Chapter 1 - Distillation PDF

CHAPTER 1: DISTILLATION
Unit operation
CHAPTER / CONTENT
Definition & General Description of the process
Physical concept of Distillation
Vapor – liquid equilibrium relationship
Flash & Batch Distillation
Continuous / Retrification Distillation
Azeotropic Distillation
Multi – component Distillation

Definition & General Description of the process
Separating the various components of a

liquid solution
Depends upon the distribution of these

components between a vapor phase and a
liquid phase.
All components presents in both phases.
Distillation is done by vaporizing a

definite fraction of a liquid mixture in
such a way that the evolved vapor is in
equilibrium with the residual liquid.
The equilibrium vapor is then separated

from the equilibrium residual liquid by
condensing the vapor.
Physical concept of Distillation
Carried out by either two principal

method
First method: based on the production of

a vapor by boiling the liquid mixture to
be separated and condensing the vapors
without allowing any liquid to return to
the still – no reflux (Eg. Flash
distillation)
Second method: Based on the return part

of the condensate to the still under such
condition that this returning liquid is
brought into intimate contact with the
vapors on their way to the condenser –
conducted as continuous or batch process
(Eg. Continuous distillation).
VAPOR – LIQUID EQUILIBRIUM
DEFINITION
EVAPORATION – The phase transformation processes from liquid to
gas or vapor phase.
VOLATILITY – The tendency of liquid to change form to gas
VAPOR – LIQUID EQUILIBRIUM OF AN ORDINARY BINARY

LIQUID MIXTURE
PREDICTION OF VAPOR – LIQUID EQUILIBRIUM

COMPOSITIONS FOR ORDINARY BINARY MIXTURES
RELATIVE VOLATILITY OF A MIXTURE

VAPOR – LIQUID EQUILIBRIUM OF AN ORDINARY BINARY
LIQUID MIXTURE
A binary liquid mixture – consist of two different liquids. Can be classified into
homogeneous mixtures or non – homogeneous (heterogeneous) mixtures.
Low boiler liquid (A) – liquid that vaporized easily (low boiling point or high vapor
pressure)
High boiler liquid (B) – liquid which have higher boiling point or low vapor pressure
Homogeneous mixtures – mix at all proportions resulting in one continuous phase.
Heterogeneous mixtures – do not mix uniformly resulting in more than one distinct
phases.
Equilibrium curve – shows the relationship between composition of residual liquid and
vapor that are in dynamic phase equilibrium. This curve will be very useful in calculations
to predict the number of the ideal stages required for a specified distillation process.
Equilibrium mole fraction of A in vapor is larger than mole fraction of A in liquid phase.
This is expected since that A has lower boiling point than B, A would vaporize more than
B.
Raoult’s Law for ideal solution & Dalton’s Law of partial pressure can be
manipulated in order to calculate compositions of liquid and vapor, which are in
equilibrium.
Raoult’s Law – the partial pressure of a component in the vapor phase is equal to
the mole fraction of the component in the liquid multiplied by its pure vapor
pressure at that temperature.
pA  xA  PAo
p A = partial pressure of A in vapor phase
xA = mole fraction of A in liquid phase
PAo = vapor pressure of A at that temperature

For a mixture of the different gases inside a close container, Dalton’s law stated
that the resultant total pressure of the container is the summation of partial
pressures of each of all the gases that make up the gas mixture.
PT  p A  p B
Dalton also stated that the partial pressure of gas (pA) is:
p A  y A  PT
y A = mole fraction of A in vapor phase
PT = Total pressure of the system

For a mixture of the different gases inside a close container, Dalton’s law stated
that the resultant total pressure of the container is the summation of partial
pressures of each of all the gases that make up the gas mixture.
PT  p A  p B
Dalton also stated that the partial pressure of gas (pA) is:
p A  y A  PT
y A = mole fraction of A in vapor phase
PT = Total pressure of the system

Separations of components by distillation process depend on the differences in

volatilities of components that make up the solution to be distilled.
The greater difference in their volatility, the better is separation by heating

(distillation). Conversely if their volatility differ only slightly, the separation by
heating becomes difficult.
Equilibrium diagram for n-heptane n-octane mixture at 101.3 kPa
1.00
0.80
0.60
yA
y= x
0.40
0.20
0.00
0.00 0.20 0.40 0.60 0.80 1.00
xA
In figure above, the greater the distance between the equilibrium line and the 45o line,
the greater the difference between the vapor composition and a liquid composition.
Separation is more easily made.
A numerical measure of ‘how easy’ separation – relative volatility, AB.
Relative volatility, AB - ratio of the concentration of A in the vapor to the

concentration of A in the liquid divided by the ratio of the concentration B in the vapor
to the concentration of B in the liquid.
yA xA yA xA
 AB  
y B x B 1  y A  1  x A 
AB - relative volatility of A with respect to B in the binary system.
If the system obeys Raoult’s Law for an ideal system:

P x Px PA x A
yA  A A yB  B B  AB  yA 
PT PT PB 1    1x A
Separation is possible for > 1.0
For non – ideal solution, the values of change with temperature. For ideal
solution, the values of doesn’t change with temperature. For a solution that
approaches ideal solution, its would fairly constant.
Flash & Batch Distillation
FLASH (EQUILIBRIUM) DISTILLATION
SIMPLE BATCH DISTILLATION

Flash distillation – a single stage process because it has only one vaporization
stage (means one liquid phase is exposed to one vapor phase.
Flash distillation is done by vaporizing a definite fraction of a liquid mixture in

such a way that the evolved vapor is in equilibrium with the residual liquid.
The equilibrium vapor is then separated from the equilibrium residual liquid by
condensing the vapor.
Flash distillation can be either by batch or continuous
Figure 1: A typical flow chart of a continuous flash distillation

As illustrated in Figure 1, a liquid mixture feed, with initial mole fraction of

A at xF, is pre-heated by a heater and its pressure is then reduced by an
expansion valve.
At lower pressure, the hot liquid will boil at lower temperature inside a
separator drum. In contrast to that of a simple batch distillation, the evolved
vapor is allowed to attain equilibrium with remaining liquid inside the flash
drum (separator).
Now we are interested to predict the composition (x* and y*) of these vapor
and liquid that are in equilibrium with each other.
Prediction of an equilibrium composition of vapor and liquid for a flash

distillation of an ordinary binary mixture
Consider a binary liquid mixture which is to be separated by a flash distillation

process as shown in Figure 1. Binary is composed of two components; A as low
boiler (more volatile) and B as a high boiler.
Total mass balance: F  V L
Mass balance on more volatile component (A): Fx F  y * V  x * L

