using k in place of k,
(10.8)
Adding Eqs. (10.8) gives
flT + flY, + flY, = qj!A + qB!!B + qe!!e = flT
A B e AkA AkB Ake
Since, in steady heat flow, all the heat that passes through the first resistance
must pass through the second and in turn pass through the third, qA' qB' and qe
are equal and all can be denoted by q. Using this fact and solving for q/A gives
q flT flT flT
-=---;~-=-~--=~ = =~ (10.9)
A BA/kA + BB/kB + Bc/ke RA + RB + Re R
where RA, Rn, Rc = resistance of individual layers
R = overall resistance
HEAT TRANSFER BY CONOUCTION 295
Equation (10.9) shows that in heat flow through a series of layers the overall
thermal resistance equals the sum of the individual resistances.
The rate of flow of heat through several resistances in series clearly is
analogous to the current flowing through several electric resistances in series. In
an electric circuit the potential drop over anyone of several resistances is to the
total potential drop in the circuit as the individual resistances are to the total
resistance. In the same way the potential drops in a thermal circuit, which are the
temperature differences, are to the total temperature drop as the individual thermal
resistances are to the total thermal resistance. This can be expressed mathematic-
ally as
(10.10)
Figure 10.2 also shows the pattern of temperatures and the temperature
gradients. Depending on the thickness and thermal conductivity of the layer, the
temperature drop in that layer may be a large or small fraction of the total
temperature drop; a thin layer of low conductivity may well cause a much larger
temperature drop and a steeper thermal gradient than a thick layer of high
conductivity.
Example 10.2. A ftat furnace wall is constructed of a 4.5-in. (114-mm) layer of Sil-o-cel
brick, with a thermal conductivity of 0.08 Btu/ft-h-oF (0.138 W/m-°C) backed by a
9-in. (229-mm) layer of common brick, of conductivity 0.8 Btu/ft-h_oF (1.38 W/m-0c).
The temperature ofthe inner face ofthe wall is 1400°F (760'C), and that of the outer
face is 170°F (76.6'C). (a) What is the heat loss through the wall? (b) What is the
temperature of the interface between the refractory brick and the common brick? (c)
Supposing that the contact between the two brick layers is poor and that a "contact
resistance" of 0.50°F-h-ft'/Btu (0.088°C-m'jW) is present, what would be the heat
loss?
Sollltion
(a) Consider I fe of wall (A ~ I ft'). The thermal resistance of the Sil-o-cel layer is
4.5/12
R ~--~4.687
A 0.08
and that of the common brick is
9/12
Rn ~ -~ 0.938
0.8
The total resistance is
R ~ RA + Rn ~ 4.687 + 0.938 ~ 5.625°F-h-ft'/Btu
The overall temperature drop is
!J.T ~ 1400 - 170 ~ 1230°F
296 HEAT TRANSFER AND ITS APPLICATIONS
Substitution in Eq. (10.9) gives, for the heat loss from 1 ft' of wall,
1230
q = - - = 219 Btufh (64.2 W)
5.625
(b) The temperature drop in one of a series of resistances is to the individual
resistance as the overall temperature drop is to the overall resistance, or
"'TA 1230
--=--
4.687 5.625
from which
"'TA = 1025'F
The temperature at the interface is 1400 - 1025 = 375'F (190.6'C).
(c) The total resistance, which now includes a contact resistance, is
R = 5.625 + 0.500 = 6.125
The heat loss from 1 ft2 is
1230
q= - = 201 Btu/h (58.9 W)
6.125
\/
, . THROUGH A CYLINDER. Consider the hollow cylinder represented
HEAT FtOW
by Fig. 10:3. The inside radius of the cylinder is ri, the outside radius is r" and
the length of the cylinder is L. The thermal conductivity of the material of which
the cylinder is made is k. The temperature of the outside surface is 7;" and that
of the inside surface is T,. It is desired to calculate the rate of heat flow outward
for this case.
Consider a very thin cylinder, concentric with the main cylinder, of radius
r, where r is between ri and r,. The thickness of the wall of this cylinder is dr; and
FIGURE 10.3
Flow of heat through thick-walled cylinder.
HEAT TRANSFER BY CONDUCTION 297
if dr is small enough with respect to r for the lines of heat flow to be considered
parallel, Eq. (10.2) can be applied and written in the form
dT
q=-k-2rrrL (10.11)
dr
since the area perpendicular to the heat flow is equal to 2rrrL and the dn of Eq.
(10.2) is equal to dr. Rearranging Eq. (10.11) and integrating between limits gives
'f·
rl
dr 2rrLk
-=--
T
r
q
, f To
dT
2rrLk
In r, - In r, = -q- (T, - 7;,)
k(2rrL)(T, - 7;,)
q= (10.12)
In (r,/rJ
Equation (10.12) can be used to calculate the flow of heat through a thick-walled
cylinder. It can be put in a more convenient form by expressing the rate of flow
of heat as
(10.13)
This is of the same general form as Eq. (10.5) for heat flow through a flat wall
with the exception of AL , which must be so chosen that the equation is correct.
The term AL can be determined by equating the right-hand sides of Eqs. (10.12)
and (10.13) and solving for AL'
- 2rrL(r, - r,)
AL = --:--':-"--c--:-"- (10.14)
In (r,/r,)
Note from Eq. (10.14) that AL is the area of a cylinder of length L and radius rL ,
where
_ To - rj
rL = (10.15)
In (r,/r,)
The form of the right-hand side of Eq. (10.15) is important enough to repay
memorizing. It is known as the logarithmic mean, and in the particular case of Eq.
(10.15) rL is called the logarithmic mean radius. It is the radius that, when applied
to the integrated equation for a flat wall, will give the correct rate of heat flow
through a thick-walled cylinder.
The logarithmic mean is less convenient than the arithmetic mean, and the
latter can be used without appreciable error for thin-walled tubes, where r,/r, is
nearly 1. The ratio of the logarithmic mean rL to the arithmetic mean ra is a
function of r,/r" as shown in Fig. lOA. Thus, when r,/r, = 2, the logarithmic mean
is 0.96i'a and the error in the use of the arithmetic mean is 4 percent. The error is
1 percent where r,/r, = lA.
298 HEAT TRANSFER AND ITS APPLICATIONS
1.0.
0.95
""
0.9
r
0..85 - L
r;,
"" "" I'-...
~
0..8
0..75
'" ~ ...........
-...........
0..7
2 3 4
ro
ri
5 6 7 8 9
r--
I~
FIGURE lOA
Relation between logarithmic and arithmetic means.
Example 10.3. A tube 60 mm (2.36 in.) OD is insulated with a 50-mm (1.97-in.) layer
of silica foam, for which the conductivity is 0.055 W/m-oC (0.032 Btu/ft-h-OF),
followed with a 40-mm (1.57-in.) layer of cork with a conductivity of 0.05 W/m-oC
(0.03 Btu/ft-h-OF). If the temperature of the outer surface of the pipe is 150°C (302°F)
and the temperature of the outer surface of the cork is 30°C (86°F), calculate the
heat loss in watts per meter of pipe.
Solution
These layers are too thick to use the arithmetic mean radius, and the logarithmic
mean radius should be used. For the silica layer
_ 80 - 30
r - 50.97 mm
L - In (80/30)
and for the cork layer
120 - 80
r = = 98.64 mm
L In (120/80)
Call silica substance A and cork substance B. From Eq. (10.13)
XB
where 1'.-.; is the temperature at the interface between the silica and the cork. From
Eqs. (10.14) and (10.15),
AA = 2n(0.05097)L = 0.3203L AB = 2n(0.09864)L = 0.6198L
HEAT TRANSFER BY CQNOUCfION 299
Then
0.055 x 0.3203L(7; - T,,)
qA = 0.3522(7; - Txl
0.050
0.05 x 0.6198(T" - 7;)
qB = 0.040
= 0.7748(T.x - T)
0
Hence
2.839qjL = 7; - T" 1.291qjL = T" - 7;
Adding these gives
4.13qjL = 7; - 7; = 150 - 30 = 120
qjL = 29.1 Wjm (30.3 Btujft-h)
UNSTEADY-STATE CONDUCTIO~ . .
A full treatment of unsteady-state heat conductIOn IS not m the field of this text. 2 - 4
A derivation of the partial differential equation for one-dimensional heat flow and
the results of the integration of the equations for some simple shapes are the only
subjects covered in this section. It is assumed throughout that k is independent
of temperature.
EQUATION FOR ONE-DIMENSIONAL CONDUCTION. Figure 10.5 represents a
section through a large slab of material of thickness 2s, initially all at a uniform
temperature T.,. At the start of heating both surface temperatures are quickly
increased to and subsequently held at temperature T.,. The temperature pattern
shown in Fig. 10.5 reflects conditions after a relatively short time tT has elapsed
since the start of heating.
Focus attention on the thin layer of thickness dx located at distance x from
the left side of the slab. The two sides of the element are isothermal surfaces. The
temperature gradient at x is, at a definite instant of time, aT/ax, and the heat
input in time interval dt at x is -kA(aT/ax) dt, where A is the area of the layer
perpendicular to the flow of heat and k is the thermal conductivity of the solid.
The gradient at distance x + dx is slightly different from that at x and may be
represented as
aT a aT
-+--dx
ax ax ax
The heat flow out of the layer at x + dx is, then,
aT a aT )
-kA ( - + - - d x dt
ax ax ax
300 HEAT TRANSFER AND ITS APPLICATIONS
T. T.
[
[
[
-- Temperature
I
Heat flow -+-off-;.. [ _-+- Heat flow
I 25
-
x
FIGURE 10.5
dx Unsteady-state conduction in solid slab.
The excess of heat input over heat output, which is the accumulation of heat in
layer dx, is
2 2
aT
-kA-dt + kA (aT
- +-2
a Tdx) dt =
a -
kA T dxdt
ax ax ax ax 2
The accumulation of heat in the layer must increase the temperature of the
layer. If cp and p are the specific heat and density, respectively, the accumulation
is the product of the mass (volume times density), the specific heat, and the increase
in temperature, or (pA dx)cp(aTjat) dt. Then, by a heat balance,
a2 T aT
k A -2 dx dt = pCpA dx- dt
ax at
or, after division by pc,A dx dt,
aT k a2 T a2 T
-=--=IX- (10.16)
at pC p ax 2 ax 2
The term IX in Eq. (10.16) is called the thermal diffusivity of the solid and is
a property of the material. It has the dimensions of area divided by time.
General solutions of unsteady-state conduction equations are available for
certain simple shapes such as the infinite slab, the infinitely long cylinder, and the
sphere. For example, the integration of Eq. (10.16) for the heating or cooling of
an infinite slab of known thickness from both sides by a medium at constant
HEAT TRANSFER BY CONDUcrlON 301
(10.17)
where 7; = constant average temperature of surface of slab
7; = initial temperature of slab
T" = average temperature of slab at time IT
N Fo = Fourier number, defined as alT/s2
a = thermal diffusivity
IT = time of heating or cooling
s = one-half slab thickness
a, = (n/2j2
Equation (10.17) may also be used for a slab heated from one side only, provided no
heat is transferred at the other side and 8T/8x = 0 at that surface. Here s is the
full slab thickness.
For an infinitely long solid cylinder of radius I'm the average temperature T"
is given by the equation"
T.-T"
-,_ _ = 0.692e- S.78N ,o + 0.131e- 3o . sN ,o + 0.0534e- 74 . 9N ,o + ... (10.18)
~-I:
where N Fo = aIT/r;'. For a sphere of radius I'm the corresponding equation is 2 '
T.-T.
-'--' = 0.608e- 9 . 87N ,o + 0.152e- 39 . sN ,o + 0.0676e- 88 •8N ,o + ... (10.19)
~-Ya
When N Fo is greater than about 0.1, only the first term of the series in Eqs.
(10.17) to (10.19) is significant and the other terms may be ignored. Under these
conditions the time required to change the temperature from 7; to T" can be found
by rearranging Eq. (10.17), with all except the first term of the series omitted, to
give for the slab
1
IT = - -
(2S)28(7; - 7;)
In --:::2c"::--~ (10.20)
a n n (7; - 11,)
For the infinite cylinder the corresponding equation, found from Eq. (10.18),
is
1';' I 0.692(7; - 7;)
IT = - - n --='-"=-=- (10.21)
5.78a 11, - 11,
For a sphere,t from Eq. (10.19),
1';' 0.608(7; - 7;)
IT = - - In --"--'=-=- (10.22)
9.87a 7; - T.
t An alternate treatment of this problem in terms of heat-transfer coefficients is given in Chap. 11,
p.327.
302 HEAT TRANSFER AND ITS APPLICATIONS
Figure 10.6 is a plot of Eqs. (10.17) to (10.19). The ordinate of this figure is
known as the lInaccomplished temperatllre change, i.e., the fraction of the total
possible temperature change that remains to be accomplished at any time. Except
at very low values of NFo> Eqs. (10.20) to (10.22) apply and all three semilogarithmic
plots are straight lines.
Equations (10.17) to (10.19) apply only when the surface temperature is
constant, so 7; can be equal to the temperature of the heating or cooling medium
only when the temperature difference between the medium and the solid surface
is negligible. This implies that there is negligible thermal resistance between the
1.0.
0..9
0..8
0..7 1\
0..6
1\ "\
0..5 ,\
0..4 I'"
0.3 \ 1\\ I"
I"
0..2 ~
1~Ih.O 1\
1\ I'"
t<
Slob [Eq.(IO -m]
1 I
~ 1--<1)
0..09
0.0.8
0..0.7
O. I 1\
'" "\
11 ylinl1er
0..06 [Eq.(IO-18J]
0..0.5 \ 1\
\ "\
0..04 \
"\
0..03 1\ '\
\
0..0.2
1\
sPkeref;\
[rl'9(J 1\
0..0 I
1\
0. 0..1 0..2 0..3 0..4 0..5 0..6 0..7 0..8 0..9 1.0. 1.1 1.2 1.3 lA
af r air
Ne
,-0
= 52
--or --
rm2
FIGURE 10.6
Average temperatures during unsteadywstate heating or cooling of a large slab, an infinitely long
cylinder, or a sphere.
HEAT TRANSFER BY CONDUCTION 303
surface and the medium. Equations and graphs S , similar to Eqs. (10.17) to (10.19)
and Fig. 10.6 are available for local temperatures at points inside slabs and
cylinders, for temperatures in spheres and other shapes, and for situations in which
the thermal resistance at the surface is large enough to cause variations in the
surface temperature. Temperature distributions in heterogeneous solids or bodies
of complex shape are found by fluid or electrical analogs or numerical approxima-
tion methods.'
The total heat Qr transferred to the solid in time t r through a unit area of
surface is often of interest. From the definition of average temperature the heat
required to raise the temperature ofa unit mass of solid from 7;, to T, is cp(T, - 7;,).
For a slab of thickness 2s and density p the total surface area (both sides) of a
unit mass is lisp. The total heat transferred per unit area is therefore given by
Qr -
A = spcp;' - 7;,) (10.23)
The corresponding equation for an infinitely long cylinder is
Qr
(10.24)
A
For a sphere the equation is
(10.25)
Example 10.4. A flat slab of plastic initially at 70'F (21.1 'C) is placed between two
platens at 250'F (121.1'C). The slab is 1.0 in. (2.54 cm) thick. (a) How long will it
take to heat the slab to an average temperature of 210'F (98.9'C)? (b) How much
heat, in Btu, will be transferred to the plastic during this time per square foot of
surface? The density of the solid is 56.2lb/ft' (900 kg/m'), the thermal conductivity
is 0.075 Btu/ft-h-'F (0.13 W/m-'C), and the specific heat is 0.40 Btu/lb-'F (1.67 J/g-
'c).
Solution
(a) The quantities for use with Fig. 10.6 are
k = 0.075 Btu/ft-h-'F p = 56.2 Ib/ft' Cp = 0.40 Btu/lb-'F
0.5
s = - = 0.0417 ft
12
Then
_1',_-_-_7b = 250 - 210 = 0.222 k 0.075
a=-= 0.00335
250 -70 pc p 56.2 x 0.40
From Fig. 10.6, for a temperature~difference ratio of 0.222,
0.00335tT
N F, = 0.52 = 0.0417' tT = 0.27 h = 16 min
304 HEAT TRANSFER AND ITS APPLICATIONS
(b) Substitution in Eq. (10.23) gives heat flow per total surface area
QT ~ 0.0417 x 56.2 x 0.40(210 - 70) ~ 131 Btu/ft' (1487 kl/m')
A
SEMI-INFINITE SOLID. Sometimes solids are heated or cooled in such a way that
the temperature changes in the solid are confined to the region near one surface.
Consider, for example, a very thick flat wall of a chimney, initially all at a uniform
temperature 7;,. Suppose that the inner surface of the wall is suddenly heated to,
and held at, a high temperature 7;, perhaps by suddenly admitting hot flue gas
to the chimney. Temperatures inside the chimney wall will change with time,
rapidly near the hot surface and more slowly farther away. If the wall is thick
enough, there will be no measurable change in the temperature of the outer surface
for a considerable time. Under these conditions the heat may be considered to be
"penetrating" a solid of essentially infinite thickness. Figure 10.7 shows the
temperature patterns in such a wall at various times after exposure to the hot
gas, indicating the sharp discontinuity in temperature at the hot surface immedi-
ately after exposure and the progressive changes at interior points at later times.
For this situation integration of Eq. (10.16) with the appropriate boundary
conditions, gives, for temperature T at any point a distance x from the hot surface,
the equation
7;- T
--~-
2 f.Z e -z' dZ (10.26)
7;-7;, In 0
where Z ~ x/2fo, dimensionless
a = thermal diffusivity
x = distance from surface
t = time after change in surface temperature, h
Solid surface
Solid
Initial temperature distribution
Temperature distribution at
successive times
FIGURE 10.7
Temperature distributions in unsteady~state
Distance, x ~ heating of semi-infinite solid.
HEAT TRANSFER BY CONDUCTION 305
1.0
...-
V
"",
1--.0 /
~
:s; 05 /
,
I--.
1--..
'- /
I
oI1
o 1.0 20 FIGURE 10.8
Z~_x_
Unsteady-state heating or cooling of semi-
2,..;at infinite solid.
The function in Eq. (10.26) is known as the Gauss error integral or probability
integral. Equation (10.26) is plotted in Fig. 10.8.
Equation (10.26) indicates that at any time after the surface temperature is
changed there will be some change in temperature at all points in the solid, even
points far removed from the hot surface. The actual change at such distant points,
however, is negligibly small. Beyond a certain distance from the hot surface not
enough heat has penetrated to affect the temperature significantly. This penetration
distance xp is arbitrarily defined as that distance from the surface at which the
temperature change is 1 percent of the initial change in surface temperature. That
is to say, (T - T,,)j(T, - TJ = om or (T, - T)/(T, - TJ = 0.99. Figure 10.8 shows
that the probability integral reaches a value of 0.99 when Z = 1.82, from which
xp = 3.64fo (10.27)
Example 10.5. A sudden cold wave drops the atmospheric temperature to - 20°C
(-4'F) for 12 h. (a) If the ground was initially all at 5'C (41'F), how deep would
a water pipeline have to be buried to be in no danger of freezing? (b) What is the
penetration distance under these conditions? The thermal diffusivity of soil is
0.0011 m'/h (0.0118 ft'fh).
Solution
(a) Assume that the surface of the ground quickly reaches and remains at - 20°C.
Unless the temperature at the location of the pipe is below ooe, there is no danger
of freezing. The quantities required for use with Fig. 10.8 are therefore
T, = -20'C
t = 12h "= 0.0011 m'fh
T,-T -20-0
---= 0.80
T,-T,. -20-5
306 HEAT TRANSFER AND ITS APPLICATIONS
From Fig. 10.8, Z = 0.91. The depth x is therefore
x = 0.91 x 2fo = 0.91 x 2JO.0011 x 12 = 0.21 m (0.69 ft)
(b) From Eq. (10.27) the penetration distance is
xp = 3.64JO.0011 x 12 = 0.419 m (1.37 ft)
To find the total heat transferred to a semi-infinite solid in a given time it
is necessary to find the temperature gradient and heat flux at the hot surface as
a function of time. The temperature gradient at the surface is found by differentia-
ting Eq. (10.26) to give
(10.28)
The heat flow rate at the surface is therefore
(-Aq)x=o - (aT) k(T, - 7;,)
-k - (10.29)
ax x=o ~
After substitution of dQ/dl for q, Eq. (10.29) can be integrated to give the
total quantity of heat transferred per unit area, QT/A, in time IT' as follows:
QT = k(T, - 7;,)
A ;;;
f" ~jt
0
= 2k(T, - 7;,) (t;
..,;-;;.
(10.30)
SYMBOLS
A Area, m 2 or re; AL ) logarithmic mean
a Constant in Eq. (10.3)
a! (n/2)2
B Thickness of slab, m or ft; BA' BB' Bc, of layers A, B, C, respectively
b Constant in Eq. (10.3)
cp Specific heat at constant pressure, J/g-"C or Btu/lb-"F
e Base of Naperian logarithms, 2.71828 ...
g, Newton's-law proportionality factor, 32.174 ft-lb/lb r s 2
k Thermal conductivity, W/m-"C or Btu/ft-h-"F; k A , k B , kc, of layers
A, B, C, respectively; k, average value
L Length of cylinder, m or ft
N F" Fourier number, dimensionless; alrls2 for slab; (J.tT/r~ for cylinder or
sphere
n Distance measured normally to surface, m or ft
Q Quantity of heat, J or Btu; QT' total quantity transferred
q Heat flow rate, W or Btu/h; qA, qB, qc, in layers A, B, C, respectively
R Thermal resistance, m2-"C/W or ft2-"F-h/Btu; RA' R B , Rc, of layers
A, B, C, respectively
HEAT TRANSFER BY CONDUCfION 307
l' Radial distance or radius, m or ft; 1\, inside radius; I'rn' radius of solid
cylinder or sphere; 1"0' outside radius; rL' logarithmic mean; ra, arith-
metic mean
s Half-thickness of slab, m or ft
T Temperature, °e or of; ~, initial temperature; 7;" average temperature
at end of time t T ; ~, of inside surface; ~, of outside surface; Ys. surface
temperature; T" T2 , at locations 1,2, respectively
t Time, s or h; tT, time required to heat or cool
u Velocity, m/s or ft/s
x Distance from surface, m or 'ft; Xl, X 2 , at locations 1, 2, respectively; x P'
penetration distance in semi-infinite solid
y Distance, m or ft
Z x/2fo, dimensionless
Greek letters
a Thermal diffusivity, k/pc p , m 2/s or ft2jh
6.T Overall temperature drop; 6.TA , 6.T., 6.Tc , in layers A, E, C, respec-
tively
J1 Absolute viscosity, Pa' s or Ib/ft-h
p Density, kg/m' or Ib/ft'
r Shear stress, N/m 2 or Ib r/ft2
PROBLEMS
10.1. A furnace wall consists of 200 mm of refractory fireclay brick, 100 mm of kao-
lin brick, and 6 mm of steel plate. The fire side of the refractory is at 1150°C,
and the outside of the steel is at 30°C. An accurate heat balance over the fur-
nace shows the heat loss from the wall to be 300 Wjm 2 • It is known that there
may be thin layers of air between the layers of brick and steel. To how many
milIimeters of kaolin are these air layers equivalent? See Appendix 11 for thermal
conductivities.
10.2. A standard I-in. Schedule 40 steel pipe carries saturated steam at 250°F, The pipe is
Jagged (insulated) with a 2-in. layer of 85 percent magnesia pipe covering, and outside
this magnesia there is a ~-in. layer of cork, The inside temperature of the pipe wall
is 249°F, and the outside temperature of the cork is 900F. Thermal conductivities,
in Btujft-h-OF, are: for steel, 26; for magnesia, 0.034; for cork, 0.03. Calculate (a) the
heat loss from lOO it of pipe in Btu per hour; (b) the temperatures at the boundaries
between metal and magnesia and between magnesia and cork.
10.3. Derive the equation for steady-state heat transfer through a spherical shell of inner
radius r 1 and outer radius 1'2' Arrange the result for easy comparison with the
solution for a thick-walled cylinder.
10.4. A very long, wide sheet of plastic 4 mm thick and initially at 200 e is suddenly exposed
on both sides to an atmosphere of steam at 102°C. (a) If there is negligible thermal
resistance between the steam and the surfaces of the plastic, how long will it take
for the temperature at the centerline of the sheet to change significantly? (b) What
308 HEAT TRANSFER AND ITS APPLICATIONS
would be the bulk average temperature of the plastic at this time? For the plastic,
k = 0.138 W/m-oC and a = 0.00035 m 2/h.
10.5. A long steel rod 1 in. in diameter is initially at a uniform temperature of 1200°F. It
is suddenly immersed in a quenching bath of oil at 150°F. In 4 min its average
temperature drops to 250°F. How long would it take to lower the temperature from
1200 to 250°F (a) if the rod were 2! in. in diameter? (b) If it were 5 in. in diameter?
For steel, k = 26 Btu/ft-h_oF; p = 486 Ib/ft 3 : cp = 0.11 Btu/Ib-oF.
10.6. Steel spheres 3 in. in diameter heated to 700°F are to be cooled by immersion in an
oil bath at 125°F. Ilthere is negligible thermal resistance between the oil and the steel
surfaces, (a) calculate the average temperature of the spheres 10 sand 1 and 6 min
after immersion. (b) How long would it take for the unaccomplished temperature
change to be reduced to 1 percent of the initial temperature difference? The steel has
the same thermal properties as in Prob. 10.5.
10.7. Under the conditions described in Example 10.5, what is the average rate of heat loss
per unit area from the ground to the air during the 12-h period? The thermal
conductivity of soil is 0.7 W/m-°C.
10.S. For the same initial temperatures Ts and Ta and at the same Fourier number, would
the average temperature of a sphere be higher or lower than that of a cylinder or a
slab? (See Fig. 10.6.) What are the physical reasons that would lead you to expect
this?
10.9. The heat transfer rate to the jacket of an agitated polymerization kettle is 7.4 kW/m'
when the polymerization temperature is 50°C and the water in the jacket is at 20°C.
The kettle is made of stainless steel with a wall 12 mm thick, and there is a thin layer
of polymer (k = 0.16 W/m-°C) left on the wall from previous runs. (a) What is the
temperature drop across the metal wall? (b) How thick would the polymer deposit
have to be to account for the rest of the temperature difference? (c) By what factor
could the heat flux be increased by using a stainless-clad reactor with a 3-mm
stainless-steel layer bonded to a 9-mm mild-steel shell?
10.10. (a) Compare the thermal conductivities and thermal diffusivities of air and water at
100°F. (b) Calculate the penetration distances in a stagnant mass of air and one of
water, at 50°F and 1 atm, each of which is exposed for 10 s to a hot metal surface
at lOO°F. Comment on the difference.
REFERENCES
1. Carnahan, B., H. A. Luther, and J. O. Wilkes: Applied Numerical Methods, WiJey, New York, 1969.
2. Carslaw, H. S., and J. C. Jaeger: Conduction of Heat in Solids, 2nd ed., Oxford University Press,
Fair Lawn, NJ., 1959; (a) pp. 6-8, (b) p. 234.
3. Faucier, J.: The Analytical 17leory of Heat, trans. by A. Freeman, Dover, New York, 1955.
4. Gebhart, B.: Heat Transfer, 2nd ed., McGraw-Hill, New York, 1971.
5. McAdams, W. H.: Heat Transmission, 3rd ed., McGraw-Hill, New York, 1954; (a) pp. 35-43,
(b) p. 232.
CHAPTER
11
PRINCIPLES
OF HEAT
FLOW IN
FLUIDS
Heat transfer from a warmer fluid to a cooler fluid, usually through a solid wall
separating the two fluids, is common in chemical engineering practice. The heat
transferred may be latent heat accompanying a phase change such as condensation
or vaporization or it may be sensible heat from the rise or fall in the temperature
of a fluid without any phase change. Typical examples are reducing the tempera-
ture of a fluid by transfer of sensible heat to a cooler fluid, the temperature of
which is increased thereby; condensing steam by cooling water; and vaporizing
water from a solution at a given pressure by condensing steam at a higher pressure.
All such cases require that heat be transferred by conduction and convection.
TYPICAL HEAT-EXCHANGE EQUIPMENT. To establish a basis for specific
discussion of heat transfer to and from flowing fluids, consider the simple tubular
condenser of Fig. 11.1. It consists essentially of a bundle of parallel tubes A, the
ends of which are expanded into tube sheets E, and E 2 • The tube bundle is inside
a cylindrical shell C and is provided with two channels D, and D 2 , one at each
end, and two channel covers E, and E 2 • Steam or other vapor is introduced
through nozzle F into the shell-side space surrounding the tubes, condensate is
withdrawn through connection G, and any noncondensable gas that might enter
with the inlet vapor is removed through vent K. Connection G leads to a trap,
which is a device that allows flow of liquid but holds back vapor. The fluid to be
heated is pumped through connection H into channel D 2 • It flows through the
309
310 HEAT TRANSFER AND ITS APPLICATIONS
Vapor
8, Oullet
~
\.1'- A A
Vent
tK
liquid £
~,~ I!=-~ IV~
tJ I
)
FIrV f> "1 f
...
Inlet liquid Condensate
FIGURE 11.1
Single-pass tubular condenser: A, tubes; B I , B 2 , tube sheets; C, shell; D I • D 2 , channels; El. E 2 , channel
covers; F, vapor inlet; G, condensate outlet; H, cold-liquid inlet; J, warm-liquid outlet; K, non-
condensed-gas vent.
tubes into the other channel D 1 and is discharged through connection J. The
two fluids are physically separated but are in thermal contact with the thin metal
tube walls separating them. Heat flows through the tube walls from the condensing
yapor to the cooler fluid in the tubes.
If the yapor entering the condenser is not superheated and the condensate
is not subcooled below its boiling temperature, the temperature throughout the
shell side of the condenser is constant. The reason for this is that the temperature
of the condensing yapor is fixed by the pressure of the shell-side space, and the
pressure in that space is constant. The temperature of the fluid in the tubes
increases continuously as the fluid flows through the tubes.
The temperatures of the condensing yapor and of the liquid are plotted
against the tube length in Fig. 11.2. The horizontal line represents the temperature
TEMP. OF CONDENSING VAPOR = 7h
Tc
I
I
Direction of )
flow
I
I
IL
LENGTH OF TUBES
FIGURE 11.2
Temperature-length curves for condenser.
PRINCIPLES OF HEAT FLOW IN FLUIDS 311
of the condensing vapor, and the curved line below it represents the rising
temperature of the tube-side fluid. In Fig. 11.2, the inlet and outlet fluid tempera-
tures are 7;, and 7;b, respectively, and the constant temperature of the vapor is
7;,. At a length L from the entrance end of the tubes, the fluid temperature is 7;,
and the local difference between the temperatures of vapor and fluid is 7;, - 7;.
This temperature difference is called a point temperature difference and is denoted
by ~ T. The point temperature difference at the inlet of the tubes is Th - 7;a, denoted
by ~Tl' and that at the exit end is T" - 7;b' denoted by ~T2. The terminal point
temperature differences ~ Tl and ~ 72 are called the approaches.
The change in temperature of the fluid, 7;b - 7;" is called the temperature
range or, simply, the range. In a condenser there is but one range, that of the cold
fluid being heated.
In this text the symbol ~T is used exclusively to signify a temperature
difference between two objects or two fluids. It does not denote the temperature
change in a given fluid.
A second example of simple heat-transfer equipment is the double-pipe
exchanger shown in Fig. 11.3. It is assembled of standard metal pipe and
standardized return bends and return heads, the latter equipped with stuffing
boxes. One fluid flows through the inside pipe and the second fluid through the
annular space between the outside and the inside pipe. The function of a heat
exchanger is to increase the temperature of a cooler fluid and decrease that of a
hotter fluid. In a typical exchanger, the inner pipe may be li in. and the outer
pipe 2! in., both IPS. Such an exchanger may consist of several passes arranged
in a vertical stack. Double-pipe exchangers are useful when not more than 100 to
150 ft2 of surface is required. For larger capacities, more elaborate shell-and-tube
exchangers, containing up to thousands of square feet of area, and described on
pages 428 to 433, are used.
FluId A inlet
~. Flutd
P, ~:iiiF=7;;;::;;;;;mr-'1 --d!.t
Fluid
---1:>"
BdJrn___-"
s;:~
: _. ElV
inlet ~
I Fluid A
... out/et
FIGURE 11.3
Double-pipe heat exchanger.
312 HEAT TRANSFER AND ITS APPLICATiONS
COUNTERCURRENT AND PARALLEL-CURRENT FLOWS. The two fluids enter
at different ends of the exchanger shown in Fig. 1(3 and pass in opposite directions
through the unit. This type of flow is that commonly used and is called coulllerflow
or countercurrent flow. The temperature-length curves for this case are shown in
Fig. 11.4a. The four terminal temperatures are denoted as follows:
Temperature of entering hot fluid, 7;..
Temperature of leaving hot fluid, 7;,b
Temperature of entering cold fluid, 7;.
Temperature of leaving cold fluid, 7;b
Direction of flow
( Worm fluid
DIrection of flow
)
Cold fluid
DISTANCE FROM COLD-FLUID INLET ~
(a)
Tho DIrection of flow
)
Warm fluid
W
0:
~
W
a.
:;;
w
I-
~o C=~ ________________________________
DISTANCE FROM COLD-FLUID INLET-
(b)
FIGURE 11.4
Temperatures in (a) countercurrent and (b) parallel flow.
PRINCIPLES OF HEAT FLOW IN FLUIDS 313
The approaches are
7;.a - 7;b = t,. T, and (11.1)
The warm-fluid and cold-fluid ranges are 7;.a - 1/'b and 7;b - 7;., respectively.
If the two fluids enter at the same end of the exchanger and flow in the same
direction to the other end, the flow is called parallel. The temperature-length curves
for parallel flow are shown in Fig. 11 Ab. Again, the subscript a refers to the entering
fluids and subscript b to the leaving fluids. The approaches are t,. T, = 1/,. - 7;a
and t,. T, = 7;.b - 7;b·
Parallel flow is rarely used in a single-pass exchanger such as that shown in
Fig. 11.3 because, as inspection of Fig. I1.4a and b will show, it is not possible
with this method of flow to bring the exit temperature of one fluid nearly to the
entrance temperature of the other and the heat that can be transferred is less than
that possible in countercurrent flow. In the multipass exchangers, described on
pages 430 and 431, parallel flow is used in some passes, largely for mechanical
reasons, and the capacity and approaches obtainable are thereby affected. Parallel
flow is used in special situations where it is necessary to limit the maximum
temperature of the cooler fluid or where it is important to change the temperature
of at least one fluid rapidly.
In some exchangers one fluid flows across banks of tubes at right angles to
the axis of the tubes. This is known as crossjlow.
ENERGY BALANCES
Quantitative attack on heat-transfer problems is based on energy balances and
estimations of rates of heat transfer. Rates of transfer are discussed later in this
chapter. Many, perhaps most, heat-transfer devices operate under steady-state
conditions, and only this type of operation will be considered here.
ENTHALPY BALANCES IN HEAT EXCHANGERS. In heat exchangers there is no
shaft work, and mechanical, potential, and kinetic energies are small in comparison
with the other terms in the energy-balance equation. Thus, for one stream through
the exchanger
1;,(Hb - Ha) = q (11.2)
where I;' = flow rate of stream
q = Q/t = rate of heat transfer into stream
Ha, Hb = enthalpies per unit mass of stream at entrance and exit, respectively
Equation (11.2) can be written for each stream flowing through the exchanger.
A further simplification in the use of the heat-transfer rate q is justified. One
of the two fluid streams, that outside the tubes, can gain or lose heat by transfer
with the ambient air if the fluid is colder or hotter than the ambient. Heat transfer
to or from the ambient is not usually desired in practice, and it is usually reduced
to a small magnitude by suitable insulation. It is customary to neglect it in
314 HEAT TRANSFER AND ITS APPLICATIONS
comparison with the heat transfer through the walls of the tubes from the warm
fluid to the cold fluid, and q is interpreted accordingly.
Accepting the above assumptions, Eq. (11.2) can be written for the warm
fluid as
,n,,(H',b - H,,,) = q" (11.3)
and for the cold fluid as
(11.4)
where m" 'h" = mass flow rates of cold fluid and warm fluid, respectively
Hea, H,,, = enthalpy per unit mass of entering cold fluid and entering warm
fluid, respectively
H,b' H"b = enthalpy per unit mass of leaving cold fluid and leaving hot fluid,
respectively
q" q" = rates of heat addition to cold fluid and warm fluid, respectively
The sign of q, is positive, but that of q" is negative because the warm fluid loses,
rather than gains, heat. The heat lost by the warm fluid is gained by the cold fluid,
and
Therefore, from Eqs. (11.3) and (11.4),
(11.5)
Equation (11.5) is called the overall enthalpy balance.
If only sensible heat is transferred and constant specific heats are assumed,
the overall enthalpy balance for a heat exchanger becomes
(11.6)
where cP' = specific heat of cold fluid
cp " = specific heat of warm fluid
ENTHALPY BALANCES IN TOTAL COND~RS. For a condenser
1il!,A = 1jlcCpc(~b - ~a) = q (11.7)
where 1ilh = rate of condensation of vapor
A = latent heat of vaporization of vapor
Equation (11.7) is based on the assumption that the vapor enters the
condenser as saturated vapor (no superheat) and the condensate leaves at conden-
sing temperature without being further cooled. If either of these sensible-heat
effects is important, it must be accounted for by an added term in the left-hand
side of Eq. (11.7). For example, if the condensate leaves at a temperature 1/,b that
PRINCIPLES OF HEAT FLOW IN FLUIDS 315
is less than T,,, the condensing temperature of the vapor, Eq. (11.7) must be written
,n,,[.l + Cph(T" - T"b)] = rilhi7;b - 7;a) (11.8)
where Cph is now the specific heat of the condensate.
RATE OF HEAT TRANSFER
HEAT FLUX. Heat-transfer calculations are based on the area of the heating
surface and are expressed in watts per square meter or Btu per hour per square foot
of surface through which the heat flows. The rate of heat transfer per unit area is
called the heatfiux. In many types of heat-transfer equipment the transfer surfaces
are constructed from tubes or pipe. Heat fluxes may then be based on either the
ii
inside area or the outside area of the tubes. Although the choice is arbitrary, it
must be clearly stated, because the numerical magnitude of the heat fluxes will
not be the same for both.
AVERAGE TEMPERATURE OF FLUID STREA . When a fluid is being heated or
cooled, the temperature will vary throughout th ' cross section of the stream. If
the fluid is being heated, the temperature of the fluid is a maximum at the wall
of the heating surface and decreases toward the center of the stream. If the fluid
is being cooled, the temperature is a minimum at the wall and increases toward
the center. Because of these temperature gradients throughout the cross section
of the stream, it is necessary, for definiteness, to state what is meant by the
temperature of the stream. It is agreed that it is the temperature that would be
attained if the entire fluid stream flowing across the section in question were
withdrawn and mixed adiabatically to a uniform temperature. The temperature
so defined is called the average or mixing-cup stream temperature. The tempera-
tures plotted in Fig. 11.4 are all average stream temperatures.
Overall Heat-Transfer Coefficie~
!
As shown in Chap. 10, Eqs. (10.5) anct' (10.9), the heat flux through layers of solids
in series is proportional to a driving force, the overall temperature difference !!.T.
This also applies to heat flow through liquid layers and solids in series. In a heat
exchanger the driving force is taken as T" - 7;, where 7;, is the average tempera-
ture of the hot fluid and 7; is that of the cold fluid. The quantity T;, - 7; is the
overall local temperature difference !!.T. It is clear from Fig. 11.4 that !!.T can vary
considerably from point to point along the tube, and therefore, since the heat flux
is proportional to !!. T, the flux also varies with tube length. It is necessary to start
with a differential equation by focusing attention on a differential area dA through
which a differential heat flow dq occurs under the driving force of a local value
of!!. T. The local flux is then dq/dA and is related to the local value of !!.T by the
equation
dq
- = U !!.T = U(7;, - 7;) (11.9)
dA
316 HEAT TRANSFER AND ITS APPLICATIONS
The quantity U, defined by Eq. (11.9) as a proportionality factor between dq/dA
and Ll T, is called the local overall heat-transfer coefficient.
To complete the definition of U in a given case, it is necessary to specify the
area. If A is taken as the outside tube area A" U becomes a coefficient based on
that area and is written U,. Likewise, if the inside area A, is chosen, the coefficient
is also based on that area and is denoted by U,. Since LlT and dq are independent
of the choice of area, it follows that
U, = dA, = D,
(11.10)
U, dA, D,
where D, and D, are the inside and outside tube diameters, respectively.
\ I
INTEGR)<'rION OVER TOTAL SURFACE; LOGARITHMIC MEAN TEMPERA-
TURE DIFFERENCE. To apply Eq. (11.9) to the entire area of a heat exchanger,
the equation must be integrated. This can be done formally where certain
simplifying assumptions are accepted. The assumptions are (1) the overall coeffi-
cient U is constant, (2) the specific heats of the hot and cold fluids are constant,
(3) heat exchange with the ambient is negligible, and (4) the flow is steady and either
parallel or countercurrent, as shown in Fig. 11.4.
The most questionable of these assumptions is that of a constant overall
coefficient. The coefficient does in fact vary with the temperatures of the fluids,
but its change with temperature is gradual, so that when the temperature ranges
are moderate, the assumption of constant U is not seriously in error.
Assumptions 2 and 4 imply that if 7; and 'I/, are plotted against q, as shown
in Fig. 11.5, straight lines are obtained. Since 7; and 'I/, vary linearly with q, LlT
,
I
LlT,;
~-
w
a: 0 vs q
:::>
~
a:
w
CL
::;;
w
f- 7;,0
LlTvsq
Llf
0
0 q q~
2
FIGURE 115
Temperature vs. heat flow rate in countercurrent flow.
PRINCIPLES OF HEAT FLOW IN FLUIDS 317
does likewise and d( ATJ/dq, the slope of the graph of AT vs. q, is constant.
Therefore
d(AT) = ATz - AT!
(11.11)
dq qT
where ATb ATz = approaches
qT = rate of heat transfer in entire exchanger
Elimination of dq from Eqs. (11.9) and (11.11) gives
d(ATJ AT, - AT!
(11.12)
U ATdA qT
The variables AT and A can be separated, and if U is constant, the equation can be
integrated over the limits AT and 0 for A and ATz and AT!, where AT is the total
area of the heat-transfer surface. Thus
or
ATz U(ATz - AT!)
In-= AT (11.13)
AT, qT
Equation (11.13) can be written
ATz-AT! _
qT = UA T In (ATz/AT,) UA T ATL (11.14)
where
..-- ATz - AT!
'-' TL = - - " - - - - ' - (11.15)
In (ATz/AT!)
Equation (11.15) defines the logarithmic mean temperature difference
(LMTD). It is of the same form as that of Eq. (10.15) for the logarithmic mean
radius of a thick-walled tube. When AT! and AT, are nearly equal, their arithmetic
average can be used for ATL within the same limits of accuracy given for Eq.
(10.15), as shown in Fig. 10.4.
If one of the fluids is at constant temperature, as in a condenser, no difference
exists among countercurrent flow, parallel flow, or mUltipass flow, and Eq. (11.15)
applies to all of them. In countercurrent flow, ATz , the warm-end approach, may
be less than AT!, the cold-end approach. In this case, for convenience and to
eliminate negative numbers and logarithms, the subscripts in Eq. (11.15) may be
interchanged. The LMTD is not always the correct mean temperature difference
to use. It should not be used when U changes appreciably or when AT is not a
linear function of q. As an example, consider an exchanger used to cool and
condense a superheated vapor, with the temperature diagram shown in Fig. 11.6.
318 HEAT TRANSFER AND ITS APPLICATIONS
Cooling
section
>--
Vi
e
0
Condensing section
;; Too
0;
Co
E
$ I1T,
f-
Tu
Rate of heat flow, q
FIGURE 11.6
Temperature profiles in cooling and condensing superheated vapor.
The !;'T driving force is a linear function of q while the vapor is being cooled,
but !;'T is a different linear function of q in the condensing section of the exchanger.
Furthermore, U is not the same in the two parts of the exchanger. The cooling and
condensing sections must be sized separately using the appropriate values of q,
U, and LMTD rather than some kind of average U and an overall LMTD.
The LMTD is also incorrect when heat is transferred to or from a reacting
fluid in a jacketed reactor. Figure 11.7 shows the temperature profiles for an
exothermic reaction in a water-cooled reactor-the lower line shows the tempera-
ture of the coolant, the upper line that of the reacting mixture. Because of heat
generated by the reaction, the reactant temperature rises rapidly near the reactor
inlet, and then, as the reaction slows, the reactant temperature drops. The !;. T's
FIGURE 11.7
Temperature patterns in jacketed tubular
DISTANCE FROM INLET, L reactor.
PRINCIPLES OF HEAT FLOW IN FLUIDS 319
at both the reactor inlet and outlet are relatively small. Clearly the average
temperature drop is much greater than the drop at either end of the reactor
and cannot be found from the logarithmic mean of the terminal 11 T's.
VARIABLE OVERA\.l VOEFFICIENT. When the overall coefficient varies regu-
larly, the rate of h~;,r;./r~fer may be predicted from Eq. (11.16), which is based
on the assumption that"Uvaries linearly with the temperature drop over the entire
heating surface! :
U 2 1lT1 - U , IlT2
qT = AT c-=:-:'---'-=-:-::-:'--:-:~ (11.16)
In (U 2 IlTr/U 1 IlT2 )
where U I' U 2 = local overall coefficients at ends of exchanger
11 T1 , 11 T2 = temperature approaches at corresponding ends of exchanger
Equation (11.16) calls for use of a logarithmic mean value of the U IlT cross
product, where the overall coefficient at one end of the exchanger is multiplied by
the temperature approach at the other. The derivation of this equation requires
that assumptions 2 to 4 above be accepted.
In the completely general case, where none of the assumptions is valid and
U varies markedly from point to point, Eq (11.9) can be integrated by evaluating
local values of U, 11 T, and q at several intermediate points in the exchanger.
Graphical or numerical evaluation of the area under a plot of I/U IlT vs. q,
between the limits of zero and qT, will then give the area AT of the heat-transfer
surface required.
MULTIPASS EXC\:XGERS. In multipass shell-and-tube exchangers the flow
pattern is compl;'x:Zi~~arallel, countercurrent, and crossflow all present. Under
these conditions, even when the overall coefficient Uis constant, the LMTD cannot
be used. Calculation procedures for muItipass exchangers are given in Chap. 15.
Individual Heat-Transfer Coefficients
The overall coefficient depends upon so many variables that it is necessary to
break it into its parts. The reason for this becomes apparent if a typical case is
examined. Consider the local overall coefficient at a specific point in the double-
pipe exchanger shown in Fig. 11.3. For definiteness, assume that the warm fluid
is flowing through the inside pipe and that the cold fluid is flowing through the
annular space. Assume also that the Reynolds numbers of the two fluids are
sufficiently large to ensure turbulent flow and that both surfaces of the inside tube
are clear of dirt or scale. If, now, a plot is prepared, as shown in Fig. 11.8, with
temperature as the ordinate and distance perpendicular to the wall as the abscissa,
severa1.important facts become evident. In the figure, the metal wall of the tube
separates the warm fluid on the right from the cold fluid on the left. The change
in temperature with distance is shown by the line T;r"T"/,T,,,T,T,. The tempera-
ture profile is thus divided into three separate parts, one through each of the two
320 HEAT TRANSFER AND ITS APPLICATIONS
F2
I Worm fluid
I _ _ _M
I li,
I
I
I
Cool fluid
• Distonce
FIGURE 11.8
Temperature gradients in forced convection.
fluids and the other through the metal wall. The overall effect, therefore, should
be studied in terms of these individual parts.
H was shown in Chap. 5 that in turbulent flow through conduits three zones
exist, even in a single fluid, so that the study of one fluid is, itself, complicated. In
each fluid shown in Fig. 11.8 there is a thin sublayer at the wall, a turbulent core
occupying most of the cross section of the stream, and a buffer zone between them.
The velocity gradients were described in Chap. 5. The velocity gradient is large
near the wall, small in the turbulent core, and in rapid change in the buffer zone.
PRINCIPLES OF HEAT FLOW IN FLUIDS 321
It has been found that the temperature gradient in a fluid being heated or cooled
when flowing in turbulent flow follows much the same course. The temperature
gradient is large at the wall and through the viscous sublayer, small in the turbulent
core, and in rapid change in the buffer zone. Basically, the reason for this is that
heat must flow through the viscous sublayer by conduction, which calls for a steep
temperature gradient in most fluids because of the low thermal conductivity,
whereas the rapidly moving eddies in the core are effective in equalizing the
temperature in the turbulent zone. In Fig. 11.8 the dashed lines F,F, and F2F2
represent the boundaries of the viscous sublayers.
The average temperature of the warm stream is somewhat less than the
maximum temperature 7; and is represented by the horizontal line MM, which is
drawn at temperature 7;,. Likewise, line NN, drawn at temperature 7;, represents
the average temperature of the cold fluid.
The overall resistance to the flow of heat from the warm fluid to the cold
fluid is a result of three separate resistances operating in series. Two resistances
are those offered by the individual fluids, and the third is that of the solid wall.
In general, also, as shown in Fig. 11.8, the wall resistance is small in comparison
with that of the fluids. The overall coefficient is best studied by analyzing it in
terms of the separate resistances and treating each separately. The separate
resistances can then be combined to form the overall coefficient. This approach
requires the use of individual heat-transfer coefficients for the two fluid streams.
The individual, or surface, heat-transfer coefficient h is defined generally by
the equation
(11.17)
where dq/dA = local heat flux, based on the area in contact with fluid
T = local average temperature of fluid
7;, = temperature of wall in contact with fluid
The reciprocal of this coefficient, l/h, is called a thermal resistance. For
conduction through a solid, such as a metal wall of thickness x" and thermal
conductivity k, the thermal resistance equals xw/k. Appropriately corrected for
changes in area, the individual resistances may be added to give the overall
resistance I/U.
A second expression for h is derived from the assumption that there are no
velocity fluctuations normal to the wall at the surface of the wall itself. The
mechanism of heat transfer at the wall is then by conduction, and the heat flux
is given by Eq. (10.2), noting that the normal distance n may be replaced by y,
the normal distance measured into the fluid from the wall in the direction of the
flow of heat. Thus
(11.18)
322 HEAT TRANSFER AND ITS APPLICATiONS
The subscript IV calls attention to the fact that the gradient must be evaluated
at the wall. Eliminating dq/dA from Eqs. (11.17) and (11.18) gives
h = _ k ~(d~T'..:./d:o.Y)~" (11.19)
T- ~I'
Note that h must always be positive. Equation (11.19) can be put into a
dimensionless form by multiplying by the ratio of an arbitrary length to the
thermal conductivity. The choice of length depends on the situation. For heat
transfer at the inner surface of a tube, the tube diameter D is the usual choice.
Multiplying Eq. (11.19) by DJk gives
hD = _ D (dT/dy)"
(11.20)
k T- ~I'
On the cold-fluid side of the tube wall T < 1;" and the denominator in Eqs.
(11.19) and (11.20) becomes 1;, - T. The dimensionless group IlD/k is called a
Nusselt number NNu' That shown in Eq. (11.20) is a local Nusselt number based
on diameter. The physical meaning of the Nusselt number can be seen by
inspection of the right-hand side of Eq. (11.20). The numerator (dT/dy)" is, of
course, the gradient at the wall. The factor (T - 1;,)/D can be considered the
average temperature gradient across the entire pipe, and the Nusselt number is
the ratio of these two gradients.
Another interpretation of the Nusselt number can be obtained by considering
the gradient that would exist if all the resistance to heat transfer were in a laminar
layer of thickness x in which heat transfer was only by conduction. The heat-
transfer rate and coefficient follow from Eqs. (10.1) and (11.17):
dq k(T - 1;')
(11.21)
dA x
k
h=- (11.22)
x
From the definition of the Nusselt number,
hD kD D
-=NN = - - = - (11.23)
k u xk x
The Nusselt number is the ratio of the tube diameter to the equivalent
thickness of the laminar layer. Sometimes x is called the film thickness, and it is
generally slightly greater than the thickness of the laminar boundary layer because
there is some resistance to heat transfer in the buffer zone.
Equation (11.17), when applied to the two fluids of Fig. 11.8, becomes, for
the inside of the tube (the warm side in Fig. 11.8),
dq/dA,
(11.24)
PRINCIPLES OF HEAT FLOW IN FLUIDS 323
and for the outside of the tube (the cold side)
h = dq/dA,
(11.25)
o ~vc - T::
where A, and A, are the inside and outside areas of the tube, respectively.
The cold fluid could, of course, be inside the tubes and the warm fluid outside.
Coefficients h, and h, refer to the inside and .the outside of the tube, respectively,
and not to a specific fluid.
CALCULATION OF OV\AALL COEFFICIENTS FROM INDIVIDUAL COEFFI-
CIENTS. The overall coelill(ient is constructed from the individual coefficients and
the resistance of the tubb wall in the following manner.
The rate of heat transfer through the tube wall is given by the differential
form of Eq. (10.13),
(11.26)
where Twh - Tw, = temperature difference through tube wall
km = thermal conductivity of wall
Xw = tube-wall thickness
dq/dA L = local heat flux, based on logarithmic mean of inside and outside
areas of tube
If Eqs. (11.24) to (11.26) are solved for the temperature differences and the
temperature differences added, the result is
(T" - Tw,,) + (T"" - T,,,) + (T,,, - 7;) = 1/, - 7; = 11 T
=dq (1 --+~+-
dA,",
Xw
dALk m
1)
dA,h,
(11.27)
Assume that the heat-transfer rate is arbitrarily based on the outside area. If Eq.
(11.27) is solved for dq, and if both sides of the resulting equation are divided by
dAo, the result is
dq 1/,-7;
(11.28)
dA, 1 (dA,) Xw (dA,) 1
h, dA, + km dAL + ~
Now
dA, D, dA, D,
and
dA, D, dAL = DL
where Do> Db and DL are the outside, inside, and logarithmic mean diameters of the
tube, respectively. Therefore
dq
(11.29)
dA,
324 HEAT TRANSFER AND ITS APPLTCA TIONS
Comparing Eq. (11.9) with Eq. (11.29) shows that
1
(11.30)
U, = -1 (D,)
- +-x" (D,)
- +-1
hi Dj !cm DL ho
If the inside area A; is chosen as the base area, division of Eq. (11.27) by dA; gives
for the overall coefficient
1
(11.31)
U; = 1 x" (D;) 1 (D,)
~ +!cm DL + ho Do
\(
RESISTANCE F()1RM OF OVERALL COEFFICIENT. A comparison of Eqs. (10.9)
and (11.30) sugie'sIS that the reciprocal of an overall coefficient can be considered
to be an overall resistance composed of three resistances in series. The total, or
overall, resistance is given by the equation
1 Do Xw Do 1
-=-+-~+ (11.32)
Vo Dihj km DL ho
The individual terms on the right-hand side of Eq. (11.32) represent the individual
resistances of the two fluids and of the metal wall. The overall temperature drop is
proportional to I/U, and the temperature drops in the two fluids and the wall are
proportional to the individual resistances, or, for the case of Eq. (11.32),
flT = flT, d7;\J dI'a
(11.33)
I/U, D,/D,", (x,Jkm)(D,/D L ) = l/h,
where fl T = overall temperature drop
fl T, = temperature drop through inside fluid
fl 7;, = temperature drop through metal wall
fl 7; = temperature drop through outside fluid
FOULING FACTORS. In actual service, heat-transfer surfaces do not remain clean.
Scale, dirt, and other solid deposits form on one or both sides of the tubes, provide
additional resistances to heat flow, and reduce the overall coefficient. The effect
of such deposits is taken into account by adding a term l/dA hd to the term in
parentheses in Eq. (11.27) for each scale deposit. Thus, assuming that scale is
deposited on both the inside and the outside surface of the tubes, Eq. (11.27)
becomes, after correction for the effects of scale,
(l1.3 t )
where hd, and "d, are the fouling factors for the scale deposits on the inside and
outside tube surfaces, respectively. The following equations for the overall coeffi-
PRINCIPLES OF HEAT FLOW IN FLUIDS 325
cients based on outside and inside areas, respectively, follow from Eq. (11.34):
and
1
U = (11.36)
, (l/hdi) + (l/h,) + (xw/km)(D,fDL) + (D,fD,h,) + (D,fD,h d ,)
The actual thicknesses of the deposits are neglected in Eqs. (11.35) and (11.36).
Numerical values of fouling factors are given in Ref. 3 corresponding to
satisfactory performance in normal operation, with reasonable service time be-
tween cleanings. They cover a range of approximately 600 to 11,000 W/m2_oC (100
to 2000 Btu/ft 2-h-OF). Fouling factors for ordinary industrial liquids fall in the
range 1700 to 6000 W/m2_oC (300 to 1000 Btu/ft2-h-OF). Fouling factors are
usually set at values that also provide a safety factor for design.
Example 11.1. Methyl alcohol flowing in the inner pipe of a dOUble-pipe exchanger
is cooled with water flowing in the jacket. The inner pipe is made from I-in. (25-mm)
Schedule 40 steel pipe. The thermal conductivity of steel is 26 Btu/ft-h-'F (45 W/m-
QC). The individual coefficients and fouling factors are given in Table 11.1. What is
the overall coefficient, based on the outside area of the inner pipe?
Solution
The diameters and wall thickness of I-in. Schedule 40 pipe, from Appendix 5, are
1.049 1.315 0.133
Di = - - = 0.0874 ft D, = - - = 0.1096 ft Xw = - - = 0.0111 ft
12 12 12
The logarithmic mean diameter DL is calculated as in Eq. (10.15) using diameter
in place of radius:
D, - D, 0.1096 - 0.0874
0.0983 ft
In (D,/D,) In (0.1096/0.0874)
TABLE 11.1
Data ,for Example 11.1
Coefficient
Alcohol coefficient hi 180 !O20
Water coefficient h" 300 1700
Inside fouling factor lid! 1000 5680
Outside fouling factor lido 500 2840
326 HEAT TRANSFER AND ITS APPLICATIONS
The overall coefficient is found from Eq. (11.35):
U,=--~~----~~--~~~~~~--~
0.1096 0.1096 0.0111 x 0.1096 1 1
+ + +--+--
0.0874 x 1000 0.0874 x 180 26 x 0.0983 300 500
= 71.3 Btu/ft'-h-'F (405 W/m'-'C)
SPECIAL C ¥ * THE OVERALL COEFFICIENT. Although the choice of area
to be used as the basis of an overall coefficient is arbitrary, sometimes one
particular area is more convenient than others. Suppose, for example, that one
individual coefficient, h" is large numerically in comparison with the other, h"
and that fouling effects are negligible. Also, assuming the term representing the
resistance of the metal wall is small in comparison with l/h" the ratios D,/D, and
D,(15L have so little significance that they can be disregarded, and Eq. (11.30) can
be replaced by the simpler form
1
U, = -c=---:-:---c-::- (11.37)
l/h, + x,,/km + l/h,
In such a case it is advantageous to base the overall coefficient on that area that
corresponds to the largest resistance, or the lowest value of h.
For large-diameter thin-walled tubes, flat plates or any other case where a
negligible error is caused by using a common area for A" AL , and A" Eq. (11.37)
can be used for the overall coefficient, and U, and U, are identical.
Sometimes one coefficient, say, h" is so very small in comparison with both
x,,/k and the other coefficient h, that the term l/h, is very large compared with
the other terms in the resistance sum. When this is true, the larger resistance is
called the controlling resistance, and it is sufficiently accurate to equate the overall
coefficient to the small individual coefficient, or in this case, h, = U,.
CLASSIFICATION OF INDIVIDUAL HEAT-TRANSFER COEFFICIENTS. The
problem of predicting the rate of heat flow from one fluid to another through a
retaining wall reduces to the problem of predicting the numerical values of the
individual coefficients of the fluids concerned in the overall process. A wide variety
of individual cases is met in practice, and each type of phenomenon must be
considered separately. The following classification will be followed in this text:
1. Heat flow to or from fluids inside tubes, without phase change
2. Heat flow to or from fluids outside tubes, without phase change
3. Heat flow from condensing fluids
4. Heat flow to boiling liquids
MAGNITUDE OF HEAT- TRANL~R
COEFFICIENTS. The ranges of values cov-
ered by the coefficient h vary gr~;,
depending upon the character of the process. 2
Some typical ranges are shown in Table 11.2.
PRINCIPLES OF HEAT FLOW IN FLUIDS 327
TABLE 11.2
Magnitudes of heat-transfer coefficientst
Range of values of !J
Type of processes Btu/ft2-h-CF
Steam (dropwise condensation) 30,000-100,000 5000-20,000
Steam (film-type condensation) 6000-20,000 1000-3000
Boiling water 1700-50,000 300-9000
Condensing organic vapors 1000-2000 200-400
Water (heating or cooling) 300-20,000 50-3000
Oils (heating or cooling) 50-1500 10-300
Steam (superheating) 30·100 5-20
Air (heating or cooling) 1-50 0.2-10
t By permission of author and publisher from W. H. McAdams, Heat Trallsmis-
sion, 3rd ed., p. 5. Copyright by author, 1954, McGraw-HiIl Book Company.
Effective
Heat Transfer j
coe;;Ui~.e.J for
\-'0; f Unsteady-State
In some cases it is convenient to treat unsteady-state heat transfer using an effective
coefficient rather than the exact equations or plots such as Fig. 10.6. For example,
the rate of heat transfer to a spherical particle can be approximated using an
internal coefficient equal to Sklr m and the external area 4m·;;,. The unsteady-state
heat balance for a sphere then becomes
•
pcl3mm)~
.3 dT,,_
- iliA IlT
dt
Sk.2 -
= - (4m m)(T, - 7;) (11.38)
l'm
After rearranging and integrating, with Ta the initial temperature,
T, - T,) ISkt ISat
In ( - - = = --2 = -2- (11.39)
T; -1b PCprm rm
Equation (11.39) is fairly close to the exact solution, Eq. (10.19), when at/r~ is
greater than 0.1. One advantage of using an effective coefficient for the internal
heat transfer is that the effect of external resistance is easily accounted for by
making use of an overall coefficient. Thus for a sphere being heated with air at
temperature T,I'
q = UA(T" - T,,) (11.40)
where A = 4nr;
I/U = (l/il,) + (r"JSk)
328 HEAT TRANSFER AND ITS APPLICATIONS
SYMBOLS
A Area m 2 or ft2; AT' total area of heat-transfer surface; Ai' of inside of
tube; A" of outside of tube; flu logarithmic mean
cp Specific heat at constant pressure, J/g-'C or Btu/lb-'F; cp" of cool
fluid; cph , of warm fluid
D Diameter, m or ft; Db inside diameter of tube; Do, outside diameter of
tube; 15L, logarithmic mean
H Enthalpy, J/g or Btuflb; Ho> at entrance; Hb, at exit; H,a' H,b' of cool
fluid; Hila, Hhb , of warm fluid
h Individual or surface heat-transfer coefficient, W/m2_'C or Btu/ft'-h-'F;
hi' for inside of tube; h" for outside of tube
hd Fouling factor, W/m2_'C or Btu/ft2-h-'F; hdi , inside tube; hdo> outside
tube
k Thermal conductivity, W/m-'C or Btu/ft-h-'F; km' of tube wall
L Length, m or ft
In Mass flow rate, kg/h or Ib/h; In" of cool fluid; li1h' of warm fluid
NNa Nusselt number, hD/k, dimensionless
Q Quantity of heat, J or Btu
q Heat flow rate, W or Btu/h; qT, total in exchanger; q" to cool fluid; qh,
to warm fluid
rm Radius of spherical particle, m or ft
T Temperature, OF or °C; Ta, at inlet, or initial value; T;" at outlet; r::, of
cool fluid; 7;0> at cool-fluid inlet; 7;b, at cool-fluid outlet; 7;" of warm
fluid; Ti/Q' at warm-fluid inlet; ~b' at warm-fluid outlet; 7;, of surface;
~v, of tube wall; ~l'C' on cool-fluid side; ~vll' on warm-fluid side; ~,
bulk average temperature of solid sphere
t Time, h or s
U Overall heat-transfer coefficient, W/m2-'C or Btu/ft2-h-'F; U i , based
on inside surface area; Uo, based on outside surface area; UI> U z , at
ends of exchanger
x Film thickness, m or ft [Eqs. (11.21) to (11.23)]
Xw Thickness of tube wall, m or ft
y Distance into fluid normal to tube wall, m or ft, measured in direction
of heat flow
Greek letters
a Thermal diffusivity, k/pc p , m 2/s or ft2/h
I!.T Overall temperature difference, T;, - 7;, 'C or 'F; I!. 7;, between tube
wall and fluid inside tube; I!.T", between tube wall and fluid outside
tube; I!. Tw, through the tube wall; I!. T" I!. T2 , at ends of exchanger;
I!. Tu logarithmic mean
A Latent heat of vaporization, J/g or Btuflb
p Density of spherical particle, kg/m' or Ib/ft 3
PRINCIPLES OF HEAT FLOW IN FLUIDS 329
PROBLEMS
11.1. Calculate the overall heat-transfer coefficients based on both inside and outside areas
for the following cases.
Case 1 Water at lOoC flowing in a :t-in. 16 BWG condenser tube and saturated steam
at lOSOC condensing on the outside. hi = 12 kW/m2_0C, ho = 14 kW/m2_oC, km =
120 W/m-oC.
Case 2 Benzene condensing at atmospheric pressure on the outside of a 2S-mm steel
pipe and air at 15°C flowing within at 6 m/so The pipe wall is 3.5 mm thick.
hi = 20 W/m2_0 C. ho = 1200 W/m2_oC. km = 45 W/m-°C.
Case 3 Dropwisecondensation from steam at a pressure of 50 Ibf /in. 2 gauge on a I-in.
Schedule 40 steel pipe carrying oil at 100°F. ho = 14,000 Btu/ft2-h-oF. hi =
130 Btu/ft 2-h-oF. km = 26 Btu/ft-h-oF.
11.2. Calculate the temperatures of the inside and outside surfaces of the metal pipe or
tubing in cases 1 to 3 of Prob. 11.1.
11.3. Aniline is to be cooled from 200 to 150°F in a double-pipe heat exchanger having a
total outside area of 70 ft2. For cooling, a stream of toluene amounting to 8600 lbjh
at a temperature of 100°F is available. The exchanger consists of li-in. Schedule 40
pipe in 2-in. Schedule 40 pipe. The aniline flow rate is 10,000Ib/h. (a) If flow is
countercurrent, what are the toluene outlet temperature, the LMTD, and the overall
heat-transfer coefficient? (b) What are they if flow is parallel?
11.4. In the exchanger described in Prob. 11.3, how much aniline can be cooled if the
overall heat-transfer coefficient is 70 Btufft2-h-OF?
11.5. Carbon tetrachloride flowing at 19,000 kgfh is to be cooled from 85 to 40°C using
13,500 kgjh of cooling water at 20°C. The film coefficient for carbon tetrachloride,
outside the tubes, is 1700 W/m2_oC. The wall resistance is negligible, but hi on the
water side, including fouling factors, is 11,000 W/m2_oC, (a) What area is needed for
a counterflow exchanger? (b) By what factor would the area be increased if parallel
flow were used to get more rapid initial cooling of the carbon tetrachloride?
REFERENCES
1. Colburn, A. P.: Ind. Eng. Chem., 25:873 (1933).
2. McAdams, W. H.: Heat Transmission, 3rd ed., McGraw-Hill, New York, 1954, p. 5.
3. Perry, 1. H. (ed.): Chemical Engineers' HandboOk, 6th ed., McGraw-Hill, New York, 1984, p.l0-43.
CHAPTER
12
HEAT
TRANSFER
TO FLUIDS
WITHOUT
PHASE
CHANGE
In a great many applications of heat exchange, heat is transferred between fluid
streams without any phase change in the fluids, This is especially important in
heat recovery operations, as when the hot effluent from an exothermic reactor is
used to preheat the incoming cooler feed. Other examples include the transfer of
heat from a stream of hot gas to cooling water, and the cooling of a hot liquid
stream by air. In such situations the two streams are separated by a metal wall,
which constitutes the heat-transfer surface. The surface may consist of tubes or
other channels of constant cross section, of flat plates, or in such devices as jet
engines and advanced power machinery, of special shapes designed to pack a
maximum area of transfer surface into a small volume.
Most fluid-to-fluid heat transfer is accomplished in steady-state equipment,
but thermal regenerators, in which a bed of solid shapes is alternately heated by
a hot fluid and the hot shapes then used to warm a colder fluid, are also used,
especially in high-temperature heat transfer. Cyclical unsteady-state processes such
as these are not considered in this book.
REGIMES OF HEAT TRANSFER IN FLUIDS. A fluid being heated or cooled may
be flowing in laminar flow, in turbulent flow, or in the transition range between
330
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 331
laminar and turbulent flow. Also, the fluid may be flowing in forced or natural
convection. In some instances more than one flow type may occur in the same
stream; for instance, in laminar flow at low velocities, natural convection may be
superimposed on forced laminar flow.
The direction of flow of the fluid may be parallel to that of the heating
surface, so that boundary-layer separation does not occur, or the direction of flow
may be perpendicular or at an angle to the heating surface, and then boun<iary-
layer separation does take place.
At ordinary velocities the heat generated from fluid friction is usually
negligible in comparison with the heat transferred between the fluids. In most
cases frictional heating may be neglected. It may be important, however, in
operations involving very viscous fluids such as the injection molding of polymers.
In gas flow at high velocities, at Mach numbers above a few tenths, frictional heat
becomes appreciable and cannot be ignored. At very high velocities frictional
heating may become of controlling importance.
Because the conditions of flow at the entrance to a tube differ from those
well downstream from the entrance, the velocity field and the associated tempera-
ture field may depend on the distance from the tube entrance. Also, in some
situations the fluid flows through a preliminary length of unheated or uncooled
pipe so that the fully developed velocity field is established before heat is
transferred to the fluid, and the temperature field is created within an existing
velocity field.
Finally, the properties of the fluid-viscosity, thermal conductivity, specific
heat, and density-are important parameters in heat transfer. Each of these,
especially viscosity, is temperature dependent. Since the temperature varies from
point to point in a flowing stream undergoing heat transfer, a problem appears
in the choice of temperature at which the properties should be evaluated. For
small temperature differences between fluid and wall and for fluids with weak
dependence of viscosity on temperature, the problem is not acute, but for highly
viscous fluids such as heavy petroleum oils or where the temperature difference
between the tube wall and the fluid is large, the variations in fluid properties within
the stream become large, and the difficulty of calculating the heat-transfer rate is
increased.
Because of the various effects noted above, the entire subject of heat transfer
to fluids without phase change is complex and in practice is treated as a series of
special cases rather than as a general theory. All cases considered in this chapter
do, however, have a phenomenon in common: in all of them the formation of a
thermal bonndary layer, analogous to the hydrodynamic Prandtl boundary layer
described in Chap. 3, takes place; it profoundly influences the temperature field
and so controls the rate of heat flow.
THERMAL BOUNDARY LAYER. Consider a flat plate immersed in a stream of
fluid in steady flow and oriented parallel to the plate, as shown in Fig. 12.1a.
Assume that the stream approaching the plate does so at velocity Uo and
temperature Too and that the surface of the plate is maintained at a constant
332 HEAT TRANSFER AND ITS APPLICATIONS
~------------X--------------~>
(aJ
u=Q T=Tw
FIGURE 12.1
Thermal and hydrodynamic
f..--=----J---- X ----~ boundary layers on flat plate:
(a) entire plate heated; (b) un-
(b) heated length = Xo.
temperature Tw' Assume that Tw is greater than Tro, so that the fluid is heated
by the plate. As described in Chap. 3, a boundary layer develops within which the
velocity varies from II = 0 at the wall to II = llO at the outer boundary of the layer.
This boundary layer, called the hydrodynamic boundary layer, is shown by line OA
in Fig. 12.10. The penetration of heat by transfer from the plate to the fluid changes
the temperature of the fluid near the surface of the plate, and a temperature
gradient is generated. The temperature gradient also is confined to a layer next
to the wall, and within the layer the temperature varies from Tw at the wall to
Tro at its outside boundary. This layer, called the thermal boundary layer, is shown
as line OB in Fig. 12.1a. As drawn, lines OA and OB show that the thermal
boundary layer is thinner than the hydrodynamic layer at all values of x, where
x is the distance from the leading edge of the plate.
The relationship between the thicknesses of the two boundary layers at a
given point along the plate depends on the dimensionless Prandtl number, defined
as cpp/k. When the Prandtl number is greater than unity, which is true for most
liquids, the thermal layer is thinner than the hydrodynamic layer, as shown in Fig.
12.10. The Prandtl number of a gas is usually close to 1.0 (0.69 for air, 1.06 for
steam), and the two layers are about the same thickness. Only in heat transfer to
liquid metals, which have very low Prandtl numbers, is the thermal layer much
thicker than the hydrodynamic layer.
Most liquids have higher Prandtl numbers than gases because the viscosity
is generally two or more orders of magnitude higher than for gases, which more
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 333
than offsets the higher thermal conductivity of liquids. With a high-viscosity fluid,
the hydrodynamic boundary layer extends further from the surface of the plate,
which can perhaps be understood intuitively. Imagine moving a flat plate through
a very viscous liquid such as glycerol: fluid at a considerable distance from the
plate will be set in motion, which means a thick boundary layer.
The thickness of the thermal boundary layer increases with thermal con-
ductivity, since a high conductivity leads to greater heat flux and to temperature
gradients extending further into the fluid. The very high conductivity of liquid
metals makes the temperature gradients extend well beyond the hydrodynamic
boundary layer.
In Fig. 12.1a it is assumed that the entire plate is heated and that both
boundary layers start at the leading edge of the plate. If the first section of the
plate is not heated and if the heat-transfer area begins at a definite distance Xo
from the leading edge, as shown by line 0'B in Fig 12.1b, a hydrodynamic
boundary layer already exists at xo, where the thermal boundary layer begins to
form.
The sketches in Fig. 12.1 exaggerate the thickness of the boundary layers for
clarity. The actual thicknesses are usually a few percent of the distance from the
leading edge of the plate.
In flow through a tube, it has been shown (Chap. 3) that the hydrodynamic
boundary layer thickens as the distance from the tube entrance increases, and
finally the layer reaches the center of the tube. The velocity profile so developed,
called jilily developed jlow, establishes a velocity distribution that is unchanged
with additional pipe length. The thermal boundary layer in a heated or cooled
tube also reaches the center of the tube at a definite length from the entrance of
the heated length of the tube, and the temperature profile is fully developed at
this point. Unlike the velocity profile, however, the temperature profile flattens as
the length of the tube increases, and in very long pipes the entire fluid stream
reaches the temperature of the tube wall, the temperature gradients disappear, and
heat transfer ceases.
HEAT TRANSFER BY FORCED
CONVECTION IN LAMINAR FLOW
In laminar flow, heat transfer occurs only by conduction, as there are no eddies
to carry heat by convection across an isothermal surface. The problem is amenable
to mathematical analysis based on the partial differential equations for continuity,
momentum, and energy. Such treatments are beyond the scope of this book and
are given in standard treatises on heat transfer. 6a Mathematical solutions depend
on the boundary conditions established to define the conditions of fluid flow and
heat transfer. When the fluid approaches the heating surface, it may have an
already completed hydrodynamic boundary layer or a partially developed one.
Or the fluid may approach the heating surface at a uniform velocity, and both
boundary layers may be initiated at the same time. A simple flow situation where
the velocity is assumed constant in all cross sections and tube lengths is called
334 HEAT TRANSFER AND ITS APPLICATIONS
plug or rodlike jlow. Independent of the conditions of flow, (1) the heating surface
may be isothermal; or (2) the heat flux may be equal at all points on the heating
surface, in which case the average temperature of the fluid varies linearly with tube
length. Other combinations of boundary conditions are possible. 6 , The basic
differential equation for the several special cases is the same, but the final integrated
relationships differ.
Most of the simpler mathematical derivations are based on the assumptions
that the fluid properties are constant and temperature independent and that flow
is truly laminar with no crosscurrents or eddies. These assumptions are valid when
temperature changes and gradients are small, but with large temperature changes
the simple model is not in accord with physical reality for two reasons. First,
variations in viscosity across the tube distort the usual parabolic velocity-
distribution profile oflaminar flow. Thus, if the fluid is a liquid and is being heated,
the layer near the wall has a lower viscosity than the layers near the center and
the velocity gradient at the wall increases. A crossflow of liquid toward the wall
is generated. If the liquid is being cooled, the reverse effect occurs. Second, since
the temperature field generates density gradients, natural convection may set in,
which further distorts the flow lines of the fluid. The effect of natural convection
may be small or large, depending on a number of factors to be discussed in the
section on natural convection.
In this section three types of heat transfer in laminar flow are considered:
(1) heat transfer to a fluid flowing along a flat plate, (2) heat transfer in plug flow
in tubes, and (3) heat transfer to a fluid stream that is in fully developed flow at the
entrance to the tube. In all cases, the temperature of the heated length of the plate
or tube is assumed to be constant, and the effect of natural convection is ignored.
LA!\jINAR-FLOW HEAT TRANSFER TO FLAT PLATE. Consider heat flow to the
flafplatesl\ov,:r in Fig. 12.1b. The conditions are assumed to be as follows:
Velocity of fluid approaching plate and at and beyond the edge of the
boundary layer OA: u o .
Temperature of fluid approaching plate and at and beyond the edge of the
thermal boundary layer O'B: Too.
Temperature of plate: from x = 0 to x = xo, T = Too; for x > xo, T = Tw ,
where 7;v > T<X).
The following properties of the fluid are constant and temperature In-
dependent: density p, conductivity k, specific heat c P ' and viscosity 1'.
Detailed analysis of the situation yields the equation 2
dT) = O.332(T" - Too) 3fc:i, ru;;p (12.1)
( dy w Jl - (xo/x)3/<Vk V-;;
where (dT/dy)w is the temperature gradient at the wall. From Eq. (11.19), the
relation between the local heat-transfer coefficient hx at any distance x from the
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 335
leading edge and the temperature gradient at the wall is
(12.2)
Eliminating (dT/dy)w gives
h - 0.332k :j¥C
- /1 J¥xoP
p
-
x - ,11 _ (XO/X)'/4 k /1X
This equation can be put into a dimensionless form by mUltiplying by x/k, giving
hxx = 0.332 3fcj. Juoxp (12.3)
k ,11 - (XO/X)3/4-JT /1
The left-hand side of this equation is, from Eq. (11.20), a Nusselt number
corresponding to the distance x, or NNu.x' The second group is the Prandtl number
N p " and the third group is a Reynolds number corresponding to distance x,
denoted by NR,.x' Equation (12.3) then can be written
N _ 0.332 3fj/ ~ (12.4)
Nu,x - 3/ 3/4 V lYPr V lYRe,x
vi - (xo/x)
The local Nusselt number can be interpreted as the ratio of the distance x to the
thickness of the thermal boundary layer, since conduction through a layer of
thickness y would give a coefficient k/y. Thus
hxx kx X
NNu.x = T yk y (12.5)
When the plate is heated over its entire length, as shown in Fig. 12.la, Xo = 0 and
Eq. (12.4) becomes
NNu.x = O.332~ JNRe,x (12.6)
Equation (12.6) gives the local value of the Nusselt number at distance x
from the leading edge. More important in practice is the average value of NNu
over the entire length of the plate Xl' defined as
hXl
NNu=T (12.7)
where
- JX< hxdx
h =1
Xl 0
Equation (12.3) can be written for a plate heated over its entire length, since Xo = 0,
as
C
h =-
xJx
336 HEAT TRANSFER AND ITS APPLICATIONS
where C is a constant containing all factors other than hx and x. Then
C rxo dx 2C 2C
h=xIJo Jx=-;;F,= F,= 2hxo (12.8)
The average coefficient is clearly twice the local coefficient at the end of the plate,
and Eq. (12.6) gives
NNu = 0.664.jN;:; JNR,.x, (12.9)
These equations are valid only for Prandtl numbers of 1.0 or greater, since the
derivation assumes a thermal boundary layer no thicker than the hydrodynamic
layer. However, they can be used for gases with Np , '" 0.7 with little error. The
equations are also restricted to cases where the Nusselt number is fairly large, say,
10 or higher, since axial conduction, which was neglected in the derivation, has a
significant effect for thick boundary layers.
LAMINAR-FLOW HEAT TRANSFER IN TUBES. The simplest situation of lami-
nar-flow heat transfer in tubes is defined by the following conditions. The velocity
of the fluid throughout the tube and at all points in any cross section of the stream
is constant, so that u = Uo = V; the wall temperature is constant; and the
properties of the fluid are independent of temperature. Mathematically this model
is identical to that of heat flow by conduction into a solid rod at constant surface
temperature, using as heating time the period of passage of a cross section of the
fluid stream at velocity V through a tube of length L. This time period is
IT = LjV, Equation (10.18), then, can be used for plug flow of a fluid by substituting
L/Vfor IT in the Fourier number, which becomes
alT 4klT 4kL
NF = .._ = - - = (12.10)
o ,.2 C pD2 C pD2V
m p p
S THE GRAETZ AND PECLET NUMBERS. Two other dimensionless groups are
commonly used in place of the Fourier number in treating heat transfer to fluids.
The Graetz number is defined by the equation
_ ri1C p
N Gz = kL (12.11)
where ril is the mass flow rate. Since lit = ("j4)pVD2,
VC 2
N Gz -- "4 p kL.D (12.12)
The Peclet "umber Np , is defined as the product of the Reynolds number
and the Prandtl number, or
(12.13)
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 337
The choice among these groups is arbitrary. They are related by the equations
nD n
N Gz-
-- 4LNPe-
-N- (12.14)
Fo
In the folJowing discussion the Oraetz number is used.
'>"..j
PLU~OW.
.
EquatIOn (10.18) becomes, for plug flow,
/-
~\/-7b 0.692e-5.78n/NG, + 0.131e-3o.5n/NG, + 0.0534e-74.9n/NG, + ... (12.15)
Tw - T:
Here 7;, and To are the inlet and average outlet fluid temperatures, respectively.
Plug flow is not a realistic model for newtonian fluids, but it does apply to
highly pseudoplastic liquids (n' "" 0) or to plastic liquids having a high value of
the yield stress '0'
FULLY -KLOPED FLOW. With a newtonian fluid in fully developed flow, the
actual YlI:c:t; distribution at the entrance to the heated section and the theoretical
distribution throughout the tube are both parabolic. For this situation the
appropriate boundary conditions lead to the development of another theoretical
equation, of the same form as Eq. (12.15). This is"
Tw - To 0.81904e-3.657n/NG, + 0.09760e-22.3h/NG, + 0.01896e- 53n /NG , + ...
(12.16)
Because of distortions in the flow field from the effects of temperature on
viscosity and density, Eq. (12.16) does not give accurate results. The heat-transfer
rates are usually larger than those predicted by Eq. (12.16), and empirical
correlations have been developed for design purposes. These correlations are based
on the Oraetz number, but they give the film coefficient or the Nusselt number
rather than the change in temperature, since this permits the fluid resistance to
be combined with other resistances in determining an overall heat-transfer coeffi-
cient.
The Nusselt number for heat transfer to a fluid inside a pipe is the film
coefficient multiplied by D/k:
h·D
NNu=-t- (12.17)
The fihn coefficient hi is the average value over the length of the pipe and
is calculated as follows for the case of constant wall temperature:
h. = ,heir" - 7;,) (12.18)
• nDL /lTL
338 HEAT TRANSFER AND ITS APPLICATIONS
Since
Ll TL = (7;. - 7'..) - (7;. - T,) (12.19)
In (7;, - 7'..)
~,,-~
(12.20)
and
NNu = mc p In (7;, - 7'..) (12.21)
nkL 7;, - 1b
or
(12.22)
Using Eqs. (12.22) and (12.16), theoretical values of the Nusselt number can
be obtained, and these values are shown in Fig. 12.2. At low Graetz numbers, only
the first term of Eq. (12.16) is significant, and the Nusselt number approaches a
limiting value of 3.66. It is difficult to get an accurate measurement of the
heat-transfer coefficient at low Graetz numbers, since the final temperature
difference is very small. For example, at N Gz = 1.0, the ratio of exit to inlet driving
forces is only 8.3 x 10- 6 •
60
40 I 1.1.
_L ~t'Q't>J.,e
~'Q~~~J..
'3,(1" /
20
(Is:""
CO,.. .)~
~\~frr~(\~~;e('Q\U(e
'Q\\
0
--
\e(fl
s't'Q(I\ ~
COO
6-Theory,
4
-constant flux
- \neO(""
2
Vha D
/
/
1 / I1 10 100 1,000
FIGURE 12.2
Heat transfer for laminar flow in tubes with a parabolic velocity profile. (Does not include effects of
natural convection or viscosity gradients.)
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 339
For Graetz numbers greater than 20, the theoretical Nusselt number in-
creases with about the one-third power of N Gz ' Data for air and for moderate-
viscosity liquids follow a similar trend, but the coefficients are about 15 percent
greater than predicted from theory. An empirical equation for moderate Graetz
numbers (greater than 20) is
(12.23)
The increase in film coefficient with increasing Graetz number or decreasing
length is a result of the change in shape of the temperature profile. For short
lengths, the thermal boundary layer is very thin, and the steep temperature
gradient gives a high local coefficient. With increasing distance from the entrance,
the boundary layer becomes thicker and eventually reaches the center of the pipe,
giving a nearly parabolic temperature profile. The local coefficient is approximately
constant from that point on, but the average coefficient continues to decrease with
increasing length until the effect of the high initial coefficient is negligible. In
practice, the change in local coefficient with length is usually not calculated, and
the length-average film coefficient is used in obtaining the overall coefficient.
CORREC ON FOR HEATING OR COOLING. For very viscous liquids with large
tempera re drops, a modification of Eq. (12.23) is required to account for
differences bet een heating and cooling. When a liquid is being heated, the lower
viscosity near the wall makes the velocity profile more like that for plug flow, with
a very steep gradient near the wall and little gradient near the center. This leads
to a higher rate of heat transfer, as can be shown by comparing temperature
approaches calculated from Eqs. (12.15) and (12.16). When a viscous liquid is
cooled, the velocity gradient at the wall is decreased, giving a lower rate of heat
transfer. A dimensionless, but empirical, correction factor <p, accounts for the
difference between heating and cooling:
_(1'- )0.14
<p, = (12.24)
I'w
This factor is added to Eq. (12.23) to give the final equation for laminar-f1ow
heat transfer:
N Nu = 2( 'he
-p
kL
)1/3(- I' )0.14 = 2N' /3"
Gz 0/11
(12.25)
I'w
In Eqs. (12.24) and (12.25), I' is the viscosity at the arithmetic mean
temperature of the fluid, er.. + Tj,)/2, and I'w is the viscosity at the wall temperature
7;,. For liquids I'w < I' and <p, > 1.0 when the liquid is being heated, and I'w > I'
and <p, < 1.0 when the liquid is being cooled. The viscosity of a gas increases with
temperature, so these inequalities are reversed for a gas. The change in viscosity
of a gas, however, is relatively small, and the term <p, is usually omitted when
dealing with gases. The change in gas density with temperature is of more
importance, and this will be discussed when dealing with natural convection.
340 HEAT TRANSFER AND ITS APPLICATIONS
The coefficients presented in Eqs. (12.17) to (12.25) are based on a logarithmic
mean driving force!'. TL • Some workers have presented correlations for a coefficient
ho based on the arithmetic mean driving force, !'.1'". When the Graetz number is
10 or larger, the ratio of inlet to exit driving forces is less than 2.0, and there is
little difference between !'.TL and!'. 1'" or between hand h o • However, at low Graetz
numbers the temperature approach becomes very small, and the coefficient ho
varies inversely with the Graetz number, as shown in Fig. 11.2. There is no
apparent advantage to using ho, and h is recommended for design calculations.
The equations and experimental results discussed up to this point are for
constant wall temperature and would apply for heating a fluid with a condensing
vapor. If a counterflow exchanger is used, the wall temperature will change along
the length of the exchanger, and this will affect the film coefficient for laminar
flow. If the two streams have about the same flow rate and heat capacity, the
temperature driving force and the heat flux will be nearly constant. The theoretical
equation for constant heat flux and parabolic flow gives a limiting Nusselt number
of 4.37, compared to 3.66 for constant Tw. At high Graetz numbers, the predicted
coefficient for constant flux is also higher than for constant wall temperature, but
there are not enough experimental results to develop a separate equation for the
case of constant flux.
HEAT iR~SFER TO NON-NEWTONIAN LIQUIDS IN LAMINAR FLOW. For
heat tr~sfeNo and from liquids that follow the power-law relation [Eq. (3.7)],
Eq. (12.25) is modified to 10
liD =
_._ 2~1/3 ('ile )1 /3( )0.14
_P _tn (12.26)
k kL tnw
where" = (311' + 1)/411'
m= K,sn' -1, at arithmetic mean temperature
mw = value of m at Tw
K' = flow consistency index
11' = flow behavior index
For shear-thinning fluids (n' < 1), the non-newtonian behavior makes the
velocity profile more like that for plug flow and increases the heat-transfer
coefficient. When n' = 0.1, the coefficient for large Graetz numbers is about 1.5
times that for parabolic flow (n' = 1.0). The limit of n' = 0 corresponds to true
plug flow and the coefficients can be as large as twice those for parabolic flow.
Figure 12.2 shows the Nusselt number for plug flow as a dashed line, the slope
of which approaches 0.5 at high Graetz numbers.
HEAT TRANSFER BY FORCED
CONVECTION IN TURBULENT FLOW
Perhaps the most important situation in heat transfer is the heat flow in a stream
of fluid in turbulent flow in a closed channel, especially in tubes. Turbulence is
encountered at Reynolds numbers greater than about 2100, and since the rate of
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 341
heat transfer is greater in turbulent flow than in laminar flow, most equipment is
operated in the turbulent range.
The earliest approach to this case was based on empirical correlations of
test data guided by dimensional analysis. The equations so obtained still are much
used in design. Subsequently, theoretical study has been given to the problem. A
deeper understanding of the mechanism of turbulent-flow heat transfer has been
achieved, and improved equations applicable over wider ranges of conditions have
been obtained.
DIMENSIO~NALYSIS METHOD. Dimensional analysis of the heat flow to
a fluid in tl) u nt flow in a long, straight pipe yields the dimensionless relation-
ship
hD = <1>(DV p Cpfl) = <1>(DG Cpfl) (12.27)
k fl'k fl'k
Here the mass velocity G is used in place of its equal Vp. Dividing both
sides of Eq. (12.27) by the product (DGIf1)(cpfl/k) gives an alternate relationship
~= <1>1(DG, Cpfl) (12.28)
cpG fl k
The three groups in Eq. (12.27) are the Nusselt, Reynolds, and Prandtl
numbers, respectively. The left-hand group in Eq. (12.28) is called the Stanlon
number N st . The four groups are related by the equation
(12.29)
Thus, only three of the four are independent.
EMPIRICAiYQUATIONS. To use Eq. (12.27) or (12.28), the function <1> or <1>,
must be 7no~. One empirical correlation for long tubes with sharp-edged
entrances is the'Dittus-Boelter equation
hiD
-=0.023 (DG)0.S(Cpfl)'/3
- - (12.30)
le fl k
This is the dimensionless form of Eq. (1.42) in Chap. 1, Example 1.2. Equation
(12.30) has been modified to allow for heating and cooling, as in Eq. (12.25) for
laminar flow. The modified rela~nship for. turbulent flowS is known as the
Sieder-Tate equation. It is ' /A?e ')0/',,-
'/
Pc'NI',
hP
-=0.023 (DG)0.S(Cpfl)'/3Gfl
- - - )0.'. (12.31)
k fl k w
An alternate form of Eq. (12.31) is obtained by dividing both sides by
(DG/fl)(cpfl/k) and transposing, to give the Colburn equation:
/
~ (C pl')2 3(flw)0." = 0.023 (12.32)
cpG k I' (DG/fl)0.2
342 HEAT TRANSFER AND ITS APPLICATIONS
In using these equations, the physical properties of the fluid, except for J1.w,
are evaluated at the bulk temperature T. Equations (12.31) and (12.32) can be
written in more compact form as
(12.33)
and
N 8t N Pr
2 / 3 -1.- 1 = 0023N-o. 2
'Pv . Re (12.34)
Equations (12.31) to (12.34) are not fundamentally different equations; they
are merely alternative ways of expressing the same information. They should not
be used for Reynolds numbers below 6000 or for molten metals, which have
abnormally low Prandtl numbers.
Eff;~~Ube length. Near the tube entrance, where the temperature gradients are
stIly(o;,nmg, the local coeffiCIent hx IS greater than hoo for fully developed flow.
At the entrance itself, where there is no previously established temperature
gradient, hx is infinite. Its value drops rapidly toward hoo in a comparatively short
length of tube. Dimensionally, the effect of tube length is accounted for by another
dimensionless group, xlD, where x is the distance from the tube entrance. The
local coefficient approaches hoo asymptotically with increase in x, but it is
practically equal to hoo when xlD is about 50. The average value of hx over the
tube length is denoted by hi' The value of hi is found by integrating hx over the
length of the tube. Since hx -+ hoo as x -+ 00, the relation between hi and hoo is of the
form 6b
h·
-'-=I+ljJ -
!zoo D
(L) (12.35)
An equation for short tubes with sharp-edged entrances, where the velocity
at entrance is uniform over the cross section, is
hi
-=1+ (D)O.7
- (12.36)
hoo L
The effect of tube length on hi fades out when LID becomes greater than about
50.
" IVALUE OF IIi IN TURBULENT FLOW. Since the temperature of the
AVERAG-l{
fluid c;I1ang~ from one end of the tube to the other and the fluid properties J1., k,
and t{p are all functions of temperaturc, the local valuc of hi also varics from point
to point along the tube. This variation is independent of the effect of tube length.
The effect of fluid properties can be shown by condensing Eq. (12.31) to read,
assuming (J1.1J1.w) = 1,
(12.37)
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 343
For gases the effect of temperature on hi is smalL At constant mass velocity
in a given tube, hi varies with k2/3C!/3/l-0.47. The increase in thermal conductivity
and heat capacity with temperature offset the rise in viscosity, giving a slight
increase in hi For example, for air hi increases about 6 percent when the
<
temperature changes from 50 to 100'C.
For liquids the effect of temperature is much greater than for gases because
of the rapid decrease in viscosity with rising temperature. The effects of k, cP' and
I' in Eq. (12.37) all act in the same direction, but the increase in hi with temperature
is due mainly to the effect of temperature on viscosity. For water, for example, hi
increases about 50 percent over a temperature range from 50 to 100'C. For viscous
oils the change in hi may be two- or threefold for a 50'C increase in temperature.
In practice, unless the variation in hi over the length of the tube is more than
about 2: 1, an average value of hi is calculated and used as a constant in calculating
the overall coefficient U. This procedure neglects the variation of U over the tube
length and allows the use of the LMTD in calculating the area of the heating
surface. The average value of hi is computed by evaluating the fluid properties cp ,
k, and I' at the average fluid temperature, defined as the arithmetic mean between
the inlet and outlet temperatures. The value of hi calculated from Eq. (12.31), using
these property values, is called the average coefficient. For example, assume that
the fluid enters at 30'C and leaves at 90'C. The average fluid temperature is
(30 + 90)/2 = 60'C, and the values of the properties used to calculate the average
value of hi are those at 60'C.
For larger changes in hi' two procedures can be used: (1) The values of hi
at the inlet and outlet can be calculated, corresponding values of U, and U2 found,
and Eq. (11.16) used. Here the effect of L/D on the entrance value of hi is ignored.
(2) For even larger variations in hi' and therefore in U, the tube can be divided
into sections and an average U used for each section. Then the lengths of the
individual sections can be added to account for the total length of the tu be.
ESTIMATION OF WALL TEMPERATURE T,... To evaluate I'w, the viscosity of the
fluid at the wall, temperature 7;, must be found. The estimation of 7;, requires an
iterative calculation based on the resistance equation (11.33). If the individual
resistances can be estimated, the total temperature drop !;'T can be split into the
individual temperature drops by the use of this equation and an approximate
value for the wall temperature found. To determine Tw in this way, the wall
resistance (xw/km)(D Jf5L ) can usually be neglected, and Eq. (11.33) used as follows.
From the first two members of Eq. (11.33)
!;.T, = D,/Dihi!;'T (12.38)
, I/U,
Substituting l/U, from Eq. (11.30) and neglecting the wall-resistance term gives
!;. T, = l/hi !;. T (12.39)
, l/hi + DJD,h,
344 HEAT TRANSFER AND ITS APPLICATIONS
In qualitative terms Eq. (12.39) may be written
inside resistance
LlY, = LlT
overall resistance
Use of Eq. (12.39) requires preliminary estimates of the coefficients hi and h,.
To estimate hi' Eq. (12.31) can be used, neglecting <Po. The calculation of h, will
be described later. The wall temperature 7;, is then obtained from the following
equations:
For heating: (12.40)
For cooling: (12.41)
where T is the average flnid temperature.
If the first approximation is not sufficiently accurate, a second calculation
of 7;, based on the results of the first can be made. Unless the factor <p, is quite
different from unity, however, the second approximation is unnecessary.
~ample 12.1. Toluene is being condensed at 230°F (110°C) on the outside of i-in.
(19-mm) BWG 16 copper condenser tubes through which cooling water is flowing
at an average temperature of 80°F (26.7°C). Individual heat-transfer coefficients are
given in Table 12.1. Neglecting the resistance of the tube wall, what is the tube-wall
temperature?
Solution
From Appendix 6, Di = 0.620 in.; D, = 0.750 in. Hence, from Eq. (12.39)
1/400 (230 _ 80) = 90.3'F
1/400 + 0.620/(0.750 x 500)
Since the water is being heated by the condensing toluene, the wall temperature
is found from Eq. (12.40) as follows:
Tw = 80 + 90.3 = 170.3'F (76.8'C)
CROSS SECTIONS OTHER THAN CIRCULAR. To use Eq. (12.31) or (12.32) for
cross sections other than circular, it is only necessary to replace the diameter D
in both Reynolds and Nusselt numbers by the equivalent diameter D eo defined as
~ IJ (°3
TABLE 12.1
Data for Example 12.1
Heat-transfer coefficient
For cooling water hi 400 2270
For toluene h" 500 2840
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 345
4 times the hydraulic radius rH' The method is the same as that used in calculating
friction loss.
, ~Ie 12.2. Benzene is cooled from 141 to 79"F (60.6 to 21.1"C) in the inner pipe
V :t:":t~uble-pipe exchanger. Cooling water flows countercurrently to the benzene,
entering the jacket at 65"F (18.3"C) and leaving at 75"F (23.9"C). The exchanger
consists of an inner pipe of t-in (22.2-mm) BWG 16 copper tubing jacketed with
It-in (38.1-mm) Schedule 40 steel pipe. The linear velocity of the benzene is 5 ft/s
(1.52 m/s). Neglecting the resistance of the wall and scale films and assuming
LID> 150 for both pipes, compute the film coefficients of the benzene and water
and the overall coefficient based on the outside area of the inner pipe.
Solution
The average temperature of the benzene is (141 + 79)/2 ~ 1l0"F; that of the water
is (65 + 75}j2 ~ 70"F. The physical properties at these temperatures are given in
Table 12.2. The diameters of the inner tube are
0.745 0.875
D" ~ -- ~ 0.0621 ft D" ~ - - ~ 0.0729 ft
12 12
The inside diameter of the jacket is, from Appendix 5
1.610
D.. ~ - - ~ 0.1342 ft
IJ 12
The equivalent diameter of the annular jacket space is found as follows. The
cross-sectional area is (1</4)(0.1342 2 - 0.0729 2) or 0.00997 ft'. The wetted perimeter is
1t(0.1342 + 0.0729). The hydraulic radius is
(1t/4)(0.1342' - 0.0729')
r 1l = HO.1342 - 0.0729) = ~ x 0.0613 ft
1t(0.1342 + 0.0729)
The equivalent diameter De = 4rH = 0.0613 ft.
TABLE 12.2
Data for Example 12.2
Value at average fluid temperature
Property Benzene Watert
Density p, Ib/ft 3 53.1 62.3
Viscosity p, Ib/ft-h 1.16t 2.42 x 0.982 = 2.34
Thermal conductivity k, Btu/ft-h_oF 0.089§ 0.346
Specific heat cp. Btuf1b-cF 0.4351[ 1.000
t Appendix 14.
:j: Appendix 9.
§ Appendix 13.
'if Appendix 16.
346 HEAT TRANSFER AND ITS APPLICATIONS
First the velocity of the water must be computed from the heat flow and the
temperature rise in the water. The heat flow, in turn, is found from the mass flow
rate of the benzene, Inb' given by
where S is the inside sectional area of the copper tube. From Appendix 6, for a
il-in. BWG i6 tube, S = 0.00303 ft2. Thus
/i" = 5 x 53.1 x 0.00303 = 0.804 Ibis
The rate of heat flow q, found by multiplying the mass flow, specific heat, and
temperature change of the benzene, is
q = 0.804 x 0.435 x (141 - 79)..
= 21.68 Btu/s
The mass flow rate of the water 1hw is then
. 21.68
mw = 1.000 x (75 _ 65) 2.168 Ibis
The water velocity 17w is
_ 2.168
V. = 3.49 ft/s
w 0.00997 x 62.3
The Reynolds number and Prandtl number of each stream are next computed:
D"Vp 0.0621 x 5 x 3600 x 53.1
Benzene: N R• = - - = 5.12 X 104
I' 1.16
cpl' 0.435 x 1.16
Np, = - = =5.67
k 0.089
D,Vp 0.0613 x 3.49 x 3600 x 62.3
Water: N Re = - - 2.05 X 104
I' 2.34
1.00 x 2.34
Np, = = 6.76
0.346
Preliminary estimates of the coefficients are obtained from Eq. (12.32) omitting
the correction for viscosity ratio:
0.023 x 5 x 3600 x 53.1 x 0.435
Benzene: hi = --:-::-:c:--=c-:;---;-:::;;;;-- 344 Btu/ft 2 -h-'F
(5.12 x 104 )°.2 x 5.67 2 /3
0.023 x 3.49 x 3600 x 62.3 x 1.000
Water: ho = ---:::-:-::--==:----:c::-:-;;-;;;--- 691 Btu/ft2-h-'F
(2.05 x 104 )°.2 x 6.762 / 3
In these calculations use is made of the fact that G = V p.
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 347
The temperature drop over the benzene resistance, from Eq. (12.39), is
1/344
t.T= (110-70) = 28.l°F
, 1/344 + 0.0621/(0.0729 x 691)
Tw = 110 - 28.1 = 81.9°F
The viscosities of the liquids at Tw are now found.
1.45 Ib/ft-h for benzene
{
I'w = 0.852 x 2.42 = 2.06Ib/ft-h for water
The viscosity-correction factors c/Jv, from Eq. (12.24), are
-
1.16)0.,4 =0.969 for benzene
1.45
{(
r/>, = (2.34)0'"
- = 1.018 for water
2.06
The corrected coefficients are
Benzene: hi = 344 x 0.969 = 333 Btu/ft'-h-oF (1891 W/m'-°C)
Water: ho = 691 x 1.018 = 703 Btu/ft'-h-oF (3992 W/m'-°C)
The temperature drop over the benzene resistance and the wall temperature
become
1/333
t.T = (110 - 70) = 28SF
, 1/333 + 0.0621/(0.0729 x 703)
Tw = 110 - 28.5 = 81SF
This is so close to the wall temperature calculated previously that a second
approximation is unnecessary.
The overall coefficient is found from Eq. (11.29) neglecting the resistance of
the tube wall:
0.0729 I
--,--- + - = 0.00495
Uo 0.0621 x 333 703
I
U = - - = 202 Btu/ft'-h-oF (1147 W/m'-°C)
° 0.00495
ROUGHNESS. For equal Reynolds numbers the heat-transfer coeffi-
bulent flow is somewhat greater for a rough tube than for a smooth
ect of roughness on heat transfer is much less than on fluid friction,
and econ mic ally it is usually more important to use a smooth tube for minimum
friction foss than to rely on roughness to yield a larger heat-transfer coefficient.
The effect of roughness on hi is neglected in practical calculations.
HEAT TRA¥~R AT HIGH VELOCiTIES. When a fluid flows through a tube at
high velocjties, temperature gradients appear even when there is no heat transfer
348 HEAT TRANSFER AND ITS APPLICATIONS
through the wall and q = O. In injection molding, for example, polymer melt flows
into the cavity at a very high velocity and the steep velocity gradients in the viscous
liquid cause heat to be generated in the fluid by what is called viscous dissipation.
In the high-velocity flow of compressible gases in pipes, friction at the wall raises
the temperature of the fluid at the wall above the average fluid temperature." The
temperature difference between wall and fluid causes a flow of heat from wall to
fluid, and a steady state is reached when the rate of heat generation from friction
at the wall equals the rate of heat transfer back into the fluid stream. The constant
wall temperature thus attained is called the adiabatic wall temperature. Further
treatment of this subject is beyond the scope of this text. The effect becomes
appreciable for Mach numbers above approximately 0.4, and appropriate equa-
tions m~st be used in this range of velocities instead of Eqs. (12.31) and (12.32).
",
.,
'',. j
Transfer IJ».,Turbulent Eddies and Analogy between
Transfer of Momentum and Heat
On pages 92 to 98 the distribution of velocity and its accompanying momentum
flux in a flowing stream in turbulent flow through a pipe was described. Three
rather ill-defined zones in the cross section of the pipe were identified. In the first,
immediately next to the wall, eddies are rare, and momentum flow occurs almost
entirely by viscosity; in the second, a mixed regime of combined viscous and
turbulent momentum transfer occurs; in the main part of the stream, which
occupies the bulk of the cross section of the stream, only the momentum flow
generated by the Reynolds stresses of turbulent flow is important. The three zones
are called the viscous sublayer, the buffer zone, and the turbulent core, respectively.
In heat transfer at the wall of the tube to or from the fluid stream, the same
hydrodynamic distributions of velocity and of momentum fluxes still persist, and
in addition, a temperature gradient is superimposed on the turbulent-Iaminar
velocity field. In the following treatment both gradients are assumed to be
completely developed and the effect of tube length negligible.
Throughout the stream of fluid, heat flow by conduction occurs in accor-
dance with the equation
q, dT
-=-k- (12.42)
A dy
where q, = rate of heat flow by conduction
k = thermal conductivity
A = area of isothermal surface
dT/dy = temperature gradient across isothermal surface
The isothermal surface is a cylinder concentric with the axis of the pipe and
located a distance y from the wall, or I' from the center of the pipe. Here I' + y = I' w'
where rw is the radius of the pipe.
In addition to conduction, the eddies of turbulent flow carry heat by
convection across each isothermal area. Although both mechanisms of heat flow
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 349
may occur wherever a temperature gradient exists (dT/dy 'i' 0), their relative
importance varies greatly with distance from the wall. At the tube wall itself eddies
very rarely exist, and the heat flux is entirely due to conduction. Equation (12.42)
written for the wall is
(12.43)
where (q/A)w = total heat flux at wall
(dT/dy)w = temperature gradient at wall
These quantities are identical with those in Eqs. (11.18) and (11.19).
Within the viscous sublayer heat flows mainly by conduction, but eddies are
not completely excluded from this zone, and some convection does occur. The
relative importance of turbulent heat flux compared with conductive heat flux
increases rapidly with distance from the wall. In ordinary fluids, having Prandtl
numbers above about 0.6, conduction is entirely negligible in the turbulent core,
but it may be significant in the buffer zone when the Prandtl number is in the
neighborhood of unity. Conduction is negligible in this zone when the Prandtl
number is large.
The situation is analogous to momentum flux, where the relative importance
of turbulent shear to viscous shear follows the same general pattern. Under certain
ideal conditions, the correspondence between heat flow and momentum flow is
exact, and at any specific value of r/rw the ratio of heat transfer by conduction to
that by turbulence equals the ratio of momentum flux by viscous forces to that
by Reynolds stresses. In the general case, however, the correspondence is only
approximate and may be greatly in error. J:he study of the relationship between
heat and momentum flux for the entire spectrum of fluids leads to the so-called
analogy theory, and the equations so derived are called analogy equations. A
detailed treatment of the theory is beyond the scope of this book, but some of the
more elementary relationships are considered.
Since eddies continually cross an isothermal surface from both directions,
they carry heat between layers on either side of the surface, which are at different
average temperatures. At a given point the temperature fluctuates rapidly about
the constant mean temperature at that point, depending on whether a "hot" or
a "cold" eddy is crossing through the point. The temperature fluctuations form a
pattern with respect to both time and place, just like the fluctuations in velocity
and pressure described on pages 50 to 54. The instantaneous temperature T, at
the point can be split into two parts, the constant average temperature T at the
point and the fluctuating or deviating temperature T', or
T,=T+T' (12.44)
The time average of the deviating temperature T', denoted by T', is zero, and
the time-average value of the total instantaneous temperature, denoted by T" is
T. The average temperature T is that measured by an ordinary thermometer. To
350 HEAT TRANSFER AND ITS APPLICATIONS
measure T, and so find T' requires special sensing devices that can follow rapid
temperature changes.
)C
THE ;EDDr DIFFUSIVITY OF HEAT. When there is no temperature gradient
across the iSbthermal surface, all eddies have the same temperature independent
of the point of origin, dT(dy = 0, and no net heat flow occurs. If a temperature
gradient exists, an analysis equivalent to that leading to Eq. (3.17) shows that the
eddies carry a net heat flux from the higher temperature to the lower, in accordance
with the equation
q, -
- = -c pv'T' (12.45)
A p
where v' is the deviating velocity across the surface and the overbar indicates the
time average of the product v'T'. Although the time averages i7 and T'individually
are zero, the average of their product is not, because a correlation exists between
these deviating quantities when dT(dy # 0, in the same way that the deviating
velocities u' and v' are correlated when a velocity gradient du(dy exists.
On page 55 an eddy diffusivity for momentum transfer BM was defined. A
corresponding eddy diffusivity for heat transfer BH can be defined by
~ == -B
H
dT = -v'T' (12.46)
cppA dy
The subscript t refers to the fact that Eq. (12.46) applies to turbulent convection
heat transfer. Since conduction also takes place, the total heat flux at a given
point, denoted by q, is, from Eqs. (12.42) and (12.46),
q q, q, dT dT
- = - + - = - k - - c PBH-
A A A dy p dy
or
(12.47)
where a is the thermal diffusivity, k(cpp. The equation for the total momentum
flnx corresponding to Eq. (12.47) is Eq. (3.20) written as
'g, du
(12.48)
- = (v +SM)-
p dy
where v is the kinematic viscosity, 1'(p.
SIGNIFICANC1bF PRANDTL NUMBER; THE EDDY DIFFUSIVITIES. The
physical signifia . ce, of the Prandt! number appears on noting that it is the ratio
via; it is therefo e a'measure of the magnitude of the momentum diffusivity relative
to that of the tliermal diffusivity. Its numerical value depends on the temperature
and pressure of the fluid, and therefore it is a true property. The magnitude of the
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 351
Prandtl numbers encountered in practice covers a wide range. For liquid metals
it is of the order 0.01 to 0.04. For diatomic gases it is about 0.7, and for water at
70°C it is about 2.5. For viscous liquids and concentrated solutions it may be as
large as 600. Prandtl numbers for various gases and liquids are given in Appendixes
17 and 18.
The eddy diffusitives for momentum and heat, eM and eH, respectively, are not
properties of the fluid but depend on the conditions of flow, especially on all factors
that affect turbulence. For simple analogies, it is sometimes assumed that eM and
eH are both constants and equal, but when determined by actual velocity and
temperature measurements, both are found to be functions of the Reynolds
number, the Prandtl number, and position in the tube cross section. Precise
measurement of the eddy diffusivities is difficult, and not all reported measure-
ments agree. Results are given in standard treatises·' The ratio eH/eM also varies
but is more nearly constant than the individual quantities. The ratio is denoted
by .p. For ordinary liquids, where N p , > 0.6, .p is close to 1 at the tube wall and
in boundary layers generally and approaches 2 in turbulent wakes. For liquid
metals .p is low near the wall, passes through a maximum of about unity at
y/rw "" 0.2, \decre~:.es toward the center of the pipe."
THE REYNOLDtAIlPGY. The simplest and oldest analogy equation is that of
Reynolds, whicJr~l\derived for flow at high Reynolds numbers in straight round
tubes. It is based, however, on several questionable assumptions:
1. The ratio of the two molecular diffusivities equals that of the two eddy
diffusivities, or
2. The heat flux q/A varies linearly with radius r.
3. The point where the local fluid temperature equals the average bulk tempera-
ture T is at the same radial distance from the tube wall as the point where
u=v.
Applying these assumptions to Eqs. (12.47) and (12.48) leads to the relation
~N -£
cpG Pr - 2
(12.49)
For the special case where N p , = 1 and eM = eH'
~=N
CpG -
-£2
SI -
(12.50)
This is the usual form of the Reynolds analogy equation. It agrees fairly well with
experimental data for most gases, which have Prandtl numbers of about unity,
provided the temperature drop Tw - T is not large.
352 HEAT TRANSFER AND ITS APPLICATIONS
\ /
.
THE CUi-BURN ANALOGY; COLBURN j FACTOR. Over a range of Reynolds
numbertirom 5000 to 200,000 the friction factor for smooth pipes is adequately
given by the empirical equation
DG)-O.2
f = 0.046 ( -;; (12.51)
Comparison of Eq. (12.51) with Eq. (12.32) for heat transfer in turbulent flow
inside long tubes shows that
~ N2f3(I'W)O.'4
P,
=' _ £
-lH- (12.52)
cp G I' 2
Eqnation (12.52) is a statement of the Colbum analogy between heat transfer
and fluid friction. The factor jH' defined as (hlcpG)(cpl'lkj'f3(l'wll')o.14, is called the
Colburn j factor. It is used in a number of other semiempirical equations for heat
transfer. While the Reynolds analogy [Eq. (12.50)] applies only to fluids for which
the Prandtl number is close to unity, the Colburn analogy [Eq. (12.52)J applies
over a range of Prandtl numbers from 0.6 to about 100.
Equation (12.32) can be written in j-factor form as follows:
(12.53)
MORE ACCURATE ANALOGY EQUATIONS. A number of more elaborate anal-
ogy equations connecting friction and heat transfer in pipes, along flat plates, and
in annular spaces have been published. They cover wider ranges of Reynolds and
Prandtl numbers than Eq. (12.52) and are of the general form
N _ fl2 (12.54)
SI - <J>(Np,)
where <J>(Np,) is a complicated function of the Prandtl number. One example,
by Friend and Metzner,' applying to fully developed flow in smooth pipe is
fl2
Ns, = ----;====------ (12.55)
1.20 + Jiii(N p , - 1)(Np ,)-lf 3
The friction factor f used in this equation may be that given by Eq. (12.51) or,
for a wider range of Reynolds numbers from 3000 to 3 X 106, by the equation
0.125
f = 0.00140 + ----0.32 (12.56)
N R,
Equation (12.55) is said to apply over a range of Prandtl numbers from 0.5 to
600.
All analogy equations connecting f and h have an important limitation. They
apply only to wall, or skin, friction and must not be used for situations where form
drag appears.
353
3
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE
Heat Transfer in Transition Region between
Laminar and Tnrbulent Flow
Equation (12.32) applies only for Reynolds numbers greater than 6000 and Eq.
(12.25) only for Reynolds numbers less than 2100. The range of Reynolds numbers
between 2100 and 6000 is called the transition region, and no simple equation
applies here. A graphical method therefore is used. The method is based on graphs
of Eqs. (12.25) and (12.32) on a common plot of the Colburn j factor vs. N R " with
lines of constant values of LID. To obtain an equation for the laminar-flow range,
it is necessary to transform Eq. (12.25) in the following manner. Substituted for
the Graetz number, using Eqs. (12.13) and (12.14), is the quantity (nDI4L)NR,Np ,.
The result is
_ (nD
NNu - 2 NReNpr
)1 /3(!!:...)O.'4
4L I'w
This relation is multiplied by (lINR,)(lINp ,) to give the j factor. The final
equation can be written
-
h; (C- l')2 /3(l'w)O.'4.
p
- =JH =
(D)' /3(DG)-Z
1.86 - -
I3
(12.57)
cpG k I' L I'
Equation (12.57) shows that for each value of the length-diameter ratio LID,
a logarithmic plot of the left-hand side vs. N R , gives a straight line with a slope
of -j. 'rhe straight lines on the left-hand portion of Fig. 12.3 are plots of this
equation for a few values of LID. The lines terminate at a Reynolds number of2100.
Equation (12.57) should not be used for LID> 100, since it may give
coefficients smaller than the limiting values shown in Fig. 12.2.
Equation (12.32), when plotted for long tubes on the same coordinates, gives
a straight line with a slope of - 0.20 for Reynolds numbers above 6000. This
line is drawn in the right-hand region of Fig. 12.3.
The curved lines between Reynolds numbers of 2100 and 6000 represent
the transition region. The effect of LID is pronounced at the lower Reynolds
numbers in this region and fades out as a Reynolds number of 6000 is approached.
Figure 12.3 is a summary chart that can be used for the entire range of
Reynolds numbers from 1000 to 30,000. Beyond its lower and upper limits, Eqs.
(12.25) and (12.32) respectively, can be used.
Exam~12.3. A light motor oil with the characteristics given below and in Table
12.3 j t be heated from 150 to 250'F (65.5 to 121.1 'C) in a tin. (6.35-mm)
Schedule 4 pipe 15 ft (4.57 m) long. The pipe wall is at 350'F (176.7'C). How much
oil can be heated in this pipe, in pounds per hour? What coefficient can be expected?
The properties of the oil are as follows: The thermal conductivity is 0.082 Btujft-h_oF
(0.142 Wjm-'C). The specific heat is 0.48 BtujIb-'F (2.01 Jjg-'C).
Solution
Assume the flow is laminar and that the Graetz number is large enough for Eq.
(12.25) to apply.
:154 HEAT TRANSFER AND ITS APPLICATIONS
0.01
~''sO
~~ /':: / °0
~ /
e--
----
0.001 3
10
FIGURE 12.3
Heat transfer in transition range. (By permission of author andpublisher,from W. H. McAdams, Heat
Transmission, 3rd ed. Copyright by author, 1954, McGraw-Hill Book Company.)
Data for substitution into Eq. (12.25) are
6.0 + 3.3 0.364
I' = --::-- 4.65 cP I'w = 1.37 cP D = - - = 0.0303 ft (Appendix 5)
2 12
/l )0.14 (4.65)0.14
</>, = ( - = - = 1.187 k = 0.082 c, = 0.48
/lw 1.37
TABLE 12.3
Data for Example 12.3
Temperature
Viscosity, cP
150 65.5 6.0
250 121.1 3.3
350 176.7 1.37
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 355
From Eq. (12.25)
0.0303h /
--= 2 x 1.187( -0.48,n
--
)' 3
0.082 0.082 x 15
1 3
From this, h = 4.69IiI /
Data for substitution into Eq. (12.18) are
11T. = 350 - 150 - (350 - 250) = 144'F
L In (200/100)
L= 15 D = 0.0303 Tb - T. = 250 - 150 = 100'F
From Eq. (12.18)
0.48 x 100,n
h = = 0.233ri1
nO.0303 x 15 x 144
Then
4.69ri1 '/3 = 0.233ri1
4.69 )3 ' /
,n = ( - - = 90.31bjh (41.0 kgjh)
0.233
and
h = 0.233 x 90.3 = 21.0 Btu/ft'-h-'F (119 W/m'-'C)
rilep 90.3 x 0.48
N G. = kL = 0.082 x 15 35.2
This is large enough so that Eq. (12.25) applies. To check the assumption of
laminar flow, the maximum Reynolds number, which exists at the outlet end of the
pipe, is calculated:
DG D,n 4 x 90.3
N R, = -1'- = -n(:::D"".C'jC4C):-1' n x 0.0303 x 3.3 x 2.42
=475
This is well within the laminar range.
Transfer to ~~etals
Liquid metals :e\,\ed for high-temperature heat transfer, especially in nuclear
reactors. Liquid mercury, sodium, and a mixture of sodium and potassium called
NaK are commonly used as carriers of sensible heat. Mercury vapor is also used
as a carrier of latent heat. Temperatures of 1500'F and above are obtainable by
using such metals. Molten metals have good specific heats, low viscosities, and
high thermal conductivities. Their Prandtl numbers are therefore very low in
comparison with those of ordinary fluids.
Equations such as (12.32), (12.34), and (12.55) do not apply at Prandtl
numbers below about 0.5, because the mechanism of heat flow in a turbulent
356 HEAT TRANSFER AND ITS APPLICATIONS
stream differs from that in fluids of ordinary Prandtl numbers. In the usual fluid,
heat transfer by conduction is limited to the viscous sublayer when N p, is unity
or more and occurs in the buffer zone only when the number is less than unity.
In liquid metals, heat transfer by conduction is important throughout the entire
turbulent core and may predominate over convection throughout the tube.
Much study has been given to liquid-metal heat transfer in recent years,
primarily in connection with its use In nuclear reactors. Design equations, all based
on heat-momentum analogies, are available for flow in tubes, in annuli, between
plates, and outside bundles of tubes. The equations so obtained are of the form
(12.58)
where C(, p, and y are constants or functions of geometry and of whether the
wall temperature or the flux is constant and lfi is the average value of eH/eM
across the stream. For circular pipes, et = 7.0, P= 0.025, and y = 0.8. For other
shapes, more elaborate functions are needed. A correlation for lii is given by the
equation 1
(12.59)
The quantity (eMMm is the maximum value of this ratio in the pipe, which is
reached at a value of y/rw = #. Equation (12.58) becomes, then,
1.82NR,]O.8
NNu = 7.0 + 0.025 [ N p, - 14- (12.60)
(eM Mm'
A correlation for (eMMm as a function of the Reynolds number is given in Fig.
12.4.
THE C~\l'nCAL PECLET NUMBER. For a given Prandtl number, the Peclet
number is;'proportional to the Reynolds number, because N p, = Np/VR,' At a
definite vilueof N p , the bracketed term in Eq. (12.60) becomes zero. This situation
corresponds to the point where conduction controls and the eddy diffusion no
longer affects the heat transfer. Below the critical Peclet number, only the first
term in Eq. (12.60) is needed, and NNu = 7.0.
For laminar flow at uniform heat flux, by mathematical analysis NNu =
¥I: = 4.37. This has been confirmed by experiment.
INTERPRETATION OF DIMENSIONLESS GROUPS. The relationships among
several ophe.common dimensionless groups can be made clearer by considering
them as :ratios ofvarious arbitrarily defined fluxes-that is, rates of flow per unit
area9 The fluxes are:
A convective flux, Jcv
A conductive flux, l,
A wall-transfer flux, 1 w
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 357
4
10
7
2
V
10
, /
7
10' V
7
2 /'
10
, /
2 4 7
10' 10'
FIGURE 12.4
Values of (eAtiv)m for fully developed turbulent flow of liquid metals in circular tubes.
These are defined as follows for a fluid flowing in fully developed flow in a long,
straight pipe at velocity V and temperature T. The temperature of the fluid at
the wall is 7;,. Assume that the fluid is being cooled, so that T > Tw'
convectiv~es. The mass velo?ity G is the mass rate of flow. of the fluid per
umt cross-sectIOnal area of the pipe; It IS therefore the convective flux of mass.
Each kilogram or pound of fluid carries with it a certain amount of momentum,
depending on the fluid velocity, so the convective flux of momentum can be
approximated by the product of the mass flux and the velocity to give GV or its
equivalent pV ' . In the same way, the convective flux of heat, arbitrarily based on
Tw as the reference or base temperature, is GciT - Tw) or pV ciT - Tw)'
Convective fluxes are vectors in the direction of the fluid flow.
conduct~to':~. In Chap. 3, p. 47, it was pointed out that a shear stress reSUlting
from viscous action may be considered to be a flux of momentum in the direction
of the ,!elocity gradient [see Eq. (3.4)]. The conductive flux of momentum is
therefore defined here as I'V/D, where I' is the fluid viscosity and V/D is arbitrarily
taken as a measure of the velocity gradient. The corresponding conductive flux of
heat (q/A), equals k(T - Tw)/D, where (T - Tw)/D is an arbitrary measure of the
temperature gradient [see Eq. (10.2)].
358 HEAT TRANSFER AND ITS APPLICATIONS
TABLE 12.4
Dimensionless flux ratios
For momentum For heat
Flux transfer transfer
Convective, JCI) pV 2 pVc,(T - Tw)
Conductive, Jc pV/D k(T - TwVD
Wall transfer, J w ·wgc h(T - Tw)
Conductive fluxes are in the direction normal to the direction of the fluid
flow.
Wall-transfer fluxes. Also normal to the fluid-flow direction are the transfer fluxes
at the pipe wall. These are the rates of transfer to or from the fluid per unit wall
area. The wall flux of momentum is simply the shear stress '" (in fps units, '"g,).
The wall flux of heat (qj A)" is h(T - 7;,), where h is the inside heat transfer
coefficient.
These fluxes are summarized in Table 12.4.
Dimensionless groups.
I. For momentum transfer the ratio of the wall-transfer flux l" to the
convective flux Jcv is
J w T: w 9c f
(12.61)
J,,=py 2 =2
For heat transfer the same ratio is
J" h(T - 7;') It
-- ---N (12.62)
J" - pVciT - 7;,) - cpG - s,
Il. The ratio of l," to J, for momentum transfer is
J" py2 DYp
- = - = - = - - = N Re (12.63)
J, I'(VjD) I'
For heat transfer it is
pYcp(T- 7;,) DVpc p
k[(T - 7;,)jD] = - k - = N p , (12.64)
Ill. Finally, the ratios of J" to l, are:
For momentum transfer
(12.65)
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 359
For heat transfer
lw h(T - 7;') hD
-k--N Nu (12.66)
l, k[(T - Tw}/D]
The dimensionless ratio in Eq. (12.65), unlike the other five, has not been
given a name.
HEATING AND COOLING OF FLUIDS IN
FORCED CONVECTION OUTSIDE TUBES
The mec.hanism of heat flow in forced convection outside tubes differs from that
of flow inside tubes, because of differences in the fluid-flow mechanism. As has
been shown on pages 59 and 106 no form drag exists inside tubes except perhaps
for a short distance at the entrance end, and all friction is wall friction. Because
of the lack of form friction, there is no variation in the local heat transfer at
different points in a given circumference, and a close analogy exists between friction
and heat transfer. An increase in heat transfer is obtainable at the expense of added
friction simply by increasing the fluid velocity. Also, a sharp distinction exists
between laminar and turbulent flow, which calls for different treatment of heat-
transfer relations for the two flow regimes.
On the other hand, as shown on pages 143 to 151, in the flow of fluids across
a cylindrical shape boundary-layer separation occurs, and a wake develops that
causes form friction. No sharp distinction is found between laminar and turbulent
flow, and a common correlation can be used for both low and high Reynolds
numbers. Also, the local value of the heat-transfer coefficient varies from point to
point around a circumference. In Fig. 12.5 the local value of the Nusselt number
is plotted radially for all points around the circumference of the tube. At low
Reynolds numbers, NNu.O is a maximum at the front and back of the tube and a
minimum at the sides. In practice, the variations in the local coefficient ho are
often of no importance, and average values based on the entire circumference are
used.
Radiation may be important in heat transfer to outside tube surfaces. Inside
tubes, the surface cannot see surfaces other than the inside wall of the same tube,
and heat flow by radiation does not occur. Outside tube surfaces, however, are
necessarily in sight of external surfaces, if not nearby, at least at a distance, and
the surrounding surfaces may be appreciably hotter or cooler than the tube wall.
Heat flow by radiation, especially when the fluid is a gas, is appreciable in
comparison with heat flow by conduction and convection. The total heat flow is
then a sum oftwo independent flows, one by radiation and the other by conduction
and convection. The relations given in the remainder of this section have to do
with conduction and convection only. Radiation, as such and in combination with
conduction and convection, is discussed in Chap. 14.
360 HEAT TRANSFER AND ITS APPLICATIONS
600
500v-~"
100~----4-----+P~~--~----+-~
FIGURE 12.5
Local Nusselt number for airflow normal to
a circular cylinder. (Adapted with permission
°0l--L--~40~-L~8~0~~-"12hO~L-~1*60~~ from W. H. Giedt, Trans. ASME, 71:375.
Angular coordinate. 0 1949,)
FLUIDS FLOWING NORMALLY TO A SINGLE TUBE. The variables affecting
the coefficient of heat transfer to a fluid in forced convection outside a tube are D",
the outside diameter of the tube; cp , Il, and k, the specific heat at constant pressure,
the viscosity, and the thermal conductivity, respectively, of the fluid; and G, the
mass velocity of the fluid approaching the tube, Dimensional analysis gives, then,
an equation of the type of Eq. (12.27):
h,D, = ,I. (D,G Cpll) (12,67)
k '1'0 Il' le
Here, however, ends the similarity between the two types of process-the flow
of heat to fluids inside tubes and the flow of heat to fluids outside tubes-and the
functional relationships in the two cases differ.
For simple gases, for which the Prandtl number is nearly independent of
temperature, the Nusselt number is a function only of the Reynolds number.
Experimental data for air are plotted in this way in Fig. 12.6. The effect of radiation
is not included in this curve, and radiation must be calculated separately,
The sUbscriptfon the terms kl and III indicates that in using Fig. 12,6 these
terms must be evaluated at the average film temperature TI midway between the
600
400
300 /'
200
,/
100
80
60
40
,/
<$' 1 ...... 20
4::.,0 ~
10
8
6
4
2 ../
...-r-
0.8
0.6
0.4
0.3 ,
0.1 )3 104 10 5
DoG
1'/
FIGURE 12.6
Heat transfer to air flowing normally to a single tube. (By permission of author and publisher. from W. H. McAdarns, Heat Transmission, 3rd
ed, Copyright by author, 1954, McGraw~HiIl Book ComparlY.)
-
~
362 HEAT TRANSFER AND ITS APPLICATIONS
wall temperature and the mean bulk temperature of the fluid T. Therefore, Tf
is,given by the equation
(12.68)
Figure 12.6 can be used for both heating and cooling.
For heating and cooling liquids flowing normally to single cylinders the
following equation is used":
h,D, (CP l'f)-0.3 = 0.35 + 0.56(D,G)0.52 (12.69)
lef lef I'f
This equation can also be used for gases from N R• = 1 to N R • = 104 , but it
gives lower values of the Nusselt number than Fig. 12.6 at higher Reynolds
numbers. Equation (12.69) is plotted in j-factor form in Fig. 21.4, in the section
of Chap. 21 dealing with the analogies between heat and mass transfer.
Heat-transfer data for flow normal to cylinders of noncircular cross section
are given in the literature.4b Banks of tubes across which the fluid flows are
common in industrial exchangers. Problems of heat flow in tube banks are
discussed in Chap. 15.
FLOW PAST SINGLE SPHERES. For heat transfer between a flowing fluid and
the surface of a single sphere the following equation is recommended:
hD
-'--I'- = 2.0 + 0.60(D_P- " )'/3
G)0.50(C.J'!::.£ (12.70)
lef I'f lef
where D P is the diameter of the sphere. In a completely stagnant stream the
Nusselt number,h,Dp/kf , is equal to 2.0. A plot ofEq. (12.70) is given in Fig. 21.5.
HEAT TRANSFER IN PACKED BEDS. Data for heat transfer between fluids and
beds of various kinds of particles can be obtained from Fig. 21.5 or from Eq.
(21.62) by replacing N s• with N p, and NSh with NN"'
N~tL CONVECTION
As an example of natural convection, consider a hot, vertical plate in contact with
the air in a room. The temperature of the air in contact with the plate will be that
of the surface of the plate, and a temperature gradient will exist from the plate
out into the room. At the bottom of the plate, the temperature gradient is steep,
as shown by the full line marked "Z = 10mm" in Fig. 12.7. At distances above
the bottom of the plate, the gradient becomes less steep, as shown by the full curve
marked" Z = 240 mm" of Fig. 12.7. At a height of about 600 mm from the bottom
of the plate, the temperature-distance curves approach an asymptotic condition
and do not change with further increase in height.
The density of the heated air immediately adjacent to the plate is less than
that of the unheated air at a distance from the plate, and the buoyancy of the hot
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 363
480 120
I\. _ _ Temperature
1\\ I
"
___ Velocity
400
.P
100
\ \1 ,
~ uT 1\
~ 320!5 80
I- 1\
,
~ ;i ,
U
g
240);' 60
::;; ,
~
..J
160
~
<i 40
I
!
\
"" Z=240mm
5 L _I
g
80
l)
g
20
I
It
! /-,
"
'f.-.. i'--- i-
... ,
I'....
Z=IOmm
,-.
Z=240mm
Z=IOmm I I
o 2 4 6 8 ~ 12
DISTANCE FROM PLATE SURFACE, MM
FIGURE 12.7
Velocity and temperature gradients, natural convection from heated vertical plate. (By permission of
author and publisher, from W. H. McAdams, Heat Transmission, 3rd ed. Copyright by author, 1954,
McGralV~Hill Book Company.)
air causes an unbalance between the vertical layers of air of differing density. The
unbalanced forces generate a circulation by which hot air near the plate rises and
cold air flows toward the plate from the room to replenish the rising airstream.
A velocity gradient near the plate is formed. Since the velocities of the air in contact
with the plate and that out in the room are both zero, the velocity is a maximum
at a definite distance from the wall. The velocity reaches its maximum a few
millimeters from the surface of the plate. The dashed curves in Fig. 12.7 show the
velocity gradients for heights of 10 and 240 mm above the bottom of the plate.
For tall plates, an asymptotic condition is approached.
The temperature difference between the surface of the plate and the air in
the room at a distance from the plate causes a transfer of heat by conduction into
the current of gas next to the wall, and the stream carries the heat away by
convection in a direction parallel to the plate.
The natural convection currents surrounding a hot, horizontal pipe are more
complicated than those adjacent to a vertical heated plate, but the mechanism of
the process is similar. The layers of air immediately next to the bottom and sides
of the pipe are heated and tend to rise. The rising layers of hot air, one on each
side of the pipe, separate from the pipe at points short of the top center of the
pipe and form two independent rising currents with a zone of relatively stagnant
and unheated air between them.
Natural convection in liquids follows the same pattern, because liquids are
also less dense hot than cold. The buoyancy of heated liquid layers near a hot
surface generate convection currents just as in gases.
364 HEAT TRANSFER AND ITS APPLICATIONS
s On the assumption that h depends upon pipe diameter, specific heat, thermal
conductivity, viscosity, coefficient of thermal expansion, the acceleration of gravity,
and temperature difference, dimensional analysis gives
hD, = <l>(Cpll D:p2g p!!. T) (12.71)
k k' Jl.2 '
Since the effect of Pis through buoyancy in a gravitational field, the product
gp !!.T acts as a single factor, and the last two groups fuse into a dimensionless
group called the Grashofnumber N G ,.
For single horizontal cylinders, the heat-transfer coefficient can be correlated
by an equation containing three dimensionless groups, the N usselt number, the
Prandtl number, and the Grashof number, or specifically,
(12.72)
where h = average heat-transfer coefficient, based on entire pipe surface
D, = outside pipe diameter
kf = thermal conductivity of fluid
cp = specific heat of fluid at constant pressure
pf = density of fluid
p = coefficient of thermal expansion of fluid
g = acceleration of gravity
!!. T, = average difference in temperature between outside of pipe and fluid
distant from wall
Il f = viscosity of fluid
The fluid properties Ilf, Pf, and k f are evaluated at the mean film tempera-
ture [Eq. (12.68)]. Radiation is not accounted for in this equation.
The coefficient of thermal expansion p is a property of the fluid, defined as
the fractional increase in volume at constant pressure of the fluid per degree of
temperature change, or mathematically,
p= (av/aT)p
(12.73)
v
where v = specific volume of fluid
(av/oTJp= rate of change of specific volume with temperature at constant
pressure
For liquids, p can be considered constant over a definite temperature range
and Eq. (12.73) written as
p = !!.v~!!. T (12.74)
v
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 365
where ii is the average specific volume. In terms of density.
f! = 1/P2 - l/p,
(12.75)
(T2 - T,)(l/ p, + 1/P2)/2
where Pa = (p, + P2)/2
p, = density of fluid at temperature T,
P2 = density of fluid at temperature Tz
For an ideal gas, since v = RT/p,
and using Eq. (12.73),
R/p 1
f! = RT/p = T (12.76)
The coefficient of thermal expansion of an ideal gas equals the reciprocal of the
absolute temperature.
In Fig. 12.8 is shown a relationship, based on Eq. (12.72), which satisfactorily
correlates experimental data for heat transfer from a single horizontal cylinder to
1.8
1.6 ~
V
1.4
1.2 ~
1.0 /
ZZ
~
0.8 /
o
(!)- 0.6 /
S /
0.4
0.2 ./
o V
V
-0. 2 V
I-
~
-0.4
-4 -3 -2 -I 0 I 2 3 4 5 6 7 8
LOG,o [NGr X N pr]
FIGURE 12.8
Heat transfer between single horizontal cylinders and fluids in natural convection.
366 HEAT TRANSFER AND ITS APPLICATIONS
liquids or gases. The range of variables covered by the single line of Fig. 12.8 is
very great.
For magnitudes of log!o NG,Np , of 4 or more, the line of Fig. 12.8 follows
closely the empirical equation 7'
NNu = O.53(N G ,Np ,)J· 25 (12.77)
N}~AL CONVECTION TO AIR FROM VERTICAL SHAPES AND HORIZON-
TALPLANES. Equations for heat transfer in natural convection between fluids
and solids of definite geometric shape are of the form 7"
hL = b[L3p'r9~f!J.T(Cpf.l) J" (12.78)
kf f.lf k f
where b, 11 = const
L = height of vertical surface or length of horizontal square surface
Properties are taken at the mean film temperature. Equation (12.78) can be
written
(12.79)
Values of the constants band n for various conditions are given in Table 12.5.
EF~S OF NATURAL CONVECTION IN LAMINAR-FLOW HEAT TRANS-
FE~;:n.minar flow at low velocities, in large pipes, and at large temperature
drops, natural convection may occur to such an extent that the usual equations
for laminar-flow heat transfer must be modified. The effect of natural convection
in tubes is found almost entirely in laminar flow, as the higher velocities character-
istic of flow in the transition and turbulent regimes overcome the relatively gentle
currents of natural convection.
The effect of natural convection on the coefficient of heat transfer to fluids
in laminar flow through horizontal tubes can be accounted for by multiplying the
TABLE 12.5
Values of constants in Eq. (12.79)t
System Range of NG~l'r b n
Vertical plates, vertical cylinders 104 _10 9 0.59 0.25
10 9 _10 12 0.13 0.333
Horizontal plates:
Heated, facing upward or
cooled, facing down 10 5 _2 x 10 7 054 0.25
2 x 101-3 X 1010 0.14 0.333
Cooled, facing upward or
heated, facing down 3 x 10 5-3 X 10 10 0.27 0.25
t By permission of author and publishers, from W. H. McAdams, Heat Transmis~
sion, 3rd ed., pp. 172, 180. Copyright by author, 1954, McGraw~Hill Book Company.
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 367
coefficient hi' computed from Eq. (12.57) or Fig. 12.3, by the factor'
2.25(1 + 0.010NY;)
'" = =-'---'----'--""-'- (12.80)
n logio N Re
Natural convection also occurs in vertical tubes, increasing the rate of heat
flow, when the fluid flow is upward, to above that found in laminar flow only.
The effect is marked at values of N G , between 10 and 10,000 and depends 7 ' on
the magnitude of the quantity NG,Np,D/L.
EX~ 12.4. Air at 1 atm pressure is passed through a horizontal 2-in (51-mm)
sc~7c:~40 steam-jacketed steel pipe at a velocity of 1.5 ft/s (0.457 m/s) and an inlet
temperature of 68'F (20'C). The pipe-wall temperature is 220'F (!o4.4'C). If the
outlet air temperature is to be 188°F (86.7°C), how long must the heated section be?
Solution
To establish the flow regime, the Reynolds number based on the average temperature
is calculated. The quantities needed are
_ 68 + 188 2.067
T = 128'F D = - - = 0.1723 ft (Appendix 5)
2 12
I' (at 128'F) = 0.019 cP (Appendix 8)
29 492
p (at 68'F) = = 0.0753 1b/ft'
35968 + 460
VP = G = 1.5 x 0.0753 x 3600 = 406.4 Ib/ft'-h
DG 0.1723 x 406.4
N R• =- = 1522
I' 0.019 x 2.42
Hence flow is laminar, and Eq. (12.25) applies. The results may later require
correction for the effect of natural convection using Eq. (12.80). To use Eq. (12.25),
the following quantities are needed:
c,(at 128'F) = 0.25 Btujlb-':F (Appendix 15)
k (at 128'F) = 0.0163 Btu/ft-h-'F (Appendix 12)
(By linear interpolation)
I'w (at 220'F) = 0.021 cP (Appendix 8)
The internal cross-sectional area of pipe is
S = 0.02330 ft' (Appendix 5)
The mass flow rate is
m= GS = 406.4 x 0.02330 = 9.47 lb/h
The heat load is
q= rilclt, - 7;) = 9.47 x 0.25(188 - 68) = 284.1 Btu/h
368 HEAT TRANSFER AND ITS APPLICATIONS
The logarithmic mean temperature difference is
t.T1 = 220 - 188 = 32"F t.T, = 220 - 68 = 152"F
_ 152-32
t. T. = 77.0"F
L In (152/32)
The heat-transfer coefficient h = q/A t.TL • From Appendix 5, for 2-in. Schedule
40 pipe, A = 0.541L. Hence
h= 284.1 6.820
0.541L x 77 L
Also, from Eq. (12.25), the heat-transfer coefficient is
h=~(~zr(f:J14
= 2 x 0.0163 (9.47 x 0.25)1 /'(0.019)°.14 = 0.9813
0.1723 0.0163L 0.021 U/3
Equating the two relationships for h gives
0.9813 6.820
from which L = 18.32 ft (5.58 m).
This result is now corrected for the effect of natural convection using Eq. (12.80).
This requires calculation of the Grashof number, for which the additional quantities
needed are
fJ (at 128"F) = 1 = 0.0017"R- 1
460 + 128
t.T = 220 - 128 = 92"F p (at 128"F) = 0.0676 Ib/ft'
The Grashof number is therefore
D'p'gfJ t.T
N or = 2
J.l
0.1723' X 0.0676' x 32.174 x 0.0017 x 92
0.7192 X 106
(0.019 x 6.72 x 10 4)'
Hence, from Eq. (12.80),
2.25[1 + 0.01(0.7192 x 10 6 )1/'J
4>. = 1.34
IOg10 1522
This factoris used to correct the value of L. Hence L = 18.32/1.34 = 13.7 ft(4.17 m).
HEAT TRANSFER TO FLUIDS WITliOUT PHASE CHANGE 369
SYMBOLS
A Area, m 2 or ft 2
b Constant in Eq. (12.78)
C Constant
cp Specific heat at constant pressure, Jjg_OC or Btu/lb-oF
D Diameter, m or ft; Din equivalent diameter, 4rH ; Di , inside diameter;
Du, inside diameter of jacket; Dio inside diameter of inner tube; Do,
outside diameter; D,,, outside diameter of inner tube; Dp' of spherical
particle; D L , logarithmic mean
J Fanning friction factor, dimensionless
G Mass velocity, kgjm 2-s or Ibjft2-s
g Gravitational acceleration, mjs2 or ftjs2
g, Newton's-law proportionality factor, 32.174 ft-Ib/lb rs2
h Individual heat-transfer coefficient, Wjm 2 _OC or Btujft'-h_oF; h"
based on arithmetic mean temperature drop; hi' average over inside of
tube; ho, for outside of tube or particle; hx' local value; hXl' at trailing
edge of plate; hoo, for fully developed flow in long pipes; ho, local
value outside tube
J Flux, rate per unit area; Jc ' conductive flux; JCIl ' convective flux; J w ,
wall transfer flux
jH Colburnj factor, Nst(Np ,)2/34>" dimensionless
K' Flow consistency index of non-newtonian fluid
k Thermal conductivity, Wjm_OC or Btujft-h_oF; kf' at mean film tem-
perature; km' of tube wall
L Length, m or ft
In Parameter in Eq. (12.26), K'8·· -1; mw, value at 7;,
ril Mass flow rate, kgjh or lbjh
N Fo Fourier number, 4kLjcppD 2 V, dimensionless
N G, Grashofnumber, D3p2gfJ IlT/J.!.2, dimensionless
N Gz Graetz number, rilcp/kL, dimensionless
NNu Nusselt number, hDjk, dimensionless; NNu.f' at mean film tempera-
ture; NNu.x> local value on flat plate; NNu.O, local value on outside of
tube
Np , Peelet number, pVcvD/k, dimensionless
Np, Prandtl number, cpJ.!.jk, dimensionless
N R, Reynolds number, DGjJ.!., dimensionless; NR,.x> local value on flat
plate, uoxpjJ.!.; N Ro • x1 , at trailing edge of plate
N st Stanton number, hjcpG, dimensionless
/1 Constant in Eq. (12.78)
/1' Flow behavior index of non-newtonian fluid, dimensionless
p Pressure, Njm 2 or Ibf jft2
q Heat flow rate, W or Btujh; q" by conduction; q" by turbulent con-
vection
R Gas-law constant
370 HEAT TRANSFER AND ITS APPLICATIONS
r Radius, m or ft; rH, hydraulic radius of channel; 'm' of tube; l'w,
radius of pipe
S Cross-sectional area of tube, m 2 or ft 2
T Temperature, °C or OF; Y'a, at inlet; Tb, at outlet; Tf , mean film
temperature; 7;, instantaneous value; ~I" at wall or plate; Ta;, of
approaching fluid; T, average fluid temperature in tube; 7;" bulk
average fluid temperature at outlet; 7;, time average of instantaneous
values; T fluctuating component; T time average of fluctuating
I
,
I
,
component
tT Total time of heating or cooling, s or h
U Overall heat-transfer coefficient, W/m2_oC or Btu/ft'-h_oF; U" based
on outside area; U l' U 2, at ends of exchanger
u Fluid velocity, m/s or ft/s; U o, of approaching fluid; u', fluctuating
component
V Volumetric average fluid velocity, m/s or ft/s
v Specific volume, m 3/kg or ft'jlb for liquids, m 3/kg mol or ft3j1b mol
for gases; V, average value
v' Fluctuating component of velocity in y direction; v', time-average
value
x Distance from leading edge of plate or from tube entrance, m or ft;
x"' wall thickness; Xo, at start of heated section; Xl' length of plate
y Radial distance from wall, m or ft; also, boundary-layer thickness
Z Height, m or ft
Greek letters
Cl. Thermal diffusivity, k/pc p , m2 /h or ft 2/h; also constant in Eq. (12.58)
{3 Coefficient of vol umetric expansion, IfR or I/K; also constant in Eq.
(12.58); {3 I' at mean film temperature
y Constant in Eq. (12.58)
I!.T Temperature drop, °C or OF; I!. T" from inner wall of pipe to fluid;
I!.T" from outside surface to fluid distant from wall; I!.T" arithmetic
mean temperature drop; I!.TL> logarithmic mean temperature drop
Parameter in Eq. (12.26), (3n' + 1)/4n'
S Turbulent diffusivity, m 2jh or ft'/h; SH, of heat; SM, of momentum
e Angular position on outside of tube
I' Absolute viscosity, kg/m-s or lb/ft-s; 1'1' average value of liquid film;
1'", value at wall temperature
v Kinematic viscosity, m2 /h or ft>/h
p Density, kg/m 3 or lb/ft'; PI' of liquid film; PO' arithmetic average
value
T Shear stress, N/m2 or lb//ft2; T", shear stress at pipe wall; To, yield
stress of plastic fluid
Function
Natural-convection factor [Eq. (12.80)]
Viscosity-correction factor, (1'/1',,)0.14
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 371
1/1 Function in Eq. (12.35); also ratio of turbulent diffusivities, BH/B M; Vi,
average value
1/10 Function in Eq. (12.67)
PROBLEMS
12.1. Glycerin is flowing at the rate of 700 kgjh through a 30-mm-ID pipe. It enters a
heated section 2.5 m long. the walls of which are at a uniform temperature of 11SOC.
The temperature of the glycerin at the entrance is 15°e. (a) If the velocity profile is
parabolic, what would be the temperature of the glycerin at the outlet of the heated
section? (b) What would the outlet temperature be if flow were rodlike? (c) How
long would the heated section have to be to heat the glycerin essentially to 115°C?
12.2. Oil at 50°F is heated in a horizontal 2-in Schedule 40 steel pipe 60 ft long having a
surface temperature of 120°F. The oil flow rate is 150 galfh at inlet temperature.
What will be the oil temperature as it leaves the pipe and after mixing? What is the
average heat-transfer coefficient? Properties of the oil are given in Table 12.6.
TABLE 12.6
Data for Prob. 12.2
Specific gravity, 60"F/60 F
Q
0.79 0.74
Thennal conductivity, Btu/ft-h-OF 0.072 0.074
Viscosity, cP 18 8
Specific heat, Btuflb-"f 0.75 0.75
12.3. Oil is flowing through a 75-mm-lD iron pipe at I m/so It is being heated by steam
outside the pipe, and the steam-film coefficient may be taken as 11 kW/m2_oC. At
a particular point along the pipe the oil is at 50°C, its density is 880 kg/m 3 , its
viscosity is 2.1 cP, its thermal conductivity is 0.135 W/m-oC, and its specific heat is
2.17 J/g_0C. What is the overall heat-transfer coefficient at this point based on the
inside area of the pipe? If the steam temperature is 120oe, what is the heat flux at
this point based on the outside area of the pipe?
12.4. Kerosene is heated by hot water in a shell-and-tube heater. The kerosene is inside
the tubes, and the water is outside. The flow is countercurrent. The average
temperature of the kerosene is 110°F, and the average linear velocity is 8 ft/so The
properties of the kerosene at 110°F are specific gravity 0.805, viscosity 1.5 cP, specific
heat 0.583 Btujlb-oF, and thermal conductivity 0.0875 Btu/ft-h-oF. The tubes are
low-carbon steel i in. OD by BWG 16. The heat-transfer coefficient on the shell
side is 300 Btu/ft 2-h-oF. Calculate the overall coefficient based on the outside area
of the tube.
12.5. Assume that the kerosene of Prob. 12.4 is replaced with water at 110°F and flowing
at a velocity of 8 ft/so What percentage increase in overall coefficient may be expected
if the tube surfaces remain clean?
12.6. Both surfaces of the tube of Prob. 12.5 become fouled with deposits from the water.
The fouling factors are 330 on the inside and 200 on the outside surfaces, both in
372 HEAT TRANSFER AND ITS APPLICATIONS
Btu/ft 2 -h-OF. What percentage decrease in overall coefficient is caused by the fouling
of the tube?
12.7. From the Col burn analogy, how much would the heat-transfer coefficient inside a
I-in. Schedule 40 steel pipe differ from that inside a I-in. BWG 16 copper tube if
the same fluid were flowing in each and the Reynolds number in both cases was
4 x 104 ?
12.8. Water must be heated from 15 to 50°C in a simple double-pipe '] ~at exchanger at a
rate of 3500 kgjh. The water is flowing inside the inner tube with steam condensing
at 110°C on the outside, The tube wall is so thin that the wall resistance may be
neglected, Assume that the steam-film coefficient ho is 11 kW/m2_ 0 C. What is the
length of the shortest heat exchanger that will heat the water to the desired
temperature? Average properties of water are as follows:
p = 993 kg/m' k = 0.61 W/m-"C J1. = 0.78 cP cp = 4.19 J/g-"C
Hint: Find the optimum diameter for the tube.
12.9. Since the Prandtl number and the heat capacity of air are nearly independent of
temperature, Eq. (12.32) seems to indicate that h j for air increases with pO.2, (a)
Explain this anomaly and determine the approximate dependence of hj on tempera-
ture, using hi oc T n, (b) How does hi for air vary with temperature if the linear velocity,
rather than the mass velocity, is kept constant?
12.10. Air is flowing through a steam-heated tubular heater under such conditions that the
steam and wall resistances are negligible in comparison with the air-side resistance.
Assuming that each of the following factors is changed in turn but that all other
original factors remain constant, calculate the percentage variation in q/iJ..tL that
accompanies each change. (a) Double the pressure on the gas but keep fixed the mass
flow rate of the air. (b) Double the mass flow rate of the air. (c) Double the number
of tu1:es in the heater. (d) Halve the diameter of the tubes.
12.11. A sodium-potassium alloy (78 percent K) is to be circulated through ~-in.-ID tubes
in a reactor core for cooling. The liquid-metal inlet temperature and velocity are to
be 580°F and 32 ft/so If the tubes are 3 ft long and have an inside surface temperature
of 720°F, find the coolant temperature rise and the energy gain per pound of liquid
metal. Properties of NaK (78 percent K) are as follows:
p = 45 Ib/ft' k = 179 Btu/ft-h-"F J1. = 0.16 cP cp = 0.21 Btuflb-"F
12.12. In a catalytic cracking regenerator, catalyst particles at 600°C are injected into air
at 700°C in a fluidized bed. Neglecting the chemical reaction, how long would it
take for a 50-pm particle to be heated to within 5°C of the air temperature? Assume
the heat-transfer coefficient is the same as for a spherical particle falling at its terminal
velocity.
12.13. In a pilot plant, a viscous oil is being cooled from 200 to 11O"C in a l.O-in. jacketed
pipe with water flowing in the jacket at an average temperature of 30°C. To get
greater cooling of the oil, it has been suggested that the exchanger be replaced with
one having a greater inside diameter (1.5-in.) but the same length. (a) If the oil is in
laminar flow in the 1.0-in. pipe, what change in exit temperature might result from
using the larger exchanger? (b) Repeat assuming the oil is in turbulent flow.
12.14. In the manufacture of nitric acid, air containing 10 percent ammonia is passed
through a pack of fine-mesh wire screens of Pt/Rh alloy. (a) Calculate the heat-
transfer coefficient for air at 500"C flowing at a superficial velocity of 20 ft/s past
HEAT TRANSFER TO FLUIDS WITHOUT PHASE CHANGE 373
wires 0.5 mm in diameter. (b) If the surface area of the wire screen is 3.7 cm 2 /cm 2 of
cross section, what is the temperature change in air, initially at 500°C, flowing
through one screen if the surface of the wires is at 900°C?
12.15. Water at 15'C is flowing at right angles across a heated 25-mm-OD cylinder, the
surface temperature of which is 120°C. The approach velocity of the water is 1 m/so
(a) What is the heat flux, in kilowatts per square meter, from the surface of the
cylinder to the water? (b) What would be the fiux if the cylinder were replaced by
a 25-mm-OD sphere, also with a surface temperature of 120°C?
12.16. Water is heated from 15 to 65'C in a steam-heated horizontal 50-mm-ID tube. The
steam temperature is 120°C. The average Reynolds number of the water is 450. The
individual coefficient of the water is controlling. By what percentage would natural
convection increase the total rate of heat transfer over that predicted for purely
laminar flow? Compare your answer with the increase indicated in Example 12.4.
12.17. A large tank of water is heated by natural convection from submerged horizontal
steam pipes. The pipes are 3-in Schedule 40 steel. When the steam pressure is
atmospheric and the water temperature is 80°F, what is the rate of heat transfer to
the water in Btu per hour per foot of pipe length?
12.18. Calculate (a) the overall coefficient U for heat transfer through a vertical glass
window from a room at 70°F to still air at OaF. Assume that a single pane of glass
is kin. thick and 4 ft high. (b) Calculate U for a thermopane window with a i-in.
air space between the two panes. For this glass k = 0.4 BtuJh-ft-oF.
12.19. How does U for a thermopane window depend on the spacing between the panes?
REFERENCES
1. Dwyer, O. E.: AIChE J., 9:261 (1963).
2. Eckert, E. R. G., and 1. F. Gross: Introduction to Heal and Mass Transfer, McGraw-Hill, New
York, 1963 pp. 110-114.
3. Friend, W. L., and A. B. Metzer: AIChE J., 4:393 (1958).
4. Gebhart, B.: Heat Transfer, 2nd ed., McGraw-Hill, New York, 1971; (a) p. 272, (b) p. 274, (c) p. 283.
5. Kern, D. Q" and D. F, Othmer: TraIlS. AIChE, 39:517 (1943).
6, Knudsen, 1. G., and D. L Katz: Fluid Dynamics and Heal Transfer, McGraw-Hill, New York,
1958; (a) pp. 361-390, (b) pp. 400-403, (c) p. 439.
7. McAdams, W. H: Heat Transmission, 3rd ed" McGraw-HiII, New York, 1954; (a) pp. 172, 180,
(b) p. 177, (c) p. 215. (d) p. 230, (e) p. 234.
8. Sieder, E. N,. and G. E. Tate: Ind. £ng, Chem., 28:1429 (1936).
9. Smith, J. C.: Can. J. Chem. Eng., 39:106 (1961).
10, Wilkinson, W. L: Non-NelVlonian Fluids, Pergamon, London, 1960, p. 104.
CHAPTER
13
HEAT
TRANSFER
TO FLUIDS
WITH
PHASE
CHANGE
Processes of heat transfer accompanied by phase change are more complex than
simple heat exchange between fluids. A phase change involves the addition or
subtraction of considerable quantities of heat at constant or nearly constant
temperature. The rate of phase change may be governed by the rate of heat transfer,
but it is often influenced by the rate of nucleation of bubbles, drops: or crystals
and by the behavior of the new phase after it is formed. This chapter covers
condensation ofvapors and boiling ofliquids. Crystallization is discussed in Chap.
27.
HEAT TRANSFER FROM CONDENSING
VAPORS
The condensation of vapors on the surfaces of tubes cooler than the condensing
temperature of the vapor is important when vapors such as those of water,
hydrocarbons, and other volatile substances are processed. Some examples will
be met later in this text, in discussing the unit operations of evaporation,
distillation, and drying.
374
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 375
The condensing vapor may consist of a single substance, a mixture of
condensable and noncondensable substances, Or a mixture of two or more
condensable vapors. Friction losses in a condenser are normally small, so that
condensation is essentially a constant-pressure process. The condensing tempera-
ture of a single pure substance depends only on the pressure, and therefore the
process of condensation of a pure substance is isothermal. Also, the condensate
is a pure liquid. Mixed vapors, condensing at constant pressure, condense over a
temperature range and yield a condensate of variable composition until the entire
vapor stream is condensed, when the composition of the condensate equals that
of the original uncondensed vapor.t A common example of the condensation
of one constituent from its mixture with a second non condensable substance is
the condensation of water from a mixture of steam and air.
The condensation of mixed vapors is complicated and beyond the scope of
this text.'3b The following discussion is directed to the heat transfer from a single
volatile substance condensing on a cold tube.
DROPWISE AND FILM-TYPE CONDENSATION. A vapor may condense on a
cold surface in one of two ways, which are well described by the terms dropwise
and film type. In fihn condensation, which is more common than dropwise
condensation, the liquid condensate forms a film, or continuous layer, of liquid
that flows over the surface of the tube under the action of gravity. It is the layer
of liquid interposed between the vapor and the wall of the tube that provides the
resistance to heat flow and therefore fixes the magnitude of the heat-transfer
coefficient.
In dropwise condensation the condensate begins to form at microscopic
nucleation sites. Typical sites are tiny pits, scratches, and dust specks. The drops
grow and coalesce with their neighbors to form visible fine drops like those often
seen on the outside of a cold-water pitcher in a humid room. The fine drops, in
turn, coalesce into rivulets, which flow down the tube under the action of gravity,
sweep away condensate, and clear the surface for more droplets. During dropwise
condensation, large areas of the tube surface are covered with an extremely thin
film of liquid of negligible thermal resistance. Because of this the heat-transfer
coefficient at these areas is very high; the average coefficient for dropwise
condensation may be 5 to 8 times that for film-type condensation. On long tubes,
condensation on some of the surface may be film condensation and the remainder
dropwise condensation.
The most important and extensive observations of dropwise condensation
have been made on steam, but it has also been observed in ethylene glycol, glycerin,
nitrobenzene, isoheptane, and some other organic vapors. ' 7 Liquid metals usually
condense in the dropwise manner. The appearance of dropwise condensation
t Exceptions to this statement are found in the condensation of azeotropic mixtures, which are
discussed in a later chapter,
376 HEAT TRANSFER AND ITS APPLICATIONS
depends upon the wetting or non wetting of the surface by the liquid, and
fundamentally, the phenomenon lies in the field of surface chemistry. Much of the
experimental work on the dropwise condensation of steam is summarized in the
following paragraphs 5 :
1. Film-type condensation of water occurs on tubes of the common metals if both
the steam and the tube are clean, in the presence or absence of air, on rough
or on polished surfaces.
2. Dropwise condensation is obtainable only when the cooling surface is not
wetted by the liquid. In the condensation of steam it is often induced by
contamination of the vapor with droplets of oil. It is more easily maintained
on a smooth surface than on a rough surface.
3. The quantity of contaminant or promoter required to cause dropwise condensa-
tion is minute, and apparently only a monomolecular film is necessary.
4. Effective drop promotors are strongly adsorbed by the surface, and substances
that merely prevent wetting are ineffective. Some promoters are especially
effective on certain metals, e.g., mercaptans on copper alloys; other promoters,
such as oleic acid, are quite generally effective. Some metals, such as steel and
aluminum, are difficult to treat to give dropwise condensation.
5. The average coefficient obtainable in pure dropwise condensation may be as
high as 115 kW/m2-oC (20,000 Btu/ft2_0F).
Although attempts are sometimes made to realize practical benefits from
these large coefficients by artificially inducing dropwise condensation, this type of
condensation is so unstable and the difficulty of maintaining it so great that the
method is not common. Also the resistance of the layer of steam condensate even
in film-type condensation is ordinarily small in comparison with the resistance
inside the condenser tube, and the increase in the overall coefficient is relatively
small when dropwise condensation is achieved. For normal design, therefore,
film-type condensation is assumed.
COEFFICIENTS FOR FILM-TYPE CONDENSATION. The basic equations for the
rate of heat transfer in film-type condensation were first derived by Nusselt l l •13 ,.15
The Nusselt equations are based on the assumption that the vapor and liquid at
the outside boundary of the liquid layer are in thermodynamic equilibrium, so
that the only resistance to the flow of heat is that offered by the layer of condensate
flowing downward in laminar flow under the action of gravity. It is also assumed
that the velocity of the liquid at the wall is zero, that the velocity of the liquid at
the outside of the film is not influenced by the velocity of the vapor, and that the
temperatures of the wall and the vapor are constant. Superheat in the vapor is
neglected, the condensate is assumed to leave the tube at the condensing tempera-
ture, and the physical properties of the liq\1id are taken at the mean film
temperature.
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 377
Vertical tubes. In film-type condensation, the Nusselt theory shows that the
condensate film starts to form at the top of the tube and that the thickness of the
film increases rapidly near the top of the tube and then more and more slowly in
the remaining length. The heat is assumed to flow through the condensate film
solely by conduction, and the local coefficient hx is therefore given by
h = kf (13.1)
x iJ
where iJ is the local film thickness.
The local coefficient therefore changes inversely with the film thickness. The
variations of both hx and" with distance from the top of the tube are shown for
a liquid like methanol in Fig. 13.1.
0. ......
/
I1 \
0.5
f-
le
w- 1.0
(!J
::>
f-
le
r- ~
o r- !!!
<L r- ',g
Q)
l=' 1.5 r- 8
::;; r- '- ~
a! -l!? ..:;;
I- §'"
~
le
W r-
U
Z r- ""
t; .§
;: 2.0. l-
(/)
:'/! ii:
is
2.5
3.0 0. 400 800 120.0. 160.0. 20.0.0. FIGURE 13.1
Film thickness and local coefficients, descending film
Co.EFFICIENT, BTU/H-FT2.OF
-4 of condensate. (By permission,jrom D. Q. Kern, Process
0. 0..8 1.6 2.4 3.2 4.oXI0. Heat Trallsfer. Copyright, 1950, McGraw-Hill Book
FILM THICKNESS, FT Company.)
378 HEAT TRANSFER AND ITS APPLICATIONS S
Film thickness J is typically two or three orders of magnitude smaller than
the tube diameter; it can therefore be found, for flow either inside or outside a
tube, from the equation for a flat plate, Eq. (5.77). Since there is a temperature
gradient in the film, the properties of the liquid are evaluated at the average film
temperature Tr , given by Eq. (13.11). For condensation on a vertical surface, for
which cos [J = 1, Eq. (5.77) becomes
J= (3r)l.r)1/3 (13.2)
Plg
where r is the condensate loading, the mass rate per unit length of periphery.
Substitution for J in Eq. (13.1) gives for the local heat-transfer coefficient, at
a distance L from the top of the vertical surface, the equation
Pfg
h =k ( - -
)1 /3 (13.3)
x r 3r)l.r
Equation (13.3) applies to condensation either inside or outside a tube. Pure
vapors are usually condensed on the outside of tubes; for this situation, for vertical
tubes, the local coefficient is given by the relations
h = dq (13.4)
x flY" dA, fl y" nD, dL
where). = heat of vaporization
In = local flow rate of condensate
Since minD, = r, Eq. (13.4) may be written
Adr
h =-- (13.5)
x flY"dL
The average coefficient h for the entire tube is defined by
qT rilTA rb A
h=--= =-- (13.6)
A, fly" nD,LT flY" LT fly"
where qT total rate of heat transfer
=
mT = total rate of condensation
LT = total tube length
rb = condensate loading at bottom of tube
Eliminating hx from Eqs. (13.3) and (13.5) and solving for fl T, gives
flY = (3r)l.r)'/3 Adr (13.7)
, p}g krdL
Substituting flY" from Eq. (13.7) into Eq. (13.6) gives
r k
h - --'!....£ L
(p g)1 /3
2
dL
(13.8)
- LT 3)l.r r l/3 dr
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 379
Rearranging Eq. (13.8) and integrating between limits leads to
h f'
r 113 dr = -"-.£ jg)1 3f.LT dL
r k ( P2 1
f.
o LT 3/1j 0
from which
h = 4k j ( p}g )1 13 (13.9)
3 3rb/1j
Thus the average coefficient for a vertical tube, provided that flow in the
condensate film is laminar, is ~ times the local coefficient at the bottom of the
tube.
Equation (13.9) can be rearranged to give
h(-'!L)113
3
kjpjg
_1.47(4rb)-113
2
/1j
- (13.10)
On the assumption that the temperature gradient is constant across the film
and that 1(/1 varies linearly with temperature, the reference temperature for
evaluating /1j' kj' and Pj is given by the equation 13 •
H7;,
T.--- (13.11)
" 4
where Tj = reference temperature
7;, = temperature of condensing vapor
Tw = temperature of outside surface of tube wall
Equation (13.10) is often used in an equivalent form, in which the term rb
has been eliminated by combining Eqs. (13.6) and (13.10) to give
1
h = 0.943(k}P}g2)1 4 (13.12)
fl7;, L/1j
Horizontal tubes. Corresponding to Eqs. (13.10) and (13.12) for vertical tubes, the
following equations apply to single horizontal tubes:
(13.13)
and
h= 0.725( k}p}g2 )114 (13.14)
fl7;,D,/1j
where r' is the condensate loading per unit length of tube riIIL and all the other
symbols have the usual meaning.
Equations (13.10) and (13.13) closely resemble each other and can be made
identical by using the coefficient 1.5 for each. They apply in different regimes of
380 HEAT TRANSFER AND ITS APPLICATIONS
Reynolds number, however, for r' for horizontal tubes is typically only about
one-tenth rb for vertical tubes. On horizontal tubes the flow of the condensate
film is virtually always laminar, whereas on vertical tubes it may not be and Eqs.
(13.10) and (13.12) may not apply. Films in turbulent flow are discussed later.
PR~'cAL USE OF NUSSELT EQUATIONS. In the absence of high vapor
veTo~s, experimental data check Eqs. (13.13) and (13.14) well, and these equa-
tions can be used as they stand for calculating heat-transfer coefficients for
film-type condensation on a single horizontal tube. Also, Eq. (13.14) can be used
for film-type condensation on a vertical stack of horizontal tubes, where the
condensate falls cumulatively from tube to tube and the total condensate from
the entire stack finally drops from the bottom tube. The average coefficient
hN for the stack oftubes is less than that for one tube; it is given by the equation'6
hN = h,N-'/4 (13.15)
where hN = average coefficient for entire stack
h, = condensing coefficient for top tube in stack
N = number of tubes in stack
For a stack of tubes Eq. (13.14) becomes 9
hN = 0.725( k}p}g), )'/4 (13.16)
N !!. T" D,I'f
Equations (13.10) and (13.12), for vertical tubes, were derived on the assump-
tion that the condensate flow was laminar. This limits their use to cases where
4rb /l'f is less that 2100. For long tubes, the condensate film becomes sufficiently
thick and its velocity sufficiently large to cause turbulence in the lower portions
of the tube. Also, even when the flow remains laminar throughout, coefficients
measured experimentally are about 20 percent larger than those calculated from
the equations. This is attributed to the effect of ripples on the surface of the falling
film. For practical calculations the coefficients in Eqs. (13.10) and (13.12) should
be taken as 1.76 and 1.13, respectively. When the velocity of the vapor phase in
the condenser is appreciable, the drag of the vapor induces turbulence in the
condensate layer. The coefficient of the condensing film is then considerably larger
than predicted by Eqs. (13.10) and (13.12).
In Fig. 13.2 is plotted h(I'}/kJp}g)'/3 vs. N Ro • Line AA is the theoretical
relation for both horizontal and vertical tubes for magnitudes of N Ro less than
2100 [Eqs. (13.10) and (13.13)]. This line can be used directly for horizontal tubes.
Line BB, based on Eq. (13.10) with a coefficient of 1.76 instead of 1.47 to allow
for the effect of ripples, is recommended for vertical tubes when flow in the
condensate film is laminar throughout.
Turbule~{ljow in films. When the Reynolds number defined by Eq. (5.78) exceeds
abouvi100, flow in the film becomes turbulent. For magnitudes of 4rb /l'f greater
tharf2100 the coefficient h increases with increase in the Reynolds number. Line
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 38i
1.0
0.8 C
~ 0.6
'~"
I\r<t OA B
"',
--- - A-- r-- ......
~
......
S°.2 c
<:
O. I
2
k ~,-
B
A
10
FIGURE 13.2
Heat-transfer coefficients in film condensation: line AA, theoretical relation for laminar flow, horizontal
and vertical tubes; also, recommended relation for horizontal tubes; line BB, recommended relation
for laminar flow, vertical tubes; line CC, approximate relation for turbulent flow, vertical tubes.
CC in Fig. 13.2 can be used for calculation of values of h when the value of 41,/J1.f
exceeds 2100. This value is not reached in condensation on horizontal pipes, and
a line for turbulent flow is not needed. The equation for line CC is 7'
J1.} )' /3 _
h( -3-'- - 0.0076 -
(41,)0.• (13.17)
kfpfg J1.f
For a given substance over a moderate pressure range the quantity
(k}p}g/J1.})'/3 is a function of temperature. Use of Fig. 13.2 is facilitated if this
quantity, which can be denoted by '"f' is calculated and plotted as a function of
temperature for a given substance. QUlllltity '"f has the same dimensions as a
heat-transfer coefficient, so that both the ordinate and abscissa scales of Fig. 13.2
are dimensionless. Appendix 14 gives the magnitude of",f for water as a function
of temperature. Corresponding tables can be prepared for other substances when
desired.
/
EX1Im~3.1. A shell·and-tube condenser with vertical tin. (19-mm) BWG 16
copia!r tubes has chlorobenzene condensing at atmospheric pressure in the shell. The
latent heat of condensation of chlorobenzene is 139.7 Btujlb (324.9 Jjg). The tubes
are 5 ft (1.52 m) long. Cooling water at an average temperature of 175°F (79.4°C) is
flowing in the tubes. If the water-side coefficient is 400 Btujft'-h-OF (2270 Wjm'-°C),
(a) what is the coefficient of the condensing chlorobenzene; (b) what would the
coefficient be in a horizontal condenser with the same number of tubes if the average
number of tubes in a vertical stack is 6? Neglect fouling factors and tube-wall
resistance.
Solution
(a) Equation (13.12) applies, but the properties of the condensate must be evaluated
at reference temperature Tf , which is given by Eq. (13.11). In computing Tf the wall
temperature ~\' must be estimated from 11, the condensate-film coefficient. A trial-
and-error solution is therefore necessary.
382 HEAT TRANSFER AND ITS APPLICATIONS
The quantities in Eq. (13.12) that may be specified directly are
,! ~ 139.7 Btu/lb 9 ~ 4.17 X 10 8 ft/h' L ~ 5 ft
The condensing temperature 1h is 270°F.
The wall temperature Tw must be between 175 and 270°F. The resistance of a
condensing film of organic liquid is usually greater than the thermal resistance of
flowing water; consequently Tw is probably closer to 175°F than it is to 270°F. As
a first approximation. Tw will be taken as 205°F.
The temperature difference A4 is 270 - 205 = 65°F.
The reference temperature, from Eq. (13.11), is
TJ ~ 270 - i(270 - 205) ~ 221 'F
The density and thermal conductivity of liquids vary so little with temperature
that they may be assumed constant at the following values:
PJ ~ 65.4lb/ft3 kJ ~ 0.083 Btu/ft-VF (Appendix 13)
The viscosity of the film is
PJ ~ 0.30 x 2.42 ~ 0.726Ib/ft-h (Appendix 9)
The first estimate of h, using coefficient 1.13, as recommended on page 380, is
0.083 3 x 65.4' x 4.17 x 108 x 139.7)"4
h ~ 1.13 ( ~ 179 Btu/ft'-h-'F
65 x 5 x 0.726
The corrected wall temperature is found from Eq. (12.39). The outside diameter
of the tubes D, is 0.75/12 ~ 0.0625 ft. The inside diameter D; is 0.0625-
(2 x 0.065)/12 ~ 0.0517 ft.
The temperature drop over the water resistance is, from Eq. (12.39),
1/400
!lT~ (270-175)~33'F
, 1/400 + 0.0517/(0.0625 x 179)
The wall temperature is
Tw ~ 175 + 33 ~ 208'F
This is sufficiently close to the estimated value. 205°F (96.1°C). to make further
calculation unnecessary. The coefficient Iz is 179 Btu/ft'-h-'F (1016 W/m'-'C).
Finally, check to see that flow is laminar throughout. The outside surface area
of each tube (Appendix 6) is
A, ~ 0.1963 x 5 ~ 0.9815 ft'
The rate of heat transfer is then
q ~ 179 x 0.9815(270 - 208)
~ 10,893 Btu/h
Thus In T is 10,893/139.7 ~ 78.0 Ib/h, and
78.0
rb ~ n(0.75/12) 397.2Ib/ft-h
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 383
and
4r, = 4 x 397.2
2188
fl 0.726
Since this is only slightly above the critical value of 2100, laminar flow may be
assumed throughout.
(b) For a horizontal condenser, Eq. (13.16) is used. The coefficient of the
chlorobenzene is probably greater than in part (a), so the wall temperature 7;v is now
estimated to be 215°F. The new quantities needed are
N=6 AT" = 270 - 215 = 55°F Do = 0.0625 ft
TJ = 270 - £(270 - 215) = 229°F
flJ = 0.280 x 2.42 = 0.68Ib/ft-h (Appendix 16)
0.083 3 x 65.4 2 x 4.17 X 10 8 x 139.7)"4
11 = 0.725 ( = 230 Btu/ft 2-h-oF
6 x 55 x 0.0625 x 0.68
_ _ _-'=1'--/4~00~_ _ _ 95 = 390F Tw = 175 + 39 = 214°F
1/400 + 0.0517/(0.0625 x 230)
This closely checks the assumed value, 215°F (101.70C), and no further
calculation is needed. The coefficient h is 230 Btu/ft 2-h-oF (1310 W/m2_0C).
In general, the coefficient of a film condensing on a horizontal tube is
considerably larger than that on a vertical tube under otherwise similar conditions
unless the tubes are very short or there are very many horizontal tubes in each
stack. Vertical tubes are preferred when the condensate must be appreciably
subcooled below its condensation temperature. Mixtures of vapors and non-
condensing gases are usually cooled and condensed inside vertical tubes, so that
the inert gas is continually swept away from the heat-transfer surface by the
incoming stream. "
---...c>
CONDENSATION OF SUPERHEATED VAPORS. If the vapor entering a con-
denser is superheated, both the sensible heat of superheat and the latent heat of
condensation must be transferred through the cooling surface. For steam, because
of the low specific heat of the superheated vapor and the large latent heat of
condensation, the heat of superheat is usually small in comparison with the latent
heat. For example, 50°C of superheat represents only 100 Jig, as compared with
approximately 2300 Jig for latent heat. In the condensation of organic vapors, such
as petroleum fractions, the superheat may be appreciable in comparison with the
latent heat. When the heat of superheat is important, either it can be calculated
from the degrees of superheat and the specific heat of the vapor and added to the
latent heat, or if tables of thermal properties are available, the total heat transferred
per pound of vapor can be calculated by subtracting the enthalpy of the condensate
from that of the superheated vapor.
The effect of superheat on the rate of heat transfer depends upon whether
the temperature of the surface of the tube is higher or lower than the condensation
384 HEAT TRANSFER AND ITS APPLICATIONS
temperature of the vapor. If the temperature of the tube is lower than the
temperature of condensation, the tube is wet with condensate, just as in t\le
condensation of saturated vapor, and the temperature of the outside boundary of
the condensate layer equals the saturation temperature of the vapor at the pressure
existing in the equipment. The situation is complicated by the presence of a thermal
resistance between the bulk of the superheated vapor and the outside of the
condensate film and by the existence of a temperature drop, which is equal to the
degrees of superheat in the vapor, across that resistance. Practically, however, the
net effect of these complications is small, and it is satisfactory to assume that the
entire heat load, which consists of the heats of superheat and of condensation, is
transferred through the condensate film; that the temperature drop is that across
the condensate film; and that the coefficient is the average coefficient for condens-
ing vapor as read from Fig. 13.2. The procedure is summarized by the equation
q = hA(T" - 7;,) (13.18)
where q = total heat transferred, including latent heat and superheat
A = area of heat-transfer surface in contact with vapor
h = coefficient of heat transfer, from Fig. 13.2
T" = saturation temperature of vapor
Tw = temperature of tube wall
When the vapor is highly superheated and the exit temperature of the cooling
fluid is close to that of condensation, the temperature of the tube wall may be
greater than the saturation temperature of the vapor, condensation cannot occur,
and the tube wall will be dry. The tube wall remains dry until the superheat has
been reduced to .a point where the tube wall becomes cooler than the condensing
temperature of the vapor, and condensation takes place. The equipment can be
considered as two sections, one a desuperheater and the other a condenser. In
calculations, the two sections must be considered separately. The desuperheater
is essentially a gas cooler. The logarithmic mean temperature difference applies,
and the heat-transfer coefficient is that for cooling a fixed gas. The condensing
section is treated by the methods described in the previous paragraphs.
Because of the low individual coefficient on the gas side, the overall coefficient
in the desuperheater section is small, and the area of the heating surface in that
section is large in comparison with the amount of heat removed. This situation
should be avoided in practice. Superheat can be eliminated more economically by
injection of a spray of liquid directly into the superheated vapor, since small drops
evaporate very rapidly, cooling the vapor to the saturation temperature. The
desuperheating section is thereby eliminated, and condensation occurs with high
coefficients.
s:
EFFECT OF NONCONDENSABLE GASES ON RATE OF CONDENSATION. The
presence of even small amounts of noncondensing gas in a condensing vapor
seriously reduces the rate of condensation. The partial pressure of the condensing
vapor at the surface of the condensate must be less than it is in the bulk gas phase
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 385
FIGURE 13.3
PA . C Profiles of partial pressure and temperature in a condenser
T, when noncondensables are present: PA, partial pressure of
condensable vapor in bulk gas phase; PA,c' partial pressure at
surface of condensate layer; 7;" temperature of bulk gas phase;
Tube Layer of 7;$' temperature at condensate surface; T...i , temperature inside
wall condensate tube wall; 7;"0' temperature outside tube wall; 7;, temperature
of coolant.
in order to provide the driving force for mass transfer through the gas film. This
lower partial pressure means a lower condensing temperature, which decreases the
driving force for heat transfer. There is also a temperature difference across the
gas film and some heat is transferred to the condensate surface by conduction-
convection. This is of minor importance when the amount of noncondensable is
small, since the heat of condensation released at the condensate surface carries
nearly all the heat from the gas phase to the condensate. When the gas is largely
depleted of condensable vapor, however, the heat transferred across the gas film
by conduction-convection may be a significant part of the total.
Figure 13.3 shows the profiles of temperature and partial pressure in such a
condenser. The condensing temperature is not constant as it is in condensing a
pure vapor; instead it drops as the composition of the gas-vapor mixture, and
hence its dew point, changes as condensation proceeds. Rigorous methods of
solving the general problem are based on equating the heat flow to the condensate
surface at any point to the heat flow away from the surface. This involves
trial-and-error solutions for the point temperature of the condensate surface and
from these an estimation of the point values of the heat flux U !J. T. The values of
1(( U !J. T) for each point are plotted against the heat transferred to that point and
the area of the condenser surface found by numerical integration"
A condenser for mixtures of vapors and noncondensable gases is illustrated
in Fig. 15.9, p. 441.
HEAT TRANSFER TO BOILING LIQUIDS
Heat transfer to a boiling liquid is a necessary step in evaporation and distillation
and also in steam generation, petroleum refining, and control of the temperature
of a chemical reaction. The boiling liquid may be contained in a vessel equipped
with a heating surface fabricated from horizontal or vertical plates or tubes, which
supplies the heat necessary to boil the liquid. Or the liquid may flow through
heated tubes, under either natural or forced convection, and the heat transferred
to the fluid though the walls of the tubes. An important application of boiling in
386 HEAT TRANSFER AND ITS APPLICATIONS
tubes is the evaporation of water from solution. Evaporation is the subject of
Chap. 16.
When boiling is accomplished by a hot immersed surface, the temperature
of the mass of the liquid is the same as the boiling point of the liquid under the
pressure existing in the equipment. Bubbles of vapor are generated at the heating
surface, rise through the mass of liquid, and disengage from the surface of the
liquid. Vapor accumulates in a vapor space over the liquid; a vapor outlet from
the vapor space removes the vapor as fast as it is formed. This type of boiling can
be described as pool boiling of saturated liquid since the vapor leaves the liquid in
equilibrium with the liquid at its boiling temperature.
When a liquid is boiled under natural circulation inside a vertical tube,
relatively cool liquid enters the bottom of the tube and is heated as it flows upward
at a low velocity. The liquid temperature rises to the boiling point under the
pressure prevailing at that particular level in the tube. Vaporization begins, and
the upward velocity of the two-phase liquid-vapor mixture increases enormously.
The resulting pressure drop causes the boiling point to fall as the mixture proceeds
up the tube and vaporization continues. Liquid and vapor emerge from the top
of the tubes at very high velocity.
With forced circulation through horizontal or vertical tubes the liquid may
also enter at a fairly low temperature and be heated to its boiling point, changing
into vapor near the discharge end of the tube. Sometimes a flow-control valve is
placed in the discharge line beyond the tube so that the liquid in the tube may
be heated to a temperature considerably above the boiling point corresponding
to the downstream pressure. Under these conditions there is no boiling in the
tube: the liquid is merely heated, as a liquid, to a high temperature, and flashes
into vapor as it passes through the valve. Natural- and forced-circulation boilers
are called calandrias; they are discussed in detail in Chap. 15.
In some types of forced-circulation equipment the temperature of the mass
of the liquid is below that of its boiling point, but the temperature of the heating
surface is considerably above the boiling point of the liquid. Bubbles form on the
heating surface but on release from the surface are absorbed by the mass of the
liquid. This type of boiling is called subcooled boiling.
POOL BOILING OF SATURATED LIQUID. Consider a horizontal wire immersed
in a vessel containing a boiling liquid. Assume that q/A, the heat flux, and 11T,
the difference between the temperature of the wire surface, T,,, and that of the
boiling liquid, T, are measured. Start with a very low temperature drop 11 T. Now
raise Tw and increase the temperature drop by steps, measuring q/A and I1T at
each step, until very large values of I1T are reached. A plot of q/A vs. I1T on
logarithmic coordinates will give a curve of the type shown in Fig 13.4. This curve
can be divided into four segments. In the first segment, at low temperature drops,
the line AB is straight and has a slope of 1.25. This is consistent with the equation
'i = a 11 T U5 (13.19)
A
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 387
o6r---------,----~~~~~~----~~--
Maximum flux for E
nucleate boiling
~ I05~--------+-~~----+_--------~---------
,
Le
,
1:
:::J
f-
co
",-
~I04r-------,A--------_+--------~--------
FIGURE 13.4
Heat flux vs. temperature drop, boiling water at 212"F on an electrically heated wire: AB, natural
convection; BC, nucleate boiling; CD, transition boiling; DE, film boiling, (After MeA dams et al. 14)
where a is a constant. The second segment, line BC, is also approximately
straight, but its slope is greater than that of line AB. The slope of the line BC
depends upon the specific experiment; it usually lies between 3 and 4. The second
segment terminates at a definite point of maximum flux, which is point C in Fig.
13.4. The temperature drop corresponding to point C is called the critical
temperature drop, and the flux at point C is the peak flux. In the third segment,
line CD in Fig. 13.4, the flux decreases as the temperature drop rises and reaches
a minimum at point D. Point D is called the Leidenji-ost point. In the last segment,
line DE, the flux again increases with!;.T and, at large temperature drops, surpasses
the previous maximum reached at point C.
Because, by definition, h = (q(A)(!;'T, the plot of Fig. 13.4 is readily convert-
ible into a plot of h vs. !;. T. This curve is shown in Fig. 13.5. A maximum and a
minimum coefficient are evident in Fig. 13.5. They do not, however, occur at the
same values of the temperature drop as the maximum and minimum fluxes
indicated in Fig. 13.4. The coefficient is normally a maximum at a temperature
drop slightly lower than that at the peak flux; the minimum coefficient occurs at
a much higher temperature drop than that at the Leidenfrost point. The coefficient
is proportional to !;. TO. 2S in the first segment of the line in Fig. 13.4 and to between
!;. T2 and!;, T' in the second segment.
Each of the four segments of the graph in Fig. 13.5 corresponds to a definite
mechanism of boiling. In the first section, at low temperature drops, the mechanism
is that of heat transfer to a liquid in natural convection, and the variation of h
with !;'T agrees with that given by Eq. (12.78). Bubbles form on the surface of the
388 HEAT TRANSFER AND ITS APPLICATIONS
104 , -________, -________- ,________- ,________- - ,
C',
,u.,
N
I-
u. B
± 103
"-
::0 D
I-
CD
£
E
10 2
2 4
10 10 10' 10
iJ T,°F
FIGURE 13.5
Heat-transfer coefficients vs. !J.T, boiling of water at 1 atm.
heater, are released from it, rise to the surface of the liquid, and are disengaged
into the vapor space; but they are too few to disturb appreciably the normal
currents of free convection.
At larger temperature drops, lying between 5 and 25°C (9 and 45°F) in the
case shown in Fig. 13.5, the rate of bubble production is large enough for the
stream of bubbles moving up through the liquid to increase the velocity of the
circulation currents in the mass of liquid, and the coefficient of heat transfer
becomes greater than that in undisturbed natural convection. As IJ.T is increased,
the rate of bubble formation increases and the coefficient increases rapidly.
The action occurring at temperature drops below the critical temperature
drop is called nucleate boiling, in reference to the formation of tiny bubbles, or
vaporization nuclei, on the heating surface. During nucleate boiling, the bubbles
occupy but a small portion of the heating surface at a time, and most of the surface
is in direct contact with liquid. The bubbles are generated at localized active sites,
usually small pits or scratches on the heating surface. As the temperature drop is
raised, more sites become active, improving the agitation of the liquid and
increasing the heat flux and the heat-transfer coefficient.
Eventually, however, so many bubbles are present that they tend to coalesce
on the heating surface to form a layer of insulating vapor. This layer has a highly
unstable surface, from which miniature "explosions" send jets of vapor away from
the heating element into the bulk of the liquid. This type of action is called
transition boiling. In this region increasing the temperature drop increases the
thickness of the vapor film and reduces the number of explosions that occur in a
given time. The heat flux and heat-transfer coefficient both fall as the temperature
drop is raised.
Near the Leidenfrost point another distinct change in mechanism occurs.
The hot surface becomes covered with a quiescent film of vapor, through which
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 389
heat is transferred by conduction and (at very high temperature drops) by
radiation. The random explosions characteristic of transition boiling disappear
and are replaced by the slow and orderly formation of bubbles at the interface
between the liquid and the film of hot vapor. These bubbles detach themselves
from the interface and rise through the liquid. Virtually all the resistance to heat
transfer is offered by the vapor sheath covering the heating element. As the
temperature drop increases, the heat flux rises, slowly at first and then more rapidly
as radiation heat transfer becomes important. The boiling action in this region is
known as film boiling.
Film boiling is not usually desired in commercial equipment because the
heat-transfer rate is low for such a large temperature drop. Heat-transfer apparatus
should be so designed and operated that the temperature drop in the film of boiling
liquid is smaller than the critical temperature drop, although with cryogenic liquids
this is not always feasible.
The effectiveness of nucleate boiling depends primarily on the ease with
which bubbles form and free themselves from the heating surface. The layer of
liquid next to the hot surface is superheated by contact with the wall of the heater.
The superheated liquid tends to form vapor spontaneously and so relieve the
superheat. It is the tendency of superheated liquid to flash into vapor that provides
the impetus for the boiling process. Physically, the flash can occur only by forming
vapor-liquid interfaces in the form of small bubbles. It is not easy, however, to
form a small bubble in a superheated liquid, because at a given temperature the
vapor pressure in a very small bubble is less than in a large bubble or that from
a plane liquid surface. A very small bubble can exist in equilibrium with super-
heated liquid, and the smaller the bubble, the greater the equilibrium superheat
and the smaller the tendency to flash. By taking elaborate precautions to eliminate
all gas and other impurities from the liquid and to prevent shock, it is possible
to superheat water by several hundred degrees Fahrenheit without formation of
bubbles.
A second difficulty appears if the bubble does not readily leave the surface
once it is formed. The important factor in controlling the rate of bubble detach-
ment is the interfacial tension between the liquid and the heating surface. If this
interfacial tension is large, the bubble tends to spread along the surface and blanket
the heat-transfer area, as shown in Fig. 13.6c, rather than. leaving the surface to
make room for other bubbles. If the interfacial tension between liquid and solid
FIGURE 13.6
Effect on bubble formation of interfacial tension between
liquid and heating surface. (After Jakob and Fritz. lo )
390 HEAT TRANSFER AND ITS APPLICATIONS
is low, the bubble will pinch off easily, in the manner shown in Fig. 13.6a. An
example of intermediate interfacial tension is shown in Fig. 13.6b.
The high rate of heat transfer in nucleate boiling is primarily the result of
the turbulence generated in the liquid by the dynamic action of the bubbles. 6
The coefficient obtained during nucleate boiling is sensitive to a number of
variables, including the nature of the liquid, the type and condition of the heating
surface, the composition and purity of the liquid, the presence or absence of
.agiation, and the temperature or pressure. Minor changes in some variables cause
major changes in the coefficient. The reproducibility of check experiments is poor.
Qualitatively, the effects of some variables can be predicted from a considera-
tion of the mechanisms of boiling. A roughened surface provides centers for
nucleation that are not present on a polished surface. Thus roughened surfaces
usually give larger coefficients than smooth surfaces. This effect, however, is often
due to the fact that the total surface of a rough tube is larger than that of a smooth
surface of the same projected area. A very thin layer of scale may increase the
coefficient of the boiling liquid, but even a thin scale will reduce the overall
coefficient by adding a resistance that reduces the overall coefficient more than
the improved boiling liquid coefficient increases it. Gas or air adsorbed on the
surface of the heater or contaminants on the surface often facilitate boiling by
either the formation or the disengaging of bubbles. A freshly cleaned surface may
give a higher or lower coefficient than the same surface after it has been stabilized
by a previous period of operation. This effect is associated with a change in the
condition of the heating surface. Agitation increases the coefficient by increasing
the velocity of the liquid across the surface, which helps to sweep away bubbles.
MAXIMUM FLUX AND CRITICAL TEMPERATURE DROP. The maximum flux
(qjA)m" depends somewhat on the nature of the boiling liquid and on the type of
heating surface but is chiefly sensitive to pressure. It is a maximum at an absolute
pressure about one-third of the thermodynamic critical pressure p, and decreases
toward zero at very low pressures and at pressures approaching the critical
pressure. 7 , If the maximum flux is divided by the critical pressure of the boiling
substance, a curve is obtained, shown in Fig. 13.7, which is about the same for
many pure substances and mixtures. The corresponding critical temperature drop
(not to be confused with "critical temperature") also varies with pressure, from
large values at low pressures to very small ones near the critical pressure. At
pressures and temperatures above the critical values, of course, there is no
difference between liquid and vapor phases, and "vaporization" has no meaning.
At atmospheric pressure the critical temperature drop for water is usually between
40 and 50°C (72 and 90°F); for common organic liquids it is often between 22 and
28°C (40 and 50°F).
The critical temperature drop can be exceeded in actual equipment unless
precautions are taken. If the source of heat is another fluid, such as condensing
steam or hot liquids, the only penalty for exceeding the critical temperature drop
is a decrease in flux to a level between that at the peak and that at the Leidenfrost
point. If the heat is supplied by an electric heater, exceeding the critical temperature
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 391
500 100
400 BO
~
V
"7 60
K 1\
i'-
,-"<J
40
\
~ r- 1\
100 20
~
o
o 0.2 0.4 0.6 0.8
~ 1.0
o
REDUCED PRESSURE,P/Pc
FIGURE 13.7
Maximum boiling heat flux and critical ~ T as functions of reduced pressure. (After M. T. Cichelli and
C. F. ROJ/ilIa, Trans. AIChE, 41:755,1945.)
drop may burn out the heater, as the boiling liquid cannot absorb heat fast enough
at a large temperature drop, and the heater immediately becomes very hot.
The peak flux at the critical temperature drop is large. For water it is in the
range 350 to 1250 kW/m2 (111,000 to 397,000 Btu/ft2-h) depending on the purity
of water, the pressure, and the type and condition of the heating surface. For
organic liquids, the peak flux lies in the range 125 to 400 kW/m2 (40,000 to
127,000 Btu/ft2-h). These limits apply to boiling under atmospheric pressure.
Many correlations have been proposed for estimating the peak flux from the
properties of the fluid, based on various models of the physical phenomena. In
one approach it is assumed that near the critical temperature drop the streams of
bubbles characteristic of nucleate boiling are progressively replaced by jets of
vapor leaving the heat-transfer surface. These must, of course, be accompanied by
streams of liquid flowing toward the surface. At the peak value of the heat flux,
the countercurrent flows of vapor and liquid reach a limiting condition, the process
becomes unstable, and the jets of vapor collapse to form a continuous vapor
sheath. The phenomenon is analogous to the flooding in a packed tower described
in Chap. 22 20 Using this model, Zuber 19 has derived the following dimensionally
consistent equation for maximum heat flux, (q/A)m,,:
(Aq) mall
= 24
n'\ ( P
[l1g,g(PL - PV)]1/4p}12 1 +-.!::
PL
)1/2 (13.20)
where 11 is the interfacial tension between liquid and vapor, PL and Pv are the
densities of liquid and vapor, respectively, and the other symbols have their usual
392 HEAT TRANSFER AND ITS APPLICATIONS
meanings. Increasing the pressure on the system increases Pv without greatly
affecting the other terms in Eq. (13.20) and consequently increases the maximum
heat flux. If the pressure is increased sufficiently. the latent heat of vaporization
tends toward zero, so that ultimately a reduction in the peak flux occurs, as
shown in Fig. 13.7.
~ple 13.2. Benzene is boiling at 2 atm in a kettle-type reboiler with horizontal
!tu"iJe"s. (a) Estimate the maximum heat flux, the critical temperature difference, and
the film coefficient of the boiling liquid. (b) What would be the maximum heat flux
with benzene boiling at 0.2 atm?
Solution
(a) Use Fig. 13.7. The critical pressure of benzene is 47.7 atm, and pip, = 2/47.7 =
0.042. From Fig. 13.7 the ordinate (q/A)m,'/P, is about 190, and
(q/A)m" = 190 x 47.7 x 14.696
= 133,000 say, 130,000 Btu/h-ft 2 (410,000 W/m2)
Also from Fig. 13.7,
!1 T, = 62'F (WC)
The film coefficient is
(q/A)m" 130,000
h=---=---
!1T, 62
=2096 say, 2100 Btufh-ft2-'F (12,000 W/m2-'C)
(b) At a pressure of 0.2 atm, pip, is only 0.0042 and (q/A)m" cannot be read
from Fig. 13.7. Equation (13.20) is therefore used, noting that )., (J, and PL are all nearly
constant, and that PL ~ Pv- Under these conditions
(q/A)m" _ piP _ pll2
Then
(q/A)m" = 130,000 x (0;2)"2
= 41,000 Btu/h-ft2 (130,000 W/m2)
Note that the critical temperature difference at a pressure of 0.2 atm would be
greater than 100'F (56'C) and the film coefficient would be less than 410 Btufh-ft2-'F
(2300 W/m2-'C)
M.\L).'M HEAT FLUX AND FILM BOILING. When film boiling is established,
u;lu~~ns of a characteristic wavelength form in the interface between liquid
and vapor. These undulations grow into bubbles, which leave the interface at
regularly spaced intervals. The diameter of the bubbles is approximately one-half
the wavelength of the undulations. Consideration of the dynamics of this process
leads to the following equation for the minimum heat flux necessary for stable
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 393
film boiling on a horizontal plate 7.
('i) m'.
A
= "APV [(5g,g(PL -
24 (PL
~V)J'/4
+ Pv)
(13.21)
where (q/A)m'. is the minimum heat flux.
Film boiling is a more orderly process than either nucleate boiling or
transition boiling and has been subjected to considerable theoretical analysis. Since
the heat-transfer rate is governed solely by the vapor film, the nature of the heating
surface has no effect in film boiling. For film boiling on a submerged horizontal
tube, the following equation applies with considerable accuracy over a wide range
of conditions 2 :
/
ha[, A,l'v 11T J' 4 = 0.59 + 0.069 A, (13.22)
kVPy{PL - Pv)A'g Da
where ha= heat-transfer coefficient
I'v = viscosity of vapor
11 T = temperature drop across vapor film
kv = thermal conductivity of vapor
PLo Pv = densities of liquid and vapor, respectively
Da = outside diameter of heating tube
In Eq. (13.22) A' is the average difference in enthalpy between the liquid and
the superheated vapor. It is given by the following equation, which is Hsu and
Westwater's modificationS ofBromley's approximation to the rigorous solution':
(13.23)
where A = latent heat of vaporization
cp = specific heat of vapor at constant pressure
The term A, in Eq. (13.22) is the wavelength of the smallest wave that can
grow in amplitude on a flat horizontal interface. It is related to the properties of
the fluid by the equation
(5g J' /2 (13.24)
A = 2" [ '
, g(PL - Pv)
where (5 is the interfacial tension between liquid and vapor. Eq. (13.22) does
not include the effect of heat transfer by radiation.
In Eqs. (13.20) through (13.24) the vapor properties are evaluated at the
arithmetic average of the wall temperature and the boiling point of the liquid. The
liquid properties PL, A, and (5 are evaluated at the boiling point.
Equations have also been developed for film boiling from submerged vertical
tubes, 8 but they have less general validity than Eq. (13.22). Vapor disengages from
a vertical surface in a more complicated fashion than from a horizontal surface,
and the theoretical analysis of the process is correspondingly mOre difficult.
394 HEAT TRANSFER AND ITS APPLlCATfONS
SUBCOOLED BOILING: ENHANCEMENT OF PEAK FLUX. Subcooled boiling
can be demonstrated by pumping a gas-free liquid upward through a vertical
annular space consisting of a transparent outer tube and an internal heating
element and observing the effect on the liquid of a gradual increase in heat flux
and temperature of the heating element. It is observed that when the temperature
of the element exceeds a definite magnitude, which depends on the conditions of
the experiment, bubbles form, just as in nucleate boiling, and then condense in
the adjacent cooler liquid. Under these conditions a small change in temperature
drop causes an enormous increase in heat flux. Fluxes greater than
150 x 106 W/m2 (50 x 106 Btu/ft 2-h) have been reported. 7 , Subcooled boiling is
important for heat-transfer equipment that must pack great capacity into a small
space.
Other methods of obtaining high fluxes, in excess of the normal peak flux
in pool boiling, includes the use of porous coatings on the heating surface, 1 finned
tubes of various designs,18 and for liquids of low electrical conductivity, the
application of high-voltage electric fields. '2
SYMBOLS
A Area, m 2 or ft2; A" outside of tube
a Constant in Eq. (13.19)
cp Specific heat at constant pressure, J/g_OC or Btujlb-oF
D Diameter, m or ft; Dj, inside diameter of tube; Do, outside diameter
9 Gravitational acceleration, m/h2 or ft/h 2
g, Newton's-law proportionality factor, 4.17 x 108 ft-Ibjlb r h 2
h Individual heat-transfer coefficient, W/m2_oC or Btu/ft2-h_oF; hN ,
average for stack of tubes; h" outside tube; h" local value; h" for top
tube in stack
k Thermal conductivity, W/m-oC or Btu/ft-h_oF; ky, of vapor; k f , of
condensate film
L Length, m or ft; LT' total length of tube
In Mass flow rate, kgjh or lb/h; rn T, total condensate flow rate from stack
of tubes
N Number of tubes in vertical stack
NRo Reynolds number of condensate film, 4f"/Pf' dimensionless
P Pressure, atm or Ib f /in. 2 ; PC) critical pressure
q Rate of heat transfer, J/s or Btujh; qT, total rate of heat transfer in
condenser tube
T Temperature, °C or of; Tf , average temperature of condensate film; 1/"
saturation temperature of vapor; Tw ) wall or surface temperature
U Overall heat-transfer coefficient, W/m2_oC or Btu/fe-h-'F
Greek letters
f3 Angle with vertical
r Condensate loading, kg/m-h or lb/ft-h; rb' at bottom of vertical tube;
r', per unit length of horizontal tube
HEAT TRANSFER TO FLUIDS WITH PHASE CHANGE 395
!iT Temperature drop, °C or of; !iT" drop across condensate film,
~ - 7;v; !J. 7;;, critical temperature drop
o Thickness of condensate film, m or ft
A Heat of vaporization, J/g or Btujlb; A', average difference in enthalpy
between boiling liquid and superheated vapor, defined by Eq. (13.23)
A, Wavelength of smallest wave that can grow on flat horizontal surface,
m or ft [Eq. (13.24)]
/l Absolute viscosity, P or lb/ft-h; /lv, of vapor; /If, of condensate film
P Density, kg/m 3 or Ib/ft 3 ; PL, of liquid; Pv, ofvapor Pf' of condensate film
(J Interfacial tension between liquid and vapor, N/m or lbf/ft
'"f Condensation parameter, (k}p}g//lJl' /3, W/m2_oC or Btu/ftl-h_oF
PROBLEMS
13.1. A I-in. BWG 14 copper condenser tube, 3 m long, is to condense ethyl alcohol at
atmospheric pressure. CooJing water inside the tube keeps the metal surface at
an essentially constant temperature of 25 C. (a) How much vapor, in kilograms
Q
per hour, will condense if the tube is vertical? (b) How much wi1l condense if
the tube is horizontal?
13.2. A vertical tubular condenser is to be used to condense 2100 kgjh of ethyl alcohol,
which enters at atmospheric pressure. Cooling water is to flow through the tubes at
an average temperature of 30"C. The tubes are 31 mm OD and 27 mm ID. The
water-side coefficient is 2800 W1m2_ C. Fouling factors and the resistance of the tube
Q
wall may be neglected. If the available tubes are 3 m long, how many tubes will be
needed? Data are as follows:
Boiling point of alcohol: T" = 78.4'C
Heat of vaporization: A = 856 J/g
Density of liquid: Pj = 769 kg/m'
13.3. A horizontal shel1-and-tube condenser is to be used to condense saturated ammonia
vapor at 145Ibj /in.' abs (T" = 82'F). The condenser has 19 steel tubes (1.5 in. OD,
1.3 in. ID) 14 ft long through which cooling water is flowing. The tubes are arranged
hexagonally on 2-in. centers. The latent heat of ammonia at these conditions may be
taken as 500 Btuflb. The cooling water enters at 70°F. Determine the capacity of the
condenser for these conditions.
