DISTILLATION

Contents

11.1 vapor-liquid equilibrium relations

11.2 Single Stage Equilibrium contact stages

11.3 Simple Distillation Methods

11.4 Distillation with reflux and McCABE-THIELE method

11.5 Ponchon-Savarit method

11.6 Distillation and Absorption Efficiencies for tray and packed towers

11.7 Fractional distillation using enthalpy-concentration method

11.8 Multi component distillation

11.1 vapor-liquid equilibrium relations
11.1.1 Phase rule and Raoult`s Law
As the gas-liquid systems , the equilibrium in vapor-liquid system is restricted by the
phase rule .
An ideal Law , Raoult`s Law , can be defined for vapor- liquid phases equilibrium

p
A
=P
A
.x
A
Where
p
A
=partial pressure of component A in the vapor (atm)
P
A
=the vapor pressure of pure A (atm)
x
A
=mole fraction of A in the liquid

11.1.2 Boiling-point diagrams and x-y plots

For example ; the system benzene-toluene follows Raoult`s law . So the
following equation can be used to calculate the boiling-point Diagram
P
x P
P
p
y
P x P x P
P p p
A A A
A
A B A A
B A



) 1 (
Example 11.1.1
Calculate the vapor pressure and liquid composition in equilibrium at 95C
o
(368.2
K) for benzene- toluene using the vapor pressure from table 11.1.1 at 101.32kPa

Solution
from table 11.1.1
For benzene P
A
=155.7 kPa
For toluene P
B
= 63.3 kPa

155.7(x
A
) + 63.3 (1-x
A
)=101.32 kPa
x
A
=0.411 and
x
B
= 1-0.411=0.589 kPa

y
A
=(P
A
x
A
)/P = (155.7 x 0.411)/101.32 = 0.632

P x P x P
A B A A
) 1 (
11.2 Single Stage Equilibrium contact stages

If a vapor-liquid system is being considered , where the stream V
2
is the vapor
and L
o
is the liquid, and the two streams are brought into contact in a single
equilibrium stage , the boiling point or the x-y equilibrium relation similar to
henry`s law is not available

Since we are considered only two components A and B only the following
equations are used for the material balance
AM A A A Ao o
o
Mx y V x L y V x L
M V L V L


1 1 1 2 2
1 1 2
1
If sensible heat effects are small and the latent heats of both compounds
are the same , then when 1 mol of A condenses , 1mol of B must vaporized .
Hence the total moles of vapor V
2
entering will equal V
1
leaving and L
o
=L
1
.
This case is called one of the constant molal overflow

Example 11.2.1
A vapor at the Dew point and 101.32 kPa contains a mole fraction of 0.4
benzene (A) and 0.6 toluene (B) and 100kg mol total brought into contact with
110 kg mol of a liquid at the boiling point containing a mole fraction of 0.3
benzene and 0.7 toluene . The two streams are connected in a single stage,
and the outlet streams leave in equilibrium with each other .
Assume constant molal overflow
Calculate the amounts of compositions of the exit streams
Solution
V
2
=100 kgmol
y
A2
= 0.4
L
o
=110
x
Ao
= 0.3

For constant molal overflow
V
2
=V
1
and L
o
=L
1
1 1
1 1 1 2 2
100 110 ) 4 . 0 ( 100 ) 3 . 0 ( 110
1
A A
A A A Ao o
y x
y V x L y V x L


To solve the equation , the equilibrium relation between y
A1
and x
A1
in figure
11.1.1 must be used . This is by trial and error

1. Assume x
A1
=0.2
2. Sub. In the equation then y
A1
=0.51
3. Plot the equilibrium relation
4. Plot x
A1
and y
A1
on the graph
5. It is evident that y
A1
=0.51 and x
A1
=0.2 do not fall on the curve
6. Assume x
A1
=0.4 then y
A1
=0.29 plot this point on the graph
7. Assume x
A1
=0.3 then y
A1
= 0.4 . Plot this point on the graph
8. At the intersection of this line with the equilibrium curve , y
A1
= 0.455 and x
A
=0.25


