INTRODUCTION

TYPES OF SEPARATION
PROCESSES

Separation
Separation
Separation
Separation
Separation
Gradient

by
by
by
by
by

Phase Creation
Phase Addition
Barrier
solid
External Field or

SEPARATING AGENTS
ENERGY SEPARATING AGENTS
MASS SEPARATING AGENTS
DISADVANTAGES:
Need for an additional separator to recover
the MSA for recycle.
Need for MSA make up
Possible MSA product contamination
More difficult design procedures

SEPARATION PROCESSES

DISTILLATION
ABSORPTION/STRIPPING
LIQUID LIQUID EXTRACTION
SOLID LIQUID EXTRACTION

Distillation

Gibbs Phase Rule and

Equilibrium
Phase Rule
Degree of Freedom
F=CP+2
Example: gas-liquid system of CO2 air
water
What is the degree of freedom?
What variables can be set to define the
system?

EQUILIBRIUM VS STEADY
STATE
EQUILIBRIUM
All properties of the system are identical in
all phases and on the macroscopic scale. No
further changes in these properties with time
and no differences in properties within the
system
STEADY STATE
No changes of properties with time only but
there can be differences in any properties
within the system.

RELATIVE VOLATILITY
Mole fraction in vapour and liquid
phase

must be greater than 1.0 for

separation to be possible.
If Raoults Law applies,

RAOULTS LAW
VAPOR
LIQUID equilibrium relation

To establish equilibrium, what factors can be

set?
Assumptions:
The gas phase is an ideal gas
The liquid phase is an ideal mixture

Applicable to solutions where the components

are almost the same structure: benzenetoluene, hexane-heptane, methyl alcohol ethyl
alcohol
Daltons Law: PT = PA + PB
Equilibrium relations:

VAPOR PRESSURE
Define:
Vapor pressure
Volatile liquids
Bubble point
Dew point

AZEOTROPIC SYSTEMS
WHAT IS AN AZEOTROPE?
Point at which mole fraction in vapour is
equal to mole fraction in liquid
Azeotropic-forming mixtures exhibit either
minimum or maximum boiling points at
some composition with deviations from
Raoults Law.
Vapor and Liquid compositions are identical
thus relative volatility is equal to 1.( What is
the implication of this?)

EQUILIBRIUM BOILING POINT

DIAGRAM
The ease for a liquid to boil depends
on its volatility

BINARY VAPOR LIQUID

SYSTEMS
Experimental vapour-liquid
equilibrium data for binary systems
are represented in terms of four
intensive variables: T, P, y and x.
Types of equilibrium data
Isothermal: P y x
Isobaric: T y x

If P and T are fixed phase

compositions are completely defined
Separation factor is fixed (relative

SINGLE-STAGE EQUILIBRIUM CONTACT FOR GASLIQUID SYSTEM

Liquid and vapor are made in contact

and allow to attain equilibrium. The
liquid and vapor will come out of the
contacting system in equilibrium.
V1, y1

V2, y2

Lo,
xo

L1, x1

OMB:
Component Balance:

RELATIVE VOLATILITY (> 10,000) ALMOST PERFECT SEPARATION IN A SINGLE S

DISTILLATION
Single stage or still distillation that
does not involve rectification
Equilibrium or Flash Distillation
Simple Batch or Differential Distillation
Steam Distillation

Equilibrium or Flash
Distillation

ed is partially vaporized to give a vapour richer in the more volatile comp

an the remaining liquid. (flashed adiabatically to a lower pressure)

Simple Batch or Differential

Distillation

L1 = L 2 + V
x1 L1 = x2L2 + (L1 -L2)y2v

There is no reflux,
At any instant, vapour leaving the still pot
with composition, yD is assumed to be in
equilibrium with the liquid in the still.

EXAMPLE FOR DIFFERENTIAL

DISTILLATION
A mixture of 100 moles containing
50 mol% n-pentane and 50 mol% nheptane is distilled under the
differential conditions at 101.3 Kpa
until 40 moles is distilled. What is the
average composition of the total
vapor distilled and the composition of
the liquid left?

x 1.0 0.867 0.594 0.398 0.254 0.145

Given below is the equilibrium data for n0.059 0
pentane.
y 1.0 0.984 0.925 0.836 0.701 0.521

Plate-to-Plate
Calculations
Sorel Method
Without the assumption of constant molal overflow
Uses material and enthalpy balances with equilibrium
calculation to determine flow of liquid and vapor for the
plate, temperature of the plate, and the composition of
each stream for the plate
Rigorous and tedious
Assumes operation pressure, reflux ratio, temperature or
enthalpy of the reflux stream, and the use of total
condenser.

Lewis Method
Assumes constant molal overflow (CMO) equimolal
latent heats and heat capacities and no heat of mixing
The reflux Lo is saturated liquid.

Plate-to-Plate
Calculations
Graphical Methods for Binary Systems
Ponchon-Savarit
Uses H-concentration diagram
No CMO assumption
Mc-Cabe-Thiele
CMO equimolal latent heats and heat
capacities and no heat of mixing
The reflux Lo is a saturated liquid.
Column pressure is constant.
Reflux ratio is assumed.

McCabe-Thiele Method

Constant Molal Overflow

(CMO)

Distillation processes

Distillation is a process where

a feed mixture of two or more
components is separated into
products, of compositions
different from the feed. This
process takes advantage of the
differences in distribution of
components between the
vapour and liquid phase.

Va, ya
condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, zf

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

The feed is introduced at one

or more points along the
column.
Liquid runs down the column
from tray to tray, whereas
vapour is ascending along the
column.
At each tray vapour and liquid
contact and mix with each
other

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, zf

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

Liquid at the bottom of the

column is partially vaporized in
a heated
reboiler.

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

The boil-up is send back to the

column.
The rest is withdrawn as
bottoms, or bottoms product

F, zf

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

Vapour at the top of the

column is cooled and
condensed in the overhead
condenser.

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

Part of this liquid is returned

back to the column and the
rest is withdrawn as distillate
or overhead product

F, zf

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

At each stage of the column

two phases come in contact
with each other, mix, approach
thermal and composition
equilibrium to the extent which
depends on the efficiency of
the contact stage

Va, ya
condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, zf

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Lin,xin

Lout,xout

Vout,yout

Vin,yin

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Definition of a stage in a process

Lin,xin

Vout,yout

Lout,xout

Vin,yin

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
with new compositions

- Mass balance
Overall
Components

Lin Vin Lout Vout

Lin xin Vin y in Lout xout Vout yout

- Energy balance
Lin,hin

Vout,hout

Lout,hout

Vin,hin

Lin hin Vin h in Q Lout hout Vout hout

Equilibrium stage processes

Lin,xin

Streams leaving the stage are in thermodynamic

equilibrium with each other
Vout,yout

Lout,xout

Vin,yin
Streams coming to the stage: not in equilibrium

Va, ya
condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, zf

R=La/D

Overhead product D, xd

The idea is then to consider a

hypothetical column, composed
of equilibrium stages

Vn+1
yn+1

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

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

This idealistic design can be

converted to the actual design via
analysis of tray efficiency

Distillation processes

Va, ya

The lighter component tends

to accumulate in the vapour
phase
The heavier component tends
to accumulate in the liquid
phase

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

F, zf

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

In general, the overall separation

process depends on:

condenser
La, xa=xd=y1=ya

- relative volatilities

Ln-1 xn-1
Vn yn
Ln xn

- number of contacting
stages
- ratio of liquid and
vapour flowrates

F, zf

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

Distillation processes

Va, ya

If the feed is introduced at one

point, it divides the column into a
rectifying and stripping
sections

condenser
La, xa=xd=y1=ya
Ln-1 xn-1
Vn yn
Ln xn

But usually there are multiple

feed location and various side
streams

F, zf

R=La/D

Overhead product D, xd

Vn+1
yn+1

Lm-1 xm-1
Vm ym

Bottom product B, xb

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

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 analysi

to equilibrium stage design

Design of equilibrium stage distillation:

Binary Mixtures Review
Va, ya
La, xa=xd
Ln-1 xn-1

Ln xn

condenser
Overhead product

Vn yn

D, x d

Vn+1 yn+1

F, zf
Lm-1 xm-1
Vm ym

Bottom product

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

B, xb

Operating lines
Rectifying section

Va, ya
La, xa=xd=y1=ya
Ln-1 xn-1

Ln xn

R=La/D

Vn yn

condenser
Overhead product

D, x d

Vn+1 yn+1

F, zf
Lm-1 xm-1
Vm ym

Bottom product

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

B, xb

Operating lines
Vn 1 yn 1 Ln xn Dx D yn 1

Ln
D

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

yn 1

Va, ya

L
D

xn
xD
V
V

La, xa
Ln xn

L
;
D

yn 1

R=L/D

Overhead product

Vn+1 yn+1

L
L
L/D
R

V L D L / D D / D R 1

R
1

xn
xD
R 1
R 1

condenser

Reflux ratio

D, xd

Operating lines

yn 1

R
1

xn
xD
R 1
R 1
y

slope=R/(R+1)

1
xD
R 1
xD
x

Operating lines
Va, ya
La, xa
Ln-1 xn-1

Ln xn

R=La/D

Vn yn

condenser
Overhead product

D, x d

Vn+1 yn+1

Stripping section

F, zf
Lm-1 xm-1
Vm ym

Bottom product

Lm xm
Vm+1 ym+1

Vb, yb
Lb, xN

boiler

B, xb

Operating lines

L xm V y m 1 Bx B

L
B
yn 1 xm xB
V
V

Lm xm
Vm+1 ym+1

Bottom product
boiler

slope=V

yB

B, xb

Operating line equation: Stage-by-stage

L a, xa
y

L1, x1

ya

Va, ya
Plate 1

Plate 2

Plate 3

x
1

x
a

Operating line equation: Stage-by-stage

L a, xa
y

L1, x1

ya

Va, ya
Plate 1

Plate 2

Plate 3

x
1

x
a

Operating line equation: Stage-by-stage

y
ya

L a, xa

Va, ya

L1, x1

V2, y2

Plate 1

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.

x
1

x
a

This process can be continued to

calculate the number of theoretical
stages. This method of graphical
construction of theoretical stages is called
McCabe Thiele method

Feed stage considerations

L

V
F

dew point
vapour feed

bubble point
liquid feed

subcooled
liquid feed

superheated
vapour feed

partially vaporized
feed

Feed stage considerations

L

L L
V V
q
1
F
F

Feed stage considerations

L

V
F

bubble point
liquid feed

subcooled
liquid feed

q>1

dew point
vapour feed

q=1

q=0

L L
F

superheated
vapour feed

q<
0

partially vaporized
feed

0<q<1

McCabe Thiele method

The condition of the feed is very important
It determines the q-line
q is the moles of liquid in stripping
section resulting from the introduction
of a mole of feed
(a) Cold feed
q>1
(b) Feed at bp
q=1
(c) Feed part vapor
0<q<1
(d) Feed at dp
q=0
(e) Feed superheated vap q<0

q = 1 + [cpV(Tbp-TF]/ cold liquid

q = - [cpV(TF-Tdp]/s/htd vapor
q = 1- f
mixed
Lm
= Ln +qF
Vm Vn = qF - F

q-line
Q is the moles of liquid in stripping
section resulting from the introduction
of a mole of feed
(a) Cold feed
q>1
(b) Feed at bp
q=1
(c) Feed part vapor
0<q<1
(d) Feed at dp
q=0
(e) Feed superheated vap q<0

Vnyq = Lnxq + Dxd

Vmyq =Lmxq Wxw
yq(Vm-Vn)=(Lm- Ln)xq(Dxd+Wxw)
Vm Vn = Lm Ln F
Lm = Ln +qF ; Vm Vn = qF
F
Derive the equation forFx
yFq = Dxd +Wxw
y = [q/(1-q)] x + x /(1-

Feed stage considerations

F

L L qF L L F
V V (1 q ) F V V (1 q ) F

Vy Lx Dx D rectifying section

V y L x Bx B

stripping section

y (V V ) ( L L ) x Dx D Bx B
q
zF
y
x
q 1
1 q

FzF
Feed line

D
F
B

q
zF
y
x
q 1
1 q
x=zf

q
zF
y
zF
zF
q 1
1 q

q>1
x

q=1

y=

Feed line behavior

0<q<1
q=0
x=zf

q<0

y=zf
x

Complete picture
yn 1

R
1

xn
xD
R 1
R 1

q
zF
y
x
q 1
1 q

L
B
yn 1 xm xB
V
V

y
y1

zf

yB
1
xD
R 1
xB xN

zf

xD
x

Complete picture
yn 1

R
1

xn
xD
R 1
R 1

L
B
yn 1 xm xB
V
V
q
zF
y
x
q 1
1 q

y
y1

zf

yB
xB xN

zf

xD
x

Limiting cases
y
R=L/D
slope=R/(R+1)

xD
x

Limiting cases
y
R=L/D

slope=R/(R+1)

Total reflux
Total reflux=Minimum number of stages
D=0
R=L/D=
L/V=1

F=0

y
y1

Ln D Vn 1
Ln Vn 1
B=0

Total reflux

yn 1

R
1

xn
xD
R 1
R 1

zf

yB

If R=L/D= then R/(R+1)=1; also L=V

yn 1 xn

xB

xN

zf

xD
x

Total reflux
Total reflux=Minimum number of stages
D=0
R=L/D=
L/V=1

F=0

y
y1

Ln D Vn 1
Ln Vn 1
B=0

Total reflux

yn 1

R
1

xn
xD
R 1
R 1

zf

yB

If R=L/D= then R/(R+1)=1; also L=V

yn 1 xn

xB

xN

zf

xD
x

Minimum number of stages

a) Graphical methods

D, xD
F, z

R=L/D

B, xB
xB

b) Short cut methods: Fenske Equation

xD

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:

AB

yA / xA
y
y
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 everythi
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:

So

yn 1 xn

xn
xn 1
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

N min

ln[ xD (1 xB ) / xB (1 xD )]

1
ln AB
Fenske equation

Limiting cases: minimum reflux

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

xD
x

Limiting cases: minimum reflux

If we decrease the reflux ratio, then

y
R=L/D

slope=R/(R+1)

Limiting cases: minimum reflux

If we decrease the reflux ratio, then

q
zF
y
x
q 1
1 q
yn 1

R
1

xn
xD
R 1
R 1

L
B
yn 1 xm xB
V
V

y
y1

zf

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
intersect at the equilibrium line.

y
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

yn 1

R
1

xn
xD
R 1
R 1

y
y1

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

y*

Rmin
1
y*
x*
xD
Rmin 1
Rmin 1
x y*
Rmin D
y * x *

zf

yB
xB xN

zf
x*

xD
x

Feed Condition

q-value

q-line

q>1

Line in second quadrant

q=1

Vertical line

0<q<1

Line in third quadrant

Saturated vapor

q=0

Horizontal line

Superheated vapor

q<0

Line in the fourth quadrant

Liquid below boiling point

(Subcooled Liquid)
Liquid at boiling point
Liquid + Vapor

(Seader and Henley, Separation Process Principles, 2 nd

ed., p 261)

Value of q
Subcooled
Liquid:

Saturated Liquid:

q=1

Partially Vaporized Feed:

Saturated Vapor:

q=0

Superheated Vapor:

Tb= bubble point temperature

Td= dew-point temperature

fL= liquid fraction in the feed

Shifting is
done the
moment
the
intersecti
on is
passed.

Reboiler and Partial

Condenser
Reboiler: Subtract 1 stage from N if
there is a reboiler.
Partial Condenser: Vapor is
withdrawn in the condenser, not all
liquid. Add 1 stage to N if the
condenser is a partial condenser.

Total Reflux

Number of theoretical plates is minimum.

Tower diameter is infinite.
Slope of OL:
OL is the 45o-line (y=x).

If relative volatility is approximately constant:

Fenske Equation

Total Reflux

Minimum Reflux Ratio

reflux ratio that will require an infinite
The

Minimum vapor flow in the tower

Minimum reboiler and condenser sizes

Pitch point (x, y) when the OLs touch

the EC or, in case of inflection in the EC,
when the OL of the rectifying section
touches the EC.

Minimum Reflux Ratio

Perfect Separation

xD=1, xB=0
No of plates in rectifying section =
No of plates in stripping section=
is evaluated at the feed condition

OPTIMUM REFLUX RATIO

Heuristics: 1.2Rm to 1.5Rm

Overall Energy Balance

QB= reboiler duty
QC= condenser duty
QL= heat loss to the surroundings

Condenser Duty
Total Condenser
If no subcooling of the condensate:

=latent heat of condensation of the overhead

vapor

Partial Condenser

Reboiler Duty