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
Multicomponent distillation Part
5
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)

1.3: Vapor liquid equilibrium
DEFINITION:
EVAPORATION: The phase
transformation processes from liquid to
gas/vapor phase
VOLATILITY: The tendency of liquid to
change form to gas/vapor phase
a) VAPOR LIQUID EQUILIBRIUM OF AN
ORDINARY BINARY LIQUID MIXTURE
b) PREDICTION OF VAPOR LIQUID
EQUILIBRIUM COMPOSITIONS FOR
ORDINARY BINARY MIXTURES
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 compostions 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 = xA PA
o

pA = partial pressure of A in a vapor phase
xA = mole fraction of A in liquid phase
PA
o
=
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



Phase Rule
Example:
Calculate the vapor and liquid compositions in
equilibrium at 95
o
C (368.2K) for benzene-
toluene using the vapor pressure from Table
11.1-1 at 101.32 kPa.
Table 11.1-1
Solution
1.4: 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 & 45
o
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
concentration of B in the liquid:
Relative volatility () of a
mixture


AB relative volatility of A with respect to B in
the binary system
If the system obeys Raoults law for an
ideal system:


Separation is possible for > 1.0

A
A
A
B
A
AB
T
B B
B
T
A A
A
x
x
y
P
P
P
x P
y
P
x P
y
) 1 ( 1 +
= = = =
o
o
o
) 1 /( ) 1 (
/
/
/
A A
A A
x B
x A
AB
x y
x y
y
y
B
A

= = o
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


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
Use the following list of vapor pressure for pure n-heptane & n-octane
at various temperature.
Solution
Vapor Pressure
Temperature n-Hexane (A) n-Octane (B)
(C) kPa X
A
Y
A
kPa X
B
Y
B
68.7 101.3 1 1 16.1 0 0
79.4 136.7 0.6884 0.9290 23.1 0.3116 0.071
93.3 197.3 0.4007 0.7804 37.1 0.5993 0.2196
107.2 284.0 0.1920 0.5383 57.9 0.8080 0.4617
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
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
30
o
C 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) x
A
y
A
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
o
C
0
0.2
0.4
0.6
0.8
1
1.2
0 0.2 0.4 0.6 0.8 1 1.2
y
,

m
o
l

f
r
a
c
t
i
o
n

o
f

n
-
h
e
p
t
a
n
e

i
n

v
a
p
o
r

x, mol fraction of n-heptane in liquid
Determination of vapor-liquid equilibrium
composition for a flash distillation of n-heptane/n-
octane mixture
Figure: Equilibrium curve and operating line
370
375
380
385
390
395
400
370
375
380
385
390
395
400
0 0.2 0.4 0.6 0.8 1
T
e
m
p
e
r
a
t
u
r
e

(
K
)

Mol fraction of n-heptane in vapor (y) and liquid (x)
Determination of equilibrium temperature for a
flash distillation of n-heptane-n-octane mixture
x
y
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
vapor and liquid are kept in contact with
each
other until vaporization is complete.
Determine the composition of the vapor
and
liquid.
The equilibrium data are as follows,
where
x and y are mole fraction of n-pentane.
x (mol fraction of n-
pentane in liquid)
y (mol fraction of n-
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:
x
A =
0.430
y
A =
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 product
becomes leaner in A.
Simple batch distillation
Simple batch distillation
1. Raleigh equation for ideal and non-ideal
mixtures
Consider a typical differential distillation at an
instant time, t
1
as shown below:






Simple batch distillation
Now consider that the differential distillation at certain infinitesimal time
lapse,(dt), at t2 where t
2
=t
1
+ 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 y
av
can be obtained by material
balance: (integrate from Rayleigh
equation)
av
y L L x L x L ) (
2 1 2 2 1 1
+ =
av
Vy x L x L + =
2 2 1 1
Simple batch distillation
2. Simplified Raleigh equation for ideal
mixture

Consider a simple batch distillation
process at
an initial time, t
1
, as shown below
Simple batch distillation
L
1
=no of moles of binary mixture
containing A and B at t
1
A
1
= no of moles comp A in L
1
at
t
1
B
1
= no of moles comp B in L
1
at
t
1
x
1
= mol fraction of A in L
1
at t
1
dL= infinitesimal amount of liq
that has vaporized
dA=infinitesimal amount of A that
has vaporized
dB = infinitesimal of B that has
vaporized
L
1
= A
1
+ B
1
X
1


dL= dA + dB
y
Simple batch distillation
We know from definitions,


Since is constant for an ideal mixture,


After simplifying,

Rearranging,
|
.
|

\
|
+
= |
.
|

\
|
+
=
|
.
|

\
|
+
= |
.
|

\
|
+
=
B A
B
x
B A
A
x
dB dA
dB
y
dB dA
dA
y
B A
B A
AB
o
B A
A
dB dA
dB
B A
B
dB dA
dA
x y
x y
B B
A A
AB
+

