CHAPTER 1: DISTILLATION

Part 1
Definition
& process
description
Physical concept of
distillation
Vapor-liquid equilibrium
relationship
Relative volatility
Batch distillation Part 2
Continuous distillation Part
3
Azeotropic distillation -Part 4
COURSE LEARNING OUTCOME
CHAPTER 1
-Distillation
Student should be able to :
1. Define and describe distillation process
2. Explain the physical concepts of distillation including
vapor-liquid equilibrium and relative volatility, batch
distillation and use Rayleigh equation, continuous
distillation, the equipment used and reflux ratio
3. Determine the number of the theoretical stages in a
distillation column using McCabe-Thiele and Lewis Sorel
method
4. Calculate the overall plate efficiency, and minimum reflux
ratio
5. Explain Azeotropic mixtures and the distillation method ,
how multi component mixtures are fractionated in
1.1: Definition & process
description
Distillation is a process of separating
various components of a liquid solution
by heating the liquid to forms its vapors
and then condensing the vapors to form
the liquid.
It is use to separate 2 or more
substances present in the liquid OR for
purification purpose.
Distillation is a commonly used method
for purifying liquids and separating
mixtures of liquids into their individual
components
All components presents in both
phases
Familiar examples include
1) distillation of crude fermentation
broths into alcoholic spirits such as
gin and vodka
2) fractionation of crude oil into useful
products such as gasoline and
heating oil.
3) In the organic lab, distillation is used
for purifying solvents and liquid
reaction products.
1.1: Definition & process
description
Other definition
Distillation is done by vaporizing a
definite fraction of a liquid mixture in a
such 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
Laboratory / Testing
1.2: Physical Concept of distillation
Carried out by either 2 principal
methods
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 (E.g. Flash, simple
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 / batch
process (E.g. 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 2 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
a) VAPOR LIQUID EQUILIBRIUM OF
AN ORDINARY BINARY LIQUID
MIXTURE
Equilibrium curve: shows the relationship
between composition of residual liquid and
vapor that are in dynamic phase equilibrium.
The curve will be very useful in calculations to
predict the number of stages required for a
specified distillation process.
VAPOR LIQUID EQUILIBRIUM
CURVE
 b) Prediction of vapor-liquid
equilibrium compositions for
ordinary binary mixtures
Raoults Law for ideal solution & Daltons Law of partial
pressure can be manipulated in order to calculate
compositions of liquid and vapor, which are in
equilibrium.
Raoults 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 the temperature:
pA = x A P A o
pA = partial pressure of A in a vapor phase
xA = mole fraction of A in liquid phase
PAo vapor pressure of A at the temperature
=
Prediction of vapor-liquid equilibrium
compositions for ordinary binary mixtures
For a mixture of the different gases inside a close
container, Daltons law stated that the resultant total
pressure of the container is the summation of partial
pressures of each of all gases that make up the gas
mixture:
PT = pA + pB
Dalton also state that the partial pressure of gas (pA) is:

pA = yA PT
pA = partial pressure of A in vapor phase
yA = mole fraction of A in vapor phase
PT = total pressure of the system
Example:
Calculate the vapor and liquid
compositions in equilibrium at 95oC
(368.2K) for benzene-toluene using the
vapor pressure from Table 11.1-1 at
Table 11.1-1
101.32 kPa.
Phase Rule
Relative volatility () of a
mixture
Separations of components by
distillation process depends 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.
Relative volatility () of a
mixture
The greater the distance between the
equilibrium line & 45o line, the greater
the difference the vapor composition
and a liquid composition. Separation is
more easily made.
A numerical measure of how easy
separation relative volatility, AB
AB relative volatility of A with respect
to B in the binary system
Relative volatility ratio of the
concentration of A in the vapor to the
concentration of A in liquid divided by the ratio
of the concentration B in the vapor to the
Relative volatility () of a
mixture
y A / xA y A / xA
AB
y B / xB (1 y A ) /(1 x A )
AB relative volatility of A with respect
to B in the binary system
Ifthe system obeys Raoults law for
an ideal system:
PA x A PB xB PA x A
yA yB AB yA
PT PT PB 1 ( 1) x A

