Inttroducction too Separration Proces

P
ses
Whaat are sseparattion prrocessees?
thhose ooperatioons whhich trransform
m a m
mixturee of
substances into tw
wo or more
m
prooducts which differ from
eachh other iin compposition.

A geeneral vview off separration proces

p
ses

Two important questions in separation processes

1. How much separating agent is required?
2. How fast can the separation be achieved?
The keys to these questions are the mass balance
analysis.

Processing methods
1. Single-stage process (batchwise or continuously)
2. Multiple-stage process (batchwise or continuously)
Equilibrium relations between phases
1. Phase rule and equilibrium
2. Gas-liquid equilibrium

Figu
ure 1.

Generral sepaaration process

Figuure 1 sshows a simpple schhematicc of a separation

process. It com
mprises four sectionns: thee feed,, the
separration device, thee sepaaration agentt and the
prodducts. The ffeed may
m
coonsist of
o one stream
m of
matter or off severaal streaams, whhich ennters thee separation
devicce andd is forced to be sepparatedd into aat leastt two
prodduct sttreams of differen
d
nt com
mpositiion, bby a
separration aagent. The separati
s
ion ageent can be a strream
or ennergy and
of matter
m
a
geenerallyy will causee the
form
mation oof a seccond phhase of matter.
5

App
plicatioon of Separaation Processses

Distiilled Water

Typ
pes of S
Separaation Proces
P
sses
(1) Distilla
D
tion prrocessees:
* most
m popular separattion proocess,
* capablee of prooducingg pure substan
s
nce from
m mixtture,
* require
r
es two pphases: liquid and vaapor,
* uses
u ennergy too accom
mplish separattion.
Prodduction processses usiing disttillationn
* oil
o prodductionn,
* air sepaarationn,
* distilla
d
tion off wine to cognac and spirits..

10

(2) Absorp
A
ption/sttrippin
ng proccesses:
* popula
p
r in envvironm
mental applicat
a
tions,
* transfe
t
r gas coomponnent from
m gas to
t liquiid
or vicee versa,
* require
r
es two pphases: liquid and gaas,
* uses
u thhe differrent afffinity gas
g com
mponentt
for gass and liqquid.
Prodduction processses usiing absoorber
* scrubbiing smookestaccks,
* remova
r
al of am
mmoniaa from refinery
r
y,
* remove
r
e CO2 ffrom aiir.

11

(3) LiquidL
-liquid extracction:
* used
u
foor proceesses thhat requuires loow tempperaturre
operatiion,
r solubble com
* transfe
t
mponentt from one
o liquuid to
anotherr,
* require
r
es two pphases: two im
mmiscibble or ppartiallyy
miscible liquiids,
* uses
u thhe differrent afffinity componnents foor
separattion.
Prodduction processses usiing extrraction
* food prrocessinng,
p
aceutical sepaaration,
* pharma
* oil
o puriificatioon.

12

(4) Solid-li
S
quid exxtractiion:
* used
u
liqquid too extracct compponent from
f
a solid
matrix,,
r solubble com
* transfe
t
mponentt from solid
s
too liquidd,
* require
r
es two pphases: solid aand liquuid,
* uses
u thhe solubbility off the coomponeent for separattion.

Phasse Tran
nsform
mation
Diagram
m of Water
W
Phase D

Prodduction processses usiing leacching

* mining
m
g,
* food prrocessinng,
* pharma
p
aceutical.

13

14

uilibriu
um
Phasse Equ

peratioon
Equilibrium-Stagged Op
Single Stagedd Unit

15

16

Equilibrium-Stagged Op
peratioon

Different Representation of VLE Data

(1) Ideal solution & Raoult's Law:

Multipple Stagged Uniit

Raoult's Law states that, for an ideal solution, the

equilibrium partial pressure of a component at a fixed
temperature T equals the product of its vapor pressure
(when it is pure) and its mole fraction in the liquid:
For component A,
PA = YAPT = PA*XA
YA = (PA*/PT)XA
where
PA = equilibrium partial pressure of component-A
in the gas at temperature T
PA* = vapor pressure of pure liquid A at temperature T
XA = liquid-phase mole fraction of component-A
at temperature T
YA = gas-phase mole fraction of component-A
at temperature T
PT = system total pressure
Note: The vapor pressure is a constant at constant
temperature.
Hence, from the equation, we see that Raoult's Law
predicts a linear equilibrium relationship between P
and X.