13.4. A study of heat transmission from condensing steam to cooling water in a single-tube
condenser gave results for both clean and fouled tubes. For each tube the overall
coefficient U was determined at a number of water velocities. The experimental results
were represented by the following empirical equations:
l
I
O.00092+~
268V .,
fouled tube
-=
U, I
0.00040 + 268VO.' clean tube
where U0 = overall heat-transfer coefficient, Btu/ft2-h_oF
V= water velocity, ftls
396 HEAT TRANSFER AND ITS APPLICATIONS
The tubes were 0.902 in. ID and 1.000 in. OD, made of admiralty metal, for which
k ~ 63 Btujft-h-oF. From these data calculate (a) the steam-film coefficient (based on
steam-side area), (b) the water-film coefficient when the water velocity is 1 ft/s (based
on water-side area), (c) value of hdo for the scale in the fouled tube, assuming the
clean tube was free of deposit.
13.5. What heat-transfer coefficient would be expected for natural convection to water at
212°F and 1 atm, outside a 1-in. horizontal pipe with a surface temperature of 213°F?
Compare with Fig. 13.5 and comment on the difference.
13.6. A 25-mm-OD copper tube is to be used to boil water at atmospheric pressure. (a)
Estimate the maximum heat flux obtainable as the temperature of the copper surface
is increased. (b) If the temperature of the copper surface is 210°C, calculate the boiling
film coefficient and the heat flux. The interfacial tension of water at temperatures
above SO°C is given by
(J ~ 7S.38(1 - 0.0025T)
where (J = interfacial tension, dyn/cm
T = temperature, °C
13.7. Steam containing 2 percent air is condensed at atmospheric pressure inside 2S-mm
tubes in a water-cooled condenser. The vertical tubes are 3 m long; the coefficient
and temperature of the cooling water are 2500 W1m2_cC and 30°C, respectively.
Calculate the condensation rate expected if no air was present, and use this value
to estimate the Reynolds number of the vapor at the tube inlet. If 96 percent of
the steam was condensed, what would be the vapor Reynolds number at the tube
outlet? Calculate the equilibrium condensation temperature of the exit vapor, and
show why the actual temperature at the vapor-liquid interface in the condenser
would be lower than this value.
REFERENCES
1. Bergles, A. E., and M.-C. Chyu: AIChE Symp. Series, 77(208):73 (1981).
2. Breen, B. P., and 1. W. Westwater: Cllem. ElIg. Prog., 58(7):67 (1962).
3. Bromiey, L. A.: Ind. Eng. Chem., 44:2966 (1952).
4. Col burn, A. P., and O. A. Hougen: bid. Eng. Chem., 26: 1178 (1934).
5. Drew, T. B., W. M. Nagie, and W. Q. Smith: Trans. AIChE, 31:605 (1935).
6. Forster, H. K., and N. Zuber: AIChE l., 1:531 (1955).
7. Gebhart, B.: Heat Transfer, 2nd ed., McGraw-Hill, New York, 1971; (a) pp. 424-426. (b) p. 446.
8. Hsu, Y. Y., and J. W. Westwater: ClIem. Ellg. Prog. Symp. Ser., 56(30): 15 (1960).
9. Incropera, F. P., and D. P. DeWitt: Fundamenta/sof Heat Transfer, WHey, New York. 1981, p. 492.
10. Jakob, M., and W. Fritz: VDI-ForsclIungsh, 2:434 (1931).
11. Kern, D. Q.: Process Heat Trans/er, McGraw-Hill, New York, 1950, pp. 313ft'.
12. Markels, M. Jr., and R. L. Durfee: AIChE l., 10: 106 (1964).
13. McAdams, W. H.: Heat Transmissi01I, 3rd ed., McGraw-Hill, New York, 1954; (a) pp. 330ff., (b)
pp. 351ff.
14. McAdams, W. H., J. N. Addoms, P. M. Rinaldo, and R. S. Day: Chem. Eng. PMg., 44:639 (1948).
15. Nusselt, W.: VDI z., 60:541, 569 (1916).
16. Perry, 1. H. (ed.): Chemical Engineers Handbook, 6th ed., McGraw-Hill, New York, 1984, p.l0-21.
17. Welch, J. F., and 1. W. Westwater: Proc. Jnt. Heat Transfer Con! £ond., 1961-1962, p. 302 (1963).
18. Yilmaz, S., and 1. W. Westwater: AICbE Symp. Series, 77(208):74 (1981).
19. Zuber, N.: Trans. ASME, 80:111 (1958).
20. Zuber, N., J. W. Westwater, and M. Tribus: Proc. Jnt. Heat Transfer COil! LOlld. 1961-1962, p.
230 (1963).
CHAPTER
14
RADIATION
HEAT
TRANSFER
Radiation, which may be considered to be energy streanting through space at the
speed of light, may originate in various ways. Some types of material will emit
radiation when they are treated by external agencies, such as electron bombard-
ment, electric discharge, or radiation of definite wavelengths. Radiation due to
these effects will not be discussed here. All substances at temperatures above
absolute zero emit radiation that is independent of external agencies. Radiation
that is the result of temperature only is called thermal radiation, and this
discussion is restricted to radiation of this type.
FUNDAMENTAL FACTS CONCERNING RADIATION. Radiation moves through
space in straight lines, or beams, and only substances in sight of a radiating body
can intercept radiation from that body. The fraction of the radiation falling on a
body that is reflected is called the reflectivity p. The fraction that is absorbed is
called the absorptivity c(. The fraction that is transmitted is called the transmissivity
,. The sum of these fractions must be unity, or
C(+p+,=1 (14.1)
Radiation as such is not heat, and when transformed into heat on absorption,
it is no longer radiation. In practice, however, reflected or transmitted radiation
usually falls on other absorptive bodies and is eventually converted into heat,
perhaps after many successive reflections.
397
398 HEAT TRANSFER AND ITS APPLICATIONS
The maximum possible absorptivity is unity, attained only if the body
absorbs all radiation incident upon it and reflects or transmits none. A body that
absorbs all incidient radiation is called a blackbody.
The complex subject of thermal radiation transfer has received much study
in recent years and is covered in a number of texts. 5.8.9 The following introductory
treatment discusses the following topics: emission of radiation, absorption by
opaque solids, radiation between surfaces, radiation to and from semitransparent
materials, and combined heat transfer by conduction-convection and radiation.
EMISSION OF RADIATION
The radiation emitted by any given mass of material is independent of that being
emitted by other material in sight of, or in contact with, the mass. The net energy
gained or lost by a body is the difference between the energy emitted by the body
and that absorbed by it from the radiation reaching it from other bodies. Heat
flow by conduction and convection may also be taking place independently of the
radiation.
When bodies at different temperatures are placed in sight of one another
inside an enclosure, the hotter bodies lose energy by emission of radiation faster
than they receive energy by absorption of radiation from the cooler bodies, and
the temperatures of the hotter bodies decrease. Simultaneously the cooler bodies
absorb energy from the hotter ones faster than they emit energy, and the
temperatures of the cooler bodies increase. The process reaches equilibrium when
all the bodies reach the same temperature, just as in heat flow by conduction and
convection. The conversion of radiation into heat on absorption and the attain-
ment of temperature equilibrium through the net transfer of radiation justify the
usual practice of calling radiation "heat."
WAVELENGTH OF RADIATION. Known electromagnetic radiations cover an
enormous range of wavelengths, from the short cosmic rays having wavelengths of
about 10- 11 cm to longwave broadcasting waves having lengths of 1000 m or
more.
Radiation of a single wavelength is called monochromatic. An actual beam
of radiation consists of many monochromatic beams. Although radiation of any
wavelength from zero to infinity is, in principle, convertible into heat on absorption
by matter, the portion of the electromagnetic spectrum that is of importance in
heat flow lies in the wavelength range between 0.5 and 50 I'm. Visible light covers
a wavelength range of about 0.38 to 0.78 I'm, and thermal radiation at ordinary
industrial temperatures has wavelengths in the infrared spectrum, which includes
waves just longer than the longest visible waves. At temperatures above about
500°C heat radiation in the visible spectrum becomes significant, and the phrases
"red heat" and "white heat" refer to this fact. The higher the temperature of the
radiating body, tlle shorter the predominant wavelength of the thermal radiation
emitted by it.
RADIATION HEAT TRANSFER 399
For a given temperature, the rate of thermal radiation varies with the state
of aggregation of the substance. Monatomic and diatomic gases such as oxygen,
argon, and nitrogen radiate weakly, even at high temperatures. Under industrial
conditions, these gases neither emit nor absorb appreciable amounts of radiation.
Polyatomic gases, including water vapor, carbon dioxide, ammonia, sulfur dioxide,
and hydrocarbons emit and absorb radiation appreciably at furnace temperatures
but only in certain bands of wavelength. Solids and liquids emit radiation over
the entire spectrum.
EMISSIVE POWER. The monochromatic energy emitted by a radiating surface
depends on the temperature of the surface and on the wavelength of the radiation.
At constant surface temperature, a curve can be plotted showing the rate of energy
emission as a function of the wavelength. Typical curves of this type are shown
in Fig. 14.1. Each curve rises steeply to a maximum and decreases asymptotically
to zero emission at very large wavelengths. The unit chosen for measuring the
monochromatic radiation is based on the fact that, from a small area of a radiating
surface, the energy emitted is "broadcast" in all directions through any hemisphere
centered on the radiation area. The monochromatic radiation emitted in this
manner from unit area in unit time divided by the wavelength is called the
monochromatic radiating power W,. The ordinates in Fig. 14.1 are values of w,..
For the entire spectrum of the radiation from a surface, the total radiating
power W is the sum of all the monochromatic radiations from the surface, or
mathematically,
(14.2)
Graphically, W is the entire area under any of the curves in Fig. 14.1 from
wavelengths of zero to infinity. Physically, the total radiating power is the total
radiation of all wavelengths emitted by unit area in unit time in all directions
through a hemisphere centered on the area.
BLACKBODY RADIATION; EMISSIVITY. As shown later [Eq. (14.10)], a black-
body has the maximum attainable emissive power at any given temperature and
is the standard to which all other radiators are referred. The ratio of the total
emissive power W of a body to that of a blackbody w" is by definition the
emissivity 8 of the body. Thus,
W
e=- (14.3)
w"
The monochromatic emissivity 8, is the ratio of the monochromatic emissive
power to that of a blackbody at the same wavelength, or
(14.4)
400 HEAT TRANSFER AND ITS APPLICATIONS
25
20
r0
~
I
Q
0::
W
I: ~I
I
V2000°F
f-
w
:;;
0
15
I
\
,
0::
U I
~ I \
\ vGray body
N
f-
LL
, I
2000 OF
.. =090
I \
I 10
'.\\
,,,
I
~
::>
1'\
(])
'--'
:s,-< ,
, l~kOF
5
"~ '~
/1000 of ~~
I t--.:: ~ b-
o J' . / t..-- t--
-
o 2 3 4 5 6 7 8 9
A, MICROMETERS
FIGURE 14.1
Energy distribution in spectra of blackbodies and gray bodies.
If the monochromatic emissivity of a body is the same for all wavelengths,
the body is called a gray body.
EMISSIVITIES OF SOLIDS. Emissivities of solids are tabulated in standard refer-
ences·· 7 Emissivity usually increases with temperature. Emissivities of polished
metals are low, in the range 0.03 to 0.08. Those of most oxidized metals range
RADIATION HEAT TRANSFER 401
from 0.6 to 0.85, those of nonmetals such as refractories, paper, boards, and
building materials, from 0.65 to 0.95, and those of paints, other than aluminum
paint, from 0.80 to 0.96.
PRACTICAL SOURCE OF BLACKBODY RADIATION. No actual substance is a
black body, although some materials, such as certain grades of carbon black, do
approach blackness. An experimental equivalent of a black body is an isothermal
enclosure containing a small peephole. If a sight is taken through the peephole
on the interior wall of the enclosure, the effect is the same as viewing a blackbody.
The radiation emitted by the interior of the walls or admitted from outside through
the peephole is completely absorbed after successive reflections, and the overall
absorptivity of the interior surface is unity.
LAWS OF BLACKBOuSADIATION. A basic relationship for blackbody radia-
tion is the Stefan-Boltzmann law, which states that the total emissive power of a
black body is proportional to the fourth power of the absolute temperature, or
Wb = aT' (14.5)
where a is a universal constant depending only upon the units used to measure
T and w.. The Stefan-Boltzmann law is an exact consequence of the laws of
thermodynamics and electromagnetism.
The distribution of energy in the spectrum of a blackbody is known
accurately. It is given by Planck's law,
2nhc2), -5
W.b, A. -- '770-=--
ehc{klT _1 (14.6)
where W..l = monochromatic emissive power of blackbody
h = Planck's constant
c = speed of light
,\ = wavelength of radiation
k = Boltzmann's constant
T = absolute temperature
Equation (14.6) can be written
(14.7)
where Cl and C 2 are constants. The units of the various quantities and magnitudes
of the constants in Eqs. (14.5) and (14.6) are given in the list of symbols,
page 423.
Plots of Wh• l vs. ,\ from Eq. (14.6) are shown as solid lines in Fig. 14.1 for
blackbody radiation at temperatures of 1000, 1500, and 2000°F. The dotted line
shows the monochromatic radiating power of a gray body of emissivity 0.9 at
2000'F.
402 HEAT TRANSFER AND ITS APPLICATIONS
Planck's law can be shown to be consistent with the Stefan-Boltzmann law
by substituting w",A from Eq. (14.6) into Eq. (14.2) and integrating.
At any given temperature, the maximum monochromatic radiating power is
attained at a definite wavelength, denoted by Am,,' Wien's displacement law states
that Am" is inversely proportional to the absolute temperature, or
(14.8)
The constant C is 2890 when Am" is in micrometers and T is in kelvins or
5200 when T is in degrees Rankine.
Wien's law also can be derived from Planck's law [Eq. (14.6)] by differentia-
ting with respect to A, equating the derivative to zero, and solving for Am,,'
C
~BSORPTION OF RADIATION BY
OPAQUE SOLIDS
When radiation falls on a solid body, a definite fraction p may be reflected and
the remaining fraction 1 - p enters the solid to be either transmitted or absorbed.
Most solids (other than glasses, certain plastics, quartz, and some minerals) absorb
radiation of all wavelengths so readily that, except in thin sheets, the transmissivity
r is zero, and all nonreflected radiation is completely absorbed in a thin surface
layer of the solid. The absorption of radiation by an opaque solid is therefore a
surface phenomenon, not a volume phenomenon, and the interior of the solid is
not of interest in the absorption of radiation. The heat generated by the absorption
can flow into or through the mass of an opaque solid only by conduction.
REFLECTIVITY AND ABSORPTIVITY OF OPAQUE SOLIDS. Since the transmis-
sivity of an opaque solid is zero, the sum of the reflectivity and the absorptivity
is unity, and the factors that influence reflectivity affect absorptivity in the opposite
sense. In general, the reflectivity of an opaque solid depends on the temperature
and character of the surface, the material of which the surface is made, the
wavelength of the incident radiation, and the angle of incidence. Two main types
of reflection are encountered, specular and diffuse. The first is characteristic of
smooth surfaces such as polished metals; the second is found in reflection from
rough surfaces or from dull, or matte, surfaces. In specular reflection, the reflected
beam makes a definite angle with the surface, and the angle of incidence equals
the angle of reflection. The reflectivity from these surfaces approaches unity, and
the absorptivity approaches zero. Matte, or dull, surfaces reflect diffusely in all
directions, there is no definite angle of reflection, and the absorptivity can
approach unity. Rough surfaces, in which the scale of roughness is large in
comparison with the wavelength of the incident radiation, will reflect diffusely
even if the radiation from the individual units of roughness is specular. Re-
flectivities of rough surfaces may be either large or small, depending upon the
reflective characteristic of the material itself. Most industrial surfaces of interest
to the chemical engineer give diffuse reflection, and in treating practical cases, the
important simplifying assumption can usually be made that reflectivity and
RADIATION HEAT TRANSFER 403
absorptivity are independent of angle of incidence. This assumption is equivalent
to the cosine law, which states that for a perfectly diffusing surface the intensity
(or brightness, in the case of visible light) of the radiation leaving the surface is
independent of the angle from which the surface is viewed. This is true whether
the radiation is emitted by the surface, giving diffuse radiation, or is reflected by
it, giving diffilse reflection.
The reflectivity may vary with the wavelength of the incident radiation, and
the absorptivity of the entire beam is then a weighted average of the monochro-
matic absorptivities and depends upon the entire spectrum of the incident
radiation.
The absorptivity of a gray body, like the emissivity, is the same for all
wavelengths. If the surface of the gray body gives diffuse radiation or reflection,
its monochromatic absorptivity is also independent of the angle of incidence of
the radiant beam. The total absorptivity equals the monochromatic absorptivity
and is also independent of the angle of incidence.
KIRCHHOFF'S L~n important generalization concerning the radiating pow-
er of a substance is Kirchhofl's law, which states that, at temperature equilibrium,
the ratio of the total radiating power of any body to its absorptivity depends only
upon the temperature of the body. Thus, consider any two bodies in temperature
equilibrium with common surroundings. Kirchhofl's law states that
W, W2
(14.9)
where W" W2 = total radiating powers of two bodies
"'" "2 = absorptivities of two bodies
This law applies to both monochromatic and total radiation.
If the first body referred to in Eq. (14.9) is a black body, "I = 1, and
W1=Wi,=-
Wz (14.10)
"2
where Wi, denotes the total radiating power of a black body. Thus
2 W
<X 2 = - (14.11)
Wi,
But, by definition, the emissivity of the second body 82 is
W2
82 =- = <X2 (14.12)
Wi,
Thus, when any body is at temperature equilibrium with its surroundings, its
emissivity and absorptivity are equal. This relationship may be taken as another
statement of Kirchhofl's law. In general, except for blackbodies or gray bodies,
absorptivity and emissivity are not equal if the body is not in thermal equilibrium
with its surroundings.
404 HEAT TRANSFER AND ITS APPLICATIONS
The absorptivity and emissivity, monochromatic or total, of a blackbody
are both unity. The c9sine law also applies exactly to a black body, as the
reflectivity is zero for all wavelengths and all angles of incidence.
Kirchhoffs law applies to volumes as well as to surfaces. Since absorption
by an opaque solid is effectively confined to a thin layer at the surface, the radiation
emitted from the surface of the body originates in this same surface layer. Radiating
substances absorb their own radiation, and radiation emitted by the material in
the interior of the solid is also absorbed in the interior and does not reach the
surface.
Because the energy distribution in the incident radiation depends upon the
temperature and character of the originating surface, the absorptivity of the
receiving surface may also depend upon these properties of the originating surface.
PEAK WAVELENGTH, MICROMETERS
5 3 12
1.0
i'- ~ ~ r--..
~
0.8
paper,~ '" ,~'feename/
~
cloth, etc.
i= 0.6
""
'"~--
'>
;:::
a.
Q:
o(f) !"-
ro
<! 0.4
0.2
~
Polished
aluminu'('
--
o 1000 2000 3500 5000
SOURCE TEMPERATURE, OR
FIGURE 14.2
Absorptivities of various solids vs. source temperature and peak wavelength of incident radiation. (By
permission of author and publisher, from H. C Hotte!, p. 62 in W. H. McAdams, Heat Transmission.
Copyright by author, 1954, McGralV-HiIl Book Company.)
RADIATION HEAT TRANSFER 405
Kirchhoffs law does not, therefore, always apply to noneqnilibrinm radiation. If,
however, the receiving surface is gray, a constant fraction, independent of wave-
length, of the incident radiation is absorbed by the receiving surface, and Kirch-
holfs law applies whether or not the two surfaces are at the same temperature.
The majority of industrial surfaces, unfortunately, are not gray, and their
absorptivities vary strongly with the nature of the incident radiation. Figure 14.2
shows how the absorptivity of various solids varies with the peak wavelength of
the incident radiation and thus with the temperature of the source. 4 ' A few solids,
such as slate, are almost truly gray, and their absorptivities are almost constant.
For polished metallic surfaces the absorptivity a 2 rises with the absolute tempera-
ture of the source T, and also that of surface T2 according to the equation
(14.13)
where k, is a constant. For most surfaces, however, the absorptivity follows a
curve like that indicated for paper, wood, cloth, etc. Such surfaces have high
absorptivities for radiation of long wavelengths originating from sources below
about 1000'F (540'C); as the source temperature rises above this value, the
absorptivity falls, sometimes very markedly. With a few materials the absorptivity
rises once again when the source temperature is very high.
~.~
--':~:
RADIATION BETWEEN SURFACES
The total radiation for a unit area of an opaque body of area A" emissivity 8"
and absolute temperature T, is
-q = ers!
T41 (14.14)
A,
Most surfaces, however, that emit radiation also receive radiation from other
surfaces at different temperatures. Some of this incoming radiation is absorbed
and must be allowed for in determining the total flux of radiant energy. For
example, a steam line in a room is surrounded by the walls, floor, and ceiling of
the room, all of which are radiating to the pipe, and although the pipe loses more
energy than it absorbs from its surroundings, the net loss by radiation is less than
that calculated from Eq. (14.14). Even when a surface is radiating to a clear night
sky, the radiated energy is partially absorbed by the water and carbon dioxide in
the atmosphere, and part of this absorbed energy is radiated back to the surface.
In furnaces and other high-temperature equipment, where radiation is
particularly important, the usual objective is to obtain a controlled rate of net
heat exchange between one or more hot surfaces, called sources, and one or more
cold surfaces, called sinks. In many cases the hot surface is a flame, but exchange
of energy between surfaces is common, and a flame can be considered to be a
special form of translucent surface. The following treatment is limited to the
radiant-energy transfer between opaque surfaces in the absence of any absorbing
medium between them.
406 HEAT TRANSFER AND ITS APPLICATIONS
The simplest type of radiation between two surfaces is where each surface
can see only the other, e.g., where the surfaces are very large parallel planes, as
shown in Fig. 14.3a, and where both surfaces are black. The energy emitted per
unit area by the first plane is crTt; that emitted by the second plane is crT~. Assume
that Tl > T2 • All the radiation from each of the surfaces falls on the other surface
and is completely absorbed. Since the areas of the two surfaces are equal, the net
Hot surface
Cold surface .~
//////;;;;;;;;)7))'///;;#/////// ,./
/V'<- /,~
.......
Hot surface Cold surface
(0) (C)
Ho! ,
/
surface
Hot surface
~/
/
/
/
/
/
Cold surface
(b) (d)
FIGURE 14.3
Angle of vision in radiant heat flow.
RADIATION HEAT TRANSFER 407
loss of energy per nnit area by the first plane and the net gain by the second is
erTi - erT1, or cr(Ti - T~).
Actual engineering problems differ from this simple situation in the following
ways: (1) One or both of the surfaces of interest see other surfaces. In fact, an
element of surface in a concave area sees a portion of its own surface. (2) No actual
surface is exactly black, and the emissivities of the surfaces must often be
consid~red.
ANGLE¥~ VISION. Qualitatively, the interception of radiation from an area
elemel1( of ~·surface by another surface of finite size can be visualized in terms of
the an'gle of vision, which is the solid angle subtended by the finite surface at the
radiating element. The solid angle subtended by a hemisphere is 2" steradians.
This is the maximum angle of vision that can be subtended at any area element
by a plane surface in sight of the element. It wiIl be remembered that the total
radiating power of an area element is defined to take this fact into account. If the
angle of vision is less than 2" steradians, only a fraction of the radiation from the
area element will be intercepted by the receiving area and the remainder will pass
on to be absorbed by other surfaces in sight of the remaining solid angle. Some
of the hemispherical angle of vision of an element of a concave surface is
subtended by the originating surface itself.
Figure 14.3 shows several typical radiating surfaces. Figure 14.3a shows how,
in two large parallel planes, an area element on either plane is subtended by a
solid angle of 2" steradians by the other. The radiation from either plane cannot
escape being intercepted by the other. A point on the hot body of Fig. 14.3b sees
only the cold surface, and the angle of vision is again 2" steradians. Elements of
the cold surface, however, see, for the most part, other portions of the cold surface,
and the angle of vision for the hot body is small. This effect of self-absorption is
also shown in Fig. 14.3c, where the angle of vision of an element of the hot surface
subtended by the cold surface is relatively small. In Fig. 14.3d, the cold surface
subtends a small angle at the hot surface, and the bulk of the radiation from the
hot surface passes on to some undetermined background. Figure 14.3e shows a
simple muffle furnace, in which the radiation from the hot floor, or source, is
intercepted partly by the row of tubes across the top of the furnace, which form
the sink, and partly by the refractory walls and the refractory ceiling behind the
tubes. The refractory in such assemblies is assumed to absorb and emit energy at
the same rate, so the net energy effect at the refractory is zero. The refractory
ceiling absorbs the energy that passes between the tubes and reradiates it to the
backs of the tubes.
If attention is to be focused on the net energy received by the cold surface,
the words hot and cold in Fig. 14.3 may be interchanged, and the same qualitative
conclusions hold.\ ~
SQUARE-OF-THE~IST NCE EFFECT. The energy from a small surface that is
intercepted by a larg~? e depends only upon the angle of vision. It is independent
of the distance betwee the surfaces. The energy received per unit area of the
408 HEAT TRANSFER AND ITS APPLICATIONS
dAZ =brrZsin,pd,p
o
FIGURE 14.4
Diffuse ra?iation to a hemispherical surface.
receiving surface, however, is inversely proportional to the square of the distance
between the surfaces, as shown by the following discussion.
The rate of energy received per unit area of the receiving surface is called
the intensity I of the radiation. For diffuse radiation the cosine law can be used
to find how the intensity of radiation varies with distance and orientation of the
receiving surface from the emitting surface. Consider the element of emitting
surface dAl shown in Fig. 14.4 at the center ofa hemispherical surface A2 with a
radius ,.. The ring-shaped element of the receiving surface dA z has an area
2n,.2 sin </> d</>, where </> is the angle between the normal to dA 1 and the radius
joining dAl and dA z . The intensity at the point directly above dAl is denoted by
dlo; that at any other point above A 1 is dl. By the cosine law of diffuse radiation
dI = dlo cos </> (14.15)
The relation between emissive power W1 of the emitting surface and the
intensity is found as follows. The rate of energy reception by the element of area
dA z , dqdA" is, by Eq. (14.15),
dqdA, = dI dA 2 = dl o cos </> dA 2 (14.16)
Since dA 2 = 2n,.2 sin </> d</>,
dqdA, = dl o 2n,.2 sin </> cos </> d</> (14.17)
The rate of emission from area dA 1 must equal the rate at which energy is
received by the total area A 2, since all the radiation from dAl impinges on some
part of A 2. The rate of reception by A2 is found by integrating dqdA, over area A 2.
Hence,
"/2
W1 dA 1 =
f A,
dqdA, =
1 0
2n dl o ,.2 sin </> cos </> d</>
(14.18)
Thus
W1
dlo =-2dA1 (14.19)
n,.
RADIATION HEAT TRANSFER 409
By substitution from Eq. (14.15)
W,
dI = - , dA, cos 4> (14.20)
nr
QUANTITATIVE\ticULATION OF RADIATION BETWEEN BLACK SUR-
FACES. The above\~onsiderations can be treated quantitatively by setting up a
differential equation for the net radiation between two elementary areas and
integrating the equation for definite types of arrangement of the surfaces. The two
plane elements of area dA, and dA 2 in Fig. 14.5 are separated by a distance rand
are set at any arbitrary orientation to one another that permits a connecting
straight line to be drawn between them. In other words, element dA, must see
element dA 2; at least some of the radiation from dA, must impinge upon dA 2.
Angles 4>, and 4>2 are the angles between the connecting straight line and the
normals to dA, and dA 2, respectively.
Since the line connecting the area elements is not normal to dA, as it is in
Fig. 14.4, the rate of energy reception by element dA 2 of radiation originating at
dA, is
dqdA,~dA' = dI, cos 4>2 dA2 (14.21)
where dI, is the intensity, at area dA 2, of radiation from area dA,. From Eqs.
(14.20) and (14.21), since element dA, is black,
W,
dqdA,~dA, = -2 dA, cos 4>, cos 4>2 dA 2
nr
aTj
= --2 cos 4>, cos 4>2 dA, dA 2 (14.22)
nr
FIGURE 14.5
Differential areas for radiation.
410 HEAT TRANSFER AND ITS APPLICATIONS
Similarly, for radiation from dA 2 which impinges on dA,
aTj:
dqdA , -dA, = --2
nr
cos 1>, cos 1>2 dA, dA 2 (14.23)
The net rate of transfer dq '2 between the two area elements is then found
from the difference between the rates indicated in Eqs. (14.22) and (14.23), to give
cos 1>, cos 1>2 dA, dA 2 4 4
dq'2 = (J 2 (T, - T 2) (14.24)
nr
The integration of Eq. (14.24) for a given combination of finite snrfaces is
usually a lengthy multiple integration based on the geometry of the two planes
and their relation to each other. The resulting equation for any of these situations
can be written in the form
(14.25)
where q '2= net radiation between two surfaces
A= area of either of two surfaces, chosen arbitrarily
F = dimensionless geometric factor
The factor F is called the view factor or angle factor; it depends upon the
geometry of the two surfaces, their spatial relationship with each other, and the
surface chosen for A.
If surface A, is chosen for A, Eq. (14.25) can be written
(14.26)
If surface A2 is chosen,
q'2 = (JA 2 F 2 ,(Tt - T1) (14.27)
Comparing Eqs. (14.26) and (14.27) gives
(14.28)
Factor F'2 may be regarded as the fraction of the radiation leaving area A,
that is intercepted by area A 2 • If surface A, can see only surface A 2 , the view
factor F'2 is unity. If surface A, sees a number of other surfaces and if its entire
hemispherical angle of vision is filled by these surfaces,
Fll + F'2 + F13 + ... = 1.0 (14.29)
The factor F" covers the portion of the angle of vision subtended by other
portions of body A,. If the surface of A, cannot see any portion of itself, Fll is
zero. The net radiation associated with an F11 factor is, of course, zero.
In some situations the view factor may be calculated simply. For example,
consider a small black body of area A2 having no concavities and surrounded by
a large black surface of area A,. The factor F 2 , is unity, as area A2 can see nothing
RADIATION HEAT TRANSFER 411
but area Al' The factor F12 is, by Eq. (14.28),
F2lA2 A2
F12 = - - - = - (14.30)
Al Al
By Eq. (14.29),
A2
Fl1=I-F12=I-- (14.31)
Al
As a secoud example consider a long duct, triangular in cross section, with its
three walls at different temperatures. The walls need not be flat, but they must
have no concavities; i.e., each wall must see no portion of itself. Under these
conditions the view factors are given by4b
_A-'.I_+-,---A--,2c..-_A-:!3
F12 =
2AI
F _ Al + A3 - A2
(14.32)
13 - 2AI
A2 + A3 - Al
F 23 = -"--''----'
2A2
The factor F has been determined by Hottel 2 for a number of important
special cases. Figure 14.6 shows the F factor for equal parallel planes directly
1.0
8
7
0.8
'''- ,~\
0::
0 0.6
"-0:: Radiation belween parallel
g planes, direclly opposed
L>
04
Lt 1-2-3-4 Direcl radialion
4 belween Ihe planes, F
5-6-7-8 Planes cannecled by
3 non-conducting but
0.2
2 reradialing walls, F
I I, 5 Disks 3, 7 2.'1 Reclanqle
I 2, 6 Squares 4,8 Long narrow reclangles
0
0 2 3 4 5 6 7
SMALLER SIDE OR DIAMETER
RATIO,
DISTANCE BETWEEN PLANES
FIGURE 14.6
View factor and interchange factor, radiation between opposed parallel disks, rectangles, and squares.
412 HEAT TRANSFER AND ITS APpLlCATroNS
opposed. Line 1 is for disks, line 2 for squares, line 3 for rectangles having a ratio
of length to width 2:1, and line 4 is for long, narrow rectangles. In all cases, the
factor F is a function of the ratio of the side or diameter of the planes to the
distance between them. Figure 14.7 gives factors for radiation to tube banks backed
by a layer of refractory that absorbs energy from the rays that pass between the
tubes and reradiates the absorbed energy to the backs of the tubes. The factor
given in Fig. 14.7 is the radiation absorbed by the tubes calculated as a fraction
ofthat absorbed by a parallel plane of area equal to that of the refractory backing.
ALLOWA~(zEFOR REFRACTORY SURFACES. When the source and sink are
connectedj6y\,efr~ctory walls in the manner shown in Fig. 14.3e, the Qtctor F can
, by an analogous factor, called the interchange factor F, and Eqs.
be replaced
(14.26) and (14.27) written as
(14.33)
~ecLrL ha
///~ 'l'/////////////////////
if)
w
z
0 0 0 0
<{
..J First row 'J 0 0 0 0 0
Q.
..J
W
..J
..J
<{ 1.0 (6) TOlallo .?
rr~:'
0: Radiating plane
et ~ --3 6''''2
,.
0
f- 0.8 ~~
\0.
'0
-
~r~
0
0-::>(.<:>
~~s
Or:
6'..o.....~
-:;: ""0 RS~
,.
I
t:
',\~oS'......
·"-o::-r
,"f ./P~
~4-::
~
0"..1
.......
t-- t-
z 0.6 ?--o-?
'f'"" ~ . ..ores
J~
0 '- .;~/IY. /sA
if)
ii: " f"~ 0 .....6'_ .....6'S6'.-?/
et d r"'.~,
rOW " r--.r-...
:2 0.4
0
u
(l se;t
o(~
es GO!.'. ent
.--. ·P'i'5'.;;1::..:.-1-'-+-,-
. '- :::::1-. ('3) .
•
u.
0 ~o~ ~o/ O/rec/j,-. _
0:
0 0.2
V ~'Y'
~ ~.
-- --(I}DireCI
c,- -._ 1 "1 Ol'/rsl;.O"'---_
-~ . - _
f-
u ..,?/ rao>aIron I~ secrn;;> ~w - --
11:
If
oI 4 7
2 3 5 6
RATIO' CENTER- TO-CENTER DISTANCE
TUBE DIAMETER
FIGURE 14.7
View factor and interchange factor between a parallel plane and rows of tubes.
RADIATION HEAT TRANSFER 413
The interchange factor F has been determined accurately for some simple situa-
tions' Lines 5 to 8 of Fig. 14.6 give values of F for directly opposed parallel
planes connected by refractory walls. Line 5 applies to disks, line 6 to squares,
line 7 to 2:1 rectangles, and line 8 to long, narrow rectangles.
An approximate equation for F in terms of F is
-F _
,z -
42 - A,FIz (14.34)
A, + A z - 2A,F,z
Equation (14.34) applies where there is but one source and one sink, where
neither area A, nor A z can see any part of itself. It is based on the assumption
that the temperature of the refractory surface is constant. This last is a simplifying
assumption, as the local temperature ofthe refractory usually varies between those
of the source and the sink.
//'"'
NONBLACK SURFKCES. The treatment of radiation between nonblack surfaces,
in the general case where absorptivity and emissivity are unequal and both depend
upon wavelength and angle of incidence, is obviously complicated. Several impor-
tant special cases can, however, be treated simply.
A simple example is a small body that is not black surrounded by a black
surface. Let the areas of the enclosed and surrounding surfaces be A, and A z ,
respectively, and let their temperatures be T, and Tz , respectively. The radiation
from surface A z falling on surface A, is oAzFz , T~. Of this, the fraction "" the
absorbtivity of area A, for radiation from surface A z , is absorbed by surface A,.
The remainder is reflected back to the black surroundings and completely
reabsorbed by the area A z . Surface A, emits radiation in amount aA,s, Tt, where
s, is the emissivity of surface A,. All this radiation is absorbed by the surface A z ,
and none is returned by anothetr~flection. The emissivity s, and absorptivity",
are not in general equal, because the two surfaces are not at the same temperature.
The net energy loss by surface A, is
(14.35)
But by Eq. (14.28), AzFz , = A" and after elimination of AzFz " Eq. (14.35)
becomes
q,z = erA,(., n - ", T~) (14.36)
If surface A, is gray, " = ", and
q,z = erA,E,(n - T~) (14.37)
In general, for gray surfaces, Eqs. (14.26) and (14.27) can be written
q,z = erA,%dn - Ti) = erAz%z,(n - T~) (14.38)
where $'",z and $'"z, are the overall interchange Jactors and are functions of E, and
'z. The value of er is 5.672 x 10- 8 W/mZ_K4, or 0.1713 x 10-' Btu/ftz_h_oR4
414 HEAT TRANSFER AND ITS APPLICATIONS
Surface I .,,$;===='7T1i~7T717T777T7177777777=,;iz.,m7»r.====7777
(a)
;f
/
/
/
/
r,
Surface I -df,'ll7l'll7l'll7l'll7l7T71~77777777777777777777=='7T1i¥''ll1i'777imJ7m7m
(b)
FIGURE 14.8
Evaluation of overall interchange factor for large gray parallel planes: (a) energy originating at surface
I, which is absorbed by unit area of surface 2; (b) energy originating at surface 2, which is reabsorbed
by surface 2.
Two large parallefplanes. In simple cases the factor % can be calculated directly.
Consider tw>Y'Iarge gray parallel planes at absolute temperatures T, and T2 , as
indicated in Fig: 14.8, with emissivities 8, and 8 2 , respectively. The energy radiated
from a unit area of surface 1 equals aTt8,. Part of this energy is absorbed by
surface 2, and part is reflected. The amount absorbed, as shown in Fig. 14.8a,
equals aTt8,8 2 • Part of the reflected beam is reabsorbed by surface 1 and
part is re-reflected to surface 2. Of this re-reflected beam an amount
aTt8,8 2 (1 - 8,)(1 - 82) is absorbed. Successive reflections and absorptions lead to
the following equation for the total amount of radiation originating at surface 1
that is absorbed by surface 2:
q'~2 = aTt8,82[1 + (1 - 8,)(1 - 82) + (1 - 8,l'(1 - 82l' + .. -]
Some of the energy originating at surface 2, as shown in Fig. 14.8b, is reflected
by surface 1 and returns to surface 2, where part of it is absorbed. The amount
of this energy, per unit area, is
q2~2 = -aT1[8 2 - 8~(l - 8,) - 8~(l - 8,l'(1 - 82) - ... ]
The total amount of energy absorbed by a unit area of surface 2 is therefore
q'2 = q'~2 + q2~2
= aTt8,8 2 [1 + (1 - 8,)(1 - 82) + (1 - 8,)2(1 - 82)2 + .. -]
- aT~{ 82 - d(1 - 8,)[1 + (1 + 8,)(1 - 82) + ...]}
RADIATION HEAT TRANSFER 415
Let
y = (1 - B1)(1 - BZ)
Then
q12 = O-TtBIB2(1 + y + y2 + ...) - aT~[Bz - B~(1 - B1)(1 + y + yZ + ...)J
But, since y < 1,
1
l+y+yz+ ... = _ _
l-y
Thus
4 1
QlZ = aT1BIBZ - - - aT z Bz - B2(1 - Bl)--
l-y l-y
4[ Z IJ
Substituting for y and simplifying give
a(T1-
Q 1 Z = --,-c'---'--,---:---'''-_
n)
(1/8 1) + (I/B z ) - 1
Comparison with Eq. (14.38) shows that
1
ffl Z = -::(1-:/B-c)c-+--c(1:-:/B-Z'--)------:-1
(14.39)
I
..
One gray surfacei:onipletely surrounded by another. Let the area of the enclosed
body be Al and that of the enclosure be A z . The overall interchange factor for
this case is given by
1
!!F12 = ---------- (14.40)
(I/B 1) + (A 1 /A z)[(1/8 z) - IJ
Equation (14.40) applies strictly to concentric spheres or concentric cylinders,
but it can be used without serious error for other shapes. The case of a gray body
surrounded by a black one can be treated as a special case of Eq. (14.40) by setting
BZ = 1.0. Under these conditions ff12 = B1·
For gray surfaces in general the following approximate equation may be
used to calculate the overall interchange factor:
1
i71 2 = '""'O-,----::::-:-c-C--,::---:--:--:-:-=-:-:--::: (14.41)
(I/F d + [(1/81) - IJ + (AdA z)[(I/B z) - IJ
where Bl and BZ are the emissivities of source and sink, respectively. If nO
refractory is present, F is used in place of F.
Gebhart 1a describes a direct method for calculating ff in enclosures of gray
surfaces where more than two radiating surfaces are present. Problems involving
nongray surfaces are discussed in the literature'"
416 HEAT TRANSFER AND ITS APPLICATIONS
\~Xample 14.1. A chamber for heat curing large aluminum sheets, lacquered black
on both sides, operates by passing the sheets vertically between two steel plates
150 mm apart. One of the plates is at 300°C and the other, exposed to the atmosphere,
is at 25°C. (a) What is the temperature of the lacquered sheet? (b) What is the heat
transferred between the walls when equilibrium has been reached? Neglect convection
effects. Emissivity of steel is 0.56; emissivity of lacquered sheets is 1.0.
Solution
(a) Let subscript 1 refer to hot plate, 2 to lacquered sheets, and 3 to cold plate:
" ~ 1.0
T, ~573K T3 ~ 298 K
From Eq. (14.38)
q12 = aA 1 ff12(Ti - Ti)
q23 ~ aA 2#23(Ti - 1j)
At equilibrium q'2 ~ q23' From Eq. (14.39)
I
ff12 = 0.56 = ff23
1 1
-+--1
0.56 1.0
Since Al = A2 •
5.73
4
- C~S ~ c~r - 2.98
4
T2 ~ 490.4 K ~ 217.4°C
(b) From Eq. (14.38) the heat flux is
q'2 ~ 5.672 X 0.56(5.73 4 _ 4.9044) ~ 1587 Wjm 2 (503 Btujh-ft2)
A
Check:
q23 ~ 5.672 X 0.56(4.9044 _ 2.98 4 )
A
~ 1587 Wjm 2
Note: If the lacquered sheet is removed, q'3 ~ 3174 Wjm' (1006 Btujh-ft 2).
RADIATION TO SEMITRANSPARENT
MATERIALS
Many substances of industrial importance are to some extent transparent to the
passage of radiant energy. Solids such as glass and some plastics, thin layers of
RADIATION HEAT TRANSFER 417
liquid, and many gases and vapors are semitransparent materials. Their transmis-
sivity and absorptivity depend on the length of the path of the radiation and also
on the wavelength of the beam.
'\~\ . may have
ATTENTUATlON: !3S0RPTlON LENGTH. As shown below, a matenal
very different abs rptivities for radiation of different wavelengths. To classify a
given material qtantitatively as to its ability to absorb or transmit radiation of
wavelength ?C, ieis necessary to define an absOIption length (or optical path length)
LA in the material. This length is the distance of penetration into the material at
which the incident radiation has been attenuated a given amount; Le., the intensity
of the radiation has been reduced to a given fraction of the intensity of the incident
beam. The fraction usually used is lie, where e is the base of natural logarithms.
The attenuation of an incident radiant beam with a monochromatic intensity
I O• A is shown in Fig. 14.9. At distance x from the receiving surface the intensity is
reduced to I,. By assumption, the attentuation per unit length dIAldx at any given
value of x is proportional to the intensity I, at that location, or
(14.42)
where!l, is the absOIption coefficient for radiation of wavelength Jc. Separating the
variables in Eq. (14.42) and integrating between limits, with the boundary condi-
tion that 7, = 1'.0 at x = 0, gives
I =
_A. e-JtlX (14.43)
10 .,
~--- L -----I
~ l~dX
X-I
FIGURE 14.9
Attenuation of radiant beam in absorbing material.
418 HEAT TRANSFER AND ITS APPLICATIONS
The absorption length L, is the value of x such that the attenuation is l/e.
Setting the left-hand side ofEq. (14.43) equal to e- 1 and setting x equal to L, give
1
L i. = - (14.44)
1',
The absorption length is therefore the reciprocal of the absorption coefficient.
If the total thickness L of the material is many times larger than L" the
material is said to be opaque to radiation of that wavelength. Most solids are
opaque to thermal radiation of all wavelengths. If L is less than a few multiples
of L" however, the material is said to be transparent or semitransparent. The
absorption length L, varies not only with wavelength of the incident radiation
but may also vary with the temperature and density of the absorbing material.
This is especially true of absorbing gases.
\ ,.-..
\./
RADIATION TO LAYERS OF LIQUID OR SOLID. In moderately thick layers
nearly ill solids and liquids are opaque and totally absorb whatever radiation
passes/into them. In thin layers, however, most liquids and some solids absorb
only a fraction of the incident radiation and transmit the rest, depending on the
thickness of the layer and the wavelength of the radiation. The variation of
absorptivity with thickness and wavelength for thin layers of water is shown in
Fig. 14.10. Very thin layers (0.01 mm thick) transmit most of the radiation of
wavelengths between 1 and 8 I'm, except for absorption peaks at 3 and 6 I'm.
Layers a few millimeters thick, however, are transparent to visible light (0.38 to
0.78 I'm) but absorb virtually all radiant energy with wavelengths greater than
1.0
0.8
4mm \
22 "!" 001 mm \
£' "-
r-- I-
- -
/
0.2
/
o
o
t rV --
2 3 4 5 6 7 8
WAVELENGTH, MICROMETERS
FIGURE 14.10
Spectral distribution of absorptivity of thin layers of water. (By permission from H. Grober, S. Erk,
and U. Grigull, Fundamentals of Heat Transfer, 3rd ed., p. 442. Copyright, 1961, McGraw-Hill Book
Company.)
RADIATION HEAT TRANSFER 419
1.5 pm. For heat-transfer purposes, therefore, such layers of water may be con-
sidered to have an absorptivity of 1.0.
Layers of solids such as thin films of plastic behave similarly, but the
absorption peaks are usually less well marked. Ordinary glass is also transparent
to radiation of short wavelengths and opaque to that of longer wavelengths. This
is the cause of the so-called greenhouse effect, in which the contents of a
glass-walled enclosure exposed to sunlight become hotter than the surroundings
outside the enclosure. Radiation from the sun's surface, at about 5500 K (10,0000R),
is chiefly shortwave and passes readily through the glass; radiation from inside
the enclosure, from surfaces at say, 30°C (86°F), is of longer wavelength and cannot
pass through the glass. The interior temperature rises until convective losses from
the enclosure equal the input of radiant energy.
\ /!
RADIATION TO ABSORBING GASES. M · an d d
onatomlC · · gases, such as
Iatomlc
hydrogen, oxy~er( helium, argon, and nitrogen, are virtually transparent to
infrared radiation. More complex polyatomic molecules, including water vapor,
carbon dioxide, and organic vapors, absorb radiation fairly strongly, especially
radiation of specific wavelengths. The fraction of the incident radiation absorbed
by a given amount of a gas or vapor depends on the length of the radiation path
and on the number of molecules encountered by the radiation during its passage,
i.e., on the density of the gas or vapor. Thus the absorptivity of a given gas is a
strong function of its partial pressure and a weaker function of its temperature.
If an absorbing gas is heated, it radiates to the cooler surroundings, at the
same wavelengths favored for absorption. The emissivity of the gas is also a
function of temperature and pressure. Because of the effect of path length, the
emissivity and absorptivity of gases are defined arbitrarily in terms of a specific
geometry.
Consider a hemisphere of radiating gas of radius L, ·with a black element of
receiving surface dA 2 located on the base of the hemisphere at its center. The rate
of energy transfer dq12 from the gas to the element of area is then
dq12 4
- - = aTGBG (14.45)
dA 2
where TG = absolute temperature of gas
eG = emissivity of gas (by definition)
Emissivity eG is therefore the ratio of the rate of energy transfer from the gas
to the surface element to the rate of transfer from a black hemispherical surface
of radius L and temperature TG to the same surface element. Figure 14.11 shows
how eG for carbon dioxide varies with radius L and partial pressure PG. Figure
14.11 applies at a total pressure p of 1 atm; Fig. 14.12 gives the correction factor
C, for finding eG at other total pressures.
When the gas temperature TG and the surface temperature Tz are the same,
the gas absorptivity a G, by Kirchhoff's law, equals the emissivity eG. When these
temperatures differ, a G and eG are not equal; however, Fig. 14.11 can be used to
420 HEAT TRANSFER AND ITS APPLICATIONS
0.3
PG~~5.0 A
0.2
;s ---- 3.0 ~'"
~ I-- 2.,,;-:- ~
I.o-,:s'~ t---
~ ~ o.~~ §§§;?0
O. I~ ---= 0.3.
a",
0.08 ."-
....... ....... ....., 1'--,....... --......,.~
":-:::--.
i"-.i"-
:---- ---
..---:: G.7Q/s :--........... ,,:---... r---. ,........ r---. ........ .......
",:::-- L.":'-- .:--: ~ .......
0.06
""
0.- o.~
...........
--~"" ::----....'~--.. ~---
0.0;::"
........... '--......... ,........... ~
r----.......
"
•_ 0.04
0.05
---
,
---- Qo..:>o
c:::;: f'-.....
--------
~
0 ~~ ~
-;~0 ~ ~ ~
>-
f-
2: 0.03
--:~~
(f)
(f)
::;0
0.02
~~~
W
~ ~~
0.0 I ~~~ ~ ~ ~ ~ ;" t.:'--, , ,
0.008
....... .00 > -'"
1'-
I" .::"
'-,
"
.::".:--
~ ~
""
" .::""
--'"
""-
Ra-"<" '-
'- '- '-'-
~ ~""
0.006
4(~ 1"- ' ~
"'" ,,"'"~
0.005
0.004
~o"'i ~ ~ ~
0.003
500 1000 1500
M~
2000 2500
TEMPERATURE, OR
3000
~ ~
3500 ~"'" 4000 4500 5000
FIGURE 14.1I
Emissivity of carbon dioxide at a total pressure of 1 atm. (By permission of author and publisher, from
W. H. MeA dams, Heat Transmission, 3rd ed. Copyright by author, 1954, MeGraw-Hill Book Company.)
find the gas absorptivity at a total pressure of 1 atm by evaluating "G as the
emissivity at T2 and at 'PGL(T2/TG)' instead of at PGL, and mUltiplying the result
by (TG /T2 )o.6S. For total pressures other than 1 atm Fig. 14.12 again applies.
Charts similar to Figs. 14.11 and 14.12 are available for water vap6r. 4d When
both carbon dioxide and water vapor are present, the total radiation is somewhat
less than that calculated from the two gases separately, since each gas is somewha'.
opaque to radiation from the other. Correction charts to allow for this interaction
have been published.4d
RADIATION HEAT TRANSFER 421
1.5
Cc
3.0 5.0
p ~ TOTAL PRESSURE, ATM
FIGURE 14.12
Correction factor Cc for converting emissivity of COt at 1 atm total pressure to emissivity at p
atmospheres. (By permission of author and publisher,from W. H. McAdams, Heat Transmission, 3rd ed.
Copyright by all/hor, 1954, McGraw-HilI Book Company.) .
\. /)
EFFECT OF GEOMETRY ON GAS RADIATION. The rate of transfer from a
radiating gas to the surface of an enclosure depends on the geometry of the system
and on the partial pressure of the gas, PG' In general, the emissivity of a given
quantity of gas must be evaluated using a mean beam length L, which is a
characteristic of the particular geometry. Length L has been computed for several
special cases. For low values of the product P~ it may be shown that L equals
4VjA, where V is the volume of radiating gas and A is the total surface area of
the enclosure. For average values of liGL the mean beam length is 0.85 to 0.90
times that when PGL = O. Values of L for a few geometries are given in Table 14.1.
Other cases, including radiation to only part of the enclosing surface, are covered
in the literature. 4d
TABLE 14.1
Mean beam lengths for gas radiation to entire surface area of enclosuret
Mean beam length, L
For average
Shape of enclosure WhenpoL =0 values of PGL
Sphere, diameter D O.667D O.60D
Infinite cylinder, diameter D D 090D
Right circular cylinder, height = diameter = D O.667D O.60D
Cube, side D O.667D O.S7D (CO,)
Infinite parallel planes, separated by distance D 2D 1.7D (H,O)
l.S4D (CO,)
t By permission of author and publisher, rrom W. H. McAdams, Heal Transmission, 3rd ed., p. 88.
Copyright by author, 1954, McGraw-HiII Book Company.
422 HEAT TRANSFER AND ITS APPLICATIONS
COMBINED HEAT TRANSFER BY
CONDUCTION-CONVECTION AND
RADIATION
The total heat loss from a hot body to its surroundings often includes appreciable
losses by conduction-convection and radiation. For example, a hot pipeline in a
room loses heat nearly equally by each of the two mechanisms. Since the two
types of heat transfer occur in parallel, the total loss is, assuming black surround-
ings,
qT = 'I< + 'i>: = h (T _ T) + aB (T4 _ T4) (14.46)
AAA ell' II'W
where qr/A = total heat flux
qJA = heat flux by conduction-convection
q,/A = heat flux by radiation
he = convective heat-transfer coefficient
Sw = emmissivity of surface
Tw = temperature of surface
T = temperature of surroundings
Equation (14.46) is sometimes written
qT
A= (h< + h,)(7;, - T) (14.47j
where h, is a radiation heat-transfer coefficient, defined by
(14.48)
This coefficient depends strongly on the absolute magnitude of Tw and to
some extent on the temperature difference Tw - T However, when the tempera-
ture difference is small, the value of h, can be approximated from a simple equation
using only one temperature. Expansion of the fourth-power term in Eq. (14.46)
gives
(14.49)
If Tw - T is very small, T can be replaced by Tw in all but one term of Eq.
(14.49) to give
(14.50)
From the definition of h" Eq. (14.48),
(14.51)
RADIATION HEAT TRANSFER 423
If the temperature difference 7;, - T is more than a few degrees but less than
20 percent of the absolute temperature 7;" the arithmetic average of 7;, and T
can be used to improve the accuracy of Eq. (14.51).
Equations (14.46) and (14.51) apply to a small area completely surrounded
by a surface of much larger area, so that only the emissivity of the small area
influences the heat flux. For surfaces of nearly equal area, the term Sw should be
replaced by 1/[(1ls') + (1Isz) - 1], as indicated by Eq. (14.40).
/.-''.
\ / I
RADIATION Ir~.J<:ILM BOILING. In film boiling at a very hot surface a major
fraction of the h~at transfer occurs by radiation from the surface to the liquid.
Equation (14.46) applies to this situation, since the surrounding liqnid, as discussed
earlier, has an absorptivity of unity. When radiation is active, the film of vapor
sheathing the heating element is thicker than it would be if radiation were absent
and the convective heat-transfer coefficient is lower than it would be otherwise.
For film boiling at the surface of a submerged horizontal tube, Eq. (13.22) predict~
the convective heat-transfer coefficient h" in the absence of radiation. When
radiation is present, the convective coefficient is changed to he, which must
be found by trial from the equation lb
(14.52)
where h" is found from Eq. (13.22) and h, from Eq. (14.48) or (14.51). Substitution
of h, and h, into Eq. (14.47) then gives the total rate of heat transfer to the boiling
liquid.
SYMBOLS
A Area, m 2 or ftz; A" of surface 1; A z, of surface 2
C Constant in Eq. (14.8), 2890 /lm-K or 5200 /lm-"R; C" correction factor
for radiation to gases at pressures other than 1 atm; C" constant in
Eq. (14.7), 3.742 x 10- 16 W_mZ; C z , constant in Eq. (14.7), 1.439 cm-K
c Speed of light, 2.998 x 10' mls or 9.836 x 10' ftls
D Diameter, side of cube, or distance between planes, m or ft
F View factor or angle factor, dimensionless; F11, F 12' F13, for radiation
from surface 1 to surfaces 1, 2, 3, respectively; F Zl ' F Z3 ' from surface 2
to surfaces 1 and 3, respectively
Interchange factor for systems involving refractory surfaces, dimension-
less; P,Z , from surface 1 to surface 2; PZl ' from surface 2 to surface 1
Overall interchange factor, dimensionless; :F,Z ' from surface 1 to surface
2; :Fzl , from surface 2 to surface 1
h Planck's constant, 6.626 x 1O- 34 1_s
h Individual heat-transfer coefficient, W/mZ-"C or Btu/ftz-h_oF; h" for
convection in the presence of radiation; h,. for radiation; ho, for boiling
liquid in the absence of radiation
424 HEAT TRANSFER AND ITS APPLICATIONS
I Radiation intensity, W/m2 or Btu/ft2-h; 10, at point on normal to radiat-
ing surface; I I, at surface 2 of radiation from surface 1
I, Monochromatic intensity in absorbing material, W/m2 or Btu/ft2-h;
10 " , at surface of material
k Boltzmann constant, 1.380 x 10- 23 J/K
k, Constant in Eq, (14.13)
L Thickness of material, radius of hemisphere or mean beam length in
radiating gas, m or ft
LA Absorption length, m or ft
p Pressure, atm; PG, partial pressure of radiating gas
q Heat flow rate, W or Btu!h; qr, total; qc, by conduction-convection; qr'
by radiation; Q12, net exchange between surfaces 1 and 2; QI~2' radia-
tion originating at surface 1 that is absorbed by surface 2; Q2~2'
radiation originating at surface 2 that returns to surface 2 and is
absorbed
r Radius of hemisphere or length of straight line connecting area elements
of radiating surfaces, m or ft
T Temperature, K or oR; TG , of radiating gas; ~'" of wall to surface; Tt,
of surface 1; T2 , of surface 2
V Volume of radiating gas, m 3 or ft3
W Total radiating power, W/m2 or Btu/ft2-h; w", of blackbody; WI , of
surface 1; W 2 , of surface 2
w,. Monochromatic radiating power, W/m 2-f1m or Btu/ft2-h-f1m; w"", of
blackbody
x Distance from surface of absorbing material, m or ft
y Variable, set equal to (1 - ed(l - e2 )
Greek letters
0:: Absorptivity, dimensionless; Ci. G , of gas; (Xl> of surface 1; (X2' of surface 2;
IX" for wavelength ), .
8 Emissivity, dimensionless; 8 G , of gas; 8 w , of wall; 8 t , of surface 1; 82 , of
surface 2
8). Monochromatic emissivity, dimensionless
A Wavelength, I'm; Am,,' wavelength at which w"" is a maximum
f1A Absorption coefficient, m-I or ft-I
p Reflectivity, dimensionless
a Stefan-Boltzmann constant, 5,672 x 10- 8 W/m2_K4 or 0,1713 x 10- 8
Btu/ft2_h_OR4
r Transmissivity, dimensionless
</> Angle with normal to surface; </>" to surface 1; <k2, to surface 2
PROBLEMS
14.1. Determine the net heat transfer by radiation between two surfaces A and B, expressed
as watts per square meter of area B, if the temperatures of A and Bare 500 and
RADIATION HEAT TRANSFER 425
200°C, respectively, and the emissivities of A and Bare 0.90 and 0.25, respectively.
Both surfaces are gray. (a) Surfaces A and B are infinite parallel planes 3 m apart. (b)
Surface A is a spherical shell 3 m in diameter, and surface B is a similar shell
concentric with A and 0.3 m in diameter. (c) Surfaces A and B are flat parallel squares
2 by 2 m, one exactly above the other, 2 m apart. (cl) Surfaces A and B are concentric
cylindrical tubes with diameters of 300 and 275 mm, respectively. (e) Surface A is an
infinite plane, and surface B is an infinite row of loo-mm-OD tubes set on 200-mm
centers. (f) Same as (e) except that 200 mm above the centerlines of the tubes is
another infinite plane having an emissivity of 0.90, which does not transmit any of
the energy incident upon it. (g) Same as (f) except that surface B is a double row of
loo-mm-OD tubes set on equilateral 200-mm centers.
14.2. The black flat roof of a building has an emissivity of 0.9 and an absorptivity of 0.8 for
solar radiation. The sun beats down at midday with an intensity of 300 Btu/fe-h. (a)
If the temperature of the air and of the surroundings is 68°F, if the wind velocity is
negligible, and if no heat penetrates the roof, what is the equilibrium temperature of
the roof? For the rate of heat transfer by conduction-convection use q/A =
0.38(.11)1.25. where AT is the temperature drop between roof and air in degrees
Fahrenheit. (b) What fraction of the heat from the roof is lost by radiation?
14.3. The roof of Prob. 14.2 is painted with an aluminum paint, which has an emissivity
of 0.9 and an absorptivity for solar radiation of 0.5. What is the equilibrium
temperature of the painted roof?
14.4. A 3-in Schedule 40 iron pipeline carries steam at 6 atm gauge. The line is uninsulated
and is 70 m long. The surrounding air is at 25°e. The emissivity of the pipe wall is
0.70. How many kilograms of steam will condense per hour? What percentage of the
heat loss is from conduction-convection?
14.5. A radiant-heating system is installed in the plaster ceiling of a room 18 ft long by
18 ft wide by 8 ft high. The temperature of the concrete floor is maintained at 65°F.
Assume that no heat flows through the walls, which are coated with a reradiating
material. The temperature of the air passing through the room is held at 65°F. If the
required heat supply to the floor is 3500 Btu/h, calculate the necessary temperature
at the ceiling surface. How much heat is transferred to the air, in Btu per hour?
Emissivity of plaster is 0.93; absorptivity of concrete is 0.63. The convective heat-
transfer coefficient between the ceiling and the air is given by the equation hI: =
0.20(" T)'/4 Btujft'-h-oF.
14.6. On a clear night, when the effective blackbody temperature of space is - 70°C, the
air is at l5°C and contains water vapor at a partial pressure equal to that of ice or
liquid water at O°e. A very thin film of water, initially at 15°C, is placed in a very
shallow well-insulated pan. placed in a spot sheltered from the wind with a full view
of the sky. If h, ~ 2.6 Wjm'_OC, state whether ice will form, supporting the conclusion
with suitable calculations.
14.7. Air leaves a heat exchanger at about 300°C and 1.5 atm, and the temperature is
measured using a thermocouple inside a i-in.-diameter thermowell mounted normal
to the air flow. If the gas velocity is 25 ftjs and the pipe wall temperature is 270°C,
what error in temperature measurement does radiation cause? (Ignore conduction
along the axis of the thermowell,)
14.8. In an uninsulated house, there is a 90-mm air gap between the plaster wan and the
wooden siding. When the inside wall is at 18°C and the outer wall at - 9°C, what
is the heat loss in watts per square meter by radiation and by natural convection?
426 HEAT TRANSFER AND ITS APPLICATIONS
By what factor would the heat loss be reduced by covering the inside wall with
aluminum foil? Would it be better to put the aluminum foil halfway between the two
walls? (Correlations for natural convection at vertical surfaces give a film coefficient
of 3.9 W/m'-oC for each wall.)
14.9. In boiling water at 1 atm pressure outside a stainless steel tube with a surface
temperature of 410°F, the heat-transfer coefficient h in the absence of radiation is
32 Btujh-ft2_oF. If the emissivity of the stainless steel is 0.8, would radiation signi-
ficantly augment the rate of boiling (that is, by more than 5 percent)? Assume that
the vapor film is transparent to radiation and the boiling liquid is opaque.
REFERENCES
1. Gebhart, R: Heat Transfer, 2nd ed., McGraw-Hill, New York, 1971; (a) pp. 150ft'., (b) p. 421.
2. Houel, H. c.: Mech. El/g., 52:699 (1930).
3. Hottel, H. C: Notes on Radiant Heat Transmission, rev. ed., Department of Chemical Engineering,
Massachusetts Institute of Technology, Cambridge, Mass., 1951.
4. HotteI, H. C: in W. H. McAdams, Heat Transmission, 3rd ed., McGraw-HiIl, New York, 1954; (a)
p. 62, (b) pp. 66ft', (c) pp. 77ft', (d) p. 86.
5. Hottell, H. C, and A. F. Sarofim: Radialive Trans/er, McGraw-Hill, New York, 1967.
6. McAdams. W. H.: Heat Transmission, 3rd ed., McGraw-Hill, New York, 1954, pp. 472ft'.
7. Perry,J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York,1984, p. 10-51.
8. Sparrow, E. M., and R. D. Cess: Radiation Heat Transfer, augmented ed., Hemisphere Publishing,
Washington, D.C., 1978.
9. Spiegel, R., and J. R. Howell, Thermal Radiation Heal Transfer, 2nd ed., McGraw-HiIl, New York,
1981.
CHAPTER
15
HEAT-EXCHANGE
EQUIPMENT
In industrial processes heat energy is transferred by a variety of methods, including
conduction in electric~resistance heaters; conduction-convection in exchangers,
boilers, and condensers; radiation in furnaces and radiant-heat dryers; and by
special methods such as dielectric heating. Often the equipment operates under
steady-state conditions, but in many processes it operates cyclically, as in regenera-
tive furnaces and agitated process vessels.
This chapter deals with equipment types that are of most interest to a process
engineer: tubular and plate exchangers; condensers; boilers and calandrias;
extended surface equipment; mechanically aided heat-transfer devices; and
tubular chemical reactors. Evaporators are described in Chap. 16. Information
on all types of heat-exchange equipment is given in engineering texts and
handbooks. 14 ,18.20c,30
GENERAL DESIGN OF HEAT-EXCHANGE EQUIPMENT. The design and testing
of practical heat-exchange equipment are based on the general principles given in
Chaps. 11 to 14. First, material and energy balances are set up. From these results
the required heat-transfer area is calculated. The quantities to be calculated are
the overall heat-transfer coefficient, the average temperature difference, and in
cyclic equipment, the cycle time. In simple devices these quantities can be evaluated
easily and with considerable accuracy, but in complex processing units the
evaluation may be difficult and subject to considerable uncertainty. The final
design is nearly always a compromise, based on engineering judgment, to give the
best overall performance in the light of the service requirements.
427
428 HEAT TRANSFER AND ITS APPLICATIONS
Sometimes the design is governed by considerations that have little to do
with heat transfer, such as the space available for the equipment or the pressure
drop that can be tolerated in the fluid streams. Tubular exchangers are, in general,
designed in accordance with various standards and codes, such as the Standards
of the Tubular Exchanger Manufacturers Association (TEMAf8 and the ASME-
API Unfired Pressure Vessel Code.!
In designing an exchanger many decisions-some of them arbitrary-must
be made to specify the materials of construction, tube diameter, tube length, baffle
spacing, number of passes, and so forth. Compromises must also be made. For
example, a high fluid velocity inside small tubes leads to improved heat-transfer
coefficients and a small required area but increases the friction losses and pumping
costs. The design of an individual exchanger may be optimized by a formal
procedure to balance the heat-transfer area, and hence the price of the equipment
and the fixed costs, against the cost of energy to pump the fluids.21 In processing
plants, however, the exchangers are components of a complex network of heat-
transfer equipment, and it is the network, not the individual units, that is optimized
to give minimum investment and operating costS. 5
HEAT EXCHANGERS
Heat exchangers are so important and so widely used in the process industries
that their design has been highly developed. Standards devised and accepted by
the TEMA are available covering in detail materials, methods of construction,
technique of design, and dimensions for exchangers.'" The following sections
describe the more important types of exchanger and cover the fundamentals of
their engineering, design, and operation.
SINGLE-PASS 1-1 EXCHANGER. The simple dOUble-pipe exchanger shown in Fig.
11.3 is inadequate for flow rates that cannot readily be handled in a few tubes. If
several double pipes are used in parallel, the weight of metal required for the outer
tubes becomes so large that the sheIl-and-tube construction, such as that shown
in Fig. 15.1, where one shell serves for many tubes, is more economical. This
exchanger, because it has one shell-side pass and one tube-side pass, is a 1-1
exchanger.
In an exchanger the shell-side and tube-side heat-transfer coefficients are of
comparable importance, and both must be large if a satisfactory overall coefficient
is to be attained. The velocity and turbulence of the shell-side liquid are as
important as those of the tube-side fluid. To promote crossflow and raise the
average velocity of the shell-side fluid, baffles are installed in the shell. In the
construction shown in Fig. 15.1, the baffles A consist of circular disks of sheet
metal with one side cut away. Common practice is to cut away a segment having
a height equal to one-fourth the inside diameter of the shell. Such baffles are called
25 percent baffles. The baffles are perforated to receive the tubes. To minimize
leakage, the clearances between baffles and shell and tubes should be small. The
baffles are supported by one or more guide rods C, which are fastened between
HEAT_EXCHANGE EQUIPMENT 429
the tube sheets D and D' by setscrews. To fix the baffles in place, short sections
of tube E are slipped over the rod C between the baffles. In assembling such an
exchanger, it is necessary to do the tube sheets, support rods, spacers, and baffles
first and then to install the tubes.
The stuffing box shown at the right-hand end of Fig. 15.1 provides for
expansion. This construction is practicable only for small shells.
Tubes and tube sheets. As described in Chap. 8, tubes are drawn to definite wall
thickness in terms of BWG and true outside diameter (OD), and they are available
in all common metals. Tables of dimensions of standard tubes are given in
Appendix 6. Standard lengths of tubes for heat-exchanger construction are 8, 12,
16, and 20 ft. Tubes are arranged on triangular or square pitch. Unless the shell
side tends to foul badly, triangular pitch is used, because more heat-transfer area
can be packed into a shell of given diameter than in square pitch. Tubes in
triangular pitch cannot be cleaned by running a brush between the rows, because
no space exists for cleaning lanes. Square pitch allows cleaning of the outside of
the tubes. Also, square pitch gives a lower shell-side pressure drop than triangUlar
pitch.
TEMA standards specify a minimum center-to-center distance 1.25 times the
outside diameter of the tubes for triangUlar pitch and a minimum cleaning lane
of ±in. for square pitch.
Shell and baffles. Shell diameters are standardized. For shells up to and including
23 in. the diameters are fixed in accordance with American Society for Testing
and Materials (ASTM) pipe standards. For sizes of 25 in. and above the inside
diameter is specified to the nearest inch. These shells are constructed of rolled
plate. Minimum shell thicknesses are also specified.
The distance between baffles (center to center) is the baffle pitch, or baffle
spacing. It should not be less than one-fifth the diameter of the shell or more than
the inside diameter of t!le shell.
Tubes are usually attached to the tube sheets by grooving the holes circum-
ferentially and rolling the tube ends into the holes by means of a rotating
FIGURE 15.1
Single-pass 1-1 counterflow heat exchanger: A, baffles; B, tubes; e, guide rods; D, D', tube sheets; E,
spacer tubes.
430 HEAT TRANSFER AND ITS APPLICATIONS
tapered mandrel, which stresses the metal of the tube beyond the elastic limit, so
the metal flows into the grooves. In high-pressure exchangers, the tubes are welded
or brazed to the tube sheet after rolling.
ALTERNATE DESIGN. Another type of shell-and-tube exchanger is the ROD-
baffle heat exchanger developed by Phillips Petroleum Company. Metal rods
rather than sheet metal baffles are used to support the tubes and direct the liquid
flow in the shell. The tubes are arranged in square pitch, and rods with a diameter
equal to the clearance between tube rows are inserted between alternate tubes in
both the horizontal and vertical directions. A cutaway view of the exchanger is
shown in Fig. 15.2. The tube is supported on all four sides, which minimizes
vibration failure. Flow is primarily parallel to the tube axis, but flow across the
rods leads to vortex formation and improved heat transfer. Exchangers of
this type are said to have low pressure drop, give good heat transfer, and require
low maintenance. 8
1-2 PARALLEL-COUNTERFLOW HEAT EXCHANGER. The 1-1 exchanger has
limitations. Higher velocities, shorter tubes, and a more satisfactory solution to
the expansion problem are realized in multipass construction. Multipass construc-
tion decreases the cross section of the fluid path and increases the fluid velocity,
with a corresponding increase in the heat-transfer coefficient. The disadvantages
are that (1) the exchanger is slightly more complicated and (2) the friction loss
through the equipment is increased because of the larger velocities, the longer
path, and the multiplication of exit and entrance losses. For example, the average
velocity in the tubes of a four-pass exchanger is 4 times that in a single-pass
exchanger having the same number and size of tubes and operated at the same
liquid flow rate. The tube-side coefficient of the four-pass exchanger is approx-
imately 4°·8 = 3.03 times that for the single-pass exchanger, or even more if the
FIGURE 15.2
RODbaffle exchanger, cutaway
view. (Phillips Petroleum Co.)
HEAT-EXCHANGE EQUIPMENT 431
~ ~ ~I~ ~
\... 11
t
••
111111111111'1122'1"1111 1111111111
•
~~
• • • •
•
r •
• ••
•
•
••
•
•
•
•••
•
~ i ~1~222?222222222221'222211222221222121j ~ ~~
•••
•• J
FIGURE 15.3
1-2 paraIJel-counterflow exchanger.
velocity in the single-pass unit is sufficiently low to give laminar flow. The
pressure drop per unit length is 41.8 times greater, and the length is increased by
4 times; consequently the total friction loss is 4 2 . 8 = 48.5 times that in the
single-pass unit, not including the additional expansion and contraction losses.
The most economic design calls for such a velocity in the tubes that the increased
cost of power for pumping is offset by the decreased cost of the apparatus.
An even number of tube-side passes is used in multi pass exchangers. The
shell side may be either single-pass or muItipass. A common construction is the
1-2 parallel-counterflow exchanger, in which the shell-side liquid flows in one
pass and the tube-side liquid in two passes. Such an exchanger is shown in Fig.
15.3. In multipass exchangers, floating heads are frequently used, and the bulge
in the shell of the condenser in Fig. 11.1 and the stuffing box shown in Fig. 15.1
are unnecessary. The tube-side liquid enters and leaves through the same head,
which is divided by a baffle to separate the entering and leaving tube-side streams.
2-4 EXCHANGER. The 1-2 exchanger has an important limitation. Because of the
parallel-flow pass, the exchanger is unable to bring the exit temperature of one
fluid very near to the entrance temperature of the other. Another way of stating
the same limitation is that the heat recovery of a 1-2 exchanger is inherently poor.
A better recovery can be obtained by adding a longitudinal baffle to give
two shell passes. A 2-2 exchanger of this kind closely approximates the perfor-
mance of a double-pipe heat exchanger, but because of the cost of the shell-side
baffle, 2-2 exchangers are not often used. Much more common is the 2-4 exchanger,
which has two shell-side and four tube-side passes. This type of exchanger also
gives higher velocities and a larger overall heat-transfer coefficient than a 1-2
exchanger having two tube-side passes and operating with the same flow rates.
An example of a 2-4 exchanger is shown in Fig. 15.4.
432 HEAT TRANSFER AND ITS APPLICATIONS
(i
FIGURE 15.4
2-4 exchanger.
TEMPERATURE PATTERNS IN MULTIPASS EXCHANGERS. Temperature-
length curves for a 1-2 exchanger are shown in Fig. 15.5a using the following
temperature designations:
Inlet temperature of hot fluid T",
Outlet temperature of hot fluid T"b
Inlet temperature of cold fluid 7;,
Outlet temperature of cold fluid 7;.
Intermediate temperature of cold fluid 7;,
Curve T",-T". applies to the shell-side fluid, which is assumed to be the hot fluid.t
Curve 7;,-7;, applies to the first pass of the tube-side liquid, and curve 7;,-7;. to
the second pass of the tube-side liquid. In Fig. 15.5a curves T",-T"b and 7;,-7;,
taken together are those of a parallel-flow exchanger, and curves T",-T"b and 7;,-7;.
taken together correspond to a countercurrent exchanger. The curves for a 2-4
exchanger are given in Fig. 15.5b. The dotted lines refer to the shell-side fluid and
the solid lines to the tube-side fluid. Again it is assumed that the hotter fluid is in
the shell. The hotter pass of the shell-side fluid is in thermal contact with the two
hottest tube-side passes and the cooler shell-side pass with the two coolest
tube-side passes. The exchanger as a whole approximates a true countercurrent
unit more closely than is possible with a 1-2 exchanger.
HEAT-TRANSFER COEFFICIENTS IN SHELL-AND-TUBE EXCHANGER. The
heat-transfer coefficient h, for the tube-side fluid in a shell-and-tube exchanger can
be calculated from Eq. (12.31) or (12.32). The coefficient for the shell-side h, cannot
t For reasons of safety and heat economy the hot fluid is usually put inside the tubes and the cooler
fluid put in the shell.
HEAT-EXCHANGE EQUIPMENT 433
IJf ~1'Jt~L====~il"
~o 'hb
TUBE LENGTH TUBE LENGTH
(0) (h)
FIGURE 155
Temperature-length curves: (a) 1-2 exchanger; (b) 2-4 exchanger.
be so calculated because the direction of flow is partly parallel to the tubes and
partly across them and because the cross-sectional area of the stream and the mass
velocity of the stream vary as the fluid crosses the tube bundle back and forth
across the shell. Also, leakage between baffles and shell and between baffles and
tubes short-circuits some of the shell-side liquid and reduces the effectiveness of
the exchanger. An approximate but generally useful equation for predicting
shell-side coefflcients is the Danohue equation' (15.4), which is based on a weighted
average mass velocity G, of the fluid flowing parallel with the tubes and that
flowing across the tubes. The mass velocity Gb parallel with the tubes is the mass
flow rate divided by the free area for flow in the baffle window Sb' (The baffle
window is the portion of the shell cross section not occnpied by the baffle.) This
area is the total area of the baffle window less the area occupied by the tubes, or
1tD2 1tD2
Sb=ib--' -Nb--' (15.1)
4 4
where Ji, = fraction of cross-sectional area of shell occupied by baffle window
(commonly 0.1955)
D, = inside diameter of shell
Nb = number of tubes in baffle window
D, = outside diameter of tubes
434 HEAT TRANSFER AND ITS APPLICATIONS
In crossflow the mass velocity passes through a local maximum each time
the fluid passes a row of tubes. For correlating purposes the mass velocity G, for
crossflow is based on the area S, for transverse flow between the tubes in the row
at or closest to the centerline of the exchanger. In a large exchanger S, can be
estimated from the equation
(15.2)
where p = center-to-center distance between tubes
P = baffie pitch
The mass velocities are then
ri,
Gb = - and (15.3)
Sb
The Donohue equation is
h,:, O.2(D:G,tCrr,(:J'4
= (15.4)
where G, = JGbG,. This equation tends to give conservatively low values of h"
especially at low Reynolds numbers. More elaborate methods of estimating
shell-side coefficients are available for the specialis!,ob. Inj-factor form Eq. (15.4)
becomes
h (c fl)2I'(fl~)0.,4 =jH=O.2(D~G )-0.4
-'- ~
cpG, k fl fl (15.5)
After the individual coefficients are known, the total area required is found
in the usual way from the overall coefficient using an equation similar to Eq.
(11.14). As discussed in the next section, the LMTD must often be corrected for
the effects of crossflow.
Example 15.1. A tubular exchanger 35 in. (889 mm) ID contains eight hundred and
twenty-eight i-in. (19-mm) OD tubes 12 ft (3.66 mm) long on a I-in. (25-mm) square
pitch. Standard 25 percent baffles are spaced 12 in. (305 mm) apart. Liquid benzene
at an average bulk temperature of 60'F (15.6'C) is being heated in the shell side of
the exchanger at the rate of 100,000 IbJh (45,360 kgjh). If the outside surfaces of the
tubes are at 140°F (60°C), estimate the individual heat-transfer coefficient of the
benzene.
Solution
The shell-side coefficient is found from the Donohue equation (15.4). The sectional
areas for flow are first calculated from Eqs. (15.1) and (15.2). The quantities needed are
0.75
D, =- = 0.0625 ft D, = il = 2.9167 ft
12
P= ,', = 0.0833 ft P = 1 ft
HEAT-EXCHANGE EQUIPMENT 435
From Eq. (15.2), the area for crossHow is
S, ~ 2.9167 x 1 (1 _ 0.0625) ~ 0.7292 ft'
0.0833
The number of tubes in the baffle window is approximately equal to the
fractional area of the window f times the total number of tubes. For a 25 percent
baffle,f ~ 0.1955. Hence
Nb ~ 0.1955 x 828 ~ 161.8, say, 161 tubes
The area for How in the baffle window, from Eq. (15.1), is
1t x 2.9167
2 1t X 0.0625' 2
Sb ~ 0.1955 - 161 ~ 0.8123 It
4 4,
The mass velocities are, from Eq. (15.3),
G, ~ 100,000 ~ 137,137Ib/ft2-h Gb ~ 100,000 ~ 123,107Ib/ft2-h
0.7292 0.8123
G, ~ JGbG, ~ J137,137 x 123,107 ~ 129,933Ib/ft 2-h
The additional quantities needed for substitution in Eq. (15.4) are
I' at 60'F ~ 0.70 cP I' at 140'F ~ 0.38 cP (Appendix 9)
Cp ~ 0.41 Btu/lb-'F (Appendix 16)
k ~ 0.092 Btu/ft-h-'F (Appendix 13)
From Eq. (15.4)
h,D, ~ 0.2(0.0625 x 129,933)0"(0.41 x 0.70 x 2.42)0.33(0.70)0."
k 0.70 x 2.42 0.092 0.38
~ 68.59
Hence
68.59 x 0.092
h, ---- ~ 101 Btu/ft 2-h-'F (573 W/m2-'C)
. 0.0625
COEFFICIENTS FOR CROSSFLOW. In some exchangers snch as air heaters
the shell is rectangular and the number of tubes in each row is the same.
Flow is directly across the tubes, and baffles are not needed. For such crossflow
conditions the following equation is recommended';
h,:, ~ 0.287(D:Gr61(c~r3 Fp (15.6)
where G is the mass velocity outside the tubes, based on the minimum area for
flow in any tube row, and Fa is an "arrangement factor" that depends on N Re and
the tube spacingp. The other symbols are the same as in Eq. (15.4). Typical values
of Fp are given in Table 15.1.
436 HEAT TRANSFER AND ITS APPLICATIONS
TABLE 15.1
Arrangement factor Fa for crossflow with square pitcht
plD., NR~ = 2000 N Rt = 8000 N Re = 20,000 NR~ = 40,000
1.25 0.85 0.92 1.03 1.02
1.5 0.94 0.90 1.06 1.04
2.0 0.95 0.85 1.05 1.02
t After Ref. 2.
CORRECTION OF LMTD FOR CROSSFLOW. If a fluid flows perpendicularly to a
heated or cooled tube bank, the LMTD, as given by Eq. (11.15), applies only if the
temperature of one of the fluids is constant. If the temperature of both fluids
change, the temperature conditions do not correspond to either countercurrent or
parallel flow but to what is called crossflow. In a 1-2 or 2-4 exchanger the flow
is partly parallel, partly countercurrent, and partly crossflow.
When flow types other than countercurrent or parallel appear, it is customary
to define a correction factor F G , which is so determined that when it is multiplied
by the LMTD for countercurrent flow, the product is the true average temperature
drop. Figure 15.6 shows a correlation for FG for crossflow derived on the
assumption that neither stream mixes with itself during flow through the ex-
changer. 3 Each curved line in the figure corresponds to a constant value
of the dimensionless ratio Z, defined as
(15.7)
and the abscissas are values of the dimensionless ratio qH' defined as
(15.8)
The factor Z is the ratio of the fall in temperature of the hot fluid to the rise in
temperature of the cold fluid. The factor qH is the heating effectiveness, or the ratio
of the actual temperature rise of the cold fluid to the maximum possible tempera-
ture rise obtainable if the warm-end approach were zero (based on countercurrent
flow). From the numerical values of qH and Z the factor FG is read from Fig. 15.6,
interpolating between lines of constant Z where necessary, and multiplied by the
LMTD for counterflow to give the true mean temperature drop.
Figure 15.7a and b show the factor FG for 1-2 and 2-4 exchangers,
respectively, derived on the assumptions that the overall heat-transfer coefficient is
constant and that all elements of a given fluid stream have the same thermal
history in passing through the exchanger.2o, As before, FG is so defined that when
HEAT-EXCHANGE EQUIPMENT 437
1.0
0.9
~ ~ R ~ -0 :::---..
1\ \ '\ "\ ~ ~ ~
- '-.....
\
"'.. '"If " "" "" " co , "''"." \. ""
0.8 I '\
'"
"l <\i -..: <:5 <:5 <:5 <:i
\ \
\ \ \\ \\ \
0.7
0.6
0.5
\ \ \\
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
~H
FIGURE 15.6
Correction of LMTD for crossflow. (From R. A. Bowman, A. C. Muel/er, and W. M. Nag/e, Tram.
ASME, 61:283, 1940. Courtesy of American Society of Mechanical Engineers.)
it is mUltiplied by the counterflow LMTD, the product is the correct mean
temperature drop.
Factor F G is always less than unity. The mean temperature drop, and
therefore the capacity of the exchanger, is less than that of a countercurrent
exchanger having the same LMTD. When FG is less than about 0.8, the exchanger
should be redesigned with more passes or larger temperature differences; otherwise
the heat-transfer surface is inefficiently used and there is danger that small changes
in conditions may cause the exchanger to become inoperable. When FG is less
than 0.75, it falls rapidly as 'IH increases, so that operation is sensitive to small
changes. In this region, also, any deviations from the basic assnmptions on which
the charts are based become important, especially that of a uniform thermal history
for all elements of fluid. Leakage through and around the baffles may partially
invalidate this assumption.
Other combinations of shell-side passes and tube-side passes are used, but
the 1-2 and the 2-4 types are the most common.
Example 15.2. In the 1-2 exchanger sketched in Fig. 15.5a, the values of the
temperatures are 'fca = 70"C; ~b = 130"C; 'Iha = 240"C; ~b = 120"C. What is the
correct mean temperature drop in this exchanger?
Solution
The correction factor FG is found from Fig. 15.7a. For this case, from Eqs. (15.7) and
(15.8),
130 - 70 = 0.353 240 - 120
Z= = 2.00
240 -70 130 -70
438 HEAT TRANSFER AND ITS APPLICATIONS
1.0.
0..9
0..8
",'"
0..7
0..6
0..5
0. 0..1 0..2 0.3 0..4 0.5 0..6 0..7 0..8 0..9 1.0
'1H
(a)
1.0.
0..9
0..8
'"'" 0..7
0..6
0..5
0. 0..1 0..2 0..3 0..4 0.5 0..6 0..7 0..8 0..9 1.0
'1H
(b)
FIGURE 15.7
Correction of LMTD: (a) 1~2 exchangers; (b) 2-4 exchangers. (From R. A. Bowman, A. C. Muel/er,
and W. M. Nagle, Trans. ASME, 61:283,1940. Courtesy of American Societyo! Mechanical Engineers.)
From Fig. 15.7a, FG = 0.735. The temperature drops are
At shell inlet: !1T ~ 240 - 130 ~ 1!O°C
At shell outlet: !1T ~ 120 - 70 ~ 50°C
!1T ~ 110 - 50 = 760C
L In (110/50)
HEAT·EXCHANGE EQUIPMENT 439
The correct mean is 6.T = 0.735 x 76 = 56°C. Because of the low value of Fa, a
1-2 exchanger is not suitable for this duty.
Example 15.3. What is the correct mean temperature difference in a 2-4 exchanger
operating with the same inlet and outlet temperatures as in the exchanger in Example
15.27
Solution
For a 2-4 exchanger, when 'lH = 0.353 and Z = 2.00, the correction factor from
Fig. 15.7b is FG = 0.945. The ATL is the same as in Example 15.2. The correct mean
!; T ~ 0.945 x 76 ~ n'c.
PLATE-TYPE EXCHANGERS. For heat transfer between fluids at low or moderate
pressures, below about 20 atm, plate-type exchangers are competitive wth shell-
and-tube exchangers, especially where corrosion-resistant materials are required.
Metal plates, usually with corrugated faces, are supported in a frame; hot fluid
passes between alternate pairs of plates, exchanging heat with the cold fluid in the
adjacent spaces. The plates are typically 5 mm apart. They can be readily separated
for cleaning; additional area may be provided simply by adding more plates.
Unlike shell-and-tube exchangers, plate exchangers can be used for multiple duty;
i.e., several different fluids can flow through different parts of the exchanger and
be kept separate from one another. The maximum operating temperature is about
150°C (302'F); maximum heat-transfer areas are about 500 m 2 (5400 [(2). Plate
exchangers are effective with viscous fluids, with viscosities up to about 300 P.
Other special and compact exchangers, which provide large heat-transfer
areas in a small volume, are described in the literature.'3
CONDENSERS
Special heat-transfer devices used to liquefy vapors by removing their latent heats
are called condensers. The latent heat is removed by absorbing it in a cooler liquid
called the coolant. Since the temperature of the coolant obviously is increased in
a condenser, the unit also acts as a heater, but functionally it is the condensing
action that is important, and the name reflects this fact. Condensers fall into two
classes. In the first, called shell-and-tube condensers, the condensing vapor and
coolant are separated by a tubular heat-transfer surface. In the second, called
contact condensers, the coolant and vapor streams, both of which are usually
water, are physically mixed and leave the condenser as a single stream.
SHELL-AND-TUBE CONDENSERS. The condenser shown in Fig. ILl is a single-
pass unit, since the entire stream of cooling liquid flows through all the tubes in
parallel. In large condensers, this type of flow has a serious limitation. The number
of tubes is so large that in single-pass flow the velocity through the tubes is too
small to yield an adequate heat-transfer coefficient, and the unit is uneconomically
440 HEAT TRANSFER AND ITS APPLICATIONS
Vent for
no,"c'>no~m'~b'/e5" r7:7A~~~g liquid inlet
Condensate outlet
"-"-"--~-::'~nQ liquid outlet
FIGURE 15.8
Two-pass floating-head condenser.
large. Also, because of the low coefficient, long tubes are needed if the cooling
fluid is to be heated through a reasonably large temperature range, and such long
tubes are not practicable.
To obtain larger velocities, higher heat-transfer coefficients, and shorter
tubes, the mUltipass principle used in heat exchangers may also be used for the
coolant in a condenser. An example of a two-pass condenser is shown in Fig. 15.8.
Provision for thermal expansion. Because ofthe differences in temperature existing
in condensers, expansion strains may be set up that are sufficiently severe to buckle
the tubes or pull them loose from the tube sheets. The most common method of
avoiding damage from expansion is the use of the floating-head construction, in
which one of the tube sheets (and therefore one end of the tubes) is structurally
independent of the shell. This principle is used in the condenser of Fig. 15.8. The
figure shows how the tubes may expand or contract, independent of the shell. A
perforated plate is set over the vapor inlet to prevent cutting of the tubes by
drops of liquid that may be carried by the vapor.
DEHUMIDIFYING CONDENSERS. A condenser for mixtures of vapors and non-
condensable gases is shown in Fig. 15.9. It is set vertically, not horizontally like
most condensers for vapor containing no noncondensable gas; also, vapor is
condensed inside the tubes, not outside, and the coolant flows through the shell.
This provides a positive sweep of the vapor gas mixture through the tubes and
avoids the formation of any stagnant pockets of inert gas that might blanket the
heat-transfer surface. The modified lower head acts to separate the condensate
from the uncondensed vapor and gas.
CONTACT CONDENSERS. An example of a contact condenser is shown in Fig.
15.10. Contact condensers are much smaller and cheaper than surface condensers.
HEAT·EXCHANGE EQUIPMENT 441
Vopor inlet
~~, __Woter outlet
Floating tube
sheet
Stuffing box
Topped holes_!!-.-'·~1tUiLJIt~-RingS of square
for stud balls packing
Follower
Floating-tube- Slip-on backing
sheet skirt flange
Vapor oullet
./
Split shear ring
Vapor liquid
separating cone oullel FIGURE 15.9
Outside packed dehumidifying
Floating head cover cooler-condenser.
Vopor inlet
Water
mlet ---+-
(jel)
FIGURE 15.10
Contact condenser. (Sclmlte and Koerting Div.,
Ketema, Inc.)
442 HEAT TRANSFER AND ITS APPLICATIONS
In the design shown in Fig. 15.10, part of the cooling water is sprayed into the
vapor stream near the vapor inlet, and the remainder is directed into a discharge
throat to complete the condensation. When a shell-and-tube condenser is operated
under vacuum, the condensate is usually pumped out, but it may be removed by
a barometric leg. This is a vertical tube about 10 m (34 ft) long, sealed at the
bottom by a condensate-receiving tank. In operation the level of liquid in the leg
automatically adjusts itself so that the difference in head between levels in leg and
tank corresponds to the difference in pressure between the atmosphere and the
vapor space in the condenser. Then the liquid flows down the leg as fast as it is
condensed without breaking the vacuum. In a direct-contact condenser the
pressure regain in the downstream cone of the venturi is often sufficient to eliminate
the need for a barometric leg.
BOILERS AND CALANDRIAS
In process plants liquids are boiled in kettle-type boilers containing a pool of
boiling liquid or in vertical-tube calandrias though which the liquid and vapor
flow upward through the tubes. Sometimes, as described in Chap. 16, the liquid
is heated under pressure to a temperature well above its normal boiling point and
then allowed to flash (partially vaporize) by reducing the pressure at a point
external to the heat-transfer equipment.
KETTLE-TYPE BOILERS. A kettle-type boiler, or reboiler as it is called when
connected to a distillation column, is shown in Fig. 15.11. A horizontal shell
contains a relatively small tube bundle, two-pass on the tube side, with a floating
head and tube sheet. The tube bundle is submerged in a pool of boiling liquid,
Vapor
outlet
Shell
Steam
inlet
\
Tube
sheet
Auxiliary
nozzles
Tubes
Condensate Liquid Tube Hot liquid
outlet feed supports outlet
FIGURE 15.11
Kettle~type
reboiler.
HEAT-EXCHANGE EQUIPMENT 443
"- ~
Botto m of
_____ ~istilla tion
1
colum n
Liquid [evel in column
Steam
;------~--,.'"
matically
contro lied)
calandrl8
~
rp~~== -\ Bottom produ et
Condensate '.
Liquid driving head
FIGURE 15.12
Calandria reboiler.
the depth of which is set by the height of an overflow weir. Feed is admitted to
the liquid pool from the bottom. Vapor escapes from the top of the shell; any
unvaporized liquid spills over the weir and is withdrawn from the bottom of the
shell. The heating fluid, usually steam, enters the tubes as shown; steam condensate
is removed through a trap. The auxiliary nozzles shown in Fig. 15.11 are for
inspection, draining, or insertion of instrument sensing elements.
CALANDRIAS. Vertical shell-and-tube units, known as calandrias, natural-circula-
tion or thermosiphon reboilers, are generally the tnost economical vaporizers for
distillation and evaporation operations. A typical arrangement is shown in Fig.
15.12. Liquid from an evaporator or distillation column enters the bottom of the
unit and is partially vaporized in the heated tubes; the reduction in density causes
the vapor-liquid mixture to rise and draw in additional feed liquid. Liquid and
vapor leave the top of the tubes at high velocity; they are separated and the liquid
is recycled.
Configurations and thermal ratings of industrial calandrias fall in a relatively
narrow range. The tubes are typically 25 mm (1 in.) in diameter, sometimes as
large as 50 mm (2 in.). They are 2.5 to 3.5 m (8 to 12 ft) long, seldom longer; short
tubes 1.2 to 1.8 m (4 to 6 ft) long are sometimes used in vacuum service.
Heat-transfer rates depend on the properties of the vaporizing liquid,
especially its reduced temperature T"t and on its tendency to foul the heat-
transfer surface 6 •11 Typical overall coefficients for steam-heated calandrias are
given in Table 15.2. They are relatively insensitive to changes in tube length or
tube diameter. When the operating pressure is 1 atm abs or greater, the coefficients
are also insensitive to changes in the liquid "driving head" indicated in Fig. 15.12.
t Reduced temperature is the ratio of the actual temperature to the critical temperature of the liquid,
both in kelvins or degrees Rankine.
444 HEAT TRANSFER AND ITS APPLICATIONS
TABLE 15.2
Typical overall coefficients in calandria boilers
Overall coefficient U
Service Bto/ft'-b-of
Heavy organic chemicals 570-900 100-160
Light hydrocarbons 900-1250 160-220
Water, aqueous solutions 1250-2000 220-350
20,000
18,000
r,. =0.6
16,000
N
f-
14,000
u.
I
I
-..
::J
12,000
f-
en
I
10,000
'x"
::J
~
8,000
...J
U.
f-
<! 6,000
w
I
4,000
2,000
120 140
OVERALL TEMPERATURE DIFFERENCE, OF
FIGURE 15.13
Heat flux in natural-circulation calandrias. (After Frank and Prickelt. 6 )
HEAT-EXCHANGE EQUIPMENT 445
This head is defined as the distance from the bottom tube sheet to the level of the
liquid in the column. Under these pressure conditions the liquid level is typically
maintained near the level of the top tube sheet to ensure that the heat-transfer
surface is completely wetted and to establish reasonably high circulation rates.
When operation is under vacuum, however, the performance of the reboiler
is sensitive to changes in the liquid driving head, especially in the distillation of
multicomponent mixtures. The optimum liquid level for vacuum service is midway
between the tube sheets, with about 50 percent of the liquid vaporized per pass.!2
For usual applications with saturated steam on the shell side the heat flux
can be estimated from Figure 15.13, which is based on BWG 14 stainless-steel
I-in. (25-mm) tubes 8 ft (2.44 m) long. The curves are drawn for pure liquids; if
mixtures are used, the reduced temperature should be that of the component
having the lowest value of T,.. The chart should not be used for absolute pressures
below 0.3 atm, nor should the curves be extrapolated.
EXTENDED SURFACE EQUIPMENT
Difficult heat-exchange problems occur when one of two fluid streams has a much
lower heat-transfer coefficient than the other. A typical case is heating a fixed gas,
such as air, by means of condensing steam. The individual coefficient for the
steam is typically 100 to 200 times that for the airstream; consequently, the overall
coefficient is essentially equal to the individual coefficient for the air, the capacity
of a unit area of heating surface will be low, and many meters or feet of tube will
be required to provide reasonable capacity. Other variations of the same problem
are found in heating or cooling viscous liquids or in treating a stream of fluid at
low flow rate, because of the low rate of heat transfer in laminar flow.
To conserve space and to reduce the cost of the equipment in these cases,
certain types of heat-exchange surfaces, called extended surfaces, have been
developed in which the outside area of the tube is multiplied, or extended, by fins,
pegs, disks, and other appendages and the outside area in contact with the fluid
thereby made much larger than the inside area. The fluid stream having the lower
coefficient is brought into contact with the extended surface and flows outside the
tubes, while the other fluid, having the high coefficient, flows through the tubes.
The quantitative effect of extending the outside surface can be seen from the overall
coefficient, written in the following form, in which the resistance of the tube wall
is neglected,
1
V· = -.,..-"::"""'.........,c-c (15.9)
, (l/h,) + (A,(A,h,)
Equation (15.9) shows that if h, is small and h, large, the value of V, will be
small; but if the area A, is made much larger than A" the resistance A,(A,h,
becomes small and V, increases just as if h, were increased, with a corresponding
increase in capacity per unit length of tube or unit of inside area.
446 HEAT TRANSFER AND ITS APPLICATIONS
FIGURE 15.14
Types of extended surface: (a)
longitudinal fins; (b) transverse
(0) (b) fins.
TYPES OF EXTENDED SURFACE. Two common types of extended surfaces are
available, examples of which are shown in Fig. 15.14. Longitudinal fins are used
when the direction offlow of the fluid is parallel to the axis of the tube; transverse
fins are used when the direction of flow of the fluid is across the tubes. Spikes,
pins, studs, or spines are also used to extend surfaces, and tubes carrying these
can be used for either direction of flow. In all types, it is important that the fins
be in tight contact with the tube, both for structural reasons and to ensure good
thermal contact between the base of the fin and the wall.
FIN EFFICIENCY. The outside area of finned tube consists of two parts, the area
of the fins and the area of the bare tube not covered by the bases of the fins. A
unit area of fin surface is not so efficient as a unit area of bare tube surface because
of the added resistance to the heat flow by conduction through the fin to the tube.
Thus, consider a single longitudinal fin attached to a tube, as shown in Fig. 15.15,
and assume that the heat is flowing to the tube from the fluid surrounding the
fin. Let the temperature of the fluid be T and that of the bare portion of the tube
7;,. The temperature at the base of the fin will also be 7;,. The temperature drop
available for heat transfer to the bare tube is T - 7;" or 11 7;. Consider the heat
transferred to the fin at the tip, the point farthest away from the tube wall. To
reach the wall of the tube, this heat must flow by conduction through the entire
Local fin
temp TF
FlUId temperature T
Wall
temperature Tw
FIGURE 15.15
Tube and single longitudinal fin.
HEAT-EXCHANGE EQUIPMENT 447
length of the fin, from tip to base. Other increments of heat, entering the fin at
points intermediate between tip and base, also must flow through a part of the
fin length. A temperature gradient will be necessary, therefore, from the tip of the
fin to the base, and the tip will be warmer than the base. If TF is the temperature
of the fin at a distance x from the base, the temperature drop available for heat
transfer from fluid to fin at that point will be T - TF. Since TF> Tw ,
T - TF < T - 7;, = !IT,,, and the efficiency of any unit area away from the fin
base is less than that of a unit area of bare tube. The difference between T - TF
and !l T" is zero at the base of the fin and is a maximum at the tip of the fin. Let
the average value of T TF , based on the entire fin area, be denoted by !lTF . The
efficiency of the fin is defined as the ratio of !lTF to!lT" and is denoted by ryF. An
efficiency of unity (or of 100 percent) means that a unit area of fin is as effective
as a unit area of bare tube as far as temperature drop is concerned. Any actual
fin will have an efficiency smaller than 100 percent.
CALCULATIONS FOR EXTENDED-SURFACE EXCHANGERS. Consider, as a
basis, a unit area of tube. Let AF be the area of the fins and Ab the area of the
bare tube. Let h, be the heat transfer coefficient of the fluid surrounding the fins
and tube. Assume that h, is the same for both fins and tube. An overall coefficient,
based on the inside area Ai, can be written
(15.10)
To use Eq. (15.10) it is necessary to know the values of the fin efficiency 'IF
and of the individual coefficients hi and h,. The coefficient hi is calculated by the
usual method. The calculation of the coefficient h, will be discussed later.
The fin efficiency ryF can be calculated mathematically, on the basis of certain
reasonable assumptions, for fins of various types'" For example, the efficiency of
longitudinal fins is given in Fig. 15.16, in which ryF is plotted as a function of the
quantity aFxF , where X F is the height of the fin from base to tip and a F is defined
by the equation
(15.11)
where h, = coefficient outside tube
km = thermal conductivity of metal in fin
Lp = perimeter of fin
S= cross-sectional area of fin
The product aFxF is dimensionless.
Fin efficiencies for other types of extended surface are available. 7 Figure
15.16 shows that the fin efficiency is nearly unity when aFxF < 0.5. Extended
surfaces are neither efficient nor necessary if the coefficient h, is large. Also, fins
increase the pressure drop.
448 HEAT TRANSFER AND ITS APPLICATIONS
1.0 ........
o.8 "-
'" '" r--...
-......
02
00 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 FIGURE 15.16
of xF Fin efficiency, longitudinal fins.
The coefficient Iz, cannot be accurately found by the use of the equations
normally used for calculating the heat-transfer coefficients for bare tubes. The fins
change the flow characteristics of the fluid, and the coefficient for an extended
surface differs from that for a smooth tube. Individual coefficients for extended
surfaces must be determined experimentally and correlated for each type of surface,
and such correlations are supplied by the manufacturer of the tubes. A typical
correlation for longitudinal finned tubes is shown in Fig. 15.17. The quantity D,
is the equivalent diameter, defined as usual as 4 times the hydraulic radius, which
is, in turn, the cross section of the fin-side space divided by the total perimeter of
fins and tube calculated as in Example 15.4.
Example 15.4. Air is heated in the shell of an extended-surface exchanger. The inner
pipe is l1-in. IPS Schedule 40 pipe carrying 28 longitudinal fins 1 in. high and
0.035 in. thick. The shell is 3-in. Schedule 40 steel pipe. The exposed outside area of
~
c 24 Fins
-.,.
~ 28Ans
~ "
~
'"~
"-
~"-
" .Olf----+---~,.,__-___,I_--_+----l
'~"G'
'"
.-'"!; .001'----"-----"-----"-----1--,----'
I 10 100 1000 10,000 100,000
FIGURE 15.17
Heat-transfer coefficients, longitudinal finned tubes; Itin. IPS with !-by-O.035-in. fins in 3-in. IPS
shell. (Brown Fintube Co.)
HEAT-EXCHANGE EQUIPMENT 449
the inner pipe (not covered by the fins) is 0.416 ft' per linear foot; the total surface
area of the fins and pipe is 2.830 ft2jft. Steam condensing at 2500F inside the inner
pipe has a film coefficient of 1500 Btu/ft'-h-'F. The thermal conductivity of steel is
26 Btu/ft-h-'F. The wall thickness of the inner pipe is 0.145 in. If the mass velocity
of the air is 5000 Ibjh-ft2 and the average air temperature is 130°F, what is the overall
heat-transfer coefficient based on the inside area of the inner pipe? Neglect fouling
factors.
Solution
The film coefficient hI) of the air is found from Fig. 15.17. To use this correlation the
Reynolds number of the air must first be calculated as follows. The viscosity of air
at 130'F is 0.046Ib/ft-h (Appendix 8). The equivalent diameter of the shell space is
3.068
ID of shell (Appendix 5) = - - = 0.2557 ft
12
1.900
OD of inner pipe (Appendix 5) = -- = 0.1583 ft
12
The cross-sectional area of the shell space is
n(0.2557' - 0.1583') 28 x 0.5 x 0.035
0.0282 ft'
4 144
The perimeter of the air space is
nO.2557 + 2.830 = 3.633 ft
The hydraulic radius is
0.0282
r ll = - - = 0.00776 ft
3.633
The equivalent diameter is
D, =4 x 0.00776 = 0.0310 ft
The Reynolds number of air is therefore
0.0310 x 5000
N - 3.37 X 10'
R. - 0.046
From Fig. 15.17, the heat-transfer factor is
jll = ~ (Cpl')'I'(_~)-O.14 = 0.0031
cpG k fJ.w
The quantities needed to solve for hI) are
Cp = 0.25 Btuflb-'F (Appendix 15)
k = 0.0162 Btu/ft-h-'F (Appendix 12)
450 HEAT TRANSFER AND ITS APPLICATIONS
In computing Pw the resistance of the wall and the steam film are considered
negligible, so 7;, = 250°F and I'w = 0.0528Ib/ft-h:
1')0.,4 (0.046-)0.,4 =0.981 Cpl' 0.25 x 0.046
(-I'w = - 0.0528
N p, = - =
k 0.0162
=0.710
0.0031 x 0.25 x 5000 x 0.981 ,
110 = '/3 = 4.78 Btu/ft oh_oF
0.710
For rectangular fins, disregarding the contribution of the ends of the fins to
the perimeter, Lp = 2L, and S = LYF, where YF is the fin thickness and L is the length
of the fin. Then, from Eq. (15.11),
2 x 4.78
I-:-:-~~-:c = 0.467
26(0.035/12)
From Fig. 15.16, '1F = 0.93.
The overall coefficient is found from Eq. (15.10). The additional quantities
needed are
1.610
D. = - - = 0.1342 ft (Appendix 5)
, 12
__ 0.1583 - 0.1342
D = = 0.1454 ft
L In (0.1583/0.1342)
Ai = nO.1342 x 1.0 = 0.422 ft'jlineal ft
AF + Ab = 2.830 ft'jlineal ft
AF = 2.830 - 0.416 = 2.414 ft'jlineal ft
1.900 - 1.610
0.0121 ft
2 x 12
Ui=------~~~------~~~--~~--~-
0.422 0.0121 x 0.1342 1
----c------- + +-
4.78(0.93 x 2.414 + 0.416) 26 x 0.1454 1500
= 29.2 Btu/ft'-h-oF (166 W/m'-°C)
The overall coefficient, when based on the small inside area of the inner pipe,
may be much larger than the air-film coefficient based on the area of the extended
surface.
AIR-COOLED EXCHANGERS. As cooling water has become scarcer and pollution
controls more stringent, the use of air-cooled exchangers has increased. These
consist of bundles of horizontal finned tubes, typically 25 mm (1 in.) in diameter
and 2.4 to 9 m (8 to 30 ft) long, through which air is circulated by a large fan. Hot
process fluids in the tubes, at temperatures from 100 to 400'C (212 to 750'F) or
more, can be cooled to about 40°F above the dry-bulb temperature of the air.
Heat-transfer areas, based on the outside surface of the tubes, range from 50 to
HEAT-EXCHANGE EQUIPMENT 451
500 m2 (500 to 5000 ft'); the fins multiply this by a factor of 7 to 20. Air flows
between the tubes at velocities of 3 to 6 mls (10 to 20 ft/s). The pressure drop and
power consumption are low, but sometimes to reduce the fan noise to an
acceptable level, the fan speed must be lower than that for minimum power
consumption. In air-cooled condensers the tubes are usually inclined. Detailed
design procedures are given in the literature?·16
HEAT TRANSFER IN AGITATED VESSELS
Heat-transfer surfaces, which may be in the form of heating or cooling jackets or
coils of pipe immersed in the liquid, are often used in the agitated vessels described
in Chap. 9.
HEAT-TRANSFER COEFFICIENTS. In an agitated vessel, as shown in Chap. 9, the
dimensionless group D;llplJ1. is a Reynolds number useful in correlating data on
power consumption. This same group has been found to be satisfactory as a
correlating variable for heat transfer to jackets or coils in an agitated tank. The
following equations are typical of those that have been offered for this purpose.
For heating or cooling liquids in a baffied cylindrical tank equipped with a
helical coil and a turbine impeller,
h,D, = 0.17(D;n p)0.6'(C J1.)0.37(D )O.I(D,)O.5(!!.-)b
p a
(15.12)
k J1. k D, D, J1.w
where h, is the individual heat-transfer coefficient between coil surface and
liquid. The exponent b on the viscosity ratio was reported to be higher for thin
liquids than for viscous oils,19 but a value of 0.24 is suggested to be consistent
with the following equation for the jacket coefficient. The coil coefficients for a
pitched turbine are about 0.85 times and those for a propeller 0.70 times the values
for a standard turbine of the same diameter. 15
For heat transfer to or from the jacket of a baffied tank, the following
equation applies if a standard turbine is used27:
hp,
-=0.76 - -
(D;n p)2/3(C- J1.)1 /3(-J1. )0.24
p
(15.13)
k J1. k J1.w
where hj is the coefficient between the liquid and jacketed inner surface of the
vessel. The jacket coefficients for a pitched turbine are 0.9 times, and for a propeller
0.6 times, the values for a standard turbine. 15 The standard turbine, however, has
a much higher power consumption (see Table 9.3).
When the liquid is very viscous, an anchor agitator is used, which sweeps
with close clearance at fairly low speeds over the entire heat-transfer surface. Data
for anchor agitators are well correlated by the equation 29 '
(15.14)
452 HEAT TRANSFER AND ITS APPLICATIONS
where K = 1.0, a = i for 10 < N., < 300; where K = 0.36, a = ~ for
300 < N., < 40,000.
Equations of this type are generally not applicable to situations differing
significantly from those for which the equations were derived. Equations for
various types of agitators and arrangements of heat-transfer surface are given in
the literature. 29 ,
When a liquid is heated in a stirred tank by condensing a vapor in the jacket,
the controlling resistance is usually that of the liquid in the tank. When a heating
or cooling liquid is passed through the jacket without a phase change, however,
the jacket-side resistance may be controlling. With a simple open jacket the liquid
velocity is so low that heat transfer is predominantly by natural convection. The
mixing caused by natural convection also makes the average temperature in the
jacket close to that at the exit, so that the temperature difference at the exit should
be used, not the logarithmic mean. To increase the heat-transfer coefficient in large
vessels, the coolant in the jacket is often sprayed on the outer surface of the vessel
or spiral baffles are inserted in the jacket to give a higher liquid velocity and
prevent backmixing.
TRANSIENT HEATING OR COOLING IN AGITATED VESSELS. Consider a well-
agitated vessel containing In kilograms or pounds of liquid of specific heat cp. It
contains a heat-transfer surface of area A heated by a constant-temperature
medium such as condensing steam at temperature T,. If the initial temperature of
the liquid is T,., its temperature 7;, at any time IT can be found as follows. The
basic relation for unsteady-state heat transfer is
Rate of accumulation of energy = energy input - energy output
For a batch of liquid with no flow in or out of the tank and no chemical reaction,
the only energy input is the heat transferred through the area A, and there is no
output. The accumulation term is the rate of change of the enthalpy of the liquid
in the tank:
dT
mc p - = UA(T, - T) (15.15)
dl
If U is constant (usually a reasonable assumption), Eq. (15.15) can be
integrated between the limits I = 0, T = T,. and I = IT' T = Tb to give
T, - T,. UAI T
In---=-- (15.16)
1's - 1b mc p
Equation (15.16) is often used to determine overall coefficients from the time
required to heat a known mass of liquid.
If the heat-transfer medium is not at a constant temperature but is a liquid
(such as cooling water) of specific heat cp , entering at temperature 7;, and flowing
at a constant rate m" the corresponding equation for the liquid temperature is
7;, -Yea rncc pc K1 - 1
(15.17)
In =-- IT
1b - Yea mc p Kt
HEAT-EXCHANGE EQUIPMENT 453
where
(15.18)
Equations for other situations involving transient heat transfer are available
in the literature. 14a
SCRAPED-SURFACE EXCHANGERS
In vessels containing anchor agitators, scrapers are sometimes attached to the
anchor arms to prevent degradation of the liquid in contact with the heated surface.
This is especially useful with food products and similar heat-sensitive materials.
Scrapers give a modest increase in the heat-transfer coefficient when used with
newtonian liquids and may raise the coefficient by as much as 5 times with
non-newtonian liquids. 29b
Anchor-agitated vessels are nearly always operated batchwise; in continuous
processes, heat transfel to or from viscous liquids is often accomplished in
scraped-surface exchangers. Typically these are double-pipe exchangers with a
fairly large central tube 100 to 300 mm (4 to 12 in.) in diameter jacketed with
steam or cooling liquid. The inside surface of the central tube is wiped by one or
more longitudinal blades mounted on a rotating shaft.
The viscous liquid is passed at low velocity through the central tube. Portions
of this liquid adjacent to the heat-transfer surface are essentially stagnant, except
when disturbed by the passage of the scraper blade. Heat is transferred to the
viscous liquid by unsteady-state conduction. If the time between disturbances is
short, as it usually is, the heat penetrates only a small distance into the stagnant
liquid, and the process is exactly analogous to unsteady-state heat transfer to a
semi-infinite solid.
HEAT-TRANSFER COEFFICIENTS IN SCRAPED-SURFACE EXCHANGERS}O
Assume that the bulk temperature of the liquid at some location along the
exchanger is T, and the temperature of the heat-transfer surface is Tw' Assume for
the present that T," > T. Consider a small element of area of the heat-transfer
surface over which the blade has just passed. Any liquid that was previously on
this surface element has be<!ri removed by the blade and replaced by other liquid
at temperature T. Heat flows from the surface to the liquid during the time interval
IT, which is the time until the next scraper blade passes the surface element,
removes the liquid, and redeposits new liquid on the surface.
From Eq. (10.30), the total amount of heat QT transferred during time
interval IT is given by
QT = 2k(Tw _ T) (t;
A ,;~
where k = thermal conductivity of liquid
a = thermal diffusivity of liquid
A = area of heat-transfer surface
454 HEAT TRANSFER AND ITS APPLICATIONS
The heat-transfer coefficient averaged over each time interval is, by definition,
QT
h,=-:-:::::'-:= (IS.19)
tTA(T" - T)
Substitution from Eq. (10.30) into Eq. (IS.19), noting that Cl. = k/pc p ' gives
hi = 2JkPCp (IS.20)
ntl'
The time interval between the passage of successive blades over a given
element of area is
1
t 1, = - (IS.21)
nB
where n = agitator speed, r/h
B = number of blades carried by shaft
Combining Eqs. (IS.20) and (IS.21) gives, for the heat-transfer coefficient,
h, = 2 JkPc;nB (IS.22)
Equation (IS.22) shows that the heat-transfer coefficient on a scraped surface
depends on the thermal properties of the liquid and the agitator speed and implies
that it does not depend on the viscosity of the liquid or its velocity through the
exchanger. Actually, although Eq. (IS.22) gives a good approximation in many
cases, it is somewhat of an oversimplification. The liquid at the heat-transfer
surface is not all well mixed with the bulk of the fluid, as assumed, especially with
viscous liquids, but is partly redeposited behind the scraper blades. Hence the
coefficient for a viscous liquid is lower than predicted by Eq. (IS.22) and is
somewhat affected by changes in liquid viscosity; it also is a function of the liquid
velocity in the longitudinal direction and of the diameter and length of the
exchanger. An empirical equation for the heat-transfer coefficient incorporating
these variables is 2 •
hj~a = 4.9(D p)0.57(C~)0.47(Dvn)0.17 (~)0.37
a:
(IS.23)
where V = bulk average longitudinal velocity
. L = length of exchanger
Da = diameter of scraper (also equal to inside diameter of shell)
Equation (IS.23) applies to a small high-speed unit known as a Votator. Data
for laminar-flow heat transfer in large slow-speed exchangers are given in Ref. 24.
Scraped-surface devices for evaporating viscous liquids are described in Chap. 16.
HEAT·EXCHANGE EQUIPMENT 455
HEAT TRANSFER IN PACKED BEDS
Many catalytic reactions are carried out in multitubular reactors that are similar
to shell-and-tube exchangers. The solid catalyst particles are packed in the tubes,
and the reactant gases enter and leave through headers at the ends of the reactor.
For an exothermic reaction, the heat of reaction is removed by a circulating
coolant or a boiling fluid on the shell side. For an endothermic reaction, the
energy needed for the reaction is transferred from hot fluid in the shell to the
catalyst particles in the tube. The limiting heat-transfer coefficient is usually on
the tube side, and the tube size and mass flow rate are often chosen to ensure
a nearly constant reaction temperature or to prevent the maximum catalyst
temperature from exceeding a safe value. In the following discussion, an exothermic
reaction is used as an example, because this is the more common case and because
too low an overall coefficient can lead to an uncontrollable rise in reactor
temperature or a "runaway" reaction.
TEMPERATURE AND VELOCITY PROFILES. The radial temperature profile for
an exothermic reaction in a packed tube has the shape shown in Fig. 15.18a. There
is a steep gradient near the inside wall and a nearly parabolic temperature profile
over the rest of the catalyst bed. The velocity profile (Fig. 15.18b) has a peak near
the wall, since the particles are packed more loosely in this region than in the rest
of the tube. The temperature and velocity profiles for an empty tube with turbulent
flow and a homogeneous reaction would have almost all of the gradient near the
wall.
HEAT-TRANSFER COEFFICIENTS. For a simple one-dimensional treatment of
packed tubes, the heat-transfer coefficient is based on a radial average temperature
of the gas, where T is the temperature that would result from mixing all the gas
flowing through the tube at a given distance along the tube. Thus
dq = U dA(f - 7j) (15.24)
where dA = nD, dL, and
FIGURE 15.18
Temperature and velocity profiles in
lal Ibl a packed~tube reactor.
456 HEAT TRANSFER AND ITS APPLICATIONS
In this simple treatment, the gas and solid temperatures are assumed to be the
same, even though, with an exothermic reaction, the catalyst particle must be
hotter than the surrounding gas. The difference between gas and solid temperatures
can be calculated using correlations in Chap. 21; this difference is generally only
a few degrees compared to a typical driving force (1' - 1]) of 20 to 30'C.
The presence of solid particles makes the inside coefficient much greater than
for an empty tube at the same flow rate, since the actual gas velocity between the
particles is up to several times the superficial velocity. For air in tubes packed
with spheres, the coefficients are 5 to 10 times those for an empty pipe. The
coefficients increase with about the 0.6 power of the flow rate and decrease more
with increasing tube size than for an empty tube.
The coefficients for a packed tube are highest when the ratio Dp/D, is about
0.15 to 0.2, as shown by the results in Fig. 15.19. For very small particles, the
turbulent mixing in the bed is depressed, and there is a large resistance to heat
transfer in the central region, which leads to a temperature profile similar to that
for laminar flow. For very large particles, there is rapid mixing and almost no
gradient in the center of the tube, but there is a thick region of high void fraction
near the wall; most of the resistance to heat transfer is in this region in this case.
The dip in the curves at Dp/D, ~ 0.3 was attributed to an increase in the void
fraction.22
To predict the rate of heat transfer for different particle and tube sizes, gas
flow rates, and gas properties, the coefficient h, is split into two parts to account
for the resistance in the region very near the wall and for the resistance in the rest
of the packed bed:
(15.25)
50 -
I
40
.~
~
I
30
- - ~
~ r-2-in.p~
I
..JJ -'" """-
0
..0-
. 4-in. pipe
------ -0...
1-in. pipe
0
o 0.1 0.2 0.3 0.5 0.6 0.7 O.B
FIGURE 15.19
Heat-transfer coefficients for tubes packed with alumina spheres. Air flow, 3000 Ib/ft 2_h (4.07 kg/m 2 -s).
HEAT·EXCHANGE EQUIPMENT 457
The bed coefficient is obtained from an effective thermal conductivity k,. The
following equation applies if the temperature profile in the bed is parabolic:
4k,
hbed =- (15.26)
r
The effective bed conductivity has a static or zero-flow term, which is usually
about 5kg when the particles are a porous inorganic material such as alumina,
silica gel, or an impregnated catalyst, and kg is the thermal conductivity of the
gas. The turbulent flow contribution to the conductivity is proportional to the
mass flow rate and particle diameter, and the factor 0.1 in the following equation
agrees with the theory for turbulent diffusion in packed beds 17 :
k,
k"" 5 + O.INR,.pN p, (15.27)
9
Note that the particle diameter is used in calculating the Reynolds number for
Eq. (15:27), but only the gas properties are used in calculating the Prandtl number.
The bed coefficient is obtained by using Eq. (15.27) and the gas conductivity to
get k" and then Eq. (15.26) gives the value of hb,d'
The coefficient hw can be estimated from the following empirical equation,
which was determined by subtracting the calculated bed resistance from the
measured overall resistance23 :
(15.28)
Equation (15.28) in combination with the equations for hb,d explains why the
combined coefficient h, goes through a maximum when DplD, is between 0.1 and
0.2. When D plD, is small, the bed resistance is the more important, and increasing
Dp increases NR,.p and hb,d' With large D plD, the wall film controls, and increasing
Dp leads to a lower hw and a lower h" since, as shown by Eq. (15.28), hw varies
with D;O.5. Equation (15.28) was based on results for spheres, but it gives a fairly
good fit to the data for cylinders and ring-shaped packings. 23 For packed tubes
operating at 200'C or higher, radiation between particles and from the particles
to the wall becomes significant, and predicted overall coefficients should be
corrected for this effect. 25
SYMBOLS
A Area, m 2 or ft2; A F , of fin; Ab, of bare tube; A" of inside of tube;
A" of outside of tube
a Exponent in Eq. (15.14)
aF Fin factor [Eq. (15.11)]
B Number of scraper blades
b Exponent in Eq. (15.12)
cp Specific heat at constant pressure, J/g-OC or Btuflb-OF; cp" of
cooling liquid
458 HEAT TRANSFER AND ITS APPLICATIONS
D Diameter, m or ft; Da, of impeller or scraper; Dc. outside diameter
of coil tubing; De, equivalent diameter of noncircular channel; D"
inside diameter of tube; D of outside of tube; Dp , of particle; Ds.
Q•
inside diameter of exchanger shell; D" of agitated vessel; 15L , logar-
ithmic mean of inside and outside diameters of tube
F, Tube arrangement factor for crossflow [Eq. (15.6)]
FG Correction factor for average temperature difference in crossflow or
multipass exchangers, dimensionless
.f" Fraction of cross-sectional area of shell occupied by baffle window
G Mass velocity, kg/m 2 -s or Ib/ft 2 -h; Gb' in baffle window; GO' in
crossflow; Ge , effective value in exchanger, JGbG c
h Individual heat-transfer coefficient, W/m2_'C or Btu/ft 2 -h-oF; ho, for
outside of coil; hi' for inside of tube; hi' for inner wall of jacket; h"
for outside of tube; "w, of gas film near tube wall; "bed' of packed
bed
j factor, dimensionless, for shell-side heat transfer
Coefficient in Eq. (15.14); K" in Eq. (15.17)
Thermal conductivity, W/m-oC or Btu/ft-h-oF; k" effective value for
packed bed; kg, of gas; km' of tube wall
L Length of fin or exchanger, m or ft; Lp, perimeter of fin
LMTD Logarithmic mean temperature difference, t.T"
m Mass of liquid, kg or lb
Flow rate, kg/h or lb/h; til" of cooling fluid
Number of tubes in baffle window
Prandtl number, cpl'lk
Reynolds number, DGII' or D;;npll'; NR,.p' for packed bed, DpGII'
n Impeller or scraper speed, rls or rjh
p Baffle pitch, m or ft
p Center-to-center distance between tubes, m or ft
Q Quantity of heat, J or Btu; QT, total amount transferred during
time interval tT
q Rate of heat transfer, W or Btu/h
I' Inside radius of tube, m or ft; rH, hydraulic radius
S Cross-sectional area, m2 or fe; Sb' area for flow in baffle window;
SO' area for crossflow in exchanger shell
T Temperature, °C or OF; TF , at distance x from base of fin; I'a, initial
value; '1/" final value; 7;" at cool-fluid inlet; 7;b, at cool-fluid outlet;
7;;j. intermediate cool-fluid temperature; 1ha, at wann-fluid inlet;
Thb, at warm-fluid outlet; ~. in jacket; 7;., reduced temperature; ~,
temperature of constant-temperature heating fluid; Tw> of surface or
bare portion of finned tube; T, average value in packed bed
t Time, s or h; tT, length of time interval
U Overall heat-transfer coefficient, W/m2_oC or Btu/ft2-h_OF; U i ,
based on inside area
11 Fluid velocity, m/s or ft/s
HEAT-EXCHANGE EQUIPMENT 459
V Average fluid velocity in longitudinal direction, mfs or rtfs
XF Fin height, m or ft; x w , thickness of tube wall
YF Fin thickness, m or ft
Z Ratio of temperature ranges in crossflow or multipass exchanger,
dimensionless [Eq. (15.7)]
Greek letters
a Thermal diffusivity, m 2fh or ft2fh
!!. T Temperature difference, 'c or 'F; !!. 1'" between fluid and wall of
finned tube; !!.T, corrected overall average value; !!.TF , average
difference between fluid and fins; !!.TL , logarithmic mean value
'IF Fin efficiency, !!.Td!!.1',
'IH Heating effectiveness, dimensionless [Eq. (15.8)J
I' Absolute viscosity, cP or lbfft-h; I'w, at wall or surface temperature
p Density, kgfm' or lbfft'
PROBLEMS
15.1. Air is blown at a rate of 3 m 3 js (measured at ooe and 1 atm) at right angles to a
tube bank 10 pipes and 10 spaces wide and 10 rows deep. The length of each pipe
is 3.5 m. The tubes are on triangular centers, and the center-to-center distance is
75 mm. It is desired to heat the air from 20 to 40°C at atmospheric pressure. What
steam pressure must be used? The pipes are 25-mm-OD steel pipe.
15.2. Crude oil at the rate of 150,000 kg/h is to be heated from 20 to 57'C by heat exchange
with the bottom product from a distillation unit. The product at 129,000 kg/h is to
be cooled from 146 to 107°C. There is available a tubular exchanger with steel tubes
with an inside shell diameter of 23! in., having one pass on the shell side and two
passes on the tube side. It has 324 tubes, ~ in. OD, BWG 14, 12 ft long arranged
on a l-in.-square pitch and supported by baffles with a 25 percent cut, spaced at
9-in. intervals. Would this exchanger be suitable; i.e., what is the al10wable fouling
factor? The average properties are shown in Table 15.3.
TABLE 15.3
Data for Prob. 15.2
Product, outside tubes Crude, inside tubes
'" J/g_OC 2.20 1.99
/1,CP 5.2 2.9
p, kg/m 3 867 825
k, W/m-oC 0.119 0.137
15.3. A vertical-tube two-pass heater is used for heating gas oil. Saturated steam at
100 IbI/in.' gauge is used as a heating medium. The tubes are 1 in. OD by BWG 16
and are made of mild steel. The oil enters at 60°F and leaves at 150°F. T-he
viscosity-temperature relation is exponential. The viscosity at 60°F is 5.0 cP and at
460 HEAT TRANSFER AND ITS APPLICATIONS
150°F is 1.8 cP. The oil is 37° API (specific gravity 0.840) at 60°F. The flow of oil
is 150 bbljh (1 bbl ~ 42 gal). Assume the steam condenses in film condensation. The
thermal conductivity of the oil is 0.078 Btu/ft-h-oF, and the specific heat is
0.480 Btu/lb-oF. The velocity of the oil in the tubes should be approximately 4 ft/so
CaIculate the length of tubes needed for this heater.
15.4. A petroleum oil having the properties given in Table 15.4 is to be heated in a
horizontal multipass heater with steam at 60 Ibj /in. 2 gauge. The tubes are to be steel,
~ in. OD by BWG 16, and their maximum length is 15 ft. The oil enters at 100°F,
leaves at 180°F. and enters the tubes at about 4 ft/so The total flow rate is
200 galjmin. Assuming complete mixing of the oil after each pass, how many passes
are required?
TABLE 15.4
Data for Prob. 15.4
Temperature, Thermal conductivity, Kinematic viscosity, Density, Specific heat,
OF Btu/ft·h-oF 105 ft2/S lb/ft' Btu/lb·OF
100 0.0739 36.6 55.25 0.455
120 0.0737 21.8 54.81 0.466
140 0.0733 14.4 54.37 0.477
160 0.0728 10.2 53.92 0.487
180 0.0724 7.52 53.48 0.498
200 0.0719 5.70 53.03 0.508
220 0.0711 4.52 52.58 0.519
240 0.0706 3.67 52.13 0.530
260 0.0702 3.07 0.540
15.5. Compare the coefficients predicted by the Donohue equation [Eq. (15.4)] with those
found from Eq. (12.69) for flow normal to a single cylinder. Can the difference be
reconciled by considering the maximum and average mass velocities in the shell side
of the exchanger?
15.6. A shell-and-tube exchanger is used to cool an aqueous stream from 95 to 30°C using
cooling water at 20 o e. If the flow rate of the cooling water is twice that of the process
stream, would a higher overall coefficient be obtained with cooling water in the
tubes or in the shell?
15.7. A steam-heated natural-circulation calandria is to be designed to boil 5000 kgjh of
chlorobenzene at atmospheric pressure. (a) Approximately how much heat-transfer
surface will be required? (b) How much area would be required if the average pressure
in the calandria were 0.5 atm abs? The normal boiling point of chlorobenzene is
132.0°C; its critical temperature is 359.2°C.
15.8. Liquid styrene at 60 e is being heated in a 2-m-diameter steam-jacketed kettle
0
equipped with a standard six·blade turbine. (a) Calculate the film coefficient for the
inside walllzj if the stirrer speed is 140 r/min. (b) If a pitched-blade turbine were used
with the same power input, how would the coefficient compare with that for the
standard turbine?
15.9. A turbine-agitated vessel 2 m in diameter contains 5500 kg of a dilute aqueous
solution. The agitator is ~ m in diameter and turns at 140 r/min. The vessel is
HEAT-EXCHANGE EQUIPMENT 461
jacketed with steam condensing at 110°C; the heat-transfer area is 12 m 2. The steel
walls of the vessel are 10 mm thick. If the solution is at 40°C and the heat-transfer
coefficient of the condensing steam is 10 k W/m2_oC, what is the rate of heat transfer
between steam and liquid?
15.10. Under the conditions given in Prob. 15.9. how long would it take to heat the vessel
contents (a) from 20 to 60°C, (b) from 60 to 100°C?
15.11. Compare Eqs. (15.22) and (15.23) with respect to the effect of the following variables
on the predicted heat-transfer coefficient: (a) thermal conductivity, (b) specific heat,
(c) liquid density, (dJ agitator speed, (e) agitator diameter, (f) longitudinal fluid
velocity.
15.12. A gas-phase exotherrnic reaction is carried out in a multitube reactor with the
catalyst in I-in. tubes and boiling water in the jacket. The feed temperature and the
jacket temperature are 240°C. The average reactor temperature rises to 250°C a
short distance from the inlet and then gradually decreases to 24PC at the reactor
exit. The resistance to heat transfer is about equally divided between the bed and
the film at the wall. If the tube diameter were increased to 1.5 in. with the same
catalyst, what should the jacket temperature be to keep the peak reactor temperature
at 250°C? Sketch the temperature profiles for the two cases. What pressure steam
would be generated for the two cases?
15.13. Air for a pilot-plant reactor is passed through a 50-mm pipe equipped with electric
heaters strapped to the outside. By what factor could the overall heat-transfer
coefficient be increased by filling the pipe with 12-mm particles of alumina? The
Reynolds number based on the empty pipe is 12,000.
REFERENCES
I. American Society of Mechanical Engineers: Boiler and Pressure Vessel Code. ASME, New York,
1989.
2. Babcock and Wilcox Co.: Steam-Its Generation and Use, 38th ed., Babcock and Wi1cox, New
York, 1972.
3. Bowman, R. A., A. C. Mueller, and W. M. Nagle: Trans. ASME, 62:283 (1940).
4. Donohue, D. A.: Ind. Eng. Chem., 41:2499 (1949).
5. Douglas, J. M.: Conceptual Design of Chemical Processes, McGraw-Hill, New York, 1988, Chap. 8.
6. Frank, 0., and R. D. Prickett: Chem. Eng., 80(20):107 (1973).
7. Gardner, K. A.: Trans. ASME, 67:621 (1945).
8. Gentry, C. c.: Chem. Eng. Prog., 86(7):48 (1990).
9. Gianolio, E., and F. Cuti: Heat Trans. Eng., 3(1):38 (1981).
10. Harriott, P.: Chem. Eng. Prog. Symp. Ser., 29:137 (1959).
11. Hughmark, G. A.: Chem. Eng. Prog., 60(7):59 (1964).
12. Johnson, D. L., and Y. Yukawa: Chem. Eng. Prog., 75(7):47 (1979).
13. Kays, W. M., and A. L. London: Compact Heat Exchangers, 2nd ed., McGraw-HiII, New York,
1964.
14. Kern, D. Q.: Process Heat Transfer, McGraw-HiIl, New York. 1950: (a) pp. 626-637.
15. Kung, D. M., and P. Harriott: Ind. Eng. Chem. Res., 26:1654 (1987).
16. Lerner, J. E.: Hydrocarbon Proc., 51(2):93 (1972).
17. Li, C. H., and B. A. Finlayson: Chem. Eng. ScL, 32:1055 (1977).
18. McAdams, W. H.: Heat Transmission, 3rd ed., McGraw-HilI, New York, 1954.
19. Oldshue, J. Y., and A. T. Gretton: Chem. Eng. Prog., 50:615 (1954).
20. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York, 1984; (a) p.
10-25, (b) pp. 10-29 to 10-31, (c) p. 11-3ff.
462 HEAT TRANSFER AND ITS APPLICATIONS
21. Peters, M. S., and K. D. Timmerhaus, Plant Design and Economics for Chemical Engineers, 3rd
ed., McGraw-Hill, New York, 1980, pp. 678-695.
22. Peters, P. E., M. S. thesis, Cornell Univ., Ithaca, N.Y., 1982.
23. Peters, P. E., R. S. Schiffino, and P. Harriott: Ind. Eng. Chem. Res., 27:226 (1988).
24. Ramdas, V., V. W. Uhl, M. W. Osborne, and 1. R. Ortt: Heat Trans. Eng., 1(4):38 (1980).
25. Schotte, W.: AIChE J., 6:63 (1960).
26. Skelland, A. H. P.: Chem. Eng. Sci., 7:166 (1958).
27. Strek, F., and S. Masiuk: 11111. Chem. Eng., 7:693 (1967).
28. Tubular Exchangers Manufacturers Association: Standards of the TEMA, 7th ed., TEMA, New
York, 1988.
29. Uhl, V. W., and 1. B. Gray: Mixing, vo!' 1, Academic, New York, 1966; (a) p. 284; (b) pp. 298-303.
30. Walas, F. M.: Chemical Process Equipment, Butterworths, Stoneham, MA, 1988, Chap. 8.
CHAPTER
16
EVAPORATION
Heat transfer to a boiling liquid has been discussed generally in Chap. 13. A special
case occurs so often that it is considered an individual operation. It is called
evaporation and is the subject of this chapter.
The objective of evaporation is to concentrate a solution consisting of a
nonvolatile solute and a volatile solvent. In the overwhelming majority of evapora-
tions the solvent is water. Evaporation is conducted by vaporizing a portion of
the solvent to produce a concentrated solution of thick liquor. Evaporation differs
from drying in that the residue is a liquid-sometimes a highly viscous one-rather
than a solid; it differs from distillation in that the vapor usually is a single
component, and even when the vapor is a mixture, no attempt is made in the
evaporation step to separate the vapor into fractions; it differs from crystaIlization
in that emphasis is placed on concentrating a solution rather than forming and
building crystals. In certain situations, e.g., in the evaporation of brine to produce
common salt, the line between evaporation and crystallization is far from sharp.
Evaporation sometimes produces a slurry of crystals in a saturated mother liquor.
In this book such processes are considered in Chap. 27, which is devoted to
crystallization.
Normally, in evaporation the thick liquor is the valuable product and the
vapor is condensed and discarded. In one specific situation, however, the reverse
is true. Mineral-bearing water often is evaporated to give a solid-free product for
boiler feed, for special process requirements, or for human consumption. This
technique is often ca!led water distillation, but technically it is evaporation.
Large-scale evaporation processes have been developed and used for recovering
potable water from seawater. Here the condensed water is the desired product.
Only a fraction of the total water in the feed is recovered, and the remainder is
returned to the sea.
463
464 HEAT TRANSFER AND ITS APPLICATIONS
LIQUID CHARACTERISTICS. The practical solution of an evaporation problem
is profoundly affected by the character of the liquor to be concentrated. It is the
wide variation in liquor characteristics (which demands judgment and experience
in designing and operating evaporators) that broadens this operation from simple
heat transfer to a separate art. Some of the most important properties of
evaporating liquids are as follows.
Concentration. Although the thin liquor fed to an evaporator may be sufficiently
dilute to have many of the physical properties of water, as the concentnftion
increases, the solution becomes more and more individualistic. The density and
viscosity increase with solid content until either the solution becomes saturated
or the liquor becomes too viscous for adequate heat transfer. Continued boiling
of a saturated solution causes crystals to form; these must be removed or the tubes
clog. The boiling point of the solution may also rise considerably as the solid
content increases, so that the boiling temperature of a concentrated solution may
be much higher than that of water at the same pressure.
Foaming. Some materials, especially organic substances, foam during vaporiza-
tion. A stable foam accompanies the vapor out of the evaporator, causing heavy
entrainment. In extreme cases the entire mass of liquid may boil over into the
vapor outlet and be lost.
Temperature sensitivity. Many fine chemicals, pharmaceutical products, and foods
are damanged when heated to moderate temperatures for relatively short times.
In concentrating such materials special techniques are needed to reduce both the
temperature of the liquid and the time of heating.
Scale. Some solutions deposit scale on the heating surface. The overall coefficient
then steadily diminishes, until the evaporator must be shut down and the tubes
cleaned. When the scale is hard and insoluble, the cleaning is difficult and
expensive.
Materials of construction. Whenever possible, evaporators are made of some kind
of steel. Many solutions, however, attack ferrous metals or are contaminated by
them. Special materials such as copper, nickel, stainless steel, aluminum, imper-
vious graphite, and lead are then used. Since these materials are expensive, high
heat-transfer rates become especially desirable to minimize the first cost of the
equipment.
Many other liquid characteristics must be considered by the designer of an
evaporator. Some of these are specific heat, heat of concentration, freezing point,
gas liberation on boiling, toxicity, explosion hazards, radioactivity, and necessity
for sterile operation. Because ofthe variation in liquor properties, many different
evaporator designs have been developed. The choice for any specific problem
depends primarily on the characteristics of the liquid.
EVAPORATION 465
SINGLE- AND MULTIPLE-EFFECT OPERATION. Most evaporators are heated
by steam condensing on metal tubes. Nearly always the material to be evaporated
flows inside the tubes. Usually the steam is at a low pressure, below 3 atm abs;
often the boiling liquid is under moderate vacuum, at pressures down to about
0.05 atm abs. Reducing the boiling temperature of the liquid increases the tempera-
ture difference between the steam and the boiling liquid and thus increases the
heat-transfer rate in the evaporator.
When a single evaporator is used, the vapor from the boiling liquid is
condensed and discarded. This method is called single-effect evaporation, and
although it is simple, it utilizes steam ineffectively. To evaporate 1 kg of water
from a solution calls for from 1 to 1.3 kg of steam. If the vapor from one evaporator
is fed into the steam chest of a second evaporator and the vapor from the second
is then sent to a condenser, the operation becomes double-effect. The heat in the
original steam is reused in the second effect, and the evaporation achieved by a
unit mass of steam fed to the first effect is approximately doubled. Additional
effects can be added in the same manner. The general method of increasing the
evaporation per kilogram of steam by using a series of evaporators between the
steam supply and the condenser is called multiple-effect evaporation.
TYPES OF EVAPORATORS
The chief types of steam-heated tubular evaporators in use today are
1. Long-tube vertical evaporators
a. Upward flow (climbing-film)
b. DOIfnward flow (falling-film)
c. For~ed circulation
2. Agitated-film evaporators
ONCE-THROUGH AND CIRCULATION EVAPORATORS. Evaporators may be
operated either as once-through or as circulation units. In once-throngh operation
the feed liquor passes through the tubes only once, releases the vapor, and leaves
the unit as thick liquor. All the evaporation is accomplished in a single pass. The
ratio of evaporation to feed is limited in single-pass units; thus these evaporators
are well adapted to multiple-effect operation, where the total amount of concentra-
tion can be spread over several effects. Agitated-film evaporators are always
operated once through; falling-film and climbing-film evaporators can also be
operated in this way.
Once-through evaporators are especially useful for heat-sensitive materials.
By operating under high vacuum, the temperature of the liquid can be kept low.
With a single rapid passage through the tubes the thick liquor is at the evaporation
temperature but a short time and can be quickly cooled as soon as it leaves the
evaporator.
466 HEAT TRANSFER AND ITS APPLICATIONS
In circulation evaporators a pool of liquid is held within the equipment.
Incoming feed mixes with the liquid from the pool, and the mixture passes through
the tubes. Unevaporated liquid discharged from the tubes returns to the pool, so
that only part of the total evaporation occurs in one pass. All forced-circulation
evaporators are operated in this way; climbing-film evaporators are usually
circulation units.
The thick liquor from a circulation evaporator is withdrawn from the pool.
All the liquor in the pool must therefore be at the maximum concentration. Since
the liquid entering the tubes may contain several parts of thick liquor for each
part of feed, its viscosity is high and the heat-transfer coefficient tends to be low.
Circulation evaporators are not well suited to concentrating heat-sensitive
liquids. With a reasonably good vacuum the temperature of the bulk of the liquid
may be nondestructive, but the liquid is repeatedly exposed to contact with hot
tubes. Some of the liquid, therefore, may be heated to an excessively high
temperature. Although the average residence time of the liquid in the heating zone
may be short, part of the liquid is retained in the evaporator for a considerable
time. Prolonged heating of even a small part of a heat-sensitive material like a
food can ruin the entire product.
Circulation evaporators, however, can operate over a wide range of con-
centration between feed and thick liquor in a single unit, and are well adapted to
single-effect evaporation. They may operate either with natural circulation, with
the flow through the tubes induced by density differences, or with forced circula-
tion, with flow provided by a pump.
LONG-TUBE EVAPORATORS WITH UPWARD FLOW. A typical long-tube verti-
cal evaporator with upward flow of the liquid is shown in Fig. 16.1. The essential
parts are (I) a tubular exchanger with steam in the shell and liquid to be
concentrated in the tubes, (2) a separator or vapor space for removing entrained
liquid from the vapor, and (3) when operated as a circulation unit, a return leg
for the liquid from the separator to the bottom of the exchanger. InlEts are
provided for feed liquid and steam, and outlets are provided for vapor, thick liquor,
steam condensate, and noncondensable gases from the steam.
The tubular heater operates in exactly the same way as the natural-
circulation calandria described in Chap. 15, p. 443. The tubes, however, are larger
than in a calandria: they are typically 25 to 50 mm (I to 2 in.) in diameter and 3 to
10 m (10 to 32 ft) long. Dilute feed enters the system and mixes with the liquid
draining from the separator. Concentrated liquor is withdrawn from the bottom
of the heater; the remaining liquor is partially vaporized as it rises through the
tubes. The mixture of liquid and vapor from the top of the tubes flows into the
separator, where its velocity is greatly reduced. To aid in eliminating liquid
droplets the vapor impinges on and then passes around sets of baffle plates before
leaving the separator. The evaporator shown in Fig. 16.1 can be operated only as
a circulation unit.
Long-tube vertical evaporators are especially effective in concentrating
liquids that tend to foam. Foam is broken when the high-velocity mixture ofliquid
and vapor impinges against the vapor-head baffle.
EVAPORATION 467
Vapor
oul
Y-tmniTr+-~ Venl
Feed
in
1~--SI,9aln in
Uquid_--;~
return
~ Condensate
t
Concentrate
FIGURE 16.1
Climbing-film, long-tube vertical evapor-
aul ator.
FALLING-FILM EVAPORATORS."· Concentration of highly heat-sensitive
materials such as orange juice requires a minimum time of exposure to a heated
surface. This can be done in once-through falling-film evaporators, in which the
liquid enters at the top, flows downstream inside the heated tubes as a film, and
leaves from the bottom. The tubes are large, 50 to 250 mm (2 to 10 in.) in diameter.
Vapor evolved from the liquid is usually carried downward with the liquid and
leaves from the bottom of the unit. In appearance these evaporators resemble long,
vertical, tubular exchangers with a liquid-vapor separator at the bottom and a
distributor for the liquid at the top.
The chief problem in a falling-film evaporator is that of distributing the liquid
uniformly as a film inside the tubes. This is done by a set of perforated metal
plates above a carefully leveled tube sheet, by inserts in the tube ends to cause the
liquid to flow evenly into each tube, or by "spider" distributors with radial arms
from which the feed is sprayed at a steady rate on the inside surface of each tube.
Still another way is to use an individual spray nozzle inside each tube.
When recirculation is allowable without damaging the liquid, distribution
of liquid to the tubes is facilitated by a moderate recycling of liquid to the tops
of the tubes. This provides a larger volume of flow through the tubes than is
possible in once-through operation.
For good heat transfer the Reynolds number 4r/p of the falling film should
be greater than 2000 at all points in the tube' During evaporation the amount
of liquid is continuously reduced as it flows downward, and too great a reduction
can lead to dry spots near the bottom of the tube. Thus the amount of concentra-
tion that can be done in a single pass is limited.
468 HEAT TRANSFER AND ITS APPLICATIONS
Falling-film evaporators, with no recirculation and short residence times,
handle sensitive products that can be concentrated in no other way. They are also
well adapted to concentrating viscous liquids.
FORCED-CIRCULATION EVAPORATORS. In a natural-circulation evaporator'
the liquid enters the tubes at 0.3 to 1.2 m/s (1 to 4 ft/s). The linear velocity increases
greatly as vapor is formed in the tubes, so that in general the rates of heat transfer
are satisfactory. With viscous liquids, however, the overall coefficient in a natural-
circulation unit may be uneconomically low. Higher coefficients are obtained in
forced-circulation evaporators, an example of which is shown in Fig. 16.2. Here a
centrifugal pump forces liquid through the tubes at an entering velocity of 2 to
5.5 m/s (6 to 18 ft/s). The tubes are under sufficient static head to ensure that there
is no boiling in the tubes; the liquid becomes superheated as the static head is
reduced during flow from the heater to the vapor space, and it flashes into a
mixture of vapor and spray in the outlet line from the exchanger just before
entering the body of the evaporator. The mixture of liquid and vapor impinges
on a deflector plate in the vapor space. Liquid returns to the pump inlet, where
it meets incoming feed; vapor leaves the top of the evaporator body to a condenser
or to the next effect. Part of the liquid leaving the separator is continuously
withdrawn as concentrate.
Vapor
out
Deflector
plate
'---cl" Concentrate
~F'-II\1 aut
Feed in
FIGURE 16.2
Forced-circulation evaporator with separate two-pass horizontal ,beating element.
EVAPORATION 469
In the design shown in Fig. 16.2 the exchanger has horizontal tubes and is
two-pass on both tube and shell sides. In others vertical single-pass exchangers
are used. In both types the heat-transfer coefficients are high, especially with thin
liquids, but the greatest improvement over natural-circulation evaporation is with
viscous liquids. With thin liquids the improvement with forced circulation does
not warrant the added pumping costs over natural circulation, but with viscous
material the added costs are justified, especially when expensive metals must be
used. An example is caustic soda concentration, which must be done in nickel
equipment. In multiple-effect evaporators producing a viscous final concentrate
the first effects may be natural-circulation units and the later ones, handling viscous
liquid, forced-circulation units. Because of the high velocities in a forced-circula-
tion evaporator, the residence time of the liquid in the tubes is short-about 1 to
3 s-so that moderately heat-sensitive liquids can be concentrated in them. They
are also effective in evaporating salting liquors or those that tend to foam.
AGITATED-FILM EVAPORATOR. The principal resistance to overall heat transfer
from the steam to the boiling liquid in an evaporator is on the liquid side. One
way of reducing this resistance, especially with viscous liquids, is by mechanical
agitation of the liquid film, as in the evaporator shown in Fig. 16.3. This is a
modified falling-film evaporator with a single jacketed tube containing an internal
agitator. Feed enters at the top of the jacketed section and is spread out into a
thin, highly turbulent film by the vertical blades of the agitator. Concentrate leaves
Feed_iO-.,;iIl
inlel
FIGURE 16.3
AgitatedMfilm evaporator.
470 HEAT TRANSFER AND ITS APPLICATIONS
from the bottom of the jacketed section; vapor rises from the vaporizing zone into
an unjacketed separator, which is somewhat larger in diameter than the evaporat-
ing tube. In the separator the agitator blades throw entrained liquid outward
against stationary vertical plates. The droplets coalesce on these plates and return
to the evaporating section. Liquid-free vapor escapes through outlets at the top
of the unit.
The chief advantage of an agitated-film evaporator is its ability to give high
rates of heat transfer with viscous liquids. The product may have a viscosity as
high as 1000 P at the evaporation temperature. For moderately viscous liquids
the heat-transfer coefficient may be estimated from Eq. (15.22). As in other
evaporators, the overall coefficient falls as the viscosity rises, but in this design
the decrease is slow. With highly viscous materials the coefficient is appreciably
greater than in forced-circulation evaporators and much greater than in natural-
circulation units. The agitated-film evaporator is particularly effective with such
viscous heat-sensitive products as gelatin, rubber latex, antibiotics, and fruit juices.
Its disadvantages are high cost; the internal moving parts, which may need
considerable maintenance; and the small capacity of single units, which is far below
that of multitubular evaporators.
PERFORMANCE OF TUBULAR
EVAPORATORS
The principal measures of the performance of a steam-heated tubular evaporator
are the capacity and the economy. Capacity is defined as the number of kilograms
of water vaporized per hour. Economy is the number of kilograms vaporized per
kilogram of steam fed to the unit. In a single-effect evaporator the economy is
nearly always less than 1, but in multiple-effect equipment it may be considerably
greater. The steam consumption, in kilograms per hour, is also important. It equals
the capacity divided by the economy.
Evaporator Capacity
The rate of heat transfer q through the heating surface of an evaporator, by the
definition of the overall heat-transfer coefficient given in Eq. (11.9), is the product
of three factors: the area of the heat-transfer surface A, the overall heat-transfer
coefficient U, and the overall temperature drop !J. T, or
q=UA!J.T (16.1)
If the feed to the evaporator is at the boiling temperature corresponding to
the absol ute pressure in the vapor space, all the heat transferred through the
heating surface is available for evaporation and the capacity is proportional to q.
If the feed is cold, the heat required to heat it to its boiling point may be quite
large and the capacity for a given value of q is reduced accordingly, as heat used
to heat the feed is not available for evaporation. Conversely, if the feed is at a
temperature above the boiling point in the vapor space, a portion of the feed
EVAPORATION 471
evaporates spontaneously by adiabatic equilibration with the vapor-space pressure
and the capacity is greater than that corresponding to q. This process is called
flash evaporation.
The actual temperature drop across the heating surface depends on the
solution being evaporated, the difference in pressure between the steam chest and
the vapor space above the boiling liquid, and the depth of liquid over the heating
surface. In some evaporators the velocity of the liquid in the tubes also influences
the temperature drop because the frictional loss in the tubes increases the effective
pressure of the liquid. When the solution has the characteristics of pure water, its
boiling point can be read from steam tables if the pressure is known, as can the
temperature of the condensing steam. In actual evaporators, however, the boiling
point of a solution is affected by two factors, boiling-point elevation and liquid
head.
BOILING-POINT ELEVATION AND DOHRING'S RULE. The vapor pressure of
aqueous solutions is less than that of water at the same temperature. Consequently,
for a given pressure the boiling point of the solutions is higher than that of pure
water. The increase in boiling point over that of water is known as the boiling-poi1ll
elevation (BPE) of the solution. It is small for dilute solutions and for solutions
of organic colloids but may be as large as SO'C (144'F) for concentrated solutions
of inorganic salts. The BPE must be subtracted from the temperature drop that
is predicted from the steam tables.
For strong solutions the BPE is best found from an empirical rule known
as Du/wing's rule, which states that the boiling point of a given solution is a
linear function of the boiling point of pure water at the same pressure. Thus if the
boiling point of the solution is plotted against that of water at the same pressure
a straight line results. Different lines are obtained for different concentrations.
Over wide ranges of pressure the rule is not exact, but over a moderate range the
lines are very nearly straight, though not necessarily parallel. Figure 16.4 is a set of
Diihring lines for solutions of sodium hydroxide in water 6 The use of this figure
may be illustrated by an example. If the pressure over a 25 percent solution of
sodium hydroxide is such that water boils at IS0'F (S2.2'C), by reading up from
the x axis at IS0'F to the line for 25 percent solution and then horizontally to
the y axis it is found that the boiling point of the solution at this pressure is 200'F
(93.3'C). The BPE for this solution at this pressure is therefore 20'F (11.1 'c).
EFFECT OF LIQUID HEAD AND FRICTION ON TEMPERATURE DROP. If the
depth of liquid in an evaporator is appreciable, the boiling point corresponding
to the pressure in the vapor space is the boiling point of the surface layer of liquid
only. A mass of liquid at a distance Z meters or feet below the surface is under
a pressure of the vapor space plus a head of Z meters or feet ofliquid and therefore
has a higher boiling point. In addition, when the velocity of the liquid is large,
frictional loss in the tubes further increases the average pressure of the liquid. In
any actual evaporator, therefore, the average boiling point of the liquid in the
tubes is higher than the boiling point corresponding to the pressure in the vapor
472 HEAT TRANSFER AND ITS APPLICATIONS
450
/ / /,t
/ / [/, ~
400
aY /.:"i ~
'\
~ a.~'i'Vj 1/
LL 350 ~a a· a
°z /1. '0'1 a<j ~o~10- ~
Q
~<>'V~~
v?a~ '1a·a·')974
,~~~v~~
r-
=> 300
--'
\1 a -
0
C/)
LL
0 250
j. .a
/%~v,v;
w
a: 0 V ~ /:: ~ W
=>
~
a: 200
w
v: /:: ~ /.: ~ V
/, // ~ / ~ W
D-
::;
W
r- 150 ~ ['l.: /. ~ (f'
'"z 1% v/ ~ ~
::;
is
al 100
"
0- 'i ~ ~
50
0 ~
o 50 100 150 200
BOILING TEMPERATURE OF WATER,oF
250 300 350
FIGURE 16.4
Diihring lines, system sodium hydroxide-water. (After M cCabe. 6 )
space. This increase in boiling point lowers the average temperature drop between
the steam and the liquid and reduces the capacity. The amount of reduction cannot
be estimated quantitatively with precision, but the qualitative effect of liquid head,
especially with high liquor levels and high liquid velocities, should not be ignored.
Figure 16.5 relates the temperatures in an evaporator with the distance along
the tube, measured from the bottom. The diagram applies to a long-tube vertical
evaporator with upflow of liquid. The steam enters the evaporator at the top of
the steam jacket surrounding the tubes and flows downward. The entering steam
may be slightly superheated at 7;.. The superheat is quickly given up, and the
steam drops to saturation temperature 7;. Over the greater part of the heating
surface this temperature is unchanged. Before the condensate leaves the steam
space, it may be cooled slightly to temperature 7;.
The temperature history of the liquor in the tubes is shown by lines abc and
ab'c in Fig. 16.5. The former applies at low velocities, about 1 m/s, and the latter
EVAPORATION 473
1l!
:::>
b
-r r.
>-..
'I
t b' f-
!J....,;;;:::;:::~;;~~=-~H.3Iq~h~Ve~/o~c;ily~~__~~~ l
W
Z
a ---------------,--
BPE
_ L __ _
eT
T'
o
DISTANCE ABOVE TUBE INLET
FIGURE 16.5
Temperature history of liquor in tubes and temperature drops in long-tube vertical evaporator.
at high velocities, above 3 m/s, both velocities based on the flow entering the
bottom of the tube 2 It is assumed that the feed enters the evaporator at about
the boiling temperature of the liquid at vapor-space pressure, denoted by T. Then
the liquid entering the tube is at T, whether the flow is once through or circulatory.
At high velocities, the fluid in the tube remains liquid practically to the end of the
tube and flashes into a mixture of liquid and vapor in the last few inches of the
tube. The maximum liquid temperature occurs at point b', as shown in Fig. 16.5,
almost at the exit from the tube.
At lower velocities, the liquid flashes at a point nearer the center of the tube
and reaches its maximum temperature, as shown by point b in Fig. 16.5. Point b
divides the tube into two sections, a.nonboiling section below point b and a boiling
section above this point.
At both high and low velocities the vapor and concentrated liquid reach
equilibrium at the pressure in the vapor space. If the liquid has an appreciable
BPE, this temperature T is greater than T, the boiling point of pure water at the
vapor-space pressure. The difference between T and T' is the BPE.
The temperature drop, corrected for BPE, is T, - T. The true temperature
drop, corrected for both boiling elevation and static head, is represented by the
average distance between T, and the variable liquid temperature. Although some
correlations are available 2 for determining the true temperature drop from the
operating conditions, usually this quantity is not available to the designer and the
net temperature drop, corrected for BPE only, is used.
The pressure history of the fluid in the tube is shown in Fig. 16.6, in which
pressure is plotted against distance from the bottom of the tube. The velocity is
such that boiling starts inside the tube. The total pressure drop in the tube,
neglecting changes in kinetic energy, is the sum of the static head and the friction
loss. The mixture of steam and water in the boiling section has a high velocity,
474 HEAT TRANSFER AND lTS APPLICATIONS
50
<f)
<D
I I I
I I I I I
'"~ m~5500Ib/hr
~
~30
m;2ioO)b},r r- - -0
......
-... f',.
W-
o: r-.- 1'\
:::l
(f)
(f)
W
i"-:
0:
"-
10
o 5 10 15 20
DISTANCE ABOVE TUBE INLET, FT
FIGURE 16.6
Pressure history of liquor in tubes of long-tube vertical evaporator. (By permission of author and
pubUsher, from W H. McAdams, Heat Transmission, 3rd ed., p. 403. Copyright by author, 1954,
McGraw-Hill Book Company.)
and the friction loss is large in this section. As shown by the curves in Fig. 16.6,
the pressure changes slowly in the lower half of the tubes, where the liquid is not
boiling and the velocity is low, and more rapidly in the boiling section, where the
velocity is high.
HEAT-TRANSFER COEFFICIENTS. As shown by Eq. (16.1), the heat flux and the
evaporator capacity are affected by changes both in the temperature drop and in
the overall heat-transfer coefficient. The temperature drop is fixed by the properties
of the steam and the boiling liquid and except for the effect of hydrostatic head
is not a function of the evaporator construction. The overall coefficient, on the
other hand, is strongly influenced by the design and method of operation of the
evaporator.
As shown in Chap. 11 [Eq. (11.35)], the overall resistance to heat transfer
between the steam and the boiling liquid is the sum of five individual resistances:
the steam-film resistance; the two scale resistances, inside and outside the tubes;
the tube-wall resistance; and the resistance from the boiling liquid. The overall
coefficient is the reciprocal of the overall resistance. In most evaporators the
fouling factor of the condensing steam and the resistance of the tube wall are very
small, and they are usually neglected in evaporator calculations. In an agitated-film
evaporator the tube wall is fairly thick, so that its resistance may be a significant
part of the to tal.
Steam-film coefficients. The steam-film coefficient is characteristically high, even
when condensation is filmwise. Promoters are sometimes added to the steam to
give drop wise condensation and a still higher coefficient. Since the presence of
noncondensable gas seriously reduces the steam-film coefficient, provision must
EVAPORATION 475
be made to vent noncondensables from the steam chest and to prevent leakage of
air inward when the steam is at a pressure below atmospheric.
Liquid-side coefficients. The liquid-side coefficient depends to a large extent on
the velocity of the liquid over the heated surface. In most evaporators, and
especially those handling viscous materials, the resistance of the liquid side controls
the overall rate of heat transfer to the boiling liquid. In natural-circulation
evaporators the liquid-side coefficient for dilute aqueous solutions is between 1500
and 3000 W/m2_"C (300 and 600 Btu/ft 2-h-"F). The heat flux may be conservatively
estimated for nonfouling solutions from Fig. 15.13.
Forced circulation gives high liquid-side coefficients even though boiling
inside the tubes is suppressed by the high static head. The liquid-side coefficient
in a forced-circulation evaporator may be estimated by Eq. (12.32) for heat transfer
to a nonboiling liquid if its constant 0.023 is changed to 0.028. 1
The formation of scale on the tubes of an evaporator adds a thermal
resistance equivalent to a fouling factor.
OVERALL COEFFICIENTS. Because of the difficulty of measuring the high in-
dividual film coefficients in an evaporator, experimental results are usually
expressed in terms of overall coefficients. These are based on the net temperature
drop corrected for boiling-point elevation. The overall coefficient, of course, is
influenced by the same factors influencing individual coefficients; but if one
resistance (say, that of the liquid film) is controlling, large changes in the other
resistances have almost no effect on the overall coefficient.
Typical overall coefficients for various types of evaporators""' are given in
Table 16.1. These coefficients apply to conditions under which the various
evaporators are ordinarily used. A small accumulation of scale reduces the
coefficients to a small fraction of the clean-tube values. An agitated-film evaporator
gives a seemingly low coefficient with a liquid having a viscosity of 100 P, but this
coefficient is much larger than would be obtained in any other type of evaporator
which could handle such a viscous material at all.
TABLE 16.1
Typical overall coefficients in evaporators
Overall coefficient U
Type
Long-tube vertical evaporators
Natural circulation 1000-2500 200-500
Forced circulation 2000-5000 400-1000
Agitated-film evaporator, newtonian liquid, viscosity
1 eP 2000 400
1P 1500 300
lOOP 600 120
476 HEAT TRANSFER AND ITS APPLICATIONS
Evaporator Economy
The chief factor influencing the economy of an evaporator system is the number
of effects. By proper design the enthalpy of vaporization of the steam to the first
effect can be used one or more times, depending on the number of effects. The
economy also is influenced by the temperature of the feed. If the temperature is
below the boiling point in the first effect, the heating load uses a part of the
enthalpy of vaporization of the steam and only a fraction is left for evaporatiou;
if the feed is at a temperature above the boiling point, the accompanying flash
contributes some evaporation over and above that generated by the enthalpy of
vaporization in the steam. Quantitatively, evaporator economy is entirely a matter
of enthalpy balances.
ENTHALPY BALANCES FOR SINGLE-EFFECT EVAPORATOR. In a single-effect
evaporator the latent heat of condensation of the steam is transferred through a
heating surface to vaporize water from a boiling solution. Two enthalpy balances
are needed, one for the steam and one for the vapor or liquid side.
Figure 16.7 shows diagrammatically a vertical-tube, single-effect evaporator.
The rate of steam flow and of condensate is rn,: that of the thin liquor, or feed,
is rnJ' and that of the thick liquor is .n. The rate of vapor flow to the condenser,
assuming that no solids precipitate from the liquor, is rnJ - .n. Also, let T, be the
condensing temperature of the steam, T the boiling temperature of the liquid in
the evaporator, and TJ the temperature of the feed.
Vapor
--+-(m,-m)lb/hr
Hv Btu/lb
Vapor - liquid
separator
Condensate
ms Ib/hr
He Btu/lb
I
-+- i¥f"="1:3===:i:)3;oJ
- - ~Thick liquor
mlb/hr
Feed H Blu/lb
(thin liquor)""':::;';' FIGURE 16.7
HfBlu/lb Material and enthalpy balances in
rhf Ib/hr evaporator.
EVAPORATION 477
It is assumed that there is no leakage or eutrainment, that the flow of
noncondensables is negligible, and that heat losses from the evaporator need not
be considered. The steam entering the steam chest may be superheated, and the
condensate usually leaves the steam chest somewhat subcooled below its boiling
point. Both the superheat and the subcooling of the condensate are small, however,
and it is acceptable to neglect them in making an enthalpy balance. The small
errors made in neglecting them are approximately compensated by neglecting heat
losses from the steam chest.
Under these assumptions the difference between the enthalpy of the steam
and that of the condensate is simply A" the latent heat of condensation of the
steam. The enthalpy balance for the steam side is
q, = ril,(H, - H,) = ril,A, (16.2)
where q, = rate of heat transfer through heating surface from steam
H" = specific enthalpy of steam
H, = specific enthalpy of condeusate
A, = latent heat of condensation of steam
ril, = rate of flow of steam
The enthalpy balance for the liquor side is
q = (ril f -,;,)H" -,hfHf + rilH (16.3)
where q = rate of heat transfer from heating surface to liquid
H" = specific enthalpy of vapor
H f = specific enthalpy of thin liquor
H = specific euthalpy of thick liquor
In the absence of heat losses, the heat transferred from the steam to the tubes
equals that transferred from the tubes to the liquor, and q, = q. Thus, by combining
Eqs. (16.2) and (16.3),
(16.4)
The liquor-side enthalpies H", H f , and H depend upon the characteristics
of the solution being concentrated. Most solutions when mixed or diluted at
constant temperature do not give much heat effect. This is true of solutions of
organic substances and of moderately concentrated solutions of many inorganic
substances. Thus sugar, salt, and paperrnill liquors do not possess appreciable
heats of dilution or mixing. Sulfuric acid, sodium hydroxide, and calcinm chloride,
on the other hand, especially in concentrated solutions, evolve considerable heat
when diluted and so possess appreciable heats of dilution. An equivalent amount
of heat is required, in addition to the latent heat of vaporization, when dilute
solutions of these substances are concentrated to high densities.
ENTHALPY BALANCE WITH NEGLIGIBLE HEAT OF DILUTION. For solutions
having negligible heats of dilution, the enthalpy balances over a single-effect
evaporator can be calculated from the specific heats and temperatures of the
478 HEAT TRANSFER AND ITS APPLICATIONS
solutions. The heat-transfer rate q on the liquor side includes qf' the heat
transferred to the thin liquor to change its temperature from Tf to the boiling
temperature T, and q" the heat to accomplish the evaporation. That is,
(16.5)
If the specific heat of the thin liquor is assumed constant over the temperature
range from Tf to T, then
(16.6)
Also,
q" = (Ih f - m),," (16.7)
where cpf = specific heat of thin liquor
"" = latent heat of vaporization from thick liquor
If the boiling-point elevation of the thick liquor is negligible, "" = '" the
latent heat of vaporization of water at the pressure in the vapor space. When the
boiling-point elevation is appreciable, the vapor leaving the solution is superheated
by an amount, in degrees, equal to the boiling-point elevation, and "" differs slightly
from ". In practice, however, it is nearly always sufficiently accurate to use '" which
may be read directly from steam tables (see Appendix 7).
Substitution from Eqs. (16.6) and (16.7) into Eq. (16.5) gives the final equation
for the enthalpy balance over a single-effect evaporator when the heat of dilution
is negligible:
(16.8)
If the temperature Tf of the thin liquor is greater than T, the term cpfmf(T - Tf ) is
negative and is the net enthalpy brought into the evaporator by the thin liquor.
This item is the flash evaporation. If the temperature Tf of the thin liquor fed to
the evaporator is less than T, the term mfC pf(T - TA is positive and for a given
evaporation additional steam will be required to provide this enthalpy. The term
IhfcpiT - Tf ) is therefore the heating load. In words, Eq. (16.8) states that the
heat from the condensing steam is utilized (1) to vaporize water from the solution
and (2) to heat the feed to the boiling point; if the feed enters above the boiling
point in the evaporator, part of the evaporation is from flash.
ENTHALPY BALANCE WITH APPRECIABLE HEAT OF DILUTION; ENTHALPY-
CONCENTRATION DIAGRAM. If the heat of dilution of the liquor being con-
centrated is too large to be neglected, an enthalpy-concentration diagram is used
for the values of H f and H in Eq. (16.4). In an enthalpy-concentration diagram
the enthalpy, in Btu per pound or joules per gram of solution, is plotted against
concentration, in mass fraction or weight percentage of solute 6 Isotherms drawn
on the diagrams show the enthalpy as a function of concentration at constant
temperature.
Figure 16.8 is an enthalpy-concentration diagram for solutions of sodium
hydroxide and water. Concentrations are in mass fraction of sodium hydroxide,
500
450
z 400
Q
f-
:;)
c5
if)
350
co
--'
""- 300
£'
co
)--
':; 250
'"
I
I-
Z
w 200
"'-
150
100
50
0.
0 0.1 0.2 0.3 0.4 C 0.5 0.6 07
x, MASS FRACTIQN NaOH
~ F[GURE [6.8
Enthalpy~concentration diagram, system sodium hydroxide-water. Dashed lines represent extrapolated data. (After McCabe 6 .)
480 HEAT TRANSFER AND ITS APPLICATIONS
temperatures in degrees Fahrenheit, and enthalpies in Btu per pound of solution.
The enthalpy of water is referred to the same datum as in the steam tables, namely,
liquid water at 32°F (O°C), so enthalpies from the figure can be used with those
from the steam tables when liquid water or steam is involved in the calculations.
In finding data for substitution into Eq. (16.4), values of HI and H are taken from
Fig. 16.8, and the enthalpy Ho of the vapor leaving the evaporator is obtained
from the steam tables.
The curved boundary lines on which the isotherms of Fig. 16.8 terminate
represent conditions of temperature and concentration under which solid phases
form. These are various solid hydrates of sodium hydroxide. The enthalpies of all
single-phase solutions lie above this boundary line. The enthalpy-concentration
diagram can also be extended to include solid phases.
The isotherms on an enthalpy-concentration diagram for a system with no
heat of dilution are straight lines. Enthalpy-concentration diagrams can be
constructed, of course, for solutions having negligible heats of dilution, but they
are unnecessary in view of the simplicity of the specific-heat method described in
the last section.
SINGLE-EFFECT CALCULATIONS. The use of material balances, enthalpy bal-
ances, and the capacity equation (16.1) in the design of single-effect evaporators
is shown in Example 16.1.
Example 16.1. A single-effect evaporator is to concentrate 20,000 Ibfh (9070 kgfh) of
a 20 percent solution of sodium hydroxide to 50 percent solids. The gauge pressure
of the steam is to be 20Ibf /in. 2 (1.37 atm); the absolute pressure in the vapor space
is to be 100 mm Hg (1.93Ibf /in. 2). The overall coefficient is estimated to be
250 Btu/ft2-h_oF (1400 W/m2_0C). The feed temperature is 100°F (37.8°C). Calculate
the amount of steam consumed, the economy, and the heating surface required.
Solution
The amount of water evaporated is found from a material balance. The feed contains
~g = 4th of water per pound of solid; the thick liquor contains ;g
= lIb of water
per pound of solid. The quantity evaporated is 4 - 1 = 3 lb of water per pound of
solid, or
3 x 20,000 x 0.20 = 12,000 Ib/h
The flow rate of thick liquor ril is
20,000 - 12,000 = 8000 lbfh (3630 kgfh)
Steam consumption Since with strong solutions of sodium hydroxide the heat of
dilution is not negligible, the rate of heat transfer is found from Eq. (16.4) and Fig.
16.8. The vaporization temperature of the 50 percent solution at a pressure of 100 mm
Hg is found as follows.
Boiling point of water at 100 mm Hg = 124°F (Appendix 7)
Boiling point of solution = 197°F (Fig. 16.4)
Boiling-point elevation = 197 - 124 = 73"F
EVAPORATION 481
The enthalpies of the feed and thick liquor are found from Fig. 16.8:
Feed, 20% solids, lOO°F: HJ = 55 Btuflb
Thick liquor, 50% solids, 197°F: H = 221 Btuflb
The enthalpy of the vapor leaving the evaporator is found from steam tables.
The enthalpy of superheated water vapor at 19JOF and 1.93IbJ /in.' is 1149 Btu/lb;
this is the H, of Eq. (16.4).
The heat of vaporization of steam As at a gauge pressure of 20 lb j/in. 2 is, from
Appendix 7, 939 Btuflb.
The rate of heat transfer and the steam consumption can now be found from
Eq. (16.4):
q = (20,000 - 8000X1149) + 8000 x 221 - 20,000 x 55 = 14,456,000 Btu/h
In, = 6,0,-,0...:.0
_14.:...,4:::5:-0 15,400 lb/h (6990 kg/h)
939
Economy The economy is 12,000/15,400 = 0.78.
Heating surface The condensation temperature of the steam is 259°F. The heating
area required is
A -_ 14,456,000 930 ft 2 (86 .4 m 2)
250(259 - 197)
If the enthalpy of the vapor Hv were based on saturated vapor at the pressure
in the vapor space, instead of on superheated vapor, the rate of heat transfer would
be 14,036,000 Btufh (4,115.7 kW) and the heating area would be 906 ft' (84.2 m 2 ).
Thus the approximation would introduce an error of only about 3 percent.
MULTIPLE-EFFECT EVAPORATORS. Figure 16.9 shows three long-tube natural-
circulation evaporators connected together to form a triple-effect system. Connec-
tions are made so that the vapor from one effect serves as the heating medium
for the next. A condenser and air ejector establish a vacuum in the third effect in
the series and withdraw noncondensables from the system. The first effect of a
multiple-effect evaporator is the effect to which the raw steam is fed and in which
the pressure in the vapor space is the highest. The last effect is that in which the
vapor-space pressure is a minimum. In this manner the pressure difference between
the steam and the condenser is spread across two or more effects in the multiple-
effect system. The pressure in each effect is lower than that in the effect from which
it receives steam and above that of the effect to which it supplies vapor. Each
effect, in itself, acts as a single-effect evaporator, and each has a temperature
drop across its heating surface corresponding to the pressure drop in that
effect. Every statement that has so far been made about a single-effect evaporator
applies to each effect of a multiple-effect system. Arranging a series of evaporator
bodies into a multiple-effect system is a matter of interconnecting piping, and not
of the structure of the individual units. The numbering of the effects is independent
of the order liquor is fed to them-they are always numbered in the direction of
decreasing pressure. In Fig. 16.9 dilute feed enters the first effect, where it is partly
~
To vacuum
pump
Contact
Water_~ condenser
Jl JII
P, T, P2 T2 P 3 T3
P, T1
Condensate Condensate
to pump
_ _ __ To pump
F,
FIGURE 16.9
Triple-effect evaporator: I, I1, Ill, first, second, and third effects; F" F 2 , F), feed or liquor control valves; SI' steam valve; Ps,PPP2,P3, pressures;
7;, Tlo T2 , T3 , temperatures.
EVAPORATION 483
concentrated; it flows to the second effect for additional concentration and then
to the third effect for final concentration. Thick liquor is pumped out of the third
effect.
In steady operation the flow rates and evaporation rates are such that
neither solvent nor solute accumulates or depletes in any of the effects. The
temperature, concentration, and flow rate of the feed are fixed, the pressures
in steam inlet and condenser established, and all liquor levels in the separate
effects maintained. Then all internal concentrations, flow rates, pressures, and
temperatures are automatically kept constant by the operation of the process itself.
The concentration of the thick liquor can be changed only by changing the rate
of flow of the feed. If the thick liquor is too dilute, the feed rate to the first effect
is reduced, and if the thick liquor is too concentrated, the feed rate is increased.
Eventually the concentration in the last effect and in the thick-liquor discharge
will reach a new steady state at the desired level.
The heating surface in the first effect will transmit per hour an amount
of heat given by the equation
(16.9)
If the part of this heat that goes to heat the reed to the boiling point is
neglected for the moment, it follows that practically all of this heat must
appear as latent heat in the vapor that leaves the first effect. The temperature
of the condensate leaving the second effect is very near the temperature T1
of the vapors from the boiling liquid in the first effect. Therefore, in steady
operation practically all of the heat that was expended in creating vapor in
the first effect must be given up when this same vapor condenses in the second
effect. The heat transmitted in the second effect, however, is given by the equation
q2 = A 2U 2 /lT2 (16.10)
As has just been shown, q1 and q2 are nearly equal, and therefore
A 1U 1 /lT1 = A 2U 2 /lT2 (16.11)
This same reasoning may be extended to show that, roughly,
A 1U 1 /lT1 =A 2U 2 /lT2 =A,U,/lT, (16.12)
It should be understood that Eqs. (16.11) and (16.12) are only approximate
equations that must be corrected by the addition of terms which are, however,
relatively small compared to the quantities involved in the expressions above.
In ordinary practice the heating areas in all the effects of a multiple-
effect evaporator are equal. This is to obtain economy of construction. Therefore,
from Eq. (16.12) it follows that, since q1 = q2 = q, = q,
(16.13)
From this it follows that the temperature drops in a multiple-effect evapor-
ator are approximately inversely proportional to the heat-transfer coefficients.
484 HEAT TRANSFER AND ITS APPLICATIONS
Example 16.2. A triple-effect evaporator is concentrating a liquid that has no
appreciable elevation in boiling point. The temperature of the steam to the first effect
is 108°C, the boiling point of the solution in the last effect is 52°C. The overa11
heat-transfer coefficients, in W/m 2 .oC, are 2500 in the first effect, 2000 in the second
effect, and 1000 in the third effect. At what temperatures will the liquid boil in the
first and second effects?
Solution
The total temperature drop is 108 - 52 = 56"C. As shown by Eq. (16.13), the
temperature drops in the several effects will be approximately inversely proportional
to the coefficients. Thus, for example,
2500
56 = 11.8"C
1 1 1
--+--+--
2500 2000 1000
In the same manner LiT2 = 14.7"C and liT, = 29.5"C. Consequently the boiling
point in the first effect will be 108 - 11.8 = 96.2"C, and that in the second effect,
81.5"C.
METHODS OF FEEDING. The usual method of feediug a multiple-effect evapor-
ator is to pump the thin liquid into the first effect and send it in turn through the
other effects, as shown iu Fig. 16.10a. This is calledforwardfeed. The concentration
of the liquid increases from the first effect to the last. This pattern of liquid flow
is the simplest. It requires a pump for feediug dilute solution to the first effect,
since this effect is often at about atmospheric pressure, and a pump to remove
thick liquor from the last effect. The transfer from effect to effect, however, can be
done without pumps, since the flow is in the direction of decreasing pressure, and
control valves in the transfer line are all that is required.
Another common method is backward feed, in which dilute liquid is fed to
the last effect and theu pumped through the successive effects to the first, as shown
in Fig. 16.lOb. This method requires a pump between each pair of effects in addition
to the thick-liquor pump, since the flow is from low pressure to high pressure.
Backward feed often gives a higher capacity than forward feed when the thick
liquor is viscous, but it may give a lower economy than forward feed when the
feed liquor is cold.
Other patterns of feed are sometimes used. In mixed feed the dilute liquid
enters an intermediate effect, flows in forward feed to the end of the series, and 'is
then pumped back to the first effects for final concentration, as shown in Fig.
16.lOc. This eliminates some of the pumps needed in backward feed and yet permits
the final evaporation to be done at the highest temperature. In crystallizing
evaporators, where a slurry of crystals and mother liquor is withdrawn, feed may
be admitted directly to each effect to give what is called parallel feed, as shown
in Fig. 16.lOd. In parallel feed there is no transfer of liquid from one effect to
another.
EVAPORATION 485
Vapor to Vapor to
condenser condenser
hed Thick
liquor Thick liquor Feed
lal Ibl
To condenser To condenser
11 III
Steam
"ne
liquor
Thick liquor Feed
Feed
IcI
FIGURE 16.10
Patterns of liquor flow in multiple~effect evaporators: (a) forward feed; (b) backward feed; (c) mixed
feed; (d) parallel feed. ( _ ) Liquor streams. ( - - ) Steam and vapor condensate streams.
CAPACITY AND ECONOMY OF MULTIPLE-EFFECT EVAPORATORS. The
increase in economy through the use of multiple-effect evaporation is obtained at
the cost of reduced capacity. It might be thought that by providing several times
as much heating surface the evaporating capacity would be increased, but this is
not the case. The total capacity of a multiple-effect evaporator is usually no greater
than that of a single-effect evaporator having a heating surface equal to one of
the effects and operating under the same terminal conditions, and, when there is
an appreciable boiling-point elevation, is often considerably smaller. When the
boiling-point elevation is negligible, the effective overall t,.T equals the sum of the
t.. T's in each effect, and the amount of water evaporated per unit area of surface in
an N-effect multiple-effect evaporator is approximately (ljNJth that in the single
effect. This can be shown by the following analysis.
If the heating load and the heat of dilution are neglected, the capacity
of an evaporator is directly proportional to the rate of heat transfer. The
heat transferred in the three effects in Fig. 16.9 is given by the equations
(16.14)
486 HEAT TRANSFER AND ITS APPLICATIONS
The total capacity is proportional to the total rate of heat transfer qT,
found by adding these equations.
(16.15)
Assume that the surface area is A square meters in each effect and that the
overall coefficient Uis also the same in each effect. Then Eq. (16.15) can be written
qT = UA(tlT, + tlT2 + tlT3 ) = UA tlT (16.16)
where tlT is the total temperature drop between the steam in the first effect
and the vapor in the last effect.
Suppose now that a single-effect evaporator with a surface area A is operating
with the same total temperature drop. If the overall coefficient is the same as in
each effect of the triple-effect evaporator, the rate of heat transfer in the single
effect is
qT=UAtlT
This is exactly the same equation as for the multiple-effect evaporator. No
matter how many effects are used, provided the overall coefficients are the same,
the capacity will be no greater than that of a single effect having an area equal
to that of each effect in the multiple unit. The boiling-point elevation tends to
make the capacity of a multiple-effect evaporator less than that of the correspond-
ing single effect. Offsetting this are the changes in overall coefficients in a
multiple-effect evaporator. In a single-effect unit producing 50 percent NaOH, for
example, the overall coefficient U for this viscous liquid would be small. In a
triple-effect unit, the coefficient in the final effect would be the same as that in the
single effect, but in the other effects, where the NaOH concentration is much lower
than 50 percent, the coefficients would be greater. Thus the average coefficient for
the triple-effect evaporator would be greater than that for the single effect. In some
cases this overshadows the effect of boiling-point elevation, and the capacity of a
multiple-effect unit is actually greater than that of a single effect.
Elfect of liquid head and boiling-point elevation. The liquid head and the boiling-
point elevation influence the capacity of a multiple-effect evaporator even more
than they do that of a single effect. The reduction in capacity caused by the liquid
head, as before, cannot be estimated quantitatively. The liquid head reduces the
temperature drop available in each effect of a multiple-effect evaporator, as does
the boiling-point elevation.
Consider an evaporator that is concentrating a solution with a large
boiling-point elevation. The vapor coming from this boiling solution is at the
solution temperature and is therefore superheated by the amount of the boiling-
point elevation. As discussed in Chap. 13, pages 383 and 384, superheated steam
is essentially equivalent to saturated steam at the same pressure when used as a
heating medium. The temperature drop in any effect, therefore, is calculated from
the temperature of saturated steam at the pressure of the steam chest, and not
from the temperature of the boiling liquid in the previous effect. This means that
EVAPORATION 487
the boiling-point elevation in any effect is lost from the total available temperature
drop. This loss occurs in every effect of a multiple-effect evaporator, and the
resulting loss of capacity is often important.
The influence of these losses in temperature drop on the capacity of a
multiple-effect evaporator is shown in Fig. 16.11. The three diagrams in this figure
represent the temperature drops in a single-effect, double-effect, and triple-effect
evaporator. The terminal conditions are the same in all three; i.e., the steam
pressure in the first effect and the saturation temperature of the vapor evolved
from the last effect are identical in all three evaporators. Each effect contains a
liquid with a boiling-point elevation. The total height of each column represents
the total temperature spread from the steam temperature to the saturation
temperature of the vapor from the last effect.
Consider the single-effect evaporator. Of the total temperature drop of 181
degrees the shaded part represents the loss in temperature drop due to boiling-
point elevation. The remaining temperature drop, 105 degrees, the actual driving
force for heat transfer, is represented by the unshaded part. The diagram for the
double-effect evaporator shows two shaded portions because there is a boiling-
point elevation in each of the two effects, and the residual unshaded part, totaling
85 degrees, is smaller than in the diagram for the single effect. In the triple-effect
evaporator there are three shaded portions since there is a loss of temperature
drop in each of three effects, and the total net available temperature drop, 79
degrees, is correspondingly smaller.
In extreme cases of a large number of effects or very high boiling-point
elevations the sum of the boiling-point elevations in a proposed evaporator could
STEAM TO 1st EFFECT
C=:J TEMPERATURE
DROP
~ BOILING-POINT
ELEVATIONS
SATURATION TEMPERATURE OF
VAPOR FROM LAST EFFECT
SINGLE DOUBLE TRIPLE
FIGURE 16.11
Effect of boiling-point elevation on capacity of evaporators.
488 HEAT TRANSFER AND ITS APPLICATIONS
be greater than the total temperature drop available. Operation under such
conditions is impossible. The design or the operating conditions of the evaporator
would have to be revised to reduce the number of effects or increase the total
temperature drop.
The economy of a multiple-effect evaporator is not influenced by boiling-
point elevations if minor factors, such as the temperature of the feed and changes
in the heats of vaporization, are neglected. A kilogram of steam condensing in the
first effect generates about a kilogram of vapor, which condenses in the second
effect generating another kilogram there, and so on. The economy of a multiple-
effect evaporator depends on heat-balance considerations and not on the rate of
heat transfer. The capacity, on the other hand, is reduced by the boiling-point
elevation. The capacity of a double-effect evaporator concentrating a solution with
a boiling-point elevation is generally less than half the capacity of two single effects,
each operating with the same overall temperature drop. The capacity of a triple
effect is generally less than one-third that of three single effects with the same
terminal temperatures.
Optimum number of effects. The cost of each effect of an evaporator per square
meter or square foot of surface is a function of its total area Bb and decreases with
area, approaching an asymptote for very large installations. Thus the investment
required for an N-effect evaporator is about N times that for a single-effect
evaporator of the same capacity. The optimum number of effects must be found
from an economic balance between the savings in steam obtained by multiple-effect
operation and the added investment required.
MULTIPLE-EFFECT CALCULATIONS. In designing a multiple-effect evaporator
the results usually desired are the amount of steam consumed, the area of the
heating surface required, the approximate temperatures in the various effects, and
the amount of vapor leaving the last effect. As in a single-effect evaporator, these
quantities are found from material balances, enthalpy balances, and the capacity
equation (16.1). In a multiple-effect evaporator, however, a trial-and-error method
is used in place of a direct algebraic solution.
Consider, for example, a triple-effect evaporator. There are seven equations
which may be written: an enthalpy balance for each effect, a capacity equation
for each effect, and the known total evaporation, or the difference between the
thin- and thick-liquor rates. If the amount of heating surface in each effect is
assumed to be the same, there are seven unknowns in these equations: (1) the rate
of steam flow to the first effect, (2) to (4) the rate of flow from each effect, (5) the
boiling temperature in the first effect, (6) the boiling temperature in the second
effect, and (7) the heating surface per effect. It is possible to solve these equations
for the seven unknowns, but the method is tedious and involved. Another method
of calculation is as follows:
1. Assume values for the boiling temperatures in the first and second effects.
EVAPORATION 489
2. From enthalpy balances find the rates of steam flow and of liquor from effect
to effect.
3. Calculate the heating surface needed in each effect from the capacity equations.
4. If the heating areas so found are not nearly equal, estimate new values for the
boiling temperatures and repeat items 2 and 3 until the heating surfaces are
equal.
In practice these calculations are done by computer. Results of a typical
calculation are shown in the following example.
Example 16.3. A triple-effect forced-circulation evaporator is to be fed with
60,000 Ibjh (27,215 kgJh) of 10 percent caustic soda solution at a temperature 180'F
(82.2'C). The concentrated liquor is to be 50 percent NaOH. Saturated steam at
50Ibf /in. 2 (3.43 atm) a'\ls is to be used, and the condensing temperature of vapor
from the third effect is to be lOO'F (37.8'C). The feed order is 11, Ill, I. Radiation
and undercooling of con9-ensate may be neglected. Estimated overall coefficients
corrected for boiling-point elevation are given in Table 16.2. Calculate (a) the heating
surface required in each effect, assuming equal surfaces in each, (b) the steam
consumption, (c) the steam e~onomy.
Solution
The total rate of evaporation is calculated from an overall material balance, assuming
that the solids go through the evaporator without loss (Table 16.3).
Repeated calculations lead to the temperatures, enthalpies, and flow rates
shown in Table 16.4. Note that the steam fed to I becomes the condensate from I,
the vapor from I becomes the condensate from 11, and the vapor from 11 becomes
TABLE 16.2
Overall coefficient
Effect Btu/ft2-h-OF
700 3970
II 1000 5680
III 800 4540
TABLE 16.3
Flow rate, Ib/h
Material Total Solid Water
Feed solution 60,000 6,000 54,000
Thick liquor 12,000 6,000 6,000
Water evaporated 48,000 48,000
490 HEAT TRANSFER AND ITS APPLICATIONS
TABLE 16.4
Temperatures, enthalpies, and flow rates for Example 16.3
Temperature Saturation Concentration, Enthalpy, Flow rate,
Stream of temperature, of weight fraction B'ullb Ib/h
Steam 281 281 1174 19,370
Feed to I 113 0.228 68 26,300
Vapor from I 245 170 1170 14,300
Condensate from I 281 249 19,370
Thick liquor from I 246 0.50 249 12,000
Raw feed to II 180 0.10 135 60,000
Vapor from n 149 142 1126 16,340
Liquid from 11 149 0.137 101 43,660
Condensate from II 170 138 14,300
Vapor from III 114 100 1111 17,360
Condensate from III 142 110 16,340
the condensate from Ill. From these results the answers to the problems are found
to be
(a) Area per effect: 719 ft' (66.8 m')
(b) Steam consumption: 19,370 Ib/h (8786 kg/h)
(c) Economy: 48,000/19,370 = 2.48
VAPOR RECOMPRESSION
The energy in the vapor evolved from a boiling solution can be used to vaporize
more water provided there is a temperature drop for heat transfer in the desired
direction. In a multiple-effect evaporator this temperature drop is created by
progressively lowering the boiling point of the solution in a series of evaporators
through the use of lower absolute pressures. The desired driving force can also be
obtained by increasing the pressure (and, therefore, the condensing temperature)
of the evolved vapor by mechanical or thermal recompression. 1 The compressed
vapor is then condensed in the steam chest of the evaporator from which it came.
MECHANICAL RECOMPRESSION, The principle of mechanical vapor recom-
pression is illustrated in Fig. 16.12. Cold feed is preheated almost to its boiling
point by exchange with hot liquor and is pumped through a heater as in a
conventional forced-circulation evaporator. The vapor evolved, however, is not
condensed; instead it is compressed to a somewhat higher pressure by a positive-
displacement or centrifugal compressor and becomes the "steam" which is fed to
the heater. Since the saturation temperature of the compressed vapor is higher
than the boiling point of the feed, heat flows from the vapor to the solution,
generating more vapor. A small amount of makeup steam may be necessary. The
optimum temperature drop for a typical system is about S°c. The energy
utilization of such a system is very good: based on the steam equivalent of the
EVAPORATION 491
t t t Body
- t tt
Compressor t t
Motor or
turbine
Thick liquor
~
discharge
Makeup steom--
Condensate I
FIGURE 16.12
Mechanical recompression applied to forced-circulation evaporator.
power required to drive the compressor, the economy corresponds to that of an
evaporator containing 10 to 15 effects. The most important applications of
mechanical-recompression evaporation are the concentration of very dilute radio-
active solutions and the production of distilled water.
THERMAL RECOMPRESSION. In a thermal recompression system the vapor is
compressed by acting on it with high-pressure steam in a jet ejector. This results
in more steam than is needed for boiling the solution, so that excess steam must
be vented or condensed. The ratio of motive steam to the vapor from the solution
depends on the evaporation pressure; for many low-temperature operations, with
steam at 8 to 10 atm pressure, the ratio of steam required to the mass of water
evaporated is about 0.5.
Since steam jets can handle large volumes of low-density vapor, thermal
recompression is better suited than mechanical recompression to vacuum evapora-
tion. Jets are cheaper and easier to maintain than blowers and compressors. The
chief disadvantages of thermal recompression are the low efficiency of the jets and
lack of flexibility in the system toward changed operating conditions.
492 HEAT TRANSFER AND ITS APPLICATIONS
SYMBOLS
A Area of heat-transfer surface, m 2 or ft2; AI' A 2 , A 3 , in effects I, 11, III
BPE Boiling-point elevation, °C or of
cp Specific heat at constant pressure, J/g-OC or Btujlb-oF; cpl , of feed
H Enthalpy of thick liquor, Jig or Btujlb; Ho, of condensate; HI' of feed;
H" of saturated steam; H" of vapor or superheated steam
,i! Mass flow rate, kg/h or lb/h; of liquor leaving single-effect evaporator;
mI' of feed; m" of steam and steam condensate
N Number of evaporator effects
P Pressure, atm or Ibr /ft 2 ; Ps. of steam; Pl, P2, P3' in vapor spaces of
effects I, 11, III
q Rate of heat transfer, W or Btu/h; qT' total rate; ql' to thin liquor; q"
from steam; qv, for vaporization; qt, q2, Q3, in effects I, 11, III
T Temperature, °C or OF; boiling temperature in, and of liquor leaving,
single-effect evaporator; T", temperature of condensate; TI , of feed; 7;"
of entering steam; 7;, of saturated steam; T, boiling temperature of
water at pressure of vapor space; T I , T2 , T3 , boiling temperature in,
and of liquor leaving, effects I, 11, III
U Overall heat-transfer coefficient, W/m2-oC or Btu/ft 2 -h-oF; U I , U 2 ,
U 3, in effects, I, 11, III
Z Distance below liquid surface, m or ft
Greek letters
r Liquid loading on tube, kg/h per meter of perimeter or lb/h per foot of
perimeter
/l,.T Temperature drop, °C or OF; total overall corrected temperature drop,
all effects; /l,.TI , /l,.T2 , /l,.T3 , temperature drop in effects I, 11, III
A Latent heat, Jig or Btujlb; A" latent heat of condensation of steam; A"
of vaporization from thick liquor
f1 Absolute viscosity, cP or Ib/ft-h
PROBLEMS
16.1. A solution of organic colloids in water is to be concentrated from 8 to 45 per-
cent solids in a single-effect evaporator. Steam is available at a gauge pressure of
1.03 atm (120SC). A pressure of 102 mm Hg ab, is to be maintained in the vapor
space: this corresponds to a boiling point for water of 51.7°C. The feed rate to the
evaporator is 20,000 kgfh. The overall heat-transfer coefficient can be taken as
2800 W/m2_ cc. The solution has a negligible elevation in boiling point and a negligible
heat of dilution. Calculate the steam consumption, the economy. and the heating
surface required if the temperature of the feed is (a) 51.7°C, (b) 21.1'C, (c) 93.3°C. The
specific heat of the feed solution is 3.77 J/g_OC, and the latent heat of vaporization of
the solution may be taken equal to that of water. Radiation losses may be neglected.
16.2. A solution of organic colloids is to be concentrated from 15 to 50 percent solids in
a vertical-tube evaporator. The solution has a negligible elevation in boiling point,
EVAPORATION 493
and the specific heat of the feed is 0.93. Saturated steam is available at 0.8 atm abs,
and the pressure in the condenser is 100 mm Hg abs. The feed enters at 15°C. The
overall coefficient is 1700 WIm2-oC. The evaporator must evaporate 25,000 kg of
water per hour. How many square meters of surface are required, and what is the
steam consumption in kilograms per hour?
16.3. A forced-circulation evaporator is to concentrate 60,000 kgjh of 44 percent NaOH
to 65 percent using steam at 3 atm pressure. The feed temperature and the condensing
temperature are both 40'C. The density of the feed solution is 1450 kg/m'. !f the
overall heat-transfer coefficient is 2000 Wjm 2_OC, calculate (a) the steam requirement,
in kilograms per hour; (b) the heat-transfer area required.
16.4. Vertical tubes 100 mm in diameter and 6 m long are used to concentrate a dilute
aqueous solution in a once-through falling-film evaporator. The flow rate per'tube- is
3000 kgjh, and the viscosity of the solution at the initial boiling point is 2.5 cP. (a)
What would be the average residence time of the liquid in the tube if no evaporation
occurred? (b) What fraction of the water would be evaporated if the overall D.T is
90'C and the overall heat-transfer coefficient is 3500 W/m'-'C? (c) !fthe same fraction
evaporated could be achieved in an upftow evaporator of the same size, what would
be the average residence time? (Assume the fluid in the tube is two-thirds liquid and
one-third vapor.)
16.5. A triple-effect evaporator of the long-tube type is to be used to concentrate
35,000 galjh of a 17 percent solution of dissolved solids to 38 percent dissolved solids.
The feed enters at 60°F and passes through three tube-and-shell heaters, a, b, and c,
in series and then through the three effects in order n, Ill, I. Heater a is heated by
vapor taken from the vapor line between the third effect and the condenser, heater
b with vapor from the vapor line between the second and third effects, and heater c
with vapor from the line between the first effect and the second. In each heater the
warm-end temperature approach is 100F. Other data are given below and in Table
16.5.
TABLE 16.5
Concentration Specific Specific heat,
solids, % gravity Btu/lb--°F
10 1.02 0.98
20 1.05 0.94
30 1.10 0.87
35 1.16 0.82
40 1.25 0.75
Steam to I, 230°F, dry and saturated.
Vacuum on In, 28 in., referred to a 3D-in. barometer.
Condensates leave steam chests at cond~nsing temperatures.
Boiling-point elevations, 1°F in n. 5°F in Ill, 15°F in I.
Coefficients, in Btujft2-h_oF, corrected for boiling-point elevation, 450 in I, 700 in 11,
500 in Ill.
All effects have equal areas of heating surface.
494 HEAT TRANSFER AND ITS APPLICATIONS
Calculate (a) the steam required in pounds per hour, (b) the heating surface per effect,
(c) the economy in pounds per pound of steam, (c) the latent heat to be removed in
the condenser.
16.6. An agitated-film evaporator 120 mm in inside diameter contains a four-blade
agitator turning at 400 r/min. It is vaporizing ethylene dichloride from a polymer
solution with an average viscosity of 100 cP. The properties of the liquid film are:
k ~ 0.15 Btujh-ft-OF; p ~ 60 Ib/ft 3 ; cp ~ 0.3 Btu/lb-oF. (a) Estimate the heat-transfer
coefficient of the agitated liquid film. (b) Compare your result with the data in Table
16.1 and comment on the discrepancy, if any.
16.7. A triple-effect evaporator is to be used to produce a 50 percent NaOH solution from
a feed containing 25 percent NaOH. Steam is available at 320°F, and the vapor from
the last stage is condensed at 120°F. Backward feed is used. (a) If equal amounts of
water are removed in each effect, what would be the concentrations in the intermediate
effects, the boiling-point elevation in each effect, and the net temperature differences
available for heat transfer? (b) With the same terminal temperatures and more than
three effects, what would be the maximum number of effects that could be used?
16.8. A triple-effect standard vertical-tube evaporator, each effect of which has 140 m2 of
heating surface, is to be used to concentrate from 4 percent solids to 35 percent solids
a solution possessing negligible boiling-point elevation. Forward feed is to be used.
Steam is available at 120°C, and the vacuum in the last effect corresponds to a boiling
temperature of 40°C. The overall coefficients, in Wjm2_0C, are 2950 in I, 2670 in n,
and 1360 in Ill; all specific heats may be taken as 4.2 J/g_OC, and radiation is
negligible. Condensates leave at condensing temperature. The feed enters at 90°C.
Calculate (a) the kilograms of 4 percent liquor that can be concentrated per hour, (b)
the steam consumption in kilograms per hour.
16.9. A vapor-recompression evaporator is to concentrate a very dilute aqueous solution.
The feed rate is to be 30,000Ib/h; the evaporation rate will be 20,000Ib/h. The
evaporator will operate at atmospheric pressure, with the vapor mechanically com-
pressed as shown in Fig. 16.12 except that a natural-circulation calandria will be used.
If steam costs $8 per 10001b, electricity costs 3 cents per kilowatthour, and heat-
transfer surface in the heater costs $70 per square foot, calculate the optimum pressure
to which the vapor should be compressed. The overall compressor efficiency is 72
percent. Assume all other costs are independent of the pressure of the compressed
vapor. To how many effects will this evapon~tor be equivalent?
REFERENCES
I. Beagle, M. J.: Chem. Eng. Prog., 58(10):79 (1962).
2. Boarts, R. M., W. L. Badger, and S. J. Meisenburg: TrailS. AIChE, 33:363 (1937).
3. Foust, A. S., E. M. Baker, and W. L. Badger: Trans. AIChE, 35:45 (1939).
4. Lindsey, E.: Chem. Eng., 60(4):227 (1953).
5. McAdams, W. H.: Heat Trallsmission, 3rd ed., McGraw-Hill, New York, 1954, pp. 398ff.
6. McCabe, W. L.: TrailS. AIChE, 31:129 (1935).
7. Moore, J. G., and W. E. Hesler: Chem. Eng. Prog., 59(2):87 (1963).
8. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York, 1984; (a) p.
11l-35, (b) p. 11--42.
9. Sinek, J. R., and E. H. Young: Chem. Ellg. Prog., 58(12):74 (1962).
SECTION
IV
MASS
TRANSFER
AND ITS
APPLICATIONS
A group of operations for separating the components of mixtures is based on
the transfer of material from one homogeneous phase to another. Unlike
purely mechanical separations, these methods utilize differences in vapor pressure,
solubility, or diffusivity, not density or particle size. The driving force for transfer
is a concentration difference or a difference in activity, much as a temperature
difference or a temperature gradient provides the driving force for heat transfer.
These methods, covered by the term mass-transfer operations, include such tech-
niques as distillation, gas absorption, dehumidification, adsorption, liquid ex-
traction, leaching, crystallization, membrane separations and a number of others
not discussed in this book.
The function of distillation is to separate, by vaporization, a liquid mixture
of miscible and volatile substances into individual components or, in some cases,
into groups of components. The separation of a mixture of alcohol and water into
its components; of liquid air into nitrogen, oxygen, and argon; and of crude
495
496 MASS TRANSFER AND ITS APPLICATIONS
petroleum into gasoline, kerosene, fuel oil, and lubricating stock are examples of
distillation.
In gas absorption a soluble vapor is absorbed by means of a liquid in which
the solute gas is more or less soluble, from its mixture with an inert gas. The
washing of ammonia from a mixture of ammonia and air by means of liquid water
is a typical example. The solute is subsequently recovered from the liquid by
distillation, and the absorbing liquid can be either discarded or reused. When a
solute is transferred from the solvent liquid to the gas phase, the operation is
known as desorption or stripping. In dehumidification a pure liquid is partially
removed from an inert or carrier gas by condensation. Usually the carrier gas is
virtually insoluble in the liquid. Removal of water vapor from air by condensation
on a cold surface and the condensation of an organic vapor such as carbon
tetrachloride out of a stream of nitrogen are examples of dehumidification. In
humidification operations the direction of transfer is from the liquid to the gas
phase. In the drying of solids, a liquid, usuall{' water, is separated by the use of
hot, dry gas (usually air) and so is coupled with the humidification ofthe gas phase.