Separation is possible for > 1.0

Relative volatility () of a
mixture
Separation is possible for > 1.0
For non-ideal solution, the values of
change with temperature.
For ideal solution, the values of
doesnt change with temperature.
For solution that approaches ideal
solution, its would fairly constant.
Relative volatility () of a
mixture
Example:
Using the data from table below,
determine
the relative volatility for the
benzene-
toluene system at 85C and 105C
Exercise 1
A liquid mixture is formed by mixing n-hexane
(A) & n-octane (B) in a closed container at
constant pressure of 1 atm (101.3kPa).
i. Calculate the equilibrium vapor and liquid
composition of the mixture at each
temperature
ii. Plot a boiling point diagram for n-hexane
iii. Plot an equilibrium diagram for the mixture
iv. Calculate the AB at 100 C
Use the following list of vapor pressure for pure n-hexane & n-octane
at various temperature.

Vapor Pressure

Temperature n-Hexane n-Octane

(C) kPa mm Hg kPa mm Hg

68.7 101.3 760 16.1 121

79.4 136.7 1025 23.1 173

93.3 197.3 1480 37.1 278

107.2 284.0 2130 57.9 434

125.7 456.0 3420 101.3 760

 Solution
Vapor Pressure
Temperatur n-Hexane (A) n-Octane (B)
e
(C) kPa XA YA kPa XB YB

68.7 101.3 1 1 16.1 0 0

79.4 136.7 0.6884 0.929 23.1 0.3116 0.071
0
93.3 197.3 0.4007 0.780 37.1 0.5993 0.2196
4
107.2 284.0 0.1920 0.538 57.9 0.8080 0.4617
3
125.7 456.0 0 0 101.3 1 1
PART 2
Flash & batch distillation
Flash(equilibrium) distillation
Simple batch distillation
Flash (Equilibrium) Distillation
Flash distillation a single stage process
because it has only one vaporization stage
(means one liquid phase is expected to one
vapor phase)
The vapor is allowed to come to equilibrium with
the 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
 Flash (Equilibrium) Distillation
(cont.)

As illustrated in Figure 3, 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.
Because of the large drop in pressure, part of liquid vaporizes.
The vapor is taken off overhead, while the liquid drains to the
bottom of the drum
The system is called flash distillation because the vaporization
is extremely rapid after the feed enters the drum.
Now, we interested to predict the composition (x and y) of these
vapor and liquid that are in equilibrium with each other.
Flash (Equilibrium) Distillation
Flash (Equilibrium) Distillation
Example
A liquid mixture containing 70 mol% n-
heptane (A) and 30 mol % n-octane (B)
at 30oC is to be continuously flash at the
standard atmospheric pressure
vaporized 60 mol% of the feed.
Determine
1) the compositions of vapor and liquid
for n-heptane
2) temperature of the separator for an
equilibrium stage?
The equilibrium data for n-heptane n-
octane mixture at 1 atm and 30C is
given as follows:
T (K) xA yA
371.6 1 1
374 0.825 0.92
377 0.647 0.784
380 0.504 0.669
383 0.387 0.558
386 0.288 0.449
389 0.204 0.342
392 0.132 0.236
395 0.068 0.132
398.2 0 0
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 fine the equilibrium composition of liquid and

liquid; y* & x*

The operating line: y* = (0.6-1)x* + 0.7

0.6 0.6
= -0.667x* + 1.167
From the intersection of the operating line & the
equilibrium curve as shown in the graph:
equilibrium mol fraction of n-heptane in liquid, x* =
0.62
equilibrium mol fraction of n-heptane in vapor, y* =
0.76
the temperature of the separator at equilibrium 378 oC
Determination of vapor-liquid equilibrium

y , m o l f r a c t io n o f n - h e p t a n e in
composition for a flash distillation of n-
heptane/n-octane mixture

1.2

0.8

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2

x, mol fraction of n-heptane in liquid

Figure: Equilibrium curve and operating line

Determination of equilibrium temperature
for a flash distillation of n-heptane-n-octane
mixture

405 405

400 400

395 395
Temperature (K)