17

18

Vapoor presssures oof pure liquid can

c be estimatted usinng
Antoin
ne Equ
uation:
ln P
/

For a binary mixture of A and B;

wherre A, B and C are constantss.

The partial pressures PA and PB vary linearly with XA.

This is shown as PA vs. X and PB vs. X respectively in
the Figure.

Comp
pound

Benzene

13.85
594

2773.78

220.07
7

Ethan
nol

16.67
758

3674.49

226.45
5

n-hep
ptane

13.85
587

2991.32

216.64
4

Tolue
ene

14.00
098

3103.01

219.79
9

16.2
262

3799.89

226.35
5

Wate
er

The constaant-tem
mperatu
ure phaase diaagram for an iideal
soluttion is sshown in the Figure
F
below..

PA = PA*XA ; PB = PB*XB = PB*(1 - XA)

For ideal gas mixture, the total pressure is the sum of

the partial pressures.
Total pressure

PT = PA + PB

Replacing for the partial pressures and re-arrange, we

have:
PT = ( PA* - PB* ) XA + PB*

The total pressure varies linearly with XA . This is

shown as PT vs. X in the Figure.
In addition, PA = YA PT thus PA*XA = YA PT, and we
have:

Substitute into earlier equation to remove XA:

19

20

PT PA* = (PA* - PB* ) ( YA PT ) + PA* PB*

Phasse Diaggram (pressuree is connstant):

PT PA* - (PA* - PB* ) ( YA PT ) = PA* PB*

The total pressure varies nonlinearly with YA. This is

shown as PT vs. Y in the Figure.
Also, since PA* XA = YA PT ; we have ,

All the above equations are useful in determining the

equilibrium variables X and Y.
Boiling Points of Mixture of Liquids
Even at constant pressure, depending on relative
concentrations of each component in the liquid, many
boiling point temperatures are possible for mixture of
liquids (solutions). For mixture, we use the term bubble
point when the liquid starts to boil, and dew point
when the vapor starts to condense. For liquid solution,
bubble points need not be the same as dew points.
Indeed, boiling of a liquid mixture takes place over a
range of boiling points. Likewise, condensation of a
vapor mixture takes place over a range of condensation
points.

21

22

Ideall Solutiion: bennzene and

a toluuene

Example 1: Determine the T-x-y relationship for

ethanol and water using Antoine Equation assuming
that ethanol-water form an ideal solution. Plot the
resulting data. Please use ambient pressure.
Solution: Ambient pressure = 101.3 kPa
Take an example of 82.63185oC:

16.6758 3674.49/(82.63185 + 226.45)=4.7874

PE* = 119.9885
lnPW*=16.2620 3799.89/(82.63185 + 226.35)=
PW* = 52.66227

101.3 52.66227
119.9885 52.66227
119.9885
0.722419
101.3

0.722419
0.855695

XW = 1- XE = 1- 0.722419 = 0.277581
YW = 1- YE = 1- 0.855695 = 0.144305
Repeat this process for other temperatures, we have the
following table:

23

24

Example 2: For the system of ethanol-water mixture at

ambient pressure, determine
1) What is the boiling point of pure ethanol and water?
2) What is the bubble point temperature of a mixture
containing 0.25 mole fraction of ethanol? What is its
dew point temperature?
3) What are the bubble and dew point temperatures of a
solution containing 30 wt.% water?

Y plot iss as beloow:

The T-X-Y

Solution: Ambient pressure = 101.3 kPa

1)

For pure ethanol,

101.3 4.618
= 16.6758 3674.49/(T + 226.45)
The normal boiling point of ethanol is T = 78.3 oC

For pure water,

101.3 4.618
= 16.2620 3799.89/(T + 226.35)
The normal boiling point of water is T = 100 oC

2)
Bubble point at XE = 0.25: from the Figure, TB = 92 oC,
the equilibrium YE = 0.46
Dew point at YE = 0.25: from the Figure, TD = 96 oC,

25

26

3) 300% w/w
w waterr = 30 g waterr + 70 g ethanool:
xW = 0.3, connvert to moles
30w%
% wateer =30/18 molles wateer + 700/46 mooles ethhanol
= 1.667 molees wateer + 1.552 molees ethannol
Totaal moless = 3.199
XW = 1.667/3.19 = 0.52235
XE = 1 - XW = 0.4765
0
Bubbble poinnt at XE = 0.4765: TB = 87.5 oC, thhe
equillibrium
m YE = 0.68
0
Dew
w point at YE = 0.4765: TD = 91.8 oC

(2) Tabulated data:

