Separation Process

CHEN 312
American University of Beirut
Chemical Engineering Department
Spring 2022/23
Dr. Ahmad B. Albadarin
 Separation Process Engineering CHEN 312

Textbook:
Wankat, Phillip C. Separation Process Engineering, Third Edition, Pearson Education, Inc., New Jersey, 2011.
Course Outline:
• Introduction to Separation Processes (Chapter 1)
• Vapor/Liquid Equilibria and Flash Distillation (Chapter 2)
• Distillation Column (Chapters 3 & 4)
• Multi-Component Distillation (Chapters 5 & 7)
• Staged and Packed Columns (Chapters 10)
• Absorption and Stripping (Chapter 12)
• Liquid/Liquid extraction (Chapter 13)

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 Course Objectives

• To understand the fundamental principles of phase equilibrium

• To construct overall and stage-wise mass balances for distillation systems through an
understanding of the basic principles of mass transfer
• To use the McCabe-Thiele method to design binary distillation systems
• To extend the principles learned in distillation to design separation equipment for dilute and
concentrated systems
• To understand the basic chemical principles governing separation processes and identify the
specialized equipment required for their use
• To use the principles of the extraction process to design and analyze multi-component systems.

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 Assessment Weight Due Date
Assignments and Attendance 20% Assigned throughout the semester
First Exam 20% 5th week, around 1st of March
Second Exam (Project) 25% 9th week, around 31st of March
Final Exam 35% Early May

• Unless expected excuses, no make-up exams will be given.

• All make-up exams will be given on campus.
• Assignments and suggested problems will be provided for you to practice and gain
experience; it is expected that you will solve the problems independently and you can
discuss your solution with me during the online office hours.

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 Introduction: What are separation processes?

• Separation processes are defined as those operations which transform a mixture of

substances into two or more products which differ from each other in composition.

• Separations are crucial in chemical engineering. A typical chemical plant is a chemical

reactor surrounded by separators, where raw materials are prepurified in separation
devices and fed to the reactor; by-products are separated from the reaction products
whereas unreacted feeds are separated and recycled back to the reactor.

• Chemical plants commonly have from 40% to 70% of both capital and operating costs in
separations.

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Schematic of the functions of separations in manufacturing.

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Functions of separation processes

Purification:

Undesired components in the feed mixture are removed from the desired species.

Concentration:

Higher concentration of the desired components, which are initially dilute, are obtained.

Fractionation:

Two or more components are segregated into product streams of different composition.

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Separation processes

• Separation processes can involve two phases (gas and liquid, liquid and solid, gas
and solid or two immiscible liquids)

• Relatively easy to separate two phases due to density difference.

• Difficult to separate components from a single phase.

• Aim of most processes designed to separate a mixture of components is to get

the components into different phases and then to separate the phases.

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Examples of Separation processes

• Separation of blood.
• Purification of active pharmaceutical
ingredients (APIs).
• Purification of metals e.g., Au, Ag, Ti.
• Refining of crude oil.
• DNA testing.
• Purification of organic material.
• Purification of water.

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 METALS

ENERGY PRODUCTS

CRYSTALS
WATER DYES & FLAVORS
Processing sequence for producing sugar from sugar beets Refinery for converting crude oil into products

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Modes of Operation
Separation processes can be run in various modes of operation:

• Batch-wise: no flows
• Continuous: continuous flows in and out of separations
• Semi-continuous: pauses in flows.

Operations are classified as key operations and auxiliary operations:

▪ Key Operation: involves a change in chemical composition such as:

• Chemical reaction and Separation of mixtures of chemicals.
Examples: leaching, distillation, and gas absorption.

▪ Auxiliary Operation: which is required to carry out the key operations

Examples: pumps, heaters, and compressors.
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15
Mechanism of Separation

• The mixing of chemicals to form a mixture is a spontaneous and natural process.

• The inverse process (the separation of the mixture into its constituent chemical
species) is not a spontaneous process, it requires an expenditure of energy.

• A mixture to be separated usually originates as a single homogenous phase (solid,

liquid, or gas).
• If it exists as two or more immiscible phases, they must be first separated by some
mechanical means based on gravity, centrifugal force, pressure reduction, electric or
magnetic field. Then appropriate separation techniques are applied to each phase.

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• Distillation is a method of separation of liquid mixtures into its various components. It relies
on differences in volatility of the components to distribute them in varying proportions
between vapour and liquid to accomplish a separation. This difference is the driving force
basis for the separation, and it is equilibrium based.