390 390

385 385

380 380
y
375 375

370 370

365 365

360 360

355 355
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Mol fraction of n-heptane in vapor (y) and liquid (x)

x
Exercise 11.2-1 (page
752)
A mixture of 100 mol containing 60
mol%
n-pentane (A) and 40 mol% n-
heptane (B) is
vaporized at 101.32 kPa abs
pressure until 40
mol of vapor and 60 mol of liquid in
equilibrium with each other are
produced.
This occur in a single stage system,
and the
The equilibrium data are as
follows, where
xx and y are of
(mol fraction mole fraction
n- y (mol fractionof n-
of n-
pentane in liquid)
pentane. pentane in vapor)

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
Answer:
xA = 0.430
yA = 0.854
Simple batch distillation
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 stream-jacketed-kettle
(pot) and the vapor generated is withdrawn
and condensed (distillate) as fast as it
forms.
The first portion of vapor condensed will be
richest in the more volatile component A. As
the vaporization proceeds, the vaporized
Simple batch distillation
Simple batch distillation
1. Raleigh equation for ideal and non-ideal
mixtures
Consider a typical differential distillation
at an instant time, t1 as shown below:
Simple batch distillation
Now consider that the differential distillation at certain infinitesimal time lapse,
(dt), at t2 where t2=t1 + dt, after an infinitesimal amount of liquid has vaporized
as shown below:
Simple batch distillation

Applicable for ideal and

non-ideal solution
Simple batch distillation
The average composition of total
material
distilled yav can be obtained by
material
L x L x (L L ) y
balance:
1 1 (integrate
2 2 1from Rayleigh
2 av
equation)
L1 x1 L2 x2 Vy av
2. Simplified Raleigh equation for ideal
mixture
Consider a simple batch distillation process
at
an initial time, t1, as shown below
L1=no of moles of binary
mixture containing A and B
at t1
dL= dA + dB A1= no of moles comp A in L1
y
at t1
B1= no of moles comp B in L1
at t1
x1= mol fraction of A in L1 at
L1= A1 + B1
X1 t1
dL= infinitesimal amount of
liq that has vaporized
dA=infinitesimal amount of A
that has vaporized
Simple batch distillation
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, y A / xA
dA

B
AB dA dB A B
y B / xB dB A

dA dB A B

After simplifying, B dA
AB
A dB

Rearranging,
dB

dA
AB
B A
Simple batch distillation
Integrating within the limits of t 1 and t2,
B2 A2
dB dA

B1
B
AB
A1
A
Since AB is constant,
B2 A2
dB dA
AB
B1
B

A1
A
AB ln B BB2 ln A AA2
1 1

B2 A2
AB ln ln
Eq.(5)
B1 A1
Equation 5 known as simplified Raleigh
equation for simple batch distillation
which applicable for ideal solution.
 Simple batch distillation
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 n-pentane in 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
xA yA 1/(yA xA)

1.000 1.000 -

0.867 0.984 8.5470

0.594 0.925 3.0211

0.398 0.836 2.2831

0.254 0.701 2.2371

0.145 0.521 2.6596

0.059 0.271 4.7170

0 0 -
Solution
Given L1 = 100 mol V (mol distilled) = 40
mol
L1 L2 V L2 L1 V 100 40
From L2 60 mol
material balance:

Substiting
L1 into
x1
1Eq.
(4) 100 0 .5
1
ln
L2
y x
x2
dx ln
60
x2
dx
yx
0. 5
1
0.510
x2
dx
y x

The unknown, x2 is the composition n of

the liquid L2 at the end of batch
distillation.
Solution 0 .5
1 1
versus
dx
By plotting graph
y x x, the
yx
x2
value is referring to the value of area
under the curve.
From the graph, area under curve =
0.510 at x2 = 0.277. Composition of the
liquid L2, x2 = 0.277.
From material balance on more volatile
component:
x1L1 x 2L2 0.5 100 0.277 60
x1L1 x 2L2 y av V y av y av
V 40
y av 0.835