V L
* denote ‘at state of equilibrium xF  y *  x*  Eq. (1)
F F
Assign f to denote fraction of the feed which has been vaporized. f is defined
mathematically as:
V
f
F
And substituting f in the total mass balance:
F  V L V L
1 
F F
L L  Eq. (2)
1 f   1 f
F F
Substituting Eq. 2 into Eq. (1) to obtain:
x F  y * f  x * (1  f )
y* 
f  1x *  x F  Eq. (3)
f f
Eq. (3) called operating line equation (y = mx + c) for a flash distillation process.
Since xF and f do not change throughout the process, only y* and x* are the
variables. A straight line with a negative slope should be obtained from the
operating line. The line gives all locus point (x*, y*) that satisfy the operating line.
Figure 2: Graphical method to determine equilibrium compositions in a flash

Example 1
A liquid mixture containing 70 mol% n-heptane (A) and 30 mol% n-octane at
30OC is to be continuously flash – vaporized at the standard atmospheric pressure
to vaporize 60 mol% of the feed.
What will be the compositions of the vapor and liquid and the temperature in
the separator for an equilibrium stage?
The equilibrium data for n-heptane-n-octane mixture at 1 atm and 30OC is given
as follows:
T (K) xA yA
371.6 1.000 1.000
374.0 0.825 0.920
377.0 0.647 0.784
380.0 0.504 0.669
383.0 0.387 0.558
386.0 0.288 0.449
389.0 0.204 0.342
392.0 0.132 0.236
395.0 0.068 0.132
398.2 0.000 0.000
Solution
Basis  100 moles of liquid feed (F)

Given, xF  0.7
V  0.6100   60 moles f  V F  60 100  0.6
We want to find equilibriu m compositio ns of vapor and liquid; y * and x *
The operating line : y* 

0.6  1x *0 .7

0 .6 0 .6
y *  0.667 x * 1.167
From the intersection of the operating line and the equilibriu m curve as
shown in the graph,
equilibriu m mol fraction of n - heptane in liquid, x*  0.62
equilibriu m mol fraction of n - heptane in vapor, y*  0.76
the temperatur e of the separator at equilibriu m  378 O C
Determination of vapor-liquid equilibrium composition

for a flash distillation of n-heptane-n-octane mixture
1
y, mol fraction of n-heptane in vapor
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x,mol fraction n-heptane in liquid

Simple batch distillation which is also known as differential distillation refer to a

batch distillation in which only one vaporization stage (or one exposed liquid
surface) is involved.
Simple batch distillation is done by boiling a liquid mixture in a steam-jacketed-

kettle (pot) and the vapor generated is withdrawn and condensed (distillate) as fast
as it forms so that the vapor and the liquid do not have sufficient time to reach its
equilibrium.
The first portion of vapor condensed will be richest in the more volatile
component A. As the vaporization proceeds, the vaporized product becomes leaner
in A.
Raleigh equation for ideal and non – ideal mixtures
Consider a typical differential distillation at an instant time, t1 as shown below:
Where L = number of moles of liquid mixture in the pot

x = mol fraction of a more – volatile component (component A)
dx = infinitesimal change of mol fraction of A
Now consider that the differential distillation at certain infinitesimal time lapse
(t) at t2 where t2 = t1 + t, after an infinitesimal amount of liquid has vaporized as
shown below:
Mass balance of component A will yield:

xL  x  dx L  dL   ydL 
xL  xL  xdL  Ldx  dxdL  ydL

Cancel out Negligible
Ldx  xdL  ydL

Ldx  y  x dL
dL dx

L y  x 
Integrating both sides within limits initial t1 and final t2:
L1 x1
 1   1   1 
x1 x1
 1
  dL    dx  
L1
ln L L 2   dx ln L 1  ln L 2   dx
L2  L  x2  y  x  x 2
y  x  x 2
y  x 
 L1  x1 1 
ln   
 2  x2
L  y 
 x
dx
  Eq. (4)
Where L1 = number of moles of liquid at t1

L2 = number of moles of liquid at t2
x1 = mol fraction of A in liquid at t1
x2 = mol fraction of A in liquid at t2
Eq. (4) known as Raleigh equation – applicable for both an ideal solution (
constant) or non – ideal solution ( non - constant).
Thelnterm
L1   1  must be evaluated graphically by determining an area under
x1
  
   dx
 L2  x 2
y  x
 L1  x1 1 
the ln
graph
 L 2
of

   y  x dxversus
 x 2 
x between the limit x1 and x2.
Simplified Raleigh equation for ideal mixtures
For an ideal solution ( constant), the Raleigh equation can be simplified.
Consider a simple batch distillation process at an initial time, t1 as shown below:
L1 = number of moles of binary liquid mixture containing A and B at t1

A1 = number of moles component A in L1 at t1
B1 = number of moles component B in L1 at t1
x1 = mol fraction of A in in L1 at t1
dL = infinitesimal amount of liquid that has vaporized
dA = infinitesimal amount of A that has vaporized
dB = infinitesimal amount of B that has vaporized
We know from definitions,

 dA   dB 
yA    yB   
 dA  dB   dA  dB 
 A   B 
xA    xB   
A B  A B
Since AB is constant for an ideal mixture,

dA B

 dA  dB A  B
yA xA
 AB 
yB xB dB A

dA  dB A  B
After simplifying,
B  dA
 AB 
A  dB
Rearranging,
dB dA
  AB 
B A
Integrating within the limits of t1 and t2,

B2 A2
dB dA

B1
B
  AB  
A1
A
Since AB is constant,

B2 A2
dB dA B
 AB ln B B2  ln A AA12
 AB 
B1
B
 
A1
A 1
B  A 
 AB ln 2   ln 2   Eq. (5)
 B1   A1 
Equation 5 known as simplified Raleigh equation for simple batch distillation

which applicable for ideal solution.
Example 1
A mixture of 100 mol containing 50 mol% n-pentane and 50 mol% n-heptane is

distilled under differential (batch) conditions at 101.3 kPa until 40 mol is distilled.
What is the average composition of the total vapor distilled and the composition
of the liquid left?
The equilibrium data as follows, where x and y are mole fractions of n-pentane:
xA yA
1.000 1.000
0.867 0.984
0.594 0.925
0.398 0.836
0.254 0.701
0.145 0.521
0.059 0.271
0 0
Solution
Given L1  100 mol V(mol distilled)  40 mol
From material balance :

L1  L 2  V L 2  L1 - V  100 - 40 L 2  60 mol
Substituting into Eq. 4 ,

L 
x1 0.5
 1   100   1 

ln 1    dx
 L2  x 2 y  x 
ln
 60 
  
x2 
dx
yx
0.5
 1 
0.510   
x2 
y  x
dx

The unknown, x 2 is the composition of the liquid L 2 at the end

of batch distillation.
Solution
0.5
 1   1 
By plotting graph 
 yx

 versus x, the 
x2 
 dx value is referring
yx
to the value of area under the curve.
From the graph, area under curve  0.510 at x 2  0.277.

