Chemical separation processes

Objective:
take a mixture of components and
produce one or more products with
desired composition/purity
n1
A B
- A and B an be somehow different:
- boiling points
A+B - size
- polarity
zF
- etc.
B A
n2
 UNIT 1
DISTILLATION
 Lesson Outcomes
• Student should be able:
– Briefly explain the concept closed and open
system in distillation process.
– Calculate composition more volatile component in
liquid, x and in vapor, y and also relative
volatility,α
– Draw equilibrium diagram and boiling point
diagram.
TOPIC 1: DISTILLATION

Vapor – Liquid equilibrium of pure Liquid

• Mostliquid can change forms to gas phase or vapor phase.

These phase transformation process are called evaporation.

•The tendency of a liquid to change form to gas is called

volatility (α ).

•At the same temperature and pressure, different liquids have

different evaporation rate because they have different
volatility.

•Liquid that boil at higher temperature are normally less

volatility ( ↓ volatility) than those liquids that boils at lower
temperature.
Closed System: An ordinary Binary Liquid Mixture
 Fora closed system, and ordinary binary mixture
evaporates and keeps evaporating.

At any time, more of vapor A is present than B

because A vaporize faster than B.

Vapor B condense at a faster rate than vapor A

because B is a high boiler.

Evaporation and condensation processes keep going

and the composition of vapor and liquid keep changing.

When the rate of evaporation exactly matches the rate

of condensation, the system has reached a dynamic
equilibrium state.
Equilibrium State

At this state, the compositions of vapor and liquid

phase do not change any longer.

Rate of evaporation A = Rate of Condensation A

Rate of Evaporation B = Rate of Condensation B

In other word:

Phase Equilibrium: Exist when 2 or more phase are

kept in contact with each other for along enough period
of time

 So that all compositions of all phase stop changing.

 Vapor – Liquid Equilibrium of an ordinary
binary liquid mixture
 A binary liquid mixture consist of two different liquids.
Binary mixture an ordinary defined as:
- A mixture consisting as two component ( A & B) which mix
uniformly at all proportion resulting in a homogenous phase.

Example:
If you mixed Ethanol and water you will get binary mixture.

Can be classified as:

1) Homogenous – one continuous phase ( mix uniformly)
Example: Ethanol and water.
2) Non Homogenous – Mixture not mix uniformly.
Example : Chloroform and water.
 Liquid: Vapor pressure and Boiling Point
 Vapor pressure is dependent on two factor:
1) Temperature of the liquid
2) Nature of the liquid

 As the temperature of the liquid is raised, the vapor

pressure increase because the average kinetic energy of the
molecules is increased causing more of them to escape from
the liquid.
 When the vapor pressure has increased until it equals the
pressure of the atmosphere above it, the liquid boils.
 The temperature at which the vapor pressure equals exactly
one atmosphere is called the normal boiling point.
• Each liquid has a unique pattern of vapor pressure behavior.
• Liquid , which have a relatively high vapor pressure, evaporate easily and
are said to be volatile.
• In comparing two liquids at a given temperature, the more volatile liquid
will have a higher vapor pressure.
• As consequence of its higher vapor pressure the more volatile liquid will
boil at lower temperature.

 Separation of components from a liquid mixture via

distillation depends on:

1) the differences in boiling points of the individual

components.

2) the vapor pressure characteristics of the mixture.

 Summary: Some important points regarding vapor
pressure:
• Vapor pressure is related to boiling.
• A liquid is said to ‘boil’ when its vapor pressure equals the surrounding
pressure.
• The ease with which a liquid boils depend on its volatility.
• Liquid with high vapor pressure (volatile liquid) will boil at lower
temperature.
• The vapor pressure and hence the boiling point of a liquid mixture
depends on the relative amounts of the compositions in the mixture.

In this study consider:

A – Liquid high vapor pressure (low b.p)

B – Liquid low vapor pressure (high b.p)
 Thermodynamic considerations and phase
equilibria: Binary fluids boiling point diagram
Boiling point diagram shows
T how the equilibrium
Vapor compositions of the
Tb(B) Saturated vapor
components in a liquid mixture
VLE line/dew point line vary with temperature at a fixed
pressure.
Saturated liquid
line/buble point line Tb(A) Consider an example of a
liquid mixture containing 2
component ( A and B).
Liquid

V
x* y* xA T, P
L
5 separated region:

 Saturated vapor line/ Dew point line

- is the temperature at which the saturated vapor starts
to condense.

 Saturated liquid line/ Boiling point line

- is the temperature at which the liquid starts to boil.

 Vapor – Liquid Equilibrium region (VLE)

- the region enclosed in b/w upper dew point line and
lower bubble point line is the region where vapor and
liquid coexist in dynamic phase equilibrium.
- This region is of utmost importance in distillation.
 Lets consider a binary mixture AB, where B is a heavy component (high boiling
point) and A is a light component (low boiling point). A T-x phase diagram of AB
mixture, where x is a mole fraction of component A might look like this at some
constant pressure P.

This phase diagram can be also transformed in y-x diagram where composition of
vapour phase in terms of mole fraction of component A is plotted as function of the
liquid phase composition. This diagram known as Equilibrium curve/diagram

T
Tb(B) yA T4
V
T1 T3

T2

T3 T2
T4 y=x

L Tb(A)
T1

x1 x2 x3 y1 x4 y2 y3 y4
xA xA
Binary fluids: Examples

Benzene-toluene binary mixture

 Equilibrium Curve/Diagram
 Equilibrium curve shows the relationship between
compositions of residual liquids and vapor that are in dynamic
phase equilibrium.
 In distillation processes which involves many vaporization
stages, where equilibrium occurs in each of these stages.
 Very useful in calculations to predicts the number of ideal
stages required for a specified distillation process.
 Determination of vapor phase equilibrium data (VLE) has
done by experiments.
 We would also predict the equilibrium data by calculations
using Raoult’s Law and Dalton’s Law.
 Roult’s Law & Dalton Law’s
Calculation Compositions of liquid & vapor

PA = xA . P ◦ A Roult’s law states that:

- The partial pressure of a
P◦A= Vapor pressure of pure A at
the temperature composition in the vapor phase is
equal to the mole fraction of the
PT = P +P component in the liquid phase
A B

Dalton’s Law
PA = yA . P T - For amixture of different gases inside
a closed container, Dalton’s Law
Where:
states that the resultant total
PA = partial pressure of A in
vapor phase pressure of the container is the
xA = mol fraction A in liquid phase combination of partial pressure of
yA = mol fraction A in vapor phase each of the all the gases that make
P◦A = partial pressure of A in vapor up the gas mixture.
phase
P◦A = partial pressure of A in vapor
phase
Manipulate equations Dalton’s
& Roult’s Law

You will get: If given : PT, P◦ A, P◦ B

 We can calculate equilibrium
xA = (PT – P◦ B / (P◦ A – P◦ B) compositions of the vapor and
liquid at the temperature:

AND
 Then we can construct:

1) Boiling point diagram of the

yA = xA . P◦ A
system by plotting x versus
PT temperature.
2) Equilibrium diagram by plotting
x versus y
• This particular VLE plot shows a binary mixture that has a
uniform vapour-liquid equilibrium that is relatively easy to
separate.
• The next two VLE plots below on the other hand, shows non-
ideal systems which will present more difficult separations.
We can tell from the shapes of the curves and this will be
explained further later on.
 Assigment 1
• Find Information about:

Azeotropic system/distillation
 Relative Volatility (α AB)
 Separations of components by distillation process depend on the
differences in volatilities of components that make up the solution to be
distilled.
 The greater is the differences in their volatilities; the better is the
separation by heating ( distillation). Conversely if their volatility differ only
slightly, the separation by heating becomes difficult.
 One way to measure the difference in volatility of components in a binary
solution is by calculating the relative volatility of component A to B; α AB
 Relative volatility of A to B; α AB measures how many times component A is
more volatile than component B.
 The value of α AB = unity (1) means that component A is as volatile as B
and the heating separation by heating becomes impossible.
۞ The greater the value of αAB, the better and
easier is the separation by heating.

۞ Relative volatility of A to B is expressed

mathematically as;

αAB = yA / xA
yB / xB

= yA . xB
yB . xA
1) Calculate the vapor and liquid compositions in equilibrium at 95 ◦C
(368.2 K) for benzene – Toluene using the vapor pressure from table 1.0 at 101.32
kPa.

VAPOR PRESSURE
Temperature Benzene Toluene
K C kPa mm Hg kPa mm Hg
353.3 80.1 101.32 760
358.2 85 116.9 877 46.0 345
363.2 90 135.5 1016 54.0 405
368.2 95 155.7 1168 63.3 475
373.2 100 179.2 1344 74.3 557
378.2 105 204.2 1532 86.0 645
383.8 110.6 240.0 1800 101.32 760

2) Using data above:

a) Boiling point diagram

b) Plot Equilibrium curve ,
c) calculate the relative volatility for n-Benzene – Toluene binary mixture
at 1 atm.
DISTILLATION UNIT
 Lesson Outcomes
• Student should be able:
– Briefly explain the concept Distillation Column
– Apply the operating line equation of enriching,
stripping and feed column to calculate number of
stages/equilibrium in distillation process.
 Distillation processes

Distillation is a process where a Va, ya

feed mixture of two or more
La, xa=xd=y1=ya
condenser
components is separated into
products, of compositions different Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
from the feed. This process takes Ln xn
Vn+1
advantage of the differences in F, zf yn+1

distribution of components between

the vapour and liquid phase. Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

The feed is material is introduced Va, ya

at one or more points along the
La, xa=xd=y1=ya
condenser
column.
Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
Liquid runs down the column from Ln xn
Vn+1
tray to tray, where as vapour is F, zf yn+1

ascending along the column.

Lm-1 xm-1
Vm ym
At each tray vapour and liquid Lm xm Bottom product B, xb
contact and mix with each other Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

Liquid at the bottom of the column Va, ya

is partially vaporized in a heated
La, xa=xd=y1=ya
condenser
reboiler.
Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
The boil-up is send back to the Ln xn
Vn+1
column. F, zf yn+1

The rest is withdrawn as bottoms, Lm-1 xm-1

Vm ym
or bottoms product Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

Vapour at the top of the column is Va, ya

cooled and condensed in the
La, xa=xd=y1=ya
condenser
overhead condenser.
Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
Part of this liquid is returned back Ln xn
Vn+1
to the column and the rest is F, zf yn+1

withdrawn as distillate or overhead

product Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

At each stage of the column two Va, ya

phases come in contact with each
La, xa=xd=y1=ya
condenser
other, mix, approach thermal and
composition equilibrium to the Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
extent which depends on the Ln xn
Vn+1
efficiency of the contact stage F, zf yn+1

Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Lin,xin Vout,yout Vm+1 ym+1
boiler
Vb, yb

Lb, xN
Lout,xout Vin,yin
Types of trays

1. Sieve plates

2. Bubble-cap plates

3. Valve plates
Types of trays
 Definition of a stage in a process

Lin,xin Vout,yout A single stage is a device or a subunit of the process,

where two (or more) phases of a different composition
come in contact with each other, exchange and leave
Lout,xout Vin,yin with new compositions

- Mass balance
• Overall Lin  Vin  Lout  Vout
• Components Lin xin  Vin y in  Lout xout  Vout yout

- Energy balance
Lin,hin Vout,hout Q
Lin hin  Vin hin Q  Lout hout  Vout hout
Lout,hout Vin,hin
 Equilibrium stage processes

Lin,xin Vout,yout

Streams leaving the stage are in thermodynamic

equilibrium with each other
Lout,xout Vin,yin

Streams coming to the stage: not in equilibrium

Va, ya
La, xa=xd=y1=ya
condenser The idea is then to consider a
Ln-1 xn-1
hypothetical column, composed
Vn yn
R=La/D Overhead product D, xd of equilibrium stages
Ln xn
Vn+1
F, z f yn+1

This idealistic design can be

Lm-1 xm-1
Vm ym converted to the actual design via
Lm xm
Vm+1 ym+1
Bottom product B, xb analysis of tray efficiency
boiler
Vb, yb

Lb, xN
 Distillation processes

The lighter component tends to Va, ya

accumulate in the vapour phase
La, xa=xd=y1=ya
condenser

The heavier component tends to Ln-1 xn-1

Vn yn
R=La/D Overhead product D, xd
accumulate in the liquid phase Ln xn
Vn+1
F, zf yn+1

Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

In general, the overall separation Va, ya

process depends on:
La, xa=xd=y1=ya
condenser

- relative volatilities Ln-1 xn-1

Vn yn
R=La/D Overhead product D, xd
Ln xn
Vn+1
- number of contacting F, zf yn+1

stages
Lm-1 xm-1
Vm ym
- ratio of liquid and Lm xm Bottom product B, xb
vapour flowrates Vm+1 ym+1
boiler
Vb, yb

Lb, xN
 Distillation processes

If the feed is introduced at one point, it Va, ya

divides the column into a rectifying
La, xa=xd=y1=ya
condenser
and stripping sections
Ln-1 xn-1
Vn yn
R=La/D Overhead product D, xd
But usually there are multiple feed Ln xn
Vn+1
location and various side streams F, zf yn+1

Lm-1 xm-1
Vm ym
Lm xm Bottom product B, xb
Vm+1 ym+1
boiler
Vb, yb

Lb, xN
Distillation process design

Step 1: Thermodynamics data and methods to predict equilibrium

phase compositions

Step 2: Design of equilibrium stage separation

• Design problem type 1: To determine the number

of equilibrium stages required to accomplish the
desired separations

• Design problem type 2: Given a particular column

design, determine separation that can be accomplished

Step 3: Develop an actual design by applying the stage efficiency analysis

to equilibrium stage design
Design of equilibrium stage distillation: Binary
Mixtures Review
Va, ya

Ln, xn=xd
condenser

Ln-1 xn-1
Vn yn Overhead product D, xd

Ln xn
Vn+1 yn+1

F, xf

Lm-1 xm-1
Vm ym

Bottom product B, xb
Lm xm
Vm+1 ym+1

Vb, yb boiler

Lb, xN
 Operating lines
Va, ya
Rectifying section

La, xa=xd=y1=ya
condenser

Ln-1 xn-1
Overhead product D, xd
Vn yn
R=La/D
Ln xn
Vn+1 yn+1

F, z f

Lm-1 xm-1
Vm ym

Bottom product B, xb
Lm xm
Vm+1 ym+1

Vb, yb boiler

Lb, xN
 Operating lines
Ln D
Vn 1 yn 1  Ln xn  Dx D  yn 1  xn  xD
Vn 1 Vn 1

This equation is a straight line (V=const, L=const, L/V=const) if:

- Two components have similar and constant molar

enthalpies of vaporization (latent heats)

- Component sensible enthalpies changes and heats of mixing

are negligible (compared to latent heats)

- The column is well insulated (adiabatic)

- Pressure is uniform throughout the column

Operating lines

Va, ya
L D
yn 1  xn  xD La, xa condenser
V V Overhead product D, xd
R=L/D
Ln xn Vn+1 yn+1

L L L L/ D R
R ;    Reflux ratio
D V L  D L / D  D / D R 1

R 1
yn 1  xn  xD
R 1 R 1
Operating lines

R 1
yn 1  xn  xD
R 1 R 1
y

slope=R/(R+1)

1
xD
R 1

xD
x
 Operating lines
Va, ya

La, xa
condenser

Ln-1 xn-1
Overhead product D, xd
Vn yn
R=La/D
Ln xn
Vn+1 yn+1

F, z f

Lm-1 xm-1
Stripping section

Vm ym

Bottom product B, xb
Lm xm
Vm+1 ym+1

Vb, yb boiler

Lb, xN
Operating lines

L xm  V ym1  BxB Lm xm
Vm+1 ym+1
Bottom product B, xb
boiler

L B
yn 1  xm  xB y

V V
L
slope= V

yB

xB x
Operating line equation: Stage-by-stage

La, xa Va, ya

y L1, x1
Plate 1

ya Plate 2

Plate 3

x1 xa
x
Operating line equation: Stage-by-stage

La, xa Va, ya

y L1, x1
Plate 1

ya Plate 2

Plate 3

x1 xa
x
Operating line equation: Stage-by-stage

La, xa Va, ya

y L1, x1 V2, y2
Plate 1

ya Plate 2

Plate 3

Using the operating line equation we can

calculate y2 from x1. This step is depicted
by think green line in the graphs.

This process can be continued to

calculated the number of theoretical
x1 xa stages. This method of graphical
x construction of theoretical stages is called
McCabe Thiele method
 Effect of feed condition
Condition of the feed – by quantity q
Defined as:
q = heat needed to vaporize 1 mol of feed at entering condition
Molar latent heat of vaporization

for case subcooled liquid feed

Hv = enthalpy of feed dew point

 H  H  c
HL = enthalpy of feed boiling point
(TB  TF ) TF = inlet feed temperature
q
v L pL
TB = Boiling point of feed
Hv  HL
For case partially vaporized feed

q = 1 - fraction vapour
= fraction liquid
 L L
Feed stage considerations q
L V
F
L V L V

F F F

dew point
bubble point
q=1 vapour feed q=0
liquid feed

L V L V L V

F F F

subcooled superheated partially vaporized

liquid feed
q>1 vapour feed
q<0 feed 0<q<1
Feed stage considerations
F
L V
L  L  qF  L  L  F
V  V  (1  q) F  V  V  (1  q) F
L V

Vy  Lx  Dx D rectifying section

V y  L x  BxB stripping section

D
y(V  V )  ( L  L ) x  DxD  BxB F

FzF B
xF
q x
q 1 1  q
Feed line equation*
 y q>1
Feed line behavior
q=1
q xF
y x 0<q<1
q 1 1  q
q=0
x=zf

q<0

x
Complete picture

R 1
yn 1  xn  xD
R 1 R 1
y
q zF
y x y1
q 1 1  q

L B
yn 1  xm  xB
V V zf

1 yB
xD
R 1
xB xN zf xD
x
Complete picture

R 1
yn 1  xn  xD
R 1 R 1
y
L B
yn 1  xm  xB y1
V V
q zF
y x
q 1 1  q zf

yB

xB xN zf xD
x
A distillation column operating at 1 atm is to be designed for separating an ethanol-water mixture. The
feed is 20 mole% ethanol and the feed flow rate is 1000 kg-mole/hr of saturated liquid. A distillate
composition of 80 mole% ethanol and a bottoms composition of not more than 2 mole% ethanol are
desired. The reflux ratio is 5/3.

Determine:
(a) the total number of equilibrium stages required
(b) the optimum feed plate location
(c) the distillate and bottoms flow rates in kg-mole/hr

Equilibrium data for ethanol-water system at 1 atm pressure are in Table E-4 given below:
SOLUTION
Analysis of
Design:
Limiting cases

R=L/D
slope=R/(R+1)

xD
x
Limiting cases

R=L/D

slope=R/(R+1)

x
 Total reflux

Total reflux=Minimum number of stages

D=0
y
F=0 R=L/D=∞
y1
L/V=1
Ln  D  Vn 1
Ln  Vn 1
B=0
zf
Total reflux
R 1
yn 1  xn  xD
R 1 R 1 yB
If R=L/D= ∞ then R/(R+1)=1; also L=V

xB xN zf xD
yn1  xn x
 Total reflux

Total reflux=Minimum number of stages

D=0
y
F=0 R=L/D=∞
y1
L/V=1
Ln  D  Vn 1
Ln  Vn 1
B=0
zf
Total reflux
R 1
yn 1  xn  xD
R 1 R 1 yB
If R=L/D= ∞ then R/(R+1)=1; also L=V

xB xN zf xD
yn1  xn x
Minimum number of stages

a) Graphical methods y

D, xD

F, z R=L/D

B, xB
xB xD
x

b) Short cut methods: Fenske Equation

Fenske Equation
Under the total reflux condition: operating line equations become:

yn1  xn
ym1  xm
Consider a relative volatility coefficient for a binary mixture of A and B:

y A / xA y y
 AB    AB B  A
y B / xB xB x A
For a binary mixture, yA+yB=1, and xA+xB=1, so skipping the A, B subscripts and rewriting everything
for the light component A:

1 y y
 AB 
1 x x
 Fenske Equation

1 y y
 AB 
1 x x
For a particular stage n+1:

1  yn 1 yn 1 yn 1 xn 1
 n 1, AB     n 1, AB
1  xn 1 xn 1 1  yn 1 1  xn 1
At the same time: yn1  xn
xn xn 1
So   n 1, AB
1  xn 1  xn 1
Fenske Equation

xn xn 1
  n 1, AB
1  xn 1  xn 1

xD x1
 1, AB
1  xD 1  x1

x1 x2
  2, AB
1  x1 1  x2

xD xn 1
 1, AB 2, AB  n 1, AB
1  xD 1  xn 1
Fenske Equation

xD xB
 1, AB 2, AB  N 1, AB
1  xD 1  xB

xD xB
 ( ) N min 1

1  xD 1  xB

ln[ xD (1  xB ) / xB (1  xD )
N min  1
ln  AB
Fenske equation
Limiting cases: minimum reflux

R=L/D
slope=R/(R+1)

xD
x
Limiting cases: minimum reflux
If we decrease the reflux ratio, then

R=L/D

slope=R/(R+1)

x
Limiting cases: minimum reflux

If we decrease the reflux ratio, then

y
q zF
y x y1
q 1 1  q

R 1
yn 1  xn  xD
R 1 R 1 zf
L B
yn 1  xm  xB
V V yB

xB xN zf xD
x
Limiting cases: minimum reflux

If we decrease the reflux ratio, then we

are arriving at a condition where both
the rectifying, stripping and feed line y
intersect at the equilibrium line.
y1

In order for this process to take place we

need an infinite number of plates

zf

The minimum reflux

ratio condition
yB

xB xN zf xD
x
 Limiting cases: minimum reflux

R 1
yn 1  xn  xD
R 1 R 1 y
y1

At this point: xn=x* and yn+1=y*

y*
Rmin 1
y*  x* xD zf
Rmin  1 Rmin  1
xD  y *
Rmin  yB
y *X *
xB xN zf xD
x* x
A plant must distill a mixture containing 60 mole % benzene and the
rest is toluene in order to give a product of 93 % purity.
The feed enters as an equilibrium mixture of 30 % vapor and 70 percent
liquid. The value of reflux ratio is twice of the minimum. The
equilibrium diagram for Benzene-toluene at 1 atm. is given to you
before ( refer your example 1):

Determine:
•The value of q
•The value of minimum reflux ratio and reflux ratio R
•The number of theoretical plates
•The position of feed tray.
•If the overall efficiency (Eo) is given as 70 %, What would the real tray
be?