+
+

+
= =
/
/
o
dB A
dA B
AB

= o
A
dA
B
dB
AB
= o
Simple batch distillation
Integrating within the limits of t1 and t2,


Since is constant,




Equation 5 known as simplified Raleigh
equation for simple batch distillation
which applicable for ideal solution.
} }
=
2
1
2
1
B
B
A
A
AB
A
dA
B
dB
o
2
1
2
1
2
1
2
1
ln ln
A
A
B
B
AB
A
A
B
B
AB
A B
A
dA
B
dB
= =
} }
o o
AB
o
) 5 .( ln ln
1
2
1
2
Eq
A
A
B
B
AB

|
|
.
|

\
|
=
|
|
.
|

\
|
o
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
From material balance:

Substiting into Eq. (4)




The unknown, x2 is the composition n of the
liquid L2 at the end of batch distillation.
mol L V L L V L L 60 40 100
2 1 2 2 1
= = = + =
} }
|
|
.
|

\
|

= |
.
|

\
|
|
|
.
|

\
|

=
|
|
.
|

\
|
1
2
5 . 0
2
2
1
1
60
100
ln
1
ln
x
x x
dx
x y
dx
x y L
L
dx
x y
x
}
|
|
.
|

\
|

=
5 . 0
2
1
510 . 0
Solution
By plotting graph versus x, the
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:


Average composition of total vapor distilled,
yav = 0.835
|
|
.
|

\
|
x y
1
dx
x y
x
}
|
|
.
|

\
|

5 . 0
2
1
835 . 0
40
60 277 . 0 100 5 . 0
2 2 1 1
2 2 1 1
=

=

= + =
av
av av av
y
y
V
L x L x
y V y L x L x


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)
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 leaves in equilibrium.
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 (reflux) will
supply the bulk of liquid need to mix with vapor.
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:

Conditions for constant molal overflow:
Heat loses negligible (achieved more easily in
industrial column)
Negligible heat of mixing
Equal or close heats of vaporization

. .... . ....
1 1 1 1
etc V V V etc L L L
n n n n n n
= = = = = =
+ +
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 L
n+1
from plate n+1 above, and
vapor, V
n-1
from plate n-1 below.
Plate n supplies liquid L
n
to plate n-1, and vapor V
n

to plate n+1
Action of the plate is to bring about
mixing so that the vapor V
n
of
composition y
n
reaches equilibrium with
the liquid Ln of composition x
n
.


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 x
F
.
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 (V
n
) in the enriching
section, as well as between L
m
and L
n
.
The intersection of operating lines,
q



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 flows above & below
entrance of feed:

Rewrite the equations of enriching & stripping
without the tray subscripts:

Subtracting (3) from (4)


feed of on vaporizati of heat latent molar
conditions entering at feed of mol vaporize to needed heat
q
1
=
L v
F v
H H
H H
q

=
) 2 ( ) 1 (
) 1 (
F q V V
qF L L
m n
n m
+ =
+ =
) 4 (
) 3 (
w m m
D n n
Wx x L y V
Dx x L y V
=
+ =
) 5 ( ) ( ) ( ) (
w D n m n m
Wx Dx x L L y V V + =
The intersection of operating
lines, q
Substituting: , Eq. (1) & (2) into (5)
will produce:


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 45
o
line is y = x = x
F
, where
x
F
is the overall composition of the feed.
Slope = q/(q-1).
A convenient way to locate a stripping line
operating line is 1
st
to plot the enriching operating
line and then q-line.
w D F
Wx Dx Fx + =
) (
1 1
equation line q
q
x
x
q
q
y
F

=
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/Distillation/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, R
m
(b) Minimum number of theoretical
plates at total reflux
(c) Theoretical number of trays at an
operating reflux ratio of 1.5R
m
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 stages needed
and the position of entry for the feed.
Example
Solution
Feed, x
F
= 0.4
Product, x
D
= 0.9
Bottom, x
w
= 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);



