The Distillation Process

Separation Processes
Lecture 6
The Distillation Process

A less abstract representation

Some questions .
At what temperature(s) should I operate this
process?
At what pressure(s)?
What compositions of products can I expect
to achieve?
How much of each product can I get?

Vapour-Liquid Phase Equilibrium

When two phases are in equilbrium there is no net
exchange of any property between them.
Thus the driving forces causing transfer of all
properties must be equal in both phases.
The driving force for transfer of material is fugacity.
Thus for phases in equilibrium, the fugacity of each
species in a phase must be equal to that of the same
species in the other phase.

Vapour-Liquid Phase
Equilibrium, Summary
Condition for phase equilibrium is:
Fugacity of species i in vapour phase =
Fugacity of species i in liquid phase
fG,i = fL,i

For a gas or vapour:

fG,i pi = P yi

Here P is pressure and yi is mole fraction in

vapour of species i (yi=1 for pure i).

Vapour-Liquid Phase
Equilibrium, Summary
For an ideal liquid mixture:

Mixtures of Two Components

With only two species present:
y1 = P*1(T).x1/P
y2 = P*2(T).x2/P

fL,i P'i = P*i(T) xi

Here P*i(T) is vapour pressure of pure i at

temperature T and xi is liquid mole fraction.
Hence:
yi P = xi P*i(T)

or:
yi = P*i(T).xi/P

Mixtures of Two Components

Mole fractions sum to 1 in a mixture:

x1 + x2 = 1
y1 + y2 = 1

Where one component is more volatile

choose this to be the reference (m.v.c.)

Some Consequences
The two equations:
x = (P P*2(T))/(P*1 P*2(T))
y = P*1(T).x/P

Hence:
y = P*1(T).x/P
(1 y) = P*2(T). (1 x)/P

Thence:
x = (P P*2(T))/(P*1(T) P*2(T))
y = P*1(T).x/P

Some Consequences
The calculation of y from x and vice versa
at a given pressure P turns out to be so
useful that it is often presented graphically.
An xy graph is produced by taking a range
of temperatures between the boiling points
of the two species and calculating x with the
first equation and y with the second.
Corresponding x and y values are then
plotted.

imply that given any two of x, y, T, P we

can calculate all the others, e.g. given T and
P calculate x then y.
Only the above calculation is easy, all
others require numerical solution.

Computer generated Vapour-liquid

equilibrium data at fixed pressure
PPDS VLE PACKAGE: V7.07

METHOD:

RKS

GIVEN PRESSURE: 1013250.00 N/M2 (10 Atm)

KEY COMPOUND: PROPANE (+ pentane)

CALC TEMPERATURE LIQUID VAPOUR PHASE

NO
1
2
3
4
5

K
397.9392
390.0381
382.4341
375.2158
368.4410

(X)
0.0000
0.0400
0.0800
0.1200
0.1600

(Y)
0.0000
0.1492
0.2807
0.3940
0.4901

BUBBLE
BUBBLE
BUBBLE
BUBBLE
BUBBLE

Computer generated Vapour-liquid

equilibrium data at fixed pressure
CALC
NO
6
7
8
9
10
11
12
13
14
15

TEMPERATURE
K
(X)
362.1386 0.2000
356.3145 0.2400
350.9549 0.2800
346.0339 0.3200
341.5194 0.3600
337.3757 0.4000
333.5667 0.4400
330.0578 0.4800
326.8169 0.5200
323.8135 0.5600

LIQUID VAPOUR PHASE

(Y)
0.5707 BUBBLE
0.6380 BUBBLE
0.6939 BUBBLE
0.7404 BUBBLE
0.7792 BUBBLE
0.8118 BUBBLE
0.8392 BUBBLE
0.8625 BUBBLE
0.8825 BUBBLE
0.8996 BUBBLE

Vapour-liquid equilibrium
diagram at fixed pressure

Computer generated Vapour-liquid

equilibrium data at fixed pressure
CALC
NO
16
17
18
19
20
21
22
23
24
25
26

TEMPERATURE
K
(X)
321.0208 0.6000
318.4138 0.6400
315.9701 0.6800
313.6693 0.7200
311.4931 0.7600
309.4244 0.8000
307.4475 0.8400
305.5479 0.8800
303.7120 0.9200
301.9270 0.9600
300.1810 1.0000