• If two phases are at equilibrium, the temperatures, pressures and fractions of them cease to
change. Although molecules keep moving from one phase to another, but in the same rate.

• The equilibrium stage concept is applicable when the process can be constructed as a series
of discrete stages in which the two phases are contacted and then separated. The two
separated phases are assumed to be in equilibrium with each other.

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The feed mixture may be vapor, liquid or solid,
Top product
while the two or more products may differ in
(vapor phase)
composition and in phase state from each
97.6% Bz
other and / or from the feed. 3.4% Tol

Feed
liq.
50% Bz
50% Tol

Bottom product
(liquid phase)
98.6% Tol
Block Flow Diagram 1.4% Bz
for Distillation

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This simplifies the design and analysis of chemical engineering separations and unifies the basic
design principles and methods for a given separation method (unit operation). Unit Operations
is a method of analysis and design of chemical engineering processes in terms of individual
tasks/operations.

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Equilibrium conditions can be subdivided into:

Thermal: heat transfer stops and the temperature of the two phases are equal.

Tliquid = T vapor (at equilibrium)

Mechanical: the forces (usually pressure) between two phases balance.

Pliquid = pvapor (at equilibrium)

Phase equilibrium: the rate at which each species is vaporizing is just equal to the rate
at which it is condensing. Thus, there is no change in composition.

(chemical potential i)liquid = (chemical potential i)vapor

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 Ideal Solution & Raoult's Law

➢ Raoult's Law states that, for an ideal solution, the equilibrium partial pressure of a component at a
fixed temperature T equals the product of its vapor pressure (when it is pure) and its mole fraction in
the liquid: 𝑝𝐴 = 𝑃𝑂𝐴 𝑥𝐴
where
pA = equilibrium partial pressure of component-A in the gas at temperature T
POA = vapor pressure of pure liquid A at temperature T

xA = liquid-phase mole fraction of component-A at temperature T

Note: The vapor pressure is a constant at constant temperature.

Hence, from the equation, we see that Raoult's Law predicts a linear equilibrium relationship
between pA and xA.
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Ideal Binary Mixtures
• The vapour-liquid equilibrium (VLE) relationship for an ideal liquid in equilibrium with an ideal gas:
Raoult’s Law:
PA = x A PAsat

Dalton’s Law :
P =  Pi

And:
PA = y A P

Combining gives: x A PAsat

yA =
P
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Ideal Binary Mixtures

As, for a binary mixture,

y A + yB = 1

x A PAsat x B PBsat x A PAsat ( 1 - x A ) PBsat

+ = + =1
P P P P

PA = Partial pressure of component A in vapour phase (N/m2)

xA = Mole fraction of component A in liquid phase
yA
= Mole fraction of component A in vapour phase
sat
PA
= Vapour pressure of component A at system temperature (N/m2)
P
= Total system pressure (N/m2)

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 Ideal Binary Mixtures

• Rearrangement gives: P - PBsat

xA = sat
PA - PBsat

• Thus, in the case of an ideal binary mixture with liquid in equilibrium with vapour, the composition of
the liquid phase can be found if the system pressure and temperature are known, as the vapour
pressures of the two components are temperature-dependent.

• The system has two degrees of freedom, as predicted by the Gibbs Phase Rule once temperature
and pressure are defined; all other intensive variables (e.g. phase composition, density, specific
enthalpy) are also defined.

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• Problem:
• Find the liquid and vapour component mole fractions for a mixture of octane
and decane in equilibrium at a temperature of 180°C and an absolute
pressure of 2 bar (i.e. 200 kPa). The vapour pressures of octane and decane
at 180°C are 371.659 kPa and 117.296 kPa respectively. Ideal behaviour in
both phases may be assumed.

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• Solution:

• Conventionally the most volatile component is defined as component A. This will be octane in this case as it has the highest
vapour pressure.
P - PBsat 200 - 117.296
xA = sat sat
= = 0.325
PA - PB 371 .659 - 117.296

• From Raoult’s Law:

x A PAsat (0.325)(37 1.659)
yA = = = 0.604
P 200

• Thus the theory predicts a higher concentration of the more volatile component (MVC) in the vapour phase, as might be
expected.

• The mole fractions of decane in the liquid and vapour phases are 0.675 and 0.396 respectively, i.e. (1 - xA) and (1 - yA).

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Relative Volatility

• The ratio of the vapour phase partial pressure to the liquid phase mole fraction may be defined as
volatility as follows:

• Volatility of A = PA/xA
• Volatility of B = PB/xB
• Then the relative volatility (  ) of component A with respect to component B is given by:
PA x B y A xB
α = =
x A PB yB xA
yA x yA
= α A xA =
yB xB  - ( - 1) y A

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• For an ideal mixture: PA x B x A PAsat x B PAsat
α = = sat
= sat
x A PB x A x B PB PB

so that the relative volatility equals the ratio of the vapour pressures.