Average composition of total vapor

distilled, yav = 0.835
 PART 3
Continuous distillation
Continuous / retrification
distillation
Continuous / retrification
distillation
Retrification(fractionation) - or stage
distillation with reflux can be considered as a
process in which a series of flash
vaporization stages are arranged in a series in
such a manner that the vapor and liquid
products from each stage flow counter-current
to each other.
Continuous distillation - the 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)
Thefractionator consists of many trays which
have holes to permit the vapor, V which rises
Continuous / retrification
distillation
During the mixing, the vapor will pick up more
of component A from the liquid while the liquid
will richer and richer in component B. As the
vapor rises, 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 to
the fractionator. The recycled distillation
Continuous / retrification distillation
Continuous / retrification
distillation
The feed stream is introduced on some
intermediate tray where the liquid has
approximately the same composition as the feed.
The system is kept steady-state: quantities (feed
input rate, output stream rates, heating and cooling
rates, reflux ratio, and temperatures, pressures, and
compositions at every point) related to the process do
not change as time passes during operation.
With constant molal overflow assumption:
Ln 1 Ln Ln 1 ....etc. Vn 1 Vn Vn 1 ....etc.
Conditions for constant molal overflow :
Heat loses negligible (achieved more easily in
industrial column)
Negligible heat of mixing
Equal or close heats of vaporization
Continuous / retrification distillation
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.
Continuous / retrification
distillation
Design and operation of a
distillation column depends on the
feed and desired products
A continuous distillation is often a
fractional distillation and can be a
vacuum distillation or a steam
distillation.
Calculation for number of plates:
Mc-Cabe & Thiele
Lewis-Sorel Method
Continuous / retrification
distillation
Mc-Cabe Thiele Method
The intersection of operating
lines, q
Feed enters as liquid at its boiling point
that the two operating lines intersect at
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.
The condition of the feed (F) determines
the relation between the vapor (V m) in the
stripping section and (Vn) in the enriching
section, as well as between L m and Ln.
The intersection of operating
lines, q
heat needed to vaporize 1 mol of feed at entering conditions
q
molar latent heat of vaporizati on of feed
Hv H F
q
Hv H L
q also as the no. of moles of saturated liquid
produced on the feed plate by each mole of feed
added to tower.
The relationship between
Lm Ln qFflows (above
1) & below
entrance of feed: Vn Vm (1 q )F (2)

Rewrite the equations

Vn y of
Ln x enriching
Dx D (3) & stripping
without the tray subscripts:
Vm y Lm x Wx w ( 4)

(Vm V(3)
Subtracting n )y (Lm (4)
from Ln )x (Dx D Wx w ) (5 )
The intersection of operating lines, q
Substituting:Fx F Dx D Wx w , Eq. (1) & (2) into
(5) will produce:
q x
y x F (q line equation )
q 1 q 1
The equation locus of the intersection of the
two operating lines
Setting y = x in the equation, the intersection of
the q-line equation with the 45o line is y = x = xF,
where xF is the overall composition of the feed.
Slope = q/(q-1).
A convenient way to locate a stripping line
operating line is 1st to plot the enriching
operating line and then q-line.
The intersection of operating
lines, q
Depending on the
state of the feed, the
feed lines will have
different slopes:
q = 0 (saturated vapour)
q = 1 (saturated liquid)
0 < q < 1 (mix of liquid
and vapour)
q > 1 (subcooled liquid)
q < 0 (superheated
vapour)
Animation of the construction
of enriching, stripping & q
operating lines
http://www.separationprocesses.com/Distillat
ion/DT_Animation/McCabeThiele.html
Exercise
1) 11.4-1
2) 11.4-2
Steps of McCabe Thiele
Method
1. Plot equilibrium mole fraction for
component that more volatile.
[ y(mole fraction A in vapor) vs
x(mole fraction A in liquid)]
2. Make 45 line (x=y)
3. Plot enriching line;
4. Plot q line
5. Plot stripping line
6. Determine the stages
7. Feed tray location
Tutorial
11.4-5
Exercise 11.4-6
Repeat Problem 11.4-1 but use a
feed that
is saturated vapor at dew point.
Determine
(a) Minimum reflux ratio, Rm
(b) Minimum number of theoretical
plates at total reflux
(c) Theoretical number of trays at
an operating reflux ratio of
1.5Rm
Example
A mixture of benzene and toluene
containing 40 mole% benzene is to be
separated to give a product of 90 mole%
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
Example
Solution
Feed, xF = 0.4
Product, xD = 0.9
Bottom, xw = 0.10
Taking basis; 100 kmol of feed. A total
mass balance:
F = D + W hence; W = 100 D (Eq. 1)
A balance on MVC (benzene);
F x F D x D W xw 100 (0.4) D(0.9) W (0.1)
40 0.9D 0.1W (Eq.2)