X (e th a n o l)
0
0 .0 1 9
0 .0 7 2 1
0 .0 9 6 6
0 .1 2 3 8
0 .1 6 6 1
0 .2 3 7 7
0 .2 6 0 8
0 .3 2 7 3
0 .3 9 6 5
0 .5 0 7 9
0 .5 1 9 8
0 .5 7 3 2
0 .6 7 6 3
0 .7 4 7 2
0 .8 9 4 3
1

X (w a te r) Y (e th a n o l)
1
0
0 .9 8 1
0 .1 7
0 .9 2 7 9
0 .3 8 9 1
0 .9 0 3 4
0 .4 3 7 5
0 .8 7 6 2
0 .4 7 0 4
0 .8 3 3 9
0 .5 0 8 9
0 .7 6 2 3
0 .5 4 4 5
0 .7 3 9 2
0 .5 5 8
0 .6 7 2 7
0 .5 8 2 6
0 .6 0 3 5
0 .6 1 2 2
0 .4 9 2 1
0 .6 5 6 4
0 .4 8 0 2
0 .6 5 9 9
0 .4 2 6 8
0 .6 8 4 1
0 .3 2 3 7
0 .7 3 8 5
0 .2 5 2 8
0 .7 8 1 5
0 .1 0 5 7
0 .8 9 4 3
0
1

Y (w a te r)
1
0 .8 3
0 .6 1 0 9
0 .5 6 2 5
0 .5 2 9 6
0 .4 9 1 1
0 .4 5 5 5
0 .4 4 2
0 .4 1 7 4
0 .3 8 7 8
0 .3 4 3 6
0 .3 4 0 1
0 .3 1 5 9
0 .2 6 1 5
0 .2 1 8 5
0 .1 0 5 7
0

T (C )
100
9 5 .5
89
8 6 .7
8 5 .3
8 4 .1
8 2 .7
8 2 .3
8 1 .5
8 0 .7
7 9 .8
7 9 .7
7 9 .3
7 8 .7 4
7 8 .4 1
7 8 .1 5
7 8 .3

The experimental VLE data are usually obtained using

special stills where the temperature, pressure and
concentrations of the components in liquid and vapor
phases could be accurately determined.
X, Y (mole fraction) x, y (mass fraction)
for binary mixture (2-components):
x = X*MWA/(X *MWA + (1-X) *MWB)
** derive the equations for n-component and for x X

27

28

(3) G
Graphiccal reprresentattion:
T-x-y ddiagram
m

Exam
mple 33: Deterrmine the
t conncentraation off an alccohol
soluttion iff its buubble point
p
ttemperaature is 92.5 oC?
Whaat shouuld be the ethhanol contentt of thhe vapoor at
equillibrium
m with this
t soluution?
Whaat is thee bubblle pointt tempeerature of 78 aand 95 wt%
alcohhol?

Soluution:
At TB = 92..5 oC: xA = 0.004, yA = 0.28
Wheen xA = 0.78 : TB = 78.3 oC
Wheen xA = 0.95 : TB = 78.3 oC

29

30

(3) Graphic
G
cal reprresentattion:
X-Y orr McCaabe-Thiiele diaagram

mpositiion of thhe vapoor at eqquilibriuum

Deteermine the com
with an 30, 60, 800 and 900 mol.%
% ethannol soluution.

31

32

(4) Relative Volatility (AB)

AB = (YA XB)/(YB XA)
YA = AB XA/(1 + (AB -1)XA)

Exam
mple 44: Plot X-Y
X diaagram ffor isobbutane--isopenntane
mixtture if tthe relaative voolatilityy is known to bbe 1.7
X ic 4

T(C)

Kic4

10
20
30
40
50
60
70
80
90

KC6

1.1
1.5
2
2.5
3
3.8
4.6
5.5
6.5

33

Y ic 4

alpha

0.06
0.095
0.15
0.2
0.3
0.4
0.54
0.7
0.9

18.33333
15.78947
13.33333
12.5
10
9.5
8.518519
7.857143
7.222222

0
0
0
0
0
0
0
0
0

0
.1
.2
.3
.4
.5
.6
.7
.8
.9
1

0 .1 5
0 .2 9
0 .4 2
0 .5
0 .6
0 .7
0 .7 9
0 .8 7
0 .9

8
8
1
3
2
1
8
1
3

8
2
4
1
9
8
6
7
8

7
4
8
2
6
3
5
9
6

34

0
9
6
8
5
3
1
8
5
5
1