• Note that, for a component in an ideal mixture which follows Raoult’s Law,
Volatility of A = PA
= PAsat
xA

• Similarly, the volatility of B is numerically equal to the vapour pressure of B.

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Question:

• For the octane-decane system in equilibrium at 180°C and 2 bar described in Worked
Example 1, the liquid phase mole fraction of octane was found to be 0.325. The vapour
pressures of octane and decane at 180°C were given as 371.659 kPa and 117.296 kPa
respectively.

• Find the mole fraction of octane in the vapour phase using relative volatility, then find the
equilibrium coefficient K for octane.

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• Solution:
PAsat / PBsat
 xA (3.169)(0. 325)
• For an ideal system, relative volatility  yA =
1 + ( - 1) x A
=
1 + (3.169 - 1)(0.325)
= 0.604

yA 0.604
K= = = 1.86
x A 0.325
• In this case,  = 371.659/117.296 = 3.169
• This is the same answer as that obtained in the previous example.
• The higher the relative volatility, the easier it will be to separate two components.

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 Bubble Point

• When a liquid mixture, initially at a temperature below the boiling point, is heated at
constant pressure, the temperature at which the first bubble of vapour forms is called the
bubble point.

• This will occur when the pressure exerted by the liquid at the vapour-liquid interface equals
the system pressure. The vapour formed is in equilibrium with liquid at the bubble point. For
an ideal mixture of two liquids, at the bubble point:

x A PAsat + xB PBsat = PA + PB = P

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 Dew Point

• When a mixture of components in the vapour phase, initially at a temperature above the
condensation point, is cooled at constant pressure, the temperature at which the first drop
of condensate is formed is called the dew point.

• The liquid formed is in equilibrium with the vapour. For an ideal mixture of two condensable
components, at the dew point:

yA P yB P
sat
+ sat
= xA + xB = 1
PA PB

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 Txy Diagram for Octane-Decane at 1 Bar

Vapour - Liquid Equilibrium Diagrams

175

170

165

• This is a T-x-y diagram for the ideal system octane- 160

decane at an absolute pressure of 1 bar. 155

Temperature (C)
• The lower line is the bubble point line while the 150

upper line is the dew point line. For the pure 145

components (x and y equal to 0 or 1), the bubble

and dew point lines converge and the liquid and
140

vapour phases have the same composition (either 135

pure octane or pure decane). 130

125
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Mole Fraction of Octane (x or y)

 Vapour - Liquid Equilibrium Diagrams

• It is convenient to represent the vapour-liquid equilibrium behavior of binary systems

diagrammatically. If bubble and dew point temperatures are plotted against phase
composition at a specified pressure, a T-x-y diagram is produced a result.

• If a binary liquid mixture is charged to a batch still and distilled with continuous removal of
the vapour formed, the concentration of the more volatile component (MVC) in the still
liquor falls over time because the distillate is enriched in this MVC.

• The distillation temperature will therefore rise during the run and can be predicted using a
T-x-y diagram.

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 Vapour Liquid Equilibrium, VLE

• It is convenient to represent the vapour-liquid equilibrium behavior of binary systems

diagrammatically. In general, when a liquid mixture is partially vaporised, the vapour phase (y)
will have a different composition from the residual liquid (x) as the different components vary in
‘volatility’, a measure of the ease with which they vaporise.

• For a mixture of ethanol and water, the following are equivalent statements:
✓ Ethanol is more volatile than water.
✓ At a given temperature, Ethanol has a higher vapour pressure than water
✓ At a given pressure, ethanol boils at a lower temperature than water.
✓ When a liquid ethanol/water mixture is partially vaporised, the vapour is richer in ethanol than
the residual liquid.
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Temperature-composition diagram

• Typically, the mole fraction of the more volatile component is plotted. It is also called
McCabe-Thiele diagram.
• Pressure is constant, but the temperature is different at each point on the equilibrium
curve.
• Points on the curve represents two phases in equilibrium.
• Any point not on the equilibrium curve represents a system that may have both liquid and
vapor, but they are not in equilibrium.
• Minimum boiling azeotrope: where the liquid and vapor are of exactly the same
composition. It can be found by drawing the y = x line and finding the intersection with the
equilibrium curve.
• Below the azeotrope composition, ethanol is the more volatile component; above it,
ethanol is the less volatile component. The existence of the azeotrope sets a limit to the
distillate ethanol concentration that can be achieved when the ethanol in an ethanol-water
mixture is concentrated by distillation.

