Wha

th
subs
each


A ge


Figu


Figu
proc
separ
prod
matt
devic
prod
separ
of m
form
Int
at are s
hose o
tances
h other i
eneral v
ure 1.
ure 1 s
ess.
ration
ducts.
er or of
ce and
duct st
ration a
matter
mation o
troduc
separat
operatio
into tw
in comp
view of
Gener
shows
It com
devic
The f
f severa
d is for
treams
agent.
or en
of a sec
ction to
tion pr
ons wh
wo or m
positio
f separ
ral sepa
a simp
mprises
e, the
feed m
al strea
ced to
of d
The s
nergy a
cond ph
5
o Separ
rocesse
hich tr
more pro
n.
ration p
aration
ple sch
four
e sepa
may co
ams, wh
be sep
differen
separati
and ge
hase of
ration P
es?
ransform
oducts
proces
proces
hematic
section
aration
onsist o
hich en
parated
nt com
ion age
enerally
matter
Proces
m a m
which
ses
s
c of a
ns: the
agent
of one
nters the
d into a
mpositi
ent can
y will
.
ses
mixture
differ
separ
e feed,
t and
stream
e separ
at least
ion, b
be a str
cause
e of
from

ation
, the
the
m of
ation
t two
by a
ream
e the
6


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




App



plicatioon of SSepara

7
ation PProcessses







8



Disti


illed WWater

9


Typ

(1) D
* m
*
* r
* u

Prod
* o
*
* d



pes of S
Distilla
most p
capable
require
uses en
duction
oil prod
air sepa
distilla
Separa
tion pr
opular
e of pro
es two p
nergy to
proces
duction
aration
tion of
ation P
rocesse
separat
oducing
phases:
o accom
sses usi
n,
n,
f wine t

10
Proces
es:
tion pro
g pure s
liquid
mplish
ing dist
o cogn
sses
ocess,
substan
and va
separat
tillation
ac and
nce from
apor,
tion.
n
spirits.
m mixt
.
ture,


(2) A
* p
* t
* r
* u

Prod
*
* r
* r


Absorp
popula
transfe
or vice
require
uses th
for gas
duction
scrubbi
remova
remove
ption/st
r in env
r gas co
e versa,
es two p
he differ
s and liq
proces
ing smo
al of am
e CO
2
f
trippin
vironm
ompon

phases:
rent aff
quid.
sses usi
okestac
mmonia
from ai

11
ng proc
mental a
nent from
liquid
finity g
ing abso
cks,
a from r
ir.
cesses:
applicat
m gas t
and ga
gas com
orber
refinery

tions,
to liqui
as,
mponent
y,
id
t


(3) L
* u
* t
* r
* u

Prod
*
* p
* o


Liquid-
used fo
operati
transfe
another
require
miscib
uses th
separat
duction
food pr
pharma
oil puri
-liquid
or proce
ion,
r solub
r,
es two p
le liqui
he differ
tion.
proces
rocessin
aceutic
ificatio
extrac
esses th
ble com
phases:
ids,
rent aff
sses usi
ng,
al sepa
on.
12
ction:
hat requ
mponent
two im
finity c
ing extr
aration,
uires lo
t from o
mmiscib
ompon
raction
ow temp
one liqu
ble or p
nents fo
peratur
uid to
partially
or
re

y


(4) S
* u
* t
* r
* u

Prod
* m
*
* p



Solid-li
used liq
matrix,
transfe
require
uses th
duction
mining
food pr
pharma
quid ex
quid to
,
r solub
es two p
he solub
proces
g,
rocessin
aceutic
xtracti
o extrac
ble com
phases:
bility of
sses usi
ng,
al.

13
ion:
ct comp
mponent
solid a
f the co
ing leac
ponent f
t from s
and liqu
ompone
ching
from a
solid to
uid,
ent for
solid
o liquid
separat
d,
tion.

Phas

se Tran

Phase D

nsform
Diagram
mation
m of W

14
Water



Phas



se Equuilibriuum

15



Equ





ilibriu
Single
m-Stag
Staged
ged Op
d Unit

16
peratioon


Equ




ilibriu
Multip
m-Stag
ple Stag
ged Op
ged Uni

17
peratio
it
on

18

Different Representation of VLE Data

(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,
P
A
= Y
A
P
T
= P
A
*X
A
Y
A
= (P
A
*/P
T
)X
A
where
P
A
= equilibrium partial pressure of component-A
in the gas at temperature T
P
A
* = vapor pressure of pure liquid A at temperature T
X
A
= liquid-phase mole fraction of component-A
at temperature T
Y
A
= gas-phase mole fraction of component-A
at temperature T
P
T
= 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.



Vapo


wher
The
solut
Comp
Benz
Ethan
n-hep
Tolue
Wate
or press
Antoin

re A, B
consta
tion is s
pound
ene
nol
ptane
ene
er
sures o
ne Equ
lnP
A

B and C
ant-tem
shown
of pure
uation:
A

(kPo)
C are co
mperatu
in the F
A
13.85
16.67
13.85
14.00
16.2
19
liquid c
) = A -
nstants
ure pha
Figure
B
594 27
758 36
587 29
098 31
262 37
can be
- B(I
s.
ase dia
below.
B
73.78
74.49
91.32
03.01
99.89
estimat
I(oC) +
agram
.

C
220.07
226.45
216.64
219.79
226.35
ted usin
+ C)

for an i
7
5
4
9
5
ng
ideal
20

For a binary mixture of A and B;
P
A
= P
A
*X
A
; P
B
= P
B
*X
B
= P
B
*(1 - X
A
)
The partial pressures P
A
and P
B
vary linearly with X
A
.
This is shown as P
A
vs. X and P
B
vs. X respectively in
the Figure.
For ideal gas mixture, the total pressure is the sum of
the partial pressures.
Total pressure P
T
= P
A
+ P
B

Replacing for the partial pressures and re-arrange, we
have:
P
T
= ( P
A
* - P
B
* ) X
A
+ P
B
*
X
A
=
P
1
- P
B

P
A

- P
B

The total pressure varies linearly with X
A
. This is
shown as P
T
vs. X in the Figure.
In addition, P
A
= Y
A
P
T
thus P
A
*X
A
= Y
A
P
T
, and we
have:
X
A
=

A
P
1
P
A

Substitute into earlier equation to remove X
A
:
P
1
= (P
A

- P
B

) _

A
P
1
P
A

_ + P
B

21

P
T
P
A
* = (P
A
* - P
B
* ) ( Y
A
P
T
) + P
A
* P
B
*
P
T
P
A
* - (P
A
* - P
B
* ) ( Y
A
P
T
) = P
A
* P
B
*
P
1
=
P
A

P
B

P
A

-
A
(P
A

- P
B

)

The total pressure varies nonlinearly with Y
A
. This is
shown as P
T
vs. Y in the Figure.
Also, since P
A
* X
A
= Y
A
P
T
; we have ,

A
= _
P
A

P
1
_ X
A

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.


Phas

se Diaggram (pressure

22
e is connstant):


Ideal



l Solutiion: bennzene a

23
and toluuene


24

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 82.63185
o
C:
lnP
L

=16.6758 3674.49/(82.63185 + 226.45)=4.7874

P
E
* = 119.9885
lnP
W
*=16.2620 3799.89/(82.63185 + 226.35)=
P
W
* = 52.66227
X
L
=
P
1
- P
w

P
L

- P
w

=
1u1.S - S2.66227
119.988S - S2.66227
= u.722419

L
= _
P
L

P
1
_ X
L
= _
119.988S
1u1.S
_ u.722419 = u.8SS69S
X
W
= 1- X
E
= 1- 0.722419 = 0.277581

Y
W
= 1- Y
E
= 1- 0.855695 = 0.144305

Repeat this process for other temperatures, we have the
following table:





The


T-X-YY plot iss as belo

25
ow:


26

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)
For pure ethanol, lnP
L

= ln1u1.S = 4.618
= 16.6758 3674.49/(T + 226.45)
The normal boiling point of ethanol is T = 78.3
o
C

For pure water, lnP
w

= ln1u1.S = 4.618
= 16.2620 3799.89/(T + 226.35)
The normal boiling point of water is T = 100
o
C

2)
Bubble point at X
E
= 0.25: from the Figure, T
B
= 92
o
C,
the equilibrium Y
E
= 0.46
Dew point at Y
E
= 0.25: from the Figure, T
D
= 96
o
C,



3) 30
30w%

Tota


Bubb
equil
Dew


0% w/w
x
W
= 0
% wate

al moles
X
W
X
E
ble poin
librium
w point
w water
.3, con
er =30/
= 1.6
s = 3.19
W
= 1.6
E
= 1 - X
nt at X
E
m Y
E
= 0
at Y
E
=
r = 30 g
nvert to
18 mol
67 mole
9
67/3.19
X
W
= 0
E
= 0.4
0.68
= 0.476

27
g water
moles
les wate
es wate
= 0.52
0.4765
765: T
B
5: T
D
=
r + 70 g
er + 70
er + 1.5
235
B
= 87.
= 91.8
o
g ethano
0/46 mo
52 mole
5
o
C, th
o
C
ol:
oles eth
es ethan
he
hanol
nol

28

(2) Tabulated data:



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*MW
A
/(X *MW
A
+ (1-X) *MW
B
)

** derive the equations for n-component and for x X


X ( e t h a n o l ) X ( w a t e r ) Y ( e t h a n o l ) Y ( w a t e r ) T ( C )
0 1 0 1 1 0 0
0 . 0 1 9 0 . 9 8 1 0 . 1 7 0 . 8 3 9 5 . 5
0 . 0 7 2 1 0 . 9 2 7 9 0 . 3 8 9 1 0 . 6 1 0 9 8 9
0 . 0 9 6 6 0 . 9 0 3 4 0 . 4 3 7 5 0 . 5 6 2 5 8 6 . 7
0 . 1 2 3 8 0 . 8 7 6 2 0 . 4 7 0 4 0 . 5 2 9 6 8 5 . 3
0 . 1 6 6 1 0 . 8 3 3 9 0 . 5 0 8 9 0 . 4 9 1 1 8 4 . 1
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
0 . 3 2 7 3 0 . 6 7 2 7 0 . 5 8 2 6 0 . 4 1 7 4 8 1 . 5
0 . 3 9 6 5 0 . 6 0 3 5 0 . 6 1 2 2 0 . 3 8 7 8 8 0 . 7
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

(3) G





Graphic
T-x-y d
cal repr
diagram
resentat
m

29
tion:


Exam
solut
Wha
equil
Wha
alcoh


Solu
At T
Whe
Whe


mple 3
tion if
at shou
librium
at is the
hol?
ution:
T
B
= 92.
en x
A
=
en x
A
=
3: Deter
f its bu
uld be
m with t
e bubbl
.5
o
C: x
0.78 :
0.95 :
rmine t
ubble p
the eth
this solu
le point
x
A
= 0.0
T
B
= 7
T
B
= 7

30
the con
point t
hanol
ution?
t tempe
04, y
A
=
8.3
o
C
8.3
o
C
ncentra
tempera
content
erature
= 0.28
ation of
ature i
t of th
of 78 a
f an alc
s 92.5
he vapo
and 95
cohol
o
C?
or at
wt%


(3) G



Dete
with


Graphic
X-Y or
ermine
an 30,
cal repr
r McCa
the com
60, 80
resentat
abe-Thi
mpositi
0 and 90

31
tion:
iele dia
ion of th
0 mol.%
agram
he vapo
% ethan
or at eq
nol solu
quilibriu
ution.

um



32


33

(4) Relative Volatility (
AB
)

AB
= (Y
A
X
B
)/(Y
B
X
A
)
Y
A
=
AB
X
A
/(1 + (
AB
-1)X
A
)




T(C) Kic4 KC6 alpha
10 1.1 0.06 18.33333
20 1.5 0.095 15.78947
30 2 0.15 13.33333
40 2.5 0.2 12.5
50 3 0.3 10
60 3.8 0.4 9.5
70 4.6 0.54 8.518519
80 5.5 0.7 7.857143
90 6.5 0.9 7.222222

Exam
mixt


X i c
mple 4
ture if t
c 4
4: Plot X
the rela
Y
0
0 . 1
0 . 2
0 . 3
0 . 4
0 . 5
0 . 6
0 . 7
0 . 8
0 . 9
1
X-Y dia
ative vo
Y i c 4
0 . 1 5
0 . 2 9
0 . 4 2
0 . 5
0 . 6
0 . 7
0 . 7 9
0 . 8 7
0 . 9
34
agram f
olatility
0
8 8 7 9
8 2 4 6
1 4 8 8
3 1 2 5
2 9 6 3
1 8 3 1
8 6 5 8
1 7 9 5
3 8 6 5
1
for isob
y is kno

butane-
wn to b
-isopen
be 1.7
ntane