From the calculations;

D = 37.5 kmol, W = 62.5 kmol
Solution
Using notation from reflux:
Ln
R Ln RD Ln 3D Ln 3(37 .5)
D
Ln 112 .5

From material balance at the top

stage;Vn 1 Ln D Vn 1 150 kmol

Thus,
y the
Ln
x operating

D
x y line

112 .5 equation:
x
D
xD
n 1 n D n 1 n
Vn 1 Vn 1 150 Vn 1
y n 1 0.75 x n 0.225
Solution
Since the feed is all liquid at its
boiling point, it will all run down as
increased reflux to the plate below:
Lm Ln F Lm 112 .5 100 Lm 212 .5kmol

The material balance at the bottom:

Lm Vm 1 W Vm 212 .5 62 .5 Vm 150 kmol Vn

Bottom operating line equation:

Lm W 212 .5 62 .5
y m 1 xm xw y m 1 xm (0.1)
Vm 1 Vm 1 150 150
y m 1 1.417 x m 0.0417
Example
11,200 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. Determine;
The flowrate of distillate and bottom product (kg/h)
The minimum reflux ratio, Rm.
The number of theoretical stages required if the
reflux ratio used is 1.5 times the minimum reflux
ratio
The position of the feed tray
The MW of Benzene = 78
The MW of Toluene = 92
Solution
xF = 0.5
xD = 0.94
Xw = 0.02
From the total & component
material balance:
D = 5739.1 kg/h, W = 5260.9
kg/h
Convert mass fraction to mol
fraction. (Basis of calculation =
100kg)
Solution
Find q-line. Feed enters at 75%
vapor.
q 0.75(q ) 0.25(q )
vapor liquid

q 0.75(0) 0.25(1.0) q 0.25

q line equation
q x
y q x q f
q 1 q 1
0.25 0.54
yq xq y q 0.333 x q 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 (0.3, 0.62 ) forq line
Solution
From the graph, y intercept for q-
line = 0.36
x
0.36D0.95
0.36 R 1.64 m
Rm 1 Rm 1

The number of theoretical stages

required if the reflux ratio used is 2
times
R the
2Rmin minimum reflux ratio
2(1.64 ) R 3.28
R 1
y n 1 xn xD
R 1 R 1
3.28 1
y n 1 xn (0.95 )
3.28 1 3.28 1
y n 1 0.766 x n 0.222
At x 0.5, y n 1 0.766 (0.5) 0.222 y n 1 0.605
Plot (0.95, 0.95 ) and (0.5, 0.605 ) for enriching OL
Solution
The number of theoretical stages
required = 10.5 stages including
boiler
Feed plate location: 5 from top.
Q1 Final Exam Jan 2012
A distillation column with a total conden
and partial reboiler is used to separate
ethanol-water mixture. The feed contain
20 mole% ethanol enters the column at
rate 1000 kg.moles/hr. A distillate comp
of 80 mole% ethanol and bottom compo
of 2.0 mole% ethanol are desired. The e
reflux ratio is 5/3 and it is returned as a
saturated liquid. It is assumed the cond
at constant molal overflow.
Given;
Enthalpy of feed at dew point, Hv =485
kJ/kg.mol
Enthalpy of feed at boiling point, HL =70
kJ/kg.mol
Enthalpy of feed at entrance condition, HF =15
kJ/kg.mol
The equilibrium curve of ethanol-water is
provided in
Appendix 1.
Determine;
i) The minimum number of tray
ii) The total number of equilibrium tray
 Q2, Final Exam Jan 2013
A total feed of 500 kmol/hr having an
overall composition of 55 mol% heptane
and 45mol% ethyl benzene is to be
fractionated at 1.0 bar to give a distillate
containing 95 mol% heptane and bottom
containing 2 mol% heptane. The feed enters
the tower at equimolar vapor and liquid.
The molecular weight of heptane = 100.2
kg/kmol and ethyl benzene =106.6 kg/kmol.
Equilibrium data for heptane-ethylbenzene is
given in Table 1.
Determine
a) The flowrates of distillate and
bottom product in kg/hr
b) The minimum reflux ratio
c) The number of theoretical
stages if the reflux ratio used is
1.3 times the minimum reflux
ratio.
Table 1: Equilibrium data for heptane
ethylbenzene
Temperature Mole fraction
(C) XH YH