In membrane separations, including gas separations, reverse osmosis, and
ultrafiltration, one component of a liquid or gaseous mixture passes through a
selective membrane more readily than the other components. The fundamental
driving force is the difference in thermodynamic activity, but in many cases the
driving force can be expressed as a difference in concentration or partial pressure.
In adsorption a solute is removed from either a liquid or a gas through contact
with a solid adsorbent, the surface of which has a special affinity for the solute.
In liquid extraction, sometimes called solvent extraction, a mixture of two
components is treated by a solvent that preferentially dissolves one or more of
the components in the mixture. The mixture so treated is called the raffinate and
the solvent-rich phase is called the extract. The component transferred from
raffinate to extract is the solute, and the component left behind in the raffinate is
the diluent. The solvent in the extract leaving the extractor is usually recovered
and reused. In extraction of solids, or leaching, soluble material is dissolved from
its mixture with an inert solid by means of a liquid solvent. The dissolved material,
or solute, can then be recovered by crystallization or evaporation. Crystallization
is used to obtain materials in attractive and uniform crystals of good purity,
separating a solute from a melt or a solution and leaving impurities behind.
The quantitative treatment of mass transfer is based on material and energy
balances, equilibria, and rates of heat and mass transfer. Certain concepts applic-
able generally are discussed here. The individual operations are discussed in the
following chapters.
TERMINOLOGY AND SYMBOLS
It is convenient to refer generally to the two streams in anyone operation as the
L phase and the V phase. It is also customary to choose the stream having the
higher density as the L phase and the one having the lower density as the V phase.
An exception may appear in liquid extraction, where the raffinate always is taken
MASS TRANSFER AND ITS APPLICATIONS 497
TABLE A
Terminology for streams in mass-transfer operations
Operation V phase L phase
Distillation Vapor Liquid
Gas absorption, dehumidification Gas Liquid
Membrane separations Gas or liquid Gas or liquid
Adsorption Gas or liquid Solid
Liquid extraction Extract Raffinate
Leaching Liquid Solid
Crystallization Mother liquor Crystals
Drying Gas (usually air) Wet solid
as the L phase and the extract as the V phase, even when the raffinate happens
to be lighter than the extract. In drying, the L phase is the stream consisting of
the solid and the Hq uid retained in or on the solid. Table A shows how the streams
are designated in the various operations.
NOTE ON CONCENTRATIONS. Strictly speaking, concentration means mass per
unit volume. Mass may be in kilograms or pounds and volume in cubic meters
or cubic feet. Kilogram moles or pound moles are often used for mass. In this
book the context will make clear what quantity-mole or ordinary mass-is used.
It is convenient to extend the use of the word concentration to include mole or
mass fractions. The relation between concentration and mole or mass fraction of
a component i is
where Xi = mole or mass fraction of component i
p = molar or mass density of mixture
Ci = corresponding concentration of component i
The mole fraction is the ratio of the moles of the component to the total
number of moles in the mixture, with a corresponding definition for mass fraction.
By definition, all mole or mass fractions in a mixture sum to unity. If there are r
components, r - 1 of the mole fractions may be chosen independently; the mole
fraction of the remaining component is thereby fixed and equals 1 less the sum of
the others.
General symbols are needed for flow rates and concentrations. For all
operations, use V and L for the flow rates of V and L phases, respectively. Use
A, B, C, etc., to refer to the individual components. If only one component is
transferred between phases, choose component A as that component. Use x for
the concentration of a component in the L phase, and y for the concentration in
the V phase. Thus, y A is the concentration of component A in a V phase and x.
is that of component B in an L phase. When only two components are present in
a phase, the concentration of component A is x or y, and that of component B is
1 - x or 1 - y, and the subscripts A and B are unnecessary.
498 MASS TRANSFER AND ITS APPLICATIONS
TABLE B
Terminal quantities for countercurrent flow
Concentration
Stream Flow rate component A
L phase, entering L" x A"
L phase, leaving L, XAb
V phase, entering V. YAb
V phase, leaving v" YA"
TERMINAL QUANTITIES. Since in steady-flow mass-transfer operations there are
two streams and each must enter and leave, there are four terminal quantities. To
identify them, use subscript a to refer to that end of the process where the L phase
enters and b to refer to that end where the L phase leaves. Then, for countercurrent
flow, the terminal quantities are as shown in Table B. If there are only two
components in a stream, the subscript A can be dropped from the concentration
terms.
DlFFUSIONAL PROCESSES AND
EQUILIBRIUM STAGES
Mass-transfer problems can be solved by two distinctly different methods, one
utilizing the concept of equilibrium stages, the other based on diffusional rate
processes. The choice of the method depends on the kind of equipment in which
the operation is carried out. Distillation, leaching, and sometimes liquid extraction
are performed in equipment such as mixer-settler trains, diffusion batteries, or
plate towers, which contain a series of discrete processing units, and problems in
these areas are commonly solved by equilibrium-stage calculations. Gas absorp-
tion and other operations which are carried out in packed towers and similar
equipment are usually handled using the concept of a diffusional process. All
mass-transfer calculations, however, involve a knowledge of the equilibrium
relationships between phases.
Phase Equilibria
A limit to mass transfer is reached if the two phases come to equilibrium and the
net transfer of material ceases. For a practical process, which must have a
reasonable production rate, equilibrium must be avoided, as the rate of mass
transfer at any point is proportional to the driving force, which is the departure
from equilibrium at that point. To evaluate driving forces, a knowledge of
equilibria between phases is therefore of basic importance. Several kinds of
equilibria are important in mass transfer. In nearly all situations two phases are
involved, and all combinations are found except two solid phases. In phases in
bulk the effects of surface area or surface curvature are negligible, and the
MASS TRANSFER AND ITS APPLICATIONS 499
controlling variables are the intensive properties temperature, pressure, and
concentrations. Equilibrium data can be shown in tables, equations, or graphs.
For most operations considered in this text, the pertinent equilibrium relationships
can be shown graphically.
CLASSIFICATION OF EQUILIBRIA. To classify equilibria and to establish the
number of independent variables or degrees of freedom available in a specific
situation, the phase rule is useful. It is
ff=0'-&,+2
where ff = number of degrees of freedom
0' = number of components
&' = number of phases
In the following paragraphs the equilibria used in mass transfer are analyzed
in terms of the phase rule. Usually there are two phases, and so ff = 0'.
The number of degrees of freedom, or variance ff, is the number of
independent intensive variables-temperature, pressure, and concentrations-that
must be fixed to define the equilibrium state of the system. Iffewer than ff variables
are fixed, an infinite number of states fits the assumptions; if too many are
arbitrarily chosen, the system will be overspecified. When there are only two
phases, as is usually the case, ff = 0'; in systems of two components, therefore,
ff = 2. If the pressure is fixed, only one variable-the liquid-phase concentration,
for example-can be changed independently; the temperature and gas-phase
composition (if the two phases are liquid and gas) must follow. For such systems
equilibrium data are presented in temperature-composition diagrams which apply
at constant pressure, or by plotting y" the V-phase concentration, against x" the
L-phase composition. Such plots are called equilibrium curves. If there are more
than two components, the equilibrium relationship cannot be represented by a
single curve.
Applications of the phase rule to three typical operations follow.
DISTILLATION. Assume that there are two components, so 0' = 2, &' = 2, and
ff = 2. Both components are found in both phases. There are four variables:
pressure, temperature, and the concentrations of component A in the liquid and
vapor phases (the concentrations of component B are unity less those of compo-
nent A). If the pressure is fixed, only one variable, e.g., liquid-phase concentration,
can be changed independently and temperature and vapor-phase concentration
follow.
If there are three components ff = 3, and fixing the temperature and liquid
compositions X A and x B defines the system. Pressure P, liquid composition Xc,
and vapor compositions YA' YB' and Yc are then all determined.
GAS ABSORPTION. Assume that only one component is transferred between
phases. There are three components, and ff = 3. There are four variables: pressure,
500 MASS TRANSFER AND ITS APPLICA nONS
temperature, and the concentrations of component A in liquid and gas. The
temperature and pressure may be fixed: one concentration may be chosen as the
remaining independent variable. The other concentration is then determined, and
an equilibrium curve y, vs. x, plotted. All points on the curve pertain to the same
temperature and pressure. Equilibrium data for various temperatures may also be
presented in the form of solubility charts, in which the partial pressure of the
solute in the gas phase is plotted as the ordinate.
LIQUID EXTRACTION. The minimum number of components is 3, so §' = 3. All
three components may appear in both phases. The variables are temperature,
pressure, and four concentrations. Either temperature or pressure may be taken
as a constant, and two or more concentrations chosen as independent variables.
The pressure usually is assumed constant, and the temperature then varies
somewhat. The relations between these variables are given by various graphical
methods, examples of which are shown in Figs. 20.10 to 20.13.
CHAPTER
17
EQUILIBRIUM-STAGE
OPERATIONS
One class of mass-transfer devices consists of assemblies of individual units, or
stages, interconnected so that the materials being processed pass through each
stage in turn. The two streams move countercurrently through the assembly; in
each stage they are brought into contact, mixed, and then separated. Such
multistage systems are called cascades. For mass transfer to take place the streams
entering each stage must not be in equilibrium with each other, for it is the
departure from equilibrium conditions that provides the driving force for transfer.
The leaving streams are usually not in equilibrium either but are much closer to
being so than the entering streams are. The closeness of the approach to
equilibrium depends on the effectiveness of mixing and mass transfer between the
phases. To simplify the design of a cascade, the streams leaving each stage are
often assumed to be in equilibrium, which, by definition, makes each stage ideal.
A correction factor or efficiency is applied later to account for any actual
departures from equilibrium.
To illustrate the principle of an equilibrium-stage cascade, two typical
countercurrent multistage devices, one for distillation and one for leaching, are
described here. Other types of mass-transfer equipment are discussed in later
chapters.
TYPICAL DISTILLATION EQUIPMENT. A plant for continuous distillation is
shown in Fig. 17.1. Reboiler A is fed continuously with the liquid mixture to be
distilled. The liquid is converted partially into vapor by heat transferred from the
heating surface B. The vapor formed in the reboiler is richer in low boiler than
the unvaporized liquid, but unless the two components differ greatly in volatility,
501
502 MASS TRANSFER AND ITS APPLICATIONS
CONDENSER
--
HEAT
OUT
1~ REFLUX
COLUMN ~Il~
OVERHEAD
C PRODUCT
B
FEED
RE BOILER
HEAT IN=:::\;;~~!!4L_J--""BOTTOM PRODUCT
FIGURE 17.1
Reboiler with fractionating column: A, reboiler; D, heating surface; C, column; D, condenser.
the vapor contains substantial quantItIes of both components, and if it were
condensed, the condensate would be far from pure. To increase the concentration
of low boiler in the vapor, the vapor stream from the still is brought into intimate
countercurrent contact with a descending stream of boiling liquid in the column,
or tower, C. This liquid must be rich enough in low boiler so that there is mass
transfer of the low boiler from the liquid to the vapor at each stage of the column.
Such a liquid can be obtained simply by condensing the overhead vapors and
returning some of the liquid to the top of the column. This return liquid is called
reflux. The use of reflux increases the purity of the overhead product, but not
without some cost, since the vapor generated in the reboiler must provide both
reflux and overhead product, and this energy cost is a large part of the total cost
of separation by distillation.
The reflux entering the top of the column is often at the boiling point; but
if it is cold, it is almost immediately heated to its boiling point by the vapor.
Throughout the rest of the column, the liquid and vapor are at their boiling and
condensing temperatures, respectively, and the temperatures increase on going
down the column because of the increase in high boiler concentration, and in some
cases, because of increase in pressure.
Enrichment of the vapor occurs at each stage because the vapor coming to
a stage has a lower concentration of the low boiler than the vapor that would be
in equilibrium with the liquid fed to that stage. For example, the vapor coming
to the top stage is less rich than the overhead product, and the reflux, which has
the same composition as the product, has an equilibrium vapor composition which
EQUILIBRIUM_STAGE OPERATIONS 503
is even richer than the product. Therefore, vapor passing through the top stage
will be enriched in low boiler at the expense of the reflux liquid. This makes the
reflux poorer in low boiler, but if the flow rates have been adjusted correctly, the
liquid passing down to the second stage will still be able to enrich the lower quality
vapor coming up to the second stage. Then at all stages in the column, some low
boiler diffuses from the liquid into the vapor phase, and there is a corresponding
diffusion of high boiler from the vapor to the liquid. The heat of vaporization of
the low boiler is supplied by the heat of condensation of the high boiler, and the
total flow rate of vapor up the column is nearly constant.
The enrichment of the vapor stream as it passes through the column in
contact with reflux is called rectification. It is immaterial where the reflux
originates, provided its concentration in low boiler is sufficiently great to give the
desired product. The usual source of reflux is the condensate· leaving condenser
D. Part of the condensate is withdrawn as the product, and the remainder is
returned to the top of the column. Reflux is sometimes provided by partial
condensation of the overhead vapor; the reflux then differs in composition from
the vapor leaving as overhead product. Provided an azeotrope is not formed, the
vapor reaching the condenser can be brought as close to complete purity as desired
by using a tall tower and a large reflux.
From the reboiler, liquid is withdrawn which contains most of the high
boiling component, because little of this component escapes with the overhead
product unless that product is an azeotrope. The liquid from the reboiler, which
is called the bottom product or bottoms, is not nearly pure, however, because there
is no provision in the equipment of Fig. 17.1 for rectifying this stream. A method
for obtaining nearly pure bottom product by rectification is described in Chap. 18.
The column shown in Fig. 17.1 often contains a number of perforated plates,
or trays, stacked one above the other. A cascade of such trays is called a sieve-plate
column. A single sieve plate is shown in Fig. 17.2. It consists of a horizontal tray
A carrying a downpipe, or downcomer, C, the top of which acts as a weir, and a
number of holes B. The holes are all of the same size, usually! to ! in. in
'C:
,
0, LIqUId surface ' \
Weir"
k= -
- --
-- -- -
- .~
-- I
1Zl!?ll rn &':a fZj Q2]fZ2l fZZl!22l rill fill &?2l!ZZl1ZlZZ Izz
j G~S flO;
C
Yt t
-trl
Liquid flow
FIGURE 17.2
Sieve plate: A, tray or plate; E, perforations; C, downcomer to plate below; D downcomer from plate
above.
504 MASS TRANSFER AND ITS APPLICA nONS
diameter. The downcomer D from the tray above reaches nearly to tray A. Liquid
flows from plate to plate down the column, passing through downcomers D and
C and across the plates. The weir maintains a minimum depth of liquid on the
tray, nearly independent of the rate of flow of liquid. Vapor flows upward from
tray to tray through the perforations. Except at very low vapor rates, well below
the normal operating range, the vapor velocity through the perforations is
sufficient to prevent leakage or "weeping" of the liquid through the holes. The
vapor is subdivided by the holes into many small bubbles and passes in intimate
contact through the pool of liquid on the tray. Because of the action of the vapor
bubbles, the liquid is actually a boiling frothy mass. The vapor space above the
froth contains a fine mist of droplets formed by collapsing bubbles. Most of the
drops settle back into the liquid, but some are entrained by the vapor and carried
to the plate above. Sieve-plate columns are representative of an entire class of
equipment called plate columns.
TYPICAL LEACHING EQUIPMENT. In leaching, soluble material is dissolved
from its mixture with an inert solid by means of a liquid solvent. A diagrammatic
flowsheet of a typical countercurrent leaching plant is shown in Fig. 17.3. It consists
of a series of units, in each of which the solid from the previous unit is mixed with
the liquid from the succeeding unit and the mixture allowed to settle. The solid
is then transferred to the next succeeding unit, and the liquid to the previous unit.
As the liquid flows from unit to unit, it becomes enriched in solute, and as the solid
flows from unit to unit in the reverse direction, it becomes impoverished in solute.
The solid discharged from one end of the system is well extracted, and the solution
leaving at the other end is strong in solute. The thoroughness of the extraction
depends on the amount of solvent and the number of units. In principle, the
unextracted solute can be reduced to any desired amount if enough solvent and
a sufficient number of units are used.
Fresh
solvent
Extracted
solids
Concentrated
-==-- A solution
A A
Feed
solIds
B
c "8
c B
c B
c
FIGURE 17.3
Countercurrent leaching plant: A, launder; E, rake; C, slurry pump.
EQUILlBRJUM-5TAGE OPERATIONS 505
Any suitable mixer and settler can be chosen for the individual units in a
countercurrent leaching system. In those shown in Fig. 17.3 mixing occurs in the
feed troughs (known as "launders") leading to each tank and also in the upper
parts of the tanks themselves. Rakes B move settled solids to the discharge, and
pumps C move the slurry from tank to tank.
PRINCIPLES OF STAGE PROCESSES
In the sieve-plate tower and the countercurrent leaching plant shown in Figs. 17.1
and 17.3, the cascade consists of a series of interconnected units, or stages. Study
of the assembly as a whole is best made by focusing attention on the streams
passing between the individual stages. An individual unit in a cascade receives
two streams, one a V phase and one an L phase, from the two units adjacent to
it, brings them into close contact, and delivers L and V phases, respectively, to
the same adjacent units. The fact that the contact units may be arranged either
one above the other, as in the sieve-plate column, or side by side, as in a stage
leaching plant, is important mechanically and may affect some of the details of
operation of individual stages. The same material-balance equations, however, can
be used for either arrangement.
TERMINOLOGY FOR STAGE-CONTACT PLANTS. The individual contact units
in a cascade are numbered serially, starting from one end. In this book, the stages
are numbered in the direction of flow of the L phase, and the last stage is that
discharging the L phase. A general stage in the system is the nth stage, which is
number n counting from the entrance of the L phase. The stage immediately ahead
of stage n in the sequence is stage n - 1 and that immediately following it is stage
n + 1. Using a plate column as an example, Fig. 17.4 shows how the units in a
cascade are numbered. The total number of stages is N, and the last stage in the
plant is therefore the Nth stage.
To designate the streams and concentrations pertaining to anyone stage,
all streams originating in that stage carry the number of the unit as a subscript.
Thus, for a two-component system, Y.+ I is the mole fraction of component A in
the V phase leaving stage n + 1, and L. is the molal flow rate of the L phase
leaving the nth stage. The streams entering and leaving the cascade and those
entering and leaving stage n in a plate tower are shown in Fig. 17.4. Quantities
v." L b , Ya, and Xb in Table B, page 498, are equal to VI' L N , YI, and XN, respectively.
This can be seen by reference to Fig. 17.4.
MATERIAL BALANCES. Consider the portion of the cascade that includes stages
1 through n, as shown by the section enclosed by the dashed line in Fig. 17.4. The
total input of material to this section is La + V.+ I moles per hour and the total
output is L" + v., moles per hour. Since, under steady flow, there is neither
accumulation nor depletion, the input and the output are equal and
(17.1)
506 MASS TRANSFER AND ITS APPLICATIONS
1&= V,
tYo:J/
1--+ ----,
I
La
Xa ---4I Plote I I
I
I
I
I I
I I
I Ln _1 ~
n n+
P/olen+!
PloteN
-.r. ...,.
- N+/
Lb =LN FIGURE 17.4
xb =AN Material-balance diagram for plate column.
Equation (17.1) is a total material balance. Another balance can be written by
equating input to output for component A. Since the number of moles of this
component in a stream is the product of the flow rate and the mole fraction of A
in the stream, the input of component A to the section under study, for a
two-component system, is Laxa + ~+ lYn+ 1 moles per hour, the output is
Lnxn + YaYa moles per hour, and
(17.2)
A material balance can also be written for component B, but such an equation
is not independent of Eqs. (17.1) and (17.2), since if Eq. (17.2) is subtracted from
Eq. (17.1), the result is the material-balance equation for component B. Equations
(17.1) and (17.2) yield all the information that can be obtained from material
balances alone written over the chosen section.
Overall balances covering the entire cascade are found in the same manner:
Total material balance: L, + Vb = Lb + v;, (17.3)
Component A balance: L,x, + Y"Yb = LbXb + v;,y, (17.4)
ENTHALPY BALANCES. In many equilibrium-stage processes the general energy
balance can be simplified by neglecting mechanical potential energy and kinetic
EQUILIBRIUM-STAGE OPERATIONS 507
energy. If, in addition, the process is workless and adiabatic, a simple enthalpy
balance applies. Then, for a two-component system, for the first n stages,
L,H L., + v,,+lH v .n+1 = LnHL.n + v"H v ., (17.5)
where HL and Hv are the enthalpies per mole of the L phase and V phase,
respectively. For the entire cascade,
L,H L., + V,H v ., = L,H L., + v"H v ., (17.6)
GRAPHICAL METHODS FOR TWO-COMPONENT SYSTEMS. For systems COn-
taining only two components it is possible to solve many mass-transfer problems
graphically. The methods are based on material balances and equilibrium relation-
ships; some more complex methods require enthalpy balances as well. These more
complex methods will be discussed in Chap. 18. The principles underlying the
simple graphical methods are discussed in the following paragraphs. Their detailed
applications to specific operations are covered in later chapters.
OPERATING-LINE DIAGRAM. For a binary system, the compositions of the two
phases in a cascade can be shown on an arithmetic graph where x is the abscissa
and Y the ordinate. As shown by Eq. (17.2), the material balance at an intermediate
point in the column involves x" the concentration of the L phase leaving stage n,
and Yn+ " the concentration of the V phase entering that stage. Equation (17.2)
can be written to show the relationship more clearly:
(17.7)
Equation (17.7) is the operating-line equation for the column; if the points
Xn and Y,+1 for all the stages are plotted, the line through these points is called
the operating line. Note that if Ln and v,,+l are constant throughout the column,
the equation is that of a straight line with slope L/V and intercept y, - (L/V)x"
and the line is easily located. For this case the operating line can also be drawn
as a straight line connecting the terminal compositions (x" Y,) and (Xb' y,). To
understand why this is true, extend the dashed rectangle in Fig. 17.4 to include
plate N and consider that the stream Vi, coming to the bottom stage is equivalent
to a stream from a hypothetical stage N + 1, so that Yb corresponds to YN+ 1 and
Xb to X N • Similarly, the stream L, at the top of the column can be considered to
come from a hypothetical stage numbered zero so that the point (XO,y,) or (x"y,)
locates the true upper end of the operating line.
When the flow rates are not constant in the column, the operating line on
a simple arithmetic plot is not straight. The terminal compositions may still be
used to locate the ends of the line, and material-balance calculations over sections
of the column are made to establish a few intermediate points. Often only one or
two other points are needed because usually the operating line is only slightly
curved.
508 MASS TRANSFER AND ITS APPLICATIONS
The position of the operating line relative to the equilibrium line determines
the direction of mass transfer and how many stages are required for a given
separation. The equilibrium data are found by experiment, by thermodynamic
calculations, or from published sources, 2 and the equilibrium line is just a plot of
the equilibrium values of Xc and Ye' For rectification in a distillation column, the
operating line must lie below the equilibrium line, as shown in Fig. 17.5a. Then
the vapor coming to any plate contains less of the low boiler than the vapor in
equilibrium with the liquid leaving the plate, so that vapor passing through the
liquid will be enriched in the low-boiling component. The relative slopes of the
lines are not important as long as the lines do not touch; the operating line could
be less steep than the equilibrium line and progressive enrichment of the vapor
would still take place. The driving force for mass transfer is the difference,
Ye - Yn+l, as shown in Fig. 17.5a.
When one component is to be transferred from the V phase to the L phase,
as in the absorption of soluble material from an inert gas, the operating line must
lie above the equilibrium line as in Fig. 17.5b. The driving force for mass transfer
is now Yn+l - y" or the difference between the actual vapor composition and the
vapor composition in equilibrium with the liquid for that position in the column.
Equilibrium
~?f
';ne Op,,";n9
Operating
line
lIme '..
y Yn~l y
Equilibrium
x" line
x x
lal Ibl
Equilibrium
line
--...
y
~ qperat'mg
lme
x
Icl
FIGURE 17.5
Operating and equilibrium lines: (a) for rectification, (b) for gas absorption, (c) for desorption.
EQUILIBRIUM-STAGE OPERATIONS 509
In the design of gas absorbers the liquid rate is usually chosen to make the
operating line somewhat steeper than the equilibrium line, which gives a moder-
ately large driving force in the bottom part of the column and permits the desired
separation to be made with relatively few stages.
In absorbing one component of the gas into a nonvolatile solvent, the total
gas rate decreases and the total liquid rate increases as the two phases pass through
the column. Therefore the operating line is usually curved, though the percentage
change in slope, or L/V, is not as great as the change in either L or V, since both
L and Vare largest at the bottom of the column and smallest at the top. A method
of calculating intennediate points on the operating line is shown later in Example
17.l.
The reverse of gas absorption is called desorption or stripping, an operation
catried out to recover valuable solute from the absorbing solution and regenerate
the solution. The operating line must then lie below the equilibrium line, as in
Fig. 17.5c. Usually the temperature or pressure is changed to make the equilibrium
curve much steeper than for the absorption process.
IDEAL CONTACT STAGES. The ideal stage is a standard to which an actual stage
may be compared. In an ideal stage, the V phase leaving the stage is in equilibrium
with the L phase leaving the same stage. For example, if plate n in Fig. 17.4 is an
ideal stage, concentrations x. and Y. are coordinates of a point on the curve of
x, vs. y, showing the equilibrium between the phases. In a plate column ideal
stages are also called perfect plates.
To use ideal stages in design it is necessary to apply a correction factor,
called the stage efficiency or plate efficiency, which relates the ideal stage to an
actual one. Plate efficiencies are discussed in Chap. 18, and the present discussion
is restricted to ideal stages.
DETERMINING THE NUMBER OF IDEAL STAGES. A problem of general impor-
tance is that of finding the number of ideal stages required in an actual cascade
to cover a desired range of concentration Xa to Xb or Ya to Yb' If this number can
be determined, and if information on stage efficiencies is available, the number of
actual stages can be calculated. This is the usual method of designing cascades.
A simple method of determining the number of ideal stages when there are
only two components in each phase is a graphical constructipn using the oper-
ating-line diagram. Figure 17.6 shows the operating line and the equilibrium curve
for a typical gas absorber. The ends of the operating lice are point a, having
coordinates (x" Ya), and point b, having coordinates (x b, Yb). The problem of
determining the number of ideal stages needed to accomplish the gas-phase
concentration change Y. to Ya and the liquid-phase concentration change Xa to x.
is solved as follows.
The concentration of the gas leaving the top stage, which is stage 1, is y"
or Y l ' If the stage is ideal, the liquid leaving is equilibrium with the vapor leaving,
so the point (X 1'Y1) must lie on the equilibrium curve. This fact fixes point rn,
510 MASS TRANSFER AND ITS APPLICATIONS
Vb ------------ b
Y,
Y ,I
Equilibrium curve
I
I
I
I
I
I
I
I
x, FIGURE 17.6
x Operating-line diagram for gas absorber.
found by moving horizontally from point a to the equilibrium curve. The abscissa
of point m is x,. The operating line is now used. It passes through all points
having coordinates of the type (x.,Y.+,), and since x, is known, Y2 is found by
moving vertically from point m to the operating line at point n, the coordinates
of which are (x" y,). The step, or triangle, defined by points a, m, and n represents
one ideal stage, the first one in this column. The second stage is located graphically
on the diagram by repeating the same construction, passing horizontally to the
equilibrium curve at point 0, having coordinates (x 2 ,y,), and vertically to the
operating line again at point p, having coordinates (X2' y,). The third stage is
found by again repeating the construction, giving triangle pqb. For the situation
shown in Fig. 17.6, the third stage is the last, as the concentration of the gas leaving
that stage is Yb, and the liquid leaving it is x b, which are the desired terminal
concentrations. Three ideal stages are required for this separation.
The same construction can be used for determining the number of ideal
stages needed in any cascade, whether it is used for gas absorption, rectification,
leaching, or liquid extraction. The graphical step-by-step construction utilizing
alternately the operating and equilibrium lines to find the number of ideal stages
was first applied to the design of rectifying columns, and is known as the
McCabe-Thiele method' The construction can be started at either end of the
column, and in general the last step will not exactly meet the terminal concentra-
tions, as was the case in Fig. 17.6. A fractional step may be assigned, or the number
of ideal stages may be rounded up to the nearest whole number.
Example 17.1. By means of a plate column, acetone is absorbed from its mixture
with air in a nonvolatile absorption oil. The entering gas contains 30 mole percent
acetone, and the entering oil is acetone free. Of the acetone in the air 97 percent is
to be absorbed, and the concentrated liquor at the bottom of the tower is to contain
10 mole percent acetone. The equilibrium relationship is Ye = 1.9xe . Plot the opera-
ting line and determine the number of ideal stages.
EQUILIBRIUM-STAGE OPERATIONS 511
Solution
Choose 100 mol of entering gas as a basis, and set this equal to Vb. The acetone
entering is then 0.3 x 100 = 30 mol; the air entering is 100 - 30 = 70 mol. With 97
percent absorbed, the acetone leaving is 0.03 x 30 = 0.9 mol and y, = 0.9/70.9 =
0.0127; the acetone absorbed is 30 - 0.9 = 29.1 mol. With 10 percent acetone in the
leaving solution and no acetone in the entering oil, O.lLb = 29.1, and Lb = 291 mol.
Then L, = 291 - 29.1 = 261.9 mol.
To find an intermediate point on the operating line, make an acetone balance
around the top part of the tower, assuming a particular v~lue of y V, the moles of
acetone left in the gas. For 10 mol left in the gas,
10
y=--=0.125
10 + 70
The moles of acetone lost by the gas in this section, 10 - 0.9, or 9.1, must equal the
moles gained by the liquid. Hence where y = 0.125,
9.1
x = = 0.0336
261.9 + 9.1
Similar calculations for yV = 20 and x = 19.1/(261.9 +
give y = 20/90 = 0.222
19.1) = 0.068.
The operating line is plotted in Fig. 17.7. Note that it is only slightly curved,
even though the gas flow rate changes almost 30 percent.
The number of ideal stages is 4 and a fraction. Based on the required change
in x relative to the change that would be made in a full step, the fraction is Id12' or
0.27. A similar construction based on changes in y gives the fraction 0.33; the values
differ because the operating and equilibrium lines are not parallel. The answer would
be given as 4.3 stages.
0.31;------,-------,,,..-------,
Operating line
0.2'f--------+-+---+-+~----_j
y 4
~ Equilibrium line
O"'li==ir----i--- 3
0.05 0.10 0.15
x
FIGURE 17.7
Diagram for Example 17.1,
512 MASS TRANSFER AND ITS APPLICATIONS
ABSORPTION-FACTOR METHOD FOR CALCULATING THE NUMBER OF
IDEAL STAGES. When the operating and equilibrium lines are both straight over
a given concentration range x, to X b, the number of ideal stages can be calculated
by formula and graphical construction is unnecessary. Formulas for this purpose
are derived as follows.
Let the equation of the equilibrium line be
Ye = mXe +B (17.8)
where, by definition, m and B are constant. If stage n is ideal,
Yn = nlX n +B (17.9)
Substitution for x. into Eq. (17.7) gives, for ideal stages and constant L/V,
L(y. - B) Lx,
Y.+l= mV +y,-V (17.10)
It is convenient to define an absorption factor A by the equation
L
A=- (17.11)
mV
The absorption factor is the ratio of the slope of the operating line, L/V, to
that of the equilibrium line, m. It is a constant when both of these lines are straight.
Equation (17.10) can be written
Y.+l = A(y. - B) + y, - Amx,
= Ay. - A(mx, + B) + y, (17.12)
The quantity mx, + B is, by Eq. (17.8), the concentration of the vapor that is
in equilibrium with the inlet L phase, the concentration of which is x,. This can
be seen from Fig. 17.8. The symbol y* is used to indicate the concentration of a
V phase in equilibrium with a specified L phase. Then
(17.13)
and Eq. (17.12) becomes
(17.14)
Equation (17.14) can be used to calculate, step by step, the value of Y.+1 for
each stage starting with stage 1. The method may be followed with the aid of Fig.
17.8.
For stage 1, using n = 1 in Eq. (17.14) and noting that Yl = y, gives
Y2 = Ay, - Ay: + y, = y,(1 + A) - Ay:
For stage 2, using n = 2 in Eq. (17.14) and eliminating yz gives
Y3 = Ayz - Ay: + y, = A[yotl + A) - Ay:] - Ay: + y,
= yotl + A + AZ) - y:(A + AZ)
EQUILIBRIUM-5TAQE OPERATIONS 513
+,_ __ - - - - -
Yb=YN
N
----r---"
Operating, xn vs. y,,+!
Equilibrium, XnV5.Yn I
I
I
I
I
x__
FIGURE 17.8
Derivation of absorption~factor equation.
These equations can be generalized for the nth stage, giving
y,+, = Ya(l + A + A2 + ... + A') - y:(A + A2 + ... + A') (17.15)
For the entire cascade, n = N, the total number of stages, and
YII+l = YN+l = Yb
Then
(17.16)
The sums in the parentheses of Eq.· (17.16) are both sums of geometric series.
The sum of such a series is
a,(l - r')
s, =
1-r
where SIl = sum of first n terms of series
a, = first term
r = constant ratio of each term to preceding term
Equation (17.16) can then be written
1_A N+' 1_AN
Yb-y
- a 1-A
-y*A---
a 1-A
(17.17)
Equation (17.17) is a form of the Kremser equation 3 It can be used as such or in
the form of a chart relating N, A, and the terminal concentrations.'·5 It can also
be put into a simpler form by the following method.
514 MASS TRANSFER AND ITS APPLICATIONS
Equation (17.14) is, for stage N,
Yb = AYN - Ay: + Y. (17.18)
Figure 17.8 shows that YN = yt and Eq. (17.18) can be written
Y. = Yb - A(yt - Y:) (17.19)
Collecting terms in Eq. (17.17) containing A N + 1 gives
A N+ 1(y. - Y:) = A(Yb - Y:) + (y. - Yb) (17.20)
Substituting Ya - Yb from Eq. (17.19) into Eq. (17.20) gives
~h-~=h-~-~+~=h-~ (17.21)
Taking logarithms of Eq. (17.21) and solving for N gives
N = In [(h - yt)/(Ya - Y:)]
(17.22)
In A
and from Eq. (17.19)
Yb - Ya = A (17.23)
yt - y:
Equation (17.22) can be written
N = In [(h - yt)/(Ya - y:J]
(17.24)
In [(Yb - Ya)/(yt - Y:)]
The various concentration differences in Eq. (17.24) are shown in Fig. 17.9.
When the operating line and the equilibrium line are parallel, A is unity and
Eqs. (17.22) and (17.24) are indeterminate. In this case the number of steps is just
the overall change in concentration divided by the driving force, which is constant.
Thus,
N = Yb - Ya = Yb - Ya (17.25)
Ya - Y: Yb - yt
If the operating line has a lower slope than the equilibrium line, A is less
than 1.0, but Eqs. (17.22) and (17.24) can still be used by inverting both terms to
give
N = In [(y. - Y:)/(h - ytJ]
(17.26)
In (I/A)
or
N = In [(Ya - Y:)/(Yb - ~)]
(17.27)
In [(yt - y:l!(Yb - Ya)]
In the design of an absorber, the liquid rate is usually chosen to make the
operating line steeper than the equilibrium line or to make A greater than unity.
EQUILlBRIUM-5TAGE OPERATIONS 515
-----------.!f"
,II .!f,-Y
b
.
I
y,*,
0,
Operating line t
I
Y 1
lb
j-Ya
Equilibrium IlfJe
1 y,
11b ~y,' a
Ya
- ,
I
YfJ&~Ya*- __ ___________ ~ __
FIGURE 17.9
Concentration differences in Eq. (17.24).
Values of A less than 1.0 can arise when dealing with two or more absorbable
components. If the value of A is slightly greater than 1.0 for the major solute, a
second component with a much lower solubility (higher value of m) will have a
value of A appreciably less than 1.0. If the gas stream and the solution are dilute,
the preceding equations can be applied to each component independently.
L-PHASE FORM OF EQ. (17.24). The choice of y as the concentration coordinate
rather than x is arbitrary. It is the conventional variable in gas-absorption
calculations. It may be used for stripping also, but in practice equations in x are
more common. They are
N = In [(x. - x;)!(x b - xm
In [(x. - Xb)/(X; - xt)]
In [(x. - x;)/(x b - xi)]
(17.28)
In S
where x, = equilibrium concentration corresponding to y
S = stripping Jactor
The stripping factor S is defined by
1 mV
S=-=- (17.29)
A L
516 MASS TRANSFER AND ITS APPLICATIONS
~-------------X;-Xb------------~·~~
I~----------------xo-Xb----------------~'I
x----_+_
FIGURE 17.10
Concentration differences in Eq. (17.2~).
The stripping factor is the ratio of the slope of the equilibrium line to that
of the operating line, and the conditions are usulllly chosen to make S greater
than uuity. The concentration differences in Eq. (1728) are shown in Fig. 17.10.
As shown in the derivations, it is not assumed that the equilibrium line passes
through the origin. It is only necessary that the line be linear in the range where
the steps representing the stages touch the line, as shown by line AB in Fig. 17.10.
Thus an equilibrium line that is almost linear near the origin but curves at higher
concentrations is sometimes fitted by a straight line over part of its range to permit
use of the Kremser equation.
The various forms of the Kremser equation were derived using concentra-
tions in mole fractions, which is the usual choice for distillation or absorption.
For some operations, including extraction and leaching, the concentrations may
be expressed using mole ratios or mass ratios, defined as the amount of diffusing
component divided by the amount of inert nondiffusing components. If this choice
of units gives straight equilibrium and operating lines, the same Kremser equations
can be used to find the number of ideal stages.
In the design of a plant, N is calculated from the proposed terminal
concentrations and a selected value of A or S. Equation (17.22) or (17.24) is used
for absorption and Eq. (17.28) for stripping. In estimating the effect of a change
in operating conditions of an existing plant, Eq. (17.21) or the following equation
EQUILIBRIUM-STAGE OPERATIONS 517
in x coordinates is used:
(17.30)
Example 17.2. Ammonia is stripped from a dilute aqueous solution by countercurrent
contact with air in a column containing seven sieve trays. The equilibrium relation-
ship is Ye = 0.8xe, and when the molar flow of air is 1.5 times that of the solution,
90 percent of the ammonia is removed. (a) How many ideal stages does the column
have, and what is the stage efficiency? (b) What percentage removal would be obtained
if the air rate were increased to 2.0 times the solution rate?
Solution
(a) The stripping factor is
mV
S=-=0.8x1.5=1.2
L
All concentrations can be expressed in terms of X a , the mole fraction of NH3
in the entering solution:
xt = 0, since Yb = 0
From an ammonia balance, V 8.y = VYa = L 8.x = L(0.9xa)' Hence
L 0.9
Ya = - (0.9xa) = - Xa = 0. 6xa
V 1.5
Also,
Ya 0. 6x a
x* =-=--=0.75x
a m 0.8 a
From Eq. (17.28),
In [(x. - 0.75x.)/(0.lx. - 0)]
N = -'''--''---=-'--''--'''-
InS
In (0.25x./0.lx.)
5.02
In 1.2
The separation corresponds to 5.02 ideal stages, so the stage efficiency is 5.02/7 = 72
percent.
(b) If V/L is increased to 2.0 and the number of ideal stages N does not cbange,
S = 0.8 x 2.0 = 1.6. Then
x -x*
In _._ _• = 5.02 In 1.6 = 2.36
Xb
x_
_. -x*
_• = 10.59
Xb
518 MASS TRANSFER AND ITS APPLICATIONS
Let/be the fraction of NH3 removed. Then Xb = (1 - J)xa . By a material balance,
y, = v
L
(x, - Xb)
= J[X, - (1 - f)x,] = yx,
y, O.5/X,
x: = - = - - = 0.625Jx a
In 0.8
Thus
x, - x: = (1 - 0.625f)x,
Also,
x, - x: = 1O.59x, = 10.59(1 - f)x,
From these, / = 0.962, or 96.2 percent is removed.
The conditions for the original case and the new case are sketched in Fig. 17.11.
Equilibrium-Stage Calculatious for
Multicomponent Systems
For systems containing more than two or three components graphical procedures
are ordinarily of little value, and the number of ideal stages required in a given
problem must be found by algebraic calculations. These involve knowledge and
application of the equilibrium relationships; material balances [Eqs. (17.1) and
(17.2)J; and (sometimes) enthalpy balances [Eqs. (17.5) and (17.6)]. The calculations
are begun at some point in the cascade where conditions are known. On the basis
of certain assumptions the conditions on succeeding stages which satisfy the
equilibrium requirements and the material and energy balances are found mathe-
matically, usually by iteration. The calculations are continued, stage by stage, until
the desired terminal conditions are reached or, as often happens, it becomes evident
that they cannot be reached. If this occurs, the underlying assumptions are
modified and the entire calculation repeated until the problem is solved. For
preliminary calculations on multicomponent systems certain approximate me-
thods are available which greatly reduce the labor involved, but the rigorous
Equilibrium
line
_--I
1_-< Higher V/L
_-- I
-- I
x; FIGURE 17.11
x Diagram for Example 17.2.
EQUILTBRIUM-5TAGE OPERATIONS 519
computation of multi component cascades is an important application of computer
techniques. (See Chap. 19.)
SYMBOLS
A Absorption factor, L/m V, dimensionless
a1 First term of geometric series
B Constant in Eq. (17.8)
J Fraction of ammonia absorbed (Example 17.2)
H Specific enthalpy, J/g or Btujlb; H L , of L phase; H L . " at entrance;
BL,b' at exit; BL,n, of L phase leaving stage n; B v , of V phase; B V• a, at
exit; H V • b , at entrance; H V .,+l, of V phase leaving stage n + 1
L Flow rate of L phase, kg moljh or lb mol/h; L N , from final stage of
cascade; La, at entrance; Lb. at exit; Ln. from stage n
11 , I, Lengths of line segments in Fig. 17.7
m Slope of equilibrium curve, dYe/dxe
N Total number of ideal stages
n Serial number of ideal stage, counting from inlet of L phase
r Ratio of succeeding terms of geometric series
S Stripping factor, In V/L, dimensionless
Sn Sum of first 11 terms of geometric series
V Flow rate of V phase, kg mol/h or lb moljh; V" at exit; Vb' at
entrance; v" + 1, from stage 11 + 1; VI' leaving first stage of cascade
x Mole fraction in L phase; used for component A when only two
components are present; XN, in L phase from final stage of cascade;
X a , at entrance; Xb, at exit; Xe, at equilibrium; X n , mole fraction in L
phase from stage n; x*, mole fraction in L phase in equilibrium with
specified stream of V phase; x:, in equilibrium with Ya; X6, in
equilibrium with y,; x o, in L phase entering first stage of cascade; Xl'
x" in L phase leaving first and second stages, respectively
Y Mole fraction in V phase; used for component A when only two
components are present; YN + l' in V phase entering stage N of cascade;
Ya, at exit; Yb, at entrance; Ye' at equilibrium; Yn. in V phase from
stage n; y*, mole fraction in V phase in equilbrium with specified
stream of L phase; Y:, in equilibrium with xa; Y6, in equilibrium with
x b ; YI, y" in V phase leaving first and second stages, respectively
PROBLEMS
17.1. Calculate the number of ideal stages for the system described in Example 17.1 if
the conditions are changed to the following:
Acetone in entering gas, 25 mole percent
Acetone in entering oil, 1.5 mole percent
Acetone in bottoms liquor, 8 mole percent
Acetone absorbed, 96 percent
520 MASS TRANSFER AND ITS APPLICATIONS
17.2. What are the effects on the concentrations of the exit gas and liquid streams of the
following changes in the operating conditions of the column of Example 17.2? (a) A
drop in the operating temperature that changes the equilibrium re1ationship to
Y. = O.6x•. Unchanged from the original design: N, LjV,y" and x,. (b) A reduction
in the LjV ratio from 1.5 to 1.25. Unchanged from original design: temperature, N, y"
and X". (c) An increase in the number of ideal stages from 5.02 to 8. Unchanged from
original design: temperature, L/V, Yb. and X".
REFERENCES
1. Brown, G. G., M. Souders, Jr., and H. V. Nyland: 1nt. Eng. Chem., 24:522 (1932).
2. Gmehling, 1., U. Onken, et at: Vapor Liquid Equilihria Data Collection, DECHEMA, Frankfurt,
1977.
3. Kremser, A.: Natl. Petr. News, 22(21):42 (May 21, 1930).
4. McCabe, W. L., and E. W. Thiele: Ind. Eng. Chem., 17:605 (1925).
5. Perry, 1. H. (ed.): Chemical Engineers' Handbook, 6th cd., McGrawMHiIl, New York, 1984, p. 1S-1().
CHAPTER
18
DISTILLATION
In practice, distillation may be carried out by either of two principal methods.
The first method is based on the production of a vapor by boiling the liquid
mixture to be separated and condensing the vapors without allowing any liquid
to return to the still. There is then no reflux. The second method is based on the
return of part of the condensate to the still under such conditions that this
returning liquid is brought into intimate contact with the vapors on their way to
the condenser. Either of these methods may be conducted as a continuous process
or as a batch process. The first two sections of this chapter deal with continuous
steady-state distillation processes, including single-stage partial vaporization with-
out reflux (flash distillation) and continuous distillation with reflux (rectification),
for systems containing only two components. (Multicomponent distillation is
discussed in Chap. 19.) The third section is concerned with the design and
performance of sieve-tray distillation columns and the last section with batch
distillation.
FLASH DISTILLATION
Flash distillation consists of vaporizing a definite fraction of the liquid in such a
way that the evolved vapor is in equilibrium with the residual liquid, separating
the vapor from the liquid, and condensing the vapor. Figure 18.1 shows the
elements of a flash-distillation plant. Feed is pumped by pump a through heater
b, and the pressure is reduced through valve c. An intimate mixture of vapor and
liquid enters the vapor separator d, in which sufficient time is allowed for the
vapor and liquid portions to separate. Because of the intimacy of contact of liquid
and vapor before separation, the separated streams are in equilibrium. Yapor
leaves through line e and liquid through line g.
522 MASS TRANSFER AND ITS APPLICATIONS
Vaporlo
e condenser
L fmole
YD
b 1~
)
.c
----1
,
d
( )
Feed" r )
, g
Imole L
xF // g LiqUId
I~ (I-f) mole
~ " xB
FIGURE IS.1
Plant for flash distillation.
FLASH DISTILLATIONt OF BINARY MIXTURES. Consider 1 mol of a two-
component mixture fed to the equipment shov,'n in Fig. 18.1. Let the concentration
of the feed be X p , in mole fraction of the more volatile component. Let f be the
molal fraction of the feed that is vaporized and withdrawn continuously as vapor.
Then 1 - f is the molal fraction of the feed that leaves continuously as liquid. Let
YD and XB be the concentrations of the vapor and liquid, respectively. By a material
balance for the more volatile component, based on 1 mol of feed, all of that
component in the reed must leave in the two exit streams, or
XF = fYD + (1 - f)XB (18.1)
There are two unknowns in Eq. (18.1), X B and YD. To use the equation, a second
relationship between ihe unknowns must be available. Such a relationship is
provided by the equilibrium curve, as YD and XB are coordinates of a point on this
curve. If X B andYD are replaced by x andy, respectively, Eq. (18.1) can be written
1- f Xp
Y= - - - X + - (18.2)
f J
The fraction f is not fixed directly but depends on the enthalpy of the hot
incoming liquid and the enthalpies of the vapor and liquid leaving the flash
t Flash distillation is used on a large scale in petroleum refining, in which petroleum fractions
are heated in pipe stills and the heated fluid flashed into overhead vapor and residual-liquid
streams, each containing many components.
DISTILLATION 523
chamber. For a given feed condition, the fraction I can be increased by flashing
to a lower pressure.
Equation (18.2) is the equation of a straight line with a slope of -(1 - I)!I
and can be plotted on the equilibrium diagram. The coordinates of the intersection
of the line and the equilibrium curve are x = x B and Y = YD' The intersection of
this material-balance line and the diagonal x = Y can be used conveniently as a
point on the line. Letting x = XF in Eq. (18.2) gives
1- I XF
y= --I- xF +7
from which Y = XF = x. The material-balance line crosses the diagonal at x = XF
for all values of f
Example 18.1. A mixture of 50 mole percent benzene and 50 mole percent toluene
is subjected to flash distillation at a separator pressure of 1 atm. The vapor-Iiquid
equilibrium curve and boiling-point diagram are shown in Figs. 18.2 and 18.3. Plot
the following quantities, all as functions of f, the fractional vaporization: (a) the
temperature in the separator, (b) the composition of the liquid leaving the separator,
and (c) the composition of the vapor leaving the separator.
1.0
(:02 (=0
/ '~
0.9 (=
4\ 1\ ./
V
/
0.8
(=06
0.7 ~ 1\\ \ V 1/
~ k\ /
i'--.
0.6 (=08
>- 0.5
NO
--- r----. ~N /
04 / 1/
0.3 //
0.2 V 1/
O.1/ /
W 0.1 0.2 Q.3 0.4 0.5 06 07 OB 09 1.0
x
FIGURE 18.2
Equilibrium curve, system benzene-toluene. Graphical construction for Example 18.l.
524 MASS TRANSFER AND ITS APPLICATIONS
115
110.
10.5
~ t'-
l)
W 100 i'-
~ ~
~ 95
"-
"'i5
Q
90.
85
i'- "-
'-
~ 80.
:::"
75
70.
65
0. 0..2 0..4 0..6 0..8 IQ FIGURE 18.3
Co.NCENTRATlo.N, Mo.LE FRACTlo.N Boiling-point diagram (system benzene-
BENZENE toluene at 1 atm).
Solution
For each of several values of/corresponding quantities - [(I/!) - 1J are calculated.
Using these quantities as slopes, a series of straight 1ines each passing through point
(xP. x F) is drawn on the equilibrium curve of Fig. 18.2. These lines intersect the
equilibrium curve at corresponding values of Xn and YD' The temperature of each
vaporization is then found from Fig. 18.3. The results are shown in Table 18.1 and
plotted in Fig. 18.4. The limits for 0 and lOO percent vaporization are the bubble and
dew points, respectively.
I00
~
~
Temperature 96
b 0.8
~w 0.7
cl
'"
~0..6
- r-- eo~ ~ ~/]I/C:7bo,.,
0/';'''-,ene
•
~
~0.5
w
~0..4
8
0..3
- r- e""""
-.:..:..::: nb-onon 0/49.
~"~r--
--....::::: "-'ene
-:':::':'::"'//7. liquid
r-.::.;...
0..2
0. 0..1 0..2 0..3 0..4 0..5 0..6 0..7 0..8 0..9 1.0
I-MCLES VAPCRIZED PER MCLE CF FEED
FIGlIRE 18.4
Results for Example 18.1.
DISTILLATION 525
TABLE 18.1
Data for Example 1S.1
Concentration,
mole fraction C6H6
Fraction 1-1 Temperature,
vaporizedf Slope--- Liquid XB Vapor YD °c
I
0 00 0.50 0.71 92.2
0.2 -4 0.455 0.67 93.7
0.4 -1.5 0.41 0.63 95.0
0.6 -0.67 0.365 0.585 96.5
0.8 -0.25 0.325 0.54 97.7
1.0 0 0.29 0.50 99.0
CONTINUOUS DISTILLATION WITH
REFLUX (RECTIFICATION)
Flash distillation is used most for separating components that boil at widely
different temperatures. It is not effective in separating components of comparable
volatility, since then both the condensed vapor and residual liquid are far from
pure. By many successive redistillations small amounts of some nearly pure
components may finally be obtained, but this method is too inefficient for
industrial distillations when nearly pure components are wanted. Methods now
used in both laboratory and plant apply the principle of rectification, which is
described in this section.
RECTIFICATION ON AN IDEAL PLATE. Consider a single plate in a column or
cascade of ideal plates. Assume that the plates are numbered serially from the top
down and that the plate under consideration is the nth plate from the top. It is
shown diagrammatically in Fig. 18.5. Then the plate immediately above this plate
is plate n - 1 and that immediately below it is plate n + 1. Subscripts are nsed
on all quantities showing the point of origin of the quantity.
Two fluid streams enter plate n, and two leave it. A stream of liquid, L"-1
mol/h, from plate n - 1, and a stream of vapor, v" + 1 mOl/h, from plate n + 1, are
brought into intimate contact. A stream of vapor, v" mol/h, rises to plate n - 1,
and a stream of liquid, L" mol/h, descends to plate n + 1. Since the vapor streams
are the V phase, their concentrations are denoted by y. The liquid streams are the
L phase and their concentrations are denoted by x. Then the concentrations of
the streams entering and leaving the nth plate are as follows:
Vapor leaving plate, y"
Liquid leaving plate, x"
Vapor entering plate, y"+1
Liquid entering plate, X"_1
526 MASS TRANSFER AND ITS APPLICATIONS
Xn _2
I ~P/ole n-/
r-'
xn _/ Yn
Vnf
-+--P/ole n
~r'r
In-l-/
1: +--P/ole n+1
I lj;+2 I
FIGURE IS.S
Material-balance diagram for plate n.
Figure 18.6 shows the boiling-point diagram for the mixture being treated.
The four concentrations given above are shown in this figure. By definition of an
ideal plate, the vapor and liquid leaving plate 1Z are in equilibrium, so x" and Y"
represent equilibrium concentrations. This is shown in Fig. 18.6. Since concentra-
tions in both phases increase with the height of the column, x" - I is greater than
x" and y" is greater than Y,,+I' Although the streams leaving the plate are in
equilibrium, those entering it are not. This can be seen from Fig. 18.6. When the
vapor from plate 1Z + 1 and the liquid from plate 1Z - 1 are brought into intimate
contact, their concentrations tend to move toward an equilibrium state, as shown
by the arrows in Fig. 18.6. Some of the more volatile component A is vaporized
from the liquid, decreasing the liquid concentration from X"_I to x"; and some
of the less volatile component B is condensed from the vapor, increasing the vapor
concentration from Y"+I to Y", Since the liquid streams are at their bubble points
and the vapor streams at their dew points, the heat necessary to vaporize
component A must be supplied by the heat released in the condensation of
component B. Each plate in the cascade acts as an interchange apparatus in which
component A is transferred to the vapor stream and component B to the liquid
stream. Also, since the concentration of A in both liquid and vapor increases with
column height, the temperature decreases, and the temperature of plate 1Z is greater
than that of plate 1Z - 1 and less than that of plate n + 1.
COMBINATION RECTIFICATION AND STRIPPING. The plant described on
pages 501 to 504, in which the feed to the unit is supplied to the still, cannot
produce a nearly pure bottom product because the liquid in the still is not subjected
DISTILLATION 527
w
a::
:::J
~W
CL
::;;
W
f-
I
I
I
I
I
I
I
I
I
I
I
I I
I I
~-I IYn+J Yn
OA 'WOA
1.008 CONCENTRATION, MOLE FRACTION A 0B
FIGURE 18.6
Boiling-point diagram showing rectification on ideal plate.
to rectification. This limitation is removed by admitting the feed to a plate in the
central portion of the column. Then the liquid feed flows down the column to the
still, which in this type of plant is called the reboiler, and is subjected to rectification
by the vapor rising from the reboiler. Rectification in the lower section of the
column is called stripping. Since the liquid reaching the reboiler is stripped of
component A, the bottom product can be nearly pure B.
A typical continuous fractionating column equipped with the necessary
auxiliaries and containing rectifying and stripp}ng sections is shown in Fig. 18.7.
The column A is fed near its center with a definite flow of feed of definite
concentration. Assume that the feed is a liquid at its boiling point. The action in
the column is not dependent on this assumption, and other conditions of the feed
will be discussed later. The plate on which the feed enters is called the feed plate.
All plates above the feed plate constitute the rectifying section, and all plates below
the feed, including the feed plate itself, constitute the stripping section. The feed
flows down the stripping section to the bottom of the column, in which a definite
level of liquid is maintained. Liquid flows by gravity to reboiler B. This is a
steam-heated vaporizer that generates vapor and returns it to the bottom of the
column. The vapor passes up the entire column. At one end of the reboiler is a
weir. The bottom product is withdrawn from the pool of liquid on the downstream
528 MASS TRANSFER AND ITS APPLICATIONS
Vapor
J Condenser C
(I H
-,--- - Accumulotor D
J-- (1:-,- - -- --- -- 0\
A r
't' Cooler E
-~ ""
0 <::: ~
(I Cold
woter
:.::: -!:?
Q!"
t
~
~
'-
'-'
Reflux
t Overheod
product
3- pump F
·LFeed
Plote
~ .!:?
<:::
:~ Vapor
;:::
i?; ~ .- - _.
ReboilerB
..--
--_.. .. --- ~ Steam
--- ---- 1&
.. --
'- r-- ./ Liquid
Trap
-- Condensate
Bottoms
1- ~ coolerG
I Bottoms
Feed P'l"oduct
FIGURE 18.7
Continuous fractionating column with rectifying and stripping sections.
side of the weir and flows through the cooler G. This cooler also preheats the feed
by heat exchange with the hot bottoms.
The vapors rising through the rectifying section are completely condensed
in condenser C, and the condensate is collected in accumulator D, in which a
definite liquid level is maintained. Reflux pump F takes liquid from the accumula-
tor and delivers it to the top plate of the tower. This liquid stream is called reflux.
It provides the downflowing liquid in the rectifying section that is needed to act
on the upflowing vapor. Without the reflux no rectification would occur in the
rectifying section and the concentration of the overhead product would be no
DISTILLATION 529
greater than that of the vapor rising from the feed plate. Condensate not picked
up by the reflux pump is cooled in heat exchanger E, called the product cooler,
and withdrawn as the overhead product. If no azeotropes are encountered, both
overhead and bottom products may be obtained in any desired purity if enough
plates and adequate reflux are provided.
The plant shown in Fig. 18.7 is often simplified for small installations. In
place of the reboiler, a heating coil may be placed in the bottom of the column
and generate vapor from the pool of liquid there. The condenser is sometimes
placed above the top of the column and the reflux pump and accumulator are
omitted. Reflux then returns to the top plate by gravity. A special valve, called a
reflux splitter, may be used to control the rate of reflux return. The remainder of the
condensate forms the overhead product.
Material Balances in Plate Columns
OVERALL MATERIAL BALANCES FOR TWO-COMPONENT SYSTEMS. Figure
18.8 is a material-balance diagram for a typical continuous-distillation plant. The
column is fed with F moljh of concentration XF and delivers D moljh of overhead
product of concentration X D and B moljh of bottom product of concentration XB'
Two independent overall material balances can be written
Total-material balance F=D+B (18.3)
Component A balance: (18.4)
Eliminating B from these equations gives
D Xp - XB
-= (18.5)
F XD-X B
Eliminating D gives
B XD - Xp
(18.6)
F XD - XB
Equations (18.5) and (18.6) are true for all values of the flows of vapor and
liquid within the column.
NET FLOW RATES. Quantity D is the difference between the flow rates of tbe
streams entering and leaving the top of the column. A material balance around
the condenser and accumulator in Fig. 18.8 gives
D= Y,,-La (18.7)
The difference between the flow rates of vapor and liquid anywhere in the
upper section of the column is also equal to D, as shown by considering the part
of the plant enclosed by control surface I in Fig. 18.8. This surface includes the
condenser and all plates above n + 1. A total-material balance around this control
530 MASS TRANSFER AND JTS APPLICATIONS
,---- ------ - - ---------1
: ~ Condenser
,
r Heoloul
Control
Vc ,,, -qc
surface
1
.--.!t I
I
f
~
(I
I~A
, ccumulator
I
I
,
I
Overhead
""- Reflux I product
n I D
Xo
.f--,----,+m
r
;mt___J ~%~j_____ _______ -, If
I m+1
Control : v"
surface [ /~--_+_- RebOiler
If : Heal in
I
qr
,I I
I Lb
xb
IL. ______________________ --1
Bol/oms producl
B
xB
FIGURE 18.8
Material-balance diagram for continuous fractionating column.
surface gives
(18.8)
Thus quantity D is the net flow rate of material upward in the upper section
of the column. Regardless of changes in V and L, their difference is constant and
equal to D.
Similar material balances for component A gives the equations
(18.9)
Quantity DXD is the net flow rate of component A upward in the upper section
of the column. It, too, is constant throughout this part of the equipment.
In the lower section of the column the net flow rates are also constant but
are in a downward direction. The net flow rate of total material equals B; that of
DISTILLATION 531
component A is BXB' The following equations apply:
B = Lb - Jtb = Lm - Vm+ 1 (18.10)
BXB = LbXb - YbYb = Lmxm - Vm+ 1Ym+l (18.11)
Subscript m is used in place of n to designate a general plate in the: tripping
section.
OPERATING LINES. Because there are two sections in the column, there are also
two operating lines, one for the rectifying section and the other for the stripping
section. Consider first the rectifying section. As shown in Chap. 17 [Eq. (17.7)],
the operating line for this section is
(18.12)
Substitution for v"Ya - Laxa from Eq. (18.9) gives
Ln DXD
Yn+l =--xa+-- (18.13)
v,; + 1 v,; + 1
The slope of the line defined by Eq. (18.13) is, as usual, the ratio of the flow
of the liquid stream to that ofthe vapor stream. For further analysis it is convenient
to eliminate v" + I from Eq. (18.13) by Eq. (18.8), giving
Ln DXD
Yn+ 1 = Ln + D Xn + Ln + D (18.14)
For the section of the column below the feed plate, a material balance over
control surface II in Fig. 18.8 gives
Vm+ 1 Ym+l = Lmxm - BXB (18.15)
In a different form, this becomes
Lm BXn
y ---x --- (18.16)
m+l - V + m V +
m 1 m 1
This is the equation for the operating line in the stripping section. Again the
slope is the ratio of the liquid flow to the vapor flow. Eliminating Vm+ 1 from Eq.
(18.16) by Eq. (18.10) gives
(18.17)
Number of Ideal Plates; McCabe-Thiele Method
When the operating lines represented by Eqs. (18.14) and (18.17) are plotted with
the equilibrium curve on the X-Y diagram, the McCabe-Thiele step-by-step
construction can be used to compute the number of ideal plates needed to
532 MASS TRANSFER AND ITS APPLICATIONS
accomplish a definite concentration difference in either the rectifying or the
stripping section. 8 Equations (18.14) and (18.17), however, show that unless L, and
Lm are constant, the operating lines are curved and can be plotted only if the
change in these internal streams with concentration is known. Enthalpy balances
are required in the general case to determine the position of a curved operating line,
and a method of doing this is described later in this chapter.
CONSTANT MOLAL OVERFLOW. For most distillations, the molar flow rates of
vapor and liquid are nearly constant in each section of the column, and the
operating lines are almost straight. This results from nearly equal molar heats of
vaporization, so that each mole of high boiler that condenses as the vapor moves
up the column provides energy to vaporize about 1 mol oflow boiler. For example,
the molar heats of vaporization of toluene and benzene are 7960 and 7360 calfmol,
respectively, so that 0.92 mol of toluene corresponds to 1.0 mol of benzene.t
The changes in enthalpy of the liquid and vapor streams and heat losses from the
column often require slightly more vapor to be formed at the bottom, so the molar
ratio of vapor flow at the bottom of a column section to that at the top is even
closer to 1.0. In designing columns, therefore, the concept of constant molal overflow
is generally used, which means simply that in Eqs. (18.8) to (18.17), subscripts n,
n + 1, n - 1, m, m + 1, and m-Ion L and V may be dropped. In this simplified
model the material-balance equations are linear and the operating lines straight.
An operating line can be plotted if the coordinates of two points on it are known.
Then the McCabe-Thiele method is used without requiring enthalpy balances.
REFLUX P. \ TIO. The analysis of fractionating columns is facilitated by the use
of a quantity called the reflux ratio. Two such quantities are used. One is the ratio
of the reflux to the overhead product, and the other is the ratio of the reflux to
the vapor. Both ratios refer to quantities in the rectifying section. The equations
for these ratios are
L V-D L L
Rn =-=-- and R ----- (18.18)
D D v-V-L+D
In this text only Rn will be used.
If both numerator and denominator of the terms on the right-hand side of
Eq. (18.14) are divided by D, the result is, for constant molal overflow,
(18.19)
t For benzene-toluene and for many other pairs of similar hycrocarbons, the heat of vaporization
per unit mass is higher for the low boiler. but the ratio is still close to 1.0. and operating lines based
on mass fraction would be almost straight. For systems such as ethanol-water, however, the heats of
vaporization are about the same per mole but quite different per unit mass. so the use of molar
quantities is advantageous for distillation calculations.
DISTILLATION 533
Equation (18.19) is an equation for the operating line of the rectifying section.
The y intercept of this line is xn/(Rn + 1). The concentration xn is set by the
conditions of the design; and Rn, the reflux ratio, is an operating variable that
can be controlled at will by adjusting the split between reflux and overhead product
or by changing the amount of vapor formed in the reboiler for a given flow rate
of the overhead product. A point at the upper end of the operating line can be
obtained by setting x" equal to Xn in Eq. (18.19):
Rn xn xn(Rn + 1)
(18.20)
Y"+l = Rn + 1 Xn + Rn + 1 = Rn + 1
or
Yn+l = xD
The operating line for the rectifying section then intersects the diagonal at
point (xn' xn)· This is true for either a partial or a total condenser. (Partial
condensers are discussed in the next section.)
CONDENSER AND TOP PLATE. The McCabe-Thiele construction for the top
plate does depend on the action of the condenser. Figure 18.9 shows material-
balance diagrams for the top plate and the condenser. The concentration of the
vapor from the top plate is Y1, and that for the reflux to the top plate is x,. In
accordance with the general properties of operating lines, the upper terminus of
the line is at the point (x" y,),
The simplest arrangement for obtaining reflux and liquid product, and one
that is frequently used, is the single total condenser shown in Fig. 18.9b, which
condenses all the vapor from the column and supplies both reflux and product.
When such a single total condenser is used, the concentrations of the vapor from
the top plate, of the reflux to the top plate, and of the overhead product are equal
and can all be denoted by Xn. The operating terminus of the operating line becomes
point (xn' x n ), which is the intersection of the operating line with the diagonal.
Triangle abe in Fig. 18.lOa then represents the top plate.
0 Vopor
y/
Liquid
Liquid 0
Le Xc
Le Xo
xC=xD=Y' Fino// Liquid
condenser 0 Xo
(o) (b) (c)
FIGURE 18.9
Material-balance diagrams for top plate and condenser: (a) top plate; (b) total condenser; (c) partial
and final condensers.
534 MASS TRANSFER AND ITS APPLICATIONS
Y'=XD-b - - - - - 0
° t
I I
b.' I I
y,-*------,"':al>" I
I
I
c' I
I
Xo
(0) (b)
FIGURE 18.10
Graphical construction for top plate: (a) using total condenser; (b) using partial and final condensers.
When a partial condenser, or dephlegmator, is used, the liquid reflux does
not have the same composition as the overhead product; that is, x, oft XD'
Sometimes two condensers are used in series, first a partial condenser to provide
reflux, then a final condenser to provide liquid product. Such an arrangement is
shown in Fig. 18.9c. Vapor leaving the partial condenser has a composition y',
which is the same as X D . Under these conditions the diagram in Fig. 18.lOb applies.
The operating line passes through the point (xD , x D) on the diagonal, but as far
as the column is concerned, the operating line ends at point a', which of course
has the coordinates (x" YI)' Triangle db'c' in Fig. 18.lOb represents the top plate
in the column. Since the vapor leaving a partial condenser is normally in
equilibrium with the liquid condensate, the vapor composition y' is the ordinate
value of the equilibrium curve where the abscissa is x" as shown in Fig. 18.10b.
The partial condenser, represented by the dotted triangle aba' in Fig. 18.10b, is
therefore equivalent to an additional theoretical stage in the distillation apparatus.
In the preceding treatment it is assumed that the condenser removes latent
heat only and that the condensate is liquid at its bubble point. Then the refiux L
is equal to Loo the refiux from the condenser, and V = VI' If the refiux is cooled
below the bubble point, a portion of the vapor coming to plate 1 must condense
to heat the refiux; so VI < V and L > L,. The additional amount />,.L that is
condensed inside the column is found from the equation
/>,.L = L,cp,(TI - 7;) (18.21)
}"
where cp , = specific heat of condensate
TI = temperature of liquid on top plate
7; = temperature of returned condensate
}" = heat of vaporization of condensate
DISTILLATION 535
The actual reflux ratio in the column is then
L L, + /l,.L L,[1 + cp,( T, - 7;)/}.J
-= = (18.22)
D D D
Temperature T, is not usually known, but it normally almost equals 1/,,,
the bubble-point temperature of·the condensate. Thus 1/" is commonly used in
place of T, in Eqs. (18.21) and (18.22).
BOTTOM PLATE AND REBOILER. The action at the bottom of the column is
analogous to that at the top. Thus, Eq. (18.17), written for constant molal overflow,
becomes, with I and later 17 used to denote flow rates in this section,
I Ex.
Ym+'=I_Exm-I_E (18.23)
If xm is set equal to x. in Eq. (18.23), Ym+' is also equal to x., so the
operating line for the stripping section crosses the diagonal at point (XB, x B). This
is true no matter what type of reboiler is used, as long as there is only one bottom
product. The lower operating line could then be constructed using the point
(XB, x.) and the slope I/(I - E), but a more convenient method is described in the
discussion on feed plates in the next section.
The material-balance diagram for the bottom plate and the reboiler is shown
in Fig. 18.11. The lowest point on the operating line for the column itself is the
point for the bottom plate (x b , y,), where Xb and y, are the concentrations in the
liquid leaving the bottom plate and the vapor coming from the reboiler. However,
as shown earlier, the operating line can be extended to cross the diagonal at point
(XB' x B )·
Plate b
!;b vt Steam
Yr "-
-
---=------ 4'1 r -- - - --
----- ---- - ---I
..... ----------~)
,..-----------
'-- ------
--- -- - -
----- 'f --- Condensate
L B
xb xB
FIGURE 18.11
Material-balance diagram for bottom plate and reboiler.
536 MASS TRANSFER AND ITS APPLICATIONS
EquilIbrium curve Operating
y Ime
x_
FIGURE IB.12
Graphical construction for bottom plate and reboiler: triangle ede. reboiler; triangle abe, bottom plate.
In the common type of reboiler shown in Figs. 18.7 and 18.11, the vapor
leaving the reboiler is in equilibrium with the liquid leaving as bottom product.
Then xn and y, are coordinates of a point on the equilibrium curve, and the
reboiler acts as an ideal plate. In Fig. 18.12 is shown the graphical construction
for the reboiler (triangle cde) and the bottom plate (triangle abc). Such a reboiler
is called a partial reboiler. Its construction is shown in detail in Fig. 15.11.
FEED PLATE. At the plate where the feed is admitted, the liquid rate or the vapor
rate or both may change, depending on the thermal condition of the feed. Figure
18.13 shows diagrammatically the liquid and vapor streams into and out of the
feed plate for various feed conditions. In Fig. 18.13a, cold feed is assumed, and
the entire feed stream adds to the liquid flowing down the column. In addition,
some vapor condenses to heat the feed to the bubble point; this makes the liquid
flow even greater in the stripping section and decreases the flow of vapor to the
rectifying section.
In Fig. 18.13b the feed is assumed to be at its bubble point. No condensation
is required to heat the feed, so V = V and I = F + L. If the feed is partly
vapor, as shown in Fig. 18.13c, the liquid portion of the feed becomes part of I
and the vapor portion becomes part of V. If the feed is saturated vapor, as shown
in Fig. 18.13d, the entire feed becomes part of V, so L = I and V = F + V. Finally,
if the feed is superheated vapor, as shown in Fig. 18.13e, part of the liquid from
the rectifying column is vaporized to cool the feed to a state of saturated vapor.
DISTILLATiON 537
v ~
V
~
L 1 L V L ~+
I I
1 t
F
"-Y-'
T
(a)
rl I
I
I
17
Ft
~
I
(b)
I
I
I
1
V
i#+t er'
L
(c)
_I
V
V V
L ,..c-,
L~
t+1 I ' I
'I i
I I I ill
~" ~ I
F. I I
--~ [ F~---'i
I I
I I
L V L 17
(d) (e)
FIGURE 18.13
Flow through feed plate for various feed conditions: (a) feed cold liquid; (b) feed saturated liquid; (c)
feed partially vaporized; (d) feed saturated vapor; (e) feed superheated vapor.
Then the vapor in the rectifying section consists of (1) the vapor from the stripping
section, (2) the feed, and (3) the extra moles vaporized in cooling the feed. The
liquid flow to the stripping section is less than that in the rectifying section by the
amount of additional vapor formed.
All five of the feed types can be characterized by the use of a single factor,
denoted by q and defined as the moles of liquid flow in the stripping section that
result from the introduction of each mole of feed. Then q has the following
numerical limits for the various conditions:
Cold feed, q > 1
Feed at bubble point (saturated liquid), q = 1
Feed partially vapor, 0 < q < 1
Feed at dew point (saturated vapor), q = 0
Feed superheated vapor q < 0
If the feed is a mixture of liquid and vapor, q is the fraction that is liquid.
Such a feed may be produced by an equilibrium flash operation, so q = 1 - J,
where f is the fraction of the original stream vaporized in the flash.
538 MASS TRANSFER AND ITS APPLICATIONS
The value of q for cold-liquid feed is found from the equation
CpLCT. - TF )
q= 1+ -'='--":--~ (18.24)
A
For superheated vapor the equation is
Cpy{TF - 7;,)
q= - (18.25)
A
where cpL , cpv = specific heats of liquid and vapor, respectively
Tp = temperature of feed
7;" T" = bubble point and dew point of feed, respectively
A = heat of vaporization
FEED LINE. The value of q obtained from Eq. (18.24) or (18.25) can be used with
the material balances to find the locus for all points of intersection of the operating
lines. The equation for this line of intersections can be found as follows.
The contribution of the feed stream to the internal flow of liquid is qF, so
the total flow rate of reflux in the stripping section is
I=L+ qF and I-L=qF (18.26)
Likewise, the contribution of the feed stream to the internal flow of vapor is
F(1 - q), and so the total flow rate of vapor in the rectifying section is
v= V + (1 - q)F and v- V = (1 - q)F (18.27)
For constant molal overflow, the material-balance equations for two sections
are
VYrz = LXrz + 1 + DXD (18.28)
VYm = LXm+l - BXn (18.29)
To locate the point where the operating lines intersect, letYn = Ym and X n+ 1 = X m+ 1
and subtract Eq. (18.29) from Eq. (18.28):
y(V - 17) = (L - I)x + DXD + Bx. (18.30)
From Eq. (18.4), the last two terms in Eq. (18.30) can be replaced by FXF. Also,
substituting for L - I from Eq. (18.26) and for V - V from Eq. (18.27) and
simplifying leads to the result
q Xp
y= - - - x + - - (18.31)
1-q 1-q
Equation (18.31) represents a straight line, called the feed line, on which all
intersections of the operating lines must fall. The position of the line depends only
on Xp and q. The slope of the feed line is - ql(1 - q), and as can be demonstrated
by substituting x for Y in Eq. (18.31) and simplifying, the line crosses the diagonal
DISTILLATION 539
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
Xo ,I
x.....
FIGURE 18.14
Effect of feed condition on feed line: ra, feed cold liquid; rh, feed saturated liquid; rc, feed partially
vaporized; rd, feed saturated vapor; re, feed superheated vapor.
CONSTRUCTION OF OPERATING LINES. The simplest method of plotting the
operating lines is (1) locate the feed line; (2) calculate the y-axis intercept
xD/(R D + 1) of the rectifying line and plot that line through the intercept and the
point (x D, x D); (3) draw the stripping line through point (x B, x B) and the intersection
of the rectifying line with the feed line. The operating lines in Fig 18.14 show the
result of this procedure.
In Fig. 18.14 are plotted operating lines for various types of feed, on the
assumption that X F , x., X D , L, and D are all constant. The corresponding feed
lines are shown. If the feed is a cold liquid, the feed line slopes upward and to the
right; if the feed is a saturated liquid, the line is vertical; if the feed is a mixture
of liquid and vapor, the line slopes upward and to the left and the slope is the
negative of the ratio of the liquid to the vapor; if the feed is a saturated vapor,
the line is horizontal; and finally, if the feed is superheated vapor, the line slopes
downward and to the left.
FEED-PLATE LOCATION. After the operating lines have been plotted, the number
of ideal plates is found by ihe usual step-by-step construction, as shown in Fig.
18.15. The construction can start either at the bottom of the stripping line or at
the top of the rectifying line. In the following it is assumed that the construction
540 MASS TRANSFER AND ITS APPLICATIONS
FIGURE 18.15
Optimum feed~plate location: - - , with feed on plate 5 (optimum location); ~-----, with feed on
plate 7.
begins at the top and also that a total condenser is used. As the intersection of
the operating lines is approached, it must be decided when the steps should transfer
from the rectifying line to the stripping line. The change should be made in such
a manner that the maximum enrichment per plate is obtained so that the number
of plates is as small as possible. Figure 18.15 shows that this criterion is met if
the transfer is made immediately after a value of x is reached that is less than the
x coordinate of the intersection of the two operating lines. The feed plate is always
represented by the triangle that has one corner on the rectifying line and one on
the stripping line. At the optimum position, the triangle representing the feed plate
straddles the intersection of the operating lines.
The transfer from one operating line to the other, and hence the feed-plate
location, can be made at any location between points a and b in Fig. 18.15, but
if the feed plate is placed anywhere but at the optimum point, an unnecessarily
large number of plates is called for. For example, if the feed plate in Fig. 18.15 is
number 7, the smaller steps shown by the dashed lines make the number of ideal
plates needed about eight plus a reboiler, instead of seven plus a reboiler when
the feed is on plate number 5. Note that the liquid on the feed plate does no!have
the same composition as the feed except by coincidence, even when the feed plate
location is optimum.
When analyzing the performance of a real column, the switch from one
operating line to another must be made at a real feed plate. Because of changes
DISTILLATION 541
in feed composition and uncertainties in plate efficiency, large columns are often
operated with the feed entering a few plates above or below the optimum location.
If large changes in feed composition are anticipated, alternate feed locations can
be provided.
HEATING AND COOLING REQUIREMENTS. Heat loss from a large insulated
column is relatively small, and the column itself is essentially adiabatic. The heat
effects of the entire unit are confined to the condenser and the reboiler. If the
average molal latent heat is ,\ and the total sensible heat change in the liquid
streams is small, the heat added in the reboiler q, is 17'\, either in watts or Btu per
hour. When the feed is liquid at the bubble point (q = 1), the heat supplied in
the reboiler is approximately equal to that removed in the condenser, but for other
values of q this is not true. (See page 554.)
If saturated steam is used as the heating medium, the steam required at the
reboiler is
17'\
m=-
, '\, (18.32)
where Ins = steam consumption
V= vapor rate from reboiler
'\, = latent heat of steam
,\ = molal latent heat of mixture
If water is used as the cooling medium in the condenser and the condensate
is not subcooled, the cooling-water requirement is
- V,\ V,\
= (18.33)
where In = water consumption .. ,i;.~;,
T2 - Tl = temperature rise of cooling water
Example 18.2. A continuous fractionating column is to be designed to separate
30,000 kgjh of a mixture of 40 percent benzene and 60 percent toluene into an
overhead product containing 97 percent benzene and a bottom product containing
98 percent toluene. These percentages are by weight. A reflux ratio of 3.5 mol to 1
mol of product is to be used. The molal latent heats of benzene and toluene are 7360
and 7960 caljg mol, respectively. Benzene and toluene fonn an ideal system with a
relative volatility of about 2.5; the equilibrium curve is shown in Fig. 18.16. The feed
has a boiling point of 9SOC at a pressure of 1 atm. (a) CalCrllate the moles of overhead
product and bottom product per hour. (b) Determine the number of ideal plates and
the position of the feed plate (I) if the feed is liquid and at its boiling point; (b) if the
feed is liquid and at 20'C (specific heat 0.44 cal/g-'C); (ib) if the ,feed is a mixture of
two-thirds vapor and one-third liquid. (c) If steam at 20 IbJ /in. 2 (1.36 atm) gauge is
used for heating, how much steam is required per hour for each of the above three
cases, neglecting heat losses and assuming the reflux is a saturated liquid? (d) If
cooling water enters the condenser at 25°C and leaves at 40°C, how much cooling
water is required, in cubic meters per hour?
542 MASS TRANSFER AND ITS APPLICATIONS
FIGURE 18.16
Example 18.2. part (b)(r).
Solution
(a) The molecular weight of benzene is 78 and that of toluene is 92. The concentra-
tions of feed, overhead, and bottoms in mole fraction of benzene are
40
78
XF = 40 60 = 0.440
78 + 92
2
XB = 2 78 98 = 0.0235
78+92
The average molecular weight of the feed is
The average heat of vaporization of the feed is
). ~ 0.44(7360) + 0.56(7960) ~ 7696 caVg mol
The reed rate F is 30,000/85.8 ~ 350 kg mol/h. By an overall benzene balance,
using Eq. (18.5).
D ~ 350 0.440 - 0.0235
153.4 kg mol/h
0.974 - 0.0235
B ~ 350 - 153.4 ~ 196.6 kg mol/h
DISTILLATION 543
(b) Next we determine the number of ideal plates and position of the feed plate.
(1) The first step is to plot the equilibrium diagram and on it erect verticals at
xv, XF, and Xs. These should be extended to the diagonal of the diagram. Refer to
Fig. 18.16.
The second step is to draw the feed line. Here,! = 0, and the feed line is vertical
and is a continuation of line x = X F .
The third step is to plot the operating lines. The intercept of the rectifying line
on the y axis is, from Eq. (18.19), 0.974/(3.5 + 1) = 0.216. From the intersection of
this operating line and the feed line the stripping line is drawn.
The fourth step is to draw the rectangular steps between the two operating
lines and the equilibrium curve. In drawing the steps, the transfer from the rectifying
line to the stripping line is at the seventh step. By counting steps it is found that,
besides the reboiler, 11 ideal plates are needed and feed should be introduced on the
seventh plate from the top.t
(ill The latent heat of vaporization of the feed J. is 7696/85.8 = 89.7 cal/g.
Substitution in Eq. (18.24) gives
0.44(95 - 20)
q = 1+ = 1.37
89.7
From Eq. (18.31) the slope of the feed line is -1.37/(1 - 1.37) = 3.70. When
steps are drawn for this case, as shown in Fig. 18.17, it is found that a reboiler
and 10 ideal plates are needed and that the feed should be introduced on the fifth
plate.
(iil) From the definition of q it follows that for this case q = t and the
slope of the feed line is -0.5. The solution is shown in Fig. 18.18. It calls for a
reboiler and 12 plates, with the feed entering on the seventh plate.
(c) The vapor flow V in the rectifying section, which must be condensed
in the condenser, is 4.5 mol per mole of overhead product, or 4.5 x 153.4 =
690 kg mol/h. From Eq. (18.27),
V = 690 - 350(1 - q)
Using the heat of vaporization of toluene rather than that of benzene to be
slightly conservative in design, A = 7960 cal/g mol. The heat from 1 Ib of steam
at 20 Ibf/in' gauge, from Appendix 7, is 939 Btujlb; hence J. s = 939/1.8 = 522 cal/g.
The steam required, from Eq. (18.32), is
7960_
rn, = - V = 15.25[690 - 350(1 - q)] kg/h
522
The results are given in Table 18.2.
t To fulfill the conditions of the problem literally, the last step, which represents the reboiler,
should reach the concentration Xn exactly. This is nearly true in Fig. 18.16. Usually, Xn does
not correspond to an integral number of steps. An arbitrary choice of the four quantities X n , X F , X B ,
and Rn is' not necessarily consistent with an integral number of steps. An integral number can be
obtained by a slight adjustment of one of the four quantities, but in view of the fact that a plate
efficiency must be applied before the actual number of plates is established, there is little reason for
making this adjustment.
544 MASS TRANSFER AND ITS APPLICATIONS
FIGURE 18.17
Example 18.2, part (bXitJ.
(cl) The cooling water needed, which is the same in all cases, is, from Eq.
(18.33),
mw ~ 7960 x 690 ~ 366,160 kgjh
40 -25
The density of water at 25°C (77°F), from Appendix 14, is 62.241b/ft', or
62.24 x 16.018 ~ 996.3 kg/m'. The water requirement is 366,160/996.3 ~ 367.5 m'/h.
The use of cold feed, case (il), requires the smaIlest number of plates but the
greatest amount of reboiler steam. The total energy requirement for the reboiler
and the preheater is about the same for all three cases. The reasons for preheating
the feed, in most cases, are to keep the vapor flow rate about the same in both
TABLE 18.2
Solution to Example 18.2, part (c)
Reboiler steam mso Number of
Case q kg/h ideal plates
(i) 1.0 10,520 11
(ii) 1.37 12,500 10
(iii) 0.333 6,960 12
DISTILLATION 545
5.
Feed line
I'IGURE 18.18
Example 18.2, part (b)(iU).
sections of the column and to make use of the energy in a hot-liquid stream such
as the bottom product.
MINIMUM NUMBER OF PLATES. Since the slope of the rectifying line is
RD/(RD + 1), the slope increases as the reflux ratio increases, until, when RD is
infinite, V = L and the slope is 1. The operating lines then both coincide
with the diagonal. This condition is called total reflux. At total reflux the
number of plates is a minimum, but the rates of feed and of both the overhead
and bottom products are zero. Total reflux represents one limiting case in
the operation of fractionating columns. The minimum number of plates required
for a given separation may be found by constructing steps on an x-y diagram
between compositions x D and x B using the 45' line as the operating line for both
sections of the column. Since there is no feed in a column operating under total
reflux, there is no discontinuity between the upper and lower sections.
For the special case of ideal mixtures, a simple method is available for
calculating the value of N min from the terminal concentrations X B and X D •
This is based on the relative volatility of the two components a AB, which is
defined in terms of the equilibrium concentrations
Ci. AB = YocA""",/X-,A=, (18.34)
YBe!xne
546 MASS TRANSFER AND ITS APPLICATIONS
An ideal mixture follows Raoult's law, and the relative volatility is the ratio of
the vapor pressures. Thus
PA
YA=-
P
PB
YB=p
YA/XA P~/P p~
IX AB = - - = - - = - (18.35)
YB/XB P~/P p~
The ratio P~/PB does not change much over the range of temperatures encountered
in a typical column, so the relative volatility is taken as constant in the following
derivation.
For a binary system YA/YB and XA/X B may be replaced by YA/(l - YA)
and x A /(l - x A ), so Eq. (18.34) can be written for plate 11 + 1 as
Yn+l Xn+ 1
= IXAB (18.36)
l-YII+l l-xlI + 1
Since at total reflux D = 0 and L/V = 1, y,+ 1 = x,. See Eq. (18.13), and note
that the operating line is the 45' line; this leads t,o
(18.37)
At the top of the column, if a total condenser is used, y, = XD, so Eq. (18.36)
becomes
(18.38)
Writing Eq. (18.37) for a succession of n plates gives
(18.39)
If Eq. (18.38) and all the equations in the set of Eqs. (18.39) are multiplied
together and all the intermediate terms canceled,
(18.40)
DISTILLATION 547
To reach the bottom discharge from the column, Nm,o plates and a reboiler
are needed, and Eq. (18.40) gives
~ = (a AB)Nmin+l ~
1 - Xn 1 - XB
Solving the equation for N m'o by logarithms gives
N m'o = In [xn(l - XB)/XB(l - xn)J 1 (18.41)
In IXAB
Equation (18.41) is the Fenske equation, which applies when IJ(AB is constant.
If the change in the value of IJ(AB from the bottom of the column to the top is
moderate, a geometric mean of the extreme values is recommended for IXAB'
MINIMUM REFLUX. At any reflux less than total, the number of plates needed
for a given separation is larger than at total reflux and increases continuously as
the reflux ratio is decreased. As the ratio becomes smaller, the number of plates
becomes very large, and at a definite minimum, called the minimum reflux ratio,
the number of plates becomes infinite. All actual columns producing a finite
amount of desired top and bottom products must operate at a reflux ratio between
the minimum, at which the number of plates is infinity, and infinity, at which the
number of plates is a minimum. If L"/D is the operating reflux ratio and (L"/D)m'o
the minimum reflux ratio,
(-L")
D min
L"D
<-<00 (18.42)
The minimum reflux ratio can be found by foHowing the movement of the
operating lines as the reflux is reduced. In Fig. 18.19 both operating lines coincide
with the diagonal ajb at total reflux. For an actual operation lines ae and eb are
typical operating lines. As the reflux is further reduced, the intersection of the
operating lines moves along the feed line toward the equilibrium curve, the area
on the diagram available for steps shrinks, and the number of steps increases.
When either one or both of the operating lines touch the equilibrium curve, the
number of steps necessary to cross the point of contact becomes infinite. The reflux
ratio corresponding to this situation is, by definition, the minimum reflux ratio.
For the normal type of equilibrium curve, which is concave downward
throughout its length, the point of contact, at minimum reflux, of the operating
and equilibrium lines is at the intersection of the feed line with the equilibrium
curve, as shown by lines ad and db in Fig. 18.19. A further decrease in reflux brings
the intersection of the operating lines outside of the equilibrium curve, as shown
by lines age and cb. Then even an infinite number of plates cannot pass point g,
and the reflux ratio for this condition is less than the minimum.
The slope of operating line adin Fig. 18.19 is such that the line passes through
the points (x', y') and (xn, x n ), where x' and y' are the coordinates of the intersection
of the feed line and the equilibrium curve. Let the minimum reflux ratio be Rnm.
548 MASS TRANSFER AND ITS APPLICATIONS
o
I
I
I
I
I
y' ------------ I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
'B '0
FIGURE 18.19
Minimum reflux ratio.
Then
R Dm XD - y'
R Dm +1 XD - x'
or
XD - y'
R Dm =-,--, (18.43)
y -x
Equation (18.43) cannot be applied to all systems. Thus, if the equilibrium
curve has a concavity upward, e.g., the curve for ethanol and water shown in Fig.
18.20, it is clear that the rectifying line first touches the equilibrium curve between
abscissas X F and XD and line ac corresponds to minimum reflux. Operating lirte
ab is drawn for a reflux less than the minimum, even though it does intersect the
feed line below point (x', y'). In such a situation the minimum reflux ratio must
be computed from the slope of the operating line ac that is tang,nt to the
equilibrium curve.
INVARIANT ZONE. At minimum reflux ratio an acute angle is formed at the
intersection of an operating line and the equilibrium curve, as shown at point d
DISTILLATION 549
1.00
0.90
1/
a:
o
~0.80
,Va I
'"
;;; 0.70
.
:? -.7 I
I
o-'
~
~
/ /
: I
is 0.60 e-
::l
<l
1---
yl
/' 7 //
,/
1/ : I
zO.50 1/
V
o
>=
~ 0.40
I
er'
I
I
/
a:
LL
w 0.30 I I
I V
~
-'
o
:;;
" 0.20 :
0.10
1/ ,I
,
I
/
o 0.20
: XF=X'
0.40 0.60 0.80
I'D
1.00
x, MOLE FRACTION ALCOHOL IN LIQUID
FIGURE 18.20
Equilibrium diagram (system ethanol~water).
in Fig. 18.19 or at the point of tangency in Fig. 18.20. In each angle an infinite
number of steps is called for, representing an infinite number of ideal plates, in
all of which there is no change in either liquid or vapor concentrations from plate
to plate, so X n - 1 = X" and Yn+ 1 = Yn' The tenn invariant zone is used to describe
these infinite sets of plates. A more descriptive term, pinch point, also is used.
With a normal equilibrium curve it is seen from Fig. 18.19 that at minimum
reflux ratio the intersection of the q line and the equilibrium curve gives the
concentrations of liquid and vapor at the feed plate (and at an infinite number of
plates on either side of that plate). So an invariant zone forms at the bottom of
the rectifying section and a second one at the top of the stripping section. The
two zones differ only in that the liquid-vapor ratio is LjV in one and Llv in the
other.
OPTIMUM REFLUX RATIO. As the reflux ratio is increased from the minimum;
the number of plates decreases, rapidly at first and then more and more slowly
until, at total reflux, the number of plates is a minimum. It will be shown later
that the cross-sectional area of a column usually is approximately proportional
to the flow rate of vapor. As the reflux ratio increases, both V and L increase for
a given production, and a point is reached where the increase in column diameter
is more rapid than the decrease in the number of plates. The cost of the unit is
550 MASS TRANSFER AND ITS APPLICATIONS
Minimum reflux ratio
'/
I
I
I
I
I
I
I
I
t I
I heating and
I cooling
I
I
I
I
I
I c
b
I
FIGURE IS.21
Reflux ratio ----+- Optimum reflux ratio.
roughly proportional to the total plate area, that is, the number of plates times the
cross-sectional area of the column, so the fixed charges for the column first decrease
and then increase with reflux ratio. The cost of the heat exchange equipment-the
reboiler and condenser-increases steadily with reflux ratio. This cost may be a
small part of the total at low reflux ratios, but at high reflux ratios it becomes
significant and contributes to the upturn in the curve for fixed charges (line abe
in Fig. 18.21).
The reflux is made by supplying heat at the reboiler and withdrawing it at
the condenser. The costs of both heating and cooling increase with reflux, as shown
by curve de in Fig. 18.21. The total cost of operation is the sum of the fixed charges
and the cost of heating and cooling, as shown by curve fgh. Curve fgh has a
minimum at a definite reflux ratio not much greater than the minimum reflux.
This is the point of most economical operation, and this reflux is called the
optimum reflux ratio; it is usually in the range of 1.1 to 1.5 times the minimum
reflux ratio. Actually, most plants are operated at reflux ratios somewhat above
the optimum. The total cost is not very sensitive to reflux ratio in this range, and
better operating flexibility is obtained if a reflux greater than the optimum is
used·t
Example 18.3. What is (a) the minimum reflux ratio and (b) the minimum number
of ideal plates for cases (b)(l), (b)(b), and (b)(iil) of Example 18.2?
t Because of deviations in the column from constant molal overflow, the true minimum reflux
ratio may be larger than that predicted from the McCabe-Thiele diagram. (See p. 559.)
DISTILLATION 551
TABLE 18.3
Case x' y' RDm
(b)(i) 0.440 0.658 1.45
(b)(ii) 0.521 0.730 1.17
(b)(iii) 0.300 0.513 2.16
Solution
(a) For minimum reflux ratio use Eq. (18.43). Here XD = 0.974. The results are
given in Table 18.3.
(b) For minimum number of plates, the reflux ratio is infinite, the operating
lines coinicide with the diagonal, and there are no differences between the three cases.
The plot is given in Fig. 18.22. A reboiler and eight ideal plates are needed.
NEARLY PURE PRODUCTS. When either the bottom or overhead product is
nearly pure, a single diagram covering the entire range of concentrations is
impractical as the steps near x = 0 and x = 1 become small. Auxilliary diagrams
for the ends of the construction range may be prepared, on a large scale, so that
the individual steps are large enough to be drawn. In practice, however, the
Xs
X--~)
FIGURE 18.22
Example 18.3, part (b).
552 MASS TRANSFER AND ITS APPLICATIONS
calculations are usually done by computer, and the scale may easily be expanded
to cover the desired range. (With computer calculations, of course, it is not
necessary to display the McCabe-Thiele diagram to find the number of plates
needed, but it is often helpful to do so in order to visualize the solution to the
problem.)
Another method of treating nearly pure products is based on the principle
that Raoult's law applies to the major component and Henry's law to the minor
component at each end of the equilibrium curve. In these regions, therefore, both
the equilibrium and the operating lines are straight, so Eq. (17.27) can be used,
and no graphical constuction is required. The same equation may be used
anywhere in the concentration range where both the operating and equilibrium
lines are straight or nearly so.
Example 18.4. A mixture of 2 mole percent ethanol and 98 mole percent water is to
be stripped in a plate column to a bottom product containing not more than 0.01
mole percent ethano1. Steam, admitted through an open coil in the liquid on the
bottom plate, is to be used as a source of vapor. The feed is at its boiling point. The
steam flow is to be 0.2 mol per mole of feed. For dilute ethanol-water solutions, the
equilibrium line is straight and is given by Ye = 9.0xe' How many ideal plates are
needed?
Solution
Since both equilibrium and operating lines are straight, Eq. (17.27) rather than
a graphical construction may be used. The material-balance diagram is shown in Fig.
18.23. No reboiler is needed, as the steam enters as a vapor. Also, the liquid flow in
L:/ ~ V:0.2 FIGURE 18.23
xb
:0000/
'
-IL.::o::=:J<---v:o
/b Material-balance diagram for Example 18.4.
DISTILLATION 553
the tower equals the feed entering the column. By conditions of the problem
Yb =0 XII = 0.02
x, = 0.0001 m = 9.0 Y: = 9.0 x 0.02 = 0.18
Yi = 9.0 x 0.0001 = 0.0009
To use Eq. (17.27), YII' the concentration of the vapor leaving the column, is
needed. This is found by an overall ethanol balance
V(y. - y,) = L(x. - x,) 0.2(y. - 0) = 1(0.02 - 0.0001)
from which y. = 0.0995. Substituting into Eq. (17-27) gives
N = In [(0.0995 - 0.18)/(0 - 0.0009)]
In [(0.0009 - 0.18)/(0 - 0.0995)]
In 89.4
= - - = 7.6 ideal plates
In 1.8
Enthalpy Balances for Fractionating Colnmns
The actual variations in the V and L streams in a distillation column depend
on the enthalpies of the vapor and liquid mixtures. The limitations imposed
by assuming constant molal overflow can be removed by enthalpy balances
used in conjunction with material balances and phase equilibria. The enthalpy
data may be available from an enthalpy-concentration diagram, such as the one
in Fig. 18.24. Since benzene-toluene solutions are ideal, this diagram was con-
structed using molar average heat capacities and heats of vaporization. Some
10,000
8.000
0 6 ,000
E
- -- - r--
Vapor
!'!:
11
::r:' 4,000
2,00 0
r-- Liquid
FIGURE 18.24
o 1.0 Enthalpy-concentration diagram
o 0.2 0.4 0.6 0.8
xory for benzene-toluene at 1 atm.
554 MASS TRANSFER AND ITS APPLICATIONS
sample calculations are given in Example IS.5. The reference temperature was
taken as SO'C, the boiling point of benzene, to simplify further calculations.
The enthalpy values in Fig. IS.24 are for liquid mixtures at the bubble
point and for vapor mixtures at the dew point, both at 1.0 atm. Thus each
point on the line is for a different temperature between 110.6 and SO'C, but
the temperature for x = 0.5 is not the same as for y = 0.5, as shown by the
difference between bubble and dew points in Fig. IS.3. The slight curvature
in the enthalpy-concentration graphs is due to the nonlinear change in bubble
point and dew point with mole fraction benzene.
Consider an overall enthalpy balance for the system shown in Fig. IS.8.
In addition to the quantities shown in the figure, let H F, Hv, and HB represent
the specific enthalpies of the feed, overhead product, and bottom product,
respectively, all in energy per mole. The enthalpy balance for the entire system is
(IS.44)
When the feed is liquid at the boiling point, HF is between Hv and H B, and
the terms FHF and (DHv + BH B) nearly cancel, making the heat supplied at the
reboiler q, about equal to that removed in the condenser q,.
For given feed and product streams, only one of heat effects, q, or q" is
independent and subject to choice by the designer or operator. In designing a
column, q, is usually chosen to correspond to the desired reflux ratio and moles
of overhead vapor. Then q, can be calculated from Eq. (IS.44). However, in
operating a column, q, is often varied to change the vapor flow rate and reflux
ratio, and changes in q, then follow.
ENTHALPY BALANCES IN RECTIFYING AND STRIPPING SECTIONS. Refer-
ring again to Fig. IS.S, let H y ., + 1 be the specific enthalpy of vapor rising from
plate n + 1 and H x ., the specific enthalpy of liquid leaving plate n. The enthalpy
balance for the section within control surface I is
~+lHy.n+l = LnHx.n + DHD + qc (IS.45)
An alternate form is obtained by eliminating q, using the relation
q, = Y"H y., - RHv - DHv (IS.46)
~+lHy.n+l = LnHx.n + YaHy.a - RHD (IS.47)
Equation (IS.47) could also have been derived by making a balance over the
top part of the column without including the condenser. Note that the reflux is
assumed to be at the same temperature as the distillate product, so HR = Hv.
In using Eq. (IS.47), the terms Y"Hy., and RHv are known, and the terms
v,,+1 and L, are to be determined. If a value x, is chosen, H x ., is obtained from
an enthalpy-concentration diagram, or it is calculated from the average specific
heat and the bubble point. The value of H y ,,+ 1 depends on y,+ l' which is not
known until the operating line has been drawn on the McCabe-Thiele diagram
or values of v" + 1 and L, specified for the operating-line equation.
DISTILLATION 555
An exact value of v" + 1 calls for a trial-and-error solution using Eq. (18.47),
the enthalpy-concentration diagram, and the following equations for the individual
and overall material balances:
(18.48)
(18.49)
However, a satisfactory value of v" + 1 can usually be obtained on the first trial by
using the flows at the top of the column L. and v" to calculate y,+ 1 from x, in
Eq. (18.48) (this corresponds to using a straight operating line based on constant
molal overflow). Then Hp+ 1 is evaluated from Y,+l and Eq. (18.47) is solved for
v" + 1 after L, is replaced by v" + 1 - D.
Only a few values of v" + 1 and L, are needed to establish a slightly curved
operating line. For a plate-by-plate calculation, the values of v" + 1 and L, would
be obtained by using the corresponding values for the previous plate, v" and L,-1'
in the calculation of y,+ 1 from Eq. (18.48).
In the stripping section of the column, the flow rates at an intermediate plate
m are calculated using an enthalpy balance for control surface II in Fig. 18.8:
Vm+lHy.m+l = LmHx.m + qr - BHB (18.50)
Lm Bx.
Ym+l =-v. xm--v. (18.51)
m+ 1 m+ 1
(18.52)
Following the same approach as before, a value of Xm is chosen and Ym+1
calculated from Eq. (18.51) using Lb and V. to approximate Lm and Vm+1. Then
Vm+1 is calculated from Eq. (18.50) using the specific enthalpies H x. m and Hy.m+1
and substituting (Vm+1 + B) for Lm.
Example 18.5. A mixture of 50 mole percent benzene and toluene is to be separated
by distillation at atmospheric pressure into products of 98 percent purity using a
reflux ratio 1.2 times the minimum value. The feed is liquid at the boiling point. Use
enthalpy balances (Table 18.4) to calculate the flows of liquid and vapor at the top,
middle, and bottom of the column, and compare these values with those based on
TABLE 18.4
Data for Example 18.5
Specific heat at constant
pressure, callg mol-cC
Enthalpy of vaporization, Boiling point,
Component callg mol Liquid Vapor °c
Benzene 7360 33 23 80.1
Toluene 7960 40 33 110.6
556 MASS TRANSFER AND ITS APPLICATIONS
constant molal overflow. Estimate the difference in the number of theoretical plates
for the methods.
Solution
XF = 0.50 XD = 0.98 XB = 0.02
From Eq. (18.5)
_0_.5_-_0_.0_2 = 0.50
0.98 - 0.02
Basis: F = 100mo! D = 50 mol B = 50 mol
From Eq. (18.3)
XD- y' L
R Dm =-,--, based on - = const
y -x V
For this feed, q = 1.0 and x' = x F = 0.50
From the equilibrium curve, y' = 0.72, and
0.98 - 0.72
---=1.18
0.72 - 0.50
RD = 1.2(1.18) = 1.42
R = 1.42(50) = 71 mol
At top of column
VI = R +D= 71 + 50 = 121 mol
Enthalpy balance Choose 80°C as a reference temperature so that the reflux and
distillate product at SO°C have zero enthalpy. For benzene vapor, the enthalpy is the
heat of vaporization at 80°C plus the sensible heat of the vapor:
H, = 7360 + 23(T - 80) calfmo!
For toluene vapor, the enthalpy of vaporization at SO°C is calculated from the
value at the boiling point:
I1H, = I1H,.b + (C p.1 Cp.XI; - T)
For toluene at T = 80'e, I1H, = 7960 + (40 - 33)(30.6) = 8174 calfmo!. For toluene
at T'e, H, = 8174 + 33(T - 80).
From Eq. (18.47) with HD = 0 and v., = VI
Vn+ 1Hy,n+l = LnHx.n + VI R y. 1
Assume the top plate temperature is about 80°C to evaluate Hy • 1 · Since Yl =
Xo = 0.98,
H y = 0.98(7360) + 0.02(8174) = 7376 calfmol
Pick x, = 0.5, and get 'I; = 92'e from Fig. 18.3. Then
H x ., = [(0.5 x 33) + (0.5 x 40)](92 - 80)
= 438 cal/mo!
DISTILLATION 557
To estimate Yn+l, use the operating line for constant molal overflow (dashed
line in Fig. 18.25):
Yn+l ~ 0.70 7; '" 9)oC from Fig. 18.3
H, .• +l = 0.7[7360 + (23 x 13)] + 0.3[8174 + (33 x 13)]
= 7942 cal/mol
Since L. = v" + 1 - D, from Eq. (18.47)
v" + 1(7942) = (v" + 1 - 50)(438) + 121(7376)
870,596
v" + 1 = --- = 116.0 mol L. = 66.0 mol
7504
From Eq. (18.48)
66 50(0.98)
Y.+l =-(0.50)+--=0.707
116 116
This is close enough to 0.70.
A similar calculation for Xn = 0.7 gives
v,,+l = 118 L.= 68 Y.+ 1 = 0.818
The operating line, shown in Fig. 18.25 as a solid line, is almost straight but lies
above the operating line based on constant molal overflow (dashed line).
To get the vapor rate at the reboiler, an overall balance is made to get qr:
FHF + q, = DHD + BHB + q,
For feed at 92°C,
H F = [(0.5 x 33) + (0.5 x 40)](92 - 80)
= 438 cal/mol
1.o,---,----.-----,----,--"'"
FIGURE 18.25
McCabe~Thiele diagram for
Example 18.5 benzene~toluene
distillation: ~ ~ ~ w,
w based
_
on constant molal overflow;
~--..fo---,!-.----,&---n'o--...,,1.0 - - , based on enthalpy bal~
x ance.
558 MASS TRANSFER AND ITS APPLICATIONS
For bottoms at 111 "C,
HB ~ [(0.02 x 33) + (0.98 x 40)](111 - 80)
~ 1236 caIJmol
q, ~ 121 x 7376 ~ 892,496 cat
q, ~ (50 x 0) + (50 x 1236) + 892,496 - (100 x 438)
~ 910,496 cat
An enthalpy balance around the reboiler is then made:
qr + LbHx,b = ~Hy,b + BHb
The vapor from the reboiler is about 5 percent benzene at 111°C, and
H y ., ~ 0.05[7360 + (23 x 31)] + 0.95[8174 + (33 x 31)]
~ 9141 caIJmol
The liquid to the reboiler is about 4 percent benzene at 110°C, and
H x ., ~ 0.04(33 x 30) + 0.96(40 x 30) ~ 1192 caIJmol
Since L, ~ V, + 50, and Hr., - H •. , ~ 9141 - 1192 ~ 7949 caIJmol,
V. _ 910,496 + 50(1192) 50(1236)
114.3
, - 7949
L, ~ 114.3 + 50 ~ 164.3
Approximately the same value for Jt;, could have been obtained from qr and
the heat of vaporization of toluene:
q, 910,496 ..
v,,,,-~---~ 114.4
AH, 7960
Use Eq. (18.50) to get an intermediate value of Vm+ 1:
For xm = 0.4, Ym+l = 0.55 (from the operating line in Fig. 18.25); also
Tm ~ 95"C
H y• m + 1 ~ 0.55[7360 + 23(97 - 80)] + 0.45[8174 + 33(17)] ~ 8194 caIJmol
H •. m ~ [(0.4 x 33) + (0.6 x 40)](95 - 80)
~ 558 caIJmol
From Eq. (18.50),
8194Vm + 1 ~ 558(Vm+l + 50) + 910,496 - (1236 x 50)
Vm + 1 = 114.8 mol
Lm ~ 164.8 mol
DISTILLATION 559
Note that in this case there is almost no change in L and V in the stripping section,
in contrast to the 7 percent decrease in L in the rectifying section. The lower operating
line can be drawn as a straight line to the intersection of the upper operating line
and the q line.
Counting steps, about 27 ideal stages are required for this separation, compared
to 21 based on the assumption of constant molal overflow. The difference would be
smaller if a higher reflux ratio were used. The calculations were based on 1.2 times
the nominal value of Rmin , but this really corresponds to about 1.1 times the true
minimum reflux, as can be seen from Fig. 18.25.
In Example 18.5, the molar liquid rate decreased about 7 percent in going
from the top plate to the feed plate, mainly because of the higher molar heat of
vaporization of toluene. The terms for the change in sensible heat of the liquid
and vapor streams nearly cancel, since the liquid has a higher heat capacity but
a lower flow rate than the vapor. In the stripping section of the column, there was
almost no change in liquid rate, although the vapor composition changed even
more than in the rectifying section. The liquid flow rate in the stripping section
is always greater than the vapor rate, and in Example 18.5, the product of flow
rate and heat capacity for the liquid was 1.73 times that for the vapor. Only part
of the energy needed to heat the liquid from the feed plate temperature to the
reboiler temperature could be supplied by cooling the vapor, and the rest came
from condensation of vapor in the column. The difference between the heat of
condensation of toluene and the heat of vaporization of benzene was nearly used
up in providing the extra energy needed to heat the liquid, so that there was only
a slight increase in vapor flow from the reboiler to the feed plate.
Similar changes in Land Vare likely to be observed for other ideal mixtures.
The more volatile component has a lower molal heat of vaporization, since the
heat of vaporization is roughly proportional to the normal boiling point (Trouton's
rule). The change in V will be greatest in the upper section of the column, where
L is less than V, and may be ahnost zero in the lower secttion, where LjV> 1.0.
The percentage change in (LjV) will be smaller than the change in L or V, but
the slight upward shift of the operating lines may be important when operating
close to the minimum reflux ratio, as was the (:ase in Example 18.5. For operation
at twice the minimum reflux ratio or greater, the effect of operating-line curvature
would be very small.
The slope of a straight operating line is LjV for that section of the column,
but the local slope of a curved operating line is not equal to the local value of
LjV. Starting with the equation for the rectifying section, Eq. (18.48), the following
equations can be obtained by replacing first L. and then v" + 1 with v,,+1 - D and
L.+D:
v,,+lY.+l = (v" + 1 - D)x. + DXn
or v,,+l(Y.+l - x.) = D(xn - x.) (18.53)
(L. + D)Y.+l = L.x. + DXn
or L.(Y.+l - x.) = D(XD - Y.+l) (18.54)
560 MASS TRANSFER AND ITS APPLICATIONS
Dividing Eq. (18.54) by Eq. (18.53),
~=XD-Yn+l (18.55)
Vn + 1 XD - Xn
Thus L,/v,,+ 1 is the slope of the chord connecting points (XD, XD) and (y,+ l' X,).
A similar derivation for the stripping section shows that
~=Ym+l-XB
(18.56)
Vm + 1 Xm - X B
DESIGN OF SIEVE-PLATE COLUMNS
To translate ideal plates into actual plates, a correction for the efficiency of the
plates must be applied. There are other important decisions, some at least as
important as fixing the number of plates, that must be made before a design is
complete. A mistake in these decisions results in poor fractionation, lower-than-
desired capacity, poor operating flexibility, and with extreme errors, an inoperative
column. Correcting such errors after a plant has been built can be costly. Since
many variables that influence plate efficiency depend on the design of the
individual plates, the fundamentals of plate design are discussed first.
The extent and variety of rectifying columns and their applications are
enOrmous. The largest units are usually in the petroleum industry, but large and
very complicated distillation plants are encountered in fractionating solvents, in
treating liquefied air, and in general chemical processing. Tower diameters may
range from 1 ft (0.3 m) to more than 30 ft (9 m) and the number of plates from a
few to about a hundred. Plate spacings may vary from 6 in. or less to several feet.
Formerly bubble-cap plates were most common; today most columns contain
sieve trays or lift-valve plates. Many types of liquid distribution are specified.
Columns may operate at high pressures or low, from temperatures of liquid gases
up to 900°C reached in the recification of sodium and potassium vapors. The
materials distilled can vary greatly in viscosity, diffusivity, corrosive nature,
tendency to foam, and complexity of composition. Plate towers are as useful in
absorption as in rectification, and the fundamentals of plate design apply to both
operations.
Designing fractionating columns, especially large units and those for unusual
applications, is best done by experts. Although the number of ideal plates and the
heat requirements can be computed quite accurately without much previous
experience, other design factors are not precisely calculable, and a number of
equally sound designs can be found for the same problem. In common with most
engineering activities, sound design of fractionating columns relies on a few
principles, on a number of empirical correlations (which are in a constant state of
revision), and much experience and judgment.
The following discussion is limited to the usual type of column, equipped
with sieve plates, operating at pressures not far from atmospheric, and treating
mixtures having ordinary properties.
DISTILLATION 561
NORMAL OPERAnON OF SIEVE PLATE. A sieve plate is designed to bring a
rising stream of vapor into intimate contact with a descending stream of liquid.
The liquid flows across the plate and passes over a weir to a downcomer leading
to the plate below. The flow pattern on each plate is therefore crossflow rather
than countercurrent flow, but the column as a whole is still considered to have
countercurrent flow of liquid and vapor. The fact that there is crossflow of liquid
on the plate is important in analyzing the hydraulic behavior of the column and
in predicting the plate efficiency.
Figure 18.26 shows a plate in a sieve-tray column in normal operation. The
downcomers are the segment-shaped regions between the curved wall of the
column and the straight chord weir. Each downcomer usually occupies 10 to 15
percent of the column cross section, leaving 70 to 80 percent of the column area
for bubbling or contacting. In small columns the downcomer may be a pipe welded
to the plate and projecting up above the plate to form a circular weir. For very
large columns, additional downcomers may be provided at the middle of the plate
to decrease the length of the liquid flow path. In some cases an underflow weir
or tray inlet weir is installed as shown in Fig. 18.26 to improve the liquid
distribution and to prevent vapor bubbles from entering the down corner.
The vapor passes through the perforated region of the plate, which occupies
most of the space between downcomers. The holes are usually 5 to 12 mm (10 to
1in.) in size and arranged in a triangular pattern. One or two rows of holes
may be omitted near the overflow weir to permit some degassing of the liquid
before it passes over the weir. Some holes may also be omitted near the liquid
inlet to keep vapor bubbles out of the downcomer. Under normal conditions, the
vapor velocity is high enough to create a frothy mixture of liquid and vapor that
has a large surface area for mass transfer. The average density of the froth may
r
oowncomer Pressure'" Pn_l
~~
~"-r-.- ~
/ /" .---..-.-... -.. ~ Weir
:=~--~
1----1.- --, _-y-,ri~Platen - 1
Pressure'" Pn r- 0
;0,,0 0 "
0 11 Zc
~~
0
g
£"C
/~---
_ --.. Froth
~
r--
-y--
-
::::.......
0 0
"I>
o.
Z hd
+
T-ht,L
Rjhow!K~
7
0
"I 2"lh w + h 0"' I
'f"
1
h w '{ Und"flow we;, - I ,
Plate n
Pressure'" Pn+l
FIGURE 18.26
Nonna! operation of sieve plate.
562 MASS TRANSFER AND ITS APPLlCA nONS
be as low as 0.2 of the liquid density, and the froth height is then several times
the value corresponding to the amount of liquid actually on the plate.
VAPOR PRESSURE DROP. The flow of vapor through the holes and the liquid
on the plate requires a difference in pressure. The pressure drop across a single
plate is usually 50 to 70 mm H 2 0, and the pressure drop over a 40-plate column
is then about 2 to 3 m H 2 0. The pressure required is automatically developed by
the reboiler, which generates vapor at a pressure sufficient to overcome the
pressure drop in the column and condenser. The overall pressure drop is calculated
to determine the pressure and temperature in the reboiler, and the pressure drop
per plate must be checked to make sure the plate will operate properly, without
weeping or flooding.
The pressure drop across the plate can be divided into two parts, the friction
loss in the holes and the pressure drop due to the hold-up of liquid on the plate.
The pressure drop is usually given as an equivalent head in millimeters or inches
of liquid:
h, = lId + hI (18.57)
where h, = total pressure drop per plate, mm of liquid
hd = friction loss for dry plate, mm of liquid
hI = equivalent head of liquid on plate, mm of liquid
The pressure drop through the holes can be predicted from a modification
of Eq. (8.37) for flow through an orifice:
hd = (~~)(2:;J = 51.0(~~)(;:) (18.58)
where U o = vapor velocity through holes, m/s
Pv = vapor density
PL = liquid density
Co = orifice coefficient
Equation (18.58) gives hd in millimeters of liquid. The coefficient comes from
1000 mm/m = 51.0
2 x 9.8 m/s 2
If Uo is expressed in feet per second and hd in inches, the coefficient becomes
12
0.186
2 x 32.2
Orifice coefficient Co depends on the fraction open area (the ratio of the total
cross-sectional area of the holes to the column cross section) and on the ratio of
tray thickness to hole diameter, as shown in Fig. 18.27. The increase in Co with
open area is similar to the change in Co for single orifices as the ratio of orifice
diameter to pipe diameter increases. The coefficients vary with plate thickness, but
for most sieve plates the thickness is only 0.1 to 0.3 times the hole size. For these
DISTILLATION 563
0.90
cf
,.:
z
w
u 0.80
u.
u.
w
0
U
w
'"
c:
<>:
:I:
u 0.70
!!2
Cl
0.60,'ne-_ _ _ _--.""".---_ _ _ _-"i;,,-_ _ _ _""""'"
0.05 0.10 0.15 0.20
Hole area/Column area
FIGURE 18.27
Discharge coefficients for vapor flow, sieve trays. [I. Liebson, R. E. Kelley, and L. A. Bullington, Petrol.
Refin., 36(2):127,1957; 36(3):288,1957.]
thicknesses and the typical fraction open area of 0.08 to 0.10, the value of Co is
0.66 to 0.72.
The amount of liquid on the plate increases with the weir height and with
the flow rate of liquid, but it decreases slightly with increasing vapor flow rate,
because this decreases the density of the froth. The liquid holdup also depends on
the physical properties of liquid and vapor, and only approximate methods of
predicting the holdup are available. A simple method of estimating h, uses the
weir height hw, the calculated height of clear liquid over the weir h"" and
an empirical correlation factor [3:
(18.59)
The height over the weir is calculated from a form of the Francis equation,
which for a straight segmental weir is
qL)2/3
how = 43.4 ( - (18.60)
Lw
where how = height, mm
qL = flow rate of clear liquid, m 3(min
Lw = length of weir, m
564 MASS TRANSFER AND ITS APPLICATIONS
If qdLw is in gallons per minute per inch, a coefficient of 0.48 in Eq. (18.60)
gives how in inches.
The actual height of froth over the weir is greater than h,w, since the vapor
has only partially separated from the liquid, making the volumetric flow rate at
the weir greater than that of the liquid alone. However, the actual height over the
weir is not needed in estimating hi' since the effect of froth density is includ~d in
the correlation factor {3. For typical weir heights of 25 to 50 rna, (1 to 2 in.) and
the normal range of vapor velocities, values of {3 are 0.4 to 0.7. The change in {3
with flow rates of vapor and liquid is complex, and there is no generally accepted
correlation. For design purposes, a value of {3 = 0.6 can be used in Eq. (18.59),
and some error can be tolerated since most of the pressure drop at high vapor
flows is due to the holes.
When h,w is small relative to h,,, Eq. (18.59) shows that hi may be less than
hw, which means less liquid on the tray than corresponds to the weir height. This
is a fairly common situation.
DOWNCOMER LEVEL. The level of liquid in the downcomer must be con,
siderably greater than that on the plate because of the pressure drop across the
plate. Referring to Fig. 18.26, note that the top of the downcomer for plate 11 is
at the same pressure as plate 11 - 1. Therefore, the equivalent level in the
down corner must exceed that on the plate by an amount h, plus any friction losses
in the liquid hl . L • The total height of clear liquid Z, is
Z, = {3(h" + h,w) + h, + hI.L (18.61)
Using Eqs. (13.57) and (18.59) for h,
Z, = 2{3(h" + h,w) + hd + hl . L (18.62)
The contributions to Z, are shown in Fig. 18.26. Note that an increase in hw
or h,w comes in twice, since it increases the level of liquid on the plate and increases
the pressure drop for vapor flow. The term for hI.L is usually small, corresponding
to one to two velocity heads based on the liquid velocity under the bottom of the
downcomer.
The actual level of aerated liquid Z in the downcomer is greater than Z,
because of the entrained bubbles. If the average volume fraction liquid is <Pd, the
level is
(18.63)
When the height of aerated liquid becomes as great as or greater than the plate
spacing, the flow over the weir on the next plate is hindered, and the column
becomes flooded. For conservative design, a value of <Pd = 0.5 is assumed, and the
plate spacing and operating conditions are chosen so that Z is less than the plate
spacing.
DISTILLAT10N 565
OPERATING LIMITS FOR SIEVE TRAYS. At low vapor velocities, the pressure
drop is not great enough to prevent liquid from flowing down through some of
the holes. This condition is called weeping and is more likely to occur if there is
a slight gradient in liquid head across the plate. With such a gradient, vapor will
tend to flow through the region where there is less liquid and therefore less
resistance to flow, and liquid will flow through the section where the depth is
greatest. Weeping decreases the plate efficiency, since some liquid passes to the
next plate without contacting the vapor. The lower limit of operation could be
extended by using smaller holes or a lower fraction open area, but these changes
would increase the pressure drop and reduce the maximum flow rate. A sieve tray
can usually be operated over a three- to fourfold range of flow rates between the
weeping and flooding points. If a greater range is desired, other types of plates
such as valve trays can be used. (See page 576.)
The upper limit of the velocity in a sieve-tray column is determined by the
flooding point or by the velocity at which entrainment becomes excessive. Flooding
occurs when the liquid in the downcomer backs up to the next plate, and this is
determined mainly by the pressure drop across the plate and the plate spacing.
Near the flooding point, most of the pressure drop comes from the term hd in Eq.
(18.57), so the total pressure drop varies approximately with the square of the
velocity and the ratio of vapor and liquid densities. A long-established empirical
correlation consistent with the above reasoning states that the maximum permis-
sible vapor velocity is proportional to J(PL - Pvl/pv' Thus
u, = K;JPL - Pv (18.64)
Pv
where u, = maximum permissible velocity based on bubbling or active area
K~ = empirical coefficient
Coefficient K', has been evaluated from plant data and correlated with operating
variables such as plate spacing and flow rates. A correlation 2 that includes the
effect of surface tension is given below [Eq. 18.65]; values of K, for use with this
equation are shown in Fig. 18.28. A value of (5 = 20 dyn/cm is typical of organic
liquids, and the correlation shows that the flooding velocity with such liquids is
about 20 percent lower than that for water, for which (5 is about 72 dyn/cm. The
correlation is not recommended for liquids of very low surface tension or for
systems that foam easily:
Uc
=
Kv f¥xL
- Pv (-,,-)0.2 (18.65)
Pv 20
The term PL - Pv appears in Eqs. (18.64) and (18.65) because it was once
thought that entrainment of liquid drops determined the limiting vapor velocity,
and the setting velocity of drops depends on this density difference. The term
PL - p, is practically the same as PL in most cases; the effect of vapor density is
reflected primarily in the terms involving jP;" which show that the flooding
566 MASS TRANSFER AND ITS APPLICATIONS
o. 7
O. 6 , ,
Plate spacing ~
O. 5
,-36 2~-
O. 4
-- --,
-- --
24 in.
O. 3 ,IS in.
•o
>
"-
o. 2
-- --
112 ir.
9 in.
6 in.
--- ~
"
-----::: ;:c:------
"-
'-,-
I
"- " o. 1
I--
S;: ,',- """
"
1
11
~>.
0.0 7
0.0 6
'-'- ~
0.05 ....0-."
.-
'~
0.0 4
0.0 3
0.01 0.02 0.03 0.05 0.07 0.1 0.2 0.3 0.5 0.7 1.0 2.0
FIGURE 18.28
Values of Kv at flooding conditions for sieve plates; LI V = ratio of mass flow rate of liquid to vapor,
u is in feet per second, and d is in dynes per centimeter. [J. R. Fair, Petrol. Chem. Eng., 33(10):45,
1961. Courtesy Petroleum Engineer.]
velocity is appreciably lower in columns operated at high pressure than those at
atmospheric pressure or below.
Example 18.6. A sieve-plate column operating at atmospheric pressure is to produce
nearly pure methanol from an aqueous feed containing 40 mole percent methanol.
The distillate product rate is 5800 kg/h. (a) For a refiux ratio of 3.5 and a plate
spacing of 18 in., calculate the allowable vapor velocity and the column diameter.
*
(b) Calculate the pressure drop per plate jf each sieve tray is in. thick with i-in.
holes on a i-in. triangular spacing and a weir height of 2 in. (c) What is the froth
height in the downcomer?
Solution
Physical properties ofmethanol: Molecular weight is 32, normal boiling point is 65°C,
and the density of vapor is
32 x 273
Pv= = 1.15 kg/m'
22.4 x 338
From Perry, Chemical Engineers' Handbook, 6th ed., p. 3·188, the density of liquid
methanol is 810 kg/m' at O°C and 792 kg/m' at 20°C. At 65°C, the estimated density
PL is 750 kg/m'. Lange's Handbook of Chemistry, 9th ed., 1956, p. 1650, gives
the surface tension of methanol at 20 and 100°C. By interpolation, at 65°C,
(J = 19 dyn/cm.
(a) Vapor velocity and column diameter In Fig. 18.28 the abscissa is
(pv)'/2 = -3.5 (1.15)'/2
-L - - = 3.04 X 10- 2
V PL 4.5 750
DISTILLATION 567
For 18-in. plate spacing,
Pv )112(20)0.2
Kv = 0.29 (Pv - PL
= lie - - - -
(J
Allowable vapol' velocity:
2
750 - 1.15)" (19)°.2
lie = 0.29 ( -
1.15 20
= 7.32 It/s or 2.23 m/s
Vaporflow rate:
v = D(R + 1) = 4.5D
= 5800 x 4.5 = 6.30 m'/s
3600 x 1.15
Cross-sectional area of column:
Bubbling area = 6.30/2.23 = 2.83 m 2
If the bubbling area is 0.7 of the total column area,
Column area = 2.83/0.7 = 4.04 m 2
Column diameter:
Dc= (
4 X 4.04)1 /2= 2.27 m
"
(b) Pressure drop The plate area of one unit of three holes on a triangular
i-in. pitch is ~ x i(i x }3/2) = 9}3/64 in. 2. The hole area in this section (hall a hole)
is ~ x ,,/4 X (;\)2 = ,,/128 in.'. Thus the hole area is ,,/128 x 64/9}3 = 0.1008, or
10.08 percent 01 the bubbling area.
Vapor ve/ocity through holes:
Uo = 2.23/0.1008 = 22.1 m/s
Use Eq. (18.58) lor the pressure drop through the holes. From Fig. 18.27, Co = 0.73.
Hence
51.0 X 22.12 x 1.15
lId = - - - -2: - - - - 71.7 mm methanol
0.73 x 750
Head of liquid on plate:
Weir height: IIw = 2 x 25.4 = 50.8 mm
Height of liquid above weir: Assume the downcomer area is 15 percent of the column
area on each side of the column. From Perry, 6th ed., page 1-26, the chord length for
such a segmental downcomer is 1.62 times the radius of the column, so
Lw = 1.62 x 2.23/2 = 1.81 m
568 MASS TRANSFER AND ITS APPLICATIONS
Liquid flow rale:
5800 x 4.5 3.
qL = = 0.58 m/mm
750 x 60
From Eq. (18.60),
h.w = 43.4(0.58/1.81)2/3 = 20.3 mm
From Eq. (18.59), with P= 0.6,
h, = 0.6(50.8 + 20.3) = 42.7 mm
Total height of liquid [from Eq. (18.57)]:
h, = 71.7 + 42.7 = 114.4 mm
(c) Froth height in dowllcomer Use Eq. (18.62). Estimate hi . f, = 10 mm metha-
nol. Then
Z, = (2 x 42.7) + 71.7 + 10 = 167.1 mm
From Eq. (18.63),
Z = 167.1/0.5 = 334 mm (13.2 in.)
Plate Efficiency
To translate ideal plates into actual plates, the plate efficiency must be known.
The following discussion applies to both absorption and fractionating columns.
TYPES OF PLATE EFFICIENCY. Three kinds of plate efficiency are used: (1)
overall efficiency, which concerns the entire column; (2) Murphree efficiency, which
has to do with a single plate; and (3) local efficiency, which pertains to a specific
location on a single plate.
The overall efficiency 'I.
is simple to use but is the least fundamental.
It is defined as the ratio of the number of ideal plates needed in an entire
column to the number of actual plates· For example, if six ideal plates are
called for and the overall efficiency is 60 percent, the number of actual plates
is 6/0.60 = 10.
The Murphree efficiency! 0 th, is defined by
Yn-Yn+l
~M= (18.66)
Y; - Yn+l
where y" = actual concentration of vapor leaving plate n
y .. +! = actual concentration vapor entering plate n
y; = concentration of vapor in equilibrium with liquid leaving downpipe
from plate n
The M urphree efficiency is therefore the change in vapor composition
from one plate to the next divided by the change that would have occurred
DISTILLATION 569
if the vapor leaving were in equilibrium with the liquid leaving. The liquid
leaving is generally not the same as the average liquid on the plate, and this
distinction is important in comparing local and Murphree efficiencies.
The Murphree efficiency is defined using vapor concentrations as a matter
of custom, but the measured efficiencies are rarely based on analysis of the vapor
phase because of the difficulty in getting reliable samples. Instead, samples are
taken of the liquid on the plates, and the vapor compositions are determined from
a McCabe-Thiele diagram. A plate efficiency can be defined using liquid concentra-
tions, but this is used only occasionally for desorption or stripping calculations.
Columns operated at high velocity will have significant entrainment, and this
reduces the plate efficiency, because the drops of entrained liquid are less rich in
the more volatile component than is the vapor. Although methods of allowing for
entrainment have been published,l most empirical correlations for the Murphree
efficiency are based on liquid samples from the plates, and this includes the effect
of entrainment.
The local efficiency ~' is defined by
, Y~-Y~+l
tT = I ,
(18.67)
Yen - Yn+l
where y; = concentration of vapor leaving specific location on plate 11
Y;+ 1 = concentration of vapor entering plate n at same location
y;. = concentration of vapor in equilibrium with liquid at same location
Since y; cannot be greater than y;., a local efficiency cannot be greater than 1.00,
or 100 percent.
Relation between Murphree and local efficiencies. In small columns, the liquid on
a plate is sufficiently agitated by vapor flow through the perforations for there to
be no measurable concentration gradients in the liquid as it flows across the plate.
The concentration of the liquid in the downpipe x. is that of the liquid on the
entire plate. The change from concentration x. to X.+ 1 occurs right at the exit
from the downcomer, as liquid leaving the downcomer is vigorously mixed with
the liquid on plate n + 1. Since the concentration of the liquid on the plate is
everywhere the same, so is that of the vapor from the plate and no gradients exist
in the vapor streams. A comparison of the quantities in Eqs. (18.66) and (18.67)
shows that Yn = Y;pYn+l =Y~+1> and y~ = Y~n' Then tTM = tT', and the local and
Murphree efficiencies are equal.
In larger columns, liquid mixing in the direction of flow is not complete, and
a concentration gradient does exist in the liquid on the plate. The maximum
possible variation is from a concentration of x._ 1 at the liquid inlet to a
concentration of x. at the liquid outlet. To show the effect of such a concentration
gradient, consider a portion of the McCabe-Thiele diagram, as shown in Fig. 18.29.
This diagram corresponds to a Murphree efficiency of about 0.9, with y. almost
equal to Y~. However, if there is no horizontal mixing of the liquid, the vapor
near the liquid inlet would contact liquid of composition x.- 1 and be considerably
570 MASS TRANSFER AND ITS APPLICATIONS
Equilibrium
line
Operating
line
FIGURE 18.29
Local and average vapor compositions for an
x unmixed plate.
richer than vapor contacting liquid of composition x. near the exit. To be
consistent with an average vapor composition y., the local vapor composition
must range from y. near the liquid exit to Yb near the liquid inlet. The local
efficiency is therefore considerably lower than the Murphree efficiency, and ry'
would be about 0.6 for this example.
When the local efficiency is high, say, 0.8 or 0.9, the presence of concentration
gradients in the liquid sometimes gives an average vapor concentration greater
than y~, and the Murphree efficiency is then greater than 100 percent. An example
of this is shown later in Fig. 18.34.
The relation between ryM and ry' depends on the degree of liquid mixing and
whether or not the vapor is mixed before going to the next plate. Calculations
have shown 7 only a small difference in efficiency for completely mixed vapor or
unmixed vapor, but the effect of no liquid mixing can be quite large. Most studies
have assumed complete vapor mixing in order to simplify the calculations for
various degrees of liquid mixing. A correlation based on plug flow of liquid across
the plate with eddy diffusion in the liquid phase was developed by workers at the
University of Delaware' and is given in Fig. 18.30. The abscissa is (m VjL)ry', and
the parameter on the graphs is a Peelet number for axial dispersion:
N Pe -
zf- (18.68)
- D t
EL
where Z, = length of liquid flow path, m
DE = eddy diffusivity, m 2 js
tL = residence time of liquid on plate, s
For distillation at atmospheric pressure in a column 0.3 m (1 ft) in diameter
the Peelet number is about 10, based on empirical correlations for dispersion on
bubble-cap and sieve trays.'·3 This is in the range where significant enhancement
of the efficiency should result because of gradients on the plate. For a column 1 m
or larger in diameter, the Peelet number would be expected to be greater than 20,
DISTILLATION 571
3.5,---,-----,----,---,
3.01-----f-·--- - -_.
2.51-----+---
:0:,
" 2.01----+-- -+----/'--4--/----1
5
1. 5 i---t--z01':7""'--+-:=.oj2
1~§:=f==t==J,
:: 0.5
1.0 1.5 2.0
FIGURE 18.30
Relationship between Murphree and local
(mV/L)1j' efficiencies.
and the efficiency should be almost as high as it would be with no mixing in the
direction of flow. Tests on very large columns, however, sometimes show lower
plate efficiencies than for medium-size columns, probably because of departure
from plug flow. With a large column and segmental downcomers the liquid flowing
around the edge of the bubbling area, as shown in Fig. 18.31, has an appreciably
longer flow path than liquid crossing the middle, and a wide distribution of
residence times or even some backflow of liquid may result. These effects can be
minimized by special plate design.
USE OF MURPHREE EFFICIENCY. When the Murphree efficiency is known, it
can readily be used in the McCabe-Thiele diagram. The diagram for an actual
plate as compared with that for an ideal plate is shown in Fig. 18.32. Triangle acd
represents the ideal plate and triangle abe the actual plate. The actual plate, instead
FIGURE 18.31
Possible liquid flow patterns in a large column.
572 MASS TRANSFER AND ITS APPLICATIONS
ry
FIGURE 18.32
Use of Murphree efficiency on x~y diagram. Dashed line is effective equilibrium curve, Y." vs. x" for
'lltI = 0.60; ba/ca = yzjxz = 0.60.
of enriching the vapor from Y.+ 1 to y~, shown by line segment ac, accomplished
a lesser enrichment, Y. - Y.+1> shown by line segment ab. By definition of ~M'
the Murphree efficiency is given by the ratio ab/ac. To apply a known Murphree
efficiency to an entire column, it is necessary only to replace the true equilibrium
curve Ye vs. Xc by an effective equilibrium curve y~ vs. Xc, whose ordinates are
calculated from the equation
(18.69)
In Fig. 18.32 an effective equilibrium curve for 'lA,
= 0.60 is shown. Note that
the position of the y;-vs.-x, curve depends on both the operating line and the true
equilibrium curve. Once the effective equilibrium curve has been plotted, the usual
step-by-step construction is made and the number of actual plates determined.
The reboiler is not subject to a discount for plate efficiency, and the true
equilibrium curve is used for the last step in the stripping section.
Relation between Murphree and overall efficiencies. The overall efficiency of a
column is not the same as the average Murphree efficiency of the individual plates.
The relation between these efficiencies depends on the relative slopes of the
equilibrium line and the operating line. When the equilibrium line is steeper than
the operating line, which is typical for stripping columns, the overall efficiency is
DISTILLATION 573
greater than the Murphree efficiency if q" is less than 1.0. Consider a portion of
the column where the liquid composition changes from X 12 to X IO , a change
requiring 1.0 ideal stage as shown in Fig. 18.33a. If two plates are actually required
for this change, the overall efficiency for that portion of the column is 50 percent.
However, if two partial steps are drawn assuming qM = 0.50, as shown by the
dashed line, the predicted value or XIO is too high, since the first step would go
halfway from x 12 to XlO and the second step would be a much larger change. The
correct value of '1" is about 0.40, as shown in the steps drawn with a solid line.
When the equilibrium line is less steep than the operating line, as usually
occurs near the top of the rectifying section, the overall efficiency is less than the
Murphree efficiency, as illustrated in Fig. 18.33b. For this case, two ideal plates
are needed to go from Xl to X" and if four actual plates are required, the overall
efficiency is 0.50. By trial and error, a Murphree efficiency of 0.6 is found to give
the correct value of x, after four partial steps.
For columns with both a stripping and a rectifying section, the overall value
of q, may be fairly close to the average value of '1 M' since the higher value of '1,
in the stripping section, where mVjL > 1, tends to offset the lower value of q, in
the rectifying section, where mVjL < 1. For this reason, the difference between q,
and ry" is sometimes ignored in designing a column. However, in analyzing the
Equilibrium line
Operating
line
y
x
la)
y
Operating line
FIGURE 1833
x Relationship between Murphree and overall efficiencies: (a)
Ib) l1M < '10; (b) l1M > '1 0.
574 MASS TRANSFER AND ITS APPLICATIONS
performance of a real column or a section of the column, where the composition
change over several plates is measured, the correct value of ~M should be
determined by trial rather than just determining 'I, and assuming ~, = 'I".
For the special case where the equilibrium and operating lines are straight,
the following equation can be applied:
In [1 + '1,,(mV/L - 1)]
(18.70)
110 =
In (mV/L)
Note that when mV/L = 1.0 or when ~M '" 1.0, 'IM = ~,.
FACTORS INFLUENCING PLATE EFFICIENCY. Although thorough studies of
plate efficiency have been made,5 .•. 13 the estimation of efficiency is largely
empirical. Sufficient data are at hand, however, to show the major factors involved
and to provide a basis for estimating the efficiencies for conventional types of
columns operating on mixtures of common substances.
The most important requirement for obtaining satisfactory efficiencies is that
the plates operate properly. Adequate and intimate contact between vapor and
liquid is essential. Any misoperation of the column, such as excessive foaming or
entrainment, poor vapor distribution, or short-circuiting, weeping, or dumping of
liquid, lowers the plate efficiency.
Plate efficiency is a function of the rate of mass transfer between liquid and
vapor. The prediction of mass-transfer coefficients in sieve trays and their relation-
ship to plate efficiency are discussed in Chap. 21. Some published values of the
plate efficiency of a 1.2-m column are shown in Fig. 18.34. This column had sieve
trays with 12.7-mm holes and 8.32 percent open area, a 51-mm weir height, and
0.61-m tray spacing. The data are plotted against a flow parameter F, which tends
to cover about the same range for different total pressures, since the flooding
velocity varies inversely with jP;, as shown by Eq. (18.65). Parameter F, generally
known as the "Ffactor," is defined as follows:
F == ujP; (18.71)
The normal range of F for sieve trays is 1 to 3 (m/s) (kg/m')o." or 0.82 to
2.46 (ft/s) (lb/ft,)o.5.
Example 18.7. What is the F factor at the top of the column in Example 18.6 if the
vapor velocity is the maximum allowable?
Solution
From Eq. (18.71) the F factor is
F ~ u,JP;,
~ 2.23jUs ~ 2.39
As shown by Fig. 18.34, this is a reasonable value for a sieve-plate column at
1 atm pressure.
DISTILLATION 575
140
~2 atm
120
,lohutane-n-butane, 11
,
lOO
/ 1,63 atm
J
.•
>-
u
c 80 I ------- CYCIOheXane-n-heptan
.
.g
ii; 60
}~ ~ ~ \
0.34 atm
.::
40
( C
20
2 3 4
F,lm/sl {kg/m 3)o.5
FIGURE 18.34
Efficiency of sieve trays in a 1.2-m column. (From M. Sakata and T. Yanagi, 3rd Int. Symp. Dist., p.
3.2/21, ICE, 1979.)
The efficiency does not change much with vapor rate in the range between the
weeping point and the flooding point. The increase in vapor flow increases the froth
height, creating more mass transfer area, so that the total mass transferred goes up
about as fast as the vapor rate. The data for Fig. 18.34 were obtained at total reflux,
so the increase in liquid rate also contributed to the increase in interfacial area. The
sharp decrease in efficiency near the flooding point is due to entrainment.
The data for cyclohexane-n-heptane show a lower efficiency for operation at
a lower pressure, which has been confirmed by tests on other systems. Lowering the
pressure decreases the concentration driving force in the vapor phase but increases
the vapor diffusivity. It also lowers the temperature, which increases the liquid
viscosity and surface tension and decreases the diffusion coefficients in the liquid.
The decrease in efficiency is due to a combination of these effects.
Efficiencies greater than 100 percent for the isobutane-butane system show
the effect of liquid concentration gradients; the local efficiency for this case may
be in the range 0.7 to 0.9. A somewhat smaller difference between '1.[ and ~'
probably exists for the cyclohexane-heptane system, since the liquid flow is less,
which decreases the Peclet number and makes the conditions on the plate closer
to complete mixing.
SPECIAL SIEVE TRAYS." In some columns equipped with sieve trays no down-
corners are used. There is no crossflow of the liquid; the liquid and vapor pass
576 MASS TRANSFER AND ITS APPLICATIONS
countercurrently through relatively large holes in the tray. Liquid drains through
some holes at one instant, through others somewhat later, with the vapor passing
upward through the remainder. Such columns have some advantages in cost over
conventional columns and do not foul easily, but their turndown ratio (the ratio
of the maximum allowable vapor velocity to the lowest velocity at which the
column will operate satisfactorily) is low, usually 2 or less.
In a valve-tray column the openings in the plate are quite large, typically
it in. (38 mm) for circular perforations and ! by 6 in. (13 by 150 mm) for
rectangular slots. The openings are covered with lids or "valves," which rise and
fall as the vapor rate varies, providing a variable area for vapor passage.
Downcomers and crossflow of the liquid are used in the regular sieve trays. Valve
trays are more expensive than conventional trays but have the advantage of a
large turndown ratio, up to 10 or more, so the operating range of the column is
large. Counterflow trays and valve trays are nearly always of proprietary design.
Rectification in Packed Towers
Packed columns are often used for distillation operations when the separation is
relatively easy and the required column diameter is not very large. Packed columns
are generally less expensive than plate columns and have lower pressure drop. The
main disadvantage is the difficulty in getting good liquid distribution, particularly
for large diameter columns or very tall columns. Even if liquid is spread evenly
over the packing at the top of the column, liquid tends to move toward the wall
and to flow through the packing in preferred channels. Regions of high liquid flow
tend to have low vapor flow, and the local variations in L/V decrease the
separation that can be achieved.' To minimize this effect, tall columns are often
split into sections, with redistributors every 3 to 4 m.
A packed distillation column can be designed with the same methods used
for absorption columns, as discussed in Chap. 22. The height of the column can
be based on the number of transfer units and the height of a transfer unit, but it
is usually based on the number of theoretical plates and the height equivalent
to a theoretical plate (HETP). Values of HETP are generally in the range 0.5 to
1 m (1.5 to 3 ft) for random dumped packings such as Pall rings or Intalox
saddlesp·l'.15 Typical values for HETP are shown in Fig. 22.25, p. 732. Lower
values of HETP can be obtained using structured packings, which are made from
crimped or perforated metal sheets arranged to form a regular structure with a
high surface area. These packings are finding increasing use for vacuum distillation
because of the low pressure drop.
BATCH DISTILLATION
In some small plants, volatile products are recovered from liquid solution by batch
distillation. The mixture is charged to a still or reboiler, and heat is supplied
through a coil or through the wall of the vessel to bring the liquid to the boiling
point and then vaporize part of the batch. In the simplest method of operation,
DISTILLATION 577
,
Batch still
~-l_~~ ,_ Product
receiver
Steam-M-+----.,..
FIGURE 18.35
Simple distillation in a batch still.
the vapors are taken directly from the still to a condenser, as shown in Fig. 18.35.
The vapor leaving the still at any time is in equilibrium with the liquid in the still,
but since the vapor is richer in the more volatile component, the compositions of
liquid and vapor are not constant.
To show how the compositions change with time, consider what happens if
no moles are charged to a batch still. Let n be the moles of liquid left in the still at
a given time and y and x be the vapor and liquid compositions. The total moles
of component A left in the still nA will be
nA = xn (18.72)
If a small amount of liquid dn is vaporized, the change in the moles of
component A is y dn, or dnA" Differentiating Eq. (18.72) gives
dnA = d(xn) = n dx + x dn (18.73)
Henee
ndx+xdn=ydn
By rearrangement,
dn dx
-=-- (18.74)
n y-x
Equation (18.74) is integrated between the limits of Xo and X" the initial and
final concentrations,
"f ' dn
no -;;
r"
= JXo Y -
dx
X
n,
= In no
(18.75)
Equation (18.75) is known as the Rayleigh equation. The function dx/(y - x)
can be integrated graphically or numerically using tabulated equilibrium data or
an equilibrium curve.
A simple alternative to the Rayleigh equation can be derived for an ideal
mixture based on the relative volatility. Although the temperature in the still
increases during a batch distillation, the relative volatility, which is the ratio of
vapor pressures, does not change much and an average value can be used. From
Eq. (18.34),
YA XA
-=IX
AB
- (18.76)
YB xB
578 MASS TRANSFER AND ITS APPLICATIONS
If the mixture has /lA mol of A and liB mol of B, the ratio nA/nn is equal to
xA/x.; when dn mol is vaporized, the change in A is YA dll or dnA' and the change
in B is YB dn or dll n. Substituting these terms into Eq. (18.76) gives
dnA/dn dnA nA
--- = - = CX
AB
-
dnB/dn dnB ".
dnA dn.
or - = r : J . AB - (18.77)
HA nB
After integration between limits
HA HB
In - = CX AB In- (18.78)
HOA llOB
~ = (~)l/aAB
or (18.79)
nOB llOA
Equation (18.79) can be plotted as a straight line on logarithmic coordinates
to help follow the course of a batch distillation or it can be used directly if the
recovery of one of the components is specified.
Example 18.8. A batch of crude pentane contains 15 mol percent l1-butane and 85
percent l1-pentane. If a simple batch distillation at atmospheric pressure is used to
remove 90 percent of the butane, how much pentane would be removed? What would
be the composition of the remaining liquid?
Solution
The final liquid is nearly pure pentane, and its boiling point is 36°C. The vapor
pressure of butane at this temperature is 3.4 atm, giving a relative volatility of 3.4.
For the initial conditions, the boiling point is about 27°C, and the relative volatility
is 3.6. Therefore, an average value of 3.5 is used for lX AY '
Basis: 1 mol feed
nOA = 0.15 (butane) nA = 0.015 non = 0.85 (pentane)
From Equation (18.72)
~ = 0.1 ' /3.5 = 0.518 nn = 0.518(0.85) = 0.440
0.85
0.015
n = 0.44 + 0.015 = 0.455 mol x A = - - = 0.033
0.455
BATCH DISTILLATION WITH REFLUX. Batch distillation with only a simple
still does not give a good separation unless the relative volatility is very high. In
many cases, a rectifying column with reflux is used to improve the performance
of the batch still. If the column is not too large, it may be mounted on top of the
still, as shown in Fig. 17.1, or it may be supported independently, with connecting
pipes for the vapor and liquid streams.
DISTILLATION 579
The operation of a batch still and column can be analyzed using a McCabe-
Thiele diagram, with the same operating-line equation that was used for the
rectifying section of a continuous distillation:
RD XD
Y"+ 1 = RD + I x" + RD + I (18.19)
The system may be operated to keep the top composition constant by
increasing the reflux ratio as the composition of the liquid in the reboiler changes.
The McCabe-Thiele diagram for this case would have operating lines of different
slope positioned such that the same number of ideal stages was used to go from
x D to x B at any time. A typical diagram is shown in Fig. 18.36 for a still with five
ideal stages including the reboiler. The upper operating line is for the initial
conditions, when the concentration of low boiler in the still is about the same as
the charge composition. (The concentration X B is slightly lower than XF because
of the holdup of liquid on the plates.) The lower operating line and the dashed
line steps show conditions when about one-third of the charge has been removed
as overhead product.
To determine the reflux ratio needed for a constant X D and given X B requires
a trial-and-error calculation, since the last step on the assumed operating line must
end exactly at x B • However, once the initial reflux ratio is chosen by this method,
the value of x B for a later stage in the distillation can be obtained by assuming a
value of R D , constructing the operating line, and making the correct number of
steps ending at X B • By a material balance, Eqs. (18.5) and (18.6), the amount of
product and remaining charge can be calculated.
An alternative method of running a batch distillation is to fix the reflux ratio
and let the overhead product purity vary with time, stopping the distillation when
the amount of product or the average concentration in the total product reaches
FIGURE 1836
McCabe-Thiele diagrams for a batch
distillation. Upper operating line and solid
lines: initial conditions; lower operating line
and dashed lines: after one-third of the
charge has been removed.
580 MASS TRANSFER AND ITS APPLICATIONS
a certain value. To calculate the performance of the still, operating lines of constant
slope are drawn starting at different values of X D and the actual number of stages
is stepped off to determine X B • The total number of moles left in the still is then
calculated by integration ofEq. (18.75), where X D is equal to y and x is equal to X B .
SYMBOLS
Flow rate of bottoms product, mOl/h, kg/h or lblh
Discharge coefficient, flow through perforations of sieve plate
Specific heat at constant pressure, J/g.oC or Btu/lb-oF; cp" of con-
densate; c pL , of liquid; Cpy, of vapor
Flow rate of overhead product, mol(h, kg(h or lblh
Diameter of column, m or ft
Eddy diffusivity, m 2 /s
Feed rate, mol(h, kg/h or lb/h; also factor for estimating column
capacity, defined by Eq. (18.71)
f Fraction of feed that is vaporized
9 Acceleration of gravity, m/s2 or ft/s2
H Enthalpy, energy per mole or per unit mass; H B , of bottom product;
H D , of overhead product; H F , of feed; HR' of reflux; Hxo of
saturated liquid; H x "" of liquid from plate m of stripping column;
Hw of liquid from plate n of rectifying column; H y, of saturated
vapor; Hy,(I' of vapor entering column; H y(m+l)' of vapor from plate
m + 1 of stripping column; H Y(,,+l)' of vapor from plate n + 1 of
rectifying column; H y1 , ofval?or from top plate
HETP Height of packing equivalent to a theoretical plate
" Pressure drop or head, mm of liquid; hd' for dry plate; hf . L , friction
loss in liquid; h/o equivalent head of liquid on plate; how, height of
clear liquid over weir; h" total drop per plate; hw, height of
weIr
K,. Coefficient in Eq. (18.65); K;, in Eq. (18.64)
L Flow rate of liquid in general or in rectifying column, mol/h, kg/h,
or lb/h; L", entering top of column; L b , leaving bottom of column;
L" of reflux from condenser; Lm, from plate m of stripping column;
L., from plate n of rectifying column; I, in stripping column
Length of weir, m
Serial number of plate in stripping column, counting from feed
plate; also, slope of equilibrium curve, dy,ldx,
Mass flow rate, kg/h or lb(h; m" of steam to reboiler; In w , of cooling
water to condenser
Number of ideal plates; N rnin> minimum number of ideal plate,
Peclet number for axial dispersion, Z~/DEtL
Serial number of plate in rectifying column, counting from top; also,
number of moles in still or mixture; nA, nB' of components A and B,
DISTILLATION 581
respectively; no. moles charged to still; 11 0A , non. of components A
and B, respectively; ni' final value
p Pressure, N/m2 or lb f/ft 2 ; P,-1' P", P ,+ I' in vapor space above plates
n - 1, n, and n + 1, respectively; pI, vapor pressure; P A, PH, of
components A and B, respectively
PA,PB Partial pressure of components A and B, respectively, N/m2 or
lbf/ft>
q Rate of heat flow, W or Btujh; qc, heat removed in condenser; q"
heat added at reboiler; also, moles of liquid to stripping section of
column per mole of feed
Volumetric flow rate of liquid in downpipe, m 3/s or ft3/S
Reflux ratio; RD = L/D; Ry = L/V; R Dm , minimum reflux ratio
Temperature, 'c or 'F; TF , of feed; 1/" bubble point; 1/,<> bubble point
of condensate; 7;, of condensate; 'Id, dew point;·l1, of liquid on top
plate; also, entering temperature of cooling water; T2 - TI , tempera-
ture rise of cooling water
Residence time of liquid on plate, s
Linear velocity, m/s or ft/s; U" maximum permissible vapor velocity,
based on area of bubbling section; Uo, vapor velocity through per-
forations in sieve plate
v Flow rate of vapor, in general or in rectifying column, mol/h, kgjh
or lb/h; v;, , from top of column; v" , entering bottom of column;
V,n+l' from plate m + 1 in stripping column; ~, ~+1> from plates
nand n + 1, respectively, in rectifying column; VI> from top plate to
condenser; V, in stripping column
x Mole fraction or mass fraction in liquid; X A , of component A; X Ae ,
in equilibrium with vapor of concentration YAe; X B , in bottoms pro-
duct, also, of component B in liquid; X n" in equilibrium with vapor
of concentration YBc; XD, in overhead product; Xp, in feed; Xa • in
liquid entering single-section column; Xb, in liquid leaving single-
section column; Xl:' in reflux from condenser; xc, in equilibrium with
vapor of composition Ye; X m, in liquid from plate m of stripping
column; xn - 1 , X n • in liquid from plates n - 1 and n, respectively, of
rectifying column; x', at intersection offeed line and equilibrium curve;
Xo, XI' initial and final values in batch distillation
Y Mole fraction or mass fraction in vapor; YA' Yn, of components A and
B, respectively; YAe' Yn" in equilibrium with liquids of concentration
xAc • x Bc • respectively; YD. in vapor overhead product; Ya, in vapor
leaving single-section column; Yb, in vapor entering single-section
column; y" from reboiler; y" in equilibrium with liquid of concen-
tration Xe; Ym+l, of vapor from plate m + 1 in stripping column; Yn'
Y,+I, in vapor from plates nand n + 1, respectively, in rectifying
column; y*, in vapor in equilibrium with specific stream of liquid;
Y:, in equilibrium with Xa; yt, in equilibrium with X b; Y:, in equilib-
rium with X,; YI, in vapor from top plate; y', at intersection of feed
582 MASS TRANSFER AND ITS APPLICATIONS
line and equilibrium curve; also, of vapor leaving partial condenser;
y~, pseudoequilibrium value [Eq. (18.69)]; y~,,, in equilibrium with
liquid at a specific location on plate 11; y;, in vapor leaving a specific
location on plate n; Y~+l' entering plate n at same location as for Y;I
Z Height of liquid in downcomer, m or ft; actual height of aerated
liquid; Z" height of clear liquid
Z/ Length of liquid flow path, m
Greek letters
aA • Relative volatility, component A relative to component B
{3 Correction factor in Eq. (18.59)
AH" Enthalpy of vaporization, cal/mol; AH".b, at boiling point
AL Additional liquid condensed in column from cold condensate
[Eq. (18.21)]
'1 Efficiency; ~M' Murphree plate efficiency; ~" overall plate efficiency;
,]" local plate efficiency
), Latent heat of vaporization, energy per unit mass; '\" of condensate;
}"s, of steam
P Density, kg/m' or Ib/ft'; PL' of liquid; Pv, of vapor
I] Surface tension, dyn/cm
I/>, Volume fraction liquid in aerated mixture
PROBLEMS
18.1. A liquid containing 25 mole percent toluene, 40 mole percent ethyl benzene, and 35
mole percent water is subjected to a continuous flash distillation at a total pressure
of 0.5 atm. Vapor-pressure data for these substances are given in Table 18.5.
Assuming that mixtures of ethylbenzene and toluene obey Raoult's law and that the
hydrocarbons are completely immiscible in water, calculate the temperature and
TABLE 18.5
Vapor pressures of ethylbenzene, toluene, and
water
Vapor pressure, mm Hg
Temperature,
'C Ethylbeozeoe Toluene Water
50 53.8 92.5
60 78.6 139.5 149.4
70 113.0 202.4 233.7
80 166.0 289.4 355.1
90 223.1 404.6 525.8
100 307.0 557.2 760.0
110 414.1
110.6 760.0
120 545.9
DISTILLATION 583
compositions of liquid and vapor phases (a) at the bubble point, (b) at the dew point,
(c) at the 50 percent point (one-half of the feed leaves as vapor and the other half
as liquid).
18.2. A plant must distill a mixture containing 75 mole percent methanol and 25 percent
water. The overhead product is to contain 99.99 mole percent methanol and the
bottom product 0.002 mole percent. The feed is cold, and for each mole of feed 0.15
mol of vapor is condensed at the feed plate. The reflux ratio at the top of the column
is 1.4, and the reflux is at its bubble point. Calculate (a) the minimum number of
plates; (b) the minimum reflux ratio; (c) the number of plates using a total condenser
and a reboiler, assuming an average Murphree plate efficiency of 72 percent; (d) the
number of plates using a reboiler and a partial condenser operating with the reflux
in equilibrium with the vapor going to a final condenser. Equilibrium data are given
in Table 18.6.
TABLE 18.6
Equilibrium data for methanol-water
x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y 0.4t7 0.579 0.669 0.729 0.780 0.825 0.871 0.915 0.959 1.0
18.3. The boiling point-equilibrium data for the system acetone-methanol at 760 mm Hg
are given in Table 18.7. A column is to be designed to separate a feed analyzing 25
mole percent acetone and 75 mole percent methanol into an overhead product
containing 78 mole percent acetone and a bottom product containing 1.0 mole
percent acetone. The feed enters as an equilibrium mixture of 30 percent liquid and
70 percent vapor. A reflux ratio equal to twice the minimum is to be used. An external
rebotler is to be used. Bottom product is removed from the reboiler. The condensate
(reflux and overhead product) leaves the condenser at 25°C, and the reflux enters
the column at this temperature. The molal latent heats of !loth components are
7700 g cal(g mol. The Murphree plate efficiency is 70 percent. Calculate (a) the
number of plates required above and below the feed; (b) the heat required at the
reboiler, in Btu per pound mole of overhead product; (c) the heat removed in the
condenser, in Btu per pound mole of overhead product.
TABLE 18.7
System acetone-methanol
Mole fraction acetone Mole fraction acetone
Temperature, Temperature,
'C Liquid Vapor 'C Liquid Vapor
64.5 0.00 0.000 56.7 0.50 0.586
63.6 0.05 0.102 56.0 0.60 0.656
62.5 0.10 0.186 55.3 0.70 0.725
60.2 0.20 0.322 55.05t 0.80 0.80
58.65 0.30 0.428 56.1 1.00 1.00
57.55 0.40 0.513
t Azeotrope.
584 MASS TRANSFER AND ITS APPLICATIONS
18.4. An equimolal mixture of benzene and toluene is to be separated in a bubble-plate
tower at the rate of 100 kg moljh at 1 atm pressure. The overhead product must
contain at least 98 mole percent benzene. The feed is saturated liquid. A tower is
available containing 24 plates. Feed may be introduced either on the eleventh or the
seventeenth plate from the top. The maximum vaporization capacity of the reboiler
is 120 kg moljh. The plates are about 50 percent efficient. How many moles per hour
of overhead product can be obtained from this tower?
18.5. An aqueous solution of a volatile component A containing 7.94 mole percent A
preheated to its boiling point is to be fed to the top of a continuous stripping column
operated at atmospheric pressure. Vapor from the top of the column is to contain
11.25 mole percent A. No reflux is to be returned. Two methods are under
consideration, both calling for the same expenditure of heat, namely, a vaporization
of 0.562 mol per mole feed in each case. Method 1 is to use a still at the bottom of
a plate column, generating vapor by use of steam condensing inside a closed coil in
the still. In method 2 the still and heating coil are omitted, and live steam is injected
directly below the bottom plate. Equilibrium data are given in Table 18.8. The usual
simplifying assumptions may be made. What are the advantages of each method?
TABLE 18.8
Equilibrium data in mole fraction A
x 0.0035 0.0077 0.0125 0.0177 0.0292 0.0429 0.0590 0.0784
y 0.0100 0.0200 0.0300 0.0400 0.0600 0.0800 0.1000 0.1200
18.6. A tower containing six ideal plates, a reboiler, and a total condenser is used to
separate, partially, oxygen from air at 65 Ibf/in. 2 gauge. It is desired to operate at
reflux ratio (reflux to product) of 2.6 and to produce a bottom product containing
51 weight percent oxygen. The air is fed to the column at 65IbJ /in. 2 gauge and 30
percent vapor by mass. The enthalpy of oxygen-nitrogen mixtures at this pressure
is given in Table 18.9. Compute the composition of the overhead if the vapors are
just condensed but not cooled.
TABLE 18.9
Enthalpy of oxygen-nitrogen at 65 Ibiin.2 gauge
Liquid Vapor
Temperature,
°c NI. wt % #n cal/g mol NI. wt % By. callg mol
-163 00 420 0.0 1840
-165 7.5 418 19.3 1755
-167 17.0 415 35.9 1685
-169 27.5 410 50.0 1625
171 39.0 398 63.0 1570
-173 52.5 378 75.0 1515
-175 68.5 349 86.0 1465
-177 88.0 300 95.5 1425
-178 100.0 263 100.0 1405
DISTILLATION 585
18.7. A rectifying column containing the equivalent of three ideal plates is to be supplied
continuously with a feed consisting of 0.4 mole percent ammonia and 99.6 mole
percent water. Before entering the column, the feed is converted wholly into saturated
vapor, and it enters between the second and third plates from the top of the column.
The vapors from the top plate are totally condensed but not cooled. Per mole of
feed, 1.35 mol of condensate is returned to the top plate as reflux, and the remainder
of the distillate is removed as overhead product. The liquid from the bottom plate
overflows to a reboiler, which is heated by closed steam coils. The vapor generated
in the reboiler enters the column below the bottom plate, and bottom product is
continuously removed from the reboiler. The vaporization in the reboBer is 0.7 mol
per mole of feed. Over the concentration range involved in this problem, the
equilibrium relation is given by the equation
y = 12.6x
Calculate the mole fraction of ammonia in (a) the bottom product from the
reboiler, (b) the overhead product, (c) the liquid reflux leaving the feed plate.
18.8. It is desired to produce an overhead product containing 80 mole percent benzene
from a feed mixture of 68 mole percent benzene and 32 percent toluene. The following
methods are considered for this operation. All are to be conducted at atmospheric
pressure. For each method calculate the moles of product per 100 mol of feed and
the number of moles vaporized per 100 mol feed. (a) Continuous equilibrium
distillation. (b) Continuous distillation in a still fitted with a partial condenser, in
which 55 mole percent of the entering vapors are condensed and returned to the
still. The partial condenser is so constructed that vapor and liquid leaving it are in
equilibrium and holdup in it is negligible.
18.9. The operation of a fractionating column is circumscribed by two limiting reflux
ratios: one corresponding to the use of an infinite number of plates and the other
a total-reflux, or infinite-reflux, ratio. Consider a rectifying column fed at the bottom
with a constant flow of a binary vapor having a constant composition, and assume
also that the column has an infinite number of plates. (a) What happens in such a
column operating at total reflux? (b) Assume that a product is withdrawn at a
constant rate from the top of this column. What happens as more and more product
is withdrawn in successive steps if each step achieves steady state between changes?
18.10. A laboratory still is charged with 10 L of a methanol-water mixture containing 0.70
mole fraction methano1. This is to be distilled batchwise without reflux at 1 atm
pressure until 5 L of liquid remains in the still, that is, 5 L has been boiled off. The
rate of heat input is constant at 4 kW. The partial molar volumes are 40.5 cm 3/g
mol for methanol and 18 cm 3/g mol for water. Neglecting any volume changes on
mixing and using an average heat of vaporization of 40 kJ/g mol, calculate (a) the
time tT required to boil off 5 L; (b) the mole fraction of methanol left in the still at
times t T /2, 3tT/4, and tT; (c) the average composition of the total distillate at time
tT' Equilibrium data for the system methanol-water are given in Table 18.6.
18.11. An equimolal mixture of A and B with a relative volatility of 2.3 is to be separated
into a distillate product with 98.5 percent A, a bottoms product with 2 percent A,
and an intermediate liquid product that is 80 percent A and has 40 percent of the
A fed. (a) Derive the equation for the operating line in the middle section of the
column, and sketch the three operating lines on a McCabe-Thiele diagram. (b)
Calculate the amounts of each product per 100 mol of feed, and determine the
586 MASS TRANSFER AND ITS APPLICATIONS
minimum reflux rate if the feed is liquid at the boiling point. (c) How much greater
is the minimum reflux rate because of the withdrawal of the side-stream product?
18.12. Distillation is used to prepare 99 percent pure products from a mixture of n-butane
and n-pentane. Vapor pressures taken from Perry's Handbook are given below.
Temperature, °C
P, atm n-C4H tO n-CsH 12
0.526 -16.3 18.5
I - 0.5 36.1
2 18.8 58.0
5 50.0 92.4
10 79.5 124.7
20 116.0 164.3
(a) Plot the vapor pressures in a form that permits accurate interpolation, and
determine the average relative volatility for columns operating at 1, 2, and 8 atm.
(b) Determine the minimum number of ideal plates for the separation at these three
pressures, What is the main advantage of carrying out the separation at above
atmospheric pressure?
18.13. Ethyl benzene (boiling point 136.2'C) and styrene (boiling point 145.2'C) are
separated by continuous distillation in a column operated under a vacuum to keep
the temperature under 110°C and to avoid styrene polymerization. The feed is
30,000 kgfh with 54 percent ethyl benzene and 46 percent styrene (weight percent),
and the products have 97 percent and 0.2 percent ethyl benzene. The relative
volatility is 1.37, and with a reflux ratio of 6.15, about 70 plates are needed. The
top of the column operates at 50 mm Hg and 58°C, and the average pressure drop
per tray is 2.5 mm Hg. (a) If the column is designed to have an F factor of 2.8
(m/s)(kgfm')O.5 at the top, what diameter column is needed? (b) For a uniform
diameter column, what would be the F factor at the bottom of the column? (c) If
the column was built in two sections. with a smaller diameter for the bottom section,
what diameter should be used so that F is never greater than 2.8? (See C. J. King,
Separation Processes, McGraw-Hill, New York, 1971, p. 608, for more about this
system.)
18.14. A plant has two streams containing benzene and toluene, one with 37 percent
benzene and one with 68 percent benzene. About equal amounts of the two streams
are available, and a distillation tower with two feed points is proposed to produce
98 percent benzene and 99 percent toluene in the most efficient manner. However,
combining the two streams and feeding at one point would be a simpler operation.
For the same reflux rate, calculate the number of ideal stages required for the two
cases.
18.15. Toluene saturated with water at 30'C has 680 ppm H 2 0 and is to be dried to 0.3 ppm
H 2 0 by fractional distillation. The feed is introduced to the top plate of the column,
and the overhead vapor is condensed, cooled to 30°C, and separated into two layers.
The water layer is removed, and the toluene layer, saturated with water, is recycled.
The average relative volatility of water to toluene is 120. How many theoretical
DISTILLATION 587
stages are required if 0.25 mol of vapor are used per mole of liquid feed? (Neglect
the change in LjV in the column.)
18.16. A sieve-tray column with 15 plates is used to prepare 99 percent methanol from a
feed containing 40 percent methanol and 60 percent water (mole percent). The plates
have 8 percent open area, i-in. holes, and 2-in. weirs with segmental downcomers.
(a) If the column is operated at atmospheric pressure, estimate the flooding limit
based on conditions at the top of the column. What is the F factor and the pressure
drop per plate at this limit? (b) For the flow rate calculated in part (a) determine
the F factor and the pressure drop per plate near the bottom of the column. Which
section of the column will flood first as the vapor rate is increased?
REFERENCES
1. AIChE: Bubble Tray Desigll Manual, New York, 1958.
2. Fair, J. R.: Petrol. Chem. Eng., 33(10):45 (1961).
3. Gerster, J. A.: /Ild. Eng. Cllem., 52:645 (1960).
4. Harriott, P.: Ellviron. Sci. Teclmol., 23:309 (1988).
5. Jones, J. B., and C. Pyle: Chem. Eng. Prog., 51:424 (1955).
6. Lewis, W. K.: /Ild. Eng. Cllem., 14:492 (1922).
7. Lewis, W. K., Jr.: lnd. Eng. Cllem., 28:399 (1936).
8. McCabe, W. L., and E. W. Thiele: llld. Eng. Chem., 17:605 (1925).
9. McFarland, S. A., P. M. Sigmund, and M. Van Winkle: Hydro. Proc., 51(7):111 (1972).
10. Murphree, E. V.: llld. ElIg. ClIem., 17:747 (1925).
11. Smith, B. D.: Design of Equilibriil1n Stage Processes, McGraw-Hill, New York, 1963, pp. 565-567.
12. Strigle, R. F., Jr., and F. Rukovena, Jr.: ClIem. Eng. Prog., 75(3):87 (1979).
13. Vital, T. 1., S. S. Grossel, and P.!' Olsen: Hydro. Proc., 63{1l):147 (1984).
14. Vital, T. J., S. S. Grosscl, and P. I. Olscn: Hydro. Proc., 63(12):75 (1984).
15. Walas, S. M.: Chemical Process Equipment, Butterworths, Stoneham, MA, 1988, p. 453.
CHAPTER
19
INTRODUCTION
TO
MULTICOMPONENT
DISTILLATION
In multicomponent distillation, as in the distillation of binary mixtures, the
calculation of equilibrium stages uses mass and enthalpy balances and vapor-liquid
equilibria. A mass balance can be written for each component for the column as
a whole or for a single stage, but there is only one enthalpy balance for the column
or for each stage. The phase equilibria are much more complex than for binary
systems, because of the several components and because the equilibria depend on
temperature, which changes from stage to stage. In binary systems the temperature
and equilibria also change from stage to stage, but except with azeotropes, the
more volatile component is more volatile than the other component throughout
the column. In multicomponent mixtures one component may be more volatile
than the average in one part of the column and less volatile than the average in
another part, which leads to complex concentration profiles.
In practice the field is dominated by the use of digital computers because of
the mass of numbers needed to quantify the operating and engineering variables
and the many iterations required to obtain convergence of the solutions to the
equations. This is not a book on computers, but all computers must be fed with
programs based squarely on the principles to which this text is devoted.
PHASE EQUILIBRIA IN MULTICOMPONENT DISTILLATION. The vapor-liquid
equilibria for a mixture are described by distribution coefficients or K factors,
INTRODUCTION TO MULTICOMPONENT DISTILLATION 589
where K for each component is the ratio of mole fractions in the vapor and liquid
phases at equilibrium:
(19.1)
If Raoult's law and Dalton's law hold, values of K, can be calculated from the
vapor pressure and the total pressure of the system:
(19.2)
p,
Y'=p (19.3)
(19.4)
Raoult's law is a good approximation for mixtures of similar compounds, such
as the paraffins found in the low-boiling fractions of petroleum or the aromatics
recovered from coke production. However, at high pressures, K factors do not
vary exactly inversely with total pressure because of compressibility effects.
Nomographs of K values for some paraffins and olefins are given in Appendixes
21 and 22.
The K factors are strongly temperature dependent because of the change in
vapor pressure, but the relative values of K for two components change only
moderately with temperature. The ratio of K factors is the same as the relative
volatility of the components:
(19.5)
When Raoult's law applies,
(i ..
r
= -• (19.6)
IJ p'.
J
As will be shown later, the average relative volatility of a key component in
the overhead or distillate product to that of a key component in the bottoms
product can be used to estimate th.,.. minimum number of stages for a multi-
component distillation.
BUBBLE-POINT AND DEW-POINT CALCULATION. Determination of the
bubble point (initial boiling point of a liquid mixture) or the dew point (initial
condensation temperature) is required for a flash-distillation calculation and for
each stage of a multicomponent distillation. The basic equations are, for the bubble
point,
N~ N~
I: y, = I: K,x, = 1.0 (19.7)
i= 1 i=l
590 MASS TRANSFER AND ITS APPLICATIONS
and, for the dew point,
Ne Ne y.
l: Xi = l: -'- = 1.0 (19.8)
j=l i=l Kj
where N, is the number of components.
To use Eq. (19.7), a temperature is assumed, and values of Ki are obtained
from published tables or from vapor pressure data and the known total pressure.
If the summation of Kix i exceeds 1.0, a lower temperature is chosen and the
calculation repeated until Eq. (19.7) is satisfied. If the bubble-point temperature
is determined exactly (l: Kix i = 1.00), the composition of the vapor in equilibrium
with this liquid is given directly by the terms Kix i. However, when the summation
is close to 1.0, the vapor composition can be determined with little error from the
relative contribution of each term to the summation:
KjX j
Yi = Ne (19.9)
L Kjx i
i=l
A similar procedure is used to determine the dew point of a vapor mixture
and the composition of the liquid in equilibrium with this mixture.
10
9
8 ,
7
./ n-Pentane
6
!
5 /
4. 0 ./ I
/'
3. 0 /' /
n-Hexane
oV /
V
2.
~ / /
ui 1. 5
a:
:J
"'"'a:w
1. 0
O.9
/ V n-Heptane
-
~ O. 8
a: O. 7
0
O. 6 /' n-Octane-
~
"
> O. 5 r7
O. 4 / /'
O. 3 / V
/'
/
o. 2
/'
0.1 5
O. 1
60
v 70 80 90
TEMPERATURE,oC
100 110 120 130 FIGURE 19.1
Diagram for Example 19.1.
INTRODUCfION TO MULTICOMPONENT DISTILLATION 591
Example 19.1. Find the bubble-point and the dew-point temperatures and the
corresponding vapor and liquid compositions for a mixture of 33 mole percent
n-hexane. 37 mole percent n-heptane, and 30 mole percent n-octane at 1.2 atm total
pressure.
Solution
Plot the vapor pressures of the three components as a semilogarithmic plot of log P
vs. T(Fig. 19.1) or log P vs. 1l'Tabs. where ~bs is the absolute temperature in Kelvins.
Bubble point Choose T = 105°C, where the vapor pressure of heptane, the
middle component, is 1.2 atm.
Component P'; at 105°C, atm K; = P';11.2 Xi Yi= K;x;
1. Hexane 2.68 2.23 0.33 0.7359
2. Heptane 1.21 1.01 0.37 0.3737
3. Octane 0.554 0.462 0.30 0.1386
I ~ 1.248
Since LYiis too large, try a lower temperature. Since the major contribution
comes from the first term, pick a temperature where Ki is lower by a factor 1/1.24.
Choose T = 96°C, where P: = 2.16 atm.
Component P'; at 96°C Ki Xi K;x; Yi
2.16 1.8 0.33 0.5940 0.604
2 0.93 0.775 0.37 0.2868 0.292
3 0.41 0.342 0.30 0.1025 0.104
I ~ 0.9833 1.000
Since I Kixi = 0.9833, Yi ~ KiXJO.9833.
By interpolation, the bubble point is 97°C, close enough to 96°C so that the
vapor compositions can be calculated using Eq. (19.9). The vapor in equilibrium with
the liquid is 60.4 mole percent n-hexane, 29.2 mole percent n-heptane, and 10.4 mole
percent n-octane.
Dew point The dew point is higher than the bubble point, so use 105°C as a
first guess.
Component Ki Yi YiIK;
1 2.23 0.33 0.1480
2 1.01 0.37 0.366
3 0.458 0.30 0.655
I ~ 1.169
Since the sum is too high, choose a higher temperature. Pick T = 110°C, where
K3 is 17 percent higher.
592 MASS TRANSFER AND ITS APPLICATIONS
Component P, Ki Yi y;IK; Xi
1 3.0 2.5 0.33 0.132 0.130
2 1.38 1.15 0.37 0.3217 0.317
3 0.64 0.533 0.30 0.5625 0.553
L: ~ 1.0162 1.000
By extrapolation, the dew point is 1l0.5°C, and the composition of the liquid
in equilibrium with the vapor is obtained by dividing the values of yJKi by 1.0162.
FLASH DISTILLATION OF
MULTICOMPONENT MIXTURES
Equation (18.2) can be written for each component m a flash distillation in
the form
XFi 1- I
YDi=7-jX Bi (19.10)
Since the distillate and bottom streams are in equiIibrinm, this equation may be
changed to
YDi
xm
= Ki = ~ (XFi + I -
f XBi
1) (19.11)
Solving Eq. (19.11) for x Bi and summing over n, components give
Ne Ne X
I X Bi = 1= I Fi
--:-:-::::---,"':----c (19.12)
i=l i=l I(K i - 1) +1
This equation is solved by iteration in the same manner as the dew-point
calculation using Eq. (19.8), and the final values of T and Ki are used to
calculate the compositions of the product streams.
Example 19.2. The mixture of Example 19.1 is subjected to a flash distillation at
1.2 atm pressure, and 60 percent of the feed is vaporized. (a) Find the temperature
of the flash and the composition of the liquid and vapor products. (b) To what
temperature must the feed liquid be heated for 60 percent vaporization on flashing?
Solution
(a) The flash temperature must lie between the bubble point (97'C) and the
dew point (110.5'C). Assume T = 105'C, which is 97 + 0.6(110.5 - 97). From Fig.
19.1, Kl = 2.68/1.2 = 2.23, Kz = 1.21/1.2 = 1.01, and K, = 0.554/1.2 = 0.462. The
value ofJis 0.6. The right-hand side of Eq. (19.12) becomes
0.33 0.37 0.30
==::---:-:---:- + + .,-,-.,.,---,:-:----c-:--
0.6 (2.23 - 1) + 1 0.6 (1.01 - I) + 1 0.6 (0.462 - 1) + 1
= 0.190 + 0.368 + 0.443 = 1.001
INTRODUCTION TO MULTICOMPONENT DISTILLATION 593
The flash temperature is 105°C. The composition of the liquid product is n-hexane,
19.0 mole percent; n-heptane, 36.8 mole percent; and'n-octane, 44.2 mole percent.
The composition of the vapor product is computed from the values of K and x:
,,-hexane, y ~ 0.190(2.23) ~ 0.424
n-heptane, y ~ 0.368(1.01) ~ 0.372
n-octane, y = 0.442(0.462) ~ 0.204
1.000
(b) To determine the temperature of the feed before flashing, an enthalpy balance is
made using 105°e as the reference temperature. The heats of vaporization at 105°C
and the average heat capacities of the liquid from 105 to 200 0 e are obtained
from the literature.
Cp. cal/mol·OC AH~, cal/mol
n-hexane 62 6370
n-heptane 70 7510
n-octane 78 8560
Based on liquid at 105°C, the enthalpies of the product are
H.,po, = 0.6[(0.424 x 6370) + (0.372 x 7510) + (0.204 x 8560)]
Hvapor = 4345 cal Hnquid = 0
For the feed,
Cp = (0.33 x 62) + (0.37 x 70) + (0.30 x 78)
= 69.8 cal/mol-°C
69.8(To - 105) = 4345
To = 167°C = preheat tmnperature
For a more accurate answer, the liquid heat capacities could be reevaluated for
the range 105 to 1700C.
FRACTIONATION OF
MULTICOMPONENT MIXTURES
As in the fractionation of binary mixtures, ideal plates are assumed in the design
of cascades, and the number of stages is subsequently corrected for plate efficien-
cies. The two limiting conditions of total reflux and minimum reflux are also
encountered.
Calculations for distillation plants are made by either of two methods. In
the first, a desired separation of components is assumed and the numbers of plates
above and below the feed are calculated from a chosen reflux ratio. In the second,
the number of plates above and below the feed is assumed, and the separation of
594 MASS TRANSFER AND lTS APPLICATIONS
components is calculated using assumed flows of reflux from the condenser and
vapor from the reboiler. In binary distillation the first method is the more common;
in mnlticomponent cases the second approach is preferred, especially in computer
calculations.
In final computer calculations, neither constant molal overflow nor temper-
ature-independent K factors are assumed, and plate efficiencies are also introduced,
but in preliminary estimates the simplifying assumptions are common. When the
activity coefficients are assumed to be temperature independent, group methods
are used in which the number of ideal stages in a cascade is the dependent variable.
The calculation gives this number without solving for either the plate temperature
or the compositions of the interstreams between plates. If IX values are temperature
dependent, these simple methods are not used and plate-by-plate calculations are
necessary. The temperature and liquid composition for plate 11 + 1 are calculated
by trial from those already known for plate 11, and the calculation proceeds from
plate to plate up or down the column.
In the rest of this chapter these methods are sampled in the following way:
the estimates of the minimum number of plates at infinite reflux and of minimum
reflux with an infinite number of plates are made by group methods on the
assumption of constant relative volatilities and are based on a design point of
view. An empirical relation for the number of plates at an operating reflux is
described.
KEY COMPONENTS. The objective of distillation is the separation of the feed
into streams of nearly pure products. In binary distillation, the purity is usually
defined by specifying X D and X B , the mole fraction of light component in the
distillate and bottoms products. As shown by Eq. (18.5), fixing these concentrations
fixes the amounts of both products per unit of feed. The reflux ratio is then chosen,
and the number of theoretical stages is calculated.
In multicomponent distillation, there are three or more components in
the products, and specifying the concentrations of one component in each
does not fully characterize these products. However, if the concentrations of
two out of three or three out of four components are specified for the distillate
and bottoms products, it is generally impossible to meet these specifications
exactly. An increase in reflux ratio or number of plates would increase the
sharpness of the separation, and the desired concentration of one component
in each product could be achieved, but it would be a coincidence if the other
concentrations exactly matched those specified beforehand. The designer generally
chooses two components whose concentrations or fractional recoveries in the
distillate and bottoms products are a good index of the separation achieved. After
these components are identified, they are called key components. Since the keys
must differ in volatility, the more volatile, identified by subscript L, is called the
light key, and the less volatile, identified by subscript H, is called the heavy key.
Having chosen the keys, the designer arbitrarily assigns small numbers
to X H in the distillate (XDH) and to XL in the bottoms (X BL), just as small
numbers are assigned to XDB and XBA in binary distillation. Choosing small
INTRODUCTION TO MULTICOMPONENT DISTILLATION 595
values for X BL and X VH means that most of the light key ends up in the
distillate and most of the heavy key in the bottoms. The distillate may be
nearly pure light key if the keys are the two most volatile components, since
components heavier than the heavy key will tend to concentrate in the liquid
phase and not be carried much above the feed plate. Often there are components
lighter than the light key, and these are nearly completely recovered in the
distillate. Any components heavier than the heavy key are usually completely
recovered in the bottoms. The exceptions to these generalizations are encountered
in distillation of very close boiling materials, such as mixtures of isomers.
Unlike the binary case, the choice of two keys does not give determinate
mass balances, because not all other mole fractions are calculable by mass
balances alone and equilibrium calculations are required to calculate the con-
centrations of the dew-point vapor from the top plate and the bubble-point liquid
leaving the reboiler.
Although any two components can be nominated as keys, usually they
are adjacent in the rank order of volatility. Such a choice is called a sharp
separation. In sharp separations the keys are the only components that appear in
both products in appreciable concentrations.
MINIMUM NUMBER OF PLATES. The Fenske equation (18.41) applies to any
two components, i and j, in a conventional plant at infinite reflux ratio. In this
case, the equation has the form
Xm/XBi
In - - -
XVj!XBj _ 1
N min = (19.13)
In rJ.ij
(19.14)
The subscripts D, F, and B in Eq. (19.14) refer to the temperatures of the
distillate, feed plate, and bottoms in the column.
Example 19.3. A mixture with 33 percent n-hexane, 37 percent n-heptane, and 30
percent n-octane to be distilled to give a distillate product with 0.01 mole fraction
n-heptane and a bottoms product with 0.01 mole fraction n-hexane. The column will
operate at 1.2 atm with 60 percent vaporized feed. Calculate the complete product
compositions and the minimum number of ideal plates at infinite reflux.
Solution
The n-hexane is the light key (LK), the n-heptane is the heavy key (HK), and the
12-octane is a heavy nonkey (HNK), which goes almost entirely to the bottoms. The
product compositions are found by mass balance assuming no n-octane and 0.99
mole fraction n-hexane in the distillate. Basing the calculations on a feed rate of
100 mol/h,
F = D + B = 100
596 MASS TRANSFER AND lTS APPLICATIONS
For hexane,
100 x 0.33 = 0.99D + (100 - D)(O.OI)
32
D= - = 32.65 mol/h
0.98
B = 100 - D = 67.35 molfh
The amount of hexane in the overhead is
DXD = 32.65 x 0.99 = 32.32 mol/h
The composition of the bottoms product can be calculated directly since this
stream contains all the octane, all but O.OID of the heptane, or 37 - 0.01(32.65) =
36.67 mol/h, and 0.68 mol/h hexane. Table 19.1 gives the compositions.
The minimum number of plates is obtained from the Fenske equation [Eq.
(19.13)J using the relative volatility of the light key to the heavy key, which is the
ratio of the K factors. The K values at the flash temperature were taken from Example
19.2 and are given in Table 19.1:
2.23
aLK.HK = 1.01 = 2.21
°
In-:---:-.9:-":9/0":'0:.,:,1
_ _0_.0--,1/_0._54_4
N min = - 1 = 10.8 1 = 9.8
In 2.21
The r,:inimum number of ideal stages is 9.8 plus a reboiler.
A more accurate estimate of N min can be obtained using a mean relative
volatility based on values at the top, middle, and bottom of the column. The top
temperature is about 75°C, the boiling point of n-hexane at 1.2 atm, and the relative
volatility is 2.53 from the vapor pressures in Fig. 19.1. The bottom temperature is
about 115°C, by a bubble-point calculation for the bottoms product, giving a relative
volatility of 2.15. From Eq. (19.14),
"LK.HK = .j2.53 x 2.21 x 2.15 = 2.29
Using In 2.29 in the denominator of Eq. (19.13) gives Nm;o = 9.4.
TABLE 19.1
Distillate Bottoms
Kat 105"C,
Component Feed, mol Moles x Moles x 1.2 atm
LK n-hexane 33 32.32 0.99 0.68 0.010 2.23
HK lI-heptane 37 0.33 0,01 36.67 0.544 1.01
HNK lI-octane 30 0 0 30 0.446 0.462
100 32.65 67.35
INTRODUCTION TO MULTICOMPONENT DISTILLATION 597
To check the assumption of no octane in the distillate, Eq. (19.13) can be
applied to heptane and octane using a = K2 /K, = 1.01(0.462 = 2.19:
In 0.01(0.544
x D ,(0.446
N min + 1 = 10.4
In 2.19
from which X D3 = 2.4 X 10- 6, which is negligible.
MINIMUM REFLUX RATIO. The minimum reflux ratio for a multicomponent
distillation has the same significance as for binary distillation; at this reflux ratio,
the desired separation is just barely possible, but an infinite number of plates is
required. The minimum reflux ratio is a guide in choosing a reasonable reflux
ratio for an operating column and in estimating the number of plates needed for
a given separation at certain values of the reflux ratio.
For a multicomponent system, the desired separation usually refers to
the amount of light key recovered in the distillate and the amount of heavy
key recovered in the bottoms. For example, the specifications might call for
98 percent recovery of the light key in the distillate and 99 percent recovery
of the heavy key in the bottoms. The actual mole fractions of the key components
in the products are not usually specified, since they depend on the amounts of
nonkey components in the feed. Small changes in these nonkey components in
the feed would change the product compositions without significantly affecting
the basic separation of the light and heavy keys.
Although the separation achieved in a column depends to some extent
on all components in the feed, an approximate value of the minimum reflux
ratio can be obtained by treating the mixture as a pseudo binary. Taking only the
moles oflight key and heavy key to make a new pseudofeed, product compositions
could be calculated along with a vapor-liquid equilibrium curve based on "LK-HK'
Then R Dm could be obtained using Eq. (18.43) as illustrated in Fig. 18.19. An
alternate equation for a saturated liquid feed 3 gives the minimum ratio of liquid
rate to feed rate for a binary mixture of A and B:
Lm;n (DXDA/FxFA) - "AB(DxDBIFxFB)
(19.15)
F "AB - 1
The terms in parentheses in Eq. (19.15) are the fractional recovery of A and Bin
the distillate product. For a multicomponent mixture, these terms would be the
specified recovery of light key in the distillate and the fraction of heavy key in the
feed that is allowed in the distillate. Note that the minimum value of L depends
mainly on the relative volatility. Changing the recovery of light key from 0.95 to
0.99 or even 0.999 changes Lm;nlF only about 4 to 5 percent, since the term
"AB(DxDBIFxFB ) is usually quite small. The feed composition has little effect in Eq.
(19.15), but when X'A is low, D will be small and the reflux ratio LID will be
greater than for a richer feed.
Equation (19.15) gives a good approximation for multicomponent mixtures
if the key components make up 90 percent or more of the feed. It generally
598 MASS TRANSFER AND ITS APPLICATIONS
overestimates the value of L needed for these cases, since components more
volatile than the light key or heavier than the heavy key are more easily separated
than the keys themselves. For other mixtures, the distribution of nonkey compo-
nents in the products must be estimated as a first step in a more rigorous
calculation of the minimum reflux ratio. The complete composition of the products
cannot be specified beforehand, and the amounts of nonkey components in the
products change with reflux ratio, even when the number of plates is adjusted to
maintain the desired separation of the key components. To help estimate the
product compositions at minimum reflux, the concepts of distributed and undistri-
buted components are introduced.
DISTRIBUTED AND UNDISTRIBUTED COMPONENTS. A distributed com-
ponent is found in both the distillate and bottoms products, whereas an undistri-
buted component is found in only one product. The light key and heavy key are
always distributed, as are any components having volatilities between those two
keys. Components more volatile than the light key are almost completely recovered
in the distillate, and those less volatile than the heavy key are found almost
completely in the bottoms. Whether such components are called distributed or
undistributed depends on the interpretation of the definition. For a real column
with a finite number of plates, all components are theoretically present in both
products, though perhaps some are at concentrations below the detectable limit.
If the mole fraction of a heavy nonkey component in the distillate is 10- 6 or less,
the component may be considered undistributed from a practical standpoint.
However, in order to start a plate-by-plate calculation to get the number of plates
for the column, this small but finite value needs to be estimated.
For the case of minimum reflux, the distinction between distributed and
undistributed components is clearer, since heavy nonkey components are generally
absent from the distillate, and light nonkey components are not present in the
bottoms. The concentrations of these species can go to zero because of an infinite
number of plates in the column and conditions that lead to a progressive reduction
in concentration for each plate beyond the feed plate.
Consider what is required for a heavy component to be completely absent
from the distillate. If X D is zero and constant molal overflow is assumed, the
material-balance equation for the upper part of the column [Eq. (18.14)] becomes
Y,+l =(~},X' (19.16)
For an ideal stage, Yn = Kx n, and the ratio of vapor concentrations for successive
plates is
y, KV
--=- (19.17)
Yn+l L
If K for the component being considered is less than L/V, y" will be smaller
than y,+l,and if this is true for all plates above the feed, an infinite number of
INTRODUCTION TO MULTICOMPONENT DISTILLATION 599
plates will make y go to zero. Of course, K is a function of temperature, but if K
is less than LIV at the feed-plate temperature, it will be even smaller for plates
above the feed, where the temperature is lower, and the decrease in y from plate
to plate will be more rapid. Heavy components will generally be undistributed if
K is more than 10 percent below the K for the heavy key or if the relative volatility
based on the heavy key is less than 0.9.
Light components are undistributed at minimum reflux if the value of
K is high enough for plates below the feed plate. If x. is assumed zero, Eq.
(18.16) leads to
I
Ym+l=yXm (19.18)
Thus,
Ym+lL
-=KV (19.19)
Ym
If K is always greater than IIV in the bottom section of the column, y will become
zero, justifying the assumption that x. = O. In practice, a K value or relative
volatility 10 percent greater than that of the light key nearly always means
an undistributed component. For a feed with components only slightly more
volatile than the light key or slightly less volatile than the heavy key, there are
techniques for calculating whether such components distribute and for estimating
their concentrations in the products'
CALCULATION OF MINIMUM REFLUX RATIO. At the minimum reflux ratio,
there are invariant zones above and below the feed plate where the composition
of the liquid and vapor do not change from plate to plate. These zones are similar
to the "pinch" regions shown in Fig. 18.19, but they do not necessarily occur at
the feed plate, as they do in binary distillation. If there are undistributed
components in the feed, their concentrations change from plate to plate near the
feed, and the concentrations have been reduced to zero when the invariant zone
is reached. Thus for a feed with both light and heavy undistributed components,
the liquid in the upper invariant zone will have all components except the heavy
undistributed ones.
At the lower invariant zone, all components except the light undistri-
buted ones will be present. The two invariant zones will be at different tempera-
tures and have different liquid and vapor compositions because of the undistri-
buted components. If the undistributed components are a small fraction of the
feed, the temperatures of the two invariant zones are nearly the same, and the
calculation of the minimum reflux ratio is relatively easy. When these temperatures
differ considerably, exact calculation of the minimum reflux is difficult because the
relative volatilities in the two zones are different. The following analysis is intended
to give the concepts underlying the determination of the minimum reflux ratio
and a convenient approximate equation. The complete derivation of the equation
for R Dm is beyond the scope of this text.
600 MASS TRANSFER AND ITS APPLICATIONS
The material-balance equation for each component in the upper section
of the column [Eq. (18.14)] can be written with y,IK in place of x" which
assumes perfect equilibrium between vapor and liquid:
L'Y'i D
V.n,iYn+l,i=T+ (19.20)
X Di
•
In the invariant zone, there is no change in composition from plate to plate, so
Y,+ l.i = Y'i and is designated Yroi. The subscript
00 denotes an infinite number of
plates. Equation (19.20) then becomes
L",Yroi D
VroYroi = - - + X Di (19.21)
KWi
Rearrangment of this equation leads to
(19.22)
or
D X Di
Ywi=- (19.23)
Vro 1 - (Lro/VroKroi)
Equation (19.23) is summed for all components appearing in the distillate,
and the sum must equal 1.0:
(19.24)
A similar treatment for the lower section of the column leads to
(19.25)
(19.26)
(19.27)
Equation (19.27) is summed over all the components appearing in the
bottoms product, and the signs are changed to make the denominator positive:
B xo·
LY",i=1.0=Vro L(L co IV~)-1
co COl
(19.28)
To determine the mlmmum reflux ratio using Eq. (19.24), a value of
RD is assumed, which gives LIV and DIV. The temperature at which Eq. (19.24)
is satisfied with all terms positive is determined by trial. Other sets of K values
INTRODUCTION TO MULTICOMPONENT DISTILLATION 601
will give a sum equal to 1.0 but with some negative terms, which have no physical
significance.
The flow rates in the lower section of the column are then calculated
from the feed condition: L = L + qF, 17 = V - (1 - q)F, where q is the number
of moles of liquid entering the stripping section per mole of feed [see Eqs. (18.24)
and (18.25)]. The temperature that satisfies Eq. (19.28) with all terms positive is
found. The temperature in the lower invariant zone should be higher than that
found for the upper invariant zone if there are some undistributed components.
If the calculated temperatures are the same or are in the wrong order, the assumed
RD is incorrect, and the calculations are repeated for a lower value of RD' Figure
19.2 shows how this procedure would apply to a binary system. For any selected
value of RD or L/V, a temperature would be found that corresponds to a pinch,
where the operating line touches the equilibrium line. For a higher R D , the upper
pinch occurs at a lower value of x or a higher temperature, and the lower pinch
occurs at a higher x and lower temperature. For a binary, the two pinch points
coincide at the true minimum reflux, but for a multicomponent feed, the invariant
zones differ in temperature and composition. Unfortunately, there is no simple
method of determining the temperature separation, and plate-to-plate calculations
are needed in the region between these zones to get the exact value of R Dm .
An approximate but fairly accurate method of determining R Dm was devel-
oped by Underwood. 6 The relative volatility for each component is taken to be
the same in the upper and lower invariant zones, and constant molal overflow is
assumed. The equations for the invariant zones are written in terms of the relative
volatility ai' where ai = K.!K"" with the heavy key generally taken as the reference
component. The two equations are combined with an overall material balance
and the feed-quality equation to give an equation that must be solved by trial.
The correct root", of this equation lies between the values of a for the keys. Other
FIGURE 19.2
Invariant zones in a binary system.
602 MASS TRANSFER AND ITS APPLICATIONS
values of 4> satisfy the equation but have no physical significance. The equation is
1- q = L: (X,XF' = L: J. (19.29)
(Xi - 4>
The value of 4> is then used to get Vmin/D:
Vrnin = RDm + 1= L C't.jXDi (19.30)
D (X, - 4>
Note that all components of the feed are included in the summation of Eq.
(19.29), but only those found in the distillate are included in Eq. (19.30). If there
are one or more compounds in the feed between the light and heavy keys, there
are two or more values of 4> between the (X values of the keys that will satisfy Eq.
(19.29). The correct value of 4> must then be found by solving Eqs. (19.29) and
(19.30) simultaneously.
Example 19.4. A mixture with 4 percent n-pentane, 40 percent n-hexane, 50 percent
n-heptane, and 6 percent n-octane is to be distilled at 1 atm with 98 percent of the
hexane and 1 percent of the heptane recovered in the distillate. (a) What is the
minimum reflux ratio for a liquid feed at the boiHng point? (b) What are the
temperatures and compositions in the upper and lower invariant zones?
Solution
The keys are n-hexane and n-heptane, and the other components are sufficiently
different in volatility to be undistributed. Below are given the moles in the products
per lOO mol of feed along with K values at 80n C.
XF FXF Moles in D XD Moles in B XB K 80 • KXF
ri-Cs 0.04 4 4 0.092 0 0 3.62 0.145
LK n-C6 0.40 40 39.2 0.897 0.8 0.014 1.39 0.556
HK n-C 7 0.50 50 0.5 0.011 49.5 0.879 0.56 0.280
ri-Cs 0.06 6 0 0 6 0.107 0.23 0.014
D ~ 43.7 B ~ 56.3 0.995
(a) The bubble point is 80n C, and at this temperature .LK-HK is 1.39/0.56 ~ 2.48.
For an approximate solution, use Eq. (19.15):
Lmin 0.98 - 2.48(0.01) ~ 0.645
F 2.48-1
Lmin = L min ~ = 0.645 _1_ = 1.48
D F D 0.437
To use the Underwood method, the K values at 80°C are converted to relative
volatilities and the root of Eq. (19.29) between 1 and 2.48 is found by trial. Since
q = 1.0, the terms must sum to zero.
INTRODUCTION TO MULTICOMPONENT DISTILLATION 603
~;
x" [;, q,= 15 [;, q, = 1.48
n-Cs 6.46 0.04 0.052 0.052
n-C6 2.48 0.40 1.012 0.992
n-C 7 1.0 0.50 -1.00 -1.042
n-C s 0.41 0.06 -0.023 -0.023
0.041 -0.021
By further trials or interpolation, q, = 1.487. From Eq. (19.30),
R Dm + 1=I lXiXDi
" - 1.487
6.64(0.092) 2.48(0.897) 1(0.011)
6.64 - 1.487 + 2.48 - 1.487 + I - 1.487
= 0.119 + 2.24 - 0.023 = 2.336
R Dm = 1.34
Note this is 10 percent less than the approximate value obtained using Eq.
(19.15).
(b) To get the conditions in the upper invariant zone, use Eq. (19.24) with the
fonowing flow ratios:
v D
- = Rn + I = 2.34 - = 0.427
D V
V VD
- = - - = 2.34 X 0.437 = 1.02 !:. = ~ = 1.34 = 0.573
F DF V RD +1 2.34
D XDi
y,= VI-LjVK,
xni Kw· y, Ks1 ' y, Ks1 •2' y, y;at81.1°C
n-C s 0.092 3.62 0.047 3.72 0.046 3.74 0.046 0.046
LK n-C6 0.897 1.39 0.652 1.43 0.639 1.44 0.636 0.637
HK n-C 7 0.011 0.56 -0.202 0.58 0.389 0.584 0.249 0.317
1.074 0.931 1.00
For an assumed T = 80°C, the calculated y for heptane is negative, so the
temperature must be slightly higher (so that K j > LjV). The term for heptane is very
sensitive to the assumed temperature, and the K values would have to be given to
four significant figures to make the summation 1.00. From the above values
T upper zone::::::: 81.PC
The vapor compositions in this zone (Yi in the final column) are corrected to the
correct sum by making most of the adjustment to the value for heptane.
604 MASS TRANSFER AND ITS APPLICATIONS
The vapor composition and temperature in the lower invariant zone are
obtained using Eq. (19.28) with the following flow ratios. For q = 1.0,
L=L+F
B BF 0.563 L L F 1
= = -= = - - = 0.552 = =- +- = 0.573 + - = 1.55
V FV 1.02 VVV 1.02
B x Bi
y; = V (LjVK;) - 1
;'COi Ku' y; K"". y; Yi at 83.3°C
LK II~C6 0.014 1.52 0.392 1.53 0.591 0.662
HK II~C7 0.879 0.618 0.322 0.622 0.325 0.326
n~C8 0.107 0.258 0.012 0.26 0.012 0.012
0.726 0.928 1.000
Here the tenn for hexane changes most rapidly with temperature, and the
final values of Yi are adjusted accordingly:
T lower zone", 83.rC
The liquid compositions in the invariant zones are calculated from Xj = yi/Kj •
Lower zone Upper zone
T,°C 83.3 81.1
LK x 0.433 0.442
Y 0.662 0.637
HK x 0.524 0.543
Y 0.326 0.317
C(LK_HK 2.46 2.47
YLK/YHK 2.03 2.01
Between the lower and upper invariant zones, the mole fraction of both keys
in the vapor phase decreases, and the ratio of light key to heavy key decreases. This
region of the column serves to remove the light nonkey components from the liquid
flowing down and the heavy nonkey component from the material that will flow up
and form the distillate. The small amount of reverse fractionation shown for the key
components is an interesting phenomenon that is often found in real columns
operating at close to the minimum reflux ratio.
CALCULATION OF REQUIRED REFLUX RATIO AND CONCENTRATION PRO-
FILES. The number of plates needed for a specified separation at a selected reflux
ratio can be determined by a plate-by-plate calculation called the Lewis-Matheson
method.' The amount of all components in the products must be specified to start
the calculation. From the composition of the distillate (which is the same as the
vapor from the top if a total condenser is used), the temperature and liquid
INTRODUCTION TO MULTICOMPONENT D1STILLATION 605
composition on the top plate can be determined by a dew-point calculation:
LX, = 1.0 = L y, (19.8)
K,
The K factors are stored as a table of values or calculated from empirical
equations for a given temperature and pressure. If the mixtures are nonideal,
equations for the activity coefficients are also required.
From the liquid composition on the top plate and the distillate composition,
material-balance equations are used to get the composition of the vapor from
plate 2:
(19.31)
Equal-molal overflow could be assumed, but if the calculations are done by
computer, an enthalpy balance would probably be made and the change in
pressure from stage to stage would also be allowed for. The calculations are
continued in this fashion, alternating the use of equilibrium and material-balance
relationships, until the composition is close to that of the feed. Similar calculations
are carried out for the lower section of the column starting with an estimated
reboiler or bottoms composition. The next step is to match the (!ompositions at
the feed stage for the two sets of calculations. Based on the differences for individual
components, the product compositions are adjusted and the calculations repeated
until all errors fall below a specifi,d value. In some procedures, the number of
plates and the feed plate are fixed beforehand, and the calculations are repeated
for different reflux ratios until the desired match is obtained at the designated feed
·plate.
Convergence to the specified conditions at the feed plate is easy when the
nonkeys are all heavy or all lightS'. In other situations it may be very difficult,
even when constant molal overflow or constant relative volatilities may be
assumed. For the general caSe it is necessary to use rather elaborate matrix
methods that form the basis of commercially available computer software. These
methods are discussed in Ref. 8b.