LIQUID
(Y)
0.9145
0.9276
0.9391
0.9493
0.9585
0.9669
0.9745
0.9815
0.9880
0.9942
1.0000

VAPOUR PHASE
BUBBLE
BUBBLE
BUBBLE
BUBBLE
BUBBLE
BUBBLE
BUBBLE
BUBBLE
BUBBLE
BUBBLE
BUBBLE

Single Stage Equilibrium Separation

Processes: Simple Distillation
In any single stage equilibrium separation
process the two product streams leave in
phase equilibrium.
This determines the operating
characteristics of the process, and in
particular the limitations of the process.

Single Stage Equilibrium Separation

Processes: Simple Distillation
Vapour-liquid phase equilibrium data,
measured, calculated by hand or computer,
and presented graphically or in tabular
form, provides nearly all the information
required to understand the process.

Using Equilibrium Data

Diagrams and tables are normally produced
at a specified fixed pressure. (We shall see
why later.)
Data relates:
liquid mole fraction x
vapour mole fraction y
temperature T

Some examples Fill in the values

Using Equilibrium Data
For any given liquid composition x we can
immediately determine the vapour
composition y and vice versa.
On the diagram the curve of y against x lies
above the diagonal line y=x
The diagram does not show temperature,
but its variation from the boiling point of
l.v.c. to that of m.v.c. is implicit.

Some examples Fill in the values

0.787
x
0.5000 0.086
0.1000 0.288
0.34
0.963
y
0.3000
0.7000
0.87
381
379
350
T, K 328.5
310
Then estimate temperatures from tabulated data.
20
21

311.4931 0.7600 0.9585 BUBBLE

309.4244 0.8000 0.9669 BUBBLE

13
14

330.0578 0.4800 0.8625 BUBBLE

326.8169 0.5200 0.8825 BUBBLE

3
4

382.4341 0.0800 0.2807 BUBBLE

375.2158 0.1200 0.3940 BUBBLE

8
9

350.9549 0.2800 0.6939 BUBBLE

346.0339 0.3200 0.7404 BUBBLE

Some other mixtures

x
0.5000 0.086
0.1000 0.288
0.87
0.34
y
0.3000
0.7000
T, K
310
Then estimate temperatures from tabulated data.

Some other mixtures

The following are sketch graphs of VLE
data for four two component mixtures.
Consider the following questions:
Rank in terms of ease of separation:
ethane and ethene
ammonia and water
propane and pentane
hexane and ethanol

Could this have been deduced from the pure

components' boiling points?

Ranking

The following are sketch graphs of VLE

data for four two component mixtures.
Consider the following questions:
What vapour product would you expect
from distillation units at these pressures
when liquid product contains m.v.c.:
0.2 mole fraction,
0.9 mole fraction?

Why were these particular pressures chosen

for each mixture?

Ethene-Ethane

Ammonia-Water

TB=133K at 1bar
TB=130K at 10bar
TB=15K at 1bar
TB=22K at 20bar

x=0.2, y=0.88
x=0.9, y=0.99

x=0.2, y=0.26
x=0.9, y=0.93

1 atm boiling points: ethene 169.2K, ethane 184.5K

Propane-Pentane

1 atm boiling points: ammonia 239.7K, water 373K

Hexane-Ethanol

Azeotrope

TB=78K at 1bar
TB=98K at 10bar

x=0.2, y=0.48
x=0.9, y=0.99

1 atm boiling points: propane 231K, pentane 309K

TB=9.4K at 1bar

x=0.2, y=0.51
x=0.9, y=0.78

1 atm boiling points: hexane 342.1K, ethanol 351.5K

Approximate Boiling Points at

elevated pressure
At 10 atm, approximately:
propane 300K, pentane 398K
ethene 220K, ethane 239K
ammonia 298K, water 428K
hexane 444K, ethanol 456K

At 20 atm, approximately:
propane 330K, pentane 441K
ethene 241K, ethane 263K
ammonia 323K, water 485K

At 50 atm, approximately:
ethene 278K, ethane 302K