MODULE 2 – Process Units and Degree of Freedom 1

Engr. Caesar Pobre Llapitan

TOPICS
I. Process Units and Basic Functions
II. Problem Specification and Degrees of Freedom
III. Multi-Unit Process Flow Diagram
IV. DFA in Multi-Unit Process

Process flow diagrams (PFD) are used extensively in solving chemical

engineering problems. The PFD depicts the process route, showing the
flows of material and energy between those process units that make up
the plant. This module provides an introduction to process flow diagrams
and the procedure to draw single and multiple unit processes. Basic
functions of the commonly encountered unit operations in chemical
engineering calculations are described. And systematic analysis of
material balances problems is explained using the degree of freedom
analysis for single and multiple unit processes.

I. PROCESS UNITS AND BASIC FUNCTIONS

Learning Objectives
At the end of this section, the students should be able to
1. Describe by schematic diagram the different unit operations frequently
used for transports processes, with or without chemical reactions.
2. Discuss the different functions of the different unit operations commonly
encountered in chemical engineering calculations.
3. Draw the process flow diagrams of commonly used unit operations in
chemical and process engineering.

A. Process Units and Basic Functions

In this section, a brief description is given of the most frequently used unit
operations in chemical engineering processes. The explanation is focused on
typical operations involving the transfer of mass through physical or chemical
routes

1. Divider/Splitter
A splitter is used to divide the flow rate in a certain stream into two or more streams
with different flow rates.

Splitter Feed, Splitter Exit 2,

A C

Splitter Exit 1,
B

a. The total balance is A = B + C

b. Composition of streams A, B and C is the same for each.
c. There in only one independent material balance since all
compositions are equal.
 MODULE 2 – Process Units and Degree of Freedom 2
Engr. Caesar Pobre Llapitan

2. Mixer (Blender)

Mixer Feed 2,
B
Mixer Feed 1,
F MIXER
Mixer Product,
E
a. There are two or more entering streams.
b. There is only one exit stream, a “mixed” stream.
c. The streams can be any phase, gas, liquid or solid.

3. Dryer (Direct Heating)

Drying is a mass transfer process resulting in the removal of moisture by
evaporation from a solid, semisolid, or liquid to produce a solid state. To
achieve this operation, the dryer is supplied with a source of heat. Vapor
is produced in the process.

Solvent, S

Dryer Feed, D DRYER

Dried Product,
E
a. Solvent stream leaves as a pure vapor and is solids free.
b. Exit dried solids are in the solid phase.
c. Dried solids may not be solvent free.
d. Feed can be solid, slurry or solution.

4. Filter
Filtration is a technique used either to remove impurities from a liquid or
to isolate a solid from a fluid. Filtration is commonly a mechanical or a
physical operation that is used for the separation of solids from fluids
(liquids or gases) by interposing a medium through which only the fluid
can pass.

Filtration can also be used to separate particles that are suspended in a

fluid, where the latter can be a liquid, a gas, or a supercritical fluid.
Depending on the application, either one or both of the components may
be isolated.

Feed FILTER
Solution or
Filtrate, E
Slurry, D
(Exit
Liquid)
Filter Cake,
S
(Wet Solid)
a. Filtrate, the exit liquid, is solids free.
b. Filtrate is saturated with soluble component.
c. The filter cake leaves with some liquid attached.
d. Concentration of stream E and liquid attached to the filter cake is
the same.
 MODULE 2 – Process Units and Degree of Freedom 3
Engr. Caesar Pobre Llapitan

5. Evaporator
Similar to drying, except both process streams are liquids. The process of
evaporation is used in the different branches of the industry for food or
chemicals processes, in which the concentration of the solutions is
required.

Solvent,

EVAPORATOR
Evaporator Feed, Dried Product, E
D

a. Single-effect evaporator
Single-effect evaporators are used when:
- The throughput is low.
- When a cheap supply of steam is available.
- When expensive materials of construction must be used as is the
case with corrosive feedstock and when the vapor is so
contaminated so that it cannot be reused

Single effect units may be operated in batch, semi-batch or continuous

batch modes or continuously.
- In a single effect evaporator, the condensate product and the
solution in the evaporator have the same composition and
temperature T1 (Boiling point of solution).
- The temperature of vapor is also T1 since it is in equilibrium with
boiling solution.
- The pressure is P1, which is the vapor pressure of the solution at
T1.
- The solution in evaporator is assumed to be completely mixed.

b. Multi-effect evaporator
Theoretically, multiple-effect evaporators allow decreased consumption of
energy for a concentration almost proportionally equal to the number of
effects (evaporators). However, being expensive, evaporators require the
reduction in the number of effects, in order to be cost-effective. The
optimal number of effects is generally determined via calculations.
 MODULE 2 – Process Units and Degree of Freedom 4
Engr. Caesar Pobre Llapitan

6. Distillation
Distillation is a method of separating chemical substances based on
differences in their volatilities. Distillation usually forms part of a larger
chemical process. In the distillation column, more volatile components
are in the distillate, while less volatile components are in the bottoms.
Separation is accomplished by boiling. However, perfect separation is not
possible

Each tray accomplishes a fraction of the separation task by transferring

the more volatile species to the gas phase and the less volatile species to
the liquid phase. Material and energy balances can be performed on an
individual tray, the column, bottom reboiler, or top condenser, or the
entire system.

a. The more volatile components are in the distillate.

b. The less volatile components are in the bottoms.
c. Separation is accomplished by boiling.
 MODULE 2 – Process Units and Degree of Freedom 5
Engr. Caesar Pobre Llapitan

d. Perfect separation is not possible.

7. Dehumidifier
It is a device that reduces the level of humidity in air or a gas stream.

Feed Gas
Moist Gas, D DEHUMIDIFIER Exit Gas,
E
Condensate
Liquid, S

a. Feed stream contains a condensable component and a non-

condensable component.
b. Condensate is a liquid with the condensable component only.
c. The “dry gas” exit stream is saturated with the condensable
component at the T and P of the process.

8. Humidifier
Humidifier is a device that increases the amount of moisture in indoor air
or a stream of air. It operates by allowing water to evaporate from a pan
or a wetted surface, or by circulating air through an air-washer com-
partment that contains moisture.