98.3 1.00 1.00

102.8 0.79 0.90
110.6 0.49 0.73
119.4 0.25 0.51
129.4 0.08 0.23
136.1 0.00 0.00
AZEOTROPIC DISTILLATION
Azeotrope mixtures
Minimum boiling point
Maximum boiling point
Azeotropic Distillation
Azeotrope mixtures
Liquid and vapor are exactly the same
at a certain temperature
It is a special class of liquid mixture
that boils at a constant temperature at
a certain composition
Cannot be separated by a
simple/conventional distillation
Azeotropic Distillation
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
The purpose of the introduction of entrainer
is to break an azeotrope from being formed
by the original feed mixture
Function of entrainer:
To separate one component of a closely boiling
point
To separate one component of an azeotrope
Azeotropic Distillation
Azeotropic distillation is a widely practiced
process for the dehydration of a wide range of
materials including acetic acid, chloroform,
ethanol, and many higher alcohols.
The technique involves separating close boiling
components by adding a third component,
called an entrainer, to form a minimum boiling.
Normally ternary azeotrope which carries the
water overhead and leaves dry product in the
bottom.
The overhead is condensed to two liquid phases;
the organic, "entrainer rich" phase being
refluxed while the aqueous phase is decanted.
Azeotropic Distillation
A common example of distillation with an
azeotrope is the distillation of ethanol
and water.
Using normal distillation techniques,
ethanol can only be purified to
approximately 89.4%
Further conventional distillation is
ineffective.
Other separation methods may be used
are azeotropic distillation or solvent
extraction
Azeotropic Distillation
The concentration in the vapor phase is
the same as the concentration in the
liquid phase (y=x)
At this point, the mixture boils at
constant temperature and doesnt
change in composition
This is called as minimum boiling point
(positive deviation)
Azeotropic Distillation
The characteristic of such mixture is
boiling point curve goes through
maximum phase diagram
Example: Acetone-chloroform
Azeotropic Distillation
The most common examples:
Ethanol-water (89.4 mole%, 78.25 oC, 1
atm)
Carbon Disulfide-acetone (61 mol% CS2,
39.25oC, 1 atm)
Benzene-water (29.6 mol% water, 69.25
o
C, 1 atm)
Azeotropic Distillation
Let say binary mixture: A-B formed an
azeotrope mixture
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
Azeotropic Distillation
Example: Acetic acid-water using
entrainer n-butyl acetate
Boilingpoint of acetic acid is 118.1 oC, water is
100 oC & n-butyl acetate is 125 oC
The addition of the entrainer results in the
formation of a minimum boiling point azeotrope
with water with a boiling point = 90.2 oC.
The azeotropic mixture therefore be distilled
over as a vapor product & acetic acid as a
bottom product
The distillate is condensed and collected in a
decanter where it forms 2 insoluble layers
 Azeotropic Distillation
Example: Acetic acid-water using
entrainer n-butyl acetate
Top layer consist of nearly pure n-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)
Determination of Boiling Point
Temperature in multi component
distillation
The calculation is a trial and error
process
where
1. T is assumed
2. Value of relative volatility of
each component are then
calculated using K values at the
assume T.
3. Then calculate value of Kc
where
4. Find the T that corresponds to the
calculated value of Kc
5. Compare with T value read from
table that corresponds to the Kc.
6. If value is differ, the calculated T
is used for the next iteration.
7. After the final T is known, the
vapor composition is calculated
from
Yi= (relative volatility x liq mole
fraction)/(relative volatility x liq
mole fraction)
Example 11.7-1
Bubble point@boiling
point
Bubble point@boiling point
=temperature at which liquid
begins to vaporize
Dew point
=temperature at which liquid
begins to condense out of the
vapor