Composition of the liquid L 2 ,x 2  0.277.
From material balance on more volatile component,

x 1L 1  x 2 L 2 0.5  100  0.277  60
x1L1  x 2 L 2  y av V y av  y av 
V 40
y av  0.835
Average composition of total vapor distilled, y av  0.835.

Retrification (fractionation) – or stage distillation with reflux, from a

simplified point of view, can be considered to be a process in which a series
of flash – vaporization stages are arranged in a series in such manner that
the vapor and liquid products from each stage flow counter – current to
each other.
In contrast with flash dist., continuous dist. process is more suitable for
mixtures of about the same volatility and the condensed vapor and residual
liquid are more pure (since it is re-distilled).
The fractionator consists of many trays which have holes to permit the
vapor, V which rises up from the lower tray to bubble through and mixes
with the liquid, L on the upper tray and equilibrated, and V and L stream
leave in equilibrium.
During the mixing, the vapor will pick up more of component A from
the liquid while the liquid will be richer with component B. As the vapor
rises further up, it becomes richer and richer in component A but poorer
with component B.
Conversely, as the liquid falls further down, it becomes poorer with A

but richer in B. Thus we obtain a bottom product and an overhead product
of higher purity in comparison to those obtained by single – stage simple
batch or flash distillation.
Note: fractionation refers to a process where a part or whole of distillate

is being recycled back to the fractionator. The recycled distillation (known
as reflux) will supply the bulk of liquid needed to mix with vapor.
Where;
F = Feed flow rate (kmols/hr)
xf = m.v.c. composition of feed
(mole fraction or mol percentage)
V = Vapour flow rate (kmols/hr)
L = Reflux flow rate (kmols/hr)
D = Top Product flow rate
(kmols/hr)
xD = m.v.c. composition of top
vapour stream, top product, and
reflux (mole fraction or mol
percentage)
V" = Reboiler exit stream flow rate
(kmols/hr)
W = Bottom-product flow rate
(kmols/hr)
xW = m.v.c. composition of bottom
product and feed to reboiler (mole
fraction or mol percentage)
Consider of fractionating column of N plates, where the condenser and

reboiler are counted as ‘plates’. A typical ‘nth’ plate has the streams shown
below associated with:
The feed stream is introduced on some intermediate tray where the liquid
has approximately the same composition as the feed. The part of column
above feed point – rectifying section; the lower portion – stripping section.
With constant molal overflow assumption:

Ln-1 = Ln = Ln+1 = ... etc. Vn-1 = Vn = Vn+1 = ... etc.
Conditions for Constant Molal Overflow
Heat losses negligible (achieved more easily in industrial columns)
Negligible heat of mixing
Equal or close heats of vaporisation

Number of Plates Required in a Distillation Column
Four streams are involved in the transfer of heat and material across a
plate, as shown in figure above:
Plate n receives liquid Ln+1 from plate n+1 above, and vapor Vn-1 from plate
n-1 below.
Plate n supplies liquid Ln to plate n-1, and vapor Vn to plate n+1.
Action of the plate is to bring about mixing so that the vapor Vn, of
composition yn, reaches equilibrium with the liquid Ln, of composition xn.
CALCULATION FOR NUMBER OF PLATES
NUMBER OF PLATES BY LEWIS – SOREL METHOD
NUMBER OF PLATES BY Mc – CABE & THIELE

From figure above, binary feed F is distilled to give a top product D and a
bottom product W, with xf , xd , and xw as the corresponding mole fraction of
more volatile component.
The vapor Vt rising from top plate is condensed, and part is run back as
liquid at its boiling point to the column as reflux, the remain withdrawn as
product.
A material balance above plate n c gives:

A material balance above plate n gives:
Vn  Ln 1  D ynVn  Ln 1 xn 1  Dxd (M.V.C Balance)

Ln 1 D
yn  xn 1  xd
Vn Vn
Since moles of liquid overflow are constant, Ln may be replaced by Ln+1

and:
 Eq. 6 
Ln D
Vn Vn
A material balance for bottom to above plate m (indicated by loop II) and
note that Lm = Lm+1.
Lm  Vm  W ymVm  Lm xm 1  Wx w (M.V.C Balance)
Eq. 7 
Lm W
ym  xm 1  xw 
Vm Vm
Eq. 6 (above feed point) and Eq. 7 (below feed point) – operating lines.
Equilibrium data are used to find the composition of the vapor above the
liquid, and the enrichment line to calculate the composition of liquid on the
next plate.
Example
A mixture of benzene and toluene containing 40 mole% benzene is to be

separated to give a product of 90 mole% of benzene at the top, and a bottom
product with not more than 10 mole% of benzene. The feed is heated so that it
enters the column at its boiling point, and the vapor leaving the column is
condensed but not cooled, and provides reflux and product.
It is proposed to operate the unit with a reflux ratio of 3 kmol/kmol

product. It is required to find the number of theoretical plates needed and the
position of entry for the feed. The equilibrium diagram for operating at 1 bar
pressure is shown in Figure below.
Solution
Feed : 40 mol% benzene (A), xf = 0.40

Product : 90 mol% benzene (A), xd = 0.90
Bottom : 10 mol% benzene (A), xw = 0.10
Do a basis: 100 kmol of feed. A total material balance gives:

F DW 100  D  W W  100 - D  Eq. a 
A balance on M.V.C (benzene) gives:
F  xf  D  xd  W  x w 1000.4   D0.9   W 0.1
40  0.9D  0.1W  Eq. b 
Insert Eq. a  into Eq. b 

40  0.9D  0.1100 - D 
D  37.5 kmol.
From Eq. a , W  100 - 37.5
W  62.5 kmol
Using a notation from reflux,
Ln
R L n  RD L n  3D L n  337.5 L n  112 .5
D
From Material balance at top stage,

Vn  L n  D Vn  112.5  37.5 Vn  150 kmol
Thus, the top operating line equation (Eq. 6) :

112.5 37.5
yn 
Ln
xn 1 
D
xd yn  xn 1  0.9 
Vn Vn 150 150
y n  0.75 xn 1  0.225
Since the feed is all liquid at its boiling point, it will all run down as
increased reflux to the plate below. Thus:
Lm  Ln  F L m  112.5  100 L m  212.5 kmol
From materialbalance at Bottom,