Concentration profiles calculated 7 for a depropanizer operating at 300 psia
are shown in Fig. 19.3. There are 40 stages counting the reboiler and condenser,
with feed entering as liquid on stage 20. The reflux ratio is 2.62, which is 1.25RDm •
The concentration profiles are characteristic of systems with components both
lighter and heavier than the keys. The maxima shown for the light key and the
heavy key and the shape of the other profiles can be better understood by
examining the operating lines and the equilibrium relationships for individual
components on a y-x diagram.
In the upper section of the column, LjV is nearly constant, and the operating
line for ethane is
Yn+ 1 = 0.724Xn + 0.061
The equilibrium relationship y = Kx is shown in Fig. 19.4a as a family of
straight lines, with the slope increasing as n increases. Each of the straight lines
606 MASS TRANSFER AND ITS APPLICATIONS
12 0
o~
0
~
60
~ [\..
40
'\
o.8
Propane, 11/\
o. 6 ~
~ ~Butane.HK
11
o.
41~ \
o. 2 ~ !\\~
~entane ~ne
.(
o ';;.L t- , FIGURE 19.3
40 30 20 10 o Temperature and concentration profiles for a
Stage number depropanizer.
is used only once for the appropriate plate number. Starting from Xn = 0.222, only
a few plates are needed to reduce x to about 0.05, which results in a "pinch." The
pinch shifts to lower values of x as the temperature increases and K increases, but
the change from plate to plate is very small, as shown in Fig. 19.3. At the feed
plate, the calculation is switched to the lower operating line, which gives a rapid
decrease in x and values less than 10- 6 at the bottom of the column.
A portion of the y-x diagram for propane is shown in Fig. 19.4b. The
equilibrium curve is shown as a line connecting the points for the individual plates,
each at a different temperature. From the feed plate up to plate 6, the temperature
is high enough so that K exceeds 1.0, and the vapor is richer in propane than the
liquid. The enrichment from plate to plate is nearly constant in this region. For
plate 5 and above, K is less than 1.0, and the increase in x and y per stage becomes
smaller. At plate 3, the equilibrium curve intersects the operating line, which in a
binary mixture would mean no further change in concentration. However, in this
INTRODUCTION TO MULTICOMPONENT DISTILLATION 607
0.5~--~--~--~---,
131
K:::: 2.25
0.1 0.2 0.3 0.4
x
lal
1.0,-----;;-----;------,------,---"
0.911----1----1----1-----,1<'----1
FIGURE 19.4
0.6 0.7 O.B 0.9 1.0 Operating-line diagrams for individual
x
components in a depropanizer; (a) for
Ibl C2 H 6 ; (b) for C3HS'
multicomponent system, the further decrease in temperature puts the equilibrium
curve below the operating line, and more steps can be made between the two lines,
which brings x back to lower values and gives a product with 77 percent propane.
The top plates of the column thus serve to enrich the distillate in ethane, mainly
by reducing the amount of propane. It would not be possible to get 90 percent
propane just by eliminating these few plates, since all the ethane ends up in the
608 MASS TRANSFER AND ITS APPLICATIONS
distillate product, and the peak propane concentration would just shift a few plates
closer to the feed. It would be possible to take a sidestream product a few plates
from the top that would be richer in propane, but for pure products, it would be
better to send the crude propane to a de-ethanizer column.
The concentration profile for the heavy key i-butane seems normal from the
top of the column to plate 15. In this region K is less than 0.7, and the operating
line lies above the equilibrium curve, so x decreases going up the column. From
the feed plate to plate 15 the temperature is high enough to make K> 0.7, and
the equilibrium line shifts to give values above the operating line. Therefore
i-butane increases in concentration on going up from the feed plate. The change
in plate temperature in this region is strongly influenced by the decrease in the
heavy nonkey components ll-butane and "-pentane. Without these or similar
components the heavy key would not show any maximum concentration. With a
relatively large amount of heavy nonkey components, ihe heavy key not only
shows a maximum but may increase more rapidly than the light key and exhibit
reverse fractionation for a few stages.
The first few plates above the reboiler show sharp changes in the concentra-
tions of ll-pentane and n-butane, similar to that shown by ethane near the top of
the column, and this results in a maximum concentration of i-butane at plate 34.
The concentration of ll-pentane is nearly constant from plate 35 to the feed plate
because of a pinch, and changes slowly as the temperature gradually decreases.
The n-butane does not show such a plateau because its volatility is about 0.8 that
of i-bntane, the heavy key.
NUMBER OF IDEAL PLATES AT OPERATING REFLUX. Although the precise
calculation of the number of plates in multicomponent distillation is best accom-
plished by computer, a simple empirical method due to GiIIiland 2 is much used
for preliminary estimates. The correlation requires knowledge only of the mini-
mum number of plates at total reflux and the minimum reflux ratio. The
correlation is given in Fig. 19.5 and is self-explanatory. An alternate method
devised by Erbar and Maddox! is especially useful when the feed temperature is
between the bubble point and dew point.
Example 19.5. Estimate the number of ideal plates required for the separation
specified in Example 19.3 if the reflux ratio is 1.5RDm _
Solution
From Example 19.3, the minimum number of ideal stages is 9.4 plus a reboiler. or
10.4. The value of RDm is obtained by the Underwood method.
XF XD
LK nwHexane 0.33 0.99 2.23 2.21
HK n-Heptane 0.37 0.01 1.01 1.0
n-Octane 0.30 0 0.462 0.457
INTRODUCTION TO MULTICOMPONENT DISTILLATION 609
1.0
0.8
0.6 -
0.4
r--
0.2
S
<-
'" + O. 1
;!, '" 0.08
0.06
0.04
0.02
0.01
0.01 0.02 0.04 0.10 0.2 0.4 0.6 1.0
RO-ROm FIGURE 19.5
Ro+1 Gilliland correlation.
For a liquid feed, q = 1,
By trial, q, = 1.45:
RDm + 1 = L C(jXDi :-2-::c.2,-:1(,-0',...99-,:) + 1.0(0.01) = 2.86
(Xi - 1.45 2.21 - 1.45 1 - 1.45
Rnm = 1.86
Rn = 1.5 X 1.86 = 2.79
RD - R Dm 2.79 - 1.86
0.245
RD +1 3.79
From Fig. 19.5,
N - N min
0.41
N +1
N - 10.4 = 0.41N + 0.41
10.81
N = - - = 18.3 stages
0.59
AZEOTROPIC AND EXTRACTIVE
DISTILLATION
The separation of components that have nearly the same boiling points is difficult
by simple distillation even if the mixtures are ideal, and complete separation may
610 MASS TRANSFER AND ITS APPLICATIONS
be impossible because of azeotrope formation. For such systems the separation
can often be improved by adding a third component to alter the relative volatility
of the original components. The added component may be a higher boiling liquid
or "solvent" that is miscible with both of the key components but is chemically
more similar to one of them. The key component that is more like the solvent
will have a lower activity coefficient in the solution than the other component, so
the separation is enhanced. This process is called extractive distillation and is like
liquid-liquid extraction with an added vapor phase.
One example of extractive distillation is the use of furfural to permit the
separation of butadiene from a mixture coniaining butane and butenes. Furfural,
which is a highly polar solvent, lowers the activity of butadiene more than it does
for butenes or butane, and the butadiene is concentrated in the furfural-rich stream
from the bottom of the column. Butadiene is distilled from the furfural, which is
returned to the top of the extractive distillation column. This column would
operate with a reflux containing butane and butenes, but the total liquid rate in
the top section of the column would be the reflux rate plus the flow rate of furfural.
Separation of the original mixture may also be enhanced by adding a solvent
that forms an azeotrope with one of the key components. This process is called
azeotropic distillation. The azeotrope forms the distillate or bottoms product from
the column and is later separated into solvent and key component. Usually the
material added forms a low-boiling azeotrope and is taken overhead, and such
materials are called "entrainers." The azeotrope will of course contain some of all
components in the feed, but it will have a much different ratio of the keys than
the feed.
An example of azeotropic distillation is the use of benzene to permit the
complete separation of ethanol and water, which forms a minimum-boiling azeo-
trope with 95.6 weight percent alcohol. The alcohol-water mixture with about 95
percent alcohol is fed to the azeotropic distillation column with a benzene-rich
stream added at the top. The bottom product is nearly pure alcohol, and the
overhead vapor is a ternary azeotrope. The overhead vapor is condensed and
separated into two phases. The organic layer is refluxed, and the water layer is
sent to a benzene recovery column. All the benzene and some alcohol is taken
overhead and sent back to the first column, and the bottoms stream is distilled in
a third column to give pure water and some of the binary azeotrope.
SYMBOLS
B Flow rate of heavy or bottom product, mol(h
Cp Molar heat capacity, calfg mol-oC; Cp , average value
D Flow rate of light or overhead product, molfh
F Feed rate, molfh
J Fraction of feed that is vaporized; j" of component i
H Enthalpy of stream, calfg mol or Btu/lb mol
K Equilibrium ratio, Ye/xe; K i • K j • of components i and j; K rer , of
INTRODUCTION TO MULTICOMPONENT DISTILLATION 611
reference component; Ka:;, for an infinite number of plates; K, strip-
ping section
L Flow rate of liquid, in general or in rectifying section, mOl/h; L min ,
minimum flow rate [Eq. (19.15)]; Lro, for an infinite number of plates;
"E, in stripping section
m Plate number in stripping section
N Number of ideal plates; N min, minimum number at total reflux
N, Number of components
n Plate number in rectifying section
P Total pressure, atm or lb f lft2; P', vapor pressure; P;, Pj, of com-
ponents i and j
P Partial pressure, atm or lbflft2; Pb of component i
q Moles of liquid to stripping section per mole of feed
RD Reflux ratio, LID; R Dm , minimum value
T Temperature, °C or of; J:bs' absolute temperature, K or oR; To, pre-
heat temperature (Example 19.2b)
V Flow rate of vapor, in general or in rectifying section, mOl/h; Vmin , at
minimum reflux ratio [Eq. 19.30)]; V.+ 1 , from plate n + 1; Vro ' for an
infinite number of plates; V, in stripping section
x Mole fraction of component in liquid phase; X B , in bottoms; XD, in
overhead; X DA , X DB • of components A and B in overhead; X F , in feed;
X H , of heavy key; XL, of light key; x,, of liquid in equilibrium with
vapor of composition Ye; Xi> of component i; Xle' equilibrium value for
component i; Xj' of component j; X m • X,!) on plates In and n
Y Mole fraction of component in vapor phase; YD, in overhead; y" of
vapor in equilibrium with liquid of composition X,; Yb Yj, of com-
ponents i and j; Yle' equilibrium value for component i; Ym, Yn. from
plates In and n; Yllb of component i from plate n; Yc:ol, for an infinite
number of plates
Greek letters
(J. Relative volatility, dimensionless; (J.AB, of component A relative to
component B in binary system; aB. aD' aF, in bottoms, overhead, and
feed, respectively; (J.LK.HK, of light key relative to heavy key; (J.i, of
component i, defined as KJ K",; (J.;j, of component i relative to compo-
nentj; "fi,j, average value, defined by Eq. (19.14)
f1H" Heat of vaporization, cal/mol
r/> Root of Eq. (19.29)
PROBLEMS
19.1 The feed to a conventional distillation column and the relative volatilities are
shown in Table 19.2. The recovery of component 2 in the distillate is 99 percent,
and 98 percent of component 3 is to leave in the bottoms. Calculate the minimum
number of plates.
612 MASS TRANSFER AND ITS APPLICATIONS
TABLE 19.2
Component XFi a;
1 0.05 2.1
2 0.42 1.7
3 0.46 1.0
4 0.07 0.65
19.2 For the conditions of Prob. 19.1, estimate the minimum reflux ratio if the feed is liquid
at the bubble point. About how many plates would be required at a reflux ratio 1.3
times the minimum?
19.3 The feed to a distillation column operating at 270 psia contains 10 percent ethane, 45
percent propane, 30 percent i-butane, and 15 percent n-hutane. Calculate the bubble
point of the feed and the fraction vaporized if the feed is heated 20°C above the bubble
point.
19.4 A five-component mixture is to be distilled with 99 percent recovery of the light and
heavy keys in the distillate and bottoms (Table 19.3). Calculate the product composi-
tions for the case of infinite reflux. Explain how these concentrations would shift as
the reflux ratio was decreased using the compositions at minimum reflux as a guide.
TABLE 19.3
Component XFi a;
1 0.06 2.6
LK 2 0.40 1.9
3 0.05 1.5
HK 4 0.42 1.0
5 0.07 0.6
19.5 A mixture of xylenes plus other aromatics is separated in a large fractionating column
operating at atmospheric pressure. Calculate the minimum number of plates and the
minimum reflux ratio for the conditions in Table 19.4. Use the GiIIiland correlation to
estimate the reflux ratio that will permit the separation to occur in 100 ideal stages. The
relative volatilities are calculated for 18 psia and 150°C, the estimated conditions near
the feed tray.
TABLE 19.4
Component bp,oC XFi a; % recovery in D
Ethyl benzene 136.2 0.054 1.23
p-Xylene 138.5 0.221 1.15
LK m-Xylene 139.1 0.488 1.13 99.0
HK o-Xylene 144.4 0.212 1.0 3.8
n-Propyl benzene 159.3 0.025 0.70
INTRODUCTION TO MULTICOMPONENT DISTILLATION 613
REFERENCES
1. Erbar, J. H., and R. N. Maddox: Petrol. Refiner, 40{5): 183 (1961).
2. GiIIiland, E. R.: [nd. Eng. Chem., 32:110 (1940).
3. King, C. J.: Separation Processes, 2nd ed., McGraw-Hill, New York, 1980, p. 416.
4. Lewis, W. L., and G. L. Matheson: Ind. Eng. Chem., 24:494 (1932).
5. Shiras, R. N., D. N. Hanson, and C. H. Gibson: Ind. Eng. Chem., 42:871 (1950).
6. Underwood, A. J. V.: Chem. Eng. Pwg., 44:603 (1948).
7. Vorhis, F. H., Chevron Research Co., private communication, 1983.
8. Wankat, P. C.: Equilibrium Staged Separations, Elsevier, New York, 1988; (a) p. 243, (b) pp. 251-263.
CHAPTER
20
LEACHING
AND
EXTRACTION
This chapter discusses the methods of removing one constituent from a solid
or liquid by means of a liquid solvent. These techniques fall into two categories.
The first, called leaching or solid extraction, is nsed to dissolve soluble matter from
its mixture with an insoluble solid. The second, called liquid extraction, is used to
separate two miscible liquids by the use of a solvent that preferentially dissolves
one of them. Although the two processes have certain common fundamentals, the
differences in equipment and, to some extent, in theory are sufficient to justify
separate treatment.
LEACHING
Leaching differs very little from the washing of filtered solids, as discussed in
Chap. 30, and leaching equipment strongly resembles the washing section of
various filters. In leaching, the amount of soluble material removed is often rather
greater than in ordinary filtration washing, and the properties of the solids may
change considerably during the leaching operation. Coarse, hard, or granular feed
solids may disintegrate into pulp or mush when their content of soluble material
is removed.
LEACHING AND EXTRACTION 615
Leaching Eqnipment
When the solids form an open, permeable mass throughout the leaching operation,
solvent may be percolated through an unagitated bed of solids. With impermeable
solids or materials that disintegrate during leaching, the solids are dispersed into
the solvent and are later separated from it. Both methods may be either batch or
continuous.
LEACHING BY PERCOLATION THROUGH STATIONARY SOLID BEDS.
Stationary solid-bed leaching is done in a tank with a perforated false bottom to
support the solids and permit drainage of the solvent. Solids are loaded into the
tank, sprayed with solvent until their solute content is reduced to the economical
minimum, and excavated. In some cases the rate of solution is so rapid that one
passage of solvent through the material is sufficient, but countercurrent flow of
solvent through a battery of tanks is more common. In this method, fresh solvent
is fed to the tank containing the solid that is most nearly extracted; it flows through
the several tanks in series and is finally withdrawn from the tank that has been
freshly charged. Such a series of tanks is called an extraction battery. The solid in
anyone tank is stationary until it is completely extracted. The piping is arranged
so that fresh solvent can be introduced to any tank and strong solution withdrawn
from any tank, making it possible to charge and discharge one tank at a time.
The other tanks in the battery are kept in countercurrent operation by advancing
the inlet and drawoff tanks one at a time as the material is charged and removed.
Such a process is sometimes called a Shanks process.
In some solid-bed leaching the solvent is volatile, necessitating the use of
closed vessels operated under pressure. Pressure is also needed to force solvent
through beds of some less permeable solids. A series of such pressure tanks
operated with countercurrent solvent flow is known as a diffusion battery.
MOVING-BED LEACHING.' In the machines illustrated in Fig. 20.1 the solids are
moved through the solvent with little or no agitation. The Bollman extractor (Fig.
20.1a) contains a bucket elevator in a closed casing. There are perforations in the
bottom of each bucket. At the top right-hand corner of the machine, as shown in
the drawing, the buckets are loaded with flaky solids such as soybeans and are
sprayed with appropriate amounts of half miscella as they travel downward. Half
miscella is the intermediate solvent containing some extracted oil and some small
solid particles. As solids and solvent flow concurrently down the right-hand side
of the machine, the solvent extracts more oil from the beans. Simultaneously the
fine solids are filtered out of the solvent, so that clean full miscella can be pumped
from the right-hand sump at the bottom of the casing. As the partially extracted
beans rise through the left side of the machine, a stream of pure solvent percolates
countercurrently through them. It collects in the left-hand sump and is pumped
to the half-miscella storage tank. Fully extracted beans are dumped from the
buckets at the top of the elevator into a hopper from which they are removed by
616 MASS TRANSFER AND ITS APPLICATIONS
o Half misce//a
Extracted
+-- reed
meal
flake JL-~=:~==~~
We! SOlven]
---'>-
hopper
Oil and
,-+
. Solvent
--.l::::::~~~~
Full misce//a
(0) (b)
FIGURE 20.1
Moving~bed leaching equipment: (a) Bollman extractor; (b) Hildebrandt extractor.
paddle conveyors. The capacity of typical units is 50 to 500 tons of beans per 24-h
day.
The Hildebrandt extractor shown in Fig. 20.1b consists of a U-shaped screw
conveyor with a separate helix in each section. The helices turn at different speeds
to give considerable compaction of the solids in the horizontal section. Solids are
fed to one leg of the U and fresh solvent to the other to give countercurrent flow.
DISPERSED-SOLID LEACHING. Solids that form impermeable beds, either before
or during leaching, are treated by dispersing them in the solvent by mechanical
agitation in a tank or flow mixer. The leached residue is then separated from the
strong solution by settling or filtration.
Small quantities can be leached batchwise in this way in an agitated vessel
with a bottom drawoff for settled residue. Continuous countercurrent leaching is
obtained with several gravity thickeners connected in series, as shown in Fig. 17.3,
or when the contact in a thickener is inadequate by placing an agitator tank in
the equipment train between each pair of thickeners. A still further refinement,
used when the solids are too fine to settle out by gravity, is to separate the residue
from the miscella in continuous solid-bowl helical-conveyor centrifuges. Many
other leaching devices have been developed for special purposes, such as the
solvent extraction of various oilseeds, with their specific design details governed
by the properties of the solvent and of the solid to be leached. 5 The dissolved
material, or solute, is often recovered by crystallization or evaporation.
LEACHING AND EXTRACTION 617
Principles of Continuous Countercurrent Leaching
The most important method of leaching is the continuous countercurrent method
using stages. Even in an extraction battery, where the solid is not moved physically
from stage to stage, the charge in anyone cell is treated by a succession of liquids
of constantly decreasing concentration as if it were being moved from stage to
stage in a countercurrent system.
Because of its importance, only the continuous countercurrent method is
discussed here. Also, since the stage method is normally used, the differential-
contact method is not considered. In common with other stage cascade operations,
leaching may be considered, first, from the standpoint of ideal stages and, second,
from that of stage efficiencies.
IDEAL STAGES IN COUNTERCURRENT LEACIDNG. Figure 20.2 shows a
material-balance diagram for a continuous countercurrent cascade. The stages
are numbered in the direction of flow of the solid. The V phase is the liquid that
overflows from stage to stage in a direction counter to that of the flow of the solid,
dissolving solute as it moves from stage N to stage 1. The L phase is the solid
flowing from stage 1 to stage N. Exhausted solids leave stage N, and concentrated
solution overflows from stage 1.
It is assumed that the solute-free solid is insoluble in the solvent and that
the flow rate of this solid is constant throughout the cascade. The solid is porous
and carries with it an amount of solution that mayor may not be constant. Let
L refer to the flow of this retained liquid and V to the flow of the overflow solution.
The flows V and L may be expressed in mass per unit time or may be based on
a definite flow of dry solute-free solid. Also, in accordance with standard nomen-
clature, the terminal concentrations are as follows:
Solution on entering solid Xa
Solution on leaving solid Xb
Fresh solvent entering the system Yb
Concentrated solution leaving the system Ya
As in absorption and distillation, the quantitative performance of a counter-
current system can be analyzed by utilizing an equilibrium line and an operating
1;
~Lb
N
L-_--'
~~ nr'
xb
FIGURE 20.2
Countercurrent leaching cascade.
618 MASS TRANSFER AND ITS APPLICATIONS
line, and as before, the method to be used depends on whether these lines are
straight or curved.
EQUILIBRIUM. In leaching, provided sufficient solvent is present to dissolve all
the solute in the entering solid and there is no adsorption of solute by the solid,
equilibrium is attained when the solute is completely dissolved and the concentra-
tion of the solution so formed is uniform. Such a condition may be obtained simply
or with difficulty, depending on the structure of the solid. These factors are
considered when stage efficiency is discussed. At present, it is assumed that the
requirements for equilibrium are met. Then thc concentration of the liquid retained
by the solid leaving any stage is the same as that of the liquid overflow from the
same stage. The equilibrium relationship is, simply, x, = y,.
OPERATING LINE. The equation for the operating line is obtaiued by writing
material balances for that portion of the cascade consisting of the first n units, as
shown by the control surface indicated by the dashed lines in Fig. 20.2. These
balances are
Total solution: ~+1 +La= Ya+L" (20.1)
Solute: ~+lYII+l + Laxa = L xn + YaYa
ll (20.2)
Solving for y,+ 1 gives the operating-line equation, which is the same as that
derived earlier for the general case of an equilibrium-stage cascade [Eq. (17.7)]:
_ (~) L,x,
Yn+l - Xn + v..Yc - (20.3)
Vn + 1 Vn+ 1
As usual, the operating line passes through the points (x" y,) and (x b, Yb)' and
if the flow rates are constant, the slope is (LjV).
CONSTANT AND VARIABLE UNDERFLOW. Two cases are to be considered. If
the density and viscosity of the solution change considerably with solute con-
centration, the solids from the lower numbered stages may retain more liquid than
those from the higher numbered stages. Then, as shown by Eq. (20.3), the slope
of the operating line varies from unit to unit. If, however, the mass of solution
retained by the solid is independent of concentration, L, is constant, and the
operating line is straight. This condition is called constant solution underfiow. If
the underflow is constant, so is the overflow. Constant and variable underflow are
given separate consideration.
NUMBER OF IDEAL STAGES FOR CONSTANT UNDERFLOW. When the operat-
ing line is straight a McCabe-Thiele construction can be used to determine the
number of ideal stages, but since in leaching the equilibrium line is always straight,
Eq. (17.24) can be used directly for constant underflow. The use of this equation
is especially simple here because Y: = x, and yt = X b •
LEACHING AND EXTRACfION 619
Equation (17.24) cannot be used for the entire cascade if La, the solution
entering with the unextracted solids, differs from L, the underfiows within the
system. Equations have been derived for this situation,'·8 but it is easy to calculate,
by material balances, the performance of the first stage separately and then to
apply Eq. (17.24) to the remaining stages.
Example 20.1. By extraction with kerosene, 2 tons of waxed paper per day is to be
dewaxed in a continuous countercurrent extraction system that contains a number
of ideal stages. The waxed paper contains, by weight, 25 percent paraffin wax and
75 percent paper pulp. The extracted pulp is put through a dryer to evaporate the
kerosene. The pulp, which retains the unextracted wax after evaporation, must not
contain over 0.21b of wax per 100 lb of wax-free pulp. The kerosene used for the
extraction contains 0.05 lb of wax per 100 lb of wax-free kerosene. Experiments show
that the pulp retains 2.0 lb of kerosene per pound of kerosene- and wax-free pulp as
it is transferred from cell to cell. The extract from the battery is to contain SIb of
wax per 100lb of wax-free kerosene. How many stages are required?
Solution
Any convenient units may be used in Eq. (17.24) as long as the units are consistent
and as long as the overflows and underflows are constant. Thus, mole fractions, mass
fractions, or mass of solute per mass of solvent are all permissible choices for
concentration. The choice should be made that gives constant underflow. In this
problem, since it is the ratio of kerosene to pulp that is constant, flow rates should
be expressed in pounds of kerosene. Then, all concentrations must be in pounds of
wax per pound of wax-free kerosene. The unextracted paper has no kerosene, so the
first cell must be treated separately. Equation (17.24) can then be used for calculating
the number of remaining units.
The flow quantities and concentrations for this cascade are shown in Fig. 20.3.
The kerosene in with the fresh solvent is found by an overall wax balance. Take a
basis of 100 lb of wax- and kerosene-free pulp, and let s be the pounds of kerosene
So/vent Extroct
a0.51b wax 51b wax
10.0. Ib kerosene 1000.Ib kerasene
~
A"rst
rN-I) stages
stage
k-.,...
Extracted
pulp o.21b wax
1000.Ibpulp
51bwax 7 Wax paper 2 T/day
25% wax
T5 •% pulp
lOO /b kerosene
21b kerosene
I/bpulp
FIGURE 20.3
Material-balance diagram for Example 20.1.
620 MASS TRANSFER AND ITS APPLICATIONS
fed in with the fresh solvent. The wax balance, in pounds, is as follows:
Wax in with pulp, lOO x ~ = 33.33
Wax in with solvent, 0.0005s
Total wax input, 33.33 + 0.0005s
Wax out with pulp, 100 x 0.002 = 0.200
Wax out with extract, (s - 200)0.05 = 0.05s - 10
Total wax output, 0.05s - 9.80
Therefore
33.33 + 0.0005s = 0.05s - 9.80
From this s = 871 lb. The kerosene in the exhausted pulp is 2001b, and that in the
strong solution is 871 - 200 = 671 lb. The wax in this solution is 671 x 0.05 =
33.55 lb. The concentration in the underflow to the second unit equals that of the
overflow from the first stage, or 0.051b of wax per pound of kerosene. The wax in
the underflow to unit 2 is 200 x 0.05 = 10 lb. The wax in the overflow from the
second cell to the first is, by a wax balance over_ the- first unit,
10 + 33.55 - 33.33 = 1O.221b
The concentration of this stream is, therefore, 10.22/871 = 0.0117. The quantities
for substitution in Eq. (17.24) are
Y. = 0.0117
0.2
x, = yt = - = 0.001 Yo = 0.0005
200
Equation (17.24) gives, since stage 1 has already been taken into account,
N _ I = In [(0.0005 - 0.001)/(0.0117 - 0.05))
In [(0.0005 - 0.0117)/(0.001 - 0.050))
In [(0.05 - 0.0117)/(0.001 - 0.0005)) = 3
In [(0.050 - 0.001)/(0.01 17 - 0.0005)J
The total number of ideal stages is N = 1 + 3 = 4.
NUMBER OF IDEAL STAGES FOR VARIABLE UNDERFLOW. When the under-
flow and overflow vary from stage to stage, a modification of the McCabe-Thiele
graphical method may be used for calculations. The terminal points on the
operating line are determined using material balances, as was done in Example
20.1. Assuining the amounts of underflow L is known as a function of underflow
composition, an intermediate value of x. is chosen to fix L" and v" + 1 is calculated
from Eq. (20.1). The composition of the overflow Y.+ 1 is then calculated from Eq.
(20.2), and the point (x" Y.+ ,) is plotted along with the terminal compositions to
give the curved operating line. Unless there is a large change in L and V or the
operating line is very close to the equilibrium line, only one intermediate point
need be calculated.
LEACHING AND EXTRAcrlON 621
Example 20.2. Oil is to be extracted from meal by means of benzene using a
continuous countercurrent extractor. The unit is to treat 1000 kg of meal (based on
completely exhausted solid) per hour. The untreated meal contains 400 kg of oil and
25 kg of benzene. The fresh solvent mixture contains 10 kg of oil and 655 kg of
benzene. The exhausted solids are to contain 60 kg of unextracted oil. Experiments
carried out under conditions identical with those of the projected battery show that
the solution retained depends on the concentration of the solution, as shown in Table
20.1. Find (a) the concentration of the strong solution, or extract; (b) the concentration
of the solution adhering to the extracted solids; (c) the mass of solution leaving with
the extracted meal; (d) the mass of extract; (e) the number of stages required. All
quantities are given on an hourly basis.
Solution
Let x and y be the mass fractions of oil in the underflow and overflow solutions.
At the solvent inlet,
Vb = 10 + 655 = 665 kg solutionfh
10
Yb = - = 0.015
665
Determine the amount and composition of the solution in the spent solids by trial.
If Xb = 0.1, the solution retained, from Table 20.1, is 0.505 kg/kg. Then
Lb = 0.505(1000) = 505 kgfh
60
Xb =- = 0.119
505
From Table 20.1, the solution retained is 0.507 kg/kg:
Lb = 0.507(1000) = 507
60
Xb = - = 0.118 (close enough)
507
Benzene in the underllow at 4 is 507 - 60 = 447 kgfh.
At the solid inlet,
L. = 400 + 25 = 425 kg solutionfh
400
x.=- = 0.941
425
TABLE 20.1
Data for Example 20.2
Concentration, Solution retained, Concentration, Solution retained,
kg oil/kg solution kg/kg solid kg oil/kg solution kg/kg solid
0.0 0.500 0.4 0.550
0.1 0.505 0.5 0.571
0.2 0.515 0.6 0.595
0.3 0.530 0.7 0.620
622 MASS TRANSFER AND ITS APPLICATIONS
Oil in extract = oil in -60 = 10 + 400 - 60 = 350 kg/h. Benzene in extract =
655 + 25 - 447 = 233Ib/h.
v" = 350 + 233 = 583 kg/h
350
y.=-=0.600
583
The answers to parts (a) to (d) are
(a) Y. = 0.60
(b) x, = 0.118
(c) L, = 507 kg/h
(d) V. = 583 kg/h
(e) To determine an intermediate -point on the operating line, choose XII = 0.50:
L, = solution retained = 0.571(1000) = 571 kg/h
By overall balance, [Eq. (20.1)],
v" + 1 = 583 + 571 - 425 = 729 kg/h
An oil balance gives
= 571(0.5) + 583(0.6) - 400
= 235.3 kg/h
235.3
Y,+l = - - = 0.323
729
The points (xn'YII+d plus the points (xa,Ya) and (Xb,Yb) define a slightly curved
operating line, as shown in Fig. 2004. Slightly more than four stages are required:
N=4
SATURATED CONCENTRATED SOLUTION. A special case of leaching is en-
countered when the solute is of limited solubility and the concentrated solution
reaches saturation. This situation can be treated by the above methods. 7 The
solvent input to stage N should be the maximum that is consistent with a saturated
overflow from stage 1, and all liquids except that adhering to the underflow from
stage 1 should be unsaturated. If too little solvent is used and saturation is attained
in stages other than the first, all but one of the "saturated" stages are unnecessary,
and the solute concentration in the underfiow from stage N is higher than it needs
to be.
STAGE EFFICIENCIES. In some leaching operations the solid is entirely imper-
vious and inert to the action of the solvent and carries a film of strong solution
on its surface. In such a case the process simply involves the equalization of
concentrations in the bulk of the extract and in the adhering film. Such a process
LEACHING AND EXTRACTION 623
1.0
0.9 /
0.8 /
o. 7 /
o. 6 / I
I
y
o. 5
1/ /'
/'
o. 4
, V /'
o. 3 / /
/ V
o. 2
o. L V
~V Iv
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 O.B 0.9 1.0
FIGURE 20.4
McCabe·Thiele diagram for leach·
x ing (Example 20.2).
is rapid, and any reasonable time of contact will bring about equilibrium. The
countercurrent leaching process shown in Fig. 17.3 is of this type, and the stage
efficiency is taken as unity in calculations for such processes.
In other situations the solute is distributed through a more or less permeable
solid. Here the rate of leaching is largely governed by the rate of diffusion through
the solid, as discussed in Chap. 21.
LIQUID EXTRACTION
When separation by distillation is ineffective or very difficult, liquid extraction
is one of the main alternatives to consider. Close-boiling mixtures or substances
that cannot withstand the temperature of distillation, even under a vacuum, may
often be separated from impurities by extraction, which utilizes chemical differ-
ences instead of vapor-pressure differences. For example, penicillin is recovered
from the fermentation broth by extraction with a solvent such as butyl acetate,
after lowering the pH to get a favorable partition coefficient. The solvent is then
treated with a buffered phosphate solution to extract the penicillin from the solvent
and give a purified aqueous solution, from which penicillin is eventually produced
by drying. Extraction is also used to recover acetic acid from dilute aqueous
solutions; distillation would be possible in this case, but the extraction step
considerably reduces the amount of water to be distilled.
One of the major uses of extraction is to separate petroleum products
that have different chemical structures but about the same boiling range. Lube oil
fractions (bp> 300°C) are treated with low-boiling polar solvents such as phenol,
furfural, or methyl pyrrolidone to extract the aromatics and leave an oil that
624 MASS TRANSFER AND ITS APPLICATIONS
contains mostly paraffins and naphthenes. The aromatics have poor viscosity-
temperature characteristics, but they cannot be removed by distillation because
of the overlapping boiling-point ranges. In a similar process, aromatics are
extracted from catalytic reformate using a high-boiling polar solvent, and the
extract is later distilled to give pure benzene, toluene, and xylenes for use as
chemical intermediates. An excellent solvent for this use is the cyclic compound
C.H BS0 2 (Sulfolane), which has high selectivity for aromatics and very low
volatility (bp, 290°C).
When either distillation or extraction may be used, the choice is usually
distillation, in spite of the fact that heating and cooling are needed. In extraction
the solvent must be recovered for reuse (usually by distillation), and the combined
operation is more complicated and often more expensive than ordinary distillation
without extraction. However, extraction does offer more flexibility in choice of
operating conditions, since the type and amount of solvent can be varied as well
as the operating temperature. In this sense, extraction is more like gas absorption
than ordinary distillation. In many problems, the choice between methods should
be based on a comparative study of both extraction and distillation.
Extraction may be used to separate more than two components; and
mixtures of solvents, instead of a single solvent, are needed in some applica-
tions. These more complicated methods are not treated in this text.
Extraction Equipment'O
In liquid-liquid extraction, as in gas absorption and distillation, two phases
must be brought into good contact to permit transfer of material and then
be separated. In absorption and distillation the mixing and separation are
easy and rapid. In extraction, however, the two phases have comparable densities,
so that the energy available for mixing and separation-if gravity flow is used-is
small, much smaller than when one phase is a liquid and the other is a gas. The
two phases are often hard to mix and harder to separate. The viscosities of both
phases, also, are relatively high, and linear velocities through most extraction
equipment are low. In some types of extractors, therefore, energy for mixing and
separation is supplied mechanically.
Extraction equipment may be operated batchwise or continuously.
A quantity of feed liquid may be mixed with a quantity of solvent in an agitated
vessel, after which the layers are settled and separated. The extract is the
layer of solvent plus extracted solute, and the raffinate is the layer from which
solute has been removed. The extract may be lighter or heavier than the raffinate,
and so the extract may be shown coming from the top of the equipment in some
cases and from the bottom in others. The operation may of course be repeated if
more than one contact is required, but when the quantities involved are large and
several contacts are needed, continuous flow becomes economical. Most extraction
equipment is continuous with either successive stage contacts or differential
contacts. Representative types are mixer-settlers, vertical towers of various kinds
LEACHING AND EXTRACTION 625
TABLE 20.2
Performance of commercial extraction equipment
Liquid Plate Spacing
capacity 0' between
of combined stage plates or
streams, HTU,t efficiency, stages, Typical
Type ft'fft'-h ft % in. applications
Mixer-settler 75-100 Duo-Sollube-oil process
Spray column 50-250 10-20 Ammonia extraction of
salt from caustic soda
Packed column 20-150 5-20 Phenol recovery
Perforated-plate 10-200 1-20 6-24 30-70 Furfurallube-oil process
column
Baffle column 60-105 4-6 5-10 4-6 Acetic acid recovery
Agitated tower 50-100 1-2 80-100 12-24 Pharmaceuticals and
organic chemicals
t HTUs arc discussed in Chap. 22, page 704.
that operate by gravity flow, agitated tower extractors, and centrifugal extractors.
The characteristics of various types of extraction equipment are listed in Table
20.2. Liquid-liquid extraction can also be carried out using porous membranes as
described in Chap. 26. The method has promise for difficult separations.
MIXER-SETTLERS. For batchwise extraction the mixer and settler may be the
same unit. A tank containing a turbine or propeller agitator is most common. At
the end of the mixing cycle the agitator is shut off, the layers allowed to separate
by gravity, and extract and raffinate drawn off to separate receivers through a
bottom drain line carrying a sight glass. The mixing and settling times required
for a given extraction can be determined only by experiment; 5 min for mixing
and 10 min for settling are typical, but both shorter and much longer times are
common.
For continuous flow the mixer and settler are usually separate pieces of
equipment. The mixer may be a small agitated tank provided with inlets and a
drawoff line and baffles to prevent short-circuiting or it may be a motionless
mixer or other flow mixer. The settler is often a simple continuous gravity decanter.
With liquids that emulsify easily and have nearly the same density it may be
necessary to pass the mixer discharge through a screen or pad of glass fiber to
coalesce the droplets of the dispersed phase before gravity settling is feasible. For
even more difficult separations, tubular or disk-type centrifuges are employed.
If, as is usua~ several contact stages are required, a train of mixer-settlers is
operated with countercurrent flow, as shown in Fig. 20.5. The raffinate from each
settler becomes the feed to the next mixer, where it meets intermediate extract or
fresh solvent. The principle is identical with that of the continuous countercurrent
stage leaching system shown in Fig. 17.3.
626 MASS TRANSFER AND ITS APPLICATIONS
Final exlracl
Feed
Final
ra!finole
Solvenl
Mixer No.1 Mixer No.2 Mixer No 3
FIGURE 205
Mixer~settler extraction system.
SPRAY AND PACKED EXTRACTION TOWERS. These tower extractors give
differential contacts, not stage contacts, and mixing and settling proceed simultan-
eously and continuously. In the spray tower shown in Fig. 20.6, the lighter liquid
is introduced at the bottom and distributed as small drops by the nozzles A. The
drops oflight liquid rise through the mass of heavier liquid, which flows downward
as a continuous stream. The drops are collected at the top and form the stream
of light liquid leaving the top of the tower. The heavy liquid leaves the bottom of
the tower. In Fig. 20.6, light phase is dispersed and heavy phase is continuous.
This may be reversed, and the heavy stream sprayed into the light phase at the
top of the column, to fall as dispersed phase through a continuous stream of light
liquid. The choice of dispersed phase depends on the flow rates, viscosities, and
wetting characteristics of both phases and is usually based on experience. The
phase with the higher flow rate may be dispersed to give a greater interfacial area,
but if there is a significant difference in viscosities, the more viscous phase may
be dispersed to give a higher settling rate. Some say that in packed towers the
continuous phase should wet the packing, but this need not be true for good
performance. Whichever phase is dispersed, the movement of drops through the
column constantly brings the liquid in the dispersed phase into fresh contact with
the other phase to give the equivalent of a series of mixer-settlers.
There is continuous transfer of material between phases, and the composition
of each phase changes as it flows through the tower. At any given level, of course,
equilibrium is not reached; indeed, it is the departure from equilibrium that
provides the driving force for material transfer. The rate of mass transfer is
relatively low compared to distillation or absorption, and a tall column may be
equivalent to only a few perfect stages.
In actual spray towers, contact between the drops and the continuous phase
often appears to be most effective in the region where the drops are formed. This
could be due to a higher rate of mass transfer in the newly formed drops or to
LEACHING AND EXTRACfION 627
Heavy liquid Light liquid oul/el
inlet
Heavy liqUid
I
Light
liquid
outlet
FIGURE 20.6
inlet Spray tower; A, nozzle to distribute light liquid.
backmixing of the continuous phase. In any case, adding more height does not
give a proportional increase in the number of stages; it is much more effective to
redisperse the drops at frequent intervals throughout the tower. This can be done
by filling the tower with packing, such as rings or saddles. The packing causes the
drops to coalesce and reform and, as shown in Table 20.2, may increase the number
of stages in a given height of column. Packed towers approach spray towers in
simplicity and can be made to handle almost any problem of corrosion or pressure
at a reasonable cost. Their chief disadvantage is that solids tend to collect in the
packing and cause channeling.
Flooding velocities in packed towers. If the flow rate of either the dispersed phase
or the continuous phase is held constant and that of the other phase gradually in-
creased, a point is reached where the dispersed phase coalesces, the holdup of that
phase increases, and finally both phases leave together through the continuous-
phase outlet. The elfect, like the corresponding action in an absorption column,
628 MASS TRANSFER AND ITS APPLICATIONS
I""
10
10 10 2 103
f./v;; +Ad) 2,oc
°vPc
FIGURE 20.7
Flooding velocities in packed extraction towers.
is called flooding. The larger the flow rate of one phase at flooding, the smaller
is that of the other. A column obviously should be operated at flow rates below
the flooding point.
Flooding velocities in packed columns· can be estimated from Fig. 20.7. In
this figure the abscissa is the group
(JI[ + A.)2 p,
The ordinate is the group
!± (!!..)O.2(a,)1.5
!J.p p, e
where v,., V,.d = superficial velocities of continuous and dispersed phases, respec-
tively, ft/h
/1, = viscosity of continuous phase, lb/ft-h
(J = interfacial tension between phases, dyn/cm
p, = density of continuous phase, lb/ft'
!J.p = density difference between phases, lb/ft'
a, = specific surface area of packing, ft>/ft'
e = fraction voids or porosity of packed section
LEACHING AND EXTRAcnON 629
The groups in Fig. 20.7 are not dimensionless, and the proper units must be
used.
PERFORATED-PLATE TOWERS. Redispersion of liquid drops is also done by
transverse perforated plates like those in the sieve-plate distillation tower described
in Chap. 17. The perforations in an extraction tower are 1! to 4! mm in
diameter. Plate spacings are 150 to 600 mm (6 to 24 in.). Usually the light liquid
is the dispersed phase, and down corners carry the heavy continuous phase from
one plate to the next. As shown in Fig. 20.8a, light liquid collects in a thin layer
beneath each plate and jets into the thick layer of heavy liquid above. A modified
design is shown in Fig. 20.8b, in which the perforations are on one side of the
plate only, alternating from left to right from one plate to the next. Nearly all the
extraction takes place in the mixing zone above the perforations, with the light
liquid (oil) rising and collecting in a space below the next higher plate, then flowing
transversely over a weir to the next set of perforations. The continuous-phase
heavy liquid (solvent) passes horizontally from the mixing zone to a settling zone
in which any tiny drops of light liquid have a chance to separate and rise to the
plate above. This design often greatly reduces the quantity of oil carried downward
by the solvent and increases the effectiveness of the extractor.
BAFFLE TOWERS. These extraction towers contain sets of horizontal baffle plates.
Heavy liquid flows over the top of each baffle and cascades to the one beneath;
light liquid flows under each baffle and sprays upward from the edge through the
heavy phase. The most common arrangements are disk-and-doughnut baffles and
segmental, or side-to-side, baffles. In both types the spacing between baffles is 100
to 150 mm (4 to 6 in.).
Baffle towers contain no small holes to clog or be enlarged by corrosion.
They can handle dirty solutions containing suspended solids; one modification of
the disk-and-doughnut towers even contains scrapers to remove deposited solids
from the baffles. Because the flow of liquid is smooth and even, with no sharp
Layer of Perforoted
light liq",U/",d.-f.7~;qfi9 plate
Downcomer
(0)
(b)
FIGURE 20.8
Perforated-plate extraction towers: (a) perforations in horizontal plates; (b) cascade weir tray with
mixing and settling zones. (After Bushel! and Fiocco. 4 )
630 MASS TRANSFER AND ITS APPLICATIONS
changes in velocity or direction, baffle towers are valuable for liquids that emulsify
easily. For the same reason, however, they are not effective mixers, and each baffle
is equivalent to only a 0.05 to 0.1 ideal stage.!'
AGITATED TOWER EXTRACTORS. Mixer-settlers supply mechanical energy for
mixing the two liquid phases, but the tower extractors so far described do not.
They depend on gravity flow both for mixing and for separation. In some tower
extractors, however, mechanical energy is provided by internal turbines or other
agitators, mounted on a central rotating shaft. In the rotating-disk contactor
shown in Fig. 20.9a, flat disks disperse the liquids and impel them outward toward
the tower wall, where stator rings create quiet zones in which the two phases can
Variable speed
drive unit
- Light ___ Light phase
Interface, phase Interface outlet
can be at outlet can be at
top or top or
bottom bottom
Heavy Heavy _
phase phase Shaft
-'
inlet inlet York mesh ™
knitted mesh
Shaft Agitator
impeller
Rotor
disk Inner stators
Stator Outer stator
Mixing zone
Settfing zone
_ Light phase
inlet
inlet Manway
; Guide
bushing bushing
Heavy phase Heavy phase
outlet outlet
lal Ibl
FIGURE 20.9
Agitated extraction towers: (a) rotating-disk unit; (b) York-Scheibel extractor.
LEACHING AND EXTRACTION 631
separate. In other designs, sets of impellers are separated by calming sections to
give, in effect, a stack of mixer-settlers one above the other. In the York-Scheibel
extractor illustrated in Fig. 20.9b, the regions surrounding the agitators are packed
with wire mesh to encourage coalescence and separation of the phases. Most of
the extraction takes place in the mixing sections, but some also occurs in the
calming sections, so that the efficiency of each mixer-settler unit is sometimes
greater than 100 percent. Typically each mixer-settler is 300 to 600 mm (1 to 2 Ft)
high, which means that several theoretical contacts can be provided in a reasonably
short column. The problem of maintaining the internal moving parts, however,
particularly where the liquids are corrosive, may be a serious disadvantage.
PULSE COLUMNS. Agitation may also be provided by external means, as in a
pulse column. A reciprocating pump "pulses" the entire contents of the column
at frequent intervals, so that a rapid reciprocating motion of relatively small
amplitude is superimposed on the usual flow of the liquid phases. The tower may
contain ordinary packing or special sieve plates. In a packed tower the pulsation
disperses the liquids and eliminates channeling, and the contact between the phases
is greatly improved. In sieve-plate pulse towers the holes are smaller than in
nonpulsing towers, ranging from 1.5 to 3 mm in diameter, with a total open area
in each plate of 6 to 23 percent of the cross-sectional area of the tower. Such
towers are used almost entirely for processing highly corrosive radioactive liquids.
No downcomers are used. Ideally the pulsation causes light liquid to be dispersed.
into the heavy phase on the upward stroke and the heavy phase to jet into the
light phase on the downward stroke. Under these conditions the stage efficiency
may reach 70 percent. This is possible, however, only when the volumes of the
two phases are nearly the same and when there is almost no volume change
during extraction. In the more usual case the successive dispersions are less
effective, and there is backmixing of one phase in one direction. The plate efficiency
then drops to about 30 percent. Nevertheless, in both packed and sieve-plate pulse
columns the height required for a given number of theoretical contacts is often
less than one-third that required in an unpulsed columnY
CENTRIFUGAL EXTRACTORS. The dispersion and separation of the phases may
be greatly accelerated by centrifugal force, and several commercial extractors make
use of this. In the Podbielniak extractor a perforated spiral ribbon inside a heavy
metal casing is wound about a hollow horizontal shaft through which the liquids
enter and leave. Light liquid is pumped to the outside of the spiral at a pressure
between 3 and 12 atm to overcome the centrifugal force; heavy liquid is fed to the
center. The liquids flow countercurrently through the passage formed by the
ribbons and the casing walls. Heavy liquid moves outward along the outer face
of the spiral; light liquid is forced by displacement to flow inward along the inner
face. The high shear at the liquid-liquid interface results in rapid mass transfer.
In addition, some liquid sprays through the perforations in the ribbon and
increases the turbulence. Up to 20 theoretical contacts may be obtained in a single
machine, although 3 to 10 contacts are more common. Centrifugal extractors are
632 MASS TRANSFER AND ITS APPLICATIONS
expensive and find relatively limited use. They have the advantages of providing
many theoretical contacts in a small space and of very short holdup times-about
4 s. Thus they are valuable in the extraction of sensitive products such as vitamins
and antibiotics.
AUXILIARY EQUIPMENT. The dispersed phase in an extraction tower is allowed
to coalesce at some point into a continuous layer from which one product stream
is withdrawn. The interface between this layer and the predominant continuous
phase is set in an open section at the top or bottom of a packed tower; in a'
sieve-plate tower it is set in an open section near the top of the tower when the light
phase is dispersed. If the heavy phase is dispersed, the interface is kept near the
bottom of the tower. The interface level may be automatically controlled by a
vented overflow leg for the heavy phase, as in a continuous gravity decanter. In
large columns the interface is often held at the desired point by a level controller
actuating a valve in the heavy-liquid discharge line.
In liquid-liquid extraction the solvent must nearly always be removed from
the extract or raffinate or both. Thus auxiliary stills, evaporators, heaters, and
condensers form an essential part of most extraction systems and often cost much
more than the extraction device itself. As mentioned at the beginning of this
section, if a given separation can be done either by extraction or distillation,
economic considerations usually favor distillation. Extraction provides a solution
to problems that cannot be solved by distillation alone but does not usually
eliminate the need for distillation or evaporation in some part of the separation
system.
Principles of Extraction
Since most continuous extraction methods use countercurrent contacts between
two phases, one a light liquid and the other a heavier one, many of the
fundamentals of countercurrent gas absorption and of rectification carry over into
the study of liquid extraction. Thus questions about ideal stages, stage efficiency,
minimum ratio between the two streams, and size of equipment have the same
importance in extraction as in distillation.
EQUILIBRIA AND PHASE COMPOSITIONS. The equilibrium relationships in
liquid extraction are generally more complicated than for other separations,
because there are three or more components present, and some of each component
is present in each phase. The equilibrium data are often presented on a triangular
diagram, such as those shown in Figs. 20.10 and 20.11. The system acetone-
water-methyl isobutyl ketone (MIK), Fig. 20.10, is an example of a type I system,
which shows partial miscibility of the solvent (MIK) and the diluent (water) but
complete miscibility of the solvent and the component to be extracted (acetone).
Aniline-n-heptane-methylcyclohexane (MeR) form a type II system (Fig. 20.11),
where the solvent (aniline) is only partially miscible with both the other compo-
nents.
LEACHING AND EXTRACTION 633
100 Acetone
" ' " (a)
09 '\01
) /
MIK 100
(5) A 09 08 07 06 05 04 03 0.2 01 (b)
MASS FRACTION MIK
FIGURE 20.10
System acetone-MIK-water at 25"C. (After Othmer, White, and Trueger. 9 )
Some of the features of an extraction process can be illustrated using Fig.
20.10. When solvent is added to a mixture of acetone and water, the composition
of the resulting mixture lies on a straight line between the point for pure solvent
and the point for the original binary mixture. When enough solvent is added so
that the overall composition falls under the dome-shaped curve, the mixture
separates into two phases. The points representing the phase compositions can be
joined by a straight tie line, which passes through the overall mixture composition.
For clarity, only a few such tie lines are shown, and others can be obtained by
interpolation. The line ACE shows compositions of the MIK layer (extract), and
line BDE shows compositions of the water layer (raffinate). As the overall acetone
content of the mixture increases, the compositions of the two phases approach
each other, and they become equal at the point E, the plait paint.
The tie lines in Fig. 20.10 slope up to the left, and the extract phase is richer
in acetone than the raffinate phase. This suggests that most of the acetone could
be extracted from the water phase using only a moderate amount of solvent. If
the tie lines were horizontal or sloped up to the right, extraction would still be
possible, but more solvent would have to be used, since the final extract would
not be as rich in acetone.
The ratio of desired product (acetone) to diluent (water) should be high for
a practical extraction process. The solubility of water in MIK solvent is only 2
634 MASS TRANSFER AND ITS APPLICATIONS
LOO Aniline
f\ (s)
Af- ~EXlraCI phase
09 0.1
17
Iv 0.8f)(.
I. "~B02
!\' ,\\'
~.
,107 IVII
J .J\~03 ~
~ I .X 'Yr.
,,~ 0.61\, ,\:\0.4ll'1>
~ 1,/
It OS/,\: ~ '\ '\ [\X\ O.S '0
& 04 /\lIY 7 J '\\;\\ 1\ ~
0.6 ~
$ "1 lA '\ '\ ,I
/'\: 77:1\1 ,\7 J ,V ,/\ Se-
0.3 / \7
<7\1 7\ '\ ''I, '\1' 0.7
I , IV7 Jf '\1 '\ r\ ,\1 J V .1\/\/ 0.8
0.2/\ 'Y/V/./\/\ fV j
,/\ '\ '\ "".xV J
o I\lV/\lYj\/\/l7\ '\
.1 '\IV l/\X\ '\ D.
,\0.9
\1
7\1\1 \1\1\1 f!,affinale phas~J\I ,1\/\. '\ ,/\
LOO 0.9 0.8 0.7 0.6 O.S 0.4 0.3 0.2 0.1 1.00
MCH
H7t?ne MASS FRACTION HEPTANE (a)
FIGURE 20.11
System aniline-Il-heptane-MCH at 25°C: a, solute, MCH: b, diluent, Il-heptane; s, solvent, aniline.
(After Varteressian and Fenske. 1 $)
percent, but as the acetone concentration increases, the water content of the extract
phase also increases. The data from Fig. 20.10 are replotted in Fig. 20.12 to show
the gradual increase in water content YH,O with acetone content YA. The ratio
Y A/YH,O goes through a maximum at about 27 weight percent acetone in the
extract phase. A higher concentration of acetone could be obtained, but the greater
amount of water in the extract product would probably make operation at these
conditions undesirable.
o. 3 6
5
"'G...
o. 2 /' K
V
o.1 7
/
/ 2
~ 1
()o
FIGURE 20.12
0 o
o 0.1 0.2 0.3 0.4 0.5 Composition of extract phase for
YA MIK-acetone-HzO.
LEACHING AND EXTRACTION 635
The phase compositions resulting from a single-stage extraction are easily
obtained using the triangular diagram. For example, if a mixture with 40 percent
acetone and 60 percent water is contacted with an equal mass of MIK solvent,
the overall mixture is represented by point M in Fig. 20.10. A new tie line is drawn
to show that the extract phase would be 0.232 acetone, 0.043 water, and 0.725
MIK. The raffinate phase would be 0.132 acetone, 0.845 water, and 0.023 MIK.
Repeated contacting of the raffinate phase with fresh solvent, a process called
crosscurrent extraction, would permit recovery of most of the acetone, but this
would be less efficient than using a countercurrent cascade because of the large
volume of solvent needed.
USE OF McCABE-THIELE METHOD. The separation achieved for a given number
of ideal stages in a counterflow cascade can be determined by using a triangular
diagram and special graphical techniques, but a modified McCabe-Thiele method,
which is the approach used here, is simple to use and has satisfactory accuracy
for most cases. The method focuses on the concentration of solute in the extract
and raffinate phases, and the diagram does not show the concentration of the
diluent in the extract or the concentration of solvent in the raffinate. However,
these minor components of both phases are accounted for in determining the total
flow of extract and raffinate, which affects the position of the operating line.
To apply the McCabe-Thiele method to extraction, the equilibrium data are
shown on a rectangular graph, where the mass fraction of solute in the extract or
V phase is plotted as the ordinate and the mass fraction of solute in the raffinate
phase as the abscissa. For a type I system, the equilibrium line ends with equal
compositions at the plait point. The use of only one concentration to characterize
a ternary mixture may seem strange, but if the phases leaving a given stage are
in equilibrium, only one concentration is needed to fix the compositions of both
phases.
The operating line for the extraction diagram is based on Eq. (20.3), which
gives the relationship between the solute concentration leaving stage n in the L
phase and that coming from stage n + 1 in the V.phase. The terminal points on
the operating line, (x" y,) and (Xb' y.), are usually determined by an overall material
balance, taking into account the ternary equilibrium data. Because of the decrease
in the raffinate phase (L) and the increase in the extract phase (V) as they pass
through the column, the operating line is curved. A material balance over a portion
of the cascade is made to establish one or more intermediate points on the
operating line. The number of ideal stages is then determined by drawing steps in
the normal manner.
If the number of ideal stages is specified, the fraction of solute extracted and
the final compositions are determined by trial and error. The fraction extracted
or the final extract composition is assumed, and the curved operating line is
constructed. If too many stages are required, a smaller fraction extracted is
assumed and the calculations are repeated. Computer programs for extraction
calculations are available.'6
636 MASS TRANSFER AND ITS APPLICATIONS
Example 20.3. A countercurrent extraction plant is used to extract acetone (A) from
its mixture with water by means of methyl isobutyl ketone (MIK) at a temperature
of 25°C. The feed consists of 40 percent acetone and 60 percent water. Pure solvent
equal in mass to the feed is used as the extracting liquid. How many ideal stages are
required to extract 99 percent of the acetone fed? What is the extract composition
after removal of the solvent?
Solution
Use the data in Fig. 20.10 to prepare a plot of the equilibrium relationship YA vs.
X A•which is the upper curve in Fig. 20.13. The terminal points for the operating line
are determined by material balances with allowance for the amounts of water in the
extract phase and MIK in the raffinate phase. Basis: F = 100 mass units per hour.
Let n = mass flow rate of H 2 0 in extract
m = mass flow rate of MIK in raffinate
For 99 percent recovery of A, the extract has 0.99 x 40 = 39.6A, and the raffinate
has OAA. The total flows are
At the top, L. = F = 100 = 40A + 60 H,O
V. = 39.6A + 11 H,O + (100 - m)MIK = 139.6 + 11 - m
At the bottom, Vb = 100 MIK
Lb = OAA + (60 - II)H,O + mMIK = 60.4 +m- 11
Since n and m are small and tend to cancel in the summations for Ya and La, the
. total extract flow v" is about 140, which would make YA .• '" 39.6/140 = 0.283. The
value of XA,b is about 0.4/60 = 0.0067. These estimates are adjusted after calculating
values of nand m.
o. 5
o. 4
~t
o. 3
/1
o. 2 / /
o. 1 / /
/ ./'
o~ 0.1 0.2 0.3 0.4 0.5
FIGURE 20.13
McCabe-Thiele diagram for
extraction (Example 20.3).
LEACHING AND EXTRACTION 637
From Fig. 20.10 for YA ~ 0.283, YH,O ~ 0.049,
0.049
n ~ (39.6 + 100 - m)
1 - 0.049
If m is very small, n '" (0.049/0.951)(139.6) ~ 7.2.
From Fig. 20.10 for X A ~ 0.007, XMIK ~ 0.02,
0.02
m~ (0.4 + 60 - n)
1 - 0.02
0.02
'" - (0.4 + 52.8) ~ 1.1
0.98
Revised n ~ (0.049/0.951)(139.6 - 1.1) ~ 7.1:
V. ~ 139.6 + 7.1 - 1.1 ~ 145.6
39.6
YA , ~ -- ~ 0.272
. 145.6
Lb ~ 60.4 + 1.1 - 7.1 ~ 54.4
0.4
XA b ~ - ~ 0.0074
. 54.4
Plot points (0.0074,0) and (0.40,0.272) to establish the ends of the operating line.
For an intermediate point on the operating line, pick YA = 0.12 and calculate
V and L. From Fig. 20.10, YH,O ~ 0.03, and YMIK ~ 0.85. Since the raffinate phase
has only 2 to 3 percent MIK, assume that the amount of MIK in the extract is 100,
the same as the solvent fed:
100
V", - ~ 117.6
0.85
By an overall balance from the solvent inlet (bottom) to the intermediate point,
v;,+L~Lb+ V
L", 54.4 + 117.6 - 100 ~ 72.0
A balance on A over the same section gives x A :
LXA '" 0.4 + 117.6(0.12) - 0
14.5
xA '" - ~ 0.201
72
This value is probably accurate enough, but corrected values of V. L, and X A can
be determined. For x A ~ 0.201, XMIK '" 0.03 (Fig. 20.10). A balance on MIK from
638 MASS TRANSFER AND ITS APPLICATIONS
the solvent inlet to the intermediate point gives
Vz, + LX~UK = LbxMIK,b + VYMIK
VYMIK ~ 100 + 72(0.03) - 1.1
101.1
Revised V ~ -- ~ 118.9
0.85
Revised L ~ 54.4 + 118.9 - 100 ~ 73.3
. d
ReVlse X A =
0.4 + 118.9(0.12) 0.200
73.3
Plot X A ~ 0.20, YA ~ 0.12, which gives a slightly curved operating line. From Fig.
20.13, N ~ 3.4 stages.
COUNTERCURRENT EXTRACTION OF TYPE II SYSTEMS USING REFLUX.
Just as in distillation, reflux can be used in countercurrent extraction to improve
the separation of the components in the feed. This method is especially effective
in treating type II systems, because with a center-feed cascade and the use of reflux,
the two feed components can be separated into nearly pure products.
A flow diagram for countercurrent extraction with reflux is shown in
Fig. 20.14. To emphasize the analogy between this method and fractionation, it
is assumed that the cascade is a plate column. Any other kind of cascade, however,
may be used. The method requires that sufficient solvent be removed from the
extract leaving the cascade to form a raffinate, part of which is returned to the
cascade as reflux, the remainder being withdrawn from the plant as a product.
Raffinate is withdrawn from the cascade as bottoms product, and fresh solvent is
admitted directly to the bottom of the cascade. None of the bottom raffinate needs
to be returned as reflux, for the number of stages required is the same whether or
not any of the raffinate is recycled to the bottom of the cascade.''' The situation
is not the same as in continuous distillation, in which part of the bottoms must
be vaporized to supply heat to the column.
The solvent separator, which is ordinarily a still, is shown in Fig. 20.14. As
also shown in Fig. 20.14, solvent may be removed from both products by stripping,
or in some cases by water washing, to give solvent-free products.
The close analogy between distillation and extraction, both using reflux, is
shown in Table 20.3. Note that the solvent plays tlie same part in extraction that
heat does in distillation.
LIMITING REFLUX RATIOS. Just as in distillation, two limiting cases exist in
operating a countercurrent extractor with reflux. As the reflux ratio RD becomes
very great, the number of stages approaches a minimum, and as RD is reduced, a
minimum value of the reflux ratio is reached where the number of stages becomes
infinite. The minimum number of stages and the minimum reflux ratio are found
by exactly the same methods used to determine the same quantities in distillation.
LEACHING AND EXTRACTION 639
Solvent
t
01 Solvent I
Solvent La+ O
Solvent
So
separator I stripper
t Va ·vI
Reflux
tOIvent-free
exlract DI
is La
""~ I
:s'"
.~ 2
~
~
g n
_~_Ln
'"
~
Vn+I..l
nTI
F
Feed
.§ plate
<:;
'"'"
'"
.~ m
~
~
Vmrir _i!m m+1
-;;; .....
~
"
.S;
::::
~ N
tsolvent
t LN" Lb BJ Solvent I
. I stripper
FIGURE 20.14
Solvent sa ~ Solvent -free Countercurrent extraction with
raff/note B I reflux.
PRACTICAL EXAMPLES OF EXTRACTION WITH REFLUX. There are few, if
any, practical examples of reflux in the simple manner shown in Fig. 20.14. For
systems such as aniline-heptane-methylcyclohexane (Fig. 20.11), the ratio of MCH
to heptane in the extract is only modestly greater than in the raffinate, so a great
many stages would be needed for high-purity products. Furthermore, the low
solubility of both solutes in aniline would mean a very large flow of solvent to
be handled. However, a modification of the reflux concept has been applied in
several industrial processes for extractive separation. Enrichment of the extract is
accomplished by countercurrent washing with another liquid, chosen so that the
small amounts of this liquid that dissolve in the extract can be easily removed.
The Sulfolane process for extraction of aromatics is an example of this type.
640 MASS TRANSFER AND ITS APPLICATIONS
TABLE 20.3
Comparison of extraction with distillation, both using
reflux
Distillation Extraction
Vapor flow in cascade V Extract flow in cascade V
Liquid flow in cascade L Raffinate flow in cascade L
Overhead product D Extract product D
Bottom product B Raffinate product B
Condenser Solvent separator
Bottom~product cooler Raffinate solvent stripper
Overhead-product cooler Extract solvent stripper
Heat to reboiler q, Solvent to cascade Sn
Heat removal in condenser qc Solvent removal in separator SD
Reflux ratio RD = LaiD Reflux ratio RD = L"./D
Rectifying section Extract~enriching section
Stripping section Raffinate-stripping section
Sulfolane process. A flow sheet for the Sulfolane process' is shown in Fig. 20.15.
The hydrocarbon feed is introduced near the middle of the extractor and the heavy
solvent is fed at the top. In the top section, nearly all the aromatics are extracted
from the raffinate, but the solvent at this point also contains a few percent paraffins
and naphthenes. The boiling point ranges overlap, so preparation of pure aro-
matics by distillation of this material is not practical. Also, Sulfolane and the
Nonaromatic product
Wash
column
Raffinate
Extractor
Feed Extract
distillation recovery
column column
L--'----l-l
Aromatic
product
Extract
Lean solvent
FIGURE 20.15
Sulfolane extraction process. (After Broughton and Asselin. 3 )
LEACHING AND EXTRACfION 641
hydrocarbons form a type I system with a plait point, so paraffin-free aromatics
cannot be obtained by refluxing some of the solvent-free extract product.
In the lower section of the extractor, medium- and high-boiling paraffins are
displaced from the extract phase by contact with a low-boiling hydrocarbon
fraction prepared by distillation of the extract. Water is present in this system and
forms a low-boiling azeotrope with the lighter hydrocarbons, so the distillation is
actually an azeotropic distillation (see Chap. 19). Vapors from the column are
condensed and separated into two phases, and the hydrocarbon phase is returned
to the extractor as backwash. In the lower section of the extractor, enough stages
are provided for nearly complete transfer of the medium and heavy paraffins to
the raffinate phase. The extract leaves saturated with light hydrocarbons, but these
are removed in the azeotropic distillation column.
Solvent is recovered in the second distillation coluljlD, which is a vacuum
steam-distillation column, with reflux of the organic phase to get high-purity
aromatics. The final column is a multistage extraction column, where water is used
to wash the solvent from the raffinate. There is a closed cycle for water to minimize
solvent loss, and a small amount of water can be tolerated in the extraction solvent.
The backwash stream is sometimes called countersolvent or reflux, but the
term "reflux" should be reserved for streams having the same composition as the
product. The backwash need not be a low-molecular-weight material; in one
version of the Sulfolane process, the backwash is a heavy paraffinic fraction, which
is easily removed from both extract and raffinate.
SUPERCRITICAL FLUID EXTRACTION
Certain compounds may be separated from solids or liquids by extraction with a
solvent held at a pressure and temperature above the critical point of the solvent.
Such a process, when used with either solids or liquids, is known as supercritical
fluid extraction. In addition to its selective dissolving power, a supercritical fluid
has several advantages over conventional liquid solvents. Its density and viscosity
are low, and the diffusivities of solutes in it are high-about 100 times greater
than those in ordinary liquids. Consequently, the supercritical fluid easily pene-
trates porous or fibrous solids. Solutes can be recovered from a supercritical fluid
merely by changing the temperature or the pressure, although other ways are also
used. The chief disadvantage of supercritical fluid extraction is the high pressure
required.
PHASE EQUILIBRIA. A useful solvent for supercritical extraction, especially in
food processing, is carbon dioxide, which has a critical point of 31.06'C and 73.8
bars (10701bf /in. 2 ). The phase diagram for pure CO 2 (Fig. 20.16) shows the
equilibrium regions of solid, liquid, and gas and the conditions under which a
supercritical fluid exists. In the supercritical region there is no distinction between
liquid and gas and no phase transition from one to the other; the supercritical
fluid acts like a very dense gas or a light, mobile liquid.
Solubility and selectivity in a supercritical fluid are strong functions of
temperature and pressure. For nearly total extraction of solutes by supercritical
642 MASS TRANSFER AND ITS APPLICATIONS
400
350
300
I
I
~ 250 I
~ I
I
200 I 0;
Triple Critical: ~
:: y::::~: ~ ~,~~"t=;,~~ no
,
i
-60 -40 -20 o 20 40 60
Temperature ("C)
FIGURE 20.16
Phase diagram for carbon dioxide, illustrating regions useful for food-processing applications. ll
CO 2 , as indicated in Fig. 20.16, the highest pressure is used, since 'here the
solubilities are highest. The loaded solvent may then be passed through a series
of separation vessels in which the temperature or pressure is changed stepwise, to
give what is called multistage fractionation. For selective removal of odor-
producing volatile components conditions close to the critical point are advanta-
geous. Here the solubilities are smaller but the selectivity for the most volatile
compounds is much higher.
Equilibrium phase diagrams for one or more solutes in supercritical CO 2
and other solvents can be very complicated. 2 Relatively little equilibrium informa-
tion has been published; this lack coupled with the cost of high-pressure equipment
and the difficulties of scaleup have to date limited the commercial applications of
supercritical fluid extraction.
COMMERCIAL PROCESS. l l A practical example of a supercritical fluid extraction
process is the decaffeination of coffee. Coffee beans are first soaked in water to
make the extraction more selective and then are loaded into an extraction vessel
through which supercritical CO 2 is circulated to dissolve the caffeine. In a separate
scrubbing vessel the caffeine is transferred from the CO 2 to water, also at high
pressure. Extraction is continued until the caffeine content of the beans, originally
0.7 to 3 percent, is reduced to less than 0.02 percent. At the end of the batch cycle
the water is depressurized and distilled away from the caffeine. In an alternative
process the caffeine is separated from the CO 2 by adsorption on activated carbon.
In either case the supercritical fluid extraction is said not to affect the characteristic
flavor and aroma of the coffee.
LEACHING AND EXTRACfION 643
SYMBOLS
a, Specific surface of packing, m 2/m 3 or ft2/ft3
B Bottom product, kg or lb base mixture per hour; B', bottom product
leaving stripper
D Overhead product, kg or lb base mixture per hour; D', overhead
product leaving solvent stripper
F Feed to extraction cascade, kg or lb base mixture per hour
HTU Height of a transfer unit, m or ft
L Underflow, or raffinate phase, kg or lb total or base mixture per
hour; LN , leaving final stage; La, entering cascade; Lb , leaving cas-
cade; L m , leaving stage m; L n , leaving stage n
m Stage number in stripping section; also, mass flow rate of MIK in
raffinate (Example 20.3), kg/h or lb/h
N Number of ideal stages
n Stage number in rectifying section; also mass flow rate of water In
extract (Example 20.3), kgjh or lb/h
P, Critical pressure, bars
q Heat added, J/g or Btu/lb; -q" to condenser; q" to reboiler
RD Reflux ratio
S Pounds of kerosene in solvent (Example 20.1); s., solvent added to
bottom product, kg/h or lb/h; SD, solvent removed from overhead
product, kg/h or lb/h
Critical temperature, °C
Overflow, or extract phase, mass or moles base mixture per hour; Va ,
leaving cascade; v" , entering cascade; v,n+ 1, leaving stage 111 + 1;
v" + l ' leaving stage n + 1
Superficial velocity, based on cross section of column, m/h or ft/h; v,.,
of continuous phase; V,.d of dispersed phase
x Mass fraction of solute in underflow or L phase; x A, XM1K, mass frac-
tion of acetone, MIK, respectively, based on entire L phase; x" at
entrance; X b , at exit; Xc, equilibrium value; X n , leaving stage n
y Mass fraction of solute in overflow or V phase; YA' YH 20 , YMIK' mass
fraction of acetone, water, MIK, respectively, based on entire V phase;
Ya' at exit; Yb' at entrance; Yc. equilibrium value; Yn+l, leaving stage
n+1
y* Concentration of overflow solution in equilibrium with specific under-
flow solution; y~, in equilibrium with Xa; yt, in equilibrium with Xb
Greek letters
I'lp Density difference between phases, kg/m 3 or Ib/ft 3
e Fraction voids in packed section
/1, Viscosity of continuous phase, kg/m-s or lb/ft-h
p, Density of continuous phase, kg/m 3 or Ib/ft 3
(J Interfacial tension, dyn/cm or lbf/ft
644 MASS TRANSFER AND ITS APPLICATIONS
PROBLEMS
20.1. Roasted copper ore contammg the copper as CuS0 4 is to be extracted in a
countercurrent stage extractor. Each hour a charge consisting of 10 tons of gangue,
1.2 tons of copper sulfate. and 0.5 ton of water is to be treated. The strong solution
produced is to consist of 90 percent H 2 0 and 10 percent CuSO. by weight. The
recovery of CuS0 4 is to be 98 percent of that in the ore. Pure water is to be used as
the fresh solvent. After each stage, 1 ton of inert gangue retains 2 tons of water plus
the copper sulfate dissolved in that water. Equilibrium is attained in each stage. How
many stages are required?
20.2. A five-stage countercurrent extraction battery is used to extract the sludge from the
reaction
Na,CO, + CaO + H 2 0 -+ CaCO, + 2NaOH
The CaC0 3 carries with it 1.5 times its weight of solution in flowing from one
unit to another. It is desired to recover 99 percent of the NaOH. The products from
the reaction enter the first unit with no excess reactants but with 0.6 kg of H 2 0 per
kilogram of CaC0 3 • (a) How much wash water must be used per kilogram of calcium
carbonate? (b) What is the concentration of the solution leaving each unit, assuming
that CaC0 3 is completely insoluble?
20.3. In Prob. 20.2 it is found that the sludge retains solution varying with the concentration
as shown in Table 2004. If a 12 percent solution of the NaOH is to be produced, how
many stages must be used to recover 97 percent of the NaOH?
TABLE 20.4
NaOH, wt % o 5 10 15 20
Kg solutionfkg CaCO J 1.50 1.75 2.20 2.70 3.60
20.4. Oil is to be extracted from halibut livers by means of ether in a countercurrent
extraction battery. The entrainment of solution by the granulated liver mass was
found by experiment to be as shown in Table 20.5. In the extraction battery, the
charge per cell is to be 100 lb, based on completely exhausted livers. The unextracted
livers contain 0.043 gal of oil per pound of exhausted material. A 95 percent recovery
of oil is desired. The final extract is to contain 0.65 gal of oil per gallon of extract.
TABLE 20.5
Solution Solution Solution Solution
retained by concentration, retained by concentration,
1 lb exhausted gal oil/gal 1 Ib exhausted gal oil/gal
livers, gal solution livers, gal solution
0.035 0 0.068 0.4
0.042 0.1 0.081 0.5
0.050 0.2 0.099 0.6
0.058 0.3 0.120 0.68
LEACHING AND EXTRACfION 645
The ether fed to the system is oil free. (a) How many gallons of ether are needed per
charge of livers? (b) How many extractors are needed?
20.5. In a continuous countercurrent train of mixer-settlers, 100 kgjh of a 40:60 acetone-
water solution is to be reduced to 10 percent acetone by extraction with pure
1,1,2-trichloroethane at 25°C. (a) Find the minimum solvent rate. (b) At 1.8 times the
minimum (solvent rate)/(feed rate), find the number of stages required. (c) For
conditions of part (b) find the mass flow rates of all streams. Data are given in Table
20.6.
TABLE 20.6
Equilibrium data
Limiting solubility curve
Water, wt % Acetone, wt %
94.73 0.26 5.01
79.58 0.76 19.66
67.52 1.44 31.04
54.88 2.98 42.14
38.31 6.84 54.85
24.04 15.37 60.59
15.39 26.28 58.33
6.77 41.35 51.88
1.72 61.11 37.17
0.92 74.54 24.54
0.65 87.63 11.72
0.44 99.56 0.00
Tie lines
Weight % in
Weight % in water layer trichloroethane layer
CzH)Cl) Water Acetone CzH)CI) Water Acetone
0.52 93.52 5.96 90.93 0.32 8.75
0.73 82.23 17.04 73.76 1.10 25.14
1.02 72.06 26.92 59.21 2.27 38.52
1.17 67.95 30.88 53.92 3.11 42.97
1.60 62.67 35.73 47.53 4.26 48.21
2.10 57.00 40.90 40.00 6.05 53.95
3.75 50.20 46.05 33.70 8.90 57.40
6.52 41.70 51.78 26.26 13.40 60.34
20.6. A spray-tower extractor operates at 30°C with hydrocarbon drops dispersed in water.
The density of the hydrocarbon phase is 53 lb/ft'. If the average drop size is 2.0 mm,
calculate the terminal velocity of the drops. If the slip velocity is assumed to be
independent of the holdup and if the dispersed-phase volumetric flow rate is taken
to be twice that of the continuous phase. at what flow rate of the dispersed phase
646 MASS TRANSFER AND ITS APPLICATIONS
would the fraction holdup be 0.30 (close to flooding)? For different ratios of flow
rates, is either the sum of the flow rates or the sum of their square roots nearly
constant at a given holdup? (Note the correlation in Fig. 20.7.)
20.7. Estimate the flooding velocity for an extraction column packed with i5-mm spheres
and operating with water and toluene at 30°C. Toluene is dispersed and has a flow
rate twice that of the water phase.
20.S. A mixture containing 40 weight percent acetone and 60 weight percent water is
contacted with an equal amount of MIK. (a) What fraction of the acetone can be
extracted in a single-stage process? (b) What fraction of the acetone could be extracted
if the fresh solvent were divided into two parts and two successive extractions used?
REFERENCES
1. Baker, E. M.: Trans. AIChE, 32:62 (1936).
2. Brennecke, J. F., and C. A. Eckert: A/ChE J .., 35:1409 (1989).
3. Broughtan, D. B., and G. F. Asselin: Proc. Seventh World Petroleum Congress, vaL 4, Elsevier,
Ncw York, 1967, p. 65.
4. Bushnell, J. D., and R. J. Fiocco: Hydrocarbon Proc., 59(5):119 (1980).
5. Cofield, E. P., Jr.: Chem. Eng., 58(1):127 (1951).
6. Crawford, J. W., and C. R. Wilkc: Chem. Eng. Prog., 47:423 (1951).
7. Elgin, J. c.: Trans. AIChE, 32:451 (1936).
8. Grosbcrg, J. A.: /nd. Eng. Chem., 42:154 (1950).
9. Othmer, D. F., R. E. White, and E. Trucger: /lId. Ellg. Chem., 33:1240 (1941).
10. Perry, J. H. (cd.): Chemical Engineers' Handbook, 6th cd., McGraw-Hill, New York, 1984, pp.
21-57 to 21-83.
11. Rivzi, S. S., A. L. Benado, J. A. Zollweg, and J. A. Daniels: Food. Tech., 40(6):55 (1986).
12. Sage, G., and F. W. Woodfield: Chem. Eng. Prog., 50:396 (1954).
13. Skelland, A. H. P.: Ind. Eng. Chem., 53:799 (1961).
14. Treybal, R. E.: Liquid Extraction, 2nd ed., McGraw-Hill, New York, 1963.
15. Varteressian, K. A., and M. R. Fenske: /nd. Erzg. Chem., 29:270 (1937).
16. Walas, S. M.: Chemical Process Equipment, Butterworths, Stoneham, MA, 1988, p. 474.
CHAPTER
21
PRINCIPLES
OF DIFFUSION
AND MASS
TRANSFER
BETWEEN
PHASES
Diffusion is the movement, under the influence of a physical stimulus, of an
individual component through a mixture. The most common cause of diffusion is
a concentration gradient of the diffusing component. A concentration gradient
tends to move the component in such a direction as to equalize concentrations and
destroy the gradient. When the gradient is maintained by constantly supplying
the diffusing component to the high-concentration end of the gradient and
removing it at the low-concentration end, the flow of the diffusing component is
continuous. This movement is exploited in mass-transfer operations. For example,
a salt crystal in contact with a stream of water or a dilute solution sets up a
concentration gradient in the neighborhood of the interface, and salt diffuses
through the liquid layers in a direction perpendicular to the interface. The flow
of salt away from the interface continues until the crystal is dissolved. When the
saIt is intimately mixed with insoluble solid, the process is an example ofleaching.
Although the usual cause of diffusion is a concentration gradient, diffusion
can also be caused by an activity gradient, as in reverse osmosis, by a pressure
gradient, by a temperature gradient, or by the application of an external force
field, as in a centrifuge. 1 Molecular diffusion induced by temperature is thermal
648 MASS TRANSFER AND ITS APPLICATIONS
diffusion, and that from an external field is forced diffusion. Both are uncommon
in chemical engineering. Only diffusion under a concentration gradient is con-
sidered in this chapter.
Diffusion is not restricted to molecular transfer through stagnant layers of
solid or fluid. It also takes place in fluid phases by physical mixing and by the
eddies of turbulent flow, just as heat flow may occur by convection. This is called
eddy diffusion. Sometimes the diffusion process is accompanied by bulk flow of
the mixture in a direction parallel to the direction of diffusion, and it is often
associated with heat flow.
ROLE OF DIFFUSION IN MASS TRANSFER. In all the mass-transfer operations,
diffusion occurs in at least one phase and often in both phases. In gas absorption,
solute diffuses through the gas phase to the interface between the phases and
through the liquid phase from the interface. In distillation, the low boiler diffuses
through the liquid phase to the interface and away from the interface into the
vapor. The high boiler diffuses in the reverse direction and passes through the
vapor into the liquid. In leaching, diffusion of solute through the solid phase is
followed by diffusion into the liquid. In liquid extraction, the solute diffuses
through the raffinate phase to the interface and then into the extract phase. In
crystallization, solute diffuses through the mother liquor to the crystals and
deposits on the solid surfaces. In humidification or dehumidification there is no
diffusion through the liquid phase because the liquid phase is pure and no
concentration gradient through it can exist; but the vapor diffuses to or from the
liquid-gas interface into or out of the gas phase. In drying, liquid water diffuses
through the solid toward the surface of the solid, vaporizes, and diffuses as vapor
into the gas. The zone of vaporization may be either at the surface of the solid or
within the solid, depending upon factors that are discussed in Chap. 24. When the
vaporization zone is in the solid, vapor diffusion takes place in the solid between
the vaporization zone and the surface and diffusion of both vapor and liquid
occurs within the solid.
THEORY OF DIFFUSION
In this section quantitative relationships for diffusion are discussed. Attention is
focused on diffusion in a direction perpendicular to the interface between the phases
and at a definite location in the equipment. Steady state is assumed, and the
concentrations at any point do not change with time. This discussion is restricted
to binary mixtures.
COMPARISON OF DIFFUSION AND HEAT TRANSFER. There is an analogy
between flow of heat and diffusion. In each, a gradient is the cause of the flow.
In heat transfer a temperature gradient is the driving force; in diffusion the force
is a concentration gradient. In each case the flux is directly proportional to the
gradient. The analogy cannot be carried further, however, for the reason that heat
is not a substance: it is energy in transit. When heat flows from one point to
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 649
another, it leaves no space behind, nor does it require space in its new location.
The velocity of heat flow has no meaning. Diffusion is a physical flow of matter,
which occnrs at a definite velocity. A diffusing component leaves space behind it,
and room must be found for it in its new location.
The material natnre of diffusion and the resulting flow lead to three types
of sitnations:
1. Only one component A of the mixture is transferred to or from the interface,
and the total flow is the same as the flow of A. Absorption of a single component
from a gas into a liquid is an example of this type.
2. The diffusion of component A in a mixtnre is balanced by an equal and opposite
molar flow of component B, so that there is no net molar flow. This is generally
the case in distillation, and it means there is no net volume flow in the gas
phase. However, there is generally a net volume or mass flow in the liquid phase
because of the difference in molar densities.
3. Diffusion of A and B takes place in opposite directions, but the molar fluxes
are unequal. This situation often occnrs in diffusion of chemically reacting
species to and from a catalyst snrface, but the equations are not covered in this
text.
DIFFUSION QUANTITIES. Five interrelated concepts are used in diffusion theory:
1. Velocity u, defined as usual by length/time.
2. Flux across a plane N, moles/area-time.
3. Flux relative to a plane of zero velocity J, moles/area-time.
4. Concentration c and molar density PM, moles/volume (mole fraction may also
be used).
5. Concentration gradient dc/db, where b is the length of the path perpendicular
to the area across which diffusion is occnrring.
Appropriate subscripts are used when needed. The equations apply equally well
to SI, cgs, and fps units. In some applications, mass, rather than molal units, may
be used in flow rates and concentrations.
VELOCITIES IN DIFFUSION. Several velocities are needed to describe the move-
ments of individual substances and of the total phase. Since absolute motion has
no meaning, any velocity must be based on an arbitrary state of rest. In this
discussion "velocity" without qualification refers to the velocity relative to the
interface between the phases and is that apparent to an observer at rest with
respect to the interface.
The individual molecules of anyone component in the mixture are in random
motion. If the instantaneous velocities of the components are summed, resolved
in the direction perpendicular to the interface, and divided by the number of
650 MASS TRANSFER AND ITS APPLICATIONS
molecules of the substance, the result is the macroscopic velocity of that compo-
nent. For component A, for instance, this velocity is denoted by UA'
MOLAL FLOW RATE, VELOCITY, AND FLUX. If the total molal flux, in moles
per unit time per unit area in a direction perpendicular to a stationary plane, is
denoted by N and the volumetric average velocity by uo,
(21.1)
where PM is the molar density of the mixture.
For components A and B crossing a stationary plane, the molal fluxes are
NA = CAU A (21.2)
NB = CBll B (21.3)
Diffusivities are defined, not with respect to a stationary plane, but relative
to a plane moving at the volume-average velocity uo. By definition there is no net
volumetric flow across this reference plane, although in some cases there is a net
molar flow or a net mass flow. The molar flux of component A through this
reference plane is a diffusion flux designated J A and is equal to the flux of A for
a stationary plane [Eq. (21.2)] minus the flux due to the total flow at velocity U o
and concentration CA:
JA = CAU A - CAU o = CA(U A - Uo) (21.4)
JB = CBUB - CBUO = Cn(UB - Uo) (21.5)
The diffusion flux J A is assumed to be proportional to the concentration gradient
de A/db, and the diffusivity of component A, in its mixture with component
B, is denoted by DAB' Thus,
(21.6)
A similar equation applies for component B:
(21.7)
Equations (21.6) and (21.7) are statements of Fick's first law of diffusion for a
binary mixture. Note that this law is based on three decisions:
1. The flux is in moles per unit area per unit time.
2. The diffusion velocity is relative to the volume-average velocity.
3. The driving potential is in terms of the molar concentration (moles cif compo-
nent A per unit volume).
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 651
The dimensions of DAB are length squared divided by time, usually given as square
meters per second or square centimeters per second.
RELATIONS BETWEEN DIFFUSIVITlES. The relationship between DAB and DBA
is easily determined for ideal gases, since the molar density does not depend on
the composition:
(21.8)
For diffusion of A and B in a gas at constant temperature and pressure,
(21.9)
Choosing the reference plane for which there is zero volume flow, the sum of
the molar diffusion fluxes of A and B can be set to zero, since the molar volumes
are the same:
(21.10)
Since dC A = -dcB , the diffusivities must be equal; that is,
DAB=DBA (21.11)
When dealing with liquids, the same result is found if all mixtures of A and B
have the same mass density.
cAM A + cBM. = P = const (21.12)
MAdc A + M.dc. = 0 (21.13)
For no volume flow across the reference plane, the sum of the volumetric flows
due to diffusion is zero. The volumetric flow is the molar flow times the molar
volume M/p and
(21.14)
Substituting Eq. (21.13) into Eq. (21.14) gives
DAB=D. A (21.15)
Other equations can be derived for diffusion in liquids where the density
changes, but for most practical applications, equal diffusivities are assumed when
dealing with binary mixtures. In the following equations a volumetric diffusivity
D, is used, with the subscript v used as a reminder that the driving force for
652 MASS TRANSFER AND ITS APPLICATIONS
diffusion is based on concentration differences in moles per volume. A common
form of the diffusion equation gives the total flux relative to a fixed plane:
(21.16)
For gases it is often convenient to use mole fractions rather than molar
concentrations, and since CA = PMYA and Uo = N/PM' Eq. (21.16) becomes
(21.17)
Equation (21.17) is sometimes applied to liquids, though it is only ap-
proximate if the molar density is not constant.
INTERPRETATION OF DIFFUSION EQUATIONS. Equation (21.16) is the basic
equation for mass transfer in a non turbulent fluid phase. It accounts for the
amount of component A carried by the convective bulk flow of the fluid and the
amount of A being transferred by molecular diffusion. The vector nature of the
fluxes and concentration gradients must be understood, since these quantities are
characterized by directions and magnitudes. As derived, the positive sense of the
vectors is in the direction of increasing b, which may be either toward or away
from the interface. As shown in Eq. (21.6), the sign of the gradient is opposite to
the direction of the diffusion flux, since diffusion is in the direction of lower
concentrations, or "downhill," like the flow of heat "down" a temperature
gradient.
There are several types of situations covered by Eq. (21.16). The simplest
case is zero convective flow and equimolal counterdiffusion of A and B, as occurs
in the diffusive mixing of two gases. This is also the case for the diffusion of A
and B in the vapor phase for distillations that have constant molal overflow. The
second common case is the diffusion of only one component of the mixture, where
the convective flow is caused by the diffusion of that component. Examples include
evaporation of a liquid with diffusion of the vapor from the interface into a gas
stream and condensation of a vapor in the presence of a noncondensable gas.
Many examples of gas absorption also involve diffusion of only one component,
which creates a convective flow toward the interface. These two types of mass
transfer in gases are treated in the following sections for the simple case of
steady-state mass transfer through a stagnant gas layer or film of known thickness.
The effects of transient diffusion and laminar or turbulent flow are taken up later.
EQUIMOLAL DIFFUSION. For equimolal diffusion in gases, the net volumetric
and molar flows are zero, and Eq. (21.16) or Eq. (21.17) can be used with the
convective term set to zero, which makes them equivalent to Eq. (21.6). Using a
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 653
mole-fraction gradient for convenience, dC A = PM dYA' Eq. (21.6) is integrated over
a film thickness B T , assuming a constant flux lA:
(21.18)
where YA = mole fraction of A at outer edge of film
YAi = mole fraction of A at interface or inner edge of film
Integration of Eq. (21.18) and rearrangement gives
1 D"PM ( ) (21.19)
A=B;YAi-YA
or
D" (21.20)
lA = -(C Ai - CA)
BT
The concentration gradient for A is linear in the film, and the gradient for
B has the same magnitude but the opposite sign, as shown in Fig. 21.1a.
ONE-COMPONENT MASS TRANSFER (ONE-WAY DIFFUSION). When only
component A is being transferred, the total molal flux to or away from the
interface, N, is the same'as N A , and Eq. (21.17) becomes
dYA
NA = yAN A - D"PM (21.21)
db
1.0
1;
0.8
is
ti06 1l
<1
0: -l?,
"- ~
~O.4
0
::;; "
0.2
y Cone. of stagnant Camp' B y
O~ __~__~__~__~__~
o DISTANCE FROM INTERFACE
o DISTANCE FROM INTERFACE
(a)
• (6)
•
FIGURE 21.1
Concentration gradients for equimolal and unicomponent diffusion; (a) components A and B diffusing
at same molal rates ~n opposite directions; (b) component A diffusing, component B stationary with
respect to interface.
654 MASS TRANSFER AND ITS APPLICATIONS
Rearranging and integrating,
dYA
N A (l- YA) = -D,PM (21.22)
db
NABT
DvPM = -
fY
' dYA 1-YA
YA/1-YA =In l-YAi
(21.23)
or
NA=D,PM ln 1-YA (21.24)
BT 1-YA'
For a constant flux, the gradient is not linear but is steeper at low values of Y A,
as shown in Fig. 21.1b. The convective flow contribution to the flux, Y AN, becomes
smaller as Y A decreases, so the gradient becomes steeper, reflecting an increased
contribution from the diffusion term - D,PM dy A/db. The example in Fig. 21.1b
is for a very large change in concentration across the layer, such as might occur
in the evaporation of a liquid near the boiling point into a large stream of air. If
the mole fraction of A was much smaller, say, in the range 0 to 0.2, which is typical
of gas absorption, the gradient would be nearly linear. In the limit as Y A' and Y A
become very small, Eq. (21.24) becomes the same as Eq. (21.19), since
In(l - YA) '" - Y A and - In(l - YA') '" YA'·
Note that the gradient for B can be obtained directly from the gradient for
A, since YA + YB = 1.0 or CA + CB = PM. There is no transfer of B toward the
interface in spite of the large concentration gradient shown in Fig. 21.1b. The
explanation is that B tends to diffuse toward the region of lower concentration,
but the diffusion flux is just matched by the convective flow carrying B in the
opposite direction.
Example 21.1. (a) For the diffusion of solute A through a layer of gas to an absorbing
liquid, with YA = 0.20 and YAi = 0.10, calculate the transfer rate for one-way diffusion
compared to that for equimolal diffusion. (b) What is the value of YA halfway through
the layer for one-way diffusion?
Solution
(a) From Eq. (21.19) for equimolal diffusion,
JA ~ D,PM (0.20 - 0.10)
BT
From Eq. (21.24) for one-way diffusion,
NA ~ D,PM In 0.9 ~ D,PM 0.1178
BT 0.8 BT
(The concentration terms in both equations are reversed to make the flux toward
the interface positive.)
NA 0.1178
-~--~ 1.18
JA 0.10
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 655
In this case the transfer rate with one-way diffusion is about 18 percent greater
than that with equimolal diffusion.
(b) When b = B T /2,
1- YA BT NA 0.1178
In - - = - - - = - - = 0.0589
0.8 2 D,PM 2
1- YA = 0.8485 YA = 0.1515
The concentration at the midpoint is only slightly greater than if the gradient
were linear (yA = 0.150).
PREDICTION OF DIFFUSIVITIES. Diffusivities are best established by experi-
mental measurements, and where such information is available for the system of
interest, it should be used directly. Often the desired values are not available,
however, and they must be estimated from published correlations. Sometimes a
value is available for one set of conditions of temperature and pressure; the
correlations are then useful in predicting, from the known value, the desired values
for other conditions.
DIFFUSIVITIES IN GASES. Values of D, for some common gases diffusing
in air at ooe and 1 atm are given in Appendix 19. At pressures below about
5 atm, D, may be considered to be independent of concentration. Diffusivities
in gases can be predicted with considerable accuracy from kinetic theory 2.2o;
the theoretical correlations have been modified in the light of experimental
information to give the semiempirical equation 4
O.01498T1.81(1/M A + 11MB)".'
D = (21.25)
, P(T;A T;B)O.1405(V~A4 + V~B4)2
whereD, = diffusivity, cm 2 /s
T = temperature, K
MA, MB = molecular weights of components A and B, respectively
T;A' T;B = critical temperatures of A and B, K
~A' ~B = critical molar volumes of A and B, cm 3 /g mol
P = pressure, atm
Example 21.2. Estimate the volumetric diffusivity Dv for the system fluorotri-
chloromethane-nitrogen at 100ae and 10 atm. The critical temperatures and densities
are given in Table 21.1.
TABLE 21.1
Component
CFCI, 198 0.552
N, -147 0.311
656 MASS TRANSFER AND ITS APPLICATIONS
Solution
Equation (21.25) will be used. The quantities needed for substitution are
T = 373.16 K 7;A = 471.16 K 7;8 = 126.16 K
MA = 137.5 M8=28
137.5 28
V,A = - - = 249.1 cm'/g mol
0.552 .
V,8 = 0.311 = 90.03 cm'/g mol
Substitution in Eq. (21.25) gives
0.01498 x 373.16""(1/137.5 + 1/28)°·'
D =-----~~~~~~~~
, 10(471.16 X 126.16)°·14°'(249.1°·4 + 90.03°·4),
= 1.31 X 10-' cm'/s
LIQUID DIFFUSIVITIES. The theory of diffusion in liquids is not as advanced or
the experimental data as plentiful as for gas diffusion. The diffusivities in liquids
are generally four to five orders of magnitude smaller than in gases at atmospheric
pressure. Diffusion in liquids occurs by random motion of the molecules, but the
average distance traveled between collisions is less than the molecular diameter,
in contrast to gases, where the mean free path is orders of magnitude greater than
the size of the molecule.
Diffusivities for dilute liquid solutions can be calculated approximately
from the equation 2 •
(21.26)
whereD, = diffusivity, cm 2/s
T = absolute temperature, K
Jl = viscosity of solution, cP
VA = molar volume of solute as liquid at its normal boiling point, cm'/g mol
"'B= association parameter for solvent
M B = molecular weight of solvent
The recommended values of", Bare 2.6 for water, 1.9 for methanol, 1.5 for ethanol,
and 1.0 for benzene, heptane, ether, and other unassociated solvents. Equation
(21.26) is valid only at low solute concentrations and does not apply when the
solution has been thickened by addition of high-molecular-weight polymers. Small
amounts of polymer can raise the solution viscosity more than lOO-fold or even
gel the solution, but the diffusivity of small solutes is only slightly reduced, because
the polymer chains are too far apart to obstruct the movement of the solute
molecules. •
For values of VA larger than 500 cm'/mol, the Stokes-Einstein equation [Eq.
(30.54) on p. 1041] should be used for the diffusivity.
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 657
TABLE 21.2
Limiting ionic conductances in water
at 25°C21
Cation l'+ Anion l'
H+ 349.8 OH- 197.6
Li+ 38.7 CI- 76.3
Na+ 50.1 Br- 78.3
K+ 73.5 1- 76.8
NHt 73.4 NO; 71.4
The diffusion coefficient for dilute solutions of completely ionized univalent
electrolytes is given by the Nemst equation:
D = =-~_2_R:c-T~-=-= (21.27)
o [(1;;'~) + (1/2':)]F;
where 2~, 2': = limiting (zero-concentration) ionic conductances, A/cm2-(V/cm)-
(g equivalent/cm 3 )
R = gas constant, 8.314 J/K-g mol
F o = Faraday constant, = 96,500 C/g equivalent
Table 21.2 lists values of 2° at 25°C. Values for higher temperatures can be
estimated from the change in T //1.
For dilute aqueous solutions of nonelectrolytes a simpler equation can be
used 1?:
13.26 x 10- 5
D = ----;--;-:;-:-=;;;- (21.28)
v Jl1.14V~.589
where /1B = viscosity of water, cP
VA = molar volume of solute at normal boiling point, cm 3 /g mol
Note that unlike the case for binary gas mixtures the diffusion coefficient for
a dilute solution of A in B is not the same as for a dilute solution of B in A, since
/1, M B, and VA will be different when the solute and solvent are exchanged. For
intermediate concentrations, an approximate value of Do is sometimes obtained
by interpolation between the dilute solution values, but this method can lead to
large errors for nonideal solutions.
Example 21.3. Estimate the diffusivity of benzene in toluene and toluene in benzene
at 110°C. The physical properties are as follows:
VA at bp, pa.110°C
M bp,OC cm)/mol cP
Benzene 78.11 80.1 96.5 0.24
Toluene 92.13 110.6 118.3 0.26
658 MASS TRANSFER AND ITS APPLICATIONS
Solution
Equation (21.26) will be used. For benzene in toluene,
7.4 x 10- 8 (92.13)1/2383
D = 6.74 X 10- 5 cm 2 /s
" 0.26(96.5)°·6
For toluene in benzene,
7.4 x 10- 8 (78.11)1/2383
D = 5.95 X 10- 5 cm 2 /s
" 0.24(118.3)°·6
TURBULENT DIFFUSION. In a turbulent stream the moving eddies transport
matter from one location to another, just as they transport momentum and heat
energy. By analogy with Eqs. (3.18) and (12.46) for momentum transfer and heat
transfer in turbulent streams the equation for mass transfer is
de
J A" = -eN db (21.29)
where J A., = molal flux of A, relative to the phase as a whole, caused by turbulent
action
eN = eddy diffusivity
The total molal flux, relative to the entire phase, becomes
de
J A = -(D, + eN)PM db (21.30)
The eddy diffusivity depends on the fluid properties but also on the velocity
and position in the flowing stream, Therefore Eq, (21.30) cannot be directly
integrated to determine the flux for a given concentration difference. This equation
is used with theoretical or empirical relationships for eN in fundamental studies of
mass transfer, and similar equations are used for heat or momentum transfer in
developing analogies between the transfer processes, Such studies are beyond the
scope of this text, but Eq. (21.30) is useful in helping to understand the form of
some empirical correlations for mass transfer.
MASS-TRANSFER COEFFICIENTS AND
FILM THEORY
For steady-state mass transfer through a stagnant layer of fluid Eq. (21.19)
or Eq. (21.24) can be used to predict the mass-transfer rate provided BT is
known. However, this is not a common situation, because in most mass-transfer
operations turbulent flow is desired to increase the rate of transfer per unit area
or to help disperse one fluid in another and create more interfacial area. Further-
more, mass transfer to a fluid interface is often of the unsteady-state type, with
continuously changing concentration gradients and mass-transfer rates. In spite
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES' 659
of these differences, mass transfer in most cases is treated using the same type of
equations, which feature a mass-transfer coefficient k. This coefficient is defined as
the rate of mass transfer per unit area per unit concentration difference and is
usually based on equal molal flows. The concentrations can be expressed in moles
per volume or mole fractions, with subscript c indicating concentration and y or
x mole fractions in the vapor or liquid phase:
JA
k,= --"~ (21.31)
C Ai - CA
or
(21.32)
YAi - YA
Since k, is a molar flux divided by a concentration difference, it has
the units of velocity, such as centimeters per second or meters per second:
mol
k = = cm/s
c s, cm 2 , molfcm 3
For ky or kx the units are the same as for J A, moles per area per time,
since the mole fraction driving force is dimensionless. It is apparent that k,
and ky are related by the molar density as follows:
k,P
ky = k,PM = RT (21.33)
(21.34)
The significance of k, is brought out by combining Eq. (21.31) with Eq.
(21.20) for steady-state equimolal diffusion in a stagnant film. This gives
DJCAi - CA) 1
ET cAI-C A
D, (21.35)
=-
ET
Thus the coefficient k, is the molecular diffusivity divided by the thickness
of the stagnant layer. When dealing with unsteady-state diffusion or diffusion in
flowing streams, Eq. (21.35) can still be used to give an effective film thickness
from known values of k, and D,.
The basic concept of the film theory is that the resistance to diffusion
can be considered equivalent to that .in a stagnant film of a certain thickness.
The implication is that the coefficient k, varies with the first power of D"
which is rarely true, but this does not detract from the value of the theory
660 MASS TRANSFER AND ITS APPLICATIONS
FIGURE 21.2
Concentration gradient for mass transfer in a pipe with turbulent
flow of gas.
in many applications. The film theory is often used as a basis for complex
problems of multicomponent diffusion or diffusion plus chemical reaction.
For example, consider mass transfer from a turbulent gas stream to the wall
of a pipe, with the concentration gradient as shown in Fig. 21.2. There is a laminar
layer near the wall, where mass transfer is mainly by molecular diffusion, and the
concentration gradient is almost linear. As the distance from the wall increases,
turbulence becomes stronger, and the eddy diffusivity increases, which means that
a lower gradient is needed for the same flux [see Eq. (21.30)]. The value of CA is
a maximum at the center of the pipe, but this value is not used in mass-transfer
calculations. Instead the driving force is taken as CA - CAi' where CA is the
concentration reached if the stream were thoroughly mixed. This is the same as
a flow-weighted average concentration and is also the concentration to be used in
material-balance calculations. (This is analogous to the usage in heat transfer,
where the average temperature of a stream is used in defining h.)
If the gradient near the wall is linear, it can be extrapolated to CA' and
the distance from the wall at this point is the effective film thickness BT.
Generally, the resistance to mass transfer is mainly in the laminar boundary
layer very close to the wall, and BT is only slightly greater than the thickness
of the laminar layer. However, as will be brought out later, the value of BT
depends on the diffusivity D, and not just on flow parameters, such as the
Reynolds number. The concept of an effective film thickness is useful, but
values of BT must not be confused with the actual thickness of the laminar
layer.
EFFECT OF ONE-WAY DIFFUSION. As shown previously, when only com-
ponent A is diffusing through a stagnant film, the rate of mass transfer for
a given concentration difference is greater than if component B is diffusing
in the opposite direction. From Eqs. (21.19) and (21.24), the ratio of the fluxes
is
1- YA
In-"-
1- YAi
(21.36)
YAi - YA
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 661
The term Y Ai - YA can be written (1 - YA) - (1 - YAi)' and the right-hand side of
Eq. (23.36) is therefore the reciprocal of the logarithmic mean of 1 - YA and
1 - Y Ai or the mean value ofy., the mole fraction ofthe nondiffusing component:
NA = 1 1
(21.37)
J A (1 YA)L (Y.)L
This relationship, derived for molecular diffusion in a stagnant film, is assumed
to hold reasonably well for unsteady-state diffusion or a combination of molecular
and eddy diffusion. Sometimes the mass-transfer coefficient for one-way transfer
is denoted by k; or k;, and the coefficients then follow the same relationship as
the fluxes in Eq. (21.37):
(21.38)
The rate of one-way mass transfer can be expressed using either type
of coefficient:
NA = k;(YAi - YA) (21.39)
N _k,(YAi-YA)
(21.40)
A - (1 YA)L
When the value of Y A is 0.10 or less, the difference between ky and k; is small
and often ignored in design calculations. For mass transfer in the liquid phase,
the corresponding correction term for one-way diffusion (1 - XA)L is usually
omitted, because the correction is small compared to the uncertainty in the
diffusivity and the mass-transfer coefficient.
BOUNDARY-LAYER THEORY. Although there are few examples of diffusion
through a stagnant fluid film, mass transfer often takes place in a thin boundary
layer near a surface where the fluid is in laminar flow. If the velocity gradient in
the boundary layer is linear and the velocity is zero at the surface, the equations
for flow and diffusion can be solved to give the concentration gradient and the
average mass-transfer coefficient. The coefficient depends on the two-thirds power
of the diffusivity and decreases with increasing distance along the surface in the
direction of flow, because an increase in either distance or in Dv makes the
concentration gradient extend further from the surface, which decreases the
gradient dCA/db at the surface.
For flow over a flat plate or around a cylinder or sphere, the velocity
profile is linear near the surface but the gradient decreases as the velocity
approaches that of the main stream at the outer edge of the boundary layer.
Exact calculations show that the mass-transfer coefficient still varies with D;;" if
D" is low or the Schmidt number (J1./pD") is 10 or larger. For Schmidt numbers
of about 1, typical for gases, the predicted coefficient varies with a slightly lower
power of D". For boundary-layer flows, no matter what the shape of the velocity
662 MASS TRANSFER AND ITS APPLICATIONS
profile or value of the physical properties, the transfer rate cannot increase with
the 1.0 power of the diffusivity, as implied by the film theory. Boundary-layer
theory can be used to estimate k, for some situations, but when the boundary
layer becomes turbulent or separation occurs, exact predictions of k, cannot be
made, and the theory serves mainly as a guide in developing empirical correlations.
PENETRATION THEORY OF
MASS TRANSFER
The penetration theory makes use of the expression for the transient rate of
diffusion into a relatively thick mass of fluid with a constant concentration at the
surface. The change in concentration with distance and time is governed by the
following equation:
(21.41)
The boundary conditions are
for t = 0
atb = 0, t > 0
The particular solution of Eq. (21.41) is the same as that for transient heat
conduction to a semi-infinite solid, Eq. (10.26).
The instantaneous flux at time t is given by the analogous form ofEq. (10.29):
(21.42)
The average flux over the time interval 0 to tT is
(21.43)
Combining Eqs. (21.31) and (21.43) gives the average mass-transfer coefficient
over the time tT:
- J!i' Jf:'
k, = 2 - = 1.13
nt T
-
tT
(21.44)
Higbie'8 was the first to apply this equation to gas absorption in a liquid,
showing that diffusing molecules will not reach the other side of a thin layer if the
contact time is short. The depth of penetration, defined as the distance at which
the concentration change is 1 percent of the final value, is 3.6)D,t T • For
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 663
D, = 10- 5 cm 2/s and IT = 10 s, the depth of penetration is only 0.036 cm. In gas
absorption equipment, drops and bubbles often have very short lifetimes because
of coalescence, and the penetration theory is likely to apply.
An alternate form of the penetration theory was developed by Danckwerts, 7
who considered the case where elements of fluid at a transfer surface are randomly
replaced by fresh fluid from the bulk stream. An exponential distribution of ages
or contact times results, and the average transfer coefficient is given by
(21.45)
where s is the fractional rate of surface renewal, in s -I,
Both Eqs. (21.44) and (21.45) predict that the coefficient varies with the
one-half power of the diffusivity and give almost the same value for a given average
contact time. A modified version of the penetration theory,15 which assumes that
eddies from a turbulent bulk fluid come to within random distances of the surface,
gives slightly higher exponents for the diffusivity, which indicates that this theory
might apply for mass transfer to pipe walls or flat surfaces such as a pool of liquid.
The various forms of the penetration theory can be classified as surface-
renewal models, implying either formation of new surface at frequent intervals or
replacement of fluid elements at the surface with fresh fluid from the bulk. The
time IT or its reciprocal, the average rate of renewal, are functions of the fluid
velocity, the fluid properties, the the geometry of the system and can be accurately
predicted in only a few special cases. However, even if IT must be determined
empirically, the surface-renewal models give a sound basis for correlation of
mass-transfer data in many situations, particularly for transfer to drops and
bubbles. The similarity between Eqs. (21.44) and (15.20) is an example of the close
analogy between heat and mass transfer. It is often reasonable to assume that IT
is the same for both processes and thus to estimate rates of heat transfer from
measured mass-transfer rates or vice versa,
EXPERIMENTAL MEASUREMENT OF
MASS-TRANSFER COEFFICIENTS
In view of the complexity of mass transfer in actual equipment, fundamental
equations for mass transfer in actual equipment are rarely available, and empirical
methods, guided by dimensional analysis and by semitheoretical analogies, are
relied upon to give workable equations. The approach to the problem has been
made in several steps in the following manner.
1. The coefficient k has been studied in experimental devices in which the area of
contact between phases is known and where boundary-layer separation does
not take place. The wetted-wall tower shown in Fig. 21.3, which is sometimes
used in practice, is one device of this type. It has given valuable information
on mass transfer to and from fluids in turbulent flow. A wetted-wall tower is
essentially a vertical tube with means for admitting liquid at the top and causing
664 MASS TRANSFER AND ITS APPLICATIONS
Gas
in or out
Gauze
Calming
section FIGURE 21.3
Gas
in or out Wetted-wall tower.
it to flow downward along the inside wall of the tube, under the influence of
gravity, and means for admitting gas to the inside of the tube, where it flows
through the tower in contact with the liquid. Generally the gas enters the
bottom of the tower and flows countercurrent to the liquid, but parallel flow
can be used. In the wetted-wall tower, the interfacial area A, except for some
complications from ripple formation, is known, and form drag is absent.
2. Mass transfer to liquids in turbulent pipe flow has been studied by using tubes
made from a slightly soluble solid and measuring the rate of dissolution of the
solid for various liquid flow rates. An alternate technique is to make a portion
of the tube wall an electrode and carry out an electrochemical reduction under
conditions where the current is limited by the rate of mass transfer of the
reacting ion to the wall.
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 665
3. External mass transfer, such as diffusion to particles or to the outside of pipes
or cylinders, requires different correlations from those for internal mass transfer,
because there is boundary-layer flow over part of the surface, and boundary-
layer separation is common. The mass-transfer coefficients can be determined
by studying evaporation of liquid from porous wet solids. However, it is not
easy to ensure that there is no effect of internal mass-transfer resistance.
Complications from diffusion in the solid are eliminated if the solid is made
from a slightly soluble substance that dissolves in the liquid or sublimes into
a gas. This method also permits measurement of local mass-transfer coefficients
for different points on the solid particle or cylinder.
4. Finally, experiments are made with actual mass-transfer devices such as packed
towers, sieve trays, and bubble columns, for which the mass-transfer area varies
with operating conditions. The mass-transfer rates are converted first to a
volumetric mass-transfer coefficient ka, where a is the transfer area per unit
volume of equipment. Sometimes a is determined from photographs, so that
separate correlations for a and k can be developed. Although there are two
fluid phases present in most cases, the resistance in one phase is usually made
negligible so that ka for the other phase can be determined. For example,
gas-film coefficients in a packed column are determined by evaporating pure
liquids into flowing gases, and there is no diffusion resistance in the liquid.
Likewise the absorption of a pure gas into water eliminates the gas-film
resistance, permitting study of the liquid-film coefficient.
Experiments conducted for obtaining numerical values for k or ka consist
in measuring experimentally the quantities N A , A, Yi' and Y and calculating k by
Eq. (21.32) or (21.40) or an integrated form of these equations, as shown in Chap.
22. If A or a is not known, the total volume of the equipment is used and ka
calculated. Dimensional analysis is used to plan the experiments and to interpret
the results in the form of dimensionless groups and equations. Analogies among
friction, heat transfer, and mass transfer are useful guides.
COEFFICIENTS FOR MASS TRANSFER
THROUGH KNOWN AREAS
In this section correlations are given for mass transfer between fluids or between
fluids and solids where the area A is known. Coefficients for equipment in which
the area between the phases is not known are discussed in subsequent chapters.
DIMENSIONAL ANALYSIS. From the mechanism of mass transfer, it can be
expected that the coefficient k would depend on the diffusivity D, and on the
variables that control the character of the fluid flow, namely, the velocity u, the
viscosity J1., the density p, and some linear dimension D. Since the shape of the
interface can be expected to influence the process, a different relation should appear
for each shape. For any given shape of transfer surface
k = Ijt(D" D, u, J1., p)
666 MASS TRANSFER AND ITS APPLICATIONS
Dimensional analysis gives
(21.46)
where G = up.
Equation (21.46) is analogous to the Colburn form of the heat-transfer
equations (12.52) and (12.53). A second dimensionless equation, analogous to the
Nusselt form of the heat-transfer equation is obtained by multiplying Eq. (21.46)
by (DGI/1)(/1lpDJ This gives
k,D
D,
= 1/12 (DO,~)
/1 pD,
(21.47)
The dimensionless groups in Eqs. (21.46) and (21.47) have been given names
and symbols. The group k,DID, is called the Sherwood number and is denoted by
NSh ' This number corresponds to the Nusselt number in heat transfer. The group
/1lpD, is the Schmidt number, denoted by Ns,' It corresponds to the Prandtl
number. Typical values of N s, are given in Appendix 19. The group DGI/1 is, of
course, a Reynolds number, NRco
When the mass-transfer coefficient depends on the two-thirds power of the
diffusivity, as is the case for some boundary-layer flows, the coefficients are often
presented in the form of ajM factor analogous to thejH factor of Eq. (12.53):
. _k,(
lAr=- -
/1 )2/3 (21.48)
u pD,
Mass Transfer to Pipes and Cylinders
FLOW INSIDE PIPES. Correlations for mass transfer to the inside wall of a pipe
are of the same form as those for heat transfer, since the basic equations for
diffusion and conduction are similar. For laminar flow, the Sherwood number
shows the same trends as the Nusselt number, with a limiting value of 3.66 for
very long tubes and a one-third-power dependence on flow rate for short tubes.
The solution shown in Figure 12.2 can be used for NSh if the Graetz number is
based on the diffusivity or on the Schmidt number as follows:
lil n D
N'a,= DL ="4 NR ,Ns'L (21.49)
, p
For moderate Graetz numbers, the theoretical equation for mass transfer is
N Sh = 1.62N~i3 (21.50)
Equation (21.50) has been used to predict the internal mass-transfer resistance
for separation processes using hollow-fiber membranes. The recommended equa-
tion for heat transfer, Eq. (12.23), has an empirical coefficient of 2.0, and this higher
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 667
value is probably due to natural convection. There are not enough data to
determine an empirical equation for mass transfer in laminar flow.
One equation for turbulent-flow mass transfer to pipe walls is a modification
of Eq. (12.31) with the Nusselt and Prandtl numbers replaced by the Sherwood
and Schmidt numbers.
NSh = 0.023N~;8N§i3
Jl
-
)0.14 (21.51)
(
Jl"
This is the simplest equation that gives a fairly good fit to the published data over
a wide range of Reynolds numbers and Schmidt numbers. An alternate form of
the correlation is obtained by dividing Eq. (21.51) by N Ro x NJi3 to give the j"
factor, which was shown by Chilton and Colburn' to be the same as}H and also
the same as J12. The term JlIJl~.14 is usually about 1.0 for mass transfer and is
omitted:
. .
JM=JH="2 If =.
0023N-o.
Re
2
(21.52)
The analogy shown in this equation is general for heat and mass transfer in the
same equipment.
Extending the analogy to include friction loss is possible for pipes only
because all the loss comes from skin friction. The analogy does not apply to total
friction loss when there is form drag from separation of flow, as occurs in flow
around objects.
In general,)" is a function of N Ro • For gas-phase mass transfer other forms
of}" can be used:
. _ k,R T 2{3 k,M 2{3
lM-p;;-N sc =G Nsc (21.53a)
. kgMP 2{3
J"=-G- Nso (21.53b)
Coefficient kg is discussed in Chap. 22.
Slightly more accurate correlations for pipe flow have been presented for
different ranges of the Schmidt number. Data for evaporation of several liquids
in wetted-wall towers (Fig. 21.3) were correlated with slightly higher exponents
for both the Reynolds and Schmidt numbers 11 :
(21.54)
The Schmidt numbers were varied from 0.60 to 2.5, and over this narrow range
the difference between the exponents of 0.44 in Eq. (21.54) and 0.33 in Eq. (21.51)
has only a small effect on the coefficient. The difference in exponents may have
fundamental significance, since transfer to a liquid surface, which can have waves
or ripples, should differ somewhat from transfer to a smooth rigid surface.
A correlation for mass transfer at high Schmidt numbers (430 to 100,000)
was obtained by measuring the rate of solution of tubes of benzoic acid in water
668 MASS TRANSFER AND ITS APPLICATIONS
and viscous liquids l6 :
(21.55)
The difference between the exponent on the Schmidt number and the usual value
of t may not be significant, but the exponent for the Reynolds number is definitely
greater than 0.80. Other studies of heat transfer with large Prandtl numbers 'o
have also shown an exponent of about 0.9 for the Reynolds number. Various
empirical equations that cover the entire range of Ns, or N p , with good accuracy
are available. 23a
Example 21.4. (a) What is the effective thickness of the gas film for the evaporation
of water into air in a 2-in.-diameter wetted-wall column at a Reynolds number of
20,000 and a temperature of 40'C? (b) Repeat the calculation for the evaporation of
ethanol under the same conditions. At 1 atm the diffusivities are 0.288 cm lis for water
in air and 0.145 cm 2 /s for ethanol in air.
Solution
For air at 40°C,
29 273.16
P = - - x - - = 1.129 X 10-' g/crn'
22,410 313.16
I' = 0.0186 cP (Appendix 8)
I'. = 1.86 X 10-'
0.165 cm'js
P 1.129 x 10 '
(a) For the air-water system,
0.165
N s, = - - = 0.573
0.288
From Eq. (21.54),
NSh = 0.023(10,000)°·81(0.573)°·44 = 31.3
In the film theory, kc = Dv/BT' and since NSh = kJJ/Dv,
D 2.0
N Sh = - or BT =- = 0.064 in.
BT 31.3
(b) For the system air-ethanol, N s, = O.l65jO.l45 = 1.14:
NSh = 0.023(10,000)°·81(1.14)°·44 = 42.3
2.0
BT = - = 0.047 in.
42.3
Thickness BT becomes smaller as the diffusivity decreases because kc varies
with only the 0.56 power of the diffusivity instead of the 1.0 power implied by the
film theory. If Eq. (21.51) were used, the corresponding values of BT would be 0.066
and 0.053 in. These are somewhat closer to each other because D;/3 is used instead
of D~·56.
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 669
FLOW OUTSIDE TUBES PARALLEL TO AXIS. Some membrane separators have
bnndles of hollow fibers in a shell-and-tnbe arrangement with liquid or gas flowing
parallel to the tube axis on the outside of the tubes. The external flow passages
are irregular in shape and not uniform, since the flbers are not held in position
as are the tubes in a heat exchanger. Empirical correlations for the external
mass-transfer coefficient have been proposed using an equivalent diameter to
calculate the Reynolds number. For a bundle of fibers with diameter d packed in
a shell with E void fraction, the equivalent diameter is
flow area 4E d_E _
d = 4 x ---,---;--;-- (21.56)
, wetted perimeter (4/d)(1 - E) l-E
FLOW NORMAL TO CYLINDERS. A correlation of jM vs. N R, for flow of
air perpendicular to single cylinders is shown in Fig. 21.4. The dashed line
shows values of jH calculated from Eq. (12.69), which was based on data for
liquids. The data for heat transfer to air, taken from Fig. 12.6, fall slightly
below the dashed line and very close to the mass-transfer data. The good
agreement shows that the analogy between mass and heat transfer holds very well
for external flows as well as for flows inside pipes.
An approximate equation for mass transfer to a single cylinder can be
used for N R , values of 10 to 10':
(21.57)
FLOW NORMAL TO TUBE BUNDLE. For flow normal to a bundle of tubes, the
average mass-transfer coefficient is higher than for a single tube at the same
superficial velocity, but the factor of increase depends on the tube spacing and the
Reynolds number. Based on heat transfer to 'tube banks, the increase could be 20
n.
I Heo
~ :!::
-Moss
nnnl
10' 10' 10' 10'
FIGURE 21.4
Heat and mass transfer, flow past single cylinders.
670 MASS TRANSFER AND ITS APPLICATIONS
to 40 percent, but there are few mass-transfer data for low Reynolds numbers,
which is the region of interest for hollow-fiber membrane devices.
Tests of a module with 2100 fibers and t = 0.6 gave NSh = 0.24, independent
of flow rate.27 Such a low Sherwood number indicates very uneven flow distribu-
tion, since the minimum value of NSh for ideal flow would be in the range 2 to 4.
The following empirical equation for a 72-fiber module 27 gives about the
same coefficients as Fig. 21.4 for NR< = 100:
(21.58)
There are no data on the effect of void fraction, and local variations in packing
density probably have a large effect on the average coefficient.
Mass Transfer to Particles
FLOW PAST SINGLE SPHERES. For mass transfer to an isolated sphere, the
Sherwood number approaches a lower limit of 2.0 as the Reynolds number
approaches zero. A simple equation that is fairly accurate for Reynolds numbers
up to 1000 is a modification of the Frossling equation 22 [compare to Eq. (12.70)
for NNo]:
(21.59)
Data for high Reynolds numbers show a gradual increase of slope on a plot
of NShvs. N R" as shown in Fig. 21.5. The exponent of ! is consistent with
Iv
. Pnrk"d beds
NSc = /0 >-
10 2 1\ /0 3 , I ".-
,/
10
V
stagnant flUId
I
I 10 102 10' 104 le
FIGURE 21.5
Heat and mass transfer, flow past single spheres (solid line) and in packed beds (dashed lines).
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 671
boundary-layer theory which applies to the front portion of the sphere, where
most of the transfer takes place at moderate Reynolds numbers. At high Reynolds
numbers mass transfer in the turbulent region becomes more important and the
effect of flow rate increases.
The correlation in Fig. 21.5 gives values that are too low for "creeping flow,"
where the Reynolds number is low and the Peclet number N p , is high (Np , =
N R , x N s, = Dpua/D,). For this case the recommended equation is'
NSh = (4.0 + 1.21NW)1/2 (21.60)
The limiting Sherwood number of 2.0 corresponds to an effective film
thickness of D p/2 if the mass-transfer area is taken as the external area of the
sphere. The concentration gradients actually extend out to infinity in this case,
but the mass-transfer area also increases with distance from the surface, so the
effective film thickness is much less than might be estimated from the shape of the
concentration profile.
MASS TRANSFER IN PACKED BEDS. There have been a great many studies of
mass transfer and heat transfer from gases or liquids to particles in packed beds.
The coefficients increase with about the square root of the mass velocity and the
two-thirds power of the diffusivity, but the correlations presented by different
workers differ appreciably, in contrast to the the close agreement found in studies
of single spheres. An equation that fairly well represents most of the data is 2 'b
jM
k
= ~ N§~3 = 1.17
(D G)-a.415
-p- (21.61)
"a f.l
This is equivalent to the equation
(21.62)
Equations (21.61) and (21.62) are recommended for spheres or roughly
spherical solid particles that form a bed with about 40 to 45 percent voids. For
cylindrical particles these equations can be used with the diameter of the cylinder
in N R, and N Sh ' For beds with higher void fractions or for hollow particles, such
as rings, other correlations are available. 12
To compare mass transfer in packed beds with transfer to a single particle,
Sherwood numbers calculated from Eq. (21.62) are plotted in Fig. 21.5 along with
the correlation for isolated spheres. The coefficients for packed beds are two to
three times those for a single sphere at the same Reynolds number. Most of this
difference is due to the higher actual mass velocity in the packed bed. The Reynolds
number is based for convenience on the superficial velocity, but the average mass
velocity is G/€, and the local velocity at some points in the bed is even higher.
Note that the dashed lines in Fig. 21.5 are not extended to low values of N R"
since it is unlikely that the coefficients for a packed bed would ever be lower than
those for single particles.
672 MASS TRANSFER AND ITS APPLICATIONS
MASS TRANSFER TO SUSPENDED PARTICLES. When solid particles are sus-
pended iu an agitated liquid, as in a stirred tank, a minimum estimate of the
transfer coefficient can be obtaiued by using the terminal velocity of the particle
in stilI liquid to calculate N R , in Eq. (21.59). The effect of particle size and density
difference on this minimum coefficient k,T is shown in Fig. 21.6. Over a wide range
of sizes, there is little change in the coefficient, because the iucrease in terminal
velocity and Reynolds number makes the Sherwood number nearly proportional
to particle diameter.
The actual coefficient is greater than k,T because frequeut acceleration and
deceleration of the particle raises the average slip velocity and because small eddies
in the turbulent liquid penetrate close to the particle surface and increase the local
rate of mass transfer. However, if the particles are fully suspended, the ratio k)k'T
falls within the relatively narrow range of 1.5 to 5 for a- wide range of particle
sizes and agitation conditions." The effects of particle size, diffusivity, and
viscosity follow the trends predicted for k,T' but the density difference has almost
no effect until it exceeds 0.3 g/cm'. For suspended particles, k, varies with only the
0.1 to 0.15 power of the power dissipation per unit volume, the higher exponent
being for large particles. Empirical correlations for predicting k, based on power
consumption are available!" but at the same power, the coefficients are higher
for larger ratios of agitator diameter to tank diameter D./D,.
0.1 0
.08
kcDp
.0 6 2
N" D•
.0 4
.02
0.0 1 ~~ DENSITY pIFF~R,E NCE
3,Og ;d~~
.008
.006 1,0 9fem 3
.004 .39 I'm
]
,
","
.002
,, 0.1 9I'm
0.00 1
.0008
.000 6
.0004
.0002
I',,
0.000 1
1 2 4 6 810 2 4681002 4 6 81,000 2 4 6 810,000
Diameter of particle, 0P' /lm
FIGURE 21.6
MassRtransfer coefficients for particles falling in water 13 (viscosity /.l = 1 cP, diffusivity D~ =
10- 5 cm 2 /s).
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 673
Power per unit volume is a satisfactory basis for scaleup when dealing with
suspended particles provided geometric similarity is maintained.
MASS TRANSFER TO DROPS AND BUBBLES. When small drops of liquid are
falling through a gas, surface tension tends to make the drops nearly spherical,
and the coefficients for mass transfer to the drop surface are often quite close to
those for solid spheres. The shear caused by the fluid moving past the drop surface,
however, sets up toroidal circulation currents in the drop that decrease the
resistance to mass transfer both inside and outside the drop. The extent of the
change depends on the ratio of the viscosities of the internal and external fluids
and on the presence or absence of substances such as surfactants that concentrate
at the interface. 14
For a low-viscosity drop falling through a viscous liquid with no surface-
active material present, the velocity boundary layer in the external fluid almost
disappears. Fluid elements are exposed to the drop for short times and the mass
transfer is governed by the penetration theory. It can be shown that the effective
contact time is the time for the drop to fall a distance equal to its own diameter,
and application of the penetration theory leads to the equation
k, = 2JD,uo (21.63)
nDp
Multiplyjng through Dp/D, gives
NSh = ~ (DpUOP -,,--)1/2
In J1 pD,
= 1.l3N~~2N§i2 (21.64)
Comparing Eq. (21.64) with Eq. (21.59) for a rigid sphere shows that internal
circulations can increase k, by a factor of about 1.8Nti6, or 5.7, when N s, = 103 •
Coefficients in agreement with Eq. (21.63) have been found for some drops
in free fall, but in many cases the high drop viscosity or impurities in the drop
reduce the circulation currents and lead to values only slightly greater than for
rigid spheres. For drops suspended in an agitated liquid, as in a stirred-tank
extractor, the coefficients generally fall between those for a solid sphere and those
for a completely circulating drop. The coefficients for drops increase with the 1.0
to 1.2 power of the stirrer speed, in contrast to the 0.4 to 0.5 power found with
solid particles, because eddies in the suspending liquid can penetrate closer to a
drop with a deformable surface than to a solid particle. 8
It is difficult to predict k, for a practical application, and the mass-transfer
calculations are generally based on a volumetric mass-transfer coefficient k,a
estimated from laboratory or pilot-plant tests.
The same uncertainties arise when dealing with mass transfer from bubbles
of gas rising through liquid. The gas in the bubbles should circulate rapidly because
of the low gas viscosity, but impurities often interfere, giving coefficients between
674 MASS TRANSFER AND ITS APPLICATIONS
those for rigid spheres and freely circulating bubbles. Bubbles 1 mm in diameter
or smaller often behave like rigid spheres and those 2 mm or larger as freely
circulating bubbles. Bubbles larger than a few millimeters in diameter, however,
are flattened in shape and may oscillate as they rise, making mass-transfer
predictions more difficult. As with transfer to liquid drops, design correlations for
bubbling systems are usually based on a volumetric coefficient.
With drops and bubbles the resistance to mass transfer in both phases may
be significant. Diffusion inside a stagnant (noncirculating) drop is an unsteady-
state process, but for convenience in combining coefficients an effective internal
coefficient can be used, as was done for heat transfer in spheres [see Eqs. (11.38)
and (11.40)]:
10D,
k·=-- (21.65)
" Dp
where kci = effective internal mass-transfer coefficient
D, = diffusivity inside the drop
D p = drop diameter
If the drop has a short lifetime, the internal coefficient will be greater than that
given by Eq. (21.65), since the concentration gradient will not extend very far into
the drop. If the lifetime is known, the penetration theory [Eq. (21.44)] can be used,
but the breakup and coalescence of the drops in agitated systems make it hard to
predict the drop lifetime. Measurements of the internal mass-transfer coefficient
k" for drops of an organic liquid in a stirred extractor were consistent with the
penetration theory and with drop lifetimes one-third to one-tenth as long as the
batch time. 24
TWO-FILM THEORY
In many separation processes, material must diffuse from one phase into another
phase, and the rates of diffusion in both phases affect the overall rate of mass
transfer. In the two-film theory, proposed by Whitman 25 in 1923, equilibrium is
assumed at the interface, and the resistances to mass transfer in the two phases
are added to get an overall resistance, just as is done for heat transfer. The
reciprocal of the overall resistance is an overall coefficient, which is easier to use
for design calculations than the individual coefficients.
What makes mass transfer between phases more complex than heat transfer
is the discontinuity at the interface, which occurs because the concentration or
mole fraction of diffusing solute is hardly ever the same on opposite sides of the
interface. For example, in distillation of a binary mixture, y~ is greater than X A ,
and the gradients near the surface of a bubble might be as shown in Fig. 21.7a.
For the absorption of a very soluble gas, the mole fraction in the liquid at the
interface would be greater than that in the gas, as shown in Fig. 21.7b.
PRINCIPLES Of DIFFUSION AND MASS TRANSFER BETWEEN PHASES 675
Liquid
Gas Liquid
lal Ib)
FIGURE 21.7
Concentration gradients near a gas-liquid interface: (a) distillation; (b) absorption of a very soluble
gas.
In the two-film theory, the rate of transfer to the interface is set equal to the
rate of the transfer from the interface:
r = kx(XA - XAi ) (21.66)
r = kiYAi - YA) (21.67)
The rate is also set equal to an overall coefficient K, times an overall driving
force Y~ - YA, where Y~ is the composition of the vapor that would be in
equilibrium with the bulk liquid of composition x A :
(21.68)
To get K, in terms of k, and k" Eq. (21.68) is rearranged and the term
Y:!! - YA replaced by (y~ - YAi) + (YAi - YA):
*
YA-YAi+YAi-YA
(21.69)
r r
Equations (21.66) and (21.67) are now used to replace r in the last two terms
of Eq. (21.69):
~= YA-YAi + Yai-YA (21.70)
K, kx(XA-XA.l k,(YAi-YA)
Figure 21.8 shows typical values of the composition at the interface, and it
is apparent that (y~ - YAi)/(XA - x Ai) is the slope of the equilibrium curve. This
slope is denoted by m. The equation can then be written
1 m 1
-=-+- (21.71)
K, kx k,
The term 1/K, can be considered an overall resistance to mass transfer, and the
terms m/kx and l/k, are the resistances in the liquid and gas films. These
"films" need not be stagnant layers ofa certain thickness in order for the two-film
theory to apply. Mass transfer in either film may be by diffusion through a laminar
676 MASS TRANSFER AND ITS APPLICATIONS
Y" \
I Equilibrium line
YA,--- I
I
I
I I
I I
YA ----1----+
I I
I
xA ,
I
xA
FIGURE 21.8
Bulk and interface concentrations typical of
distillation.
boundary layer or by unsteady-state diffusion, as in tbe penetration theory, and
the overall coefficient is still obtained from Eq. (21.71). For some problems, such
as transfer through a stagnant film into a phase where the penetration theory is
thought to apply, the penetration-theory coefficient is slightly changed because of
the varying concentration at the interface, but this effect is only of academic
interest.
STAGE EFFICIENCIES
The efficiency of a stage or plate in a distillation, absorption, Or extraction
operation is a function of the mass-transfer rates and transfer coefficients. When
material is removed from a permeable solid, as in leaching or drying operations,
the transfer rates and sometimes the stage efficiencies can be estimated from
diffusion theory.
DISTILLATION PLATE EFFICIENCY. The two-film theory can be applied to mass
transfer on a sieve tray to help correlate and extend data for tray efficiency. The
bubbles formed at the holes are assumed to rise through a pool of liquid that is
vertically mixed and has the local composition x A- The bubbles change in
composition as they rise, and there is assumed to be no mixing of the gas phase
in the vertical direction. For a unit plate area with a superficial velocity v" the
moles transferred in a thin slice dz are
Y,PM dYA = Kya(y~ - YA) dz (21.72)
Integrating over the height of the aerated liquid Z gives
'f"
yA1yj{-YA
= In y*A - YA1
dYA
yj{-YA2
(21.73)
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 677
or
Y~ - YA2 = exp ( - 5 az ) (21.74)
YA - YA! Y,PM
The local efficiency ~' is given by
, YA2-YAl
~ = (21.75)
Y~ - YAl
and
1 I Y~-YAI-YA2+YAl
- '1 = * (21.76)
YA - YAl
From Eq. (21.74),
1 - 't1' = exp ( - K
-.!~
az) = e- Noy (21.77)
Y,PM
The dimensionless group No, is called the number of overall gas-phase
transfer units, and its significance will be discussed in Chap. 22. For distillation
of low-viscosity liquids such as water, alcohol, or benzene at about lOO"C, the
value of No, is about 1.5 to 2, nearly independent of the gas velocity over the
normal operating range of the column. This gives a local efficiency of 78 to 86
percent, and the Murphree plate efficiency will be slightly higher or lower,
depending on the degree of lateral mixing on the plate and on the amount of
entrainment.
The relative importance of the gas and liquid resistances can be estimated
by assuming that the penetration theory applies to both phases and with the same
contact time. Since the penetration theory [Eq. (21.44)J gives k" and k, and kx
equal k,PM, and k,PMx> respectively,
k, = (Do,)!!2 PM, (21.78)
kx Dux PMx
Example 21.5. (a) Use the penetration theory to estimate the fraction of the total
resistance that is in the gas film in the distillation of a benzene-toluene mixture at
110°C and 1 atm pressure. The liquid viscosity J1 is 0.26 cP. The diffusivities and
densities are, for liquid,
PMx = 8.47 malfL
and, for vapor,
D" = 0.0494 cm'/s PM, = 0.0318 molfL
(b) How would a fourfold reduction in total pressure change the local efficiency
and the relative importance of the gas-film and liquid-film resistances?
678 MASS TRANSFER AND ITS APPLICATIONS
Solution
(a) Substitution into Eq. (21.78) gives
k, ( 0.0494 )"20.0318
-= , --=0.102
kx 6.74 x 10- 8.47
Thus the gas-film coefficient is predicted to be only 10 percent of the liquid-film
coefficient, and if m = 1, about 90 percent of the overall resistance to mass transfer
would be in the gas film.
(b) Assume that the column is operated at the same F factor and that this gives
the same interfacial area a and froth height Z. The boiling temperature of toluene
at 0.25 atm is 68"C, or 341 K, compared to 383 K at 1 atm.
GasfUm Since Dvl' oc T1. 81 1P, the new value of Dvl' is
341)1.81 D
D~l' = 3.24 times the old value
( -383 ----2:.
0.25
=
Assuming that the penetration theory holds with the same tT' kc increases by J3.24,
or 1.8, but at 0.25 atm and 68"C, PM" is 0.00894 mol/L, so k, changes by
1.8 x 0.00894/0.0318 = 0.506.
Liquid film Here Dvx cc Tlfl, and since fl = 0.35 cP at 68°C, the new value
of Dux is
3410.26D,x
D~x = - --- = 0.66 times the old value
383 0.35
Thus kc decreases by JO.66 = 0.81, and considering the small change in molar
density to 8.92 mol/L, kx changes by 0.81 x 8.92/8.47 = 0.86.
If the local efficiency at 1 atm pressure is 0.86, corresponding to two transfer
units, and if the relative values of kx and ky are estimated as in part (a) the new value
of K~ is obtained as follows:
k'x = 0.86kx
At 1 atm, k, = 0.102kx and K, = 0.907k,. Thus
0.86
k~ = - - k, = 8.43k,
0.102
For m = 1,
1 1 1 1 1 2.10
-=-+-=--+--=-
K; k; k'x 0.506k, 8.43k, k,
K; = 0.476k,
The ratio of the number of transfer units is the ratio of the overal coefficients
divided by the molar flow rate. If the column is operated at the same F factor, .JPl'
changes by [(383 x 0.25)j341]0., = 0.53, and V, changes by 1/0.53. If a, the area
per unit volume, is the same, the new value of N~y is
0.476
N~, = 2 x - - = 1.80 q' = 1 - e-1.80 = 0.83
0.53
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 679
Thus the local efficiency is predicted to drop from 86 to 83 percent, with 94
percent of the total resistance in the gas phase. Close agreement with the actual values
of efficiency is not expected because of the assumptions made to simplify the analysis.
but the trend is correct. as shown in Fig. 18.34, and it is clear that the gas-film
resistance is increasingly important at low pressures. For distillation at high pressures.
ky and kx are more nearly equal.
STAGE EFFICIENCIES IN LEACHING. The stage efficiency in a leaching process
depends on the time of contact between the solid and the solution and the rate
of diffusion of the solute from the solid into the liquid. If the particles of solid are
nonporous and the solute is contained only in the film of liquid around the
particles, mass transfer is quite rapid, and any reasonable time of contact will
bring about equilibrium. Such a process is really one of washing rather than
leaching, and if carried out in a series of tanks as shown in Fig. 17.3, the stage
efficiency is taken as unity. The residence time in each stage depends mainly on
the settling rate of the suspension, and small particles require longer times even
though the mass transfer is more rapid.
When most of the solute is initially dissolved in the pores of a porous
solid or is present as a separate phase inside the solid particles, the diffusion
rate from the interior to the surface of the solid is generally the controlling
step in the overall rate of leaching. Once the particles are suspended in the
liquid, increased agitation has little effect on the rate of mass transfer, but
the rate is greatly increased if the solid is finely ground. When the internal
resistance to diffusion is the only limiting factor, the time for a given degree
of approach to equilibrium varies with the square of the smallest particle dimen-
sion, whether the particles are spheres, cylinders, or thin slices. (See Fig. 10.6.)
When leaching minerals from ores, the optimum particle size is determined by the
cost of grinding as well as by the change in extraction rate with particle size.
The leaching of natural materials such as sugar beets or soybeans is
complex, because the solute is contained in vegetable cells and must first pass
through the cell walls. If the resistance for this step is relatively large, the effect
of cutting smaller particles will not be as great as for diffusion in a uniform solid.
For the extraction of oil from soybeans, the beans are crushed to break the cell
walls and release the oil, but sugar beets are sliced in a way that leaves most of
the cells intact, which retards the diffusion of high-molecular-weight impurities
more than it does the diffusion of sucrose.
Under certain idealized conditions, the stage efficiency in extracting some
(but not all) cellular materials can be estimated from experimental diffusion data
obtained under the conditions of temperature and agitation to be used in the plant.
The assumptions are as follows':
1. The diffusion rate is represented by the equation
ax a2 x
-=D'-- (21.79)
at 2
" ab
680 MASS TRANSFER AND ITS APPLICATIONS
where X = concentration of solute in solution within solid
D; = diffusivityt
b= distance, measured in direction of diffusion
2. The diffusivity is constant.
3. The solid can be considered to be equivalent to very thin slabs of constant
density, size, and shape.
4. The concentration X, of the liquid in contact with the solid is constant.
5. The initial concentration in the solid is uniform throughout the solid.
Under these assumptions, Eq. (21.79) can be integrated in exactly the same
manner as Eq. (10.16) for conduction of heat through a slab. The result may be
written
X
x-x,
_ X =
8
'2 (e-"P + ~e-90'P + "5 e - 250 ,P + ...) = 4>({3) (21.80)
o ,,,
where X = average concentration of solute in solid at time t
X 0 = uniform concentration of solute in solid at zero time
X, = constant concentration of solute in bulk of solution at all times
and
(21.81)
where 2r p is the thickness of the particle.
Note that Eq. (21.80) is Eq. (10.17) with T replaced by X and N Fo by {3.
Similar equations for long cylindrical particles and for spherical particles can be
written by analogy with Eqs. (10.18) and (10.19) for conduction of heat. These
equations for slablike, cylindrical, and spherical particles are represented by the
curves of Fig. 10.6, and this figure can therefore be used in the solution of diffusion
problems.
The M urphree stage efficiency for leaching is given by the equations
~M =
Xo-X = 1 - X-X, = 1 - 4>({3) = 1 - 4> (D;t)
-2 (21.82)
Xo-X, Xo-X, rp
Equation (21.82) follows from the fact that Xo - X is the actual concentration
change for the stage and Xo - X, is the concentration change that would be
obtained if equilibrium were reached.
t The diffusivity D~ differs from the usual volumetric diffusivity D,,: it is based on a gradient expressed
in terms of pounds of solute per pound of solute~free solvent rather than mole fraction of solute. and
the transfer is in pounds or kilograms rather than moles. Since the diffusivity D~ can be found only
by experiment on the material to be extracted, it is actually used as an empirical constant, and these
differences are unimportant in practice.
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 681
Example 21.6. Assuming, for the meal in Example 20.2, D~ = 10- 7 cm 2 /s, that the
thickness of the flakes is 0.04 cm and that the time of contact in each stage is 30 min,
estimate the actual number of stages required.
Solution
Since 2rp = 0.04, rp = 0.02 cm. Also, t = 30 x 60 = 1800 s. Then
= D;t = 10- 7 x 1,800
fJ r; 0.022
0.45
From Fig. 10.6 4>(fJ) = 0.26, and the Murphree efficiency is
'lM = 1 - 0.26 = 0.74
Here the average efficiency is nearly equal to the Murphree efficiency. The actual
number of stages is 4/0.74 = 5.4. Either five or six stages should be used.
SYMBOLS
A Area perpendicular to direction of mass transfer, m 2 or ft2
a Area of interface between phases per unit volume of equipment,
m-I or fC '
a, (n/2)2 in Eq. (21.80)
BT Thickness of layer through which diffusion occurs, m or ft
b Distance from phase boundary in direction of diffusion, m or ft
C Concentration, kg mol/m 3 or lb mol/ft 3 ; CA' of component A; CA', of
component A at interface; CAO, at time zero; CB' of component B
D Linear dimension or diameter, m or ft; Do, of agitator; Dp , of bubble,
drop, or particle; D" of tank
DAB Diffusivity of component A in component B; D BA , of B in A
Do Volumetric diffusivity, m 2/h, cm2/s, or ft 2/h; Dux> in liquid phase; Day, in
gas phase; D;, of solute through stationary solution contained in a solid;
D;x> D;y, new values (Example 21.5)
d Diameter of hollow fiber, m or ft; d" equivalent diameter
F F factor, u}p;
Fo Faraday constant, 96,500 C/g equivalent
f Fanning friction factor, dimensionless
G Mass velocity, kg/m2_s or Ib/ft 2-h
h Individual heat-transfer coefficient, W/m2_oC or Btu/ft2-h_oF
J Mass flux relative to a plane of zero velocity, kg mOl/m 2-s or lb mOl/ft 2-h;
J A' J B' of components A and B, respectively; J A' average value; J A." of
component A, caused by turbulent action
jH Colburnj factor for heat transfer, (h/c pG)(c p /l/k)2 /3, dimensionless
jM Colburn j factor for mass transfer, (ky1Vl/G)(P/pD a),/3, dimensionless
Ky Overall mass-transfer coefficient in gas phase, kg mOl/m 2 -s-unit mole
fraction or lb mol/ft'-h-unit mole fraction; K~, new value in Example 21.5
682 MASS TRANSFER AND ITS APPLICATIONS
k Individual mass-transfer coefficient; kc, cm/s or ftfs; keT' minimum coeffi-
cient for suspended particle (Fig. 21.6); k", effective internal coefficient
[Eq. (21.65)]; 7<;, average value over time tT; kz, ky, in liquid phase and
gas phase, respectively, based on mole-fraction differences, kg mol/m 2-s-
unit mole fraction or lb mol(ft2-h-unit mole fraction
k' Effective mass-transfer coefficient in one-way diffusion; k" cm/s or ft/s;
k~, in gas phase, kg mol(m 2-s-unit mole fraction or lb mol(ft2-h-unit
mole fraction; also new values in Example 21.5
L Length of pipe or tube, m or ft
M Molecular weight; MA, M n , of components A and B, respectively; M,
average value
m Slope of equilibrium curve
riz Mass flow rate, kg/s or lb/s
N Mass-transfer flux across a plane or boundary, kg mol/m 2-s or lb
mOl/ft 2-h; N A , N n, of components A and B, respectively
NFu Fourier number [see Eq. (1O.17)J
N oz Graetz number for mass transfer, ,iJ/DoLp
NNu NusseIt number, liD p/k
N p, Peclet number, Dpuo/Do
N p, Prandtl number, cpJ1./k
N R, Reynolds number, DG/J1.
N s, Schmidt number, J1./pDo
NSh Sherwood number, k,D/Do
Nay Number of overall gas-phase transfer units
P Pressure, atm or lb f/ft2
R Gas law constant, 8.314 J/g mol-K or 1545 ft-lbf/lb mol_OR
r Rate of mass transfer, kg mol(m 2-s or lb mOl/ft2-h
rp One-half particle thickness, m or ft
s Fractional rate of surface renewal, s - 1
T Temperature, °C, K, OF, or OR; T::A' T::n, critical temperatures of compo-
nents A and B, respectively
t Time, s or h; tT' residence time on transfer surface
U Velocity, m/s or ft/s; U A , Un, of components A and B, respectively; uo,
volume-average velocity of phase; also velocity past a suspended bubble,
drop, or particle; also superficial velocity in packed bed
VA Molar volume of solute as liquid at its normal boiling point: cm'/g mol
V, Critical molar volume, cm' /g mol; V,A' of component A; v'n, of compo-
nent B
V, Superficial velocity, m/s or ft/s
X Concentration of solute in solution within solid; X o, at zero time; Xl'
in bulk of solution; X, average concentration in solution within solid
at time t
x Mole fraction in liquid or L phase; X A , of component A; XAi> of compo-
nent A at interface
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 683
Y Mole fraction in gas or V phase; YA, of component A; YA', of component
A at interface; YA1, YA2, at bottom and top of aerated liquid layer,
respectively; yt of vapor in equilibrium with liquid of composition x A ;
YB' of component B; (YE)L> logarithmic mean value for nondiffusing
species;·Yh at interface
Z Depth of pool on distillation plate, m or ft
z Distance in vertical direction, m or ft
Greek letters
f! Diffusion group, D;t/r;, dimensionless
€ Void fraction, dimensionless
eN Eddy diffusivity of mass, m 2/h, cm 2/s, or ft>jh
.<0 Limiting ionic conductance, A/cm2-(V/cm)-(g equivalent/cm'); .<~, of
cation; A.~, of anion
~ Plate or stage efficiency; ~M' Murphree efficiency; ,/" local efficiency
P Viscosity, cP; PB, viscosity of water [Eq. (21.28)]; Pw, value at wall
P Density, kg/m' or lb/ft'; Px, of liquid; Py, of vapor
PM Molar density, g mol/m' or lb mOl/ft'; PMX' of liquid; PMy' of gas
<p,1/I Functions; 1/1" in Eq. (21.46); 0/2' in Eq. (21.47)
o/B Association parameter for solvent [Eq. (21.26)]
PROBLEMS
21.1. Carbon dioxide is diffusing through nitrogen in one direction at atmospheric pressure
and O°C. The mole fraction of CO 2 at point A is 0.2; at point S, 3 m away, in the
direction of diffusion, it is 0.02. The concentration gradient is constant over this
distance. Diffusivity DJ) is 0.144 cm 2/s. The gas phase as a whole is stationary; i.e.,
nitrogen is diffusing at the same rate as the carbon dioxide, but in the opposite
direction. (a) What is the molal flux of CO 2 , in kilogram moles per square meter
per hour? (b) What is the net mass flux, in kilograms per square meter per hour?
(c) At what speed, in meters per second, would an observer have to move from one
point to the other so that the net mass flux, relative to him or her, would be zero?
(d) At what speed would the observer have to move so that, relative to him or her,
the nitrogen is stationary? (e) What would be the molal flux of carbon dioxide relative
to the observer under condition (d)?
21.2. An open circular tank 8 m in diameter contains benzene at 22°C exposed to the
atmosphere in such a manner that the liquid is covered with a stagnant air film
estimated to be 5 mm thick. The concentration of benzene beyond the stagnant film
is negligible. The vapor pressure of benzene at 22°C is 100 mm Hg. If benzene is
worth $1.80 per gallon, what is the value of the loss of benzene from this tank in
dollars per day? The specific gravity of benzene is 0.88.
21.3. Alcohol vapor is being absorbed from a mixture of alcohol vapor and water vapor
by means of a nonvolatile solvent in which alcohol is soluble but water is not. The
temperature is 97°C, and the total pressure is 760 mm Hg. The alcohol vapor can
684 MASS TRANSFER AND ITS APPLICATIONS
be considered to be diffusing through a film of alcohol-water vapor mixture 0.1 mm
thick. The mole percent of the alcohol in the vapor at the outside of the fi1m is 80
percent, and that on the inside, next to the solvent, is 10 percent. The volumetric
diffusivity of alcohol-water vapor mixtures at 25°C and 1 atm is 0.15 cml/s. Calculate
the rate of diffusion of alcohol vapor in kilograms per hour if the area of the film
is 10 m 2 •
21.4. An alcohol-water vapor mixture is being rectified by contact with an alcohol-water
liquid solution. Alcohol is being transferred from gas to liquid and water from liquid
to gas. The molal flow rates of alcohol and water are equal but in opposite directions.
The temperature is 9SOC and the pressure 1 atm. Both components are diffusing
through a gas film 0.1 mm thick. The mole percentage of the alcohol at the outside
of the film is 80 percent, and that on the inside is 10 percent. Calculate the rate of
diffusion of alcohol and of water in pounds per hour through a film area of 10 m2 •
21.5. A wetted-wall column operating at a total pressure of 518 mm Hg is supplied with
water and air, the latter at a rate of 120 g/min. The partial pressure of the water
vapor in the airstream is 76 mm Hg and the vapor pressure of the liquid-water film
on the wan of the tower is 138 mm Hg. The observed rate of vaporization of water
into the air is 13.1 g/min. The same equipment, now at a total pressure of 820 mm,
is supplied with air at the same temperature as before and at a rate of 100 g/min.
The liquid vaporized is n-butyl alcohol. The partial pressure of the alcohol is
30.5 mm, and the vapor pressure of the liquid alcohol is 54.5 mm. What rate of
vaporization, in grams per minute, may be expected in the experiment with n-butyl
alcohol?
21.6. Air at 40°C and 2.0 atm is passed through a shallow bed of naphthalene spheres
12 mm in diameter at a rate of 2 m/s, based on the empty cross section of the bed. The
vapor pressure of naphthalene is 117 mm Hg. How many kilograms per hour of
naphthalene wil1 evaporate from 1 m 3 of bed, assuming a bed porosity of 40 percent?
21.7. Diffusion coefficients for vapors in air can be determined by measuring the rate of
evaporation of a Jiquid from a vertical glass tube. For a tube 0.2 cm in diameter
filled with n-heptane at 21°C, calculate the expected rate of decrease of the liquid
level when the meniscus is 1 cm from the top based on the published diffusivity of
0.071 cm'/s. At 21°C the vapor pressure and density of n-heptane are 0.050 atm
and 0.66 g/cm 3 , respectively. Would there by any advantage in using a larger
diameter tube?
21.S. Estimate the liquid-fi1m mass-transfer coefficient for 02 diffusing from an air bubble
rising through water at 20°C. Choose a bubble size of 4.0 mm; assume a spherical
shape; and assume rapid circulation of gas inside the bubble. Neglecting the change
of bubble size with distance traveled, calculate the fraction of oxygen absorbed from
the air in 1 m of travel if the water contains no dissolved oxygen.
21.9. Calculate the effect of the change in slope of the equilibrium line on the local
efficiency in a sieve-tray distillation column. Use the benzene-toluene system as an
example, and predict 1( for plates where the mixture is mostly toluene and for those
where it is mostly benzene, starting with an estimated value of 1( for the middle of
the column.
21.10. Small spheres of solid benzoic acid are dissolved in water in an agitated tank.
If the Sherwood number is nearly constant at a value of 4.0, show how the time for
complete dissolution varies with the initial size of the particle. How much time would
be required for lOO-pm particles to dissolve completely in pure water at 25°C?
Solubility: 0.43 gfl00 g H,O. D, = 1.21 x 10- 5 cm'/s.
PRINCIPLES OF DIFFUSION AND MASS TRANSFER BETWEEN PHASES 685
REFERENCES
1. Bird, R. B.: Advances in Chemical Engineering, vol. I, Academic, New York, 1956, pp. 156-239.
2. Bird, R. B., W. E. Stewart, and E. N. Lightroot: Transport Phenomena, Wiley, New York, 1960.
3. Brian, P. L. T., and H. B. Hales: AIChE J., 15:419 (1969).
4. Chen, N. H., and D. F. Othmer: J. Chem. Eng. Data, 7:37 (1962).
5. Chiltan, T. H., and A. P. Colburn: Ind Eng. Chem., 26: 1183 (1934).
6. Clough, S. B., H. E. Read, A. B. Metzner, and V. C. Behn: AIChE J., 8:346 (1962).
7. Danckwerts, P. V.: Ind. Eng. Chem., 43:1460 (1951).
8. Davies, J. T.: Turbulence Phenomena, Academic, New York, 1972, p. 240.
9. Fan. H. P., I. C. Morris, and H. Wakeman: Ind. Eng. Chem., 40:195 (1948).
10. Friend, W. L., and A. B. Metzner: AICizE J., 4:393 (1958).
11. Gil1iland, E. R., and T. K. Sherwood: Ind Eng. Chem., 26:516 (1935).
12. Gupta, A. S., and G. Thodos: Chem. Ellg. Prog., 58(7):58 (1962).
13. Harriott, P.: AIChE J., 8:93 (1962).
14. Harriott, P.: Can. J. Chem. Eng., 40:60 (1962).
15. Harriott, P.: Chem. Eng. Sci., 17:149 (1962).
16. Harriott, P., and R. M. Hamilton: Chem. Eng. Sci., 20:1073 (1965).
17. Hayduk, W., and H. Laudie: AIChE J., 20:611 (1974).
18. Higbie, R.: Trails. AIChE, 31:365 (1935).
19. Levins, D. I., and I. R. Glastonbury: Trans. Inst. Chem. Eng. Lond., 50:132 (1972).
20. Present, R. D.: Kinetic Theory o/Gases, McGraw-Hill, New York, 1958.
21. Reid, R. c., I. M. Prausnitz, and B. E. Paling: The Properties 0/ Gases and Liquids, 4th ed.,
McGraw-Hill, New York, 1987, p. 620.
22. Schlichting, H.: Boundary Laver Theory, 7th ed., McGraw-HiIl, New York, 1979, pp. 303-304.
23. Sherwood, T. K., R. L. pigrord, and C. R. Wilke: Mass Transfer, McGraw-HiII. New York, 1975:
(a) p. 169, (b) p. 242.
24. Skelland. A. H. P., and H. Xien: Illd. Ellg. Chem. Res., 29:415 (1990).
25. Whitman, W. G.: Chem. Met. Eng .• 29:146 (1923).
26. Wilke, C. R., and P. Chang: AlChE J., 1:264 (1955).
27. Yang, M. c., and E. L. Cussler, AlChE J., 32:1910 (1986).
CHAPTER
22
GAS
ABSORPTION
This chapter deals with the mass-transfer operations known as gas absorption and
stripping, or desorption. In gas absorption a soluble vapor is absorbed from its
mixture with an inert gas by means of a liquid in which the solute gas is more or
less soluble. The washing of ammonia from a mixture of ammonia and air by
means of liquid water is a typical example. The solute is subsequently recovered
from the liquid by distillation, and the absorbing liquid can be either discarded
or reused. Sometimes a solute is removed from a liquid by bringing the liquid into
contact with an inert gas; such an operation, the reverse of gas absorption, is
desorption or gas stripping.
At the end of this chapter is a section on the application of packed towers,
used chiefly in gas absorption, to distillation and liquid-liquid extraction.
DESIGN OF PACKED TOWERS
A common apparatus used in gas absorption and certain other operations is the
packed tower, an example of which is shown in Fig. 22.1. The device consists of
a cylindrical column, or tower, equipped with a gas inlet and distributing space
at the bottom; a liquid inlet and distributor at the top; gas and liquid outlets at
the top and bottom, respectively; and a supported mass of inert solid shapes, called
tower packing. The packing support is typically a screen, corrugated to give it
strength, with a large open area so that flooding does not occur at the support. The
inlet liquid, which may be pure solvent or a dilute solution of solute in the solvent
686
GAS ABSORPTION 687
and which is called the weak liquor, is distributed over the top of the packing by
the distributor and, in ideal operation, uniformly wets the surfaces of the packing.
The distributor shown in Fig. 22.1 is a set of perforated pipes. In large towers
spray nozzles or distributor plates with overflow weirs are more common.
The solute-containing gas, or rich gas, enters the distributing space below
the packing and flows upward through the interstices in the packing counter-
current to the flow of the liquid. The packing provides a large area of contact
between the liquid and gas and encourages intimate contact between the phases.
The solute in the rich gas is absorbed by the fresh liquid entering the tower, and
dilute, or lean, gas leaves the top. The liquid is enriched in solute as it flows down
the tower, and concentrated liquid, called strong liquor, leaves the bottom of the
tower through the liquid outlet.
Tower packings are divided into three principal types: those that are dumped
at random into the tower, those that must be stacked by hand, and those known
as structured or ordered packings. Dumped packings consist of units 6 to 75 mm
(i to 3 in.) in major dimension; packings smaller than 25 mm are used mainly
~~§§l~~ir Liquid distributor
Packed
section
Packed
section
+--Gas
r;==!ll====d inlet
';;:;i/~I+-'~=======:=Jk
FIGURE 22.1
Packed tower.
688 MASS TRANSFER AND ITS APPLICATIONS
in laboratory or pilot-plant columns. In stacked packings the units are 50 to
200 mm (2 to 8 in.) in size. They are much less commonly used than dumped
packings and are not discussed here.
Dumped tower packings are made of cheap, inert materials such as clay,
porcelain, or various plastics. Thin-walled metal rings of steel or aluminum are
sometimes used. High void spaces and large passages for the fluids are achieved
by making the packing units irregular or hollow, so that they interlock into open
structures with a porosity or void fraction of 60 to 90 percent.
Common dumped packings are illustrated in Fig. 22.2, and their physical
characteristics are given in Table 22.1. Ceramic Berl saddles and Raschig rings
are older types of packing that are not much used now, although they were a big
improvement over ceramic spheres or crushed stone when first introduced. Intalox
saddles are somewhat like Berl saddles, but the shape prevents pieces from nesting
closely together, and this increases the bed porosity. Super Intalox saddles are a
slight variation with scalloped edges; they are available in plastic or ceramic form.
Pall rings are made from thin metal with portions of the wall bent inward or from
plastic with slots in the wall and stiffening ribs inside. Hy-pak metal packing and
Flexirings (not shown) are similar in shape and performance to metal Pall rings.
Beds of Pall rings have over 90 percent void fraction and lower pressure drop
than most other packings of the same nominal size. Norton's new IMTP'" (Intalox
Metal Tower Packing) has a very open structure and even lower pressure drop
than Pall rings. Additional pressure-drop packing factors for many commercial
packings are given by Robbins.13
(a) (b) (c)
(d) (e) (I) (g)
FIGURE 22.2
Common tower packings: (a) Raschig rings; (b) metal Pall ring; (c) plastic Pall ring; (cl) Bed saddle;
(e) ceramic Intalox saddle; (f) plastic Super Intalox saddle; (g) metal Intalox saddle.
GAS ABSORPTION 689
TABLE 22.1
Characteristics of dumped tower packings"lZb.2l
Packing
factors:!:
Nominal Bulk Total Porosity.
Type Material size, in. density,t Ib/ft3 area,t ftl/ft3 < Fp h
Raschig rings Ceramic t 55 112 0.64 580 1.52§
I 42 58 0.74 155 1.36§
11 , 43 37 0.73 95 1.0
2 41 28 0.74 65 0.92§
Pall rings Metal 30 63 0.94 56 1.54
11, 24 39 0.95 40 1.36
2 22 31 0.96 27 1.09
Plastic 5.5 63 0.90 55 1.36
11 , 4.8 39 0.91 40 1.18
Ber! saddles Ceramic ,• 54 142 0.62 240 1.58§
I 45 76 0.68 110 1.36§
11 , 40 46 0.71 65 1.07§
Intalox saddles Ceramic t 46 190 0.71 200 2.27
I 42 78 0.73 92 1.54
11 , 39 59 0.76 52 1.18
2 38 36 0.76 40 1.0
3 36 28 0.79 22 0.64
Super Intalox Ceramic 60 1.54
saddles 2 30 1.0
IMTP~ Metal I 0.97 41 1.74
11 , 0.98 24 1.37
2 0.98 18 1.19
Hy-Pak Metal 19 54 0.96 45 1.54
11 , 29 1.36
2 14 29 0.97 26 1.09
t Bulk density and total area are given per unit volume of column.
t Factor Fp is a pressure..drop factor and JP a relative mass-transfer coefficient.
§ Based on NH)-H 2 0 data; other factors based on CO 2 -NaOH data.
Structured packings with ordered geometry evolved from the Stedman
packing of the late 1930s,20 but they found few industrial uses until the Sulzer
packing was developed about 1965." Early structured packings were fabricated
from wire gauze; most current ones are made of sheets of perforated corrugated
metal, with adjacent sheets arranged so that liquid spreads over their surfaces
while vapor flows through channels formed by the corrugations. The channels are
set at an angle of 45° with the horizontal; the angle alternates in direction in
successive layers, as shown schematically in Fig. 22.3. Each layer is a few inches
thick. Various proprietary packings differ in the size and arrangement of the
corrugations and the treatment of the packing surfaces" Typically the triangular
corrugations are 25 to 40 mm across the base, 17 to 25 mm on the side, and 10 to
15 mm high. The porosity ranges from 0.93 to 0.97 and the specific surface area
690 MASS TRANSFER AND ITS APPLICATIONS
FIGURE 223
Schematic drawing of successive layers of structured packing. Arrows indicate vapor flow; the liquid
flow is in the opposite direction.
from 60 to 76 ft2/ft3 (200 to 250 m 2/m 3). The Sulzer BX packing, fabricated from
metal gauze, provides a specific surface area of 152 ft2/ft3 (500 m 2/m 3) with a
porosity of 0.90.
CONTACT BETWEEN LIQUID AND GAS. The requirement of good contact
between liquid and gas is the hardest to meet, especially in large towers. Ideally
the liquid, once distributed over the top of the packing, flows in thin films over
all the packing surface all the way down the tower. Actually the films tend to grow
thicker in Some places and thinner in others, so that the liquid collects into small
rivulets and flows along localized paths through the packing. Especially at low
liquid rates much of the packing surface may be dry or, at best, covered by a
stagnant film of liquid. This effect is known as c"anneling; it is the chief reason
for the poor performance of large packed towers.
Channeling is severe in towers filled with stacked packing, which is the main
reason they are not much used. It is less severe in dumped packings. In towers of
moderate size channeling can be minimized by having the diameter of the tower
GAS ABSORPTION 691
at least 8 times the packing diameter. If the ratio of tower diameter to packing
diameter is less than 8 to 1, the liquid tends to flow out of the packing and down
the walls of the column. Even in small towers filled with packings that meet this
requirement, however, liquid distribution and channeling have a major effect on
column performance. 6 In large towers the initial distribution is especially impor-
tant,11 but even with good initial distribution it is necessary to include re-
distributors for the liquid every 5 to 10 m in the tower, immediately above each
packed section. Improved liquid distribution has made possible the effective use
of packed towers as large as 9 m (30 ft) in diameter.
PRESSURE DROP AND LIMITING FLOW RATES. Figure 22.4 shows typical data
for the pressure drop in a packed tower. The pressure drop per unit packing depth
comes from fluid friction; it is plotted on logarithmic coordinates against the gas
flow rate G" expressed in mass of gas per hour per unit of cross-sectional area,
based on the empty tower. Therefore, Gy is related to the superficial gas velocity
by the equation G, = UOPy, where P, is the density of the gas. When the packing
is dry, the line so obtained is straight and has a slope of about 1.8. The pressure
drop therefore increases with the 1.8th power of the velocity. If the packing is
irrigated with a constant flow of liquid, the relationship between pressure drop
and gas flow rate initially follows a line parallel to that for dry packing. The
pressure drop is greater than that in dry packing, because the liquid in the tower
reduces the space available for gas flow. The void fraction, however, does not
change with gas flow. At moderate gas velocities the line for irrigated packing
~
2.DI----------+-rl~
J-) ~~
"" ~~ "'l,,
j ~i)j 4
~/ "I" ,,,,!
!2 0 0+ 0+ 0+ (:)+ "'{:)""f})"<;J" j ...
~ l.D~~§~i~~~~1!ij~§~§~~g~~~
a...
~
0.8~
/ / / Column dia. - 30 in. _
w 0.6 // J / IL Packing height = 10ft
~ / / / I III
~ D.4 / / I
/ / /1// 'j /
~~ 0.2~-,~-+'f-~f,~Lf7hA-t++-----~~~r--t-+~
F =92 p
/~~~/I. Uqu;d ,"e. 1~/ft'- h.
L/:~/
D"//'/ "PT ete
, I I
100 200 300 400 600 1,000 2,000 5,000
AIR MASS VELOCITY, G y , Ib/ft2- h
FIGURE 22.4
Pressure drop in a packed tower for air-water system with i-in. Intalox saddles.
692 MASS TRANSFER AND ITS APPLICATIONS
gradually becomes steeper, because the gas now impedes the downflowing liquid
and the liquid holdup increases with gas rate. The point at which the liquid holdup
starts to increase, as judged by a change in the slope of the pressure-drop line, is
called the loading point. However, as is evident from Fig. 22.4, it is not easy to
get an accurate value for the loading point.
With stilI further increase in gas velocity, the pressure drop rises even more
rapidly, and the lines become almost vertical when the pressure drop is about 2
to 3 in. of water per foot of packing (150 to 250 mm of water per meter). In local
regions of the column, the liquid becomes the continuous phase, and the flooding
point has been reached. Higher gas flows can be used temporarily, but then liquid
rapidly accumulates, and the entire column may fill with liquid.
The gas velocity in an operating packed column must obviously be lower
than the flooding velocity. However, as flooding is approached, most or all of the
packing surface is wetted, maximizing the contact area between gas and liquid.
The designer must choose a velocity far enough from the flooding velocity to
ensure safe operation but not so low as to require a much larger column. Lowering
the design velocity increases the tower diameter without much change in the
required height, since lower gas and liquid velocities lead to a nearly proportional
reduction in mass-transfer rate. Decreased pressure drop is one benefit of low gas
velocity, but the cost of power consumed is usually not a major factor in optimizing
the design. The gas velocity is sometimes chosen as one-half the predicted flooding
velocity obtained from a generalized correlation. This might seem too conservative,
but there is considerable scatter in published data for flooding velocities, and the
generalized correlations are not very accurate. A closer approach to flooding may
be used if detailed performance data are available for the packing selected. Packed
towers may also be designed on the basis of a definite pressure drop per unit
height of packing.
The flooding velocity depends strongly on the type and size of packing and
the liquid mass velocity. Figure 22.5 shows data for Intalox saddles taken from
Fig. 22.4 and similar curves for other sizes. Flooding was assumed to occur at a
pressure drop of 2.0 in. H 2 0/ft of packing, since the pressure drop curves are
vertical or nearly so at this point. For low liquid rates the flooding velocity varies
with about the -0.2 to -0.3 power of the liquid rate and the 0.6 to 0.7 power of the
packing size. The effects of liquid rate and packing size become more pronounced
at high liquid mass velocities.
Several generalized correlations have been proposed for the pressure drop
and flooding velocity in packed columns. Most of these use a log-log plot with
(G x/G y)(py/Px)O.5 on the abscissa and a function containing G: on the ordinate.
Usually the flow ratio Gx/G, is known, and Gy can then be determined directly,
whereas trial-and-error solution is needed if Gy and Gx are on separate axes, as
in Fig. 22.5. The packing characteristics are accounted for by a packing factor Fp,
which decreases with increasing packing size or increasing void fraction. Packing
factors cannot be predicted from theory using the Ergun equation [Eq. (7.22)]
because of the complex shapes, and they are determined empirically. Unfortu-
nately, no single correlation for pressure drop gives a good fit to all packings, and
GAS ABSORPTION 693
5000
2000
- 1-
~
-
-- r--r-
I-.
r- -t--
'"
~
","
Z-
'0
1000
• r-
r--... .......... r-
- ~ .........
..........
~
0
a;
> " I...... ....... '\. I\,
" I'\. \ \
C>
c
'i5 500
0
0
u: \. 1~ in. 2 in.
Packing! size ~ in. ~.
1 In.
200
100
1000 2000 5000 10,000 20,000 50,000
Liquid Mass Velocity G". Ib/ffl-h
FIGURE 22.5
Flooding velocities in ceramic Intalox saddles, air-water system.
values of Fp based on fitting the data for low pressure drops may differ significantly
from values obtained by fitting the data for high pressure drops or by fitting the
flooding data,
A widely used correlation for estimating pressure drops in dumped packings
is given in Fig. 22.6 where Gx and Gy are in Ib/ft2-s, fJ.x is in cP, Px and Pr are in
lb/ft', and g, is 32.174Ibr ftjlb-s 2, Earlier versions of this correlation included a
flooding line above the line for t!.P = 1.5 in, H 20/ft of packing, but recent studies
show flooding at pressure drops of only 0,7 to 1.5 in. H 20/ft of packing for 2- or
3-in, packings. An empirical equation for the limiting pressure drop is 7
t!.Pflood = 0,115F~·7 (22.1)
where f,P flood = pressure drop at flooding, in, H 20/ft of packing
Fp = packing factor, dimensionless
Equation (22.1) can be used for packing factors from 10 to 60, For higher
values of Fp, the pressure drop at flooding can be taken as 2,0 in H 20/ft.
694 MASS TRANSFER AND ITS APPLICATIONS
0.60
0040
0.20
Parameter of curves is pressure
0.10 ~ - 1.50.
1.00.
drop in inches of water/foot
of pocked height
0.060 I - - 0.5
>-: .......
-: et
0 .. ~'" 0.040
~
~~
'- "- 0.25 i- --........:
~
Lt- "- f-
N
rt' ~ 0.020
- 0.10. ----- "-..
~ ~
0.010
0.006 1== 0.0.5
---- ....... "-
,'\.
0.004
0.002
r---.. r--- "
~ ~\
~~
0.00 I
0.01 0.020.040.060.1 0.2
Gi{~
Gy
"'"
004 0.6 1.0. 2.0
V p;:p;
4.0 6.0 10.0
FIGURE 22.6
Generalized correlation for flooding and pressure drop in packed columns. (After Eckert. 3)
An alternate correlation for the pressure drop in packed columns was
proposed by Strigle 20 and is shown in Fig. 22.7. The abscissa is essentially the
same as for Fig. 22.6, but the ordinate includes the capacity factor C, =
uoJ P,J(px - Py), where uo is the superficial velocity in ft/so The kinematic viscosity
of the liquid, v, is in centistokes. The semilog plot permits easier interpolation
than the log-log plot, though both correlations are based on the same set of data.
Example 22.1. A tower packed with I-in. (25.4-mm) ceramic Intalox saddles is to be
built to treat 25,000 ft3 (708 m3 ) of entering gas per hour. The ammonia content of
the entering gas is 2 percent by volume. Ammonia-free water is used as absorbent.
The temperature is 68°F (20°C), and the pressure is 1 atm. The ratio of gas flow to
liquid flow is I lb of gas per pound of liquid. (a) If the gas velocity is to be one-half
the flooding velocity, what should be the diameter of the tower? (b) What is the
pressure drop if the packed section is 20 ft (6.\ m) high?
Solution
The average molecular weight of the entering gas is 29 x 0.98 + 0.02 x 17 = 28.76.
Then
28.76 x 492
P, ~--c---ccc = 0.07465 Ib/ft 3
359(460 + 68)
GAS ABSORPTION 695
2.4
I'" 4P~ i.n. jif
2.0 - .....1,0,1
-:0.
I'"
1.6
'U' I-- t:-..
~ 1.2
r..; ~
t.o. .n ><. r---
0"
O.B
'0.
- r- ~
'0.' )5' I-- ..;::: S
-
0.4
0.0
0.006 0.02 0.04 0.06 0.20 0.40 10.60 2.0 4.0 I
0.005 0.01 0.03 0.05 0.10 0.30 0.50 1.0 3.0 5.0
FIGURE 22.7
Alternate generalized pressure-drop correlation.
(a) Use Fig. 22.5. When Gy = Gx for I-in. Intalox saddles, Gy = 1700Ib/ft 2-h
or 0.472lb/ft'-s. The design value is then 0.472/2 = 0.236Ib/ft2-s. The total gas flow
is 25,000 x 0.07465/3600 = 0.518Ib/s. The cross-sectional area of the tower is
0.518
S = - - = 2.19 ft'
0.236
The diameter of the tower is J2.19/0.7854 = 1.67 ft (509 mm).
(b) Use Fig. 22.4. The pressure drop for Gx = Gy = 850 Ib/ft 2-h is 0.35 in.
H 20/ft. The total pressure drop is then 20 x 0.35 = 7.0 in. H 20 (13.1 mm Hg).
This may be checked using Fig. 22.6. The additional quantities needed are
Px = 62.3 Ib/ft3 Jix=lcP
g, = 32.174 ft-Ib/lb rs2
For I-in. ceramic Intalox saddles, Fp = 92 (Table 22.1). Also
0.07465
= 0.0346
62.3 - 0.07
696 MASS TRANSFER AND ITS APPLICATIONS
Note that the ordinate value in Fig. 22.6 is not dimensionless, and the stated units
must be used. The ordinate value in Fig. 22.6 is
G;FpJl~·l 0.236 2 x 92 X 1°·1
g,(p, - p,)p, 32.174 x (62.3 - 0.07465) x 0.07465
= 0.0343
For these conditions the predicted pressure drop is about 0.23 in. H 2 0 per foot
of packed height; the total pressure drop is 20 x 0.23 = 4.6 in. H 2 0 (8.6 mm Hg). The
actual pressure drop would probably be close to the higher value found from Fig.
22.4. which is based on direct measurements for the specific packing used. (The
generalized correlation in Fig. 22.6 is in closer agreement with Fig. 22.4 when
G,/G, 'P I.)
STRUCTURED PACKINGS. Flooding velocities in several commercial structured
packings are shown in Fig. 22.8. This plot is similar to Fig. 18.28 for flooding is
sieve-plate columns. The pressure drop in structured packings may be predicted
from some rather complicated equations given by Fair and Bravo,4 but relatively
little experimental information is available. Towers containing structured packing
are best designed in collaboration with the packing manufacturer. Spiegel and
Meier '9 state that most structured packings reach their maximum capacity at a
pressure drop of about 1000 (N/m2)/m (1.22 in. H 2 0 per ft), at a vapor velocity
of 90 to 95 percent of the flooding velocity.
Example 22.2. Substitute Gempak 230 A2T packing, manufactured by Glitsch, for
the I-in. Intalox saddles in the tower of Example 22.1. (a) What increase in capacity
is expected? (b) Will the pressure drop at 50 percent of the flooding velocity be greater
or less than in the Intalox saddles?
.20
Montz 81-200
.15 Gempak 230 A2T
MontzB1-100
~
----f6;Z
- - - _ _L
-=.-..-a:.~.:::::::-!..-::::--<... y_ Mellapak 250Y
7-",__ /
E .10
- -·~ct===~-~L
"~-~~'(::---
qJ.g
.08
.06
/
Montz B1-300
---a-:---Q~ --...
-....;!&::::::;: ~...:::-
~~~
.04
.02 "-_ _--'_ _"--'-_--'_...l...-'-_ _ _.1.-_ _- - ' _ - - - '
.0.Q1 .02 .03 .04 .06 .08 .10 .20 .40 .60
G, fI5..
Gy.J~
FIGURE 22.8
Flooding velocities in structured packings. 4
GAS ABSORPTION 697
Solution
(a) Use Fig. 22.8. From Example 22.1, GJG, = 1 and
G, r;;; = 0.07465 = 0.0346
Gy YPx 62.3
From Fig. 22.8, uo.fJ(P,I(P, - Py) = 0.11. The superficial vapor velocity at flooding
is therefore
62.3 - 0.07
"O,f = 0.11 {-:0C-:.Occ74c-6:-:5- = 3.175 m/s
The allowable vapor velocity. at 50 percent of flooding, is
Uo = 3.175/2 = 1.588 m/s or 5.21 ft/s
The corresponding mass velocity is
Gy = 5.21 x 0.07465 = 0.389Ib/ft2-s
The aBowable mass velocity in Example 22.1 was 0.236Ib/ft 2 -s. The increase by
using structured packing is (0.389/0.236) - 1 = 0.65, or 65 percent.
(b) Using Spiegel and Meier's value of 1.22 in. H 2 0/ft at 90 percent of flooding,
the pressure drop in 20 ft of packing at 50 percent of flooding would be no greater
than
0.50)1.8
!1p=20 x 1.22 x ( -
0.90
= 8.47 in. H 2 0
This is 1.2 times the pressure drop of 7 in. H 2 0 in the Intalox saddles. The actual
pressure drop in the structured packing should be less than this, but it probably
would still be somewhat greater than in the saddles.
PRINCIPLES OF ABSORPTION
As shown in the previous section, the diameter of a packed absorption tower
depends on the quantities of gas and liquid handled, their properties, and
the ratio of one stream to the other. The height of the tower, and hence the
total volume of packing, depends on the magnitude of the desired concentra-
tion changes and on the rate of mass transfer per unit of packed volume.
Calculations of the tower height, therefore, rest on material balances, enthalpy
balances, and estimates of driving force and mass-transfer coefficients.
MATERIAL BALANCES. In a differential-contact plant such as the packed absorp-
tion tower illustrated in Fig. 22.9, there are no sudden discrete changes in
composition as in a stage-contact plant. Instead the variations in composi-
tion are continuous from one end of the equipment to the other. Material
balances for the portion of the column above an arbitrary section, as shown
698 MASS TRANSFER AND ITS APPLICATIONS
Va
IYa Control
,---1-- sU!Z~~1
La I
I I
I
Xa I I
I I
I I
I I
I I
I L V I
I I
I I
I
I I
I ~ I
I_~ -- =Y ___ J
r ~
11,
.If, Lb
FIGURE 22.9
xb MateriaI~balance diagram for packed column.
by the dashed line in Fig. 22.9, are as follows:
Total material: L,+ V=L+ v" (22.2)
Component A: L,x, + Vy = Lx + v"y, (22.3)
where V is the molal flow rate of the gas phase and L that of the liquid
phase at the same point in the tower. The L-phase and V-phase concentrations
x and y apply to this same location.
The overall material-balance equations, based on the terminal streams,
are
Total material: L,+ Vb=Lb+ v" (22.4)
Component A: Laxa + v;,Yb = LbXb + ~Ya (22.5)
Equations (22.4) and (22.5) are identical with Eqs. (17.3) and (17.4) for
a stage-contact column.
GAS ABSORPTION 699
The operating-line equation for a differential-contact plant, analogous to Eq.
(17.7) for a stage-contact column, is
(22.6)
In Eq. (22.6) x and Y represent the bulk compositions of the liquid and
gas, respectively, in contact with each other at any given section through the
column. It is assumed that the compositions at a given elevation are independent
of position in the packing. The absorption of a soluble component from a gas
mixture makes the total gas rate V decrease as the gas passes through the column,
and the flow of liquid L increase. These changes make the operating line slightly
curved, as shown by the example in Fig. 17.7. For dilute mixtures, containing less
than 10 percent of soluble gas, the effect of changes in total flow is usually ignored
and the design is based on the average flow rates.
LIMITING GAS-LIQUID RATIO. Equation (22.6) shows that the average slope of
the operating line is L/V, the ratio of the molal flows of liquid and gas. Thus, for
a given gas flow, a reduction in liquid flow decreases the slope of the operating
line. Consider the operating line ab in Fig. 22.10. Assume that the gas rate and
the terminal concentrations Xa, Ya, and Yb are held fast and the liquid flow L
~ ___________________ b__________ t!
,,,
,,
y ,
,,
J ---
.
Yb
I
,
I
I
I
a I
I
I
I
I
I
FIGURE 22.10
Limiting gas-liquid ratio.
700 MASS TRANSFER AND ITS APPLICATIONS
decreased. The upper end of the operating line then shifts in the direction of the
equilibrium line, and Xb, the concentration of the strong liquor increases. The
maximum possible liquor concentration and the minimum possible liquid rate
are obtained when the operating line just touches the equilibrium line, as shown
by line ab' in Fig. 22.10. At this condition, an infinitely deep packed section is
necessary, as the concentration difference for mass transfer becomes zero at the
bottom of the tower. In any actual tower the liquid rate must be greater than this
minimum to achieve the specified change in gas composition.
The L/V ratio is important in the economics of absorption in a counter-
current column. The driving force for mass transfer is y - y', which is propor-
tional to the vertical distance between the operating line and the equilibrium line
on a diagram such as Fig. 22.10. Increasing L/V increases the driving force
everywhere in the column except at the very top, and the absorption column does
not need to be as tall. However, using a larger amount of liquid gives a more
dilute liquid product, which makes it more difficult to recover the solute by
desorption or stripping. The energy cost for stripping is often a major part of the
total cost of an absorption-stripping operation. The optimum liquid rate for
absorption is found by balancing the operating costs for both units against the
fixed costs of the equipment. In general, the liquid rate for the absorber should
be between 1.1 and 1.5 times the minimum rate.
The conditions at the top of the absorber are often design variables that also
have to be set considering the balance between equipment and operating costs.
For example, if tentative specifications call for 98 percent recovery of a product
from a gas stream, the designer might calculate how much taller the column would
have to be to get 99 percent recovery. If the value of the extra product recovered
exceeds the extra costs, the optimum recovery is at least 99 percent, and the
calculation should be repeated for even higher recovery. If the unremoved solute
is a pollutant, its concentration in the vent gas may be set by emission standards,
and the required percent recovery may exceed the optimum value based on product
value and operating costs.
The diagram in Fig. 22.10 shows a significant concentration of solute in the
liquid fed to the column, and 99 percent removal from the gas would not be
possible for this case. However, a lower value of x, could be obtained by better
stripping or more complete regeneration of the absorbing liquid. The value of x,
could be optimized, considering the extra equipment and operating costs for more
complete regeneration and the savings from better operation of the absorber.
TEMPERATURE VARIAnONS IN PACKED TOWERS. When rich gas is fed to an
absorption tower, the temperature in the tower varies appreciably from bottom
to top. The heat of absorption of the solute raises the solution temperature, but
evaporation of the solvent tends to lower the temperature. Usually the overall
effect is an increase in the liquid temperature, but sometimes the temperature goes
through a maximum near the bottom of the column. The shape of the temperature
profile depends on the rates of solute absorption, evaporation or condensation of
solvent, and heat transfer between the phases. Lengthy computations are needed
GAS ABSORPTION 701
T,
T,
--------------- ~
T,
- - - - - - - - - - - - - - - T.
Vb ----------
;> Operating line
;>
I..:
y y I..:
x,
x x
la) Ib)
FIGURE 22.11
Temperature profiles and equilibrium lines for adiabatic absorption: (a) no solvent evaporation: (b)
significant solvent evaporation or cold gas feed.
to get the exact temperature profiles for liquid and gas,15.24 and in this text only
simplified examples are presented. When the gas inlet temperature is close to the
exit temperature of the liquid and the incoming gas is saturated, there is little
effect of solvent evaporation, and the rise in liquid temperature is roughly
proportional to the amount of solute absorbed. The equilibrium line is then curved
gradually upward, as shown in Fig. 22.11a, with increasing values of x correspond-
ing to higher temperatures.
When the gas enters the columns 10 to 20°C below the exit liquid tempera-
ture and the solvent is volatile, evaporation will cool the liquid in the bottom part
of the column, and the temperature profile may have a maximum as shown in
Fig. 22.11b. When the feed gas is saturated, the temperature peak is not very
pronounced, and for an approximate design, either the exit temperature or the
estimated maximum temperature can be used to calculate equilibrium values for
the lower half of the column.
The curvature of the equilibrium line complicates the determination of the
minimum liquid rate, since decreasing the liquid rate increases the temperature rise
of the liquid and shifts the position of the eqUilibrium line. For most cases, it is
satisfactory to assume the pinch occurs at the bottom of the column to calculate
L mino
RATE OF ABSORPTION
The rate of absorption can be expressed in four different ways using individual
c!Jeffkients or overall coefficients based on the gas or liquid phases. Volumetric
coefficients are used for most calculations, because it is more difficult to determine
702 MASS TRANSFER AND ITS APPLICATIONS
the coefficients per unit area and because the purpose of the design calculation is
generally to determine the total absorber volume. In the following treatment the
correction factors for one-way diffusion are omitted for simplicity, and the changes
in gas and liquid flow rates are neglected. The equations are strictly valid only for
lean gases but can be used with little error for mixtures with up to 10 percent
solute. The case of absorption from rich gases is treated later as a special case.
The rate of absorption per unit volume of packed column is given by any
of the following equations where y and x refer to the mole fradion of the
component being absorbed:
I' = k,a(y - y,) (22.7)
I' = kxa(x, - x) (22.8)
I' = Kya(y - y*) (22.9)
r= Kxa(x* - x) (22.10)
The interface composition (y" x,) can be obtained from the operating-line
diagram using Eqs. (22.7) and (22.8):
Y - Yi kxa
(22.11)
Xi - X kya
Thus a line drawn from the operating line with a slope -kxa/kya will intersect
the equilibrium line at (y" x,), as shown in Fig. 22.12. Usually it is not necessary
to know the interface compositions, but these values are used for calculations
involving rich gases or when the equilibrium line is strongly curved.
The overall driving forces are easily determined as vertical or horizontal lines
on the y-x diagram. The overall coefficients are obtained from kya and kxa using
the local slope ofthe equilibrium curve m as was shown in Chap. 21 [Eq. (21.71)]:
1 1 III
-=-+- (22.12)
Kya kya kxa
1 1 1
-=-+-- (22.13)
Kxa kxa mkya
Operating line Equilibrium
line
k"
Slope=:--
k"
y'-
I FIGURE 22.12
x
x Location of interface compositions.
GAS ABSORPTION 703
CALCULATION OF TOWER HEIGHT. An absorber can be designed using any
of the four basic rate equations, but the gas-film coefficients are most common,
and the use of K,a will be emphasized here. Choosing a gas-film coefficient does
not require any assumption about the controlling resistance. Even if the liquid
film controls, a design based on Kya is as simple and accurate as one based on
Kxa or kxa.
Consider the packed column shown in Fig. 22.13. The cross section is Sand
the differential volume in height dZ is S dZ. If the change in molar flow rate V is
neglected, the amount absorbed in section dZ is - V dy, which equals the
absorption rate times the differential volume:
- V dy = Kya(y - y*)S dZ (22.14)
This equation is rearranged for integration, grouping the constant factors V,
S, and K,a with dZ and reversing the limits of integration to eliminate the minus
sign:
(22.15)
The right-hand side of Eq. (22.15) can be integrated directly for certain cases
or it can be determined numerically. We will examine some of these cases.
L{qUfd
mlet
Xa
Gas S---
oullet+-
Jf,
Gas
inlet LiquId
Jb '"l ___~==:r-~ aut/et FIGURE 22.13
'= Ab Diagram of packed absorption tower,
704 MASS TRANSFER AND ITS APPLICATIONS
NUMBER OF TRANSFER UNITS. The equation for column height can be written
as follows:
(22.16)
The integral in Eq. (22.16) represents the change in vapor concentration
divided by the average driving force and is called the number of transfer units
(NTU) Nay- The subscripts show that Nay is based on the overall driving force
for the gas phase. The other part of Eq. (22.16) has the units of length and is called
the height of a transfer unit (HTU) Hay. Thus a simple design method is to
determine Nay from the y-x diagram and multiply it by Hay obtained from the
literature or calculated from mass-transfer correlations:
(22.17)
The number of transfer units is somewhat like the number of theoretical
stages, but these values are equal only if the operating line and equilibrium line
are straight and parallel, as in Fig. 22.14a. For this case,
N =Yb- Y. (22.18)
ay Y-Y *
When the operating line is straight but steeper than the equilibrium line, as in
Fig. 22.14b, the number of transfer units is greater than the number of ideal stages.
Note that for the example shown, the driving force at the bottom is Yb - Y.. the
same as the change in vapor concentration across the tower, which has one ideal
stage. However, the driving force at the top is Y.. which is several-fold smaller, so
the average driving force is much less than Yb - Y•. The proper average can be
Vb ---------
v,
Operating line I O~rating line
v I v
I
I
Equilibrium 1
v,
t
EquHibrium line
line
v. 1
I
x x
lal Ibl
FIGURE 22.14
Relationship between number of transfer units (NTU) and number of theoretical plates (NTP),: la)
NTU ~ NTP; (b) NTU > NTP.
GAS ABSORPTION 705
shown to be the logarithmic mean of the driving forces at the two ends of the
column.
For straight operating and equilibrium lines, the number of transfer units is
the change in concentration divided by the logarithmic mean driving force:
_ Yb - Ya
N Oy- - (22.19)
~YL
where ~YL is the logarithmic mean of Yb - yt and Ya - Y:. Equation (22.19) is
based on the gas phase. The corresponding equation based on the liquid phase is
(22.20)
When the incoming liquid is free of solute, Y; = 0, aud an alternate equation
based on the absorption factor A = Llm V [Eq. (17.11)J can be used:
A (YbIYa)(A - I) + 1
No = ~- In =='-'--,--'-- (22.21)
y A -I A
The corresponding equation for stripping with a solute-free gas is based on
the stripping factor S = mVIL [Eq. (17.29)]:
S (x",-al_xb",,)(,-S::--_I..'-)--,-+_I
__
Nox=--In- (22.22)
S-I S
The overall height of a transfer unit can be defined as the height of a packed
section required to accomplish a change in concentration equal to the average
driving force in that section. Values of Hoy for a particular system are sometimes
available directly from the literature or from pilot-plant tests, but often they must
be estimated from empirical correlations for the individual coefficients or the
individual heights of a transfer unit. Just as there are four basic types of
mass-transfer coefficients, there are four kinds of transfer units, those based on
individual or overall driving forces for the gas and liquid phases. These are as
follows:
Gas film: H =-
y
VIS
ky a
N y = -dy-
Y- y,
f (22.23)
Liquid film: H = LIS
x kxa
N =
x
f-dx-
Xj-X
(22.24)
Overall gas:
H
0)1-
_ VIS
K
ya
N oy - -f~
Y - y*
(22.25)
Overall liquid:
H _ LIS
Ox- K
xa
N Ox =f~
x* _ x (22.26)
706 MASS TRANSFER AND ITS APPLICATIONS
ALTERNATE FORMS OF TRANSFER COEFFICIENTS. The gas-film coefficients
reported in the literature are often based on a partial-pressure driving force instead
of a mole-fraction difference and are written as k,a or K,a. Their relationships to
the coefficients used heretofore are simply k,a = k,a/P and K,a = Kya/P, where P
is the total pressure. The units of k,a and K,a are commonly mOl/ft 3 -h-atm.
Similarly liquid-film coefficients may be given as kLa or KLa, where the driving
force is a volumetric concentration difference; kL is therefore the same as k, defined
by Eq. (21.31). Thus kLa and KLa are equal to kxa/PM and Kxa/PM' respectively,
where PM is the molar density of the liquid. The units of kLa and KLa are usually
mol/ft 3 -h-(mol/ft') or h - '.
If G,/M or GM is substituted for VIS in Eqs. (22.23) and (22.25), and Gx/M
for L/S in Eqs. (22.24) and (22.26), the equations for the height of a transfer unit
may be written (since MPM = Px, the density of the liquid)
GM H --GM-
H=- and (22.27)
y k aP , 0, -K,aP
H = Gx/Px and H = Gx/Px (22.28)
x "La Ox K La
The terms H G , Hu N G , and NL often appear in the literature instead of H"
H x , N y , and N x , as well as the corresponding terms for overall values, but here
the different subscripts do not signify any difference in either units or magnitude.
If a design is based on No" the value of Ho, can be calculated either from
K,a or froin values of H, and H x , as shown below. Starting with the equation for
overall resistance, Eq. (22.12), each term is multiplied by GM, and the last term is
multiplied by LM/LM, where LM = L/S = Gx/M, the molar mass velocity of the
liquid:
(22.29)
From the definitions of HTU in Eqs. (22.23) to (22.25),
(22.30)
Example 22.3. A gas stream with 6.0 percent NH3 (dry basis) and a flow rate of
4500 SCFM (ft3/min at O°C, 1 atm) is to be scrubbed with water to lower the
concentration to 0.02 percent. The absorber will operate at atmospheric pressure
with inlet temperatures of 20 and 25°C for the gas and liquid, respectively. The gas
is' saturated with water vapor at the inlet temperature and can be assumed to leave
as a saturated gas at 25°C. Calculate the value of N Oy if the liquid rate is 1.25 times
the minimum.
GAS ABSORPTION 707
Solutioll
The following solubility data are given by Perry 12a:
X Yl0'C Y311'C Y40"C
0.0308 0.0239 0.0389 0.0592
0.0406 0.0328 0.0528 0.080
0.0503 0.0417 0.0671 0.1007
0.0735 0.0658 0.1049 0.1579
For NH3 -+ NH3(aq),
I!.H ~ -8.31 kcaljg mol
The temperature at the bottom of the column must be calculated to determine
the minimum liquid rate.
Basis 100 g mol of dry gas in, containing 94 mol of air and 6 mol of NH3
(plus 2.4 mol of H 2 0). The outlet gas contains 94 mol of air.
The moles of ammonia in the outlet gas, since Ya = 0.0002, are
0.0002)
94 - - = 0.0188 mol NH,
( 0.9998
The amount of ammonia absorbed is then 6 - 0.0188 = 5.98 mol.
Heat effects The heat of absorption is 5.98 x 8310 = 49,690 cal. Call this Q,.
Then
Q,=Q"+Q,+Q,, (22.31)
where Qsy = sensible heat change in the gas
Qv = heat of vaporization
Qs~ = sensible heat change in liquid
The sensible heat changes in the gas are
Q.;,= 94 mol x 7.0 cal/mol-'C x 5'C = 3290 cal
QH,O = 2.4 x 8.0 x 5 = 96 cal
Q" = 3290 + 96 = 3390 cal
The amount of vaporization of water from the liquid is found as follows. At 20°C,
PH:!)= 17.5 mm Hg; at 25°C, PH20 = 23.7 mm Hg. The amount of water in the inlet
gas is
17.5
100 x - - = 2.36 mol
742.5
In the outlet gas it is
23.7
94.02 x - - = 3.03 mol
736.3
The amount of water vaporized is therefore 3.03 - 2.36 = 0.67 mol. Since the
heat of vaporization 8H, = 583 cal/g,
Q, = 0.67 x 583 x 18.02 = 7040 cal
708 MASS TRANSFER AND ITS API'LTCATIQNS
Solving Eq. (22.31) for Q", the sensible-heat change in the liquid, gives
Q," ~ 49,690 - 3390 - 7040 ~ 39,260 cal
The outlet temperature of the liquid T" is found by trial. Assume that for the
solution Cp = 18 caljg mol-cC; guess that 1b = 40°C and Xmax = 0.031, as estimated
from the equilibrium solubility lines on Fig. 22.15. Then the total moles ofliquid out
Lb are
5.98
Lb ~ - - ~ 192.9 mol
0.031
192.9 x 18(T" - 25) ~ 39,260
T" ~ 36.3"C
0.08
;440"C
/
/
/
0.0 7
;'
-
/
/
/
0.0 6
Op,," 9
in
lif/ 35°e
T
/
300 e
0.05
/
1/// /
/ /
/
/
0.0 4
/ ~ Il?ilib~"m line
._-
0.03
/ /j / Y
/ // /
/
//25°e
/, t/
0.0 2
/
0.0
'~ ,j
/,
;,.V
/,
o
o 0.01 0.02 0.03 0.04 0.05
FIGURE 22.15
y-x diagram for Example 22.3.
GAS ABSORPTION 709
For a revised estimate of 11. = 37°C. Xmax = 0.033,
5.98
L, = - - = 181 mol
0.033
39,260
7;, - 25 = = 12.1
181 x 18
7;, = 37"C
This procedure gives the minimum liquid rate; the minimum amount of water is
L m ," = 181 - 6 = 175 mol H 2 0
For a water rate 1.25 times the minimum, La = 1.25 X 175 = 219 mol, and Lb =
219 + 6 = 225 mol. Then, the temperature rise of the liquid is
39,260
7;, - 25 = 9.7"C
225 x 18
The liquid therefore leaves at 35"C, with x, = 5.98/225 = 0.0266 and y* '" 0.044.
To simplify the analysis, the temperature is assumed to be a linear function of
x, so that T '" 30"C at x = 0.0137. Using the data given for 30"C and interpolating
to get the initial slope for 25°C and the final value of y* for 35°C, the equilibrium
line is drawn as shown in Fig. 22.15. The operating line is drawn as a straight line,
neglecting the slight change in liquid and gas rates. Because of the curvature of the
equilibrium line, N Oy is evaluated by numerical integration or by applying Eq. (22.19)
to sections of the column, which is the procedure used here.
y y* y-y* dYL t1ylt1YL = Wo)'
0.06 0.048 0.012
0.03 0.017 0.013 0.0125 2.4
0.01 0.0055 0.0045 0.0080 2.5
0.0002 0 0.0002 0.00138 7.1
Noy = 12.0
MULTICOMPONENT ABSORPTION. When more than one solute is absorbed
from a gas mixture, separate equilibrium and operating lines are needed for each
solute, but the slope of the operating line, which is L/V, is the same for all the
solutes. A typical y-x diagram for absorption of two solutes is shown in Fig. 22.16.
In this example, B is a minor component of the gas, and the liquid rate was chosen
to permit 95 percent removal of A with a reasonable packed height. The
operating-line slope is about 1.5 times the slope of the equilibrium line for A, and
N Oy "" 5.5. The operating line for B is parallel to that for A, and since the
equilibrium line for B has a slope greater than L/V, there is a pinch at the bottom
of the column, and only a small fraction of the B can be absorbed. The operating
line for B should be drawn to give the correct number of transfer units for B, which
710 MASS TRANSFER AND ITS APPLICATIONS
YA
or
Y.
Y6,b
Y6,8
YA,a~ __~____________________________~____~
XB,b XA,IJ
FIGURE 22.16
Equilibrium and operating lines for multicomponent absorption.
is generally about the same as N oy for A. However, in this example, XB.b is
practically the same as xi!', the equilibrium value for YB.b, and the fractional
removal of B can be calculated directly from a material balance:
V(YB.b - YB.a) = L(4.b - x B • a) (22.32)
If nearly complete absorption of B is required, the operating line would
have to be made steeper than the equilibrium line for B. Then the operating
line would be much steeper than the equilibrium line for A, and the concentration
of A in the gas would be reduced to a very low value. Examples of multi component
absorption are the recovery of light hydrocarbon gases by absorption in heavy
oil, the removal of CO 2 and H 2 S from natural gas or coal gasifier products by
absorption in methanol or alkaline solutions, and water scrubbing to recover
organic products produced by partial oxidation. For some cases, the dilute-
solution approach presented here may have to be corrected for the change in
molar flow rates or the effect of one solute on the equilibria for other gases, as
shown in the analysis of a natural gasoline absorber l5 •
DESORPTION OR STRIPPING. In many cases, a solute that is absorbed from a
gas mixture is desorbed from the liquid to recover the solute in more concentrated
form and regenerate the absorbing solution. To make conditions more favorable
for desorption, the temperature may be increased or the total pressure reduced or
GAS ABSORPTION 711
both these changes may be made. If the absorption is carried out under high
pressure, a large fraction of the solute can sometimes be recovered simply by
flashing to atmospheric pressure. However, for nearly complete removal of the
solute, several stages are generally needed, and the desorption or stripping is
carried out in a column with countercurrent flow of liquid and gas. Inert gas or
steam can be used as the stripping medium, but solute recovery is easier if steam
is used, since the steam can be condensed.
Typical operating and equilibrium lines for stripping with steam are shown
in Fig. 22.17. With Xa and Xb specified, there is a minimum ratio of vapor to liquid
corresponding to the operating line that just touches the equilibrium line at some
point. The pinch may occur in the middle of the operating line if the equilibrium
line is curved upward, as in Fig. 22.17, or it may occur at the top of the column,
at (y., xa). For simplicity the operating line is shown as a straight line, though it
would generally be slightly curved because of the change in vapor and liquid rates.
In an overall process of absorption and stripping, the cost of steam is
often a major expense, and the process is designed to use as little steam as
possible. The stripping column is operated at close to the minimum vapor
rate, and some solute is left in the stripped solution, rather than trying for
complete recovery. When the equilibrium line is curved upward, as in Fig.
22.17, the minimum steam rate becomes much higher as Xb approaches zero.
The height of a stripping column can be calculated from the number
of transfer units and the height of a transfer unit, using the same equations
as for absorption. Often attention is focused on the liquid-phase concentra-
tion, and No:c and Ho:c are used:
-
ZT = Ho:cNo:c = Ho:c f - .dx
x -x
-- (22.33)
The equation corresponding to Eq. (22.30) is
LM
Ho:c=H:c+--Hy (22.34)
mG M
Equilibrium line,
p= 1 atm
y".!....~----------
Operating line for Vmin
y
Operating line,
Slope'= L!V
x. FIGURE 22.17
x Operating lines for a stripping column.