Exit Gas, E
Feed Gas, HUMIDIFIER Wetter
D Gas
Volatile
Feed
Liquid, S
a. The feed gas is not saturated.
b. The liquid is evaporated in the process unit.
c. The vapor exit product may or may not be saturated.

9. Gas dryer

Exit gas, E Feed gas,

GAS G
DRYER
Dryer feed, Dry product, P
F
a. Solvent is transferred from liquid phase to gas phase.
b. Unit can be split into two units for analysis- a direct dryer (as in 3)
and a mixer of the feed gas and the solvent mover to the gas
phase.

10. Leaching and Extraction

a. The two liquid solvents must be immiscible.

b. They must have different S.G.
c. At least one component is transferred from one solvent to the other
by difference in solubility.
d. The process is often called liquid-liquid extraction.
e. If one of the feed streams is a solid, the process is called Leaching
or liquid-solid extraction.
 MODULE 2 – Process Units and Degree of Freedom 6
Engr. Caesar Pobre Llapitan

Extract Liquid Out, Heavy Solvent Feed,

E G

Extractio
n

Column

Light Solvent Feed, Raffinate Liquid Out, R

F

11. Absorption (Gas Absorption) (desorption)

In gas absorption, a soluble component is absorbed by contact with a
liquid phase in which the component is soluble. This system is used for
absorbing impurities from a gas stream of certain components such as
hydrogen sulfide, carbon dioxide, and ammonia, using a suitable solvent.

Clean Exit Gas, E Feed Absorbing Liquid,

G

Absorptio
n

Column

Dirty Gas Feed, F Exit Liquid, P

a. Purpose of unit is to have the liquid absorb a component from the

feed gas. An absorber is often called a scrubber.
b. The liquid stream flows down through the tower by gravity.
c. The gas stream is pumped upwards through the tower.
d. No carrier gas is transferred to the liquid.
e. Generally, no liquid solvent is transferred to the gas stream (check
this assumption).
f. Desorption is the same process as gas absorption except that the
component transferred leaves the liquid phase and enters the gas
phase. A desorber is sometimes called a stripper.

12. Partial Condenser

a. The feed stream contains only condensable vapor components.

b. The exit streams, L and V, are in equilibrium.
c. Condensation is caused by cooling and/or increasing pressure.
 MODULE 2 – Process Units and Degree of Freedom 7
Engr. Caesar Pobre Llapitan

Vapor Product, V

Partial
Vapor Feed, F
Condens
er

Condensed Liquid,
L
13. Flash Vaporizer, Flash Distillation

a. Same flow sheet as a partial condenser except the feed is a liquid.

b. Vaporization is caused by reducing the pressure and/or heating.
c. The Vapor and liquid streams are in equilibrium.

Vapor Product,
V

Flash
Liquid Feed,
F Unit

Liquid Product,
L
14. Crystallizer
Crystallizers are used in industry to achieve liquid–solid separation. The
process for a crystallizer involves a crystallizer–filter combination so as to
separate solid crystals from a solution. Solid crystals are formed in the
unit by a change in temperature. Crystallization is capable of generating
high purity products with a relatively low energy input

Crystallizer Feed, Crystallizer Crystals, C

F
Slurry Product,
E

a. Solid crystals are formed in the unit by a change in temperature.

b. The flow sheet for a crystallizer is often shown as a combination
crystallizer-filter.

15. REACTOR (Chemical Reactor, combustor, furnace, reformer)

Gas Products,
G
Reactant 1 Feed,
A
Reactant 2 Feed, REACTO Liquid Products,
B R L

Recycle Feed, Solid Products,

R S
 MODULE 2 – Process Units and Degree of Freedom 8
Engr. Caesar Pobre Llapitan

a. The diagram shown is for a typical reactor that has two reactant
feed streams and a recycle stream.
b. If a single reaction takes place, put the conversion in the box.
c. A reactor is often named by the reaction taking place.
d. A reactor is sometimes preceded by a fictitious mixer if the
combined reactor feed is specified or must be determined.
e. Multiple exit streams are shown to remind you to watch for exit
streams that separate because of their different phases.

B. Process Flow Diagram

A PFD is a diagram commonly used in chemical and process engineering to
describe the general flow of plant processes and equipment. PFD displays the
relationship between major equipment of a plant facility and does not show
minor details such as piping and control designations.

Labeling a PFD
PFD identifies all processes at a facility. Each piece of equipment is labeled with
a name and a number assigned by the engineer or client and must be shown on
the PFD. Major flow streams are represented by arrow lines directed from left
to right in a diagram. Each stream line should have a specification indication as
a minimum unit number and line number.

Example
An amount of 100 kg/h of a mixture of 50% benzene and 50% toluene is
separated in a distillation column. The distillate contains 90% benzene and the
bottom stream composition is 95% toluene (compositions are in weight
percent). Draw and label the process flowchart, and specify vapor and liquid
streams.

Exercises 1
1. A process for making a single product involves reacting liquids in a
continuously agitated reactor and distilling the resulting mixture. Unused
reactants are recovered as overhead and are recycled. The product is
obtained in sufficiently pure form as bottoms from the distillation tower.
Prepare a qualitative flowsheet for the process, showing all pieces of
equipment.

2. Consider the following recipe for pizza dough:

 MODULE 2 – Process Units and Degree of Freedom 9
Engr. Caesar Pobre Llapitan

Mix 4 packages of Baker’s yeast with ¼ cup of milk and ½ cup of warm
water. Gently warm and stir for 15 minutes.
Prepare two cups of “scalded milk,” that is, milk that has been heated to
a boil for about 1 minute; add 1 tablespoon of molasses and 1 tablespoon
of salt to the milk after scalding.

Make the dough by combining the yeast mixture and the scalded milk
mixture with 6 cups of flour.

Gently knead the dough for about 5 minutes. Let the dough rise in warm,
moist air for 15 minutes. The risen dough should be about double its
initial size. There should be sufficient dough to make 4 pizzas.

Roll one quarter of the dough into a flat circle, 15 inches in diameter.
Lightly coat dough with olive oil. Bake the dough at 535 0F for 5 to 6
minutes.