Vm  L m  W Vm  212.5  62.5 Vm  150 kmol  Vn
From Bottom operating line,

212.5 62.5
ym 
Lm
xm 1 
W
xw ym  xm 1  0.1
Vm Vm 150 150
ym  1.417 xm 1  0.0417
Since all vapor from column is condensed, the composition of the vapor, yt
from top plate = product, xd and liquid returned, xr
From yn  0.75 xn 1  0.225

Let say, x n 1  x d  0.9
yn  0.75 0.9   0.225 yn  0.9
The composition xt of the liquid on the top plate is found from the
equilibrium curve and since it is in equilibrium with vapor of composition
yt = 0.90, xt = 0.79.
yt 1  0.75 xt  0.225 yt 1  0.750.79  0.225

yt 1  0.8175
From Eq. diagram at yt 1  0.8175, x t 1  0.644

yt  2  0.75 xt 1  0.225 yt 2  0.750.644  0.225

yt  2  0.708
From Eq. diagram at yt 2  0.708, x t  2  0.492
yt 3  0.75 xt  2  0.225 yt 3  0.750.492  0.225

yt 3  0.594
From Eq. diagram at yt 3  0.594, x t  3  0.382
This last value of composition is sufficiently near to the feed composition

(xf =0.4). Feed to be introduced on plate t-3.
For the lower part of the column, the bottom operating line equation will
be used.
y m  1.417 xm 1  0.0417
yt  4  1.417 xt 3  0.0417
yt  4  1.4170.382   0.0417 yt  4  0.50
From Eq. diagram,at y t  4  0.50, x t - 4  0.298
yt 5  1.417 xt  4  0.0417
yt 5  1.4170.298  0.0417 yt 5  0.379
From Eq. diagram,at y t  5  0.379 x t - 5  0.208
yt 6  1.417 xt 5  0.0417
yt 6  1.4170.208  0.0417 yt 6  0.252
From Eq. diagram,at y t 6  0.252 x t -6  0.120
yt 7  1.417 xt 6  0.0417
yt 7  1.4170.120  0.0417 yt 7  0.127
From Eq. diagram,at y t 7  0.127 x t -7  0.048
This liquid xt-7 is slightly weaker than the minimum required and maybe
withdrawn as the bottom product (the xt-7 value < xw).
Thus, xx-7 will correspond to the reboiler, and there will be seven plates in
the column.
No of theoretical stages = 7 stage + 1 reboiler.

yt = 0.9
yt-1 = 0.8175
yt-2 = 0.708
yt-3 = 0.594
xt = 0.79
xt-1 = 0.644
xt-2 = 0.492
xt-3 = 0.382
Assumption: constant molal heat of vaporization, no heat losses, no heat on

mixing, led to a constant molal vapor flow and constant molar reflux flow in
any section of column, the two enrichment equation obtained were:
 Eq. 6 
Ln D
Vn Vn
 Eq. 7 
Lm W
ym  xm 1  xw
Vm Vm
Mc Cabe and Thiele pointed out that, since these equations represent
straight lines connecting yn with xn+1 and ym with xm+1, they can be drawn on
the same diagram as the equilibrium curve to give a simple graphical solution
for the number of stages required .
In Eq. (6), if xn+1 = xd, then yn = xn+1 = xd :
Ln D  Ln  D   Ln 1  D   Vn 
yn  
x d  xd  xd  
 
 xd  
  xd    xd
Vn Vn  Vn   Vn   Vn 
In Eq. (6), if xn+1 = 0, then yn = Dxd / Vn :
yn 
Ln
0  D xd  D xd
Vn Vn Vn
The top operating line drawn through two points of coordinates (xd, xd)
and (0, Dxd / Vn)
In Eq. (7), if xm+1 = xw, then ym = xw.

Lm W  L W  V 
ym  xw  xw   m  xw   m  xw  xw
Vm Vm  Vm   Vm 
For bottom operating line passes point (xw, xw) and has a slope (Lm/Vm).
When two operating lines drawn in, the number of stages required may
be found by drawing steps between the operating line and the equilibrium
curve starting from point xd.
Limitation of method: 1.3 < relative volatility < 5, reflux ratio >1.1 minimum
reflux ratio, theoretical stages < 25
Example
A mixture of benzene and toluene containing 40 mole% benzene is to be

separated to give a product of 90 mole% of benzene at the top, and a bottom
product with not more than 10 mole% of benzene. The feed is heated so that it
enters the column at its boiling point, and the vapor leaving the column is
condensed but not cooled, and provides reflux and product.
It is proposed to operate the unit with a reflux ratio of 3 kmol/kmol

product. It is required to find the number of theoretical plates needed and the
position of entry for the feed. The equilibrium diagram for operating at 1 bar
pressure is shown in Figure below.
Solution
Feed : 40 mol% benzene (A), xf = 0.40

Product : 90 mol% benzene (A), xd = 0.90
Bottom : 10 mol% benzene (A), xw = 0.10
Do a basis: 100 kmol of feed. A total material balance gives:

F DW 100  D  W W  100 - D  Eq. a 
F  xf  D  xd  W  x x 1000.4   D0.9   W0.1
40  0.9D  0.1W  Eq. b 

40  0.9D  0.1100 - D 
D  37.5 kmol.
From Eq. a , W  100 - 37.5
W  62.5 kmol
Using a notation from reflux,
Ln
R L n  RD L n  3D L n  337.5 L n  112 .5
D
From Material balance at top stage,

Vn  L n  D Vn  112.5  37.5 Vn  150 kmol
Thus, the top operating line equation (Eq. 6) :

112.5 37.5
yn 
Ln
xn 1 
D
xd yn  xn 1  0.9 
Vn Vn 150 150
y n  0.75 xn 1  0.225
Since the feed is all liquid at its boiling point, it will all run down as
increased reflux to the plate below. Thus:
Lm  Ln  F L m  112.5  100 L m  212.5 kmol
From materialbalance at Bottom,

Vm  L m  W Vm  212.5  62.5 Vm  150 kmol  Vn
From Bottom operating line,

212.5 62.5
ym 
Lm
xm 1 
W
xw ym  xm 1  0.1
Vm Vm 150 150
ym  1.417 xm 1  0.0417
The intersection of operating lines
• Feed enters as liquid at its boiling point that the two operating lines
intersect at a point having an x – coordinate of xf.. The locus point of the
intersection of the operating lines is considerable importance since; it is
dependent on the temperature and physical condition of feed.
• If the two operating lines intersect at a point with coordinates (xq, yq), then
from equation 6 and 7:
yqVn  Ln xq  Dx d yqVm  Lm xq  Wx w
yq Vm  Vn   Lm  Ln xq  Dx d  Wx w   Eq. 8 
• A material balance over the feed plate gives:

F  Vm  Ln  Lm  Vn Vm  Vn  Lm  Ln  F  Eq. 9 
Feed is form of liquid at its boiling point, the reflux overflowing  Ln  F . If

feed is a liquid at temperature Tf, less than the boiling point, some vapor rising
from the plate below will condense to provide sufficient heat to bring the feed
liquor to the boiling point.
Let Hf = enthalpy per mol of feed, Hfs = enthalpy of one mol of feed at its
boiling point. Heat to be supplied to bring feed to its boiling point is F(Hfs - Hf ),
number of vapor mols to be condensed to provide this heat is F(Hfs - Hf ) / ,
where  is molar latent heat of vapor
Reflux liquor:
Lm  Ln  F 

F H fs  H f  Lm  Ln 

F   H fs  H f  Lm  Ln  qF  Eq. 10
 
Heat to vaporize1 mol of feed
q
Molar latent heat of feed
Insert Eq 9 into 10:

Vm  Vn  Ln  qF  Ln  F Vm  Vn  qF  F  Eq. 11
A material balance for m.v.c over whole column gives:

Fx f  Dx d  Wxw
From Eq. 8, Eq. 10 and Eq 11:
yq qF  F   qF xq  Fx f   yq q  1F  qF xq  Fx f

xf
Eq. 12 q - line equation
q
yq  xq  
q  1 q  1
If xq = xf, then yq = xf. The point of intersection of the two operating lines lies
on the straight line of slope q / (q-1) passing through point (xf, xf). When yq = 0,
xq = xf / q.
From definition of q, it follows that the slope of q – line is governed by the

nature of feed,
Total and Minimum Reflux Ratio for Mc Cabe – Thiele Method

R x
yn  xn1  d  Top operating line (rectifying section)
R 1 R 1
Total reflux –Limiting values of the reflux ratio, R = . Since R = Ln/D and
Vn=Ln+1+D, Ln+1 is very large, as is the vapor Vn. The slope of the top operating
R x
line, = 1.0, d = 0, eq. become, operating line of both sections of the
R 1 R 1
column coincide with the 45O diagonal line as shown in figure below .
The number of theoretical trays required obtained as before by stepping off

the trays from the distillate to the bottoms – gives the minimum number of
trays can possibly be used to obtain the given separation.
In actual practice – condition can be realized by returning all the overhead

condenser vapor V1 from the top to the tower back to the tower as reflux, that
is total reflux. All the liquid in the bottom is reboiled – all the production
distillate and bottoms are reduced to zero flow, as the fresh feed to the tower.
Minimum reflux ratio – reflux

ratio, Rm that will acquire an infinite
number of trays for the given
desired separation of xd and xw. This
corresponds to the minimum vapor
flow in the tower, hence minimum
reboiler and condenser size.
If R decreased, the slope of T.O.L (R/(R+1)) is decreased, T.O.L closer to the

equilibrium line. Number of steps required to give a fixed xd and xw increases.
When two operating line touch the equilibrium line, a ‚pinch point‛ at y’
and x’ occurs where the number of steps required become infinite.
The slope of T.O.L: Rm x  y'

 d
Rm  1 xd  x'
xd
The y-intercept of T.O.L: y  intercept 
Rm  1
Operating and optimum reflux ratio:
For the case of total reflux, the number of plates is a minimum, but the
tower diameter is infinite. This corresponds to an infinite cost of tower.
For minimum reflux, the number of trays infinite, gives an infinite

cost.
These are the two limits in operation of the tower. The actual reflux
ratio to use is lies between two limits.
The optimum reflux ratio between Rm total reflux. For many cases,
operating reflux ratio between 1.2Rm and 1.5Rm.
Example 2
11,000 kg/h of equal parts (in wt) of Benzene – Toluene solution is to be

distilled in a fractionating tower at atmospheric pressure.
The liquid is fed as a liquid – vapor mixture in which the feed consist of
75% vapor. The distillate contains 94 wt% Benzene whereas the bottom
products contains 98 wt% toluene. Using the equilibrium diagram of
Benzene-Toluene mixture, determine by McCabe-Thiele’s method:
The flow rate of distillate and bottom product in kg/h

The minimum reflux ratio, Rm.
The number of theoretical stages required if the reflux ratio
used is 2 times the minimum reflux ratio
The position of the feed tray.
Data:
Molecular weight of Benzene = 78
Molecular weight of Toluene = 92
Solution 2
Feed : 50 wt% benzene (A), xf = 0.50

F : 11,000 kg/h
Product : 94 wt% benzene (A), xd = 0.94
Bottom : 2 wt% benzene (A), xw = 0.02
The flow rate of distillate and bottom product in kg/h
A total material balance gives:

F DW 11000  D  W W  11000 - D  Eq. a 
F  xf  D  xd  W  x w 110000.5  D0.94  W0.02
5500  0.94D  0.02W  Eq. b 
5500  0.94D  0.0211000 - D
D  5739.1 kg/h.
From Eq. a , W  11000 - 5739.1
W  5260.9 kg/h
The minimum reflux ratio, Rm.
1) Convert mass fraction to mol fraction

Do basis calculation: 100 kg
Feed (F) Distillate (D) Bottoms (W)

Component Mwt Mass Mol Mol Mass Mol Mol Mass Mol Mol
frac. frac. frac.
Benzene (A) 78 50 0.64 0.54 94 1.21 0.95 2 0.03 0.03
Toluene (B) 92 50 0.54 0.46 6 0.07 0.05 98 1.07 0.97

Total 1.18 1.00 1.28 1.00 1.10 1.00
From conversion table, mol fraction for M.V.C:
xf = 0.54 xd = 0.95 xw = 0.03

2) Find q – line. Feed enters at 75% vapor.
q  0.75 ( qvap. )  0.25 ( qliq. )

q  0.75 (0)  0.25 (1.0) q  0.25
q line equation
 q   xf 
y q    xq   
 q 1  q 1
 0.25   0.54 
yq    xq    y q  0.333xq  0.72
 0.25  1   0.25  1 
Let x  0.3, y q  0.3330.3  0.72 y q  0.62
Plot (0.54 , 0.54) and (0.30 , 0.62) for q-line