712 MASS TRANSFER AND ITS APPLICATIONS
Stripping with air is used in some cases to remove small amounts of
gases such as ammonia or organic solvents from water. If there is no need
to recover the solute in concentrated form, the optimum amount of air used
may be much greater than the minimum, since it does not cost much to
provide more air, and the column height is considerably reduced. The following
example shows the effect of air rate in a stripping operation.
Example 22.4 Water containing 6 ppm trichloroethylene (TCE) is to be purified by
stripping with air at 20°C. The product must contain less than 4.5 ppb TCE to meet
emission standards. Calculate the minimum air rate in standard cubic meters of air
per cubic meter of water and the number of transfer units if the air rate is 1.5 to 5
times the minimum value.
Solution
The Henry's-Iaw coefficient for TCE in waterS at 20'C is 0.0075 m'-atm/mol. This
can be converted to the slope of the equilibrium line in mole-fraction units as follows,
since P = 1 atm and 1 m3 weighs 1Q6 g:
atm-m 3 1 10 6 mol H 2 0
m=0.0075---x--x =417
mol 1 atm 18 m3
With this large value of rn, the desorption is liquid-phase controlled. At the
minimum air rate, the exit gas will be in equilibrium with the incoming solution. The
molecular weight of TCE is 131.4, and
6 X 10- 6 mol TCE 18 g
XQ = x ----''-- 8.22 X 10- 7
131.4 g H2 0 mol H 2 0
y, = 417(8.22 x 10- 7 ) = 3.43 x 10- 4
Per cubic meter of solution fed, the TCE removed is
W[(6 x 10- 6 ) - (4.5 x 10- 9 )]
v. -
TeE -
-~'------:':-:-:'------=
131.4
= 4.56 x 10- 2 mol
The total amount of gas leaving is
4.56 x 10- 2
V = 132.9 mol
3.43 x 10 4
Since 1 g mol = 0.0224 std m3 and since the change in gas flow rate is very small,
F rni, = 132.9 x 0.0224 = 2.98 std m'
The density of air at standard conditions is 1.295 kgjm 3 , so the minimum rate on
a mass basis is
2.98 x 1.295
3.86 X 10-' kg air/kg water
1000
GAS ABSORPTION 713
If the air rate is 1.5 times the minimum value. then
3.43 x 10- 4
2.29 X 10- 4
1.5
2.29 X 10- 4
x* 5.49 X 10- 7
• 417
131.4
C: ~ 5.49 x 10- 7
x - - ~ 4.01
18
X 10- 6 gig ~ 4.01 ppm
C. - C: ~ I1C. ~ 6.0 - 4.01 ~ 1.99
At bottom,
Cb ~ 0.0045 ppm I1Cb ~ 0.0045 ppm
1.99 - 0.0045
(C - C*)L ~ In (1.99/0.0045) 0.3259 ppm
Using concentrations in parts per million to calculate N Ox.
No. ~ f dC
C _ C*
6 - 0.0045
C. - Cb
~ (C - C*)L
---~18.4
0.3259
Similar calculations for other multiples of the minimum flow rate give the fonowing
values. The packed height is based on an estimated value of Hox = 3 ft; this is
somewhat greater than the values reported for I-in. plastic PaU rings.
Air rate No. Z. ft
1.5Vmin 18.4 55.2
2Vmin 13.0 39
3Vmin 10.2 30.6
5V",in 8.7 26.1
Going from 1.5 to 2Vmin or from 2 to 3Vmin decreases the tower height
considerably, and the reduction in pumping work for water is more than the
additional energy needed to force air through the column. Further increase in V does
not change Z very much, and the optimum air rate is probably in the range 3 to
5Vmio ' Typical flow rates at V ~ 3Vmio might be G. ~ 10,000 Ib/ft2-h (49,000 kgjm 2-h)
and G, ~ 116Ib/ft 2-h (566 kg/m2-h).
MASS-TRANSFER CORRELATIONS
To predict the overall mass-transfer coefficient or the height of a transfer unit,
separate correlations are required for the gas phase and the liqnid phase. Such
correlatious are generally based on experimental data for systems in which one
714 MASS TRANSFER AND lTS APPLICATIONS
phase has the controlling resistance, since it is difficult to separate the two
resistances accurately when they are of comparable magnitude. The liquid-phase
resistance can be determined from the rate of desorption of oxygen or carbon
dioxide from water. The low solubility of these gases makes the gas-film resistance
negligible, and the values of Hox are essentially the same as Hx.
More accurate values of Hx are obtained from desorption measurements
than from absorption tests, because the operating lines at typical gas and liquid
rates have slopes much less than the slope of the equilibrium line. For oxygen in
water at 20o e, the equilibrium partial pressure is 4.01 x 10 4 atm per mole
fraction, and L/V might range from 1 to 100. For absorption of oxygen from air
in pure water, a "pinch" would develop at the bottom of the packed column, as
shown in Fig. 22.18. Very accurate measurements of Xb and the temperature (to
determine xt) would be needed to determine the driving force (Xb - 4). For
desorption of oxygen from a saturated solution into nitrogen, the concentration
Xb is small, but No::c can be determined with reasonable accuracy since x6' is zero.
LIQUID-FILM COEFFICIENTS. Values of Hx for the system 02-H20 with cer-
amic Raschig rings!4 are shown in Fig. 22.19. For liquid mass velocities in the
intermediate range, 500 to 1O,000Ib/ft2 -h, Hx increases with G~·4 for !-in. rings
but with G~·2 for the larger sizes. Thus for 1-, 1!-, and 2-in. rings kLa varies
with G~·8. Much of the increase in kLa is due to the increasing interfacial area a,
and the rest comes from an increase in k L . At high mass velocities, the packing is
nearly completely wetted, and there is only a slight increase in kLa with G" which
makes Hx nearly proportional to Gx . Note that as far as mass transfer is concerned,
the small packings are only slightly better than the large ones in the intermediate
range of flows, even though the total area varies inversely with the packing size.
The larger packings are generally preferred for commercial operation because of
the much higher capacity (higher flooding velocity).
The data in Fig. 22.19 were taken with gas flow rates of 100 to 230Ib/fe-h,
and there was no effect of Gy in this range. For gas flow rates between loading
and flooding, Hx is slightly lower because of the increased holdup of liquid.
However, for a column designed to operate at half the flooding velocity, the effect
of Gy on Hx can be neglected.
Equilibrium line
Operating line for desorption
FIGURE 22.18
x, Typical operating lines for absorption or desorption of a
x slightly soluble gas.
GAS ABSORPTION 715
30 300
20 - 200
i--' - /'
0C--_ -- -
, KJ·-~ 100
l-in. rings
5.0 5o
/'
, , 1
-i- /'
'" 2. 0
V 3.-
V,2
,
l' 2o
-;
Ho.
~ ~
1. 0
.-I -I- 1
2
, ,
l'
O. 5
,
Packing size, in.
O. 2
O. 1
100 1,000 10,000 100,000
LIQUID MASS VELOCITY, G"" Ib/ft2-h
FIGURE 22.19
Height of a transfer unit for desorption of oxygen from water at 25°C with Raschig ring packing.
(Note: in this system Hox ~ Hr)
The liquid-film resistance for the other systems can be predicted from
the O,-H,O data by correcting for differences in diffusivity and viscosity (for
reference, at 25"C, Do for oxygen in water is 2.41 x 10- 5 cm'/s and N s, is
381):
Hx =! (Gx)n(~)O.5
I'
Cl pDo
(22.35)
where Cl and n are empirical constants that are tabulated in the literature
for some of the older packing types. The exponent of 0.5 on the Schmidt
number is consistent with the penetration theory, which would be expected
to apply to liquid flowing for short distances over pieces of packing. The
exponent n varies with packing size and type, but 0.3 can be used as a typical
value. Equation (22.35) should be used with caution for liquids other than
water, since the effects of density, surface tension, and viscosity are uncertain.
When a vapor is absorbed in a solvent of high molecular weight, the
molar flow rate of liquid will be much less than if water were used at the
same mass velocity. However, the coefficient k,p, which is based on a mole-fraction
driving force, also varies inversely with the average molecular weight of the liquid,
716 MASS TRANSFER AND ITS APPLICATIONS
and there is no net effect of M on Hr'
k"a = kLa ~ (22.36)
H = GriM = GrlPr (22.37)
x kxa kLa
The coefficient kLa depends mainly on the volnmetric flow rate, diffusivity, and
viscosity but not on the molecular weight, so in this respect general correlations
for kLa or Hr are simpler than those for k"a.
GAS-FILM COEFFICIENTS. The absorption of ammonia in water has been
used to get data on k"a or H" since the liquid-film resistance is only about
10 percent of the overall resistance and can be easily allowed for. Data for
Ho, and corrected values of H, for l}in. Raschig rings are given in Fig.
22.20. For mass velocities up to 600 Ib/ft2-h, H, varies with about the 0.3 to
0.4 power of Gy , which means k"a increases with G~·6-0.7, in reasonable agreement
with data for mass transfer to particles in packed beds. The slopes of tlie H,
plots decrease in the loading region because of the increase in interfacial area. The
values of H, vary with the -0.7 to -0.4 power of the liquid rate, reflecting the
large effect of liquid rate on interfacial area.
The following equation is recommended 15 to estimate H, for absorp-
tion of other gases in water. The Schmidt number for the NH 3 -air-H 20 system
is 0.66 at 25°C:
H, = H,.NH,(:.~~r (22.38)
There are few data to support an exponent of! for the diffusivity or the Schmidt
number, and an exponent of t has been suggested based on boundary-layer theory
and data for packed beds. However, the Schmidt numbers for gases do not differ
6
Loading
4
p'
2
G", '" 500
.,; -""
~
~
",'
-g 1,500 ~
1
•
:r.6 o. B
o.6r4.500
- -+-
..0-_
HOy
Hy
0.4
FIGURE 22.20
I III Height of a transfer unit for the absorption of
100 200 400 600 1,000
G y , Ib/ft 2 - h ammonia in water with 1!-in. ceramic Raschig rings.
GAS ABSORPTION 717
widely, and the correction term is often small. There is more uncertainty about
the effect ofliquid properties on Hy ifliquids other than water are used as solvents.
For the vaporization of pure liquid into a gas stream, there is no mass-
transfer resistance in the liquid phase, and vaporization tests might seem a good
method of developing a correlation for gas-film resistance. However, tests with
water and other liquids give Hr values about half those for ammonia at the same
mass velocities. The difference is attributed to pockets of nearly stagnant liquid
that contribute steadily to vaporization but soon become saturated in a gas
absorption test. 17 The stagnant pockets correspond to the static holdup, liquid
that remains in the column long after the flow is shut off. The rest of the liquid
constitutes the dynamic holdup, which increases with liquid flow rate. Correlations
for the static and dynamic holdup and the corresponding interfacial areas have
been developed 16 and can be used to correlate vaporization and gas absorption
results.
PERFORMANCE OF OTHER PACKINGS. Several packings have been devel-
oped that have high capacity and better mass-transfer characteristics than Raschig
rings and Berl saddles, but comprehensive data on the gas and liquid resistances
are not available. Many of these packings have been tested for the absorption of
CO 2 in NaOH solution, a system where the liquid film has the controlling
resistance, but the gas-film resistance is not negligible. The K,a values are 20 to
40 times the normal values for CO 2 absorption in water, because the chemical
reaction between CO, and NaOH takes place very close to the interface, making
the concentration gradient for CO 2 much steeper.
Although the K,a values for the COz-NaOH system cannot be used directly
to predict the performance with other systems, they can be used for comparison
between packings. Data for several sizes of Intalox saddles and Pall rings are
shown in Fig. 22.21, along with some results for Raschig rings. The ratio of K,a
for a given packing to that for 1!-in. Raschig rings, evaluated at Gx = 1000Ib/ftz-h
and Gy = 500 Ib/ft 2 -h, is taken as a measure of performance JP and listed in Table
22.1. The value of Jp is a relative measure of the total interfacial area, since the
absorption of CO 2 into NaOH solution is an irreversible reaction that can take
place in the static as well as the dynamic holdup. Packings that have a relatively
high total interfacial area probably have a large dynamic holdup as well and a
large area for normal physical absorption. For a rough estimate of the performance
of the new packings for physical absorption, the value of Jp can be applied to H Oy
or to the overall coefficient calculated for 1.5-in. Raschig rings. The overall
coefficient would be based on data for NH, and for Oz and corrected for
changes in diffusivity, viscosity, and flow rate.
Large columns sometimes have higher apparent values of Hoy than small
columns using the same packing, and various empirical correlations for the effects
of column diameter and packed height have been presented. I2 , These effects
probably resulted from uneven liquid distribution, which tends to make the gas
flow uneven and results in local values of the operating-line slope quite far from
the average. The penalty for mal distribution is greatest when the operating line
718 MASS TRANSFER AND ITS APPLICATIONS
10.0
8.0
6.0 . --
4.0
Pall rings, Dp ' in. ~""I--
" --- =---:: :::= ~ ~ -- --11-
3.0
--t:=
'---
in. Raschig rings
E
2.0
r:;-, ~ --1.,...;::-.:::' :---
2 __ --/
" 1/f--:.:.... . . . . . .
I 1.0
~ 8.0
~... 6.0 1--
4. 0
Intalox saddles
Size, in.
, V - -....
::: -- -- --
3.0 _ 2 /'
V ~
"-
~ --- ----
2.0
r-
~
L----
1.0
1,000 2,000 3,000 6,000 10,000 20,000 30,000 60,000
G""lb/ft 2 -h
FIGURE 22.21
Mass-transfer coefficients for the absorption of CO 2 in 4 percent NaOH with metal Pall rings or
ceramic Intalox saddles (G y = 500 Ib/ft 2 -h).
is only slightly steeper than the equilibrium line and when a large number of
transfer units is needed. For these cases it is especially important to provide very
good liquid distribution, and for tall columns, as mentioned previously, it is
advisable to pack the column in 5- to lO-m sections, with redistribution of the
liquid between the sections.
Example 22.5. Gas from a reactor has 3.0 percent ethylene oxide (EO) and 10 percent
CO 2 , with the rest mostly nitrogen, and 98 percent of the EO is to be recovered by
scrubbing with water. The absorber will operate at 20 atm, using water with 0.04
mole percent EO at 30°C, and the gas enters at 30°C, saturated with water. How
many transfer units are needed if 1.4 mol H 2 0 are used per mole of dry gas? Estimate
the diameter of the column and the packed height if li-in. Pall rings are used
and the total gas feed rate is 10,000 mol/h.
Solution
Equilibrium data' for 30 and 40°C are shown in Fig. 22.22. By a heat balance similar
to that of Example 22.3, the temperature rise of the liquid was estimated to be 12SC,
GAS ABSORPTION 719
0.0 6
I .....--40°C
0.05
I ///
Z
//
0.0 4
/ . . .30°C
Yeo Eq";Hb,;"m //
;0
line,// ,./
0.03
operat;nI0// // p,.,at;n 9
line V /" ~ne
0.0 2
I~~ // 0.00' /
0.0
'[ptV'
~$
/ /f / /
0
yVEq"U;bd"m
0.001
I;n~
0.002
00 0.01 0.02 0.03 0.04 0.05 0.06 0.07
xeo
FIGURE 22.22
y-x diagram for Example 22.5.
which makes the equilibrium line for the column curve upward. The terminal points
of the operating line are determined by material balance.
Basis 100 mol dry gas in; 140 mol solution in.
In Out
87 N2 87N 2
10 CO, lOCO,
lEO 0.06 EO (~l x 0.02)
~ 97.06
Assume negligible CO 2 absorption and neglect effect of H 2 0 on gas composition.
0.06
At top: x = 0.0004 Y = - - = 0.00062
97.06
Moles o[EO absorbed: 3 x 0.98 = 2.94
Moles o[EO in water: 140 x 0.0004 = 0.056
At bottom: x 2.94 + 0.056 = 0.0210
140 + 2.94
Y = 0.030
No,=f~=L: l\y
y - y* (y Y*)L
720 MASS TRANSFER AND ITS APPLICATIONS
y y-y* ~.NOy
0.03 0.008
0.015 0.0006 2.14
0.005 0.0024 2.55
0.0006 0.0003 5.35
N Oy = 10.04 = 10.0 transfer units
Column diameter To find the column diameter, use the generalized pressure-
drop correlation, Fig. 22.6.
Based on the inlet gas,
M = 0.87(28) + 0.1(44) + 0.03(44) = 30.1
30.1 273
P, =- x 20 x - = 1.46 Ib/ft 3 (0.0234 g/cm 3)
359 313
Gx r-;;;- 1.4 x 18 1.46
1-~~=0.130
G, ",;;:=t;; = 1 x 30.1 62.2 - 1.46
From Fig. 22.6 for AP = 0.5 in. H,O/ft,
G2 F 11°·1
Y pr";c = 0.045
P,(Px - p,)g,
From Table 22.1, Fp = 40. At 40'C, J< = 0.656 cP. Therefore,
G' = 0.045(1.46)(62.2 - 1.46)(32.2) = 3.35
, 40(0.656)°·1
G, = 1.83Ib/ft'-s = 6590Ib/ft'-h
1.4 x 18 x 6590 = 5520Ib/ft'-h
1 x 30.1
For a feed rate of 10,000 x 30.1 = 3.01 x 1O'lbjh,
s _3_.0_I_x_IO_' = 54.5 ft' D = 8.3 ft.
5520
Use an 8.5-ft-diameter column.
Column height Find Hy and H;c from the data for ammonia-water and
oxygen-water, with It-in. Raschig rings. From Fig. 22.20 at G, = 500 and Gx = 1500,
Hy,NH) = 1.4 ft
The gas viscosity is assumed to be that of N, at 40'C and 1 atm, which is 0.0181 cP
(Appendix 8). The diffusivity of EO in the gas is calculated from Eq. (21.25) to be,
at 40'C and 20 atm,
D, = 7.01 X 10- 3 cm'/s
J< 1.81 x 10- 4
N =-= = 1.10
" pD, (7.01 x 10 3)(2.34 x 10-')
GAS ABSORPTION 721
From Table 22.1, f, = 1.36 for 1.5-in. Pan rings, so Hr is lower by this factor. The
quantity Hy is assumed to vary with G~·3 and G;O.4. Thus
H. = 1.4 (~)Ii2 _1_ (6590)0.3 (1500)0.4 = 1.71 ft
r. EO 0.66 1.36 500 5520
From Fig. 22.19, H,.o, = 0.9 ft at Gx = 1500. Using Eq. (21.28),
D, = 2.15 X 10-' cm'/s for EO in H,O at 40'C:
0.00656
N" = = 305
1.0 x 2.15 X 10-'
Using Eq. (22.35) with the correction factor JP and Nsc = 381 for O 2 in water at
25°C,
5520/0.656)0.3 (305)0.5 I
H x • EO = 0.9 ( 1500/0.894 381 1.36 = 0.96 ft
From Fig. 22.22, the average value of m is about 1.0, and from Eq. (22.30)
mG" 1.0 x 0.96
H oy = Hy + - - Hx = 1.71 + 2.40 ft
L" 1.4
For 10 transfer units, you need 24 ft. Use 30 ft of packing in two I5-ft sections, with
redistribution of the liquid.
Absorption in Plate Columns
Gas absorption can be carried out in a column equipped with sieve trays or other
types of plates normally used for distillation. A column with trays is sometimes
chosen instead of a packed coJumn to avoid the problem of liquid distribution in
a large diameter tower and to decrease the uncertainty in scaleup. The number of
theoretical stages is determined by stepping off plates on a y-x diagram, and the
number of actual stages is then calculated using an average plate efficiency. The
plate and local efficiencies are defined in the same way as for distillation [Eqs.
(18.66) and (18.67)], but more care must be taken in estimating the value of ~,
since plate efficiencies for absorption cover a much wider range than for distilla-
tion.
When the gas-film resistance is controlling, absorption efficiencies are gener-
ally in the range of 60 to 80 percent, about the same as for typical distillations,
which are also gas-film controlled. Slightly higher efficiencies can be expected for
low-molecular-weight solutes or when the liquid has a low viscosity or a low
surface tension. For large plates, liquid concentration gradients across the plate
could lead to efficiencies of 100 percent or more.
When the gas being absorbed is only slightly soluble, the liquid film usually
has the controlling resistance because of the high value of In [see Eq. (22.12)], and
the corresponding low value of K,a leads to a low plate efficiency [Eq. (21.77)].
The effect ofliquid viscosity is also more important when the liquid film controls,
because the lower diffusivity in the liquid phase has a more direct influence on
722 MASS TRANSFER AND ITS APPLICATIONS
the overall transfer coefficient. (If the gas film controls, the liquid viscosity only
affects the interfacial area.)
To illustrate the effect of solubility and plate efficiency, consider the absorp-
tion of CO 2 in water at 20°C and 10 atm. The value of In is 146, and the diffusion
coefficients for CO 2 in the gas and liquid are 0.0156 cm 2 /s and 1.76 x 10- 5 cm 2 /s.
The ratio of film coefficients can be estimated by applying the penetration theory,
as was done for distillation [Eq. (21.78)]:
kxa _ (D,,)0.5 PMx
(22.39)
kyQ Duy PMy
For water, PMx = 62.3/18.02 = 3.46 mol/ft'; for gas, PMy = (10/359)(273/293) = 0.026
mol/ft'. For this case, then, kxa/kp = (1.76 x 10- 5/1.56 x 10- 2)°.5 (3.46/0.026) =
4.47, which means that the liquid film would have only one-fifth of the total
resistance if In were 1.0. Allowing for the low solubility, however, makes the
liquid-film resistance In/k xa 146/4.47 = 33 times the gas-film resistance I/kya.
Taking N y = 2 as typical for a sieve tray, the effect of the liquid resistance is to
decrease Kya and Noy by a factor of 33 + I, giving Noy = 0.059. This corresponds
to a local efficiency of about 0.06 [see Eq. (21.77)]. For a value of local efficiency
that is this low, there is hardly any effect of concentration gradients across the
plate, and the plate efficiency would be about the same as the local efficiency, or
6 percent. The predicted efficiency for CO 2 absorption at 1 atm is only 2 percent.
Published data for CO 2 absorption in plate columns'o indicate efficiencies of about
this magnitude.
Absorption from Rich Gases
When the solute being absorbed is present at moderate or high concentrations in
the gas, there are several additional factors to consider in design calculations. The
decrease in total gas flow and the increase in liquid flow must be accounted for
in the material balance, and the correction factor for one-way diffusion should be
included. Also, the mass-transfer coefficients will not be constant because of the
changes in flow rate, and there may be an appreciable temperature gradient in the
column, which will change the equilibrium line.
The amount of solute absorbed in a differential height dZ is d(Vy), since
both V and y decrease as the gas passes through the tower.
dN A = d(Vy) = V dy + ydV (22.40)
If only A is being transferred, dNA is the same as dV, so Eq. (22.40) becomes
dN A = V dy + y(dN A ) (22.41)
or
Vdy
dN A = - - (22.42)
I-y
GAS ABSORPTION 723
The effect of one-way diffusion in the gas film is to increase the mass-transfer
rate for the gas film by the factor 1/(1 - Y)L, as shown by Eq. (21.39), so the effective
overall coefficient K~a is somewhat larger than the normal value of K,a:
(22.43)
In this treatment, the effect of one-way diffusion in the liquid film is neglected.
The basic mass-transfer equation is then
Vdy
dN A = - - = K~aS dZ(y - y*) (22.44)
1-y
The column height can be found by a graphical integration, allowing for changes
in V, (1 - y), (y - y*), and K~a:
ZT =
I
S
J' a
V dy
(I - y)(y - Y')(K~a)
(22.45)
If the process is controlled by the rate of mass transfer through the gas film,
a simplified equation can be developed. The term (I - y)" which strictly applies
only to the gas film, as shown in Eq. (22.43), is assumed to apply to the overall
coefficient, since the gas film is controlling. The coefficient K~a in Eq. (22.45) is
replaced by K,a/(l - y)L, which leads to
Z - -
I
T - S
J' a
V''''(I---Y)'L dy
K y a(l - y)(y - y*)
(22.46)
Since k,a varies with about VD. 7 , and K,a will show almost the same variation
when the gas film controls, the ratio V/K,a does not change much. This term can
be taken outside the integral and evaluated at the average flow rate or the values
at the top and bottom of the tower can be averaged. The term (1 - y)L is the
logarithmic mean of I - y and 1 - Yi, which is usually only slightly larger than
1 - y. Therefore the terms (1 y)L and 1 - Y are assumed to cancel, and Eq.
(22.46) becomes
ZT = (VlS) r ~
\4J,y-y*
a
(22.47a)
ZT = HoyN oy (22.47b)
This is the same as Eq. (22.17) for dilute gases, except that the first term, which
is Hoy, is an average value for the column rather than a constant. Note that Kya
from Eq. (22.12) is to be used here, and not K~a, since the (1 - y)L term was
included in the derivation.
If the liquid film has the controlling resistance to mass transfer, gas-film
coefficients could still be used for design calculations following Eq. (22.45). If
liquid-film coefficients are used, and if the factor (1 X)L is introduced to allow for
724 MASS TRANSFER AND ITS APPLICATIONS
one-way diffusion in the liquid, an equation similar to Eq. (22.47a) can be derived:
(22.48)
or
(22.49)
When the gas-film and liquid-film resistances are comparable in magnitude,
there is no simple method of dealing with absorption of a rich gas. The re-
commended method is to base the design on the gas phase and use Eq. (22.45).
Several values of Y between Ya and Yb are chosen, and values of V, K~a, and Y - y*
are calculated. As a check, the value of ZT from the integration should be compared
with that based on the simple formula in Eq. (22.47), since the difference should
not be great.
Example 22.6. A tower packed with I-in. (25.4-mm) rings is to be designed to absorb
sulfur dioxide from air by scrubbing the gas with water. The entering gas is 20 percent
S02 by volume, and the leaving gas is to contain not more than 0.5 percent S02 by
volume. The entering H 20 is S02 free. The temperature is 80°F and the total pressure
is 2 atm. The water flow is to be twice the minimum. The air flow rate (S02-free
basis) is to be 200 Ib/ft'-h (976 kg/m2-h). What depth of packing is required?
The following equations are available 25 for the mass-transfer coefficients for
absorption of S02 at 80°F in towers packed with 1-in. rings:
kLa = 0.038G~·82
koa = 0.028G~·7G~·2S
where kLa is in h-t, kga is in moljft 3 -h-atm, and Gx and Gy are in lb/ft 2-h.
The solubility of S02 in water is not quite proportional to the pressure, because
the H 2S0 3 that forms partially dissociates to H + and HSO;, and the fraction
dissociation decreases with increasing concentration. Henry's law applies to the
undissociated H,SO" and the total SO, dissolved is the sum of the H,SO, and the
HSO,. (The SOl- formed in water is negligible.) A few points for the total SO,
dissolved at 80°F are given below.
Pso p atn:t 0.04 0.08 0.12 0.16 0.20
CS02 • mol/ft 3 0.0044 0.0082 0.0117 0.0152 0.0186
xsop mole fraction 0.00127 0.00237 0.00338 0.00439 0.00538
Solution
The coefficients are first converted to mole-fraction units. At 80°F. PM for water is
62.2/18.02 = 3.45 mol/ft'. Therefore
k.a = 0.038G~·82 x 3.45 = O.13IG~·82 mOl/ft'-h
GAS ABSORPTION 725
Since the coefficients were measured at atmospheric pressure, and kya = kgaP, the
value of kga is equal to kll. However, the measured coefficients were not corrected
for one-way diffusion and thus represent ky aj{l - Y)L' The S02 concentration for the
published tests ranged from 3 to 17 percent, and the average value of {I - Y)L was
about 0.9. Therefore the published correlation is multiplied by 0.9 to give
k},a = O.025G~·7G~,2s
The next step is to plot the equilibrium curve. Since the pressure is 2 atm,
y = Pso)2. The curve is shown in Fig. 22.23. The slope of the linear portion is 20.1,
and the initial slope is 15.6. The lower end of the operating line is at y = 0.005, x = D,
and at the minimum liquid rate, the upper end of this line will touch the equilibrium
curve at y = 0.20, x = 10.36 x 10- 3. At twice the minimum liquid rate, the ratio of
FIGURE 22.23
Diagram for Example 22.6.
726 MASS TRANSFER AND ITS APPLICATIONS
water to S02 in the liquid will be twice as great. The number of moles of water fed
per mole of S02 is
0.98964
2 x - - = 191.1
0.01036
and
I
Xb = 0.0521
191.1 +I
The molal mass velocity of the feed gas GM is
200 I
- x- = 8.62 moljft'-h
29 0.8
The SO, fed is
8.62 x 0.2 = 1.724 moljft'-h
The air fed is
8.62 x 0.8 = 6.896 moljft'-h
The exit gas contains 0.5 percent S02; consequently the amount of S02 leaving is
0.005
6.896 x - - = 0.035 moljft2-h
0.995
The SO, absorbed is then 1.724 - 0.035 = 1.689 moljft 2-h. The SO, is 98 percent
absorbed. The water fed is
191.1 x 1.689 = 322.8 mol/ft 2 -h
Intermediate points on the operating line are obtained by a mass balance using
mole ratios. This leads to
322.8 -x- (y
= 6.896 - - - 0.005)
--
I - x I - y 0.995
Substituting values of y gives the following coordinates of the operating line:
0.2 0.15 0.1 0.05 0.02 0.005
5.21 3.65 2.26 1.02 0.33 o
The operating line is plotted in Fig. 22.23. It is slightly concave toward the x
axis.
The mass-transfer coefficients depend on the mass velocities, which are not
constant. The change in liquid rate is very small, and the liquid-film coefficient is
based on an average flow rate. The molecular weight of S02 is 64.1, and the average
mass velocity is
Gx = (322.8 x 18.02) + 1.689 x 64.1
2
= 5871 Ib/ft'-h
GAS ABSORPTION 727
The coefficient, assumed constant for the tower, is
k,a = 0.131 x 5871 0.82 = 161 molfft3-h
The gas-film coefficients are calculated for the bottom and top of the tower:
At bottom: G, = (6.9 x 29) + (1.724 x 64.1)
= 31O.6Ib/ft'-h
k,a = 0.025 x 310.6°·7 x 5871°·25
= 12.15 molfft 3-h
At top: G, = (6.9 x 29) + (0.035 x 64.1)
2
= 202.3 Ib/ft -h
k,a = 0.025 x 202.3°·7 x 5871°·25
= 9.0 mol/ft 3-h
The gas-film coefficients are only 6 to 8 percent as large as the liquid-film
coefficient, but the slope of the equilibrium line makes the two resistances comparable
in magnitude. Values of Yi are obtained by drawing lines of slope -k x a(l - y)dkyQ
from the operating line to the equilibrium line. This requires a preliminary estimate
of (1 - Y)L, but the lines are nearly parallel, and the first trial is usually accurate
enough. If ~ is assumed to be about 0.82 at the bottom,
k,an=YJ;: 161 x 0.82
10.87
k,a 12.15
A line from (vb, x b) with a slope of -10.9 gives y, = 0.164, and I - y, = 0.836.
The logarithmic mean of 0.80 and 0.836 is 0.818, very close to the estimated value.
From Eq. (22.43),
1 0.818 20.1
- = - - + - = 0.192
K;a 12.15 161
1
K;a = - - = 5.21 mol/ft 3-h
0.192
The fraction of the total resistance that is in the liquid is (20.1/161)/0.192 = 0.65,
or 65 percent.
Similar calculations are made for intermediate values of y, with the results
given in Table 22.2. The values of VIS are found from VIS = 6.896/(1 - y), and k,a
is calculated from the mass velocity. Note that VIS = GM' When Y > 0.05, slope m
is taken as 20.1; when y is <0.05, m = 15.6.
The column height is found as follows. From Eq. (22.45),
dZ = -;-:-_(':cV,-/S-,-)d-,-Y=-:- f'dy
(1 - y)(y - y*)K;a
Values of [' are calculated for several values of y and tabulated in Table 22.2. The
total height may be found by graphical integration of a plot of y vs. [" as shown by
the inset in Fig. 22.23, to give a total height ZT of 8.9 ft.
728 MASS TRANSFER AND ITS APPLICATIONS
TABLE 22.2
Integration for Example 22.6
V VIS
f'
y y-y* J'i (I - Y)L K~,a S (I - y)(y - y*)K;,a dZ
0.20 0.103 0.164 0.818 5.21 8.62 20,1
0,15 0.084 0.118 0.866 4.95 8.12 23.0 1.08
0.10 0.062 0.074 0.913 4.71 7.67 29.2 1.31
0.05 0.034 0.034 0.958 4.46 7.26 50.4 1.99
0.02 0.015 0.012 0.984 4.87 7.04 98.3 2.06
0.005 0.005 0.002 0.996 4.82 6.93 289.0 2.41
ZT = 8.85
Since the major resistance is in the liquid film, Eq. (22.49) can be used for a
rough check on the column height. The equation analogous to Eq. (22.43) is
1 1 (1 - y),.
-=-+---
K~a kxa mk)'Q
Hence
1 1 0.91
-=-+ = 1.04 x 10- 2
K:,a 161 20.1 x 11
K~a = 96.2 mol/ft 3 -h-unit mole-fraction difference
From Eq. (22.26),
322.8
H Ox = 96.2 = 3.36 ft
Ignoring the curvature of the equilibrium and operating lines,
0.00522
=--=3.0
0.00174
From Eq. (22.49),
ZT = 3.36 x 3.0 = 10.1 ft
ABSORPTION WITH CHEMICAL
REACTION
Absorption followed by reaction in the liquid phase is often used to get more
complete removal of a solute from a gas mixture. For example, a dilute acid
solution can be used to scrub NH3 from gas streams, and basic solutions
GAS ABSORPTION 729
are used to remove CO 2 and other acid gases. Reaction in the liquid phase
reduces the equilibrium partial pressure of the solute over the solution, which
greatly increases the driving force for mass transfer. If the reaction is essentially
irreversible at absorption conditions, the equilibrium partial pressure is zero, and
Nay can be calculated just from the change in gas composition. For y* = 0,
(22.50)
To illustrate the effect of a chemical reaction, consider the absorption
of NH, in dilute Hcr with a 300-fold reduction in gas concentration (6 to
0.02 percent). From Eq. (22.50), Nay = In 300 = 5.7, which can be compared
with Nay = 12 for the same change in concentration using water at the conditions
of Example 22.3.
A further advantage of absorption plus reaction is the increase in the
mass-transfer coefficient. Some of this increase comes from a greater effective
interfacial area, since absorption can now take place in the nearly stagnant
regions (static holdup) as well as in the dynamic liquid holdup. For NH,
absorption in H 2 S04 solutions, K,a was 1.5 to 2 times the value for absorption
in waterl7 Since the gas-film resistance is controlling, this effect must be due
mainly to an increase in effective area. The values of Kga for NH, absorption in
acid solutions were about the same as those for vaporization of water, where all
the interfacial area is also expected to be effective. The factors K,a"p/K,a,b, and
K,a,,,,,/Kga'b' decrease with increasing liquid rate and approach unity when the
total holdup is much larger than the static holdup.
The factor K,a"".(Kga'b' also depends on the concentration of reactant and
is smaller when only a slight excess of reagent is present in the solution fed to the
column. Data on liquid holdup and effective area have been published for Raschig
rings and Berl saddles, 16 but similar results for newer packings are not available.
When the liquid-film resistance is dominant, as in the absorption of CO 2 or
H 2 S in aqueous solutions, a rapid chemical reaction in the liquid can lead to a
very large increase in the mass-transfer coefficient. The coefficients shown in Fig.
22.21 for the CO 2 -H 2 0-NaOH system range from 1 to 4 molfft'-atm-h, compared
to typical values for CO 2 in water of 0.05 to 0.2 molfft'-atm-h. The rapid reaction
consumes much of the CO 2 very close to the gas-liquid interface, which makes
the gradient for CO 2 steeper and enhances the process of mass transfer in the
liquid. The ratio of the apparent value of kL to that for physical absorption defines
an enhancement factor 4>, which ranges from 1.0 to 1000 or more. Methods of
predicting 4> from kinetic and mass-transfer data are given in specialized texts 2 • 1 '
When the value of 4> is very large, the gas film may become the controlling
resistance.
When absorption is accompanied by a very slow reaction, the apparent
values of Kga may be lower than with absorption alone. An example is the
absorption of Cl 2 in water followed by hydrolysis of the dissolved chlorine. The
slow hydrolysis reaction essentially controls the overall rate of absorption.
GAS ABSORPTION 731
of both phases. It is even more difficult than in gas-liquid systems to separate
measured overall coefficients into individual coefficients, and generally only overall
coefficients K"" or Kya or the corresponding values of Hox or Hoy are reported.
The height of a transfer unit tends to be considerably greater in extraction
than for gas-liquid systems. With !-in. packings, values of 2 to 20 ft (0.6 to 6 m)
for Hoy are typical 23 for extraction of organics from water into low-viscosity
solvents. The relatively low mass-transfer rates are probably due to a combination
of only moderate interfacial area and low turbulence in the flowing liquids. If
several transfer units are needed, other types of extractors with mechanical energy
input are usually preferred.
DISTILLATION IN PACKED COLUMNS. A packed tower can be used as a
fractionating column for either continuous or batch distillation. The column height
is usually based on the number of theoretical plates and the height equivalent to
a theoretical plate (HETP). In most cases the upper operating line is slightly steeper
than the equilibrium line, and the reverse is true for the lower operating line, which
makes the average HETP about the same as H Oy. The 1!- or 2-in. sizes of the
common packings have about the same capacity as a sieve tray, and the packed
height equivalent to a theoretical plate HETP is generally in the range 1 to 2 ft.
(0.3 to 0.6 m.) The smaller packings have lower values of HETP, sometimes less
than 1.0 ft, but they also have lower capacity and are not likely to be used in a
large column. The pressure drop per equivalent theoretical plate is generally less
than that for a sieve or bubble-cap tray, which is an important advantage for
vacuum operation.
Packed distillation towers can often be operated over a moderate range of
flow rates at nearly constant separation efficiency. Data for isooctane-toluene
separation at total reflux are shown in Fig. 22.25. The three Intalox metal (IMTP)
packings numbered 25, 40, and 50 correspond to nominal sizes of 1, 1.5, and 2 in.,
respectively. As the capacity parameter increases, both the liquid rate and the
vapor rate increase, which explains why HETP is nearly constant. The gas film
has the controlling resistance to mass transfer, and Hoy increases with the 0.3 to
0.4 power of Gy, but this is offset by the decrease in Hoy with increasing Gx, as
shown in Fig. 22.20. The net effect is a nearly constant HTU or HETP over a
2- to 2.5-fold range of flows. The HETP decreases in the loading region because of
the more rapid increase in liquid holdup and wetted area, but HETP then increases
sharply as flooding is approached. With these high-capacity packings, the rise in
HETP is believed due to entrainment of the liquid. The recommended design
velocity for these packings is 20 percent less than the velocity at which HETP
starts to rise rapidly.
Structured sheet-metal packings give slightly better separation than dumped
packings, and the HETP values are nearly constant over a three- to fourfold range
of flow rates. Even more efficient are the gauze-type packings, with HETP values
that increase from about 3 to 6 in. (0.1 to 0.2 m) over a fourfold range of velocities.
The gauze is completely wetted even at low flow rates, and the HETP can be
predicted from fundamental equations for mass transfer in wetted channels. 1 There
732 MASS TRANSFER AND ITS APPLICATIONS
2.5
"a: I
p
>- 2.0 #50 size
w
:r: 0
#40 size
.... ~
1.5 0
#2 size
1 o~ Ll~
10
~
oS
1.5
•
•!Of
0
/~~
~~
ci:
e 1.0
1J'Ik
"~
~
ID
ID
~
0.5
/ ;'
IP"
L--::: ~ ~
i$-"V
a. <00.
>\<
0.05 0.1 0.15 0.2 0.25 0.03
Cs~Capacity factor, ftls
FIGURE 22.25
HETP and pressure drop in the distillation of isooctane and toluene in Intalox metal tower (IMTP)
packings.22
is no corresponding theory for other structured packings or for dumped packings,
because it is difficult to predict the wetted area. Low surface tension tends to
increase the wetted area, but too low values may lead to foaming, which increases
HETP.
SYMBOLS
A Absorption factor, L/m V
a Area of interface per unit packed volume, m 2 /m 3 or ft2/ft3; a,bp for
absorption; areact. for chemical reaction; a vap • for vaporization
C Mass concentration in liquid phase, gig, kg mOl/m 3, ppm, or lb
mOl/ft 3; CO' at liquid inlet; Cb' at liquid outlet; C*, liquid-phase
concentration in equilibrium with gas of composition y; C:, at
liquid inlet; ct, at liquid outlet
Molal heat capacity, cal/g mol-oC
Capacity factor, uoJ py/(Px - Py)
GAS ABSORPTION 733
Diameter of packing unit, mm or in.
Diffusivity, m 2!s, cm 2!s, or ft 2!h; D"X' in liquid; D"" in gas
Volume of gas fed to tower, m\ Fmin , minimum value
Packing factor for pressure drop
Relative mass-transfer coefficient (Table 22.1)
Factor (V!S)!(l - y)(y - y*)(K;a) in Example 22.6
Mass velocity based on total tower cross section, kg!m 2_h or
Ib!ft 2-h; Gx> of liquid stream; Ox> average value; G" of gas stream
Molal mass velocity, kg molfm 2-h or lb molfft2-h
Newton's-law proportionality factor, 32.174 ft-lb/lbrs2
Height of a transfer unit, m or ft; H G, alternate form of H ,; H L>
alternate form of H x; H Ox> overall, based on liquid phase; Ho"
overall, based on gas phase; H x> individual, based on liquid phase;
H y , individual, based on gas phase
HETP Height equivalent to a theoretical plate
Ka Overall volumetric mass-transfer coefficient, kg molfm'-h-unit mole
fraction or lb molfft'-h-unit mole fraction; Kxa, based on liquid
phase; K,a, based on gas phase; K~a, K;a, induding one-way diffu-
sion factors, for liquid and gas phases, respectively
Overall volumetric mass-transfer coefficient for liquid phase, based
on concentration difference, h- 1
Overall volumetric mass-transfer coefficient for gas phase, based on
partial-pressure driving force, kg molfm'-h-atm or lb molfft'-h-atm
Individual mass transfer for liquid phase, based on concentration
difference, mjh or ftjh
ka Individual volumetric mass-transfer coefficient, kg molfm'-h-unit
mole fraction or lb molfft'-h-unit mole fraction; kxa, for liquid
phase; kya, for gas phase
Individual volumetric mass-transfer coefficient for liquid phase,
based on concentration difference, h- 1
kga Individual volumetric mass-transfer coefficient for gas phase,
based on partial-pressure driving force, kg molfm'-h-atm or
lb molfft'-h-atm
L Molal flow rate of liquid, molfh; L., at liquid inlet; L b , at liquid
outlet; Lmin , minimum value
Molal mass velocity of liquid, kg molfm 2-h or lb molfft2-h
Molecular weight; M, average value
III Slope of equilibrium curve
N Number of transfer units; N G , alternate form of N y ; N L , alternate
form of N x; N Ox, overall, based on liquid phase; N Oy' overall,
based on gas phase; Nx> individual, liquid phase; N" individual,
gas phase
Mass-transfer flux of component A, kg molfm 2-s or lb molfft2-h
Schmidt number, J1!pD"
Exponent in Eq. (22.35)
734 MASS TRANSFER AND ITS APPLICATIONS
P Total pressure, atm; PA, vapor pressure of component A
PA Partial pressure of component A
Q Quantity of heat, cal; Q" heat of absorption; Q", Q,y, sensible
heat changes in liquid and gas, respectively; Q" heat of vaporization
r Rate of absorption per unit volume, kg moljm'-h or lb moljft'-h
S Cross-sectional area of tower, m 2 or ft2; also stripping factor, mVIL
T Temperature, °C or OF; 7;" at liquid inlet; 7;" at liquid outlet; 7;,
at intermediate point; Tmax , maximum_ value
Superficial gas velocity, based on empty tower, m/s or ft/s; "0,[' at
flooding
v Molal flow rate of gas, moljh; Ya, at outlet; ~, at inlet; Vmin , mini-
mum value
x Mole fraction of solute (component A) in liquid; Xa, at liquid inlet;
X b, at liquid outlet; Xi> at gas-liquid interface; X max , maximum
value; x', equilibrium concentration corresponding to gas-phase
composition Y; xt, in equilibrium with h
(1 - X)L One-way diffusion factor in liquid phase
Y Mole fraction of solute (component A) in gas; Ya, at gas outlet; h,
at gas inlet; y" at gas-liquid interface; y', equilibrium concentra-
tion corresponding to liquid-phase composition x; Y:
in equilib-
rium with xa; Y6, with Xb
(1 - Y)L One-way diffusion factor in gas phase
Z Vertical distance below top of packing, m or ft; ZT' total height of
packed section
Greek letters
a Constant in Eq. (22.35)
dC Concentration driving force, gig or ppm; dCa' at liquid inlet; dC b ,
at liquid outlet
dH Heat of solution, kcaljg mol; dH", heat of vaporization
dP Pressure drop, in. water/ft packing; dP"ood' at flooding
I1xL Logarithmic mean of X6 - Xb and x: - Xa
dYL Logarithmic mean of Yb - yt and Ya - Y:
e Porosity or void fraction in packed section
J1 Viscosity, cP or lb/ft-h; J1xo of liquid
P Density, kg/m' or lb/ft'; Pxo of liquid; P" of gas
PM Molar density, kg moljm' or lb moljft'; PMxo of liquid; PM" of gas
4> Enhancement factor in absorption with chemical reaction, dimen-
sionless
PROBLEMS
22.1. A plant design calls for an absorber that is to recover 95 percent of the acetone in
an air stream, using water as the absorbing liquid. The entering air contains 14 mole
percent acetone. The absorber has cooling and operates at 80°F and 1 atm and is
GAS ABSORPTION 735
to produce a product containing 7.0 mole percent acetone. The water fed to the
tower contains 0.02 mole percent acetone. The tower is to be designed to operate
at 50 percent of the flooding velocity. (a) How many pounds per hour of water must
be fed to the tower if the gas rate is 500 ft'lmin, measured at I atm and 32°F? (b)
How many transfer units are needed, based on the overall gas-phase driving force?
(e) !fthe tower is packed with I-in. Raschig rings, what should be the packed height?
For equilibrium Assume that PA = p~ YAX, where In YA = 1.95(1 - xf·
The vapor pressure of acetone at 80°F is 0.33 atm.
22.2. An absorber is to recover 99 percent of the ammonia in the. air-ammonia stream fed
to it, using water as the absorbing liquid. The ammonia content of the air is 20 mole
percent. Absorber temperature is to be kept at 30°C by cooling coils; the pressure
is 1 atm. (a) What is the minimum water rate? (b) For a water rate 40 percent greater
than the minimum, how many overall gas-phase transfer units are needed?
22.3. A soluble gas is absorbed in water using a packed tower. The equilibrium relationship
may be taken as Ye = 0.06xe' Terminal conditions are
Top Bottom
x o 0.08
y 0.001 0.009
If Hx = 0.24 m and H,. = 0.36 m, what is the height of the packed section?
22.4. How many ideal stages are required for the tower of Prob. 22.3?
22.5. A mixture of 5 percent butane and 95 percent air is fed to a sieve-plate absorber
containing eight ideal plates. The absorbing liquid is a heavy, nonvolatile oil having a
molecular weight of 250 and a specific gravity of 0.90. The absorption takes place at
1 atm and lYe. The butane is to be recovered to the extent of95 percent. The vapor
pressure of butane at 1YC is 1.92 atm, and liquid butane has a density of 580 kgjm 3
at 15°e. (a) Calculate the cubic meters of fresh absorbing oil per cubic meter of
butane recovered. (b) Repeat, on the assumption that the total pressure is 3 atm and
all other factors remain constant. Assume that Raoult's and Dalton's laws apply.
22.6. An absorption column is fed at the bottom with a gas containing 5 percent benzene
and 95 percent air. At the top of the column a nonvolatile absorption oil is
introduced, which contains 0.2 percent benzene by weight. Other data are as follows:
Feed, 2000 kg of absorption oil per hour
Total pressure, 1 atm
Temperature (constant), 26°C
Molecular weight of absorption oil, 230
Viscosity of absorbing oil, 4.0 cP
Vapor pressure of benzene at 26°C, 100 mm Hg
Volume of entering gas, 0.3 m 3 js
Tower packing, Intalox saddles, 1 in. nominal size
Fraction of entering benzene absorbed, 0.90
Mass velocity of entering gas, 1.1 kgjm 2 _s
Calculate the height and diameter of the packed section of this tower.
736 MASS TRANSFER AND ITS APPLICATIONS
22.7. A vapor stream containing 3.0 mole percent benzene is scrubbed with wash oil in
a packed absorber to reduce the benzene concentration in the gas to 0.02 percent.
The oil has an average molecular weight of about 250 and a density of 54.6 Ib/ft'
and contains 0.015 percent benzene. The gas flow is 1500 ft 3 jmin at 25°C and 1 atm.
(a) If the scrubber operates isothermally at 25°C with a liquid rate of 14,000 Ib/h, how
many transfer units are required? (b) If the scrubber operates adiabatically, how
many transfer units are needed? (c) What would be the major effect of operating
with an oil of lower molecular weight, say, M = 200?
22.8. An aqueous waste stream containing 1.0 weight percent NH3 is to be stripped with
air in a packed column to remove 99 percent of the NH 3 • What is the minimum air
rate, in kilograms of air per kilogram of water, if the column operates at 20°C?
How many transfer units are required at twice the minimum air rate?
22.9. An 8-ft-diameter column packed with 20 ft of I-in. BerI saddles has air at 1.5 atm
and 40°C flowing through it. The tower is apparently clo~e to flooding, since
I1p ~ 24 in. of water. The mass velocity of the liquid is 8.5 times that of the gas. (a)
If the tower were repacked with It-in. Intalox saddles, what would the pressure
drop be? (b) How much higher flow rates could be used if the pressure drop were
the same as it was with the Berl saddles?
22.10. An absorber is to remove 99 percent of solute A from a gas stream containing 4
mole percent A. Solutions of A in the solvent follow Henry's law, and the temperature
rise of the liquid can be neglected. (a) Calculate No), for operation at 1 atm using
solute-free liquid at a rate of 1.5 times the minimum value. (b) For the same liquid
rate, calculate Noy for operation at 2 atm and at 4 atm. (c) Would the effect of
pressure on Nay be partly offset by a change in Hay?
22.11. A gas containing 2 percent A and 1 percent B is to be scrubbed with a solvent in
which A is five times as soluble as B. Show that using two columns in series with
separate regeneration of the liquid from each column would permit recovery of A
and B in relatively pure form. Use a y-x diagram to show the equilibrium and
operating lines for the simultaneous absorption of A and B and estimate the ratio
of A and B in the liquid from the first absorber.
22.12. A packed column is used to reCover acrylic acid and acetic acid from a dilute gas
stream by absorption in water. For low concentrations acrylic acid is about two
times as soluble in water as acetic acid. (a) If the column is designed for 99.9 percent
recovery of acrylic acid with an absorption factor A = 1.5, how many transfer units
are needed? (b) What is the percent recovery of acetic acid?
22.13. (a) For benzene-toluene distillation in a column packed with 1.5-in. metal Pall rings,
estimate Ho), at the top of the column based on the feed and product compositions
of Example 18.2. (b) What fraction of the mass-transfer resistance is in the gas phase?
22.14. An absorber packed with l-in. Intalox saddles operates at 50°C and 10 atm with a
liquid mass velocity five times the gas mass velocity. Assuming the gas and liquid
are similar to air and water, what gas mass velocity will give a pressure drop of
0.5 in. H 2 0jft packing? Use the generalized correlations to get the effect of changed
physical properties, and apply a correction to the data of Fig. 22.4.
REFERENCES
1. Bravo, J. L., 1. A. Rocha. and J. R. Fair: Hydrocarbon Proc., 64(1): 91 (1985).
2. Danckwerts. P. V.: Gas-Liquid Reactions, McGraw-Hill. New York, 1970.
3. Eckert, J. S.: Chem. Eng. Prog., 66(3): 39 (1970).
GAS ABSORPTION 737
4. Fair, 1. F., and 1. L. Bravo: Chem. Eng. Prog., 86(1): 19 (1990).
5. Gmehling, 1., U. Onken, and W. Arlt: VaporMLiqllid Equilibria Data Collection, vol. 1, Dechema,
Frankfurt/Main. 1979.
6. Harriott, P.: Enviroll. Sci. Tech., 23:309 (1989).
7. Kister, H. Z., and D. R. Gill: Chem. Eng. Prog., 87(2):32 (1991).
8. Lincoff, A. H., and 1. M. Gossett: Imernational Symposium 011 Gas Transfer at Water Surfaces,
Cornell University, Ithaca, New York, June 1983.
9. Norton Chemical Process Products Division, Akron, Ohio, 1987.
10. O'Connell, H. E.: Trans. AIChE, 42:741 (1946).
11. Perry, D., D. E. Nutter, and A. Hale: Chem. Ellg. Prog., 86(1):30 (1990).
12. Perry, J. H.: Chemical Engineers' Handbook, 6th ed., McGrawMHill, New York, 1984, (a) p. 3-101,
(b) p. 18-23, (c) p. 18-39.
13. Robbins, L. A.: Chem. Eng. Prog., 87(5):87 (1991).
14. Sherwood, T. K., and F. A. L. Holloway: TraIlS. AICltE. 36:21, 39 (1940).
15. Sherwood, T. K., R. L. Pigford, and C. R. Wilke: Mass Transfer, McGrawMHiII, New York, 1975,
p.442.
16. Shulman, H. L., C. F. Ullrich, A. Z. Proulx, and J. O. Zimmennan: A[ChE J., 1 :253 (1955).
17. Shulman, H. L., C. F. Ullrich, and N. Wells: AIChE J., 1:247 (1955).
18. Sperandio, A., M. Richard, and M. Huber: Chem. [ng. Tech., 37:322 (1965).
19. SpiegeJ, L., and W. Meier: I. Chem. E. Symp. Ser., I04:A203 (1987).
20. Stedman, D. F.: Trails. A[ChE, 33: 153 (1937).
21. Strigle, R. F., Jr.: Random Packillgs and Packed Towers, Gulf Publishing, Houston, 1987.
22. Strigie, R. F., Jr., and F. Rukovena, Jr.: ClIent. Eng. Prog., 75(3):86 (1979).
23. TreybaJ, R. E.: Mass Transfer Operations, 2nd ed., McGrawMHiII, New York, 1968, p. 481.
24. VonStockar, U., and C. R. Wilke: 11Id. Eng. Cilem. Fund., 16:88,94 (1977).
25. Whitney, R. P., and 1. E. Vivian: Chem. Ellg. Prog., 45:323 (1949).
CHAPTER
23
HUMIDIFICATION
OPERATIONS
Humidification and dehumidification involve the transfer of material between a
pure liquid phase and a fixed gas that is insoluble in the liquid. These operations
are somewhat simpler than those for absorption and stripping, for when the liquid
contains only one component, there are no concentration gradients and no
resistance to transfer in the liquid phase. On the other hand, both heat transfer
and mass transfer are important and influence one another. In previous chapters
they have been treated separately; here and in drying of solids (discussed in Chap.
24) they occur together, and concentration and temperature change simul-
taneously.
DEFINITIONS. In humidification operations, especially as applied to the system
air-water, a number of rather special definitions are in common use. The usual
basis for engineering calculations is a unit mass of vapor-free gas, where vapor
means the gaseous form of the component that is also present as liquid and gas
is the component present only in gaseous form. In this discussion a basis of a unit
mass of vapor-free gas is used. In the gas phase the vapor will be referred to as
component A and the fixed gas as component B. Because the properties of a
gas-vapor mixture vary with total pressure, the pressure must be fixed. Unless
otherwise specified, a total pressure of 1 atm is assumed. Also, it is assumed that
mixtures of gas and vapor follow the ideal-gas laws.
Humidity !If' is the mass of vapor carried by a unit mass of vapor-free gas.
So defined, humidity depends only on the partial pressure of the vapor in the
mixture when the total pressure is fixed. If the partial pressure of the vapor is
738
HUMIDIFICATION OPERATIONS 739
PA atm, the molal ratio of vapor to gas at 1 atm is PAI(l - PAl. The humidity is
therefore
(23.1)
where M A and MB are the molecular weights of components A and E, respectively.
The humidity is related to the mole fraction in the gas phase by the equation
:It'IMA
(23.2)
y = 11M. + Y{'IM,
Since :It'IMA is usually small compared with 11MB , y may often be considered to
be directly proportional to :It'.
Saturated gas is gas in which the vapor is in equilibrium with the liquid at
the gas temperature. The partial pressure of vapor in saturated gas equals the
vapor pressure of the liquid at the gas temperature. If£; is the saturation humidity
and P~ the vapor pressure of the liquid,
MP'
Yt:= A A (23.3)
, M B(1 - P~)
Relative humidity :It'R is defined as the ratio of the partial pressure of the
vapor to the vapor pressure of the liquid at the gas temperature. It is usually
expressed on a percentage basis, so 100 percent humidity meanS saturated gas and
o percent humidity means vapor-free gas. By definition
yt:R = 100 PA (23.4)
P'A
Percentage humidity Y{'A is the ratio of the actual humidity Y{, to the
saturation humidity £; at the gas temperature, also on a percentage basis, or
Y{, P 1(1 - P ) 1 - P'A
:It'A = 100- = 100 A A = Y{'R-- (23.5)
£; P~/(l - P~) 1 - PA
At all humidities other than 0 or 100 percent, the percentage humidity is less
than the relative humidity.
Humid heat c, is the heat energy necessary to increase the temperature of
1 g or lIb of gas plus whatever vapor it may contain by 1°C or 1of. Thus
c, = cp' + cpAY{' (23.6)
where cp, and cpA are the specific heats of gas and vapor, respectively.
Humid volume Vll is the total volume of a unit mass of vapor-free gas plus
whatever vapor it may contain at 1 atm and the gas temperature. From the gas
laws, V H in fps units is related to humidity and temperatures by the equation
359T ( 1 :It')
Vll = 492 M. + MA (23.7a)
740 MASS TRANSFER AND ITS APPLICATIONS
where Tis the absolute temperature in degrees Rankine. In SI units the equation is
0.0224 T (_1_ .YE)
+ (23.7b)
273 MB MA
where vH is in cubic meters per gram and T is in Kelvins. For vapor-free gas
.Yf = 0, and Vj{ is the specific volume of the fixed gas. For saturated gas .Yf = Jf';,
and VH becomes the saturated volume.
Dew point is the temperature to which a vapor-gas mixture must be cooled
(at constant humidity) to become saturated. The dew point of a saturated gas
phase equals the gas temperature.
Total enthaipy Hy is the enthalpy of a unit mass of gas plus whatever vapor
it may contain. To calculate H y , two reference states must be chosen, one for gas
and one for vapor. Let To be the datum temperature chosen for both components,
and base the enthalpy of component A on liquid A at To. Let the temperature of
the gas be T and the humidity .Yf. The total enthalpy is the sum of three items;
the sensible heat of the vapor, the latent heat of the liquid at To, and the sensible
heat of the vapor-free gas. Then
(23.8)
where 20 is the latent heat of the liquid at To. From Eq. (23.6) this becomes
By = c,(T - To) + .Yf,lo (23.9)
PHASE EQUlLIBRIA. In humidification and dehumidification operations the
liquid phase is a single pure component. The equilibrium partial pressure of solute
in the gas phase is therefore a unique function of temperature when the total
pressure on the system is held constant. Also, at moderate pressures the equilib-
rium partial pressure is almost independent of total pressure and is virtually equal
to the vapor pressure of the liquid. By Dalton's law the equilibrium partial pressure
may be converted to the equilibrium mole fraction Ye in the gas phase. Since the
liquid is pure, Xe is always unity. Equilibrium data are often presented as plots of
Ye vs. temperature at a given total pressure, as shown for the system air-water at
1 atm in Fig. 23.1. The equilibrium mole fraction Ye is related to the saturation
humidity by Eq. (23.2); thus
(23.10)
ADIABATIC SATURATOR. Water is often sprayed into a stream of gas in a pipe
or spray chamber to bring the gas to saturation. The pipe or chamber is insulated
so that the process is adiabatic. The gas, with an initial humidity .Yf and
temperature T, is cooled and humidified. If not all the water evaporates and there
is sufficient time for the gas to come to equilibrium with the water, the exit
HUMIDIFICATION OPERATIONS 741
0.20
0.18
0",0.16
I1
:r:
i5 0.14
E 0.12 I1
<l
[ 0.10 J
V
':l 0.08
o
::;; 0.06
V
V
~0.04
0.02
.v-
I-'
0
50 7.0 90 110 130 FIGURE 23.1
TEMPERATURE, 'F Equilibria for the system air-water at 1 atm.
temperature of the gas is called the adiabatic saturation temperature, T,. The
rerr,aining liquid is also at T, and can be recirculated to the spray nozzles. The
value of T, depends on the temperature and initial humidity of the air and to a
minor extent on the initial water temperature. To simplify the analysis, the water
is often assumed to enter at T,.
An enthalpy balance can be written over this process. Pump work is
neglected, and the enthalpy balance is based on temperature T, as a datum. Then
the enthalpy of the makeup liquid is zero, and the total enthalpy of the entering
gas equals that of the leaving gas. Since the latter is at"datum temperature, its
enthalpy is simply £;.Ie" where £; is the saturation huriridity and }" is the latent
heat, both at T,. From Eq. (23.9) the total enthalpy of the entering gas is
e,(T - T,) + Ji'.Ie" and the enthalpy balance is
e,(T - T,) + .;rn, = £;.Ie,
or
:Yf - .n=: = _ S= _ cp » + cpA .1f (23.11)
T - T, },' }"
To find the adiabatic saturation temperature for gases other than air, a heat
balance similar to Eq. (23.11) is used. It may be more convenient, however, to use.
molar heat capacities, as in the following example.
Example 23.1. Flue gas at 320'F and 1 atm is to be cooled by a water spray. The
gas contains 14 percent CO" 7 percent H2 0, 3 percent 0" and 76 percent N2 • (a)
Calculate the adiabatic saturation temperature if the water spray enters at 80°F. (b)
Repeat for water entering at 7;.
742 MASS TRANSFER AND ITS APPLICATIONS
Soilltioll
(a) Basis 100 mol of gas. Guess that 7; is about 120"F and evaluate the
molar heat capacity Cp for each gas at (320 + 120)/2 = 220"F.
Number of Molar specific
Gas moles, n heat, Cp ne p
CO, 14 9.72 136.08
H,O 7 8.11 56.77
0, 3 7.14 21.42
N, 76 6.98 530.48
~> = 100 I nCp = 744.75
Make a heat balance for z moles of water evaporated:
2: nC.(T - 7;) = zi., + 18z(120 - 80)
= z(i., + 720)
At 120"F, from Appendix 7,
i., = 1025.8 x 18 = 18,464 Btujlb mol
Then 744.75(320 - 120) = z(18,464 + 720) = 19,184z
z = 7.76
Total moles of water in exit gas: 7 + 7.76 = 14.76
Partial pr,essure of water in exit gas:
PH,o = (14.76/107.76) x 760 = 104.1 mm Hg
But at 120°F, P~20 = 87.5 mm Hg (Appendix 7). Saturation temperature 1's must
be greater than 120"F. Try 7; = 126"F. Then P~,o = 103.2 mm Hg and i., =
1022.3 x 18 = 18,401 Btujlb mol. Neglecting any changes in Cp:
744.75(320 - 126) = z[18,401 + 18(126 - 80)] = 19,229z
z = 7.51
Total moles of water: 7 + 7.51 = 14.51.
PH,o = (14.51/107.51) x 760 = 102.6 mm Hg
This is close enough to the value of PH20 . Here 1's = 126°F.
(b) The last term of the heat balance is dropped if 1io = 7;. For 7; = 126"F,
744.75(320 - 126) = z(18,401)
z = 7.ji5
PH,o = (14.85/107.85) x 760 = 104.6 mm Hg
HUMIDIFICATION OPERATIONS 743
This is higher than the vapor pressure of water at ,126°F, 103.2 mm Hg, and
1; > 126'F. Try 127'F, for which p~,o = 106.0 mm Hg and )" = 18 x 1021.7 =
18,391 Btujlb mol:
Z = 744.75(320 - 127) = 7.82
18,391
PH,o = (14.82/107.82) x 760 = 104.5 mm Hg
Thus 127'F is too high and 126'F is too low. Hence 1; ~ 126.5'F.
Note that changing the inlet temperature of the water has a very sroan effect
on the adiabatic saturation temperature.
HUMIDITY CHART. A convenient diagram showing the properties of mixtures of
a permanent gas and a condensable vapor is the humidity chart. A chart for
mixtures of air and water at 1 atm is shown in Fig. 23.2. Many forms of such
charts have been proposed. Figure 23.2 is based on the Grosvenor 3 chart.
On Fig. 23.2 temperatures are plotted as abscissas and humidities as
ordinates. Any point On the chart represents a definite mixture of air and water.
The curved line marked 100 percent gives the humidity of saturated air as a
function of air temperature. By using the vapor pressure of water, the coordinates
of points on this line are found from Eq. (23.3). Any point above and to the left
of the saturation line represents a mixture of saturated air and liquid water. This
region is important only in checking fog formation. Any point below the saturation
line represents undersaturated air, and a point on the temperature axis represents
dry air. The curved lines between the saturation line and the temperature axis
marked in even percents represent mixtures of air and water of definite percentage
humidities. As shown by Eq. (23.5), linear interpolation between the saturation
line and the temperature axis can be used to locate the lines of constant percentage
humidity.
The slanting lines running downward and to the right of the saturation line
are called adiabatic-cooling lines. They are plots of Eq. (23.11), each drawn for a
given constant value of the adiabatic-saturation temperature. For a given value
of T" both H, and A, are fixed, and the line of:Yt' vs. T can be plotted by assigning
values to :Yt' and calculating corresponding values of T. Inspection of Eq. (23.11)
shows that the slope of an adiabatic-cooling line, if drawn on truly rectangular
coordinates, is -c,jA" and by Eq. (23.6), this slope depends On the humidity. On
rectangular coordinates, then, the adiabatic-cooling lines are neither straight nor
parallel. In Fig. 23.2 the ordinates are sufficiently distorted to straighten the
adiabatics and render them parallel, so interpolation between them is easy. The
ends of the adiabatics are identified with the corresponding adiabatic-saturation
temperatures.
Lines are shown on Fig. 23.2 for the specific volume of dry air and the
saturated volume. Both lines are plots of volume against temperature. Volumes
are read On the scale at the left. Coordinates of points on these lines are calculated
by use of Eq. (23.7a). Linear interpolation between the two lines, based on
percentage humidity, gives the humid volume of unsaturated air. Also, the relation
t
~ ~v mlmmmllilmllifiimlllll~IlIII!IIll!llilll!IIlUlllliljjlftp.~~;mlllll!lilllmlml1~I~jj!!l!flelm!:~I.rtl:~m"llIiili1l!illlHrtl&nlilillllllmll!l!i~u!lll. V.'4 ~
er
0
CO
-'
er
w
C>-
o-'
le
:::>
0
W
:;;
:::>
-'
0
>
TEMPERATURE. DEGREES FAHRENHEIT
FIGURE 23.2
Humidity chart. Air~water at I atm.
HUMIDIFICATION OPERATIONS 745
between the humid heat c, and humidity is shown as a line on Fig. 23.2. This
line is a plot of Eq. (23.6). The scale for c, is at the top of the chart.
USE OF HUMIDITY CHART. The usefulness of the humidity chart as a source of
data on a definite air-water mixture can be shown by reference to Fig. 23.3, which
is a portion of the chart of Fig. 23.2. Assume, for example, that a given stream of
undersaturated air is known to have a temperature T, and a percentage humidity
.Yt'A" Point a represents this air on the chart. This point is the intersection of the
constant-temperature line for T, and the constant-percentage-humidity line for
Jf'A" The humidity .Yt', of the air is given by point b, the humidity coordinate of
point a. The dew point is found by following the constant-humidity line through
point a to the left to point c on the 100 percent line. The dew point is then read
at point d on the temperature axis. The adiabatic-saturation temperature is the
temperature applying to the adiabatic-cooling line through point a. The humidity
at adiabatic saturation is found by following the adiabatic line through point a
to its intersection e on the 100 percent line and reading humidity .n'; at point f
HUMID HEAT
,s
P:C
,,
,,
,,
,
,,,
,, ,
w :
:;;; n_________ '1_ _ _ _ _ _ _ _
::J
~ vH
,,! ,/
,,, >-
!:::
Saturated vOluhle
vs. temperature ,
,,
Cl
~
:;:)
,, I
,:~/%
e
~;::..-_- -- -- '
-- --:--- f df
--- ---------- --------- s
1 ---__ 1 b
't----------:..:":-"::.. df,
,, ,10-----------------------
,
,, ,,''
,
, '
:759 :7j
TEMPERATURE
FIGURE 23.3
Use of humidity chart.
746 MASS TRANSFER AND ITS APPLICATIONS
on the humidity scale. Interpolation between the adiabatic lines may be necessary.
The adiabatic-saturation temperature T, is given by point g. If the original air is
subsequently saturated at constant temperature, the humidity after saturation is
found by following the constant-temperature line through point a to point h on
the 100 percent line and reading the humidity at point j.
The humid volume of the original air is found by locating points k and Ion
the curves for saturated and dry volumes, respectively, corresponding to tempera-
ture Tt. Point 111 is then found by moving along line Ik a distance (£A/lOO)kl
from point I, where kl is the line segment between points 1 and k. The humid
volume VH is given by point n on the volume scale. The humid heat of the air is
found by locating point 0, the intersection of the constant-humidity line through
point a and the humid-heat line, and reading the humid heat c, at point p on the
scale at the top.
Example 23.2. The temperature and dew point of the air entering a certain dryer are
150 and 60°F (65.6 and 15.6°C), respectively. What additional data for this air can
be read from the humidity chart?
Solution
The dew point is the temperature coordinate on the saturation line corresponding
to the humidity of the air. The saturation humidity for a temperature of 60°F is
0.011 Ib of water per pound (0.011 gig) of dry air, and this is the humidity of the air.
From the temperature and humidity of the air, the point on the chart for this air is
located. At .Yt = 0.011 and T = 150°F, the percentage humidity .YtA is found by
interpolation to be 5.2 percent. The adiabatic~cooling line through this point
intersects the 100 percent line at 85°F (29.4°C), and this is the adiabatic-saturation
temperature. The humidity of saturated air at this temperature is 0.026 lb of water
per pound (0.026 gig) of dry air. The humid heat of the air is 0.245 Btu/lb dry air-oF
(1.03 J/g_°C). The saturated volume at 150°F is 20.7 ft'/lb (1.29 m'/kg) of dry air, and
the specific volume of dry air at 150°F is 15.35 ft'/lb (0.958 m'/kg). The humid volume
is, then,
Vn = 15.35 + 0.052(20.7 - 15.35) = 15.63 ft'/lb dry air (0.978 m'/kg)
HUMIDITY CHARTS FOR SYSTEMS OTHER THAN AIR-WATER. A humid-
ity chart may be constructed for any system at any desired total pressure.
The data required are the vapor pressure and latent heat of vaporization of
the condensable component as a function of temperature, the specific heats
of pure gas and vapor, and the molecular weights of both components. If a
chart on a mole basis is desired, all equations can easily be modified to the
use of molal units. If a chart at a pressure other than I atm is wanted, obvious
modifications in the above equations may be made. Charts for several common
systems besides air-water have been published. 7
HUMIDIFICATION OPERATIONS 747
WET-BULB TEMPERATURE AND
MEASUREMENT OF HUMIDITY
The properties discussed above and those shown on the humidity charts are
static or equilibrium quantities. Equally important are the rates at which mass
and heat are transferred between gas and liquid not in equilibrium. A useful
quantity depending on both of these rates is the wet-bulb temperature.
WET-BULB TEMPERATURE. The wet-bulb temperature is the steady-state, non-
equilibrium temperature reached by a small mass of liquid immersed under
adiabatic conditions in a continuous stream of gas. The mass of the liquid is so
small in comparison with the gas phase that there is only a negligible change in
the properties of the gas, and the effect of the process is confined to the liquid.
The method of measuring the wet-bulb temperature is shown in Fig. 23.4. A
thermometer, or an equivalent temperature-measuring device such as a thermo-
couple, is covered by a wick, which is saturated with pure liquid and immersed
in a stream of gas having a definite temperature T and humidity ye. Assume that
initially the temperature of the liquid is about that of the gas. Since the gas is not
saturated, liquid evaporates, and because the process is adiabatic, the latent heat
is supplied at first by cooling the liquid. As the temperature of the liquid decreases
below that of the gas, sensible heat is transferred to the liquid. Ultimately a steady
Irf----· Tw
Gos • - - -.... Gos
Temperature T
Humidify d!-
•
•
•
•
--_.
- - -...
) Temperature T
•
•
Humid,fYd!-
•
FIGURE 23.4
Wet-bulb thennometer.
748 MASS TRANSFER AND ITS APPLICATIONS
state is reached at such a liquid temperature that the heat needed to evaporate
the liquid and heat the vapor to gas temperature is exactly balanced by the sensible
heat flowing from the gas to the liquid. It is this steady-state temperature, denoted
by 7;" that is called the wet-bulb temperature. It is a function of both T and .YE.
To measure the wet-bulb temperature with precision, three precautions are
necessary: (1) the wick must be completely wet so no dry areas of the wick are in
contact with the gas; (2) the velocity of the gas should be large enough to ensure
that the rate of heat flow by radiation from warmer surroundings to the bulb is
negligible in comparison with the rate of sensible heat flow by conduction and
convection from the gas to the bulb; (3) if makeup liquid is supplied to the bulb,
it should be at the wet-bulb temperature. When these precautions are taken, the
wet-bulb temperature is independent of gas velocity over a wide range of flow rateS.
The wet-bulb temperature superficially resembles the adiabatic-saturation
temperature T,. Indeed, for air-water mixtures the two temperatures are nearly
equal. This is fortuitous, however, and is not true of mixtures other than air and
water. The wet-bulb temperature differs fundamentally from the adiabatic-satura-
tion temperature. The temperature and humidity of the gas vary during adiabatic
saturation, and the end point is a true equilibrium rather than a dynamic steady
state.
Commonly, an uncovered thermometer is used along with the wet bulb to
measure T, the actual gas temperature, and the gas temperature is usually called
the dry-bulb temperature.
THEORY OF WET-BULB TEMPERATURE. At the wet-bulb temperature the rate
of heat transfer from the gas to the liquid may be equated to the product of the
rate of vaporization and the sum of the latent heat of evaporation and the sensible
heat of the vapor. Since radiation may be neglected, this balance may be written
q = MAN A[A" + cpA(T - 7;,)] (23.12)
where q = rate of sensible heat transfer to liquid
N A = molal rate of vaporization
A" = latent heat of liquid at wet-bulb temperature 7;,
The rate of heat tranfer may be expressed in terms of the area, the
temperature drop, and the heat-transfer coefficient in the usual way, or
q = hiT - T,)A (23.13)
where h, = heat-transfer coefficient between gas and surface of liquid
T, = temperature at interface
A = surface area of liquid
The rate of mass transfer may be expressed in terms of the mass-transfer
coefficient, the area, and the driving force in mole fraction of vapor, or
k,
NA = (y, - y)A (23.14)
(1 - y)L
HUMIDIFICATION OPERATIONS 749
where N A = molal rate of transfer of vapor
y, = mole fraction of vapor at interface
y = mole fraction of vapor in airstream
k, = mass-transfer coefficient, mole per unit area per unit mole fraction
~(I~_-y""",)LL = one-way diffusion factor
If the wick is completely wet and no dry spots show, the entire area of the
wick is available for both heat and mass transfer and the areas in Eqs. (23.13) and
(23.14) are equal. Since the temperature of the liquid is constant, no temperature
gradients are necessary in the liquid to act as driving forces for heat transfer within
the liquid, the surface of the liquid is at the same temperature as the interior, and
the surface temperature of the liquid T; equals T". Since the liquid is pure, no
concentration gradients exist, and granting interfacial equilibrium, y, is the mole
fraction of vapor in saturated gas at temperature T". It is convenient to replace
the mole-fraction terms in Eq. (23.14) by humidities through the use of Eq. (23.2),
noting that y, corresponds to £;" the saturation humidity at the wet-bulb
temperature. [See Eq. (23.10).] Following this by substituting q from Eq. (23.13)
and NA from Eq. (23.14) into Eq. (23.12) gives
hiT- T" ) =~~
ky( £;,
(1 y)L I/M B + .!If',,/MA
YE )
- I/MB + YE/MA [Aw + cpi T - T,,)] (23.15)
Equation (23.15) may be simplified without serious error in the usual range of
temperatures and humidities as follows: (1) the factor (1 - Y)L is nearly unity and
can be omitted; (2) the sensible-heat item cPA(T - T,,l is small in comparison with
A" and can be neglected; (3) the terms £;,/MA and YE/MA are small in comparison
with I/MB and may be dropped from the denominators of the humidity terms.
With these simplifications Eq. (23.15) becomes
or
(23.16)
For a given wet-bulb temperature, both Aw and .n"w are fixed. The relation
between .n" and T then depends on the ratio hy/k,. The close analogy between
mass transfer and heat transfer provides considerable information on the magni-
tude of this ratio and the factors that affect it.
It has been shown in Chap. 12 that heat transfer by conduction and
convection between a stream of fluid and a solid or liquid boundary depends on
the Reynolds number DG//1 and the Prandtl number cp /1/k. Also, as shown in
Chap. 21, the mass-transfer coefficient depends on the Reynolds number and the
Schmidt number WPD,. As discussed in Chap. 21, the rates of heat and mass
750 MASS TRANSFER AND ITS APPLICATIONS
transfer, when these processes are under the control of the same boundary layer,
are given by equations that are identical in form. For turbulent flow of the gas
stream these equations are
h
-y =bN"Re N-m
Pr (23.17)
Cp G
and
Mk, = bN" N-m (23.18)
G Rc Se
where b, n, In = constants
M = average molecular weight of gas stream
Substitution of hy from Eq. (23.17) and k, from Eq. (23.18) in Eq. (23.16),
assuming M = M B, gives
(23.19)
and
h, (Ns,)m (23.20)
MBky = cp N Pr
Ifin is taken as t, the predicted value of iz,/M.k, for air in water is 0.24
(0.62/0.71)2/3, or 0.22 Btu/lb-'F (0.92 J/g-'C). The experimental value' is 0.26
Btu/lb'F (1.09 J/g-'C), somewhat larger than predicted, because of heat transfer
by radiation. For organic liquids in air it is larger, in the range 0.4 to 0.5 Btuflb-'F
(1.6 to 2.0 J /g- 'c). The difference, as shown by Eq. (23.20), is the result of the
differing ratios of Prandtl and Schmidt numbers for water and for organic vapors.
PSYCHROMETRIC LINE AND LEWIS RELATION. For a given wet-bulb tempera-
ture, Eq. (23.19) can be plotted on the humidity chart as a straight line having a
slope of -hy/M",c,?" and intersecting the 100 percent line at 7;,. This line is
called the psychrometric line. When both a psychrometric line, from Eq. (23.19),
and an adiabatic-saturation line, from Eq. (23.11), are plotted for the same point
on the 100 percent curve, the relation between the lines depends on the relative
magnitudes of c, and hy/Mnky.
For the system air-water at ordinary conditions the humid heat c, is almost
equal to the specific heat cP' and the following equation is nearly correct:
hy
--:;;:;:cs (23.21)
M.ky
Equation (23.21) is known as the Lewis relation. 5 When this relation holds,
the psychrometric line and the adiabatic-saturation line becomes essentially the
same. In Fig. 23.2 for air-water, therefore, the same line may be used for both.
HUMIDIFICATION OPERATIONS 751
For other systems separate lines must be used for psychrometric lines. With nearly
all mixtures of air and organic vapors the psychrometric lines are steeper than the
adiabatic-saturation lines, and the wet-bulb temperature of any mixture other than
a saturated one is higher than the adiabatic-saturation temperature.
MEASUREMENT OF HUMIDITY. The humidit:y of a stream or mass of gas may
be found by measuring either the dew point or the wet-bulb temperature or by
direct-absorption methods.
Dew-point methods. If a cooled, polished disk is inserted into gas of unknown
humidity and the temperature of the disk gradually lowered, the disk reaches a
temperature at which mist condenses on the polished surface. The temperature at
which this mist just forms is the temperature of equilibrium between the vapor in
the gas and the liquid phase. It is therefore the dew point. A check on the reading
is obtained by slowly increasing the disk temperature and noting the temperature
at which the mist just disappears. From the average of the temperatures of mist
formation and disappearance, the humidity can be read from a humidity chart.
Psychometric methods. A very common method of measuring the humidity is to
determine simultaneously the wet-bulb and dry-bulb temperatures. From these
readings the humidity is found by locating the psychrometric line intersecting the
saturation line at the observed wet-bulb temperature and following the psychro-
metric line to its intersection with the ordinate of the observed dry-bulb temper-
ature.
Direct methods. The vapor content of a gas can be determined by direct analysis,
in which a known volume of gas is drawn through an appropriate analytical device.
EQUIPMENT FOR HUMIDIFICATION
OPERATIONS
When warm liquid is brought into contact with unsaturated gas, part of the liquid
is vaporized and the liquid temperature drops. This cooling of the liquid is the
purpose behind many gas-liquid contact operations, especially air-water contacts.
Water is cooled in large quantities in spray ponds or more commonly in tall towers
through which air passes by natural draft or by the action of a fan.
A typical forced-draft cooling tower is shown in Fig. 23.5. The purpose of a
cooling tower is to conserve cooling water by allowing the cooled water to be
reused many times. Warm water, usually from a condenser or other heat-transfer
unit, is admitted to the top of the tower and distributed by troughs and overflows
to cascade down over slat gratings, which provide large areas of contact between
air and water. The air is sent upward through the tower by the fan.
A cooling tower is, in principle, a special kind of packed tower. In older
towers the packing consisted of redwood slats on which drops of water impinged.
Such packing has now been largely replaced by cellular fill or, in tall towers with
752 MASS TRANSFER AND ITS APPLICATIONS
Air
Drift eliminators
Hot Nozzles
water
1I
Fan
Air
Basin Cold
water
FIGURE 235
Forced-draft cooling tower.
crossflow of the air, by V-shaped bars of polyvinyl chloride.' Cellular fill consists
of corrugated plastic plates with ridges set at an angle, much like the structured
packings described in Chap. 22. In the tower, part of the water evaporates into
the air, and sensible heat is transferred from the warm water to the cooler air.
Both processes reduce the temperature of the water. Only makeup water, to replace
that lost by evaporation and windage loss, is required to maintain the water
balance.
The driving force for evaporation is, very nearly, the difference between the
vapor pressure of the water and the vapor pressure it would have at the wet-bulb
temperature of the air. Obviously the water cannot be cooled to below the wet-bulb
temperature. In practice the discharge temperature of the water must differ from
the wet-bulb temperature by at least 4 or 5°F. This difference in temperature is
known as the approach. The change in temperature in the water from inlet to
outlet is known as the range. Thus if water were cooled from 95 to 80°F by
exposure to air with a wet-bulb temperature of 70°F, the range would be 15°F
and the approach 10°F.
If water from a cooling tower is to be used for process cooling, the design
of the cooling equipment must be based on the maximum expected temperature
of the cooling water. This in turn depends, not on the maximum dry-bulb
temperature of the air, but on the maximum wet-bulb temperature for that
particular locality. Tables of maximum wet-bulb temperatures have been published
for various points in the United States and other parts of the world. 6
The loss of water by evaporation during cooling is small. Since roughly
1000 Btu is required to vaporize lib of water, 100lb must be cooled 10°F to
HUMIDIFICATION OPERATIONS 753
give up enough heat to evaporate lib. Thus for a change of 10'F in the water
temperature there is an evaporation loss of 1 percent. In addition there are
mechanical spray losses, but in a well-designed tower these amount to only about
0.2 percent. Under the conditions given above, then, the total loss of water during
passage through the cooler would be approximately N x 1 + 0.2 = 1.7 percent.
In cooling other liquids by evaporation the vaporization loss, though small, is
somewhat greater than with water because of the smaller heat of vaporization.
HUMIDIFIERS AND DEHUMIDIFIERS. Gas-liquid contacts are used not only
for liquid cooling but also for humidifying or dehumidifying the gas. In a humidifier
liquid is sprayed into warm unsaturated gas, and sensible-heat and mass transfer
take place in the manner described in the discussion of the adiabatic-saturation
temperature. The gas is humidified and cooled adiabatically. It is not necessary
that final equilibrium be reached, and the gas may leave the spray chamber at less
than full saturation.
Warm saturated gas can be dehumidified by bringing it into contact with
cold liquid. The temperature of the gas is lowered below the dew point, liquid
condenses, and the humidity of the gas is reduced. After dehumidification the gas
can be reheated to its original dry-bulb temperature. Equipment for dehumidifica-
tion may utilize a direct spray of coarse liquid droplets into the gas, a spray of
liquid on refrigerated coils or other cold surface, or condensation on a cold surface
with no liquid spray. A dehumidifying cooler-condenser is shown in Fig. 15.9.
THEORY AND CALCULATION OF
HUMIDIFICATION PROCESSES
The interaction between unsaturated gas and liquid at the wet-bulb tempera-
ture of the gas has been discussed under the description of wet and dry-bulb
thermometry. The process has been shown to be controlled by the flow of
heat and the diffusion of vapor through the gas at the interface between the
gas and the liquid. Although these factors are sufficient for the discussion of
the adiabatic humidifier, where the liquid is at constant temperature, in the
case of dehumidifiers and liquid coolers, where the liquid is changing temperature,
it is necessary to consider heat flow in the liquid phase also.
In an adiabatic humidifier, where the liquid remains at a constant adiabatic-
saturation temperature, there is no temperature gradient through the liquid. In
dehumidification and in liquid cooling, however, where the temperature of the
liquid is changing, sensible heat flows into or from the liquid, and a temperature
gradient is thereby set up. This introduces a liquid-phase resistance to the flow of
heat. On the other hand, there can be no liquid-phase resistance to mass transfer
in any case, since there can be no concentration gradient in a pure liquid.
MECHANISM OF INTERACTION OF GAS AND LIQUID. It is important to
obtain a correct picture of the relationships of the transfer of heat and of vapor
in all situations of gas-liquid contacts. In Figs. 23.6 and 23.8, distances measured
Liquid Gas
Humidity, .Jf
-----
(a)
LiqUid Gas
Tempera/ure
Tempera/ure,7;
(b)
FIGURE 23.6
(a) Conditions in adiabatic humidifier. (b) Conditions in dehumidifier.
754
HUMIDIFICATION OPERATIONS 755
perpendicular to the interface are plotted as abscissas and temperatures and
humidities as ordinates. In both figures let
Tx = temperature of bulk of liquid
7; = temperature at interface
T" = temperature of bulk of gas
ff, = humidity at interface
:Jl' = humidity of bulk of gas
Broken arrows represent the diffusion of the vapor through the gas phase,
and full arrows represent the flow of heat (both latent and sensible) through gas
and liquid phases. In all processes, 7; and ff, represent equilibrium conditions
and are therefore coordinates of points lying on the saturation line on the humidity
chart.
The simplest case, that of adiabatic humidification with the liquid at constant
temperature, is shown diagrammatically in Fig. 23.6a. The latent-heat flow from
liquid to gas just balances the sensible-heat flow from gas to liquid, and there is
no temperature gradient in the liquid. The gas temperature T" must be higher
than the interface temperature 7; in order that sensible heat may flow to the
interface; and ff, must be greater than :Jl' in order that the gas be humidified.
Conditions at one point in a dehumidifier are shown in Fig. 23.6b. Here :Jl'
is greater than .Yr" and therefore vapor must diffuse to the interface. Since 7; and
ff, represent saturated gas, T" must be greater than T,; otherwise the bulk of the
gas would be supersaturated with vapor.
This reasoning leads to the conclusion that vapor can be removed from
unsaturated gas by direct contact with sufficiently cold liquids without first
bringing the bulk of the gas to saturation. This operation is shown in Fig. 23.7.
Supersaturation
region A
B
\.
L./.
/.
A
:
'
I
---------------+----
Ir [r
Ir l~
TEMPERATURE
FIGURE 23.7
Dehumidification by cold liquid.
756 MASS TRANSFER AND ITS APPLICATIONS
Point A represents the gas that is to be dehumidified. Suppose that liquid is
available at such a temperature that saturation conditions at the interface are
represented by point B. It has been shown experimentally' that in such a process
the path of the gas on the humidity chart is nearly a straight line between points
A and B. As a result of the humidity and temperature gradients, the interface
receives both sensible heat and vapor from the gas. The condensation of the vapor
liberates latent heat, and both sensible and latent heat are transfu red to the liquid
phase. This requires a temperature difference T, - T, through the liquid.
In a cooler-condenser like that shown in Fig. 15.9 the liquid flows over the
inner surface of the tubes, which are kept cold by the cooling water outside. Heat
is removed from the liquid as it flows downward; this maintains the necessary
temperature difference through the liquid and causes progressively more vapor to
condense as the gas-vapor mixture passes down through the tubes. The mixture
becomes leaner and leaner in condensable material, which it loses to the increasing
layer of liquid.
Sometimes the dehumidification process can lead to fog formation. Consider
a gas with the initial conditions represented by point A' in Fig. 23.7. In this case
the dehumidification path from A' to B reaches the equilibrium curve and then
crosses it into a region of supersaturation. The rate of heat transfer (temperature
change) outruns the mass-transfer rate (humidity change) so that the gas becomes
supersaturated. If the gas contains dust or other particles that can serve as nuclei
for droplet formation, the supersaturation may be relieved by condensation on
these particles instead of on the bulk liquid surface. This can lead to a persistent,
troublesome fog. Fog formation may be avoided by making sure that the initial
gas temperature is well above the equilibrium value, as at point A, or by adding
heat to the gas during the dehumidification process'>
In a countercurrent cooling tower the conditions depend on whether the gas
temperature is below or above the temperature at the interface. In the first case,
e.g., in the upper part of the cooling tower, the conditions are shown diagrammati-
cally in Fig. 23.8a. Here the flow of heat and of vapor (and hence the direction of
temperature and humidity gradients) are exactly the reverse of those shown in Fig.
23.6b. The liquid is being cooled both by evaporation and by transfer of sensible
heat, the humidity and temperature of the gas decrease in the direction of interface
to gas, and the temperature drop Tx - T, through the liquid must be sufficient
to give a heat-transfer rate high enough to account for both heat items.
In the lower part of the cooling tower, where the temperature of the gas is
above that of the interface temperature, the conditions shown in Fig. 23.8b prevail.
Here the liquid is being cooled; hence the interface must be cooler than the bulk
of the liquid, and the temperature gradient through the liquid is toward the
interface (T, is less than Tx). On the other hand, there must be a flow of sensible
heat from the bulk of the gas to the interface (T" is greater than n. The flow of
vapor away from the interface carries, as latent heat, all the sensible heat supplied
to the interface from both sides. The resulting temperature profile Tx T,T" has a
striking V shape, as shown in Fig. 23.8b.
HUMIDIFICATION OPERATIONS 757
Liquid Liquid
- _ Humidily,.R
Vapor ------
-------+- Vopor
------
Temperature
T,
(a) (b)
FIGURE 23.8
Conditions in cooling tower: (a) in top of tower; (b) in bottom of tower.
EQUATIONS FOR GAS-LIQUID CONTACTS. Consider the countercurrent gas-
liquid contactor shown diagrammatically in Fig. 23.9. Gas at humidity .YE" and
temperature T"b enters the bottom of the contactor and leaves at the top with a
humidity Jf;, and temperature T",. Liquid enters the top at temperature Txo and
leaves at the bottom at temperature T,b' The mass velocity of the gas is G~, the
mass of vapor-free gas per unit area of tower cross section per hour. The mass
velocities of the liquid at inlet and outlet are, respectively, Gxo and Gxb ' Let dZ
be the height of a small section of the tower at distance Z from the bottom of the
contact zone. Let the mass velocity of the liquid at height Z be Gx> the temperatures
of gas and liquid be T" and T" respectively, and the humidity be .Y(. At the
interface between the gas and the liquid phases, let the temperature be T; and the
humidity be £,. The cross section of the tower is S, and the height of the contact
section is ZT' Assume that the liquid is warmer than the gas, so the conditions
at height Z are those shown in Fig. 23.8a. The following equations can be written
over the small volume S d2.
The enthalpy balance is
(23.22)
where Hy and Hx are the total enthalpies of gas and liquid, respectively.
758 MASS TRANSFER AND ITS APPLICATIONS
Mass velocifyof vopor- free gas G;
Temperature yo Mass velocity of
liquid Gxa
+--
~
-'--h Temperature 0,a
Humidity dfa
E nlha/py Hya
dZ
.t
~~fZT
Mass veloclfy of
vopor-free gas G;
Temperature Tyb
U Mass velocity of
liquid GXb
Lf-:!----J:-~Temperature 'T,;b
Humidity Ab
Enlha/py Hyb
FIGURE 23.9
Countercurrent gas-liquid contactor, flow diagram.
The rate of heat transfer from liquid to interface is
(23.23)
where "x = heat-transfer coefficient from liquid to interface
aH = heat-transfer area per contact volume
The rate of heat transfer from interface to gas is
G~c, dT" = hPi - T,,)a H dZ (23.24)
The rate of mass transfer of vapor from interface to gas is
(23.25)
where aM is the mass-transfer area per unit contact volume. The factors aM
and aH are not necessarily equal. If the contactor is packed with solid packing,
the liquid may not completely wet the packing and the area available for heat
transfer, which is the entire area of the packing, is larger than that for mass transfer,
which is limited to the surface that is actually wet.
These equations can be simplified and rearranged. First, neglect the change
of Gx with height and write for the enthalpy of the liquid
Hx = cL(Tx - To) (23.26)
where CL = specific heat of liquid
To = base temperature for computing enthalpy
HUMIDIFICATION OPERATIONS 759
Then
d(GxHx) = Gx dH x = GxC L dTx (23.27)
Substituting d( GxHx) from Eq. (23.27) into Eq. (23.23) gives
Gh dT, = h)T, - T,)a H dZ
This may be written
(23.28)
Second, Eq. (23.24) may be rearranged to read
~= h,aH dZ (23.29)
1i - Yy csG~
Third, Eq. (23.25) may be written
dYC
(23.30)
£;-£
Finally, using Eq. (23.22), Eq. (23.27) may be written
(23.31)
Three working equations, which are applied later, can now be derived. First,
multiply Eq. (23.25) by }'o and add Eq. (23.24) to the product, giving
G;(c, dT, + Ao d£) = [AokyM.(J'tf - £)a M + "iT, - T,)aHJ dZ (23.32)
If the packing is completely wet with liquid, so that the area for mass transfer
equals that for heat transfer, aM = a H = a. When the change of c, with £ is
neglected, Eq. (23.9) gives, on differentiation,
(23.33)
From Eq. (23.33), dHy can be substituted in the left-hand side of Eq. (23.32).
This gives
(23.34)
SYSTEM AIR-WATER. For the system air-water hy can be eliminated from Eq.
(23.34) using the Lewis relation, Eq. (23.21), to give
G; dH y = k,M.a[(A o£; + c,T,) - (}'oYC + c,T,)] dZ (23.35)
If Hi is the enthalpy of the air at the interface,
Hi = Ao£; + c,(T, - To)
760 MASS TRANSFER AND ITS APPLICATIONS
From this definition of Hi and the expression for Hy given by Eq. (23.9), the
bracketed term in Eq. (23.35) is simply Hi H y. Then Eq. (23.35) becomes
G; dH y = kyMBa(Hi - Hy) dZ
or
_d_HLY_ = _ky_M_B_a dZ
(23.36)
Hj-H y G~
Second, from Eqs. (23.22) and (23.23),
G; dHy = hxCI:, - T,)a dZ (23.37)
Eliminating dZ from Eqs. (23.36) and (23.37) and rearranging gives, with the
aid of Eq. (23.21),
Hi - Hy hx hxcs
=---=-- (23.38)
T, - Tx k,M B hy
Third, Eq. (23-29) is divided by Eq. (23.36), giving
dT,/(T, - T,) _h_y_
dHy/(H i - Hy) kyMBc,
From Eq. (23.21), the right-hand side of this equation equals unity, and
dT, T, - T,
_ = =----:"- (23.39)
dH y Hi-Hy
Note that since the Lewis relation is used in their derivation, Eqs. (23.36),
(23.38), and (23.39) apply only to the air-water system and also for situations where
aM = aB' In the following section the discussion is limited to air-water contacts.
ADIABATIC HUMIDIFICATION. Adiabatic humidification is similar to adiabatic
saturation except that the air leaving the humidifier is not necessarily saturated
and, for design, rate equations must be used to calculate the size of the contact
zone. The inlet and outlet water temperatures are equal. It is assumed in the
following that the makeup water enters at adiabatic-saturation temperature and
that the volumetric-area factors aM and aB are identical. The wet-bulb and
adiabatic-saturation temperatures are equal and constant. Then
Txa = TXb = I; = Tx = 1's = const
1
where T, is the adiabatic-saturation temperature of the inlet air. Equation (23.29)
then becomes
(23.40)
HUMIDIFICATION OPERATIONS 761
With c, used as the average humid heat over the humidifier, Eq. (23.40) can
be integrated:
(23.41)
where VT = SZT = total contact volume
Tit' = G~S = total flow of dry air
An equivalent equation, based on mass transfer, can be derived from Eq.
(23.30), which is written for adiabatic humidification as
d:Yf' = k,M Ba dZ
:Yf', - YI' G~
Since Yf" the saturation humidity at T" is constant, this equation can be
integrated in the same manner as Eq. (23.40) to give
In Yf, - ye. = k,MG'
~p
Ba Z = k,M Ba VT
T
(23.42)
",p
J~s-.:na y In.,
Application of HTU method. The HTU method is applicable to adiabatic humidifi-
cation. Thus, by definition,
N - In :Yf', - Yl'b (23.43)
,- .fP ~P
.:rts - .:rta
where N, is the number of humidity transfer units. From the definition of H,
and Eqs. (23.42) and (23.43),
ZT G~
H, = - = - - (23.44)
N, k,MBa
where H, is the height of one humidity transfer unit.
The number of transfer units can also be defined on the basis of heat transfer
as follows:
(23.45)
That H, given by Eq. (23.44) is the same as that given by Eq. (23.45) can be
shown by dividing Eq. (23.44) by the value of H, from Eq. (23.45). The result is
Eq. (23.21). Also, the values of N, calculated from Eqs. (23.43) and (23.45) are the
same, because in both instances N, = ZT/H,.
The heat-transfer method using Eqs. (23.41) and (23.45) is equivalent to the
mass-transfer method using Eqs. (23.42) to (23.44). The two methods give the same
result.
762 MASS TRANSFER AND ITS APPLICATIONS
Example 23.3. For a certain process requiring air at controlled temperature and
humidity there is needed 15,000 lb (6804 kg) of dry air per hour at 20 percent humidity
and 130°F (54.4°C). This air is to be obtained by conditioning air at 20 percent
humidity and 70°F (21.1°C) by first heating, then humidifying adiabatically to the
desired humidity, and finally reheating the humidified air to 130°F (54.4°C). The
humidifying step is to be conducted in a spray chamber. Assuming the air leaving
the spray chamber is to be 4°F (2.22°C) warmer than the adiabatic-saturation
temperature, to what temperature should the air be preheated, at what temperature
should it leave the spray chamber, how much heat will be required for pre- and
reheating, and what should be the volume of the spray chamber? Take hya as
85 BtuJft'-h-oF (1583 WJm'-°C).
Solution
The temperature-humidity path of the air through the heaters and spray chamber is
plotted on the section of the humidity chart shown in Fig. 23.10. Air at 20 percent
humidity and 130°F has a humidity of 0.022. The air leaving the spray chamber is
at this same humidity, and the point representing it on the humidity chart is located
by finding the point where the coordinate for :Yt' = 0.022 is 4°F from the end of an
adiabatic-cooling line. By inspection, it is found that the adiabatic line for the process
in the spray chamber corresponds to an adiabatic saturation temperature of 81°F
and that the point on this line at :Yl' = 0.022 and T = 85°F represents the air leaving
the chamber. The original air has a humidity of 0.0030. To reach the adiabatic cooling
line for 7; = 81°F, the temperature of the air leaving the preheater must be 168°F.
The humid heat of the original air is, from Fig. 23.3, 0.241 Btujlb-o'F. The heat
required to preheat the air is, then,
0.241 x 15,000(168 - 70) = 354,000 Btufh
The humid heat of the air leaving the spray chamber is 0.250 BtujIb-oF, and the
heat required in the reheater is
0.250 x 15,000(130 - 85) = 169,000 Btufh
The total heat required is 354,000 + 169,000 = 523,000 Btufh.
+
['::
15
~
::J
I
'i-==:::::--------;"f---- ----- - ---- 0022
I::::t::fl==±=±~:::±====:::::::=±-=-=-=-=-:::::J 0003
130°
TEMPERATURE OF
FIGURE 23.10
Temperature-humidity path for Example 23.3.
HUMIDIFICATION OPERATIONS 763
To calculate the volume of the spray chamber, Eq. (23.41) may be used. The
average humid heat is
0.241 + 0.250
c, = 2 0.2455 Btujlb dry air-oF
Substituting in Eq. (23.41) gives
168 - 81 85VT
In---
85 - 81 15,000 x 0.2455
From this, the volume of the spray chamber is VT = 134 ft 3 (3.79 m 3 ).
SYMBOLS
A Surface area of liquid, m 2 or ft'
a Transfer area, m2jm 3 or ft2jft3; aH, for heat transfer; aM, for
mass transfer
b Constant in Eqs. (23.17), (23.18)
Cp Molar specific heat, J/g mol-oC or Btujlb mol-oF
CL Specific heat of liquid, J/g-T or Btu/lb-oF
cp Specific heat, J/g_OC or Btu/lb-oF; CpA, cpR , of components A and
B, respectively
c, Humid heat, J/g_OC or Btujlb-oF; c" average value
D Diameter, m or ft
D, Diffusivity, m 2/h, cm 2/s, or ft2/h
G Mass velocity, kg/m2-h or Ib/ft 2-h; Gx , ofliquid at any point; Gx ", of
liquid at entrance; G.xb' of liquid at exit; G~, of gas, mass of vapor-free
gas per unit area of tower cross section per hour
B Enthalpy, J/g or Btujlb; B" of liquid; By, of gas; By., B yb , of gas at
entrance and exit, respectively
B, Height of humidity transfer unit, m or ft
.Yf Humidity, mass of vapor per unit mass of vapor-free gas; .n:" at
top of contractor; Yt", at bottom of contactor; £" at gas-liquid
interface; ~, saturation humidity; ~I" saturation humidity at wet-
bulb temperature
yt'A Percentage humidity, 100Yt'/.n:,
Yt'R Relative humidity, 100PA/P A
h Heat-transfer coefficient, W/m2_oC or Btu/ft2-h_oF; h" liquid side; hy ,
gas side
k Thermal conductivity, W/m-oC or Btu/ft-h_oF
ky Mass-transfer coefficient, g mol/m 2-h-unit mole fraction or
Ib mOl/ft2-h-unit mole fraction
M Molecular weight; MA, M R , of components A and B, respectively; M,
average molecular weight of gas stream
m Exponent in Eqs. (23.17), (23.18)
rn' Total flow rate of dry air, kgjh or Ib/h
764 MASS TRANSFER AND ITS APPLICATIONS
NA Rate of transfer or vaporization of liquid, mol/h
N p, Prandtl number, cpl'/k, dimensionless
N R, Reynolds number, DG/I', dimensionless
Ns, Schmidt number, l'/pD" dimensionless
N, Number of humidity transfer units or heat-transfer units
Il Exponent in Eqs. (23.17), (23.18); also number of moles (Example 23.1)
P Pressure, atm; FA, vapor pressure of liquid
PA Partial pressure of vapor, atm
q Rate of sensible-heat transfer to liquid, W or Btu/h
S Cross-sectional area of tower, m 2 or ft 2
T Temperature, K, °C, oR or of; ~,at gas-liquid interface; ~,adiabatic
saturation temperature; 7;" wet-bulb temperature; Tx, of bulk of
liquid; Tx" of liquid at top of contactor; Tx., of liquid at bottom of
contactor; T", of bulk of gas; T"" of gas at top of contactor; T"., of
gas at bottom of contactor; To, datum for computing enthalpy
Total contact volume, m 3 or ft 3
Humid volume, m 3/kg or ft3 jIb
Mole fraction of liquid component ill gas stream; Ye> equilibrium
value; Yi, at gas-liquid interface
(1 - Y)L One-way diffusion factor
Z Distance from bottom of contact zone, m or ft; ZT' total height of
contact section
z Number of moles of water evaporated (Example 23.1)
Greek letters
A Latent heat of vaporization, J/g or BtujIb; A" at T,; }'w, at 7;,; Ao, at To
I' Viscosity, cP or Ib/ft-h
P Density of gas, kg/m 3 or Ib/ft 3
PROBLEMS
23.1 One method of removing acetone from cellulose acetate is to blow an airstream over
the cellulose acetate fibers. To know the properties ofthe air-acetone mixtures, the pro-
cess control department requires a humidity chart for air-acetone. After investigation,
it was found that an absolute humidity range of 0 to 6.0 and a temperature range of
5 to 55°C would be satisfactory. Construct the following portions of such a humidity
chart for air-acetone at a total pressure of 760 mm Hg: (a) percentage humidity lines
for 50 and 100 percent, (b) saturated volume vs. temperature, (c) latent heat of acetone
vs. temperature, (d) humid heat vs. humidity, (e) adiabatic-cooling lines for adiabatic-
saturation temperatures of 20 and 40°C, (I) wet-bulb temperature (psychrometric) lines
for wet-bulb temperatures of 20 and 40°C. The necessary data are given in Table 23.1.
For acetone vapor, cp ~ 1.47 J/g_OC and h/MDk, ~ 1.7 J/g_0C.
23.2. A mixture of air and benzene vapor is to be cooled from 70 to 15°C in a tubular
cooler condenser. The humidity at the inlet is 0.7 kg benzene vapor per kilogram of
air. Calculate (a) the wet-bulb temperature of the entering gas; (b) the humidity at
the outlet; and (c) the total amount of heat to be transferred per kilogram of air.
HUMIDIFICATION OPERATIONS 765
TABLE 23.1
Properties of acetone
Vapor Vapor
Temperature, pressure, Latent heat, Temperature, pressure, Latent heat,
°C mmHg Jig °C mmHg Jig
0 564 50 620.9
10 115.6 56.1 760.0 521
20 179.6 552 60 860.5 517
30 281.0 70 1,189.4
40 420.1 536 80 1,611.0 495
23.3. The following data were obtained during a test run of a packed cooling tower
operating at atmospheric pressure:
Height of packed section, 6 ft
Inside diameter, 12 in.
Average temperature of entering air, 100"F
Average temperature ofleaving air, 103"F
Average wet-bulb temperature of entering air, 80"F
Average wet-bulb temperature of leaving air, 96"F
Average temperature of entering water, 115"F
Average temperature of leaving water, 95"F
Rate of entering water, 2000 lb/h
Rate of entering air, 480 ft 3 /min
(a) Using the entering-air conditions, calculate the humidity of the exit air by
means of an enthalpy balance. Compare the result with the humidity calculated from
the wet- and dry-bulb readings.
(b) Assuming that the water-air interface is at the same temperature as the bulk
of the water (water-phase resistance to heat transfer negligible), calculate the driving
force Jfi - ff at the top and at the bottom of the tower. Using an average Jlt; -..Yt,
estimate the average value of kflo
23.4. Air is to be cooled and dehumidified by countercurrent contact with water in a packed
tower. The tower is to be designed for the following conditions:
Dry-bulb temperature of inlet air, 30"C
Wet-bulb temperature of linIet air, 25"C
Flow rate of inlet air, 900 kg/h of dry air
Inlet water temperature, 10"C
Outlet water temperature, 16"C
(a) For the entering air, find (/) the humidity, (il) the percent relative humidity, (iiO
the dew point, (iv) the enthalpy, based on air and liquid water at o°e. (b) What is the
maximum water rate that can be used to meet design requiremenls, assuming a very
tall tower? (c) Calculate the number of transfer units required for a tower that meets
design specifications when 600 kg/h of water is used and if the liquid-phase resistance
to heat transfer is negligible.
766 MASS TRANSFER AND ITS APPLICATIONS
23.5. (a) Show that for small drops of water evaporating in wann air, the evaporation time
is proportional to the square of the droplet size. (b) Calculate the evaporation time
for SO-,um drops in air at 140°F. (c) Evaluate the volumetric heat-transfer coefficient
for a spray of SO-,um drops that contains 1 percent of drops by volume.
23.6. Air at 27°C and 60 percent relative humidity is circulated past l.S-cm-O.D. tubes
through which water is flowing at 60 cmJs and 15°C. The air velocity approaching
the tubes is 1.5 m/so (a) Will water condense on the tubes? (b) What are the wall
temperature and the interface temperature if condensation occurs?
REFERENCES
1. Burger, R.: Chem. Eng. Prog., 86(9): 37 (1990).
2. Colburn, A. P., and A. G. Edison: [nd. Eng. Chem., 33:457 (1941).
3. Grosvenor, W. M.: Trans. AICltE, 1: 184 (1908).
4. Keevil, C. S., and W. K. Lewis: Ind. E11g. Chem., 20: 1058 (1928).
5. Lewis, W. K.: Trans. A/ME, 44:325 (1922).
6. Perry, J. H. (ed.): Chemical Engineers' Handbook, 5th ed., McGraw-Hill, New York, 1973, p.12-26.
7. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York, 1984,
pp. 20-7, 20-8.
8. Sherwood, T. K., and R. L. Pigrord: Absorption and Extraction, 2nd ed., McGraw-Hill, New York,
1952, pp. 97-101.
CHAPTER
24
DRYING
OF
SOLIDS
In general, drying a solid means the removal of relatively small amounts of water
or other liquid from the solid material to reduce the content of residual liquid to
an acceptably low value. Drying is usually the final step in a series of operations,
and the product from a dryer is often ready for final packaging.
Water or other liquids may be removed from solids mechanically by presses
or centrifuges or thermally by vaporization. This chapter is restricted to drying
by thermal vaporization. It is generally cheaper to remove liquid mechanically
than thermally, and thus it is advisable to reduce the liquid content as much as
practicable before feeding the material to a heated dryer.
The liquid content of a dried substance varies from product to product,
Occasionally the product contains no liquid and is called bone-dry. More com-
monly, the product does contain some liquid. Dried table salt, for example,
contains about 0.5 percent water, dried coal about 4 percent, and dried casein
about 8 percent. Drying is a relative term and means merely that there is a
reduction in liquid content from an initial value to some acceptable final value.
The solids to be dried may be in many different forms-flakes, granules,
crystals, powders, slabs, or continuous sheets-and may have widely differing
properties. The liquid to be vaporized may be on the surface of the solid, as in
drying salt crystals; it may be entirely inside the solid, as in solvent removal from
a sheet of polymer; or it may be partly outside and partly inside. The feed to some
767
768 MASS TRANSFER AND ITS APPLICATIONS
dryers is a liquid in which the solid is suspended as particles or is in solution. The
dried product may be able to stand rough handling and a very hot environment
or it may require gentle treatment at low or moderate temperatures. Consequently
a multitude of types of dryers are on the market for commercial drying. They
differ chiefly in the way the solids are moved through the drying zone and in the
way heat is transferred.
CLASSIFICATION OF DRYERS. There is no simple way of classifying drying
equipment. Some dryers are continuous, and some operate batchwise; some agitate
the solids, and some are essentially unagitated. Operation under vacuum may be
used to reduce the drying temperature. Some dryers can handle almost any kind
of material, while others are severely limited in the type of feed they can accept.
A major division may be made between (1) dryers in which the solid is directly
exposed to a hot gas (usually air) and (2) dryers in which heat is transferred to
the solid from an external medium such as condensing steam, usually through a
metal surface with which the solid is in contact. 5 Dryers that expose the solids to
a hot gas are called adiabatic or direct dryers; those in which heat is transferred
from an external medium are known as nonadiabatic or indirect dryers. Dryers
heated by dielectric, radiant, or microwave energy are also nonadiabatic. Some
units combine adiabatic and nonadiabatic drying; they are known as direct-indirect
dryers.
SOLIDS HANDLING IN DRYERS. Most industrial dryers handle particulate solids
during part or all of the drying cycle, although some, of course, dry large individual
pieces such as ceramic ware or sheets of polymer. The properties of particulate
solids are discussed in Chap. 28. Here it is important only to describe the different
patterns of motion of solid particles through dryers as a basis for understanding
the principles of drying discussed in the next section.
In adiabatic dryers the solids are exposed to the gas in the following ways:
1. Gas is blown across the surface of a bed or slab of solids or across one or both
faces of a continuous sheet or film. This process is called cross-circulation drying
(Fig. 24.1a).
2. Gas is blown through a bed of coarse granular solids that are supported on a
screen. This is known as through-circulation drying. As in cross-circulation
drying the gas velocity is kept low to avoid any entrainment of solid particles
(Fig. 24.1b).
3. Solids are showered downward through a slowly moving gas stream, often with
some undesired entrainment of fine particles in the gas (Fig. 24.1c).
4. Gas passes through the solids at a velocity sufficient to fluidize the bed, as
discussed in Chap. 7. Inevitably there is some entrainment of finer particles
(Fig. 24.ld).
5. The solids are all entrained in a high-velocity gas stream and are pneumatically
conveyed from a mixing device to a mechanical separator (Fig. 24.1e).
DRYING OF SOLIDS 769
I
-
-af _W~
~
I
lal Ibl
lel Idl lel
FIGURE 24.1
Patterns of gasMsolid interaction in dryers: (a) gas flow across a static bed of solids; (b) gas passing
through a bed of preformed solids; (c) showering action in a rotary dryer; (d) fluidized solids bed; (e)
cocurrent gasMsolid flow in a pneumatic-conveyor flash dryer.
In nonadiabatic dryers the only gas to be removed is the vaporized water
or solvent, although sometimes a small amount of "sweep gas" (often air or
nitrogen) is passed through the unit. Nonadiabatic dryers differ chiefly in the ways
in which the solids are exposed to the hot surface or other source of heat.
1. Solids are spread over a stationary or slowly moving horizontal surface and
"cooked" until dry. The surface may be heated electrically or by a heat-transfer
fluid such as steam or hot water. Alternatively, heat may be supplied by a
radiant heater above the solid.
2. Solids are moved over a heated surface, usually cylindrical, by an agitator or
a screw or paddle conveyor.
3. Solids slide by gravity over an inclined heated surface or are carried upward
with the surface for a time and then slide to a new location. (See "Rotary
Dryers," p. 795.)
PRINCIPLES OF DRYING
Because of the wide variety of materials that are dried in commercial equipment
and the many types of equipment that are used, there is no single theory of drying
that covers all materials and dryer types. Variations in shape and size of stock,
770 MASS TRANSFER AND ITS APPLICATIONS
in moistnre equilibria, in the mechanism of flow of moistnre through the solid,
and in the method of providing the heat required for the vaporization-all prevent
a unified treatment. General principles used in a semiquantitative way are relied
upon. Dryers are seldom designed by the user but are bought from companies
that specialize in the engineering and fabrication of drying equipment.
TEMPERATURE PATTERNS IN DRYERS. The way in which temperatnres vary
in a dryer depends on the natnre and liquid content of the feedstock, the
temperature of the heating medium, the drying time, and the allowable final
temperatnre of the dry solids. The pattern of variation, however, is similar from
one dryer to another. Typical patterns are shown in Fig. 24.2.
In a batch dryer with a heating medium at constant temperature (Fig. 24.2a)
the temperatnre of the wet solids rises rather quickly frorn its initial value T" to
the vaporization temperature T". In a nonadiabatic dryer with no sweep gas, T"
is essentially the boiling point of the liquid at the pressnre prevailing in the dryer.
If a sweep gas is used or if the dryer is adiabatic, T" is at or near the wet-bulb
temperatnre of the gas (which equals the adiabatic-satnration temperatnre if the
gas is air and water is the liquid being evaporated). Drying occnrs at T" for a
considerable period; that is to say, much of the liquid can be vaporized at a
temperatnre well below that of the heating medium. In the final stages of drying,
the solids temperatnre rises to T,b, which may be slightly above T" or significantly
higher. The drying mechanisms underlying these temperatnre changes are dis-
cussed later.
The drying time indicated in Fig. 24.2a may be a few seconds or many honrs.
The solids may be at T" for most of the drying cycle or for only a small fraction
of it. The temperatnre of the heating medium may be constant, as shown, or it
may be programmed to change as drying proceeds.
In a continuous dryer each particle or element of the solid passes through
a cycle similar to that shown in Fig. 24.2a on its way from the inlet to the outlet
of the dryer. In steady-state operation the temperature at any given point in a
continuous dryer is constant, but it varies along the length of the dryer. Fignre
~ Heating medium
T,
::>
~
'"w
~ T,b
T"
~ Tv
Solids Solids
>- Tu
o o 100
TIME PERCENT OF DRYER LENGTH
la) Ib)
FIGURE 24.2
Temperature patterns in dryers: (a) batch dryer; (b) continuous countercurrent adiabatic dryer.
DRYING OF SOLIDS 771
24.2b shows a temperature pattern for an adiabatic countercurrent dryer. The
solids inlet and gas outlet are on the left; the gas inlet and solids outlet are on
the right. Again the solids are quickly heated from T,a to T". The vaporization
temperature temperature 7; is again constant since the wet-bulb temperature does
not change. (If some heat were also supplied indirectly to the solids, this would
not be true.) Near the gas inlet the solids may be heated to well above 7;. Hot
gas enters the dryer at 'Ij,b, usually with low humidity; it cools, rapidly at first,
then more slowly as the temperature-difference driving force decreases. Its humid-
ity rises steadily as it picks up more and more of the vaporized liquid.
HEAT TRANSFER IN DRYERS. Drying of wet solids is by definition a thermal
process. While it is often complicated by diffusion in the solid or through a gas,
it is possible to dry many materials merely by heating them above the boiling
point of the liquid-perhaps well above, to free the last traces of adsorbed material.
Wet solids, for example, can be dried by exposure to highly superheated steam.
Here there is no diffusion; the problem is solely one of heat transfer. In most
adiabatic drying, of course, diffusion is nearly always present, but often drying
rates are limited by heat transfer, not mass transfer, and the principles given in
Chaps. 10 to 14 can be used in dryer calculations. Many, perhaps most, dryers
are designed on the basis of heat-transfer considerations alone.
Calculation of heat duty. Heat must be applied to a dryer to accomplish the
following:
1. Heat the feed (solids and liquid) to the vaporization temperature.
2. Vaporize the liquid.
3. Heat the solids to their final temperature.
4. Heat the vapor to its final temperature.
Items 1, 3, and 4 are often negligible compared with item 2. In the general case
the total rate of heat transfer may be calculated as follows. If In, is the mass of
bone-dry solids to be dried per unit time and Xa and Xb are the initial and final
liquid contents in mass of liquid per unit mass of bone-dry solid, then the quantity
of heat transferred per unit mass of solid qT/m, is
qT
-;- = Cp,(T,b - T,a) + X acpL(7; - T,a) + (Xa - X b),\
m,
+ XbCpL(T,b - 7;) + (Xa - Xb)cp,(Taa - 7;) (24.1)
where T,a = feed temperature
Yv = vaporization temperature
T,b = final solids temperature
7;; = final vapor temperature
,\ = heat of vaporization
cps ' c pL , cpv = specific heats of solid, liquid, and vapor, respectively
772 MASS TRANSFER AND ITS APPUCATIONS
Equation (24.1) is based on average specific heats for the temperature range
from inlet to outlet and on the heat of vaporization at 7;,. However, if vaporization
occurs over a range of temperatures, Eq. (24.1) still applies, because the total
enthalpy change is independent of the path followed from the initial to the final
state.
In an adiabatic dryer 7;, is the wet-bulb temperature of the gas and 7;" and
Th , are the inlet and exit gas temperatures. The heat transferred to the solids,
liquid, and vapor, as found from Eq. (24.1), comes from the cooling of the gas;
for a continuous adiabatic dryer the heat balance gives
qT = Ih,(l + .Ytb)c"(7;,, - 7;,,) (24.2)
where Ih, = mass rate of dry gas
Jfb = humidity of gas at inlet
c" = humid heat of gas at inlet humidity
Heat-transfer coefficients. In dryer calculations the basic heat-transfer equation,
a form of Eq. (11.14), applies:
(24.3)
where V = overall coefficient
A = heat-transfer area
!iT = average temperature difference (not necessarily logarithmic mean)
Sometimes A and !i T are known and the capacity of the dryer can be estimated
from a calculated or measured value of V, but often there is considerable
uncertainty in the area actually available for heat transfer. The fraction of a heated
surface in contact with solids in a conveyor dryer, for example, is difficult to
estimate; the total surface area of solid particles exposed to a heated surface or a
hot gas is rarely known.
For these reasons many dryers are designed on the basis of a volumetric
heat-transfer coefficient Va, where a is the (unknown) heat-transfer area per unit
dryer volume. The governing equation is
qT = VaV !iT (24.4)
where Va = volumetric heat-transfer coefficient, Btu/ft3-h-'F or W/m 3-,C
V= dryer volume, ft3 or m3
Because of the rather complex temperature patterns, the true average
temperature difference for the dryer as a whole is not easy to define. Sometimes,
in fact, the outlet temperature of solids and gas are so nearly the same' that the
difference between them cannot be measured. Heat-transfer coefficients are there-
fore hard to estimate and may be of limited utility. One general equation that is
useful in drying calculations is Eq. (12.70) for heat transfer from a gas to a single
or isolated spherical particle:
h,Dp = 2.0 + 0.60 (D p G)O.sO(C pl'f)1/3 (12.70)
kf I'f kf
DRYING OF SOLIDS 773
When internal heat transfer is important, Eq. (11.40) may be used. For flow
through fixed or fluidized beds of solid particles the heat-transfer correlation
shown in Fig. 21.5 is often applicable. For many dryers, however, no general
correlations are available and coefficients must be found experimentally. Empirical
coefficients are often based on more or less arbitrary definitions of heat-transfer
and average temperature difference. Examples of empirical correlations are given
later in this chapter under the discussion of the particular kind of dryer to which
they apply.
HEAT-TRANSFER UNITS. Some adiabatic dryers, especially rotary dryers, are
conveniently rated in terms of the number of heat-transfer units they contain.
Heat-transfer units are analogous to the mass-transfer units discussed in Chap.
22; one heat-transfer unit is the section or part of the equipment in which the
temperature change in one phase equals the average driving force (temperature
difference) in that section. Transfer units may be based on the temperature change
in either phase but in dryers they are always based on the gas. The number of
transfer units in the dryer is given by
dT:
f
TM
N = __
h_
(24.5)
t
T"Q
T:-T.
h s
or
N = thb - Tira (24.6)
t t;T
When the initial liquid content of the solids is high and most of the heat
transferred is for vaporization, t; T may be taken as the logarithmic mean difference
between the dry-bulb and wet-bulb temperatures. Then
- - (7;,b - Twb ) - (7;,a - Y,,.)
t; T = t; TL = (24.7)
In[7;,b - Twb)/(T,.. - Twa)]
For the system water-air TWb = Twa and Eq. (24.6) becomes
7hb - TWb
N t = In --""--"" (24.8)
7ha - TWb
The length of a transfer unit and the number of transfer units appropriate
for good design are discussed later under "Drying Equipment."
MASS TRANSFER IN DRYERS. In all dryers in which a gas is passed over or
through the solids, mass must be transferred from the surface of the solid to the
gas and sometimes through interior channels of the solid. The resistance to mass
transfer, not heat transfer, may control the drying rate. This is most often true in
cross-circulation drying of slabs, sheets, or beds of solids. From the standpoint of
the gas, this kind of drying is much like adiabatic humidification; from that of the
solid it is like evaporation when the solid is very wet and like solvent desorption
from an adsorbent when the solid is nearly dry.
774 MASS TRANSFER AND ITS APPLICATIONS
The average rate of mass transfer In. is readily calculated from the relation
In. = In,(X. - X b) (24.9)
If the gas enters at humidity ,ff" the exit humidity £" is given by
In,(X. - X b )
£,,=ff,+ .
In.
(24.10)
Prediction of mass-transfer rates per unit area or unit volume is less
straightforward. It requires a knowledge of the mechanism of liquid and vapor
motion in and through the solid and of the rather complicated phase equilibria
between a wet solid and a humid gas.
Phase Equilibria
Equilibrium data for moist solids are commonly given as relationships between
the relative humidity of the gas and the liquid content of the solid, in mass of
liquid per unit mass of bone-dry solid. t Examples of equilibrium relationships
are shown in Fig. 24.3. Curves of this type are nearly independent of temperature.
The abscissas of such curves are readily converted to absolute humidities, in mass
of vapor per unit mass of dry gas.
The remainder of the discussion in this section is based on the air-water
system, but it should be remembered that the underlying principles apply equally
well to other gases and liquids.
When a wet solid is brought into contact with air of lower humidity than
that corresponding to the moisture content of the solid, as shown by the
humidity-equilibrium curve, the solid tends to lose moisture and dry to equilibrium
with the air. When the air is more humid than the solid in equilibrium with it,
the solid absorbs moisture from the air until equilibrium is attained.
In fluid phases diffusion is governed by concentration differences expressed
in mole fractions. In a wet solid, however, the term mole fractioll may have little
meaning, and for ease in drying calculations the moisture content is nearly always
expressed in mass of water per unit mass of bone-dry solid. This practice is followed
throughout the present chapter.
EQUILIBRIUM MOISTURE AND FREE MOISTURE. The air entering a dryer is
seldom completely dry but contains some moisture and has a definite relative
humidity. For air of definite humidity, the moisture content of the solid leaving
the dryer cannot be less than the equilibrium-moisture content corresponding to
the humidity of the entering air. That portion of the water in the wet solid that
cannot be removed by the inlet air, because of the humidity of the latter, is called
the equilibrium moisture.
t A liquid content expressed in this way is said to be on a dry basis; it may, and often does, exceed
100 percent.
DRYING OF SOLIDS 775
30
I. Pope!', newsprint
28 I - 2. Wool, worsted
3. Silk
26 I - 4. Kaolin
<i 24
5. Soop
if
/
erw
t:;2 2
:;;
~ 20
j 1
ro
2j rl I1
~ 18
Q
8S 16
VI /
CL
(f)
§! 14
V } /
::0
~ 2
/ J J
f--'"
z
/
V V/ /J V
t:: 10
V
8
0: 8 / /-- V VJ
./
/
~ 6
V
/ /' V V
// /
./
2
/
I~V
L
:..---- -- V
o~
4
o 10 20 30 40 50 60 70 80 90 100
RELATIVE HUMIDITY, PER CENT
FIGURE 24.3
Equilibrium-moisture curves at 25°C.
The free water is the difference between the total-water content of the solid
and the equilibrium-water content. Thus, if X T is the total-moisture content, and
if X* is the equilibrium-moisture content, the free moisture X is
X=XT-X'
It is X, rather than X T , that is of interest in drying calculations.
BOUND AND UNBOUND WATER. If an equilibrium curve like those in Fig. 24.3
is continued to its intersection with the axis for 100 percent humidity, the moisture
content so defined is the minimum moisture this material can carry and still exert
776 MASS TRANSFER AND ITS APPLICATIONS
a vapor pressure at least as great as that exerted by liquid water at the same
temperature. If such a material contains more water than that indicated by this
intersection, it can still exert only the vapor pressure of water at the solids
temperature. This makes possible a distinction between two types of water held by
a given material. The water corresponding to concentrations lower than that
indicated by the intersection of the ~urves in Fig. 24.3 with the line for 100 percent
hnmidity is called bound water, because it exerts a vapor pressure less than that
of liquid water at the same temperature. Water corresponding to concentrations
greater than that indicated by the intersections is called unbound water. Sub-
stances containing bound water are often called /zygroscopic substances. The
condition at which wood, textiles, and other cellular materials is in equilibrium
with saturated air is called the jiber-saturation point.
Bound water may exist in several conditions. Liquid water in fine capillaries
exerts an abnormally low vapor pressure because of the highly concave curvature
of the surface; moisture in cell or fiber walls may suffer a vapor-pressure lowering
because of solids dissolved"in it; water in natural organic substances is in physical
and chemical combination, the nature and strength of which vary with the nature
and moisture content of the solid. Unbound water, on the other hand, exerts its
full vapor pressure and is largely held in the voids of the solid. Large wet particles,
such as coarse sand, contains only unbound water.
The terms employed in this discussion may be clarified by reference to Fig.
24.3. Consider, for instance, curve 2 for worsted yarns. This intersects the curve
for 100 percent humidity at 26 percent moisture; consequently, any sample of wool
that contains less than 26 percent water contains only bound water. Any moisture
that a sample may contain above 26 percent is unbound water. If the sample
contains 30 percent water, for example, 4 percent of this water is unbound and
26 percent bound. Assume, now, that this sample is to be dried with air of 30
percent relative humidity. Curve 2 shows that the lowest moisture content that
can be reached under these conditions is 9 percent. This, then, is the equilibrium-
moisture content for this particular set of conditions. If a sample containing 30
percent total moisture is to be dried with air at 30 percent relative humidity, it
contains 21 percent free water and 9 percent equilibrium moisture. Any amount
up to a concentration of 26 percent is still bound water, but most of this can be
evaporated into the air and hence is free water. Thus water can be both ·bound
and free at the same time-partially bound to the solid but free to be evaporated.
The distinction between bound and unbound water depends on the material itself,
while the distinction between free and equilibrium moisture depends on the drying
conditions.
Cross-Circulation Drying
When both heat and mass transfer are involved, the mechanism of drying depends
on the nature of the solids and on the method of contacting the solids and gas.
Solids are of three kinds: crystalline, porous, and nonporous. Crystalline particles
contain no interior liquid, and drying occurs only at the surface of the solid. A
DRYING OF SOLIDS 777
bed of such particles, of course, can be considered a highly porous solid. Truly
porous solids, such as catalyst pellets, contain liquid in interior channels. Non-
porous solids include colloidal gels such as soap, glue, and plastic clay; dense
cellular solids such as wood and leather; and many polymeric materials.
Mass transfer between the solid surface and the gas is covered by the relations
discussed in Chap. 21. The drying rate of solids containing internal liquid, however,
depends on the way the liquid moves and on the distance it must travel to reach
the surface. This is especially important in cross-circulation drying of slabs or beds
of solids. Drying by this method is slow, is usually done batch wise, and has been
displaced by other faster methods in most large-scale drying operations; it remains
important, however, in the production of pharmaceuticals and fine chemicals,
especially when drying conditions must be carefully controlled.
Constant drying conditions. Consider a bed of wet solids, perhaps 50 to 75 mm (2
to 3 in.) deep, over which air is circulated. Assume that the temperature, humidity,
and velocity and direction of flow of the air across the drying surface are constant.
This is called drying under constant drying conditions. Note that only the condi-
tions in the airstream are constant, as the moisture content and other factors in
the solid are changing.
RATES OF DRYING. As time passes, the moisture content X T typically falls as
shown by graph A in Fig. 24.4. After a short period during which the feed is heated
to the vaporization temperature, the graph becomes linear, then curves toward
the horizontal, and finally levels off. The drying rate is shown by graph B; it is
horizontal for much of its length, indicating that the drying rate is constant; later
0:
o
c:
z
~ A
Zw
ot-
uo< Total moisture
wO:
0:", content
::lz
t;>=
o~
"-''''.
g 8 Drying rate
t-
~
FIGURE 24.4
Olk-__________________ ~ _______ Typical plots of total moisture content
o t, TIME and drying rate vs. drying time.
778 MASS TRANSFER AND ITS APPLICATIONS
it curves downward and eventually, when the material has come to its equilibrium
moisture content, reaches zero.
Figures 24.5 and 24.8 show the drying rate per unit area R plotted against
the free moisture content X T - X*, or X. Figure 24.5 is the curve for a nonporous
clay slab; Fig. 24.8 is that for a porous ceramic plate. The difference in the shapes
of these curves reflects the differences in the mechanism of internal moisture flow
in the two materials.
CONSTANT-RATE PERIOD. After the preliminary adjustment period (not shown
in the figures) each curve has a horizontal segment AB that pertains to the first
major drying period. This period, which may be absent if the initial moisture
content of the solid is less than a certain minimum, is called the conslant-rale
0..35
B A
0.30.
0..25
N
I-
':00.20.
/
"-
ill
-"
w
~ -<
0:: 0..15
l
<9
z
>=
is
0:' 0.10.
V
0..0.5 /
/
0. ~
0. 0.0.5 0..10. 0..15 0.20. 0..25
X,FREE Mo.ISTURE. LB/LB DRY So.L1D
FIGURE 24S
Drying-rate curves for nonporous clay slab. (After Sherwood. 13)
DRYING OF SOLIDS 779
iperiod. It is characterized by a rate of drying independent of moisture content.
iDuring this period, the solid is so wet that a continuous film of water exists over
the entire drying surface, and this water acts as if the solid were not there. If the
solid is nonporous, the water removed in this period is mainly superficial water
on the surface of the solid. In a porous solid, most of the water removed in the
constant-rate period is supplied from the interior of the solid. The evaporation
from a porous material is by the same mechanism as that from a wet-bulb
thermometer, and the process occurring at a wet-bulb thermometer is essentially
one of contant-rate drying. In the absence of radiation or of heat transfer by
conduction through direct contact of the solid with hot surfaces, the temperature
of the solid during the constant-rate period is the wet-bulb temperature of the air.
During the constant-rate period the drying rate per unit area R, can be
estimated with fair precision from correlations developed for evaporation from a
free liquid surface. The calculations may be based on mass transfer [Eq. 24.11]
or on heat transfer [Eq. (24.12)] as follows:
(24.11)
or
. h,(T -1;)A
mv= (24.12)
where 1nv = rate of evaporation
A = drying area
hy = heat-transfer coefficient
ky = mass-transfer coefficient
M" = molecular weight of vapor
T = temperature of gas
1; = temperature at interface
y = mole fraction of vapor in gas
y, = mole fraction of vapor at interface
.1., = latent heat at temperature 1;
To estimate the coefficient for air flowing parallel with the surface of a solid
in the absence of experimental information, the following dimensional equation is
recommended 9,,:
hy = 8.8Go. 8 /D~·2 (24.13)
where hy = heat-transfer coefficient, W/m2_0C
G = mass velocity, kg/s-m2
D, = equivalent diameter of the airflow channel, m
Equation (24.13) is based on the properties of air at 95°C; it applies for Reynolds
numbers between 2600 and 22,000.
780 MASS TRANSFER AND ITS APPLICATIONS
When the flow is perpendicular to the surface, at air velocities between 0.9
and 4.5 m/s, the equation is"
(24.14)
In fps units, with h in Btu/ft 2-h- o F, Gin Ib/ft2-h, and D, in ft, the coefficient
in Eq. (24.13) is 0.01 and that in Eq. (24.14) is 0.37.
The constant drying rate R, is simply
(24.15)
In most situations, as previously mentioned, temperature T, may be assumed
to be equal to the wet-bulb temperature of the air. When radiation from hot
surroundings and conduction from solid surfaces in contact with the stock are not
negligible, however, the temperature of the interface is greater than the wet-bulb
temperature, y, is increased, and the rate of drying is, by Eq. (24.11), increased
accordingly. Methods for estimating these effects are available?'·!2
CRITICAL MOISTURE CONTENT AND FALLING-RATE PERIOD. As the mois-
ture content decreases, the constant-rate period ends at a definite moisture content,
and during further drying the rate decreases. The point terminating the constant-
rate period, shown by point B in Figs. 24.5 and 24.8, is called the critical point.
This point marks the instant when the liquid water on the surface is insufficient
to maintain a continuous film covering the entire drying area. In nonporous solids,
the critical point occurs at about the time when the superficial moisture is
evaporated. In porous solids, the critical point is reached when the rate of moisture
flow to the surface no longer equals the rate of evaporation called for by the
wet-bulb evaporative process.
If the initial moisture content of the solid is below the critical point, the
constant-rate period does not occur.
The critical moisture content varies with the thickness of the material and
with the rate of drying. It is therefore not a property of the material itself. The
critical moisture content is best determined experimentally, although some ap-
proximate data are available?'
Example 24.1. A filter cake 24 in. (610 mm) square and 2 in. (51 mm) thick, supported
on a screen, is dried from both sides with air at a wet-bulb temperature of 80°F
(26.7°C) and a dry-bulb temperature of 120°F (4S.9°C). The air flows parallel with
the faces of the cake at a velocity of 3.5 ft/s (1.07 m/s). The dry density of the cake
is 120lb/ft' (1922 kg/m'). The equilibrium-moisture content is negligible. Under the
conditions of drying the critical moisture is 9 percent, dry basis. (a) What is the drying
rate during the constant-rate period? (b) How long would it take to dry this material
from an initial moisture content of 20 percent (dry basis) to a final moisture content
of 10 percent? Equivalent diameter De is equal to 2 ft.
DRYING OF SOLIDS 781
Solution
(a) The interface temperature 7; is the wet-bulb temperature of the air, 80°F.
Then A, is, by Appendix 7, 1049 Btujlb. The mass velocity of the air is
3.5 x 29 x 492 x 3600 ,
G= = 863 Ib/ft -h
359(460 + 120)
The coefficient h" by Eq. (24.13), in fps units, is
,,= om x 863°"/2°., =1.94 Btu/ft'-h-'F
Substituting in Eq. (24.15) gives
R, = 1.94(~~; 80) 0.074Ib/ft'-h
(b) Since drying is from both faces, area A is 2 X (24/12)' = 8 ft'. The rate of
drying riIv is therefore
rn, = 0.074 x 8 = 0.591bJh
The volume of the cake is (24/12)' x (2/12) = 0.667 ft', and the mass of bone-dry
solids is 120 x 0.667 = 80 lb. The quantity of moisture to be vaporized is
80(0.20 - 0.10) = 8 lb. Drying time IT is therefore 8/0.59 = 13.5 h.
The period subsequent to the critical point is called the falling-rate period.
It is clear from Figs. 24.5 and 24.8 that the drying-rate curve in the falling-rate
period varies from one type of material to another. The shape of the curve also
depends on the thickness of the material and on the external variables. In some
situations, illustrated in Fig. 24.8, there is a distinct break in the curve during the
falling-rate period, Signifying a change in the drying mechanism. This break occurs
at what is called the second critical point, corresponding to the second critical
moisture content.
Methods of estimating drying rates in the falling-rate period depend on
whether the solid is porous or nonporous. In a nonporous material, once there is
no more superficial moisture, further drying can occur only at a rate governed by
diffusion of internal moisture to the surface. In a porous material other mechan-
isms appear, and vaporization may even take place inside the solid instead of at
the surface.
NONPOROUS SOLIDS AND DIFFUSION THEORY. The moisture distribution in
a solid giving a falling-fate curve like that of Fig. 24.5 is shown as the dotted line
in Fig. 24.6, in which the local moisture content is plotted against distance from
the surface. Its shape is qualitatively consistent with that called for by assuming
that the moisture is flowing by diffusion through the solid, in accordance with Eq.
(21.79). It differs somewhat from the theoretical curve, as explained later. Equation
(21.79) has long been used as a basis for quantitative calculations of the rate of
drying of nonporous solids.-· l l Materials drying in this way are said to be drying
782 MASS TRANSFER AND ITS APPLICATIONS
w
Actual----..,. ~ _ ~
z
::J
ffi
/
/
/
-- -- !zw
u
I
I
~~- Theoreticol
I
/
I
I
I
DISTANCE FROM SURFACE ~
FIGURE 24.6
Moisture distribution in slab dried from both faces. Moisture flow by diffusion.
by diffusion, although the actual mechanism is probably considerably more
complicated than that of simple diffusion.
Diffusion is characteristic of slow-drying materials. The resistance to mass
transfer of water vapor from the solid surface to the air is usually negligible, and
diffusion in the solid controls the overall drying rate. The moisture content at the
surface, therefore, is at or very near the equilibrium value. The velocity of the air
has little or no effect, and the humidity of the air influences the process primarily
through its effect on the equilibrium-moisture content. Since diffusivity increases
with temperature, the rate of drying increases with the temperature of the solid.
Equations for diffusion. Assuming that the diffusion law given by Eq.(21.79) applies
even though the moisture content X is based on mass, not volume, the integrated
forms of this equation can be used to relate the time of drying with the initial and
final moisture contents. Thus, if the assumptions made in integrating Eq. (21.79)
are all accepted, Eq. (21.80) is obtained on integration. For drying, the results can
be written
(24.16)
DRYING OF SOLIDS 783
where f3 = D;tT/S2
a, = (n/2)2
X T = average total moisture content at time tT h
X = average free-moisture content at time tT h
X* = equilibrium-moisture content
X T1 = initial moisture content at start of drying when t = 0
X, = initial free-moisture content
D; = diffusivity of moisture through solid
s = one-half slab thickness
All moisture contents are in mass of water per unit mass of bone-dry solid. In
Fig. 10.6, with f3 in place of N Fo and X/X, in place of (T, - T,,)(T, - 7,;), is a plot
of Eq. (24.16) for drying a large fiat slab.
The accuracy of the diffusion theory for drying suffers from the fact that the
diffusivity usually is not constant but varies with moisture content. It is especially
sensitive to shrinkage. The value of D; is less at small moisture contents than at
large and may be very small near the drying surface. Thus, the moisture distribu-
tion called for by the diffusion theory with constant diffusivity is like that shown
by the solid line in Fig. 24.6. In practice, an average value of D;, established
experimentally on the material to be dried, is used.
When f3 is greater than about 0.1, only the first term on the right-hand side
of Eq. (24.16) is significant, and the remaining terms of the infinite series may be
dropped. Solving the resulting equation for the drying time gives
4s 2 8X,
tT=--ln-- (24.17)
n2D~ n2 X
Differentiating Eq. (24.17) with respect to time and rearranging gives
_dX=("l'.)2D;X (24.18)
dt 2 S2
Equation (24.18) shows that when diffusion controls, the rate of drying is directly
proportional to the free-moisture content and inversely proportional to the square
of the thickness. Equation (24.17) shows that if time is piotted against the logarithm
of the free-moisture content, a straight line should be obtained, from the slope of
which D; can be calculated.
Example 24.2. Planks of wood 25.4 mm thick are dried from an initial moisture
content of 25 percent to a final moisture of 5 percent using air of negligible humidity.
If D; for the wood is 8.3 x 10- 6 crn 2/s, how long should it take to dry the wood?
Solution
Since the air is dry, the equilibrium-moisture content is zero, and Xl = 0.25 and
X = 0.05. Then X/X, = 0.05/0.25 = 0.20. From Fig. 10.6, P is read on the abscissa
784 MASS TRANSFER AND ITS APPLICATIONS
corresponding to the known ordinate of 0.20 and found to be 0.57. Since s =
25.4/(2 x 10) cm,
8.3 X 1O- 6 /
-:-:-:-::-::-:::-;;-'-T ~ 0.57
(12.7/10)2
Solving for IT gives a drying time of 110,765 s, or 30.8 h.
Another solution can be found by Eq. (24.17). Substituting the appropriate
values in this equation gives
4(12.7/10)2 In [(8 x 0.25)/(,,2 x 0.05)]
/ ~ ~3Q6h
T ,,2(8.3 x 10 6) x 3600
Shrinkage and casehardening. When bound moisture is removed from a colloidal
nonporous solid, the material shrinks. In small pieces this effect may not be
important, but in large units improper drying may lead to serious product
difficulties that are basically a result of shrinkage. Since the outer layers necessarily
lose moisture before the interior portions, the concentration of moisture in these
layers is less than that in the interior, and the surface layers shrink against an
unyielding, constant-volume core. This surface shrinkage causes checking, crack-
ing, and warping. Also, since the diffusivity is sensitive to moisture concentration
and generally decreases with decreasing concentration, the resistance to diffusion
in the outer layers is increased by surface dehydration. This accentuates the effect
of shrinkage by impeding the flow of moisture to the surface and so increasing
the moisture gradient near the surface.
In extreme cases, the shrinkage and drop in diffuSivity may combine to give
a skin, practically impervious to moisture, which encloses the bulk of the material
so the interior moisture cannot be removed. This is called casehardening.
Warping, checking, cracking, and casehardening can be minimized by
reducing the rate of drying, thereby flattening the concentration gradients in the
solid. Then the shrinkage of the surface is reduced, and the diffusivity throughout
the solid is more nearly constant. The moisture gradient at the surface is flattened,
and the entire piece is protected against shrinkage.
The rate of drying is controlled most readily by controlling the humidity of
the drying air. Since the equilibrium-moisture concentration X* at the surface is
fixed by the humidity of the air, increasing the humidity also increases X*. For a
given total moisture concentration X T , the free-moisture concentration X is
reduced by increasing the equilibrium moisture X*. The overall concentration
gradient of. free water is then reduced, the drying slowed, and the skin effect
minimized.
POROUS SOLIDS AND FLOW BY CAPILLARITY. The flow of liqnid through
porous solids does not conform to the solution to the diffusion equation given by
Eq. (24.16). This may be seen by comparing the moisture distribution in a solid
of this type during drying with that for diffusion. A typical moisture-distribution
curve for a porous solid is shown in Fig. 24.7. A point of inflection divides the
DRYING OF SOLIDS 785
>-
zw
>-
Z
0
'"
<I
-l
if)
u
w "-
et: 0
::J W
>-
if)
Z
:J
0
:;; et:
W
W >-
W Z
et: W
"- U
...-
DISTANCE FROM SURFACE ___
FIGURE 24.7
Moisture distribution in porous slab dried from both faces. Moisture flow by capillarity.
curve into two parts, one concave npward and one concave downward. This is
completely contrary to the distribution called for by the diffusion model, as shown
in Fig. 24.6.
Moisture flows through porous solids by capillarity'·2.• and to some extent
by surface diffusion (see Chap. 25, p. 826). A porous material contains a compli-
cated network of interconnecting pores and channels, the cross sections of which
vary greatly. At the surface are the mouths of pores of various sizes. As water is
removed by vaporization, a meniscus across each pore is formed, which sets up
capillary forces by the interfacial tension between the water and the solid. The
capillary forces possess components in the direction perpendicular to the surface
of the solid. It is these forces that provide the driving force for the movement of
water through the pores toward the surface.
The strength of capillary forces at a given point in a pore depends on the
curvature of the meniscus, which is a function of the pore cross section. Small
pores develop greater capillary forces than large ones, and small pores, therefore,
can pull water out of the large pores. As the water at the surface is depleted, the
large pores tend to empty first. Air must displace the water so removed. This air
enters either through the mouths of the larger pores at the drying surface or from
the sides and back of the material if drying is from one side only.
786 MASS TRANSFER AND ITS APPLICATIONS
The rate-of-drying curve for a typical porous solid having small pores is
shown in Fig. 24.8. As long as the delivery of water from the interior to the surface
is sufficient to keep the snrface completely wet, the drying rate is constant. The
pores are progressively depleted of water, and at the critical point the surface layer
of water begins to recede into the solid. This starts with the larger pores. The high
points on the surface of the,solid begin to emerge from the liquid, and the area
available for mass transfer from the solid into the air decreases. Then, although
the rate of evaporation per unit wetted area remains unchanged, the rate based
on the total surface, including both wet and dry areas, is less than that in the
constant-rate period. The rate continues to decrease as the fraction of dry surface
increases.
The first section of the faIling-rate period is shown by line BC in Fig, 24.8.
The rate of drying during this period depends on the same factors that are active
during the constant-rate period, since the mechanism of evaporation is unchanged
and the vaporization zone is at or near the surface, The water in the pores is the
continuous phase and the air the dispersed phase. In the first falling-rate period,
the rate-of-drying curve is usually linear.
As the water is progressively removed from the solid, the fraction of the pore
volume that is occuped by air increases. When the fraction reaches a certain limit,
there is insufficient water left to maintain continuous films across the pores and
the pores fill with air, which now becomes the continuous phase. The remaining
water is relegated to small isolated pools in the corners and interstices of the pores.
When this state appears, the rate of drying again suddenly decreases, as shown
by line CD in Fig. 24,8. The moisture content at which this break appears, shown
1.0
VB A
1
l''"
I
,LL
CD
I1
/
..J
W
!:io.5
11
0:
<.?
1
Z c
>=
0:
o
0::- /
V
0 L.-- V
°° 0.05
X,FREE MOISTURE, LB/LB DRY SOLID
0,10 0.15
FIGURE 24.8
Drying-rate curve for porous ceramic plate. (After Sherwood and Comings. 14 )
DRYING OF SOLIDS 787
by point C in Fig. 24.8, is called the second critical point, and the period that it
initiates is called the second falling-rate period.
In this final drying period the vaporization rate is practically independent
of the velocity of the air. The water vapor must diffuse through the solid, and the
heat of vaporizatiou must be transmitted to the vaporization zones by conduction
through the solid. Temperature gradients are set up in the solid, and the
temperature of the solid surface approaches the dry-bulb temperature of the air.
For fine pores, the rate-of-drying curve during the second falling-rate period
conforms to the diffusion model, and the drying-rate curve is concave upward.
CALCULATION OF DRYING TIME UNDER CONSTANT DRYING CON-
DITIONS. In the design of dryers, an important quantity is the time required for
drying the material under the conditions existing in the dryer, as this fixes the size
of the equipment needed for a given capacity. For drying under constant drying
conditions, the time of drying can be determined from the rate-of-drying curve if
it can be constructed. Often the only source of this curve is an experiment on the
material to be dried, and this gives the drying time directly. Drying-rate curves
for one set of conditions often may be modified to other conditions, and then
working back from the drying-rate curve to drying time is useful. By definition,
R= _ dm, = _ m,dX (24.19)
A dt A dt
Integrating Eq. (24.19) between X, and X"~ the initial and final free-moisture
contents, respectively,
tT = m,
A
fX
' dX
x, R
(24.20)
where tT is the total drying time. Equation (24.20) may be integrated numeri-
cally from the rate-of-drying curve or analytically if equations are available giving
R as a function of X.
In the constant-rate period R = R, and the drying time is simply
m,(X,-X ) z
t = --"'--'--"":::' (24.21)
cARe
In the falling-rate period, when diffusion controls, the drying time t f for a
slab is given by Eq. (24.17). If R is linear in X, as with many porous solids, during
the falling-rate period,
R=aX+b (24.22)
where a and b are constants, and dR = a dX. Substitution for dX in Eq. (24.20)
gives, for the time required in the falling-rate period,
t
f
= m, dRfR' = m, In R, (24.23)
aAR,R aA Rz
788 MASS TRANSFER AND ITS APPLICATIONS
where R, and R2 are the ordinates for the initial and final moistnre contents,
respectively. The constant a is the slope of the rate-of-drying curve and may be
written as
Rc- R'
a= (24.24)
Xc-X'
where R, = rate at first critical point
R' = rate at second critical point
X, = free-moisture content at first critical point
X = free-moisture content at second critical point
Substitution of a from Eq. (24.24) into Eq. (24.23) gives
rn,(X, - X) R,
If = A(R, _ R') In R2 (24.25)
When the drying process covers both a constant-rate period and a falling-rate
period, the X 2 of Eq. (24.21) equals X" and the R, of Eq. (24.25) equals Rc The
total time of drying t T is then
1-1+1--
rn,(x,-x, + X,-X'l nR,)
- (24.26)
T-, f- A R, R-R'R
, ,
Here X, is the moisture content at the start of the entire process, and R, is
the drying rate at the end of the process.
In SO'11e situations, a single straight line passing through the origin ade-
quately represents the entire falling-rate period. The point (X" R,) lies on this line.
When this approximation may be made, Eq. (24.26) may be simplified by noting
that b, R', X' dmp out, that a = R,/X" and that RJR, = XJX,. Equation (24.26)
then becomes
IT = -rn, [(X,-X,)+X,ln-
X,] (24.27)
AR, X,
Here X 2 is the moisture content at the end of the entire process.
Through-Circulation Drying
If the particles of wet solid are large enough, gas may be passed through the bed
instead of across it, usually with a significant increase in drying rate. Even if the
individual particles are too small to permit this, the material in many cases may
be "preformed" into a condition suitable for through-circulation drying. Filter
cake, for example, may be granulated or extruded into "biscuits" or spaghettilike
cylinders, perhaps 6 mm in diameter and several centimeters long. Preforms
usually retain their shape during drying and form a permeable bed of fairly high
porosity.
DRYING OF SOLIDS 789
The rates of heat and mass transfer to particle surfaces in a bed of solids
can be calculated from Eq. (21.62), as illustrated in Example 24.3 below. The results
of such calculations, however, are best used for preliminary estimates only, for it
is always advisable, and usually necessary, to make experimental tests with the
actual material to be dried.
Example 24.3. The filter cake of Example 24.1 is extruded onto a screen in the form
of cylinders i in. in diameter and 4 in. long. The solids loading is 8 pounds of dry
solids per square foot of screen surface. The bed porosity is 60 percent. Air at 120°F
(dry-bulb) and with a wet-bulb temperature of 80°F is passed through the bed at
a superficial velocity of 3.5 ft/s. How long will it take to dry the solids from 20 to
10 percent moisture?
Solution
Since the critical moisture content is less than 10 percent, all drying takes place in
the constant-rate period and the vaporization temperature, as before, is 80°F and 1
is 1049 Btuflb. Per square foot of screen surface, therefore, the mass of water to be
evaporated is 8(0.20 - 0.10) = 0.8Ib, and the quantity of heat to be transferred QT
is 0.8 x 1049 = 839 Btu.
The mass of dry solids in one cylinder is
nx(oB' 4
rnp = - - - x - x 120 = 0.0136Ib
4 x 144 12
Neglecting the ends of the pieces, the surface area of one cylinder is
1t x1 4
Ap = __4 X _ = 0.0218 ft'
12 12
The total area exposed by 8 Ib of solids is
8
A = - - x 0.0218 = 12.8 ft'
0.0136
The heat-transfer coefficient is found from the equivalent form of Eq. (21.62):
liD = 117No,ss'Nl/3
k . Re Pr
For air at 1 atm and 120°F, the properties are
29 492 3
P = 359 x 580 = 0.0685 Iblft Jl = 0.019 cP (Appendix 8)
k = 0.0162 Btu/ft_h_oF (Appendix 12) Cp = 0.25 Btujlb-oF (Appendix 15)
The Reynolds number, based on the diameter of the particles, is
Dp D;Vp
N Re = - - = - -
Jl Jl
(:la) x 3.5 x 0.0685
391
0.019 x 6.72 x 10- 4
790 MASS TRANSFER AND ITS APPLICATIONS
The Prandtl number is
0.25 x 0.019 x 2.42
0.71
0.0162
From Eq. (21.62),
0.0162 x 1.17 x 391°·585 x 0.71 1 / 3
h =------;------
= 26.7 Btu/ft'-h-oF
The heat transferred from the gas to a thin section of bed is
,ituC, dT, = hdA(1/, - Tw)
which integrates to
Per square foot of screen surface, the mass flow rate of the air is
,n, = 3.5 x 3600 x 0.0685 = 863 Ibfh
From Fig. 23.2, c, = 0.25. Then
1/" - Tw 26.7 x 12.8
In 1.58
1/,. - Tw 863 x 0.25
Since 1/" - Tw = 120 - 80 = 40°F,
40 - 8.24
20.1°F
In(40/8.24)
If qT is the rate of heat transfer and tT is the drying time,
= 26.7 x 12.8 x 20.1
= 6869 Btufh
From this, since QT = 839 Btu,
839
IT = - - = 0.122 h or 7.33 min
6869
Note that the final moisture content of 10 percent in Example 24.3 is the
average value for all the solids. The top layer, exposed to the hottest air, would
be dried to 10 percent moisture in about 3.7 min, so that at the end of the 7.33-min
drying time the top layer would be drier than the average and the bottom layer
would be somewhat wetter. Note also that the drying time in Example 24.3 is less
DRYING OF SOLIDS 791
than 1 percent of the time required with cross-circulation drying (Example 24.1).
Although the solids loading in Example 24.3 is only 40 percent of that in Example
24.1, the amount of solids dried per unit time with through-circulation drying is
30 to 40 times as much as with cross-circulation drying. It is true that this is for
constant-rate drying, but drying rates in the falling-rate period are also enhanced,
primarily because of the reduction in diffusion distance.
To estimate diffusion rates inside cylinders or spheres of nonporous solids,
equations similar to Eq. (24.16) for slabs can be written by analogy with Eqs.
(10.18) and (10.19) for heat transfer. If X, and D~ are known, these give the
drying-rate curve in the falling-rate period. With porous solids the drying-rate
.curve in the falling-rate period is best approximated, in the absence of experimental
data, by a straight line through the origin.
Drying of Suspended Particles
Mass transfer from the surface of a solid particle or a liquid drop falling through
a gas may be found from Eq. (21.59) or Fig. 21.5, provided the velocity difference
between the particle or drop and the gas is known. Often, as in a tower dryer or
rotary dryer, only part of the drying is done while the particles are being showered
through the gas, and such dryers are therefore designed using empirical equations
(see "Rotary Dryers," page 796).
Transfer to suspended particles is estimated from an equation like Eq. (21.59);
it is often appropriate simply to assume that the Nusselt or Sherwood number is
2.0, the limit for a relative velocity of zero. As discussed later under fluid-bed
dryers, however, it is not always possible to calculate an average temperature
difference or mass-transfer driving force between the gas and solid, and drying
rates must be found by experiment.
Internal diffusion in spherical particles may be estimated from an equation
analogous to Eq. (11.40).
The time required to dry individual particles is usually very short, so short,
in fact, that the terms constant rate and falling rate have no Significance. In flash
dryers and some kinds of spray dryers the drying is all finished in ! to 5 s.
DRYING EQUIPMENT
Of the many types of commercial dryers available,.··l6 only a small number of
important types will be considered here. The first and larger group comprises
dryers for rigid or granular solids and semisolid pastes; the second group consists
of dryers that can accept slurry or liquid feeds.
Dryers for Solids and Pastes
Typical dryers for solids and pastes include tray and screen-conveyor dryers for
materials that cannot be agitated and tower, rotary, screw-conveyor, fluid-bed,
and flash dryers where agitation is permissible. In the following treatment these
792 MASS TRANSFER AND ITS APPLICATIONS
types are ordered, as far as possible, according to the degree of agitation and the
method of exposing the solid to the gas or contacting it with a hot surface, as
discussed at the beginning of this chapter. The ordering is complicated, however,
by the fact that some types of dryers may be either adiabatic or nonadiabatic or
a combination of both.
TRAY DRYERS. A typical batch tray dryer is illustrated in Fig. 24.9. It consists
of a rectangular chamber of sheet metal containing two trucks that support racks
H. Each rack carries a number of shallow trays, perhaps 750 mm (30 in.) square
and 50 to 150 mm (2 to 6 in.) deep, that are loaded with the material to be dried.
Heated air is circulated at 2 to 5 m/s (7 to 15 ft/s) between the trays by fan C and
motor D and passes over heaters E. Baffles G distribute the air uniformly over
the stack of trays. Some moist air is continuously vented through exhaust duct
B; makeup fresh air enters through inlet A. The racks are mounted on truck wheels
I, so that at the end of the drying cycle the trucks can be pulled out of the chamber
and taken to a tray-dumping station.
Tray dryers are useful when the production rate is small. They can dry almost
anything, but because of the labor required for loading and unloading, they are
expensive to operate. They find most frequent application on valuable products
like dyes and pharmaceuticals. Drying by circulation of air across stationary layers
of solid is slow, and drying cycles are long: 4 to 48 h per batch. Occasionally
through-circulation drying is used, but this is usually neither economical nor
necessary in batch dryers because shortening the drying cycle does not reduce the
labor required for each batch. Energy savings may be significant, however.
o--t:::) M-s
F888 E ~ E888 11
1 o~
F 'i c rA88\
000
: Q v
11:
G :
I-H-
,7f
, I-H- C-
r/
~1,
\,
\ ,'
.
: -
-+-
~
;;r
'\
\. ~
~I
~
C-;t
,
~l r 11¥-/-"1
FIGURE 24.9
Tray dryer.
DRYING OF SOLIDS 793
Tray dryers may be operated under vacuum, often with indirect heating. The
trays may rest on hollow metal plates supplied with steam or hot water or may
themselves contain spaces for a heating fluid. Vapor from the solid is removed by
an ejector or vacuum pump. Freeze-drying is the sublimation of water from ice
under high vacuum temperatures below O°e. This is done in special vacuum tray
dryers for drying vitamins and other heat-sensitive products.
SCREEN-CONVEYOR DRYERS. A typical through-circulation screen-conveyor
dryer is shown in Fig. 24.10. A layer 25 to 150 mm (1 to 6 in.) thick of material
to be dried is slowly carried on a traveling metal screen through a long drying
chamber or tunnel. The chamber consists of a series of separate sections, each with
its own fan and air heater. At the inlet end of the dryer the air usually passes
upward through the screen and the solids; near the discharge end, where the
material is dry and may be dusty, air is passed downward through the screen. The
air temperature and humidity may differ in the various sections, to give optimum
conditions for drying at each point.
Screen-conveyor dryers are typically 2 m (6 ft) wide and 4 to 50 m (12 to
150 ft) long, giving drying times of 5 to 120 min. The minimum screen size is about
30-mesh. Coarse granular, flaky, or fibrous materials can be dried by through
circulation without any pretreatment and without loss of material through the
screen. Pastes and filter cakes of fine particles, however, must be preformed before
they can be handled on a screen-conveyor dryer. The aggregates usually retain
their shape while being dried and do not dust through the screen except in small
amounts. Provision is sometimes made for recovering any fines that do sift through
the screen.
Screen-conveyor dryers handle a variety of solids continuously and with a
very gentle action; their cost is reasonable, and their steam consumption is low,
typically 2 kg of steam per kilogram of water evaporated. Air may be recirculated
(aJ Path of travel of permeable bed
through a 3-unilthrough-
circulation dryer
r7"=~=:-:--'--:"'i' Insulated housing
1 - ,..................... . . . '\
;' Material \: Steam
t t ....... 00· ....• •••• • • • •0 heaters
Motor till I1
Fan./
___ . / ,; I , Conveyor
¥,v.k'
(C) Air flow in dry end
FIGURE 24.10
Through-circulation screen-conveyor dryer.
794 MASS TRANSFER AND ITS APPLICATIONS
through, and vented from, each section separately or passed from one section to
another countercurrently to the solid. These dryers are particularly applicable
when the drying conditions must be appreciably changed as the moisture content
of the solid is reduced. They are designed by methods similar to that illustrated
in Example 24.3.
TOWER DRYERS. A tower dryer contains a series of circular trays mounted one
above the other on a central rotating shaft. Solid feed dropped on the topmost
tray is exposed to a stream of hot air or gas that passes across the tray. The solid
is then scraped off and dropped to the tray below. It travels in this way through
the dryer, discharging as dry product from the bottom of the tower. The flow of
solids and gas may be either parallel or countercurrent.
The turbodryer illustrated in Fig. 24.11 is a tower dryer with internal
recirculation of the heating gas. Turbine fans circulate the air or gas outward
between some of the trays, over heating elements, and inward between other trays.
Gas velocities are commonly 0.6 to 2.4 m/s (2 to 8 ft/s). The bottom two trays of
the dryer shown in Fig. 24.11 constitute a cooling section for dry solids. Preheated
air is usually drawn in the bottom of the tower and discharged from the top, giving
countercurrent flow. A turbodryer functions partly by cross-circulation drying, as
in a tray dryer, and partly by showering the particles through the hot gas as they
tumble from one tray to another.
Feed r7iJrblnes (fans)
rr=~~~~~;;;~~;J~~====*~H~9 elements
I
I
I
I I
I
I
I
t: ~
21 : :
:'"·S
I
-tt I
I
3\
I
I
-flg
: ~
1, '"
.~
.....L-~
(3
FIGURE 24.11
Turbodryer.
DRYING OF SOLIDS 795
ROTARY DRYERS. A rotary dryer consists of a revolving cylindrical shell, hor-
izontal or slightly inclined toward the outlet. Wet feed enters one end of the
cylinder; dry material discharges from the other. As the shell rotates, internal
flights lift the solids and shower them down through the interior of the shell.
Rotary dryers are heated by direct contact of gas with the solids, by hot gas passing
through an external jacket, or by steam condensing in a set of longitudinal tubes
mounted on the inner sutface of the shell. The last of these types is called a
steam-tube rotary dryer. In a direct-indirect rotary dryer hot gas first passes
through the jacket and then through the shell, where it comes into contact with
the solids.
A typical adiabatic countercurrent air-heated rotary dryer is shown in Fig.
24.12. A rotating shell A made of sheet steel is supported on two sets of rollers B
and driven by a gear and pinion C. At the upper end is a hood D, which connects
through fan E to a stack, and a spout F, which brings in wet material from the
feed hopper. Flights G, which lift the material being dried and shower it down
through the current of hot air, are welded inside the shell. At the lower end the
dried product discharges into a screw conveyor H. Just beyond the screw conveyor
is a set of steam-heated extended-surface pipes that preheat the air. The air is
moved through the dryer by a fan, which may, if desired, discharge into the air
heater so that the whole system is under a positive pressure. Alternatively, the fan
may be placed in the stack as shown, so that it draws air through the dryer and
keeps the system under a slight vacuum. This is desirable when the material tends
to dust. Rotary dryers of this kind are widely used for salt, sugar, and all kinds
of granular and crystalline materials that must be kept clean and may not be
directly exposed to very hot flue gases.
The allowable mass velocity of the gas in a direct-contact rotary dryer
depends on the dusting characteristics of the solid being dried and ranges from
2000 to 25,000 kg/m2-h (400 to 5OO0Ib/ft 2-h) for coarse particles. Inlet gas tem-
peratures are typically 120 to 175°C (250 to 350°F) for steam-heated air and 550
Moist Feed
air
outlet
Dry solids dische.rg,'l
FIGURE 24.12
Countercurrent air-heated rotary dryer: A, dryer shell; B, shell-supporting rolls; C, drive gear; D,
air-discharge hood; E, discharge fan; F, feed chute; G, lifting flights; H, product discharge; J, air heater.
796 MASS TRANSFER AND ITS APPLICATIONS
to 800°C (1000 to 15OO°F) for flue gas from a furnace. Dryer diameters rauge from
1 to 3 m (3 to 10 ft); the peripheral speed of the shell is commonly 20 to 25 m/min
(60 to 75 ft/min).
Rotary dryers are designed on the basis of heat transfer. An empirical
dimensional equation for the volumetric heat-transfer coefficient Ua is 7
0.500 . 67
Ua=--- (24.28)
D
where Ua is in Btu/ft 3-h-oF, 0 is the mass velocity of the gas in Ib/ft2 -h of
dryer cross section, and D is the dryer diameter in feet. The rate of heat transfer
qT, from Eq. (24.4), is therefore
0.50 0 . 67 -
qT= D V t.T
= 0.125" DLO o.67 t.T (24.29)
where V = dryer volume, ft3
L = dryer length, ft
t.T = average temperature difference, taken as logarithmic mean of wet-bulb
depressions at inlet and outlet of dryer
The proper outlet gas temperature is a matter of economics; it may be estimated
from Eq. (24.6) or (24.8) since it has been found empirically·d that rotary dryers
are operated mo~t economically when N, is between 1.5 and 2.5.
Example 24.4. Calculate the diameter and length of an adiabatic rotary dryer to dry
2800 Ibfh (1270 kgfh) of a heat-sensitive solid from an initial moisture content of 15
percent to a final moisture content of 0.5 percent, both dry basis. The solids have a
specific heat of 0.52 BtuJlb-oF; they enter at 80'F (26.7°C) and must not be heated
to a temperature above 125°F (51.7°C). Heating air is available at 260°F (126.7'C)
and a humidity of O.oIlb of water per pound of dry air. The maximum allowable
mass velocity of the air is 700 Ib/ft2-h (3420 kgfm'-h).
Solution
In view of the heat sensitivity of the solids, cocurrent operation will be used. The
outlet gas temperature is found from Eq. (24.8) for adiabatic drying. Assume the
number of transfer units is 1.5. The inlet wet-bulb temperature Twb , from Fig. 23.2,
is 102°F. Since 1/" is 260°F, Eq. (24.8) gives
260 -102
N, = 1.5 = In - - - -
1/" - 102
From this, 1'"a = 137°F and ~b may reasonably be set at the maximum alIowable
value, 125°F.
Other quantities needed are
,! at 102°F = 1036 BtuJlb (Appendix 7)
DRYING OF SOLIDS 797
Specific heats, in Btuflb-'F,
(Appendix 15)
Also
X. = 0.15 Xb = 0.005 rn, = 2800 Ibfh
From Eq. (24.9),
'", = 2S00(0.15 - 0.005) = 4061bfh
The beat duty is found from substitution in Eq. (24.1):
qT = 0.52(125 _ 80) + 0.15 x 1.0(102 - 80)
rn,
+ (0.15 - 0.005)1036 + 0.005 x 1.0(125 - 102)
+ 0.145 x 0.45(137 - 102)
= 23.4 + 3.3 + 150.2 + 0.1 + 2.3 = 179.3 Btuflb
Only the first and third terms are significant. From this, qT = 179.3 x 2800 =
502,040 Btufh.
The flow rate of entering air is found from a heat balance and the humid heat
C,b' From Fig. 23.2, C,b = 0.245 Btuflb-'F. Tbus
rn,(1 + ,ff,) = --'''--
C,b(1/,b - 1/,,)
502,040 = 16 660 Ibfh
0.245(260 - 137) ,
Since ,ff, = 0.01, m, = 16,660/1.01 = 16,4951bfh of dry air.
The outlet humidity Jf;. is found from Eq. (24.10):
406
Jf;. = 0.01 +-- = 0.0346 Ibflb
16,495
At a dry-bulb temperature T"" of 137'F, wet-bulb temperature Tw. for Jf;. = 0.0346
is 102'F, the same as TWb (as it should be for adiabatic drying).
The dryer diameter is found from the allowable mass velocity and the flow
rate of tbe entering air. For G = 700 Ib/ft'-h, the cross-sectional area of the dryer
must be 16,660/700 = 23.S ft', and the dryer diameter is
4
D = ( x :3.8)"" = 5.50 ft (1.68 m)
The dryer lengtb is given by Eq. (24.29):
L
0.125nDGo. 67 11 T
The logarithmic mean temperature difference is
(260 - 102) - (137 - 102)
SI.6'F
In[(260 - 102)/(137 - 102)]
798 MASS TRANSFER AND ITS APPLICATIONS
Therefore,
L = _ _ _ _5-'0-'2,-'04-'0~~-
0.1251< x 5.5 X 700°·67 x 81.6
= 35.4 say, 36 ft (11.0 m)
This gives a ratio L/D of 36/5.5 = 6.54, a reasonable value for rotary dryers.
SCREW-CONVEYOR DRYERS. A screw-conveyor is a continuous indirect-heat
dryer, consisting essentially of a horizontal screw conveyor (or paddle conveyor)
enclosed in a cylindrical jacketed shell. Solid fed in one end is conveyed slowly
through the heated zone and discharges from the other end. The vapor evolved
is withdrawn through pipes set in the roof of the shell. The shell is 75 to 600 mm
(3 to 24 in.) in diameter and up to 6 m (20 ft) long; when more length is required,
several conveyors are set one above another in a bank. Often the bottom unit in
such a bank is a cooler in which water or another coolant in the jacket lowers
the temperature of the dried solids before they are discharged.
The rate of rotation of the conveyor is slow, from 2 to 30 r/min. Heat-transfer
coefficients are based on the entire inner surface of the shell, even though the shell
runs only 10 to 60 percent full. The coefficient depends on the loading in the shell
and on the conveyor speed. It ranges, for many solids, between 15 and 60 W/m2-oC
(3 and 10 Btu/ft2-h-OF).
Screw-conveyor dryers handle solids that are too fine and too sticky
for rotary dryers. They are completely enclosed and permit recovery of solvent
vapors with little or no dilution by air. When provided with appropriate feeders,
they can be operated under moderate vacuum. Thus they are adaptable to the
continuous removal and recovery of volatile solvents from solvent-wet solids, such
as spent meal from leaching operations. For this reason they are sometimes known
as desolventizers.
A related type of equipment is described later under "Thin-Film Dryers."
FLUID-BED DRYERS. Dryers in which the solids are fluidized by the drying gas
find applications in a variety of drying problems. 3 The particles are fluidized by
air or gas in a boiling-bed unit, as shown in Fig. 24.13. Mixing and heat transfer
are very rapid. Wet feed is admitted to the top of the bed; dry product is taken
out from the side, near the bottom. In the dryer shown in Fig. 24.13 there is a
random distribution of residence times; the average time a particle stays in the
dryer is typically 30 to 120 s when only surface liquid is vaporized and up to 15
to 30 min if there is also internal diffusion. Small particles are heated essentially
to the exit dry-bulb temperature of the fluidizing gas; consequently, thermally
sensitive materials must be dried in a relatively cool suspending medium. Even so
the inlet gas may be hot, for it mixes so rapidly that the temperature is virtually
uniform, at the exit gas temperature, throughout the bed. If fine particles are
present, either from the feed or from particle breakage in the fluidized bed, there
DRYING OF SOLIDS 799
Clean gas
discharge
Fluidizing Dust
chamber collector
Feeder
Distributor
plate
Heat
source
FlUIdizing
blower
Air
Inlet
FIGURE 24.13
Continuous fluid-bed dryer.
may be considerable solids carryover with the exit gas and cyclones and bag filters
are needed for fines recovery.
Some rectangular fluid-bed dryers have separately fluidized compartments
through which the solids move in sequence from inlet to outlet. These are known
as plug jiow dryers; in them the residence time is almost the <°'11e for all particles.
Drying conditions can be changed from one compartment to another, and often
the last compartment is fluidized with cold gas to cool the solids before discharge.
Heat-transfer coefficients can be estimated from Eq. (12.70) with G = pUp
where Ut is the terminal velocity of the particles (see Fig. 7.10). Dryer capacities,
however, especially with fine particles, are best established by experiment. The exit
gas is nearly always saturated with vapor for any allowable fluidization velocity.
Dryers of the kind shown in Fig. 24.13 may also be operated batchwi,·. A
charge of wet solids in a perforated container attached to the bottom of the
800 MASS TRANSFER AND ITS APPLICATIONS
fluidizing chamber is fluidized, heated until dry, then discharged. Such units have
replaced tray dryers in many processes.
FLASH DRYERS. In a flash dryer a wet pulverized solid is transported for a few
seconds in a hot gas stream. A dryer of this type is shown in Fig. 24.14. Drying
takes place during transportation. The rate of heat transfer from the gas to the
suspended solid particles is high, and drying is rapid, so that no more than 3 or
FIGURE 24.14
Flash dryer with disintegrator: A. paddle-conveyor mixer; B. oi1~fired furnace; C. hammer mill; D.
cyclone separator; E. vent fan; F. star feeder; G. solids flow divider and timer.
DRYING OF SOLIDS 801
4 s is required to evaporate substantially all the moisture from the solid. The
temperature of the gas is high-often about 650°C (1200°F) at the inlet-but the
time of contact is so short that the temperature of the solid rarely rises more than
50°C (90°F) during drying. Flash drying may therefore be applied to sensitive
materials that in other dryers would have to be dried indirectly by a much cooler
heating medium.
Sometimes a pulverizer is incorporated in the flash-drying system to give
simultaneous drying and size reduction. Such a system is shown in Fig. 24.14.
Wet feed enters mixer A, where it is blended with enough dry material to make
it free-flowing. Mixed material discharges into hammer mill C, which is swept with
hot flue gas from furnace B. Pulverized solid is carried out of the mill by the gas
stream through a fairly long duct, in which drying takes place. Gas and dry solid
are separated in cyclone D, with the cleaned gas passing to vent fan E. Solids are
removed from the cyclone through star feeder F, which drops them into solids
divider G. This divider is nearly always needed to recycle some dry solid for mixing
with the wet feed. It operates by a timer that moves a flapper valve so that for a
fixed period of time dry solid returns to the mixer and for another fixed period it
is removed as product. Usually more solid is returned to the mixer than is
withdrawn. Typical recirculation ratios are 3 to 4 kg of solid returned per kilogram
of product removed from the system.
Dryers for Solutions and Slurries
A few types of dryers evaporate solutions and slurries entirely to dryness by
thermal means. Typical examples are spray dryers, thin-film dryers, and drum
dryers.
SPRAY DRYERS. In a spray dryer a slurry or liquid solution is dispersed into a
stream of hot gas in the form of a mist of fine droplets. Moisture is rapidly
vaporized from the droplets, leaving residual particles of dry solid, which are then
separated from the gas stream. The flow of liquid and gas may be cocurrent,
countercurrent, or a combination of both in the same unit.
Droplets are formed inside a cylindrical drying chamber by pressure nozzles,
two-fluid nozzles, or, in large dryers, high-speed spray disks. In all cases it is
essential to prevent the droplets or wet particles of solid from striking solid surfaces
before drying has taken place, so that the drying chambers are necessarily large.
Diameters of 2.5 to 9 m (8 to 30 ft) are common.
In the typical spray dryer shown in Fig. 24.15 the chamber is a cylinder
with a short conical bottom. Liquid feed is pumped into a spray-disk atomizer
set in the roof of the chamber. In this dryer the spray disk is about 300 mm (12 in.)
in diameter and rotates at 5000 to 10,000 r/min. It atomizes the liquid into tiny
drops, which are thrown radially into a stream of hot gas entering near the top
of the chamber. Cooled gas is drawn by an exhaust fan through a horizontal
discharge line set in the side of the chamber at the bottom of the cylindrical section.
The gas passes through a cyclone separator where any entrained particles of solid
802 MASS TRANSFER AND ITS APPLICATIONS
Liquor or slurry
supply from Fan exhaust
storage to atmosphere
t-,
'Hot gi~~
f
..;=.....::§I!ray Exhaust fan
inlet::.'" 'dIsk
Instant drying
Slack chamber Fan platform
ttttt ~~
Furnace
Rotary
product
valve-_-i
Floor level
Molof.
Finished product to storage
FIGURE 24.15
Spray dryer with parallel flow.
are removed. Much of the dry solid settles out of the gas into the bottom of the
drying chamber, from which it is removed by a rotary valve and screw conveyor
and combined with any solid collected in the cyclone.
A dimensional equation for the volume-surface mean diameter 15, of the
drops from a disk atomizer is 6
- _ 4 (~)O.6(~)O.2(5'PLLp)o.1
D,-12.2xlOr (24.30)
PLnr 2
r r
2
where 15, = average drop diameter, I'm
r = disk radius, ft
r = spray mass rate per foot of disk periphery, Ib/ft-min
(5' = surface tension of liquid, Ib/min2
PL = density of liquid, Ib/ft 3
11 = disk speed, r/min
I' = viscosity of liquid, cP
Lp = disk periphery, 2"r, ft
The heat-transfer coefficient for the individual drops may be estimated from
Eq. (12.70). The time required to dry a drop of known diameter, however, depends
not only on Iz but also on the mixing pattern. In a dryer with a low ratio of height
to diameter, as in Fig. 24.15, there is a considerable amount of mixing near the
top and the average temperature-difference driving force is less than for true
parallel flow. It is essential, however, to evaporate to dryness the largest drop, not
DRYING OF SOLIDS 803
the average drop. Usually in calculating drying times it may be assumed that the
diameter of the largest drop is twice the value of 15, found from Eq. (24.30).
Average drop diameters in a spray dryer range from 20 flm when a disk
atomizer is used to 180 flm with a coarse spray nozzle. Residence times vary from
3 to 6 s in cocurrent dryers to as much as 25 to 30 s in countercurrent dryers.
The chief advantages of spray dryers are the very short drying time, which
permits drying of highly heat-sensitive materials, and the production of solid or
hollow spherical particles. The desired consistency, bulk density, appearance, and
flow properties of some products, such as foods or synthetic detergents, may be
difficult or impossible to obtain in any other type of dryer. Spray dryers also have
the advantage of yielding from a solution, slurry, or thin paste, in a single step, a
dry product that is ready for the package. A spray dryer may combine the functions
of an evaporator, a crystallizer, a dryer, a size-reduction unit, and a classifier.
Where one can be used, the resulting simplification of the overall manufacturing
process may be considerable.
Considered as dryers alone, spray dryers are not highly efficient. Much heat
is ordinarily lost in the discharged gases. They are bulky and very large, often 25 m
(80 ft) or more high, and are not always easy to operate. The bulk density of the
dry solid-a property of especial importance in packaged products-is often
difficult to keep constant, for it may be highly sensitive to changes in the solids
content of the feed, to the inlet gas temperature, and to other variables. 9 '
In spray-drying solutions the evaporation from the surface of the drops leads
to initial deposition of solute at the surface before the interior of the drop reaches
saturation. The rate of diffusion of solute back into the drop is slower than the
flow of water from the interior to the surface, and the entire solute content
accumulates at the surface. The final dry particles are often hollow, and the product
from a spray dryer is quite porous.
THIN-FILM DRYERS. Competitive with spray dryers in some situations are
thin-film dryers which can accept a liquid or a slurry feed and produce a dry,
free-flowing solid product. They normally are built in two sections, the first of
which is a vertical agitated evaporator-dryer similar to the device illustrated in
Fig. 16.3. Here most of the liquid is removed from the feed, and partially wet solid
is discharged to the second section, as illustrated in Fig. 24.16, in which the residual
liquid content of the material from the first section is reduced to the desired value.
The thermal efficiency of thin-film dryers is high, and there is little loss of
solids, since little or no gas needs to be drawn through the unit. They are useful in
removing and recovering solvents from solid products. They are relatively expen-
sive and are somewhat limited in heat-transfer area. With both aqueous and
solvent feeds the acceptable feed rate is usually between 100 and 200 kg/m 2 -h (20
and 40Ib/ft2-h).
DRUM DRYERS. A drum dryer consists of one or more heated metal rolls on the
outside of which a thin layer of liquid is evaporated to dryness. Dried solid is
scraped off the rolls as they slowly revolve.
804 MASS TRANSFER AND ITS APPLICATIONS
Vapor
Heating and i I
zone
Vertical
dryer
FIGURE 24.16
Solids "Combi" thjn~film dryer. (Le! Corp.)
A typical drum dryer-a double-drum unit with center feed-is shown in
Fig. 24.17. Liquid is fed from a trough or perforated pipe into a pool in the space
above and between the two rolls. The pool is confined there by stationary end
plates. Heat is transferred by conduction to the liquid, which is partly concentrated
in the space between the rolls. Concentrated liquid issues from the bottom of the
pond as a viscous layer covering the remainder of the drum surfaces. Substantially
all the liquid is vaporized from the solid as the drums turn, leaving a thin layer
of dry material that is scraped off by doctor blades into conveyors below.
Vaporized moisture is collected and removed through a vapor head above the
drums.
Double-drum dryers are "effective with dilute solutions, concentrated solu-
tions of highly solnble materials, and moderately heavy slurries. They are not
FIGURE 24.17
Conveyor Conveyor Double-drum dryer with center feed.
DRYING OF SOLIDS 805
suitable for solutions of salts with limited solubility or for slurries of abrasive
solids that settle out and create excessive pressure between the drums.
The rolls of a drum dryer are 0.6 to 3 m (2 to 10 ft) in diameter and 0.6 to
4 m (2 to 14 ft) long, revolving at 1 to 10 r/min. The time that the solid is in contact
with hot metal is 6 to 15 s, which is short enough to result in little decomposition
even of heat-sensitive products. The heat-transfer coefficient is high, from 1200 to
2000 W/m2_oC (220 to 360 Btu/ft2-h-OF) under optimum conditions, although it
may be only one-tenth of these values when conditions are adverse. IO The drying
capacity is proportional to the active drum area; it is usually between 5 and 50 kg
per square meter of drying surface per hour (1 and 101b/ft2-h).
Selection of Drying Equipmeut
The first consideration in selecting a dryer is its operability; above all else, the
equipment must produce the desired product in the desired form at the desired
rate. Despite the variety of commercial dryers on the market, the various types
are largely complementary, not competitive, and the nature of the drying problem
dictates the type of dryer that must be used, or at least limits the choice to perhaps
two or three possibilities. The final choice is then made on the basis of capital and
operating costs. Attention must be paid, however, to the costs of the entire isolation
system, not just the drying unit alone.
GENERAL CONSIDERATIONS. There are some general guidelines for selecting a
dryer, but it should be recognized that the rules are far from rigid and exceptions
not uncommon. Batch dryers, for example, are most often used when the produc-
tion rate of dried solid is less than 150 to 200 kg/h (300 to 400 Ib/h); continuous
dryers are nearly always chosen for production rates greater than 1 or 2 tons/h.
At intermediate production rates other factors must be considered. Thermally
sensitive materials must be dried at low temperature under vacuum, with a
low-temperature heating medium, or very rapidly as in a flash or spray dryer.
Fragile crystals must be handled gently as in a tray dryer, a screen-conveyor dryer,
or tower dryer.
The dryer must also operate reliably, safely, and economically. Operating
and maintenance costs must not be excessive; pollution must be controlled; energy
consumption must be minimized. As with other equipment these considerations
may conflict with one another and a compromise reached in finding the optimum
dryer for a given service.
As far as the drying operation itself is concerned, adiabatic dryers are
generally less expensive than nonadiabatic dryers, in spite of the lower thermal
efficiency of adiabatic units. Unfortunately there is usually a lot of dust carryover
from adiabatic dryers, and these entrained particles must be removed almost
quantitatively from the drying gas. Elaborate particle-removal equipment may be
needed, equipment that may cost as much as the dryer itself. This often makes
adiabatic dryers less economical than a "buttoned-up" nonadiabatic system in
which little or no gas is used. Rotary dryers are an example; they were once the
806 MASS TRANSFER AND ITS APPLICATIONS
most common type of continuous dryer, but because of the inevitable entrainment,
other types of dryers which avoid the problem of dust carryover would now, if
possible, be selected in their place. Nonadiabatic dryers are always chosen for very
fine particles or for solids that are too chemically reactive to be exposed to a
stream of gas. They are also widely used for solvent removal and recovery.
THE COMPLETE ISOLATION TRAIN; EVAPORATOR-DRYERS. Many industrial
processes involve the isolation of solids from solution in water or other solvents
to yield a dry, purified granular product suitable for packaging and sale. The
process steps needed to accomplish this are typically evaporation, crystallization,
filtration or centrifuging, drying, size reduction, and classification or screening.
Five or six pieces of equipment are needed. Sometimes an evaporator-dryer can
eliminate the need for many of these. Spray dryers, drum dryers, and thin-film
dryers can accept liquid feed and convert it directly into dry product ready for
packaging. The added cost of removing moisture thermally instead of mechanically
is more than made up by the economies of installing and operating one piece of
equipment instead of many. It may, of course, be necessary to treat the liquid feed
prior to drying to remove impurities that cannot be permitted to appear in the
dried product. It is essential, therefore, that the engineer pay attention to the Whole
isolation process and not focus narrowly on the drying step alone.
SYMBOLS
A Area for drying, m2 or ft2; A p , surface area of a single particle
a Surface area per unit volume, m 2/m 3 or ft 2/ft 3 ; also slope of drying-rate
curve [Eq. (24.22)]
a, (n/2)2
b Constant in Eq. (24.22)
Specific heat at constant pressure, J/g_OC or Btu/lb-oF; CpL' of liquid;
cp :p of solids; cpv , of vapor
C, Humid heat, J/g_OC or Btu/lb-oF; C,b' at gas inlet
D Diameter, m, .urn, or ft; De' equivalent diameter of channel, m or ft; Dp ,
of particle; 15" volume-surface mean diameter, /lm
D' Volumetric diffusivity of liquid through solid, m 2jh, cm 2/s, or ft2jh
G
" Mass velocity of gas, kg/m2-h or Ib/ft 2-h
Yf Humidity of gas, mass of vapor per unit mass of dry gas; £;" at outlet;
.n;" at inlet
h Heat-transfer coefficient, W/m2_0C or Btu/ft2-h_oF; ho, between gas and
particle; 11" between gas and surface of slab
k Thermal conductivity, W/m-oC or Btu/ft-h_oF; kf' at mean film tem-
perature
Mass-transfer coefficient, kg molfm2-h-unit mole-fraction difference or
lb molfft2-h-unit mole-fraction difference
DRYING OF SOLIDS 807
L Length of dryer, m or ft; Lp, perimeter of atomizing disk
M" Molecular weight of vapor
m Mass. kg or lb; mp, of single particle; ms. of solids; mv, of vapor
lh Mass rate of flow, kgjh or lb/h; lh g , of gas; Ih" of bone-dry solids; m"
rate of vaporization
N p, Prandtl number, cpp/k
NR , Reynolds number, DG/p
N, Number of transfer units
n Rotational speed of disk, r/min
QT Quantity of heat transferred, J or Btu
qT Rate of heat transfer, W or Btu/h
R Rate of drying, kg/m2-h or lb/ft'-h; R" in constant-rate period; R j , at
start of drying; R" at end of drying; R', at second critical moisture
content
r Radius of atomizing disk, ft
s One-half slab thickness, m or ft
T Temperature. °C or OF; Tb, of heating medium; 7hIJO at outlet; 7;,b' at
inlet; 7;, at interface; 7;. of solids; 7;;a, at inlet; Y'sb' at outlet; Tv.
vaporization temperature; 1'va, vapor temperature at outlet; Tw , wet-
bulb temperature; ~I'a' at outlet; ~I'b' at inlet
Drying time, h or s; tT, total drying time; te , in constant-rate period;
tJ, in falling-rate period
V Overall heat-transfer coefficient, W/m'-'C or Btu/ft'-h-'F
Va Volumetric heat-transfer coefficient, W/m 3_'C or Btu/ft3-h-'F
u, Terminal velocity of particle, m/s or ft/s
V Volume of dryer, m 3 or ft3
V Superficial velocity of gas, m/s or ft/s
X Free-moisture content, mass of water (or other liquid) per unit mass of
dry solid; X T , total moisture content; X Tj , X" initial total moisture
content; X b • final total moisture content; Xc. free-moisture content at
first critical point; Xl' initial value; X 2 , final value; X*, equilibrium
value; X', at second critical point
Y Mole fraction of vapor in gas phase; Yi, at interface; (1 Y)L, log mean
value of 1 - Y and 1 - Yi
Greek letters
P Dimensionless group, D;tr/s 2 in Eq. (24.16)
r Liquid rate per foot of disk periphery, lb/ft-min
Il. T Average temperature difference; Il. TL , log mean value
A Latent heat of vaporization, J/g or Btujlb; Ai, at interface temperature
T,
p Viscosity, cP, lb/ft-s or lb/ft-h; PJ, at mean film temperature
p Density, kg/m 3 or lb/ft'; PL, of liquid
u' Surface tension of liquid, lb/min'
808 MASS TRANSFER AND ITS APPLICATIONS
PROBLEMS
24.1. Fluorspar (CaF,) is to be dried from 6 to 0.4 percent moisture (dry basis) in a
countercurrent adiabatic rotary dryer at a rate of 18,000 lbjh of bone-dry solids.
The heating air enters at 1000°F with a humidity of 0.03 and a wet-bulb tem-
perature of 150°F. The solids have a specific heat of 0.48 Btujlb-oF; they enter the
dryer at 70°F and leave at 20Qo F. The maximum allowable mass velocity of the air
is 2000 Ib/ft'-h. (a) Assuming Eq. (24.8) applies, what would be the diameter and length
of the dryer if N, = 2.2? Is this a reasonable design? (b) Repeat part (a) with N, = 1.8.
24.2. A porous solid is dried in a batch dryer under constant drying conditions. Seven
hours are required to reduce the moisture content from 35 to 10 percent. The critical
moisture content was found to be 20 percent and the equilibrium moisture 4 percent.
All moisture contents are on the dry basis. Assuming that the rate of drying during
t!te falling-rate period is proportional to the free-moisture content, how long should
it take to dry a sample of the same solid from 35 to 5 percent under the same drying
conditions?
24.3. A slab with a wet weight of 5 kg originally contains 50 percent moisture (wet basis).
The slab is 600 by 900 by 75 mm thick. The equilibrium-moisture content is 5 percent
of the total weight when in contact with air of 20°C and 20 percent humidity. The
drying rate is given in Table 24.1 for contact with air of the above quality at a definite
velocity. Drying is from one face. How long will it take to dry.the slab to 15 percent
moisture content (wet basis)?
TABLE 24.1
Data for Prob. 24.3
Wet-slab weight, kg 9.1 7.2 5.3 4.2 3.3 2.9 2.7
Drying rate, kg/m2_h 4.9 4.9 4.4 3.9 3.4 2.0 1.0
24.4. A continuous countercurrent dryer is to be designed to dry 800 lb of wet porous solid
per hour from 140 percent moisture to 20 percent, both on the dry basis. Air at 120°F
dry bulb and 70°F wet bulb is to be used. The exit humidity is to be 0.012. The
average equilibrium-moisture content is 5 percent of the dry weight. The total
moisture content (dry basis) at the critical point is 40 percent. The stock may be
assumed to remain at a temperature 3°F above that of the wet-bulb temperature of
the air throughout the dryer. The heat-transfer coefficient is 12 Btu/ftl-h-oF. The area
exposed to the air is 1.1 fe· per pound of dry solids. How long must the solids remain
in the dryer?
24.5. A film of polymer 2 m wide and 0.76 mm thick leaves the surface of a heated drum
containing 30 weight percent (dry basis) of acetone. It is dried by exposing both
sides of the film to air at 1 atm and 65'::>C containing essentially no acetone vapor.
The flow of air is across the faces of the film at 3 m/so The critical acetone content
is 10 weight percent acetone (dry basis). The equilibrium acetone content is negligible.
The density of the dry solid is 800 kg/m'. (a) What would be the surface temperature
of the film during the constant-rate period? (b) What would be the constant drying
rate, in kilograms per square meter per hour? (c) How long would it take to reduce
the acetone content from 30 to 0.5 percent if the diffusivity of acetone in the solid is
8 x 10- 4 cm'/s? For acetone-air mixtures iI,/M.k, is 1.76 J/g_0C.
DRYING OF SOLIDS 809
24.6. Show that the dimensional equation for hy, Eq. (24.13), is consistent with the
dimensionless equation for turbulent flow, Eq. (12.30), for a certain range of dryer
conditions.
REFERENCES
1. Ceaglske, N. H., and O. A. Hougen: Trans. AIChE, 33:283 (1937).
2. Ceaglske, N. H., and F. C. Kiesling: Tmns. AIChE, 36:211 (1940).
3. Clark, W. E.: Chem. Eng., 74(6):177 (1967).
4. Cornings, E. W., and T. K. Sherwood: lnd. Eng. Chem., 26:1096 (1934).
5. Dittman, F. W.: Chem. Eng., 84(2):106 (1977).
6. Dittman, F. W., and E. M. Cook: Chem. Eng., 84(2):108 (1977).
7. McCormick, P. Y.: Chem. Eng. Prog., 58(6):57 (1962).
8. Newman, A. B.: Trons. AIChE, 27:203, 310 (1931).
9. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York, 1984; (a) pp.
20-12, 20-27, (b) pp. 20-14 to 20-59, 20-74, (c) p. 20-20, (dJ p. 20-32, (e) p. 20-56.
10. Riegel, E. R.: Chemical Process Machinery, 2nd ed., Reinhold, New York, 1953, Chap. 17.
11. Sherwood, T. K.: Ind. Eng. Chem., 21:12 (1929).
12. Sherwood, T. K.: Ind. Eng. Chem., 21:976 (1929).
13. Sherwood, T. K.: Ind. Eng. Chem., 24:307 (1932).
14. Sherwood, T. K., and E. W. Cornings: TrailS. AIChE, 28: 118 (1932).
15. Treybal, R. E., Mass-Transfer Operations, 3rd ed., McGraw-Hill, New York, 1980, p. 675.
16. Walas, S. M.: Chemical Process Equipment. Butterworths, Stoneham, MA, 1988, pp. 237-277.
CHAPTER
25
ADSORPTION
Adsorption is a separation process in which certain components of a fluid phase
are transferred to the surface of a solid adsorbent. Usually the small particles of
adsorbent are held in a fixed bed, and fluid is passed continuously through the
bed until the solid is nearly saturated and the desired separation can no longer
be achieved. The flow is then switched to a second bed until the saturated
adsorbent can be replaced or regenerated. Ion exhange is another process that is
usually carried out in this semibatch fashion in a fixed bed. Water that is to be
softened or deionized is passed over beads of ion-exchange resin in a column until
the resin becomes nearly saturated. The removal of trace impurities by reaction
with solids can also be carried out in fixed beds, and the removal of H 2 S from
synthesis gas with ZnO pellets is a well-known example. For all these processes,
the performance depends on solid-fluid equilibria and on mass-transfer rates. In
this chapter the emphasis is on adsorption, but the general methods of analysis
and design are applicable to other fixed-bed processes.
ADSORBENTS AND ADSORPTION PROCESSES. Most adsorbents are highly
porous materials, and adsorption takes place primarily on the walls of the pores
or at specific sites inside the particle. Because the pores are generally very small,
the internal surface area is orders of magnitude greater than the external area and
may be as large as 2000 m 2 /g. Separation occurs because differences in molecular
weight, shape, or polarity cause some molecules to be held more strongly on the
surface than others or because the pores are too small to admit the larger
molecules. In many cases, the adsorbing components (or adsorbate) is held strongly
810
ADSORPTION 811
enough to permit complete removal of that component from the fluid with very
little adsorption of other components. Regeneration of the adsorbent can then be
carried out to obtain the adsorbate in concentrated or nearly pure form.
Applications of vapor-phase adsorption include the recovery of organic
solvents used in paints, printing inks, and solutions for film casting or fabric
coating. The solvent-laden air may first be sent to a water-cooled or refrigerated
condenser to collect some of the solvent, but it is generally impractical to cool the
gas far below ambient temperature in an attempt to eliminate solvent losses. The
air with a small amount of solvent is passed through a bed of carbon adsorbent
particles, which can reduce the solvent concentration to less than 1 ppm. The
concentration may be set by government emission standards rather than by the
economics of solvent recovery. Adsorption on carbon is also used to remove
pollutants such as H 2 S, CS 2 and other odorous compounds from air circulating
in ventilation systems, and canisters of carbon are placed in most new automobiles
to prevent gasoline vapors from being vented to the air.
Drying of gases is often carried out by adsorbing the water on silica gel,
alumina, or other inorganic porous solids. The zeolites, or molecular sieves, which
are natural or synthetic aluminosilicates with a very regular, fine pore structure,
are especially effective in preparing gases with low dew points (-75°C). Adsorp-
tion on molecular sieves can also be used to separate oxygen and nitrogen, to
prepare pure hydrogen for synthesis gas, and to separate normal paraffins from
branched paraffins and aromatics.
Adsorption from the liquid phase is used to remove organic components
from aqueous wastes, colored impurities from sugar solutions and vegetable oils,
and water from organic liquids. Adsorption can also be used to recover reaction
products that are not easily separated by distillation or crystallization. Some of
the same types of solids are used for both vapor-phase and liquid-phase adsorp-
tion, though often adsorbents with larger pores are preferred for use with liquids.
ADSORPTION EQUIPMENT
FIXED-BED ADSORBERS. A typical system used for adsorption of solvent vapors
is shown in Fig. 25.1. The adsorbent particles are placed in a bed 1 to 4 ft deep
supported on a screen or perforated plate. The feed gas passes down through one
of the beds while the other is being regenerated. Downflow is preferred because
upflow at high rates might fluidize the particles, causing attrition and loss of fines.
When the concentration of solute in the exit gas reaches a certain value or at a
scheduled time, valves are automatically switched to direct the feed to the other
bed and initiate the regeneration sequence.
Regeneration can be carried out with hot inert gas, but steam is usually
preferred if the solvent is not miscible with water. Steam condenses in the bed,
raising the temperature of the solid and providing the energy for desorption. The
solvent is condensed, separated from the water, and perhaps dried before reuse.
The bed may then be cooled and dried with inert gas, but is is not necessary to
lower the entire bed to ambient temperature. If some water vapor can be tolerated
812 MASS TRANSFER AND ITS APPLICATIONS
Feed------,;---±:======::::;:-l---l
H,O
Clean gas _-~~===!===~
Steam hlnert gas
FIGURE 25.1
Vapor-phase adsorption system.
in the clean gas, evaporation of water during the adsorption cycle will help cool
the bed and partially offset the heat of adsorption.
The size of the adsorbent bed is detennined by the gas flow rate and the
desired cycle time. Usually the cross-sectional area is .,alculated to give a superficial
velocity of 0.5 to 1.5 ft/s (0.15 to 0.45 m/s), which results in a pressure drop of a
few inches of water per foot when using typical adsorbents (4 by 10 mesh or 6 by
16 mesh). For very large flow rates, a rectangular bed may be installed in the
middle of a horizontal cylinder rather than using a vertical tank with a diameter
much greater than the bed depth.
The bed depth and flow rate are generally chosen to provide an adsorption
cycle of 2 to 24 h. By using a longer bed, the adsorption cycle could be extended
to several days, but the higher pressure drop and the greater capital cost of the
adsorber would probably make this uneconomic. Using a bed only 1 ft (0.3 m) or
less in depth is sometimes recommended to decrease the pressure drop and the
size of the adsorber, but shallow beds do not give as complete a separation and
also require more energy for regeneration.
Gas-drying equipment. The equipment for drying gases is similar to that shown
in Fig. 25.1, but hot gas is used for regeneration. The moist gas from the bed being
regenerated may be vented, or much of the water may be removed in a condenser
and the gas recirculated through a heater to the bed. For small dryers, electric
heaters are sometimes installed inside the bed to provide the energy for regenera-
tion.
When regeneration is carried out at a much lower pressure than adsorption,
it may not be necessary to supply heat, since low pressure favors desorption. If a
gas dryer operates at several atmospheres pressure during the adsorption cycle,
nearly complete regeneration can be accomplished by passing part of the dry gas
through the bed at atmospheric pressure without preheating. Some of the heat of
ADSORPTION 813
adsorption, which was stored in the bed as sensible heat of the solid, becomes
available for desorption, and the bed cools during regeneration. The amount of
gas needed for regeneration is only a fraction of the gas fed in the adsorption
cycle, since the gas leaving at 1 atm will have a much higher mole fraction of water
than the feed gas. Applying the same principle, vacuum regeneration offers an
alternative to steam or hot-gas regeneration when adsorption is carried out at
atmospheric pressure.
Pressure-swing adsorption. Although adsorption is most often used as a purifica-
tion process to remove small amounts of material, a number of applications involve
separations of gas mixtures with moderate to high concentration of adsorbates.
These are called bulk separations, and they often use different operating procedures
than for gas purification. Pressure-swing adsorption (PSA) is a bulk separation
process that is used for small-scale air separation plants and for concentration of
hydrogen in process streams.
A simple PSA scheme for air separation uses two beds of moleuclar sieves,
with one adsorbing at several atmospheres pressure and the other being re-
generated at 1 atm. For the same concentration, nitrogen is adsorbed three to four
times as strongly as oxygen, so nearly pure oxygen can be produced as the product.
However, the adsorption time is quite short (less than a minute) because of the
high concentration of N 2 in air and the low capacity of the sorbent. Therefore the
holdup of gas in the bed is significant relative to the amount adsorbed, and this
gas volume must be considered in designing the adsorption cycle. After adsorption,
the bed is depressurized, which removes most of the gas holdup and some of the
adsorbed gas. The bed is purged at 1 atm with part of the product gas from the
other adsorber to finish the desorption. Then the bed is pressurized with product
gas "before being switched to air feed. More complex schemes use three or four
beds with only one bed adsorbing and the others being depressurized, purged, or
repressurized, all under control of a sequence timer.
Adsorption from liquids. An important example of adsorption from the liquid
phase is the use of activated carbon to remove pollutants from aqueous wastes.
Carbon adsorbents are also used to remove trace organics from municipal water
supplies, which improves the taste and reduces the chance of forming toxic
compounds in the chlorination step. For these uses the carbon beds are many
feet in diameter and up to 30 ft (10 m) tall, and there may be several beds operating
in parallel. Tall beds are needed to ensure adequate treatment, because the rate
of adsorption from liquids is much slower than from gases. Also the spent carbon
must be removed from the bed for regeneration, and so relatively long periods
between regeneration are desirable.