Design a process to continuously produce prebaked pizza dough a for a

major grocery chain. Your flow sheet should have labels on all units and
qualitative compositions of all streams.

3. Prepare the simplest principal type of flowsheet for the following process
and indicate the flowrates of the principal chemical components:

A refinery stream containing paraffins and a mixture of aromatics

(benzene, toluene, xylene, and heavier aromatics) is extracted with a
liquid solvent to recover the aromatics. The solvent and aromatics are
separated by distillation, with the solvent recycled to the extraction
column. The aromatics are separated in three columns, recovering
benzene, toluene, and mixed xylenes, in that order. The feed stream
consists of the following:
Paraffins 300,000 kg/h
Benzene 100,000 kg/h
Toluene 180,000 kg/h
Xylene 70,000 kg/h
Heavy aromatics 40,000 kg/h

A 3-to-1 ratio of solvent to aromatics is used.

4. Sketch a flow sheet for a process to wash clothes. Your process should
include units to perform the following operations:
a. sort the laundry into three types: white items, colored items, and
delicate items
b. wash laundry types separately
c. spin dry
d. air dry

Label all units’ operations in general terms, such as mixer, separator,

heater, and cooler. Each unit on your flow sheet should perform only one
operation, even though in actual practice one machine may perform
multiple operations in sequence. Add the necessary streams for water,
soap, bleach, and air and list the components in all streams.

II. PROBLEM SPECIFICATION AND DEGREES OF FREEDOM

 MODULE 2 – Process Units and Degree of Freedom 10
Engr. Caesar Pobre Llapitan

Learning Objectives
At the end of this section, the students should be able to
1. Define degrees of freedom in chemical engineering calculations.
2. Determine whether a set of equations is independent or not.
3. Explain the different rule of thumb used in performing the degree of
freedom analysis.
4. Conduct the degree of freedom analysis on single units with no reactions.
To avoid the onset of confusion in problem solving, a systematic approach for
solving process engineering problems is presented. This is known as the
freedom of degree analysis. A general set of procedures in using this follows.

A. Degree of Freedom Analysis

The degree of freedom analysis establishes the necessary information needed
whether a problem is solvable or not. It is structured in terms of the total
number of variables involved; then subtract from that the number of
independent equations relating the variables and the number of independent
known values.

B. Analysis of Material Balance Problems

Solving material balances problems involve the formulation of equations needed
to determine the unknown quantities. Thus, the question: How many equations
do I need, and where do these potentially come from? The DFA is used to
address these questions.

A simple index that can provide a good indication of whether the problem has
been properly set up as well as point to the most reasonable starting point for a
hand solution is the degree of freedom of the problem.

In simple terms, if you have m unknowns contained within n algebraic

equations, then the problem is uniquely solvable if m = n, under-specified if m
> n (you cannot solve for all unknown stream variables), and over-specified if n
> m (there is a redundancy or perhaps even an inconsistency in the equations).
To provide a more systematic approach, we will define the degree of freedom of
a system as

F=m-n-p–s

where
F = degree of freedom of the system
m = total number of independent stream variables
n = total number of independent balance equations
p = total number of independent stream variables for which the values
are specified in
the problem
s = total number of subsidiary relations

Criterion:
 if the degree of freedom is positive then the problem is under-specified;
 if it is negative then the problem is over-specified; and
 if the degree of freedom is zero then the problem is correctly specified
and a unique solution can be found.

A simple rule of thumb for obtaining the number of each individual terms is
explained next.

C. Rules of Thumb for Getting m, n, p, and s

 MODULE 2 – Process Units and Degree of Freedom 11
Engr. Caesar Pobre Llapitan

m:
The total number of independent stream variables. This is
found by adding up the number of components in each of the
streams that cross the system boundary.
The specific variables for each stream that are independent can be found
in one of two ways:
o Count 1 for the number of moles (or molar flow rate) for each
component
 (Note that the total flow rate is not independent in this case
because the sum of the individual component flows must add
to the total flow)
o Count 1 for the total flow rate plus an additional 1 for each of the C
 l mass fractions (or mole fractions), where C is the number of
components in that stream.
 Recall that only C – 1 of the total C mole fractions is
independent because the last one can be found from the
previous C  1 using:

n:
The total number of independent mass balance equations.
In general, the number of independent mass balances that
can be written for a system is equal to the number of
different components that cross the system boundaries.

p:
The number of independent specified stream variables; i.e.,
variables for which you have numbers.
These are the "knowns." These are stream values prescribed by the
problem, such as 10 mol% benzene, 30 moles/sec, etc. Be sure to include
the basis as a p-value whenever appropriate.

s:
The number of independent subsidiary relationships
Subsidiary relationships are additional equations that relate properties in
two streams. Often subsidiary relations are given in a problem such as a
percent conversion, a ratio of flow rates, a yield, fractional recoveries,
composition relationships, etc. Subsidiary relations come about because
of the way the apparatus is operated, because of constraints set by the
operator or equipment, or because of equilibrium relationships between
outlet streams.

The degree-of-freedom analysis for a problem becomes more and more

important as the complexity of the problem increases. This is because the
degrees of freedom tell you where to start in solving a problem (anything
with a zero degree of freedom can be solved immediately), and what to use to
solve it (n mass balance equations and s subsidiary relations).

D. Degree of Freedom Analysis on Single Units with no Reactions

A degree-of-freedom analysis can be done correctly in different ways than we
have formalized here, but the methods of counting m, n, p, and s proscribed is a
 MODULE 2 – Process Units and Degree of Freedom 12
Engr. Caesar Pobre Llapitan

good systematic way to do it. In particular, we deal completely with

independent variables to keep the number of variables as small and simple as
possible. One could formulate a similar procedure for all variables (instead of
independent ones), but that simply increases m, n, and p equivalently so that f
comes out the same.

Example 1: Problem Solving Approach

(Drying) A wet paper pulp contains 71% water. After drying, it is found that
60% of the original water has been removed. Draw and label the process
flowchart and perform DFA.