From the calculations;
D = 37.5 kmol, W = 62.5 kmol






) 2 . ( 1 . 0 9 . 0 40
) 1 . 0 ( ) 9 . 0 ( ) 4 . 0 ( 100
Eq W D
W D x W x D x F
w D F
+ =
+ = + =
Solution
Using notation from reflux:


From material balance at the top stage;

Thus, the operating line equation:


5 . 112
) 5 . 37 ( 3 3
=
= = = =
n
n n n
n
L
L D L RD L
D
L
R
kmol V D L V
n n n
150
1 1
= + =
+ +
225 . 0 75 . 0
150
5 . 112
1
1
1
1 1
1
+ =
+ = + =
+
+
+
+ +
+
n n
D
n
n n D
n
n
n
n
n
x y
x
V
D
x y x
V
D
x
V
L
y
Solution
Since the feed is all liquid at its boiling
point, it will all run down as increased
reflux to the plate below:

The material balance at the bottom:

Bottom operating line equation:


n m m m m
V kmol V V W V L = = = =
+
150 5 . 62 5 . 212
1
kmol L L F L L
m m n m
5 . 212 100 5 . 112 = + = + =
0417 . 0 417 . 1
) 1 . 0 (
150
5 . 62
150
5 . 212
1
1
1 1
1
=
= =
+
+
+ +
+
m m
m m w
m
m
m
m
m
x y
x y x
V
W
x
V
L
y
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
x
F
= 0.5
x
D
= 0.94
X
w
= 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)
Mol fraction: x
F
= 0.54, x
D
= 0.95, x
w
=
0.03
Solution
Find q-line. Feed enters at 75% vapor.



line forq and Plot
y y x Let
x y x y
q
x
x
q
q
y
equation line q
q q
q q q
q q
q q q q
f
q q
liquid vapor

= + = =
+ = |
.
|

\
|

|
.
|

\
|

=
|
|
.
|

\
|

|
|
.
|

\
|

= + =
+ =
) 62 . 0 , 3 . 0 ( ) 54 . 0 , 54 . 0 (
62 . 0 72 . 0 ) 3 . 0 ( 333 . 0 , 3 . 0
72 . 0 333 . 0
1 25 . 0
54 . 0
1 25 . 0
25 . 0
1 1
25 . 0 ) 0 . 1 ( 25 . 0 ) 0 ( 75 . 0
) ( 25 . 0 ) ( 75 . 0
Solution
From the graph, y intercept for q-line =
0.36

The number of theoretical stages
required if the reflux ratio used is 2 times
the minimum reflux ratio


64 . 1 36 . 0
1
95 . 0
36 . 0
1
m
m m
D
R
R R
x
=
+
=
+
OL enriching for and Plot
y y x At
x y
x y
x
R
x
R
R
y
R R R
n n
n n
n n
D n n
) 605 . 0 , 5 . 0 ( ) 95 . 0 , 95 . 0 (
605 . 0 222 . 0 ) 5 . 0 ( 766 . 0 , 5 . 0
222 . 0 766 . 0
) 95 . 0 (
1 28 . 3
1
1 28 . 3
28 . 3
1
1
1
28 . 3 ) 64 . 1 ( 2 2
1 1
1
1
1
min
= + = =
+ =
+
+
+
=
+
+
+
=
= = =
+ +
+
+
+
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 condenser
and partial reboiler is used to separate an
ethanol-water mixture. The feed containing
20 mole% ethanol enters the column at feed
rate 1000 kg.moles/hr. A distillate composition
of 80 mole% ethanol and bottom composition
of 2.0 mole% ethanol are desired. The external
reflux ratio is 5/3 and it is returned as a
saturated liquid. It is assumed the condition is
at constant molal overflow.
Given;
Enthalpy of feed at dew point, Hv =485 kJ/kg.mol
Enthalpy of feed at boiling point, H
L
=70 kJ/kg.mol
Enthalpy of feed at entrance condition, H
F
=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
iii) The feed location
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
(C)
Mole fraction
X
H
Y
H
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
o
C, 1 atm)
Carbon Disulfide-acetone (61 mol% CS
2
,
39.25
o
C, 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
Boiling point of acetic acid is 118.1
o
C, water is 100
o
C & n-butyl acetate is 125
o
C
The addition of the entrainer results in the
formation of a minimum boiling point azeotrope
with water with a boiling point = 90.2
o
C.
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
Kc= 1/(relative volatility x liq mole
fraction)


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
Y
i=
(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