Inttroducction too Separration Proces

P ses
Two important questions in separation processes
Whaat are sseparattion prrocessees? 1. How much separating agent is required?
thhose ooperatioons whhich trransformm a m mixturee of 2. How fast can the separation be achieved?
substances into twwo or more
m prooducts which differ from The keys to these questions are the mass balance
eachh other iin compposition. analysis.

A geeneral vview off separration proces

p ses 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 o one stream
coonsist of 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
of matter
m or ennergy anda geenerallyy will causee the
mation oof a seccond phhase of matter.
form

5 6
App
plicatioon of Separaation Processses

7 8
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..

9 10
(2) Absorp
A ption/sttrippin ng proccesses: (3) Liquid-
L -liquid extracction:
* popula
p r in envvironmmental applicat
a tions, * used
u foor proceesses thhat requuires loow tempperaturre
* transfe
t r gas coomponnent fromm gas to
t liquiid operatiion,
or vicee versa, * transfe
t r solubble com
mponentt from one o liquuid to
* require
r es two pphases: liquid and gaas, anotherr,
* uses
u thhe differrent afffinity gas
g com mponentt * require
r es two pphases: two im mmiscibble or ppartiallyy
for gass and liqquid. miscible liquiids,
* uses
u thhe differrent afffinity componnents foor
Prodduction processses usiing absoorber separattion.
* scrubbiing smookestaccks,
* remova
r al of am
mmoniaa from refinery
r y, Prodduction processses usiing extrraction
* remove
r e CO2 ffrom aiir. * food prrocessinng,
* pharma
p aceutical sepaaration,
* oil
o puriificatioon.

11 12
(4) Solid-li
S quid exxtractiion: Phasse Tran
nsform
mation
* used
u liqquid too extracct compponent from
f a solid
matrix,, Phase D
Diagram
m of Water
W
* transfe
t r solubble com
mponentt from solid
s too liquidd,
* require
r es two pphases: solid aand liquuid,
* uses
u thhe solubbility off the coomponeent for separattion.

Prodduction processses usiing leacching

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

13 14
Phasse Equ
uilibriu
um Equilibrium-Stagged Op
peratioon

Single Stagedd Unit

15 16
Equilibrium-Stagged Op
peratioon Different Representation of VLE Data

Multipple Stagged Uniit (1) Ideal solution & Raoult's Law:

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 For a binary mixture of A and B;
Antoinne Equ uation:
ln P / PA = PA*XA ; PB = PB*XB = PB*(1 - XA)

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
Comp
pound A B C the Figure.
Benzene 13.85
594 2773.78 220.07
7 For ideal gas mixture, the total pressure is the sum of
Ethan
nol 16.67
758 3674.49 226.45
5
the partial pressures.

n-hep
ptane 13.85
587 2991.32 216.64
4
Total pressure PT = PA + PB

Tolue
ene 14.00
098 3103.01 219.79
9
Replacing for the partial pressures and re-arrange, we
have:
Wate
er 16.2
262 3799.89 226.35
5
PT = ( PA* - PB* ) XA + PB*
The constaant-tem mperatu ure phaase diaagram for an iideal
soluttion is sshown in the Figure
F below..

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
0.722419
119.9885 52.66227

119.9885
0.722419 0.855695
101.3
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?

Solution: Ambient pressure = 101.3 kPa

1)
The T-X-Y
Y plot iss as beloow: 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/ww waterr = 30 g waterr + 70 g ethanool: (2) Tabulated data:
xW = 0.3, connvert to moles
30w% % wateer =30/18 molles wateer + 700/46 mooles ethhanol X (e th a n o l)
0
X (w a te r) Y (e th a n o l)
1 0
Y (w a te r)
1
T (C )
100
= 1.667 molees wateer + 1.552 molees ethannol 0 .0 1 9 0 .9 8 1 0 .1 7 0 .8 3 9 5 .5
Totaal moless = 3.199 0 .0 7 2 1 0 .9 2 7 9 0 .3 8 9 1 0 .6 1 0 9 89
0 .0 9 6 6 0 .9 0 3 4 0 .4 3 7 5 0 .5 6 2 5 8 6 .7
XW = 1.667/3.19 = 0.52235 0 .1 2 3 8 0 .8 7 6 2 0 .4 7 0 4 0 .5 2 9 6 8 5 .3
XE = 1 - XW = 0.4765
0 0 .1 6 6 1 0 .8 3 3 9 0 .5 0 8 9 0 .4 9 1 1 8 4 .1

Bubbble poinnt at XE = 0.4765: TB = 87.5 oC, thhe

0 .2 3 7 7 0 .7 6 2 3 0 .5 4 4 5 0 .4 5 5 5 8 2 .7
0 .2 6 0 8 0 .7 3 9 2 0 .5 5 8 0 .4 4 2 8 2 .3
equillibrium
m YE = 0.68
0 0 .3 2 7 3 0 .6 7 2 7 0 .5 8 2 6 0 .4 1 7 4 8 1 .5

w point at YE = 0.4765: TD = 91.8 oC

0 .3 9 6 5 0 .6 0 3 5 0 .6 1 2 2 0 .3 8 7 8 8 0 .7
Dew 0 .5 0 7 9 0 .4 9 2 1 0 .6 5 6 4 0 .3 4 3 6 7 9 .8
0 .5 1 9 8 0 .4 8 0 2 0 .6 5 9 9 0 .3 4 0 1 7 9 .7
0 .5 7 3 2 0 .4 2 6 8 0 .6 8 4 1 0 .3 1 5 9 7 9 .3
0 .6 7 6 3 0 .3 2 3 7 0 .7 3 8 5 0 .2 6 1 5 7 8 .7 4
0 .7 4 7 2 0 .2 5 2 8 0 .7 8 1 5 0 .2 1 8 5 7 8 .4 1
0 .8 9 4 3 0 .1 0 5 7 0 .8 9 4 3 0 .1 0 5 7 7 8 .1 5
1 0 1 0 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: Exam mple 33: Deterrmine the
t conncentraation off an alccohol
soluttion iff its buubble point
p ttemperaature is 92.5 oC?
T-x-y ddiagram
m 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

Deteermine the commpositiion of thhe vapoor at eqquilibriuum

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

31 32
(4) Relative Volatility (AB) Exammple 44: Plot X-YX diaagram ffor isobbutane--isopenntane
AB = (YA XB)/(YB XA) mixtture if tthe relaative voolatilityy is known to bbe 1.7
YA = AB XA/(1 + (AB -1)XA)
X ic 4 Y ic 4
T(C) Kic4 KC6 alpha
0 0
0 .1 0 .1 5 8 8 7 9
0 .2 0 .2 9 8 2 4 6
10 1.1 0.06 18.33333 0 .3 0 .4 2 1 4 8 8
20 1.5 0.095 15.78947 0 .4 0 .5 3 1 2 5
0 .5 0 .6 2 9 6 3
30 2 0.15 13.33333 0 .6 0 .7 1 8 3 1
40 2.5 0.2 12.5 0 .7 0 .7 9 8 6 5 8
50 3 0.3 10 0 .8 0 .8 7 1 7 9 5
0 .9 0 .9 3 8 6 5
60 3.8 0.4 9.5 1 1
70 4.6 0.54 8.518519
80 5.5 0.7 7.857143
90 6.5 0.9 7.222222

33 34