From the graph, y intercept for q – line = 0.36

xd 0.95
 0.36  0.36 Rm  1.64
Rm  1 Rm  1
The number of theoretical stages required if the reflux ratio used

is 2 times the minimum reflux ratio
R  2 Rmin  21.64 R  3.28
R x
yn  xn 1  d  Top operating line
R 1 R 1
3.28 0.95
yn  xn 1 
3.28  1 3.28  1
yn  0.766xn 1  0.222
Plot (0.95 , 0.95) and
At x  0.5, yn  0.7660.5  0.222 y n  0.605 (0.5, 0.605) for T.O.L
The number of theoretical stages required = 10.5 stages including

reboiler
Feed plate location: 5 from top

Azeotropic Distillation
AZEOTROPE / AZEOTROPIC MIXTURE
MINIMUM BOILING POINT (POSITIVE DEVIATION)
MAXIMUM BOILING POINT (NEGATIVE DEVIATION)
AZEOTROPIC DISTILLATION
AZEOTROPE / AZEOTROPIC MIXTURE
Very large deviations from ideally lead to a special class of mixtures known as
azeotropes.
Azeotrope is a special class of liquid mixture that boils at a constant

temperature at a certain composition.
It acts if it was one component with one constant boiling point.
In other words, vapor and liquid compositions are equal.
Cannot be separated by conventional distillation.
For example ethanol –water system, one cannot recover more than 89.4 mol%
ethanol by ordinary distillation because the mixture forms azeotropes at this point.
Other separation methods (for eg solvent extraction) or azeotropic distillation

may be used.
Two types of azeotropes known are:

(i) Minimum boiling
(ii) Maximum boiling (less common)
At point Z2, the concentration in the vapor phase is the same as the
concentration in the liquid phase (y=x) and =1.
At this point, the mixture boils at constant temperature and doesn’t change
in composition.
On the equilibrium diagram, the equilibrium crossed at 45O diagonal line.
Z2
The most common examples of this type of azeotrope are:
Ethanol – water (89.4 mol% water, 78.25OC, 1 atm)
Carbon Disulfide – Acetone (61 mole% CS2, 39.25OC, 1 atm)
Benzene – water (29.6 mole% water, 69.25OC, 1 atm)

MAXIMUM BOILING POINT (NEGATIVE DEVIATION)
At point Z2, the characteristic of such mixture is boiling point curve goes
through maximum phase diagram.
Example of this type of azeotrope is:
Acetone – chloroform
Z2
The distillation of a mixture that is azeotropic begins similarly to

conventional distillation.
The difference is that, as the process continues.

A temperature is reached at which the compositions of the vapor
phase and the liquid phase become the SAME.
Once this azeotrope has been formed, the individual components can no
longer be separated by conventional distillation.
*Note: the description of azeotrope distillation only refers to
minimum boiling distillation of azeo. only.
Recall the mixture of ethanol – water, that demonstrates azeo behaviour at

89.4 mol% at 78.15OC and 1 atm.
Therefore, by conventional distillation, the highest concentration of ethanol

achieved is the azeotropic concentration, i.e 89.4 mol%.
Azeotropic distillation refers to an introduction of a new component called

entrainer is added to the original mixture to form an azeotrope with one or more
of feed component.
The azeotrope is then removed as either the distillate or bottoms.
This type of distillation also refers to a new components (entrainer) is added to

break an azeotrope from being formed by the original feed mixture.
Entrainer – as described above has the following functions that are:
To separate one component of a closely boiling point, or

To separate one component of an azeotrope.
Recall the binary mixture, A – B that formed an ezeotropic mixture, the

entrainer C is added to form a new azeotrope with the original components,
often in the LVC, say A.
The new azeotrope (A – C) is separated from the other original component

B.
This new azeotrope is then separated into entrainer C and original

component A. Hence the separation of A and B can be achieved.
Alternative method to azeo – distillation: is when no entainer is used,

instead the column is operated at different pressure, since changing the
operating P can eliminate azeotropic behaviour in some systems.
Example of Azeotropic Distillation:
Distillation acetic – acid water using entrainer: n-butyl acetate.
Boiling point (B.P) of acetic acid is 118.1OC while water is 100OC, whereas
n-butyl acetate is 125OC.
The addition of n-butyl acetate results in

the formation of a minimum boiling
azeotrope with water with a B.P of 90.2OC.
The azeotropic mixture will therefore be

distilled over as a vapor product and acetic
acid as bottom product.
The distillate is condensed and collected in

a decanter where it forms two insoluble
layers.
Example of Azeotropic Distillation:
Distillation acetic – acid water using entrainer: n-butyl acetate.
Top layer consists of nearly pure butyl acetate in water, whereas

bottom layer of nearly pure water saturated with butyl acetate.
The liquid from top layer is returned to column as reflux and

entrainer.
The liquid from bottom layer is sent to another column to recover the
entrainer (by stream stripping).
Distillation ethanol-water system.

Entainer: Benzene with Boiling point (B.P) at 80.2OC that forms a new-
minimum boiling point azeotrope with 22.8 mol% ethanol (E), 23.3 mol%
water (W) and 53.9 mol% benzene (B) (three comp. azeotrope).
The B.P of the azeotrope mixture is 64.86OC which leaves top product and
bottom consist of nearly pure ethanol.
The condensed overhead product forms two

layer in the decanter – top and bottom layer). Top layer
*Rich in benzene.
*Returned to column as reflux
The bottom layer is sent to a 2nd column where and entrainer
benzene is stripped and returned to the 1st column.
Bottom layer
*Rich in water with a small
The bottom product (E-W) are fed to a 3rd Distill. amount of ethanol.
for further distillation.
Multi – component Distillation
INTRODUCTION OF MULTI – COMP. DISTILLATION
EQUILIBRIUM DATA IN MULTI. DISTILLATION
BOILING POINT, DEW POINT AND FLASH DISTILLATION
LIGHT AND HEAVY KEY COMPONENT

For binary mixture for constant P – vapor liquid equilibrium curve rather
unique.
With a ternary mixture, the conditions of equilibrium curve are more complex
for constant P where mol fraction of the two components in liq. phase must be
given before composition of vapor can be fixed/determine.
Therefore, the mol fraction yA not only depends on xA but also on the
proportions of the other two components.
Graphical method are not generally suitable.
The possible method used – plate to plate analysis.
For many systems consisting particularly similar chemically substances, the

relative volatilities of the components remain constant over a wide range of T and
composition.
This is illustrated by the table below:
Temperature (K)
Component 353 393 453
Phenol 1.25 1.25 1.25
o – Cresol 1 1 1
M – Cresol 0.57 0.62 0.70
Xylenols 0.30 0.38 0.42
An alternative method is to use the simple relation.
y A  K xA where K  equilibrium constant

(or Equilibrium Vaporization ratio)
Particularly useful for hydrocarbon processing in petroleum industry
The K values can be measured .