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Question:

A batch still operated without reflux is charged with a cold liquid mixture
containing 80 % octane and 20 % decane on a molar basis. The liquid is heated
to its boiling point and distillation is carried out until the octane concentration in
the liquid left in the still has fallen to 25 mole %.

Find the temperature, composition of the distillate and relative volatility  at the
start and at the end of the run.

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 Txy Diagram for Octane-Decane at 1 Bar

Solution 175

• From T-x-y diagram it can be seen that bubble point for

170

liquid containing 80 % octane is around 131.4°C. 165

• The mole fraction of octane in the first vapour formed will 160

be 0.934, i.e. an octane content of 93.4 mole %. When the 155

octane content of the still liquor has fallen to 25 mole %, the

Temperature (C)
temperature will be around 155.6°C and the distillate will 150

contain 52.9 mole % octane. 145

• Initially,  = yAxB/yBxA 140

= 0.934)(0.2)/(0.066)(0.8) = 3.54
135

130

• At end,  = yAxB/yBxA 125

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

= (0.529)(0.75)/(0.471)(0.25) = 3.37 Mole Fraction of Octane (x or y)

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 Vapour-Liquid Equilibrium Diagram for Ethanol-Water at 1
Bar

1.0

Ethanol-water
0.9

• The x-y diagram for the non-ideal system ethanol- 0.8

water at 1 bar. It can be seen that there is a high

Mole Fraction of Ethanol in Vapour Phase y

0.7

relative volatility  at low ethanol concentrations, but

 decreases with rising ethanol content until at 0.6

around 89 mole % ethanol the y = x line and

equilibrium lines converge and  becomes equal to 1.
0.5

The mixture at this point is a minimum boiling point 0.4

azeotrope.
0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mole Fraction of Ethanol in Liquid Phase x

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 Vapour-Liquid Equilibrium Diagram for Ethanol-Water at 1
Bar

1.0

Question: 0.9

0.8
Find the relative volatility  of ethanol

Mole Fraction of Ethanol in Vapour Phase y

with respect to water for liquid 0.7

ethanol-water mixtures containing 0.6

10, 40 and 80 mole % ethanol at 1
bar. 0.5

0.4

0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mole Fraction of Ethanol in Liquid Phase x

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Solution

From x-y diagram for ethanol-water at 1 bar

At 10 % ethanol,  = yAxB/yBxA = (0.44)(0.9)/(0.56)(0.1) = 7.07

• At 40 % ethanol,  = yAxB/yBxA = (0.62)(0.6)/(0.38)(0.4) = 2.45

• At 80 % ethanol,  = yAxB/yBxA = (0.82)(0.2)/(0.18)(0.8) = 1.14
• The results suggest that it becomes more difficult to separate ethanol and water by
distillation as the ethanol concentration increases.

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 Azeotropes
• If a mixture of two or more components has a bubble
point which is either higher or lower than the bubble
points of any of the pure components, the mixture is an
azeotrope.

• Minimum boiling azeotrope: where the liquid and vapor

are of exactly the same composition. It can be found by
drawing the y = x line and finding the intersection with
the equilibrium curve.

• Below the azeotrope composition, ethanol is the more

volatile component; above it, ethanol is the less volatile T-x-y diagram for the
component. The existence of the azeotrope sets a limit minimum boiling point
to the distillate ethanol concentration that can be azeotropic
achieved when the ethanol in an ethanol-water mixture is
concentrated by distillation.
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If a mixture of two or more components has a
bubble point which is either higher or lower than
the bubble points of any of the pure components,
the mixture is an azeotrope. For a binary system,
the T-x-y diagram will show either a minimum or
maximum temperature at the azeotropic point.
Hence azeotropes can be characterized as either
minimum boiling point azeotropes or maximum
boiling point azeotropes.

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• From the equilibrium curves, we see
that the greater the distance between
the equilibrium curve and the diagonal
line (where y = x), the greater the
difference in liquid and vapor
compositions and therefore the easier
the separation by distillation.

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• The larger the value of α above 1.0, the greater the
degree of separability, i.e., the easier the separation.
Recall that when a system has reached equilibrium, no
further separation can take place.

• The net transfer rate from vapor to liquid is exactly

balanced by the transfer rate from liquid to vapor.

• Separation by distillation is only feasible within the region

bounded by the equilibrium curve and the 45o diagonal
line.

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