Solution:

Basis: 100 kg feed

DOF Analysis:

m 5
n 2 W3: (60% of
original)
p 2
100 KG S2
s 1 DRYER
dof = m – n – p W1: 71% W2
0
–s P1: 29% P2

1. P balance: (0.29) (100 kg) = p2 × s2

2. Overall balance: 100 kg = w3 + s2
3. Subsidiary equation: (0.71) (100 kg) (0.6) = w3

Example 2: Simple Distillation Example

A mixture containing 10% EtOH and 90% H 2O by weight is fed to a distillation
column at the rate of 1000 kg/h. The distillate contains 60% EtOH and is
produced at a rate 1/10th that of the feed. Draw and label the process flowchart
and perform DFA.

Solution:
Basis: 1 hr D: 100
kg
DOF Analysis:
m 6 60% E
n 2 40% W
p 4
1000
s 0 kg
dof = m – n – p
0 10% E
–s
90% W
Independent Equations: B
According to the DOF analysis, we need 2 mass balances.
WE
Overall: 1000 kg = B + 100 kg B = 900 kg WB
EtOH: 100 kg = 60 kg + (wEtOHB) (900 kg) (wEtOHB) = 0.044

DOF Notes:
 MODULE 2 – Process Units and Degree of Freedom 13
Engr. Caesar Pobre Llapitan

m is the number of independent variables for all of the streams combined.

The rule for counting it is to find the number of components in each stream
and add them up. In this case, there are 2 components (E and W) in the
feed, 2 in the distillate, and 2 in the bottoms; i.e., a total of 6.

n is the number of independent mass balances that can be written for this
system. The rule for counting it is to find the number of different
components that enter or leave the system. In this case n = 2 because E and
W are the only two components that are in any of the streams.

p is the number of independent variables for which we have known values.

In this case, p = 4. Which ones are they? (1) The feed = 1000 kg, (2) The
feed composition is 10% E, (3) the distillate is 100 kg, and (4) the distillate is
60% E. What about the other two values: 90% W in the feed and 40% W in
the distillate? These are not independent of the other variables because
we may not count all C mass fractions for C components in a stream. This is
because we know they add to one. When we counted m, we counted the
mass of the stream and C-1 mass fractions (for a total of C), so we can't
count any other values that we know except those included in that
independent set.

Example 3: Washing Process

A slurry of CaCO3 (s) in NaOH and H2O is washed with an equal mass of dilute 5
wt% NaOH in water. The washed and settled slurry contains 2 lb m of solution
per lbm of solid CaCO3. The solution may be considered the same composition as
the clear solution withdrawn from the unit. If the feed slurry contained equal
mass fractions of all components, draw and label the process flowchart and
perform DFA.

Solution:

Basis: 1 lbm CaCO3 in product

F
DOF: Washer
5 % NaOH S
m 10 95% H2O
n 3 wNaOH
p 5 F wH2O
s 2
1/3 CaCO3
dof = m – n – p
0 1/3 NaOH
–s
1/3 H2O

Equations: 2 lbm solution/lbm

DOF says we need 3 mass balances + 2 subsidiaries CaCO3
P = 3 lbm
Overall: 2F = S + 3 lbm
CaCO3: (0.333) F = 1 lbm

Note: This is a tie Component

NaOH: (1/3) (3 lbm) + (0.05) (3 lbm) = wNaOH (2 lbm) + wNaOH (3 lbm)

Notes:
Basis: Because we were given that there would be 2 lb of solution for every
1 lb of solid produced, the most convenient basis is to choose 1 lb of solid
product. That way, we can immediately fill in a p value; i.e., we can set the
 MODULE 2 – Process Units and Degree of Freedom 14
Engr. Caesar Pobre Llapitan

amount of solution equal to 2 lb. If we were to choose a basis for the feed,
we would end up using a ratio between the two outlet streams as a
subsidiary relation. This would be much harder. Make life easy by choosing
a basis that makes things as simple as possible.

m is the number of independent variables for all of the streams combined.

The rule for counting it is to find the number of components in each stream
and add them up. In this case, there are 3 components (CaCO 3, NaOH and
water) in the feed, 2 in the wash water (NaOH and water), 2 in the clear
solution stream and 3 in the precipitate stream. This gives m = 10.

n is the number of independent mass balances that can be written for this
system. The rule for counting it is to find the number of different
components that enter or leave the system. In this case n = 3 for CaCO3,
NaOH and water.

p is the number of independent variables for which we have known values.

In this case, p = 5. Which ones are they? (1 & 2) Feed: 1/3 CaCO3 & 1/3
NaOH (note that 1/3 water is not independent). (3) 5% NaOH in wash water
(note that 95% water is not independent of this value), (4) 1 lb CaCO 3, and
(5) 2 lb solution that leaves with the solid. (Note that we know that this total
stream is 3 lb, but that is not independent since 2 + 1 = 3).

s is the number of independent subsidiary relations. In this case, we know

that the feed and wash streams are equal amounts and we know that the
mass fraction of NaOH is the same in the clear solution and the solution
exiting with the solid. This yields s = 2. Can you see why the fact that the
mass fractions of water in the clear solution and in the solution exiting with
the solid are the same is not an independent (new) subsidiary relation?

Example 4: Mixing Process

A manufacturer mixes three alloys to yield 10,000 lb m/h of a desired alloy. The
alloy compositions in wt% are:

components feed alloy compositions (mass product

%)
1 2 3
A 60 20 20 25
B 20 60 0 25
C 20 0 60 25
D 0 20 20 25

Solution:

Basis: 100 lbm final alloy

DOF Q1
Mixer 60%
m 13 A
n 4 20%
p 10
Q2 100 lbm
s 0 MIXE
dof = m – n – p 20% R 25 lbm A
-1 25 lbm B
–s A
60% 25 lbm C
Q3 25 lbm D
B 20%
A
 MODULE 2 – Process Units and Degree of Freedom 15
Engr. Caesar Pobre Llapitan

The DOF analysis indicates that this problem is over specified. In fact, the
problem is not only over specified; it is inconsistent and cannot be solved
uniquely. Can you see why? Note that none of the streams have a D
composition as large as the product alloy. It is impossible to get more D by
mixing these streams.