11.3 Simple Distillation Methods
11.3.1 introduction

the basic requirements for the separation of components by distillation is that the
composition of the vapor be different from the composition of the liquid with which it
is in equilibrium at the boiling point of the liquid

Distillation is concerned with solutions where all components are appreciably
volatile , where both components will be in the vapor phase

In evaporation , by contrast , of a solution of salt and water for example , the
water will vaporize but the salt will not

11.3.2 relative volatility of vapor-liquid system
the greater the difference between the equilibrium line and the 45
o
line , the
greater the difference between the vapor composition y
A
and the liquid composition
x
A
. Hence the separation will be more easily made
A numerical measure of this separation is the Relative Volatility
AB

A
A
A
B
A
AB
B B
B
A A
A
A A
A A
B B
A A
AB
x
x
y
also
P
P
P
x P
y
P
x P
y
x y
x y
x y
x y
) 1 ( 1
.
) 1 /( ) 1 (
/
/
/

Where
AB
is the relative volatility of A with respect to B in the binary system
If the system obeys Raoults Law , then
Please see example 11.3.1 P701
11.3.2 Equilibrium or flash distillation
Heater
F,x
F
L , x
V, y
Separator
In equilibrium or flash distillation, which occurs in single stage, a liquid mixture is
partially vaporized . The vapor allowed to come to equilibrium with the liquid , and
the vapor and the liquid phases are then separated.
Fx
F
= V y + L x
Since L=F-V
Then Fx
F
=V y +(F-V) x

11.3.3 Simple Batch or differential Distillation
The first portion of condensed liquid from the vapor will be of the component
with the lower volatility
L moles Liquid x
V moles vapor to
condense y
av
x
x
y L L x L x L
x y
dx
L
L
L
dL
) (
ln
2 1 2 2 1 1
2
1
1
2

The average composition of total material distilled , y
av
can be obtained by
material balance

Example 11.3.2
A mixture of 100 mol containing 50mol% n-heptane is distilled under differential
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?
For n-heptane
x y x y x y
1.000 1.000 0.398 0.836 0.059 0.271
0.867 0.984 0.254 0.701 0 0
0.594 0.925 0.145 0.521
Solution
L
1
= 100 mol
x
1
= 0.5
L
2
= 60 mol
V= 40 mol

5 . 0
2
51 . 0
60
100
ln
x
x y
dx
Sub. In the integration
X
2
is unknown and to solve this problem , we plot the equilibrium data so the values of y
can be obtained from this curve
Now we have already the Area under the curve (the value of the integration ) and the
starting point x
1
, the value of x
2
=0.277
Finally
100(0.5)=60(0.277)+40(y
AV
)
y
AV
=0.835

11.3.4 Simple Steam Distillation
Is a special type of Distillation for temperature sensitive materials like natural aromatic compounds
Many organic compounds tend to decompose at high sustained temperatures
Separation by normal distillation would then not be an option, so water or steam is introduced into the
distillation apparatus. By adding water or steam the boiling points of the compounds are depressed,
allowing them to evaporate at lower temperatures, preferably below the temperatures at which the
deterioration of the material becomes appreciable. If the substances to be distilled are very sensitive to
heat, steam distillation can also be combined with vacuum distillation . After distillation the vapors are
condensed as usual, usually yielding a two-phase system of water and the organic compounds, allowing
for simple separation.
Quiz
A continuous single-effect evaporator concentrates 6000 kg/h of a 4.0 wt %
salt solution entering at 300 K to a final concentration of 9 wt %. The vapor
space of the evaporator is at 101.325 kPa (1.0 atm abs) and the steam
supplied is saturated at 122 kPa. The overall coefficient U =1704 W/m2 .K.
Calculate the amounts of vapor and liquid product and the heat-transfer
area required. Assumed that, since it its dilute, the solution has the same
boiling point as water.