An alternative method of treating wastewaters is to add powdered carbon
to a tank of solution using mechanical stirrers or air spargers to keep the particles
suspended. With'the fine particles, the adsorption is much more rapid than with
granular carbon, but large equipment is needed to remove the spent carbon by
sedimentation or filtration, The treatment with powdered carbon can be done
814 MASS TRANSFER AND ITS APPLICATIONS
batchwise, or it can be carried out continuously, with metered addition of carbon
to the waste stream and continuous removal of the spent carbon.
CONTINUOUS ADSORBERS. Adsorption from gases or liquids can be made truly
continuous by causing the solid to move through the bed countercurrent to the
flow of the fluid. The solid particles are allowed to flow down by gravity through
the adsorption and regeneration sections and are then returned by an airlift or
mechanical conveyor to the top of the column.
With fine particles a fluidized bed can be used with baffles or multiple stages
employed to prevent end-to-end mixing. The "hypersorber" is a multistage
fluid-bed adsorber built like a distillation column, with fluidized solids passing
through downcomers from stage to stage. Some countercurrent adsorbers and
ion-exchange columns have been built, and since such schemes can make more
efficient use of the solid, they may find increasing use, particularly for large
installations.
EQUILIBRIA; ADSORPTION ISOTHERMS
The adsorption isotherm is the equilibrium relationship between the concentration
in the fluid phase and the concentration in the adsorbent particles at a given
temperature. For gases, the concentration is usually given in mole percent or as
a partial pressure. For liquids, the concentration is often expressed in mass units,
such as part per million. The concentration of adsorbate on the solid is given as
mass adsorbed per unit mass of original adsorbent.
TYPES OF ISOTHERMS. Some typical isotherm shapes are shown as arithmetic
graphs in Fig. 25.2. The linear isotherm goes through the origin, and the amount
adsorbed is proportional to the concentration in the fluid. Isotherms that are
1----------;:,,,=ev'ersible
"'ii Favorable
~ Strongly _--"7'~--
"'C favorable __
£g
'll Linear
'"
",'
U nfavorable
o~~~ ______________~ FIGURE 25.2
o c,ppm Adsorption isotherms.
ADSORPTION 815
convex upward are called favorable, because a relatively high solid loading can
be obtained at low concentration in the fluid. The Langrnuir isotherm is given by
the relation W = Wm ,,(Kc/(1 + Kc», where W is the adsorbate loading, c is the
concentation in the fluid, and K is the adsorption constant. This isotherm is of
the favorable type. When K is large and Kc ~ 1, the isotherm is strongly favorable,
and when Kc < 1, the isotherm is nearly linear. The Langmuir isotherm is derived
assuming a uriiform surface-not a valid assumption-but the relation works fairly
well for gases that are weakly adsorbed. For strongly favorable isotherms the
empirical Freundlich equation W = bern, where b and m are constants and m < 1,
is often a better fit, particularly for adsorption from liquids.
The limiting case of a very favorable isotherm is irreversible adsorption,
where the amount adsorbed is independent of concentration down to very low
values. All systems show a decrease in the amount adsorbed with an increase in
temperature, and of course adsorbate can be removed by raising the temperature
even for the cases labeled "irreversible." However, desorption requires a much
higher temperature when the adsorption is strongly favorable or irreversible than
when the isotherms are linear.
An isotherm that is concave upward is called unfavorable because relatively
low solid loadings are obtained and because it leads to quite long mass-transfer
zones in the bed. Isotherms of this shape are rare, but they are worth studying to
help understand the regeneration process. If the adsorption isotherm is favorable,
mass transfer from the solid back to the fluid phase has characteristics similar to
those for adsorption with an unfavorable isotherm.
To show the variety of isotherm shapes for a single adsorbate, data for water
adsorbed from air on three dessicants are given in Fig. 25.3. Silica gel has a nearly
40
V J-
Silica gel
o
::; 3 0
51
/
>-
'"o
01
V .
Molecular Sieve, 4 A
o ..--- /
K;n,
o 20
§
I
01
"
10
/ V
..-/
oV
o 20 40 60 80
PERCENT RELATIVE HUMIDITY
100
FIGURE 25.3
Adsorption isotherms for water in air
at 20 to 50'C.
816 MASS TRANSFER AND ITS APPLICATIONS
linear isothenn up to 50 percent relative humidity, and the ultimate capacity is
about twice that for the other solids. At high humidity, the small pores become
filled with liquid by capillary condensation, and the total amount adsorbed
depends on the volume of the small pores and not just the surface area. Water is
held most strongly by molecular sieves, and the adsorption is almost irreversible,
but the pore volume is not as great as for silica gel. The curves in Fig. 25.3 are
based on relative humidity, which makes the isothenns for a range of temperatures
fall on a single curve. Note that except for the molecular sieves, the amount
adsorbed at a given partial pressure decreases strongly with increased temperature.
For air with 1 percent H 2 0 at 20°C,.ffR = 7.6 mm Hg/17.52 x 100 = 43.4 percent,
and the amount adsorbed on silica gel is W = 0.26Ibflb. For the same concentra-
tion at 40°C, .ffR = 7.6/55.28 x 100 = 13.7 percent, and W = 0.082 lbflb.
The adsorption data for hydrocarbon vapors on activated carbon are
sometimes fitted to Freundlich isothenns, but data for a wide range of pressures
show the isothenn slopes gradually decrease as the pressure is increased. The
amount adsorbed depends primarily on the ratio of the partial pressure of the
adsorbate in the gas to the vapor pressure of the liquid at the same conditions
and on the surface area of the carbon. Generalized correlations have been
developed based on the concept ohhe adsorption potential,4,7 and some results for
a typical coal-based carbon are shown in Fig. 25.4. For a given class of materials,
the amount adsorbed depends on (T/V) log (f,lf), where T is the adsorption
temperature, in Kelvins, V is the molar volume of the liquid at the boiling point,
I, is the fugacity of the saturated liquid at adsorption temperature, and f is the
fugacity of the vapor. For adsorption at atmospheric pressure, the partial pressure
and vapor pressure can be used for the fugacities. The volume adsorbed is
converted to mass by assuming the adsorbed liquid has the same density as
liquid at the boiling point.
The curves for n-paraffins and sulfur compounds were adapted from similar
plots by Grant and Manes,." who used a different definition of the molar volume,
Limited data show that highly chlorinated hydrocarbons are more strongly
adsorbed than the sulfur compounds, as shown in Fig. 25.4, but data for vinyl
chloride fall closer to the line for paraffins, as expected. The adsorption of
oxygenated species such as ketones and alcohols on BPL carbon can be estimated
using the curve for sulfur compounds.
Example 25.1. Adsorption gn BPL carbon is used to treat an airstream containing
0.2 percent n-hexane at 20"C. (a) Estimate the equilibrium capacity for a bed operating
at 20°C. (b) How much would the capacity decrease if the heat of adsorption raises
the bed temperature to 40°C?
Solution
(a) The molecular weight of n-hexane is 86.17. At 20°C (from Perry's Chemical
Engineers' Handbook, 6th ed., p. 3-57) P' = 120 mm Hg '" J,. At the normal boiling
ADSORPTION 817
100
50
~
~ t'.
~'"
"
g'"
-g 20
'\~ "-
"E
o n-paraffin:'\ ~ ,,\HCI, , C,CI,
-0 C2 to Ca
~ 10
"
w
al
m
\.\.\.
\.\.\.
E \\'\
~
g 5
\.\. I\H 2S, CS2 • mercaptans
\', \,
l\ '\
2
\\\
\\ '\
\ ~'H'C~
1
o 5 10 15 20 25
T IV log,,(f,l~
FIGURE 25,4
Generalized adsorption correlation4 . 5 for Pittsburgh Chemical Co. BPL carbon (1040 m2 jg).
point (68.7°C), PL = 0.615 gfcm'. The adsorption pressure P is 760 mm Hg, and
86.17
p = 0.002 x 760 = 1.52 mm Hg ,., f V = - - = 140.1 cm'/g mol
0.615
T f, 293 120
- log - = - - log - = 3.97
V f 140.1 1.52
From Fig. 25.4, volume adsorbed is 31 cm' liquid per 100 g carbon:
W = 0.31 x 0.615 = 0.19 gfg carbon
818 MASS TRANSFER AND ITS APPLICATIONS
(b) At 40"C, r ~ 276 mm Hg:
T J. 313 276
-Iog- ~ --Iog- ~ 5.05
V J 140.1 1.52
Volume adsorbed, from Fig. 25.4, is 27 cm' per lOO g carbon:
W ~ 0.27 x 0.615 ~ 0.17 gig carbon
Adsorption isothenns are generally presented for a single component, but
many applications involve multicomponent mixtures. The Langmuir isotherm is
easily modified for multiple adsorbates by adding tenns to the denominator:
W1 = Wmax K,c, )
( 1 + K,c, + Kzc z + ...
As mentioned previously, however, this equation is not very satisfactory for
strongly adsorbed materials. For solutes with similar properties, the generalized
correlations of Fig. 25.4 could be used by using average values of V, PL, and J, to
estimate the total amount adsorbed. However, when solute A is much more
strongly adsorbed than solute B, separate mass transfer zones will develop, and
A will displace adsorbed B as the zone for A moves through the bed.
A common problem in removal of vapors from air is the simultaneous
adsorption of water vapor. The capacity of the carbon for organic vapors may be
reduced by 50 to 70 percent if the relative humidity is 80 percent; but there is
little effect if the relative humidity is less than 30 percent. This may make it
worthwhile to raise the temperature of the feed by 20 to 30°F, even though this
decreases the equilibrium capacity for a single adsorbate.
PRINCIPLES OF ADSORPTION
CONCENTRATION PATTERNS IN FIXED BEDS. In fixed-bed adsorption, the
concentrations in the fluid phase and the solid phase change with time as well as
with position in the bed. At first, most of the mass transfer takes place near the
inlet of the bed, where the fluid first contacts the adsorbent. If the solid contains no
adsorbate at the start, the concentration in the fluid drops exponentially with
distance essentially to zero before the end of the bed is reached. This concentration
profile is shown by curve I, in Fig. 25.5a, where c/c o is the concentration in the
fluid relative to that in the feed. After a few minutes, the solid near the inlet is
nearly saturated, and most of the mass transfer takes place further from the inlet.
The concentration gradient becomes S shaped, as shown by curve I z . The region
where most of the change in concentration occurs is called the mass-transfer zone,
and the limits are often taken as c/co values of 0.95 to 0.05.
With time, the mass-transfer zone moves down the bed, as shown by profiles
13 and I•. Similar profiles could be drawn for the average concentration of
adsorbate. on the solid, showing nearly saturated solid at the inlet, a large change
in the region of the mass-transfer zone, and zero concentration at the end of the
ADSORPTION 819
BED LENGTH, L
(al
-------------------T-----
I
I
io.s
ot t'
FIGURE 25.5
(a) Concentration profiles and (b) breakthrough curve for adsorption in a fixed bed.
bed. Instead of plotting the actnal concentration on the solid, the concentration
in the fluid phase in equilibrium with the solid is shown as a dashed line for time
12 , This concentration must always be less than the actual fluid concentration,
and the difference in concentrations, or driving force, is large where the concentra-
tion profile is steep and mass transfer is rapid.
BREAKTHROUGH CURVES. Few fixed beds have internal probes that would
permit measurement of profiles such as those in Fig. 25.5a. However, these profiles
can be predicted and used in calculating the curve of concentration vs. time for
fluid leaving the bed. The curve shown in Fig. 25.5b is called a breakthrough curve.
At times 11 and 12 , the exit concentration is practically zero, as shown also in Fig.
25.5a. When the concentration reaches some limiting permissible value, or break
point, the flow is stopped or diverted to a fresh adsorbent bed. The break point
is often taken as a relative concentration of 0.05 or 0.10, and since only the last
portion of fluid processed has this high a concentration, the average fraction of
solute removed from the start to the break point is often 0.99 or higher.
If adsorption were continued beyond the break point, the concentration
would rise rapidly to about 0.5 and then more slowly approach 1.0, as shown in
Fig. 25.5b. This S-shaped curve is similar to those for the internal concentration
profiles, and it is often nearly symmetrical. By material balance, it can be shown
that the area between the curve and a line at c/co = 1.0 is proportional to the
total solute adsorbed if the entire bed comes to equilibrium with the feed. The
amount adsorbed is also proportional to the rectangular area to the left of the
dashed line at 1*, the ideal adsorption time for a vertical breakthrough curve. For
820 MASS TRANSFER AND ITS APPLICATIONS
a symmetrical curve, t* is also the time when c/co reaches 0.5. The movement of
the adsorption front through the bed and the effect of process variables on t* can
be obtained by a simple material balance.
For a unit area of bed cross section, the solute feed rate is the product of
the superficial velocity and the concentration:
(25.1)
For an ideal breakthrough curve, all the solute fed in time t* is adsorbed,
and the concentration on the solid has increased from the initial value Wo to the
equilibrium or saturation value w,,,. Thus
(25.2)
or
t* = LPb(W,,, - Wo) (25.3)
UOC o
where Land Pb are the length and bulk density of the bed, respectively. For
fresh carbon or completely regenerated carbon, Wo = 0, but complete regeneration
is often too costly.
The break-point time tb is always less than t*, and the actual amount of
solute adsorbed at the break point can be determined by integrating the break-
through curve up to the time Ib, as shown in Fig. 25.6. If the mass-transfer zone
is narrow relative to the bed length, the breakthrough curve will be rather steep,
as in Fig. 25.6a, and most of the capacity of the solid will be utilized at the break
point. Whe1 the mass-transfer zone is almost as long as the bed, the breakthrough
curve is greatly extended, as in Fig. 25.6b, and less than half of the bed capacity
is utilized. A narrow mass-transfer zone is desirable to make efficient use of the
absorbent and to reduce the energy costs in regeneration. In the ideal case of no
mass-transfer resistance and no axial dispersion, the mass-transfer zone would be
lal
FIGURE 25.6
TIME,t Breakthrough curves for (a) a narrow and (b) a wide
Ibl mass-transfer zone.
ADSORPTION 821
of infinitesimal width, and the breakthrough curve would be a vertical line from
o to 1.0 when all the solid was saturated.
SCALE-UP. The width of the mass-transfer zone depends on the mass-transfer
rate, the flow rate, and the shape of the equilibrium curve. Methods of predicting
the concentration profiles and zone width have been published, but lengthy
computations are often required, and the results may be inaccurate because of
uncertainties in the mass-transfer correlations. Usually adsorbers are scaled up
from laboratory tests in a small-diameter bed, and the large unit is designed for
the same particle size and superficial velocity. The bed length need not be the
same, as shown in the next section.
Length of unused bed. For systems with a favorable isotherm, the concentration
profile in the mass-transfer zone soon acquires a characteristic shape and width
that do not change as the zone moves down the bed. Thus, tests with different
bed lengths give breakthrough curves of the same shape, but with longer beds, the
mass-transfer zone is a smaller fraction of the bed length, and a greater fraction
of the bed is utilized. At the break point, the solid between the inlet of the bed
and the start of the mass-transfer zone is completely saturated (at equilibrium with
the feed). The solid in the mass-transfer zone goes from nearly saturated to ahnost
no adsorbate, and for a rough average, this solid could be assumed to be about
half saturated. This is equivalent to having about half of the solid in the
mass-transfer ZOne fully saturated and half unused. The scaleup principle is that
the amount of unused solid or length of unused bed does not change with the
total bed length.'
To calculate the length of unused bed from the breakthrough curve, the total
solute adsorbed up to the break point is determined by integration. The capacity
of the solid is obtained by integration of a complete breakthrough curve or from
separate equilibrium tests. The ratio of these two quantities is the fraction of the
bed capacity utilized at the break point, and 1.0 minus this ratio is the unused
fraction. The unused fraction is converted to an equivalent length of bed (LUB),
which is assumed to be constant. The break-point time is calculated from the ideal
time and the fraction of bed utilized:
tb = t* (1 _L~B) (25.4)
As an example, if a 20-cm-deep bed gives 60 percent utilization at the break
point, the length of the unused bed is 8 cm. Increasing the bed length to 40 cm
makes the unused portion dt or 20 percent. Therefore the break-point time is
increased by a factor 40/20 x 0.8(0.6 = 2.67, because of the longer bed and the
greater fraction used.
Example 25.2. The adsorption of n-butanol from air was studied 3 in a small fixed
bed (l0.16-cm diameter) with 300 and 600 g carbon, corresponding to bed lengths of
8 and 16 cm. (a) From the following data for effluent concentration, estimate the
822 MASS TRANSFER AND ITS APPLICATIONS
saturation capacity of the carbon and the fraction of the bed used at c/co = O.OS.
(b) Predict the break-point time for a bed length of 32 cm.
Data for n-butanol on Columbia JXC 4/6 carbon are as follows:
Uo = 58 cm/s D p = 0.37 cm
Co = 365 ppm S = 1194 m'/g
T= 25°C p, = 0.461 g/cm'
P = 737mmHg e = 0.457
300g 600g
t, h clco t, h clco
0.005 5 0.00i9
1.5 0.01 5.5 0.003
2 0.027 6 0.0079
2.4 0.050 6.5 0.018
2.8 0.10 7 0.039
3.3 0.20 7.5 0.077
4 0.29 8 0.15
5 0.56 8.5 0.24
Solution
(a) The concentration profiles are plotted in Fig. 25.7 and extended to
c/co = 1.0, assuming the curves are symmetrical about c/co = 0.5.
1. 0 ,-
. //
/
/
/
/
o.8 I /
f
/
o. 6 /
/
/
l
I
o. 4 I
!~:8 cm I
I
I
I
/
I
o. 2 / ~ '" 16cm
00
V
2 4 6
t, HOURS
/ 8 10 12 14
FIGURE 25.7
Breakthrough curves for Example 25.2.
ADSORPTION 823
Per square centimeter of bed cross section, the solute feed rate is
cm (365 x 10- 6 273 737) mol
= 58- x- x- - x 74.12g(mol
s 22,400 298 760 cm'
= 6.22 X 10- 5 g(cm 2_s or 0.224 gfcm 2_h
The total solute adsorbed is the area above the graph multiplied by FA' For
the 8-cm bed, the area is
c)
f '·5 (
o 1 -;:;; dt = 4.79 11
This area corresponds to the ideal time that would be required to adsorb the
same amount if the breakthrough curve were a vertical line. The mass of carbon per
unit cross-sectional area of bed is 8 x 0.461 = 3.69 gfcm 2 . Thus
0.224 x 4.79
w,.. = = 0.291 g solute(g carbon
3.69
At the break point, where c(co = 0.05, and t = 2.4 h
f o
2 .• ( c)
1 -;:;; dt = 2.37 h
The amount adsorbed up to the break point is then
0.224 x 2.37
Wo = = 0.144 g solute(g carbon
3.69
Wo 0.144
-=--=0.495
~at 0.291
Thus 50 percent of the bed capacity is unused, which can be represented by a
length of 4 cm.
For the 16-cm bed the breakthrough curve has the same initial slope as the
curve for the 8-cm bed, and although data were not taken beyond c(co = 0.25, the
curves are assumed to be parallel.
For the entire bed,
r (I - :}t = 9.59 h
0.224 x 9.59
~at = = 0.291 g solute/g carbon
16 x 0.461
824 MASS TRANSFER AND ITS APPLICATIONS
At clco = 0.05, t = 7.1 h, and
fl (1- ~)dt = 7.07h
0.224 x 7.07
If" = 0.215 g solutelg carbon
16 x 0.461
If" 0.215
-=-=0.739
~4t 0.291
At the break point, 74 percent of the bed capacity is used, which corresponds to
an unused section of length 0.26 x 16 = 4.2 cm. Within experimental error, the
lengths of unused bed agree, and 4.1 cm is the expected value for a still longer bed.
(b) For L = 32 cm, the expected length of the fully used bed is 32 - 4.1 =
27.9 cm. The fraction of the bed used is
If" 27.9
-=-=0.872
~.. t 32
The break-point time is
27.9 x 0.461 x 0.291
16.7 h
0.224
Summary
8 16 32
2.4 7.1 16.7
0.50 0.74 0.87
Effect of feed concentration. The effect of moderate changes in feed concentration
on the breakthrough curve can be predicted, since the width of the mass-transfer
zone does not change. The equilibrium capacity is determined from the adsorption
isotherm, and the break-point time is proportional to the capacity of the solid and
to the reciprocal of the feed concentration [Eqs. (25.3) and (25.4)]. Laboratory
tests using higher than expected concentrations of a pollutant may be made to
shorten the time for a breakthrough ·test. Very large differences in concentration
may lead to errors in scaleup because of a change in the mass-transfer coefficient or
because of temperature effects.
Adsorption is an exothermic process, and a bed temperature rise of 10
to 50°C may result when treating vapors with only I percent adsorbable compo-
nent. In small-diameter beds, heat loss will limit the temperature rise, but a large
unit will operate almost adiabatically, and significant differences in performance
could result. In such cases, a large-diameter pilot column should be used or detailed
calculations made to account for heat release and heat transfer in the bed.
ADSORPTION 825
Basic Equations for Adsorption
Although adsorbers are generally designed from laboratory data, the approximate
performance can sometimes be predicted from equilibrium data and mass-transfer
calculations. In this section the basic equations are presented for isothermal
adsorption in fixed beds, and solutions are given for some limiting cases.
RATE OF MASS TRANSFER. Equations for mass transfer in fixed-bed adsorption
are obtained by making a solute material balance for a section dL of the bed, as
shown in Fig. 25.8. The rate of accumulation in the fluid and in the solid is the
difference between input and output flows. The.change in superficial velocity is
neglected:
ae aw
e dL - + (1 - e) dL Pp - = uoc - uo(e + de) (25.5)
at at
or
ae aw ae
e-+(l-e)p - = - u - (25.6)
at p at 0 aL
The term e is the external void fraction of the bed, and solute dissolved in the
pore fluid is included with the particle fraction 1 - e. For adsorption from a gas
or a dilute solution, the first term in Eq. (25.6), the accumulation in the fluid, is
usually negligible compared to the accumulation on the solid.
The mechanism of transfer to the solid includes diffusion through the
fluid film around the particle and diffusion through the pores to internal adsorp-
tion sites. The actual process of physical adsorption is practically instantaneous,
and equilibrium is assumed to exist between the surface and the fluid at each point
inside the particle. The transfer process is approximated using an overall volu-
metric coefficient and an overall driving force:
(25.7)
The mass-transfer area a is taken as the external surface of the particles, which is
6(1 - e)/Dp for spheres. The concentration e* is the value that would be in
equilibrium with the average concentration W in the solid.
£ 1- € Fraction particles
u.
c+dc
dL FIGURE 25.8
-L Mass balance for a section of a fixed bed.
826 MASS TRANSFER AND ITS APPLICATIONS
INTERNAL AND EXTERNAL MASS-TRANSFER COEFFICIENTS. The overall
coefficient Kc depends on the external coefficient kc.ex! and on an effective internal
coefficient k,.in,. Diffusion within the particle is actually an unsteady-state process.
and the value of kc,int decreases with time, as solute molecules must penetrate
further and further into the particle to reach adsorption sites. An average
coefficient can be used to give an approximate fit to uptake data for spheres:
10D,
kc.int~D (25.8)
p
This leads to
1 1 Dp
-"'--+-- (25.9)
Kc kc.ex, lODe
The effective diffusion coefficient D, depends on the particle porosity,
the pore diameter, the tortuosity, and the nature of the diffusing species. For
gas-filled pores, the above factors can be allowed for to make a reasonable
estimate of the effective diffusivity in the gas phase. However, diffusion of
adsorbed molecules along the pore walls, called surface diffusion, often contributes
much more to the total flux than diffusion in the gas phase. This is particularly
evident in the adsorption of water vapor on silica gel and the adsorption of
hydrocarbon vapors on carbon, where the measured values of K, correspond to
internal and external coefficients of comparable magnitUde or even to external
film control. For adsorption of solutes from aqueous solutions, surface migration
is much less important, and the internal diffusion resistance generally dominates
the transfer process.
Solutious to Mass-Transfer Equations
There are many solutions to Eq. (25.6) and (25.7) for different isotherm shapes
and controlling steps, and all solutions involve a dimensionless time , and
a parameter N representing the overall number of transfer units:
uoco(t - Le/uo)
, == ---''-'''--''':''''-'''-- (25.10)
pi1 - e)L/(W,,, - Wo)
(25.11)
The term Le/u o in Eq. (25.10) is the time to displace fluid from external
voids in the bed, which is normally negligible, and pp(1 - e) is the bed density
Pb. Then, is the ratio of the time to the ideal time t* from Eq. (25.3):
, = t/t* (25.12)
If there were no mass-transfer resistance, the adsorber could be operated with
complete removal of solute up to , = 1.0, and then the concentration would jump
ADSORPTION 827
from 0 to clco = 1.0. With a finite rate of mass transfer, breakthrough occurs at
, < 1.0, and the steepness of the breakthrough curve depends on the parameter
N and on the shape of the equilibrium curve.'
IRREVERSIBLE ADSORPTION. Irreversible adsorption with a constant mass-
transfer coefficient is the simplest case to consider, since the rate of mass transfer
is then just proportional to the fluid concentration. A truly constant coefficient is
obtained only when all resistance is in the external film, but a moderate internal
resistance does not change the breakthrough curve very much. Strongly favorable
adsorption gives almost the same results as irreversible adsorption, because the
equilibrium concentration in the fluid is practically zero until the solid concentra-
tion is over half the saturation value. If the accumulation term for the fluid is
neglected, Eqs. (25.6) and (25.7) are combined to give
ac
-Uo aL = K,ac (25.13)
The initial shape of the concentration profile is obtained by integration of Eq.
(25.13), which gives
ln~= _ K,aL (25.14)
Co Uo
Since the term K,flLlu o is defined as N in Eq. (25.11), the concentration at the end
of the bed is given by
(25.15)
If the bed contained only three transfer units, the exit concentration would
be 0.05c o right at the start of the test, but usually N will be 10 or more, and c at
the exit will be a very small fraction of Co, small enough to be considered zero.
The rate of mass transfer to the first layer of particles is assumed to
be constant until the particles reach equilibrium with the fluid, and until this
happens, the concentration profile in the bed remains constant. The time to
saturate the first portion of the bed t 1 is the equilibrium capacity divided by
the intial transfer rate (Wo = 0 to simplify the analysis):
w,;"pp(1 - e)
tl = (25.16)
Kcaco
After this time, the concentration profile moves steadily down the bed, keeping
the same shape. The transfer zone moves at a velocity v" which is equal to the
amount of solute removed per unit time divided by the amount retained on the
solid per unit length of bed:
(25.17)
828 MASS TRANSFER AND ITS APPLICATIONS
~====~~L=~'====~'l _______, I
" '3 I
I FIGURE 25.9
oL ___--=::::==_--=::::==-___...:::l Concentration profiles for irreversible
L , adsorption with a constant coefficient.
The concentration is constant at Co for the saturated portion of the bed and then
falls exponentially in the mass-transfer zone as shown in Fig. 25.9.
In.':.. = _-_K--,-,a-,(L_-_L",,,,,,,J (25.18)
To predict the break point, Eq. (25.18) is applied for a bed of length L with c/c o
set at 0.05 or another selected value. The length of the saturated bed is the product
of transfer-zone velocity and the time since the zone started to move:
L,,, = v,(t - t,) (25.19)
Lsat = UoCo [ t - ---"=:-:'-'----'-
W,.,p.(1 - e)]
(25.20)
pp(1 - e)W,,, K,ac o
Substituting the equation for L,,, into Eq. (25.18) and using the dimensionless
terms, and N [Eqs. (25.10) and (25.11)] gives
c
In-=-N+N,-1 (25.21)
Co
or
c
In - = N(, - 1) - 1 (25.22)
Co
The predicted breakthrough curve is shown as a solid line in Fig. 25.10. The slope
increases with time, and c/co becomes 1.0 at N(, - 1) = 1.0. In practice, the
breakthrough curves are usually S shaped, because the internal diffusion resistance
is not negligible, and it increases somewhat when the solid becomes nearly
saturated.
If pore diffusion controls the rate of adsorption, the breakthrough curve
has the opposite shape from that for external-fihn control. The corresponding
line in Fig. 25.10 was taken from the work of Hall et al.: who presented
breakthrough curves for several cases ofirreversible adsorption. For pore diffusion
control the initial slope of the curve is high, because the solid near the front of
the mass-transfer zone has almost no adsorbate, and the average diffusion distance
is a very small fraction of the particle radius. The curve has a long tail because
the final molecules adsorbed have to diffuse almost to the center of the particle.
When both internal and external resistances are significant, the break-
through curve is S shaped, as shown by the dashed line in Fig. 25.10. For
ADSORPTION 829
/~
lt~/
-
/
o.8 J.
411
III Equal resistances
r
o.6
Pore diffusion control-1
o. 4 /f
~External film control
o.2
~
1/0/
0
/,
3 2 o 2 3
N(r-1)
FIGURE 25.10
Breakthrough curves for irreversible adsorption.
this plot, the value of N is based on the overall mass-transfer coefficient given
by Eq. (25.9), or it can be expressed in Hall's terminology as .
1 1 1
=-+- (25.23)
N NJ Np
where
Example 25.3. (a) Use the breakthrough data in Example 25.2 to determine Nand
Kp for the 8-cm bed assuming irreversible adsorption. (b) Compare Kp with the
predicted kp for the external film.
Solution
(a) From Example 25.2, at clco = 0.05, WIW, .. = 0.495, < = 0.495, < - I =
-0.505. Assume equal internal and external resistances to determine N from Fig.
25.10:
c
N« -
I) = -1.6 at- = 0.05
Co
N=~=3.17=K,aL Ka=
3.17 x 58 cmls
23.0s- 1
-0.505 U o c 8 cm
830 MASS TRANSFER AND ITS APPLICATIONS
(b) Prediction of kea from N Rc • Nsc (kc is the external coefficient):
Dp = 0.37 cm
At 25'C, 1 aIm, fl/P = 0.152 cm 2/s, D, = 0.0861 cm 2/s. Then
0.37(58) 0.152
NR =---=141 N s, = - - = 1.765
, 0.152 0.0861
From Eq. (21.62), NSh = 1.17(141)0.58S(1.765)'/3 = 25.6
_ 25.6(0.0861)
k, - 0.37 5.96 cm/s
a = 6(1 - e) = 6(1 - 0.457) = 8.81 cm2/cm'
Dp 0.37
k,a = 5.96 x 8.81 = 52.5 S-l
Since Kea is slightly less than half the predicted value of kea. the external resistance
is close to half the total resistance. and the calculated value of N need not be revised.
The internal coefficient can be obtained from
1
23.0
K, =- = 2.61 cm/s
8.81
1
k,.;" = (1/2.61) _ (1/5.96) 4.64 cm/s
If diffusion into the particle occurred only in the gas phase. the maximum possible
value of De would be about D,J4. which leads to
IOD, 10 x 0.0861
k - -- 0.58 cm/s
c,illt - Dp 4 x 0.37
Since the measured value of kc,illt is an order of magnitude greater than this value.
surface diffusion must be the dominant transfer mechanism.
LINEAR ISOTHERM. Adsorption with a linear isotherm is another limiting
case for which solutions for Eqs. (25.6) and (25.7) are readily available. With
a linear isotherm, the equations are of the same form as those for passage
of a temperature wave through a fixed bed:
aT.
BC -+(l-B)pC-=-u op c -
aT, aT. (25.24)
P at P , at P aL
aT,
(1 - B)ppC, - = Ua(T. - T,) (25.25)
at
ADSORPTION 831
Solutions for the heat-transfer problem, which arises in the use of packed
beds as direct-contact recuperative heat exchangers, were presented by Furnas 2
in 1930. The parameter NH is the number of heat-transfer units. For heat transfer,
the dimensionless time r is the heat capacity of the gas times the amount of gas
that has passed through the bed divided by the total bed capacity. For N H = co,
the breakthrough curve of Yu/To vs. r would be a vertical line at r = 1.0, just as
for mass transfer. The defining equations are
r = __u-"o,-p~cp,,-t-:-::
(25.26)
p,c,(l - elL
UaL
NH =-- (25.27)
pCpu o
The breakthrough curves are complex expressions that are best presented
graphically, as in Fig. 25.11. These curves become steeper relative to bed length
for high values of N, but the absolute width of the transfer zone actually increases
with U t'- For adsorption with a linear isotherm, a very long bed is required to
make the transfer zone a small fraction of the bed width, in contrast to adsorption
with a favorable isotherm. For example, if N = 10, Fig. 25.11 shows the break
point would be reached at r = 0.35, and only about 35 percent of the bed capacity
would be utilized. Doubling the bed length to make N = 20 raises r at the break
point to only 0.50, and N would have to be over 100 to utilize 80 percent of the
bed capacity. For irreversible adsorption with equal internal and external
resistances, N = 10 gives N(r - 1) = -1.6 or r = 0.84 at the break point.
O.sf--+---j---j-----j-+-7f.rL--;..-t;.......-=+-1
~Q O.6r--t------r_----4-----~~~--f------t------r__l
J....
~Q o.4r--t------r_--::T"+:-h"--;H------f------t------r__l
O.2r--b.L---;i."'---r---I-/-f--t----+---+---t---1
5
FIGURE 25.11
Breakthrough curves for adsorption with a linear isotherm or for heat transfer, for which N = NIl'
832 MASS TRANSFER AND ITS APPLICATIONS
FAVORABLE ADSORPTION. For favorable adsorption, the break point occurs
between the values predicted for linear adsorption and irreversible adsorption.
Solutions are available for certain isothenn shapes and different values of internal
and external resistances. 6 •9 These solutions have found use for the design of ion
exchangers, where the solid-fluid equilibria and the internal diffusivities are more
readily characterized than for adsorption.
ADSORBER DESIGN
The design of an adsorber for gas or liquid purification involves choosing
the adsorbent and the particle size, selecting an appropriate velocity to get
the bed area, and either detennining the bed length for a given cycle time
or calculating the breakthrough time for a chosen length. Using a shorter
bed length means a smaller inventory of sorbent and lower pressure drop
in the bed. However, the shorter bed means more frequent regeneration and
higher regeneration costs, since a smaller fraction of the bed is saturated at
breakthrough. For gas purification, 4 x 6- or 4 x lO-mesh carbon is often chosen,
but smaller sizes can be used when better mass transfer is needed and pressure
drop is not a problem. Because the external area a varies with llDp and both
k,.". and k,.;n. increase as Dp decreases, k,a is expected to vary with the -1.5
to - 2.0 power of D p' Therefore a reduction in particle size gives a much steeper
breakthrough curve.
There have been few published studies of regeneration kinetics, since it is
difficult to match conditions for a large adiabatic bed in a laboratory adsorber
and modeling is complicated because the desorption isothenn is nonlinear and
unfavorable. For steam regeneration of carbon, reverse flow is generally used with
steam at 130 to l50'C. Regeneration is stopped soon after the temperature front
reaches the top of the bed and the typical steam consumption 8 is 0.2 to O.4lb
steamjlb carbon. Although a significant amount of absorbate remains, regenera-
tion is most complete near the bottom of the bed, so that a high percentage removal
can still be achieved in the next adsorption period. If extremely high solute removal
is needed, the bed can be aimost completely regenerated by prolonging the
steaming period or using higher temperature steam.
Example 25.4. Adsorption on activated carbon is being considered to treat a process
air stream that has 0.12 vol% methyl ethyl ketone (MEK). The gas is at 25'C and
1 atm, and the flow is 16,000 ft'/min. The pressure drop across the bed should not
exceed 12 in. H 2 0. (a) If BPL 4 x 10-mesh carbon is used, predict the saturation
capacity and the working capacity if the average bed temperature is 35°C and the
regeneration is stopped when W = t~al' (b) What gas velocity and bed size could
be used to give a reasonable cycle time if the length of unused bed is 0.5 ft? How
much carbon is needed?
Solution
J. = 151 mm Hg at 35°C and PL = 0.805 glcm'
(a) From the handbooks, P' =
at 20°C. The normal boiling point is 79.6°C, and the estimated density at this
ADSORPTION 833
temperature is PL = 0.75 gjcm 3 . The molecular weight is 72.1.
72.1
V~-~96.1 p ~ 0.0012 x 760 ~ 0.912 mm Hg ~ f
0.75
At 35°C,
T !.
-log-~-log
308 (-151
-) ~7.11
V f 96.1 0.912
From Fig. 25.4, the volume adsorbed is 24 cm' per lOO g carbon:
w;" ~ 24(0.75) ~ 18 gflOO g carbon
Wo = ~ ~Ilt = 6 gj100 g carbon
Working capacity ~ W;" - Wo ~ 12 gflOO g carbon ~ 0.121bflb carbon.
(b) Try U o ~ I ftfs:
16,000 ft' I
A ~--- x --~ 267ft'
60 s I ftfs
For a circular cross section, D = 18.4 ft. A rectangular bed 10 ft x 27 ft might be
more suitable if the bed depth is only 3 to 4 ft. Try L ~ 4 ft. From Eq. (25.3)
t* = LpbC~t;1l1 - WO)
uoco
At 25°C,
0.0012 273
Co ~ - - x -.- x 72.1 ~ 2.21 x 1O- 4 lbfft'
359 298
30 x 4 x 0.12
pil - e) ~ p, ~ 30 lbfft' t* 6.52 X 104 s ~ 18.1 h
I x 2.21 x 10 4
If the length of unused bed is 0.5 ft, 3.5 ft are used, and
3.5
t, ~ - (18.1) ~ 15.8 h
4.0
If the bed length is 3 ft with 2.5 ft used,
2.5
t, ~ -(18.1) ~ 11.3 h
4
Allowing for uncertainties in the calculations, a bed length of 3 ft would be satisfactory
with regeneration once per 8-h shift.
Check I1P using Eq. (7.22). For granular carbon, assume <11, ~ 0.7 (see Table
28.1). Assume external void fraction e ~ 0.35 (see Table 7.1). From handbooks, the
properties of air at 25°C are
Jl ~ 0.018 cP ~ 1.21 x 10-' lbfft-s p ~ 0.0741bfft'
834 MASS TRANSFER AND lTS APPLlCAT10NS
4.76 + 2.0 ,
For 4 x IO-mesh carbon, D, ~ 3.38 mm ~ 1.108 x 10- ft
2
I1P ISO x 1.0 x 1.21 X 10- 5 0.65'
1.75 x 0.074 x 12 0.65
-~ +,..,-,---------,-
L 32.2 x 0.7' x (1.108 x 10 ')' 0.35' 32.2 x 0.7 x 0.Q1108 0.35'
~ 9.23 + 7.86 ~ 17.09IbJ lft'-ft
17.09 x 12
3.29 in. H,O/ft
62.4
For L ~ 3 ft, I1P ~ 9.9 in H,O, which is satisfactory.
A velocity of 1.5 ftfs would give I1PIL ~ 6.06 in. H,O/ft and require L" 2 ft
to keep 6.P < 12 in. H2 0. However, the breakthrough time would be reduced to
11.3/1.5 x (1.5/2.5) ~ 4.5 h, and the bed would have to be regenerated twice each
shift. This design might be satisfactory but does not give as much margin for error.
The recommended design is for two beds 10 x 27 x 3 ft placed in horizontal
cylinders. The total inventory of carbon is
me ~ 2(270 x 3) ft' x 30 lb/ft' ~ 48,600 lb
SYMBOLS
A Cross-sectional area of bed, m2 or ft2
a External surface area per unit volume of bed, m -1 or ft-I
b Constant in equations for adsorption isotherms
c Concentration of adsorbate in fluid, g/cm' or ppm (mg/L); Co, in feed;
Cb cz, of components 1 and 2 of muiticomponent mixture; c*, in
equilibrium with concentration in solid
cp Heat capacity of fluid, J Ig- °C or Btu/lb-OF
c, Heat capacity of solid, J/g-OC or Btuflb-oF
D Diameter, m or ft; Dp, of particle
De Effective diffusivity, cm 2 /s or ft2/h
De Volumetric diffusivity, cm 2 /s or ft2/h
FA Feed rate of adsorbate per unit cross-sectional area of bed, g/cm 2 -s
J Fugacity, atm or mm Hg; J" of saturated liquid
£'R Relative humidity
K Constant in equation for adsorption isotherm; K 1 , K 2 , for mUltiple
adsorbates
K, Overall mass-transfer coefficient, m/s or ft/s
K,a Volumetric overall mass-transfer coefficient, S-1
k, Individual mass-transfer coefficient, m/s or ft/s; k,."" for external film;
kc,in!! for internal diffusion
k,a Volumetric individual mass-transfer coefficient, s - 1
L Distance through bed, m or ft; also total bed length
M Molecular weight
m Exponent in Freundlich equation
ADSORPTION 835
mc Total mass of carbon in bed, kg or lb
N Number of mass-transfer units; N f' based on external film; N P' based
on pore diffusion
NH Number of heat-transfer units
N R, Reynolds number, DpUop/fl
N s, Schmidt number, fl/pD,
NSh Sherwood number, k,Dp/D,
P Total pressure, atm or mm Hg; P', vapor pressure
p Partial pressure, atm or mm Hg
S Internal surface area of solid, m 2/g or ft 2jlb
T Temperature, °C, K, of, or oR; Tg , of gas; T~p of solid; To, initial value
t Time, s or h; to, at start of adsorption; t 1 , time to saturate first
portion of bed; t*, ideal adsorption time for vertical breakthrough
curve
U Overall heat-transfer coefficient, W/m2-'C or Btu/ft2-h-'F
Ua Volumetric overall heat-transfer coefficient, W/m'-'C or Btu/ft'-h-'F
Uo Superficial velocity of fluid, cm/s, m/s, or ft/s
V Molar volume at normal boiling point, cm'/g mol
v. Velocity of transfer zone, cm/s or ft/s
W Adsorbate loading, gig solid; w" at break point; Wm", maximum
value as c ~ 00; ~at' at equilibrium with the fluid; Wo, initial value;
Wi, for component 1 of multiple adsorbates
Abbreviations
LUB Length of unused bed
PSA Pressure-swing adsorption
Greek letters
8 External void fraction of bed
fl Absolute viscosity, Pa-s, cP, or lb/ft-h
p Density, kg/m' or lb/ft'; PL, of liquid; P., bulk density of bed; Pp'
density of particle
T Throughput parameter defined by Eq. (25.10), dimensionless
<1>, Sphericity, dimensionless
PROBLEMS
25.1 Adsorption on 6 x 1O-mesh activated carbon is being considered to recover methyl
ethyl ketone (MEK) from an air stream at 25°C and 1 atm. The air flow is
12,000 std ft'lmin and the air has 0.401b MEK/lOOO std ft'. If the superficial velocity
is 0.5 ft/s, and an adsorption cycle of at least 8 h is desired, about what bed dimensions
should be used? Assume the bulk density of the carbon is 30lb/ft'.
25.2 Granular carbon is used to remove phenol from an aqueous waste. If 10 x 20-mesh
carbon is used with a superficial velocity of 0.03 m/s, estimate the number of transfer
units in a bed 4 m deep. The effective diffusivity in the particles can be taken as 0.2
times the bulk diffusivity.
836 MASS TRANSFER AND ITS APPLICATIONS
25.3 Air with relative humidity of 50 percent at'20°C is compressed to 8 atm, cooled to
30°C to condense some of the water, and dried in a silica-gel dryer. What fraction of
the water in the air is removed in the condenser? Calculate the equilibrium capacity
of the silica gel if the adsorption is carried out at 30°C and if the average bed
temperature rises to 50°C.
25.4 The preliminary design for a vapor-phase adsorber speci~ a bed of 6 x 16·mesh
carbon 6 ft in diameter and 4 ft deep, with a superficial velocity of 60 ft/min, However,
the estimated pressure drop of 16 in, H 2 0 is more than twice the desired value, If the
same amount of carbon is used in a wider and shallower bed, how will that affect the
pressure drop and the steepness of the breakthrough curve? Suggest an appropriate
design for the bed.
25.5 Data for drying nitrogen with molecular sieve type 4A are given by Collins,l Calculate
the saturation capacity from the breakthrough curve, and determine the length of
unused bed based on a break-point concentration c/co of 0.05:
T = 79"F LT = 1.44 ft
P = 86 psia Pb = 44.5 lb/ft'
N 2 feed = 29.2 molfh·ft2 Co = 1490 ppm
t, h 0 10 15 15.4 15.6 15.8 16 16.2
c,ppm <1 <1 <1 5 26 74 145 260
t, h 16.4 16.6 16.8 17 17.2 17.6 18 18.5
c,ppm 430 610 798 978 1125 1355 1465 1490
25.6 (a) Use the correlation in Fig. 25.4 to predict the amount of n-butanol adsorbed
on carbon for the conditions of Example 25.2 and compare with the experimental
data, (b) Estimate the saturation capacity of the carbon for a butanol concentration
of 20 ppm in air at 30"C and I atm.
25.7 A molecular sieve adsorbent used for air separation has a maximum capacity for N2
of 0.046 gig at 30"C, and the data can be fitted to a Langmuir isotherm with
K = 0.50 atm -1. (a) What is the saturation capacity when the adsorbent is exposed
to air at 10 atm and 30"C? (b) Calculate the ideal absorption time for a bed 4 ft deep
operating with a superficial velocity of 20 ft/min. The pellet density is 1.3 gfcm'.
25.8 Granular activated carbon impregnated with sulfur is used to remove mercury vapor
from natural gas and from air. Because chemical reaction converts the mercury to
mercuric sulfide, the adsorption is irreversible, and the capacity is as high as 20 weight
percent. (a) Assuming that the adsorption rate for removal of mercury from air is
controlled by external mass transfer, calculate the overall coefficient for a bed of
4 x 6·mesh carbon at 20"C and a superficial velocity of 75 cm/so (b) If the inlet
concentration is 10 ,ugjNm 3 (micro grams per normal cubic meter, with the gas volume
evaluated at standard conditions) and the treated gas must contain less than
10-' /lgfNm', what is the minimum bed length? (c) For a bed 50 cm deep, what is the
predicted time to breakthrough?
25.9 An adsorber for removing vinyl chloride monomer (VCM) from air has two beds of
BPL carbon that are 4 ft deep, and at breakthrough, the beds have 0.09 lb VCMflb
carbon. The average bed temperature is 80°F. The beds are regenerated with air at
200°F and 120 ft/min, and the exhaust gas is incinerated. Regeneration at higher
ADSORPTION 837
temperature is being considered. (a) How fast does the temperature front move through
the bed if the bed operates adiabatically and the heat of desorption is 1.5 times the
heat of vaporization? (b) If the inlet temperature is increased to 300°F with the same
mass velocity. what is the rate of movement of the temperature front? (c) If the bed
temperature could be increased very rapidly to 200°F by using electric heaters in the
bed, what would be the equilibrium concentration of VCM in the vapor phase? If air
flow was then started at 120 ft/min and 200°F, how rapidly would the desorption front
advance through the bed? (cl) What is the main advantage of increasing the regenera-
tion temperature?
REFERENCES
I. Collins, J. J.: AIChE Symp. Ser., no. 74, 63:31 (1967).
2. Fumas, C. C.: Trails. AICIzE, 24: 142 (1930).
3. Golovy, A., and J. Braslaw: Environ. Progr., 1:89 (1982).
4. Grant, R. J., M. Manes, and S. B. Smith: AICIzE J., 8:403 (1962).
5. Grant, R. J., and M. Manes: Ind. Eng. Chem. Fund., 3:221 (1964).
6. Hall, K. R., L. C. Eagleton, A. Acrivos, and T. Vermeulen: Ind. Eng. Chem. Fund., 5:212 (1966).
7. Lewis, W. K., E. R. Gilliland, B. Chertow, and W. P. Cadogan: Ind. Eng. Clzem., 42:1326 (1950).
8. Shuliger, W. G.: Calgon Corp., personal communication.
9. Vermeulen, T., G. Klein, and N. K. Hiester, in J. H. Perry (ed.), Chemical Engineers' Handbook, 5th
ed., sec. 16, McGraw-HilI, New York, 1973.
CHAPTER
26
MEMBRANE
SEPARATION
PROCESSES
Many processes for separation of gaseous or liquid mixtures use semipermeable
membranes that allow one or more constituents of the mixture to pass' through
more readily than the others. The membranes may be thin layers of a rigid material
such as porous glass or sintered metal, but more often they are flexible films of
synthetic polymers prepared to have a high permeability for certain types of
molecules. This chapter deals with processes in which separation is due to
differences in diffusion rates through the membrane. Separation of gas mixtures
with porous or nonporous membranes is treated first. Then several processes for
liquid mixtures are discussed, including pervaporation, liquid-liquid extraction,
reverse osmosis, and dialysis. The process of ultrafiltration, where separation is
accomplished mainly by excluding large molecules or colloidal particles from the
pores of the membrane, is treated as a special case of filtration in Chapter 30.
SEPARATION OF GASES
POROUS MEMBRANES. When a. gas mixture is allowed to diffuse through a
porous membrane to a region oflower pressure, the gas permeating the membrane
is enriched in the lower molecular weight components, since they diffuse more
rapidly. When the pores are much smaller than the mean free path in the gas
phase (about 1000 A at standard conditions), the gases diffuse independently by
Knudsen diffusion, and the diffusivity in the pore is proportional to the pore size
838
MEMBRANE SEPARATION PROCESSES 839
and the average molecular velocity, which varies inversely with the square root
of the molecular weight M. For Knudsen diffusion of gas A in cylindrical pores
T )0.5 (26.1)
DA = 9700r ( MA
In Equation (26.1), r is the mean pore radius in centimeters, T is the absolute
temperature in kelvins, and DAis in cm 2 js.
The flux per unit membrane area depends on an effective diffusivity, De> that
is lower than the pore diffusivity by the factor e/r, where e is the porosity and r
the tortuosity. For membranes with about 50 percent porosity, this factor is
generally 0.2 to 0.3:
(26.2)
The flux of each gas is proportional to the concentration gradient, which is
linear if the membrane structure is uniform and the gases do not interact. Usually
the gradient is expressed as a pressure gradient, and ideal gases are assumed:
(26.3)
The composition of the permeate depends on the fluxes of all species. For a
binary system, the mol fraction of A in the permeate is
lA
(26.4)
Typical pressure gradients for a membrane exposed to an equimolar binary
mixture are shown in Fig. 26.1. For this case, gas A is assumed to have a diffusivity
2 times that of gas B (helium and methane, for example) and the upstream and
downstream pressures are 2.4 and 1.0 atm, respectively. The permeate has 60
P,atm
PAl = P Sl
1.2
Permeate 1.0
0.8
Feed
P" 0.6
P., 0.4
0.2
FIGURE 26.1
Typical pressure gradients in a porous membrane.
840 MASS TRANSFER AND ITS APPLICATIONS
percent A, which is only a slight enrichment over the 50 percent A on the feed
side. The enrichment makes the gradient for A less than that for B (t.PA =
1.2 - 0.6 = 0.6; t.PB = 1.2 - 0.4 = 0.8) so the flux of A is only 2 x (0.6/0.8) = 1.5
times that for B, giving a permeate with 60 percent A. The permeate would be
slightly richer in A if a higher feed pressure was used or if the permeate side of
the membrane was at less than atmospheric pressure. A smaller amount of purer
product could be obtained by compressing the permeate and sending it to another
membrane unit. A cascade of countercurrent stages with recycle could be designed
to produce nearly pure products at high recovery, but the membrane cost and the
cost of compression at each stage generally make such processes too expensive.
A well-known example of gas separation by porous membranes, and perhaps
the only large-scale application, is the separation of uranium isotopes using the
hexafluorides 235UF6 and 238UF6' Since natural uranium has only 0.7 percent
235U.and the diffusivities of these hexafluorides differ by only 0.4 percent, more
than a thousand stages are needed to get a product with 4 percent 235U and a
residue with 0.25 percent 235U?
POLYMER MEMBRANES. The transport of gases through dense (nonporous)
polymer membranes occurs by a solution-diffusion mechanism. The gas dissolves
in the polymer at the high-pressure side of the membranes, diffuses through the
polymer phase, and desorbs or evaporates at the low-pressure side. The rate of
mass transfer depends on the concentration gradient in the membrane, which is
proportional to the pressure gradient across the membrane if the solubility is
proportional to the pressure. Typical gradients for a binary mixture are shown in
Fig. 26.2. Henry's law is assumed to apply for each gas, and equilibrium is assumed
CA>
Po>
C" P A,
:I
P",
P.,
C., r-z-I
FIGURE 26.2
Gradients in a dense polymer membrane.
MEMBRANE SEPARATION PROCESSES 841
at the interface. The gas-film resistances are neglected for this case, so the partial
pressures at the gas-polymer interface are the same as those in the bulk. The flux
for gas A is
(26.5)
The concentrations are related to the partial pressures by a solubility coefficient
S, which has units such as mOl/cm 3-atm (S is the reciprocal of the Henry's-Iaw
coefficient):
(26.6)
Using Eq. (26.6) to replace the concentration gradient with a pressure gradient
gives
(26.7)
The product D A SA is the flux per unit pressure gradient, which is called the
permeability coefficient qA and is often expressed in Barrers, where 1 Bar-
rer = 10- 10 cm 3 (STP)-cm/cm 2-s-cm Hg. Since the actual membrane thickness is
not always known or specified for commercial membranes, it is customary to use
the flux per unit pressure difference, which will be called the permeability QA:
(26.8)
Convenient units of QA might be std ft3/ft2-h-atm or L(STP)/m2-h-atm. Units
must be checked carefully in using published values of "permeability" since
different definitions are in use.
The ratio of permeabilities for a binary mixture is the membrane selectivity
IJ. (also called the ideal separation factor):
(26.9)
A high selectivity can be obtained from either a favorable diffusivity ratio or a
large difference in solubilities. The diffusivities in the membrane depend more
strongly on the size and shape of the molecules than do gas-phase diffusivities,
and large differences may exist for molecules of almost the same size. For example,
the ratio Do,/D N , is between 1.5 and 2.5 for several polymers,4 though the O 2
molecnle is only 10 percent smaller than the N2 molecule. Values of the diffusivity
vary widely with the type of polymer, with lowest values for glassy or crystalline
polymers and Jrigh values for polymers that are above their glass transition
temperature. A few values of diffusivity are given in Table 26.1.
842 MASS TRANSFER AND lTS APPLICATIONS
TABLE 26.1
Diffusion coefficients in selected polymers'
D X 10' at 2S<>C, cm 2/s
Polymer 0, N, CO, CH,
Polyethylene terephthalate 3.6 1.4 0.54 0.17
Po1yethylene (p = 0.964 gfcm') 170 93 124 57
Po1yethylene (p = 0.914 gfcm') 460 320 372 193
Natural rubber 1580 1110 1110 890
The gas solubility also varies widely with the gas and the type of polymer.
The solubility is low for gases that have a low boiling point or critical temperature,
but the similarity of the gas and the polymer is also important. Polar gases tend
to be more soluble in polymers with a high concentration of polar groups, and
the solubility of water vapor is high in materials that can form hydrogen bonds
with water molecules. With a wide range of diffusivities and solubili'ies, it is not
surprising that some membranes have quite high selectivities for certain gas
mixtures. For silicone rubber, the selectivity is 4.9 for CO 2 /H 2 and 5.4 for CO 2 /0 2 .
For Kapton®, an aromatic polyether diimide and a glassy polymer, the permeabili-
ties are two to four orders of magnitude lower than for silicone rubber, and the
order of permeabilities is altered!D The seleclivities for Kapton® are 0.18 for
CO 2 /H 2 and 1.8 for CO 2 /0 2 • A selectivity of 4 or greater is generally needed for
a good separation, as shown in a later section.
For most gases, the permeability increases with temperature, because the
increase in diffusivity more than offsets any decrease in solubility. The change in
permeability is often correlated with an exponential equation, Q = a exp ( - E/R T),
with activation energies E that range from 1 to 5 kcaIjmol. However, an increase
in temperature usually decreases the membrane selectivity, so the operating
temperature is determined by balancing the needs for high flux and high selectivity.
MEMBRANE STRUCTURE. The flnx through a dense polymer film is inversely
proportional to the thickness [Eq. (26.7)J, so there is a strong incentive to make
the membrane as thin as possible without having holes or weak spots in it.
Gas-separation processes operate with pressure differences of 1 to 20 atm, so the
thin membrane must be supported by a porous structure capable of withstanding
such pressures but offering little resistance to the flow of gas. The support is made
from a porous ceramic, metal, or polymer, and it should have a porosity of about
50 percent. The pore size should be comparable to the thickness of the thin selective
film that Covers the support. However, handling a thin layer and bonding it to
the support without tearing is difficult, and most gas-separation membranes are
prepared with the support as an integral part of the membrane. Special methods
of casting are used to prepare asymmetric membranes, which have a thin, dense
MEMBRANE SEPARATION PROCESSES 843
FIGURE 26.3
Capillary ultrafiltration membrane. (Amicon, Inc.)
layer or skin on one side and a highly porous substructure over the rest of the
membrane. A picture of such a membrane is shown in Fig. 26.3.
Typical gas-separation membranes are 50 to 200 I'm thick with a 0.1- to
I-I'm skin.17 New techniques may permit production of commercial membranes
with a skin thinner than 0.1 I'm. Membranes with a very thin skin are more likely
to have pinholes, and since flow through such flaws is very rapid compared to
diffusion through dense polymer, only a few pinholes per unit area can lower the
selectivity appreciably. One solution to this problem is to coat the membrane with
a very permeable but nonselective polymer, which fills the pinholes and does not
greatly reduce the permeability of the rest of the membrane. 6 The asymmetric
membranes can be prepared in the form of flat sheets, tubes, or hollow fibers as
small as 40 I'm in diameter. The small hollow fibers are strong enough to withstand
high pressures without any additional support, but the flat sheets need additional
supports and spacers.
The concentration gradients in an asymmetric membrane are complex
because the driving force for diffusion in the skin layer is the concentration gradient
of gas dissolved in the dense polymer, and the driving force in the porous support
layer is a concentration or pressure gradient in the gas-filled pore. When the porous
layer is thick, diffusion does not contribute very much to the flux, and gas flows
by laminar flow in the tortuous pores. For high-flux membranes, there may also
be significant mass-transfer resistances in the fluid boundary layers on both sides.
844 MASS TRANSFER AND ITS APPLICATIONS
Boundary layer Boundary layer
\ I I I I
I I
P,
I I
I I
I
I
I CA I Feed
Permeate I I
I
I
: PA
I
I
: p.
I
I I
~
I
P, I
I
PA I I
I C.
p.
:
-Skin
-Porous laye:1
-Membrane-
FIGURE 26.4
Pressure and concentration gradients for an asymmetric membrane with boundary-layer resistance.
Figure 26.4 shows pressure and concentration gradients for an asymmetric
membrane. For this example, the permeability of A is much greater than that of
B, and the flux of A is several times that of B. The sketch shows a slight pressure
gradient for A in the feed boundary layer, but the large drop in CA shows that
the skin has most of the resistance to mass transfer. Note that the gradient for B
in the boundary layer is negative, and B is carried against its concentration
gradient by the total flow, which is mostly A.
The gases are assumed to be in equilibrium with the polymer phase on both
sides of the skin layer. The composition of the gas in the pores next to the skin
is generally not the same as the bulk composition of the permeate at that point.
The bulk composition depends on the flow arrangement of the separator, and the
bulk gas could have either more A or less A than the gas in the porous layer. The
diagram in Fig. 26.4 shows a case where the bulk permeate is about 70 percent
A, and the gas leaving the skin layer is about 90 percent A.
FLOW PATIERNS IN MEMBRANE SEPARATORS. There are several ways of
arranging the surface area in a gas separator, and some of these are illustrated in
Fig. 26.5 for hollow-fiber membranes with an external skin. Only a few fibers are
shown, and their size is greatly exaggerated for clarity. A commercial separator
has up to a million fibers in a shell several inches in diameter. The fibers are sealed
MEMBRANE SEPARATION PROCESSES 845
L,
l/
--
+-- )
v_ '\
(a) Il
L, L,
l
v_ --- --
-
__v
+--
(b)
L,
L,
~-
000/
LffiO\, )Q88 L,
\C£Q~
~s~
(c)
FIGURE 265
Flow arrangements for hollow-fiber membranes: (a) countercurrent flow; (b) parallel and counter-
current flow; (c) radial crossBow.
into a tube sheet with an epoxy potting compound at one or both ends of the
unit to keep the feed and permeate separated.
Figure 26.5a shows a separator arranged for countercurrent flow with the
feed gas on the shell side. The fibers are closed at one end, so the permeate flow
increases from zero at the closed end to the final value at the discharge end. The
feed gas has to flow across some of the fibers near the inlet and exit, so the flow
846 MASS TRANSFER AND ITS APPLICATIONS
is not always parallel to the axis, as it would be for ideal countercurrent flow.
Good distribution of flow on the shell side is a design problem for large-diameter
units.
In some separators, both ends of the fibers are open, as in Fig. 26.5b, and
permeate flows from the center toward each end. This makes the flow counter-
current in half of the separator and parallel in the other half. This arrangement
decreases the pressure drop for permeate flow inside the fibers or permits longer
nnits to be made with the same pressure drop. There is usually little difference in
the composition of the permeate for parallel or counterfiow operation when
asymmetric membranes are used, since the fluxes depend on the partial pressures
at the skin surface and not on the partial pressures in the product stream.
The problem of getting good flow distribution on the shell side is alleviated
by using a crossflow arrangement, as in Fig. 26.5c. The fibers are bundled around
a perforated discharge pipe, and feed gas flows radially from the outside of the
shell to the central pipe. With flow radially inward and the flow decreasing as gas
permeates the fibers, there is not much change in velocity past the fibers. Some
commercial separators are arranged with feed at the center and radial flow
outward, even though this makes the change in velocity greater from inlet to exit.
The fibers can be sealed in tube sheets at one or both ends of the unit.
PRODUCT PURITY AND YIELD. The compositions of the permeate and the
residue depend on the pressure difference across the membrane, the permeability
of the various species, the feed composition, and the fraction of the feed that is
recovered as permeate. With asymmetric membranes and uniform distribution of
the feed, the flow arrangement has no effect on the product purity unless there is
a significant pressure drop in the lumen or interior of the fibers or unless the
porous layer is thin enough for diffusion to moderate the concentration differences
across this layer. Equations are derived here for a binary mixture with asymmetric
membranes and negligible boundary-layer resistances. (A small boundary-layer
resistance could be allowed for by using an effective permeability.) The pressures
in the shell side and the tube side are assumed constant. The terminology is similar
to that for distillation, with x and L representing composition and molar flow rate
of the feed and y and V the composition and flow rate of the permeate. The
composition on the feed side, x, changes with length along the fiber axis, but radial
gradients in x are ignored. However, for the permeate composition at any length,
it is necessary to distinguish between the average composition of the gas, y, and
the composition of the gas on the low-pressure side of the skin layer, which is
called the local or interface composition y,. The relationship between x and y, is
not an equilibrium one but depends on the relative permeabilities and partial-
pressure differences. The fluxes are given by the following equations, where P 1 is
the feed pressure and P 2 the permeate pressure:
J A = QA(P,X - P 2 y;) (26.10)
J a = Qa[P,(1 - x) - P 2 (1 - y,)] (26.11)
MEMBRANE SEPARATION PROCESSES 847
The ratio of absolute pressures, R, is introduced into the flux equations to give
Pz
R=- (26.12)
PI
J A = QAPI(X - Ry,) (26.13)
J. = QnPI[I- x - R(1 - y,)] (26.14)
The local permeate composition y, depends on the flux ratio at that point:
JA QAPI(X-Ry,)
(26.15)
y, = J A + J. QAPI(X - Ry,) + Q.P I [1 - x - R(I- y,)]
Using" for the permeability ratio QA/Qn gives
x-Ry,
(26.16)
y, = x - Ry, + (1 - x- R + Ry,)j"
Rearrangement leads to a quadratic equation for y,:
z
(a - l)y,
(
+ 1- " -
1-
R x(" -
R
1)) y, + Rax = 0 (26.17)
Equations (26.16) or (26.17) can be used to show how the local permeate
composition depends on the pressure ratio, the selectivity, and the feed composi-
tion. In the limit as R approaches zero, Eq. (26.16) is used because Eq. (26.17)
becomes indeterminate. Then
_--,-:.x~-,--, (26.18)
y, = x + (1 - x)ja
or
ax
y, = -1-+-(a---l)-x
At a pressure ratio of 1.0, no separation occurs in a binary system, since
there is no driving force for diffusion. If a third component is added to the permeate
side as a sweep gas, the partial pressures of A and B in the permeate are lowered,
and separation of A and B can take place, but trial-and-error calculations are
needed to determine the permeate composition.
At a fixed pressure ratio, the separation improves with increasing selectivity,
but there may be an upper limit to y,. The partial pressure of A in the permeate
can never exceed that in the feed, so the maximum value of y, is found by equating
the partial pressures:
(26.19)
848 MASS TRANSFER AND ITS APPLICATIONS
For example, for a feed with 40 percent A and a pressure ratio R = 0.5, the
highest permeate concentration is 0.80 even for a very selective membrane.
However, if the pressure ratio is decreased to 0.20, nearly pure A can be obtained
if the membrane has a very high selectivity. The variation of y, with Cl is shown
in Fig. 26.6 for two values of R and x = 0.4 or 0.2.
The composition of the permeate stream at any point along the separator
is an integrated average of the incremental contributions to V;
L:~Vy,
y= (26.20)
V
or
y=--
Jy,dV (26.21)
V
The overall and component material balances for the separator are
L in = + "Yaut
Lout (26.22)
LinX in = LoutXout + V:utYout (26.23)
1.0
0.8 /'
~ - / V ~ --
~~
.....-::
-'/ ~
0.6
/1
,I'
lP Y ~:"
~~ -
0.4
0.2 ~
2 5 10 20 50 100 200 500 1000
"
FIGURE 26.6
Effects of selectivity and pressure ratio on local permeate composition.
MEMBRANE SEPARATION PROCESSES 849
When using a stepwise solution to determine separator performance, the following
equations apply, where y is the average composition of the gas diffusing through
an incremental length of separator:
L,=Lj+L'.V (26.24)
L,x, = Ljx j + L'. Vy (26.25)
Y = !(Y, + Yj) (26.26)
Replacing L j with L, - L'. V in Eq. (26.25) gives
L, (x, - x) = L'. V(y - x) (26.27)
Equations (26.17) and (26.24) to (26.27) are solved numerically to determine
the amount of permeate and its composition for chosen values of X out ' The area
needed for separation is calculated from the total flux or the flux of A:
(26.28)
or
(26.29)
An approximate area can be obtained from the permeate flow and the average
flux of the most permeable gas:
A = (VY)out = (VY)out (26.30)
(J A)", QA(P,X - P 2y,)",
If the ratio of inlet and exit driving forces is less than 2, an arithmetic average
can be used with little error. For larger driving-force ratios the logarithmic mean
could be used, though examples show that this slightly overestimates the required
area.
Multicomponent mixtures. To predict the performance of a membrane separator
for a multicomponent mixture, the flux equations for each component are written
in the same form as Eq. (26.10), and a trial-and-error procedure is used to get the
amount of permeate and the local permeate compositions for each increment of
area. To start the calculation, the permeate composition can be assumed the same
as the feed composition, which makes the estimated driving force for each species
(P, - P 2)X,. The fluxes are summed to get the total flux and the local permeate
composition, and the calculation is repeated using the corrected composition. If
p 2 ~ P" only a few trials are needed for convergence, and the residue composition
is then calculated by material balance. The procedure is continued for a succession
of area increments nntil the design goal is met. As with other multicomponent
850 MASS TRANSFER AND ITS APPLlCATrON~
separations, the complete composition of the product streams cannot be specified,
and the design goal is either a certain concentration of a key component in the
permeate or residue, a given percent recovery of one component, or a specified
stage cut, which is the molar ratio of permeate to feed.
Example 26.1 An air-separation membrane has an 02JN2 selectivity of 5.0, and the
O 2 permeability is 0.2 scf/ft 2 -h-atm. (a) For a counterftow separator operating with
a residue containing 95 percent N 2 , what is the permeate composition and the fraction
of the feed obtained as permeate if the feed pressure is 150 Ib f /in. 2 absolute and the
permeate pressure 15Ibf /in. 2 absolute? (b) What membrane area is needed for a feed
rate of 300 scfm?
Solution
R ~ 15/150 = 0.1 • = 5.0
At the feed inlet, x = 0.209, and the local permeate composition is calculated from
Eq. (26.17):
(a - I)y? + (I - a- *- x(a R I))y, +: = 0
4y? + [I - 5 - 10 - 4(0.209)(10)Jy, + 5(0.209)(10) = 0
4 y? - 22.36 y, + 10.45 = 0
From the quadratic formula using the negative root,
22.36 - [22.36 2 - 16(1O.45)Jo.,
y, = 8 0.5148
At the discharge end x = 0.05, and y, is obtained from Eq. (26.17):
4y? - 16y, + 2.5 = 0 y, = 0.1629
For an approximate solution, these terminal composItIon are averaged to give
y ~ (0.5148 + 0.1629)/2 =
0.3389. From an overall material balance using L,o =
100 scfh as a basis,
100(0.209) = V(0.3389) + (100 - V)(0.05)
20.9 = 0.3389V + 5 - 0.05V
15.9 = 0.2889V
v= 55.0. Hence the permeate is 55% of the feed.
A more accurate solution is obtained by a stepwise calculation using 11x increments
of 0.01 (0.009 for first increment):
At x = 0.20,
4y; - 22Yj + 10 = 0
Yj = 0.50
MEMBRANE SEPARATION PROCESSES 851
For the first section, ji = (0.5148 + 0.50)(2 = 0.5074. The material balance for this
section is
2.9278
(0.5074 - 0.20)
L = lOO - 2.9278 = 97.0722
The O 2 permeating this section is
"V ji = 2.9278(0.5074) = 1.4856 scfh
For the second section, at x = 0.19,
4y~ - 21.6y, + 9.5 = 0 y, = 0.4830
0.4830 + 0.50
ji = - - - - , - - - 0.4915
2
"V = 97.072(0.20 - 0.19) = 3.2196
(0.4915 - 0.19)
V= I "V = 2.9278 + 3.2196 = 6.1474
L = 100 - 6.1474 = 93.8526
"Vji = 3.2196(0.4915) = 1.5824
I ("Vji) = 1.4856 + 1.5824 = 3.068
I (" Vy) 3.068 = 0.4990
y= V 6.1474
Calculations continued in this manner give
y = 0.350 when x = 0.05
V = 52.93 or 52.93% recovered as permeate
The permeate composition differs by 3.3 percent from the approximate solu-
tion. The changes in local and cumulative permeate compositions are plotted against
the stage cut, which is defined as the fraction of feed recovered as permeate, in Fig.
26.7.
The membrane area is obtained from the flux of A using Eqs. (26.29) and (26.13):
852 MASS TRANSFER AND ITS APPLICATIONS
0.5 '-'
~
0.4
P::r--.. N
r--...
c
~ I'
0
1l 0.3 N'
.g
~
"0
"'" ~
--r--..r--...
::;
0.2
l'
0.1
0.1 0.2 0.3
r-.,x
-r-- 0.4
t-
0.5 0.6
Stage cut
FIGURE 26.7
Penneate and residue compositions for OrN2 separation with GC = 5.0.
For the first increment x = 0.2Q9 to x = 0.200
d V ~ = 1.4856 scfh for Lin = 100 scfh
At x = 0.209
x - Ry, = 0.209 - 0.1(0.5148) = 0.15752
At x = 0.200
x - Ry, = 0.20 - 0.1(0.50) = 0.15000
(x - Ry,)", = 0.15376
QA p 1 = 0.2 x 10 = 2.0 scfh/ft'
Since the specified flow is 300 scfm or 18,000 scfh and part (a) was solved for
a feed of 100 scfh, a factor of 180 is used to get the incremental area:
1 1.486
dA =- -- x 180 = 870 ft'
2.00.15376
MEMBRANE SEPARATION PROCESSES 853
The calculation is continued with 6.x increments of 0.01,
when Lin = 100 scfh
211
A =- x 180 = 18,990 It>
2.0
The change in x and y; along the length 01 the permeator is shown in Fig. 26.8,
where the abscissa scale is I AV y/(x - Ry;).
COUNTERCURRENT VERSUS PARALLEL FLOW. The solid lines in Fig. 26.8
show how the local and average penneate compositions decrease along the length
of a parallel-flow separator. The abscissa scale is I AVJiI(x - Ry;) or square feet
divided by 90. At the inlet, y; and y are the same, but the average composition y
does not decrease as rapidly with length as y;. The dashed line shows the values
of y for a counterflow separator, where the feed flow is still from left to right but
the penneate flows from right to left. The curve for y; is the same as before, since
the driving force is P ,(x - Ry;) and does not depend on y when asymmetric
0.51-""~""",:!---+----+-----l---t----1
0.4 f---+-~'+----I--=_d--~f----j
5 O.3~----~~~--~-------P~----~------+-----~
~ '- ... y
~
......
'0 Countercurrent flow
::;;
0.2 P_:--+---+----+--"'1k2"""'t----1
0.1 t---+---+---"T'..;;...=---lr---t----1
°0L-----~40~----~8LO------~12LO-------16LO----~2~0~0----~240
Membrane area, ff/90
FIGURE 26.8
Change in penneate and residue compositions with membrane area for Oz-N z separation.
854 MASS TRANSFER AND ITS APPLICATIONS
membranes are used. Therefore the final permeate composition is the same for
counterflow as for parallel flow and is 0.35 for this example.
If uniformly dense polymer membranes are used, the gradients are similar
to those shown in Fig. 26.1, and the driving force for the most permeable species
is P,(x - Ry) rather than P,(x - RyJ The fluxes then depend on the average
permeate composition at a given length, and using countercurrent flow gives a
higher average driving force than parallel flow. Calculations by Walawender and
Stern 2• for air separation in a single stage with" = 5 and R = 0.2 show the best
separation for dense membranes is obtained with a counterflow flow pattern
followed by crossflow, parallel flow, and perfect mixing. At a stage cut of 0.5, the
permeate oxygen levels were about 36 percent for countercurrent flow, 34 percent
for crossflow, and 32 percent for parallel flow.
Laboratory tests using asymmetric membranes for 02-N2 separation have
shown almost no difference between parallel-flow and counterflow operation.'·
However, for long fibers or those with a very small internal diameter, there can be
a significant effect of the flow arrangement. The pressure gradients and driving
forces for parallel and counterflow separators are sketched in Fig. 26.9. The
gradient for P 2 is zero at the closed ends of the fibers and increases gradually to
a maximum at the tube sheet. The value of P, on the shen side is assumed constant.
With parallel flow (solid lines) the lowest value of R (where R = P 2 IP,) is at the
discharge end, which tends to make the driving force x _ Ry, closer to the value
at the inlet. With counterflow (dashed lines), P 2 and R are highest at the residue
end, and the driving force x - Ry, may be very small. It is generally better to
have a nearly constant driving force than a large value at one end and a small value
at the other.
Tube sheet
Pressure
or
composition 1- . . . . . . . ..... Final driving
Final
---- force
parallel flow
driving force P,
counterflow
Permeate flow - - - . .
Length
FIGURE 26.9
Pressure gradients and driving forces in membrane separators: ( - - ) parallel flows; (~--~-~-)
counterflow.
MEMBRANE SEPARATION PROCESSES 855
APPLICATIONS. The major applications of gas-separation membranes are to
make products that are enriched in one or more components but are not of very
high purity. Products of equal or greater purity can usually be obtained by
liquefaction and distillation at low temperature, but the membrane processes have
the advantage of operation at or near room temperature.
Several companies supply permeators for air separation using membranes
with characteristics similar to those in Example 26.1. One of the main applications
is to provide nitrogen at purities of 95 to 99 percent, which is sufficient for many
inert-gas requirements. Units with capacities of 100 to 40,000 scfh (3 to 1000 m' /h)
are available, and in any unit, the nitrogen purity can be increased by reducing
the feed rate. If the goal is to make enriched oxygen for medical uses or to improve
combustion, only a small stage cut is used, and a permeate with 40 to 50 percent
O 2 is obtained. Although purer oxygen can be made by using several stages in
series, the recompression costs make this uneconomic compared to oxygen from
liquid-air plants or adsorption processes.
A combination of membrane and other technologies might be attractive for
some applications. Using membranes to prepare a gas with 50 percent O 2 as feed
to a pressure-swing adsorption plant would greatly increase the capacity of the
adsorber. Also, a gas with only a few ppm O 2 can be produced by using membranes
to get down to 0.5 percent O 2 and then removing the oxygen with added hydrogen
in a catalytic combustor. 2
There are many installations using membranes to recover hydrogen from
purge streams in ammonia, methanol, and hydrogenation plants. The selectivities
for H2 relative to CH., CO, and N2 are in the range 10 to 100, and permeate
considerably enriched in H2 can be obtained in a single stage. The compositions
reported for a petrochemical application are shown in Table 26.2.
In this example the feed pressure was 72 bars, the residue pressure was
n bars, and the permeate pressure was 31 bars. Most of the hydrogen is recovered
and recycled to the synthesis plant, and the residue is burned for fuel. There is
no need to get a very high concentration of hydrogen in the permeate. In other
applications, hydrogen concentrations of 95 to 98 percent can be obtained by
taking a lower stage cut (smaller recovery ofH 2) or operating with a lower pressure
ratio.
TABLE 26.2
Gas compositions for separation of ammonia plant
purge gas lS
Gas composition, mol %
Percentage recovery
Gas Feed Residue Permeate in permeate
H, 59 12 86 93
N, 21 43 8 24
Ar 6 II 3 32
CH. 14 34 3 14
856 MASS TRANSFER AND ITS APPLICATIONS
Example 26.2. A gas containing 70 percent H" 24 percent CH., and 6 percent C,H 6
is to be separated into a nearly pure H2 stream and a fuel gas using a hollow-fiber
permeator with a selectivity of 100 for H,/CH•. (a) If the upstream and rlownstream
pressures are 600 and 300 Ibf /in. 2 absolute, what fraction of H2 in the feed is
recovered in the permeate if the permeate is 96 percent H2? What is the stage cut?
(b) How much more H2 could be recovered by lowering the permeate pressure to
180 Ibf/in.' absolute?
Solution
(a) The mixture is treated as a pseudobinary, since the permeability of CH4 is
only slightly greater than that ofC 2H 6 . The local permeate composition is calculated
from Eq. (26.17) for a = 100 and R = 0.5. At the feed inlet, x = 0.70, and
99 yf + [1 - 100 - 2 - 2(99)(0.7)]y, + 100(0.7)(2) = 0
99yf - 239.6y, + 140 = 0
y, = 0.9860
The calculation is repeated for other values of x using increments of 0.05. For
x = 0.65
99y; - 229.7Yj + 130 = 0
Yj = 0.9793
For the first increment, y = (0.9860 + 0.9793)/2 = 0.9826. From Eq. (26.27) with
Lin = 100
~V = L~x, - x) 100(0.70 - 0.65)
15.03
Y- Xj 0.9826 - 0.65
H, in permeate = ~Vy = 15.03(0.9826) = 14.77
H, recovery = 14.77/70 = 0.211 = 21.1 %
Calculations are continued until the total H2 recovery is over 95 percent. The
results are plotted in Fig. 26.10.
For R = 0.5, the H, purity is 96 percent at a recovery of 62.5 percent.
The H, recovered per 100 mol total feed is 0.625(70) = 43.75.
The permeate flow V = 43.75/0.96 = 45.6.
The stage cut is 45.6 percent.
(b) R = 180/600 = 0.3.
At x = 0.70
,
99y, + [ 1-100----(0.7)
1 99 ] 100(0.7)
y,+--=O
0.3 0.3 0.3
y, = 0.9926
Continuing the calculations as in part (a) gives y = 0.96 at 88 percent H,
recovery.
The stage cut is 0.88(70)/0.96 = 64.2 percent.
MEMBRANE SEPARATION PROCESSES 857
100
95
-- .........
""'-'\
\.
'-
R~0.3\
'\
\
\
~$ \ \
R~0.5
E
$
c.
90
\
.~
:£
\
;;. \
\
\
85 \
\
I;
\
20 40 60 80 100
Hydrogen recovery, %
FIGURE 26.10
Permeate purity for H2 /CH 4 separation with a = 100 and Xo = 0.70.
Another indnstrial application of gas-separation membranes is the removal
of carbon dioxide from natural gas. The CO 2 /CH 4 selectivity is about 20 to 30
for polycarbonate, polysulfone, and cellulose acetate membranes at 35"C and
40 atm. A selectivity of over 60 can be obtained with Kapton@, but this polymer is
much less permeable than the others. Increasing the temperature raises the
permeability of most polymers but generally causes a .slight decrease in selectivity.
The operating temperature is chosen to be somewhat above the dew point of the
residue gas. There is considerable CO 2 absorbed in the membranes at high CO 2
partial pressures, and the plasticization effect of CO 2 increases the effective
diffusion coefficients for all gases and makes the selectivity less than that based
on pure-gas data. 7 Methods of allowing for such nonlinear effects have been
presented."
The separation of helium from natural gas is a potential application of
membrane technology. Using a membrane with a He/CH. selectivity of 190 and
a feed with only 0.82 percent He, half of the helium can be recovered in a single
stage, giving a permeate 30 times richer than the feed! 9
858 MASS TRANSFER AND ITS APPLICATIONS
SEPARATOR ARRANGEMENT. Most applications of membranes for gas or liquid
separation require multiple units, since the largest units are only about 1 ft (0.3 m)
in diameter and 10 to 15 ft (3 to 5 m) in length. A hollow-fiber module of this size
might have many thousand square feet of membrane area and be able to process
several hundred cubic feet of gas per minute. For treating the much larger flows
in a refinery or chemical plant, several units could be arranged in parallel, as
shown in Fig. 26.11a. Care must be taken in designing the feed distribution system
to ensure the same flow to all units. When operating at low capacity, some of the
units can be shut off to keep the flow per module about the same. If all units were
kept in service, the greater permeate recovery at low flow rate could lead to
condensation of liquid on the feed side.!6
;L-------.r:;-T.. Residue
Feed-JL~t=============~:?r
L _______-.J..1...--+- Permeate
ia)
Feed ---;Jt!.....----_Jlc:;---;:Jt'--_____J~:::; Residue
F----------- F--------n~!
1
VI Permeate
ib)
V2 Permeate
Reflux Feed
!
f51----------3 ' I
(----------f Residue
Permeate id)
FIGURE 26.11
Separator arrangements: (a) parallel flow; (b) series flow; (c) two~stage flow; (dJ continuous membrane
column.
MEMBRANE SEPARATION PROCESSES 859
Separators are sometimes arranged in series, as shown in Fig. 26.11b. The
frictional pressure drop on the feed side is usually small « 1 atm), so two or
three units can be put in series without having to recompress the feed. The
permeate streams differ in purity and may be used for different purposes or they
may all be combined. Another method of operation uses lower permeate pressures
in successive units. The first unit produces permeate at moderate pressure so that
the gas can be used directly without compression. The next unit operates at lower
downstream pressure to compensate for decreased feed concentration, and the
permeate is compressed for reuse. In a large plant a combined series-parallel
arrangement could be used, with several pairs of permeators connected to a
common source of feed.
To get higher purity perineate, the product from the first stage can be
compressed and sent to a second stage, as shown in Fig. 26.11c. Two or more
stages could be used in this fashion to get the desired purity, but the cost of
recompression and the increased complexity of the system makes this scheme
generally uneconomical. A novel approach that uses two separators and one
recompression step is the continuous membrane column. 8 As shown in Fig. 26.11d,
part of the permeate product from the second separator is compressed and sent
back to the other side of the membrane, where it flows countercurrently to the
permeate. This reflux action permits very high purity permeate to be obtained.
The reflux steam loses the more permeable component as it flows through the
separator and is combined with the feed to the first separator. This scheme was
demonstrated in pilot units but has not yet been used commercially.
SEPARATION OF LIQUIDS
There are several processes for the separation of liquid mixtures using porous
membranes or asymmetric polymer membranes. With porous membranes, separa-
tion may depend just on differences in diffusivity, as is the case with dialysis, where
aqueous solutions at atmospheric pressure are on both sides of the membrane.
For liquid-liquid extraction using porous membranes, the immiscible raffinate and
extract phases are separated by the membrane, and differences in the equilibrium
solute distribution as welI as differences in diffusivity determine the extract
composition.
With asymmetric membranes or dense polymer membranes, permeation of
liquids occurs by a solution-diffusion mechanism. The selectivity depends on the
solubility ratio as well as the diffusivity ratio, and these ratios are very dependent
on the chemical structure of the polymer and the liquids. The driving force for
transport is the activity gradient in the membrane, but in contrast to gas
separation, the driving force cannot be changed over a wide range by increasing
the upstream pressure, since pressure has little effect on activity in the liquid phase.
In pervaporation, one side of the membrane is exposed to the feed liquid at
atmospheric pressure, and vacuum or sweep gas is used to form a vapor phase
on the permeate side. This lowers the partial pressure of the permeating species
and provides an activity driving force for permeation. In reverse osmosis, the
860 MASS TRANSFER AND ITS APPLICATIONS
permeate is nearly pure water at about 1 atm, and very high pressure is applied
to the feed solution to make the activity of the water slightly greater than that in
the permeate. This provides an activity gradient across the membrane even though
the concentration of water in the product is higher than that in the feed.
Dialysis
Thin porous membranes are used in dialysis, a process for selectively removing
low-molecular-weight solutes from a solution by allowing them to diffuse into a
region of lower concentration. There is little or no pressure difference across the
membrane, and the flux of each solute is proportional to the concentration
difference. Solutes of high molecular weight are mostly retained in the feed solution,
because their diffusivity is Iow and because diffusion in small pores is greatly
hindered when the molecules are almost as large as the pores.
Concentration gradients for a typical dialysis experiment are shown in Fig.
26.12. The feed is assumed to contain a Iow-molecular-weight solute A, a solute
of intermediate size B, and a colloid C. There are concentration boundary layers
on both sides of the membrane, and these may contribute significantly to the
overall resistance if the membrane is thinner than the boundary layers. The
gradient for A or B in the membrane is steeper than in the boundary layers,
because the effective diffusivity is less than the bulk value, and at steady state, the
flux through the membrane equals that through the boundary layers. The values
of CA and CB in the membrane are the concentrations in the pore fluid and not
Boundary layers
I~\
Product ~ Feed
C" ------'1 I_~-----C..
1-....;----- Cc
FIGURE 26.12
Concentration gradients in dialysis.
MEMBRANE SEPARATION PROCESSES 861
the concentrations based on total membrane volume. In the pore fluid and in the
product, Cc = 0 because the colloidal particles are larger than the pore size.
The general equations for solute flux allow for three resistances in series:
lA = KA(C A1 - C A2 ) (26.31)
1 1 1 1
-=-+-+- (26.32)
KA klA k"'A k2A
The coefficients kl and k2 for the feed and product depend on the flow rates,
physical properties, and membrane geometry, and they can be predicted using the
correlations in Chap. 21. The membrane coefficient depends on the effective
diffusivity D, and the membrane thickness z:
D,
k =- (26.33)
'" z
A theoretical equation for D, is based on ..\, the ratio of molecular size to pore
size 25 :
D, = D,B (1 _ J.)2(1 - 2.104J. + 2.09J.2 - 0.95J.3) (26.34)
T
The term (1 - J.)' is the volume fraction available for a spherical molecule in
a cylindrical pore, and the last term in Eq. (26.34) is a hindered diffusion term.
For B = 0.5, T = 2, and J. = 0.1, D, = 0.164D" and for J. = 0.5, D, = 0.022D,. Since
D, is much lower than D" the diffusion flux is generally controlled by the
membrane resistance.
The best-known application of dialysis is the use of artificial kidneys to
remove waste products from the blood of persons with kidney disease. Hollow-
fiber cellulosic membranes are employed, and blood is passed through the fibers
while saline solution is circulated on the outside. Urea and other small molecules
diffuse through the membrane to the external solution, while proteins and cells
are retained in the blood. The dialyzing solution has added salts and glucose to
prevent loss of these materials from the blood.
An industrial application of dialysis is the recovery of caustic from hemi-
cellulose solutions produced in making rayon by the viscose process. Flat-
sheet membranes are placed parallel to each other in a filter-press arrangement
(see Chap. 30, p. 1004) and water is passed countercurrent to the feed solution to
produce a dialyzate with up to 6 percent NaOH. Recovery of salts or sugars from
other natural products or other colloidal solutions could he achieved by dialysis,
but ultrafiltration is more likely to be used because of the higher permeation rates
that can be obtained.
Many large-scale applications of electrodialysis use ion-selective membranes
and a potential gradient to speed migration of ions through the membranes.
Brackish water can be made potable by passage through an array with alternate
cation- and anion-permeable membranes, as shown in Fig. 26.13. In half of the
spaces, cations move out to one side and anions move out to the other side, leaving
862 MASS TRANSFER AND ITS APPLICATIONS
Concentrated brine ~
~ Desalted water
Anode Cathode
A = anion permeable
C = cation permeable
Feed solution
FIGURE 26.13
Schematic diagram of an electrodialysis cell.
purer water. Solution in the alternate spaces becomes more concentrated and is
eventually discarded. Similar units are used to concentrate salt solutions in a
variety of processes. One example is the use of electrodialysis to treat the reject
salt solution from a reverse-osmosis system. 23 The salt concentration is increased
eightfold, which reduces the disposal cost, and the reclaimed water is recycled to
the reverse-osmosis plant. In this application, the electrode polarity is reversed at
regular intervals to minimize scale problems at the high salt concentration.
Membranes for Liquid-Liquid Extraction
Extraction of a solute from water to an organic liquid, or vice versa, can be carried
out using membranes to separate the phases and provide a high surface area for
mass transfer. Hollow-fiber or flat-sheet membranes can be used, and the mass-
transfer area is then fixed by the design and does not depend on variables such
as flow rate, viscosity, and surface tension, which affect the area of liquid-liquid
dispersions. The membrane extractor can be arranged to have counterfiow of the
two phases with no flooding limitations, unlike the situation in packed or spray
columns. A further advantage is that there is no need for a settling tank or
de-emulsifier, because the phases are kept separate by the membrane. However,
the membrane does introduce an additional resistance to mass transfer, and this
must be minimized to make the process attractive.
MEMBRANE SEPARATION PROCESSES 863
If a dense polymer film were used in an extractor, the membrane resistance
would be quite large because of the very low diffusivity in solid polymers. Using
an asymmetric membrane would reduce the membrane resistance, because diffu-
sion is more rapid in the open substructure than in the dense skin. However, the
minimum resistance is obtained with a porous membrane, one that has pores
extending completely through the membrane. Phase separation is maintained by
choosing a membrane that is not wetted by one of the phases. For example,
membranes made of Tellon or polypropylene are hydrophobic, and water will
not enter the pores except at high pressure. The critical entry pressure depends
on the contact angle and the size and shape of the pores' and is as high as
50 lbJ/in 2 for some commercial membranes. .
An extractor with hollow fibres of polypropylene· could operate with the
aqueous phase inside the fibers at a pressure slightly greater than the pressure of
the organic phase on the outside. The pores of the membrane would fill with the
organic solvent, and the liquid-liquid interface would be at the pore mouths. The
concentration gradients are sketched in Fig. 26.14 for an example where the
equilibrium solute concentration is much higher in the organic phase. The overall
resistance for this case is
(26.35)
The coefficients for the water phase, k", the organic phase, le" and the membrane,
D,.o/z, are generally about the same magnitude, but if the distribution coefficient
m is large, most of the resistance is in the water phase. Here m is the ratio of the
solute concentration in the organic phase to that in the water phase.
If a hydrophilic membrane is used, the pores fill with the water phase, and
the organic phase must be kept at a high pressure to prevent water from passing
Membrane
I
..J--- Boundary layer
I
I
I
I
I
I
I
Water phase I
Organic phase
FIGURE 26.14
Liquid-liquid ex.traction with a
porous hydrophobic membrane.
864 MASS TRANSFER AND ITS APPLICATIONS
through the pores and forming drops in the organic phase. For the system shown
in Fig. 26.14, use of a hydrophilic membrane would mean two water-phase
resistances and a lower overall coefficient, as shown by the equation
(26.36)
If the distribution coefficient for the solute strongly favors the water phase
(m ~ 1), the organic phase has the controlling resistance, and a hydrophilic
membrane might be selected to make the membrane resistance smaller.
Hollow-fiber extractors have been tested in the laboratory,2UO and the mass
transfer rates are generally consistent with theory, though satisfactory correlations
for the external coefficient are not yet available (see Chap. 21). These devices should
find practical application for systems where it is difficult to get a good dispersion
or where emulsification makes the final phase separation difficult.
Pervaporation
Pervaporation is a separation process in which one or more components of a
liquid mixture diffuse through a selective membrane, evaporate under low pressure
on the downstream side, and are removed by a vacuum pump or a chilled
condenser. Composite membranes are used with the dense layer in contact with
the liquid and the porous supporting layer exposed to the vapor. The phase change
occurs in the membrane, and the heat of vaporization is supplied by the sensible
heat of the liquid conducted through the thin dense layer. The decrease in
temperature of the liquid as it passes through the separator lowers the rate of
permeation, and this usually limits the application of pervaporation to removal
of small amounts of feed, typically 2 to 5 percent for one-stage separation. If a
greater removal is needed, several stages are used in series with intermediate
heaters. Commercial units generally use flat-sheet membranes stacked in a filter-
press arrangement, with spacers acting as product channels, although spiral-wound
membranes could also be used. Hollow-fiber membranes are not as suitable
because of the pressure drop from the permeate flow through the small-bore fibers.
The flux of each component is proportional to the concentration gradient
and the diffusivity in the dense layer. However, the concentration gradient is often
nonlinear because the membrane swells appreciably as it absorbs liquid, and the
diffusion coefficient in the fully swollen polymer may be 10 to 100 times the value
in the dense unswollen polymer. Furthermore, when the polymer is swollen mainly
by absorption of one component, the diffusivity of other components is increased
also. This interaction makes it difficult to develop correlations for membrane
permeability and selectivity.
For permeation of a single species, the diffusivity can be expressed as an
exponential function of the concentration:
(26.37)
MEMBRANE SEPARATION PROCESSES 865
where {3 is a constant and Do is the diffusivity at infinite dilution. At steady
state, the flux across a film of thickness z is
Do c
J = -(e~ ' - ePC,) (26.38)
{3z
If {3C, is larger than 1.0 aud C z iS,much smaller than C" there is a several-fold
decrease in diffusivity across the membrane, and the flux is not proportional to
the concentration difference. For example, if {3C, = 2.0 and Cz = 0,5C" the flux
is (e Z - e)D o/{3z = 4,67D o/{3z, but lowering Cz to zero, which doubles the con-
centration difference, only increases the flux to 6.39D o/{3z, a 37 percent increase,
However, increasing C, by 50 percent to double the driving force raises the flux
to 17.4D o/{3z, a 3,7-fold increase,
In an early study of pervaporation 3 using lI-heptane at 1 atm and 99°C the
flux was inversely proportional to the thickness of the dense polymer fihn, as
expected, but the flux increased only slightly as the downstream pressure was
decreased from 500 to 50 mm Hg. This is consistent with Eq. (26.38) and a value
of 5 or more for {3C,. Other studies with pure feed liquids have given similar
results, and direct measurements have shown very nonlinear concentration profiles
in the membrane.' However, in commercial applications of pervaporation, the
liquid feed usually has a low concentration of the more permeable species, so the
swelling of the membrane and the resulting nonlinear effects are not as pronounced
as when testing pure liquids or solutions of high concentration.
The gradients at steady state for a typical system are shown in Fig, 26,15.
The feed is rich in E, but A is assumed to be much more soluble in the polymer,
and there is a high concentration of A at the upstream face of the membrane, The
Skin Porous support
P,
Xs
Ps,
C"
P"
XA
C'"
\
~ CA>
P2
P",
P",
C",
FIGURE 26.15
Gradients in a pervaporation membrane.
866 MASS TRANSFER AND ITS APPLICATIONS
gradient of A is small near this boundary because of the high diffusivity, but D A
decreases as CA decreases. The gradient of B has a similar shape reflecting the
change in DB through the membrane. The concentrations C A2 and C B2 are likely
to be proportional to the downstream partial pressure PA2 and P B2 , but Henry's
law may not hold at the upstream side, where the membrane is highly swollen by
solvent.
The concentration of a solvent in the membrane at the upstream side depends
on its solubility in the polymer at the operating temperature and the activity of
the solvent in the liquid. The feed is usually heated, because the membrane
permeability increases 20 to 40 percent for a lOOC increase in temperature without
much loss in selectivity. The upstream pressure is I atm or slightly higher to
prevent partial vaporization of the feed. It is not worthwhile to use very high
pressure on the upstream side, since the activity in the liquid phase increases only
a small amount for a large increase in pressure. The downstream pressure is kept
as low as possible to provide a large driving force for diffusion across the
membrane. The driving force can be expressed as a partial-pressure difference
(y AX AP~ - YAP 2), where y is the activity coefficient, P' the vapor pressure of the
pure component, and x and Y the mole fractions in the liquid and vapor. If the
nonlinear effects are neglected and average values of permeability are used, the
equations for a binary mixture become
JA= QA(YAXAP~ - y AP 2) (26.39)
J B = QB[YB(I - XA)P~ - (I - YA)P 2] (26.40)
JA
(26.41)
YA=JA+J B
These equations are similar to those for gas separation, but the pressure
ratio R is replaced by modified ratios RA and R B , which include the activity
coefficients and vapor pressures:
(26.42)
The activity coefficients and vapor pressures are also included III a modified
selectivity,
(26.43)
Combining Eqs (26.39) to (26.43) leads to a quadratic equation for y" the local
value of y A' Then
ayl + by, + c = 0 (26.44)
where a = a'RA - RB
b = RB + X - I - a'(RA + x)
c = clx
MEMBRANE SEPARATION PROCESSES 867
For plug flow of liquid through a separator the value of y, is greatest at the
feed end, and the final composition of the permeate, y, is an integrated average
of the local values. The calculations have to allow for the decrease in liquid
temperature, which decreases the driving force for diffusion and also the perme-
ability. The temperature change is calculated from an enthalpy balance:
(26.45)
where cp is the specific heat of the liquid and AH, is the enthalpy of vaporization.
The first commercial application of pervaporation was for ethanol-water
separation. The dilute solution produced by fermentation is distilled to produce
an overhead product with 90 to 95 percent alcohol (close to the azeotrope), and this
solution is fed to the membrane unit to give nearly pure ethanol (99.9 percent).
The permeate stream with about 20 to 40 percent alcohol is recyled to the
distillation column. The vapor-liquid equilibrium curve and the vapor and liquid
compositions for a poly(vinyl alcohol) membrane are shown in Fig. 26.16. 29 The
membrane gives a permeate that is always richer in water than the liquid, in
contrast to distillation, where alcohol is the more volatile component over most
of the range. The shape of the curve for permeate composition indicates strongly
1.0 ~---~--~-----.----,---.....
,,
0.8 r
1_______-}~v~a~p~or~-I~iq~u~id~eq~u~iI~ib;r;iu~m~~=---~~----~
1 atm
0.6 '---j'--l------I!------,lL----+----H
0.4 f--I---+---...,jL---+-----j----jLJ
Vapor composition for
0.21-1______7I''-::::;;;==;F!p~e~rnmeate pressure=15 mm Hg
0.2 0.4 0.6 0.8 1.0
Weight fraction alcohol in liquid
FIGURE 26.16
Permeate compositions for pervaporation with a PVA membrane and an ethanol-water feed at 60"C.
868 MASS TRANSFER AND ITS APPLICATIONS
nonlinear behavior. Between 40 and 80 percent alcohol, the alcohol content of the
vapor decreases as the concentration in the liquid increases, but not all membranes
show this type of behavior. The membrane is most selective between 80 and 85
percent alcohol, and the permeate is only about 5 percent alcohol in this range.
The curve for permeate composition would be displaced upward at higher
permeate pressures because the driving force for water permeation is more sensitive
to changes in P 2 than is the driving force for alcohol.
Example 26.3. Laboratory tests of a pervaporation membrane exposed to liquid with
90 weight percent ethanol and 10 percent water at 60°C showed a flux of 0.20 kg/m2-h
and a permeate compostion of 7.1 percent ethanol when the downstream pressure
was 15 mm Hg. (a) Calculate the permeability of the membrane to ethanol and to
water at the test conditions and the selectivity for water. (b) Predict the local permeate
composition for 90 percent ethanol and 60°C if the downstr~am pressure is kept at
30 mm Hg by a water-cooled condenser. What is the condensing temperature? (c)
Calculate the local permeate composition for 95 percent) 99 percent) and 99.9 percent
ethanol at 60°C and 30 mm Hg assuming the permeabilities are the same as for part
(a).
Sollltion
(a) The flux of each component is calculated from the total flux and the
permeate composition with A = H 2 0 and B = C 2 H sOH:
J A ~ 0.20(0.929) ~ 0.1858 kg/m2-h
J B ~ 0.20(0.071) ~ 0.0142 kg/m2_h
The vapor pressures at 60°C are p~ = 149 mm Hg and P; = 340 mm Hg. For 10
weight percent H 2 0, x ~ (10/18)1(10/18 + 90/46) ~ 0.221 mole fraction H 2 0. The
activity coefficients can be estimated from the Margules equationsro using activity
coefficients applicable at the boiling point and neglecting the change in y with
temperature.
For H 2 0, In YA ~ (0.7947 + 1.615xA)x~:
For x A ~ 0.221, YA ~ 2.01
For alcohol, In YB ~ (1.6022 - 1.615 XB)X~
For x B ~ 0.779, YB ~ 1.02
The permeate is 100 - 7.1, or 92.9 weight percent H 2 0:
92.9/18
y 0.971 mole fraction H 20
92.9/18 + 7.1/46
The driving force for water transport is
I1P A ~ 2.01(0.221)(149) - 0.971(15) ~ 51.6 mm Hg ~ 0.0679 atm
0.1858
QA ~ - - ~ 2.74 kg/m 2 -h-atm ~ 152 g mOl/m 2 -h-atm
0.0679
MEMBRANE SEPARATION PROCESSES 869
For alcohol transport
!J.Pn ~ 1.02(0.779)(340) - 0.029(15) ~ 269.7 mm Hg ~ 0.355 atm
0.0142
Qn ~ - - ~ 0.040 kgfm'-h-atm ~ 0.87 g molfm'-h-atm
0.355
The selectivity on a mass basis is QA/Qn ~ 2.74/0.040 ~ 68.5. On a molar basis,
the selectivity is 152/0.87 ~ 175.
(b) If P, ~ 30 mm Hg, the driving force for water transport is reduced, but that
for alcohol is nearly the same, because the partial pressure of alcohol in the liquid
is so much greater than P 2' The vapor composition is found using Eq. (26.44):
P, 30 P, 30
RA ~ -- ~ ~ 0.1002 Rn ~ -- ~ 0.0865
YAP~ 2.01 x 149 YnP; 1.02 X 340
, QAYAP~ 152(2.01)(149)
• ~ --- ~ 150.9
QnYnP; 0.87(1.02)(340)
a ~ .'RA - Rn ~ 150.9(0.1002) - 0.0865 ~ 15.03
b ~ Rn +x - I - .'(RA + x)
~ 0.0865 + 0.221 - I - 150.9(0.1002 + 0.221) ~ -49.16
c ~ .'x ~ 150.9(0.221) ~ 33.35
15.03yf - 49.16y, + 33.35 ~ 0
y, ~ 0.960 (0.904 weight fraction water)
This small increase in alcohol content of the permeate (from 7.1 to 9.6 percent)
might seem tolerable, but the change becomes much greater as the feed solution
becomes richer in alcohol. In practice, pressures even lower than 15 mm Hg are used
to minimize the alcohol content of the permeate.
Since the vapor is mostly water, the condensing temperature at 30 mm Hg is
estimated from the vapor pressure of water to be 29°C.
(c) For 95, 99, and 99.9 percent alcohol, the concentrations are converted to
mole fractions and new values of the activity coefficients and other parameters are
calculated. The results are given in Table 26.3.
Reducing the water content of the ethanol from 1 to 0.1 percent is difficult if
P2 = 30 mm Hg. At 0.1 percent H 2 0 the partial pressure of water over the liquid is
TABLE 26.3
Permeate compositions for pervaporation of ethanol-water mixtures, Example 26.3
wt % alcohol XH10 Y, YB RA RB a' y, wt % H2O
95 0.1186 2.15 1.0 0.0936 0.0882 164.6 0.915 80.8
99 0.0252 2.21 1.0 0.0911 0.0882 169.2 0.256 11.9
99.9 0.00255 2.21 1.0 0.0911 0.0882 169.2 0.026 1.0
99.9t 0.00255 2.21 1.0 0.00911 0.00865 169.2 0.159 6.8
t For P z = 3 mm Hg
870 'MASS TRANSFER AND ITS APPLICATIONS
only 0.84 mm Hg, and the local permeate contains only 1 weight percent H2 0. If P 2
could be reduced to 3 mm Hg, the increased driving force would raise Yi to 0.159
and the local permeate would contain 6.8 weight percent H 2 0. Therefore much less
alcohol would be removed in going to 99.9 percent alcohol.
Although membranes could be used for the entire alcohol purification
process, a great many stages would be needed, and it is cheaper to use distillation
for most of the separation. If a membrane selectively permeable to alcohol could
be developed, it might be feasible to separate alcohol from dilute solutions entirely
by membranes.
The membranes used for ethanol purification are also suitable for dehydra-
tion of many other organic solvents, including methanol, isopropanol, butanol,
methyl ethyl ketone, acetone, and chlorinated solvents. Commercial units use up
to 12 stages with reheating between stages, and product water contents lower than
100 ppm can be obtained.
Another application of pervaporation is the removal of volatile organic
contaminants from water using silicone rubber or other organophilic polymers
for the membrane. Substances such as chlorinated solvents or gasoline components
that are only slightly soluble in water have very high activity coefficients in aqueous
solution. Therefore the equilibrium concentration in the membrane may be
moderately large even with only a few ppm in the solution, and nearly complete
removal of the organic compounds can be achieved at a low stage cut (not much
removal of water). Purification of water containing traces of trichloroethylene
(TCE) was demonstrated using silicone hollow fibers at 20°C, and up to 90 percent
TCE removal was obtained in a single stage. 22
At low concentrations of nearly insoluble organic materials, the mass-transfer
resistance in the water phase may control the rate of permeation. For water flow
inside hollow fibers at low Reynolds numbers, the limiting Sherwood number is
about 4 [see Eq. (21.49) and Fig. 12.2], corresponding to a "film thickness" of id"
where d, is the inside diameter of the tube. The membrane thickness ranges from
trrd, to td" about the same magnitUde as the inside film thickness. The solute
diffusivity in the membrane is lower than in water, but this is more than offset by
the much higher concentration of solute in the membrane. As a result, the
mass-transfer resistance for solute is often greater in the water phase than in the
membrane. By contrast, the transfer of water through the membrane is completely
controlled by the membrane resistance, since the water phase contains more than
99 percent H 20. This leads to an interesting optimization problem, since doubling
the membrane thickness halves the water flux but only slightly decreases the flux
of organic solute. The lower water flux means lower costs for vapor pumping and
condensation and less water in the permeate, but the membrane area for a given
solute removal is slightly increased. In a study by Lipski and Cote,'2 the optimum
conditions for removal of volatile organics were calculated for hollow fibers with
inside flow or transverse flow of the feed. The optimum membrane thickness was
75 I'm for flow inside 500-f.lm fibers but only 30 I'm for flow transverse to the
fibers, which gave a higher mass-transfer coefficient.
MEMBRANE SEPARATION PROCESSES 871
Reverse Osmosis
When miscible solutions of different concentration are separated by a membrane
that is permeable to the solvent but nearly impermeable to the solute, diffusion
of solvent occurs from the less concentrated to the more concentrated solution,
where the solvent activity is lower. The diffusion of solvent is called osmosis, and
osmotic transfer of water occurs in many plant and animal cells. The transfer of
solvent can be stopped by increasing the pressure of the concentrated solution
until the activity of the solvent is the same on both sides of the membrane. If pure
solvent is on one side of the membrane, the' pressure required to equalize the
solvent activities is the osmotic pressure of the solution n. If pressure higher than
the osmotic pressure is applied, solvent will diffuse from the concentrated solution
through the membrane into the dilute solution. This phenomenon is called reverse
osmosis, because the solvent flow is opposite to the normal osmotic flow.
Reverse osmosis is used primarily to prepare pure water from dilute aqueous
solutions, though it could be used for purifying organic solvents. The main
advantages of the process are that separation can take place at room temperature
and there is no phase change, which would require supplying and removing large
amounts of energy. The energy for the separation of salt water into pure water
and a concentrated brine comes from the work of pressurizing the feed, and some
of this energy can be recovered with a turbine, so the thermodynamic efficiency
of the process is relatively high.
Several polymers have a high permeability for water and low permeabilities
for dissolved salts. Cellulose acetate is outstanding in these respects and relatively
inexpensive. In early work by Reid and Breton,24 dense membranes made from
cellulose acetate with 40 percent acetyl content gave salt rejections of 95 to 98
percent at pressures of 50 to 90 atm, but the water fluxes were impractically low.
Membranes with higher acetyl content gave higher salt rejection but even lower
fluxes. Reverse osmosis became a practical process with the discovery of asym-
metric cellulose-acetate membranes by Loeb and Sourirajan'3 With a skin or
dense layer thickness less than 1 !lm and a porous substructure, fluxes of 10 to
20 gal/fe-day are possible with high salt rejection. Asymmetric cellulose acetate
membranes can now be prepared by different casting techniques as flat sheets,
hollow fibers, or a coating on a porous pipe to make a tubular membrane.
Hollow-fiber membranes made by duPont from an aromatic polyamide are also
used for water purification,15 and the fluxes are 1 to 3 gal/ft 2 -day.
The mechanism of water and salt transport in reverse osmosis is not
completely understood. One theory is that water and solutes diffuse separately
through the polymer by a solution-diffusion mechanism. The concentration of
water in the dense polymer is assumed to be proportional to the activity of water
in the solution. On the low-pressure side of the dense layer, the activity is essentially
unity if nearly pure water is produced at 1 atm. On the high-pressure side, the
activity would be slightly less than 1.0 at atmospheric pressure (0.97 for a 5 percent
NaCI solution), 1.0 at the osmotic pressure, and slightly greater than 1.0 at higher
pressures. The upstream pressure is generally set at 20 to 50 atm above the osmotic
872 MASS TRANSFER AND ITS APPLICATIONS
pressure of the feed solution. At these pressures, the activity of the water a w is
only a few percent greater than for pure water at 1 atm, and the change in activity
and concentration across the membrane are small, as shown in Fig. 26.17. The
driving force for water transport is the difference in activity, which is proportional
to the pressure difference !l.P minus the difference in osmotic pressures of the feed
and product !l.n. The equation for water flux is"
J = CwDwvw (!l.P - !l.n) (26.46)
W RT z
In Eq. (26.46) Dw is the diffusivity in the membrane, Cw is the average water
concentration in gjcm 3 , and Vw is the partial molar volume of water.
The flux of solute is assumed proportional to the difference in solution
concentrations, the diffusivity, and a solubility or distribution coefficient:
(26.47)
Equation (26.46) shows that the water flux increases strongly with the pressure
difference !l.P, and the selectivity increases also, since the salt flux does not depend
on !l.P. Experiments confirm these trends, but the salt rejection with cellulose
acetate is not as high as predicted. The water content Cw is about 0.2 gjcm 3 , and
tracer tests show Dw ~ 10- 6 cm 2 js. Diffusion tests of NaCI in dense polymer
films '4 indicate S, = 0.035 and D, = 10- 9 cm 2 js. The fluxes J w and J, cannot be
predicted accurately for an asymmetric membrane, because the skin thickness z is
not known. However, the ratio of fluxes is independent of z, and the predicted salt
Bwp= CwP---+-----f1
c.,
Porous
support
Permeate Feed
c,'
FIGURE 26.17
Concentration gradients for a reverse-
osmosis membrane.
MEMBRANE SEPARATION PROCESSES 873
rejection for seawater is 99.6 percent when I;.P - I;.n = 50 atm. Early desalting
units gave only 97 to 98 percent rejection under these conditions, and it is not
clear whether the difference was due to flow through pinholes in the membrane
or to incorrect assumptions in the solution-diffusion theory. Improved membranes
are now available for producing potable water from seawater in a one-stage
separator, and this means greater than 99 percent salt rejection.
CONCENTRATION POLARIZATION. The nearly complete rejection of solute by
the membrane leads to a higher concentration at the membrane surface than in
the bulk solution, and this effect is called concentration polarization. At steady
state, the solute carried to the membrane by the water flux almost equals the
amount of solute diffusing back to the solution. The gradient may be relatively
small, as shown in Fig. 26.17, or the solute concentration at the membrane surface
may be several times the bulk concentration. Concentration polarization reduces
the flux of water because the increase in osmotic pressure reduces the driving force
for water transport. The solute rejection decreases both because of the lower water
flux and because the greater salt concentration at the surface increases the flux of
solute.
Equations for concentration polarization have been derived for simple cases
such as laminar flow of feed solution between parallel plates or inside hollow
fibers. 27 Numerical solutions were required because of the developing concentra-
tion boundary layer and the gradual decrease in solution flow rate as permeation
occurs. Exact solutions are not available for the more important cases of flow
outside hollow fibers or in the channels of a spiral-wound module, but an
approximate analysis may still be helpful.
Consider a membrane with a water flux of J w cm 3/s_cm 2 when the bulk solute
concentration is C, gfcm 3 and f is the fraction of solute rejected. Diffusion of solute
away from the membrane surface is characterized by a mass-transfer coefficient
k, and driving force C,' - C, where C,' is the solute concentration at the surface.
At steady state, the diffusion flux equals the amount of solute rejected per unit
area:
(26.48)
The polarization factor r is defined as the relative concentration difference
r c,' - C, Jwf
=-- (26.49)
C,
The mass-transfer coefficient can be predicted from correlations such as those
in Chap. 21. If the polarization factor r is less than 0.1, its effect can be neglected.
If r is large, the change in rejection and water flux can be estimated using Eqs.
(26.46), (26.47), and (26.49), or the more exact expression for the concentration
profile, Eq. (30.52), can be used. However, a large value of r is an opportunity to
improve the performance by changing the dimensions or velocities in the separator
to give better mass transfer.
874 MASS TRANSFER AND ITS APPLICATIONS
Example 26.4. A hollow-fiber permeator with d. = 300 I'm and di = 200 I'm gives a
water flux of 10 gal/day-ft2 with 0.1 M NaCI solution at 20'C. and the salt rejection
is 97 percent. Feed solution flows normal to the fibers at an average superficial
velocity of 0.5 cm/so Is concentration polarization significant?
Solution
For io gal/day-ft 2
231 x 16.3871
J w = 10 x =4.72 x 1O- 4 cm/s
24 x 3600 x 929
3 x 10- 2 cm x 0.5 cm/s x 1 gfcm 3
N Rc = = 1.5
om g/cm-s
Ds = 1.6 x 10- 5 cm 2 /s
0.01
N = =625
s~ 1 x 1.6 x 10 5
For flow nonnal to cylinders, Eq. (12.69) for heat transfer is converted to the
analogous form for mass transfer:
NShNs-:O.3 = 0.35 + 0.56N~~52
NSh = [0.35 + 0.56(1.5)°''']625°. 3 = 7.18
[use of Eq. (21.57), which may be inaccurate at NR , < 40, gives NSh = 6.38]:
7.18(1.6 x 10-')
k = = 3.83 X 10- 3 cm/s
, 0.03
From Eq. (26.49),
4.72 x 10- 4 (0.97)
r= 0.120
3.83 x 10 3
A concentration difference of 12 percent between the surface and the bulk solution
would not have much effect on the salt rejection or the water flux. The estimate of
kt; may be conservative, because the mass-transfer coefficient in a bundle of fibers
should be greater than for a single fiber. However, if good flow distribution is not
maintained, sections receiving little flow might have significant polarization.
FRICTIONAL PRESSURE DROP. Hollow-fiber membranes are generally made
with the skin on the outside, and a bundle with thousands of closely packed fibers
is sealed in a metal cylinder. Feed solution passes radially across the fibers or
flows parallel to the fibers on the shell side, and product water is collected from
the fiber lumens at one or both ends of the bundle. The diameter and length of
the fibers are chosen so that the pressure drop for product flow inside the fibers
is not large relative to the driving force for water permeation. For some units with
low water flux, fibers with d. and di as small as 50 and 25 I'm are used, but larger
diameters are employed with more permeable membranes. For high production
rates, feed water is passed in parallel through a large number of permeators, and
MEMBRANE SEPARATION PROCESSES 875
First stage
Pure water
First stage
Feed
Second stage
'--~ Residue
FIGURE 26.18
Two-stage reverse-osmosis system.
the residue streams may be combined and passed through another set of permea-
tors, as shown in Fig. 26.18. With this arrangement, the velocity on the shell side
is kept high to get good flow distribution and minimize concentration polarization.
The flow inside the fibers is laminar, and the pressure gradient caused
by skin friction is given by the derivative form of the Hagen-Poiseuille equation,
Eq. (5.16):
dp, 32VJL
-=-- (26.50)
dL gp2
where V is the average velocity, JL is the viscosity, and D is the tube diameter.
The velocity increases with distance from the closed end of the fiber, and the
. incremental change in flow rate is the flux per unit wall area times the incremental
area:
(26.51)
dV 4Jw
-=- (26.52)
dL D
The water flux J w changes along the length of the separator, since increasing
concentration of salt increases !>.rc, and pressure buildup inside the fibers decreases
!>.P. For an approximate solution, J w is assumed constant, and Eq. (26.52) is
integrated directly:
(26.53)
876 MASS TRANSFER AND ITS APPLICATIONS
Substituting Eq. (26.53) into Eq. (26.50) and integrating gives
dp, = 128JwilL
(26.54)
dL gp3
128J wll L2
I1p, --=7-
- gp3 2 (26.55)
Note that the pressure drop is just half the value that would be calculated
if the water velocity V was constant at the exit value, 4Jw L/D. This is shown by
rearranging Eq. (26.55) to give, for comparison with Eq. (26.50),
1321lL4JwL
I1p, = 2. D>
g,
D (26.56)
Example 26.5. (a) For the permeator of Example 26.4 estimate the exit velocity and
the pressure drop within the fibers if the fiber length is 3 m and the average water
flux is 10 gal/day-ft' based on the external area. (b) What is the pressure drop if the
fibers are open at both ends?
Solution
Convert the flux to J w based on inside area. Using d j = 200 pm and do =
300 pm, and the conversion factor from Example 26.4,
300
Jw = (4.72 x 10- 4 ) 200 = 7.08 X 10- 4 cm/s = 7.08 x 10- 6 m/s
Assume Jl = I cP = 10-' Pa-s.
D=d,=2oo x 1O- 6 m
From Eq. (26.53),
_ 4(7.08 x 10- 6 )(3)
V =
6
0.425m/s
200 x 10
From Eq. (26.56),
0.425(32)10-'(3) 1
/j.p
,
= (2 x 10 4)' 2
= 5.1 X 10' Pa = 5.03 atm
This is a significant pressure drop, but if the feed is at 50 atm and 8n goes from
5 atm in the feed to 10 atm at the discharge, the driving force for water transport
(8P - 8n) has a maximum value of 50 - 5 = 45 and a minimum value of
45 - 10 = 35, so the assumption of constant flux is not greatly in error.
(b) If the fibers are open at both ends, the effective length is 1.5 m and the exit
velocity is half as great. The pressure drop is one-fourth as large as it was:
5.03
/j.P = - = 1.26atm
4
Flat-sheet membranes for reverse osmosis are usually used in spiral-wound
modules. The membrane is folded over a porous spacer sheet, through which
MEMBRANE SEPARATION PROCESSES 877
product drains, and the edges are sealed. A plastic screen is placed on top to serve
as a feed distributor, and the sandwich is rolled in a spiral around a small
perforated drain pipe. The module is inserted in a small pressure vessel, and many
units are installed in parallel. The mass-transfer area is a few hundred ft2 Ift 3 , an
order of magnitude lower than for typical hollow-fiber separators,26 and the
pressure drop due to permeate flow is generally negligible. Diagrams of spiral-
wound and hollow-fiber units are shown in Fig. 26.19.
Permeate
pipe containing
collection holes Antitelescoping device
Out
Permeate flow (after passage
Permeate through membrane into permeate
collection material)
Feed channel spacer
ra)
Epoxy
Open ends
tube sheet
Concentrate of fibers
outlet
ring
End plate
rb)
FIGURE 26.19
Cutaway views of permeators; (a) spiraI~wound separator [by permission, from w. Eykamp and J.
Steen, in Handbook of Separation Process Technology, R. W. Rousseau (ed.), WHey, 1987, p. 838J; (b)
PERMASEP hollow~fiber separator (by permission, from Du Pont brochure, PERMASEP Permeators,
1990).
878 MASS TRANSFER AND ITS APPLICATIONS
SYMBOLS
A Area, m 2 or fe
a, b, c Constants in quadratic equation for Yi [Eq. (26.44)]
aw Activity of water; awl> in feed; a wp , in permeate
C Concentration, g mOI/cm 3 , kg mol/m" or lb mOl/ft'; CA' of compo-
nent A; CAo' CAw' in organic and water phases, respectively; CB. of
component B; Cc. of colloid; Cs. of solute; C sF ' in feed; CsP' in per-
meate; Cs!, at membrane surface; Csm • in membrane; C w , of water;
C wF , in feed; C wp , in permeate; CWj ' at membrane surface; Cb C 2 •
average concentrations in feed and permeate, respectively
Specific heat of liquid, J /g-°C or Btu(lb-of
Volumetric diffusivity, cm 2/s, m 2/h, or ft2(h; DA, DB' of components
A and B; De' effective diffusivity; D eA • of component A;' De,o, in
organic phase; De,w, in water phase; Ds. of salt; Dv, bulk value; Dw,
of water in membrane; Do, at infinite dilution; also, diameter, ID or ft
d Tube or fiber diameter, pm; dj, inside diameter; do. outside diameter
E Activation energy, kcal/mol
e Base of natural logarithms, 2.71828 ...
J Fraction of solute rejected
g, Newton's-law proportionality factor, 32.174 ft-lb/lb rs2
J Molar flux, mass flux, or volume flux, mOl/m 2-h, kg/m2-h, or
m 3 /m 2_h; J A, J D, of components A and E; J" of salt; J,,, of water
K Overall mass-transfer coefficient, kg mOl/m 2-s-(kg mol/m 3 ) or m/s; K A ,
of component A; Kw> based on water phase
k Individual mass-transfer coefficient; k" based on concentration [Eq.
(26.48)]; km' for membrane; k" for organic phase; kw, for water phase;
k k 2 , for phases 1 and 2
L "
Flow rate of feed or residue, mol/h, kg(h, lb(h, std ft' /h, or L(h; L i , at
station i; Li , at station j; L 1 , at entrance; L 2 • at discharge; also,
length, m or ft
M Molecular weight; M A' of component A
m Distribution coefficient for solute (ratio of concentration in organic
phase to that in water phase)
Reynolds number, dV p/I'
Schmidt number, l'/pD
Sherwood number, k,d/D
Total pressure, atm or IbJ/ft'; P upstream or of feed; P 2 , down-
stream or of permeate "
Partial pressure of components A and E, respectively, atm or
IbJ/fe; PAlo PBl' upstream or in feed; PA2 , P B2 , downstream or in
permeate
p* Vapor pressure, atm or Ib J /ft 2 ; P~, of component A; P~, of com-
ponent E
Q Permeability [flux per unit pressure difference, Eq. (26.8)], L/m 2_h_
atm or ft 3 /ft 2-h-(lbJ /ft 2); QAi Q., of components A and E
MEMBRANE SEPARATION PROCESSES 879
q Permeability coefficient (flux per unit pressure gradient; q = DS,
where S is the solubility coefficient, or Qz), cm 3/cm 2-s-(cm Hg/cm),
L/m 2 -h-(atm/m), or ft 3/ft 2 -h-[(lbf /fe)jft]; qA, of component A
R Gas constant, 8.314 J/g mol-K or 1545 ft-lbf/lb mol-oR; also, pres-
sure ratio P 2 /p!; RA, Rn, modified pressure ratios [Eq. (26.42)]
r Pore radius, J.lm or cm
S Solubility coefficient, mOl/cm 3-atm [Eq. (26.6)]; SA' Sn, of compo-
nents A and B; also distribution coefficient [Eq. (26.47)]; S" of
solute
T Absolute temperature, K
V Flow rate of permeate, mol/h, kg/h, lb/h, std ft3/h or L/h
V Average fluid velocity, m/s or ft/s
"" Partial molar volume of water, cm 3/g
x Mole fraction of more permeable species m feed or residue; x" at
station i; xi' at station j; xo. at feed inlet
Y Mole fraction of more permeable species in permeate; YA, of compo-
nent A; Yh local value at station i; Yi' at station j; Yk, at station k; ]i,
average value over incremental length
z Membrane thickness, pm; also, distance normal to surface
Greek letters
rJ. Membrane selectivity for gas separation, dimensionless [Eq. (26.9)];
modified selectivity for pervaporation [Eq. (26.43)]
rJ.',
{3 Exponent in Eq. (26.37)
r Polarization factor, dimensionless [Eq. (26.48)]
Y Activity coefficient; YA, Yn, of components A and B
!;'C Concentration difference; !;'CA, of component A; !;'C" of solute
!;'H, Enthalpy of vaporization, cal/mol, J/g, or Btu/lb
!;'P Pressure difference, atm or lbf/ft2; !;'P A, !;'P n, partial pressure differ-
ences for components A and B
!;.p, Pressure drop due to skin friction, atm or lbfife
!;.z Increment of distance, m or ft
!;.n Difference in osmotic pressures, atm or Ibf /ft2
e Porosity or void fraction, dimensionless
A Ratio of molecular size to pore size
p Viscosity, cP, Pa-s, or lb/ft-s
n Osmotic pressure, atm or lb f/ft2
P Density, g/cm" kg/m 3, or Ib/ft 3
~ Tortuosity, dimensionless
PROBLEMS
26.1 (a) If a membrane has a selectivity of 8 for air separation, what is the maximum
oxygen concentration that can be obtained for a single-stage device? (b) What is the
approximate permeate composition if 60 percent of the oxygen in the feed is recovered
in the permeate?
880 MASS TRANSFER AND ITS APPLICATIONS
26.2. Laboratory tests of a membrane for H 2 /CH 4 separation gave a permeate composi-
tion of 80 percent H, and a residue of 42 percent H, when the feed had 50 percent
H2 and the feed and permeate absolute pressures were 100 and 151bf /in. 2 . The
permeate flow was 20 percent of the feed flow. (a) What is the membrane selectivity?
(b) About what permeate composition would have been obtained if a vacuum had
been used on the downstream side?
26.3. Dialysis is being considered to recover a product A with molecular weight 150 from
a dilute aqueous stream. The principal contaminant is a polymer B with molecular
weight 15,000. Predict the initial fluxes of A and B if the membrane has a porosity
of 45 percent, a mean pore size of 0.05 pm, and a thickness of 30 pm, and the feed
solution contains 1 percent A and 1 percent B. Neglect boundary-layer resistances
and assume pure water on the product side.
26.4. A hollow-fiber separator used for reverse osmosis is suspected of having flaws in the
O.1-pm dense layer, since the salt rejection is only 97 percent when tested with sea-
water at 1000 Ibf /in. 2 abs, and the predicted rejection is 99.5 percent. The measured
product flux is 6.5 gal/day-ft'. (a) If the flaws are O.Ol-l'm pinholes in the dense layer,
how many holes per square centimeter would be needed to account for the lower
salt rejection? (b) What is the corresponding fraction hole area in the dense layer?
(c) What would be the product flux if the pinholes were sealed without increasing
the thickness of the membrane?
26.5. Show how the water flux and salt rejection would change with upstream pressure
for a perfect cellulose acetate asymmetric membrane and a feed with an osmotic
pressure of 20 atm. Use the diffusivity and solubility values for NaCI.
26.6. (a) Calculate the internal pressure drop for an oxygen-nitrogen hollow-fiber separ-
ator that has 600 pm outside diameter and 400 pm inside diameter fibers 1.0 m
long. When P, = 75Ibf /in.' abs and P, ~ l5Ibf /in.' abs, the permeate flux is
2.0 L/min-m'. (b) What would be the internal pressure drop for L = 5 m?
26.7. Pervaporation is used to produce nearly pure ethanol from a feed with 90 percent
ethanol and 10 percent water. The feed enters at 80°C, and the design calls for
reheating the liquid after the temperature has dropped to 70°C. About how many
stages and how many heaters are needed?
26.8. The permeation rates of CH4 and CO 2 in a GASEP membrane at 80°F were given
as 0.00205 and 0.0413 ft' (std conditions)/ft'-h-(lbf/in.'), respectively. At 100°F the
corresponding values were 0.00290 and 0.0425. (a) Calculate the apparent activation
energies for permeation of CH4 and CO 2 , (b) Predict the permeabilities and the
CO,/CH. selectivity at 100°F.
26.9. A three-component mixture at 600 lbf/in. 2 abs is fed to a membrane separator with
a permeate pressure of 120 Ib f /in. 2 abs. The mixture has 50 percent A, 30 percent
B, and 20 peroent C, and the permeabilities are QA = 004, Q. = 0.1, and Qc = 0.15,
all in ft' (std)/ft'-h-atm. Estimate the local composition of the permeate at the inlet
end of the separator.
26.10. (a) Use 'the data in Table 26.2 to estimate the membrane selectivity for N,/CH.
based on the average driving. force. (b) Explain why the same method cannot be
used to estimate the H,/CH. selectivity. (c) How could the H,/CH. selectivity be
determined from these data?
MEMBRANE SEPARATION PROCESSES 881
REFERENCES
1. Aptel, P., and J. Ne'el: in P. M. Bungay, H. K. Lonsdale, and M. N. dePinho (eds.): Synthetic
Membranes: Science, Engineering, and Applications, Dordrecht, Boston, 1986, p. 403.
2. Beaver, E. R., and P. V. Bhat: AIChE Symp. Ser., 84(261): 113 (1988).
3. Binning, R. C., R. J. Lee, J. F. Jennings, and E. C. Martin: fnd. Eng. Chem., 53:45 (1961).
4. Crank, J. t and G. S. Park (eds.): Diffusion in Polymers, Academic, New York, 1968.
5. Harriott, P., and B. Kim: J. Colloid Interface Sd., 115: 1 (1987).
6. Henis, J. M. S., and M. K. Tripodi: Separation Sci. Teclmol., 15: 1059 (1980).
7. Hogsett, J. E., and W. H. Mazur: Hydrocarbon Proc., 62(8):52 (1983).
8. Hwang, S. T., and J. M. Thonnan: AIChE J., 26: 558 (1980).
9. Kirk, R. E., and D. F. Othmer (eds.): Encyclopedia of Chemical Technology, 3rd ed., vol. 7, Wiley,
New York, 1979, p. 639.
10. Koros, W. J., and R. T. Chem: in R. W. Rousseau (ed.), Handbook ofSeparation Process Technology,
Wiley, New York, 1987, p. 862.
11. Lee, S. Y., and B. S. Minhas: AIChE Symp. Ser., 84(261):93 (1988).
12. Lipski, c., and P. Cote: Environ. Prog., 9:254 (1990).
13. Loeb, S., and S. Sourirajan: Adv. Chem. Ser., 38: 117 (1962).
14. Lonsdale, H. K.: in U. Merten (ed.), Desalimition by Reverse Osmosis, MIT Press, Cambridge,
MA, 1966, p. 93.
15. Lonsdale, H. K.: in P. M. Bungay, H. K. Lonsdale, and M. N. dePinho (eds.): Synthetic Membranes:
Science, Engineering, and Applications, Dordrecht, Boston, 1986, p. 307.
16. MacLean, D. L., D. J. Stookey, and T. R. Metzger: Hydrocarbon Proc., 62(8):47 (1983).
17. Matson, S. L., J. Lopez, and J. A. Quinn: Chem. ElIg. Sei., 38:503 (1983).
18. Medal™ Membrane Separation System brochure, Du Pont-Air Liquide, 1989.
19. Pan, C. Y.: AICM J., 29:545 (1983).
20. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-HilI, New York, 1984, p.13-20.
21. Prasad, R., and K. K. Sirkar: AIChE J., 33: 1057 (1987).
22. Psaume, R., P. Aptel, Y. Aurelle,J. C. Mora, and J. L. Bersillon: J. Membrane Sd., 36: 373 (1988).
23. Reahl, E. R.: Desalination, 78: 77 (1990).
24. Reid, C. E., and E. J. Breton: J. App/. Polym. Sel., 1: 133 (1959).
25. Renkin, E. M.: J. Gen. Physiol., 38:225 (1954).
26. Schell, W. J., and C. D. Houston: in T. E. Whyte, Jr., C. M. Yon, and E. H. Wagener (eds.),
Industrial Gas Separations, Am. Chem. Soc. Symp. Ser., 223: 125 (1983).
27. Sherwood, T. K., P. L. T. Brian, R. E. Fisher, and L. Dresser: Ind. Ellg. Chem. Fund., 4: 113 (1965).
28. Walawender, W., and S. A. Stern: Separation Sd, 7: 553 (1972).
29. Wesslein, M., A. Heintz, and R. N. Lichtenthaler: J. Membrane Sd., 51: 169 (1990).
30. Yang, M. c., and E. L. Cuss!er: AICizE J., 32: 1910 (1986).
CHAPTER
27
CRYSTALLIZATION
Crystallization is the formation of solid particles within a homogeneous phase. It
may occur as the formation of solid particles in a vapOf, as in snow; as
solidification from a liquid melt, as in the manufacture oflarge single crystals; or
as crystallization from liquid solution. This chapter deals mainly with the last
situation. The concepts and principles described here equally apply to the crystalli-
zation of a dissolved solute from a saturated solution and to the crystallization
of part of the solvent itself, as in freezing ice crystals from seawater or other dilute
salt solutions.
Crystallization from solution is important industrially because of the variety
of materials that are marketed in the crystalline form. Its wide use has a twofold
basis: a crystal formed from an impure solution is itself pure (unless mixed crystals
occur), and crystallization affords a practical method of obtaining pure chemical
substances in a satisfactory condition for packaging and storing.
Magma. In industrial crystallization from solution, the two-phase mixture of
mother liquor and crystals of all sizes, which occupies the crystallizer and is
withdrawn as product, is called a magma.
IMPORTANCE OF CRYSTAL SIZE. Clearly, good yield and high purity are
important objectives in crystallization, but the appearance and size range of a
crystalline product also are significant. If the crystals are to be further processed,
reasonable size and size uniformity are desirable for filtering, washing, reacting
with other chemicals, transporting, and storing the crystals. If the crystals are to
be marketed as a final product, customer acceptance requires individual crystals
882
CRYSTALLIZATION 883
to be strong, nonaggregated, uniform in size, and noncaking in the package. For
these reasons, crystal size distribution (CSD) must be under control; it is a prime
objective in the design and operation of crystallizers.
CRYSTAL GEOMETRY
A crystal is the most highly organized type of nonliving matter. It is characterized
by the fact that its constituent particles, which may be atoms, molecules, or ions,
are arranged in orderly three-dimensional arrays called space lattices. As a result
of this arrangement of the particles, when crystals are allowed to form without
hindrance from other crystals or outside bodies, they appear as polyhedrons
having sharp corners and flat sides, or faces. Although the relative sizes of the faces
and edges of various crystals of the same material may be widely different, the
angles made by corresponding faces of all crystals of the same material are equal
and are characteristic of that material.
CRYSTALLOGRAPHIC SYSTEMS. Since all crystals of a definite substance have
the same interfacial angles in spite of wide differences in the extent of development
of individual faces, crystal forms are classified on the basis of these angles. The
seven classes are cubic, hexagonal, trigonal, tetragonal, orthorhombic, monoclinic,
and triclinic. A given material may crystallize in two or more different classes
depending on the conditions of crystallization. Calcium carbonate, for example,
occurs most commonly in nature in the hexagonal form (as calcite) but also occurs
in the orthorhombic form (aragonite).
INVARIANT CRYSTALS. Under ideal conditions, a growing crystal maintains
geometric similarity during growth. Such a crystal is called invariant. Figure 27.1
shows cross sections of an invariant crystal during growth. Each of the polygons
in the figure represents the outline of the crystal at a different time. Since the
crystal is invariant, these polygons are geometrically similar and the dotted lines
connecting the corners of the polygons with the center of the crystal are straight.
The center point may be thought of as the location of the original nucleus from
which the crystal grew. The rate of growth of any face is measured by the velocity
of translation of the face away from the center of the crystal in a direction
perpendicular to the face. Unless the crystal is a regular polyhedron, the rates of
growth of the various faces of an invariant crystal are not equal.
-/-~=====~=~~~~
/ / ~ ~~-:> <;-----
-+-~---- ~~- ~"--7-7-
"-
" " _ . ---- -- _ / / FIGURE 27.1
" '-'=" ::-( /
_')....:::.-----------"""<.._ Growth of an invariant crystal.
884 MASS TRANSFER AND ITS APPLICATIONS
CRYSTAL SIZE AND SHAPE FACTORS. A single dimension can be used as the
measure of the size of an invariant crystal of any definite shape. From Eq. (7.10),
page 152, the ratio of the total surface area of a crystal sp to the crystal volume vp is
Sp 6
-=-- (27.1)
Vp CIlsDp
where <1>, is the sphericity. If the characteristic length L of a crystal is defined
as equal to <I>,Dp' then
6v
L = <I>, Dp =----E (27.2)
sp
For cubes and spheres (I>, = 1 (see Table 28.1, p. 928) and L = Dp. For
geometric solids in general, L is close to the size determined by screening."
The concept of invariant growth is useful in analyzing the crystallization
process, even though in most crystallizers the conditions are far from ideal and
growth is often far from invariant. In extreme cases one face may grow much more
rapidly than any of the others, giving rise to long needlelike crystals. Slow growth
of one face may give rise to thin-plate or disk-shaped crystals, typical of ice formed
from aqueous solution. For a disk-shaped crystal <1>, may be quite low, and length
L from Eq. (27.2) has little meaning. Disks of size D p cannot pass through a screen
of size L = <I>,Dp"
PRINCIPLES OF CRYSTALLIZATION
Crystalliz2'ion may be analyzed from the standpoints of purity, yield, energy
requirements, and rates of nucleation and growth.
PURITY OF PRODUCT. A sound, well-formed crystal itself is nearly pure, but it
retains mother liquor when removed from the final magma, and if the crop contains
crystalline aggregates, considerable amounts of mother liquor may be occluded
within the solid mass. When retained mother liquor of low purity is dried on the
product, contamination results, the extent of which depends on the amount and
degree of impurity of the mother liquor retained by the crystals.
In practice, much of the retained mother liquor is separated from the crystals
by filtration or centrifuging, and the balance is removed by washing with fresh
solvent. The effectiveness of these purification steps depends on the size and
uniformity of the crystals.
Equilibria and Yields
Equilibrium in crystallization processes is reached when the solution is saturated,
and the equilibrium relationship for bulk crystals is the solubility curve. (As shown
later, the solnbility of extremely small crystals is greater than that of crystals of
ordinary size.) Solubility data are given in standard tables.""·2l Curves showing
solubility as a function of temperature are given in Fig. 27.2. Most materials follow
CRYSTALLIZATION 885
1.00
0.90
0.80
2~
(; 0.70 ,., ~
00
c
0
:g 0.60 V
.;;:
00 0.50
1~KN03 V
00
rn
,/
E
OAO /'
~
:0
~
(;
0.30 V 3-MnS04"H 2 O
r--
'" 0.20
/' 2-NaCl r-
.,/'
0.10
o
o 10 m w ~ W 00 m w w 100 110
Temperature,OC
FIGURE 27:1.
Solubility curves for (1) KN0 3 • (2) NaCl, and (3) MnS0 4 " H 2 0 in aqueous solution.
curves similar to curve 1 for KN0 3 i.e., their solubility increases more or less
rapidly with temperature. A few substances follow curves like curve 2 for NaCl,
with little change in solubility with temperature; others have what is called an
inverted solubility curve (curve 3 for MnSO.· H 2 0), which means that their
solubility decreases as the temperature is raised.
Many important inorganic substances crystallize with water of crystalliza-
tion. In some systems, several different hydrates are formed, depending on
concentration and temperature, and phase equilibria in such systems can be quite
complicated. The phase diagram for the system magnesium sulfate-water is shown
in Fig. 27.3. The equilibrium temperature in degrees Fahrenheit is ploUed against
the concentration in mass fraction of anhydrous magnesium sulfate. The entire
area above and to the left of the broken solid line represents undersaturated
solutions of magnesium sulfate in water. The broken line eagfhij represents
complete solidification of the liquid solution to form various solid phases. The
area pae represents mixtures of ice and saturated solution. Any solution containing
less than 16.5 percent MgSO. precipitates ice when the temperature reaches line
pa. Broken line abcdq is the solubility curve. Any solution more concentrated
than 16.5 percent precipitates, on cooling, a solid when the temperature reaches
this line. The solid formed at point a is called a eutectic. It consists of an inti-
mate mechanical mixture of ice and MgSO •. 12H2 0. Between points a and
886 MASS TRANSFER AND ITS APPLICATIONS
220r-'--'--'--'--'--'--'--~nnjq,---
200 f---r--+---+--4-~--~--~M;
<::,'"
180 f--1:---+---+--+--+--+--+ Vj Soln +
f' MgSo" -1'(
160
,'---r--+--+--4-~I--~-.-Jt"''d
Cl "
"-
0 140 r---t---t--4---+--+---+-~~~Oh+M9S~4:~
w
0:: ~~l( 6HzO '
:::J 120
I-
<I
0::
W 100
"-
::2'
w
I- 80
60
40
FIGURE 27.3
Phase diagram, system MgS04~H20. [By permission, from J. H. Perry (ed.), Chemical Engineers'
Handbook, 4th ed. Copyright, 1963, McGrawRHill Book Company.]
b the crystals are MgSO •. 12H 2 0; between band c the solid phase is
MgSO.·7H 2 0 (epsom saIt); between c and d the crystals are MgSO.·6H 2 0;
and above point d they are MgSO.· H 2 0. In the area cihb, the system at equili-
brium consists of mixtures of saturated solution and crystalline MgSO.· 7H 2 0.
In area dkjc, the mixture consists of saturated solution and crystals of MgSO 4 .
6H 2 0. In area qdk, the mixture is saturated solution and MgSO.· H 2 0.
YIELDS. In many industrial crystallization processes, the crystals and mother
liquor are in contact long enough to reach equilibrium, and the mother liquor is
saturated at the final temperature of the process. The yield of the process can then
be calculated from the concentration of the original solution and the solubility at
the final temperature. If appreciable evaporation occurs during the process, this
must be known or estimated.
When the rate of crystal growth is slow, considerable time is required to
reach equilibrium. This is especially true when the solution is viscous or where
the crystals collect in the bottom of the crystallizer so there is little crystal surface
exposed to the supersaturated solution. In such situations, the final mother liquor
may retain appreciable supersaturation, and the actual yield will be less than
that calculated from the solubility curve.
CRYSTALLIZATION 887
If the crystals are anhydrous, calculation of the yield is simple, as the solid
phase contains no solvent. When the crop contains water of crystallization,
account must be taken of the water accompanying the crystals, since this water
is not available for retaining solute in solution. Solubility data are usually given
either in parts by mass of anhydrous material per hundred parts by mass of total
solvent or in mass fraction anhydrous solute. These data ignore water of crystalli-
zation. The key to calculations of yields of hydrated solutes is to express all masses
and concentrations in terms of hydrated salt and free water. Since it is this latter
quantity that remains in the liquid phase during crystallization, concentrations or
amounts based on free water can be subtracted to give a correct result.
Example 27.1. A solution consisting of 30 percent MgS04 and 70 percent H 2 0 is
cooled to 60°F. During cooling, 5 percent of the total water in the system evaporates.
How many kilograms of crystals are obtained per kilogram of original mixture?
Sollltion
From Fig. 27.3 it is noted that the crystals are MgSO.· 7H,O and that lhe
concentration of the mother liquor is 24.5 percent anhydrous MgS0 4 and 75.5
percent H 2 0. Per 1000 kg of original solution, the total water is 0.70 x 1000 =
700 kg. The evaporation is 0.05 x 700 = 35 kg. The molecular weights of MgSO. and
MgSO.· 7H 2 0 are 120.4 and 246.5, respectively, so the total MgSO.· 7H 2 0 in the
batch is 1000 x 0.30(246.5/120.4) = 614 kg, and the free water is 1000 - 35 -
614 = 351 kg. In 100 kg of mother liquor, there is 24.5(246.5/lLO.4) = 50.16 kg of
MgSO.· 7H 2 0 and 100 - 50.16 = 49.84 kg of free water. The MgSO.· 7H 2 0 in
the mother liquor, then, is (50.16/49.84)351 = 353 kg. The final crop is 614 - 353 =
261 kg.
ENTHALPY BALANCES. In heat-balance calculations for crystallizers, the heat of
crystallization is important. This is the latent heat evolved when solid forms from
a solution. Ordinarily, crystallization is exothermic, and the heat of crystallization
varies with both temperature and concentration. The heat of crystallization is
equal to the heat absorbed by crystals dissolving in a saturated solution, which
may be found from the heat of solution in a very large amount of solvent and the
heat of dilution of the solution from saturation to high dilution. Data on heats
of solution and of dilution are available,2 and these, together with data on the
specific heats of the solutions and of the crystals, can be used to construct
enthalpy-concentration charts like those of Fig. 16.8 but extended to include solid
phases. The diagram is especially useful in calculating enthalpy balances for
crystallization processes. An H-x diagram, showing enthalpies of solid phases, for
the system MgSO. and H 20 is given in Fig. 27.4. This diagram is consistent with
the phase diagram of Fig. 27.3. As before, enthalpies are given in Btu per pound.
They refer to lib of total mixture regardless of the number of phases in the mixture.
The area above line pabcdq represents enthalpies of undersaturated solutions
of MgSO. in H 20, and the isotherms in this area have the same significance
as those in Fig. 16.8. The area eap in Fig. 27.4 represents all equilibrium
mixtures of ice and freezing MgSO. solutions. Point 1l represents ice at 32°F. The
888 MASS TRANSFER AND ITS APPLICATIONS
140
120
100
80
60
z 40
0
i=
:::l 20
-'
0
U)
0
Cl
Z
:::l -20
0
Q.
0::
W
Q.
~ -60
en
>- -80
Q.
-'
<I -100
I
I-
z -120
w
-140
-160
-180
-220 L=t=:t:=t=:t=t=~?ff§.ii:'!i!.f!J.:tj
o 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50
CONCENTRATION-MASS FRACTION MgSO,
FIGURE 27.4
Enthalpy-concentration diagram, system MgS0 4 -H 2 0. Datum is liquid water at 32°F (ooq. [By
permission, from J. H. Perry (ed.), Chemical Engineers' Handbook, 4th eeL Copyright 1963, McGraw-
Hill Book Company.]
isothermal (2SOF) triangle age gives the enthalpies of all combinations of ice
with partly solidified eutectic or of partly solidified eutectic with MgS04 . 12H2 0.
Area abfg gives the enthalpy-concentration points for all magmas consisting of
MgS04 . 12H2 0 crystals and mother liquor. The isothermal (35.7°F) triangle
bhfshows the transformation of MgS04 '7H 2 0 to MgS0 4 . 12H2 0, and this area
represents mixtures consisting of a saturated solution containing 21 percent
CRYSTALLIZATION 889
MgSO., solid MgSO.· 7H 2 0, and solid MgSO •. 12H2 0. The area cihb represents
all magmas of MgSO.· 7H 2 0 and mother liquor. Isothermal (118.8°F) triangle cji
represents mixtures consisting of a saturated solution containing 33 percent
MgSO., solid MgSO.· 6H 2 0, and solid MgSO•. 7H 2 0. Area dljc gives enthalpies
of MgSO.· 6H 2 0 and mother liquor. The isothermal (154.4°F) triangle dkl
represents mixtures of a saturated solution containing 37 percent MgSO., solid
MgSO.· H 2 0, and solid MgSO.· 6H2 0. Area qrkd is part of the field representing
saturated solutions in equilibrium with MgSO.· H 2 0.
Example 27.2. A 32.5 percent solution of MgSO. at 120'F (48.9'C) is cooled, without
appreciable evaporation, to 70°F (21.1°C) in a batch water-cooled crystallizer. How
much heat must be removed from the solution per ton of crystals?
Solution
The initial solution is represented by the point on Fig. 27.4 at a concentration of
0.325 in the undersaturated-solution field on a 120°F isotherm. The enthalpy
coordinate of this point is - 33.0 BtuJlb. The point for the final magma lies on the
70"F isotherm in area cihb at concentration 0.325. The enthalpy coordinate of
this point is - 78.4. Per hundred pounds of original solution the change in enthalpy
of the solution is
100(33.0 - 78.4) = -4540 Btu
This is a heat evolution of 4540 Btu/lOO Ib (1.06 x 10' Jfkg).
The split of the final slurry between crystals and mother liquor can be found
by what is called the "eenter-of-gravity principle," which says that the masses of the
two phases, in a two-phase mixture, are inversely proportional to the differences
between their coneentrations and that of the overall mixture. This principle is applied
to the 70"F isotherm in either Fig. 27.3 or 27.4. The concentration of the mother
liquor is 0.259, and that of the crystals is 0.488. Then, the crystals are
0.325 - 0.259
lOO = 28.8 lb/loo lb slurry
0.488 - 0.259
The heat evolved per ton of crystals is (4540/28.8X2000) = 315,000 Btu/ton
10' Jfkg).
(3.66 x
SUPERSATURATION. Mass and enthalpy balances shed no light on the CSD of
the product from a crystallizer. Conservation laws are unchanged if the product
is one huge crystal or a mush of small ones.
In the formation of a crystal two steps are required: (1) the birth of a new
particle and (2) its growth to macroscopic size. The first step is called nucleation.
In a crystallizer, the CSD is determined by the interaction of the rates of nucleation
and growth, and the overall process is complicated kinetically. The driving
potential for both rates is supersaturation, and neither crystal growth nor forma-
tion of nuclei from the solution can occur in a saturated or unsaturated solution.
Of course, very small crystals can be formed by attrition in a saturated solution,
and these may act just like new nuclei as sites for further growth if the solution
later becomes supersaturated.
890 MASS TRANSFER AND ITS APPLICATIONS
In the theories of nucleation and growth, mole units are used in place of
mass units.
Supersaturation may be generated by one or more of three methods. If the
solubility of the solute increases strongly with increase in temperature, as is the
case with many common inorganic salts and organic substances, a saturated
solution becomes supersaturated by simple cooling and temperature reduction. If
the solubility is relatively independent of temperature, as is the case with common
salt, supersaturation may be generated by evaporating a portion of the solvent. If
neither cooling nor evaporation is desirable, as when the solubility is very high,
supersaturation may be generated by adding a third component. The third
component may act physically by forming, with the orginal solvent, a mixed
solvent in which the solubility of the solvent is sharply reduced. This process is
called salting. Or, if a nearly complete precipitation is required, a new solute may
be created chemically by adding a third component that will react with the orginal
solute and form an insoluble substance. This process is called precipitation. By
the addition of a third component, the rapid creation of very large supersaturations
is possible.
Units for supersaturation. Supersaturation is the concentration difference between
that of the supersaturated solution in which the crystal is growing and that of a
solution in equilibrium with the crystal. The two phases are very nearly at the
same temperature. Concentrations may be defined either in mole fraction of the
solute, denoted by y, or in moles of solute in unit volume of solution, denoted by
c. Since only one component is transferred across phase boundaries, component
subscripts are omitted. The two supersaturations are defined by the equations
.1.Y'" Y - y, (27.3)
(27.4)
where.1.y = supersaturation, mole fraction of solute
y = mole fraction of solute in solution
y, = mole fraction of solute in saturated solution
.1.c = molar supersaturation, moles per unit volume
c = molar concentration of solute in solution
Cs = molar concentration of solute in saturated solution
The supersaturations defined by Eqs. (27.3) and 27.4) are related by the equation
(27.5)
where PM and p, are the molar densities of the solution and the saturated
solution, respectively. In general, since supersaturations in crystallizers are small,
the densities PM and p, may be considered equal and PM used to designate both
quantities. Then
.1.c = PM.1.y (27.6)
CRYSTALLIZATION 891
The concentration ratio IX and the fractional supersaturation s are defined by
c !;.c y !;.y
IX=-=I+-=-=I+-=I+s (27.7)
Cs Cs Ys Ys
The quantity lOOs is the percentage of supersaturation. In practice, it is usually
less than about 2 percent.
Temperature dilference as a potential. When the solubility increases appreciably
with temperature, the supersaturation can be expressed as an equivalent tempera-
ture difference instead of a concentration difference. The relation between these
driving potentials is shown in Fig. 27.5, which contains a small section of the
solubility curve in molar concentrations. The field above the line represents
unsaturated solutions and that below the line, supersaturated solutions. Point A
refers to a saturated solution at temperature 7;, which is the temperature of the
growing crystal, and point D to the supersaturated solution at temperature T. Since
heat is evolved by the crystal as it grows, 7; is slightly larger than T, providing
the driving force !;. 7;, for heat transfer from the crystal to the liquid. This
temperature difference is typically of the order of 0.01 to O.02°C. The super-
saturation IX is normally based on the bulk temperature and, as shown by points
E and D, is slightly greater than the actual supersaturation.
Point B refers to a saturated solution of the same composition as the
supersaturated solution in which the crystal is growing. It would be at a tempera-
ture T" where T, > T. Point C refers to temperature 7; and a concentration equal
to that of the supersaturated solution.
From Eqs. (27.3) and (27.4) the supersaturation potential is represented by
line segment AC. The equivalent temperature driving potential is shown by line
segment BC. Segment AB of the solubility curve can be considered linear over
I;
T.
o Y,c FIGURE 275
y,c_ Supersaturation and temperature potentia)s.
892 MASS TRANSFER AND ITS APPLICATIONS
the small concentration spanned by line AC and the temperature potential defined
by
K
d 7; '" T, - 7; = K(y - yJ = K dy = - de (27.8)
PM
where K = slope of T-vs.-y line
PM = molar density
The temperature potential is therefore a little less than that calculated from
the actual temperature T of the solution and its saturation temperature T,. Since
d T" is so small, the difference between T, - Tand T, - 7; is usually insignificant.
Nucleation
The rate of nucleation is the number of new particles formed per unit time per
unit volume of magma or solids-free mother liquor. This quantity is the first kinetic
parameter controlling the CSD.
ORIGINS OF CRYSTALS IN CRYSTALLIZERS. If all sources of particles are
subsumed under the term nucleation, a number of kinds of nucleation may occur.
Many of these are important only as methods to be avoided. They may be classified
into three groups: spurious nucleation, primary nucleation, and secondary nuclea-
tion.
One origin of crystals is macroscopic attrition, which is more akin to
comminution than to real nucleation. Circulating magma crystallizers have inter-
nal propeller agitators or external rotary circulating pumps. On impact with these
moving parts, soft or weak crystals can break into fragments, form rounded corners
and edges, and so give new crystals, both large and small. Such effects also degrade
the quality of the product. Attrition is the only source of new crystals that is
independent of supersaturation.
Occasionally, especially in experimental work, seed crystals originating in
previous crystallizations are added to crystallizing systems. Seeds usually carry on
their surfaces many small crystals which were formed during the drying and storage
of the seeds after their own manufacture. The small crystals soon wash off and
subsequently grow in the supersaturated solution. This is called initial breeding. 2 •
It can be prevented by curing the seed crystals before using, either by contact with
undersaturated solution or solvent or by a preliminary growth in a stagnant
supersaturated solution.
Growth-related spurious nucleation occurs at large supersaturations or
accompanies poor magma circulation. It is characterized by abnormal needlelike
and whiskerlike growths from the ends of the crystals, which, under these
conditions, may grow much faster than the sides. The spikes are imperfect crystals,
which are bound to the parent crystal by weak forces and which break off to give
crystals of poor quality. This is called needle breeding. 2 •
CRYSTALLIZATION 893
Another growth-related imperfection, unrelated to nucleation, is called veiled
growth and occurs at moderate supersaturations. It is the result of the occlusion
of mother liquor into the crystal face, giving a milky surface and an impure
product. The cause of veiled growth is too rapid crystal growth, which traps mother
liquor into the crystal faces.
Figures 27.6 and 27.7, which apply to MgS0 4 ' 7H 2 0, show the appear-
ance of good and inferior crystals and the variation in quality of product at
various supersaturations.
All fonns of spurious nucleation can be avoided by growing crystals at low
supersaturations and by using only well-designed and operated pumps and
agitators.
PRIMARY NUCLEATION. In scientific usage, nucleation refers to the birth of very
small bodies of a new phase within a supersaturated homogenous existing phase.
Basically, the phenomenon of nucleation is the same for crystallization from
solution, crystallization from a melt, condensation of fog drops in a supercooled
vapor, and generation of bubbles in a superheated liquid. In all instances,
nucleation is a consequence of rapid local fluctuations on a molecular scale in a
homogenous phase that is in a state of metastable equilibrium. 7 The basic
phenomenon is called homogeneous nucleation, which is further restricted to the
fonnation of new particles within a phase uninfluenced in any way by solids of
f1 9 Good growth
6T< 4" C
t1- ?f7 Veiled growth
4<6T< 8"C
~
~ If'
f!- !!I Spikewise growth
6T> 8"C FIGURE 27.6
Illustration of growth regimes.
(After Clontz and M cCabe. 4 )
894 MASS TRANSFER AND ITS APPLICATIONS
TEMPERATURE, GROWTH NUCLEATION
'C Absence of Presence of
crystol-solid crystal-solid
Soturation, Ts contact
,r
contoct
,,
is - 1 - GOOD ,2
,Q
Best . ,
operating I
GROWTH 2
0 ,"< region :
>= 'w
« ,-'
r, - 4 w
-'
u
'u
.. ~ _____ J'
=> >-
2 u
VEILED 0 ;'!
z 2
GROWTH 0
u
T, - 8
DENDRITIC, SPLINTERING SPLINTERING
SPIKEWISE AND AND
8ROOMING ATTRITION ATTRITION
GROWTH FROM OF
SPLINTERS COLLIDING
CRYSTALS
FIGURE 27.7
1; - 16 - Effect of supersaturation on crystal
HETEROGENEOUS
growth quality and type of nucleation for
NUCLEATION
MgSO.·7H,O. (Adapted/ram Re! 5)
any sort, including the walls of the container or even the most minute particles
of foreign substances.
A variant of homogenous nucleation occurs when solid particles of foreign
substances do influence the nucleation process by catalyzing an increase of
nucleation rate at a given supersaturation or giving a finite rate at a super-
saturation where homogenous nucleation would occur only after a vast time. This
is called heterogeneous nucleation.
HOMOGENOUS NUCLEATION. In crystallization from solution, homogenous
nucleation almost never happens, except perhaps in some precipitation reactions.
The fundamentals of the phenomenon, however, are important in understanding
the more useful types of nucleation.
Crystal nuclei may form from various kinds of particles: molecules, atoms,
or ions. In aqueous solutions these may be hydrated. Because of their random
motion, in any small volume several of these particles may associate to form what
is called a ciuster-a rather loose aggregation which usually disappears quickly.
Occasionally, however, enough particles associate into what is known as an
embryo, in which there are the beginnings of a lattice arrangement and the
formation of a new and separate phase. For the most part, embryos have short
lives and revert to clusters or individual particles, but if the supersaturation is
large enough, an embryo may grow to such a size that it is in thermodynamic
equilibrium with the solutiou. It is then called a nucleus, which is the smallest
CRYSTALLIZATION 895
assemblage of particles that will not redissolve and can therefore grow to form a
crystal. The number of particles needed for a stable nucleus ranges from a few to
several hundred. For liquid water the number is about 80.
Nuclei are in a state of unstable equilibrium: if a nucleus loses units, it
dissolves; if it gains units, it grows and becomes a crystal. The sequence of stages
in the evolution of a crystal is, then,
Cluster --+ embryo --+ nucleus --+ crystal
EQUILIBRIUM. Thermodynamically, the difference between a small particle and
a large one at the same temperature is that the small particle possesses a significant
amount of surface energy per unit mass and the large one does not. One
consequence of this difference is that the solubility of a small crystal in the less
than micrometer size range is larger than that of the large crystal. Ordinary
solubility data apply only to moderately large crystals. A small crystal can be in
equilibrium with a supersaturated solution. Such an equilibrium is unstable,
because if a large crystal is also present in the solution, the smaller crystal will
dissolve and the larger one will grow until the small crystal disappears. This
phenomenon is called Ostwald ripening. The effect of particle size on solubility is
a key factor in nucleation.
Kelvin equation. The solubility of a substance is related to its particle size by the
Kelvin equation
Inex=4v",,(J (27.9)
vRTL
where L = crystal size
a = ratio of concentrations of supersaturated and saturated solutions
VM = molar volume of crystal
(J = average interfacial tension between solid and liquid
v = number of ions per molecule of solute (for molecular crystals v = 1)
Since ex = 1 + s, Eq. (27.9) shows that a very small crystal of size L can exist
in equilibrium with a solution having a supersaturation of s, relative to a saturated
solution in equilibrium with large crystals.
RATE OF NUCLEATION. The rate of nucleation, from the theory of chemical
kinetics, is given by the equation
o [161[(J3V~No ] (27.10)
B = C exp - 3v2(RT)3(ln a)2
O
where B = nucleation rate, number/cm'-s
N, = Avogadro constant, 6.0222 x 1023 molecules/g mol
R = gas constant, 8.3143 x 107 ergs/g mol-K
C = frequency factor
896 MASS TRANSFER AND ITS APPLICATIONS
The factor C is a statistical measure of the rate of formation of embryos that
reach the critical size. It is proportional to the concentration of the individual
particles and to the rate of collision of these particles with an embryo of the critical
size required to form a stable nuclus. Its value for nucleation from solutions is
not known. From analogy with nucleation of water drops from supersaturated
water vapor: it is of the order of 1025 nuclei/cm 3-s. Its accurate value is not
important, because the kinetics of nucleation is dominated by the In " term in the
exponent.
Numerical values for (f also are uncertain. The experimental determination
of solid-liquid interfacial tensions is difficult and few values are available. They
may be estimated from solid-state theory, using lattice energies. For ordinary salts,
(f is of the order 31 of 80 to 100 ergs/cm 2 . When the above values of C and (J are
used in Eq. (27.10), a value of s can be calculated that will correspond to a
nucleation rate of one nucleus per second per cubic centimeter, or B O = 1. The
calculation gives a very large value of s and one that is impossible for materials
of usual solubility. This is one reason for the conclusion that homogenous
nucleation in ordinary crystallization from solution never occurs and all actual
nucleations in these situations are heterogenous. Equation (27.10), then, does not
give actual rates of nucleation.
In precipitation reactions, where y, is very small and where large super-
saturation ratios can be generated rapidly, homogenous nucleation probably
occurs.31
HETEROGENEOUS NUCLEATION. The catalytic effect of solid particles on
nucleation rate is the reduction of the energy required for nucleation. One theory
of this effect holds that if the nucleus "wets" the surface of the catalyst, the work
of nucleus formation is reduced by a factor that is a function of the angle of wetting
between the nucleus and the catalyst. Experimental data on the heterogeneous
nucleation of potassium chloride solutions" show that the nucleation of this
substance is consistent with an apparent value of the interfacial tension in the
range 2 to 3 ergs/cm 2 for both catalyzed nucleation and nucleation without an
added catalyst. If the latter situation was actually a secondary nucleation self-
catalyzed by microscopic seeds, the value of (f for seeded solutions of KCI would
be 2.8 ergs/cm 2 at a temperature of 300 K. If (fa is used to denote the apparent
interfacial tension, if C is taken as 1025 , and if the mathematical approximation
In" = " - 1 = s is accepted for small values of" - 1, Eq. (27.10) may be written
0_ 25 [_ 161tVi,Na(f';] (27.11)
B - 10 exp 3 2 2
3(RT) v s
This equation, although it rests on incomplete data, gives results of the correct
order and does reflect the very strong effect of supersaturation on nucleation.
Example 27.3. Assuming that the rate of heterogeneous nucleation of potassium
chloride is consistent with an apparent interfacial tension of 2.5 ergs/cm 2 , determine
the nucleation rate as a function of s at a temperature of 80°F (300 K).
CRYSTALLIZATION 897
Solution
Use Eq. (27.11). The molecular weight of KCI is 74.56. The density of the crystal is
1.988 g/cm 3 • Since KCI dissociates into two ions, K+ and CI-, v = 2. Then
74.56
Vu = - - = 37.51 cm'jgmol aa = 2.5 ergs/cm 2
1.988
The exponent in Eq. (27.11) is
16n(37.51)' x 6.0222 x 10 2 ' x 2.5' 0.03575
3(300 x 8.3134 x 10 7 )'(2'82 )
For BO = 1, the value of s is given by
0.03575 0.03575
- - 2- = 57.565 s= - - = 0.02492
s 57.565
From the equation
the value of BO can be calculated for magnitudes of s around 0.025. The results
are shown in Table 27.1. The explosive increase in BO as s increases is apparent.
Example 27.4. What would, be the size of a nucleus in equilibrium with a super-
saturation of 0.029, under the conditions of Example 27.3?
Solution
This is solved from the Kelvin equation. Here" = 1 + 0.029 = 1.029. Substitution
of the values for 1'", "., D, R, and T from Example 27.3 into Eq. (27.9) gives
4 x 37.51 x 2.5
In 1.029 = --,-,..,...,.,------,-;;--:c:-::-::
2 x 8.3143 X 10 7 x 300L
From this,
L = 2.63 X 10- 7 cm or 2.63 nm
Note that this is consistent with the size of a nucleus containing a few hundred
particles about 0.3 nm in diameter. If (J were 80 ergs/cm 2 , (l would be 2.5 for a 2.63-nm
particle, and the supersaturation required would be 150 percent-dearly an impos-
sible value for a soluble salt like KC!.
TABLE 27.1
s If' s If'
0.023 4.47 x 10- 5 0.0255 13.3
0.024 1.11 x 10- 2 0.027 5.04 x 10 3
0.02492 1 0.029 3.46 x 10'
898 MASS TRANSFER AND ITS APPLICATIONS
SECONDARY NUCLEATION. The formation of nuclei attributable to the infl-
uence of the existing macroscopic crystals in the magma is called secondary
nucleation 9 •28 Two kinds are known, one attributable to fluid shear and the other
to collisions between existing crystals with each other or with the walls of the
crystallizer and rotary impellers or agitator blades.
Fluid-shear nucleation. This type is known to take place under certain conditions
and is suspected in others. When supersatured solution moves past the surface of
a growing crystal at a substantial velocity, the shear stresses in the boundary layer
may sweep away embryos or nuclei that would otherwise be incorporated into
the growing crystal and so appear as new crystals. This has been reported in work
on sucrose crystallization l3 It also has been demonstrated 25 in the nucleation of
MgSO.· 7H 2 0, if the solution is subjected to shear at the crystal face at one
supersaturation and then quickly cooled to a higher supersaturation and allowed
to stand while nuclei grow to macroscopic size.
CONTACT NUCLEATION. It has been known for a long time that secondary
nucleation is influenced by the intensity of agitation, but it was not until the 1970s
that the phenomenon of contact nucleation was isolated and studied experiment-
ally. It is the most common type of nucleation in industrial crystallizers, for it
occurs at low supersaturations where the growth rate of the crystals is at an
optimum for good quality. It is proportional to the first power of the super-
saturation, instead of the twentieth or more power for primary nucleation, so that
control is comparatively easy without unstable operation.
The energy at which a crystal must be struck is amazingly low, of the order
of a few hundred ergs, and no visible effect is observable on the crystal surface.
The position of contact nucleation in the fields of crystal growth and nucleation
is shown by the dashed area in Fig. 27.7.
In experimental studies of this phenomenon'·6.23 small rods are made to
strike, with known amounts of impact energy, selected faces of individual crystals
positioned in a flowing supersaturated solution, and the number of resulting nuclei
is measured. This number has been shown to depend only on the supersaturation
and the energy of impact. For inorganic crystals the number of nuclei per contact
N is proportional to the supersaturation s; for some organic crystals, In N is
proportional to s. For organic and hydrated inorganic crystals the number N is
directly proportional to the contact energy E over a range that is significant in
practice, but for anhydrous inorganic crystals the energy required is larger than
for other crystals, and a threshold energy is required before nucleation will take
place at all. For higher contact energies N is proportional 27 to exp E.
An appreciable healing time, usually several seconds long, is needed between
contacts if successive contacts are to give the same nucleation. 6
Contact nucleation is probably a combination of breakage of microscopic
dendritic growths on the surface of the growing crystal and an interference by the
contacting object with clusters of solute particles moving to become organized
CRYSTALLIZATION 899
into the crystal. It has been hypothesized 2 • that the action of the contacting object
deflects or dislodges particles ranging in size from embryos to small crystals much
larger than L, that is, the maximum size of a crystal that can exist in equilibrium
with the supersaturated solution, as called for by the Kelvin equation (27.9).
Particles at least as large as L survive and grow as new nuclei, while smaller ones
dissolve.
Crystal Growth
Crystal growth is a diffusional process, modified by the effect of the solid surfaces
on which the growth occurs. Solute molecules or ions reach the growing faces of
a crystal by diffusion through the liquid phase. The usual mass-transfer coefficient
k, applies to this step. On reaching the surface, the molecules or ions must be
accepted by the crystal and organized into the space lattice. The reaction occurs
at the surface at a finite rate, and the overall process consists of two steps in series.
Neither the diffusional nor the interfacial step will proceed unless the solution is
supersaturated.
INDIVIDUAL AND OVERALL GROWTH COEFFICIENTS. In mass-transfer
operations it is generally assumed that equilibrium exists at the interface between
phases. If this were true in crystallization, the concentration of the solution at the
face of the crystal would be the saturation value y" and the total driving force
for mass transfer would be y - y" where y is the concentration at a distance from
the crystal face. Because of the surface reaction, however, a driving force is needed
for the interfacial step, and the concentration at the interface is therefore y', where
y, < y' < y. Only y - y' remains as the driving force for mass transfer. This is
illustrated in Fig. 27.8.
The coefficients for both mass transfer and surface reaction differ from one
crystal face to another, but it is nearly always adequate to consider only average
1
_TbU~ _ _
I
-++--,1 1 1
1 1 1 I
1 1 I, I
Y. Y Ybulk
Y., based on Tbulk FIGURE 27.8
MOLE FRACTION, Y Temperatures and concentrations in crystallization.
900 MASS TRANSFER AND ITS APPLICATIONS
values for the entire crystal. The equation for mass transfer can then be written
NA
In
= -S = ky (y -
I
y) (27.12)
p
where N A = molar flux, moles per unit time per unit area
riJ = rate of mass transfer, molfh
sp = surface area of crystal
ky = mass-transfer coefficient defined by Eq. (21.32)
The equation for the surface reaction using the coefficient k, is
In
- = k,(y' - y,) (27.13)
sp
The resistances for the two steps may be added to give an overall coefficient
K defined by
K (27.14)
siY - y,)
Elimination of y' from Eqs. (27.12) and (27.13), followed by substitution in Eq.
(27.14), gives
1
K (27.15)
llk y + Ilk,
Growth rate. For an invariant crystal the volume of the crystal vp is proportional
to the cube of its characteristic length L; that is,
vp = aL' (27.16)
where a is a constant. If PM is the molar density, the mass of the crystal m is then
m= VpPM = aL 3 PM (27.17)
Differentiating Eq. (27.17) with respect to time gives
m= dm = 3aL2pM (dL) (27.18)
dt dt
The growth rate dLldt is denoted by the symbol G.
From Eq. (27.2), sp = 6vplL = 6aU. Substituting this for sp and In from
Eq. (27.18) into Eq. (27.14) gives
3aL2p MG
K (27.19)
6aL2(y - y,)
From this
G = 2K(y - y,) (27.20)
PM
CRYSTALLIZATION 901
Mass-transfer coefficients. For spheres or crystals with a shape factor close to 1.0,
Eq. (21.59) may be used to predict the mass-transfer coefficient k y • As discussed
on page 672, for suspended particles in an agitated system the coefficient will be
1.5 to 5 times that calculated from the terminal setting velocity of the crystals.
Surface-growth coefficients. Much research on the growth of crystals by the
interfacial reaction has been done and reported in standard monographs on
crystallization,·22.2. Although a coherent theory of crystal growth has evolved,
numerical data on k, of a kind that can be used in design are scarce.
One theory is based on the concept that growth occurs layer by layer on
the crystal face, and that each new layer begins as a two-dimensional nucleus
attached to the face. This theory predicts that growth does not start until an
appreciable threshold supersaturation is reached and that the rate of growth then
increases rapidly until, at some fairly high value of supersaturation, it becomes
linear with supersaturation. Actually, the growth rate of most crystals is linear
with supersaturation at all supersaturations, even at very low values. There seems
to be no threshold value required.
The difference between the observed and theoretical growth rates has been
reconciled by the Frank screw-dislocation theory. Actual space lattices of real
crystals are far from perfect and crystals have imperfections called dislocations.
Planes of particles on the surfaces and within the crystals are displaced, and several
kinds of dislocations are known. One common dislocation is a screw dislocation
(Fig_ 27.9), where the individual particles are shown as cubical building blocks.
The dislocation is in a shear plane perpendicular to the surface of the crystal, and
the slipping of the crystal creates a ramp. The edge of the ramp acts like a portion
of a two-dimensional nucleus and provides a kink into which particles can easily
fit. A complete face never can form, and no nucleation is necessary. As growth
FIGURE 27.9
Screw dislocation in crystal surface and movement of particle into kink.
902 MASS TRANSFER AND ITS APPLICATIONS
continues, the edge of the ramp becomes a spiral, and the continued deposit of
particles along the edge of the spiral constitutes the mechanism of crystal growth.
Since this mechanism was first suggested, many examples of screw disloca-
tions have actually been observed by electron microscopy and other methods of
very high magnification.
THE lJ.L LAW OF CRYSTAL GROWTH.' If all crystals in magma grow in a uniform
supersaturation field and at the same temperature and if all crystals grow from
birth at a rate governed by the supersaturation, then all crystals are not only
invariant but also have the same growth rate that is independent of size. This
generalization is called the AL law. When applicable, G oF J(L), the total growth
of each crystal in the magma during the same time interval !J.t is the same, and
!!.L = G!!.t (27.21)
The model underlying Eq. (27.21) is highly idealized and is certainly not
realistic in all situations. Figure 21.6 shows that the mass-transfer coefficient is
approximately constant only over a limited range of particle diameters; when the
mass-transfer resistance is significant, therefore, a constant growth rate would be
expected only for crystals between about 50 and 500 I'm in size. When Eq. (27.21)
is not applicable, G = J(L) and the growth is called size dependent. Perhaps
because of cancellation of errors, the !!.L law is sufficiently precise in many
situations to be usable, and so greatly simplifies the calculation of industrial
processes.
CRYSTALLIZATION EQUIPMENT
Commercial crystallizers may operate either continuously or batchwise. Except
for special applications, continuous operation is preferred. The first requirement
of any crystallizer is to create a supersaturated solution, because crystallization
cannot occur without supersaturation. Three methods are used to produce
supersaturation, depending primarily on the nature of the solubility curve of the
solute. (1) Solutes like potassium nitrate and sodium sulfite are much less soluble
at low temperatures than at high temperatures, so supersaturation can be produced
simply by cooling. (2) When the solubility is almost independent of temperature,
as with common salt, or diminishes as the temperature is raised, supersaturation
is developed by evaporation. (3) In intermediate cases a combination of evapora-
tion and cooling is effective. Sodium nitrate, for example, may be satisfactorily
crystallized by cooling without evaporation, evaporation without cooling, or a
combination of cooling and evaporation.
VARIATIONS IN CRYSTALLIZERS. Commercial crystallizers may also be differ-
entiated in several other ways. One important difference is in how the crystals are
brought into contact with the supersaturated liquid. In the first technique, called
the circulating-liquid method, a stream of supersaturated solution is passed through
CRYSTALLIZATION 903
a fluidized bed of growing crystals, within which supersaturation is released by
nucleation and growth. The saturated liquid then is pumped through a cooling
or evaporating zone, in which supersaturation is generated, and finally the
supersaturated solution is recycled through the crystallizing zone. In the second
technique, called the circulating-magma method, the entire magma is circulated
through both crystallization and supersaturation steps without separating the
liquid from the solid. Supersaturation as well as crystallization occurs in the
presence of crystals. In both methods feed solution is added to the circulating
stream between the crystallizing and supersaturating zones.
One type of crystallizer uses size-classification devices designed to retain
small crystals in the growth zone for further growth and to allow only crystals of
a specified minimum size to leave the unit as product. Ideally, such a crystallizer
would produce a classified product of a single uniform size. Other crystallizers are
designed to maintain a thoroughly mixed suspension in the crystallizing zone, in
which crystals of all sizes from nuclei to large crystals are uniformly distributed
throughout the magma. Ideally, the size distribution in the product from a mixed
suspension unit is identical to that in the crystallizing magma itself.
To make the average crystal size larger than that for a mixed-suspension
unit, some crystallizers are equipped with devices that segregate and remove most
of the fine crystals from the crystallizing zone. These small crystals are redissolved
and returned to the crystallizer. Other crystallizers have two take-off lines, one for
large crystals and another for small ones. The two product streams, which may
differ considerably in volume, are combined and sent to a filter or other separation
unit. These techniques of enhancing crystal size are discussed later.
Most crystallizers utilize some form of agitation to improve growth rate, to
prevent segregation of supersaturated solution that causes excessive nucleation,
and to keep crystals in suspension throughout the crystallizing zone. Internal
propeller agitators may be used, often equipped with draft tubes and baffles, and
external pumps also are common for circulating liquid or magma through the
supersaturating or crystallizing zones. The latter method is called forced circula-
tion. One advantage offorced-circulation units with external heaters is that several
identical units can be connected in multiple effect by using the vapor from one
unit to heat the next in line. Systems of this kind are evaporator-crystallizers.
VACUUM CRYSTALLIZERS. Most modern crystallizers fall in the category of
vacuum units in which adiabatic evaporative cooling is used to create super-
saturation. In its orginal and simplest form, such a crystallizer is a closed vessel
in which a vacuum is maintained by a condenser, usually with the help of a
steam-jet vacuum pump, or booster, placed between the crystallizer and the
condenser. A warm saturated solution at a temperature well above the boiling
point at the pressure in the crystallizer is fed to the vessel. A magma volume is
maintained by controlling the level of the liquid and crystallizing solid in the vessel,
and the space 'above the magma is used for release of vapor and elimination of
entrainment. The feed solution cools spontaneously to the equilibrium tempera-
ture; since both the enthalpy of cooling and the enthalpy of crystallization appear
904 MASS TRANSFER AND ITS APPLICATIONS
as enthalpy of vaporization, a portion of the solvent evaporates. The super-
saturation generated by both cooling and evaporation causes nucleation and
growth. Product magma is drawn from the bottom of the crystallizer. The
theoretical yield of crystals is proportional to the difference between the concentra-
tion of the feed and the solubility of the solute at equilibrium temperature.
Figure 27.10 shows a continuous vacuum crystallizer with the conventional
auxiliary units for feeding the unit and processing the product magma. The
essential action of a single body is much like that of a single-effect evaporator,
and in fact these units can be operated in multiple effect. The magma circulates
from the cone bottom of the crystallizer body through a downpipe to a low-speed
low-head circulating pump, passes upward through a vertical tubular heater with
condensing steam in the shell, and thence into the body. The heated stream enters
through a tangential inlet just below the level of the magma surface. This imparts
a swirling motion to the magma, which facilitates flash evaporation and equi-
librates the magma with the vapor through the action of an adiabatic flash. The
supersaturation thus generated provides the driving potential for nucleation and
growth. The volume of the magma divided by the volumetric flow rate of magma
through the slurry pump gives the average residence time.
/,Bo'rolne;'ric· condenser
Body
FIGURE 27.10
Continuous crystalIizer. (By permission,Jrom R. C. Bennett and M. Van Buren. Chem. Eng. Prog. Symp.
Ser. 95, 65:38, 1969.)
CRYSTALLIZATION 905
Feed solution enters the downpipe before the suction of the circulating pump.
Mother liquor and crystals are drawn off through a discharge pipe upstream from
the feed inlet in the downpipe. Mother liquor is separated from the crystals in a
continuous centrifuge; the crystals are taken off as a product or for further
processing, and the mother liquor is recycled to the downpipe. Some of the mother
liquor is bled from the system by a pump to prevent accumulation of impurities.
The simple form of vacuum crystallizer has serious limitations from the
standpoint of crystallization. Under the low pressure existing in the unit, the effect
of static head on the boiling point is important; e.g., water at 45°F has a vapor
pressure of 0.30 in. Hg, which is a pressure easily obtainable by steam-jet boosters.
A static head of 1 ft increases the absolute pressure to 1.18 in. Hg., where the
boiling point of water is 84°F. Feed at this temperature would not flash if
admitted at any level more than 1 ft below the surface of the magma. Admission
of the feed at a point where it does not flash, as in Fig. 27.10, is advantageous in
controlling nucleation.
Because of the effect of static head, evaporation and cooling occur only in
the liquid layer near the magma surface, and concentration and temperature
gradients near the surface are formed. Also crystals tend to settle to the bottom
of the crystallizer, where there may be little or no supersaturation. The crystallizer
will not operate satisfactorily unless the magma is well agitated, to equalize
concentration and temperature gradients and suspend the crystals. The simple
vacuum crystallizer provides no good method for nucleation control, for classifi-
cation, or for removal of excess nuclei and very small crystals.
DRAFT TUBE-BAFFLE CRYSTALLlZER. A more versatile and effective equip-
ment is the draft tube-baffle (DTB) crystallizer shown in Fig. 27.11. The crystallizer
body is equipped with a draft tube, which also acts as a baffle to control the
circulation of the magma, and a downward-directed propeller agitator to provide
a controllable circulation within the crystallizer. An additional circulation system,
outside the crystallizer body and driven by a circulating pump, contains the heater
and feed inlet. Product slurry is removed through an outlet near the bottom of
the conical lower section of the crystallizer body. For a given feed rate both the
internal and external circulations are independently variable and provide controll-
able variables for obtaining the required CSD.
Draft tube-baffle crystallizers can be equipped with an elutriation leg below
the body to classify the crystals by size and may also be equipped with a baffled
settling zone for fines removal. An example of such a unit is shown in Fig. 27.12.
Part of the circulating liquor is pumped to the bottom of the leg and used as a
hydraulic sorting fluid to carry small crystals back into the crystallizing zone for
further growth. The action here is that of hindered-settling classification described
in Chap. 30. The discharge slurry is withdrawn from the lower part of the
elutriation leg and sent to a filter or centrifuge, and the mother liquor is
returned to the crystallizer.
Unwanted nuclei are removed by providing an annular space, or jacket, by
enlarging the cone bottom and using the lower wall of the crystallizer body as a
906 MASS TRANSFER AND lTS APPLICATIONS
Cooling r-1-_ To vacuum
water equipment
"""V--:J
Barometric
condenser
""
"" it
""
"
,",
"
r To hotwell
"
" 1
r--11---
,II ":'"
I "
I ::
,
,I
,,,
I 11 I
---~ P I~
\.-~(~-,:..... ../7
_..L~.::_:_::.-
,,
'-~--Jr-~ Slurry dlsch.
Steam----, Feed
Heatln element
Purge
Condensate
Circulating pump ==~~-----'
FIGURE 27.11
Draft tube-baffle (DTB) crystallizer. (By permission,from R. C. Bennet! and M. Van Buren, Chem. Eng.
Prog. Symp. Ser. 95,65:45, 1969.)
baffle. The annular space provides a settling zone, in which hydraulic classification
separates fine crystals from larger ones by floating them in an upward-flowing
stream of mother liquor, which is withdrawn from the top of the settling zone.
The fine crystals so withdrawn are 60-mesh in size or smaller, and although their
number is huge, their mass is small, so that the stream from the jacket is nearly
solids free. When this stream-called the clear liquor recycle-is mixed with the
fresh feed and pumped through a steam heater, the solution becomes unsaturated
and most of the tiny crystals dissolve. The liquor, now essentially clear, is rapidly
mixed with the slurry circulating in the main body of the crystallizer.
By removing a large fraction of the mother liquor from the jacket in this
fashion, the magma density is sharply increased. Magma densities of 30 to 50
CRYSTALLIZATION 907
Propeller drive
To barometric
,
condenser
Balling
surface
Draft tube
Clear
Baffle
liquor
recycle Settling zone
(fines
separation)
Feed
discharge
FIGURE 27.12
Draft tube-baffle crystallizer with
internal system for fines separation and
Elutriation pump removal. (By permissioll, from A. D.
Ralldolph, Chem. Ellg., May 1970,
Circulation pump p.86.)
percent, based on the ratio of the volume of settled crystals to that of the total
magma, are achieved.
Yield of vacuum crystallizer. The yield from a vacuum crystallizer can be calcu-
lated by enthalpy and material balances. A graphical calculation based on the
enthalpy chart of Fig. 27.4 is shown in Fig. 27.13. Since the process is an adiabatic
split of the feed into product magma and vapor, points b for the feed, a for the
vapor, and e for the magma lie on a straight line. The isotherm connecting point
d for the crystals with point I for the mother liquor also passes through point e,
and this point is located by the intersection of lines ab and df From the line
segments and the center-of-gravity principle, the ratios of the various streams are
calculated.
Example 27.5. A continuous vacuum crystallizer is fed with a 31 percent MgS04
solution. The equilibrium temperature of the magma in the crystallizer is 86°F (30°C),
and the boiling-point elevation of the solution is 2°F (l.l1°e). A product magma
containing 5 tons (4536 kg) of MgSO.· 7H,O per hour is obtained. The volume
ratio of solid to magma is 0.15; the densities of the crystals and mother liquor are
105 and 82.5 lb/ft', respectively. What is the temperature of the feed, the feed rate,
and the rate of evaporation?
908 MASS TRANSFER AND ITS APPLICATIONS
1200
a
1000 1\
<D
-'
800 \
"-
"
+
<D 600 1\
;,:
"-
-' 400
«
I
\
I-
Z
w
200
1\
\
~N
0
fe
-200
o 0.1 0.2 0.3 0.4 0.5 0.6 FIGURE 27.13
WEIGHT FRACTION MgS04 Solution for Example 27.5.
Solution
Figure 27.13 shows the graphical solution of the problem. The vapor leaves the
crystal1izer at the pressure corresponding to 84°F and carries 2°F superheat, which
may be neglected. From steam tables, the enthalpy of the vapor is that of saturated
steam at 0.5771Ibf /in-', and the coordinates of point a are H = 1098 Btuflb and
c = O. The enthalpy and average concentration of the product magma are calculated
from data given by Fig. 27.4. The straight line Jd is the 86°F isotherm in the area
bcih of Fig. 27.4. The coordinates for its terminals are, for point f, H = -43 Btuflb
and c = 0.285, and for point d, H = -149 Btuflb, c = 0.488. The mass ratio of
crystals to mother liquor is
0.15 x 105
0.224
0.85 x 82.5
The rate of production of mother liquor is 10,000/0.224 = 44,520 lb/h, and the
total magma produced is 10,000 + 44,520 = 54,520 lbfh. The average concentration
of MgSO4 in the magma is
0.224 x 0.488 + 0.285 = 0.322
1.224
The enthalpy of the magma is
0.224( -149) + (-43)
- 62.4 Btu/lb
1.224
These are the coordinates of point e. The point for the feed must lie on the straight
line ae. Since the feed concentration is 0.31, the enthalpy of the feed is the ordinate
CRYSTALLIZATION 909
of point b, or -21 Btujlb. Point b is on the 130'F (94.4'C) isotherm, so this
temperature is that of the feed. By the center-of-gravity principle, the evaporation
rate is
-21 - (-62.4)
54520 2,0171bjh (915 kg/h)
, 1098-(-21)
The total reed rate is 54,520 + 2017 = 56,537Ib/h (25,645 kgjh).
APPLICATIONS OF PRINCIPLES
TO DESIGN
Once the theoretical yield from a crystallizer has been calculated from mass and
energy balances, there remains the problem of estimating the CSD of the product
from the kinetics of nucleation and growth. An idealized crystallizer model, called
the mixed suspension-mixed product removal model (MSMPR), has served well as
a basis for identifying the kinetic parameters and showing how knowledge of them
can be applied to calculate the performance of such a crystallizer.'7.'8.20
MSMPR Crystallizer
Consider a continuous crystallizer that operates in conformity with the following
stringent requirements 15 :
1. The operation is steady state.
2. At all times the crystallizer contains a mixed-suspension magma, with no
product classification.
3. At all times uniform supersaturation exists throughout the magma.
4. The I1L law of crystal growth applies.
5. No size-classified withdrawal system is used.
6. There are no crystals in the feed.
7. The product magma leaves the crystallizer in equilibrium, so the mother liquor
in the product magma is saturated.
8. No crystal breakage into finite particle size occurs.
The process is called mixed suspension-mixed product removal crystallization.
Because of the above restraints, the nucleation rate, in number of nuclei generated
in unit time and unit volume of mother liquor, is constant at all points in the
magma; the rate of growth, in length per unit time, is constant and independent
of crystal size and location; all volume elements of mother liquor contain a mixture
of particles ranging in size from nuclei to large crystals; and the particle-size
distribution is independent of location in the crystallizer and is identical to the
size distribution in the product.
910 MASS TRANSFER AND ITS APPLICATIONS
By the use of a generalized population balance the MSMPR modelt is
extended to account for unsteady-state operation, classified product removal,
crystals in the feed, crystal fracture, variation in magma volume, and time-
dependent growth rate. IS These variations are not included in the following
derivations.
POPULATION-DENSITY FUNCTION. The basic quantity in the theory of the
CSD is the population density. To understand the meaning of this variable, assume
that a distribution function of the cumulative number of crystals in the magma,
in number per unit volume of mother liquor, is known as a function of L, the
crystal size. Such a function is plotted in Fig. 27.14. The abscissa is L, and the
ordinate is N/V, where V is the volume of mother liquor in the magma and N is
the number of crystals of size L and smaller in t)le magma. At L = 0, N = 0; the
total number of crystals is N T, corresponding to the length LT of the largest crystal
in the magma.
The population density n is defined as the slope of the cumulative distribution
curve at size L, or
d(N/VJ 1 dN
11=---=-- (27.22)
dL V dL
By assumption 1, V is a constant. The function n = f(L) has a maximum value
n° where L = 0 and is zero where L = LT' In the MSMPR model, the functions
of N/V and 11 with L are invariant in both time and location in the magma. The
dimensions of n are number/volume-length.
A growing crystal moves with time along the size axis in the direction of
increasing L. A dissolving crystal moves in the other direction. For computations
in the MSMPR model a relation between population density n and size L is needed.
Consider the n dL crystals between sizes Land L + dL per unit volume of
magma in the crystallizer. In the MSMPR model, each crystal of length L has the
same age, and if tm is the age of a crystal.
(27.23)
N
t
i7
LT FIGURE 27.14
o L- Cumulative number density vs. length.
t Walas 30.. has proposed the term continuous-stirred-tank crystallizer (CSTC) in place of MSMPR.
CRYSTALLIZATION 911
Assume, now, that of the n dL crystals per unit volume of liquid, I!.n dL are
withdrawn as product during time increment !!.t. Since the operation is in steady
state, withdrawal of product does not affect the size distribution in either magma
or product, and since in the MSMPR model the discharge is accurately representa-
tive of the magma, it follows that the fraction of particles withdrawn is identical
to the ratio of the volume of product liquid taken out in time I!.t to the total
volume of liquid in the crystallizer. Then if Q is the volumetric flow rate of liquid
in the product and y" is the total volume of liquid in the crystallizer,
I!.n dL I!.n Q I!.t
---=--=-- (27.24)
ndL n y"
The time interval !!.t also is a period in the life of each crystal, and during this
time, by Eq. (27.23), the growth of each crystal is
I!.L = G !!.t (27.25)
Eliminating I!.t from Eqs. (27.24) and (27.25) gives
I!.n Qn
I!.L GY"
Letting I!.L -+ 0, so that
lim I!.n = dn
"L~O I!.L dL
leads to
dn Qn
dL GY"
The retention time ~ of the magma in the crystallizer is defined by
V,
1':=-
Q
and
dn 1
--=-dL (27.26)
n G~
Integration of Eq. (27.26) gives the function of cumulative population vs. length,
where n° is the population density at L = 0 and is assumed to represent the nuclei.
Thus
_~ r dL
I
L
"dn =
n~ n G1': Jo
n° L
In-=- (27.27)
n G~
912 MASS TRANSFER AND ITS APPLICATIONS
The quantity LIGr is dimensionless. It may be replaced by z, called the dimension-
less length, which is defined by
(27.28)
Equation (27.27) may be written
(27.29)
When plotted on semilogarithmic coordinates, the linear graph gives n° when
z = 0 and has a slope of 1/Ch. Such a graph is shown in Fig. 27.17.
MOMENT EQUATIONS. Equation (27.29) is the fund?mental relation of the
MSMPR crystallizer. From it differential and cumulative equations can be derived
for crystal population, crystal length, crystal area, and crystal mass. Also, the
kinetic coefficients G and BO are embedded in these equations.
These calculations use moments of the n-vs.-z relation of Eq. (27.29). The
normalized jth moment is defined by
J~ nzi dz
J1..= (27.30)
J - So nzi dz
Using Eq. (27.29) gives
(27.31)
Integrating this equation for values of j = 0 through j = 3 gives
J1.o = 1 - e- Z (27.32)
J1.1 = 1 - (1 - z)e-' (27.33)
J1.2 = 1 - (1 + z + !z2)e- z (27.34)
J1.3 = 1 - (1 + z + !Z2 + tz3)e-' (27.35)
The differential distributions are
dJ1.o = e- Z (27.36)
dz
dJ1.1 _,
-=ze (27.37)
dz
dJ1.2 = Z2e-,
(27.38)
dz 2
dJ13 = Z3 e -:r:
(27.39)
dz 6
CRYSTALLIZATION 913
Equations (27.32) to (27.35) give directly the distribution of the crystals from
the idealized MSMPR plant. Thus, 110 is the number distribution x"' 111 the size
distribution XL' 112 the area distribution X., and 113 the mass distribution Xm.
Likewise, the differential distributions for number, size, area, and mass are
given in Eqs. (27.36) to (27.39). Plots of Xa, Xm, dxaldz, and dXmldz are given in Fig.
27.15.
Figure 27.15a relates the cumulative mass fraction Xm to the dimensionless
length z. For given values of G and !, z may be converted by Eq. (27.28) to the
crystal size L, and Fig. 27.15a then becomes a plot of the cumulative screen
analysis. This procedure is illustrated in Example 27.6.
Since both z and 11 are dimensionless, Eqs. (27.32) to (27.39) are universally
applicable to MSMPR crystallizers.
PREDOMINANT CRYSTAL SIZE. Figure 27.15b, the differential mass distribution,
shows a node where the value of dxmldz is a maximum. Differentiating the
right-hand side of Eq. (27.39) with respect to z and setting the result equal to zero
-
(0) (c)
1.0 1.0
0.9
0.8
V 0.9
0.8
'/ '"'
0.7 0.7
0.6
I1 0.6
xmO.5 xn 0.5 /
0.4
I1 0.4
0.3 0.3
0.2
7 0.2
I
O. I O. 117
00 I 2 3 4 5 6 7 8 9 10 11 12 00 2 3 4 5 6
z z
0.50 1.0
0.45 0.9
0.40 0.8 1\
0.35 0.7 \
A 0.30 dx 0.6
uXm
'dZ 0 .25 t-..
d;0.5
\
0.20 OA
0.15
r--.. 0.3
0.10
I1 r--.. 0.2
r--... "-
0.05 O. I
1/ t--
00 I 2 3 4 5 6 7 8 9 10 11 12 00 2 3 4 5 6
z z
(b) (d)
FIGURE 27.15
Size-distribution relations, mixed suspension: (a) cumulative mass distribution; (b) differential mass
distribution; (c) cumulative population distribution; (d) differential population distribution.
914 MASS TRANSFER AND ITS APPLICATIONS
shows that the node is at abscissa zP' = 3. The predominant crystal size in the
product occurs where Lp,Gr = 3, in the sense that more of the mass is in the size
interval dz at z = 3 than in any other size interval of width dz. The most populous
size in terms of number, as shown by Figs. 27.15e and d, is the extremely small
size where z approaches zero. Differentiating Eqs. (27.37) and (27.38) shows that
nodes appear in the differential curves for the size and area distributions (not
illustrated) at z = 1 and z = 2, respectively.
KINETIC COEFFICIENTS. Clearly, to use Eq. (27.27) and its consequences in
calculations three parameters must be evaluated: the growth rate G, the nucleus
density n°, and the retention time ,. The last parameter is under the control of
the designer, but the other two are dependent variables generated by the crystalli-
zer and its contents and are functions of the engineering details of the plant, the
action of the impeller or circulating pump, and the nucleating and growth
characteristics of the crystallizing system. There is an important equation, readily
derivable from the MSMPR model, which connects the nucleation rate BO with
the zero-size particle density n°. Thus, by formal calculus,
. dN . (dLdN)
hm-=hm --
L~O dt L~O dt dL
By definition of the terms in this equation, the limits at L = 0 are dN/dt ..... B O
,
dL/dt -+ G, and dN/dL ..... n°. Therefore,
(27.40)
Number of crystals per unit mass. The number of crystals n, in a unit volume of
liquid in either magma or product is
n, = LOO n dL = nO,G LOO e-' dz = nO,G (27.41)
The total mass of product crystals in a unit volume of liquid is
rn, = LOO rnn dL = ap,(Gr)3 nOLOO Z3 e -, dz
= 6ap,nO(Gr)4
where p, is the density of the crystals. The number of crystals per unit mass is
ne nOG't 1
-= (27.42)
rn, 6ap,nO(Gr)4 6ap,(Gr)3
If the predominant size is used as a design parameter, then from the equation
Lp, = 3Gr and Eq. (27.42),
ne = __9_
(27.43)
rn, 2ap,L~,
CRYSTALLIZATION 915
The nucleation rate must be just sufficient to generate one nucleus for each
crystal in the product. If C is the mass production rate of crystals, the required
nucleation, in number per unit time and volume of mother liquor, is, from Eqs.
(27.42) and (27.43),
(27.44)
Example 27.6. In the crystallizer of Example 27.5, a growth rate G of 0.0018 ftJh
(0.00055 mjh) is anticipated, and a predominant crystal size of 20 mesh is desired.
How large must the magma volume in the crystallizer be; what nucleation rate BO
is necessary; and what is the screen analysis of the product, assuming that the
operation conforms to an the requirements of the mixed suspension-mixed product
crystallization?
Solution
The screen opening of a 20-mesh standard screen is. from Appendix 20, 0.0328 in.,
or 0.00273 ft. This dimension can be used for L, and the shape factor a [Eq. (27.16)]
is assumed to be unity. From Example 21.5. the volume flow rate of mother liquor
in the product magma is
Q = 44,520 = 540 ft' Jh
82.5
Since, when z = 3, Lp, = 0.00273, Eq. (27.28) gives for the drawdown time and
the volume of liquid in the crystallizer
Lp, 0.00273
,=-= 0.506h v, = 0.506 x 540 = 273 ft'
3G 3 x 0.0018
The total magma volume is 273/0.85 = 321 ft', or 2400 gal.
The nucleation rate is, from Eq. (27.44), since C = 10,000 IbJh,
9 x 10,000
B'=-2-x-IO-5-x-2-7~3-x-0-.-00-2-7-=3'
= 7.72 X 10' nucleijft'-h (2.74 x 109 nucleijm'-h)
By Eq. (27.40), the zero-size particle density is n' = 7.72 x 10'/0.0018 =
4.289 x 10'0 nuclei/ft'. The value of L/G< is L/(0.0018X0.506) = 1.1 x 10' L. The
equation for the number-density distribution is, from Eq. (21.21),
log n = log ,,' 1.1 x IO'L = 10.632 _ 4.777 x 10'L
2.3026
This equation is plotted in Fig. 27.16.
916 MASS TRANSFER AND ITS APPLICATIONS
1
n 0
10
"'" "-
<:
'"
o
9
"" " "-
8
"'" I"
"-
2 3 45 6
""7
i'--.
8
FIGURE 27.16
Population density vs. length (Exam-
LX10 3 ft ple 27.6).
The screen analysis is found by reading ordinates from Fig. 27.15c for values
of z corresponding to mesh openings. For example, for the 20-mesh point, where
z = 3, Xm is 0.35. In general,
L L
Z=-= 1098L
,G 0.506 x 0.0018
Details are given in Table 27.2.
TABLE 27.2
Size Screen analysis, %
Mesh ft mm z Cumulative Differential
8 0.0078 2.37 8.5 97 3
9 0.0065 1.98 7.1 93 4
10 0.0054 1.65 5.9 84 9
12 0.0046 1.40 5.0 74 10
14 0.0038 1.16 4.2 61 13
16 0.0033 1.01 3.6 48 13
20 0.0027 0.82 3.0 35 13
24 0.0023 0.70 2.5 25 10
28 0.0019 0.58 2.1 17 8
32 0.0016 0.49 1.8 11 6
35 0.0014 0.43 1.5 6 5
42 0.0011 0.34 1.2 4 2
CRYSTALLIZATION 917
INCREASING THE CRYSTAL SIZE. Two techniques are used to make crystals
larger than those from an MSMPR crystallizer. The first. known as fines destruc-
tion with solute recycle, has been described in the discussion of DTB crystallizers.
The objective is to reduce sharply the number of nuclei present so that the
remaining ones can grow. The presence of too many nuclei leads to a large surface
area and makes the supersaturation small, so the growth rate of individual crystals
is low. Fines destruction is most useful in systems involving highly soluble
materials, where the tiny crystals can easily be redissolved by heating or by adding
a small amount of solvent.
With the second technique, known as double drawoff(DDO), a large overflow
stream is removed through a classifier so that crystals larger than a certain cut
size LF are left behind. A smaller underflow stream is taken from the well-mixed
region of the crystallizer, and the large crystals that leave with this stream have
a longer average residence time than they would have in a mixed crystallizer with
a single drawoff. The overflow stream is typically 8 to 12 times as large as the
underflow stream, and the residence time for large crystals is thus increased by
about 10 times.
The classification can be accomplished by removing the overflow through a
vertical pipe or baffled segment of the tank, with the area chosen to give an upward
velocity slightly greater than the terminal velocity of crystals of size L F • Alterna-
tively, the overflow can be drawn directly from the tank and passed through a
hydroclone (see Chap. 30), with oversize particles being returned to the tank. The
overflow and underflow streams are combined outside the crystallizer and sent to
a filter or other separator.
The popUlation distribution in the combined product is strongly bimodal,
with one peak at about the same size as with MSMPR operation. The second
peak size may be several times as large as the first one, and the average size two
to three times that obtainable from an MSMPR crystallizer. This may dramatically
change the filtration characteristics ofthe product. In the disposal of waste gypsum,
for example, ordinary crystallization produced an unfilterable slime, but the
product from a DDO crystallizer, despite its high content of small crystals, filtered
"like sand."4.16
Calculation of the optimum fines cut size in a DDO crystallizer is discussed
by White and Randolph. 32 The optimum cut size for fines destruction with solute
recycle, with design charts for DDO and fines-destruction crystallizers, is given
by Sutradhar and Randolph 26
CONTACT NUCLEATION IN CRYSTALLIZERS. The contact nucleation discussed
on previous pages is based on the single-particle experiments of Clontz and
McCabe, 5 which determined the number of crystals generated by a single contact
at known supersaturation, energy, and area of contact. The results have been
applied to the construction of nucleation models for the design of magma
crystallizers.'·l1 A correlation developed by Bennet!, Fiedelman, and Randolph'
is based on the following ideas:
918 MASS TRANSFER AND ITS APPLICATIONS
1. The total generation of nuclei is proportional to the sum of the nucleation from
all crystals of all sizes each time they pass through the impeller.
2. The driving potential is the supersaturation, which is proportional to the growth
rate G.
3. The energy imparted to a crystal of size L and mass p,L' is that necessary to
accelerate the particle from the speed of the flowing magma to the speed of the
tip of the impeller.
4. The area of contact is proportional to L 2
These assumptions lead to the following equation:
(27.45)
where BO = nucleation rate per unit volume of liquid
KN = dimensional constant
UT = tip speed of impeller
tTo = turnover time
Use of this equation in practice requires empirical data from a pilot plant or
actual operation of crystallizers of the same design. In the crystallization of KCI,
for example, Randolph, White, and Low!' found that BO oc G2.77m~·91, where 111, is
the solids concentration in the crystallizer, in mass of crystals per unit volume.
CRYSTALLIZATION OF ORGANIC CHEMICALS. All the examples given in this
chapter are for inorganic salts. The principles of crystallization from solution,
however, apply equally to organic materials. Walas,ob lists a number of organic
compounds for which crystallization data are reported in the literature. Organic
compounds are also often purified by melt crystallization as discussed in the next
section.
CRYSTALLIZATION FROM MELTS
The final step in making some organic compounds is to solidify the product from
a purified molten stream. This is commonly done by freezing on a drum flaker or
a cooled vibrating conveyor or in a jacketed agitated vessel. 12b Sometimes the
liquid can be subcooled 20 or even 50°C without freezing, and mechanical agitation
or seeding of the liquid may be needed to induce crystallization.
Binary and ternary organic mixtures, especially of aromatic isomers, may be
purified by simple cooling. Unless solid solutions are formed, virtually pure crystals
of one isomer can often be produced. Mixtures of xylene isomers, for example, are
processed on a commercial scale at temperatures approaching - 60°C in a
two-stage crystallization system. Crystals ofp-xylene from each stage are separated
in a filtering centrifuge (see Chap. 30); the first crop, which is not sufficiently pure,
CRYSTALLIZATION 919
is remelted and recrystallized, and the second crop is washed with toluene or other
solvent to remove adhering mother liquor.
In other processing systems the pure product is melted and part of it is
refluxed to wash and purify the crystals. A typical unit of this type is the Bradie
Purifier, illustrated in Fig. 27.17. This consists of several scraped-surface coolers
set in series and followed by a purification column. Molten feed enters the middle
of the last cooler. Liquid flows toward the residue eJ1ll of the system where the
temperature is lowest. Crystals are moved by the conveyors toward the product
end where they discharge into a vertical purifier column. At the bottom of the
column they are melted; part of the resulting liquid is withdrawn as product and
part flows upward through the column as reflux. In the purifier the reflux washes
the crystal surfaces to remove impurities; in addition, the crystals are held at their
melting point for a time to permit occluded impurities to migrate into the reflux.
By this means p-dichlorobenzene with a purity of over 99.9 percent can be
produced from a mixture of chlorobenzene isomers. The Brodie purifier is also
used commercially to reduce the thionaphthenate content of naphthalene from 2
to 0.2 to 0.4 percent, even though these compounds form solid solutions instead
of a eutectic mixture. Io
Other countercurrent devices and melt-refining techniques are described in
the literature.12c.30c
Feed
Purification
column Jacket
coolant pump
pr"'0"id",uC=t:::::;-=,,~_Crystal melter
FIGURE 27.17
The Brodie Purifier countercurrent cooling crystallizer. (c. W. No/singer Company.)
920 MASS TRANSFER AND ITS APPLICATIONS
SYMBOLS
Shape factor, defined by Eq. (27.16), dimensionless
Nucleation rate, number/cm 3-s or number/ft'-h
Frequency factor in nucleation, number/cm 3-s; also, mass produc-
tion rate of crystals, kg/h or lbfh
c Concentration of solution, mole/unit volume or g mOl/m 3; c" in
saturated solution
D. Diameter of particle, m or ft
E Energy of contact in contact nucleation, ergs
J Function of
G Growth rate of crystal, mfh or ftfh
H Enthalpy, J /g or Btuflb
K Overall mass-transfer coefficient, g mOl/m 2-h-unit mole fraction or
lb mOl/ft2-h-unit mole fraction
Dimensional constant in Eq. (27.45)
Coefficient of interfacial reaction, g mOl/m 2-h-unit mole fraction
or lb moljft2-h-unit mole fraction
k, Mass-transfer coefficient from solution to crystal face, g moljm 2_
h-unit mole fraction or lb moljft2-h-unit mole fraction
L Linear dimension or size of crystal, m or ft; L F , cut size in DDO
crystallizer; LT' maximum size; Lp,. predominant size
m Mass, g mol or lb mol; m" total mass of crystals per unit volume
of liquid
Molal growth rate, g molfh or lb molfh
Number of crystals of size L and smaller in crystallizer; N T, total
number of crystals in crystallizer
Molar flux, g mOl/m2-h or lb mOl/ft 2-h
Avogadro constant, 6.0222 x 1023 molecules/g mol
Population density defined by Eq. (27.22) number/m 4 or number/
ft4; n°, maximum value, for nuclei
n, Number of crystals per unit mass of crystals
Q Volumetric flow of liquid in product, m 3/h or ft3fh
R Gas constant, 8.3143 x 107 ergs/g mol-K
s Fractional supersaturation, defined by Eq. (27.7); lOOs, percent
supersaturation
Surface area of crystal, m 2 or ft2
Temperature, °C or OF; 7;, of growing crystal; T" of saturated
solution
t Time; tTo' turnover time between passages of a given crystal be-
tween contacts with rotating impeller
Age of crystal
Tip speed of impeller, m/s or ft/s
Volume, m 3 or ft3; volume of liquid in magma; v." total volume
of liquid in crystallizer
CRYSTALLIZATION 921
Molar volume, I/PM' cm 3/g mol or ft3jlb mol
Volume of crystal, m 3 or ft3
Distribution relation; XL' size distribution; X,p area distribution;
Xm, mass distribution; Xn , number distribution
y Mole fraction of solute in solution, at a distance from crystal face;
y" in saturated solution; y', at interface between crystal and liquid
Z Dimensionless length, L/G~; zP" predominant value
Abbreviations
CSD Crystal size distribution
DDO Double drawoff
DTB Draft tube-baffle type of crystallizer
MSMPR Mixed suspension-mixed product removal
Greek letters
Cl Concentration ratio, defined by Eq. (27.7)
!J.c Supersaturation, g mol/m3 or lb mol/ft 3
!J.L Increase in crystal size in time increment !!.t, m or ft
!J.n Increment of population density
!J.T Temperature driving potential, °C or of; !J.T" for crystallization;
!J. T", for heat transfer from crystal to liquid
!!.t Time increment, h or s
!J.y Supersaturation, mole fraction of solute
K Slope of temperature-concentration line
I' Distribution of crystals from idealized MSMPR plant; 1'0' num-
ber distribution; 1'" size distribution; 1'2' area distribution; 1'3,
mass distribution
Normalized jth moment of crystal distribution, defined by
Eq. (27.30)
V Number of ions per molecule of solute
PM Molar density of solution, g mol/cm 3 or lb mOl/ft 3; p" of crystal;
p" of saturated solution
Interfacial energy, ergs/cm 2
Apparent interfacial tension between nucleus and catalyst,
ergs/cm 2
Retention time of magma in crystallizer, h
Sphericity [Eqs. (27.1), (27.2)]
PROBLEMS
27.1. CuSO.· H20 containing 3.5 percent of a soluble impurity is dissolved contin-
uously in sufficient water and recycled mother liquor to make a saturated solu-
tion at 80°C. The solution is then cooled to 25°C and crystals of CuSO.· 5H,O
thereby obtained. These crystals carry 10 percent of their dry weight as adhering
922 MASS TRANSFER AND ITS APPLICATIONS
mother liquor. The crystals are then dried to zero free water (CuS04 ' 5H 2 0). The
allowable impurity in the product is 0.6 percent. Calculate (a) the weight of water
and of recycled mother liquor required per 100 kg of impure copper sulfate; (b) the
percentage recovery of copper sulfate, assuming that the mother liquor not recycled
is discarded. T;,e solubility of CuS04 ' 5H 2 0 at 80'C is 120 g per 100 g of free H 2 0
and at 25'C is 40 g per 100 g of free H 2 0.
27.2. A solution of MgS0 4 containing 43 g of solid per 100 g of water is fed to a vacuum
crystallizer at 220°F. The vacuum in the crystallizer corresponds to an H 2 0 boiling
temperature of 43°F, and a saturated solution of MgS0 4 has a boiling-point elevation
of 2°F. How much solution must be fed to the crystallizer to produce 900 kg of epsom
salt (MgS0 4 ' 7H,O) per hour?
27.3. An ideal product classification in a continuous vacuum crystallizer would achieve the
retention of all crystals within the crystallizer until they attained a desired size and
then discharge them from the crystallizer. 20 The size distribution of the product would
be uniform, and all crystals would have the same value of D p' Such a process conforms
to the other constraints for the mixed suspension-mixed product crystallizer except
that the magma in the unit is classified by size and each crystal has the same retention
or growth time. For such a process show that
Lp,
and '1:=-
4G
27.4. Assume that CuS04 ' 5H 2 0 is to be crystaIIized in an ideal product-classifying
crystalIizer. A lA-mm product is desired. The growth rate is estimated to be 0.2 pm/s.
The geometric constant a is 0.20, and the density of the crystal is 2300 kg/m3. A
magma consistency of 0.35 m 3 of crystals per cubic meter of mother liquor is to be
used. What is the production rate, in kilograms of crystals per hour per cubic meter
of mother liquor? What rate of nucleation, in number per hour per cubic meter of
mother liquor, is needed?
27.5. An MSMPR crystallizer produces 1 ton of product per hour having a predominant
size of 35 mesh. The volume of crystals per unit volume of magma is 0.15. The
temperature in the crystallizer is 120°F, and the retention time is 2.0 h. The densities
of crystals and mother liquor are 105 and 82.51b/ft', respectively. (a) Plot the
cumulative screen analysis of the theoretical product. (b) Determine the required
growth rate G and the necessary nucleation rate BO.
27.6. Results have been reported on the performance of a crystallizer operating on sodium
chloride. 1 Results from one experiment are
Tip speed UT ~ 1350 ft/min Retention time = 1.80 h
Time between passages, or turnover time = 35 s
Size-distribution parameters:
n° = 1.46 x 10 6 numberJcm4 B' ~ 1.84 number/cm'-s
Crystal density ~ 2.163 gjcm'
Calculate the dimensional constant K N , using the units specified above, and the
growth rate in mil1imeters per hour.
27.7. A potassium chloride crystallizer that operates at 100°F has a fines dissolution loop
where the slurry temperature is 130'F.'9 The solubility of KCl is 39.3 g/100 g H 20 at
CRYSTALLIZATION 923
loo"F and 44 gjloo g H 2 0 at 130"F. (a) If the solution is initially supersaturated by
1.0 g/IOO g and the temperature is suddenly increased to 130"F, how long would it
take to dissolve lO-.um crystals or 50-.um crystals if the change in solution concentra-
tion is neglected? (b) If the average crystal size in the fines loop is 200 flm and the
slurry has 30 g solid/L, how close to saturation would the solution be after 10 s at
130"F?
27.8. Crystallization of gypsum takes place in a 2oo,000-gal stirred tank that is part of a
process for flue-gas desulfurization. With a single outlet to a settling tank and filter,
the slurry has 15 weight percent CaS0 4 ' 2H 2 0 and a mean particle size of about
30.um. Pilot-plant tests under similar conditions 4 but with double drawoff and an
overflow-underflow ratio of 3.5 showed a bimodal size distribution with peaks at 20
and 50.um. The classification was made with hydroclones with a cut size of 30 .urn.
(a) What is the average residence time for large crystals with DDO operation relative
to the average residence time for MSMPR operation? (b) What evidence is there that
the supersaturation is different in the two modes of operation? (c) Estimate the density
of the overflow and underflow streams and the density of the combined streams.
27.9. Use the moment equations for constant growth rate in a MSMPR crystallizer to
calculate (a) the surface-volume mean size and (b) the mass average size. (c) Compare
these values with the sizes where a maximum occurs in the corresponding distribution
curves.
REFERENCES
1. Bennett, R. C., H. Fiedelman, and A. D. Randolph: Chem. Eng. Prog., 69(7):86 (1973).
2. Bichowsky, F. R., and F. D. Rossini: Thermochemistry 0/ Chemical Substances, Reinhold, New
York, 1936.
3. Buckley, H. E.: Crystal Growth, Wiley, New York, 1951.
4. Chang, J. C. S., and T. G. Brna: Chem. E"g. Prog., 82(11):51 (1986).
5. Clontz, N. A., and W. L. McCabe: AIChE Symp. Ser., No. 110,67:6 (1971).
6. Johnson, R. T., R. W. Rousseau, and W. L. McCabe: AIChE Symp. Ser., No. 121,68:31 (1972).
7. La Mer, V. K.: Ind. Eng. Chem., 44:1270 (1952).
8. McCabe, W. L.: Ind. Eng. Chem., 21:30, 121 (1929).
9. McCabe, W. L., in J. C. Perry (ed.), Chemical Engineers' Handbook, 3rd ed., McGraw-Hill, New
York, 1950, p. 1056.
10. Meyer, D. W.: Chem. Proc., 53(1):50 (1990).
11. Ottens, E. P. K.: Nucleation in Continuous Agitated Crystallizers, Technological University, Delft,
1972
12. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-HiII, New York, 1984; (a) pp.
3-97 to 3-100; (b) pp. 11-43 to 11-45; (c) pp. 17-4 to 17-12.
13. Powers, H. E. c.: I"d. Chem., 39:351 (1963).
14. Preckshot, G. W., and G. G. Brown: Ind. Eng. Chem., 44:1314 (1952).
15. Randolph, A. D.: AIChE J., 11 :424 (1965).
16. Randolph, A. D.: private communication, 1991.
17. Randolph, A. D., and M. A. Larson: AIChE J., 8:639 (1962).
18. Randolph, A. D., and M. A. Larson: Theory 0/ Particulate Processes, Academic, New York, 1971.
19. Randolph, A. D., E. T. White, and C. ~C. D. Low: Ind. Eng. Chem. Proc. Des. Dev., 20:496 (1981).
20. Saeman, W. c.: AIChE J., 2: 107 (1956).
21. Seidell, A.: Solubi/ities, 3rd ed., Van Nostrand, Princeton, NJ, 1940 (supplement, 1950).
22. Strickland~Constable, R. F.: Kinetics and Mechanism o/Crystallization, Academic, New York, 1968.
23. Strickland~Constable, R. F., and R. E. A. Mason: Nature, 197:4870 (1963).
924 MASS TRANSFER AND ITS APPLICATIONS
24. Strickland~Constable, R. F.: AIChE Symp. Ser., No. 121,68:1 (1972).
25. Sung, C. Y., J. Estrin, and G. R. Youngquist: AfClrE J., 19:957 (1973).
26. Sutradhar, B. c., and A. D. Randolph: unpublished manuscript, Chemical Engineering Department,
University of Arizona. Tucson, AZ, 1991.
27. Tai, C. Y., W. L. McCabe, and R. W. Rousseau, AfChE J., 21:351 (1975).
28. Ting, H. H., and W. L. McCabe: lnd Eng. Chem., 26: 1201 (1934).
29. VanHook, A.: Crystallization, Theory and Practice, Wiley, New York, 1951.
30. Walas, S. M.: Chemical Process Equipment, Butterworths, Stoneham, MA, 1988; (a) p. 533; (b) p.
535; (c) pp. 543-548.
31. Walton, A. G.: Science, 148:601 (1965).
32. White, E. T., and A. D. Randolph: lnd. Eng. Chem. Res., 28(3):276 (1989).
SECTION
V
OPERATIONS
INVOLVING
PARTICULATE
SOLIDS
S olids, in general, are more difficult to handle than liquids or gases. In
processing, solids appear in a variety of forms-angular pieces, continuous
sheets, finely divided powders. They may be hard and abrasive, tough and
rubbery, soft or fragile, dusty, cohesive, free flowing, or sticky. Whatever their
form, means must be found to manipulate the solids as they occur and, if possible,
to improve their handling characteristics.
As mentioned in Chap. 27, solids in chemical processes are most commonly
in the form of particles. This section is concerned with the properties, modification,
and separation of particulate solids. General properties, handling, and mixing are
discussed in Chap. 28, size reduction in Chap. 29, and mechanical separations in
Chap. 30.
925
CHAPTER
28
PROPERTIES,
HANDLING,
AND MIXING
OF PARTICULATE
SOLIDS
Of all the shapes and sizes that may be found in solids, the most important from
a chemical engineering standpoint is the small particle. An understanding of the
characteristics of masses of particulate solids is necessary in designing processes
and equipment for dealing with streams containing such solids.
CHARACTERIZATION OF SOLID
PARTICLES
Individual solid particles are characterized by their size, shape, and density.
Particles of homogeneous solids have the same density as the bulk material.
Particles obtained by breaking up a composite solid, such as a metal-bearing ore,
have various densities, usually different from the density of the bulk material. Size
and shape are easily specified for regular particles, such as spheres and cubes, but
for irregular particles (such as sand grains or mica flakes) the terms size and shape
are not so clear and must be arbitrarily defined.
927
928 OPERATIONS INVOLVING PARTICULATE SOLIDS
PARTICLE SHAPE. As discussed iu Chap. 7, the shape of an individual particle
is conveniently expressed in terms of the sphericity <1>" which is independent of
particle size. For a spherical particle of diameter Dp, <1>, = 1; for a nonspherical
particle, the sphericity is defined by the relation
<I> = 6vp (28.1)
S - Dpsp
where D p = equivalent diameter or nominal diameter of particle
sp = surface area of one particle
vp = volume of one particle
The equivalent diameter is sometimes defined as the diameter of a sphere of
equal volume. For fine granular materials, however, it is difficult to determine the
exact volume and surface area of a particle, and Dp is usually taken to be the
nominal size based on screen analyses or microscopic examination. The surface
area is found from adsorption measurements or from the pressure drop in a bed
of particles, and then Eq. (28.1) is used to calcnlate <1>,. For many crushed materials
<1>, is between 0.6 and 0.8, as shown in Table 28.1, but for particles rounded by
abrasion <1>, may be as high as 0.95.
For cubes and cylinders for which the length L equals the diameter, the
equivalent diameter is greater than Land <1>, found from the equivalent diameter
would be 0.81 for cubes and 0.87 for cylinders. It is more convenient to use the
nominal diameter L for these shapes since the surface-to-volume ratio is 6/Dp, the
same as for a sphere, and this makes <1>, equal to 1.0. For column packiugs such
as rings and saddles the nominal size is also used in defining <1>,.
PARTICLE SIZE. In general, "diameters" may be specified for any equidimen-
sional particle. Particles that are not equidimensional, i.e., that are longer in one
direction than in others, are often characterized by the second longest major
dimension. For needlelike particles, for example, Dp would refer to the thickness
of the particles, not their length.
TABLE 28.1
Sphericity of miscellaneous materialst
Material Sphericity Material Sphericity
Spheres, cubes, short Ottawa sand 0.95
cylinders (L = Dp) 1.0 Rounded sand 0.83
Raschig rings (L = Dp) Coal dust 0.73
L = D", Dj = O.5D" 0.58t Flint sand 0.65
L = D", Dj = O.75D" 0.33t Crushed glass 0.65
Berl saddles 0.3 Mica flakes 0.28
tBy permission, from J. H. Perry (ed.), Chemical Engineers' Handbook, 6th ed., p. 5-54,
McGraw-HilI Book Company, New York, 1984.
t Calculated value.
PROPERTIES. HANDLING. AND MIXING OF PARTICULATE SOLIDS 929
By convention, particle sizes are expressed in different units depending on
the size range involved. Coarse particles are measured in inches or millimeters;
fine particles in terms of screen size; very fine particles in micrometers or
nanometers. Ultrafine particles are sometimes described in terms of their surface
area per unit mass, usually in square meters per gram.
MIXED PARTICLE SIZES AND SIZE ANALYSIS. In a sample of uniform particles
of diameter Dp the total volume of the particles is m/pp, where m and Pp are the
total mass of the sample and the density of the particles, respectively. Since the
volume of one particle is vp ' the number of particles in the sample N is
m
N=- (28.2)
Ppvp
The total surface area of the particles is, from Eqs. (28.1) and (28.2),
6m
A=Ns
p
=-=-
QJsppDp
(28.3)
To apply Eqs. (28.2) and (28.3) to mixtures of particles having various sizes and
densities, the mixture is sorted into fractions, each of constant density and
approximately constant size. Each fraction can then be weighed, or the individual
particles in it can be counted or measured by anyone of a number of methods.
Equations (28.2) and (28.3) can then be applied to each fraction and the results
added.
Information from such a particle-size analysis is tabulated to show the mass
or number fraction in each size increment as a function of the average particle
size (or size range) in the increment. An analysis tabulated in this way is called a
differential analysis. The results are often presented as a histogram, as shown in
Fig. 28.1a, with a continuous curve like the dashed line used to approximate the
distribution. A second way to present the information is through a cumulative
analysis obtained by adding, consecutively, the individual increments, starting with
that containing the smallest particles, and tabulating or plotting the cumulative
0.25 0
£
o
,t
i=
0.2 0
0.1 5
~
0
0
V- -- I--
u
~ 0.1 0 0
~
1- ho I1
~ 0.05
I l -,;. oJ
"
:::2!
0
0 10 20 30 40 50 60 70 80 90
PARTICLE SIZE, /-Im
0
o 10 20 30 40 50 60 7
PARTICLE SIZE, /-Im
80 9 o
(al (bl
FIGURE 28.1
Particle-size distribution for powder: (a) differential analysis; (b) cumulative analysis.
930 OPERATIONS INVOLVING PARTlCULATE SOLIDS
sums against the maximum particle diameter in the increment. Figure 28.1b is a
cumulative-analysis plot of the distrihution shown in Fig. 28.10. In a cnmulative
analysis the data may appropriately he represented by a continuous curve.
Calculations of average particle size, specific surface area, or particle popula-
tion of a mixture may be based on either a differential or a cumulative analysis.
In principle, methods based on the cumulative analysis are more precise than those
based on the differential analysis, since when the cumulative analysis is used, the
assumption that all particles in a single fraction are equal in size is not needed.
The accuracy of particle-size measurements, however, is rarely great enough
to warrant the use of the cumulative analysis, and calculations are nearly always
based on the differential analysis.
SPECIFIC SURFACE OF MIXTURE. If the particle density Pp and sphericity <1\
are known, the surface area of the particles in each fraction may be calculated
from Eq. (28.3) and the results for all fractions added to give Aw, the specific
surface (the total surface area of a unit mass of particles). If Pp and <il, are constant,
Aw is given by
6
= (f)spp
±
1=1
Xi
DpI
(28.4)
where subscripts = individual increments
XI = mass fraction in a given increment
n = number of increments
15pi = average particle diameter, taken as arithmetic average of
smallest and largest particle diameters in increment
AVERAGE PARTICLE SIZE. The average particle size for a mixture of particles
is defined in several different ways. Probably the most used is the volume-surface
mean diameter 15" which is related to the specific surface area Aw. [See Eqs.
(7.23), (7.24), and (9.40).] It is defined by the equation
_ 6
D, '" -=---,--- (28.5)
<l>sAwpp
Substitution from Eq. (28.4) in Eq. (28.5) gives
15 = _ _1_ _
(28.6)
, "
L (xJ15pi )
i=1
This is the same as Eq. (7.24).
If the number of particles in each fraction Ni is known instead of the mass
fraction, 15, is given by Eq. (7.23).
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 931
Other averages are sometimes useful. The arithmetic mean diameter DN is
(28.7)
where N T is the number of particles in the entire sample.
The mass mean diameter Dw is found from the equation
Dw = L" xjDpi (28.8)
1=1
Dividing the total volume of the sample by the number of particles in the
mixture (see below) gives the average volume of a particle. The diameter of such
a particle is the volume mean diameter Dy, which is found from the relation
Dy = [ 1 ] 1/3 (28.9)
it, (xJD!i)
For samples consisting of uniform particles these average diameters are, of
course, all the same. For mixtures containing particles of various sizes, however,
the several average diameters may differ widely from one another.
NUMBER OF PARTICLES IN MIXTURE. To calculate, from the differential
analysis, the number of particles in a mixture, Eq. (28.2) is used to compute the
number of particles in each fraction, and Nw, the total population in one mass
unit of sample, is obtained by summation over all the fractions. Fot a given particle
shape, the volume of any particle is proportional to its "diameter" cubed, or
vp -- aD3p (28.10)
where a is the volume shape factor. From Eq. (28.2), then, assuming that a is
independent of size,
1 "x· 1
Nw = - L: -; =---;<,
ap p i=1 Dpj appvy
(28.11)
The specific surface area, the various average diameters, and the number of
particles are readily calculated from the particle-size analyses through the use of
simple computer programs. Many measuring instruments for very fine particles
are programmed to report these quantities directly.
SCREEN ANALYSIS; STANDARD SCREEN SERIES. Standard screens are used to
measure the size (and size distribution) of particles in the size range between about
3 and 0.0015 in. (76 mm and 38 I'm). Testing sieves are made of woven wire screens,
the mesh and dimensions of which are carefully standardized. The openings are
square. Each screen is identified in meshes per inch. The actual openings are
smaller than those corresponding to the mesh numbers, however, because of the
thickness of the wires. The characteristics of one common series, the Tyler standard
932 OPERATIONS INVOLVING PARTICULATE SOLIDS
screen series, are given in Appendix 20. This set of screens is based on the opening
of the 200-mesh screen, which is established at 0.074 mm. The area of the openings
in anyone screen in the series is exactly twice that of the openings in the next
smaller screen. The ratio of the actual mesh dimension of any screen to that of
the next smaller screen is, then, j2 = 1.41. For closer sizing, intermediate screens
are available, each of which has a mesh dimension 12,
or 1.189, times that of the
next smaller standard screen. Ordinarily these intermediate screens are not used.
In making an analysis a set of standard screens is arranged serially in a stack,
with the smallest mesh at the bottom and the largest at the top. The sample is
placed on the top screen and the stack shaken mechanically for a definite time,
perhaps 20 min. The particles retained on each screen are removed and weighed,
and the masses of the individual screen increments are converted to mass fractions
or mass percentages of the total sample. Any particles that pass the finest screen
are caught in a pan at the bottom of the stack.
The results of a screen analysis are tabulated to show the mass fraction of
each screen increment as a function of the mesh size range of the increment. Since
the particles on anyone screen are passed by the screen immediately ahead of it,
two numbers are needed to specify the size range of an increment, one for the
screen through which the fraction passes and the other on which it is retained.
Thns, the notation 14/20 means "through 14 mesh and on 20 mesh."
A typical screen analysis is shown in Table 28.2. The first two columns give
the mesh size and width of opening of the screens; the third column is the mass
fraction of the total sample that is retained on the designated screen. This is Xi,
where i is the number of the screen starting at the bottom of the stack; thus i = 1
for the pan, and screen i + 1 is the screen immediately above screen i. The symbol
D pi means the particle diameter equal to the mesh opening of screen i.
TABLE 28.2
Screen analysis
Average particle Cumulative
Screen opening Mass fraction diameter in fraction
Mesh Dpi,mm retained, Xit increment, Dpil mm smaller than Dpi
4 4.699 O.OC\lO 1.0000
6 3.327 0.0251 4.013 0.9749
8 2.362 0.1250 2.845 0.8499
10 1.651 0.3207 2.007 0.5292
14 1.168 0.2570 1.409 0.2722
20 0.833 0.1590 1.001 0.1132
28 0.589 0.0538 0.711 0.0594
35 0.417 0.0210 0.503 0.0384
48 0295 0.0102 0356 0.0282
65 0.208 0.0077 0.252 0.0205
100 0.147 0.0058 0.178 0.0147
150 0.104 0.0041 0.126 0.0106
200 0.074 0.0031 0.089 0.0075
Pan 0.0075 0.037 0.0000
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 933
The last two columns in Table 28.2 show the average particle diameter [jp, in
each increment and the cumulative fractiou smaller than each value of D p " In
screen analyses cumulative fractions are sometimes written starting at the top of
the stack and are expressed as the fraction larger than a given size.
A differential plot of the data in columns 2 and 3 of Table 28.2 gives a false
impression of the particle-size distribution because the range of particle sizes
covered differs from increment to increment. Less material is retained in an
increment when the particle-size range is narrow than when it is wide. In Fig. 28.1
the ranges were all equal and the data could be plotted directly. Here, however,
a fairer picture of the distribution is given by a plot of xJ(D p ' + 1 - D p ')' where
D p'+l - D p' is the particle-size range in increment i. This is illustrated by Fig.
28.2a and b, which are direct and adjusted differential plots for the 20(28-mesh and
smaller particle sizes in Table 28.2.
,t
g0.04f----+---f----
~
'"u.~ 0.021----+---+
'"
PARTICLE SIZE, D p ' mm
(a)
E-
E
ffi~0.2+---1----+---
0. Cl'
oZ ,_
t= :t
" Cl'
~:::;.
u.. loo( o.
~
'" FIGURE 28.2
Differential screen analyses: (a) direct plot
PARTICLE SIZE, Dp , mm from Table 28.2; (b) plot adjusted for size
(b) range of increment.
934 OPERATIONS INVOLVING PARTlCULATE SOLIDS
Cl"" 1.0
,,0-
z
«
:I:
I-
oo 0 .8
W
.J
.J
11
f
«
'"'oz" O. 6
1
~
«
oo !
u. O. 4
~
'"
w
>
3o. 2
1/
::J
f.-
'"
::J
U 0
0.05 0.1 1.0 5.0
PARTICLE DIAMETER, Dp , mm
FIGURE 28.3
Cumulative screen analysis.
Cumulative plots are made from results like those in columns 2 and 5 of
Table 28.2. When the overall range of particle size is large, such plots often show
the diameter on a logarithmic scale. A semilogarithmic cumulative plot of the
analysis shown in Table 28.2 is given in Fig. 28.3. Cumulative plots may also be
made on logarithmic probability paper on which the abscissa scale is divided in
accordance with a Gaussian probability distribution. Size analyses of the product
from a crusher or grinder often give linear plots on such paper, at least over much
of the particle-size range.
SIZE MEASUREMENTS WITH FINE PARTICLES. Dry screening is useful for
sizing particles with diameters greater than about 44 I'm (325-mesh); wet-screen
analysis can be used for diameters down to 10 I'm. Particles finer than this can
be measured in a variety of ways. Optical microscopy and gravity sedimentation
are used with particles 1 to 100 I'm in diameter, as is the Coulter counter, a device
that measures changes in the resistivity of an electrolyte as it carries the particles
one by one through a small orifice. Light-scattering techniques, sedimentation in
centrifuges or ultracentrifuges, and electron microscopy are useful with even finer
particles?'
Example 28.1. The screen analysis shown in Table 28.2 applies to a sample of crushed
quartz. The density of the particles is 2650 kg/m' (0.00265 g/mm'), and the shape
factors are a = 2 and <PS" = 0.571. For the material between 4-mesh and 200-mesh in
particle size, calculate (a) Aw in square millimeters per gram and Nw in particles per
gram, (b) Dv, (c) D" (d) D.. and (e) Ni for the 150/2oo-mesh increment. (f) What
fraction of the total number of particles is in the 150/200-mesh increment?
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 935
Solution
To find Aw and Nw> Eq. (28.4) can be written
6 Xi Xi
Aw= • L:-=-=3965L:-
0.511 x 0.00265 D" 15"
and Eq. (28.11) as
1 x· x·
Nw = L: -;
2 x 0.00265 D"
= 188.7L: -;
D"
(a) For the 4/6-mesh increment J5 pi is the arithmetic mean of the mesh openings
of the defining screens, or, from Table 28.2, (4.699 + 3.327)/2 = 4.013 mm. For this
increment x, = 0.0251; hence x,f15" = 0.0251/4.013 = 0.0063 and x,15;, = 0.0004.
Corresponding quantities are calculated for the other 11 increments and summed to
give L: x,f15" = 0.8284 and L: x,f15;, = 8.8296. Since the pan fraction is excluded, the
specific surface and number of particles per unit mass of particles 200-mesh or larger
are found by dividing the results from Eqs. (28.4) and (28.11) by 1 - x, (since i = 1
for the pan), or 1 - 0.0075 = 0.9925. Then
3965 x 0.8284
0.9925
188.7 x 8.8296
Nw = = 1679 particles/g
0.9925
(b) From Eq. (28.9),
_ 1
Dv = 1/' = 0.4238 mm
8.8296
(c) The volume-surface mean diameter is found from Eq. (28.6):
_ 1
D, = - - = 1.207 mm
0.8284
(d) Mass mean diameter 15w is obtained from Eq. (28.8). For this, from the data
in Table 28.2,
L: x,15" = 15w = 1.677 mm
(e) The number of particles in the 150/200-mesh increment is found from Eq.
(28.11):
x, 0.0031
N 2 =---=3
ap,D" 2 x 0.00265 X 0.089'
= 836 particles/g
This is 836/1679 = 0.498, or 49.8 percent of the particles in the top 12 increments.
For the material in the pan fraction the number of particles and specific surface area
are enormously greater than for the coarser material, but they cannot be accurately
estimated from the data in Table 28.2.
936 OPERATIONS INVOLVING PARTICULATE SOLIDS
PROPERTIES OF PARTICULATE MASSES
Masses of solid particles, especially when the particles are dry and not sticky, have
many of the properties of a flnid. They exert pressure on the sides and walls of a
container; they flow through openings or down a chute. They differ from liquids
and gases in several ways, however, because the particles interlock under pressure
and cannot slide over one another until the applied force reaches an appreciable
magnitude. Unlike most fluids, granular solids and solid masses permanently resist
distortion when subjected to a moderate distorting force. When the force is large
enough, failure occurs and one layer of particles slides over another, but between
the layers on each side of the failure there is appreciable friction.
Solid masses have the following distinctive properties:
1. The pressure is not the same in all directions. In general, a pressure applied in
one direction creates some pressure in other directions, but it is always smaller
than the applied pressure. It is a minimum in the direction at right angles to
the applied pressure.
2. A shear stress applied at the surface of a mass is transmitted throughout a static
mass of particles unless failure occurs.
3. The density of the mass may vary, depending on the degree of packing of the
grains. The density of a fluid is a unique function of temperature and pressure,
as is that of each individual solid particle; but the bulk density of the mass is
not. The bulk density is a minimum when the mass is "loose"; it rises to a
maximum when the mass is packed by vibrating or tamping.
4. Before a mass of tightly packed particles can flow, it must increase in volume
to permit interlocking grains to move past one another. Without such dilation
flow is not possible.
Depending on their flow properties, particulate solids are divided into two
classes, cohesive and noncohesive. Noncohesive materials like grain, dry sand, and
plastic chips readily flow out of a bin or silo. Cohesive solids, such as wet clay,
are characterized by their reluctance to flow through openings.
PRESSURES IN MASSES OF PARTICLES. The minimum pressure in a solid mass
is in the direction normal to that of the applied pressure. In a homogeneous mass
the ratio of the normal pressure to the applied pressure is a constant 1(', which is
characteristic of the material. It depends on the shape and interlocking tenden-
cies of the particles, on the stickiness of the grain surfaces, and.on the degree of
packing of the material. It is nearly independent of particle size until the grains
become very small and the material is no longer free-flowing.
If the applied pressure is Pv and the normal pressure is PL, the pressure P
at any intermediate angle can be found as follows. A right-angled triangular
differential section of thickness b and hypotenuse dL is shown in Fig. 28.4a.
Pressure Pv acts on the base, PL on the side, and P on the hypotenuse. The angle
PROPERTIES, HANDLING, AND MIXING OF PARTlCULATE SOLIDS 937
PLb dL sin 9
8
P b dL sin 2 9
L
Pvb dL cos 9 Sin 9
(a) (b)
FIGURE 28.4
Stresses and forces in granular solids: (0) stresses; (b) forces.
between base and hypotenuse is e. At equilibrium the unequal pressures py and
PL cannot be balanced by a single pressure P; there must also be a shear stress <.
The forces resulting from these stresses are shown in Fig. 28.4h.
Equating the components of force at right angles to the hypotenuse gives
e + pyb dL cos e
ph dL = PLb dL sin2 2
(28.12)
Dividing by h dL and noting that sin e = 1 - cos e lead to
2 2
p = (py - pJ cos e + PL 2
(28.13)
Similarly equating for;;es parallel to the hypotenuse gives
< = (py - PL) cos e sin e (28.14)
When e = 0, P = py; when e = 90°, P = PLo In both these cases < = O. When
e has an intermediate value, there is a shear stress at right angles to p. If
e,
corresponding values ofP and < are plotted for all possible values of the resulting
graph is a circle with a radius (py - pJ/2 and its center on the horizontal axis at
P = (py + pJ/2. Such a graph is shown in Fig. 28.5; it is known as the Mohr stress
circle. 12
The ratio of < to P for any value of eis the tangent of an angle" formed by
the p axis and the line OX through the origin and the point (p, <). As increases e
from 0 to 90°, the ratio of < to p rises to a maximum and then diminishes. It is a
maximum when the line through the origin is tangent to the stress circle, as shown
by the line OA in Fig. 28.5. Under these conditions" has a maximum value "m.
938 OPERATIONS INVOLVING PARTICULATE SOLIDS
PRESSURE - p
FIGURE 28.5
Mohr stress diagram for noncohesive solids.
From Fig. 28.5 it may be seen that
.
Slna = (Pv - PL) = Pv - h (28.15)
m (Pv+h)/2 Pv+h
The lines OA and OB are tangent to all the stress circles for any value of
Pv provided the material is noncohesive. They form the Mohr rupture envelope.
With cohesive solids or solid masses the tangents forming the envelope do not
pass through the origin but intercept the vertical axis at points above and below
the horizontal axis. s
The ratio of the normal pressure to the applied pressure pJpv equals K. Then
l-K'
sina =--- (28.16)
m 1 +K'
K' = 1 - sin am
Also (28.17)
1 + sin am
Angle of internal friction and angle of repose. The angle "m
is the angle of internal
friction of the material. The tangent of this angle is the coefficient of friction
between two layers of particles. When granular solids are piled up on a flat surface,
the sides of the pile are at a definite reproducible angle with the horizontal. This
angle, "" is the angle of repose of the material. Ideally, if the mass were truly
homogeneous, et, would equal "m. In practice, the angle of repose is smaller than
the angle of internal friction because the grains at the exposed surface are more
loosely packed than those inside the mass and are often drier and less sticky. The
angle of repose is low when the grains are smooth and rounded; it is high with
PROPERTIES, HANDLING, AND MIXING OF PARTfCULATE SOLIDS 939
very fine, angular, or sticky particles. The value of K approaches zero for a
cohesive solid. For free-flowing granular materials K is often between 0.35 and
0.6, which means that am is between 15° and 30°.
Storage of Solids
BULK STORAGE. Coarse solids like gravel and coal are stored outside in large
piles, unprotected from the weather. When hundreds or thousands of tons of
material are involved, this is the most economical method. The solids are removed
from the pile by dragline or tractor shovel and delivered to a conveyor or to the
process. Outdoor storage can lead to environmental problems such as dusting or
leaching of soluble material from the pile. Dusting may necessitate a protective
cover of some kind for the stored solid; leaching can be controlled by cover-
ing the pile or by locating it in a shallow basin with an impervious floor from
which the runoff may be safely withdrawn.
BIN STORAGE. Solids that are too valuable or too soluble to expose in outdoor
piles are stored in bins, hoppers, or silos. These are cylindrical or rectangular
vessels of concrete or metal. A silo is tall and relatively small in diameter; a bin
is not so tall and usually fairly wide. A hopper is a small vessel with a sloping
bottom, for temporary storage before feeding solids to a process. All these
containers are loaded from the top by some kind of elevator; discharging is
ordinarily from the bottom. As discussed later, a major problem in bin design
is to provide satisfactory discharge.
Pressures in bins and silos. When granular solids are placed in a bin or silo, the
lateral pressure exerted on the walls at any point is less than predicted from the
head of material above that point. Furthermore there usually is friction between
the wall and the solid grains, and because of the interlocking of the particles, the
effect of this friction is felt throughout the mass. The frictional force at the wall
tends to offset the weight of the solid and reduces the pressure exerted by the mass
on the floor of the container.
The vertical pressure on the vessel floor or the packing support is much
smaller than that exerted by a column ofliquid of the same density and height. The
actual pressure from the solids depends on the value of K for the solids, the
coefficient of friction between the solids aud the vessel wall, and the way the solids
are placed in the vessel. In general, when the height of the solids column is greater
than about three times the diameter of the container, additional solids have no
effect on the pressure at the base. The total mass, of course, increases if more solids
are added, but the additional mass is carried by the walls and foundation, uot by
the floor of the vessel.
In granular solids a high pressure does not always iucrease the tendency of
the material to flow, as it does in a liquid; instead, increased pressure often packs
940 OPERATIONS INVOLVING PARTICULATE SOLIDS
the grains more tightly together and makes flow more difficult. In extreme cases
the combination of gravitational and frictional forces at some point in the
container causes the solids to arch or bridge, so that they do not fall even
when the material below them is removed. Nearly all large bins contain an
archbreaker, an upward-pointing shallow metal cone set near the bottom to keep
the solids at the discharge opening from becoming tightly packed. Granular solids,
especially with angular particles, must be loose in order to flow.
FLOW OUT OF BINS. Solids tend to flow out of any opening near the bottom of
a bin but are best discharged through an opening in the floor. Flow through a side
opening tends to be uncertain and increases the lateral pressure on the other side
of the bin while the solids are flowing. A bottom outlet is less likely to' clog and does
not induce abnormally high pressures on the wall at any point.
Except in very small bins it is not feasible to open the entire bottom for
discharge. Commonly a conical or pyramidal hopperlike section is set at the
bottom of the bin,leading to a fairly small outlet that can be closed with a valve.
Factors influencing the flow of solids out of bins have been studied by lenike
et al. 5 When the outlet at the bottom of a bin containing free-flowing solids is
opened, the material immediately above the opening begins to flow. One of two
flow patterns will develop, depending on the steepness of the walls in the bottom
section of the bin and on the coefficient of friction between the solids and the bin
walls?' Mass flow occurs in cone-bottomed bins with a tall, steep cone; all the
material moves downward uniformly from the top of the bin. Tunnel flow develops
in bins with a shallow cone angle or with vertical walls and a central opening in the
floor. Here a vertical column of solids above the opening moves downward without
disturbing the material at the sides. Eventually lateral flow begins, first from the
topmost layer of solids. A conical depression is formed in the surface of the mass.
The solids at the bin floor, at or near the walls, are the last to leave. The material
slides laterally into the central column at an angle approximating the angle of
internal friction of the solids. If additional material is added at the top of the bin
at the same rate as material is flowing out the bottom, the solids near the bin
walls remain stagnant and do not discharge no matter how long flow persists.
During flow the pressure in the solids increases from zero (atmospheric) at
the top surface to a maximum at the top of the hopper section, then drops to zero
at the discharge. (See Ref. 9c.) Arching is especially likely to occur in the hopper
section.
The rate of flow of granular solids by gravity through a circular opening in
the bottom of a bin depends on the diameter of the opening and on the
properties of the solid. Within wide limits it does not depend on the height of the
bed of solids. With free-flowing particles the rate of solids flow, rn, varies with
D~, where D, is the diameter of the discharge opening.
Exponent n varies from about 2.8 for angular particles to about 3.1 for
spheres. Detailed studies of the flow of particles through openings have been made
by Laforge and Boruff 6 and by Smith and Hattiangadi. 11
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 941
With cohesive solids it is often hard to start flow. Once flow does start,
however, it again begins in the material directly above the discharge opening.
Frequently the column of solids above the outlet moves out as a plug, leaving a
"rathole" with nearly vertical sides. Sticky solids and even some dry powders
adhere strongly to vertical surfaces and have enough shear strength to support a
plug of considerable diameter above an open discharge. Thus to get flow started
and to keep the material moving, vibrators on the bin walls, internal plows near
the bin floor, or jets of air in the discharge opening are often needed.
The discharge opening should be small enough to be readily closed when
solids are flowing yet not so small that it will clog. It is best to make the opening
large enough to pass the full desired flow when half open. It can then be opened
further to clear a partial choke. If the opening is too large, however, the shutoff
valve may be hard to close and control of the flow rate will be poor.
CONVEYORS. Pneumatic conveyors for solids are described in Chap. 7. Other
common devices for transportation include belt conveyors and bucket elevators,
closed-belt conveyors with zipperlike fasteners, and various kinds of drag and
flight conveyors. These all include a return leg that carries the empty belt or chain
back from the discharge to the loading point. Vibrating conveyors and screw
conveyors have no return leg but only operate over relatively short distances.
Pneumatic conveyors also have no return leg and are not so limited as to distance
of travel. Conveyors for solids are discussed in Ref. 9a.
MIXING OF SOLIDS
The mixing of solids, whether free flowing or cohesive, resembles to some extent
the mixing of low-viscosity liquids. Both processes intermingle two or more
separate components to form a more or less uniform product. Some of the
equipment normally used for blending liquids may, on occasion, be used to mix
solids.
Yet there are significant differences between the two processes. Liquid
blending depends on the creation of flow currents, which transport unmixed
material to the mixing zone adjacent to the irnpeller. In heavy pastes or masses
of particulate solids no such currents are possible, and mixing is accomplished by
other means. In consequence, much more power is normally required in mixing
pastes and dry solids than in blending liquids.
Another difference is that in blending liquids a "well-mixed" product usually
means a truly homogeneous liquid phase, from which random samples, even of
very small size, all have the same composition. In mixing pastes and powders the.
product often consists of two or more easily identifiable phases, each of which
may contain individual particles of considerable size. From a "well-mixed"
product of tlus kind small random samples will differ markedly in composition;
in fact, samples from any given such mixture must be larger than a certain critical
size (several times the size of the largest individual particle in the mix) if the results
are to be significant.
942 OPERAT.IONS INVOLVING PARTICULATE SOLIDS
Mixing is harder to define and evaluate with solids and pastes than it is with
liquids. Quantitative measures of mixing are discussed later in this chapter,
measures that aid in evaluating mixer performance, but in actual practice the proof
of a mixer is in the properties of the mixed material it produces. A well-mixed
product is one that does what is required and has the necessary property-visual
uniformity, high strength, uniform burning rate, or other desired characteristic. A
good mixer is one that produces this well-mixed product at the lowest overall cost.
Mixing heavy pastes, plastic solids, and rubber is more of an art than a
science. The properties of the materials to be mixed vary enormously from one
process to another. Even in a single material they may be widely different at various
times during the mixing operation. A batch may start as a dry, free-flowing powder,
become pasty on the addition of liquid, stiff and gummy as a reaction proceeds,
and then perhaps dry, granular, and free flowing once more. Indeterminate
properties of the material such as "stiffness," "tackiness," and wettability are as
significant in these mixing problems as viscosity and density. Mixers for pastes
and plastic masses must, above all, be versatile. In a given problem the mixer
chosen must handle the material when in its worst condition and may not be so
effective as other designs during other parts of the mixing cycle. As with other
equipment, the choice of a mixer for heavy materials is often a compromise.
Types of Mixers
Mixers for dry powders include some machines that are also used for heavy pastes
and some machines that are restricted to free-flowing powders. Mixing is by
slow-speed agitation of the mass with an impeller, by tumbling, or by centrifugal
smearing and impact. These mixers are of fairly light construction, and their power
consumption per unit mass of material mixed is moderate.
In mixing equipment for pastes, rubber, and heavy plastic masses the material
must all be brought to the agitator or the agitator must visit all parts of the mix.
The action in this machinery is well described as a "combination of low-speed
shear, smearing, wiping, folding, stretching, and compressing. ,,2 The mechanical
energy is applied by moving parts directly to the mass of material. In the closed
type, such as Banbury mixers, the inner wall of the casing acts as part of the
mixing means, and all mixing action occurs close to the moving parts. Clearances
between mixing arms, rotors, and wall of casing are small. The forces generated
in these mixers are large, the machinery must be ruggedly built, and the power
consumption is high. The heat evolved per unit mass of material may be sufficient
to require cooling to prevent the temperature from reaching a level dangerous to
the equipment or the material.
The boundaries between the fields of application of the various types of
mixers are not sharp. Impeller mixers of the kind described in Chap. 9 are not
often used when the viscosity is more than about 2 kP, especially if the liquid is
not newtonian. Kneaders and mixer-extruders work on thick pastes and plastic
masses; impact wheels are restricte4 to dry powders. Other mixers, however, can
blend liquids, pastes, plastic solids, and powders.
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 943
MIXERS FOR COHESIVE SOLIDS
Some of the most difficult of all mixing problems involve cohesive solids such as
pastes, plastic materials, and rubber. In some ways these substances resemble
liquids, but their enormously high viscosity means that the mixing equipment must
be different from and much more powerful than the mixers described in Chap. 9.
With cohesive solids the mixing elements cannot generate flow currents; instead
they shear, fold, stretch, and compress the material to be mixed.
The mixers described in this section are change-can mixers, kneaders,
dispersers, and masticators; continuous kneaders; mixer-extruders; mixing rolls;
muliers and pan mixers; and pugmills.
CHANGE-CAN MIXERS. These devices blend viscous liquids or light pastes, as in
food processing or paint manufacture. A small removable can 5 to 100 gal in size
holds the material to be mixed. In the pony mixer shown in Fig. 28.60 the agitator
consists of several vertical blades or fingers held on a rotating head and positioned
near the wall of the can. The blades are slightly twisted. The agitator is mounted
eccentrically with respect to the axis of the can. The can rests on a turntable driven
in a direction opposite to that of the agitator, so that during operation all the
liquid or paste in the can is brought to the blades to be mixed. When the mixing
is complete, the agitator head is raised, lifting the blades out of the can; the blades
are wiped clean; and the can is replaced with another containing a new batch.
In the beater mixer in Fig. 28.6b the can or vessel is stationary. The agitator
has a planetary motion; as it rotates, it precesses, so that it repeatedly visits all
parts of the vessel. Beaters are shaped to pass with close clearance over the side
and bottom of the mixing vessel.
KNEADERS, DISPERSERS, AND MASTICATORS. Kneading is a method of mixing
used with deformable or plastic solids. It involves squashing the mass flat, folding
it over on itself, and squashing it once more. Most kneading machines also tear
Device for
raising
agitator
Planelary
Rotating gear
change
Change
can
------~\'Aqllal,>r blades carl-~~~=i
(aJ (bJ
FIGURE 28.6
Double-motion paste mixers: (a) pony mixer; (b) beater mixer.
944 OPERATIONS INVOLVING PARTICULATE SOLIDS
the mass apart and shear it between a moving blade and a stationary surface.
Considerable energy is required even with fairly thin materials, and as the mass
becomes stiff and rubbery, the power requirements become very large.
A two-arm kneader handles suspensions, pastes, and light plastic masses.
Typical applications are in the compounding of lacquer bases from pigments and
carriers and in shredding cotton linters into acetic acid and acetic anhydride to
form ceIlulose acetate. A disperser is heavier in construction and draws more power
than a kneader; it works additives and coloring agents into stiff materials. A
masticator is still heavier and draws even more power. It can disintegrate scrap
rubber and compound the toughest plastic masses that can be worked at all.
Masticators are often caIled intensive mixers.
In all these machines the mixing is done by two heavy blades on paraIlel
horizontal shafts turning in a short trough with a saddle-shaped bottom. The
blades turn toward each other at the top, drawing the mass downward over the
point of the saddle, then shearing it between the blades and the waIl of the trough.
The circles of rotation of the blades are usuaIly tangential, so that the blades may
turn at different speeds in any desired ratio. The optimum ratio is about H:: 1. In
some machines the blades overlap and turn at the same speed or with a speed ratio
of 2: 1. A smaIl two-arm kneader with tangential blades is sketched in Fig. 28.7,
with the trough tilted upward from its normal position to show the blades.
Designs of mixing blades for various purposes are shown in Fig. 28.8. The
common sigma blade shown at the left is used for general-purpose kneading. Its
edges may be serrated to give a shredding action. The double-naben, or fishtail,
blade in the center is particularly effective with heavy plastic materials. The
dispersion blade at the right develops the high shear forces needed to disperse
powders or liquids into plastic or rubbery masses. Masticator blades are even
heavier than those shown, sometimes being little larger in diameter than the shafts
that drive them. Spiral, flattened, and eIliptical designs of masticator blades are
used.
Material to be kneaded or worked is dropped into the trough and mixed for 5
to 20 min or longer. Sometimes the mass is heated while in the machine, but more
Trough in
tilled position
Sigma'
blades _-+-"'f'
Motor
FIGURE 28.7
Twowarm kneader.
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 945
(e!
(b!
FIGURE 28.8
Kneader and disperser blades: (a) sigma blade; (b) double~naben blade; (c) disperser blade.
commonly it must be cooled to remove the heat generated by the mixing action.
The trough is often unloaded by tilting it so that its contents spill out. In kneaders
and some dispersers only one agitator blade is directly driven; the other is turned
by timing gears. In masticators both shafts are independently driven, sometimes
from both ends, so that the trough cannot be tilted and must be unloaded through
an opening in the floor.
In many kneading machines the trough is open, but in some designs, known
as internal mixers the mixing chamber is closed during the operating cycle. Thus, a
cover, the underside of which conforms to the volume swept out by the blades,
can be used on the kneader shown in Fig. 28.7. Such mixers do not tilt. This type
is used for dissolving rubber and for making dispersions of rubber in liquids. The
most common internal mixer is the Banbury® mixer, shown in Fig. 28.9. This is a
heavy-duty two-arm mixer in which the agitators are in the form of interrupted
spirals. The shafts turn at 30 to 40 r/min. Solids are charged in from above and
held in the trough during mixing by an air-operated piston under a pressure of 1
to 10 atm. Mixed material is discharged through a sliding dcoJr in the bottom of
the trough. Banbury® mixers compound rubber and plastic solids, masticate crude
rubber, devulcanize rubber scrap, and make water dispersions and rubber solu-
tions. They also accomplish the same tasks as kneaders but in a shorter time and
with smaller batches. The heat generated in the material is removed by cooling
water sprayed on the walls of the mixing chamber and circulated through the
hollow agitator shafts.
CONTINUOUS KNEADERS. The machines just described operate batchwise on
relatively small amounts of material. The more difficult the material is to mix, the
smaller the batch size must be. Many industrial processes are continuous, with
steady uniform flow into and out of units of equipment; into such processes batch
equipment is not readily incorporated. Continuous kneading machines have
developed that can handle light to fairly heavy materials. In a typical design a
single horizontal shaft slowly turning in a mixing chamber carries rows of teeth
arranged in a spiral pattern to move the material through the chamber. The teeth
on the rotor pass with close clearance between stationary teeth set in the wall of
the casing. The shaft turns and also reciprocates in the axial direction. Material
946 OPERATIONS INVOLVING PARTICULATE SOUDS
11--- Weight Cylinder
air operated
Hopper
assembly
H'-----f--- Floating weight
Body -+i'-\:,-++i-'IIil-'--- Mixing chamber
~~~~~~~=~_ Hydraulically operated
discharge door assembly
8edplate (~:~~~~~=~=~=~- Toggle latch mechanism
ll___l~===j---BedPlate
FIGURE 28.9
Banbury% internal mixer (Farrrel Corp., Ansonia, eT.)
between the meshing teeth is therefore smeared in an axial or longitudinal direction
as well as heing subjected to radial shear. Solids enter the machine near the driven
end of the rotor and discharge through an opening surrounding the shaft bearing
in the opposite end of the mixing chamber. The chamber is an open trough with
light solids, a closed cylinder with plastic masses. These machines can mix several
tons per hour of heavy, stiff, or gummy materials.
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 947
MIXER-EXTRUDERS. If the discharge opening of a continuous kneader is re-
stricted by covering it with an extrusion die, the pitched blades of the rotor build
up considerable pressure in the material. The mix is cut and folded while in the
mixing chamber and subjected to additional shear as it flows through the die.
Other mixer-extruders function in the same way. They contain one or two
horizontal shafts, rotating but not reciprocating, carrying a helix or blades set in
a helical pattern. Pressnre is built up by reducing the pitch of the helix near the
discharge, reducing the diameter of the mixing chamber, or both. Mixer-extruders
continuously mix, compound, and work thermoplastics, doughs, clays, and other
hard-to-mix materials. Some also carry a heating jacket and vapor-discharge
connections to permit removal of water or solvent from the material as it is being
processed.
MIXING ROLLS. Another way of subjecting pastes and deformable solids to
intense shear is to pass them between smooth metal rolls turning at different
speeds. By repeated passes between such mixing rolls, solid additives can be
thoroughly dispersed into pasty or stiff plastic materials. Continuous mills for
mixing pastes contain three to five horizontal rolls set one above the other in a
vertical stack; the paste passes from the slower rolls to successively faster ones.
Rubber products and pastes can be compounded on batch roll mills with two rolls
set in the same horizontal plane. Solids are picked up on the faster roll, cut at an
angle by the operator, and folded back into the "bite" between the rolls. Additives
are sprinkled on the material as it is being worked. Batch roll mills require long
mixing times and careful attention by the operator and have largely been displaced
by internal mixers and continuous kneaders.
MULLER MIXERS. A muller gives a distinctly different mixing action from that
of other machines. Mulling is a smearing or rubbing action similar to that in a
mortar and pestle. In large-scale processing this action is given by the wide, heavy
wheels of the mixer shown in Fig. 28.10. In this particular design of muller the
pan is stationary and the central vertical shaft is driven, causing the muller wheels
to roll in a circular path over a layer of solids on the pan floor. The rubbing action
results from the slip of the wheels on the solids. Plows guide the solids under the
muller wheels or to an opening in the pan floor at the end of the cycle when the
Muller
wheels
FIGURE 28.10
Muller mixer.
948 OPERATIONS INVOLVING PARTICULATE SOLIDS
mixer is being discharged. In another design the axis of the wheels is held stationary
and the pan is rotated; in still another the wheels are not centered in the pan but
are offset, and both the pan and the wheels are driven. Mixing plows may be
substituted for the muller wheels to give what is called a pan mixer. Mullers are
good mixers for batches of heavy solids and pastes; they are especially effective
in uniformly coating the particles of granular solid with a small amount of liquid.
Continuous muller mixers with two mixing pans connected ill series are also
available.
PUGMILLS. In a pugmill the mixing is done by blades or knives set in a helical
pattern on a horizontal shaft turning in an open trough or closed cylinder. Solids
continuously enter one end of the mixing chamber and discharge from the other.
While in the chamber, they are cut, mixed, and moved forward to be acted upon
by each succeeding blade. Single-shaft mills utilize an enclosed mixing chamber;
open-trough double-shaft mills are used where more rapid or more thorough
mixing is required. The chamber of most enclosed mills is cylindrical, but in some
it is polygonal in cross section to prevent sticky solids from being carried around
with the shaft. Pugmills blend and homogenize clays, break up agglomerates in
plastic solids, and mix liquids with solids to form thick, heavy slurries. Sometimes
they operate under vacuum to remove air from clay or other materials. They are
built with jackets for heating or cooling.
POWER REQUIREMENTS Large amounts of mechanical energy are needed to
mix heavy plastic masses. The material must be sheared into elements that are
moved rel~tive to one another, folded over, recombined, and redivided. In
continuous mixers the material must also be moved through the machine. Only
part of the energy supplied to the mixer is directly useful for mixing, and in many
machines the useful part is small. Probably mixers that work intensively on small
quantities of material, dividing it into very small elements, make more effective
use of energy than those that work more slowly on large quantities. Machines that
weigh little per pound of material processed waste less energy than heavier
machines. Other things being equal, the shorter the mixing time required to bring
the material to the desired degree of uniformity, the larger the useful fraction of
the energy supplied will be. Regardless of the design of the machine, however, the
power needed to drive a mixer for pastes and deformable solids is many times
greater than that needed by a mixer for liquids. The energy supplied appears as
heat, which must ordinarily be removed to avoid damaging the machine or the
material.
CRITERIA OF MIXER EFFECTIVENESS: MIXING INDEX. The performance of
an industrial mixer is judged by the time required, the power load, and the
properties of the product. Both the requirements of the mixing device and the
properties desired in the mixed material vary widely from one problem to another.
Sometimes a very high degree of uniformity is required; sometimes a rapid mixing
action; sometimes a minimum amount of power.
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 949
The degree of uuiformity of a mixed product, as measured by analysis of a
number of spot samples, is a valid quantitative measure of mixing effectiveness.
Mixers act on two or more separate materials to intermingle them, nearly always
in a random fashion. Once a material is randomly distributed through another,
mixing may be considered to be complete. Based on these concepts, a statistical
procedure for measuring mixing of pastes is as follows.
Consider a solids mixture to which has been added some kind of tracer
material for easy analysis. Let the overall average fraction of tracer in the mix be
/1. Take a number of small samples at random from various locations in the mixture
and determine the fraction of tracer Xi in each. Let the number of spot samples
be N and the average value of the measured concentrations be X. When N is
very large, x will equal /1; wI-.}n N is small, the two may be appreciably different.
If the solids were perfectly mixed (and each analysis were perfectly accurate), every
measured value of Xi would equal X. If mixing is not complete, the measured
values of Xi differ from x and their standard deviation about the average value
of x is a measure of the quality of mixing. This standard deviation is estimated
from the analytical results by the equation
N 2 - ,\,N
s=
f=l (Xi - x? = 1=1 Xi - X L..Ji=l Xi
(28.18)
N-l N-l
The value of s is a relative measure of mixing, valid only for tests of a specific
material in a specific mixer. Its significance varies with the amount of tracer in
the mix: a standard deviation of 0.001 would be far more significant if /1 were 0.01
than when /1 = 0.5. Furthermore, s diminishes toward zero as mixing proceeds, so
that a low value means good mixing. Various statistical measures that are
independent of the amount of tracer are described by Harnby et aI.' One index
that increases as mixing improves is the reciprocal of the ratio of s to the standard
deviation at zero mixing ao. Before mixing has begun, the material in the mixer
exists as two layers, one of which contains no tracer material and one of which
is tracer only. Samples from the first layer would have the analysis Xi = 0; in the
other layer Xi = 1. Under these conditions the standard deviation is given by
(28.19)
where /1 is the overall fraction of tracer in the mix. The mixing index for pastes
I p is, then, from Eqs (28.18) and (28.19),
r-;-.;:---:;-;--:c;-----;--
I = ao = (N - 1)/1(1 - Jl)
(28.20)
p s I~=lXr-xI~=lXI
The calculation of Ip from experimental data is shown by the following example.
Example 28.2. A silty soil containing 14 percent moisture was mixed in a large muller
mixer with 10.00 weight percent of a tracer consisting of dextrose and picric acid.
After 3 min of mixing, 12 random samples were taken from the mix and analyzed
colorimetrically for tracer material. The measured concentrations in the sample were,
950 OPERATIONS INVOLVING PARTICULATE SOLIDS
in weight percent tracer, 10.24, 9.30, 7.94, 10.24, 11.08, 10.03, 11.91,9.72,9.20,10.76,
10.97, 10.55. Calculate the mixing index Ip and the standard deviation s.
Solution
For this test Jl = 0.10 and N = 12; x = I xJN = 1.2194/12 = 0.101617. Also I x~ =
0.1251028. (For accurate calculations a large number of decimal places must be
retained.) Substitution in Eq. (28.20) gives
J2 = (12 - 1) x 0.10{1 - 0.10)
p 0.1251028 - (0.101617 x 1.2194)
Jp = 28.8
The standard deviation from Eq. (28.18) is 0.0104, which is 10.2 percent of x.
In any batch mixing process, Jp is unity at the start and increases as mixing
proceeds. Typical results for mixing natural soils in a small two-arm kneader, like
that in Fig. 28.7, are given in Fig. 28.11. In theory Jp would become infinite at long
mixing times; in actuality it does not, for two reasons: (1) mixing is never quite
complete; (2) unless the analytical methods are extraordinarily precise, the mea-
sured values of Xi never agree exactly with each other or with x and Jp is finite
even with perfectly mixed material. As shown in Fig. 28.11, the mixing index for
sand rises rapidly to a high value, then levels off; with finer particles and
increasingly plastic materials the pattern is the same, but mixing is slower and the
limiting value of Jp is smaller. This maximum limiting value of Jp for "completely
mixed" materials varies with the consistency of the materials being processed, the
20 0
sa~d
10 0
80 Silt
60
/
40 1 / Clay
-" f/
X
w 20
/' ---- --- Heavy clay
'~" V /
0
10
~ 8 !I
" 6
4
FIGURE 28.11
1
o 2 3 4 5 6 7 8 9 Mixing index in mixing soils in a laboratory
MIXING TIME, min two~ann kneader. (After Smith. 10)
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 951
effectiveness of the mixer, and the precision of the analytical method. Typically it
falls in the range between 10 and 150.
The rate of mixing, as measured by the rate of change of Jp with time, varies
greatly with the kind of mixer and the nature of the mixed materials. In a two-arm
mixer, for example, dry powdery clay is mixed much more rapidly than very wet,
almost liquid clay. Clay with an intermediate moisture content and in a stiff plastic
condition is mixed rapidly but with a much greater energy requirement than either
very wet or very dry clay7
The effectiveness of a given type of mixer also depends on the nature and
consistency of the mixed materials. Muller mixtures, for example, give rapid mixing
and high limiting values of Jp when operating on sandy granular solids; they give
slow, rather poor mixing with plastic or sticky pastes. '0 In contrast to this, some
continuous mixers mix plastic materials more effectively than they do granular
free-flowing solids.
The mixing index is related, in some cases at least, to the physical properties
of the mixed materiaL For example, the compressive strength of clay samples
stabilized with portland cement has been related' to the value of Jp. Low strengths
were indicated when the value of Jp was small; high values of Jp corresponded to
extraordinarily high strengths of the stabilized samples.
AXIAL MIXING. In the static mixer described in Chap. 9, page 262, two fluids are
well mixed radially at any given cross section, but there is little mixing in an axial
or longitudinal direction. The fluid behavior approximates that in plug flow, in
which there is no axial mixing whatever. In some continuous paste mixers there
is also little axial mixing, a desirable characteristic in certain mixing operations
or chemical reactions; in others the axial mixing may be significant.
In paste mixers the degree of axial mixing is measured by the injection
of a tracer, over a very short time, into the feed, followed by monitoring the
concentration of tracer in the outlet stream. Typically the tracer appears at
the outlet a little earlier than expected from the mean residence time of the
mixer contents. Its outlet concentration rises to a maximum, then decays toward
zero as time progresses. The height of the maximum and the length of time required
for all (or nearly all) of the tracer to be discharged are measures of the degree of
axial mixing.
Results of such tracer tests are normally expressed in terms of a diffusivity
E. A low diffusivity means little axial mixing; a high diffusivity means there is a
great deal. Obviously a small value of E is desirable when plug flow is best, as in
chemical reactors in which mixing of feed and product is to be avoided. A large
value of E is desirable when axial mixing is needed to blend successive portions
of the mixer feed, e.g., to dampen minor fluctuations in the feed composition or
the ratio of the feed. components. Equations are available 13 for predicting E from
the tracer-time data at the mixer outlet. For two-shaft paddle mixers E typically
equals 0.02 UL to 0.2 UL, where U is the longitudinal velocity of the material in
the mixer and L is the mixer length.
952 OPERATIONS INVOLVING PARTICULATE SOLIDS
The ratio ULjE is known as the Pedet number Np •• Thus for paddle
mixers Np • ranges from 5 to 50. With some agitator designs N p • is large and
falls as the rotor speed increases; with other designs it is small and virtually
independent of rotor speed.!3
MIXERS FOR FREE-FLOWING SOLIDS
Many of the machines described in the last section can blend solids when
they are dry and free flowing as well as when they are damp, pasty, rubbery,
or plastic. Muliers, pan mixers, and pugmills are examples. Such versatile machines
are needed when the properties of the material change markedly during the mixing
operation. In general, however, these devices are less effective on dry powders than
on other materials and are heavier and more powerful than necessary for
free-flowing particulate solids.
The lighter machines discussed here handle dry powders and-sometimes
-thin pastes. They mix by mechanical shuffling, as in ribbon blenders; by
repeatedly lifting and dropping the material and rolling it over, as in tumbling
mixers and vertical screw mixers; or by smearing it out in a thin layer over a
rotating disk or impact wheel.
RIBBON BLENDERS. A ribbon blender consists of a horizontal trough containing
a central shaft and a helical ribbon agitator. A typical mixer is shown in Fig. 28.12.
Two counteracting ribbons are mounted on the same shaft, one moving the solid
slowly in one direction, the other moving it quickly in the other. The ribbons may
be continuous or interrupted. Mixing results from the "turbulence" induced by
the counteracting agitators, not from mere motion of the solids through the trough.
Some ribbon blenders operate batchwise, with the solids charged and mixed until
satisfactory; others mix continuously, with solids fed in one end of the trough and
discharged from the other. The trough is open or lightly covered for light
duty and closed and heavy walled for operation under pressure or vacuum.
Ribbon blenders are effective mixers for thin pastes and for powders that do
not flow readily. Some batch units are very large, holding up to 9000 gal (34 m3) of
material. The power they require is moderate.
FIGURE 28.12
Ribbon mixer.
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 953
FIGURE 28.13
Internal screw mixer (orbiting type).
INTERNAL SCREW MIXERS. Free-flowing grains and other light solids are
often mixed in a vertical tank containing a helical conveyor that elevates and
circulates the material. Many different designs are commercially available. In the
type shown in Fig. 28.13 the double-motion helix orbits about the central axis of
a conical vessel, visiting all parts of the mix. Mixing is generally slower than in
ribbon blenders, but the power required is somewhat less.
TUMBLING MIXERS. Many materials are mixed by tumbling them in a partly
filled container rotating about a horizontal axis. The ball mills described in Chap.
29 are often used as mixers. Most tumbling mixers, however, do not contain
grinding elements. Tumbling barrels, for example, resemble ball mills without the
balls; they effectively mix suspensions of dense solids in liquids and heavy dry
powders. Other tumbling blenders, such as those illustrated in Fig. 28.14, handle
lighter dry solids only. The double-cone mixer shown at (a) is a popular mixer for
free-flowing dry powders. A batch is charged into the body of the machine from
above until it is 50 to 60 percent full. The ends of the container are closed and
(0) (b)
FIGURE 28.14
Tumbler mixers: (a) double-cone mixer; (b) twin-shell blender.
954 OPERATIONS INVOLVING PARTICULATE SOLIDS
the solids tumbled for 5 to 20 min. The machine is stopped; mixed material is
dropped out the bottom of the container into a conveyor or bin. The twin-shell
blender shown at (b) is made from two cylinders joined to form a V and rotated
about a horizontal axis. Like a double-cone blender, it may contain internal sprays
for introducing small amounts of liquid into the mix or mechanically driven devices
for breaking up agglomerates of solids. Twin-shell blenders are more effective in
some blending operations than double-cone blenders. Tumbling mixers are made
in a wide range of sizes and materials of construction. They draw a little less
power, ordinarily, than ribbon blenders.
One method of scaling up such mixers is based upon keeping the Froude
number n 2 L/g constant, where L is a characteristic length of the equipment, n is
the rate of rotation, and g is the gravitational acceleration. 3 Scaleup procedures
for tumbling mixers are discussed in detail by Wang and Fan. l4
IMPACT WHEELS. Fine, light powders such as insecticides may be blended
continuously by spreading them out in a thin layer under centrifugal action.
A premix of the several dry ingredients is fed continuously near the center
of a high-speed spinning disk 10 to 27 in. in diameter, which throws it outward
into a stationary casing. The intense shearing forces acting on the powders during
their travel over the disk surface thoroughly blend the various materials. The disk
in some machines is vertical; in others it is horizontal. The attrition mill shown
in Fig. 29.8 is an effective mixer of this type. In some devices, designed for mixing
and not size reduction, the premix is dropped onto a horizontal double rotor
carrying short vertical pins near its periphery to increase the mixing effectiveness.
A 14-in. disk turns at 1750 r/min for easy problems and 3500 r/min for materials
that are hard to mix. Sometimes several passes through the same machine or
through machines in series are necessary. For good results the premix fed to an
impact wheel must be fairly uniform, for there is almost no holdup of material in
the mixer and no chance for recombining material that has passed through
with that which is entering. Impact wheels blend 1 to 25 tons/h oflight free-flowing
powders.
MIXING INDEX IN BLENDING GRANULAR SOLIDS. The effectiveness of a
solids blender is measured by a statistical procedure much like that used with
pastes. Spot samples are taken at random from the mix and analyzed. The standard
deviation of the analyses s about their average value x is estimated, as with pastes,
from Eq. (28.18).
With granular solids the mixing index is based, not on conditions at
zero mixing, but on the standard deviation that would be observed with a
completely random, fully blended mixture. With pastes, assuming the analy-
ses are perfectly accurate, this value is zero. With granular solids it is not zero.
Consider, for example, a completely blended mixture of salt and sand
grains from which N spot samples, each containing n particles, are taken.
Suppose the fraction of sand in each spot sample is determined by counting
particles of each kind. Let the overall fraction, by number of particles, of
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 955
sand in the total mix be flpo If n is small (say, about 100), the measured
fraction Xi of sand in each sample will not always be the same, even when
the mix is completely and perfectly blended; there is always some chance that a
sample drawn from a random mixture will contain a larger (or smaller) proportion
of one kind of particle than the popUlation from which it is taken. Thus for any
given size of spot sample there is a theoretical standard deviation for a completely
random mixture. This standard deviation (J, is given by
(J, = (28.21)
n
For granular solids the mixing index I, is defined as (J,/s. From Eqs.
(28.18) and (28.21), I, becomes
flil - flp)(N - 1)
(28.22)
n If=l (Xi - X)2
Typical results for blending salt crystals (NaCl) with Ottawa sand in
a small tumbling blender are shown in Fig. 28.15. For the first 40 min the
mixing index I, rose from a very low value to about 0.7; it fluctuated for a
time between 0.55 and 0.7 and then, at very long mixing times, began to fall
steadily. Mixing is initially rapid, but in this type of mixer it is never perfect.
The ingredients of the mix are never blended in a completely random way.
0.9
0.8
0.7
~0.6
1\ / r'---. I--
x \./ ..............
::s 0.5
"'"
""
z
~0.4
x
::2: 0 .3
0.2
o. I
o
o 2 34567 8 9 10
MIXING TIME,HR
FIGURE 28.15
Blending salt and sand in a tumbling barrel. (After Weidenbaum and Bonilla. IS)
956 OPERATIONS INVOLVING PARTtCULATE SOLIDS
Unblending forces, usually electrostatic, are always at work in a dry solids
blender, and their effects are especially noticeable here. These forces often prevent
the mix from becoming completely blended; when the mixing time is long, they
may, as shown by Fig. 28.15 lead to a considerable degree of unmixing and
segregation.
MIXING INDEX AT ZERO TIME The equilibrium standard deviation for complete
mixing (J, is used as a reference with granular solids. With pastes the reference is
the standard deviation at zero mixing (Jo. These two references are closely related,
as shown by the similarity of Eqs. (28.19) and (28.21). In fact, if n is set equal to
1 in Eq. (28.21), the two equations become identical. This is as it should be, for if
samples of one particle each are taken from any mixture of granular solids, the
analysis will indicate Xi = 1 or Xi = 0 and nothing in between. This is the same
as with completely unmixed material with any size of sample. Equation (28.19)
may therefore be applied to granular solids before mixing begins, and the mixing
index at zero mixing becomes
(J, 1
I
s.O -
----
(fo - In (28.23)
RATE OF MIXING. In mixing, as in other rate processes, the rate is proportional
to the driving force. The mixing index I, is a measure of how far mixing has
proceeded toward equilibrium.
It has been found 15 that for short mixing times the rate of change of
I, is directly proportional to 1 - I" or
dI,
Tt = k(l- I,) (28.24)
where k is a constant. The equilibrium value of I, is 1; therefore the driving force
for mixing at any time can be considered to be 1 - I,. With rearranging and
integrating between limits, Eq. (28.24) becomes
'f
o
dt=-1
k
f" dI
--'-
1..01 - Is
(28.25)
11 1 - I, .•
from which t = - n -:---='" (28.26)
k 1 - I,
Substitution from Eq. (28.23) gives
t = ~ In 1 - I/Jn (28.27)
k 1- I,
Equation (28.27) can be nsed to calculate the time required for any desired
degree of mixing, provided k is known and unblending forces are not active.
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 957
SYMBOLS
A Area, m 2 or ft2; total surface area of particles
Aw Specific surface area of particles, m 2 /g or ft2fib
a Volume shape factor [Eq. (28.10)]
b Thickness, m or ft
D Diameter, ft or mm; Do, diameter of bin opening; Dp , particle size Dpi '
mesh opening in screen i
D Average particle size, mm, I'm, or ft; DN , arithmetic mean diameter [Eq.
(28.7)]; D pi , arithmetic mean of Dpi and D pHI ; D" mean volume-surface
diameter [Eq. (28.6)]; Dv, volume mean diameter [Eq. (28.9)]; Dw , mass
mean diameter [Eq. (28.8)]
E Diffusivity in axial mixing, m 2Is or ft2Is
9 Gravitational acceleration, m/s 2 or ft/s2
1p Mixing index for pastes, U 01s
I, Mixing index for granular solids, uJs; 1,.0' at zero time or zero mixing
Number of fraction or increment; also, screen number, counting from
smallest size
K' Ratio of pressures, PvlPL
k Constant in Eq. (28.24)
L Length, ft or m
m Mass of sample, g or lb
m Mass flow rate, lblmin
N Number of particles; N T, total number; Nw, number per unit mass
N p, Peclet number for axial mixing, ULIE, dimensionless
" Number of increments or screens; number of particles in spot sample;
also, exponent in equation for flow from bins
P Pressure, N/m2 or lbflft; PL, Py, directed pressures in stress analysis
S Strength of mixed sample (Prob. 28.5), lbflin.2
s Estimate of standard deviation [Eq. (28.18)]
sp Surface area of particle, mm 2 or ft2
t Time, s
U Longitudinal velocity of material through mixer, mls or ftls
vp Volume of particles, mm 3 or ft3
Xi Mass fraction of total sample in increment i; also, measured fraction of
tracer in spot sample; X, average measured fraction of tracer
Greek letters
a Angle; am' angle of internal friction; ar, angle of repose
o Angle; Om' maximum value in stress analysis
I' True average fraction of tracer in mix; PP' true average number fraction
of tracer particles
P Density, kg/m 3 or Ib/ft3; Ph, bulk density; Pp, density of particle
u Standard deviation; u" equilibrium value for complete mixing of granular
solids; Uo, at zero time or zero mixing
958 OPERATIONS INVOLVING PARTICULATE SOLIDS
, Shear slress, N/m 2 or Ibflft2
<1>, Sphericily of parlicle, defined by Eq. (28.1)
PROBLEMS
28.1. Calculate the arithmetic mean diameter DN for the -4- to +200-mesh fractions
of the material analyzed in Table 28.2. How does DN differ qualitatively from the
volume mean diameter Dv?
28.2. Plot the cumulative distribution given in Table 28.2 on logarithmic-probability paper.
Is the plot linear over any range of particle sizes? How does the amount of fine
material (smaller than 20-mesh) differ from what would be predicted from the size
distribution of the coarser material?
28.3. A large Banbury mixer masticates 1800 Ib of scrap rubber with a density of 70 Ib/ft'.
The power load is 6000 hp per 1000 gal of rubber. How much cooling water, in gallons
per minute, is needed to remove the heat generated in the mixer if the temperature
of the water is not to rise more than 15°F?
TABLE 28.3
Data on mixing of 35/48-mesh salt in sand in a 2-in. air-fliIidized mixer'
Mixing
Run no. time, s Number fraction of sand in spot samples
45 0.64 0.68 0.74 0.63 0.73 0.81 0.59 0.65 0.62 0.70
0.66 0.64 0.77 0.70 0.67 0.58 0.60 0.65 0.87 0.60
0.49 0.52 0.49 0.54 0.64 0.38 0.32 0.34 0.49 0.52
0.25 0.32 0.33 0.35 0.48 0.23 0.16 0.32 0.44 0.39
0.26 0.26 0.21 0.32 0.38 0.22 0.24 0.22 0.15 0.36
2 87 0.53 0.54 0.60 0.60 0.60 0.55 0.56 0.60 0.69 0.63
0.48 0.67 0.65 0.63 0.62 0.46 0.63 0.58 0.48 0.59
0.49 0.53 0.46 0.49 0.58 0.34 0.52 0.45 0.50 0.47
0.42 0.35 0.43 0.49 0.59 0.38 0.39 0.45 0.52 0.39
0.35 0.36 0.37 0.49 0.48 0.37 0.49 0.32 0.32 0.36
28.4. Data On the rate of mixing of sand and salt particles in an air-fluidized bed are given
in Table 28.3. At long mixing times it was shown that the mixing index Is closely
approaches 1.0. Assuming Eqs. (28.24) and (28.25) apply to this system, how long will
it take for the mixing index to reach 0.95? In each run the initial charge to the reactor
was 254.4 g of salt on top of 300.0 g of sand. The average number of particles in each
spot sample was 100.
28.5. The compressive strength of a cement-stabilized clay sample from a small two-arm
kneader varies with mixing index according to the relation 1
s ~ 50.07 In I p - 15.29
(a) From the curves in Fig. 28.11 for clay and fat heavy clay, what mixing time would
be required with each of these soils to give a product with a compressive strength
of 1251bf /in. 2 ? (b) What would be the maximum strength obtainable with each soil
after prolonged mixing in this mixer?
PROPERTIES, HANDLING, AND MIXING OF PARTICULATE SOLIDS 959
REFERENCES
1. Baker, C. N., Jr.: Strength of Soil Cement as a Function of Degree of Mixing, 33d Ann. Meet.
Higlnv. Res. Board, Washington, DC, January 1954.
2. Bullock, H. L: Chem. Eng. Prog., 47:397 (1951).
3. Clump, C. W.: in V. W. UhI and J. B. Gray (eds.), Mixing: Theory and Practice, vol. 2, Academic,
New York, 1967, p. 284.
4. Harnby, N., M. F. Edwards, and A. W. Nienow: Mixing in the Process Industries, Butterworths,
London, 1985, pp. 24-38, 91-93.
5. Jenike, A. W., P. J. Elsey, and R. H. Wooley: Proc. ASTM, 60:1168 (1960).
6. Laforge, R. M., and B. K. Boruff: Ind. Eng. Chem., 56(2):42 (1964).
7. Michaels, A. S., and V. Puzinauskas: Chem. Eng. Prog., 50:604 (1954).
8. Nicholson, W. J.: The Blending of Dissimilar Particles in a Gas-Fluidized Bed, Ph.D. thesis, Cornell
University, Ithaca, NY, 1965.
9. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York, 1984; (a) pp.
7-3 to 7-20; (b) pp. 7-27 to 7-28; (c) 7-29; (d) p. 20-79.
10. Smith, J. c.: IIId. El1g. Chem., 47:2240 (1955).
11. Smith, J. C., and U. S. Hattiangadi: Chem. El1g. Commun., 6:105 (1980).
12. Taylor, D, W.: Fundamentals of Soil Mechanics, Wiley, New York, 1948, chap. 13.
13. Todd, D. B., and H. F. Irving: Chem. Eng. Prog., 56(9):84 (1969).
14. Wang, R. H., and L. T. Fan: Chem. Eng., 81(11):88 (1974).
15. Weidenbaum, S. S., and C. F. Bonilla: Chem. ElIg. Prog., 51:27-J (1955).
CHAPTER
29
SIZE
REDUCTION
The term size reduction is applied to all the ways in which particles of solids are
cut or broken into smaller pieces. Throughout the process industries solids are
reduced by different methods for different purposes. Chunks of crude ore are
crushed to workable size: synthetic chemicals are ground into powder; sheets of
plastic are cut into tiny cubes or diamonds. Commercial products must often meet
stringent specifications regarding the size and sometimes the shape of the particles
they contain. Reducing the particle size also increases the reactivity of solids; it
permits separation of unwanted ingredients by mechanical methods; it reduces the
bulk of fibrous materials for easier handling and for waste disposal.
Solids may be broken in many different ways, but only four of them are
commonly used in size-reduction machines: (1) compression, (2) impact, (3)
attrition, or rubbing, and (4) cutting. A nutcracker, a hammer, a file, and a pair
of shears exemplify these four types of action. Sometimes size reduction results
from the attrition of a particle by one or more other particles or from intense
shear in the supporting fluid. In general, compression is used for coarse reduction
of hard solids, to give relatively few fines; impact gives coarse, medium, or fine
products; attrition yields very fine products from soft, nonabrasive materials.
Cutting gives a definite particle size and sometimes a definite shape, with few or
no fines.
960
SIZE REDUcnON 961
PRINCIPLES OF COMMINUTION
CRITERIA FOR COMMINUTION. Comminution is a generic term for size reduc-
tion; crushers and grinders are types of comminuting equipment. An ideal crusher
or grinder would (1) have a large capacity, (2) require a small power input per
unit of product, and (3) yield a product of the single size or the size distribution
desired. The usual method of studying the performance of process equipment is
to set up an ideal operation as a standard, compare the characteristics of the actual
equipment with those of the ideal unit, and account for the difference between the
two. When this method is applied to crushing and grinding equipment, the
differences between the ideal and the actual are very great, and despite extensive
study the gaps have not been completely accounted for. On the other hand, useful
empirical equations for predicting equipment performance have been developed
from the incomplete theory now at hand.
The capacities of comminuting machines are best discussed when the
individual types of equipment are described. The fundamentals of product size
and shape and of energy requirements are, however, common to most machines
and can be discussed more generally.
CHARACTERISTICS OF COMMINUTED PRODUCTS. The objective of crushing
and grinding is to produce small particles from larger ones. Smaller particles are
desired either because of their large surface or because of their shape, size, and
number. One measure of the efficiency of the operation is based on the energy
required to create new surface, for as shown in Chap. 28, the surface area of a
unit mass of particles increases greatly as the particle size is reduced.
Unlike an ideal crusher or grinder, an actual unit does not yield a uniform
product, whether the feed is uniformly sized or not. The product always consists
of a mixture of particles, ranging from a definite maximum size to very small
particles. Some machines, especially in the grinder class, are designed to control
the magnitude of the largest particles in their products, but the fine sizes
are not under control. In some types of grinders fines are minimized, but they are
not eliminated. If the feed is homogeneous, both in the shapes of the particles and
in chemical and physical structure, the shapes of the individual units in the product
may be quite uniform; otherwise, the grains in the various sizes of a single product
may differ considerably in shape.
The ratio of the diameters of the largest and smallest particles in a commi-
nuted product is of the order of 104 • Because of this extreme variation in the sizes
of the individual particles, relationships adequate for uniform sizes must be
modified when applied to such mixtures. The term average size, for example, is
meaningless until the method of averaging is defined, and as discussed in Chap.
28, several different average sizes can be calculated.
Unless they are smoothed by abrasion after crushing, comminuted particles
resemble polyhedrons with nearly plane faces and sharp edges and corners. The
particles may be compact, with length, breadth, and thickness nearly equal, or
they may be platelike or needlelike. For compact grains, the largest dimension or
962 OPERATIONS INVOLVING PARTICULATE SOLIDS
apparent diameter is generally taken as the particle size. For particles that are
platelike or needlelike, two dimensions should be given to characterize their size.
ENERGY AND POWER REQUIREMENTS IN COMMINUTION.' The cost of
power is a major expense in crushing and grinding, so the factors that control this
cost are important. During size reduction, the particles of feed material are first
distorted and strained. The work necessary to strain them is stored temporarily
in the solid as mechanical energy of stress, just as mechanical energy can be stored
in a coiled spring. As additional force is applied to the stressed particles, they are
distorted beyond their ultimate strength and suddenly rupture into fragments. New
surface is generated. Since a unit area of solid has a definite amount of surface
energy, the creation of new surface requires work, which is supplied by the release
of energy of stress when the particle breaks. By conservation of energy, all energy
of stress in excess of the new surface energy created must appear as heat.
Crushing efficiency. The ratio of the surface energy created by crushing to the
energy absorbed by the solid is the crushing efficiency ~,. If e, is the surface energy
per unit area, in feet times pounds force per square foot, and AWb and Awa are the
areas per unit mass of product and feed, respectively, the energy absorbed by
a unit mass of the material w" is
w:a_- e,(A w' - Awa)
(29.1)
'I,
The surface energy created by fracture is small in comparison with the total
mechanical energy stored in the material at the time of rupture, and most of the
latter is converted into heat. Crushing efficiences are therefore low. They have
been measured experimentally by estimating e, from theories of the solid state,
measuring w", A wb , and Awa, and substituting into Eq. (29.1). The precision of the
calculation is poor, primarily because of uncertainties in calculating e" but the
results do show that crushing efficiences range between 0.06 and 1 percent. 9a
The energy absorbed by the solid w" is less than that fed to the machine.
Part of the total energy input W is used to overcome friction in the bearings and
other moving parts, and the rest is available for crushing. The ratio of the energy
absorbed to the energy input is ~m' the mechanical efficiency. Then, if W is the
energy input,
W = w" = e,(Aw' - Awa) (29.2)
~lm tlmtlc
If ril is the feed rate, the power required by the machine is
P = W,n = me,(A w' - Awa) (29.3)
tlctlm
SIZE REDUCTION 963
Calculation of AWb and Awa from Eq. (28.5) and substitution in Eq. (29.3) give
p = '1~,:e;p (<I>b~'b - <l>a~J (29.4)
where 15,., 15,b = volume-surface mean diameter of the feed and product, respec-
tively
<1>., <l>b = sphericity of feed and .product, respectively
Pp = density of particle
EMPIRICAL RELATIONSHIPS: RITTINGER'S AND KICK'S LAWS. A crushing
law proposed by Rittinger in 1867 states that the work required in crushing is
proportional to the new surface created. This "law," which is really no more than
a hypothesis, is equivalent to the statement that the crushing efficiency ~, is
constant and, for a given machine and feed material, is independent of the sizes
of feed and product. s If the sphericities <l>a and <l>b are equal and the mechanical
efficiency is constant, the various constants in Eq. (29.4) can be combined into a
single constant K, and Rittinger's law written as
p
-=K 1 --
(- 1) (29.5)
m ,. DSb Dsa
In 1885 Kick proposed another "law," based on stress analysis of plastic
deformation within the elastic limit, which states that the work required for
crushing a given mass of material is constant for the same reduction ratio, that
is, the ratio of the initial particle size to the final particle size. This leads to the
relation
P Dsa
- = Kkln~ (29.6)
m Dsb
where Kk is a constant.
A generalized relation for both cases is the differential equation
d(~) =
In
_ K!.15,
D~
(29.7)
Solution of Eq. (29.7) for 11 = 1, 2 leads to Kick's law and Rittinger's law,
respectively.
Both Kick's law and Rittinger's law have been shown to apply over limited
ranges of particle size, provided Kk and K, are determined experimentally by tests
in a machine of the type to be used and with the material to be crushed. They
thus have limited utility and are mainly of historical interest.
BOND CRUSHING LAW AND WORK INDEX. A somewhat more realistic method
of estimating the power required for crushing and grinding was proposed by Bond 3
in 1952. Bond postulated that the work required to form particles of size D p from
very large feed is proportional to the square root of the surface-to-volume ratio of
964 OPERATIONS INVOLVING PARTICULATE SOLIDS
the product, sp/vp- By Eq. (28.1), sp/vp = 6!CfJ,Dp, from which it follows that
P Kb
(29.8)
;;= JD:,
where Kb is a constant that depends on the type of machine and on the material
being crushed. This is equivalent to a solution of Eq. (29.7) with n = 1.5 and a
feed of infinite size. To use Eq. (29.8), a work index W, is defined as the gross
energy requirement in kilowatthours per ton (2000 lb) of feed needed to reduce a
very large feed to such a size that 80 percent of the product passes a lOO-I'm
screen. This definition leads to a relation between Kb and w,. If Dp is in millimeters,
P in kilowatts, and min tons per hour,
Kb = J100 X 10- 3 W, = 0.3162W, (29.9)
If 80 percent of the reed passes a mesh size of Dpa millimeters and 80 percent
of the product a mesh of Dpb millimeters, it follows from Eqs. (29.8) and (29.9) that
~ - ~)
ti; = 0.3162W, ( yDpb (29.10)
yDpa
The work index includes the friction in the crusher, and the power given by Eq.
(29.10) is gross power.
Table 29.1 gives typical work indexes for some common minerals. These data
do not vary greatly among different machines of the same general type and apply
TABLE 29.1
Work indexes for dry crushingt or wet grinding~
Material Specific gravity Work index, Wi
Bauxite 2.20 8.78
Cement clinker 3.15 13.45
Cement raw material 2.67 10.51
Clay 2.51 6.30
Coal 1.4 13.00
Coke 1.31 15.13
Granite 2.66 15.13
Gravel 2.66 16.06
Gypsum rock 2.69 6.73
Iron ore (hematite) 3.53 12.84
Limestone 2.66 12.74
Phosphate rock 2.74 9.92
Quartz 2.65 13.57
Shale 2.63 15.87
Slate 2.57 14.30
Trap rock 2.87 19.32
t For dry grinding, multiply by 1-
t From AlIis-Chalmers, Solids Processing Equipment Div., Appleton,
Wisconsin, by permission.
SIZE REDUCfION 965
to dry crushing or to wet grinding. For dry grinding, the power calculated from
Eq. (29.10) is multiplied by ~.
Example 29.1. What is the power required to crush 100 tonjh of limestone if 80
percent of the feed passes a 2-in. screen and 80 percent of the product ai-in. screen?
Solution
From Table 29.1. the work index for limestone is 12.74. Other quantities for
substitution into Eq. (29.10) are
In = 100 tonjh
D", = 2 x 25.4 = 50.8 mm Dpb = 0.125 x 25.4 = 3.175 mm
The power required is
P = 100 x 0.3162 x 12.74( ~ - ~)
v 3.175 v 50.8
= 169.6 kW (227 hp)
Computer Simulation of Milling Operations
The size distribution of products from various types of size-reduction equipment
can be predicted by a computer simulation of the comminution process!··lO This
makes use of two basic concepts, that of a grinding-rate function S. and a breakage
function IlBn ••• The material in a mill or crusher at any time is made up of particles
of many different sizes, and they all interact with one another during the
size-reduction process, but for 'purposes of computer simulation the material is
imagined to be divided into a number of discrete fractions (such as the ones
retained on the various standard screens) and that particle breakage occurs in
each fraction more or less independently of the other fractions.
Consider a stack of llT standard screens, and let n be the number of a
particular screen in the stack. Here it is convenient to number the screens from
the top down, beginning with the coarsest screen. (In Chap. 28 the numbering
began at the bottom of the stack.) For any given value of n, let the upper screens,
coarser than screen n, be designated by the subscript u. (Note that u < n.) The
grinding-rate function S. is the fraction of the material of a given size, coarser
than that on screen n, which is broken in a given time. If x. is the mass fraction
retained on one of the upper screens, its rate of change by breakage to smaller
sizes is
dx.
-=-Sx
dt U U
(29.11)
Suppose, for example, that the coarsest material in the charge to a grinding
mill is 4/6-mesh, that the mass fraction of this material X, is 0.05, and that
one-hundredth of this material is broken every second. Then S. would be 0.01 s- '.
and Xl would diminish at the rate of 0.01 x 0.05 = 0.0005 S-l.
966 OPERATIONS INVOLVING PARTICULATE SOLIDS
The breakage function AB•.• gives the size distribution resulting from the
breakage of the upper material. Some of the 4/6-mesh material, after breaking,
would be fairly coarse, some very small, and some in between. Probably very little
would be as large as 6/8-mesh, and only a small amount as small as 200-mesh.
One would expect sizes in the intermediate range to be favored. Consequently
I1B•.• varies with both nand u. Furthermore it varies with the composition of the
material in the mill, since coarse particles may break differently in the presence
of large amounts of fines than they do in the absence of fines. In a batch mill,
therefore, I1B•.• (and S. also) would be expected to vary with time as well as wi!h
all the other milling variables.
If I1B•.• and S. are known or can be assumed, the rate of change of any
given fraction can be found as follows. For any fraction except the coarsest, the
initial amount is diminished by breakage to smaller sizes and simultaneously
augmented by the creation of new particles from breakage of all coarser fractions.
If the input and output from a given screen are at equal rates, the fraction retained
on that screen remains constant. Usually, however, this is not the case, and the
mass fraction retained on screen n changes according to the equation
(29.12)
Equation (29.12) can be simplified if it is assumed that S. and I1B•.• are constant,
and analytical and matrix solutions are available for this case;' but these
assumptions are highly unrealistic. In crushing coal, for particles larger than about
28-mesh, S. has been found to vary with the cube of the particle size' and the
breakage function to depend on the reduction ratio 15.i15. according to the
equation
(29.13)
where the exponent fJ may be constant or may vary with the value of B.
In Eq. (29.13), B•.• is the total mass fraction smaller than size D•. It is a
cumulative mass fraction, in contrast with Il.Bn,u, which is the fraction of size Dn
(retained between screens nand n + I) resulting from breakage of particles of size
Du·
If fJ in Eq. (29.13) is constant, this equation says that the particle-size
distribution of the crushed material is the same for all sizes of the initial material.
The value of I1B•.• in crushing 4/6-mesh material to 8/10-mesh will be the same
as in crushing 6/8-mesh particles to 10/14-mesh, since the size-reduction ratio is
the same.
Usually Eq. (29.12) is solved by the Euler method of numerical approxima-
tion, in which the changes in all fractions during successively short time intervals
M (say, 30 s) are calculated by the approximation dx./dt = Ax./M. Changes in S.
and I1B•.• with screen size and (if known) with time can be incorporated. A
computer is needed to make the lengthy calculations. The method is illustrated
in the following example.
SIZE REDUCTION 967
Example 29.2. A batch grinding mill is charged with material of the composition
shown in Table 29.2. The grinding-rate function Su is assumed to be 0.001 S-l for
the 4/6-mesh particles. Breakage function B. is given by Eq. (29.13) with fJ ~ 1.3.
Both Su and BII are assumed to be independent of time. (a) How long will it take for
the fraction of 4/6-mesh material to diminish by 10 percent? (b) Tabulate the
individual breakage functions I1B,..u for the 28/35-mesh fraction and for all coarser
fractions. (c) How will the values of x,. vary with the time during the first 6 h of
operation? Use a time interval I1t of 30 s in the calculations.
Solution
(a) For the 4/6-mesh material there is no input from coarser material and Eq.
(29.11) applies. At the end of time IT' X , will be 0.0251 x 0.9 ~ 0.02259. Thus
-Su
ndt= io.o2259 ---
d(X,)
or
io 0.0251 Xl
1 0.0251 1
IT ~ -In ----- ~ ---In I.! 11 ~ 105.3 s
S. 0.02259 0.001
(b) Assume S. varies with D;. Let S, and S2 be the values for 4/6- and 6/8-mesh
material, respectively. Then 8 1 = 10 X 10- 4 S-1, and
S2 ~ S1(D 2)3 ~ 10_ 3(2.362)3 ~ 3.578 X 10- 4 S-1
D1 3.327
Values of 8 3 to 8 7 are calculated similarly; the results are given in Table 29.2.
The breakage function I1B,.,u is found as follows. When nand u are equal, or
whenever n < u, I1B,..u = O. The total mass fraction smaller than 6/8-mesh resulting
from breakage of 4/6-mesh particles, B 2 • 1 from Eq. (29.13), is
B21 ~ (2.362)1.3 ~ 0.6407
. 3.327
Then I1B 2 • 1 , the fraction of broken material retained Oil the 8-mesh screen, is
1 - 0.6407, or 0.3593.
TABLE 29.2
Initial mass fractions and grinding-rate functions for
Example 29.2
Dp,. or Dput S,. or S., x 10",
Mesh nor u mm X,.,O s-'
4/6 1 3.327 0.0251 10.0
6/8 2 2.362 0.1250 3.578
8/10 3 1.651 0.3207 1.222
10/14 4 1.168 0.2570 0.4326
14/20 5 0.833 0.1590 0.1569
20/28 6 0.589 0.0538 0.0554
28/35 7 0.417 0.0210 0.0196
'68 OPERATIONS INVOLVING PARTICULATE SOLIDS
The total mass fraction smaller than 8/lO-mesh resulting from breakage of
4/6-mesh material, B 3 . 1 , is
1.651)1.3
B3 1 ~ = 0.4021
. (- -
3.327
In general, the individual breakage functions are found from the relation
(29.14)
Thus the mass fraction of the broken 4/6-mesh material retained on the lO-mesh
screen, !J.B3. His 0.6407 - 0.4021 = 0.2386. Other values of Bn • 1l and !J.Bn.u are found
in the same way, to give the results shown in Table 29.3. Note that when n = u, BII .u
is unity, by definition. When u ~ 1, as shown in Table 29.3, 0.6407 of the broken
particles from the 4/6-mesh material is smaller than 8-mesh, 0.4021 smaller than
lO-mesh, 0.2564 smaller than 14-mesh, and only 0.0672 smaller than 35-mesh.
(c) Let XII" be the mass fractions retained on the various screens at the end of t
time increments !J.t. Then x1.o, X2.0, etc., are the initial mass fractions given in Table
29.2.
The left-hand side of Eq. (29.12) is approximated by I1x,,/M, where 111 in this
example is 30 sand L\xn = XII,,+l - XII.,. Successive values of X on the screens can
then be calculated from the following form of Eq. (29.12):
,-1
X II. 1+ 1 = XII., - Sn!J.t x"" +!J.t L XIl.,SIl !J.B".1l
u=1
,-1
= xn.,(l - SII At) +!J.t L Xu.,Su !J.BII,u (29.15)
u= 1
TABLE 29.3
Breakage functions for Example 29.2
B",u and AB",II for n =:
U 1 2 3 4 5 6 7
1.0 0.6407 0.4021 0.2564 0.1652 0.1053 0.0672
0 0.3593 0.2386 0.1457 0.0912 0.0599 0.0381
2 0 1.0 0.6277 0.4003 0.2579 0.1643 0.1049
0 0 0.3723 0.2274 0.1424 0.0936 0.0594
3 0 0 1.0 0.6376 0.4109 0.2618 0.1671
0 0 0 0.3624 0.2267 0.1491 0.0947
4 0 0 0 1.0 0.6444 0.4106 0.2621
0 0 0 0 0.3556 0.2338 0.1485
5 0 0 0 0 1.0 0.6372 0.4067
0 0 0 0 0 0.3628 0.2305
6 0 0 0 0 0 1.0 0.6383
0 0 0 0 0 0 0.3617
7 0 0 0 0 0 0 1.0
0 0 0 0 0 0 0
SIZE REDUCTION 969
For the top screen n ~ 1 and I1B ~ O. Hence Eq. (29.15) becomes
X1.<+1 ~ x1.<(1- SIl1t) ~ xl.,[I- (10 x 1O- 4X30)]
~ 0.970x l .,
After 30 s, then, the mass fraction on the top screen is
Xl.! ~ 0.970 x 0.0251 ~ 0.02434
After 30 s more,
Xl.' ~ 0.970 x 0.02434 ~ 0.02360
and so forth. On the 8-mesh screen (n ~ 2), the mass fractions are, from Eq. (29.15),
X 2 ,1 = x 2 ,o(1- 8 2 .1.t) +.1.t x 1 ,o8 1 .1.B 2 ,l
Substituting the values of 8 1 ,82 , and x1.0 from Table 29.2 and .1.B2 . 1 from Table
29.3 gives
x,.! ~ x, .• [1 - (3.578 x 10- 4 ) x 30] + 30 x 0.0251 x (10 x 10- 4 ) x 0.359
~ 0.98926x, .• + 0.00027
Thus
X,.! ~ (0.98926 x 0.1250) + 0.00027 ~ 0.12393
Similarly,
x2.2 ~ (0.98926 x 0.12393) + (30 x 0.02434 x 10 x 10- 4 x 0.359)
~ 0.12285
TABLE 29.4
Mass fractions, Example 29_2
Time,
min x, x, x, x, x, x, x,
0 0.0251 0.1250 0.3207 0.2570 0.1590 0.0538 0.0210
0.5 0.0243 0.1239 0.3202 0.2575 0.1596 0.0542 0.0213
1 0.0236 0.1228 0.3197 0.2580 0.1602 0.0546 0.0216
2 0.0222 0.1206 0.3187 0.2590 0.1614 0.0554 0.0222
5 0.0185 0.1143 0.3153 0.2618 0.1644 0.0578 0.0240
10 0.0137 0.1042 0.3093 0.2659 0.1695 0.0619 0.0267
20 0.0074 0.0859 0.2961 0.2724 0.1788 0.0695 0.0317
30 0.0040 0.0703 0.2819 0.2772 0.1871 0.0765 0.0363
60 0.0006 0.0376 0.2379 0.2840 0.2074 0.0946 0.0485
90 0.0000 0.0197 0.1967 0.2832 0.2226 0.1097 0.0590
120 0.0000 0.0104 0.1610 0.2777 0.2341 0.1228 0.0682
180 0.0000 0.0028 0.1058 0.2585 0.2495 0.1442 0.0839
240 0.0000 0.0008 0.0687 0.2342 0.2576 0.1611 0.0971
300 0.0000 0.0002 0.0444 0.2087 0.2608 0.1748 0.1084
360 0.0000 0.0001 0.0286 0.1839 0.2605 0.1860 0.1183
970 OPERATIONS INVOLVING PARTICULATE SOLIDS
0.35
0.3 0"-...
"-...
5~ ~ x5
---I---
0.2
,0
Z-
0.2 ~
D~
~
0
f= ~
u x6
" 0.1 5
---
DO
~
~
10x 1
"'
"""' 0.1 o '\.\
5~
·0.0
D~
o
~
~
2
TIME,h
3
----- r-...
4 5
- 6
FIGURE 29.1
Mass fractions, Example 29.2, part (c). (The values of Xl have been multiplied by 10.)
The values of X3 to X7 are found in the same way. The results are given in
Table 29.4"t and illustrated in' Fig. 29.1. Initially X" X" and X, all decrease with
time and the other mass fractions increase. At the end of 1 h, 99.95 percent of the
4/6-mesh material (Xl) has disappeared and X7 has more than doubled. The fraction
of material finer than 35-mesh has increased from 0.0384 to 0.0931. During the first
hour the changes in X3 and x 7 are almost linear with time. At about 70 min x4 reaches
a maximum and then diminishes with time. If the grinding were continued, the still
finer fractions would eventually do the same.
Computer simulation is also useful in predicting the power consumption and
particle size distribution in continuous mills, in which the mass fractions are in
dynamic equilibrium and do not change with time?b
SIZE-REDUCTION EQUIPMENT
Size-reduction equipment is divided into crushers, grinders, ultrafine grinders, and
cutting machines. Crushers do the heavy work of breaking large pieces of solid
material into small lumps. A primary crusher operates on run-of-mine material,
accepting anything that comes from the mine face and breaking it into 150- to
250-mm (6- to lO-in_) lumps. A secondary crusher reduces these lumps to particles
perhaps 6 mm (ol: in_) in size. Grinders reduce crushed feed to powder. The product
t These numbers were obtained with an Apple II microcomputer. Larger computers that can handle
more significant figures give somewhat different results.
SIZE REDUCTION 971
from an intermediate grinder might pass a 40-mesh screen; most of the product
from a fine grinder would pass a 200-mesh screen with a 74-)lm opening. An
uttraftne grinder accepts feed particles no larger than 6 mm (i in.); the product size
is typically 1 to 50 )lm. Cutters give particles of definite size and shape, 2 to 10 mm
in length.
The principal types of size-reduction machines are as follows:
A. Crushers (coarse and fine)
1. Jaw crushers
2. Gyratory crushers
3. Crushing rolls
B. Grinders (intermediate and fine)
1. Hammer mills; impactors
2. Rolling-compression mills
a. Bowl mills
b. Roller mills
3. Attrition mills
4. Tumbling mills
a. Rod mills
b. Ball mills; pebble mills
c. Tube mills; compartment mills
C. Ultrafine grinders
1. Hammer mills with internal classification
2. Fluid-energy mills
3. Agitated mills
D. Cutting machines
1. Knife cutters; dicers; slitters
These machines do their work in distinctly different ways. Compression is
the characteristic action of crushers. Grinders employ impact and attrition, some-
times combined with compression; ultrafine grinders operate principally by
attrition. A cutting action is of course characteristic of cutters, dicers, and slitters.
Crushers
Crushers are slow-speed machines for coarse reduction oflarge quantities of solids.
The main types are jaw crushers, gyratory crushers, smooth-roll crushers, and
toothed-roll crushers. The first three operate by compression and can break large
lumps of very hard materials, as in the primary and secondary reduction of rocks
and ores. Toothed-roll crushers tear the feed apart as well as crushing it; they
handle softer feeds like coal, bone, and soft shale.
JAW CRUSHERS. In a jaw crusher feed is admitted between two jaws, set to form
a V open at the top. One jaw, the fixed, or anvil, jaw, is nearly vertical and does
not move; the other, the swinging jaw, reciprocates in a horizontal plane. It makes
972 OPERATIONS INVOLVING PARTICULATE SOLIDS
an angle of 200 to 300 with the anvil jaw. It is driven by an eccentric so that it
applies great compressive force to lumps caught between the jaws. The jaw faces
are flat or slightly bulged; they may carry shallow horizontal grooves. Large lumps
caught between the upper parts of the jaws are broken, drop into the narrower
space· below, and are recrushed the next time the jaws close. After sufficient
reduction they drop out the bottom of the machine. The jaws open and close 250
to 400 times per minute.
The most common type of jaw crusher is the Blake crusher, illustrated in
Fig. 29.2. In this machine an eccentric drives a pitman connected to two toggle
plates, one of which is pinned to the frame and the other to the swinging jaw. The
pivot point is at the top of the movable jaw or above the top of the jaws on the
centerline of the jaw opening. Th!: greatest amount of motion is at the bottom of
the V, which means that there is little tendency for a crusher of this kind to choke.
Some machines with a 1.8- by 2.4-m (72- by 96-in.) feed opening can accept rocks
1.8 m (6 ft) in diameter and crush 1200 tonfh to a maximum product size of 250
mm (10 in.). Smaller secondary crushers reduce the particle size of precrushed feed
to 6 to 50 mm (! to 2 in.) at much lower rates of throughput.
GYRATORY CRUSHERS. A gyratory crusher may be looked upon as ajaw crusher
with circular jaws, between which material is being crushed at some point at all
times. A conical crushing head gyrates inside a funnel-shaped casing, open at the
top. As shown in Fig. 29.3, the crushing head is carried on a heavy shaft pivoted
at the top of the machine. An eccentric drives the bottom end of the shaft. At any
point on the periphery of the casing, therefore, the bottom of the crushing head
moves toward, and then away from, the stationary wall. Solids caught in the
V-shaped space between the head and the casing are broken and rebroken until
they pass out the bottom. The crushing head is free to rotate on the shaft and
turns slowly because of friction with the material being crushed.
Pivot
Swinging jaw
Hardened
jaw faces ---;:~iFi~i£j
Stationary
Toggles
Discharge
FIGURE 29.2
Blake jaw crusher.
SIZE REDUCTION 973
shaft bearing
____ "p,aer arm
Concave .___·er/lShl"" head
~_ _-I2~.§,~8t-~laxirT1£lm opening
opemng
MinifTlum:"' _ _ '~~~f=l~~~
.___Eccenlrk
Discharge
FIGURE 29.3
Gyratory crusher.
The speed of the crushing head is typically 125 to 425 gyrations per minute.
Because some part of the crushing head is working at all times, the discharge from
a gyratory is continuous instead of intermittent as in a jaw crusher. The load on
the motor is nearly uniform; less maintenance is required than with a jaw crusher;
and the power requirement per ton of material crushed is smaller. The biggest
gyratories handle up to 4500 ton/h. The capacity of a gyratory crusher varies
with the jaw setting, the impact strength of the feed, and the speed of gyration of
the machine. The capacity is almost independent of the compressive strength of
the material being crushed.
SMOOTH-ROLL CRUSHERS. Two heavy smooth-faced metal rolls turning on
parallel horizontal axes are the working elements of the smooth-roll crusher
illustrated in Fig. 29.4. Particles of feed caught between the rolls are broken in
compression and drop out below. The rolls turn toward each other at the same
speed. They have relatively narrow faces and are large in diameter so that they
can "nip" moderately large lumps. Typical rolls are 600 mm (24 in.) in diameter
with a 300-mm (12-in.) face to 2000 mm (78 in.) in diameter with a 914-mm (36-in.)
974 OPERATIONS INVOLVING PARTICULATE SOLIDS
Flywheel
spring
DIscharge
FIGURE 29.4
Smooth-roll crusher.
face. Roll speeds range from 50 to 300 r/min. Smooth-roll crushers are secondary
crushers, with feeds 12 to 75 mm (! to 3 in.) in size and products 12 mm (! in.)
to about 1 mm.
The limiting size D P. m" of particles that can be nipped by the rolls depends
on the coefficient of friction between the particle and the roll surface, but in most
cases it can be estimated from the simple relation 9 ,
D p • m " = 0.04R +d (29.16)
where R = roll radius
d = half the width of the gap between the rolls
The maximum size of the product is approximately equal to 2d.
The particle size of the product depends on the spacing between the rolls,
as does the capacity of a given machine. Smooth-roll crushers give few fines and
virtually no oversize. They operate most effectively when set to give a reduction
ratio of 3 or 4 to 1; that is, the maximum particle diameter of the product is
one-third or one-fourth that of the feed. The forces exerted by the roll are very
great, from 8700 to 70,000 N/cm (5000 to 40,000 lbflin.) of roll width. To allow
unbreakable material to pass through without damaging the machine, at least one
roll must be spring mounted.
TOOTHED-ROLL CRUSHERS. In many roll crushers the roll faces carry corruga-
tions, breaker bars, or teeth. Such crushers may contain two rolls, as in smooth-roll
crushers, or only one roll working against a stationary curved breaker plate. A
single-roll toothed crusher is shown in Fig. 29.5. Machines known as disintegrators
contain two corrugated rolls turning at different speeds, which tear the feed apart,
or a small high-speed roll with transverse breaker bars on its face turning toward
SIZE REDUCTION 975
SJ
Flywheel----\ ~f
.~
DIscharge
FIGURE 29.5
Single-roll toothed crusher.
a large slow-speed smooth roll. Some crushing rolls for coarse feeds carry heavy
pyramidal teeth. Other designs utilize a large number of thin-toothed disks that
saw through slabs or sheets of material. Toothed-roll crushers are much more
versatile than smooth-roll crushers, within the limitation that they cannot handle
very hard solids. They operate by compression, impact, and shear, not by
compression alone, as do smooth-roll machines. They are not limited by the
problem of nip inherent with smooth rolls and can therefore reduce much larger
particles. Some heavy-duty toothed double-roll crushers are used for the primary
reduction of coal and similar materials. The particle size of the feed to these
machines may be as great as 500 mm (20 in.); their capacity ranges up to
500 tons/h.
Grinders
The term grinder describes a variety of size-reduction machines for intermediate
duty. The product from a crusher is often fed to a grinder, in which it is reduced
to powder. The chief types of commercial grinders described in this section are
hammer mills and impactors, rolling-compression machines, attrition mills, and
tumbling mills.
HAMMER MILLS AND IMPACTORS. These mills all contain a high-speed rotor
turning inside a cylindrical casing. The shaft is usually horizontal. Feed dropped
into the top of the casing is broken and falls out through a bottom opening. In
a hammer mill the particles are broken by sets of swing hammers pinned to a
rotor disk. A particle of feed entering the grinding zone cannot escape being struck
by the hammers. It shatters into pieces, which fly against a stationary anvil plate
976 OPERATIONS INVOLVING PARTICULATE SOLIDS
inside the casing and break into still smaller fragments. These in turn are rubbed
into powder by the hammers and pushed through a grate or screen that covers
the discharge opening.
Several rotor disks, 150 to 450 mm (6 to 18 in.) in diameter and each carrying
four to eight swing hammers, are often mounted on the same shaft. The hammers
may be straight bars of metal with plain or enlarged ends or with ends sharpened
to a cutting edge. Intermediate hammer mills yield a product 25 mm (1 in.) to
20-mesh in particle size. In hammer mills for fine reduction the peripheral speed
of the hammer tips may reach 110 m/s (360 ft/s); they reduce 0.1 to 15 ton/h to
sizes finer than 200-mesh. Hammer mills grind almost anything-tough fibrous
solids like bark or leather, steel turnings, soft wet pastes, sticky clay, hard rock.
For fine reduction they are limited to the softer materials.
The capacity and power requirement of a hammer mill vary greatly with the
nature of the feed and cannot be estimated with confidence from theoretical
considerations. They are best found from published information 9! or better from
small-scale or full-scale tests of the mill with a sample of the actual material to
be ground. Commercial mills typically reduce 60 to 240 kg of solid per kilowatt
hour (100 to 400Ib/hp-h) of energy consumed.
An impactol', illustrated in Fig. 29.6, resembles a heavy-duty hammer mill
except that it contains no grate or screen. Particles are broken by impact alone,
without the rubbing action characteristic of a hammer mill. Impactors are often
primary-reduction machines for rock and ore, processing up to 600 ton/h. They
give particles that are mOre nearly equidimensional (more "cubical") than the
slab-shaped particles from a jaw crusher or gyratory crusher. The rotor in an
impactor, as in many hammer mills, may be run in either direction to prolong the
life of the hammers.
ROLLING-COMPRESSION MACHINES. In this kind of mill the solid particles are
caught and crushed between a rolling member and the face of a ring or casing.
The most common types are rolling-ring pulverizers, bowl mills, and roller mills.
In the roller mill illustrated in Fig. 29.7, vertical cylindrical rollers press outward
with great force against a stationary anvil ring or bull ring. They are driven at
FIGURE 29.6
Discharge Impactor.
SIZE REDUCTION 977
Adjustable
cone
Discharge Splral--l~~;S;::::-""
Roller
~Gri."dli,g ring
~lIff/"")IVli,g bawl
.::-1It-lbnge'f)tl<,1 air
FIGURE 29.7
Roller mill.
moderate speeds in a circular path. Plows lift the solid lumps from the floor of
the mill and direct them between the ring and the rolls, where the reduction takes
place. Product is swept out of the mill by a stream of air to a classifier separator,
from which oversize particles are returned to the mill for further reduction. In a
bowl mill and some roller mills the bowl or ring is driven; the rollers rotate on
stationary axes, which may be vertical or horizontal. Mills of this kind find most
application in the reduction of limestone, cement clinker, and coal. They pulverize
up to 50 ton/h. When classification is used, the product may be as fine as 99
percent through a 200-mesh screen.
ATTRITION MILLS. In an attrition mill particles of soft solids are rubbed between
the grooved flat faces of rotating circular disks. The axis of the disks is usually
horizontal, sometimes vertical. In a single-runner mill one disk is stationary and
978 OPERATIONS INVOLVING PARTICULATE SOLIDS
one rotates; in a double-runner machine both disks are driven at high speed in
opposite directions. Feed enters through an opening in the hub of one of the disks;
it passes outward through the narrow gap between. the disks and discharges from
the periphery into a stationary casing. The width of the gap, within limits, is
adjustable. At least one grinding plate is spring mounted so that the disks can
separate if unbreakable material gets into the mill. Mills with different patterns
of grooves, corrugations, or teeth on the disks perform a variety of operations,
including grinding, cracking, granulating, and shredding, and even some opera-
tions not related to size reduction at all, such as blending and feather curling.
A single-runner attrition mill is shown in Fig. 29.8. Single-runner mills
contain disks of buhrstone or rock emery for reducing solids like clay and talc,
or metal disks for solids like wood, starch, insecticide powders, and carnauba wax.
Metal disks are usually of white iron, although for corrosive materials disks of
stainless steel are sometimes necessary. Double-runner mills, in general, grind to
finer products than single-runner mills but process softer feeds. Air is often drawn
through the mill to remove the product and prevent choking. The disks may be
cooled with water or refrigerated brine to take away the heat generated by the
reduction operation. Cooling is essential with heat-sensitive solids like rubber,
which would otherwise be destroyed.
The disks of a single-runner mill are 250 to 1400 mm (10 to 54 in.) in diameter,
turning at 350 to 700 r/min. Disks in double-runner mills turn faster, at 1200 to
7000 r/min. The feed is precrushed to a maximum particle size of about 12 mm
Hin.) and must enter at a uniform controlled rate. Attrition mills grind from
t to 8 ton/h to products that will pass a 200-mesh screen. The energy required
depends strongly on the nature of the feed and the degree of reduction accom-
plished and is much higher than in the mills and crushers described so far. Typical
values are between 8 and 80 kWh (10 and 100 hp-h) per ton of product.
--,ololc,ling disk
Stationary
disk _ _ _ _ _~
Discharge
FIGURE 29.8
Attrition mill.
SIZE REDUCTION 979
TUMBLING MILLS A typical tumbling mill is shown in Fig. 29.9. A cylindrical
shell slowly turning about a horizontal axis and filled to about half its volume
with a solid grinding medium forms a tumbling mill. The shell is usually steel,
lined with high-carbon steel plate, porcelain, silica rock, or rubber. The grinding
medium is metal rods in a rod mill, lengths of chain or balls of metal, rubber, or
wood in a ball mill, flint pebbles or porcelain or zircon spheres in a pebble mill.
For intermediate and fine reduction of abrasive materials tumbling mills are
unequaled.
Unlike the mills previously discussed, all of which require continuous feed,
tumbling mills may be continuous or batch. In a batch machine a measured
quantity of the solid to be ground is loaded into the mill through an opening in
the shell. The opening is then closed and the mill turned on for several hours; it
is then stopped and the product is discharged. In a continuous mill the solid flows
steadily through the revolving shell, entering at one end through a hollow trunnion
and leaving at the other end through the trunnion or through peripheral openings
in the shell.
In all tumbling mills, the grinding elements are carried up the side of the
shell nearly to the top, from whence they fall on the particles underneath. The
energy expended in lifting the grinding units is utilized in reducing the size of
the particles. In some tumbling mills, as in a rod mill, much of the reduction is
done by rolling compression and by attrition as the rods slide downward and roll
over one another. The grinding rods are usually steel, 25 to 125 mm (1 to 5 in.)
in diameter, with several sizes present at all times in any given mill. The rods
extend the full length of the mill. They are sometimes kept from twisting out of
line by conical ends on the shell. Rod mills are intermediate grinders, reducing a
2Q-mm (i-in.) feed to perhaps IQ-mesh, often preparing the product from a
crusher for final reduction in a ball mill. They yield a product with little oversize
and a minimum of fines.
Feed m'·!Br_---'
FIGURE 29.9
Conical ball milL
980 OPERATIONS INVOLVING PARTICULATE SOLIDS
In a ball mill or pebble mill most of the reduction is done by impact as the
balls or pebbles drop from near the top of the shell. In a large ball mill the shell
might be 3 m (10 ft) in diameter and 4.25 m (14 ft) long. The balls are 25 to 125 mm
(1 to 5 in.) in diameter; the pebbles in a pebble mill are 50 to 175 mm (2 to 7 in.)
in size. A tube mill is a continuous mill with a long cylindrical shell, in which
material is ground for 2 to 5 times as long as in the shorter ball mill. Tube mills
are excellent for grinding to very fine powders in a single pass wnere the amount
of energy consumed is not of primary importance. Putting slotted transverse
partitions in a tube mill converts it into a compartment mill. One compartment
may contain large balls, another small balls, and a third pebbles. This segregation
of the grinding media into elements of different size and weight aids considerably
in avoiding wasted work, for the large, heavy balls break only the large particles,
without interference by the fines. The small, light balls fall only on small particles,
not on large lumps they cannot break.
Segregation of the grinding units in a single chamber is a characteristic of
the conical ball mill illustrated in Fig. 29.9. Feed enters from the left through a
60° cone into the primary grinding zone, where the diameter of the shell is a
maximum. Product leaves through the 30° cone to the right. A mill of this kind
contains balls of different sizes, all of which wear and become smaller as the mill
is operated. New large balls are added periodically. As the shell of such a mill
rotates, the large balls move toward the point of maximum diameter, and the
small balls migrate toward the discharge. The initial breaking of the feed particles,
therefore, is done by the largest balls dropping the greatest distance; small particles
are ground by small balls dropping a much smaller distance. The amount of energy
expended " suited to the difficulty of the breaking operation, increasing the
efficiency of the mill.
Action in tumbling mills. The load of balls in a ball or tube mill is normally such
that when the mill is stopped, the balls occupy about one-half the volume of the
mill. The void fraction in the mass of balls, when at rest, is typically DAD. The
grinding may be done with dry solids, but more commonly the feed is a suspension
of the particles in water. This increases both the capacity and the efficiency of the
mill. Discharge openings at appropriate positions control the liquid level in the
mill, which should be such that the suspension just fills the void space in the mass
of balls.
When the mill is rotated, the balls are picked up by the mill wall and carried
nearly to the top, where they break contact with the wall and fall to the bottom
to be picked up again. Centrifugal force keeps the balls in contact with the wall
and with each other during the upward movement. While in contact with the wall,
the balls do some grinding by slipping and roIling over each other, but most of
the grinding occurs at the zone of impact, where the free-faIling balls strike the
bottom of the mill.
The faster the mill is rotated, the farther the balls are carried up inside the
mill and the greater the power consumption. The added power is profitably used
SIZE REDUCfION 981
because the higher the balls are when they are released, the greater the impact at
the bottom and the larger the productive capacity of the mill. If the speed is too
high, however, the balls are carried over and the mill is said to be centrifuging.
The speed at which centrifuging occurs is called the critical speed. Little or no
grinding is done when a mill is centrifuging, and operating speeds must be less
than the critical.
The speed at which the outermost balls lose contact with the wall of the
mill depends on the balance between gravitational and centrifugal forces. This can
be shown with the aid of Fig. 29.10. Consider the ball at point A on the periphery
of the mill. Let the radii of the mill and of the ball be Rand r, respectively. The
center of the ball is, then R - r meters (or feet) from the axis of the mill. Let the
radius AO form the angle a with the vertical. Two forces act on the ball. The first
is the force of gravity mg/g" where m is the mass of the ball. The second is the
centrifugal force (R - r) {j)2/g" where (j) = 2nn and n is the rotational speed. The
centripetal component of the force of gravity is (mg/g,) cos a, and this force
opposes the centrifugal force. As long as the centrifngal force exceeds the cen-
tripetal force, the particle will not break contact with the wall. As the angle a
decreases, however, the centripetal force increases, and unless the speed exceeds
the critical, a point is reached where the opposing forces are equal and the particle
mg
gc
FIGURE 29.10
Forces on ball in ball mill.
982 OPERATIONS INVOLVING PARTICULATE SOLIDS
is ready to fall away. The angle at which this occurs is found by equating the two
forces, giving
g m[4n 2 n 2 (R - r)]
m - cos a = -"'---'-----=
gc gc
(29.17)
g
At the critical speed, rt. = 0, cos rt. = 1, and n becomes the critical speed n,. Then
(29.18)
Tumbling mills run at 65 to 80 percent of the critical speed, with the lower
values for wet grinding in viscous suspensions. 9d
Capacity and power requirement of tumbling mills. The maximum amount of
energy that can be delivered to the solid being reduced can be computed from
the mass of the grinding medium, the speed of rotation, and the maximum distance
of fall. In an actual mill the useful energy is much smaller than this, and the total
mechanical energy supplied to the mill is much greater. Energy is required to
rotate the shell in its bearing supports. Much of the energy delivered to the grinding
medium is wasted in overgrinding particles that are already fine enough and in
lifting balls or pebbles that drop without doing much if any grinding. Good design,
of course, minimizes the amount of wasted energy. Complete theoretical analysis
of the many interrelated variables is virtually impossible, and the performance of
tumbling mills is best predicted from computer simulations based on pilot-plant
tests. Rod mills yield 5 to 200 ton/h of 10-mesh product; ball mills produce 1 to
50 ton/h of powder of which perhaps 70 to 90 percent would pass a 200-mesh
screen. The total energy requirement for a typical rod mill grinding hard material
is about 4kWh/metric ton (5 hp-h/ton); for a ball mill it is about 16kWh/metric
ton (20 hp-h/ton). Tube mills and compartment mills draw somewhat more power
than this. As the product becomes finer, the capacity of a given mill diminishes
and the energy requirement increases. (See Fig. 29.16.)
Ultrafine Grinders
Many commercial powders must contain particles averaging 1 to 20 /lm in size,
with substantially all particles passing a standard 325-mesh screen that has
openings 44 /lm wide. Mills that reduce solids to such fine particles are called
ultrafine grinders. Ultrafine grinding of dry powder is done by grinders, such as
high-speed hammer mills, provided with internal or external classification, and by
fluid-energy or jet mills. Ultrafine wet grinding is done in agitated mills.
SIZE REDUCTION 983
CLASSIFYING HAMMER MILLS. A hammer mill with internal classification is the
Mikro-Atomizer illustrated in Fig. 29.11. A set of swing hammers is held between
two rotor disks, much as in a conventional hammer mill. In addition to the
hammers the rotor shaft carries two fans, which draw air through the mill in the
direction shown in the figure and discharge into ducts leading to collectors for
the product. On the rotor disks are short radial vanes for separating oversize
particles from those of acceptable size. In the grinding chamber the particles of
solid are given a high rotational velocity. Coarse particles are concentrated along
the wall of the chamber because of centrifugal force acting on them. The airstream
carries finer particles inward from the grinding zone toward the shaft in the
direction AB. The separator vanes tend to throw particles outward in the direction
BA. Whether or not a given particle passes between the separator vanes and out
to the discharge depends on which force predominates-the drag exerted by the
air or the centrifugal force exerted by the vanes. Acceptably fine particles are
carried through; particles that are too large are thrown back for further reduction
in the grinding chamber. The maximum particle size of the product is varied by
changing the rotor speed or the size and number of the separator vanes. Mills of
this kind reduce 1 or 2 tonlh to an average particle size of 1 to 20 I'm, with an
energy requirement of about 40 kWhlmetric ton (50 hp-h/ton).
Air plate Air
FIGURE 29.11
Principle of Mikro-Atomizer'lL. (By permission, Micron Powder System, Summit, NJ)
984 OPERATIONS INVOLVING PARTICULATE SOLIDS
FLUID ENERGY MILLS. In these mills the particles are suspended in a high-
velocity gas stream. In some designs the gas flows in a circular or elliptical path;
in others there are jets that oppose one another or vigorously agitate a fluidized
bed. Some reduction occurs when the particles strike or rub against the walls of
the confining chamber, but most of the reduction is believed to be caused by
interparticle attrition. Internal classification keeps the larger particles in the mill
until they are reduced to the desired size.
The suspending gas is usually compressed air or superheated steam, admitted
at a pressure of 7 atm (100 lbf/in.2) through energizing nozzles. In the mill shown
in Fig. 29.12 the grinding chamber is an oval loop of pipe 25 to 200 mm (1 to
8 in.) in diameter and 1.2 to 2.4 m (4 to 8 ft) high. Feed enters near the bottom of
the loop through a venturi injector. Classification of the ground particles takes
place at the upper bend of the loop. As the gas stream flows around this bend at
high speed, the coarser particles are thrown outward against the outer wall while
the fines congregate at the inner wall. A discharge opening in the inner wall at
this point leads to a cyclone separator and a bag collector for the product. The
classification is aided by the complex pattern of swirl generated in the gas stream
at the bend in the loop of pipe. 2 Fluid-energy mills can accept feed particles as
large as 12 mm (! in.) but are more effective when the feed particles are no
larger than lOO-mesh. They reduce up to 1 tonlh of nonsticky solid to particles
<0." Mi11el'ial and
fluid oullel
Y-h~--t:!-Cl'ass.ifier wllel
FIGURE 29,12
Fluid-energy mill. (By permission, Fluid Energy
Energizing nozzles Processing and Equipment Co.)
SIZE REDUCfION 985
averaging i to lO!lm in diameter, using 1 to 4 kg of steam or 6 to 9 kg of air
per kilogram of product. Loop mills can process up to 6000 kg/h.
AGITATED MILLS. For some ultrafine grinding operations, small batch non-
rotary mills containing a solid grinding medium are available. The medium
consists of hard solid elements such as balls, pellets, or sand grains. These mills
are vertical vessels 4 to 1200 L (1 to 300 gal) in capacity, filled with liquid in which
the grinding medium is suspended. In some designs the charge is agitated with a
multiarmed impeller; in others, used especially for grinding hard materials (such
as silica or titanium dioxide), a reciprocating central column "vibrates" the vessel
contents at about 20 Hz. A concentrated feed slurry is admitted at the top, and
product (with some liquid) is withdrawn through a screen at the bottom. Agitated
mills are especially useful in producing particles 1 !lm in size or finer. 9,
COLLOID MILLS." In a colloid mill, intense fluid shear in a high-velocity stream
is used to disperse particles or liquid droplets to form a stable suspension or
emulsion. The final size of the particles or droplets is usually less than 5 !lm. Often
there is little actual size reduction in the mill; the principal action is the disruption
of lightly bonded clusters or agglomerates. Syrups, milk, purees, ointments, paints,
and greases are typical products processed in this way. Chemical additives are
often useful for stablizing the dispersion.
In most colloid mills the feed liquid is pumped between closely spaced
surfaces one of which is moving relative to the other at speeds of 50 m/s or more.
In the mill shown schematically in Fig. 29.13 the liquid passes through the narrow
spaces between the disk-shaped rotor and the casing. The clearances are adjustable
down to 25 !lm. Often cooling is required to remove the heat generated. The
Casing
Feed
FIGURE 29.13
Schematic drawing of colloid mill.
986 OPERATIONS INVOLVING PARTICULATE SOLIDS
capacities of colloid mills are relatively low, ranging from 2 or 3 L(min (30 to
50 gal/h) for small mills up to 440 L(min (7000 gal/h) for the largest units.
Cutting Machines ll
In some size-reduction problems the feed stocks are too tenacious or too resilient
to be broken by compression, impact, or attrition. In other problems the feed must
be reduced to particles of fixed dimensions. These requirements are met by devices
that cut, chop, or tear the feed into a product with the desired characteristics. The
sawtoothed crushers mentioned above do much of their work in this way. True
cutting machines include rotary knife cutters and granulators. These devices find
application in a variety of processes but are especially well adapted to size-
reduction problems in the manufacture of rubber and plastics. They are finding
important applications in recycling paper and plastic materials."
KNIFE CUTTERS. A rotary knife cutter, as shown in Fig. 29.14, contains a
horizontal rotor turning at 200 to 900 r(min in a cylindrical chamber. On the
rotor are 2 to 12 flying knives with edges of tempered steel or stellite passing with
close clearance over 1 to 7 stationary bed knives. Feed particles entering the
chamber from above are cut several hundred times per minute and emerge at the
bottom through a screen with 5- to 8-mm openings. Sometimes the flying knives
are parallel with the bed knives; sometimes, depending on the properties of the
feed, they cut at an angle. Rotary cutters and granulators are similar in design. A
granulator yields more or less irregular pieces; a cutter may yield cubes, thin
squares, or diamonds.
Flying Ra/or
knife -l~f~~~.~~
Bed
kmfe
FIGURE 29.14
Discharge Rotary knife cutter.
SIZE REDUCTION 987
EQUIPMENT OPERATION
For the proper selection and economical operation of size-reduction machinery,
attention must be given to many details of procedure and of auxiliary equipment.
A crusher, grinder, or cutter cannot be expected to perform satisfactorily unless (1)
the feed is of suitable size and enters at a uniform rate; (2) the product is removed
as soon as possible after the particles are of the desired size; (3) unbreakable
material is kept out of the machine; and (4) in the reduction of low-melting or
heat-sensitive products, the heat generated in the mill is removed. Heaters and
coolers, metal separators, pumps and blowers, and constant-rate feeders are
therefore important adjuncts to the size-reduction unit. Factors to consider in
specifying a size-reduction system, including energy efficiency and environmental
issues, are discussed by Kukla 8 and Hixon. 6
OPEN-CIRCUIT AND CLOSED-CIRCUIT OPERATION. In many mills the feed is
broken into particles of satisfactory size by passing it once through the mill. When
no attempt is made to return oversize particles to the machine for further
reduction, the mill is said to be operating in open circuit. This may require excessive
amounts of power, for much energy is wasted in regrinding particles that are
already fine enough. If a 50-mesh product is desired, it is obviously wasteful to
continue grinding 100- or 200-mesh material. Thus it is often economical to remove
partially ground material from the mill and pass it through a size-separation
device. The undersize becomes the product and the oversize is returned to be
reground. The separation device is sometimes inside the mill, as in ultrafine
grinders; or, as is more common, it is outside the mill. Closed-circuit operation is
the term applied to the action of a mill and separator connected so that the oversize
particles are returned to the mill.
For coarse particles the separation device is a screen or grizzly; for fine
powders it is some form of classifier. 1" A typical set of size-reduction machines
and separators operating in closed circuit is diagrammed in Fig. 29.15. The product
from a gyratory crusher is screened into three fractions, fines, intermediate, and
oversize. The oversize is sent back to the gyratory; the fines are fed directly to the
final reduction unit, a ball mill. Intermediate particles are broken in a rod mill
before they enter the ball mill. In the arrangement shown in the diagram the ball
mill is grinding wet; i.e., water is pumped through the mill with the solid to carry
the broken particles to a centrifugal classifier. The classifier throws down the
oversize into a sludge, which is repulped with more water and returned to the
mill. The undersize, or product, emerges from the classifier as a slurry containing
particles of acceptable size. Although screens are simpler to operate than classifiers,
they cannot economically make separations when the particles are smaller than
about 150- to 200-mesh. It is the overgrinding of precisely these fine particles that
results in excessive consumption of energy. Closed-circuit operation is therefore
t These devices are discussed in Chap. 30.
988 OPERATIONS INVOLVING PARTICULATE SOLIDS
Feed Coarse
Recycle
Gyratory
crusher
Screens
Coarse Rod mill
Intermediate
6nes
Centrifugal 8011 mill
classifier
Water
Repulper
Oversize
recycle
Product
slurry
FIGURE 29.15
Flow sheet for c1osed~circuit grinding.
of most value in reduction to fine and ultrafine sizes, which demands that the
separation be done by wet classifiers or air separators of the types described in
Chap. 30. Energy must of course be supplied to drive the conveyors and separators
in a closed-circuit system, but despite this, the reduction in total energy require-
ment over open-circuit grinding often reaches 25 percent.
FEED CONTROL. Of the operations auxiliary to the size reduction itself, control
of the feed to the mill is the most important. The particles in the feed must be of
appropriate size. Obviously they must not be so large that they cannot be broken
by the mill; if too many of the particles are very fine, the effectiveness of many
machines, especially intermediate crushers and grinders, is seriously reduced. With
some solids precompression or chilling of the feed before it enters the mill greatly
increases the ease with which it can be ground. In continuous mills the feed rate
must be controlled within close limits to avoid choking or erratic variations in
SIZE REDUCfION 989
load and yet make full use of the capacity of the machine. In cutting sheet material
into precise squares or thread into uniform lengths for flock, exact control of the
feed rate is obviously essential.
MILL DISCHARGE. To avoid buildup in a continuous mill the rate of discharge
must equal the rate of feed. Furthermore, the discharge rate must be such that
the working parts of the mill can operate most effectively on the material to be
reduced. In a jaw crusher, for example, particles may collect in the discharge
opening and be crushed many times before they drop out. As mentioned before,
this is wasteful of energy if many of the particles are crushed more than necessary.
Operation of a crusher in this way is sometimes deliberate; it is known as choke
crushing. Usually, however, the crusher is designed and operated so that the
crushed particles readily drop out, perhaps carrying some oversize particles, which
are separated and returned. This kind of operation is called free-discharge crushing
or free crushing. Choke crushing is used only in unusual problems, for it requires
large amounts of power and may damage the mill.
With fairly coarse comminuted products, as from a crusher, intermediate
grinder, or cutter, the force of gravity is sufficient to give free discharge. The
product usually drops out the bottom of the mill. In a revolving mill it escapes
through openings in the chamber wall at one end of the cylinder (peripheral
discharge); or it is lifted by scoops and dropped into a cone that directs it out
through a hollow trunnion (trunnion discharge). A slotted grate or diaphragm keeps
the grinding medium from leaving with the product. Peripheral discharge is
common in rod mills, trunnion discharge in ball mills and tube mills.
In discharging mills for fine and ultrafine grinding the force of gravity is
replaced by the drag of a carrier fluid. The fluid may be a liquid or a gas. Wet
grinding with a liquid carrier is common in revolving mills. It causes more wear
on the chamber walls and on the grinding medium than dry grinding, but it saves
energy, increases capacity, and simplifies handling and classification of the product.
A sweep of air, steam, or inert gas removes the product from attrition mills,
fluid-energy mills, and many hammer mills. The powder is taken out of the gas
stream by cyclone separators or bag filters.
ENERGY CONSUMPTION. Enormous quantities of energy are consumed in
size-reduction operations, especially in manufacturing cement; crushing coal, rock,
and shale; and preparing ores for making steel and copper. 7 Size reduction is
probably the most inefficient of all unit operations: over 99 percent of the energy
goes to operating the equipment, producing undesirable heat and noise, leaving
less than 1 percent for creating new surface. As processes have been developed
that require finer and finer particles as feed to a kiln or reactor, the total energy
requirement has increased, for reduction to very fine sizes is much more costly in
energy than simple crushing to relatively coarse products. This is illustrated in
Fig. 29.16, which also shows typical amounts of energy consumed per unit mass
of product by the various kinds of size-reduction equipment.
990 OPERATIONS INVOLVING PARTICULATE SOLIDS
Special Ball Rod
c Crushers
mills mills mills
,g 1000
~
~
"@
~
100
:;
::>
'"oz 0
\
">- ~ I- FIGURE 29.16
""'w
Z
1 Energy consumption vs. product size in
size~reduction equipment. (By permis~
w
10 3 10 2 10
, 10 0 10
, 10
2
10
3
sion, from Comminution and Energy
Consumption, NMAB~264, National
PRODUCT SIZE, mm Academy Press, 1981.)
REMOVAL OR SUPPLY OF HEAT. Since only a very small fraction of the energy
supplied to the solid is used in creating new surface, the bulk of the energy is
converted to heat, which may raise the temperature of the solid by many degrees.
The solid may melt, decompose, or explode unless this heat is removed. For this
reason cooling water or refrigerated brine is often circulated through coils or
jackets in the mill. Sometimes the air blown through the mill is refrigerated, or
solid carbon dioxide (dry ice) is admitted with the feed. Still more drastic
temperature reduction is achieved with liquid nitrogen, to give grinding tempera-
tures below - 75°C. The purpose of such low temperatures is to alter the breaking
characteristics of the solid, usually by making it more friable. In this way
substances like lard and beeswax become hard enough to shatter in a hammer
mill; tough plastics, which stall a mill at ordinary temperatures, become brittle
enough to be ground without difficulty.
SIZE ENLARGEMENT. To improve handling properties, reduce the pressure drop
in packed beds, increase rates of settling or drying, or prevent dusting, small
particles are often bonded together to form lumps of the desired size. This may
be accomplished by forming small pellets or larger briquets by compaction; by
extrusion through a die under high pressure; by solidification of liquid drops in
a spray dryer or prilling tower; by flocculation and coagulation of particles in a
dilute slurry; or by heat bonding in nodulization and sintering processes. It is
difficult to predict the behavior of a given material without actual tests. A binder
is often added when making pellets, briquets, or extrudates so that the particles
will stick together. Equipment for these size-enlargement operations is described
by Walas l2
SYMBOLS
A" Specific surface of particles, m 2 jg or ft2jlb; A"" for feed; A"b' for
product
B,." Total mass fraction of particles smaller than size Dp , resulting from
breakage of particles of size Dp"
SIZE REDUCTION 991
Dp Particle size, mm or ft; Dpa , of feed; Dpb , of product; Dp,max, maxi-
mum particle size nipped by rolls
Dpll Mesh opening in screen 11, mm or ft; Dp (lI+ 1)' in screen 11 + 1; DplP in
screen u
15. Arithmetic average of Dp. and Dp'.+1)' mm or ft
Ds Mean volume-surface diameter, mm or ft; Dsa , of feed; Dsb ' of product
Du Average particle diameter on screen u, which is coarser than screen n
d One-half distance between crushing rolls, m or ft
eo Surface energy per unit area, 1/m2 or ft-lb j /ft 2
g Acceleration of gravity, m/s2 or ft/s2
g, Newton's-law proportionality factor, 32.174 ft-lbfJb rs2
K Constant; K b , in Bond's law; K" in Kick's law; K" in Rittinger's law
m Mass of ball, g or lb
ri1 Feed rate to crusher, kg/s or ton/h
n Speed, r/min; screen number, counting from large screen of series;
exponent in Eq. (29.7); /IT, total number of screens; /l" critical speed
in ball min
P Power, kW or hp
R Radius of crushing rons or ball miJI, m or ft
I" Radius of balls in ball miJI, m or ft
S Grinding-rate function, S-l; SII. for screen n; Su, for screen u
sp Area of particle, m 2 or ft2
t Time, s; tT' total grinding time
U Number of screen coarser than screen n
vp Volume of particle, m' or ft'
W Energy input to crusher, J/g or ft-lbj/lb; w,,, energy absorbed by
material during crushing
W, Bond work index, kWh/ton
x Mass fraction; XII' on screen n; XII,!' on screen n after t time incre-
ments; x u , on screen u; Xl' on coarsest screen; xl.o, coarsest fraction
in feed
Greek letters
Angle between radius and vertical in ban miJI
Exponeut in Eq. (29.13)
Breakage function, fraction of particles of size 15" that are broken to
size 1511
Time increment, s
Change in x. in time At
Crushing efficiency
Mechanical efficiency of crusher
Density of particle, kg/m' or lb/ft'
Sphericity; <!la, of feed; <!lb, of product
Angular velocity, rad/s
992 OPERATIONS INVOLVING PARTICULATE SOLIDS
PROBLEMS
29.1. Trap rock is crushed in a gyratory crusher. The feed is nearly uniform 2-in. spheres.
The differential screen analysis of the product is given in column (\) of Table 29.5. The
power required to crush this material is 400 kW/ton. Of this 10 kW is needed to
operate the empty mill. By reducing the clearance between the crushing head and the
cone, the differential screen analysis of the product becomes that given in column (2)
in Table 29.5. From (a) Rittinger's law and (b) Kick's law, calculate the power required
for the second operation. The feed rate is 110 tonfh.
TABLE 29.5
Data for Prob. 29.1
Product
First grind Second grind
Mesh (1) (2)
4/6 3.1
6/8 10.3 3.3
8/10 20.0 8.2
10/14 18.6 11.2
14/20 15.2 12.3
20/28 12.0 13.0
28/35 9.5 19.5
35/48 6.5 13.5
48/65 4.3 8.5
-65 0.5
65/100 6.2
100/150 4.0
-150 0.3
29.2. Using the Bond method, estimate the power necessary per ton of rock in each of the
operations in Prob. 29.1.
29.3. Solve Example 29.2 for a mill charge consisting entirely of 4/6-mesh material. Plot
the results and compare them with Fig. 29.1.
29.4. Solve Prob. 29.3 with (a) p ~ 1.1 and (b) P~ 1.6. Plot the results. Do they vary as
you expected?
295. Solve Prob. 29.3 with P~ 1.3 and with S varying with D;
for material coarser than
lO-mesh and with D;
for the finer sizes. Are the results as you predicted?
29.6. What rotational speed, in revolutions per minute, would you recommend for a ball
mill 1200 mm in diameter charged with 75-mm balls?
REFERENCES
1. Arbiter, N., and C. C. Harris: Br. Chem. Eng., 10:240 (1965).
2. Berry, C. E.: lnd. Eng. Chem., 38:672 (1946).
3. Bond, F. C.: Trails. A/ME, TP-3308B, and Mining Eng., May 1952.
4. Galanty, H. E.: lnd. Eng. Chem., 55(1):46 (1963).
SIZE REDUCTION 993
5. Gaudin, A. M.: Principles of Mineral Dressing, McGraw~HiI1, New York, 1939, p. 136.
6. Hixon, L. M.: Chem. EIIg. Prog., 87(5):36 (1991).
7. Kapian, L. J.: Chem. EIIg., 88(26):33 (1981).
8. Kukia, R. J.: Chem. Ellg. Prog., 87(5):23 (1991).
9. Perry,J. H.(ecl.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York, 1984; (a) 8-12;
(b) p. 8-17; (c) p. 8-26; (d) p. 8-32; (c) p. 8-36; (j) pp. 8-38 to 8-42; (g) p. 8-45.
10. Reid, K. J.: Chem. Ellg. Sri., 20(11):953 (1965).
11. Sterrett, K. R., and W. M. Sheldon: [lld. El/g. Chem., SS(2):46 (1963).
12. Walas, S. M.: Chemical Process Equipment, Butterworths, Stoneham, MA, 1988, pp. 351-369.
CHAPTER
30
MECHANICAL
SEPARATIONS
Separations are extremely important in chemical mannfacture-in fact, much
processing equipment is devoted to separating one phase or one material from
another. Separations are divided into two classes. One class, known as diffusional
operations, involves the transfer of material between phases, as discussed in Chaps.
17 to 27. Another class, known as mechanical separations, is the subject of this
chapter.
Mechanical separations are applicable to heterogeneous mixtures, not to
homogeneous solutions. The techniques are based on physical differences between
the particles such as size, shape, or density. They are applicable to separating
solids from gases, liquid drops from gases, solids from solids, and solids from
liquids. Two general methods are the use of a sieve, septum, or membrane, such
as a screen or a filter, which retains one component and allows the other to pass;
and the utilization of differences in the rate of sedimentation of particles or drops
as they move through a liquid or gas. For special problems other methods, not
discussed here, are used. These special methods exploit differences in the wettability
or the electrical or magnetic properties of the substances.
SCREENING
Screening is a method of separating particles according to size alone. In industrial
screening the solids are dropped on, or thrown against, a screening surface. The
undersize, or fines, pass through the screen openings; oversize, or tails, d{) not. A
single screen can make but a single separation into two fractions. These are called
unsized fractions, because although either the upper or lower limit of the particle
MECHANICAL SEPARATIONS 995
sizes they contain is known, the other limit is unknown. Material passed through
a series of screens of different sizes is separated into sized fractions, i.e., fractions
in which both the maximum and minimum particle sizes are known. Screening is
occasionally done wet but much more commonly dry.
Industrial screens are made from woven wire, silk or plastic cloth, metal
bars, perforated or slotted metal ·plates, or wires that are wedge shaped in cross
section. Various metals are used, with steel and stainless steel the most common.
Standard screens range in mesh size from 4 in. to 400-mesh, and woven metal
screens with openings as small as I Ilm are commercially available.t Screens finer
than about ISO-mesh are not commonly used, however, because with very fine
particles other methods of separation are usually more economical.
Screening Equipment
Many varieties of screens are available for different purposes, and only a few
representative types are discussed here. In most screens the particles drop through
the openings by gravity; in a few designs they are pushed through the screen by
a brush or centrifugal force. Coarse particles drop easily through large openings
in a stationary surface, but with fine particles the screen surface must be agitated
in some way, such as by shaking, gyrating, or vibrating it mechanically or
electrically. Typical screen motions are illustrated in Fig. 30.1.
t Standard screens are discussed in Chap. 28; screen sizes are tabulated in Appendix 20.
Jikcentrlc
(c)
it
(a) (b)
/~ ~t
~~~~l~~ Eccentric (f)
vIbrator
(e)
FIGURE 30.1
Motions of screens: (a) gyrations in horizontal plane; (b) gyrations in vertical plane; (c) gyrations at
one end, shaking at other; (c) shaking; (e) mechanically vibrated; if) electrically vibrated.
996 OPERATIONS INVOLVING PARTICULATE SOLIDS
STATIONARY SCREENS AND GRIZZLIES. A grizzly is a grid of parallel metal
bars set in an inclined stationary frame. The slope and the path of the material
are usually parallel to the length of the bars. Very coarse feed, as from a primary
crusher, falls on the upper end of the grid. Large chunks roll and slide to the tails'
discharge; small lumps fall through to a separate collector. In cross section the
top of each bar is wider than the bottom, so that the bars can be made fairly deep
for strength without being choked by lumps passing partway through. The spacing
between the bars is 2 to 8 in. (50 to 200 mm). Stationary inclined woven-metal
t
screens operate in the same way, separating particles to 4 in. (12 to 100 mm)
in size. They are effective only with very coarse free-flowing solids containing
few fine particles.
GYRATING SCREENS. A heavy-duty gyrating screen is illustrated in Fig. 30.2a.
Two screens, one above the other, are held in a casing inclined at an angle between
16° and 30° with the horizontal. The feed mixture is dropped on the upper screen
near its highest point. Casing and screens are gyrated in a vertical plane about a
horizontal axis by an eccentric that is set halfway between the feed point and the
Feed
M%r
Flexible
Ball Lower connection
cleaners screen Fines Coarse
(bJ
FIGURE 30.2
(0) Heavy-duty vertically gyrated screen; (b) Electrically vibrated screen.
MECHANICAL SEPARATIONS 997
discharge. The rate of gyration is between 600 and 1800 r(min. The screens are
rectangular and fairly long, typically 1! by 4 ft (0.5 to 1.2 m) to 5 by 14 ft (1.5
to 4.3 m). Oversize particles fall from the lower ends of the screens into collecting
ducts; fines pass through the bottom screen into a discharge chute.
Finer screens are usually gyrated at the feed end in a horizontal plane. The
discharge end reciprocates but does not gyrate. This combination of motions
stratifies the feed, so that fine particles travel downward to the screen surface,
where they are pushed through by the larger particles on top. Often the screening
surface is double, and between the two screens are rubber balls held in separate
compartments. As the screen operates, the balls strike the screen surface and free
the openings of any material that tends to plug them. Dry, hard, rounded or
cubical grains ordinarily pass without trouble through screens, even fine screens;
but elongated, sticky, flaky, or soft particles do not. Under the screening action
such particles may become wedged into the openings and prevent other particles
from passing through. A screen plugged with solid particles is said to be blinded.
VIBRATING SCREENS. Screens that are rapidly vibrated with small amplitude
are less likely to blind than are gyrating screens. The vibrations may be generated
mechanically or electrically. Mechanical vibrations are usually transmitted from
high-speed eccentrics to the casing of the unit and from there to steeply inclined
screens. Electrical vibrations from heavy-duty solenoids are transmitted to the
casing or directly to the screens. Figure 30.2b shows a directly vibrated unit.
Ordinarily no more than three decks are used in vibrating screens. Between 1800
and 3600 vibrations per minute are usual. A 48- by 120-in. (1.2- to 3-m) screen
draws about 4 hp (3 kW).
CENTRIFUGAL SIFTER. In these machines the screen is a horizontal cylinder of
woven metal or plastic. High-speed helical paddles on a central shaft impel the
solids against the inside of the stationary screen; fines pass through, and oversize
is conveyed to the discharge. Plastic screens stretch a little during operation, and
the resulting minute changes in the dimensions of the openings tend to prevent
clogging or blinding. In some designs brushes attached to the paddles assist the
centrifugal action in pushing solids through the screen.
COMPARISON OF IDEAL AND ACTUAL SCREENS. The objective of a screen is
to accept a feed containing a mixture of particles of various sizes and separate it
into two fractions, an underflow that is passed through the screen and an overflow
that is rejected by the screen. Either one, or both, of these streams may be a
product, and in the following discussion no distinction is made between the
overflow and underflow streams from the standpoint of one's being desirable and
the other undesirable.
An ideal screen would sharply separate the feed mixture in such a way that
the smallest particle in the overflow would be just larger than the largest particle
in the underflow. Such an ideal separation defines a cut diameter Dp< that marks
998 OPERATIONS INVOLVING PARTICULATE SOLIDS
the point of separation between the fractions. Usually D p , is chosen to be equal
to the mesh opening of the screen.
Actual screens do not give a perfect separation about the cut diameter;
instead the cumulative screen analyses of the underflow and overflow are like
those shown in Fig. 30.3. In this typical example, the undersize contains about 19
percent of material coarser than D p" and the oversize about 15 percent that is
smaller than D p ,' The closest separations are obtained with spherical particles on
standard testing screens, but even here there is an overlap between the smallest
particles in the overflow and the largest ones in the underflow. The overlap is
especially pronounced when the particles are needlelike or fibrous or where the
particles tend to aggregate into clusters that act as large particles. Some long, thin
particles may strike the screen surface end wise and pass through easily, while other
particles of the same size and shape may strike the screen sidewise and be retained.
Commercial screens usually give poorer separations than testing screens of the
same mesh opening operating on the same mixture.
MATERIAL BALANCES OVER SCREEN. Simple material balances can be written
over a screen which are useful in calculating the ratios of feed, oversize, and
underflow from the screen analyses of the three streams and knowledge of the
desired cut diameter. Let F, D, and B be the mass flow rates of the feed, overflow,
and underflow, respectively, and X F , XD, and x. be the mass fraction of material
A in these three streams. The mass fractions of material B in the feed, overflow,
and underflow are 1 - XF, 1 - X D , and 1 - x •.
Since the total material fed to the screen must leave it either as underflow
or as overflow,
F=D+B (30.1)
O~r\
1.
Cl'
z
t" o.
IX:
w 8 \ ~ ~v"';,.
'"
IX:
"z
~
O. 6
o
\
;:
u
"... O.4
IX:
Undersize \ \
\ \'~ \
iil
""
w
>
~ o. 2
\
"'~ ~
::>
"::>u 0"
0
o 2 3 4 5 FIGURE 30.3
Analyses for Example 30.1.
MECHANICAL SEPARATIONS 999
The material A in the feed must also leave in these two streams and
FXF = DXD + Bx. (30.2)
Elimination of B from Eqs. (30.1) and (30.2) gives
(30.3)
Elimination of D givest
(30.4)
SCREEN EFFECTIVENESS. The effectiveness of a screen (often called the screen
efficiency) is a measure of the success of a screen in closely separating materials
A and B. If the screen functioned perfectly, all of material A would be in the
overflow and all of material B would be in the underflow. A common measure of
screen effectiveness is the ratio of oversize material A that is actually in the overflow
to the amount of A entering with the feed. These quantities are DXF and Fx F,
respectively. Thus
DXD
EA =-- (30.5)
FXF
where EA is the screen effectiveness based on the oversize. Similarly, an effectiveness
EB liased on the undersize materials is given by
B(1 - XB)
E. = (30.6)
F(! - x F )
A combined overall effectiveness can be defined as the product of the two
individual ratios,15 and if this product is denoted by E,
DBx (1 - x )
D B
E = EA E B = -:::;-"-'---"'-
F2xF(1 - XF)
Substitutiug DIF and BIF from Eqs. (30.3) and (30.4) into this equation gives
(XF - XB)(X D - x F)x D(1 - x.)
E= '-'-----"'-''--''-:-:;-:--'-'--'''---~ (30.7)
(XD - x.f(1 - XF)XF
Example 30.1. A quartz mixture having the screen analysis shown in Table 30.1 is
screened through a standard 10-mesh screen. The cumulative screen analysis of
overflow and underflow are given in Table 30.1. Calculate the mass ratios of the
overflow and underflow to feed and the overall effectiveness of the screen.
t Note the identity of Eqs. (30.3) and (30.4) with Eqs. (18.5) and (18.6) for distillation. Although they
are not alike physically, both operations are separation operations, and the same overall material-
balance equations apply to them.
1000 OPERATIONS INVOLVING PARTICULATE SOLiDS
TABLE 30.1
Screen analyses for Example 30.1
Cumulative fraction smaller than Dp
Mesh Dp,mm Feed Overflow Underflow
4 4.699 0 0
6 3.327 0.025 0.071
8 2.362 0.15 0.43 o
10 1.651 0.47 0.85 0.195
14 1.168 0.73 0.97 0.58
20 0.833 0.885 0.99 0.83
28 0.589 0.94 1.00 0.91
35 0.417 0.96 0.94
65 0.208 0.98 0.975
Pan 1.00 1.00
Solution
The cumulative analyses of feed, overflow, and product are plotted in Fig. 30.3. The
cut-point diameter is the mesh size of the screen, which from Table 30.1 is 1.651 mm.
Also from Table 30.1, for this screen,
XD ~ 0.85 XB ~ 0.195
From Eq. (30.3). the ratio of overflow to feed is
D 0.47 - 0.195
0.420
F 0.85 - 0.195
The ratio of underflow to feed is
B D
- ~ 1- - ~ 1 - 0.42 ~ 0.58
F F
The overall effectiveness, from Eq. (30.7), is
(0.47 - 0.195)(0.85 - 0.47)(1 - 0.195)(0.85)
E ~ ~ 0.669
(0.85 - 0.195)2(0.53)(0.47)
CAPACITY AND EFFECTIVENESS OF SCREENS. The capacity of a screen is
measured by the mass of material that can be fed per unit time to a unit
area of the screen. Capacity and effectiveness are opposing factors. To obtain
maximum effectiveness, the capacity must be small, and large capacity is obtainable
only at the expense of a reduction in effectiveness. In practice, a reasonable balance
between capacity and effectiveness is desired. Although accurate relationships are
not available for estimating these operating characteristics of screens, certain
fundamentals apply, which can be used as guides in understanding the basic factors
in screen operation.
The capacity of a screen is controlled simply by varying the rate of
feed to the unit. The effectiveness obtained for a given capacity depends on
MECHANICAL SEPARATIONS 1001
the nature of the screening operation. The overall chance of passage of a
given undersize particle is a function of the number of times the particle strikes
the screen surface aud the probability of passage during a single contact. If the
screen is overloaded, the number of contacts is small and the chance of passage
on contact is reduced by the interference of the other particles. The improvement
of effectiveness attained at the expense of reduced capacity is a result of more
contacts per particle and better chances for passage on each contact.
Ideally, a particle would have the greatest chance of passing through
the screen if it struck the surface perpendicularly, if it were so oriented that its
minimum dimensions were parallel with the screen surface, if it were unimpeded
by any other particles, and if it did not stick to, or wedge into, the screen surface.
None of these conditions applies to actual screening, but this ideal situation can
be used as a basis for estimating the effect of mesh size and wire dimensions on
the performance of screens.
Effect of mesh size on capacity of screens. The probability of passage of a particle
through a screen depends on the fraction of the total surface represented by
openings, on the ratio of the diameter of the particle to the width of an
opening in the screen, and on the number of contacts between the particle
and the screen surface. When these factors are all constant, the average number
of particles passing through a single screen opening in unit time is nearly constant,
independent of the size of the screen opening. If the size of the largest particle that
can just pass through a screen is taken equal to the width of a screen opening,
both dimensions may be represented by D p ,' For a series of screens of different
mesh sizes, the number of openings per unit screen area is proportional to l(D~.
The mass of one particle is proportional to D;,. The capacity of the screen, in
mass per unit time, is, then, proportional to (l(D;,)D;, = D po' Then the capacity
of a screen, in mass per unit time, divided by the mesh size should be constant
for any specified conditions of operation. This is a well-known practical rule of
thumb. 16
Capacities of actual screens. Although the preceding analysis is useful in analyzing
the fundamentals of screen operation, in practice several complicating factors
appear that cannot be treated theoretically. Some of these disturbing factors are
the interference of the bed of particles with the motion of anyone; blinding;
cohesion of particles to each other; the adhesion of particles to the screen surface;
and the oblique direction of approach of the particles to the surface. When large
and small particles are present, the large particles tend to segregate in a layer next
to the screen and so prevent the smaller particles from reaching the screen. All
these factors tend to reduce capacity and lower effectiveness. Moisture content of
the feed is especially important. Either dry particles or particles moving in a stream
of water screen more readily than damp particles, which are prone to stick to the
screen surface and to each other and to screen slowly and with difficulty.
Capacities of actual screens, in ton(ft2-h-mm mesh size, normally range between
0.05 and 0.2 for grizzlies to 0.2 and 0.8 for vibrating screens. As the particle size
1002 OPERATiONS INVOLVING PARTICULATE SOLIDS
is reduced, screening becomes progressively more difficult, and the capacity and
effectiveness are, in general, low for particle sizes smaller than about ISO-mesh.
FILTRATION
Filtration is the removal of solid' particles from a fluid by passing the fluid
through a filtering medium, or seplum, on which the solids are deposited.
Industrial filtrations range from simple straining to highly complex separa-
tions. The fluid may be a liquid or a gas; the valuable stream from the filter
may be the fluid, or the solids, or both. Sometimes it is neither, as when
waste solids must be separated from waste liquid prior to disposal. In industrial
filtration the solids content of the feed ranges from a trace to a very high
percentage. Often the feed is modified in some way by pretreatment to increase
the filtration rate, as by heating, recrystallizing, or adding a "filter aid" such as
cellulose or diatomaceous earth. Because of the enormous variety of materials to
be filtered and the widely differing process conditions, a large number of types of
filters has been developed,29'.35, a few of which are described below.
Fluid flows through a filter medium by virtue of a pressure differential
across the medium. Filters are also classified, therefore, into those that operate
with a pressure above atmospheric on the upstream side of the filter medium and
those that operate with atmospheric pressure on the upstream side and a vacuum
on the downstream side. Pressures above atmospheric may be developed by the
force of gravity acting on a column ofliquid, by a pump or blower, or by centrifugal
force. Centrifugal filters are discussed in a later section of this chapter. In a gravity
filter the filter medium can be no finer than a coarse screen or a bed of coarse
particles like sand. Gravity filters are therefore restricted in their industrial
applications to the draining of liquor from very coarse crystals, the clarification
of potable water, and the treatment of wastewater.
Most industrial filters are pressure filters, vacuum filters, or centrifugal
separators. They are also either continuous or discontinuous, depending on
whether the discharge of filtered solids is steady or intermittent. During much
of the operating cycle of a discontinuous filter the flow of fluid through the
device is continuous, but it must be interrupted periodically to permit discharging
the accumulated solids. In a continuous filter the discharge of both solids and
fluid is uninterrupted as long as the equipment is in operation.
Filters are divided into three main groups: cake filters, clarifying filters,
and crossflow filters. Cake filters separate relatively large amounts of solids
as a cake of crystals or sludge, as illustrated in Fig. 30Aa. Often they include
provisions for washing the cake and for removing some of the liquid from
the solids before discharge. Clarifying filters remove small amounts of solids
to produce a clean gas or a sparkling clear liquids such as beverages. The solid
particles are trapped inside the filter medium, as shown in Fig. 30Ab, or on
its external surfaces. Clarifying filters differ from screens in that the pores of
the filter medium are much larger in diameter than the particles to be removed.
In a crossflow filter the feed suspension flows under pressure at a fairly high
MECHANICAL SEPARATIONS 1003
! Suspension
j Filter
~cak' medium
~Medium
(a) (b)
o o
• ~
o •• ••• • • •• •
_..:.._-=o,---__ •• ••
• •• 0 00,:--;:,0,;;-_ Concentrated
...•
Suspension 0 .
• • 0
•
•
... .... .... ..-
•
•••
e. e • • o. •
••
• •••••
suspenSion
Memb"n. f;~t~~mi~~\~~~I~'
J
Filtrate
(c)
FIGURE 30.4
Mechanisms of filtration: (a) cake filter; (b) clarifying filter; (c) crossftow filter.
velocity across the filter medium (Fig. 30.4c). A thin layer of solids may form on
the surface ofthe medium, but the high liquid velocity keeps the layer from building
up. The filter medium is a ceramic, metal, or polymer membrane with pores small
enough to exclude most of the suspended particles. Some of the liquid passes
through the medium as clear filtrate, leaving a more concentrated suspension
behind. As discussed later, an ultrafilter is a crossflow unit containing a membrane
with extremely small openings, used for the separation and concentration of
colloidal particles and large molecules.
CAKE FILTERS
At the start of filtration in a cake filter some solid particles enter the pores
of the medium and are immobilized, but soon others begin to collect on the
septum surface. After this brief initial period the cake of solids does the filtration,
not the septum; a visible cake of appreciable thickness builds up on the surface
and must be periodically removed. Except as noted under bag filters for gas
cleaning, cake filters are used almost entirely for liquid-solid separations. As with
other filters they may operate with above-atmospheric pressure upstream from
the filter medium or with vacuum applied downstream. Either type can be
continuous or discontinuous, but because of the difficulty of discharging the solids
against a positive pressure, most pressure filters are discontinuous.
1004 OPERATIONS INVOLVING PARTICULATE SOLIDS
DISCONTINUOUS PRESSURE FILTERS. Pressure filters can apply a large pres-
sure differential across the septum to give economically rapid filtration with
viscous liquids or fine solids. The most common types of pressure filters are filter
presses and shell-and-Ieaf filters.
Filter press. A filter press contains a set of plates designed to provide a series
of chambers or compartments in which solids may collect. The plates are
covered with a filter medium such as canvas. Slurry is admitted to each compart-
ment under pressure; liquor passes through the canvas and out a discharge pipe,
leaving a wet cake of solids behind.
The plates of a filter press may be square or circular, vertical or horizontal.
Most commonly the compartments for solids are formed by recesses in the faces
of molded polypropylene plates. In other designs, they are formed as in the
plate-and·frame press shown in Fig. 30.5, in which square plates 6 to 78 in. (150 mm
to 2 m) on a side alternate with open frames. The plates are! to 2 in. (6 to
50 mm) thick, the frames! to 8 in. (6 to 200 mm) thick. Plates and frames sit
vertically in a metal rack, with cloth covering the face of each plate, and are
squeezed tightly together by a screw or a hydraulic ram. Slurry enters at one end
of the assembly of plates and frames. It passes through a channel running
lengthwise through one corner of the assembly. Auxiliary channels carry slurry
from the main inlet channel into each frame. Here the solids are deposited on the
cloth-covered faces of the plates. Liquor passes through the cloth, down grooves
or corrugations in the plate faces, and out of the press.
After assembly of the press, slurry is admitted from a pump or pressurized
tank under a pressure of 3 to 10 atm. Filtration is continued until liquor no longer
flows out the discharge or the filtration pressure suddenly rises. These occur when
the frames are full of solid and no more slurry can enter. The press is then said
to be jammed. Wash liquid may then be admitted to remove soluble impurities
from the solids, after which the cake may be blown with steam or air to displace
as much residual liquid as possible. The press is then opened, and the cake of
solids removed from the filter medium and dropped to a conveyor or storage bin.
In many filter presses these operations are carried out automatically, as in the press
illustrated in Fig. 30.5.
Thorough washing in a filter press may take several hours, for the wash
liquid tends to follow the easiest paths and to bypass tightly packed parts of the
cake. If the cake is less dense in some parts than in others, as is usually the case,
much of the wash liquid will be ineffective. If washing must be exceedingly good,
it may be best to reslurry a partly washed cake with a large volume of wash liquid
and refilter it or to use a shell-and-Ieaf filter, which permits more effective washing
than a plate-and-frame press.
Shell-and-Ieaf filters. For filtering under higher pressures than are possible in a
plate-and-frame press, to economize on labor, or where more effecti·.~ washing of
the cake is necessary, a shell-and-Ieaf filter may be used. In the horizontal-tank
design shown in Fig. 30.6 a set of vertical leaves is held on a retractable rack. The
Filtrate
/'/0 1 .L discharge
(typical)
Follower or
movable head
Control
panel
Slurry Stationary
feed head
(typical)
Polypropylene
plate
Cylinder Bracket
or tail stand
Double acting
hydraulic
cylinder
FIGURE 30.5
Filter press equipped for automatic operation. (Shriver Filters, Eimco Process Equipmelll Co.)
1006 OPERATIONS INVOLVING PARTICULATE SOLIDS
FIltrate discharge
manifold
FIGURE 30.6
Horizontal-tank pressure leaf filter.
unit shown in the figure is open for discharge; during operation the leaves are
inside the closed tank. Feed enters through the side of the tank; filtrate passes
through the leaves into a discharge manifold. The design shown in Fig. 30.6 is
widely used for filtrations involving filter aids, as discussed later in this chapter.
AUTOMATIC BELT FILTER. The Larox belt filter illustrated in Fig. 30.7 is a
discontinuous pressure filter that separates, compresses, washes, and automatically
discharges the cake. Filtration takes place in from 2 to 20 horizontal chambers,
set one above the other. A belt of filter cloth passes through the filter chambers
in turn. With the belt held stationary, each chamber is filled with solids during
the filtration cycle. High-pressure water is then pumped behind a flexible dia-
phragm in the chamber ceiling, squeezing the cake and mechanically expressing
Guide roller
Cloth length
Cake
compensator Filter cake
Cloth driving roller
Cloth centering
Counter pressure roller
Filter cloth washing ---,..,,:,,0
FIGURE 30.7
Larox automatic pressure filter showing path of filter belt and mechanism of cake discharge. (Larox,
Inc.)
MECHANICAL SEPARATIONS 1007
some of the liquid. With the diaphragm released, wash water may be passed
through the cake and the cake recompressed by the diaphragm if desired. Finally,
air is blown through the cake to remove additional liquid.
The chambers are then opened hydraulically so that the belt may be moved
a distance somewhat greater than the length of one chamber. This action
discharges cake from both sides of the filter as shown in Fig. 30.7. At the same
time, part of the belt passes between spray nozzles for washing. After all the cake
has been discharged, the belt is stopped, the chambers are closed, and the filtration
cycle is repeated. All the steps are actuated automatically by impulses from a
control panel. Filter sizes range from O.S m 2 (S.6 ft2) to 31.5 m2 (339 ft 2). The
overall cycle is relatively short, typically 10 to 30 min, so that these filters can be
used in continuous processes.
DISCONTINUOUS VACUUM FILTERS. Pressure filters are usually discontinuous;
vacuum filters are usually continuous. A discontinuous vacuum filter, however, is
sometimes a useful tool. A vacuum nutsch is little more than a large Biichner
funnel, 1 to 3 m (3 to 10 ft) in diameter and forming a layer of solids 100 to 300 mm
(4 to 12 in.) thick. Because of its simplicity, a nutsch can readily be made of
corrosion-resistant material and is valuable where experimental batches of a
variety of corrosive materials are to be filtered. Nutsches are uncommon in
large-scale processes because of the labor involved in digging out the cake; they
are, however, useful as pressure filters in combination filter-dryers for certain kinds
of batch operations 2 •
CONTINUOUS VACUUM FILTERS. In all continuous vacuum filters liquor is
sucked through a moving septum to deposit a cake of solids. The cake is moved
out of the filtering zone, washed, sucked dry, and dislodged from the septum,
which then reenters the slurry to pick up another load of solids. Some part of the
septum is in the filtering zone at all times, part is in the washing zone, and part
is being relieved of its load of solids, so that the discharge of both solids and liquids
from the filter is uninterrupted. The pressure differential across the septum in a
continnous vacuum filter is not high, ordinarily between 250 and 500 mm Hg.
Various designs of filter differ in the method 0,' admitting slurry, the shape of the
filter surface, and the way in which the solids are discharged. Most all, however,
apply vacuum from a stationary source to the moving parts of the unit through
a rotary valve.
Rotary-drum filter. The most common type of continuous vacuum filter is the
rotary-drum filter illustrated in Fig. 30.S. A horizontal drum with a slotted face
turns at 0.1 to 2 r/min in an agitated slurry trough. A filter medium, such as canvas,
covers the face of the drum, which is partly submerged in the liquid. Under the
slotted cylindrical face of the main drum is a second, smaller drum with a solid
surface. Between the two drums are radial partitions dividing the annular space
into separate compartments, each connected by an internal pipe to one hole in
the rotating plate of the rotary valve. Vacuum and air are alternately applied to
1008 OPERATIONS INVOLVING PARTICULATE SOLIDS
Liquid Rotary valve
outlets If/temol pipes to various
\ Jo.I..!IU>lc;parlmenl
Clotn-covered
outer drum
Feed pipe W
Inner drum
Slurry trough
Liquid Doctor
level blade
FIGURE 30.S
Continuous rotary vacuum filter.
each compartment as the drum rotates. A strip of filter cloth covers the exposed
face of each compartment to form a succession of panels.
Consider now the panel shown at A in Fig. 30.8. It is just about to enter
the slurry in the trough. As it dips under the surface of the liquid, vacuum is
applied through the rotary valve. A layer of solids builds up on the face of the
panel as liquid is drawn through the cloth into the compartment, through the
internal pipe, through the valve, and into a collecting tank. As the panel leaves
the slurry and enters the washing and drying zone, vacuum is applied to the panel
from a separate system, sucking wash liquid and air through the cake of solids.
As shown in the flow sheet of Fig. 30.9, wash liquid is drawn through the filter
into a separate collecting tank. After the cake of solids on the face of the panel
has been sucked as dry as possible, the panel leaves the drying zone, vacuum is
cut off, and the cake is removed by scraping it off with a horizontal knife known
as a doctor blade. A little air is blown in under the cake to belly out the cloth.
This cracks the cake away from the cloth and makes it unnecessary for the knife
to scrape the drum face itself. Once the cake is dislodged, the panel reenters the
slurry and the cycle is repeated. The operation of any given panel, therefore, is
cyclic, but since some panels are in each part of the cycle at all times, the operation
of the filter as a whole is continuous.
Many variations of the rotary-drum filter are commercially available. In
some designs there are no compartments in the drum; vacuum is applied to the
entire inner snrface of the filter medium. Filtrate and wash liquid are removed
together throngh a dip pipe; solids are discharged by air flow through the cloth
from a stationary shoe inside the drum, bellying out the filter cloth and cracking
off the cake. In other models the cake is lifted from the filter surface by a set of
closely spaced parallel strings or by separating the filter cloth from the drum
surface and passing it around a small-diameter roller. The sharp change in
direction at this roller dislodges the solids. The cloth may be washed as it returns
from the roller to the underside of the drum. Wash, liquid may be sprayed directly
on the cake surface, or, with cakes that crack when air is drawn through them, it
MECHANICAL SEPARATIONS 1009
Air connection
Continuous rotary filler
Feed
Wash
water
pump
Dry
vacuum
pump
Air
aut
Wash
Barometric
seal
FIGURE 30.9
Flow sheet for continuous vacuum filtration.
may be sprayed on a cloth blanket that travels with the cake through the washing
zone and is tightly pressed against its outer surface.
The amount of submergence of the drum is also variable. Most bottom-feed
filters operate with about 30 percent of their filter area submerged in the slurry.
When high filtering capacity and no washing are desired, a high-submergence
filter, with 60 to 70 percent of its filter area submerged, may be used. The capacity
of any rotary filter depends strongly on the characteristics of the feed slurry and
particularly on the thickness of the cake that may be deposited in practical
operation. The cakes formed on industrial rotary vacuum filters are 3 to about
40 mm (.g to It in.) thick. Standard drum sizes range from 0.3 m (1 ft) in diameter
with a O.3-m (l-ft) face to 3 m (10 ft) in diameter with a 4.3-m (14-ft) face.
Continuous rotary vacuum filters are sometimes adapted to operate under
positive pressures up to about 15 atm for situations in which vacuum filtration is
not feasible or economical. This may be the case when the solids are very fine and
filter very slowly or when the liquid has a high vapor pressure, has a viscosity
greater than 1 P, or is a saturated solution that will crystallize if cooled at all.
With slow-filtering slurries the pressure differential across the septum must be
greater than can be obtained in a vacuum filter; with liquids that vaporize or
crystallize at reduced pressure, the pressure on the downstream side of the septum
cannot be less than atmospheric. However, the mechanical problems of discharging
1010 OPERATIONS INVOLVING PARTICULATE SOLIDS
the solids from these filters, their high cost and complexity, and their small size
limit their application to special problems. Where vacuum filtration cannot be
used, other means of separation, such as continuous centrifugal filters, should be
considered.
A precoat filter is a rotary-drum filter modified for filtering small amounts
of fine or gelatinous solids that ordinarily plug a filter cloth. In the operation of
this machine a layer of porous filter aid, such as diatomaceous earth, is first
deposited on the filter medium. Process liquid is then sucked through the layer of
filter aid, depositing a very thin layer of solids. This layer and a little of the filter
aid are then scraped off the drum by a slowly advancing knife, which continually
exposes a fresh surface of porous material for the subsequent liquor to pass
through. A precoat filter may also operate under pressure. In the pressure type
the discharged solids and filter aid collect in the housing, to be removed period-
ically at atmospheric pressure while the drum is being recoated with filter aid.
Precoat filters can be used only where the solids are to be discarded or where
their admixture with large amounts of filter aid introduces no serious problem.
The usual submergence of a precoat-filter drum is 50 percent.
Horizontal belt filter. When the feed contains coarse fast-settling particles of solid,
a rotary-drum filter works poorly or not at all. The coarse particles cannot be
suspended well in the slurry trough, and the cake that forms often will not adhere
to the surface of the filter drum. In this situation a top-fed horizontal filter may
be used. The moving belt filter shown in Fig. 30.10 is one of several types of
Feed
mechanism
Drainage belt
FIGURE 30.10
Horizontal belt filter.
MECHANICAL SEPARATIONS 1011
horizontal filter; it resembles a belt conveyor, with a transversely ridged support
or drainage belt carrying the filter cloth, which is also in the form of an endless
belt. Central openings in the drainage belt slide over a longitudinal vacuum box,
into which the filtrate is drawn. Feed slurry flows onto the belt from a distributor
at one end of the unit; filtered and washed cake is discharged from the other.
Belt filters are especially useful in waste treatment, since the waste often
contains a very wide range of particle sizes.'" They are available in sizes from
0.6 to 5.5 m (2 to 18 ft) wide and 4.9 to 33.5 m (16 to 110 ft) long, with filtration
areas up to 110 m 2 (1200 fe). Some models are "indexing" belt filters, similar in
action to the Larox pressure filter described earlier; in these the vacuum is
intermittently cut off and reapplied. The belt is moved forward half a meter or so
when the vacuum is off and is held stationary while vacuum is applied. This avoids
the difficulty of maintaining a good vacuum seal between the vacuum box and a
moving belt.
Centrifugal Filters
Solids that form a porous cake can be separated from liquids in a filtering
centrifuge. Slurry is fed to a rotating basket having a slotted or perforated wall
covered with a filter medium such as canvas or metal cloth. Pressure resulting
from the centrifugal action forces the liquor through the filter medium, leaving
the solids behind. If the feed to the basket is then shut off and the cake of solids
spun for a short time, much of the residual liquid in the cake drains off the particles,
leaving the solids much "drier" than those from a filter press or vacuum filter.
When the filtered material must subsequently be dried by thermal means, consider-
able savings may result from the use of a centrifuge.
The main types of filtering centrifuges are suspended batch machines, which
are discontinuous in their operation; automatic short-cycle batch machines; and
continuous conveyor centrifuges. In suspended centrufuges the filter media are
canvas or other fabric or woven metal cloth. In automatic machines fine metal
screens are used; in conveyor centrifuges the filter medium is usually the slotted
wall of the basket itself.
SUSPENDED BATCH CENTRIFUGES. A common type of batch centrifuge in
industrial processing is the top-suspended centrifuge shown in Fig. 30.11. The
perforated baskets range from 750 to 1200 mm (30 to 48 in.) in diameter and from
18 to 30 in deep and turn at speeds between 600 and 1800 r/min. The basket is
held at the lower end of a free-swinging vertical shaft driven from above. A filter
medium lines the perforated wall of the basket. Feed slurry enters the rotating
basket through an inlet pipe or chute. Liquor drains through the filter medium
into the casing and out a discharge pipe: the solids form a cake 50 to 150 mm
(2 to 6 in) thick inside the basket. Wash liquid may be sprayed through the solids
to remove soluble material. The cake is then spun as dry as possible, sometimes
at a higher speed than during the loading and washing steps. The motor is shut
off and the basket nearly stopped by means of a brake. With the basket slowly
1012 OPERATIONS INVOLVING PARTICULATE SOLIDS
Motor
Feed
inlet
~
Wash
inlet
Casing -jf---l+I F+++-+.Salids
cake
~ Liquid Perforated
basket
drowoff
Adjus/able
~salids
unlaoder Removable
knife valve plate
discharge
FIGURE 30.11
Top-suspended basket centrifuge.
turning, at perhaps 30 to 50 rlmin, the solids are discharged by cutting them out
with an unloader knife, which peels the cake off the filter medium and drops it
through an opening in the basket floor. The filter medium is rinsed clean, the
motor turned on, and the cycle repeated.
Top-suspended centrifuges are used extensively in sugar refining, where they
operate on short cycles of 2 to 3 min per load and produce up to 5 tonlh of
crystals per machine. Automatic controls are often provided for some or all of the
steps in the cycle. In most processes where large tonnages of crystals are separated,
however, other automatic or continuous conveyor centrifuges are used.
Another type of batch centrifuge is driven from the bottom, with the drive
motor, basket, and casing all suspended from vertical legs mounted on a base
MECHANICAL SEPARATIONS 1013
plate. Solids are unloaded by hand through the top of the casing or plowed out
through openings in the floor of the basket as in top-suspended machines. Except
in sugar refining, suspended centrifuges usually operate on cycles of 10 to 30 min
per load, discharging solids at a rate of 300 to 1800 kg/h (700 to 4000 1b/h).
AUTOMATIC BATCH CENTRIFUGES. A short-cycle automatic batch centrifuge is
illustrated in Fig. 30.12. In this machine the basket rotates at constant speed about
a horizontal axis. Feed slurry, wash liquid, and screen rinse are successively
sprayed into the basket at appropriate intervals for controlled lengths of time. The
basket is unloaded while turning at full speed by a heavy knife that rises
periodically and cuts the solids out with considerable force through a discharge
chute. Cycle timers and solenoid-operated valves control the various parts of the
operation: feeding, washing, spinning, rinsing, and unloading. Any part of the cycle
may be lengthened or shortened as desired.
The basket in these machines is between 500 and 1100 mm (20 and 42 in.)
in diameter. Automatic centrifuges have high productive capacity with free-
draining crystals. Usually they are not used when the feed contains many particles
finer than ISO-mesh. With coarse crystals the total operating cycle ranges from
35 to 90 s, so that the hourly throughput is large. Because of the short cycle and
the small amount of holdup required for feed slurry, filtrate, and discharged solids,
automatic centrifuges are easily incorporated into continuous manufacturing
processes. The small batches of solid can be effectively washed with small amounts
of wash liquid, and-as in any batch machine-the amount of washing can be
temporarily increased to clean up off-quality material should it become necessary.
LI,ml
Unloader control
cylinder
Feed
valve
Unloader hy<tro<Jlic pump Liquid outlet
FIGURE 30.12
Automatic batch centrifuge.
1014 OPERATIONS INVOLVING PARTICULATE SOLIDS
Automatic centrifuges cannot handle slow-draining solids, which would give
uneconomically long cycles, or solids that do not discharge cleanly through the
chute. There is also considerable breakage or degradation of the crystals by the
unloader knife.
CONTINUOUS FILTERING CENTRIFUGES. A continuous centrifugal separator
for coarse crystals is the reciprocating-conveyor centrifuge shown in Fig. 30.13. A
rotating basket with a slotted wall is fed through a revolving feed funnel. The
purpose of the funnel is to accelerate the feed slurry gently and smoothly. Feed
enters the small end of the funnel from a stationary pipe at the axis of rotation
of the basket. It travels toward the large end of the funnel, gaining speed as it
goes, and when it spills off the funnel onto the wall of the basket, it is moving in
the same direction as the wall and at very nearly the same speed. Liquor flows
through the basket wall, which may be covered with a woven metal cloth. A layer
of crystals 25 to 75 mm (1 to 3 in.) thick is fonned. This layer is moved over the
filtering surface by a reciprocating pusher. Each stroke of the pusher moves the
crystals a few inches toward the lip of the basket; on the return stroke a space is
opened on the filtering surface in which more cake can be deposited. When the
crystals reach the lip of the basket, they fly outward into a large casing and drop
into a collector chute. Filtrate and any wash liquid that is sprayed on the crystals
during their travel leave the casing through separate outlets. The gentle accelera-
tion of the feed slurry and deceleration of the discharged solids minimize breakage
of the crystals. M ultistage units that minimize the distance of travel of the crystals
in each stage are used with solid cakes that do not "convey" properly in a
pipe
Reciprocating piston
"-"!+r-Feed funnel
i---A'm,ss door
~r--it~'<nmvnozzle
::~---*-'SnlidSdischorqe
Liquor disch£7rq,./
FIGURE 30.13
Reciprocating-conveyor continuous centrifuge.
MECHANICAL SEPARATIONS 1015
single-stage machine. Reciprocating centrifuges are made with baskets ranging in
diameter from 300 to 1200 mm (12 to 48 in.). They dewater and wash 0.3 to
25 ton/h of solids containing no more than about 10 percent by weight of material
finer than lOO-mesh.
FILTER MEDIA. The septum in any filter must meet the following require-
ments:
1. It must retain the solids to be filtered, giving a reasonably clear filtrate.
2. It must not plug or blind.
3. It must be resistant chemically and strong enough physically to withstand the
process conditions.
4. It must permit the cake formed to discharge cleanly and completely.
5. It must not be prohibitively expensive.
In industrial filtration a common filter medium is canvas cloth, either duck
or twill weave. Many different weights and patterns of weave are available for
different services. Corrosive liquids require the use of other filter media, such as
woolen cloth, metal cloth of monel or stainless steel, glass cloth, or paper. Synthetic
fabrics like nylon, polypropylene, and various polyesters are also highly resistant
chemically.
In a cloth of a given mesh size, smooth synthetic or metal fibers are less
effective than the more ragged natural fibers in removing very fine particles.
Ordinarily, however, this is a disadvantage only at the start of filtration, because
except with hard, coarse particles containing no fines the actual filtering medium
is not the septum but the first layer of deposited solids. Filtrate may first come
through cloudy, then grow clear. Cloudy filtrate is returned to the slurry tank for
refiltration.
FILTER AIDS. Slimy or very fine solids that form a dense, impermeable cake
quickly plug any filter medium that is fine enough to retain them. Practical
filtration of sucb materials requires that the porosity of the cake be increased to
permit passage of the liquor at a reasonable rate. This is done by adding a filter
aid, such as diatomaceous silica, perlite, purified wood cellulose, or other inert
porous solid, to the slurry before filtration. The filter aid may subsequently be
separated from the filter cake by dissolving away the solids or by burning out the
filter aid. Uthe solids have no value, they and the filter aid are discarded together.
Another way of using a filter aid is by precoating, i.e., depositing a layer of
it on the filter medium before filtration. In batch filters the precoat layer is usually
thin; in a continuous precoat filter, as described previously, the layer of precoat
is thick, and the top of the layer is continually scraped off by an advancing knife
to expose a fresh filtering surface. Precoats prevent gelatinous solids from plugging
1016 OPERATIONS INVOLVING PARTICULATE SOLIDS
the filter medium and give a clearer filtrate. The precoat is really a part of the
filter medium rather than of the cake.
PRINCIPLES OF CAKE FILTRATION
Filtration is a special example of flow through porous media, which was discussed
in Chap. 7 for cases in which the resistances to flow are constant. In filtration the
flow resistances increase with time as the filter medium becomes clogged or a filter
cake builds up, and the equations given in Chap. 7 must be modified to allow for
this. The chief quantities of interest are the flow rate through the filter and the
pressure drop across the unit. As time passes during filtration, either the flow rate
diminishes or the pressure drop rises. In what is called constant-pressure filtration
the pressure drop is held constant and the flow rate allowed to fall with time; less
commonly, the pressure drop is progressively increased to give what is called
constant-rate filtration.
In cake filtration the liquid passes through two resistances in series: that of
the cake and that of the filter medium. The filter-medium resistance, which is the
only resistance in clarifying filters, is normally important only during the early
stages of cake filtration. The cake resistance is zero at the start and increases with
time as filtration proceeds. If the cake is washed after it is filtered, both resistances
are constant during the washing period and that of the filter medium is nsually
negligible.
The overall pressure drop at any time is the sum of the pressure drops over
medium and cake. If Pa is the inlet pressure, p, the outlet pressure, and P' the
pressure at the boundary between cake and medium,
Ap = Pa - Pb = (Pa - p') + (p' - P.) = Ap, + APm (30.8)
where Ap = overall pressure drop
Ap, = pressure drop over cake
APm = pressure drop over medium
PRESSURE DROP THROUGH FILTER CAKE. Figure 30.14 shows diagrammati-
cally a section through a filter cake and filter medium at a definite time t from the
start of the flow of filtrate. At this time the thickness of the cake, measured from
the filter medium, is L,. The filter area, measured perpendicularly to the direction
of flow, is A. Consider the thin layer of cake of thickness dL lying in the cake at
a distance L from the medium. Let the pressure at this point be p. This layer
consists of a thin bed of solid particles through which the filtrate is flowing. In a
filter bed the velocity is sufficiently low to ensure laminar flow. Accordingly, as a
starting point for treating the pressure drop through the cake, an equation of the
form of Eq. (7.17) can be used, noting that Ap/L = dp/dL. If the velocity of the
filtrate is designated as u, Eq. (7.17) becomes
dp 150l'u(1 - e)2
(30.9)
dL gJ..if.>,Dp}'e'
MECHANICAL SEPARATIONS 1017
Flilrale
-+--- VP
Po Direction
~ ....-of
a flow of
slurry
Pb
I1
pi
'<.,l
.l1
§
~
1;j
:§-
FIGURE 30.14
Section through filter medium and cake, showing
pressure gradients; p, fluid pressure; L, distance from
filter medium.
Often the pressure drop is expressed as a function of the surface-volume ratio
instead of the particle size. Substitution of 6(vp/sp) for iI>,Dp (Eq. (7.10)) gives
dp 4.17Jlu(1 - e)'(sp/vpJ'
(30.10)
dL g,e 3
where dp/dL = pressure gradient at thickness L
Jl = viscosity of filtrate
u= linear velocity of filtrate, based on filter area
sp = surface of single particle
vp = volume of single particle
e= porosity of cake
g, = Newton's-law proportionality factor
For beds of compressible particles or beds with a very low void fraction the
coefficient in Eq. (30.10) may be much larger than 4.17.
The linear velocity u is given by the equation
u = dV/dt (30.11)
A
where V is the volume of filtrate collected from the start of the filtration to
time t. Since the filtrate must pass through the entire cake, V/A is the same for
all layers and u is independent of L.
1018 OPERATIONS INVOLVING PARTICULATE SOLIDS
The volume of solids iu the layer is A(1 - e) dL, and if Pp is the density of
the particles, the mass dm of solids in the layer is
dm = pp(l - e)A dL (30.12)
Elimination of dL from Eqs (30.10) and (30.12) gives
k,!,u(splvp)2(l - e) d
d p= m (30.13)
g,ppAe'
where k 1 is used in place of the coefficient 4.17 in Eq. (30.10).
COMPRESSIBLE AND INCOMPRESSIBLE FILTER CAKES. In the filtration under
low pressure drops of slurries containing rigid uniform particles, all factors on the
right-hand side of Eq. (30.13) except m are independent of L, and the equation is
integrable directly, over the thickness of the cake. If m, is the total mass of solids
in the cake, the resul t is
fm, dm
f
P" k,!,U(S Iv )'(1 - e)
dp = p P
p' gcppA s3 0
, k,!,u(s.lvp)'(1 - elm,
Pa - P = A ' = !1p, (30.14)
gcP P S
Filter cakes of this type are called incompressible.
For use in Eq. (30.14) a specific cake resistance Cl. is defined by the equation
!1p,g,A
C(=--- (30.15)
f.lum c
where
k,(s.lv,)2(1 - e)
a= (30.16a)
S3 pp
The cake resistance a may also be expressed in terms of the particle size D p'
with a new coefficient k 2 :
(30.16b)
For incompressible cakes a is independent of the pressure drop and of position
in the cake.
From Eq. (30.15), a is the resistance of a cake that gives a unit pressure drop
when !', u, and mjA all equal 1.0. Equation (30.16b) shows that a is influenced
solely by the physical properties of the cake, especially the particle size Dp and
the porosity e.
Most cakes encountered industrially are not made up of individual rigid
particles. The usual slurry is a mixture of agglomerates, or floes, consisting of loose
assemblies of very small particles, and the resistance of the cake depends on the
MECHANICAL SEPARATIONS 1019
properties of the floes rather than on the geometry of the individual particles.'"
The floes are deposited from the slurry on the upstream face of the cake and form
a complicated network of channels to which Eq. (30.13) does not precisely apply.
The resistance of such a sludge is sensitive to the method used in preparing the
slurry and to the age and temperature of the material. Also, the floes are distorted
and broken down by the forces existing in the cake, and the factors e, k 2 , and sp/vp
vary from layer to layer.
Such a filter cake is called compressible. In a compressible cake, " varies
with distance from the septum, since the cake nearest the septum is subject to the
greatest compressive force and has the lowest void fraction. This makes the
pressure gradient nonlinear, as shown in Fig. 30.14. The local value of" may also
vary with time. In consequence, Eq. (30.14) does not strictly apply. In practice,
however, the variations in " with time and location are ignored. An average value
is obtained experimentally for the material to be filtered, using Eq. (30.15) for the
calculation.
FILTER-MEDIUM RESISTANCE. A filter-medium resistance Rm can be defined
by analogy with the cake resistance "m,lA. The equation is
Rm == (P' - Pb)g, = !!.Pmg, (30.17)
flU flll
The dimension of Rm is [-1.
The filter-medium resistance Rm may vary with the pressure drop, since the
higher liquid velocity caused by a large pressure drop may force additional
particles of solid into the filter medium. Resistance Rm also varies with the age
and cleanliness of the filter medium, but since it is important only during the early
stages of filtration, it is nearly always satisfactory to assume that it is constant
during any given filtration and to determine its magnitude from experimental data.
When Rm is treated as an empirical constant, it also includes any resistance to
flow that may exist in the pipes leading to and from the filter.
From Eqs. (30.15) and (30.17),
(30.18)
Strictly, the cake resistance" is a function of !!.p, rather than of !!.p. During
the important stage of the filtration, when the cake is of appreciable thickness,
!!.Pm is small in comparison with !!.p" and the effect on the magnitude of " of
carrying the integration of Eq. (30.14) over a range !!.p instead of !!.p, can be safely
ignored. In Eq. (30.18), then" is taken as a function of !!.p.
In using Eq. (30.18) it is convenient to replace u, the linear velocity of the
filtrate, and m" the total mass of solid in the cake, by functions of V, the total
volume of filtrate collected to time t. Equation (30.11) relates u and V, and a
material balance relates m, and V. If c is the mass of the particles deposited in
1020 OPERATIONS INVOLVING PARTICULATE SOLIDS
the filter per unit volume of filtrate,t the mass of solids in the filter at time I is
Vc and
(30.20)
Substituting u from Eq. (30.11) and rn, from Eq. (30.20) in Eq. (30.18) gives
dl I' ("CV ) (30.21)
dV = Ag,(!lp) A + Rm
CONSTANT-PRESSURE FILTRATION. When !lp is constant, the only variables
in Eq. (30.21) are V and I. When I = 0, V = 0 and !lp = !lPm; hence
AI'~mg, = (:~) 0 :0 (30.22)
Equation (30.21) may therefore be written
dt 1 1
- = - = K V+- (30.23)
dV q , qo
where
K = 2!'C" (30.24)
, A !lpg,
Integration of Eq. (30.23) between the limits (0, 0) and (I, V) gives
!.. =
V
(K,)
2
V+ ~qo (30.25)
Thus a plot of IIV vs. V will be linear, with a slope equal to Ki2 and an
intercept of llqo. From such a plot and Eqs. (30.22) and (30.24), the values of"
and Rm may be calculated as shown in Example 30.2.
EMPIRICAL EQUATIONS FOR CAKE RESISTANCE. By conducting constant-
pressure experiments at various pressure drops, the variation of" with !lp may
be found. If " is independent of !lp, the sludge is incompressible. Ordinarily "
t The concentration of solid in the slurry fed to the filter is slightly less than c, since the wet cake
includes sufficient liquid to fill its pores, and V, the actual volume of filtrate, is slightly less than the
total liquid in the original slurry. Correction for this retention of liquid in the cake can be made by
material balances if desired. Thus, let mF be the mass of the wet cake, including the filtrate retained
in its voids, and me be the mass of the dry cake obtained by washing the cake free of soluble material
and drying. Also, let p be the density of the filtrate. Then if CF is the concentration of solids in the
slurry in kilograms per cubic meter of liquid fed to the filter, material balances give
CF
C~ ---cc--'--c:--:- (30.19)
1 - [(mF/m,) - 11cJp
MECHANICAL SEPARATIONS 1021
increases with !J.p, as most sludges are at least to some extent compressible. For
highly compressible sludges, " increases rapidly with !J.p.
Empirical equations may be fitted to observed data for !J.p vs. ", the
commonest of which is
(30.26)
where "0 and s are empirical constants. Constant s is the compressibility coefficient
of the cake. It is zero for incompressible sludges and positive for compressible
ones. It usually falls between 0.2 and 0.8. Equation (30.26) should not be used in
a range of pressure drops much different from that used in the experiments
conducted to evaluate "0 and s.
Example 30.2. Laboratory filtrations conducted at constant pressure drop on a slurry
of CaC0 3 in H,O gave the data shown in Table 30.2. The filter area was 440 cm',
the mass of solid per unit volume of filtrate was 23.5 gjL, and the temperature was
25°C. Evaluate the quantities IX and Rm as a function of pressure drop, and fit an
empirical equation to the results for IX.
Solution
The first step is to prepare plots, for each of the five constant-pressure experiments,
of (IV vs. V. The data are given in Table 30.2 and the plots are shown in Fig. 30.15.
The slope of each line is KJ2. in seconds per liter per liter. To convert to seconds per
cubic foot per cubic foot, the conversion factor is 28.31 2 = 801. The intercept of each
line on the axis of ordinates is 1jqo, in seconds per liter. The conversion factor to
TABLE 30.2
Volume-time data" for Example 30.2t
Test Test Test Test Test
Filtrate I II III IV V
volume
V, L t, , tlV t, , tlV t, , tlV t. , tlV t, , tlV
0.5 17.3 34.6 6.8 13.6 6.3 12.6 5.0 10.0 4.4 8.8
1.0 41.3 41.3 19.0 19.0 14.0 14.0 11.5 11.5 9.5 9.5
1.5 72.0 48.0 34.6 23.1 24.2 16.13 19.8 13.2 16.3 10.87
2.0 108.3 54.15 53.4 26.7 37.0 18.5 30.1 15.05 24.6 12.3
2.5 152.1 60.84 76.0 30.4 51.7 20.68 42.5 17.0 34.7 13.88
3.0 201.7 67.23 102.0 34.0 69.0 23.0 56.3 18.7 46.1 15.0
3.5 131.2 37.49 88.8 25.37 73.0 20.87 59.0 16.86
4.0 163.0 40.75 110.0 27.5 91.2 22.8 73.6 18.4
4.5 134.0 29.78 111.0 24.67 89.4 19.87
5.0 160.0 32.0 133.0 26.6 107.3 21.46
5.5 156.8 28.51
6.0 182.5 30.42
t !J.p, in Ibf {in. 2 : I, 6.7; 11, l6.2; III, 28.2; IV, 36.3; V. 49.1.
1022 OPERATIONS INVOLVING PARTICULATE SOLIDS
80
70
/o.p =S.7
so /
/
50 /
/
/ ./
/ D.p 16.2
/::,.p "" 28.2
~ :::-
30
,/ /t,p =3S.3
20 / ~
!:::.p - 49.1
~ ~ :::::::
~
10
~
o
o 2 3 4 5 6 7 FIGURE 30.15
VOLUME OF FILTRATE, V,L Plot of tlV vs. V for Example 30.2.
convert this to seconds per cubic foot is 28.31. The slopes and intercepts, in the
observed and converted units, are given in Table 30.3.
The viscosity of water is, from Appendix 14,0.886 cP, or 0.886 x 6.72 x 10- 4 =
5.95 x 1O- 4 Ib/ft-s. The filter area is 440/30.48' = 0.474 ftz. The concentration c
is (23.5 x 28.31)/454 = 1.47Ib/ft'.
From the values of Kj2 and l/g o in Table 30.3, corresponding values of R m
and a are found from Eqs. (30.22) and (30.24). Thus
R = A /;p g,(I/qo) 0.474 x 32.17 /;p (l/qo)
m Jl 5.95 x 10 4
= 2.56 x 104 /;P(:J
0.474' x 32.17 /;p K,
CJl 5.95 x 10 4 x 1.47
= 8.26 X 10' /;p K,
Table 30.3 shows the values of Kj2 and l/g o for each test, calculated by the
method of least squares. In all but test I the first point, which does not fall on the
linear graph. was omitted. Also in Table 30.3 are the values of IX and Rm. Figure
30.16 is a plot of Rm vs. /;p.
Figure 30.17 is a logarithmic plot of a vs. /;p. The points closely define a straight
line, so Eq. (30.26) is suitable as an equation for a as a function of /;p. The slope of
the line, which is the value of s for this cake, is 0.26. The cake is only slightly
compressible.
MECHANICAL SEPARATIONS 1023
TABLE 30.3
Values for Kc, lIqo, R"" and a. for Example 30.2
Pressure Intercept
drop t1p Slope K,I2 lIqo
Rm , a,
Test IbJin. 2 Ibjft' s/L2 s/ft6 slL sift' ft-I x 10- 10 ft/lb x 10- 11
6.7 965 13.02 10,440 28.21 800 1.98 1.66
Il 16.2 2,330 7.24 5,800 12.11 343 2.05 2.23
III 28.2 4,060 4.51 3,620 9.43 267 2.78 2.43
IV 36.3 5,230 3.82 3,060 7.49 212 2.84 2.64
V 49.1 7,070 3.00 2,400 6.35 180 3.26 2.80
Constant ao can be calculated by reading the coordinates of any convenient
point on the line of Fig. 30.17 and calculating "0 by Eq. (30.26). For example, when
bp ~ 1000, a ~ 1.75 x 10", and
1.75 x 10"
ao = 0 26 ~ 2.90 X 10'0 ftflb (1.95 x 10 10 mjkg)
1000 .
Equation (30.26) becomes for this cake
(J. = 2.90 X 10 10 Apo.26
o,
o
x
3
2 -"
-.--- ~ ----
1
0
o 2,000 4,000 6,000 8.000
t::"p,lb,/ft2
FIGURE 30.16
Plot of Rm vs. /!,.p for Example 30.2.
5
4
, 3
...
>- I- ~
o
x 2
• . --
1
2 4 6 8 10 FIGURE 30.17
Log~log plot of IX vs. t1p for Example 30.2.
1024 OPERATIONS INVOLVING PARTICULATE SOLIDS
CONTINUOUS FILTRATION. In a continuous filter, say, of the rotary-drum
type, the feed, filtrate, and cake move at steady constant rates. For any particular
element of the filter surface, however, conditions are not steady but transient.
Follow, for example, an element of the filter cloth from the moment it enters the
pond of slurry until it is scraped clean once more. It is evident that the process
consists of several steps in series-cake forruation, washing, drying, and dis-
charging-and that each step involves progressive and continual change in
conditions. The pressure drop across the filter during cake formation is, however,
held constant. Thus the foregoing equations for discontinuous constant-pressure
filtration may, with some modification, be applied to continuous filters.
If I is the actual filtering time (that is, the time any filter element is
immersed in the slurry), then from Eq. (30.25)
K V2 V
t=-'-+- (30.27)
2 qo
where V is the volume of filtrate collected during time I. Solving Eq. (30.27) for
V, as a quadratic equation, gives
V = (11q5 + 2K,t)'/2 - llqo (30.28)
K,
Substitution for 1/qo and K, from Eqs. (30.22) and (30.24), followed by division by
tA, leads to the equation
V [(2IJ.p g,call't) + (R.,,/t)2J'/2 - R.,,/t
-= (30.29)
tA ca
where VIt = rate of filtrate collection
A = submerged area of filter
Equation (30.29) may be written in terrus of the rate of solids produc-
tion m, and the filter characteristics: cycle time I" drum speed n, and total
filter area AT. If the fraction of the drum submerged is J,
t =/t, = -
/ (30.30)
n
The rate of solids production, from Eq. (30.20), is
(30.31)
Since AIAT = J, the rate of cake production, divided by the total area of the filter, is
In, = [2calJ.p go/nil' + (nR",)2]'/2 - nRm
(30.32)
AT a
The filter-medium resistance Rm includes that of any cake not removed
by the discharge mechanism and carried through the next cycle. When the
MECHANICAL SEPARATIONS 1025
filter medium is washed after the cake is discharged, Rm is usually negligible
and Eq. (30.32) becomes
In,= (2C IIp gJII) 1/2
(30.33)
AT aJ.l
If the specific cake resistance varies with pressure drop according to Eq.
(30.26), Eq. (30.33) may be modified to
rn, = (2C II p'-' 9JII)'/2 (30.34)
AT aoJ.l
Equations (30.32) and (30.33) apply both to continuous vacuum filters
and to continuous pressure filters. When Rm is negligible, Eq. (30.33) predicts
that the filtrate flow rate varies inversely with the square root of the viscosity
and of the cycle time. This has been observed experimentally with thick cakes
and long cycle times;27 with short cycle times, however, this is not true and
the more complicated relationship shown in Eq. (30.32) must be used.32 In
general, the filtration rate increases as the drum speed increases and the cycle
time t, diminishes, because the cake formed on the drum face is thinner than
at low drum speeds. At speeds above a certain critical value, however, the
filtration rate no longer increases with speed but remains constant, and the
cake tends to become wet and difficult to discharge.
The filter area required for a given filtration rate is calculated as shown
in Example 30.3.
Example 30.3. A rotary drum filter with 30 percent submergence is to be used to
filter a concentrated aqueous slurry of CaC0 3 containing 14.71b of solids per cubic
foot of water (236 kg/m 3 ). The pressure drop is to be 20 in. Hg. If the filter cake
contains 50 percent moisture (wet basis), calculate the filter area required to filter
10 gal/min of slurry when the filter cycle time is 5 min. Assume that the specific cake
resistance is the same as in Example 30.2 and that the filter-medium resistance Rm
is negligible. The temperature is 20°C.
Solution
Equation (30.34) wi11 be used. The quantities needed for substitution are
14.69
IIp = 20 - - x 144 = 14141bf fft2
29.92
f = 0.30 t,=5x60=300s
From Example 30.2
"0 = 2.90 X 10 '0 ft/Ib s = 0.26
Also
I' = 1 cP = 6.72 X 1O- 4 Ib/ft-s p = 62.3 Ib/ft 3
1026 OPERATIONS INVOLVING PARTICULATE SOLIDS
Quantity C is found from Eq. (30.19). The slurry concentration CF is 14.7Ib/ft'.
Since the cake contains 50 percent moisture, I11Flme = 2. Substitution of these
quantities in Eq. (30.19) gives
14.7 ,
C ~ ~ 19.24 Ib/ft
1 - (2 - 1)(14.7/62.3)
Solving Eq. (30.34) for AT gives
(30.35)
The solids production rate lile equals the slurry flow rate times its concentra-
tion CF' Thus since the density of CaCO, is 168.8Ib'/ft',
In
,
~ IOI(
-- 1
607.48 (14.7/168.8) + 1
)14.7 ~ 0.3021b s
/
Substitution in Eq. (30.35) gives
2.90 X10'° x 6.72 X10- 4
A ~ 0.302 ( -;:--:-:-::-c=..-:-=;-;--.,c:,-=:=~-::--cc=,...
)"2
T 2 x 19.24 X 1414°.74 x 32.17 x 0.30 x (1/300)
~ 81.7 ft' (7.59 m2 )
CONSTANT-RATE FILTRATION. If filtrate flows at a constant rate, the linear
velocity u is constant and
dV/dt V
U=--=- (30.36)
A At
Equation (30.15) can be written, after substituting m, from Eq. (30.20) and u from
Eq. (30.36), as
(30.37)
The specific cake resistance" is retained on the left-hand side ofEq. (30.37) because
it is a function of D.p for compressible sludges. t
If" is known as a function of D.Po and if D.p", the pressure drop through
the filter medium, can be estimated, Eq. (30.37) can be used directly to relate
the overall pressure drop to time when the rate of flow of filtrate is constant.
A more direct use of this equation can be made, however, if Eq. (30.26) is
t The concentration c may also vary somewhat with pressure drop. In operation, Cs rather than c is
constant and, by Eq. (30.19), since mF/mc changes with pressure, c also changes when [(mF/m~) - IJ(cJp)
is appreciable in comparison with unity. Any such variation in c with pressure drop can be ignored,
in view of the other approximations made in the general theory of filtration.
MECHANICAL SEPARATIONS 1027
accepted to relate a and !'.p,.22 If " from Eq. (30.26) is substituted in Eq.
(30.37), and if !'.P - !'.Pm is substituted· for !'.p" the result is
A 1-, _ aoflC t
up, - - - At
(V)2 _- (Aup-uPm
A )1-' (30.38)
g,
Again, the simplest method of correcting the overall pressure drop for
the pressure drop through the filter medium is to assume the filter medium
resistance is constant during a given constant-rate filtration. Then, by Eq. (30.17),
!'.Pm is also constant in Eq. (30.38). Since the only variables in Eq. (30.38) are !'.P
and t, the equation can be written
(30.39)
where K, is defined by
(30.40)
PRINCIPLES OF CENTRIFUGAL FILTRATION. The basic theory of constant-
pressure filtration can be modified to apply to filtration in a centrifuge. The
treatment applies after the cake has been deposited and during flow of clear filtrate
or freshwater through the cake. Figure 30.18 shows such a cake. In this figure,
r 1 = radius of inner surface of liquid
r,= radius of inner face of cake
r2 = inside radius of basket
The following simplifying assumptions are made. The effects of gravity
and of changes in kinetic energy of the liquid are neglected, and the pressure
drop from centrifugal action equals the drag of the liquid flowing through
F[GURE 30.[8
Centrifugal filter.
1028 OPERATIONS INVOLVING PARTICULATE SOLIDS
the cake; the cake is completely filled with liquid; the flow of the liquid is
laminar; the resistance of the filter medium is constant; and the cake is nearly
incompressible, so an average specific resistance can be used as a constant.
In the light of these assumptions the flow rate of liquid through the cake is
predicted as follows. Assume first that the area A for flow does not change with
radius, as would nearly be true with a thin cake in a large-diameter centrifuge.
The linear velocity of the liquid is then given by
dVldt q
U=--=- (30.41)
A A
where q is the volumetric flow rate of liquid. Substitution from Eq. (30.41) into
Eq. (30.18) gives
A
up--
_ q/l (m,a
- +- Rm) (30.42)
g, A2 A
The pressure drop from centrifugal action, from Eq. (2.9), is
pW2(1'~ - I'D
/lp = '--""-"-'::' (30.43)
2g,
where w = angular velocity, radls
p = density of liquid
Combining Eqs. (30.42) and (30.43) and solving for q gives
pw 2 (d
q = -'---'-':---'"--,-c
- I'D (30.44)
2/l(amJA 2 + R.,/A)
When the change in A with radius is too large to be neglected, it can be shown
that Eq. (30.44) should be written 18
pW2(1'~ - I'i) (30.45)
q= c:-:-'-=,,~--"-;-:-:-
2/l(amJALAa + R.,/A2)
where A2 = area of filter medium (inside area of centrifuge basket)
Aa = arithmetic mean cake area
AL = logarithmic mean cake area
The average areas Aa and AL are defined by the equations
Aa == (1', + 1'2)"b (30.46)
- 2 -;---;-1'"",)
_2"-:-b,,,('.=,·
AL== (30.47)
In (1'211',)
where b = height of basket
r i = inner radius of cake
Note that Eq. (30.45) applies to a cake of definite mass and is not an integrated
equation over an entire filtration starting with an empty centrifugal. The cake
MECHANICAL SEPARATIONS 1029
resistance <X in Eqs. (30.44) and (30.45) is generally somewhat greater than that
found in a pressure or vacuum filter under comparable conditions. Especially with
compressible cakes, <X increases with the applied centrifugal force.
WASHING FILTER CAKES. To wash soluble material that may be retained by
the filter cake after a filtration, a solvent miscible with the filtrate may be used as
a wash. Water is the most common wash liquid. The rate of flow of the wash
liquid and the volume of liquid needed to reduce the solute content of the cake
to a desired degree are important in the design and operation of a filter. Although
the following general principles apply to the problem, these questions cannot be
completely answered without experiment!
The volume of wash liquid required is related to the concentration-time
history of the wash liquid leaving the filter. During washing the concentration-time
relation is of the type shown in Fig. 30.19. The first portion of the recovered liquid
is represented by segment ab in Fig. 30.19. The effluent consists essentially of the
filtrate that was left on the filter, which is swept out by the first wash liquid without
appreciable dilution. This stage of washing, called displacement wash, is the ideal
method of washing a cake. Under favorable conditions where the particle size of
the cake is small, as much as 90 percent of the solute in the cake can be recovered
during this stage. The volume of wash liquid needed for a displacement wash is
equal to the volume of filtrate left in the cake, or iiAL, where L is the cake
thickness and ii is the average porosity of the cake. The second stage of washing,
shown by the segment bc in Fig. 30.19, is characterized by a rapid drop in
concentration of the effluent. The volume of wash liquid used in this stage is also
f-
Z
W
::J
...J
u..
u..
w a b
~
z
0
~
0:
f-
Z
W
U
Z
0
U
c
d
TIME
FIGURE 30.19
Washing filter cake.
1030 OPERATIONS INVOLVING PARTICULATE SOLIDS
of the order of magnitude of that used in the first stage. The third stage is shown
by segment cd. The concentration of solute in the effluent is low, and the remaining
solute is slowly leached from the cake. If sufficient wash liquid is used, the residual
solute in the cake can be reduced to any desired point, but the washing should
be stopped when the value of the unrecovered solute is less than the cost of
recovering it.
In most filters the wash liquid follows the same path as that of the filtrate. t
The rate of flow of the wash liquid is, in principle, equal to that of the last of the
filtrate, provided the pressure drop remains unchanged in passing from filtration
to washing. If the viscosities of filtrate and wash liquid differ, correction for this
difference can be made. This rule is only approximate, however, as during washing
the liquid does not actually follow exactly the path of the filtrate because of
channeling, formation of cracks in the cake, and short circuiting.
When a cake of porous particles is washed, solute in the pores must first
diffuse to the surface of the particles. This is a slow process compared to
displacement from the external channels in the cake. The curves of concentration
vs. time are similar to the breakthrough curves for adsorption or other fixed-bed
processes, and the equations in Chap. 25 can be applied to predict the effects of
particle size, fluid velocity, and other variables.
CLARIFYING FILTERS
Clarifying filters remove small amounts of solids or liquid droplets from either
liquids or gases. The particles are trapped inside the filter medium or on its
surfaces. Clarification differs from screening in that pores in the filter medium are
larger-sometimes much larger-than the particles to be removed. The particles
are caught by surface forces and immobilized on the surfaces or within the flow
channels, where they reduce the effective diameter of the channels but usually do
not block them completely.
Liquid Clarification
Clarifying filters for liquids include the gravity-bed filters for water treatment
mentioned earlier and a variety of small cartridge and edge filters of various
designs. Some cake filters, especially tank filters alld continuous precoat filters,
are nsed extensively for clarification. In a batch unit, the filtration rate and solids
removal efficiency are typically almost constant for a considerable period of
operation, but eventually the solids content of the effluent rises to an unacceptable
"breakthrough" value, and backwashing of the filter element becomes necessary.
A typical cartridge filter, used principally for removing small amounts of
solids from process fluids, is the filter illustrated in Fig. 30.20. The filtering cartridge
t In a filter press the wash passes through the entire thickness of the cake. The last filtrate may pass
through only one-half the final cake.
MECHANICAL SEPARATIONS 1031
FIGURE 30.20
Cartridge filter.
is a series of thin metal disks 75 to 250 mm (3 to 10 in.) in diameter set in a vertical
stack with very narrow uniform spaces between them. The disks are carried on a
vertical hollow shaft and fit into a closed cylindrical casing. Liquid is admitted to
the casing under pressure. It flows inward between the disks to openings in the
central shaft and out through the top of the casing. Solids are trapped between
the disks and remain in the filter. Since most of the solids are removed at the
periphery of the disks, this kind of device is known as an edge filter. Periodically
the accumulated solids must be dislodged from the cartridge. In the design shown
in Fig. 30.20 this is done by giving the cartridge a half turn. The stationary teeth
of a comb cleaner pass between the disks, causing the solids to drop to the bottom
of the casing, from which they may be removed at fairly long intervals.
Other cartridge filters contain tubular elements of porous metal or ceramic
material that trap the particles inside the pores. Many of the crossflow filters
described in the next section are effective liquid clarifiers.
Gas Cleaning
Filters for gas cleaning include pad filters for atmospheric dust and granular beds
and bag filters for process dusts. Air is cleaned by passing it through pads of
cellulose pulp, cotton, felt, glass fiber, or metal screening; the pad material may
be dry or coated with a viscous oil to act as a dust holder. For light duty the pads
are disposable, but in large-scale gas cleaning they are frequently rinsed and
recoated with oil.
Granular bed filters contain stationary or moving beds of granules ranging
from 30-mesh to 8-mesh in size in some designs, to 12 to 40 mm (j to 1! in.)
in others. A bag filter contains one or more large bags of felt or thin woven
fabric, mounted inside a metal housing. Dust-laden gas usually enters the bag at
the bottom and passes outward, leaving the dust behind, although sometimes the
flow is inward. Efficiencies are typically 99 percent even with extremely fine
1032 OPERATIONS INVOLVING PARTlCULATE SOLIDS
particles-far finer than the openings in the bag material. Periodically the flow
is automatically cut off and clean gas blown back or the bag mechanically shaken
to dislodge the dust for recovery or disposal. In most cases bag filters act as
clarifiers, with particles trapped within the fabric of the bag, but with heavy dust
loadings a thin but definite cake of dust is allowed to build up before it is
discharged.
In all of these filters most of the separation is by impingement, as discussed
below.
Principles of Clarification
If the solid particles being removed completely plug the pores of the filter medium
and the rate of plugging is constant with time, the mechanism is known as direct
sieving. Direct sieving is rarely encountered. Much more commonly the particles
partially block the pores, giving a gradual reduction in pore size; this is called
standard blocking. Grace!9 gives equations for flow rate through a clarifying filter
as a function of time.
Much more commonly, especially in cleaning gases, the separation is by
impingement of the particles against a solid surface placed in the flowing stream.
The particles, because of their inertia, are expected to cross the streamlines of the
fluid and strike and adhere to the solid, from which they can subsequently be
removed. The principle of impingement separation is shown in Fig. 30.21. The
solid lines are the streamlines passing around a sphere, and the dotted lines show
the paths followed by the particles. Particles initially moving along the streamlines
between A and B strike the solid and can be removed if they adhere to the wall
and are not reentrained. Particles initially following streamlines outside lines A
and B do not strike the solid and cannot be removed from the gas stream by
impingement. The target efficiency q, is defined as the fraction of the particles in
the gas stream directly approaching the separator element that strike the solid.
For particles that would settle through still fluid in the Stokes'-law range, the
target efficiencies for ribbons, spheres, and cylinders are shown in Fig. 30.22. The
Fluid sfreamline
Particle path
FIGURE 30.21
Princip1e of impingement. [By permission./rom J. H. Perry (ed.), Chemical Engineers' Handbook, 6th
ed., p. 20-81. Copyright 1984, McGraw-HiII Book Company. New York.]
MECHANICAL SEPARATIONS 1033
1.0
0.9 I
0.8 kDa V ;'
RibbonX
~o.7
l<.L1Y /'
fJher. ~.&b
GO.6
z
~ 0.S
V 1/ Cyhnder
u
/ V
E
w
0.4
f- 0.3
V
w Intercepts: / /, V
~ 0.2 - RIbbon or fy/inder'ib
;: 0.1
Sphere:ff4 ',1/ /
o 0.01 I J-±t/'
0.1 10 10 100
SEPARATION NUMBER, "t 'bIg q,
FIGURE 30.22
Target efficiency of spheres, cylinders, and ribbons. [By permission, from J. H. Perry (ed.), Chemical
Engineers' Handbook 6th ed., p. 20-83. Copyright 1984, McGraw-Hill Book Company, New York.]
abscissa is the dimensionless gronp N" called the separatioll llumber, u,uO/gDb ,
where u, is the terminal velocity of the particle in still flnid; uo is the velocity of
the fluid approaching the solid; 9 is the acceleration of gravity; and Db is the width
of the ribbon or the diameter of the sphere or cylinder.
In settling in the Stokes' -law range, the terminal velocity u, is proportional
to D;. Thus the smaller the particle, the lower the target efficiency. The target
efficiency, however, can be increased by decreasing the target size Db, and for the
collection of very small particles filter pads are made using extremely fine fibers
of glass, metal, or polymers. The overall collection efficiency depends on the target
efficiency, the solid fraction of the filter, and the depth of the filter. Even when the
target efficiency is not very high, nearly complete removal of the particles can be
accomplished by using a deep bed of fibers to give repeated chances for particle
interception.
For very small drops 0.1 /lm or so in diameter (as in a mist of H 2 SO.), the
target efficiency rises as the particle diameter decreases, contrary to what is
predicted by impingement theory. The tiny droplets move across the streamlines
by diffusion and are immobilized on the solid surfaces. Diffusion is more and more
effective as the particles become smaller, and the target efficiency is correspond-
ingly increased.
CROSSFLOW FILTRATION
The principle of crossflow filtration can be applied to concentrate suspensions of
fine particles or collodial material or to fractionate solutions of macromolecules.
The term microfiltratioll is generally used for particles in the size range 0.1 to 5 /lm.
1034 OPERATIONS INVOLVING PARTICULATE SOLIDS
Cake filtration could be used for some of these materials, but a cake of I-I'm
particles would have a high resistance to flow, and the filtration rate would be
very low. Ultrafiltration (UF) covers a wider size range, from I-I'm particles down
to molecules about 10 - 3 I'm in size (M ~ 300). The term hYPe/filtration is
sometimes used for separation of small molecules or ions, but reverse osmosis is
a more descriptive term, because the osmotic pressure has a major effect on the
flux. Furthermore, the separation in reverse osmosis occurs by a solution-diffusion
mechanism in the dense polymer rather than by a screening action at the mem-
brane surface (see Chap. 26).
Types of Membranes
The ideal membrane for crossflow filtration would have a high porosity and a
narrow pore-size distribution, with the largest pores slightly smaller than the
particles or molecules to be retained. An asymmetric membrane is preferred, with
a thin selective skin supported on a thicker layer with large pores to decrease the
hydraulic resistance. Some commercial membranes have a continuous gradation
in pore size as shown in Fig. 30.23. Several kinds of polymers are used for
ultrafiltration membranes, including cellulose acetate, polyacrylonitrile, poly-
sulfone, polyamide, and polyimide. The skin thickness and average pore size can
be varied by changing the casting conditions or postcasting treatment.
Ultrafiltration membranes have a range of pore sizes in the selective layer,
and they are often characterized by a molecular weight cutoff based on measure-
ments of fraction rejected versus molecular weight.13 Molecules larger than the
FIGURE 30.23
Cross section of a polysulfane UF membrane. (After Mulder. 25 )
MECHANICAL SEPARATIONS 1035
cutoff size are almost completely rejected, but there is a wide range of sizes for
which partial rejection occurs. Rejection curves for some membranes are shown
in Fig. 30.24, but such data should be used with caution, since the fraction rejected
for a given molecular size varies with the solvent permeation rate, the shear rate
near the surface, and the extent of membrane fouling.
Ultrafiltration and microfiltration membranes are also made from sintered
stainless steel or other metals and from porous carbon or alumina. The usual
methods of preparation give membranes. with fairly large pores (1 to 100,um), but
partially filling the surface layer with zirconium oxide or other inorganic material
produces asymmetric membranes with controlled pore size. The advantages of
inorganic membranes over polymer membranes are that they can operate at higher
temperatures and can better stand chemical cleaning or sterilization treatment.
Several types of equipment are available for laboratory use and for commer-
cial UF installations.' Small samples may be processed with flat circular mem-
branes supported on a porous disk in a cylindrical cell. A magnet-driven stirrer
above the membrane provides crossflow of the solution. Rectangular cells can also
be used with solution recirculated through the small gap between the membrane
and the top of the cell. These devices are useful for preliminary tests, but
performance data are not directly applicable to large units.
1.0
V
0.8
V~
PM~
1/ / V
"~ 0.6
.•
~
c
0
15rn
1/ I1 PM 3;
Lt 0.4
0.2
[7 7
J
o i
10' 2 5 10' 2 5 10'
Molecular weight
FIGURE 30.24
Solute rejection curves for Amicon UF membranes. (After Porter. 31)
1036 OPERATIONS INVOLVING PARTICULATE SOLIDS
0°0
=~~~~~ ~° 00° ° ~~~rane_
,0,o°0°,//
~O ~
:~,
',{) 00
Channel-----rT-
I
j
,
/0
I
/ I
' ,
Support
1- / " Intermediate layer
Permeate I-
FIGURE 30.25
Cross~sectional schematic of a monolithic multichannel element. (After Hsieh. 2t)
For industrial applications, large areas are obtained using modules with
many tubular or hollow-fiber membranes or by using large sheets in a filter-press
arrangement or a spiral-wound unit. Tubular membranes are 5 to 25 mm in inside
diameter and up to 3 m long, and velocities of 1 to 5 m(s are used to give turbulent
flow and good mass transfer. The polymer membranes are supported by porous
metal or ceramic tubes, and several tubes are clustered in a cylindrical shell.
Alumina membranes are available as single tubes or as monolithic multichannel
elements of the type shown in Fig. 30.25. Separation occurs in the thin layer of
oxide particles bound to the alumina, and the pores in the support are large enough
to have little resistance to permeate flow. Tubular membranes have the advantages
of easy membrane replacement and the feasibility of mechanical cleaning, but the
ratio of surface area to volume is relatively low.
Hollow-fiber UF membranes have diameters of 0.2 to 2.0 mm, and hundreds
or thousands of fibers are sealed in each cylindrical module. Flow through the
fibers is usually laminar, but the velocity is kept high to give high shear at the
wall and improve the flux. The area per unit volume is greatest for the smallest
fibers, but these are most susceptible to plugging by suspended matter in the feed,
and the fibers used are generally larger than those in reverse-osmosis units.
Spiral-wound modules of the type used for reverse osmosis (see Fig. 26.19)
are widely used for UFo They are not as prone to plugging as hollow-fiber units,
since the entrance is a narrow slit about 1 mm wide, but prefiltration of the feed
solution is recommended. The velocity in the feed channels corresponds to laminar
flow, but the flow disturbances caused by the spacers make the pressure drop and
the mass transfer greater than for true laminar flow.
Permeate Flux for Ultrafiltration
The performance of a UF membrane can be characterized by the permeate flux,
the percent rejection, and the concentration of solute in the retentate stream.
The permeate flux often decreases with time because of membrane foulin~. but
MECHANICAL SEPARATIONS 1037
TABLE 30.4
Conversion factors for permeate flux
rnls m/h
2.78 X to- 7 to- 3 1 0.589
4.72 X 10- 7 1.698 X 10- 3 1.698
fouling may increase the rejection. We deal first with the performance of a clean
membrane. The water is assumed to pass by laminar flow through the small pores
of the selective layer, and the driving force is the pressure difference /::.p minus the
difference in osmotic pressures across the membrane /::.n. The flux is proportional
to the void fraction e and the square of the average pore size, D. The pores are
at random angles to the surface, and the nominal thickness of the active layer L
is multiplied by a tortuosity factor r. A modified Hagen-Poiseuille equation gives
the volume flux D, which is the superficial permeate velocity normal to the surface:
(/::.p - /::.n)g,D 2 e
D= (30.48)
32Lrll
In SI units, the flux has units of m 3/s, ml, or m/s, but more common units are
L/m 2_h or galjft2-day. Conversion factors are shown in Table 30.4.
It is difficult to get independent measurements of e, D, r, and L for use in
Eq. (30.48), but these characteristics are incorporated in the membrane permeabil-
ity Qm, the flux of pure water at room temperature per unit pressure drop:
v = Qm /::.P (30.49)
For UF use, the permeate flux for a clean membrane can he predicted from
Qm, the driving force (/::.p - /::.n), and the viscosity of the permeate solution:
v = Qm(/::.P - /::.n) I'H,O (30.50)
I'
Concentration Polarization
The osmotic pressure difference /::.n depends on the solute concentration at the
membrane surface, which is often much greater than the bulk concentration,
particularly if the permeate flux is high and the solute diffusivity is low. Figure
30.26 shows concentration gradients for a UF system with partial rejection of the
solute. The concentration just inside the pores, cm' is lower than the concentration
at the surface, Cs> by the factor K, the equilibrium partition coefficient. There is a
similar discontinuity in solute concentration where the selective layer joins the
large-pore support. For cylindrical pores and spherical molecules, K = (1 - .Ie)2,
where .le is the ratio of molecular size to pore size. A low value of K contributes
to a high rejection, and there is a further effect of wall friction on the solute
diffusivity, which may make the rejection quite high even when the molecules are
less than half the size of the pores [see Eq. (26.34)].
1038 OPERATIONS INVOLVING PARTICULATE SOLIDS
Support Selective layer
\ I
c,
1
Feed
Permeate
• vcm/s
' - . , . - - - - - - - C,
c,----+------1
f--x 8
FIGURE 30.26
Concentration gradients in a UF membrane.
In Chap. 26, concentration polarization in reverse osmosis was treated using
a simple mass-transfer equation, Eq. (26.48), which is satisfactory where the surface
concentration is only moderately higher than the bulk concentration. For UF, the
large change in concentration near the surface requires integration to get the
concentration profile. The basic equation states that the flux of solute due to
convection plus diffusion is constant in the boundary layer and equal to the flux
of solute in the permeate':
dc
vc + Dv - = VC'2 (30.51)
dx
Equation (30.51) is integrated with the boundary conditions c = c, at x = 0
and c = C, at x = 0, the thickness of the concentration boundary layer. The term
D)o has the units of length per time and is defined as the mass-transfer coefficient
k,:
Cs -
In--- 2 C
=-=-
vo v
(30.52)
Cl - c 2 Dv kc
For the simple case of complete solute rejection, Cl = 0, and Eq. (30.52) becomes
(30.53)
For low values of flux, c, can be predicted from Eq. (30.53) using standard
correlations for k" and then using osmotic pressure data to get Iln, IIp can be
calculated from Eq. (30.50). If IIp is specified, a trial-and-error calculation is needed
to get v. Either approach shows that v should be nearly proportional to IIp for
MECHANICAL SEPARATIONS 1039
low values of !J.p, but the flux changes less rapidly with pressure at moderate
pressures. The flux eventually reaches a maximum, independent of !J.p, because c,
has reached cg , the solubility limit or the concentration at which a gel layer forms.
A further sudden increase in !J.p gives a temporary increase in permeate flow, but
this decreases to the maximum steady-state flux as the gel layer becomes thicker
and increases the hydraulic resistance. Figure 30.27 shows some performances
curves for ultrafiltration of skim milk, a process used for concentrating the protein
fraction. The limiting flux increases with the feed velocity, and the limit is reached
at pressure differences of 10 to 20 lbf/in. 2
Ultrafiltration systems generally operate close to the limiting flux, which
occurs at pressure differences of only 1 to 5 atm. The flux increases with velocity
past the membrane surface because of the increase in k" and the flux is lower for
high bulk concentration, as indicated by Eq. (30.53). The change in flux with
concentration is illustrated in Fig. 30.28, and semilog plots of this type can be
extrapolated to zero flux to determine cg • The gel concentration ranges from 10
to 50 weight percent for various proteins and is about 70 weight percent for latex
suspensions.
Skim milk
19.1 % TS, 60°C Velocity (m/s)
_ _ _ 1.97
0.-0
25 0 ....
5 10
30 70 110 150 (kPa)
Transmembrane pressure
FIGURE 30.27
Ultrafiltration of skim milk in a hollowMfiber UF module (Romicon HF 15-43-PM50). (After Cheryan
and Chiang. 6 )
1040 OPERATrONS rNVOLVING PARTrCULATE SOLIDS
280
260
240
o Electrodeposition primer
6. Styrene butadiene latex
220 o Human albumin
>- Cl Gelatin (at 70°C)
~ 200
"0 o
~m 180
o
160
~
'"x 140
o
'"2 120
~ 100
~ 80
5 60
40
20
0
1 2 3 4 5 6 7 8 910 20 30 40 50 80
Concentration, wt % sollds
FIGURE 30.28
Effect of solute concentration on flux. (After Porler. 31 )
For solutions of polymers and proteins up to about 300,000 in molecular
weight, some tests with tubular membranes and thin-channel cells gave limiting
fluxes in reasonable agreement (± 30 percent) with those predicted using standard
correlations for mass transfer,23.30 such as Eq. (21.50) for laminar flow and Eq.
(21.55) for turbulent flow. Others have found fluxes considerably lower than
expected using the same correlations and published diffusivities. 1 7.3 7 Some of the
differences may be due to the higher viscosity near the wall or to the variation in
diffusivity with concentration, factors not allowed for in the simple theory.
A more dramatic departure from theory occurs in the ultrafiltration of
colloidal suspensions. The limiting flux is generally larger than for protein
solutions, even though the diffusivity of the colloidal particles is an order of
magnitude lower! Figure 30.28 shows that the flux for a latex suspension, which
has particles about 0.2 /lm in diameter, is two to three times greater than for
albumin (M = 170,000) and five times greater than for gelatin (M = 350,000). Tests
with whole blood, milk, and other suspensions give similar results. Something
other than normal diffusion must be the principal mechanism for transfer of
particles from the surface of the membrane or the gel layer back to the main
stream. The enhanced flux may be due partly to the "tubular pinch" effect, the
tendency of spherical particles to move away from the wall toward the tube axis,
or to the rotation of the particles in the shear field. 30 The movement of particles
away from the wall could be an irregular process, with a gradual growth in the
gel layer interrupted by occasional eddies that sweep close to the surface and shear
MECHANICAL SEPARATIONS 1041
away a cluster of particles. The flux would then be independent of the particle
diffusivity but would depend on the packing density in the gel layer and the forces
of adhesion. More work is needed to correlate and to predict this enhanced mass-
transfer effect.
For particles or large spherical molecules, the diffusivity is given by the
Stokes-Einstein equation.
kT
D =-- (30.54)
v 6nroll
where k is the Boltzmann constant, 1.380 x 10- 23 J/K. The following con-
°
venient form of the equation gives D, in cm 2 /s when r is the radius of the particles
in cm, 1" the viscosity in cP, and T is in Kelvins:
7.32 x 1O- 16 T
D,=------ (30.55)
'011'
For random-coil polymer molecules, "0 should be taken as the radius of gyration,
which is generally two to three times the radius calculated from the molar volume.
Example 30.4. A tubular membrane with a diameter of2 cm and a water permeability
of 250 L/m 2 -h-atm is being used for UF of cheese whey. The whey proteins have an
average diffusivity of 4 x 10- 7 cm 2 ls, and the osmotic pressure in atmospheres is
given by Jonsson's equation 23 :
it = 4.4 X 1O- 3c - 1.7 X 1O- 6c 2 + 7.9 X IO-'c'
where c is the protein concentration in grams per liter. (a) Calculate the effect of
Ap on the flux for a clean membrane if the solution velocity is 1.5 mls and the protein
concentration is 10, 20, or 40 gfL. Assume the gel concentration is 400 g/L and the
rejection is 100 percent. (b) If the membrane permeability is reduced fivefold by
plugging, what is the effect on the permeate flux?
Solution
(a) Assume the bulk solutions have the same density and viscosity as water:
D =2cm j7 = 150 cm/s p = 1 g/cm' I' = 0.01 g/cm-s
0.01
N R, = 2 x 150 x 1/0.01 = 30,000 N" = I x 4 x 10 7 25,000
From Eq. (21.55),
N'h = 0.0096 X (30,000)°·913 x (25,000)°·346 = 3.9 X 10'
_3_.9_x_l_03~~_x_l_0_-~7) 4
k, = 7.8 x 10- cm/,
2
For C, = 10 g/L, pick v = 10-' cm/, or 36 L/m 2 _h. From Eq. (30.53)
10-'
-7-.8-x-l0--'4 = 1.282
c, = 3.60c 1 = 36 g/L
1042 OPERATIONS INVOLVING PARTICULATE SOLIDS
At c" n ~ 4.4 x 10- 3 X 36 - 1.7 X 10- 6 (36)2 + 7.9 X 10- 8 (36)' ~ 0.16 atm. For
complete rejection of protein 1114 = 14 = 0.16:
250 L 1
Qm ~ 2 X -- ~ 6.94 X 10-3 cm/s-atm
m -h-atm 36,000
From Eq. (30.50)
10- 3
Ap - An ~ 0.144 atm
6.94 x 10 3
Ap ~ 0.144 + 0.16 ~ 0.304 atm
Note that over half of the driving force is needed to overcome the osmotic
pressure difference caused by concentration polarization.
The maximum flux is obtained from Eq. (30.53) with c, ~ 400:
400
Vrn " ~ 7.8 X 1O- 4 1n - = 2.88 X 10- 3 cm/s = 104 L/m'-h
10
At this point,
2.88 X 10- 3
Ap - An = ~ 0.41 atm
6.94 x 10 3
For c ~ 400, n ~ 6.54 atm,
Ap = 6.54 + 0.41 = 6.95 atm
Similar calculations are made for other values of v from 10- 4 to vrnax , and the
flux is plotted against the pressure drop in Fig. 30.29. The predicted flux is constant
for IIp > 6.95, and a gel layer of increasing thickness is presumed to form as the
pressure increases, but in practice, the flux might decrease slightly because of
compression of the gel layer.
The curves for the three concentrations are similar in shape, but the flux is
zero until the pressure difference exceeds the osmotic pressure of the solution, and
the intercept is more noticeable for the higher concentrations.
(b) If Qm ~ 250/5 ~ 50 L/m 2 -h-atm, Vrn " is not changed, but a greater Ap is
needed for any value of v. For example, at v = 10- 3 cmls and c = 40 glL,
1
Qm ~ 50 x - - = 1.39 X 10- 3 cm/s-atm
36,000
10- 3
Ap - An 0.719 atm
1.39 x 10 3
2=3.6 as in part (a)
c,
c, ~ 3.6 x 40 ~ 144
n ~ 0.834 = An
Ap ~ 0.719 + 0.834 = 1.55 atm
MECHANICAL SEPARATIONS 1043
100
c 1, gll
..Co).
- -- ---
80
/
/ -<'- - - ------
.''"
E
:J
x
~
60
//W -- -- 7 r.>_ - - i ; -------
-----
'"2
m
ID
E
~
a. 40
17/ /
....... 40
--
20
il/
I
I
I
I
I
I
2 4 6 8 10
t1p, atm
FIGURE 30.29
Effects of pressure drop and concentration on flux for Example 30.4: ( - - ) Qm = 250 L/m 2 -h-atm
[part (a)]; (-------) Qm ~ 50 L/m'-h-atm [part (b)].
The dashed line in Fig. 30.29 shows that the largest effect of the lower
membrane permeability is a 30 percent reduction in flux at low pressure drops.
Partial rejection of solutes. In many applications of UF, the membrane selected has
some pores that are larger than the solute molecules, and the solute is only partially
rejected. The fraction rejected, R, is sometimes defined using the feed and permeate
concentrations:
Cp
R F == 1 - - (30.56)
cF
Since the concentrations change along the length of a separator, a more
fundamental definition of R is based on the local retentate and permeate compos-
tions, Cl and C2 (see Fig. 30.26):
R == 1 _ C2 (30.57)
Cl
1044 OPERATIONS INVOLVING PARTICULATE SOLIDS
The rejection R depends mainly on the ratio of solute size to pore size, '\,
which determines the partition coefficient K, and on the ratio vlk" which de-
termines the concentration polarization effect. From Eqs. (30.52) and (30.57)
e. = e1 (1 - R + R exp t) (30.58)
If diffusion in the membrane is negligible and solute is carried through the
pores by the permeate flow, the permeate concentration is the same as that in
equilibrium with c.:
(30.59)
Combining Eqs. (30.57), (30.58), and (30.59) leads to
1-R K v
--=--exp- (30.60)
R 1-K k,
When Eq. (30.60) applies, the rejection approaches 1 - K as vlk, approaches
zero, and the rejection decreases with increasing flux because of concentration
polarization. For UF of a very dilute dextran solution with a tabular membrane,17
the rejection varied from 77 to 93 percent with decreasing flux, in good agreement
with Eq. (30.60) and K = 0.044.
When filtering solutions of moderate or high concentration, the maximum
flux is low, and molecular diffusion in the pores may become important. The basic
equation for solute flux in the selective layer is similar to Eq. (30.51) for mass
transfer in the boundary layer, but the diffusion term adds to the convective term:
de
ve z = vc-De- (30.61)
dy
where De = DporeB/r (30.62)
y = distance from membrane surface
Integrating Eq. (30.61) and assuming the same partition factor at both boundaries
of the selective layer leads to
c2 K exp(vLID,)
= (30.63)
c. K - 1 + exp(vLID,)
where L is the thickness of the selective layer.
Where the term vLID, is less than 2.0, solute diffusion has a significant effect
on the rejection. Because diffusion lowers the rejection at low permeate flux and
concentration polarization is important at high flux, the fraction rejected is
predicted to go through a maximum with permeate flux. 20 The diffusion effect
should be quite pronounced if the active layer is very thin, say, 0.1 to 0.2 J.lm, but
there are not enough data to confirm this.
When dealing with a mixture of solutes or colloidal particles, a gel layer
formed from one material may increase the rejection for a solute of/ower molecular
MECHANICAL SEPARATIONS 1045
weight. Also, after a gel layer has formed, operation at high pressure may compress
this layer and make it less permeable to smaller solutes as well as to solvent.
Example 30.5. Ultrafiltration tests with a 1.5-cm tubular membrane at N Re = 25,000
gave a permeate flux of 40 Ljm 2 -h and 75 percent rejection for a 5 percent polymer
solution. The polymer has an average molecular weight of 30,000, and the estimated
diffusivity is 5 x 10- 7 cm'/s. (a) Neglecting the effect of molecular diffusion in the
pores, predict the fraction rejected for a flux of 20 Ljm 2 -h, and predict the maximum
rejection. (b) Estimate the fraction rejected for the low-molecular-weight fraction of
the polymer with M ~ 10,000. (c) If the selective layer· thickness is 0.2 I'm, does
molecular diffusion have a significant effect on the rejection for case (a)?
Solution
(a) Base case:
v = 40 x 2.78 X 10- 5 = 1.112 X 10- 3 cm/s
0.01
N s, = 5 x 10 7 = 20,000
From Eq. (21.55)
NSh = 0.0096(25,000)°·913(20,000)°·346 = 3060
3060(5 x 10- 7 ) -3
k, = = 1.02 x 10 cm/s
1.5
1- R 0.25 K 1.112 x 10- 3
-R- = 0.75 = 1 - K exp 1.02 x 10- 3
~=0.112
l-K
0.112
K = - - =0.101
1.112
If the flux is reduced to 20 L/m'-h or 0.556 x 10- 3 cm/s,
1 - R 0.101 0.556
- - = - - exp - - = 0.194
R 0.899 1.02
1
R=--=0.84
1.194
As the flux approaches zero, R approaches 1 - K:
R m ." = 1 - 0.101 = 0.90
(b) Use Fig. 30.24 for a rough estimate. Locate the point RI = 0.75 and
MI = 30,000 on the graph, and draw a line similar to that for PM 30. At M z = 10,000,
1046 OPERATIONS INVOLVING PARTICULATE SOLIDS
R2 ~ 0.35. For an independent calculation, predict K and k c ' If Kt = 0.101 =
(1 - )'1)2,
10,000)113
D2 ~ DI ( - - ~ 0.694DI
30,000
"2 ~ 0.682(0.694) ~ 0.473
K2 ~ (1 - 0.473)' ~ 0.278
The diffusivity of large molecules varies with -~ power of the size, and kc varies with
D~~65 or M- 0.22:
kc, ~ kC 1 X 3°·22 ~ 1.02 X 10- 3 x 1.27 ~ 1.29 x 10- 3 cm/s
At v ~ 1.112 X 10- 3 cm/s,
1 - R2 0.278 1.112
--~ exp--~0.912
R2 1 - 0.278 1.29
1
R ~--~0.52
, 1.912
This is appreciably higher than the estimate of 0.35, but in any case, a sharp
separation is not possible for molecules differing only threefold in molecular weight.
(c) For M ~ 30,000 and D, ~ 5 X 10- 7 cm 2/s, estimate
Dporc = 1 X 10- 7 cm 2 js ,~ 0.5 <~2
8
D. ~ 2.5 X 10- cm'/s
L~0.2I'm~2 x 10-' cm
vL (5.56 x 1O-'X2 x 10-')
- ~ 8 ~ 0.445
D. 2.5 x 10
From Eq. (30.63) with K ~ 0.101,
c, 0.101 exp 0.445
0.24
c, 0.101 - 1 + exp 0.445
Diffusion in the membrane makes the permeate concentrations about twice as
high as it would be if C2 = Kcs = 0.101cs ' This indicates that the partition coefficient
is lower than that estimated in part (a).
Microiiltration
There is not a sharp dividing line between microfiltration, which treats suspensions
of small particles, and ultrafiltration, which usually deals with solutions of large
molecules. For very small particles, such as O.1-pm spheres of polymer in a latex
paint, either term could be applied. However, for particles of this size or larger,
MECHANICAL SEPARATIONS 1047
the osmotic pressure can be neglected, and the molecular diffusivity is too low to
account for significant mass transfer away from the membrane surface. The solvent
flux in microfiltration is generally much less than the flux with pure water,
indicating that a layer of solids has formed at the surface. The limiting flux depends
on the type of particles and the type of membrane, and although no general
correlations are available, some theories are being developed to help interpret the
performance data.
Fundamental studies have been made for laminar flow of dilute suspensions
in thin channels or tubes. Neutrally buoyant particles in a nonporous tube tend
to move away from the wall because of an inertial lifting force, giving a particle-free
zone near the wall. This is called the tubular-pinch effect. Where the wall is porous,
as in microfiltration, flow toward the wall exerts a drag on the particles opposing
the lifting force. For particles 10 flm or greater in size, the inertial lifting force is
often large enough to keep the particle from reaching the wall! Measured
trajectories for isolated particles agree with predictions, but the theory has not
yet been extended to concentrated suspensions or turbulent flow 3
For l-flm particles, the inertial force is quite small relative to the drag
force, and rapid formation of a particle or gel layer is predicted. However,
the particle layer does not grow steadily until it plugs the channel but seems
to reach a steady-state thickness. One explanation is that the high shear rate
near the wall causes a tumbling motion of individual particles, which expands
the layer and leads to migration away from the wall.'o This shear-induced
dispersion and the particle movement toward regions of lower concentration
can be modeled with a particle diffusivity, which is proportional to the shear
rate and the square of the particle size. More work is needed to understand
the effects of particle shape and surface characteristics.
Although the permeate flux increases with crossflow velocity, velocities
greater than a few meters per second are usually impractical because of the
large pressure drop. Another way of providing high shear at the membrane
surface is to use a rotating filter plate or a rotating disc very close to the
filter plate. Several devices of this type have been tested and shown 26 to give
fluxes of 100 to 300 L/m 2 -h.
SEPARATIONS BASED ON THE
MOTION OF PARTICLES THROUGH
FLUIDS
Many methods of mechanical separation are based on the movement of solid
particles or liquid drops through a fluid. The fluid may be gas or liquid; it
may be flowing or at rest. In some situations the objective of the process is
to remove particles from a stream in order to eliminate contaminants from
the fluid or to recover the particles, as in the elimination of dust and fumes
from air or flue gas or the removal of solids from liquid wastes. In other
problems, particles are deliberately suspended in fluids to obtain separations
1048 OPERATIONS INVOLVING PARTICULATE SOLIDS
of the particles into fractions differing in size or density. The fluid is then
recovered, sometimes for reuse, from the fractionated particles.
The principles of particle mechanics that underlie the separations described
here are discussed in Chap. 7. If a particle starts at rest with respect to the fluid
in which it is immersed and is then moved through the fluid by an external force,
its motion can be divided into two stages. The first stage is a short period of
acceleration, during which the velocity increases from zero to the terminal velocity.
The second stage is the period during which the particle is at its terminal velocity.
Since the period of initial acceleration is short, usually of the order of
tenths of a second or less, initial-acceleration effects are short range. Terminal
velocities, on the other hand, can be maintained as long as the particle is
under treatment in the equipment. Equations such as (7.30) and (7.32) apply
during the acceleration period, and equations such as (7.40) and (7.43) during
the terminal-velocity period. Some separation methods, such as jigging and
tabling, depend on differences in particle behavior during the acceleration period.
Most common methods, however, including all those described here, make use of
the terminal-velocity period only.
Gravity Settling Processes
Particles heavier than the suspending fluid may be removed from a gas or
liquid in a large settling box or settling tank, in which the fluid velocity is
low and the particles have ample time to settle out. Simple devices of this
kind, however, have limited usefulness because of the incompleteness of the
separation and the labor required to remove the settled solids from the floor
of the vessel.
Industrial separators nearly all provide for the continuous removal of
settled solids. The separation may be partial or very nearly complete. A settler
that removes virtually all the particles from a liquid is known as a clarifier, whereas
a device that separates the solids into two fractions is called a classifier. The same
principles of sedimentation apply to both kinds of equipment.
GRAVITY CLASSIFIERS. Most classifiers in chemical processing separate particles
on the basis of size, in situations in which the density of the fine particles is the
same as that of the larger ones. The elutriation leg of the crystallizer shown in
Fig. 27.12 is an example. By adjusting the upward velocity of the liquid so that
it is smaller than the terminal settling velocity of acceptably large crystals, this
device carries unwanted fine crystals back to the crystallizing zone for further
growth.
Mechanical classifiers are used in closed-circuit grinding (see Fig. 29.15),
especially in metallurgical operations. Here the relatively coarse particles are called
sands and the slurry of fine particles is called slimes. Sufficient time is provided to
allow the sands to settle to the bottom of the device; the slimes leave in the effluent
liquid.
MECHANICAL SEPARATIONS 1049
In a typical mechanical classifier the settling vessel is a semicylindrical
trough set at an angle of about 12 with the horizontal, with a liquid overflow
0
at the lower end. Slurry is fed continuously to the middle of the trough. The
flow rate is adjusted so that fines do not have time to settle but are carried
out with the overflow liquid. Larger particles sink to the floor of the trough.
A rotating helical conveyor moves the settled solids upward along the floor
of the trough, out of the pool of liquid and up to the sands-discharge chute.
Such a classifier works well with coarse particles where exact splits are not
required. Typical applications are in connection with ball or rod mills for
reduction to particle sizes between 8- and 20-mesh. These classifiers have high
capacities. They lift coarse solids for return to the mill, so that auxiliary conveyors
and elevators are not needed. For close separations with finer particles, however,
other types of classifiers must be used. Modified forms of the settling basins and
sedimenting centrifuges discussed later are used for this purpose.
SORTING CLASSIFIERS. Devices that separate particles of differing densities are
known as sorting classifiers. They use one or the other of two principal separation
methods-sink-and-float and differential settling.
Sink-and-float methods. A sink-and-float method uses a liquid sorting medi-
um, the density of which is intermediate between that of the light material
and that of the heavy. Then the heavy particles settle through the medium,
and the lighter ones float, and a separation is thus obtained. This method
has the advantage that, in principle, the separation depends only on the difference
in the densities of the two substances and is independent of the particle size. This
method is also called heavyfluid separation.
Heavy-fluid processes are used to treat relatively coarse particles, usually
greater than lO-mesh. The first problem in the use of sink and float is the choice
of a liquid medium of the proper gravity to allow the light material to float and
the heavy to sink. True liquids can be used, but since the specific gravity of the
medium must be in the range 1.3 to 3.5 or greater, there are but few liquids that
are sufficiently heavy, cheap, nontoxic, and noncorrosive to be practicable.
Halogenated hydrocarbons and CaCl 2 solutions have been used for this purpose.
A more COmmon choice of medium is a pseudoliquid consisting of a suspension
in water of fine particles of a heavy mineral. Magnetite (specific gravity 5.17),
ferrosilicon (specific gravity 6.3 to 7.0), and galena (specific gravity 7.5) are used.
The ratio of mineral to water can be varied to give a wide range of medium
densities. Provision must be made for feeding the mixture to be separated, for
removing overflow and underflow, and for recovering the separating fluid, which
may be expensive relative to the value of the materials being treated. Hindered
settling is used. Cleaning coal, as shown in Fig. 30.30, and concentrating ores are
the common application of sink and float. Under proper conditions, clean
separations between materials differing in specific gravity by only 0.1 have been
claimed. 36
1050 OPERATIONS INVOLVING PARTICULATE SOLIDS
Raw / Agitator shaft
coal
r-----~------------~
!I
~
Sand
---'--
,-"')- -,...
Screen :~~-~
Sand
Spray
Clean coal
introduced
to control water to conveyor
density
Pulsators . . . . . /
to jets - -------E-o-
t-=-:-,
S............ Spray Makeup
cree~""~
'-'-'
Refuse
Sand-and-water mix
recirculated Clean water
for reuse
FIGURE 30.30
Heavy-media separation method or cleaning coal. (From Steam: lIs Generation and Use, Fig. 4, p. 8-6,
Babcock and Wilcox Co., New York, /972.)
DiWerential settling methods. Differential settling methods utilize the difference in
terminal velocities that can exist between substances of different density. The
density of the medium is less than that of either substance. The disadvantage of
the method is that since the mixture of materials to be separated covers a range
of particle sizes, the larger, light particles settle at the same rate as the smaller,
heavy ones and a mixed fraction is obtained.
In differential settling, both light and heavy materials settle through the
same medium. This method brings in the concept of equal-settling particles.
Consider particles of two materials A and B settling through a medium of
density p. Let material A be the heavier; e.g., component A might be galena
(specific gravity 7.5) and component B quartz (specific gravity 2.65). The terminal
velocity of a particle of size Dp and of density Pp settling under gravity through
a medium of density p is given by Eq. (7.40) for settling in the Stokes'-Iaw regime.
This equation can be written, for a galena particle of density PpA and diameter
DpA , as
(30.64)
For a quartz particle of density PpB and diameter D pB '
gD~B(PpB - p)
UtB = (30.65)
18,u
MECHANICAL SEPARATIONS 1051
For equal-settling particles U'A = U,B, and therefore
D pA =
DpB
JpPpApB -- PP (30.66)
For settling in the Newton's-law range the diameters of equal-settling
particles, from Eq. (7.43), are related by the equation
DpA PpB-P
--= (30.67)
DpB PpA - P
The significance in a separation process of the equal-settling ratio of
diameters is shown by Fig. 30.31, in which curves of Il, vs. Dp are plotted
for components A and E, for settling in the intermediate regime between Stokes'-
law and Newton's-law settling. Assume that the diameter range for both substances
lies between points D p1 and D p4 on the size axis. Then, all particles of the light
component E having diameters between Dp1 and Dp2 will settle more slowly than
any particle of the heavy substance A and can be obtained as a pure fraction.
Likewise, any particles of substance A having diameters between Dp3 and Dp4
settle faster than any particle of substance E and can also be obtained as a pure
fraction. But any light particle having a diameter between D p2 and D p4 settles at
the same speed as a particle of substance A in the size range between D p1 and
D p3, and all particles in these size ranges form a mixed fraction.
Equations (30.66) and (30.67) show that the sharpness of separation is
improved if the density of the medium is increased. It is also clear from Fig. 30.31
that the mixed fraction can be reduced or eliminated by closer sizing of the feed.
For example, if the size range of the feed is from Dp3 to Dp4 in Fig. 30.31, complete
separation is possible.
CLARIFIERS AND THICKENERS. Gravity separation under hindered settling
conditions is often used to convert a dilute slurry of fine particles into a clarified
liquid and a concentrated suspension. This process is carried out in large open
Settles foster
than any of B
,,
,
I
I
I Settles slower
~ ---------- -
: than any of A
,
I
:Dp4
FIGURE 3031
Dp. particle size Equal-settling particles.
1052 OPERATIONS INVOLVING PARTICULATE SOLIDS
tanks called thickeners or clarifiers. The concentrated suspension, or sludge, may
have to be filtered to produce a drier product, but the cost of the filtration step
is much lower than if the original slurry had been filtered directly. The clarified
liquid is free or nearly free of suspended particles, and it may be reused as process
water or discharged as waste.
Flocculation. If the solids in a suspension are mainly individual particles only a
few micrometers in diameter, the gravity settling rate would be very low and
perhaps too low for practical operation. Fortunately, in many fine suspensions,
the particles form agglomerates or clusters of particles that settle at reasonable
rates. Agglomeration is sometimes promoted by adding flocculating agents includ-
ing strong electrolytes, which reduce the repulsive forces between the charged
particles, or polymeric fiocculants that may be cationic, anionic, or nonionic in
character. Flocculation is also carried out by adding inexpensive materials such
as lime, alumina, or sodium silicate, which form loose agglomerates that carry
fines down with them.
Flocculated particles have different settling characteristics from suspensions
of dispersed dense solids. The aggregates have a high porosity and retain a
considerable amount of water that accompanies the floes when they settle. The
aggregates are also loosely bonded, and the sludge at the bottom of the settler
compresses under the weight of additional solids. Because the size, shape, and
effective density of the floes are not readily definable, it is riot possible to predict
the settling rate or the sludge density from theories or general correlations. The
thickener design is generally based on measurements of the settling rates obtained
from batch tests in the laboratory.
Batch sedimentation. These are several stages in the settling of a flocculated
suspension, and different zones are formed as sedimentation proceeds. Usually,
the concentration of solids is high enough that sedimentation of individual
particles or floes is hindered by other solids to such an extent that all solids at a
given level settle at a common velocity. At first, the solid is uniformly distributed
in the liquid, as shown in Fig. 30.32a. The total depth of the suspension is ZOo
After a short time, the solids have settled to give a zone of clear liquid, zone A in
Fig. 30.32b, and a zone D of settled solids. Above zone D is a transition layer,
zone C, in which the solids content varies from that in the original pulp to that in
zone D. In zone B, the concentration is uniform and equal to the original
concentration, since the settling rate is the same throughout this zone. The
boundaries between zones D and C and between C and B may not be distinct, but
the boundary between zones A and B is usually sharp.
As settling continues, the depths of zones D and A increase. The depth
of zone C remains nearly constant, and that of zone B decreases. This is
shown in Fig. 30.32c. Eventually zone B disappears and all the solids are in zones
C and D (see Fig. 30.32d). Meanwhile, the gradual accumulation of solid puts
stress on the material at the bottom, which compresses solids in layer D.
Compression breaks down the structure of the floes or aggregates, and liquid is
MECHANICAL SEPARATIONS 1053
TZo
1 (0) (b) (e) (d) (e)
FIGURE 30.32
Batch sedimentation.
expelled into the upper zones. Sometimes liquid in the flocs spurts out of zone D
like small geysers as layer D compresses. Finally, when the weight of the solid is
balanced by the compressive strength of the flocs, the settling process stops, as
shown in Fig. 30.32e. The entire process shown in Fig. 30.32 is called sedimenta-
tion.
Rate of sedimentation. A typical plot of interface height (the boundary between
zones A and Bl vs. time is shown in Fig. 30.33. During the early stages of settling
the velocity is constant, as shown by the first portion of the curve. When zone B
disappears, the rate of settling starts to decrease and steadily drops until the
ultimate height is reached. For the example shown, the interface height was still
decreasing at 20 h, and the ultimate height was only estimated.
Slurries vary greatly in their settling rates and in the relative heights
of various zones during settling. The initial rate is a function of the feed
concentration, but in the late stages, the settling rate also depends on the
initial height Zo, since compression effects are more important with the thicker
sludge layers. Experimental studies of the settling rate for different initial heights
and concentrations are needed for the design of a thickener.
EQUIPMENT FOR SEDIMENTATION; THICKENERS. Industrially, the above
process is conducted on a large scale in equipment called thickeners. For relatively
fast settling particles a batch settling tank or continuous settling cone may be
adequate. For many duties, however, a mechanically agitated thickener like that
shown in Fig. 30.34 must be employed. This is a large, fairly shallow tank with
slow-moving radial rakes driven from a central shaft. Its bottom may be flat or
a shallow cone. Dilute feed slurry flows from an inclined trough or launder into
the center of the thickener. The feed slurry, being more dense than water, tends
to flow downward until it reaches a zone of equal density. Then it moves radially
outward at a constantly decreasing velocity, and the flow gradually divides
1054 OPERATIONS INVOLVING PARTICULATE SOLIDS
50
40
E
0
'"
:c0> 1\
•• 30
\\
"ID
0
~
II
.s
.""g 20
~
ID
13 ~
10
Final height - - - -
2 4 6 B 10
Settling time, t, hours
FIGURE 30.33
Batch settling of a limestone slurry, Co = 236 g/L. (From Foust et al., "Principles of Unit Operations,"
2nd ed., WHey, New York, 1980). Copyright © 1980 by John Wiley & Sons, Inc. Reprinted by
permission of John WHey & Sons, Inc.
between the downward-moving suspension and the upward-moving flow that is
nearly free of solids. Liquor moves radially at a constantly decreasing velocity,
allowing the solids to settle to the bottom of the tank. Clear liquor spills over the
edge of the tank into a launder. The rake arms gently agitate the sludge and move
it to the center of the tank, where it flows through a large opening to the inlet of
a sludge pump. In some designs of thickener the rake arms are pivoted so that
they can ride over an obstruction, such as a hard lump of mud, on the tank floor.
Mechanically agitated thickeners are usually large, typically 10 to 100 m (30
to 300 ft) in diameter and 2.5 to 3.5 m (8 to 12 ft) deep. In a large thickener the
rakes may revolve once every 30 min. These thickeners are especially valuable
when large volumes of dilute slurry must be thickened, as in cement manufacture
or the production of magnesium from seawater. They are also used extensively in
sewage treatment and in water purification. The feed pulp is admitted at the
centerline of the unit at a depth of 1 m or so below the surface of the liquid. Above
the feed level is a clarification zone in which the liquid is almost free of solids.
Below the feed level is a zone of hindered settling and, near the bottom, a
MECHANICAL SEPARATIONS 1055
Torque indicator,
over/a ad alarm,
motor cutout
Lifting device
Overflow weir; Feed launder
f\
Vertical shaft Feed well i\
Arm
Blades
Discharge Cone scraper
cone
FIGURE 30.34
Gravity thickener. (Eimco Corp.)
compression zone in which the solids concentration is high. These sedimentation
zones are discussed later in this section.
The volume of clear liquor produced in a unit time by a continuous thickener
depends primarily on the cross-sectional area available for settling and in industrial
separators is almost independent of the liquid depth. Higher capacities per unit
of floor area are therefore obtained by using a multiple-tray thickener, with several
shallow settling zones, one above the other, in a cylindrical tank. Rake or scraper
agitators move the settled sludge downward from one tray to the next. Multistage
countercurrent displacement washing is possible in these devices. They are con-
siderably smaller in diameter, however, than single-stage thickeners.
1056 OPERATIONS INVOLVING PARTICULATE SOLIDS
Clarifier and thickener design. The principal quantities to be specified in designing
a thickener are the cross-sectional area and the depth. The area is usually based
on data from batch settling tests, even though such tests do not simulate very well
the action in a continuous thickener. In a test cylinder, there is no net volume
flow, and as solids settle out of one zone, they are replaced with an equal volume
of liquid coming up from below. The measured settling rates are valid for a
reference frame of no net flow. In .. continuous thickener, the depth of the layers
is usually constant, at least for a short time, but some liquid is flowing downward
with the solid, and the rest is flowing upward in the clarification zone. The design
is based on a one-dimensional analysis assuming upward flow in the clarifier and
downward flow in the settling zone.
In a continuous thickener the total downward solids flux is made up of two
parts: the flux of solids carried by the downflowing liquid and the additional flux
resulting from the settling of the solids through the liquid. The first is called the
transport flux G, and is the product of the solids concentration c and the downward
velocity u. The second is the settling flux G" which is the product of the solids
concentration and the settling rate, dZ/dt, as measured in batch tests,
G= G,+ G,= uc + e~} (30.68)
The settling flux goes through a maximum with increasing concentration, since
the settling rate is nearly constant at very Iow concentrations but decreases rapidly
at high concentrations. Fig. 30.35a shows data for limestone slurries derived from
the settling curve in Fig. 30.33. These data cover only the declining flux portion
of the curve, and the dashed line shows the approximate shape of the curve for
low concentrations. Usually a thickener operates at a high underflow concentra-
tion, and the design is based on the declining flux part of the curve.
Different methods have been proposed for establishing the settling flux curve,
and they often give different results. In the method of Coe and Clevenger,' the
initial settling velocity is measured for several suspensions with concentrations
between the feed and desired underflow concentrations and the settling velocity
is multiplied by the initial concentration to get the settling flux. This assumes that
the settling rate depends only on concentration, but in practice, the settling rate
may also depend on the concentration-time history of the suspension. Only one
batch settling curve is needed for the Kynch method,24 which was used to prepare
Fig. 30.35. For each of several times, a tangent is drawn to the settling curve to
get the settling rate, and the corresponding solids concentration is estimated by
the following procedure. The tangent is extended to the ordinate axis to give an
intercept Z" and the intial concentration is mUltiplied by Zo/Z, to get the
concentration at the top of the settling zone. While only one laboratory test is
needed, the measured settling rates may depend on the initial concentration and
height of the suspension because of compression effects. Recent papers give other
methods of analyzing the batch tests, and the subject of thickener analysis and
design is stilI quite controversiaI8 •12 •14
MECHANICAL SEPARATIONS 1057
50 50 ~
I
40 40
I
I
\
(
: ·~tal flux
I
I
I
\ 30
I
I [/
/ ;'j
I
I
I
I
I \settlin g flux, G,
\
.g
:fi
(!j 20
I
I
I
1/
/ransport flux, G,
I I u = 0.05 m/h
10
I
"- 10
I
~
V
I ;
o
I
i'-.. o
o
o 200 400 600 800 200 400 600 800
3 3
c, kg/m c, kg/m
la) Ib)
FIGURE 30.35
Fluxes for continuous thickening of a limestone slurry: (a) settling flux; (b) transport flux and total
flux for u = 0.05 mfh.
The transport flux increases linearly with concentration and is much lower
than the settling flux at low concentrations, but it becomes the major factor at
high concentrations. Because of this trend and the maximum in G" the total flux
goes through a maximum and then a minimum with increasing concentration, as
shown in Fig. 30.35b. The required area of the thickener is determined by the
minimum in the total flux curve, since a zone of this concentration tends to form
in a continuous thickener operating at the design capacity. If the overflow is clear
liquid, all the solids are removed in the underflow, and the required area is
determined by the amount of solid introduced in the feed, which is Fc o, and the
minimum downward solids flux:
(30.69)
The required area can be decreased by increasing the downward velocity, which
increases the solids flux, but this also decreases the underflow concentration, c•.
The effects of u and c. on the required area can be illustrated using an operating
diagram like Fig. 30.36, which is based on an alternate form of Eq. (30.68),"
G - uc = G, (30.70)
The left-hand side of Eq. (30.70) describes a straight line of slope -u, which is
called the operating line and starts at the total settling rate G. The feed rate and the
1058 OPERATIONS INVOLVING PARTICULATE SOLIDS
SOr-------,-------,--------,-------,
40
I \
.c
N'
.g
'"x
~
~
0
:2
(; 20
Cl)
10 I
I
I
I
FIGURE 30.36
Operating diagram for a fully loaded thickener.
thickener area determine G:
Fc o
G=- (30.71)
A
An operating line tangent to the settling flux curve, as in Fig. 30.36, case I, touches
the curve at the critical concentration c" which is the concentration in the hindered
settling zone of the continuous thickener. At this concentration, the settling flux is
just equal to G - !lC, as required by Eq. (30.70) for steady operation. For concentra-
tions between Co and Co, the settling flux is greater than G - UC, so zones of
intermediate concentration do not form.
The concentration of solids in the underflow, C., is indicated by the intercept
of the operating line on the abscissa, as can be shown by a simple proof. The
underfiow flux is !lCo and is the same as the total flux in the hindered settling zone,
(30.72)
G
c• =-
U
(30.73)
MECHANICAL SEPARATIONS 1059
Note that c, can be appreciably greater than c, if the settling flux is a significant
part of the total flux at the critical concentration.
If a greater thickener area is chosen for a given feed, the total flux is reduced,
and a higher underflow concentration can be obtained, as shown by case II of Fig.
30.36. With a higher underflow concentration, the volume of sludge to be handled
is reduced, and the cost of subsequent processing steps such as filtration and drying
is reduced. These advantages must be weighed against the cost of a larger thickener
in determining the optimum design.
If a thickener designed for a certain capacity and underflow concentration is
operated at lower capacity, the underflow concentration could be increased by
using a less steep operating line, and the critical concentration would be slightly
increased.
SEDIMENTATION ZONES IN CONTINUOUS THICKENERS. Typical vertical
concentration profiles are shown in Fig. 30.37. This figure shows the region of
very low solids concentration (the clarification zone) in the upper part of the
thickener; the hindered settling zone in the middle, in which the solids concentra-
tion is virtually constant; and the region of high solids concentration (the
compression zone) near the bottom, in which the solids concentration rises as the
sludge is slowly raked to the discharge. The thickness of these zones is not easily
specified, since there are radial as well as axial gradients in concentration, and
changes in the feed rate or solids concentration lead to gradual changes in average
zone thickness. The hindered settling zone may be from 0.3 to as much as 2 or
3 m thick depending on the operating history of the unit. At steady state, the
performance does not depend on the thickness of this layer, as long as it does not
extend above the feed level. If the thickener is operated for a short time at
feed rates above the design value, the settling zone gradually increases in thickness
Top of liquid
E
I\.. Feed level
~
D
\ b
•>
0
D
•
:E
0>
.~
a
I
"- Compression lzone
...........
c, Co Co
Concentration
FIGURE 30.37
Concentration profiles in a continuous thickener.
1060 OPERATIONS INVOLVING PARTICULATE SOLIDS
because the solids feed rate exceeds the limiting solids flux. Taking case II of Fig.
30.36 as the base case, going to a higher feed rate would make the operating line
intersect the G, curve at two places near c" and the required flux G - u" would
exceed the settling flux in this region. If the normal concentration profile was
similar to curve a in Fig. 30.37, satisfactory operation might continue for several
hours as the settling zone slowly increased in height. If the original concentration
profile was similar to curve b, the accumulation of solids would lead to poorer
clarification and loss of solids in the overflow.
Centrifugal Settling Processes
A .given particle in a given fluid settles under gravitational force at a fixed
maximum rate. To increase the settling rate the force of gravity acting on
the particle may be replaced by a much stronger centrifugal force. Centrifugal
separators have to a considerable extent replaced gravity separators in production
operations because of their greater effectiveness with fine drops and particles and
their much smaller size for a given capacity.
SEPARATION OF SOLIDS FROM GASES; CYCLONES. Most centrifugal separ-
ators for removing particles from gas streams contain no moving parts. They are
typified by the cyclone separator shown in Fig. 30.38. It consists of a vertical
cylinder with a conical bottom, a tangential inlet near the top, and an outlet for
dust at the bottom of the cone. The inlet is usually rectangular. The outlet pipe
is extended into the cylinder to prevent short-circuiting of air from inlet to outlet.
Gas out
~I
I
t
Dust out
FIGURE 30.38
Cyclone.
MECHANICAL SEPARATIONS 1061
The incoming dust-laden air travels in a spiral path around and down
the cylindrical body of the cyclone. The centrifugal force developed in the
vortex tends to move the particles radially toward the wall, and the particles
that reach the wall slide down into the cone and are collected. The cyclone
is basically a settling device in which a strong centrifugal force, acting radially,
is used in place of a relatively weak gravitational force acting vertically.
The centrifugal force Fe at radius l' is equal to mU~an/l'gC) where rn is
the mass of the particle and u,," is its tangential velocity. The ratio of the
centrifugal force to the force of gravity is then
Fe mU~n/rge = U~an
(30.74)
F, mg/g, I"g
For a cyclone 1 ft (0.3 m) in diameter with a tangential velocity of 50 ft/s
(15 m/s) near the wall, the ratio FJF" called the separation factor, is
2500/(0.5 x 32.2) = 155. A large-diameter cyclone has a much lower separa-
tion factor at the same velocity, and velocities above 50 to 70 ft/s (15 to 20 m/s)
are usually impractical because of the high pressure drop and increased abrasive
wear. Small-diameter cyclones may have separation factors as high as 2500. 29 ' To
handle large gas flows, a number of small-diameter cyclones may be grouped in
a single enclosure with common headers for the feed and product gases and a
single dust hopper.
The dust particles entering a cyclone are accelerated radially, but the
force on a particle is not constant because of the change in I" and also because
the tangential velocity in the vortex varies with I" and with distance below the
inlet. Calculation of particle trajectories is difficult, and the efficiency of a cyclone
is generally predicted from empirical correlations. Typical data for commercial
cyclones are given in Fig. 30.39, which shows the strong effects of particle size and
cyclone diameter on collection efficiency.
These three cyclones are of similar proportions with diameters of about
14, 31, and 70 in. (0.36, 0.79, and 1.78 m) and the lower efficiency of the larger
cyclones is mainly a result of the decrease in centrifugal force. For a given
air flow rate and inlet velocity, however, moderate increases in cyclone diameter
and length improve the collection efficiency, because the increase in surface area
offsets the decreased centrifugal force. The results in Fig. 30.39 are for intermediate
size cyclones, and higher or lower efficiencies would be expected with larger or
smaller units at the same flow rate and inlet velocity.
The decrease in efficiency with decreasing particle size is actually more
gradual than predicted by simple theories. For small particles, the radial velocity
and the collection efficiency should be a function of D"f" but agglomeration of the
fines may occur to raise the efficiency for these particles. Because of the particle
size effect, the uncollected dust leaving with the gas has a much smaller average
size than the entering dust, which may be important in setting emission limits.
Also, the overall efficiency is a function of the particle size distribution of the feed
and cannot be predicted just from the average size.
1062 OPERATIONS INVOLVING PARTICULATE SOLIDS
100
-- ,/
,,- V-
V /
° Pp '" 155 tb/ft3
Ala!/ C;
/ P '" 0.075 Ib/ft 3
°
°
I, V !/
Vf V A
Approx. Inlet
Flow rate, diameter, !1p, velocity,
Curve ft 3 /min in. in. H2O ft!,
°v
°1 2
B
C,
1,000
5,000
,25,000,
5
1.
31
70
20
6.'
6.7
6.~
59.3
60.0
59.3
50
,
-
100
FIGURE 30.39
Collection efficiency of typical cyclones. (By permission, FisherMKlosterman Inc., Louisville, KY.)
The collection efficiency of a cyclone increases with the particle density
and decreases as the gas temperature is increased because of the increase in
gas viscosity. The efficiency is quite dependent on flow rate because of the
lI~n term in Eq. (30.74). The cyclone is one of the few separation devices
that work better at full load than at partial load. Sometimes two identical
cyclones are used in series to get more complete solids removal, but the efficiency
of the second unit is less than the first, because the feed to the second unit has a
much lower average particle size.
LIQUID-SOLID SEPARATIONS; HYDROCLONES.29d • 3 ,. Cyclones are also used
for separating solids from liquids, sometimes as thickeners but much more
commonly as classifiers. In these services they are called hydrocyclones or
hydroclones. The action in a hydroclone is shown in Fig. 30AOa. Feed enters
tangentially at high velocity near the top. The liquid follows a spiral path near
the vessel wall, forming a strong downward vortex. Large or heavy solid particles
separate to the wall and are pushed downward and out of the cyclone as a slurry
or paste. A variable-discharge orifice controls the consistency of the underflow.
Most of the liquid goes back upward in an inner vortex and leaves through the
central discharge pipe, which is known as a vortex finder.
In a hydroclone it is not possible to have both good solids removal
and a high underflow concentration. In thickening operations, with nearly all the
solids removed from the overflow, the underflow concentration must be less than
about 12 percent by volume. In classifying hydroclones the underflow can be more
MECHANICAL SEPARATIONS 1063
Overflow
Vortex
finder
Classifying
Thickening
Underflow
la) Ib)
FIGURE 30.40
Hydroc1ones: (a) pattern of flow; (b) shape adapted to the kind of service. (From Walas, Chemical
Process Equipment: Selection and Di!sign,p. 329. Butterworths, Stoneham, MA, 1988.)
concentrated, up to a maximum of about 50 percent by volume for slurries of
limestone or coal. Figure 30.40b shows how the shape of a hydroclone is modified
depending on the function of the unit.
The pressure drop !J.p in a hydroclone varies with the feed rate raised
to a power between 2.0 and 3.3. For dilute feeds the cut diameter varies with
the 1.5 power of the cyclone diameter, so for a given pressure drop a small diameter
gives better separation than a large one. Hydroclones are therefore small: they
range in diameter from 10 mm (0.4 in.) to about 1.2 m (48 in.). To handle large
flows, many small hydroclones are connected in parallel, with as many as four
hundred and eighty lO-mm units manifolded in a single assembly.
The cut size is a weak function of the pressure drop; for dilute feeds it
varies with !J.p-O.2'. Hence large pressure drops are not economical. Large
hydroclones operate with a !J.p of about 1 atm; in small ones !J.p is 4 to 5 atm.
Hydroclones find applications in degritting operations in alumina produc-
tion, removing carbon in upgrading gypsum for phosphoric acid manufacture,
classifying pigments and crystal magmas, and similar process steps. They have
largely replaced mechanical classifiers in closed-circuit grinding.
CENTRIFUGAL DECANTERS. Immiscible liquids are separated industrially in
centrifugal decanters as described in Chap. 2. The separating force is much
larger than that of gravity, and it acts in the direction away from the axis
1064 OPERATIONS INVOLVING PARTICULATE SOLIDS
of rotation instead of downward toward the earth's surface. The main types
of centrifugal decanters are tubular centrifuges and disk centrifuges.
Tubular centrifuge. A tubular liquid-liquid centrifuge is shown in Fig. 30.41.
The bowl is tall and narrow, 100 to 150 mm (4 to 6 in.) in diameter, and
turns in a stationary casing at about 15,000 r/min. Feed enters from a stationary
nozzle inserted through an opening in the bottom of the bowl. It separates into
two concentric layers of liquid inside the bowl. The inner, or lighter layer spills
over a weir at the top of the bowl; it is thrown outward into a stationary discharge
cover and from there to a spout. Heavy liquid flows over another weir into a
separate cover and discharge spout. The weir over which the heavy liquid flows
is removable and may be replaced with another having an opening of a different
size. The position of the liquid-liquid interface (the neutral zone) is maintained by
a hydraulic balance as shown in Fig. 2.7 and Eq. (2.17). In some designs the liquids
discharge under pressure and the interface position is set by adjusting external
valves in the discharge lines.
I,...;,---,~.--Motor
Heavy Light
Liquid LiqUId
Rotating Bowl
Solids
l:::=:;:::== -.(- Feed FIGURE 30.41
Tubular centrifuge.
MECHANICAL SEPARATIONS 1065
Disk centrifuge. For some liquid-liquid separations the disk-type centrifuge illu-
strated in Fig. 30.42 is highly effective. A short, wide bowl 200 to 500 mm
(8 to 20 in.) in diameter turns on a vertical axis. The bowl has a flat bottom
and a conical top. Feed enters from above through a stationary pipe set into
the neck of the bowl. Two liquid layers are formed as in a tubular centrifuge;
they flow over adjustable dams into separate discharge spouts. Inside the bowl
and rotating with it are closely spaced "disks," which are actually cones of sheet
metal set one above the other. Matching holes in the disks about halfway between
the axis and the wall of the bowl form channels through which the liquids pass.
In operation feed liquid enters the bowl at the bottom, flows into the channels,
and upward past the disks. Heavier liquid is thrown outward, displacing lighter
liquid toward the center of the bowl. In its travel the heavy liquid very soon strikes
the underside of a disk and flows beneath it to the periphery of the bowl without
encountering any more light liquid. Light liquid similarly flows inward and upward
over the upper surfaces of the disks. Since the disks are closely spaced, the distance
a drop of either liquid must travel to escape from the other phase is short, much
shorter than in the comparatively thick liquid layers in a tubular centrifuge. In
addition, in a disk machine there is considerable shearing at the liquid-liquid
interface, as one phase flows in one direction and the other phase in the opposite
direction. This shearing helps break certain types of emulsions. Disk centrifuges
are particularly valuable where the purpose of the centrifnging is not complete
separation but the concentration of one fluid phase, as in the separation of cream
from milk and the concentration of rubber latex.
If the liquid fed to a disk or tubular centrifuge contains dirt or other
heavy solid particles, the solids accumulate inside the bowl and must periodically
r;====:::::;~+--F"d
Casing
Light
liquid
Heavy
liquid
Rotatl;,q bowl
FIGURE 30.42
Disk centrifuge.
1066 OPERATIONS INVOLVING PARTICULATE SOLIDS
be discharged. This is accomplished by stopping the machine, removing and
opening the bowl, and scraping out its load of solids. This becomes uneconomical
if the solids are more than a few percent of the feed.
Tubular and disk centrifuges are used to advantage for removing traces
of solids from lubricating oil, process liquids, ink, and beverages that mnst
be perfectly clean. They can take out gelatinous or slimy solids that would
quickly plug a filter. Usually they clarify a single liquid in a bowl provided
with but a single liquid overflow; however, they also may throw down solids
while simultaneously separating two liquid phases.
NOZZLE-DISCHARGE CENTRIFUGE. When the feed liquid contains more than
a few percent of solids, means must be provided for discharging the solids
automatically. One way of doing this is shown in Fig. 30.43. This separator is a
modified disk-type centrifuge with a double conical bow!. In the periphery of the
bowl at its maximum diameter is a set of small holes, or nozzles, perhaps 3 mm
in diameter. The central part of the bowl operates in the same way as the usual
disk centrifuge, overflowing either one or two streams of clarified liquid. Solids
are thrown to the periphery of the bowl and escape continuously through the
nozzles, together with considerable liquid. In some designs part of the slurry
discharge from the nozzles is recycled through the bowl to increase its concentra-
tion of solids; wash liquids may also be introduced into the bowl for displacement
Slurry dlscho'rge
FIGURE 30.43
Nozzle~discharge centrifuge.
MECHANICAL SEPARATIONS 1067
washing. In still other designs the nozzles are closed most of the time by plugs or
valves that open periodically to discharge a moderately concentrated slurry.
SLUDGE SEPARATORS. In a nozzle-discharge centrifuge the solids leave the bowl
from below the liquid surface and therefore carry with them considerable quantities
of liquid. For separating a feed slurry into a clear liquid fraction and a heavy
"dry" sludge, the settled solids must be moved mechanically from the liquid and
given a chance to drain while still under centrifugal force. This is done in
continuous sludge separators, a typical example of which is illustrated in Fig. 30.44.
In this helical-conveyor centrifuge a cylindrical bowl with a conical end section
rotates about a horizontal axis. Feed enters through a stationary axial pipe,
spraying outward into a "pond" or annular layer of liquid inside the cylindrical
bowl. Clarified liquid flows through overflow ports in the plate covering the
nonconical end of the bowl. The radial position of these ports fixes the thickness
of the annular layer of liquid in the bowl. Solids settle through the liquid to the
inner surface of the bowl; a helical conveyor turning slightly slower than the bowl
moves the solids out of the pond and up the "beach" to the discharge openings
in the small end of the cone. Wash liquid may be sprayed on the solids as they
travel up the beach, to remove soluble impurities. The wash flows into the pond
and discharges with the liquor. Drained sludge and clarified liquor are thrown
out from the bowl into different parts of the casing, from which they leave through
suitable openings.
Helic~l-conveyor centrifuges are made with maximum bowl diameters from
100 to 1400 mm (4 to 54 in.). They separate large amounts of material. A 450-mm
Effluent I head
Case top Bowl Conveyor
Adjustable
centrate
weirs
Driven sheave
Gear unit
Feed pipe
Gear torque
overload
Centrate Solids
protection
discharge discharge
FIGURE 30.44
HelicalMconveyor centrifuge (Bird Machine Co.).
1068 OPERATIONS INVOLVING PARTICULATE SOLIDS
machine, for example, might handle 1 to 2 tons of solids per hour; a 1400-mm
machine, 50 ton/h. With thick feed slurries the capacity of a given machine is
limited by the allowable torque on the conveyor. With dilute slurries the liquid-
handling capacity of the bowl and overflow ports limits the throughput.
Practical operation of a sludge separator, of course, requires that the solids
be heavier than the liquid and not be resuspended by the action of the conveyor.
A modification known as an axial-flow conveyor centrifuge (described later) is
more effective in separating fine light solids than the full-scroll centrifuge shown
in Fig. 30.44. Even so, the liquid effluent from these machines is usually not
completely free from solids and may require subsequent clarification. Within these
restrictions sludge separators solve a wide variety of problems. They separate fine
particles from liquids, dewater and wash free-draining crystals, and are often used
as classifiers.
PRINCIPLES OF CENTRIFUGAL SEDIMENTATION. In a sedimenting centrifuge
a particle of given size is removed from the liquid if sufficient time is available for
the particle to reach the wall of the separator bowl. If it is assumed that the particle
is at all times moving radially at its terminal velocity, the diameter of the smallest
particle that should just be removed can be calculated.
Consider the volume of liquid in a centrifuge bowl shown in Fig. 30.45. The
feed point is at the bottom, and the liquid discharge is at the top. Assume that
all the liquid moves upward through the bowl at a constant velocity, carrying
solid particles with it. A given particle, as shown in the figure, begins to settle at
the bottom of the bowl at some position in the liquid, say, at a distance rA from
the axis of rotation. Its settling time is limited by the residence time of the liquid
in the bowl; at the end of this time let the particle be at a distance rE from the
LiqUid discharge
I
I
\ Surface
\
\
\
~/;qU;d
I Axis of
\ ljtallon
b
~
>
1
/ Trajectory
Bowl \~
wo/! \
I
I
• ~
Feed
I
FIGURE 30.45
Particle trajectory in sedimenting centrifuge.
MECHANICAL SEPARATIONS 1069
axis of rotation. If r. < r2, the particle leaves the bowl with the liquid; if r. = r"
it is deposited on the bowl wall and removed from the liquid. If the particle settles
in the Stokes'-Iaw range, the terminal velocity at radius r is, by Eq. (7.40),
w 2r(p _ p)D2
U = p P
t 18/1
Since Ut = dr/dl,
dt = 18), dr (30.75)
w 2(pp - p)D; r
Integrating Eq. (30.75) between the limits r = r A at I = 0 and r = r. at I = IT
gives
tT =
18/1 I
n-
r. (30.76)
w 2(pp - p)D; rA
Residence time IT is equal to the volume of liquid in the bowl V divided by
the volumetric flow rate q. Volume V equals nb(d - d). Substitution into Eq.
(30.76) and rearrangement give
nbw 2(p - p)D2 d- d
q= p p (30.77)
18/1 In (rB/rA)
A cut point can be defined' as the diameter of that particle which just reaches
one-half the distance between r, and r,. If D p , is the cut diameter, a particle of
this size moves a distance y = (r, - r ,1/2 during the settling time allowed. If a
particle of diameter D pt is to be removed, it must reach the bowl wall in the
available time. Thus r. = 1'2 and I'A = (I', + r 2 )/2. Equation (30.77) then becomes
nbw'(p - p)D2 r2 _ 1"
q = p P' 2 , (30.78)
, 18/1 In [2r 2 /(r, + 1',)]
where q, is the volumetric flow rate corresponding to the cut diameter. At this
flow rate most particles whose diameters are larger than D P' will be eliminated by
the centrifuge, and most particles having smaller diameters will remain in the
liquid.
If the thickness of the liquid layer is small compared to the radius of the
bowl, 1', "" r2, and Eq. (30.78) becomes indeterminate. Under these conditions,
however, the settling velocity may be considered constant and given by the
equation
D;(pp - p)w2r,
Ut = (30.79)
18/1
Let the thickness of the liquid layer be s and the settling distance for particles
of cut diameter D P' be s/2. Then
s
U =- (30.80)
I 2tT
1070 OPERATIONS INVOLVING PARTICULATE SOLIDS
where IT is the residence time, given by
V
tr =- (30.81)
q,
Combining Eqs. (30.77) to (30.79) and solving for q, gives
2 Vu, . 2VD;(pp - P)O"'2
q =-= (30.82)
'8 18/18
Sigma value; scaleup. For application to industrial centrifuges Eq. (30.82) is
modified as follows. Radius r2 and thickness s are replaced by r, and s"
respectively, which are appropriate average values of rand s for the type of
centrifuge under consideration. The right-hand side of Eq. (30.82) is multiplied
and divided by g, the gravitational acceleration, and all factors relating to tlw
centrifuge are collected in one group and those relating to the solids and liquid
in another. This gives
2Va,z,., D;(pp - p)g
q = _ - - " --'.C'-"="-'-"'-
, gs 18/1
= 2 L ug (30.83)
where L, the so-called sigma value, is a characteristic of the centrifuge and ug
is the terminal settling velocity of the particles under gravity settling conditions.
Physically, L is the cross-sectional area of a gravity settling tank of the same
separation capacity as the centrifuge. Typical values are given in Table 30.5. A
19.5-in (O.5-m) disk centrifuge, for example, is equivalent to a gravity sedimenter
with an area of over ID· fe (ID' m 2 ). In practice the actual capacity of a centrifuge
may be somewhat less than that indicated by the L value, because of the
TABLE 30.5
Characteristics of sedimenting centrifuges29b."
Bowl speed, 1: value,
Type diameter, in. r/min ftl x 10- 4
Tubular 4.125 15,000 2.7
Disk 9.5 6,500 21.5
13.7 4,650 39.3
19.5 4,240 105
Helical
conveyor 14 4,000 1.34
25 3,000 6.1
Axial-flow
conveyor
No vanes 29 2,600 4.05
96 vanes 29 2,600 12.7
MECHANICAL SEPARATIONS 1071
complicated flow patterns in a revolving centrifuge bowl and, in some designs, the
resuspension of particles by an internal conveyor.
AXIAL-FLOW CONVEYOR CENTRIFUGES. In 1970 Schnittger 34 showed that the
actual residence time in a conveyor centrifuge is much less than that given by Eq.
(30.81). He proposed a model in which liquid flows in a thin "boundary layer"
over an essentially stagnant liquid pond. The critical separation takes place in this
layer, for once a particle moves from the boundary layer into the pond, it is
effectively removed unless later resuspended mechanically. A thin boundary layer
gives better separation than a thick one. The total pond volume is not important;
the pond needs to be no deeper than necessary to ensure that the compacted solids
are well below the surface.
In an axial-flow conveyor centrifuge the scroll is cut away in the feed and
sedimentation sections to form a ribbon conveyor operating near the bowl wall,
leaving the liquid surface undisturbed. The boundary layer can then flow in an
axial direction from the feed point to the liquid discharge. Turbulence is minimized
in the feed zone and at the liquid exit by the design of the flow channels.
Longitudinal vanes in the sedimentation section make sure the liquid in the
boundary layer rotates at full bowl speed; these vanes, set at an angle with the
radial direction, also function like the disks of a disk centrifuge, reducing the
distance a particle must settle before it strikes a solid surface. Once this occurs,
the particle is unlikely to be resuspended.
In a full-scroll centrifuge (Fig. 30.44) the liquid flows in a spiral path against
the motion of the conveyor. Under these conditions the boundary layer is as much
as 10 times as thick as it is when the layer flows only in an axial direction.
Furthermore, spiral flow induces eddies and turbulence in the boundary layer,
impeding sedimentation; with axial flow the boundary layer is in laminar flow,
and sedimentation is unimpeded. Willis and Shapiro 38 give L values for axial-flow
centrifuges. The addition of vanes can increase L by 3 to 4 times.
CENTRIFUGAL CLASSIFIERS. During the passage of the liquid through a cen-
trifuge bowl the heavier, larger solid particles are thrown out of the liquid. Finer,
lighter particles may not settle in the time available and be carried out with the
liquid effluent. As in a gravity hydraulic classifier, solid particles can be sorted
according to size, shape, or specific gravity. In a centrifugal classifier the separating
force is of the order of 600 times the force of gravity, permitting sharp separations
of particles 1 p.m or less in diameter. Much coarser particles than this, however,
are also classified in centrifugal machines.
The high settling force in a centrifuge means that practical settling rates can
be obtained with much smaller particles than in a gravity classifier. While the
higher force does not change the relative settling velocities of small particles, it
does overcome the small but disturbing effects of free convection currents and
Brownian motion in a gravity classifier, and it permits separation in some cases
where none is possible in a gravity unit. With coarse particles the settling regime
may be changed, so that a particle that settles by gravity according to Stokes' law
1072 OPERATIONS INVOLVING PARTICULATE SOLIDS
may settle in the intermediate or Newton's-law regime in a centrifuge. Thus
mixtures of equal-settling particles from a gravity unit may sometimes be partially
separated in a centrifuge. On the other hand, loose floes or weak agglomerates
which settle rapidly in a gravity thickener are often broken up in a centrifugal
classifier and settle slowly or not at all despite the increased force for sedimenta-
tion.
SYMBOLS
A Area, m 2 or ft 2; AT' total area of continuous filter; A 1> area of inner
surface of material in centrifuge; A 2 , area of outer surface of material
in centrifuge; AL , logarithmic mean of A, and A 2 ; A" arithmetic mean
of A, and A2
B Underflow from screen, kg/h or Ib/h
b Width of centrifuge basket, m or ft
C Mass of solid deposited in filter per unit volume of filtrate, kg/m 3 or
Ib/ft'; also, concentration of solids in suspension, kg/m" g/L, or Ib/ft 3;
CF , in feed; C p , in permeate; Cc, critical concentration in thickener; c g ,
concentration at which a gel layer forms in ultrafiltration; Cm, in
pores of medium; c" at surface in ultrafiltration; Co' in feed to sedi-
menter; Cl' c2 , local retentate and permeate concentrations
D Overflow from screen, kg/h or mjh; also, diameter or pore size, m, pm,
or ft
Db Width or diameter of impingement target, m or ft
Dp Particle size, m or ft; DpA ' of heavy particle; DpB , of light particle; Dp"
cut diameter
D, Volumetric diffusivity, m 2/h, cm 2/s, or ft2jh; De> effective diffusivity
defined by Eq. (30.62); D p",,, diffusivity in pores
E Screen effectiveness, dimensionless; EA' based on oversize; EB, based
on undersize
F Feed rate, kg/h or Ib/h; also force, Nor Ibf ; F" centrifugal force; F g ,
force of gravity
f Fraction of filter cycle available for cake formation
G Mass flux in sedimenter, kg/m 2-h or Ib/ft 2-h; G" settling flux; G"
transport flux
g Acceleration of gravity, m/s2 or ft/S2
g, Newton's-law proportionality factor, 32.174 ft-Ib/Ib r s 2
K Equilibrium partition coefficient in ultrafiltration
K, Constant in equation for constant-pressure cake filtration, defined by
Eq. (30.24)
K, Constant in equation for constant-rate filtration, Eq. (30.39)
k Boltzmann constant, 1.380 x 10- 23 JIK
k, Mass-transfer coefficient based on concentration, cm/s [Eq. (30.52)]
MECHANICAL SEPARATIONS 1073
Constants in Eqs. (30.13) and (30.16b), respectively
Distance in cake measured from filter medium, m or ft; also, thickness
of selective layer in ultrafiltration; L" filter cake thickness
M Molecular weight
m Mass, kg or lb; "'F, mass of wet filter cake; Ill" mass of solids in
filter cake
riJ Mass flow rate, kg(h or lb(h; lil" of solids from continuous filter
N R, Reynolds numbers, Duplll
N, Separation number, u,uolgD b
N s, Schmidt number, IllpD,
NSh Sherwood number, k,DID,
Drum speed of continuous filter, rls
"
P Pressure, atm or lbflft2; pressure in cake at distance L from filter
medium; Po> at inlet to filter; Pb' at discharge from filter; p', at boundary
between cake and medium in filter
Membrane permeability, vl!J.p [Eq. (30.49)]
Volumetric flow rate, m'/s or ft'/s; q" corresponding to removal of
particles of cut diameter; qo, at start of filtration
R Fraction of solute rejected in ultrafiltration, defined by Eq. (30.57); R F ,
based on feed and permeate [Eq. (30.56)]
Filter-medium resistance, m -1 or ft-I
Radius, ID or ft; re, effective average value; ri, of interface between cake
and liquid layer in centrifuge; r" of particle; r" inner radius of material
in centrifuge; r 2, outer radius of material in centrifuge
s Thickness of liquid layer in centrifuge, m or ft; Se> effective average
value; also, compressibility coefficient [Eq. (30.26)]
Surface area of single particle, m 2 or ft>
Absolute temperature, K
Time, h or s; tT' residence time in centrifuge; tc. cycle time in
continuous filter
U Linear velocity, m/s or ft/s; ug , settling velocity in gravity field; u"
terminal setting velocity; U,A, of heavy particle; u.. , of light particle;
U"n, tangential velocity of gas in cyclone; u., velocity of undisturbed
fluid approaching solid
v Volume, m', L, or ft'; also, volume of filtrate collected to time t
v Volume flux (superficial permeate velocity) in ultrafiltration, m/s or ft/s;
Vrnax , maximum value
Volume of single particle, m' or ft'
Mass fraction of cut in mixture of particles; X n , in underflow from
screen; X D , in overflow from screen; X F , in feed to screen; also, distance,
m or ft
y Distance from membrane surface, rn, .urn, or ft
Z Height of liquid-solid interface in sedimentation test, m or ft; Z"
intercept in Kynch method for sedimenter design; Zo, initial height
1074 OPERATIONS INVOLVING PARTICULATE SOLIDS
Greek letters
IX Specific cake resistance, mlkg or ft/lb; "'0' constant in Eq. (30.26)
IIp Overall pressure drop through filter, atm or Ibflft', Pa - Pb; IIp,,
pressure drop through cake, Pa - p'; IlPm, pressure drop through
filter medium, p' - Pb
Iln Difference in osmotic pressures, atm or Ibflft2
(j Thickness of concentration boundary layer, m, pm, or ft
8 Porosity or volume fraction voids in bed of solids, dimensionless; 8,
average porosity of filter cake
'I, Target efficiency, impingement separator
A Ratio of molecular size to pore size
p Viscosity, cP or Ib/ft-s; p', cP in dimensional equation [Eq. (30.55)]
n Osmotic pressure, atm or Ibr/ft 2
P Density, kg/m 3 or Ib/ft'; offiuid or filtrate; Pp, of particle; PpA, of heavy
particle; PpB' oflight particle
:E Sigma value for scaleup of centrifuges [Eq. (30.83)]
$, Shape factor or sphericity, defined by Eq. (28.1)
w Angular velocity, radls
PROBLEMS
30.1. It is desired to separate a mixture of crystals into three fractions, a coarse fraction
retained on an 8-mesh screen, a middle fraction passing an 8-mesh but retained on a
14-mesh screen, and a fine fraction passing a 14-mesh. Two screens in series are
used, an 8-mesh and a 14-mesh, conforming to the Tyler standard. Screen analyses of
feed, coarse, medium, and fine fractions are given in Table 30.6. Assuming the
analyses are accurate, what do they show about the ratio by weight of each of the
three fractions actually obtained? What is the overall effectiveness of each screen?
TABLE 30.6
Screen analyses for Prob. 30.1
Coarse Middle Fine
Screen Feed fraction fraction fraction
3/4 3.5 14.0
4/6 15.0 50.0 4.2
6/8 27.5 24.0 35.8
8/10 23.5 8.0 30.8 20.0
10/14 16.0 4.0 18.3 26.7
14/20 9.1 10.2 20.2
20/28 3.4 0.7 19.6
28/35 1.3 8.9
35/48 0.7 4.6
Total 100.0 100.0 100.0 100.0
MECHANICAL SEPARATIONS 1075
30.2. The screens used in Prob. 30.1 are shaking screens with a capacity of 4 metric
ton/m 2 -h-mm mesh size. How many square meters of screen are needed for each
of the screens in Prob. 30.1 if the feed to the first screen is 100 ton/h1
30.3. The data in Table 30.7 were taken in a constant-pressure filtration of a slurry of
CaC0 3 in H 20. The filter was a 6-in. filter press with an area of 1.0 ft2. The mass
fraction of solids in the feed to the press was 0.139. Calculate the values of IX. R m ,
and cake thickness for each of the experiments. The temperature is 70°F.
TABLE 30.7
Data from constant-pressure 6itrationt
5-lbJin.' 15-lbJin.' 30-lbJin.' 50-lbJin.'
pressure drop pressure drop pressure drop pressure drop
(I) (2) (3) (4)
Filtrate, Time. Filtrate, Time, Filtrate, Time, Filtrate, Time,
Ib s Ib s Ib s Ib s
0 0 0 0 0 0 0 0
2 24 5 50 5 26 5 19
4 71 10 181 10 98 10 68
6 146 15 385 15 211 15 142
8 244 20 660 20 361 20 241
10 372 25 1,009 25 555 25 368
12 524 30 1,443 30 788 30 524
14 690 35 2,117 35 1,083 35 702
16 888
18 1,188
t Mass ratio of wet cake to dry cake: (I) 1.59, (2-4), 1.47. Dry cake density: (I) 63.5, (2, 3) 73.0, (4) 73.5 Ib/ft 1•
From E. L. McMiIlen and H. A. Webber, Trolls, AIChE, 34:213 (1938).
30.4. The slurry of Prob. 30.3 is to be filtered in a press having a total area of 8 rn' and
operated at a constant pressure drop of 2 atm. The frames are 36 mm thick. Assume
that the filter-medium resistance in the large press is the same as that in the
laboratory filter. Calculate the filtration time required and the volume of filtrate
obtained in one cycle.
30.5. Assuming that the actual rate of washing is 85 percent of the theoretical rate, how
long will it take to wash the cake in the press of Prob. 30.4 with a volume of wash
water equal to that of the filtrate?
30.6. A continuous rotary vacuum filter operating with a pressure drop of 0.7 atm is to
handle the feed slurry of Prob. 30.3. The drum submergence is to be 25 percent.
What total filter area must be provided to match the overall productive capacity of
the filter press described in Prob. 30.41 Drum speed is 2 r/min.
30.7. The following relation between a and I1p for Superlight CaCO, has been de-
termined 18:
a ~ 8.8 x 1010 [1 + 3.36 x 1O-4(I1pjo.86]
where 6.p is in pounds force per square foot. This relation is followed over a pressure
range from 0 to 1000 Ibf/in.2 A slurry of this material giving 3.0 lb of cake solid per
1076 OPERATIONS INVOLVING PARTICULATE SOLIDS
cubic foot of filtrate is to be filtered at a constant pressure drop of 70 Ibf /in. 2 and
a temperature of 70°F. Experiments on this sludge and the filter cloth to be used
gave a value of Rm = 1.2 X 10 10 ft-I. A pressure filter of the tank type is to be used.
How many square feet of filter surface are needed to give 1400 gal of filtrate in a
I-h filtration? The viscosity is that of water at 70°F.
30.8. The filter of Prob. 30.7 is washed at 70°F and 70IbJ /in.' with a volume of wash
water equal to one-third that of the filtrate. The washing rate j~ 85 percent of the
theoretical value. How long should it take to wash the cake?
30.9. The filter ofProb. 30.7 is operated at a constant rate of 0.6 gal/ft 2 -min from the start
of the run until the pressure drop reaches 70 lbf/in. 2 and then at a constant pressure
drop of 70IbJ /in.' until a total of 1400 gal of filtrate is obtained. The operating
temperature is 70°F. What is the total filtration time required?
30.10. A continuous pressure filter is to yield 1400 gal/h of filtrate from the slurry described
in Prob. 30.7. The pressure drop is limited to a maximum of 50 Ib f {tn. 2 How much
filter area must he provided if the cycle time is 3 min and the drum submergence is
50 percent?
30.11. Air carrying particles of density 1800 kg/m 3 and an average diameter of 20 pm enters
a cyclone at a linear velocity of 18 m/so The diameter of the cyclone is 600 mm.
(a) What is the approximate separation factor for this cyclone? (b) What fraction of
the particles would be removed from the gas stream?
30.12. The dust-laden air of Prob. 30.11 is passed through an impingement separator at a
1inear velocity of 8 m/so The separator consists essentially of ribbons 25 mm wide.
What is the maximum fraction of the particles that can be removed by the first row
of ribbons, which covers 50 percent of the cross-sectional area of the duct?
30.13. What is the capacity in cubic meters per hour of a clarifying centrifuge operating
under the following conditions?
Diameter of bowl, 600 mm Specific gravity of liquid 1.2
Thickness of liquid layer, 75 mm Specific gravity of solid, 1.6
Depth of bowl, 400 mm Viscosity of liquid 2 cP
Speed 1200 r/min Cut size of particles, 30 pm
30.14. A batch centrifugal filter having a bowl diameter of 750 mm and a bowl height of
450 mm is used to filter a suspension having the following properties:
Liquid, water Final thickness of cake, 150 mm
Temperature, 25°C Speed of centrifuge, 2000 r/min
Concentration of solid in feed, 60 g/L Specific cake resistance, 9.5 x 10 10 ftflb
Porosity of cake, 0.835 Filter medium resistance, 2.6 x 101Oft-l
Density of dry solid in cake, 2000 kg/m'
The final cake is washed with water under such conditions that the radius of the inner
surface of the liquid is 200 mm. Assuming that the rate of flow of wash water equals
the final rate of flow of filtrate, what is the rate of washing in cubic meters per hour?
REFERENCES
1. Altena, F. W.• and G. Belrort: Chem. Ellg. Sd., 39:343 (1984).
2. Ambler, C. M.: Chem. Ellg. Prog., 48: 150 (1952).
3. Belrart, G.: J. Membrane Sd., 40:123 (1989).
MECHANICAL SEPARATIONS 1077
4. Blatt, W. F., A. David, A. S. Michaels, and L. Nelsen: in 1. E. Flinn (ed.), Membrane Science and
Technology, Plenum Press, New York, 1970.
5. Cheryan, M.: Ultrafiltration Handbook, Technomic Publishing Co., Lancaster, PA, 1986, p. 127.
6. Cheryan, M., and B. H. Chiang: in B. M. McKenna (ed.), Engineering and Food, Applied Science
Pub!., London, 1984.
7. Coe"F. S., and G. H. Clevenger: TrailS. AIME, 55:356 (1916).
8. Concha, F. A.: AfCirE J., 37:1425 (1991).
9. Crozier, H. E., and L. E. BrowneIl: Ind. Eng. Chem., 44:631 (1952).
10. Davis, R. S., and D. T. Leighton: Chem. Eng. Sci., 42:279 (1987).
11. Dick, R. I.: Fluid/Particle Separation l., 2(2):77 (1989).
12. Dixon, D. C: AfCirE J., 37:1431 (1991).
13. Fane, A. G., C. J. D. Fell, and A. G. Waters: J. Membrane Sci., 9:245 (1981).
14. Fitch, B.: AfCirE J., 36:1545 (1990).
15. Foust, A. S., L. A. Wenzel, C. W. Clump, L. Maus, and L. B. Andersen: Principles of Unit Operations,
2nd ed., WHey, New York, 1980, p. 704.
16. Gaudin, A. M.: Principles of Mineral Dressing, McGraw-Hill, New York, 1939, p. 144.
17. Goldsmith, R. L.: fnd. Eng. Chem. Fund., 10:113 (1971).
18. Grace, H. P.: Cirem. Eng. Prog., 49:303, 367, 427 (1953).
19. Grace, H. P.: AfCirE J., 2:307, 316 (1956).
20. Harriott, P.: Separation Sci., 8(3):291 (1973).
21. Hsieh, H. P.: Chem. Eng. Prog. Symp. Ser., 84(261):1 (1988).
22. Hughes, O. D., R. W. Ver Roeve, and C. D. Luke: Paper given at meeting of AIChE, Columbus,
OH, December 1950.
23. Jonsson, G.: Desalination, 51:61 (1984).
24. Kynch, G. J.: Trans. Faraday Soc., 48:161 (1952).
25. Mutder, M.: Basic Principles of Membrane Technology, Kluwer Academic Publishers, Dordrecht,
1991, p. 54.
26. Murkes, J., and C. -G. Carlsson: Crossflow Filtration Theory and Practice, WHey, New York, 1988.
27. Nickolaus, N., and D. A. DahIstrom: Chem. Eng. Prog., 52(3):87M (1956).
28. Perlmutter, B. A.: Chem. Eng. Prag., 87(7):29 (1991).
29. Perry, J. H. (ed.): Chemical Engineers' Handbook, 6th ed., McGraw-Hill, New York, 1984;
(a) pp. 19-73 to 19-88; (b) p. 19-96; (c) p. 20-83; (d) pp. 21-19 to 21-21.
30. Porter, M. C.: Ind. Eng. Chem. Prod. Res. Devel., 11:234 (1972).
31. Porter, M. C.: in P. A. Schweitzer (ed.), Handbook o/Separation Teclmiquesfor Chemical Engineers,
McGraw-Hill, New York, 1979.
32. Rushton, A., and M. S. Hameed: Filtr. Separation, 7:25 (1970).
33. Ruth, B. F.: personal communication.
34. Schnittger, J. R.: Ind Eng. Chem. Proc. Des. Dev., 9(3):407 (1970).
35. Svarovsky, L.: Chem. Eng., voL 86, 1979; (a) no. 14, p. 62; (b) no. 15, p. 101.
36. Taggart, A. F.: Handbook of Mineral Dressing: Ores and Industrial Minerals, WHey, New York,
1945, p. 11-123.
37. Van den Bers, G. B., I. G. Racz, and C. A. Smolders: J. Membrane Sci., 47:25 (1989)
38. Willis, F. F., and L. Shapiro: Technical Report No. 936, Alfa-Laval Separation, Inc., Warminster,
PA,1991.
APPENDIX
1
CGS AND SI
PREFIXES FOR
MULTIPLES AND
SUBMULTIPLES
Factor Prefix Abbreviation Factor Prefix Abbreviation
10 12 tera T to-I deci d
10' giga G 10- 2 centj c
10' mega M 10- 3 milli m
10' kilo k 10- 6 micro !'
10' hecto h 10- 9 nano n
10' deka da 10- 12 pica p
10- 15 femto f
10- 18 atto a
APPENDIX
2
VALUES
OF GAS
CONSTANT
Temperature Mass Energy R
Kelvins kg mol J 8314.47
cal'T 1.9859 x 10'
caI 1.9873 x 10'
m3 _atm 82.056 x 10 -,
gmol cm 3 -atm 82.056
Degrees Rankine Ibmol Btu 1.9858
ft-IbJ 1545.3
Hp-h 7.8045 x 10- 4
kWh 5.8198 x 10- 4
APPENDIX
3
CONVERSION
FACTORS AND
CONSTANTS
OF NATURE
To convert from To Multiply byt
acre ft' 43,560*
m' 4046.85
atm N/m' 1.01325* x 10 s
Ibf /in. 2 14.696
Avogadro number particles!g mol 6.022169 x 1023
barrel (petroleum) ft' 5.6146
gal (U.S.) 42-
m' 0.15899
bar N/m' h x lO s
Ibf /in. 2 14.504
Boltzmann constant JIK 1.380622 x 10-"
Btu cal rr 251.996
ft-lb J 778.17
J 1055.06
kWh 2.9307 x 10-'
Btufib calrr /g 0.55556
Btufib-OF calrr/g-OC h
Btu/ft'-h W/m' 3.1546
Btu/ft'-VF Wjm2_0C 5.6783
kcalfm'-h-K 4.882
Btu-ft/ft'-h_oF W-m/m2_oC 1.73073
kcalfm-h-K 1.488
(Continued)
1082 APPENDIX 3 CONVERSION FACTORS AND CONSTANTS OF NATURE
To convert from To Multiply byt
callT Btu 3.9683 x 10 -,
ft-Ib J 3.0873
J 4.1868.
cal J 4.184*
cm in. 0.39370
ft 0.0328084
cm' ft' 3.531467 x 10-'
gal (U.S) 2.64172 x 10- 4
cP (centipoise) kg/m-s h x 10- 3
Ib/ft-h 2.4191
Ib/ft-s 6.7197 x 10- 4
eSt (centistoke) m 2 /s h x 10- 6
faraday Cfg mol 9.648670 x J04
ft m 0.3048.
ft-Ib J Btu 1.2851 X 10- 3
callT 0.32383
J 1.35582
ft-lbJ /s Btu/h 4.6262
hp 1.81818 x 10- 3
ft'/h ml/s 2.581 x 10- 5
cm 2 js 0.2581
ft' cm' 2.8316839 x 10 4
gal (U.s.) 7.48052
L 28.31684
ftl-atm Btu 2.71948
caIIT 685.29
J 2.8692 x JO'
ft3js gal (U.S)fmin 448.83
gal (U.S.) ft' 0.13368
in. 3 23h
gravitational constant N_m 2jkg 2 6.673 x 10- 11
gravity acceleration, standard m/5 2 9.80665.
h min 60.
s 3600*
hp Btu/h 2544.43
kW 0.74624
hp/1000 gal kW/m' 0.197
in. cm 2.54*
in. 3 cm' 16.3871
J erg h x 10 7
ft-IbJ 0.73756
kg Ib 2.20462
kWh Btu 3412.1
L m' h x 10- 3
Ib kg 0.45359237.
Ib/ft' kg/m' 16.018
gJcm J 0.016018
Ib f /in. 2 N/m 2 6.89473 x JO'
Ib mOl/ft 2-h kg mOI/m 2 _s 1.3562 x 10-'
g mOl/cm 2-s 1.3562 x 10- 4
light, speed of m/s 2.997925 x 10'
(Continued)
APPENDIX 3 CONVERSION FACTORS AND CONSTANTS OF NATURE 1083
To convert from To Multiply byt
m It 3.280840
in. 393701
rn' ft' 35.3147
gal (U.S.) 264.17
N dyn h x 105
Ibf 0.22481
N/m 2 Ibj /in. 2 1.4498 x 10- 4
Planck constant J-s 6.626196 x 10-"
proof (U.S.) percent alcohol by volume 0.5
ton (long) kg 1016
Ib 2240*
ton (short) Ib 2000.
ton (metric) kg 1000*
Ib 2204.6
yd ft 3.
m 0.9144.
t Values that end in an asterisk are exact, by definition.
APPENDIX
4
DIMENSIONLESS
GROUPS
Symbol Name Definition
2FD gc
CD Drag coefficient
pu~Ap
!J.p,gjJ
f Fanning friction factor
2LpV'
hi Heat-transfer factor ~(Cp~r(~J>4
cpG k I-l
jM Mass-transfer factor kM(J'_)'"
G D,p
NFo F ourier number
.,
r'
u'
N F, Froude number
gL
L'p'Pg !J.T
N G, Grashof number
~'
mcp
N G, Graetz number
kL
m
NG~ Graetz number for mass transfer
pDIJL
(Continued)
APPENDIX 4 DIMENSIONLESS GROUPS 1085
Symbol Name Definition
u
NM• Mach number
a
I,D
NNo Nusselt number
k
Pg,
N, Power number
pn 3 D5
DV
N p, Pec1et number
"
cpP
N p, Prandtl number
k
DG
N" Reynolds number
P
Il f Uo
N. Separation number
gDp
P
N s, Schmidt number
Dop
k,D
NSh Sherwood number
Do
DpV 2
Nw, Weber number
ag,
APPENDIX
5
DIMENSIONS,
CAPACITIES,
AND WEIGHTS
OF STANDARD
STEEL PIPEt
c,=- Circumference, ft Capacity at 1 ftls
sectional
or surface, (t2/ft velocity
Nominal Outside Wall Inside area of Inside Pipe
of length
pipe diameter, Schedule thickness, diameter, metal, s«:tional U.S. Water, weight
size, in. in. no. in. in. in.1 area, ftl Outside Inside gal/min Ib/h Ibler
t 0.405 40 0.068 0.269 0.072 0.00040 0.106 0.0705 0.179 89.5 0.24
80 0.095 0.215 0.093 0,1)0025 0.106 0.0563 0.113 56.5 0.31
"• 0.540 40
80
0.088
0.119
0.364
0.302
0.125
0.157
0.00072
0.00050
0.141
0.141
0.095
0.079
0.323
0.224
161.5
112.0
0.42
0.54
i 0.675 40 0.091 0.493 0.167 0.00133 0.177 0.129 0.596 298.0 0.57
80 0.126 0.423 0.217 0.00098 0.177 0.111 0.440 220.0 0.74
t 0.840 40 0.109 0.622 0.250 0.00211 0.220 0.163 0.945 472.0 0.85
, 80 0.147 0.546 0.320 0.00163 0.220 0.143 0.730 365.0 1.09
• 1.050 40
80
0.113
0.154
0.824
0.742
0.333
0.433
0.00371
0.00300
0.275
0.275
0.216 1.665 832.5 1.13
0.194 1.345 6725 1.47
1.315 40 0.133 1.049 0.494 000600 0.344 0.275 2.690 1,345 1.68
80 0.179 0.957 0.639 0.00499 0.344 0.250 2.240 1,120 2.17
1. 1.660 40 0.140 1.380 0.668 0.01040 0.435 0.361 4.57 2,285 2.27
80 0.191 1.278 0.881 0.00891 0.435 0.335 3.99 1,995 3.00
1t 1.900 40 0.145 1.610 0.800 0.01414 0.497 0.421 6.34 3,170 2.72
80 0.200 1.500 1.069 0.01225 0.497 0.393 5.49 2,745 3.63
(Continued)
APPENDIX 5 DIMENSIONS, CAPACITIES, AND WEIGHTS OF STANDARD STEEL PIPE 1087
c,""" Circumference, ft Capacity at 1 ftls
sectional
or surface, ftllft velocity
Nominal Outside Wall Inside area of Inside Pipe
of length
pipe diameter, Schedule thickness, diameter, metal, sectional V.S. Water, weight
size, in. I... 00. I... in. in.2 area, ft2 Outside Inside gal/min Ib/h Iblft
2 2.375 40 0.154 2.067 1.075 0.02330 0.622 0.541 10.45 5,225 3.65
80 0.218 1.939 1.477 0.02050 0.622 0.508 9.20 4,600 5.02
2t 2875 40 0.203 2,469 1.704 0.03322 0.753 0.647 14.92 7,460 5.79
80 0.276 2.323 2.254 0.02942 0.753 0.608 13.20 6,600 7.66
3 3.500 40 0.216 3.068 2.228 0.05130 0.916 0.803 23.00 11,500 7.58
80 0.300 2.900 3.016 0.04587 0.916 0.759 20.55 10,275 10.25
31 4.000 40 0.226 3.548 2.680 0.06870 1.047 0.929 30.80 15,400 9.11
80 0.318 3.364 3.678 0.06170 1.047 0.881 27.70 13,850 12.51
4 4.500 40 0.237 4.026 3.17 0.08840 1.178 1.054 39.6 19,800 10.79
80 0.337 3.826 4.41 0.07986 1.178 1.002 35.8 17,900 14.98
5 5.563 40 0.258 5.047 4.30 0.1390 1.456 1.321 62.3 31,150 14.62
80 0.375 4.813 6.11 0.1263 1.456 1.260 57.7 28,850 20.7&
6 6.625 40 0.280 6.065 5.58 0.2006 1.734 1.588 90.0 45,000 18.97
80 0.432 5.761 8.40 0.1810 1.734 1.508 81.1 40,550 28.57
8 8.625 40 0.322 7.981 8.396 0.3474 2.258 2.089 155.7 77,850 28.55
80 0.500 7.625 12.76 0.3171 2.258 1.996 142.3 71,150 43.39
10 10.75 40 0.365 to.020 11.91 0.5475 2.814 2.620 246.0 123,000 40.48
80 0.594 9.562 18.95 0.4987 2.814 2.503 223.4 111,700 64.40
12 12.75 40 0.406 11.938 15.74 0.7773 3.338 3.13 349.0 174,500 53.56
80 0.688 11.374 26.07 0.7056 3.338 298 316.7 158,350 88.57
t Based on ANSI B36.1O~1959 by permission of ASME.
APPENDIX
6
CONDENSER
AND
HEAT-EXCHANGER
TUBE DATAt
Wan
thickness
....
"'sectional Circwnf'ereatce, ft
Velocity,
or surface, (f/rl ftls
Capacity at 1 ftls
velocity
Outside Inside a... Inside forl
of Ioogth
diameter, BWG diameter, metal, sectional U.s. US. Water, Weight.
m. DO. m. in. m.' area, rtl Outside Inside gal/miD gal/miD Ib/h Ib/ftt
i 12 0.109 0.407 0.177 0.Q00903 0.1636 O.lQ6<; 2.468 0.4053 202.7 0.602
14 0.083 0.459 0.141 0.00115 0.1636 0.1202 1.938 0.5161 258.1 0.479
16 0.065 0.495 0.114 0.00134 0.1636 0.1296 1.663 0.6014 300.7 0.388
18 0.049 0.527 0.089 0.00151 0.1636 0.1380 1.476 0.6777 338.9 0.303
•> 12
14
0.109 0.532
0.083 0.584
0.220
0.174
0.00154
0.00186
0.1963
0.1963
0.1393
0.1529
1.447
1.198
0.6912
0.8348
345.6 0.748
417.4 0.592
16 0.065 0.620 0.140 0.00210 0.1963 0.1623 1.061 0,9425 471.3 0.476
18 0.049 0.652 0.108 0.00232 0.1963 0.1707 0.962 1.041 520.5 0.367
12 0.109 0.657 0.262 0.00235 0.2291 0.1720 0.948 1.055 527.5 0.891
14 0.083 0.709 0107 0.00274 0.2291 0.1856 0.813 1.230 615.0 0.704
16 0.065 0.745 0.165 0.00303 0.2291 0.1950 0.735 1.350 680.0 0.561
18 0.049 0.777 0.127 0.00329 0.2291 02034 0.678 1.477 738.5 00432
10 0.134 0.732 0.364 0.00292 0.2618 0.1916 0.763 1.310 655.0 1.237
12 0.109 0.782 0.305 0.00334 0.2618 0.2047 0.667 1.499 750.0 1.037
14 0.083 0.834 0.239 0.00379 0.2618 0.2183 0.588 1.701 850.5 0.813
16 0.065 0.870 0.191 0.00413 0.2618 0.2278 0.538 1.854 927.0 0.649
(Continued)
APPENDIX 6 CONDENSER AND HEAT·EXCHANGER TUBE DATA 1089
OOM- Velocity,
Wall Circumference, et Capacity at 1 ftls
thickness
sectional
or surface. ((11((
COs
velocity
Outside Inside area Inside for 1
of length
diameter, BWG diameter, metal, sectional u.s. U.s. Water, Weight,
in. no. in. in. in.z area, ft 2 Outside Inside gal/min gal/min Ib/h Ib/ft~
It 10 0.[34 0.982 0.470 0.00526 0.3272 0.2571 0.424 2.361 1,181 1.598
[2 0.109 1.032 0.391 0.00581 0.3272 0.2702 0.384 2.608 1,304 1.329
[4 0.083 1.084 0.304 0.00641 0.3272 0.2838 0.348 2.877 1,439 1.033
[6 0.065 1.120 0.242 0.00684 0.3272 0.2932 0.326 3.070 1,535 0.823
Ij 10 0.134 1.232 0.575 0.00828 0.3927 0.3225 0.269 3.716 1,858 1.955
[2 0.109 1.282 0.476 0.00896 0.3927 0.3356 0.249 4.021 2,01l 1.618
[4 0.083 1.334 0.370 0.00971 0.3927 0.3492 0.229 4.358 2,176 1.258
2 10 0.134 1.732 0.7855 0.0164 0.5236 0.4534 0.136 7.360 3,680 2.68
12 0.109 1.782 0.6475 0.0173 0.5236 0.4665 0.129 7.764 3,882 2.22
t Condensed, by permission, from J. H. Perry (ed.), Chemical Engineers' Handbook, 5th ed., p. 1l~12. Copyright © 1973,
McGraw-Hill Book Company, New York.
t For steel; for copper, multiply by 1.14; for brass, mUltiply by 1.06.
APPENDIX
7
PROPERTIES
OF SATURATED
STEAM AND
WATERt
Temperature Vapor
Specific volume, ftl/lb Enth.lpy, Btu/lb
T, pressure PA , Liquid Saturated vapor Liquid Vaporization Saturated yapor
of Ibp in. 2 "x "y Hx 1 Hy
32 0.08859 0.016022 3305 0 1075.4 1075.4
35 0.09992 0.016021 2948 3.00 1073.7 1076.7
40 0.12166 0.016020 2445 8.02 1070.9 1078.9
45 0.14748 0.016021 2037 13.04 1068.1 1081.1
50 0.17803 0.016024 1704.2 18.06 1065.2 1083.3
55 0.2140 0.016029 1431.4 23.07 1062.4 1085.5
60 0.2563 0.016035 1206.9 28.08 1059.6 1087.7
65 0.3057 0.016042 1021.5 33.09 1056.8 1089.9
70 0.3632 0.016051 867.7 38.09 1054.0 1092.0
75 0.4300 0.016061 739.7 43.09 1051.1 1094.2
80 0.5073 0.016073 632.8 48.09 1048.3 1096.4
85 0.5964 0.016085 543.1 53.08 1045.5 1098.6
90 0.6988 0.016099 467.7 58.07 1042.7 1100.7
95 0.8162 0.016114 404.0 63.06 1039.8 1102.9
100 0.9503 0.016130 350.0 68.05 1037.0 1105.0
110 1.2763 0.016166 265.1 78.02 1031.4 1109.3
( COlltinued)
APPENDIX 7 PROPERTIES OF SATURATED STEAM AND WATER 1091
Specific 'Volume, ft3/1b Enthalpy, Btu/lb
Temperature Vapor
T, pressure PA! Liquid Saturated vapor Liquid Vaporization Saturated vapor
of IbJin.2 Vx Vy Hx 1 Hy
120 1.6945 0.016205 203.0 88.00 1025.5 1113.5
130 2.225 0.016247 157.17 97.98 1019.8 1117.8
140 2.892 0.016293 122.88 107.96 1014.0 1121.9
150 3.722 0.016343 96.99 117.96 1008.1 1126.1
160 4.745 0.016395 77.23 127.96 1002.2 1130.1
170 5.996 0.016450 62.02 137.97 996.2 1134.2
180 7.515 0.016509 50.20 147.99 990.2 1138.2
190 9.343 0.016570 40.95 158.03 984.1 1142.1
200 11.529 0.016634 33.63 168.07 977.9 1145.9
210 14.125 0.016702 27.82 178.14 971.6 1149.7
212 14.698 0.016716 26.80 180.16 970.3 1150.5
220 17.188 0.016772 23.15 188.22 965.3 1153.5
230 20.78 0.016845 19.386 198.32 958.8 1157.1
240 24.97 0.016922 16.327 208.44 952.3 1160.7
250 29.82 0.017001 13.826 218.59 945.6 1164.2
260 35.42 0.017084 11.768 228.76 938.8 1167.6
270 41.85 0.017170 10.066 238.95 932.0 1170.9
280 49.18 0.017259 &650 249.18 924.9 1174.1
290 57.53 0.017352 7.467 259.44 917.8 1177.2
300 66.98 0.017448 6.472 269.73 910.4 1180.2
310 77.64 0.017548 5.632 280.06 903.0 1183.0
320 89.60 0.017652 4.919 290.43 895.3 1185.8
340 117.93 0.017872 3.792 311.30 879.5 1190.8
350 134.53 0.017988 3.346 321.80 871.3 1193.1
360 152.92 0.018108 2.961 332.35 862.9 1195.2
370 173.23 0.018233 2.628 342.96 854.2 1197.2
380 195.60 0.018363 2.339 353.62 845.4 1199.0
390 220.2 0.018498 2.087 364.34 836.2 1200.6
400 247.1 0.018638 1.8661 375.12 826.8 1202.0
410 276.5 0.018784 1.6726 385.97 817.2 1203.1
420 308.5 0.018936 1.5024 396.89 807.2 1204.1
430 343.3 0.019094 1.3521 407.89 796.9 1204.8
440 381.2 0.019260 1.2192 418.98 786.3 1205.3
450 422.1 0.019433 1.1011 430.2 775.4 1205.6
t Abstractep from Steam Tables, by Joseph H. Keenan, Frederick G. Keyes, Philip G. Hill, and Joan G. Moore,
John Wiley & Sons, New York, 1969, with the permission of the publisher.
APPENDIX
8
VISCOSITIES
OF GASESt
No. Gas X Y No. Gas X Y
1 Acetic acid 7.7 14.3 29 Freon-113 11.3 14.0
2 Acetone 8.9 13.0 30 Helium 10.9 20.5
3 Acetylene 9.8 14.9 31 Hexane 8.6 11.8
4 Air 11.0 20.0 32 Hydrogen 11.2 12.4
5 Ammonia 8.4 16.0 33 3H z + N2 11.2 17.2
6 Argon 10.5 22.4 34 Hydrogen bromide 8.8 20.9
7 Benzene 8.5 13.2 35 Hydrogen chloride 8.8 18.7
8 Bromine 8.9 19.2 36 Hydrogen cyanide 9.8 14.9
9 Butene 9.2 13.7 37 Hydrogen iodide 9.0 21.3
10 Butylene 8.9 13.0 38 Hydrogen sulfide 8.6 18.0
11 Carbon dioxide 9.5 18.7 39 Iodine 9.0 18.4
12 Carbon disulfide 8.0 16.0 40 Mercury 5.3 22.9
13 Carbon monoxide 11.0 20.0 41 Methane 9.9 15.5
14 Chlorine 9.0 18.4 42 Methyl alcohol 8.5 15.6
15 Chlorofonn 8.9 15.7 43 Nitric oxide 10.9 20.5
16 Cyanogen 9.2 15.2 44 Nitrogen 10.6 20.0
17 Cyclohexane 9.2 12.0 45 Nitrosyl chloride 8.0 17.6
18 Ethane 9.1 14.5 46 Nitrous oxide 8.8 19.0
19 Ethyl acetate 8.5 13.2 47 Oxygen 11.0 21.3
20 EUtyl alcohol 9.2 14.2 48 Pentane 7.0 12.8
21 Ethyl chloride 8.5 15.6 49 Propane 9.7 12.9
22 Ethyl ether 8.9 13.0 50 Propyl alcohol 8.4 13.4
23 Ethylene 9.5 15.1 51 Propylene 9.0 13.8
24 Fluorine 7.3 23.8 52 Sulfur dioxide 9.6 17.0
25 Freon-I! 10.6 15.1 53 Toluene 8.6 12.4
26 Freon-12 11.1 16.0 54 2,3,3-Trimethylbutane 9.5 10.5
27 Freon-21 10.8 15.3 55 Water 8.0 16.0
28 Freon-22 10.1 17.0 56 Xenon 9.3 23.0
Coordinates for use with figure on next page.
t By permission, from J. H. Perry (ed.), Chemical Engineers' Handbook, 5th cd., pp. 3·210 and 3·211. Copyright © 1973,
McGraw-HiII Book Company, New York.
APPENDIX 8 VISCOSITIES OF GASES 1093
Temperature Viscosity
Deg.C Deg. F. Centipoises
-100 0.1
0.09
-100 0.08
0.07
0.06
0
0 0.05
30
100 28 0.04
26
100 200
24
0.03
22
300
20
200 400 18
0.02
500 16
Y
300 600 14
700 12
400
800 10
900 8
500
1000 0.01
6
1100 0.009
600
4 0.008
1200
700 1300 2
0.007
1400 0
800 1500 0 2 4 6 8 10 12 14 16 18 0.006
1600 X
900
1700
1000 1800 0.005
Viscosities of gases and vapors at 1 atm; for coordinates, see table on previous page.
APPENDIX
9
VISCOSITIES
OF LIQUIDSt
No. Liquid X Y No. Liquid X Y
1 Acetaldehyde 15.2 4.8 22 Butyl acetate 12.3 11.0
2 Acetic acid, 100% 12.1 14.2 23 Butyl alcohol 8.6 17.2
3 Acetic acid, 70% 9.5 17.0 24 Butyric acid 12.1 15.3
4 Acetic anhydride 12.7 12.8 25 Carbon dioxide 11.6 0.3
5 Acetone, 100% 14.5 7.2 26 Carbon disulfide 16.1 7.5
6 Acetone, 35% 7.9 15.0 27 Carbon tetrachloride 12.7 13.1
7 Allyl acohol 10.2 14.3 28 Chlorobenzene 12.3 12.4
8 Ammonia, 100% 12.6 2.0 29 Chloroform 14.4 10.2
9 Ammonia, 26% 10.1 13.9 30 Chlorosulfonic acid 11.2 18.1
10 Amyl acetate 11.8 12.5 31 o·Chlorotoluene 13.0 13.3
11 Amyl alcohol 7.5 18.4 32 m·Chlorotoluene 13.3 12.5
12 Aniline 8.1 18.7 33 p-Chlorotoluene 13.3 12.5
13 Anisole 12.3 13.5 34 m-Cresol 2.5 20.8
14 Arsenic trichloride 13.9 14.5 35 Cyclohexanoi 2.9 24.3
15 Benzene 12.5 10.9 36 Dibromoethane 12.7 15.8
16 Bimethyl oxalate 12.3 15.8 37 Dichloroethane 13.2 12.2
17 Biphenyl 12.0 18.3 38 Dichloromethane 14.6 8.9
18 Brine, eael2-. 25% 6.6 15.9 39 Diethyl oxalate 11.0 16.4
19 Brine, NaCl, 25% 10.2 16.6 40 DipropyJ oxalate 10.3 17.7
20 Bromine 14.2 13.2 41 Ethyl acetate 13.7 9.1
21 Bromotoluene 20.0 15.9 42 Ethyl alcohol, 100 % 10.5 13.8
(Continued)
APPENDIX 9 VISCOSITIES OF LIQUIDS 1095
No. Liquid X Y No. Liquid X Y
43 Ethyl alcohol, 95% 9.8 14.3 77 Nitric acid, 60% 10.8 17.0
44 Ethyl alcohol, 40% 6.5 16.6 78 Nitrobenzene 10.6 16.2
45 Ethyl benzene 13.2 11.5 79 Nitrotoluene 11.0 17.0
46 Ethyl bromide 14.5 8.1 80 Octane 13.7 10.0
47 Ethyl chloride 14.8 6.0 81 Octyl alcohol 6.6 21.1
48 Ethyl ether 14.5 5.3 82 Pentachloroethane 10.9 17.3
49 Ethyl formate 14.2 8.4 83 Pentane 14.9 5.2
50 Ethyl iodide 14.7 10.3 84 Phenol 6.9 20.8
51 Ethylene glycol 6.0 23.6 85 Phosphorus tribromide 13.8 16.7
52 Formic acid 10.7 15.8 86 Phosphorus trichloride 16.2 10.9
53 Freon-Il 14.4 9.0 87 Propionic acid 12.8 13.8
54 Freon-12 16.8 5.6 88 Propyl alcohol 9.1 16.5
55 Freon-21 15.7 7.5 89 Propyl bromide 14.5 9.6
56 Freon-22 17.2 4.7 90 Propyl chloride 14.4 7.5
57 Freon-113 12.5 11.4 91 Propyl iodide 14.1 11.6
58 Glycerol, 100% 2.0 30.0 92 Sodium 16.4 13.9
59 Glycerol, 50% 6.9 19.6 93 Sodium hydroxide, 50% 32 25.8
60 Heptane 14.1 8.4 94 Stannic chloride 13.5 12.8
61 Hexane 14.7 7.0 95 Sulfur dioxide 15.2 7.1
62 Hydrochloric acid, 31.5% 13.0 16.6 96 Sulfuric acid, 110% 7.2 27.4
63 Isobutyl alcohol 7.1 18.0 97 Sulfuric acid, 98% 7.0 24.8
64 Isobutyric acid 12.2 14.4 98 Sulfuric acid, 60% 10.2 21.3
65 Isopropyl alcohol 8.2 16.0 99 Sulfuryl chloride 15.2 12.4
66 Kerosene 10.2 16.9 100 Tetrachloroethane 11.9 15.7
67 Linseed oil, raw 7.5 27.2 101 Tetrachloroethylene 14.2 12.7
68 Mercury 18.4 16.4 102 Titanium tetrachloride 14.4 12.3
69 Methanol, 100% 12.4 10.5 103 Toluene 13.7 10.4
70 Methanol, 90% 12.3 11.8 104 Trichloroethylene 14.8 10.5
71 Methanol, 40% 7.8 15.5 105 Turpentine 11.5 14.9
72 Methyl acetate 14.2 8.2 106 Vinyl acetate 14.0 8.8
73 Methyl chloride 15.0 3.8 107 Water 10.2 13.0
74 Methyl ethyl ketone 13.9 8.6 108 o-Xylene 13.5 12.1
75 Naphthalene 7.9 18.1 109 m-Xylene 13.9 10.6
76 Nitric acid, 95% 12.8 13.~ 110 p-Xylene 13.9 10.9
Coordinates for use with figure on p. 1096.
t By permission,
from J. H. Perry (ed.), Chemical Engineers' Handbook, 5th ed., pp. 3-212 and 3-213. Copyright ©
1973, McGraw-HilI Book Company, New York.
1096 APPENDIX 9 VISCOSITIES OF LIQUiDS
Temperature Viscosity
Deg. C. Deg. F Centipoises
200
190 380
180 360
170 340
160 320 40
150 300
140 280
130 ;- 20
260
120
240
110
220 30
100
200 28
90
26
180
80
24
70 160
22
60 140
20
50 120 18
I:- 2
40 16 E-
100
Y
30 14 1::- 1
80 E-
F- 0.8
12
20 I-
60 10 I- 0.6
10 -
8
40 0.4
0 6
20 4
-10
E- 0.2
0 2
-20 0
0 2 4 6 8 10 12 14 16 18 20
-20 X - 0.1
-30
Viscosities of liquids at 1 atm. For coordinates, see table on previous page.
APPENDIX
10
THERMAL
CONDUCTIVITIES
OF METALSt
Thermal conductivity kt
Metal 3ZOF 64°F 21ZOF
Aluminum 117 119
Antimony 10.6 9.7
Brass (70 copper, 30 zinc) 56 60
Cadmium 53.7 52.2
Copper (pure) 224 218
Gold 169.0 170.0
Iron (cast) 32 30
Iron (wrought) 34.9 34.6
Lead 20 19
Magnesium 92 92 92
Mercury (liquid) 4.8
Nickel 36 34
Platinum 40.2 41.9
Silver 242 238
Sodium (liquid) 49
Steel (mild) 26
Steel (1 % carbon) 26.2 259
Stee1 (stainless, type 304) 9.4
Steel (stainless, type 316) 9.4
Steel (stainless, type 347) 9.3
Tanta1um 32
Tin 36 34
Zinc 65 64
t Based on W. H. McAdams, Heat Transmission, 3rd ed., McGraw-Hill
Book Company. New York. 1954, pp. 445-447.
1: k = Btu/ft-h-oF.
APPENDIX
11
THERMAL
CONDUCTIVITIES
OF VARIOUS
SOLIDS AND
INSULATING
MATERIALSt
Apparent Thermal
density Temperature conductivity k,
Material p, Ib/f!' T, °c Btu/b-ft'-CF/ft)
Asbestos 29 -200 0.043
36 0 0.087
36 400 0.129
Bricks
Alumina 1315 2.7
Building brick work 20 0.4
Carbon 96.7 3.0
Fire clay (Missouri) 200 0.58
1000 0.95
1400 1.02
Kaolin insulating firebrick 19 200 0.050
19 760 0.113
(Continued)
APPENDIX 11 THERMAL CONDUCfIVITIES OF VARIOUS SOLIDS AND INSULATING MATERIALS 1099
Apparent Thermal
density Temperature conductivity k,
Material p, Ib/f" T, QC Btu/h-ft'-CF/ft)
Silicon carbide, recrystallized 129 600 10.7
129 1000 8.0
129 1400 6.3
Cardboard, corrugated 0.37
Concrete
Clinker 0.20
Stone 0.54
1:4dry 0.44
Cork, ground 9.4 30 0.025
Glass
Borosilicate 139 30-75 0.63
Window 0.3-0.61
Granite 1.0-2.3
Ice 57.5 0 1.3
Insulating materials
Fiberglass batts:J: 6 20 0.019
6 150 0.027
6 200 0.035
9 20 0.018
9 150 0.023
Kapok 0.88 20 0.020
Polystyrene foam§ 20 0.023
2-5 20 0.020
Polyurethane foam§ (made 1.3-3.0 0.014
fluorocarbon gas) 4-8 0.018
Polyurethane foam§ (made 1.3--3.0 0.018
with CO,)
Wall board 14.8 21 0.028
Magnesia, powdered 49.7 47 0.35
Paper 0.75
Porcelain 200 0.88
Rubber, soft 21 0.075-0.092
Snow 34.7 0 0.27
Wood (across grain)
Oak 51.5 15 0.12
Maple 44.7 50 0.11
Pine, white 34.0 15 0.087
Wood (parallel to grain)
Pine 34.4 21 0.20
t From 1. H. Perry (ed.), Chemical Engineers' 6th ed., McGraw-HiII, New York, p. 3-260, except
as noted.
t From Heat Trallsfer alld Fluid Data Book, vol. 1, Genium Publishing Corp., Schenectady, NY,
1984, sect. 515.24. p. 1.
§ From Modern Plastics Encyclopedia, vol. 65. no. 11, McGraw-HiII Book Co., New York, 1988.
p.657.
APPENDIX
12
THERMAL
CONDUCTIVITIES
OF GASES
AND VAPORSt
Thermal conductivity kt
Substance 32°F 212'F
Acetone 0.0057 0.0099
Acetylene 0.0108 0.0172
Air 0.0140 0.0184
Ammonia 0.0126 0.0192
Benzene 0.0103
Carbon dioxide 0.0084 0.0128
Carbon monoxide 0.0134 0.0176
Carbon tetrachloride 0.0052
Chlorine 0.0043
Ethane 0.0106 0.0175
Ethyl alcohol 0.0124
Ethyl ether 0.0077 0.0131
Ethylene 0.0101 0.0161
Helium 0.0818 0.0988
Hydrogen 0.0966 0.1240
Methane 0.0176 0.0255
Methyl alcohol 0.0083 0.0128
Nitrogen 0.0139 0.0181
Nitrous oxide 0.0088 0.0138
Oxygen 0.0142 0.0188
Propane 0.0087 0.0151
Sulfur dioxide 0.0050 0.0069
Water vapor (at 1 atm abs pressure) 0.0136
t Based on W. H. McAdams, Heat Transmission, 3rd cd., McGraw-HiJI
Book Company, New York, 1954. pp. 457-458.
t k = Btu/ft-h_cF.
APPENDIX
13
THERMAL
CONDUCTIVITIES
OF LIQUIDS
OTHER THAN
WATERt
Liquid Temperature, of kt
Acetic acid 68 0.099
Acetone 86 0.102
Ammonia (anhydrous) 5-86 0.29
Aniline 32-68 0.100
Benzene 86 0.092
n-Butyl alcohol 86 0.097
Carbon bisulfide 86 0.093
Carbon tetrachloride 32 0.107
Chlorobenzene 50 0.083
Ethyl acetate 68 0.101
Ethyl alcohol (absolute) 68 0.105
Ethyl ether 86 0.080
Ethylene glycol 32 0.153
Gasoline 86 0.078
Glycerine 68 0.164
n-Heptane 86 0.081
Kerosene 68 0.086
Methyl alcohol 68 0.124
Nitrobenzene 86 0.095
n-Octane 86 0.083
Sulfur dioxide 5 0.128
Sulfuric acid (90%) 86 0.21
Toluene 86 0.086
Trichloroethylene 122 0.080
o-Xylene 68 0.090
t Based on W. H. McAdams, Heat Transmission, 3rd cd.,
McGraw-HiII Book Company, New York, 1954. pp. 45~56.
t k = Btufft-h_oP.
APPENDIX
14
PROPERTIES
OF LIQUID
WATER
Temperature T, Viscosityt JI,
Thermal
conductivity:j: k, Density§ p, if'f= - (k'P'g)'"
of cP Btu/ft_h_oF Ib/ft' ,r
32 1.794 0.320 62.42 1,410
40 1.546 0.326 62.43 1,590
50 1.310 0.333 62.42 1,810
60 1.129 0.340 62.37 2,050
70 0.982 0.346 62.30 2,290
80 0.862 0.352 62.22 2,530
90 0.764 0.358 62.11 2,780
100 0.682 0.362 62.00 3,020
120 0.559 0.371 61.71 3,530
140 0.470 0.378 61.38 4,030
160 0.401 0.384 61.00 4,530
180 0.347 0.388 60.58 5,020
200 0.305 0.392 60.13 5,500
220 0.270 0.394 59.63 5,960
240 0.242 0.396 59.10 6,420
260 0.218 0.396 58.53 6,830
280 0.199 0.396 57.94 7,210
300 0.185 0.396 57.31 7,510
t From International Critical Tables, vol. 5, McGraw~HiIl Book Company, New York, 1929, p. 10.
t From E. Schmidt and W. Sellschopp. Forse". Geb. IngenieurlV., 3:277 (1932).
§ Calculated from J. H. Keenan and F. G. Keyes. TiJermodynamic Properties of Steam. John WHey &
Sons.. Inc.. New York. 1937.
SPECIFIC APPENDIX
HEATS OF
GASESt 15
4.0
2
o 3.0
c
Cp = Specific heat"" Btu/lb-of = cal/g_OC
Deg F 2.0
o-
-
200
:::
400 -
:-: 7
0
1.0
600
::: 48
3 5
o , 6 80 0.9
800 :-:
0 0.8
0 11 6'~
:-: N. RANGE' DE .
31- ''0
~
1,000 -
-: I. ACETYLENE
15
16
... 390 - 750
750 -1550
~OO 0
0
14 0.7
0.6
27 AIR 3'2 -1550 15 01'
- 12 AMMONIA 32 - 1110
1,200 - I'
CARBON DIOXIDE
1110-1550
32 - 750
0" 0.5
-:
1,400 :-:
"
24
" (ARBON MONOXIDE
32 CHlORINE
750 -2550
32 -'2550
31 - 390
17A
o 17C IS 2. 0.4
M 390 -2550 17~O 0 0
1,600 ....: , .
3 ETHANE 32 - 390
HO - 1110
1\ 10 - 2550
17.
I'
o
21 0
024
230 0~~26 8
8
-
1,800 -:
• -
11
13
ETHYLENE 31 - )<)0
390-lI1O
1110 -2550
22
0 25 27 S:9
0.3
32 - 300
2,000 -::-: 178
170
17A
170
FRE"ON-ll (CCI F)
fREON-21 (CHtI 2 F~
FREON'22{CHCI f;
fREON '1I3({(!2f -CCI f2)
32 - 300
32 - ~,OO
31 - :.00
3.
S
- I HYDROGEN 32 - LIlO 32 'I 0.2
2,200 -
- ,.
35
2 -
HYDROGEN BROMIDE
HYDROGEN CHLORIDE
1110 - 2550
31 - '2550
32 - '2550
0
2,400 - 12 ~~ggg~~N FJ-81%~IOE
lZ - 2550
32 -1550 0 "
-
2,600 -
19
21
5
HYDROGEN SULPHIDE
METHt..NE
. 32 - 1190
1290-'2550
3'2 - 570
3+0
6 570 - 12'10 35
7 1290 - '2500 0
25 NITRIC OXIDE 32 - 1'290 0.1
28 1190 - '2550 0.09
26 NITROGEN 3'2 - 2550
2l OXYGEN 3'2 - '130
930 - 2550 56
0.08
29
SULPHUIi' 570 - 2550 0
""
'I
17
SULPHUR DIOX.lO£
WATER
. 32 - 750
750 - 2550
32 - 2550
0.07
0.06
0.05
True specific heats cp of gases and vapors at 1 atm pressure.
t Courtesy of T. H. ChiftOll.
APPENDIX SPECIFIC
HEATS OF
16 LIQUIDSt
Specific heat = Btu/lb-oF = calfg-OC
NO. U UID RANGE " Specific
~ ~lHh~~CID 100% ,g: ~
- 70- SO
Heat
52 AMMONIA
Deg F Po
30
~~\i ~tWm'
ANILINE
- '8: I!~ 1
400 73 BENZENE 18: liS 0.2
TT BEN2YLAlCOHOl. -70- 30 I
4'~ B~"J8§HL.RIDE
I , 'lbCCI~
51 BRINE,2S% Net
:.!8: r.
-.ro- 20 bO~
lA •
0-100
"'31 ~il~M~f.l1.~~'DE "'18: 1!g 4OO4A
CARBON TETRA~LORIDE
~ ~~(8N8'.,\\,~"E 8-••
- 5. 50
0.3
-60- 25
300 21
B~1tL~1wrntANe -30- 60 '0
0"
5 DICHlOROMETHANE ·.40- 50 7 7A
15 DIPHENYL 60-120
22 DIPHENYlMETHANE 30-100 0 0 ~o 010
I. DIPHENYl. OXIDE 0-200 08 0.4
.,,. ~~J.HA1~¥A~E
12
I. _J: 2Ff
30-' 80
110 0 ol3A
Hc;,I!"O
ETHYl.ALCOHOl. 100"1'0
46
50
ETHYl.AlCOHOl. 95"10
ETHYl. ALCOHOL 50'70
20- 80
20- 80 "<0\ 0'.
021
200 25
1
ETHYl. 8ENZENE
ETHYl. ROM1DE
0-100
5- 25
'I'lO~F ~ 0'. 0.5
13 ETHYL CHLORIDE -30- ~ 250 026
m:~t fJ6Ifi! !
;y !I '9&~034
-100-
0-1 •
39 ETHYlENE GlYCOL ....0-200
280 '32 35
330
36 0.6
100
04'1
0.7
0
050 510 0.8
-100 0.9
so 550
o 1.0
t Courtesy of T. H. Chi/ton.
APPENDIX
17
PRANDTL
NUMBERS
FOR GASES
AT 1 ATM
AND 100° et
Gas NPr = CpP
k
Air 0.69
Ammonia 0.86
Argon 0.66
Carbon dioxide 0.75
Carbon monoxide 0.72
Helium 0.71
Hydrogen 0.69
Methane 0.75
Nitric oxide, nitrous oxide 0.72
Nitrogen 0.70
Oxygen 0.70
Water vapor 1.06
t Based on W. H. McAdams. Heat Transmission,
3rd ed., McGrawwHiII Book Company, New York,
1954. p. 471.
APPENDIX
18
PRANDTL
NUMBERS
FOR
LIQUIDSt
CpP
N Pr = -
k
Liquid 60"F 21rF
Acetic acid 14.5 10.5
Acetone 4.5 2.4
Aniline 69 9.3
Benzene 7.3 3.8
n~Butyl alcohol 43 11.5
Carbon tetrachloride 7.5 4.2
Chlorobenzene 9.3 7.0
Ethyl acetate 6.8 5.6
Ethyl alcohol 15.5 10.1
Ethyl ether 4.0 2.3
Ethylene glycol 350 125
n·Heptane 6.0 4.2
Methyl alcohol 7.2 3.4
Nitrobenzene 19.5 6.5
n-Octane 5.0 3.6
Sulfuric acid (98%) 149 15.0
Toluene 6.5 3.8
Water 7.7 1.5
t Based on W. H. McAdams, Heat Transmission, 3rd ed., McGraw-HiII
Book Company, New York, 1954, p. 470.
APPENDIX
19
DIFFUSIVITIES
AND SCHMIDT
NUMBERS
FOR GASES
IN AIR AT
O°C AND
Volumetric 1 ATMt
diffusivity Dv. Jl
N&=-t
Gas n2/b pD,
Acetic acid 0.413 1.24
Acetone 0.32§ 1.60
Ammonia 0.836 0.61
Benzene 0.299 1.71
Il-Butyl alcohol 0.273 1.88
Carbon dioxide 0.535 ·0.96
Carbon tetrachloride 0.26§ 1.97
Chlorine 0.43§ 1.19
Chlorobenzene 0.24§ 2.13
Ethane 0.49§ 1.04
Ethyl acetate 0.278 1.84
Ethyl alcohol 0.396 1.30
Ethyl ether 0.302 1.70
Hydrogen 2.37 0.22
Methane 0.74§ 0.69
Methyl alcohol 0.515 1.00
Naphthalene 0.199 2.57
Nitrogen 0.70§ 0.73
Il-Qctane 0.196 2.62
Oxygen 0.690 0.74
Phosgene 0.31§ 1.65
Propane 0.36§ 1.42
Sulfuf dioxide 0.44§ 1.16
Toluene 0.275 1.86
Water vapor 0.853 0.60
t By permission, from T. K. Sherwood and R. L. Pigford, Absorption and Extraction,
2nd cd., p. 20. Copyright 1952. McGraw-HiII Book Company, New York.
:j:The value of pip is that for pure air, 0.512 ftlfh.
§ Calculated by Eq. (21.25)
APPENDIX
20
TYLER
STANDARD
SCREEN
SCALE
This screen scale has as its base an opening of 0.0029 in., which is the opening in
200-mesh 0.0021-in. wire, the standard sieve, as adopted by the National Bureau of
Standards.
Clear Clear Approximate Wire
Mesh opening, in. opening, mm opening, in. diameter, in.
1.050 26.67 0.148
,
t 0.883
0.742
22.43
18.85 •, 0.135
t 0.624 15.85 •i 0.135
0.120
0.525 13.33 ,.•, 0.105
t 0.441 11.20 TO 0.105
0.371 9.423 i, 0.092
2it 0.312 7.925 0.088
3 0.263 6.680 "i, 0.070
3it 0.221 5.613
,
li 0.065
4 0.185 4.699 0.065
5t 0.156 3.962 "-fi 0.044
6
7t
0.131
0.110
3.327
2.794 ••, 0.036
0.0328
8
9t
0.093
0.078
2.362
1.981
'"f2, 0.032
0.033
10 0.065 1.651 '"•
TO 0.035
12t 0.055 1.397 0.028
(Continued)
APPENDIX 20 TYLER STANDARD SCREEN SCALE 1109
Clear Clear Approximate Wire
Mesh opening, in. opening, mm opening, in. diameter, in.
14 0.046 1.168 l4 0.025
16t 0.0390 0.991 0.0235
20 0.0328 0.833 -b 0.0172
24t 0.0276 0.701 0.0141
28 0.0232 0.589 0.0125
32t 0.0195 0.495 0.0118
35 0.0164 0.417 ..!. 0.0122
64
42t 0.0138 0.351 0.0100
48 0.0116 0.295 0.0092
60t 0.0097 0.246 0.0070
65 0.0082 0.208 0.0072
80t 0.0069 0.175 0.0056
100 0.0058 0.147 0.0042
1I5t 0.0049 0.124 0.0038
150 0.0041 0.104 0.0026
170t 0.0035 0.088 0.0024
200 0.0029 0.074 0.0021
For coarser sizing: 3- to l!-in. opening
3 0.207
2 0.192
11, 0.148
t These screens, for closer sizing, are inserted between the sizes usually considered as
the standard series. With the inclusion of these screens the ratio of diameters of
openings in two successive screens is as 1:if2 instead of 1:J2.
APPENDIX K VALUES
FOR LIGHT
21 HYDROCARBONS
(LOW TEMPERATURES)t
. · . . .
· c •
~:;;
~.
oc
~~
· ".. " ~
~~ ·
c c
c c
~~ ~
C
~
,., •
• ..
00
u:iUJ rt~lJ,f_z
, • .• , "
o
"z
.
z z z
, •, , ,. ~ ~
-~
~
" " c'
"
,00
~
"
, , .' H.f
• .<
.' .. .. .. ~
~
"
"
..
~
00'
,'.', ., "" " .,
"
·•
00
" ", ." ... ,.- "
" ," , • ., ."
~,
" " • ,
B
" " "
" ",• .....
", , , "
" " • , " ,, . "
So
., " ,
, f ..
S
, • •., .,
~
" , z
'" c , , ••
.•<fI'"'
'0
" 'flS. " , ,
'" ,e " :c- -"
~ z e
:;.
'" ~
11
~
"
",
.•
"•
~
E
>-•
-SQ
'" "' " • -"
• •
'" , .. , -50
.S
'" , .
• c -H
c
'" ". ~ !
... w •
-ro
F
'"
.. K=y/x •
M' " ~
-M
~
-"
t By permission,jrom C. L. DePriester, Chem. Eng. Prog. Symp. Ser., 49(7): 1.1953.
Courtesy oJ AIChE.
K VALUES APPENDIX
FOR LIGHT
HYDROCARBONS
(HIGH TEMPERATURES)t
22
-
'"
u.
".
,~
'"
'"
"
"
" "• •
•
,. ,,
•, • .'
'"
'"
"
'"
.
" , , '"
J: "," ;:80
" "
15
,, ••, • '"
",
" '"
,,' ,, •, ,.,
'"
'" " 2D ID
', , , '"
• ""
" ~
"
,4
, '"
"
" c
~
" , .'• ,
, ." ""• '". . .. '"
'"
"- " , J
'eo
" "•,
4 ,
, •, ".
'" "e " 4 J
.' " ."" " ",
". '"
'"
"" " ,..
.~ 'SO
~
e
~
"
, ,.
,•
" " ~ ""~
.,
. ,0: ,
~
,;
e•
;; ..
'",
.,.
~ ,Il ",1
0
1.5 :r " _D15 .... -1:0: ~
'SO
'"
.,~~
" • , ."
,oS ,,,,, ,I!<l'~
•
e-
E <ZO
, ., " " ." ~
.• , , ".. •• po;
'"
"
, ., ' ..••
.a ~
"..
.M
."
.•' •• . .,'"
~
.,
" " .-
, "
.• .. ... ,
4
" .J .15
," " .• .c" '"... " "
~
"
a ..
~~
~n:
., "
'" " '"
'"
K=y/x "
"
t By permission,jrom C. L. DePriester, Cllem. ElIg. Prog. Symp. Ser., 49(7): 1, 1953. Courtesy of
AICIzE.
INDEX
Absorption (see Gas absorption) Adsorption (Cont.)
Absorption factor, 512-517 isotherms, 814-818
application of: to distillation, 574 length of unused bed (LUB), 821-824
to leaching, 618 with linear isotherm, 830-831
Acetone~methanol system, 583 mass~transfer coefficients in, 826
Acetone-methyl isobutylketone~water masHransfer rate, 825
system, 633 masHransfer zone, 818
Acetone~trichloroethane~water system, 645 pressure~swing, 813
Acoustic velocity, 122, 123 principles of, 818-834
(See also Fluid flow, compressible fluids) regeneration, 811
Activity coefficient, 866, 868 scaleup of fixed beds, 821
Adiabatic compression, 209 temperature rise in, 824
Adiabatic cooling line, 743 Aggregative fluidization, 169
Adiabatic saturation temperature, 741 Agitated mills, 985
Adsorbents, 810 Agitated vessels, 236
alumina, 815 baffles, 240
carbon, 816-818, 821 circulation rate in, 243
molecular sieves, 815-816 dimensional analysis in, 249
silica gel, 815 dispersion in, 269-277
Adsorption: gases, 269
breakthrough curves, 819-824, 828, 829 liquids, 275
effect of feed concentration, 824 draft tubes in, 241
equipment for, 811-814 flow number in, 243
c6ntinuous adsorbers, 814 flow patterns in, 239-242
fixed beds, 811 prevention of swirling, 240
gas dryers, 812 heat transfer in, 451
stirred tanks, 813 transient conditions, 452
irreversible, equations for, 827-828 power consumption in, 248
1114 INDEX
Agitated vessels (COllt.) Blending: stratified, in storage tanks, 261
scaleup of, 277 (See also Mixing)
velocity gradients in, 246, 255 Blowers, 206-208
average, non-newtonian fluids, 256 centrifugal, 206
Agitation, 236 equations for, 208
equipment for, 236-238 positive-displacement, 206
purposes of, 235 (See also Compressors)
Reynolds number in, 249,256 Bluff bodies, 149
(See also Agitators; Mixing) Boiling liquids, 385-394
Agitators: critical temperature drop, 387, 390
impellers, 237-238, 259 film boiling, 389, 392
anchor, 238 minimum heat flux, 392
helical, 259 pool boiling, 386--393
paddles, 237 enhancement of flux, 394
propellers, 237 maximum flux, 390
turbines, 238 nucleate boiling, 388
standard turbine design, 242 pressure effect on, 390
Air separation with membranes, 850-855 transl •• ~ t.."Iiiing, 388
Air-cooled exchangers, 450 subcooled boiling, _.
Air-water system (see Gas-liquid contact; Boiling-point diagrams, 524, ;).4,
Humidity; Humidity chart) (See also Vapor-liquid equilibria)
Ammonia, absorption of, 706-709 Boiling-point elevation (BPE), 471
Ammonia-water system, 707 BoIlman extractor, 616
Analogy theory, 658 Bond's crushing law, 963
Colburn equations, 352, 666 Boundary layer:
Angle: formation around sphere, 146--149
of internal friction, 938 fonnation in tube, 59
of repose, 938 hydrodynamic, 56
Angular momentum, 79 laminar and turbulent flow in, 57-59
Aniline-heptane-methyl cyc10hexane system, 634 mass transfer in, 661, 860, 863
Annular space, heat transfer in, 344 separation of, 60
Arching, in bins, 940 from velocity decrease, 110
Association parameter, 656 thermal, 331
Asterisk condition, 124 transition length, 59
Azeotropic distillation, 609 Bubble-point, 524
of mUlticomponent mixtures, 589
Bubbles:
Ball valves, 187 average diameter of, 269
Banbury mixer, 946 behavior of, 269
Barometric equation, 31 diameter, in agitated vessels, 271
Batch distillation, 576 from submerged orifices, 269
application of McCabe-Thiele method to, 579 in fluidized beds, 169, 172
with reflux, 578 mass transfer to, 673
Benzene-toluene system, 523-524 rise velocity of, 164
enthalpy-concentration diagram, 553 shape, 162-164
Bernoulli equation, 70--79 Bubbling fluidization, 169, 172
correction:' for effect of solid boundaries, 73 Buffer layer, 92
for fluid friction, 75 Burke-Plummer equation, 154
effect of fonn friction in, 107
in potential flow, 70--74
pump work in, 77 CaJandrias,442
Bin storage. 939 Carbon dioxide: absorption of, 718
Bingham plastic, 89 removal with membranes, 857
Blenders (see Mixers) Cascades, 501
INDEX 1115
Case hardening in drying, 784 Comminution (Cont.)
Cavitation, 191 criteria for, 961
Center·of·gravity principle, 889 crushing efficiency, 962
Centrifugal blowers, 206 energy requirements, 962-965, 989
Centrifugal classifiers, 1071 equipment for, 970
Centrifugal compressors, 207 general methods, 960
Centrifugal decanters, 37, 1063 products from: characteristics of, 961
Centrifugal extractors, 631 particle·size distribution, prediction of, 965
Centrifugal filters, 1011-1014 Compressibility factor, 19
Centrifugal filtration (see Centrifuges) Compressible fluids, flow of (see Fluid flow)
Centrifugal pumps: Compressors, 208-212
characteristic curves of, 202-203 centrifugal, 207
effect of speed change, 201 efficiency, 210
head losses in, 201 multistage, 207
high·energy, 203 positive-displacement, 208
impeJlers, 196 reciprocating, 208
Jeakproof, 203 theory, 208-210
multistage, 203 (See also Blowers; Pumps)
power losses in, 203 Computer simulation of milling operations,
priming, 204 965-970
theory, 197-201 breakage function, 965
volute, 196 grinding-rate function, 965
Centrifugal sifter, 997 Concentration, units of, 497
Centrifuges: Concentration polarization, 873-874, 1037
automatic batch, 1013 Condensers, 439-442
axial·flow conveyor, 1071 contact, 440
continuous filtering, 1014 dehumidifying, 440
disk, 1065 enthalpy balances in, 314
helical conveyor, 1067 shell·and-tube, 439
nozzle discharge, 1066 temperature in, 310
scaleup, 1070 tubes and tubing, data, 1088
sigma value, 1070 Condensing vapor, 374-385
sludge separators, 1067 dropwise condensation, 375
suspended batch, 1011 film-type condensation, 375
tubular, 1064 on horizontal tubes, 379
valve discharge, 1067 noncondensabJe gases, effect of, 384
Chemical engineering, 3 superheated vapor, 383
Clarification: on vertical tubes, 377-379
by filtration, 1030-1032 Conduction (see Heat)
by sedimentation, 1051 Constant-rate period in drying, 778
Classifiers, 1048-1051, 1071 Continuity, 65
centrifugal, 1071 equation for compressible flow, 121
differential-settling, 1050 (See also Mass balance in fluid flow)
equal·settIing particles, 1050 Controlling resistances, 326
sink-and-float, 1049 Convection, 286
sorting, 1049 (See also Natural convection to air)
Col burn analogy, 352 Conversion factors, 1081
Colloid mills, 985 Cooling towers, 751
Columns: action in, 756
continuous membrane, 859 equations for, 757-759
fractionating (see Fractionating columns) forced draft, 751
sieve-plate (see Sieve·plate columns) Coriolis meters, 228
Comminution: Couette flow, 112
computer simulation, 965-970 Coulter counter, 934
1116 INDEX
Countercurrent flow, 312 Crystallization (Cont.)
Creeping flow, 671 predominant crystal size, 913
Critical moisture content in drying, 780 product purity, 884
Crossflow: heat transfer in, 435-437 yields in, 886
Crossl'low filtration, 1033 (See also CrystalIizers; Crystals)
Crushers and grinders: Crystallizers, 902
agitated mills, 985 circulating liquid, 902
attrition mills, 977 circulating magma, 903
fluid-energy mills, 984 contact nucleation in, 917
gyratory crushers, 972 design of,909-916
hammer mills, 975 moment equations, 912
with internal classification, 983 double-drawolf (DDO), 917
impactors, 975 draft-tube baffle (DTB), 905
jaw crushers, 971 enthalpy balances in, 887
operation of, 987-990 fines-destruction, 917
feed control, 988 increasing crystal size in, 917
heat supply and removal, 990 MSMPR (mixed-suspension-mixed-
methods of discharge, 989 product-removal) crystallizer, 909
open-circuit versus closed-circuit, 987 origin of crystals in, 892
wet versus dry grinding. 965 types of, 902-903
rolling compression machines, 976 vacuum, 903-907
smooth-ron crushers, 973 yield in, 907
limiting feed size in, 974 (See also Crystallization)
toothed-roll crushers, 974 Crystals:
tumbling mills, 979-982 crystallographic systems, 883
action in, 980 growth, 899-902
ball mills, 980 coefficients, 899-901
capacity and power requirements, 982 overall, 899
centrifuging in, 981 surface, 901
compartment mills, 980 McCabe llL Jaw, 902
conical mills, 980 rate and equations, 900
critical speed, 981 invariant, 883
pebble mills, 980 shape factors of, 884
tube mills, 980 surface energy, 895
types of, 971 Cutting machines, 986
ultrafine grinders, 982-985 Cyclones, 1060
Crushing (see Comminution) collection efficiency of, 1062
Crystal growth (see Crystals) separation factor in, 1061
Crystallization, 496, 882 Cylinders:
enthalpy balances in, 887 heat conduction in: steady state, 296-299
ideal batch, 922 unsteady state, 301
importance of supersaturation in, 889 mass-transfer coefficients to, 669
Kelvin equation, 895
kinetic coefficient, 914
from melts, 918 Darcy's law, 153
mixed-suspension mixed-product removal Decaffeination of coffee, 642
(MSMPR),909-917 Decanters:
area distribution, 912 centrifugal, 37, 1063
mass distribution, 912 continuous gravity, 35
number distribution, 912 separation time in, 36
population density functions, 910 Dehumidification, 440, 738, 753
size distribution, 912 phase equilibria in, 740
nucleation in, 892-899 Dehumidifiers, 753
objectives of, 882 (See also Condensers, dehumidifying)
phase equilibria in, 884--886 Dehydration of solvents. 870
INDEX 1117
Demister, 179 Distillation, 495, 499, 521
Dephlegmators. 534 application of absorption factor to, 574
Desolventizers, 798 azeotropic, 609
Desorption or stripping, 509, 710 batch,576
with air, 712 with reflux, 578
oxygen desorption data, 714-715 combined rectification and stripping, 526
with steam, 711 equipment for, 521, 527-528
of trichloroethylene, 712 extractive, 609
Dew point, 524 flash: of binary mixtures, 521
gas-liquid system, 740 of multicomponent mixtures, 592
of multicomponent mixtures, 589 of multicomponent mixtures, 588
Dialysis, 860-862, 880 bubble and dew points, 589
Diaphragm pumps, 193 concentration profiles, 605
Differential contact plant, 697-698 distributed and undistributed components,
material balance, 697 598
Diffusion: flash distillation, 592
comparison with heat transfer, 648 fractionation in, 593
in drying, 781-783 Gilliland correlation, 608-609
equations for, 782 invariant zones, 599
equation, interpretation of, 652 key components, 594
equimoJaJ, 652 minimum number of plates, 595
Fick's law, 650 minimum reflux ratio, 597, 599
in gases, 655 relative volatilities, 589
in liquids, 656 reverse fractionation, 604
one-way diffusion factor, 661 in packed columns, 576, 731
one-way or one-component, 653 stage efficiency in, 676-679
effect of, 660 (See also Fractionating columns; Sieve-plate
role in mass transfer, 648 columns)
turbulent, 658 Distribution coefficients, 588, 1110-1111
velocities in, 649 Drag:
Diffusivities: fono, 144, 149
eddy (see Eddy diffusivity) reduction of, 101
effective, in porous solids, 826 Newton's law of, 160
in membranes, 839, 861, 863 wall, 144
of gases, 655, 1109 Drag coefficients, 145-149
Knudsen, 839 of particles in fluid: spheres, 147, 158
of liquids, 656 various shapes, 147
in polymers, 842 Drops, mass transfer to, 673
prediction of, 655 Dryers:
relations between, 651 classification of, 768
volumetric, 650 drum, 803
Dilatant fluids, 45 enthalpy balances in, 771
Dimensional analysis, 16-18 evaporator-, 806
in agitated vessels, 249 fixed-bed, 812
in heat transfer: inside tubes, 341 (See also Adsorption)
outside tubes, 360 flash, 800
in mass transfer, 665 fluid-bed, 798
Dimensional equations, 15 heat transfer in, 771-773
Dimensionless groups, 15 mass transfer in, 773, 779
interpretation of, 356-359 rotary, 795
named, 18 design of, 796
Disintegrators, 974 screen-conveyor, 793
Dispersion operations, 269-277 screw-conveyor, 798
of gases, 270-275 selection of, 805
of liquids, 275-277 solids handling in, 768
1118 INDEX
Dryers (Cont.) Enthalpy balances (Cont.)
spray, 801 in evaporators, 476--481
temperature patterns in, 770 in fractionating columns, 553
thin-film, 803 Enthalpy-concentration diagram, 478, 888
tower, 794 application of: to crystallization, 888
tray, 792 to evaporation, 478
turbodryer, 794 system benzene-toluene, 553
(See a/so Drying) system magnesium sulfate-water, 888
Drying: system sodium hydroxide-water, 479
adiabatic, 768 Equal-setting particles, 1050
case hardening in, 784 Equations:
constan~ drying conditions, 777 dimensional, 15
constant-rate period, 778 dimensionless, 14
critical moisture content, 780 of state, 18
cross-circulation, 776 Equilibrium:
diffusion in, 781-783 hydrostatic, 29
direct, 768 in centrifugal field, 31
effect of shrinkage, 784 (See also Gas-solid equilibria; Liquid-solid
falling-rate period, 780 equiJibria in leaching; Vapor-liquid
in fluidization, 798 equilibria)
freeze, 793 Ergun equation, 154
heat-transfer units in, 773 application to fluidized beds, 166
indirect, 768 for mixtures of particles, 155
mechanisms of, 776 Ethanol-water separation by membranes,
nonadiabatic.768 867-870
of nonporous solids, 781 Ethanol-water system, 549
objective of, 767 Ethyl benzene-toluene-water system, 582
phase equilibria in, 774-776 Evaporation:
bound and unbound water, 775 importance of liquid characteristics, 464
of porous solids, 784-787 mUltiple-effect, 465, 481
effect of capillarity on, 785 objective of, 463
rate-or-drying curves, 777, 786 single-effect, 465
of suspended particles, 791 (See also Evaporators)
through-circulation, 788 Evaporator-dryers, 806
(See also Dryers) Evaporators;
Diihring's rule, 471 agitated-film, 469
capacity: effect of boiling-point elevation on,
485-486
Eddy diffusivity: effect of liquid head on, 486
of heat, 350 circulation versus once-through, 465
of mass, 658 economy, 476, 485
of momentum, 55 enthalpy balances for, 476-481
Eddy viscosity, 55 without heat of dilution, 477
Ejectors (see Steam-jet ejectors) forced-circulation, 468
Electrodialysis, 862 heat-transfer coefficients in, 474
Energy balance: long-tube: climbing-film, 466
in flow processes, 20 falling-film, 467
mechanical: in compressible flow, 122 multiple-effect, 481--490
in incompressible flow, 72 calculations for, 488--490
total, 122 capacity of, 485
Enthalpy, stagnation, 124 capacity versus economy, 485
Enthalpy balances: in condensers, 314 methods of feeding, 484
in crystalIizers, 887 optimum number of effects, 488
in dryers, 771 principle of, 481--483
INDEX 1119
Evaporators (Cont.) Filters, 1002-1047
versus single-effect, 485-488 automatic belt, 1006
temperature drops in, 483 bag, 1031
once-through, 465 cake, 1003
single-effect calculations, 480 centrifugal, 1011-1014
temperature drop in, effect of liquid head, 473 automatic batch, 1013
vapor recompression, 490-491 continuous, 1014
mechanical, 490 principles of, 1027
thermal, 491 reciprocating-conveyor, 1014
Exchangers (see Heat exchangers) suspended batch, 1011
Extraction: clarifying, 1030
application of McCabe-Thiele method to, 635 cartridge, 1030
equipment for, 624-632 gas cleaning, 1031
agitated tower extractors, 630 principles of, 1032
auxiliary equipment, 632 continuous pressure, 1009
baffle towers, 629 continuous vacuum, 1007-1011
centrifugal extractors, 631 automatic belt, 1006
mixer-settlers, 625 rotary-drum, 1007
packed towers, 626-628 crossflow, to33
perforated plate towers, 629 discontinuous pressure, 1004
performance of, 625 discontinuous vacuum, 1007
pulse columns, 631 filter press, 1004
rotating disk contactors, 630 granular bed, 1031
spray towers, 626 horizontal belt, 1010
York-Scheibel extractors, 630 precoat, 1010
flooding velocities, 627 shell-and-leaf, 1004
HTU in, 625 types of, 1002
mass transfer in, 730 ultrafilters, 1034-1046
mass-transfer coefficients in, 730 (See also Filtration; Microfiltration)
McCabe-Thiele method, use in, 635 Filtration:
objective of, 496, 623 cake resistance, 1018
phase equilibria in, 632-635 equations for, 1020
reflux in, 638-640 compressibility coefficient, 1021
comparison with distillation, 640 of compressible cakes, 1018-1019
limiting reflux ratios, 638 constant-pressure, 1020
practical examples of, 639 constant-rate, 1026
solid (see Leaching) continuous, 1024
stage efficiency in, 625 crossflow, 1033
Extraction battery, 615 of incompressible cakes, 1018
Extractive distillation, 609 pressure drop, 1016
Extractors (see Extraction, equipment for) principles, to16
Extruders (see Mixer-extruders) purposes of, 1002
washing of cake, 1029
(See also Filters)
Fin efficiency, 446
Fans, 204-206 Fittings, 183
(See also Blowers) resistance of, 107
Feed line (see Fractionating columns) Flash evaporation, 478
Fenske equation, 547 Flocculation, 1052
application to mUlticomponent systems, 595 Flooding velocities:
Fick's law, 650 in packed absorption towers, 692
Filter aids, 1015 in packed extraction towers, 627
Filter media, 1015 Flow meters (see FuIJ-bore flow meters; Insertion
resistance of, 1019 meters)
1120 INDEX
Flow number, 245 Fluid flow (Cont.)
Flow patterns in membrane separators, 844 average velocity, 95
Fluid flow: kinetic-energy correction factor, 96
compressible fluids: maximum velocity, 97
adiabatic flow with friction, 126, 133-137 momentum correction factor, 96
in beds of solids, 155 Reynolds number-friction factor law, 96
change in gas properties, 134 universal velocity equations, 93
mass velocity, 135 velocity distribution, 92
maximum conduit length, 155 Reynolds stresses in, 55
asterisk condition, 124 scale of,54
friction parameter, 133 statistical nature of, 53
isentropic flow, 126-133 temperature fluctuations in, 349
change in gas properties, 129 Fluid friction:
critical pressure ratio, 128, 130 in beds of solids, 151-155
effect of cross~sectional area, 130 for compressible fluids, 155
mass velocity. 130 effect of particle shape, 152
velocity in nozzle, 129 in mixtures of particles, 155
isothermal flow with friction, 126. 137-139 from changes in velocity or direction, 105-110
heat transfer in, 139 minimizing of, 111
stagnation point, 150 from sudden contraction, 106
enthalpy, 124 from sudden expansion, 105
pressure, 150 contraction-loss coefficient, 106
temperature, 124 expansion-loss coefficient, 105
fields of: in fittings and valves, 107
shear-stress, 44 relations among parameters, 86
velocity, 43 skin friction and wall shear, 85
velocity gradient, 43 stress distribution in pipes, 84
kinetic energy of stream, 74 Fluidization, 165-177
correlation factor for, 74, 88, 96 aggregative, 169
laminae, 41 applications of, 173
in hollow fibers, 874 bubble velocity in, 173
newtonian fluids, 86--89 bubbling, 169, 172
average velocity, 87 conditions for, 165
kinetic-energy correction factor, 88 drying in, 798
momentum correction factor, 88 expansion of beds, 170
transition to turbulent flow, 58,101, 115 minimum bed porosity, 166
non-newtonian fluids, 89-91 minimum velocity for, 166
transition to turbulent flow, 101 particulate, 170-172
in layers, 112-115 pressure drop in beds, 166
within pipes, 115 slugging in, 169
transition to turbulent flow, 115 types of, 169
mass balance in, 64--66 velocity range in, 170-173
momentum balance, 68-72 Fluids:
momentum correction factor, 69, 87-88, 96 compressible, 27
one-dimensional, 43 (See also Fluid flow)
time-dependent, 45 incompressible, 27
transfer of momentum, 47 (See also Fluid flow)
turbulent: nature of, 27
deviating velocities in, 51 newtonian, 45
diffusion in, 658 non-newtonian, 45
intensity of, 54 rate of shear versus shear stress, 48
isotropic turbulence, 54 Force, 6, 11
nature of, 50 Form drag, 144, 149
in pipes, 92-98 Fouling factors, 324
INDEX 1121
Fourier number, 301, 336 Gas absorption (COllt.)
Fourier's law, 289 material balances, 697
Fractionating columns: multicomponent, 709
analysis by McCabe-Thiele method, 531-553 number of transfer units, 704
condenser, 533 relation to theoretical plates, 704
constant molal overflow, 532 phase equilibria in, 508
construction of operating lines, 539 in plate columns, 721
feed line and feed plate location, 538-541 plate efficiency in, 721
feed plate, 536-541 rate of, 701
heating and cooling requirements, 541 HTU method, 704-709
invariant zone, 548 application to rich gases, 723
minimum number of plates, 545 definitions, 705
minimum reflux ratio, 547 experimental values, 715-716
nearly pure products, 557 overall HTUs, 705
optimum reflux ratio, 549 individual and overall coefficients. 701-702
partial condenser, 534 interface composition, 702
reboiler, 535 two-film theory, 674
reflux ratio, 532 use of overall coefficients, 703
enthalpy balances in, 553 from rich gases, 722
material balances in, 529 stage efficiency in, 676-679
net flow rates, 529 temperature variations in, effect of, 700, 706
operating lines, 531, 539 Gas constant, 10, 1080
(See also Distillation) Gas law, ideal, 19, 123
Francis equation for weir flow, 563 (See also Ideal gas)
Free settling, 159 Gas-liquid contact, 690
Free turbulence, 50 Gas-solid equilibria, 774, 814
Freundlich equation, 815 adsdrption isotherms, 814-818
Freundlich isotherm, 816 bound water versus unbound water, 775
Friction, fluid (see Fluid friction; Friction factor) equilibrium moisture content, 774
Friction factor: free moisture, 774
Blasius,85 Gases:
charts for, 99, 101 compressibility factor, 19
newtonian fluids, 99 equations of state, 18
non-newtonian fluids, 101 virial coefficients, 18
Darcy,85 (See also Ideal gas)
with drag reduction, 102 Gel concentration, 1039
effect of heat transfer on, 102 Gel layer, 1044
effect of roughness, 97 Graetz number, 336
Fanning, 85 Grashof number, 364
for noncircular channels, 103 Greenhouse effect, 419
in supersonic flow, 133 Grinders (see Crushing and grinding)
Friction parameter, compressible fluids, 133 Grinding (see Comminution)
Frossling equation, 670
Froude number, 249, 251, 258
significance of, 250
Full-bore flow meters, 214-229 Hagen-Poiseuille equation, 88, 875, 1037
Heat:
conduction of, 289
Gas absorption, 496, 686, 697 one-dimensional, 290
with chemical reaction, 728 in solids: through cylinder, 296
cocurrent flow, 730 series resistances, 293
HTU in, 704-709 steady-state, 292
limiting gas-liquid ratio, 699 unsteady-state, 299
logarithmic mean driving force, 705 (See also Slab; Sphere)
1122 INDEX
Heat exchange equipment, 309, 427 Heat transfer (Cont.)
design of, 427 at high velocities, 347-348
extendedMsurface, 445-451 in turbulent flow:
calculations for, 447 analogy with momentum transfer, 348-352
fin efficiency, 446 Col burn analogy, 352
types of, 446 Friend and Metzner analogy, 352
temperature approach in, 311 Reynolds analogy, 351
temperature range in, 311 (See also Analogy theory)
(See also Condensers; Heat exchangers) dimensional analysis of, 341
Heat exchangers: Heat-transfer coefficients:
airMcooled, 450 in agitated vessels, 451
crossflow, 436 in dryers, 772
correction of LMTD in, 436 effective, in unsteady-state heat transfer, 327
double~pipe, 311 in evaporators, 474
enthalpy balances in, 313 in film boiling, 392
heat-transfer coefficients in, 432 in film-type condensation, 376-383
multipass, 319, 430 on horizontal tubes, 379
correction of LMTD in, 436 on vertical tubes, 377
parallel-countercurrent 1-2 type, 430 in heat exchangers, 432
2-4 type, 431 individual, 319-323
plate type, 439 classification of, 326
RODbaffie, 430 magnitude of, 326
scraped-surface, 453 in laminar flow, 334-340
single-pass 1-1 type, 428 correction for heating or cooling, 339
standards for, 428 in non-newtonian fluids, 340
tubes and tubing, data, 1088 in liquid metals, 355
Heat flux, 315 in nucleate boiling, 388
Heat of vaporization, 532 overall,315
Heat transfer: calculation from individual coefficients,
dimensional analysis in, 341, 360 323-325
in dryers, 771-773 resistance form, 324
effect on friction factor, 102 special cases, 326
estimation of wall temperature, 343 variation aIong heating surface, 319
in fluids, regimes of, 330 in packed beds, 455
interpretation of dimensionless groups in, in shell-and-tube exchangers, 432
356-359 in turbulent flow: average value of, 342
in laminar flow, 333-340 effect of roughness, 347
effect of natural convection, 366 effect of temperature, 343
to flat plate, 334 effect of tube length, 342
in tubes, 336, 340 empirical equations for, 341
to liquid metals, 355 in noncircular cross sections, 344
critical Peclet number, 356 (See also Boiling liquids; Condensing vapor;
in natural convection, 362 368 Natural convection to air)
to non-newtonian fluids, 340 Heat-transfer units, in dryers, 773
outside tubes, 359, 432-435 Heavy-fluid separation, 1049
to single tube, 360 Helium separation with membranes, 857
in packed beds, 362, 455-457 Henry's law, 552, 840
penetration theory in, 453 HETP (height equivalent to a theoretical plate),
in plug flow, 337 731
by radiation (see Radiation) High-energy pumps, 203
in recuperative exchangers, 831 Hildebrandt extractor, 616
to single sphere, 362 Hindered settling, 159
in transition region of flow, 353 HTU (height of a transfer unit):
in tubes, 336-359 in adiabatic humidification, 761
INDEX 1123
HTU (COIlt.) Kelvin equation, 895
in extraction, 625 Kick's crushing law, 963
in gas absorption, 704-709 Kinetic-energy correction factor, 74, 88, 96
overall,705 Kinetics of nucleation, 895
for packed columns, 625, 704-709 Kirchhoff's law of radiation, 403
Humid heat, 739 Kneaders. 943-946
Humid volume, 739 continuous, 945
Humidifiers, 753 Knudsen diffusivity, 839
action in, 753 Kozeny-Carman equation, 153
adiabatic, 760 Kremser equation, 513
use of HTU, 761
Humidity, 738
measurement of, 747
percentage, 739 Laminar flow (see Fluid flow, laminar)
relative, 739 Laminar sublayer (see Viscous sublayer)
Humidity chart, 743 Langmuir isotherm, 815
air-water system, 744 Lantern gland, 185
construction of, 746 Layer flow:
use of, 745 free surface, 112
Hydraulic radius, 103 in pipes, 115
Hydraulic transport, 175 Reynolds number in, 114
Hydrogen recovery with membranes, 855-857, transition to turbulent flow, 115
880 Leaching, 614-623
Hypersorber,814 application of absorption factor to, 618
continuous countercurrent, 617-623
application of McCabe-Thiele method to,
Ideal contact stages, 501, 509, 525 618
determination of number of, 509-511 equipment for, 615
absorption factor method, 512-517 for dispersed solids, 616
McCabe-Thiele method, 510, 531-553 moving bed, 615
rectification on, 525 Shanks process, 615
Ideal gas, 19,31, 123 stationary solid beds, 615
Mach number of, 123 ideal stages with variable underflow, 620
velocity of sound in, 124 liquid-solid equilibria in, 618
Ideal plate (see Ideal contact stages) in saturated solutions, 622
Impingement, separation by, 1032 stage efficiency in, 622, 679
Initial breeding, in crystallization, 892 Leakage:
Insertion meters, 229-231 prevention of, 184
Ion exchange, 810, 832 by mechanical seals, 185
backwashing of beds, 172 by stuffing boxes, 184
Isentropic compression, 209 Leakproof pumps, 203
Isolation train, for solids from solution, 806 Leidenfrost point, 387
Isothermal compression, 209 Lewis relation, 750
Liquid extraction (see Extraction)
Liquid-liquid equilibria, 632
Jet ejector, 212 plait point, 633
Jet mixers, 261 tie lines, 633
ju-factor, 352 triangular coordinates for, 632
jArfactor, 667 types of systems, 632
Liquid-solid equilibria in leaching, 618
LMTD (see Logarithmic mean, temperature
K values, 588, 1110-1111 dilference)
(See also Distribution coefficients; Logarithmic mean:
Vapor-liquid equilibria) concentration difference, 705
1124 INDEX
Logarithmic mean (Cam.) Mass-transfer operations:
radius, 297 definitions, 495
relation to arithmetic mean, 297-298 terminology and symbols for, 497
temperature difference, 316 Mass velocity, 66
correction for crossflow in heat exchangers, Material balances, 64-67, 505, 529, 697
436 McCabe /).L law of crystal growth, 902
where not used, 317 McCabe-Thiele method, 510, 531-553
LUB (length of unused bed), 821-824 application to batch distillation, 579
based on enthalpy balances, 554
use in extraction, 635
use in leaching, 618
Mach number, 120, 123 Mechanical energy (see Energy balance,
Magnesium sulfate-water system: mechanical)
enthalpy-concentration diagram, 888 Membrane separators: How patterns in, 844
phase diagram, 886 for gas separation, 838-859
Magnetic flow meters, 227 for liquid separation, 859-877
Manometers, 33-35 multicomponent separations in, 849
inclined, 34 radial-flow, 845
Mass, conservation of, 20 for solid-liquid separation, 1034-1047
Mass balance in fluid flow, 64-67 stage cut in, 850
Mass flow from bins, 940 Membranes, 838-877, 1034-1047
Mass transfer: alumina, 1036
in boundary layers, 661, 860, 863 asymmetric, 842, 844, 854, 859, 871, 1034
dimensional analysis in, 665 hollow fiber, 874
to drops and bubbles, 673 hydrophilic, 863
in dryers, 773, 779 hydrophobic, 863
in extraction, 730 nonporous, 840
film theory, 658 polymer, 840, 1036
one-way diffusion, effect of, 660 porous, 838
in packed beds, 671, 713-718 selectivity, 841
Peclet number for, 671 sintered metal, 1035
penetration theory of, 662 solute rejection by, 1035, 1043
role of diffusion in, 648 spiral-wound, 876, 1036
on sieve plates, 676 structure of, 842
to suspended particles, 672 Metals, liquid, heat transfer in, 355
to tube bundles, 669 Methanol-water system, 583
two-film theory, 674 Microfiltration, 1033
Mass-transfer coefficients, 658 Mikro-atomizer, 983
in adsorption, 826 Mixer-extruders, 947
alternate forms of, 706 Mixers:
boundary-layer theory, 661 for free-flowing solids, 952-956
for cylinders, 669 impact wheel, 954
definitions, 659 internal scrcw, 953
for drops and bubbles, 673 ribbon,952
in extraction, 730 tumbling (see Tumbling mixers)
for known areas, 665 motionless, 262
measurement of, 663-665 for pastes and plastic masses, 943-952
nonnal to cylinders, 669 axial mixing in, 951
overall, 675 change-can, 943
in packed beds, 671, 713-718 continuous kneaders, 945
inside pipes, 666 dispersers, 943
for spheres, 670 double-motion, 943
for suspended particles, 672 internal, 945
in wetted-wall tower, 668 kneaders, 943
INDEX 1125
Mixers (COllt.) Newton's law (Cont.)
masticators, 943 of motion, 6
mixing rolls, 947 conversion factors for, 12
mullers, 947 Non-newtonian fluids, 45, 50, 89-91, 100-101,
power requirements, 948 255-256, 340
pugmill,948 transition to turbulent flow, 101
(See also Agitated vessels; Agitation; Mixing) Nozzles. flow of compressible fluids in, 126-133
Mixing, 257-263, 941-956 NPSH (Net positive suction head), 191
axial: on distillation trays, 570 Nucleation, 892-899
of pastes, 951 contact, 898, 917
characteristics of materials, 942 factors influencing, 892
comparison with blending, 941 heterogeneous, 896
criteria for, 257, 948 homogeneous, 894
effectiveness, 948-951 primary, 893
in fluidized beds, 958 rate of, 895
by jets, 261 secondary, 898
of miscible liquids, 257-263 fluid-shear, 898
of pseudoplastics, 260 (See also Crystallization; Crystallizers)
rate of: for free-flowing solids, 956 Nusselt equations, 376-380
for pastes and plastic masses, 951 Nusselt number, 322, 341
selection of equipment for, 262 interpretations of, 322, 335, 359
stratified, in storage tanks, 261 limiting values of, 338
times: of dispersions, 260 Nutsch, 1007
of liquids, 258-260
of solids, 956
Operating lines, 507-509
(See also Agitated vessels; Agitation; Mixing)
constru-ction of, for fractionating columns, 531.
Mixing index:
539
for granular solids, 954
Orifice coefficient, 219
for pastes and plastic masses, 949
Orifice meters, 217
Mohr rupture envelope, 938
equations for, 219, 222
Mohr stress circle, 938
expansion factor for, 222
Moisture:
pressure recovery in, 220
bound versus unbound, 775
vena contracta in, 219
capillary flow of, 784
Orifice taps, 218-219
equilibrium: air-solid systems, 774, 815
Osmotic pressure, 871
free moisture, 774
Ostwald ripening, 895
Molecular sieves, 815-816
Ostwald-de Waele equation, 48
(See also Adsorbents)
Overall coefficients (see Heat-transfer
Momentum, 6
coefficients; Mass-transfer coefficients)
angular, 79
Oxygen-nitrogen system, 584
Momentum balance, 68-72
momentum correction factor, 69, 87-88, 96
Momentum flux, 47 Packed beds:
Motionless mixers, 262 effective thermal conductivity in, 457
Multicomponent systems, 518, 588-610, 849 heat transfer in, 362, 455-457
heat-transfer coefficients in, 455
mass transfer in, 671, 713-718
Natural convection to air, 366 mass-transfer coefficients in, 671, 713-718
heat transfer in, 362-368 radiation in, 457
Needle breeding, in crystallization, 892 Reynolds number for, 146, 151
Net positive suction head (NPSH), 191 temperature and velocity profiles in, 455
Newtonian fluids, 45, 86-89 void fraction in, 155
Newton's law: wall coefficients in, 456-457
of drag, 160 (See also Packed columns)
1126 INDEX
Packed columns: Pipe (Cont.)
channeling in, 690 selection of, 182
design of, 686-697 sizes of, 182
distillation, use for, 731 standard steel, data on, 1086
gas-liquid contact in, 690 Pipe fittings, 183
HTUs for, 625, 704-709 Pipe joints, 183
limiting flow rates in, 691 Pitot tube, 229
loading and flooding in, 692 Planck's law, 401
pressure drop in, 691 Plate columns:
temperature variation in, 700 design of, 529-575
(See also Packed beds) in gas absorption, 721
Parallel-current flow, 312 (See also Fractionating columns; Sieve-plate
Particles: columns)
average size of, 930 Plate efficiency, 568-575
characterization of, 927 effect of mixing, 570
masses of, 936-939 factors influencing, 574
pressures in, 936 in gas absorption, 721
properties of, 936 local,569
mean diameters, 930 Murphree, 568
measurement of fine particles, 934 overall, 568
mixed sizes, 929 prediction of, 676
motion through fluids, 155-163 use of, 571
from centrifugal force, 157 (See also Stage efficiency)
from gravitational force, 157 Plug cocks, 187
terminal velocity of, 157 Plug flow, heat transfer in, 337
in hindered settling, 162 Pneumatic transport, 174
number in mixture, 931 Podbelniak centrifugal extractor, 631
shape, 928 Polarization factor, 873
size, 928 Polytropic compression, 210
distributions of, 929 Porosity of beds of solids, 152
slurry transport of, 175 Potential flow, 42, 70--74
specific surface, 930 Pound force, 11
sphericity, 928 Power number, 249-252
Particulate fluidization, 170--172 effect of system geometry on, 252
Pedet number, 336, 356, 570,671 significance of, 250
for liquid-metal heat transfer, 356 Power-law fluids, 48
for mass transfer, 671 Prandtl number, 332, 341
on sieve plate, 570 of gases, 1105
Penetration theory: of liquids, 1106
in heat transfer, 453 significance of, 350
in mass transfer, 662 Pressure, 28
Permeability, 841 Pressure-swing adsorption, 813, 855
coefficient, 841 Pseudoplastic fluids, 45
Permeate composition, 839, 847 Psychrometric line, 750
Penneate flux, 1036 Pumps:
Pervaporation, 864-870 cavitation in, 191
Phase rule, 498-500 centrifugal (see Centrifugal pumps)
Piezometer ring, 214 comparison of types of, 213
Pipe, 181-184 developed head of, 189
allowance for expansion, 184 efficiency of, 78, 193, 203
economic size of, 182 high-energy, 203
materials of construction for, 182 leakproof, 203
recommended practice, 187 NPSH,191
schedule number of, 182 positive-displacement, 193-195
INDEX 1127
Pumps (Cont.) Reflux, 502
reciprocating, 193 Reflux ratio, 532
rotary, 195 (See also Extraction; Fractionating columns)
volumetric efficiency of, 194 Relative volatility, 545
power requirements of, 190, 203 Resistance, thermal, 293
suction lift. 191 Reverse osmosis, 859, 871
vacuum, 212 Reynolds analogy, 351
(See also Blowers; Compressors) Reynolds' experiments, 48
Reynolds number, 49, 58
in agitation, 249. 256
Quantity: in layer flow, 114
dimensions of, 17 for non-newtonian fluids, 50, 100
physical,S for particles or packed beds, 146, 151
transition of laminar to turbulent flow, 49, 58,
101, 115
Radial-flow membrane separator, 845 Reynolds stresses, 55
Radiation: Rheopectic fluid, 46
absorption coefficient, 417 Rittinger's crushing law, 963
absorption length, 417 Rotameters, 223-225
absorptivity, 397, 402 theory and calibration of, 224
attenuation of, 417 Roughness parameter in pipes, 98
black-body, 399
practical source of, 401
combined with conduction-convection, 422 Scaleup:
cosine law of, 403, 408 of adsorbers, 821
emissive power, 399 of agitated vessels, 277
emissivity: of centrifuges, 1070
monochromatic, 399 in solids suspensions, 266
of solids, 400 of tumbling mixers, 954
in film boiling, 423 Schmidt number, 666
intensity, 408 of gases, 1107
monochromatic, 399 Screen analyses. 931-934
nature of, 397 cumulative, 934
in packed beds, 457 differential, 933
Planck's law, 401 Tyler standard screens, 931, 1108
reflectivity of solids, 402 Screens, 931, 994
to semitransparent materials, 406--421 actual versus ideal, 997
absorbing gases, 419-421 blinding, 997
effect of geometry. 421 capacity of, 1000
layers of liquid or solid, 418 centrifugal sifter, 997
spectrum of, 400-401 effectiveness of, 999
Stefan-Boltzmann law, 401 grizzlies, 996
between surfaces, 405-416 gyrating, 996
angle of vision, 407 material balances over, 998
nonblack surfaces, 413 mesh size, effect of, 1001
with refractory surfaces, 412 particle-size limitations of, 995
square-of-distance effect, 407 standard, 931, 1108
transmissivity of, 397 vibrating, 997
Wien's displacement law, 402 Seals, mechanical, 185
Raoult's Jaw, 546, 552, 589 Sedimentation, 1049-1072
Rayleigh equation, 577 centrifugal,1060-1072
Rectification, 503, 525 principles of, 1068
combined with stripping, 526 equipment, 1053
on ideal plate, 525 flocculation in, 1052
1128 INDEX
Sedimentation (COlIC.) Solubility: coefficient, 841
heavy-fluid methods, 1049 curves, 885
mechanism of, 1052 effect of particle size on, 895
rate of, 1053 Solute rejection by membranes, 1035, 1043
sink-aod-float methods, 1049 Solution-.diffusion mechanism, 840, 859
(See also Thickeners) Solvent extraction (see Extraction)
Selectivity of membranes, 841 Sorting classifiers, 1049
Semi-infinite solid, heat conduction in, 314 Space lattice, 883
Separation: Specific heats:
by differential settling, 1050 of gases, 1103
factor, in cyclones, 1061 of liquids, 1105
heavy-fluid methods, 1049 Specific surface of particles, 930
by impingement, 1032 Sphere:
of solids from gases, 1031, 1060 drag coefficient for, 147, 158
(See also Sedimentation) heat conduction in, unsteady state, 301, 327
Settling criterion, 160 mass-transfer coefficient for, 670
Settling tanks, 1048 Sphericity, 152, 928
Shanks process, 615 Stage cut, in membrane separations, 850
Shape faclors, 152, 249, 884, 928 Stage efficiency:
Shear rate (see Velocity gradients) in distillation and absorption, 676-679
Shear-induced dispersions, 1047 in extraction, 625
Sherwood number, 666 in leaching, 622, 679
SI units, 5 of sieve plates, 574-575, 676
Sieve-plate columns: (See also Plate efficiency)
design of, 560-576 Stage operations:
counterflow trays, 575 enthalpy balances, 506
downcomer level, 564 material balances, 505
heads in downcomers, 564 mUlticomponent systems, 588-610
limiting vapor velocity, 565 tenninoiogy for, 505
pressure drop across plate, 562 Stagnation point, 150
valve trays, 576 enthalpy, 124
weir height, 563 pressure, 150
flow patterns in large columns, 571 temperature, 124
holdup of liquid, 563 Stanton number, 341
nonnal operation, 561 Steam properties, 1090
pressure drops in, 562 Steam-jet ejectors, 212
Sieve plates, 561 Stefan-Boltzmann law of radiation, 401
mass transfer on, 676 Stokes' law, 146, 160
operating limits of, 565 Stokes-Einstein equation, 1041
Peclet number on, 570 Storage of solids (see Solids storage)
stage efficiency of, 574-575, 676 Stream tube, 64
Sigma value, 1070 Streamlines, 64
Size reduction (see Comminution) Streamlining, 149
Slab: Stripping (see Desorption)
heat conduction in, unsteady state, 300-303 Stripping factor, 515
penetration of heat into, 304 Structured packings, 689
Slugging, 169 Suction lift, 191
Slurry transport, 175 Sulfolane process, 640
Sodium hydroxide-water system: Sulfur dioxide, absorption of, 724
boiling points, 471-472 Supercritical fluid extraction, 641
enthalpy-concentration diagram, 478-479 commercial process, 642
Solids storage: decaffeination of coffee, 642
in bins, 939 phase equilibria, 641
flow from, 940 Supersaturation, methods of generating, 890
bulk,939 Suspension of solid particles, 264--268
INDEX 1129
Suspension of solid particles (Cont.) Turbulence, 50--54
critical stirrer speed for, 265 isotropic, 54
degrees of, 264 Tyler standard screens, 931,1108
power requirements, 266-267
scaleup, 266
Ultrafiltration, 1034-1046
of cheese whey, 1041
of milk, 1039
of polymer solutions, 1040
Target efficiency, 1032
Ultrasonic meters, 227
Target meters, 226
Underwood equation, 601-602
Temperature of liquid stream, average, 315
Unit operations, 4
Terminal velocity, 157, 162, 167
foundations of, 4
Thermal boundary layer, 331
Unit systems, 5
Thermal conductivity, 291
cgs, 9
effective, in packed beds, 457
fps, 11
of gases, 1100
SI,5
of liquids, 1101-1102
Units, 5
of metals, 1097
consistent, 14
of various solids and insulating materials, 1098
conversion of, 12
Thermal diffusivity, 300
factors for, 1081
Thermal expansion, coefficient of, 364-365
multiples and submultiples, 1079
Thermal flow meters, 229
Unsteady-state heat transfer, 299-306, 327
Thermal resistance, 293
effective coefficients in, 327
Thickeners, 1051-1060
Uranium isotope separation, 840
design of, 1056
limiting flux in, 1057
mechanically agitated, 1053 V-element meters, 222
zones in, 1059 Vacuum pumps, 212
Thixotropic fluids, 46 Valves: ball, 187
Tie lines, 633 check, 187
Time-dependent flow, 45 gate, 186
Torque, 80 globe, 186
Tortuosity, 153, 839, 861, 1037 plug cocks, 187
Tower packings, 686--690 Vapor-liquid equilibria:
characteristics of, 689 boiling-point diagrams, 524, 527
requirements for, 688 bubble-point curve, 527
Transfer units (see HTU) dew-point curve, 527
Transition: distribution coefficients (K values), 1110--1111
laminar to turbulent flow, 49, 58, 101, 115 in humidification, 744
length,59 y-x diagrams, 523, 549
Trichloroethylene, stripping of, 712 Vapor recompression (see Evaporators)
Tubes and tubing, 181-182 Velocity:
condenser, data, 1088 in diffus.ion, 649
heat-exchanger, data, 1088 of fluids., average, 87, 95
(See also Pipe) terminal, 157, 162, 167
Tubular pinch effect, 1047 universal distribution of, in pipes, 93
Tumbling mills (see Crushers and grinders) Velocity gradients, 43, 87
Tumbling mixers, 953 in agitated vessels, 246, 255
scaJeup of, 954 in non-newtonian fluids, 89-91, 255-256
Tunnel flow from bins, 940 Velocity heads, use of, in design, 110
Turbine impellers: Vena contracta, 106
gas-handling capacity, 273 in orifice meters, 219
power input, dispersers, 271 Venturi meters, 214-216
standard design, 242 coefficients for, 216
Turbine meters, 227 expansion factor for, 222
1130 INDEX
Venturi meters (COllt.) Wake formation (see Boundary layer, separation
flow rates in, 216 of)
pressure recovery in, 216 Wall turbulence, 50
Virial equation, 18 Water, properties of, 1090, 1102
Viscosity, 46 Weber lumber, 276
of gases, 47, 1092 Wet-~lb temperature, 747-750
kinematic, 48 thJory of, 748
of liquids, 47, 1094 W tted-wall tower, 664
of suspensions, 163
7
mass-transfer coefficients in, 668
Viscous dissipation, 348 Wien's displacement law of radiation, 402
Viscous subJayer, 57, 92 Wark index for crushing, 963
Void fraction: for dumped packing, 155
for fluidized beds, 166, 170
von Karman equation, 96
Vortex street, 148 Zero velocity at wall: anomaly with
Vortex-shedding meters, 226 non-newtonian fluids, 91
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