Notes:
m is the number of independent variables for all of the streams combined.
The rule for counting it is to find the number of components in each stream
and add them up. In this case, there are 3 components in each of the 3 feed
streams and 4 components in the mixed stream; i.e., (3)(3) + 4 = 13.

n is the number of independent mass balances that can be written for this
system. The rule for counting it is to find the number of different
components that enter or leave the system. In this case n=4 for the four
different components (all of which appear in the mixed product stream in
this case).

p is the number of independent variables for which we have known values.

In this case, p = 10. Which ones are they? The top feed (Q1) has 2 (60% A
and 20% B), the next feed has 2 (20% A and 60% B), the bottom feed has 2
(20% A and 60% C), and the mixed product has 4 (25 lb of each of the 4
components). This gives p = (3)(2) + 4 = 10.

Example 5: Multi-component distillation

A feed stock available at the rate of 1000 mol/h and consisting of
20 % Propane (C3)
30 % Isobutane (i-C4)
20 % Isopentane (i-C5)
30 % Normal pentane (C5)

is to be separated into two fractions by distillation. The distillate is to contain all

of the propane fed to the unit and 80 % of the isopentane fed to the unit and is
to consist of 40 % isobutane. The bottoms stream is to contain all the normal
pentane fed to the unit. Draw and label the process flowchart and perform DFA.

Solution:

Basis: 1000 mol/h final alloy

D

C3
i-C4 = 40 %
i-C5 = 0.6 – C3

1000 mol/h

C3 = 20 %
i-C4 = 30 %
i-C5 = 20 %
C5 = 30 %
B

x i-C4
x C5
x i-C = 1 – x i-C – x
 MODULE 2 – Process Units and Degree of Freedom 16
Engr. Caesar Pobre Llapitan

DOF Analysis:
m 10 No. of stream variables
n 4 No. independent balance equations
No. of specified streams (4 compositions and
p 5
1 flow)
s 1 Subsidiary relation (80% of isopentane)
dof = m – n – p
0
–s

Alternate DAF analysis:

Checklist of variables and equations to consider:

Variables
 Flow variables
- Species (or total flow) entering and leaving for each subsystem
- Species (or total flow) entering and leaving the overall system
 Reaction variables
- Extents of reactions (if any) in the minimal set of each subsystem

Equations
 Basis for each subsystem or the overall system
 Material balances (species or elements)
- For each species of element (or their total) in each subsystem
- For each species of element (or their total) in the overall system
 Specifications
- Specified compositions
- Specified flow rates
- Specified flow ratios
- Specified conversions of extent of reactions
- Splitter restrictions
 Implicit equations (sum of mole or mass fraction)

Example 6: Binary Separation Process

Feed stream to a distillation column flows at a rate of 300 mol/h and contains 50
mol% of component A and 50 mol% of component B. The distillate flow is at a
rate of 200 mol/h and contains 60 mol% of component A. Draw and label the
process flowchart. Perform a DFA.

Solution:
D = 200
mol/h

xA, D = 0.6
xB, F = 0.4

F = 300
mol/h

xA, F = 0.5
xB, F = 0.5
B=?

xA, B = ?
xB, B = ?
 MODULE 2 – Process Units and Degree of Freedom 17
Engr. Caesar Pobre Llapitan

DFA analysis
# DFA No. Justification
1 Number of unknowns 2 B, xA,B only, xB,B = 1−xA,B
2 Number of independent 2 Overall + one of the components A
equations or B
3 Number of relations 0 No auxiliary relations
4 NDF 0 NDF = 2 − 2 − 0 = 0

The number of unknowns is equal to the number of components. Since we have

two components, two independent equations can be written: one is the overall
material balance and the second is the component balance for one of either
components.

Example 7: Binary Separation Process

A feed stream flowing at a rate of 300 mol/h contains 20 mol% of components 1
and 80 mol% component 2. The distillate flow rate is 200 mol/h. Draw and label
the process flowchart and perform DFA.

Solution:
D = 200
mol/h

xA, 2
xB, 2 = 1 - xA, 2

F = 300
mol/h

xA, 1 = 0.2
xB,1 = 0.8
B (mol/h)

xA,3
xB,3 = 1 -
xA,3
DFA analysis
# DFA No. Justification
1 Number of unknowns 3 B, xA,2, xA,3
2 Number of independent Overall + one of the components A
2
equations or B
3 Number of relations 0 No auxiliary relations
4 NDF 1 NDF = 3 − 2 − 0 = 1

Comments: NDF is greater than 0 and, accordingly, the problem is under-

specified. One extra piece of information is needed for the problem to be
solvable.

Example 8: Multicomponent Separation Process

A feed stream to a distillation column contains three components (A, B, and C).
Component A’s mass flow rate is 100 kg/s, and the flow rates of components B
and C are unknown. The distillate flow rate is 100 kg/s and contains 60 kg/s of
component A and 40 kg/s of component B. It has been found that 40% of
component A in the feed stream ends up in the bottom stream. The distillate
 MODULE 2 – Process Units and Degree of Freedom 18
Engr. Caesar Pobre Llapitan

and bottoms flow rates are equal. Draw and label the process flowchart, and
perform DFA

Solution:
Distillate = 100
kg/s

nA, 2 = 60 kg/s
nB, 2 = 40 kg/s

Feed (kg/s) 40% of A ends up in

the
nA, 1 = 100 bottom. Distillate
kg/s and
nB, 1 = ?
nC, 1 = ?
Bottoms
(kg/s)

nA, 3 = 3
nB, 3 = ?
nC, 3 = ?
DFA analysis
# DFA No. Justification
1 Number of unknowns 5 F, nB,1, B, nA,3, nB,3
2 Number of independent
3 Overall + two of three components
equations
3 Number of relations 2
40% of A in the feed ends up in the
bottom, D and B are equal
4 NDF 0 NDF = 5 − 3 − 2 = 0

In the feed stream, two unknowns are considered because the component flow
rates are related; that is, their sum is equal to the feed flow rate, F. The same is
applied for the bottom stream.