The feed and Product Compositions
Gilliand and Reed have determined the no. of freedom, F for multi –
component Distillation (MCD).
For the common case:

where Feed composition, nature of feed and operating pressure are given,
there remain only four variables to be selected.
If the reflux ratio, R is fixed, the no. of plate above and below the feed plate
are chosen to give the best used of plates, then only two variables remains.
This means that the top and bottom product composition has been
determined by trial and error method.
This problem of Trial and Error method can rather be simplified by

assuming MVC appears at top and LVC appears on bottom product.
Consider as ideal mixture, we can apply Raoult’s Law to determine the

composition of vapor in equilibrium with liquid.
Consider a four – component (A,B,C,D) mixture:
p A  x A PAo p B  xB PBo pC  xC PCo p D  xD PDo

p A PAo PBo PCo PDo
yA   xA yB  xB yC  xC yD  xD
P P P P P
In hydrocarbon system, because nonidealities, the equilibrium data are often

represented by:
y A  K A xA y B  K B xB yC  K C xC y D  K D xD
KA is the vapor – liquid equilibrium constant or distribution coefficient for
component A.
Pi o for component i individual component.

Ki 
P
K value is easily determined (refer K-chart) for hydrocarbons system but need
to be calculated for other system.
The relative volatility, i for each individual component in a multi component

mixture can be defined in a similar manner to that of a binary mixture.
Need to select a base component, say component C:
Ki K KB KC KD
αi  , hence α A  A αB  αC   1.0 αD 
KC KC KC KC KC
The values of Ki depend strongly on T.

Boiling Point.
At a specified pressure, the boiling point or bubble point of a given multi –
component mixture satisfy the relation  yi = 1.0. For a mixture A, B, C, and D,
with C as the base component,
 yi   K i xi  K C  αi xi  1.0
The calculation is a trial – and – error process where:

T is assumed.
Values of i are then calculated using K values at the assume T.
Then calculate value of KC where
1.0
KC 
 αi xi
Find the T that corresponds to the calculated value of KC

Compare with T value read from table that corresponds to the KC
(calculated)
Boiling Point.
If values is differ, the calculated T is used for next iteration.

After the final T is known, the vapor composition is calculated from:
αi xi
yi 
 αi xi
Dew Point.
Also based on the trial and error method:

yi  1   yi 
 xi    
K i  K C 
 
 αi
  1.0

The values of KC is calculated from:
1.0
KC 
 αi xi
After the final T is known, the liquid composition is calculated from:

yi αi
xi 
 yi αi
Example 3
A liquid feed to a distillation tower at 405.3 kPa abs is fed to a distillation

tower. The composition in mol fractions is as follows:
n – butane (xA = 0.40) n –pentane (xB = 0.25)

n – hexane (xC = 0.20) n – heptane (xD = 0.15)
Calculate the boiling point and the vapor in equilibrium with liquid.
Solution 3
Assume first trial and error temperature, let say T=65OC. Find the values of
K from Figure B1
Using component C (n – hexane) as base component, the following values

are calculated for the first trial:
Figure B1: Equilibrium K values for light hydrocarbon system at 405.3 kPa absolute.
Assume first trial and error temperature, let say T=65OC.
Set n-hexane as base component. Initial Kc = Ki (hexane) = 0.245

Ki
αi 
KC
Ki 1.68
For n - butane,α    6.857
K C 0.245
Do same calculation for n-pentane, n-hexane and n-heptane
For the first trial (T=65OC),
Component xi Ki (from chart) i=Ki/KC ixi

n-butane (xA) 0.40 1.68 6.857 2.743
n-pentane (xB) 0.25 0.63 2.571 0.643
n-hexane (xC) 0.20 0.245 1.000 0.200
n-heptane (xD) 0.15 0.093 0.380 0.057
1.00 ixi = 3.643
1 1
From table above, K C    0.2745
  i xi 3.643
From graph, for n-hexane at K = 0.275, T = 69OC
Using T = 69OC for trial 2, a temperature of 70OC is obtained.
Using T = 70OC for trial 3, the calculation shown final value of 70OC,
which is bubble point.
Values y is calculated from: yi=ixi/ixi
From trial 3,
Component xi Ki (from chart) i=Ki/KC i x i yi

n-butane (xA) 0.40 1.86 6.607 2.643 0.748
n-pentane (xB) 0.25 0.710 2.522 0.631 0.178
n-hexane (xC) 0.20 0.2815 1.000 0.200 0.057
n-heptane (xD) 0.15 0.110 0.391 0.059 0.017
1.00 ixi = 3.533 1.000
The essential requirement in Multi – comp. Distillation is to separate the two

components.
These components are called key component.
Suppose a four component mixture A-B-C-D where:
A is MVC where the mixture is to

B is LVC be separated as below:
Feed Top Product Bottom Product

A A
B B B
C C C
D D
Then; B – is the lightest comp. in bottom and called Light Key Component (LKC)
C – is the heaviest comp. in top / distillate and called Heavy Key Component (HKC)
The main purpose of fractionating is to separate B from C

The calculation of No. of plates required.

Developed by Lewis and Matheson (which is based on Lewis – Sorel
method).
This L – M method illustrates that:

if the comp. of liquid on any plate is known, then the vapor
component can be calculated using the vapor pressure @  of individual
components.
Suppose: a component mixture A-B-C-D with liquid composition xA, xB, xC,
xD,& etc. and vapor comp. yA, yB, yC, yD ,& etc. Then…..
The calculation of No. of plates required.

From the relation of vapor pressure, mole fraction, relative volatility (α)
and the K value:
Let say B is the bas e (referen ce) compon ent

xB x A AB xC CB x D DB
yB  yA  yC  yD 
  x 
i i   i xi    i xi    i xi 
Example 4
A mixture of ortho (o), meta (m), and para (p) mononitrotoluenes with mole
percentage as below:
ortho (o) (xo = 0.60) para (p) (xp = 0.36)

meta (m) (xm = 0.04)
is to be continuously distilled to give a top product of 98 mol% ortho, and

the bottom is to contain 12.5 mol% ortho.
The mixture is to be distilled at temperature of 410 K requiring a pressure
in the boiler of about 0.06 bar.
If a reflux ratio of 5 is used, calculate:
a) The number of plates will be required

b) The approximate compositions of product streams
The volatility of ortho relative to para isomer is taken as 1.70 and the
volatility of meta relative to para is 1.16 over the temperature range of 380 to
415 K
Solution 4
As a first estimate, suppose the distillate to contain 0.6 mol% meta and 1.4
mol% para.
Material balance will give the composition of the bottom.
Do overall material balance to find the amount of Distillate and Bottom

Product
F=D+W 100 = D + W D = 100-W
Material balance on Ortho component

0.6100   0.98D   0.125 W 
60  0.98100  W   0.125W
W  44.44 mol
D  55.56 mol
Solution 4
Calculate material balance for other component
Meta 4=0.11+xWM(44.44) xWM= 0.083