Example 9: Tertiary Component Separation Process

A feed to a distillation column contains 60 kg/s of benzene (B) and 10 kg/s of
toluene (T), and a small amount of xylene (X). The distillate contains pure
benzene. The bottom stream flow rate is 100 kg/s. Hundred percent of toluene
in the feed ends up in the bottom. Draw and label the process flowchart, and
perform DFA.

Solution:

Distillate, D
(kg/s)

nB, 2 = 100 %

Feed, F 100 % of T in the feed ends

(kg/s) up in B.
D is pure component B.
nB, 1 = 60 kg/s
nT, 1 = 10 kg/s
nX, 1
Bottoms, B (100
kg/s)

nB, 3 = 3
nT, 3 = ?
nX, 3 = ?
 MODULE 2 – Process Units and Degree of Freedom 19
Engr. Caesar Pobre Llapitan

DFA analysis
# DFA No. Justification
1 Number of unknowns 4 F, D, nB,3, nT,3
2 Number of independent
3 Overall + two of three components
equations
3 Number of relations Two auxiliary relations but one is
1 already used (distillate contains pure
B)
4 NDF 0 NDF = 4 − 3 − 1 = 0

The first relationships have useful information, so it is considered as one

relationship. The second relationship (distillate contains pure B) is already
specified in the chart as 100% component B.

Example 10: Distillation Column

A feed stream flows at a molar flow rate of 100 mol/h and contains three
components (20% component A, 30% component B, and the balance, component
C). Note that 80% of A in the feed and 50% of feed rate end up in the distillate.
The bottom stream contains 10% A, 70% B, and 20% C (by moles). Draw and
label the process flowchart and perform DFA.

Solution:

Distillate
(mol/h)

nA, 2 = ?
nB, 2 = ?
nC, 2 = ?
Feed = 100 mol/h 80% 0f 1 ends up in
distillate.
nA, 1 = 0.2 50% of F ends up in
nB, 1 = 0.3
nC, 1 = ?

Bottoms (mol/h)

nA, 3 = 0.1
nB, 3 = 0.7
nC, 3 = 0.2
DFA analysis
# DFA No. Justification
1 Number of unknowns 4 D, xA,2, xB,2, B
2 Number of independent
3 Overall + two of three components
equations
3 Number of relations Auxiliary relations shown in the
2
diagram
4 NDF -1 NDF = 4 − 3 − 2 = - 1

This problem is over-specified since the number of pieces of information given is

more than the number of unknowns.

Classroom Activity
1. An ethanol (E)–methanol (M) stream is fed at a rate of 1000 kg/h to be
separated in a distillation column. The feed has 40% ethanol and the
distillate has 90% methanol. The flow rate of the bottom product is 400
kg/h. Draw and label the PFD and perform DFA.
 MODULE 2 – Process Units and Degree of Freedom 20
Engr. Caesar Pobre Llapitan

2. Two hundred kilograms of wet leather is to be dried by heating in a dryer.

The wet leather enters the drier with 1.5 g H2O per gram bone dry
leather (BDL). The leather is to be dried to residual 20% moisture. Draw
and label the process flowchart, and perform DFA.
3. A stream of ethanol–methanol mixture (40 wt% ethanol, 60 wt%
methanol) is fed at a rate of 100 kg/h to a distillation column. The dis -
tillate has 90% methanol and the balance is ethanol. Eighty percent of
methanol fed to the distillation column is to be recovered in the distillate.
Draw and label the process flowchart, and perform DFA.
4. One hundred kilograms of wet slurry is to be dried by heating in a fur-
nace. The wet slurry is placed in the furnace with 60% moisture and 40%
dry solid (S). Note that 90% of the water is removed. Draw and label the
process flowchart, and perform DFA.
5. A hydrocarbon feed consisting of a mixture of 20 wt% propane (C3), 30
wt% isobutene (iC4), 20 wt% isopentane (iC5), and 30 wt% n-pentane
(nC5) is fractionated at a rate of 100 kg/h into a distillate. The latter con-
tains all the propane and 78% of the isopentane in the feed. The mole
fraction of isobutane in the distillate is 0.378. The bottom stream contains
all the n-pentane fed to the unit. Draw and label the process flowchart
and perform DFA.

III. MULTI-UNIT PROCESS FLOW DIAGRAM

Learning Objectives
At the end of this section, the students should be able to
1. Construct a process flowchart and label all known qualities and unknown
quantities for a multiunit process with recycles and purge.

PFDs for single unit or multiple units differ in their structure and implemen-
tation. PFDs for multiple units do not include detailed information and are
known as the schematic flow diagrams or block flow diagrams. The main reason
for using process flowchart is to show the relation between major parts of the
system. Process flowchart is used primarily in process engineering and
chemical industry, where there is a requirement of depicting the relationship
between major components only.

A. Special Multi-Unit Processes

Recycle and Bypass Streams

 Recycle  bringing a process output stream (or part of stream) back to mix
with the feed stream to the same or another unit in the process

 By-pass  splitting a process feed stream to allow part to "bypass" a unit

Recycle
Split Mix
PROCESS
PROCESS
Mix Split
By-pass
These are particularly useful for reactors, where they allow better control
of reactor selectivity when multiple reactions occur.
 MODULE 2 – Process Units and Degree of Freedom 21
Engr. Caesar Pobre Llapitan

When we study recycle systems, we are often asked to calculate the recycle
ratio. Usually, this is found by dividing the mass flow of the recycle stream by
the mass flow of the "fresh feed" entering the system. In the industrial world,
recycle ratios have important a consequence for system performance and
operating costs.

A common recycle structure is the reactor/separator which is used to recover

un-reacted material and return it to the reactor. The "separator" may be a
single piece of equipment or it may be an entire process on its own.

One use of bypass is to obtain precise control of the output stream, as when a
small wet air stream bypasses a drier so that the output humidity can be
regulated.

Fresh Feed
REACTOR SEPARATOR
Product
Purge
A purge stream is a small stream bled off from a recycle loop to prevent buildup
of inert or impurities in the system. Often, the purge flow rate is so much
smaller than the recycle flow rate that it can be neglected in the steady-state
overall material balance of the process

Make-up
A makeup stream is required to replace losses to leaks, carryover, etc., within
the recycle loop. Proper sizing and location of makeup and purge streams can
prevent many problems within process plants.

Example 1 Extraction Process

 MODULE 2 – Process Units and Degree of Freedom 22
Engr. Caesar Pobre Llapitan

A stream containing 10.0 wt% acetone and the balance water enters a
liquid/liquid extraction column where acetone is extracted with methyl isobutyl
ketone (MIBK). The solvent is a fresh feed of MIBK and a recycled stream
consisting of MIBK with a small amount of acetone. There are two streams
leaving the liquid–liquid extraction process: a raffinate stream that contains
only acetone and water, and an extract stream that contains only acetone and
MIBK. The extract stream goes to a distillation process. The overhead stream
from the distillation process is mainly acetone with some MIBK. The bottoms
stream contains mainly MIBK with some acetone and is recycled to the liquid–
liquid extraction process. The overhead stream from the distillation tower
contains 90% of the acetone in stream 1. The overhead stream from the
distillation tower also contains four times as much acetone as it contains MIBK.
Draw a flow diagram for the process labeling all processing units and all
streams. Give the information of the flow rate and/or composition. For each
stream in this process, indicate as much information as you know about that
stream as given in the process description.

Example 2 Process Flow Sheet

The process for producing pure ethanol starts with a fresh feed stream that
contains 96% ethanol and 4% water. The stream is fed to a distillation tower
along with a stream of benzene plus a small amount of ethanol (this stream is
being recycled from another portion of the system). This distillation tower
produces two outgoing streams: the overhead stream (all vapor) is a mixture of
water, benzene, and ethanol, and the bottom stream (all liquid) is 100% ethanol.
The overhead stream is condensed to an all-liquid stream. The liquid stream is
sent to a decanter where it separates into two distinct liquid phases. The top
layer in the decanter consists primarily of benzene with a small amount of
ethanol and is sent back to the first distillation tower to be mixed with the
incoming ethanol/water mixture being fed to the system. The bottom layer from
the decanter contains ethanol, water, and benzene. This stream is fed to a
second distillation tower. The overhead stream from this second distillation
tower is also all vapors and consists of ethanol, water, and benzene. This vapor
stream is mixed with the overhead vapor stream from the first distillation tower
before both streams are condensed prior to the decanter. The bottoms stream
from this second tower (again all liquid) consists of water and ethanol. This
bottoms stream is fed to a third distillation tower. The overhead product from
this third distillation tower is a 96 wt% ethanol, 4.0 wt% water stream that is
sent to the start of the entire process to be mixed with the incoming feed of
ethanol and water. The bottoms stream from the third distillation tower is all
water. Draw a flow diagram for the process described earlier clearly labeling all
processing units and all streams. For each stream in this process, you should
 MODULE 2 – Process Units and Degree of Freedom 23
Engr. Caesar Pobre Llapitan

indicate as much information as you know about that stream as given in the
process description. If you know the flow rate and/or composition, give this
information. If all you know about a stream are its components, indicate those.

IV.DFA IN MULTI-UNIT PROCESS

Learning Objectives
At the end of this section, the students should be able to
1. Perform degree-of-freedom analysis in multi-unit operations.

The DFA for a single-unit process can be easily extended to multiunit processes.
There are three ways to describe a problem in terms of its solvability:
1. If the problem has a unique set of solutions, then it is called well-
defined.
2. The problem is over-specified; that is, you have too much information
and it is either redundant or inconsistent. It could be fixed by removing
an assumption about the system that one had made.
3. The problem is under-specified; that is, you do not have enough
information to solve for all your unknowns. There are several ways to
deal with this. The most obvious is to gather additional information,
such as measuring additional process variables (e.g., temperatures,
flow rates, etc.), until you have a well-defined problem. Another way is
to use additional equations or information about what we want to
achieve out of a process (e.g., conversion level of a reaction, efficiency
of a separation unit, etc.). Finally, we can make assumptions in order to
simplify the equations, and perhaps they will simplify enough that they
become solvable.

Multiunit process systems are more involved in their analysis than single-unit
systems, but they can be analyzed, provided a structured approach is followed.
The next few steps can prove to be extremely useful:
1. Label a flowchart completely with all the relevant unknowns for all
units and streams.
2. Perform a DFA on each unit operation.
3. Determine the NDF for each unit and the overall system.

Example 1 Degree of Freedom Analysis on a Multi-unit process

 MODULE 2 – Process Units and Degree of Freedom 24
Engr. Caesar Pobre Llapitan

Consider a separation train consisting of two distillation columns which are

designed to separate a three-component mixture of benzene, toluene, and
xylene into three streams, each rich in one of the species as shown below.
Given a feed rate of 1000 mol/h of a 20 mol% benzene, 30 mol% toluene
mixtures, a bottoms product of 2.5 mol% benzene and 35 mol% toluene from the
first unit, and an overhead product of 8 mol% benzene and 72 mol% toluene
from the second unit. Draw and completely label a flow sheet of the process and
perform a DFA.
Solution:

n2 n4

XB XB = 0.08
toluene XT = 0.72
xylene
Uni Uni
1000 mol/h
t1 t2
XB = 0.2
XT = 0.3
xylene

n3 n5

XB = 0.025 XT
XT = 0.35 xylene
xylene

DOF Unit 1 Unit 2 Block Process

m 8 8 10 13
n 3 3 3 6
p 5 4 5 7
s 0 0 0 0
f 0 1 2 0

What does the above DOF table tell us?

 The process has a unique solution (f = 0 for process)
 We should start by solving Unit 1 by itself first (f = 0 for Unit 1)
 3 material balance equations can be used to completely solve Unit 1. The
other process units cannot yet be solved independent of each other.
 Once Unit 1 has been solved, it will provide another p value connected
with Unit 2. This will reduce that unit's DOF to 0 so it will be solved next.

Test your understanding

DFA for a Multiunit Process
An absorber–stripper system is used to remove carbon dioxide and hydrogen
sulfide from a feed consisting of 30% CO 2 and 10% H2S in nitrogen. In the
absorber, a solvent selectively absorbs hydrogen sulfide and carbon dioxide.
The absorber overhead contains only 1% CO2 and no H2S. N2 is insoluble in
the solvent. The rich solvent stream leaving the absorber is flashed, and the
overhead stream consists of 20% solvent, and contains 25% of the CO 2 and
15% of the H2S in the raw feed to the absorber. The liquid stream leaving
the flash unit is split into equal portions, one being returned to the absorber.
The other portion, which contains 5% CO 2, is fed to the stripper. The liquid
 MODULE 2 – Process Units and Degree of Freedom 25
Engr. Caesar Pobre Llapitan

stream leaving the stripper consisting of pure solvent is returned to the

absorber along with makeup solvent. The stripper overhead contains 30%
solvent. Draw and completely label a flow sheet of the process and perform a
DFA.

DOF Absorber Flash Stripper Splitter Mixer Overall

m
n
p
s
f

Exercises 2
1. Air containing 3% acetone and 2% water is fed to an absorber column.
The mass flow rate of air is 1000 kg/h. Pure water is used as absorbent to
absorb acetone from air. The air leaving the absorber should be free of
acetone. The air leaving the absorber was found to contain 0.5% water.
The bottom product of the absorber is sent to a distillation column to
separate acetone from water. The bottom of the distillation column was
found to contain 4% acetone, and the balance is water. The vapor from
the head of the absorber is condensed. The concentration of the
condensate is 99% acetone and the balance is water. Draw and label a
process flowchart, and perform a DFA.
2. A liquid mixture containing 38 mol% benzene (B), 35.0 mol% toluene (T),
and 27.0 mol% xylene (X) is fed to a distillation column. The bottom
product contains 97.0 mol% X and the balance is T, bearing in mind that
93.0% of X in the feed is recovered in this stream. The overhead product
is fed to a second column. The overhead product from the second column
contains 95 mol% B and 5.0 mol% T, bearing in mind that 96.0 mol% of
the benzene fed to the system is recovered in this stream. Draw and
completely label a flow sheet of the process, and perform a DFA.
3. A copper ore contains 1.00 wt% copper and 99.0 wt% rock. The crushed
ore is mixed with a stream of fresh acid plus a recycled stream. The rock
is allowed to settle out of the copper/acid solution completely. The rock
 MODULE 2 – Process Units and Degree of Freedom 26
Engr. Caesar Pobre Llapitan

leaving this stage contains all of the rock in the ore as well as some of the
copper/acid solution produced in this stage. Every 3.00 lb of rock that
leaves this stage contains 1.00 lb of the copper/acid solution. It is desired
that only 10% of the copper originally contained in the ore be lost in this
stream. The remaining copper/acid solution, containing no rock, is sent to
an electrical recovery process where pure copper is separated and a
solution containing copper and acid is generated. In the electrical
recovery process, 90% of the copper that enters the electrical recovery
process is recovered as the pure copper product. The copper/acid
solution generated in the electrical recovery process is recycled and
mixed with the fresh acid stream entering the mixing stage. For every
2000 lb of ore that enters this process, draw and label the PFD.
4. A chemical A is to be removed from its ore. Hundred kilograms per hour
of ore is fed to a dissolution tank where it is mixed with a stream of pure
water (W) and a recycle stream. The tank is heated to 90°C so that all of
A (but none of the other junk, J) dissolves, forming a saturated solution.
The material exits the tank and is sent to a filter (separator) where all of
the junk and a small portion of the (still saturated) solution are removed.
Finally, the remaining solution is fed to a crystallizer where it is cooled to
25°C in order to form some solid A, which is shipped off to be packaged
and sold (some filtrate also leaves with the solid). The remaining filtrate,
now saturated at 25°C, is recycled to the dissolution tank. Upon
analyzing the products from the filter and crystallizer, it is determined
that the waste stream from the filter contains 40.0 kg/h of J, 12 kg/h of A,
and 4 kg/h of water (W), and that the final product stream from the
crystallizer contains 42 kg/h, 6 kg/h A, and 6 kg/h W. From the process
description, draw a flowchart that concisely summarizes each stage of the
process (properly labeling all streams and species within the streams).
5. An absorber–stripper system is used to remove carbon dioxide and
hydrogen sulfide from a feed consisting of 30% CO 2 and 10% H2S in
nitrogen. In the absorber, a solvent selectively absorbs hydrogen sulfide
and carbon dioxide. The absorber overhead contains only 1% CO 2 and no
H2S. N2 is insoluble in the solvent. The rich solvent stream leaving the
absorber is flashed, and the overhead stream consists of 20% solvent, and
contains 25% of the CO2 and 15% of the H2S in the raw feed to the
absorber. The liquid stream leaving the flash unit is split into equal
portions, one being returned to the absorber. The other portion, which
contains 5% CO2, is fed to the stripper. The liquid stream leaving the
stripper consists of pure solvent and is returned to the absorber along
with makeup solvent. The stripper overhead contains 30% solvent. Draw
and completely label a PFD of the process and perform a DFA.
6. Fresh feed containing 20% by weight KNO 3 (K) in H2O (W) is combined
with a recycle stream and fed to an evaporator. The concentrated
solution leaving the evaporator, containing 50% KNO3, is fed to a
crystallizer. The crystals obtained from the crystallizer are 96% KNO 3 and
4% water. The supernatant liquid from the crystallizer constitutes the
recycle stream and contains 0.6 kg KNO3 per 1.0 kg of H2O. Draw and
label the process flowchart and perform a DFA.

References:
[1] Felder, R.M. and R.W. Rousseau (2005). Elementary Principles of
Chemical Processes (3rd Edition). New York: Wiley
[2] Ghasem, Nayef and Redhouane Henda (2015). Principles of Chemical
Engineering Processes – Material and Energy Balances (2nd Edition),
CRC Press
 MODULE 2 – Process Units and Degree of Freedom 27
Engr. Caesar Pobre Llapitan

[3] Himmelblau, D.M. and James B. Riggs (2005). Basic Principles and
Calculations in Chemical Engineering (7th Edition). Upper Saddle
River, NJ: Prentice-Hall
[4] Reklaitis, G.V. (1983), Introduction to Material and Energy
Balances. New York: John Wiley & Sons