Para 36=1+xWP(44.44) xWP= 0.792
Feed (F) Distillate (D) Bottom (W)

Component Mole xf Mole xd Mole xw
Ortho 60 0.600 54.450 0.980 5.555 0.125
Meta 4 0.040 0.333 0.006 3.667 0.083
Para 36 0.360 0.778 0.014 35.222 0.793
Total 100 1.000 55.560 1.000 44.440 1.000
Solution 4
Equation of operating lines

Above the feed point:
Liquid downflow, Ln = 5D = 5 (55.56) = 277.8
Vapor up, Vn = Ln + D = 5D + D = 6D = 6 (55.56)
Vapor up, Vn = 333.3
Below feed point:
Liquid downflow, Lm = Ln + F = 277.8 + 100 = 377.80
Vapor up, Vm =Lm - W = 377.8 - 44.44 = 333.36
Solution 4
The equation of operating lines below the feed plate can be written as:
Lm W
ym  x m 1  xw
Vm Vm
Ortho y mo 
377 .8
xm 1 
44.44
0.125  y mo  1.133 x m 1  0.0167
333 .36 333 .36
Meta y mm 
377 .8
xm1 
44.44
0.083  y mm  1.133 x m 1  0.011
333 .36 333 .36
Para y mp 
377 .8
xm1 
44.44
0.792  y mp  1.133 xm1  0.105
333 .36 333 .36
Solution 4
The equation of operating lines above the feed plate can be written as:
Ln D
yn  x n 1  xd
Vn Vn
Ortho y no 
277 .8
xn 1 
55.56
0.98  y no  0.833 x n 1  0.163
333 .36 333 .36
Meta y no 
277 .8
xn 1 
55.56
0.006  y nm  0.833 x n 1  0.001
333 .36 333 .36
Para y np 
277 .8
xn 1 
55.56
0.014  y np  0.833 xn1  0.003
333 .36 333 .36
Solution 4
Start the calculation from bottom plate (below the feed plate)
Component  xs xs ys x1
Ortho 1.7 0.125 0.213 0.193 0.185
Meta 1.16 0.083 0.096 0.087 0.087
Para 1 0.792 0.792 0.719 0.728
1.101 1.000 1.000
Component x1 x 1 y1 x2
Ortho 0.185 0.315 0.275 0.258
Meta 0.087 0.101 0.088 0.088
Para 0.728 0.728 0.637 0.655
1.000 1.143 1.000 1.000
Solution 4
Continue the calculation until x > xf
Component x6 x 6 y6 x7
Ortho 0.564 0.96 0.68 0.617
Meta 0.064 0.07 0.05 0.056
Para 0.372 0.37 0.26 0.326
1.000 1.40 1.00 1.000
The feed will be introduce at plate 7 since the liquid on this plate has a
composition with the ratio of concentration ortho and para about that in the
feed.
Continue the Calculation above the feed plate.

Solution 4
Continue the Calculation above the feed plate
Component  x7 x 7 y7 x8
Ortho 1.7 0.617 1.049 0.728 0.678
Meta 1.16 0.056 0.065 0.045 0.053
Para 1 0.326 0.326 0.227 0.270
1.000 1.441 1.000 1.001
Continue the Calculation until x > xd
Component y15 x16 x16 y16

Ortho 0.970 0.969 1.647 0.980
Meta 0.011 0.012 0.014 0.008
Para 0.019 0.020 0.020 0.012
1.000 1.001 1.681 1.000
The vapor from the sixteenth plate has the required concentration of the
ortho isomer.
16 ideal stages is required for the separation.

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CHAPTER 1: DISTILLATION

Definition & General Description of the process

Physical concept of Distillation

Vapor – liquid equilibrium relationship

Flash & Batch Distillation

Continuous / Retrification Distillation

Multi – component Distillation

Separating the various components of a

Depends upon the distribution of these

All components presents in both phases.

Distillation is done by vaporizing a

The equilibrium vapor is then separated

Carried out by either two principal

First method: based on the production of

Second method: Based on the return part

VOLATILITY – The tendency of liquid to change form to gas

VAPOR – LIQUID EQUILIBRIUM OF AN ORDINARY BINARY

PREDICTION OF VAPOR – LIQUID EQUILIBRIUM

RELATIVE VOLATILITY OF A MIXTURE

Homogeneous mixtures – mix at all proportions resulting in one continuous phase.

xA = mole fraction of A in liquid phase

PAo = vapor pressure of A at that temperature

p A = partial pressure of A in vapor phase

y A = mole fraction of A in vapor phase

PT = Total pressure of the system

p A = partial pressure of A in vapor phase

y A = mole fraction of A in vapor phase

PT = Total pressure of the system

Separations of components by distillation process depend on the differences in

The greater difference in their volatility, the better is separation by heating

Equilibrium diagram for n-heptane n-octane mixture at 101.3 kPa

A numerical measure of ‘how easy’ separation – relative volatility, AB.

Relative volatility, AB - ratio of the concentration of A in the vapor to the

AB - relative volatility of A with respect to B in the binary system.

If the system obeys Raoult’s Law for an ideal system:

Separation is possible for > 1.0

FLASH (EQUILIBRIUM) DISTILLATION

SIMPLE BATCH DISTILLATION

Flash distillation is done by vaporizing a definite fraction of a liquid mixture in

Flash distillation can be either by batch or continuous

Figure 1: A typical flow chart of a continuous flash distillation

As illustrated in Figure 1, a liquid mixture feed, with initial mole fraction of

Prediction of an equilibrium composition of vapor and liquid for a flash

Consider a binary liquid mixture which is to be separated by a flash distillation

Total mass balance: F  V L

Mass balance on more volatile component (A): Fx F  y * V  x * L

And substituting f in the total mass balance:

Substituting Eq. 2 into Eq. (1) to obtain:

Figure 2: Graphical method to determine equilibrium compositions in a flash

Basis  100 moles of liquid feed (F)

We want to find equilibriu m compositio ns of vapor and liquid; y * and x *

The operating line : y* 

Determination of vapor-liquid equilibrium composition

x,mol fraction n-heptane in liquid

Simple batch distillation which is also known as differential distillation refer to a

Simple batch distillation is done by boiling a liquid mixture in a steam-jacketed-

Raleigh equation for ideal and non – ideal mixtures

Consider a typical differential distillation at an instant time, t1 as shown below:

Where L = number of moles of liquid mixture in the pot

Mass balance of component A will yield:

xL  xL  xdL  Ldx  dxdL  ydL

Ldx  xdL  ydL

Integrating both sides within limits initial t1 and final t2: