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Polysulfane (PS).
Polyamide (PA).
Polycarbonate.
Polyacrylonitrile.
1. Inorganic: Used at high temp. also about 100
0
C.
Alumina.
Zirconia.
Stainless Steel.
Carbon Composite.
Silica.
Membrane Materials
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
40
0
C 80
0
C 140
0
C
Temp. Limits:
CA
PS, PA
Ceramic (130
0
C)
0
7
14
Ceramic
PS, PA
CA
P
H
Limits:
Working Range
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Chlorine
(ppm)
1
10
Time of
exposure
PS
PA
CA
Chlorine limits:
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
CA PA PS Ceramic
Water
Acid
Alkali
Butanol
Ethanol
Solvent Stability:
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1. Manufacturing technique: Pressing & Sintering of polymers.
.............
:::::::::::::::::::::::::::::
::::::::::::::::::::::::::::
Pressurizing (also heating just
below the MP of Powder)
Plates 100-500 m
Fine Powder.
Homogeneous solution put above glass plate & add precipitating agent.
Annealing.
100-500 m Skin layer
formed.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Types of Asymmetric membrane:
1. Finger structure:
Good for ultra filtration.
2. Sponge structure (kept in wet condition):
mix
=
1
+
2
+
3
+ +
n
= Density of the mixture
C
mix
= c
1
+ c
2
+ c
3
+ + c
n
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
*
i
i
v V
v V
ur ur
uur
ur
1 2 3
*
1 2 3 1
1
......
n
i
i
n
n i
n
mix
i
i
c v
c v c v c v c v
V
C
c
+ + +
r
r r r r
uur
1 2 3
1 2 3 1
1
....
n
i
i
n
n i
n
mix
i
i
v
v v v v
V
+ + + +
r
r r r r
ur
Mass average velocity:
Molar average velocity:
Hypothetical velocities, it cant be measured by instrument
Diffusion velocities of component i
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
* *
( )
( )
i i
i
i i i
i i
i
i i
i
n v
N c v
J v V
J c v V
r r
uur r r
ur r ur
uur uur
r
+
+
r r ur
uur
uur uur
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
1
1
1
1
( )
i i
i i
i i i
n
j
j
j
i i
i
n
j
j
n
i
i i j
n
j
j
j
n
i i j
i
j
v v v v
v v v v
v
n J
n J n
n J w n
+
+
+
+
+
r r r r
r r r r
r
r ur
r ur r
r ur r
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
* *
* *
1
*
1
*
1
1
*
1
( )
i i
i i
i i i
n
j
j
j
i i
i
n
j
j
n
i
i i j
n
j
j
j
n
i i j
i
j
v v v v
c v c v v c v
c v
N J c
c
c
N J N
c
N J x N
+
+
+
+
+
uur uur
r r
uur uur
r r
r
uur
uur
uur
uur uur
uur
uur uur
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Equation of continuity
r
i
(gm/cm3-s)
v
i
(cm/s)
i
(gm/cm3)
z
x
y
y
x
z
Conservation of mass:
Accumulation = Inflow Outflow + Generation
( )
i
i ix i ix i iy i iy
x x x
y y y
x y z
v y z v y z v x z v x z
t
+
+
V
V
V V V
V V V V V V V V
i iz i iz i
z z z
v x y v x y r x y z
+
+ +
V
V V V V V V V
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( ) ( ) ( )
( )
( ) ( ) ( )
( )
i iy
i i ix i iz
i
iy
i ix iz
i
i
i
i
v
v v
r
t x y z
n
n n
r
t x y z
n r
t
ur r
Dividing both sides by x y z & taking x 0, y 0, z 0
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
1
1
1
2
2
( )
( )
( )
( )
1, (1)
( )
2, (2)
( )
, ( )
i
i
i
i i
i i
i i
i i
i
i i i
i
i
i
n
n
n
M
M r n
M M
t M M
c M
N M RM
t
c
N R
t
i n r
t
i n r
t
i n n r n
t
r
ur
ur uur
ur uur
ur r
L L
ur r
L L
M M
ur r
L L
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1 2
1 1 1 2
1 2
1 2
1 2
( )
( ) 0
( )
( )
0
n
n n
n
n
n
n n n
t
n n n v v v
v v v
v
v
t
v
t
+ + + +
+ + + + + +
+ + +
ur r r r
L L
r r r r r r
Q L L L L
r r r
L L
r
ur r
ur r
Adding above equations:
This is known as equation of continuity
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
*
A
A AB A
A
A AB A
J D w
J c D x
ur ur
ur ur
Ficks law
Valid only for binary system
D
AB
= D
BA
*
i
i im i
i
i im i
J D w
J c D x
ur ur
ur ur
General equation of Ficks law
Ficks Law
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
*
A
A AB A
J c D x
ur ur
*
AB
A
A A
D
J c
RT
ur ur
, ,
j
t
i
i
n T P
G
x
ln (1)
ln (2)
i
i i
o o
i
d RTd f
d RTd f
L L
L L
,
ln
ln
ln
i
i
i
i
o
i
i
o
i
i i i
o
i
o
i i
o
i i
T P
f
d d RTd
f
f
a x
f
d d RTd a
RTd a
+
+
+
Ideal gas
Real gas or Liquid
Mixture
Pure
By (1) (2)
f = Fugacity
a = Activity
= Activity
coefficient
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
*
*
ln
ln( )
ln
A A
A A
A A
A
A
AB
A
A A
A
A
A AB A
RT a
RT x
RT x
RT
x
x
D RT
J c x
RT x
J c D x
ur ur
ur
ur ur
ur
ur ur
ur ur
A
=1, for ideal solution
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
If pressure changes
( ) ( ) ( )
*
*
*
, , ln
ln
1
A
A
T
o o o
A
A A A
A A A A
A
A A
A
A
A
A AB
A A
AB A A
A
AB
A A
AB A A
AB
A A
AB A A
V
P
T P T P RT a V P P
a x x
RT x V P
RT x V P
x
c D
J D x c V P
x RT
D
J cD x c V P
RT
D
J cD x c V P
RT
+ +
+
+
ur ur ur
ur ur
ur ur ur
ur ur ur
ur ur ur
For ideal gas,
A
=1
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
P
1
C
B1
C
A1
2
P
2
C
B2
C
A2
X=
X=0
Semi permeable
membrane
*
2 1 2 1
1 2 2 1
1 2 2 1
*
2 1 1 2
*
*
2 1 1 2
*
1 2
1 2
0
A AB
A
A AB A
A A AB
A
AB A
B B AB
A
AB A
B B AB
A
AB A
B B AB
A
A AB A
B B AB
A
A AB A
B B
A
dx D dP
J cD c V
dx RT dx
x x D P P
cD c V
RT
cx cx D P P
D c V
RT
c c D P P
D c V
RT
c c D P P
J D c V
RT
c c D P P
J D c V
RT
c c
P P
c
+
+
1 2
*
1 2 1 2
B B
A
RT c RT c RT
V
P P
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
*
*
A AB A
A A
A
B BA B
B B
B
c D dx RT dP
J V
RT x dx dx
c D dx RT dP
J V
RT x dx dx
1
+
1
]
1
+
1
]
ur
ur
Dilute Solution: A Solvent : x
A
1;
B Solute : x
B
0.
In this case pressure is not a deciding
factor in flux calculation.
A
*
= Electro-Chemical
Potential
= Electrical Potential
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Temperature gradient Mass flux Sorret effect
Concentration gradient Heat flux Dufour effect
ur uur
ur uur
ur uur
M M
ur uur
Flux
Forces
Onsager 1931
Works when system near to equilibrium
1, 1
1
1
1 2 3 1
11 12 13 1
1 2 3 2
21 22 23 2
n
j i
i j
n
i i
i
n
i i
ik
k
n
n
n
n
T J X
J X
J L X
J L X L X L X L X
J L X L X L X L X
+ + + +
+ + + +
ur uur
&
ur uur
ur uur
ur uur uur uur uur
L
ur uur uur uur uur
L
= Rate of dissipation of Free energy
= Rate of change of Entropy
L
ik
= Phenomenological Coefficient
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
L
ik
(Phenomenological coefficient) determined by experiment.
Theory of Irreversible T/D doesnt say anything about L
ik
.
Relation between L
ik
:
2
0
ii
ii kk ik
ik ki
L
LL L
L L
>
g
g
g
Curie principle : Flux J
i
will depend on driving force x
J
iff they have the same
tensorial order or they differ by 2.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Force
Flux
V T C
q
k D
A
T
J
D
A
T
D
AB
r
J
1
1
J
2
2
1
1
2
2
x 0
x
0
i
i
dx
x
+
+
+
ur ur
ur ur
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Stefan Maxwell equation
Forces are given in terms of Flux, where as in Theory of
Irreversible T/D Flux is given in terms of Forces.
1, 1
,
,
( )
ln
ln
ln
ln ln
1
n
j i
i
i i j
i j
ij
i i
i i
i TP
i i
i
i TP
i
i
i
i i i i i
i i
i
i
i
v v
x d xx
D
d RTd a
RT a
cRTd c
c
d
cRT
c
RT a
cRT
x x x x
x x
x
d x
r r
ur ur
ur ur
ur ur
Q
ur ur
ur
ur ur
ur
ur ur
Concentration is the only driving force
(Assuming ideal mixture)
D
ij
= Binary diffusion coefficient
v
i
, v
j
= velocities
x
i
, x
j
= concentrations
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
For two component mixture :
2
1
1 1
1
1
2 1
1 2
12
2 1 2 1
1 2
1 2
12 12
2 1
1 1
12
1 2 1
12 1 1
1 1 2
1 12 1
( )
( )
0
( )
(1 )
( )
( )
j
j
j
j
v v
x x x
D
v v
x x
D
x N x N v v
cx x
cD cD
x N x N
cD
cD x x N N N
N x N N cD x
+
+
+
r r
ur
r r
uur uur r r
uur uur
ur uur uur uur
uur uur uur ur
Bulk flow term Diffusion term
Ficks law of diffusion
including mass flux diffusion
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
For three component mixture :
3
1
1 1 1
1
1
2 1 3 1
1 2 1 3
12 13
2 1 3 1
1 1 1 2 1 3
12 13
*
( )
( ) ( )
0
( ) ( )
j
j
j
j
i ik i
i ik k
v v
d x x x
D
v v v v
x x x x
D D
v v v v
d x x x x x
D D
J L x
x R J
+ +
+
r r
ur
r r r r
r r r r
ur
In Stefan-Maxwell Forces are
given in terms of Flux.
In Theory of Irreversible T/D Flux is
given in terms of Forces.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
1
1
1
1
(1)
& ( ) (2)
( )
1
n
i j
i im i
j
n
j i
i
j
i
im
n
i j
j i
i
j
ij
n
i j
j i
j
ij
n
im
j i
i
j
N x N cD x
x N N
x
cD
x x
x v v
D
x x
v v
D
cD
x N N
uur uur ur
uur uur
ur
L L
ur r r
L L
r r
uur uur
By solving (1) & (2)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Examples:
1. Components 2, 3, , n are in trace amount in nearly pure component 1.
i.e. x
2
, x
3
, , x
n
<< 1 or x
1
1 & N
2
, N
3
, , N
n
<< N
1
1
1
1 1
1
( )
1
n
i j
j i
j
ij
n
im
j i
i
j
n n
j i
i j i j
j j
ij ij
n
j i
i
j
x x
v v
D
cD
x N N
x x cv x x v
cD D
x N N
r r
Q
uur uur
r r
uur uur
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
1 1
1
1
1
1 1
1
1
1
1
1
1
1
1
1
1 1
1 1
1
n n
j
j
i
i i
j j
ij ij
n
j i
i
j
i
i i
i i
i
im
i
i
i
i
im i
i
im i
im i
x
N
x x v
cD D
x N N
x N
x x v
cD D
cD
x N N
x N x N
cD cD
x N N
x
cD cD
D D
uur
r
uur uur
uur
r
uur uur
uur uur
uur uur
Q
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
1
1
1
1
1
( )
1
1
( )
( )
1
n
i j
j i
j
ij
n
im
j i
i
j
n
i j
j i
j
ij
n
j i
i
j
n
i
j
j
i
j
n
ij
j i
i
j
xx
v v
D
cD
x N N
cxx
v v
D c
x N N
x N
xN
c c
D
x N N
r r
Q
uur uur
r r
uur uur
uur
uur
uur uur
2. If D
ij
s are same
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1 1
1
1 1
1
1
1 1
1 1
1 1
1
n n
i
j
j
i
j j
n
im ij
j i
i
j
n n
j i
i j
j j
n
im ij
j i
i
j
n
j
j
im ij
im ij
x N
x N
c c
cD D
x N N
x N N x
cD cD
x N N
x
cD cD
D D
_
,
uur
uur
uur uur
uur uur
uur uur
Q
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
3. Components 2, 3, 4, , n are moving with same velocity.
i.e. v
2
= v
3
= = v
n
= v & v
1
v
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
( )
1
( )
1
( )
(1)
n
i j
j i
j
ij
n
im
j i
i
j
n
j
j
j
j
n
m
j
j
n
j
j
j
n
j
j
x x
v v
D
cD
x N N
x x
v v
D
cD
x N N
x
x v v
D
x N N
r r
Q
uur uur
r r
uur uur
r r
L L L
uur uur
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1 1 2 3 1
1 1 1 2 3 1
1
1 1
1 1 1 2 1 3 1 1
1
1 1 1 1
1
1 1
1
1
1
1
1
1 1
[ ... ]
[ ... ]
[ (1 ) (1 )]
(1 )( ) (2)
( )
1
(1 )( )
(1
n
j n
n
j
n
n
j
j
j
im
x N N x c v c v c v c v c v
c x x v x x v x x v x x v x v
c x v x vx x
cx x v v
x
x v v
D
cD
cx x v v
+ + + +
+ + + +
+
uur uur r r r r r
r r r r r
r r
r r
L L L
r r
r r
1
1
1
)
n
j
j
im j
x
x
D D
(From 1 & 2)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Reverse Osmosis
Applications:
1. Water purification ( Potable water or drinking water) : Municipalities,
restaurants, hotels, homes, offshore oil rigs.
2. Ultra pure water : Semiconductor industries, hem-dialysis, drug
formulation, boiler feed water.
3. Concentrate or dewatering applications in food industry : Milk
concentration (whey), concentration of juices (coffee), de-
alchoholizing of wines & beers.
4. Pollution control of waste water from industry : Textile industry, pulp
& paper industry, metal industry.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Membrane materials:
1. Cellulosic :
Cellulose acetate & Cellulose tri-acetate.
Magged, relatively chlorine insensitive, & inexpensive.
Dont have high fluxes and restricted to narrow P
H
range.
2. Non-cellulosic :
Polyamide, polyacrylonitrile, polyvinyl alcohol, polysulfone.
Not magged, relatively chlorine sensitive, & expensive.
Higher fluxes and can be used for wide PH range.
Tubular module
I D > 1/2 , 20 ft long
Hollow fiber membrane
Axial flow hollow
fiber module
Radial flow hollow
fiber module
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Flow directions inside the shell of a hollow-fibre
module
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Flow pattern in a parallel-flow hollow-fibre module
(fibre-side feed).
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Flow pattern in a radial-flow hollow-fibre module
(shell-side feed).
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Parameters
Modules
Packing
density
(ft
2
/ft
3
)
Water flux at
600 psi
(gal/ft
2
-d)
Salt
rejection
Water output
Per unit vol.
(1gal/ft
3
-d)
Flow channel
size (inch)
Ease of
cleaning
Tubular 30-50 10 Good 300-500 0.5-1 Very good
Spiral-bound 250 10 Good 2500 0.1 Fair
Hollow fiber
(axial)
1000 5 Good 5000 0.254 Fair
Hollow fiber
(radial)
5000 1-3 Good 5000-15000 0.002 Poor
Plate &
frame
35 10 Good 350 0.01 Good
Comparison of RO Modules
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Osmotic pressure
' ''
' ''
( )
i i
i i i
cRT
RTc c
Where
i
= Vont Hoff factor
= No. of ions present in a molecule of salt
e.g. For NaCl,
i
= 2
BaCl
2
,
i
= 3
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Expression for work required to separate salt from water
Water(2) (pure)
Salt + Water(1)
Salt
'
'
'
(1)
( )
( )
(2)
(3)
dQ
ds
T
dU dQ dw a
dw PdV dw b
dQ dU PdV dw
Tds dU PdV dw
t
+
+
L L
L L
L L
L L
L L
( + for work on the system
- for work by the system)
From (a) & (2)
From (1) & (2)
Combined statement of 1
st
& 2
nd
Law of Thermodynamics (T/D)
Equal sign for reversible process & inequality sign for irreversible process
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
'
,
'
,
'
,
'
1 2
' '
2 1
' '
1 2
(4)
( ) (5)
( )
( )
T P
T P
T P
Tds dU PdV dw
G H Ts
U PV Ts
dG dU PdV Tds
dG dw
dG dw
G G w
G G w w
G G w w
+
+
L
L
From (3)
From (4) & (5)
Integrating both sides
= Work done on the system for
required change
= Useful work obtained from the
system
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Transport Model
Support
Dense Layer
Z = 0
Z = L
Low pressure
side
High pressure
side
C
ij C
22
(C
22
)
m
Feed
Permeate (C
23
)
m
(C23) C23
Main Resistance
This resistance can
be neglected
Asymmetric Membrane
i = Component
i = 1 Solvent
i = 2 Solute
j = Location
Turbulent flow
All mass transfer resistance lies in a film near the surface
Film is stagnant
Membrane
Film
C
21
= Conc. At high
pressure side
C
21
= Interphase
Conc.
C
23
(C
23
)
m
(C
22
)
m
Z = 0
Z =
C
22
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2
c
t
0
2
2
N R
+
ur uur
0
2
2 2
2
2
*
1
2
2 2 1 2 21
0
0 .
,
( ) (1)
y
x z
z
z
i
i i j
j
z z z
N
N N
x y z
N
N Constt
z
as N x N J
x
N x N N cD
z
+ +
ur
L
By equation of continuity
At steady state
Considering only z direction
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
22
21
2 1 2 23
2
21 1 2 2 23
2 1 2
2 23 21
1 2
2 23
21
0
22 23 1 2
21 23 21
22 23 1 2 1 2
21 23 21
, ( ) (2)
( )( )
ln( )
ln
ln
( / )
z z z
z z
z z
z
x
z z
x
z
z z
z z z z
also N N N x
x
cD N N x x
z
dx N N
dz
x x cD
N N
x x z
cD
x x N N
x x cD
c c N N N N
c c cD ck
k
+
1
+
1
]
1
+ +
1
L
21
22 23 1 2
21 23
/
exp
z z
D
c c N N
c c ck
+
1
1
]
From (1) & (2)
After integrating
both sides
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
(N
1z
+ N
2z
) / c = [gmol / (area-time)] / [gmol / vol.]
= vol. / (area-time)
(N
1z
+ N
2z
) / c = J
v
For laminar flow also (A) can be used but result will not be fully correct
C
22
/C
21
should be as less as possible because if any opening in
membrane all salt concentration will goes to other side
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
C
21
= Interphase
Conc.
C
23
(C
23
)
m
(C
22
)
m
C
22
C
21
In this region we assume liquid is stagnant
So, k = (f / 2) u Sc
2/3
2/ 3
22 23
21 23
2
exp
v
c c J Sc
c c
f u
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
22 23 23
22 22
21 23 23
21 21
22 23
21 23
22 23 21 22
22 21 23 21
23 22
23 21
23
23
21
22
1
1
, exp
exp
1
exp
1
exp
obs
v
v
v
obs
v
obs
c c c
R
c c
c c c
R
c c
c c J
as
c c k
c c J c c
c c c c k
c J c
R
R c c k
c J R
c
R c k
c
,
_
,
_
,
Rejection:
What membrane
actually does
We can
observe this
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
(1 ) exp
(1 )
(1 ) (1 )
exp
1 1
ln ln
v
obs
obs
obs v
obs
obs v
obs
J R
R
R R k
R J R
R R k
R J R
R R k
_
,
_
,
_
_
+
,
,
Model based on Mechamstic (Role model)
N
1
= A ( P -
i
)
Model based on theory of Irreversible T/D
N
2
= B C
As we increase no. of parameters model predicts better but at the cost of
complex problem, 3 parameters problem gives good result
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Solution Diffusion Model
C
23
(C
23
)
m
(C
22
)
m
C
22
x = 0 x = x
2
1
Homogeneous membrane i.e. no big pore i.e. there
is only diffusion takes place in the membrane
P = P
1
P
2
C = C
22
C
23
$
$
$
( )
( )
1
1
1
1
1 1 1
1 1
1 1
2 2
2 2
(1)
ln
ln
ln
. . (2)
(3)
&
i
i
i i
i i
i
i
i
i
x
x
D
N c
RT
d RTd a vdP
d d a dP
RT v
dx dx dx
d d a dP
ie RT v
dx dx dx
D
N c
RT
Dd
N c
RT dx
D d
N c
RT dx
+
+
+
uur ur
L
L
ur
L
From (1)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
$
$
$
( )
$
$
( )
( )
$
$ 1
2
1
1 1
1 1
0 1
1
1
1
1 1 2 1
1
0
1
1 1
1
1 1 2
1
0
1
0
1
1
0
ln
ln
ln (4)
ln
l
x
x x
x
x x
x
x x
critical
N
x
D
Ndx c RTd a vdP dx
RT
a
D
N x c RT v P P
RT
a
a
cD
N RT v P P
xRT
a
a
RT
P
v
a
RT
1
+
]
1
_
1
+
1
1
, ]
1 _
1
+
1
1
,
]
_
,
L
$
$
[ ]
1
1
1
0
1 1
1 1
1
1
1
1 1
n (5)
,
x x
x
a
v
a
cD
N v v P
xRT
N A P
cvD
where A
xRT
,
1
+
]
L
From (2) & (3)
From (4) & (5)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
$
2 2
2
ln d RTd a v dP +
$
0
2
2
2 2 2
2 2
2
2 2 2
2
2 2 2
2
2
2 2
2
2
2 2
2 2 2
ln
ln ln
,
d d a
RT
dx dx
d x d x
RT RT
dx dx
d dx RT
dx x dx
c D d
as N
RT dx
c D dx RT
N
RT x dx
D dx
cx
x dx
dcx dc
N D D
dx dx
For ideal dilute solution
2
= 1 For ideal solution
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
23 22
2 2
22 23
2 2
22 23
1 2
22 23
1 2
22 23
2 2
2
2 22 23
2
2
( ) ( )
( ) ( )
( ) ( )
&
( )
,
m m
m m
m m
c c
N D
x
c c
N D
x
c c
k k
c c
k k k
kc kc
N D
x
Dk
N c c
x
N Bc
Dk
whereB
x
_
_
+
,
,
L
1 2
22
22 23 2
22 22
( )
1 1
v v
N N
c
Bc c N
Jc Jc
+
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
23
22
1 1
1
1 1
1
1
1 1
1 1 1 (2)
1
ln ln From (1) & (2)
1
ln ln
v
v
v
v
v v
obs v
obs v
obs v
v
obs
c B
R
J c
B
R R
J
B
R
J
R
B
J
R B B
R R J J
R J B
R J k
R J
J B
R k
_
,
_
+
,
+
+
_ _
+
, ,
_
_
+
,
,
L
ln B
1
ln
obs
v
obs
R
J
R
_
_
,
,
J
v
From Tan = 1/k
1
ln
obs
v
obs
R
J
R
_
_
,
,
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
K = a Q
b
Q
1
K
1
, Q
1
K
1
, Q
1
K
1
, ..
a
ln k
ln Q
Turbulent b = 0.8
Laminar b = 0.33
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Kedem Katchelky model
Based on Theory of Irreversible Thermodynamics (1954)
ur ur
ur ur
Q
x
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( ) ( )
0
0
0
1 2
( )
( , ) (1)
, , ln
ln
&
x
n
ix
i
x
n
ix i i i i
x x x
i
m w w s s
w ww w wp s
s pw w pp s
m
o o o
i
i i i
w
w w
s
d
J dx
dx
d
J dx
dx
J J w water s salt
J L L
J L L
J c J p
T P T P RT a V P P
RT a V P
RT
+
+
+
+
+
+ +
+
Q
L
Q
ln
s
s
a V P +
J
s
J
w
w
,
c
w
, p
x = x x = 0
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
[ ]
( )
w
0
0 0
ln ln
ln ln (2)
L
Q
0
1 1
( )
ln
s s s
x x x
s
w
c c c
c c
c
a
c
1
]
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
( )
( )
( )
( )
( )
0
ln
0
ln
ln
0
ln
ln
ln ln
ln ln
ln
ln
1 1
s s
s s
x x x
s
s
s s
s x x x
s s
s
s
x
s
x x
w s
m w s w s s
s
s w
w s
m w s
s
m v
a x
x x
x c
x c
c c
c
a c
c
c
c
J V J V P RT J J c
c c
J J
J V J V P
c c
J P
_
,
,
1
+ + +
1
1
]
1
+ +
1
1
]
+
g
Q
D
J
From (2)
J
w
V
w
= vol. flux of water
J
s
V
s
= vol. flux of salt
V
i
= partial molar vol. of i
J
v
= vol. flux
J
D
= Drift flux
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
[ ]
( )
ln
(3)
( )
1
v P PD
D DP D
PD DP
PD
v P
P
P
PD
P
D P D
s
w w
D w
s
J L P L
J L P L
L L
L
J L P
L
L P
L
where
L
J L P L
and
J
J J V V
c c
+
+
1
+
1
]
+
_
,
L
Q
L
P
= Direct coefficient for J
v
L
D
= Direct coefficient for J
D
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
( ) ( )
ln
ln
w
s D w s
P D v s
w s
v w s
J J J V c
L P L J c
J J V J V
+
+ +
+ Q
( ) ( )
( )
0
ln
ln
w
w
s P D P s
v
P
v
P
v
s P D v s
P
J V
J L P L L P c
J
P
L
J
P
L
J
J L L J c
L
,
+ + 1
]
+
1
_
+ + +
1
,
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
( ) ( ) ( )
{
( ) ( )
( )
2
ln
2
ln ln
ln
1
1
s v v P D s
D P s v s
s v s
Diffusion part
Convective part
v P
J J J L L c
L L c J c
J W J c
and J L P
1 + +
]
+
+
1 442 4 43
L
P
= Hydrodynamic permeability
W = Solute permeability
= Reflection coefficient
_
,
+
_
,
_
,
ur ur
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
x=x x=0
Cs
Cs
( )
( )
( )
( )
( )
( ) { }
( )
{ }
( )
{ }
( )
"
'
"
'
0
" '
1
1
1
1
1
ln 1
1
1
ln 1 ln 1
s
s
s
s
s v s
s
s s v
s
s s v s
c
x
s
s v s s
c
c
s v s
v s
c
v
s v s s v s
s
d
J W J c
dx
dc
P c J
dx
dc
P c J J
dx
dc dx
c J J P
x
c J J
J P
J x
c J J c J J
P
+
+
1
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( ) { }
( )
( )
"
'
" "
' "
"
" "
' "
"
" '
"
'
"
'
1 1
ln
1
1 1
ln
1
1 1
ln
1
1
ln
1
ln
1
s v s v
s v s s
s v v s v
s v v s s
s v s
s s v
s s s
v
s
s s s
s
s
s
s
cJ J J x
cJ J P
cJ Jc J x
cJ Jc P
J Jc
c c J x
c c P
J x c
P c c
c
c
c
c
1
1
]
1
1
]
1
1
]
1
1
1
]
1
Q
( )
( ) ( )
"
'
1
1 1
ln
1 1
1
v
s
v
s
s
s
J x
P
R J x
R P
c
R
c
1
1
1
1
]
1
1
+
]
_
,
Q
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( )
( )
( )
( )
( )
( )
( )
1 1
ln
1
ln
1
1
exp
1
1
1
1
v
s
v
v
R J
P
P
R P x
J
R
R P
J
R
F
R P
R F FR
R F F
F
R
F
1
_
1
,
]
1
]
_
Q
L
P
= Hydrodynamic permeability
= Reflection coefficient
P = Solute permeability
3 parameters of
SK model
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
N
1
= A ( P - )
N
2
= B ( C)
2
1 1
ln ln
1
ln ln
,
0
1
0
1 1
0
1 1
obs v
obs
obs v
obs v
Y
m m
v
v
v v
v
v
v
R J R
R R k
R J B
R J k
To find Min or Max valueof Y
dY
dJ
J dY B
dJ B J k
J k
J k
J k
_
_
+
,
,
_ _
+
, ,
+
+
1 4 2 4 3
From slide 82 & 83
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
J
V
J
V
R
ob
At J
V
= k, will have maximum or minimum value
1
ln
obs
obs
R
R
_
,
1
ln
obs
obs
R
R
_
,
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Design of RO System
Low pressure
side
High pressure
side
C
22
(C
22
)
m
Permeate side
(C
23
)
m
(C23)
(C23)
avg
Q
P
Total permeate
flow rate
Feed side
X = 0
X = L
V
x
, C
21
, (1-Q
F
) ,
V
xf
, C
21f
, Q
F
Q
F
( )
( ) ( )
( )
( )
( )
22 23 1 2
21 23
1
22 23
2 22 23
2
23
1 2
exp 1
{ ( )} 2
( ) 3
4
P
F
Q
Q
c c N N
c c ck
N A P A P b c
A P b c c
N B c B c c
cN
c
N N
+
1
+
L L
L L
L L
L L
Recovery i.e. for 50% recovery
=0.50
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
X
21
V
x
V
x
+ d V
x
X
21
+ d X
21
S = surface area per unit length of the membrane
AV
x
C X
11
It is coming
A = Cross Sectional area feed channel
( ) ( )
( ) ( ) [ ]
( )
( )
( )
( )
11 11 11 1
11 11 1
11 1
11 1 1
21 2 2
5
x x x
x x
x x dx
x
x
x
AV CX A V dV C X dX N Sdx
AC V X V X N Sdx
d V X N S
C
dx A
d V X N S N
C
dx A h
d V X N S N
and C
dx A h
+
+ +
L
(S/A*L/L=S/A=Surface/Vol.
of the module=1/h)
For Solvent :
For Solute
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
For Tubular module and
axial flow Hollow module
2B
L
( )
( )
2
22 21 23
11
1
21
2
22 23
2 2 1
2 1
2
x
x
R F P
S RL
A RL R h
WL S
and
BWL A B
c c c
d VX
N
dx ch
d VX
N
dx ch
c c c
Q Q Q
>
Q
0
21
21 21
21
21
21
21
0
.
1
1
1
x
x xf f
x
xf f
ch
VX Constt
VX VX
V X
V X
VX
X
V
+
+
+ +
+
Dimensionless parameters:
Dimensionless Osmotic Pressure
Dimensionless Mass Transfer Co-efficient
Solute Diffusivity Parameter
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
[ ]
1 22 23
22 23
1
( )
(
1
N A P bc c
bc c
N AP
Q
0
22
22
22
21
21
1 22
2
22 23
)
1
1
1
1
&
(
f
f
P
bc
AP
P
cX b
AP
P
X bc
AP X
X P
N AP X
N Bc
Bc c
+
1
1
1
]
1
]
1
]
1
1
1
]
1
]
0
22
2 21 22
)
f
BcX
N BcX X
1 2
0
exp
N N
0
22 22 1
21 21
22
22
21
22 22
21
exp
1
exp
1
exp
ck
c cX N
c cX ck
A P X
X
X ck
X X
X
+
+
+
+ +
+
1
1
1
]
1
1
]
1
1
]
1
1
]
1
1
]
( )
1
22
1
x
xf
dV N
and
dx ch
A P X d V V
X
ch
d
1
]
_
,
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
22
22
22
22 22
21
1
1
1
1
, exp
xf
xf
xf
A P X
dV
V
dX ch
A P X
A P dV
V
chV dX ch
dV
X
dX
X X
as
X
+
+
+
+ +
+
1
]
1
]
1
]
1
1
]
22
X
+
21
22
X
X
+
+
V
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Q
22
1
exp
X
+
1
1
]
1
exp
V
V
1
1
1
1
]
1 ln
( )
6
. 0 0, 1
x xf
BCx X V V V
L
1
1
+
[ ]
.
V
If Turbulent Cond
1
1
+
V
1
1 1
V
_
+ +
,
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
, as V
1 ln
dV
d
1 ln
1
+
1 ln
( )
2
1 ln
dV
d
1 ln
+
( )
2
d
1 ln and
1
V
ln
V
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
22
1
1
dV
X
dX
dV
dX
+
1
]
Q
[ ]
1
For any
V
dV
1
1
]
1 0
[ ,
1 ]
1
e
V
L
xe R
e
xf F
F P F F
F F
dx
V
V Q A
X L L V
V A Q
Q Q Q Q
Q Q
dV
L
+
+
+
( )
1
1
7
V
L
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
From (6) & (7)
( ) ( )
( )
( ) ( )
1
1 1 1 2 1 2
1
ln
i i
L e E u E u E w E w
w
+
+
+ + 1 1
] ]
1 ln
, u
( )
23
1 0
2
, 0& 0
1
1
, ln
1
1
at inlet x
at outlet x L
E Exponential Function
If u w
Then L
L
and X
+
+
+
+
_
+
,
1
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
x=0
x=L
1
2
1
dV
dX
Q
2
1
1
V
dV
dX
1
1
]
2
1
1 ln
V
L
( )
d
1 ln
+
( )
2
d
ln
1
1
1
]
2
1
d
L
+
ln 1 ln
( )
2
1
d
ln 1 ln
( )
2
2
1
d
L
+
ln 1 ln
( )
1
2
1
I
d
1 4 4 4 2 4 4 4 3
ln 1 ln
( )
2
2
2
1
I
1 4 442 4 4 43
L
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
d
I
ln 1 ln
( )
2
1
d
ln
d
+
1 ln
( )
2 2
1 1
,
ln
Lets assume
1
1
]
w
w
e d
1 ln
,
w
e dw
and
ln u
1 u
1 1 u
u
e e e d
1
1
2 2
1
1 1
u
w u
e e du
e dw e du
I e
w u
1
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Exponential Integrals
( )
( )
( ) ( ) ( )
( ) ( )
( ) ( )
1
2 2
1 1
2
1 2
1
2
2 1
1
,
u
u
w
w
i
b c b
a a c
w w w
w
i i
w
i i
e
E u du
u
e
andE w dw
w
as f x dx f x dx f x dx
e dw e dw e dw
w w w
e dw
E w E w
w
e dw
E w E w
w
+
+
+
+
+
+
+
+
+
+ + 1 1
] ]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
ln w 1
2
, ln w 2
1
1 ln
u
1
2
1 ln
, u
2
, as
1
exp
V
For
1
1
1
1
]
1 0 . . 1 atx ieV
1
1
exp
1
1
For
1
1
1
1
]
2 . . 1 atx LieV
2
1
exp
2
1
1
1
1
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
, As
1
exp
, 0& 0,
V
For u w
1
1
1
1
]
1
1
+
V
( )
2
1
1
1
V
V
dV
andL dX
+
+
2
1
1
V
dV
L
( )
2
1
2
1
V
V
L dV
V
+
+
+
+
+
+
+
1
+
1
]
1
+ +
1
]
+ 1
+
1
]
+ 1
+
1
]
+
_
+
,
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
x
22
Permeate side
x
23
x
23
= avg.
Q
P
Total permeate
flow rate
Feed side
X = 0
X = L
Q
F
V
x
, x
21
Q
R
23
23
23
23
21 21
'
'
2
23
2
1
2
23
2
1
2
22
1
,
, /
.
f f
P F xf
P
xf
X X
X X
X X
Q Q VA
A AreaofFeedChannel S surfacearealength
cX Q NSdx Totalamtof SaltinPermeate
cXVA NSdx
Bc Sdx
+
+
Q
V
xf
, x
21f
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2
'
23
22
1
'
23
xf
xf
cX V A BcX Sdx
cX V A Bc
2
21
1
X Sdx
Q
22
21
22 22
21
21 21
21
'
23
f
f
xf
X
X
X X
X
X X
X
cX V A BcS
+
+
1
1
1
1
]
[ ]
2
21
21
21 1
21 '
23
f
f
f
xf
X X
X d
X
x X
BcSX
cX V A
Q
2
21
1
X dX
+
2
21
1
23
21 f
xf
X dX
X BS
X
V
+
'
xf
A P
A
chV
_
,
2
21
1
23
'
1
X dX
cB hS
X
A P A
+
+
_ _
, ,
2
21
1
23
X dX
X
+
+
2
21
'
1
1
I
S
X dX
A h
I
+
1
1
]
Q
14243
2
21
1
X dX
I
+
2
21
1
1
dX X
V V
+
1
1
]
Q
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
I
2
1
1
dV
V
1
V
dV
dX
1
1
1
1
]
Q
1
dV
dX
V
1
1
]
1
V
I
1
1
1
1
1
1
1
]
]
2
1
1
dV
V
1
1 1
V
I
2
1
1
dV
V
1
_
1
,
]
( )
2
1
1
1
V
dV
I dV
2
1
V
1
1
1
1
]
+
+
+
+
+
+
+
+
1
]
1
]
1
]
1
]
1
]
1
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( )
( )
( ) ( )
1
1 1 1 2 1 2
23
1
1
1 ln
1 ,
i i
L e E u E u E w E w
L
X u
+
+
+
+
+ + 1 1
] ]
1
1
]
1
1
, ln w
( )
( )
( )
( )
( )
( )
( )
1
'
1
1
'
1
' '
1
'
1
1, ln
!
1, ln
!
0, 0,
ln , 0.56 .
ln
n
n
n
n
i
n
i
u
Foru E u u
n n
w
and for w E w w
n n
If u w Then
E u u u Where Constt
and E w w w
<
< + +
1 +
]
+ +
Design Equations:
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Liquid Membrane
It is used in place of polymer membrane.
As diffusivity is more in liquid than solid.
It is of two types:
1. SLM Supportive Liquid Membrane
2. ELM Emulsion Liquid Membrane
Org.
aq.
Org./aq.
aq. phase
Org. phase
Gas
aq. phase
Org. phase
Gas
Feed Phase
Receiving Phase
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Formation method :
1. Take a micro porous membrane and put liquid membrane material in its pores.
2. Surfactants are used It is a sort of double emulsion process
3. Hollow fiber liquid membrane
LM
LM
LM
Organic or Solid support
Carrier B should be very mobile i.e. higher molecular carrier & it should
combine with A easily.
We use external energy to maintain both interfaces conditions.
A + B AB
AB
B
LM Feed Side Receiving Side
A + B AB
As AB is formed so
AB conc. is high here
Carrier B should
not leak out
from LM
AB A + B
Conc. of B is
maximum here
A
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
(b) Coupled Transport
In this case one component transport from feed side to permeate side & second
component from receiving side to feed side simultaneously.
A + CB CA + B
C Carrier complex
CA
CB
A
B
B
A
Feed Side LM Receiving Side
Example: separation of metal ion
Cu
++
+ 2HR CuR
2
+ 2H
+
Carrier complex
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
(c) Photo Facilitation
At cathode: A + C
+
AC
+
& AC
+
+ e
-
AC
At anode: AC AC
+
+ e
-
& AC
+
A + C
+
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Property of carrier:
TBP (Tri-n-butylphosphane)
Grown ethers It is basically monocyclic polyether
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Method of preparation (Emulsion Liquid Membrane):
1. Emulsification
2. Emulsion external phase contacting
3. Settling
4. Demulsification
e.g.: De aromatization of Kerosene
1. Emulsification:
Emulsion Feed Kerosene
Aqueous surfactant
Micro drops of kerosene
Aqueous phase
Oil Water (O/W) Emulsion
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2. Gas oil external phase:
Here should not more mixing because that results to breaking of drops and
eventually lost separation.
Gas oil
O/W Emulsion
Receiving phase O/W Emulsion
Gas oil
Double Emulsion
Feed
LM
3. Settling:
Gas oil + aromatics
O/W Emulsion
Separate them
Aromatic compounds transferred from feed to gas oil.
Separate the 2 phases Now O/W Emulsion needs to be Demulsified.
Commercial applications:
Phases
Applications
Phase I
(Feed)
Phase I I
(LM)
Phase I I I
(Receiving Ph.)
Copper
extraction
Aq. phase containing
metal ions
Kerosene, SPAN80, ECA4360
J, LIX64N
0.5 mol/l H
2
SO
4
Phenol
separation
Aq. phase 1000 ppm
Phenol
Kerosene, ECA4360J, Liq.
Paraffin
NaOH solution
Hydrocarbon
separation
n Heptane solution Aq. solution of non ionic
surfactant + up to 10 % N
methyl pyrolidone
Dodecane
Ammonia
separation
0.1 mol/l NH
3
Paraffin oil, SPAN80,
ECA4360J
0.2 % wt H
2
SO
4
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
SLM (Supported Liquid Membrane):
Cellulose triacetate can be used as a for aqueous LM i.e. for hydrophilic LM.
Poly propylene can be used as a support for organic LM i.e. hydrophobic LM.
P 1/R
pore
If some pore are too small then some pore may remain W/O LM. Smaller pore
size also reduce the vapor pressure of LM.
Porosity should be high as much as possible.
Tortuosity should be small else fluxes will reduce
Bis-(2-
ethylhexyl)phosp
horic acid
()
SO
2
in flue
gas
Water NaHSO
4
Helium
()
Cu
++
in plating
bath
Kerosene Phenyl alkyl
Ketone
dil. H
2
SO
4
Teflon 5 60 12.5
(Flat sheet)
K
+
, Li
+
, Na
+
,
Sr
+
in aq. Sol.
Phenyl
Hexane
Crown ether De-ionized
Water
Polypropyle
ne
0.3 40 30
(Hollow
fiber)
Example of SLM
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Advantages:
0
2
1 2
2
( . )
i
A
A
A A B AB
N R at S S
d C
A D k C C k C
dx
+
ur uur
B AB A
D D D
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2
1 2
2
2
1 2
2
2
2 1
2
0
0
, & '
&
A
A A B AB
B
B A B AB
AB
AB AB A B
B B
x x L
AB AB
x x L
d C
A D kCC k C
dx
d C
B D kCC k C
dx
d C
AB D k C kCC
dx
As B ABdon tleakthroughthemembrane
dC dC
dx dx
dC dC
dx dx
+
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
As, we have linear conc. profile
( )
0
0
1 2
1 2
2
1 2
1
1
2
2
.
0
.
0
( )
1
1
&
1
L
AB AB
x x L A A
A A AB
A B AB
T B AB
A B T B
T
B
A
T T
B
A
A
A
AB T
A
C C
C C
N D D
L L
Atall pts inmembrane
kCC k C
Total conc of Bis
C C C
kCC k C C
k C
C
kC k
C C k
C k
k
kC k
C
k
kC
C C
kC
+
+
+
+
+
_
+
,
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( ) ( )
( )
( ) ( )
( ) ( )
0
0 0
0
0
0
0
0
0
0
0
0
1 1
1 1
,
1 1
1
1 1
T
L
T A T A
L L
A A A A
A A AB
L
L
T A A
A A
A A AB
L
A A
A
A
C
L
L
T A A
A A
A AB
L
A A
L
A A
A
T
L
A A
C kC C kC
C C kC kC
N D D
L L
kC C C
C C
N D D
L L kC kC
N
As Enhancement factor
N
kC C C
C C
D D
L L kC kC
C C
D
L
kC
kC kC
+ +
+
' )
+
+ +
+
+ +
+
+ +
( )
A AB
D D Q
After putting the
values of C
AB
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Thus from above expressions we can say that:
More the conc. Of B more is the transfer of species A i.e. more is the
enhancement.
++ +
++ +
+ +
1 1 1
] ] ]
MX
2
HX
M
2+
2H
+
2H
+
M
2+
m
1b
m
2b
m
1
m
1
m
2
m
2
1
2 3
4
5
a
1
a
2
0
1. Boundary layer resistance
2. Reaction between metal ions and carrier complex
3. Diffusion of metal ion complex
4. Reverse reaction takes place
5. Transfer to bulk phase of receiving side
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Here we assume that the thickness of membrane is very small & so we
consider linear concentration profile
( )
1
1
1 2
0
0
1 1 2
0
0
2
1
1
2
0 0
1 1 2
2 2
m
m
k
k
D
J m m
D
J m m m
Cu HX CuX H
From kinetic data
R R k Cu HX H k CuX HX H
++ +
+ + +
1
]
+ +
1 1 1
1 1 1
] ] ]
] ] ]
Q ?
ur su
Cases:
1. Fast interfacial reaction no resistance in the diffusion layer.
Thus R
0
R
0
= 0 and m
1b
= m
1
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
0 0
1
1
2
1 1 2
1
1
1
1 1 1 1 1
1
1 1
1
1 1
1 1
2 2
1 1
1
2 2
1 1
2
1
0
2
0 1
, 0
0
0
eq b eq
b eq
m
As R R
k Cu HX H k CuX HX H
k m HX h k m HX h
HX
k h
m m
k h
HX
mk HX m k HX
m
h h
m k HX
D
J
h
+ + +
1 1 1
1 1 1
] ] ]
] ] ]
1 1
] ]
1
]
1
]
1 1
] ]
1
]
ur su
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
0
1
2
2
0 1
2
,
.
( )
b
eq
m
Flux
As Permeability
Conc
J
P
m
k HX
D
P
h
a P HX
1
]
]
Log [HX]
Log P
Tan= 2
2. Slow chemical reaction & no resistance in diffusion
layer.
Thus m
1b
= m
1
but R
0
R
0
0
Net transported = Net reacted
0 0
0
1
1
1 1
1 1 1 1 1
0
i
m
J J R R
D
m k m HX h k m HX h
1 1
] ]
ur su
1 1
] ]
1 1
+ +
] ]
1
1
1
]
1
1
1
+
1 ]
]
1
1
1
]
1
1
1
+
1 ]
]
1
]
2
arg ,
P HX
If HX L e Then P HX
1
]
1 1
] ]
Log [HX]
Log P
Tan
1
= 2
Tan
2
= 1
2
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
3. Slow reaction, resistance in the diffusion layer.
( )
( )
1 1
1
1
1 0
1 0
1 1
1
1 0
1
1 1
1
1 0
0
1
1
1 1
1 1 1 1 1
0
.
,
b
m
a
m
i
b
m
m
a
a m b m
m a
i
m
m m
J D
D diffusivityof metal ioninaq phase
J J J
as J J
D m m
D m
D m
Dm
m
D
and J J
D
m km HX h k m HX h
1
1
1
]
1 1
] ]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
1
1
1 1
1 1
1 1 1 1
0 1 0
1
1 1
1
1
1 1 1 1 1 1 1
0 0
1
1 1 1
1
1
1
1
1 1 1 1
0 0
1
1
m a m b m
m a
m a m
b
m
b
m a m
m
D D m
D m
m k HX h k m HX h
D
D D
m k HX h k HX h km HX h
D
km HX h
m
D D
k HX h k HX h
D
k
m
1
1 1
1
] ]
1
]
1
1 1 1
+ +
1
] ] ]
]
1
]
1
1 1
+ +
1
] ]
]
2
1
2
2
1
1 1 1 1
0 0
2
1 1
0
2
2 0
1
1 1 1 1
0 0
b
m a m
m
b
m
m a m
m
m HX
D D
HX h k HX k h
D
km HX
D
J
D D
HX h k HX k h
D
1
]
1
1 1
+ +
1
] ]
]
1
]
1
1 1
+ +
1
] ]
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2
1 1
0
2
2
1 0
1 1 1 1
2
1
0
2
1
2
0 1
1 1 1 1
2
0
,
arg ,
b
a
m
m
b
a
m
m
k m HX
J
HX h k HX k h
D D
k HX
J
Thus P
m
k h k HX h HX
D D
If HX Small Then P HX
If HX L e Then P HX
1
]
1
1 1
+ +
1
] ]
1
]
1
]
1
1 1
+ +
1
] ]
1
]
1 1
] ]
1 1
] ]
Log [HX]
Log P
Tan
1
= 2
Tan
2
= 0
1
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Electro dialysis
Electrically charge membranes are used to remove electrically charge species.
Made in one step. Consists of two layers, one is CEM & other is AEM.
If it form by joining CEM & AEM then it will not work, because it will require
very high potential to keep them altogether.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Production of H
2
SO
4
and NaOH
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Cathode
+
Anode
H
+
,OH
-
BM
CEM CEM AEM AEM
Na+ Na+
Na+
H
+
OH
-
SO
4
2-
SO
4
2-
SO
4
2-
Na
2
SO
4
H
2
SO
4
NaOH
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
+
CEM
Water Brine
Na
+
Cl
-
H
+
OH
-
Na
+
Dilute brine Conc. Caustic Soda (Na
+
+ OH
-
NaOH)
We use high Electric Potential & hence water splits
CEM are PEM:
1. Nefion per fluoro sulphonic acid
2. Flemion per fluoro carbon
3. Nefion + Teflon + Flemion
Membrane cell process for caustic soda production:
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Ion Exchange Membrane (IEM) Properties:
1. High selectivity for opposite charged ions and high permeability.
2. Low electrical resistance.
3. High mechanical strength and stability.
Types of IEM:
1. Heterogeneous membrane
2. Homogeneous membrane
Procedures to produce Heterogeneous membrane:
1. Dry modeling
2. Polymer solution + ion exchange powder Cast the film Evaporate
3. Partially polymerized film + ion exchange powder Complete
polymerization.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Procedures to produce Homogeneous membrane:
1. Polymerization of mixture of reactants that can undergo condensation
polymerization. One of reactants must contain a moety (charged
group), can made up of anionic or cationic.
2. Introduction of anionic or cationic moety into a polymer by technique
such as graft polymerization. Dissolve in solvent Cast the film
And evaporate the film.
Moety:
1. -SO
3
2-
, -CO
2
-
, -PO
3
2-
, -HPO
2
, -ASO
3
2-
, SeO
3
-
for CEM
2. -NR
3
+
, -R
3
N
2
+
, -R
3
P
+
, -R
2
S
+
for AEM
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Transport phenomena in electro dialysis:
i
= Chemical potential in membrane phase
i
= Chemical potential in solution phase
i = anions/cations
i
=
i
CEM
Solution
+
ln ln
i i i
RT m RT Z + +
' ' '
& ln ln
i
i i i
F
RT m RT Z
+ +
( )
'
'
2
2
'
'
.
,
. ( )
(1): in 2 ( )
i
i i
sol
I
in
R I
F
As
Conc of anions inthe membrane
Case Salt dissociate ions like NaCl
C
Co
M
,
Where,
m
i
= molar Conc.
= Electrical potential (EP)
in membrane phase
F = Faradays constt.
M
R
= Charge on membrane
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Nernst Plank ion flux equation:
i
i i
diffusion part
dc
J D Z
dx
14243
.
i
i
i
becoz of EP across the mem
D d
Fc
RT dx
I Z
1 4 42 4 43
.
i
i
i
J F
Current carried out
by the particular ion
Transport No
Total current
F Z
t
i
i
J F Z
I
i
i
J
F Z i
i
J
AEM CEM
Ideally t
+
= 0 t
+
= 1
Ideally t
-
= 1 t
-
= 0
Really t
+
= 0.04 t
+
= 0.95
Really t
-
= 0.94 t
-
= 0.05
This should be as
low as possible
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1. Cations flow in a Cation Exchange Membrane (CEM):
CEM
Cathode
+
Anode
x = 0
x =
x =
1
x = 0
Cation
C
D,b
C
D,m
C
B,m
C
B,b
C
D,b
Dilute
Bulk
Solution
i
FZ
t Q
i
i
i
i
J
I
It
J
FZ
'
( )
i
t i
FluxinSolution Feed
Z
+
{
'
'
i
FluxduetoEP
dc
D
F dx
t i
Fluxinmembrane
Z
+
i
dc
D
F dx
0
t
+
is large and D (dc/dx) is
very small in membrane
Dilute side
Brine side
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
'
, As FluxinSolution Fluxinmembrane
t i
Z
+
'
'
i
t i dc
D
F dx Z
+
'
i F
t i
Z
+
i
t i
F Z
+
{
{
'
'
' '
,
' '
,
'
'
'
0,
,
i
Db
Dm
inmembrane
insolution
dc
D
F dx
At x c c
At x c c
t t
dc i
D
dx Z
+
+
>
( )
'
,
'
,
'
'
Dm
Db
i
c
c
t t
F
i
dc
Z
+
+
( )
'
0
t t
F
+
+
+
( )
'
0.95 & 0.5 t t
+
+
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
' '
, ,
'
D m D b
i
c c
D Z
( )
'
' '
, ,
'
D m D b
t t
F
i
c c
D Z
+
+
+
( )
'
'
,
' '
,
lim
0
D m
D b
t t
F
c
c D Z
i
+
+
+
Q
( )
'
' '
, ,
'
B m B b
F
t t
For brine side
i
c c
D Z
+
+
+
+
( )
'
i
t t
F
t i
J
Z
+
+
+
+
F +
For limiting current
)
will increase gradually & a point
will reach the C
D,m
= 0 & if i
further increases then water will
start splitting & electro dialysis
will not take place.
Normally we use 75 % of i
lim
Applications:
1. H
2
recovery from purge gases.
2. CO
2
separation e.g. Tertiary oil recovery.
3. Air separation: (a) N
2
enriched (b) O
2
enriched air
4. SO
2
removed from smelter gas
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
5. H
2
S & water removal from natural gas.
6. NH3 removal from recycle stream in Ammonia synthesis.
7. Olefin / Paraffin separation in hydrocarbon processing
8. Pollution control: (a) Hydrocarbons (b) Chlorofloro carbons
9. Dehydration of natural gas convention: Glycol dehydration process
Benzene, Toluene
Low Pressure
Side
High Pressure
Side
Reject
Feed
M
e
m
b
r
a
n
e
There should not be any pin hole in the membrane
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Transport Mechanism:
1. Knudson diffusion
l
A
+ l
B
> r
P
, l
A
& l
B
are mean free path, r
P
= Pore radius
Permeation 1/M
W
Air + CO
2
CO
2
has less permeation
2. Molecular sieving
Pore radius < 7
3. Solution Diffusion Mechanism
Diffusion coefficient can not assumed to be constant and are function of
concentration in membrane, position and may also be of time.
A B
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Solution Diffusion Mechanism:
If T < T
g
polymer becomes crystalline
1. Type I diffusion
If T > T
C
(Critical temperature), T > T
g
(Glass transition temperature)
(a) Henrys law is obeyed
(b) Diffusion coefficients are constant
2. Type II diffusion
T < T
C
, T > T
g
All simple gases with low critical temperature as compare to ambient
temperature. E.g. Diffusion of C
4
in natural rubber
(a) Henrys law is obeyed
(b) Concentration dependent diffusion coefficient
i
i i
dc
J D Non fician
dx
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
3. Type III diffusion
T T
C
, T < T
g
E.g. Organic vapor of C
5
C
8
in Polyethylene
(a) Henrys law is not obeyed
(b) Concentration dependent diffusion coefficient
4. Type IV diffusion
T > T
C
or T < T
g
Unexplainable situation
E.g. Organic vapors in ethylene cellulose
(a) Henrys law is not obeyed
(b) Diffusion coefficients are concentration and time dependent
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Permeability of gases:
x = 0 x =
C
li
C
hi
P
hi
P
li
Low pressure
side
High pressure
side
( )
0
.
.
'
li
hi
hi
li
i
i i
c
i i i
c
c
i i i
c
i
i i hi li
hi hi hi
li li li
dc
J D
dx
J dx Ddc
J Ddc if flux is constt
If D constt
J D c c
c k P
if Henry s lawis applicable
c k P
_
,
+ +
+
V
f
= Total free volume available
V
f
*
= At std. state (no gas inside polymer)
V = Volume occupied by gas
K
0
= Solubility using Henrys law
= Conc. Coefficient
= Thermal expansion coefficient
= Compressibility coefficient
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
( )
*
2
*
2 *
*
*
*
:
1
(2)
3
.
,
1 2
(1)
,
(2)
,
h
o
h
o
h
o
h
c
f
Pvs P
If k
P thenP
If k
P thenP
If k
P thenP Constt
CalculateT fromfollowingequation
T
T
T
V
If T T
As T thenP
If T T
As T thenP
<
>
>
<
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Engineering consideration in gas permeability:
Separation factor:
,
1,
1,
A
A B
B
A
A
A B
A B
P
Selectivity
P
Where P Permeability of A
and P Permeability of A
If then Acomes as permeate
If then B comes as permeate
?
=
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Michaels (1966)
1. A membrane is selectively permeable towards that component of gaseous
mixture that has highest critical temperature, the smallest molecular diameter
or both.
2. Selectivity of membrane invariably decreases with increasing temperature
(fluxes increases with temperature).
3. Stiff chain polymer membranes although less permeable gases than flexible
chain polymer of similar chemical constituent, are more selective towards
smaller molecules relative to longer ones.
Flow patterns:
1. Fully mixed flow pattern
Least efficiency
Driving is force same every where
Feed
Composition is same due to mixing
Un permeated stream
Permeate stream
Composition is same every where
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2. Cross flow pattern
= Stage cut
A = Area of the membrane
L
ol
, y
oA
, y
oB
L
oh
, x
oA
, x
oB
L
il
, y
iA
, y
iB
P
l
P
h
( )
( ) ( )
( )
,
,
1
, 1
oA
oA
ol oA
oA
A h oA l oA
oA
ol oA A h oA l oA
ol oB ol oA
If known find A y
If Aknown find y
Amount of Aout L y
P
J Px Py
AP
L y AJ Px Py
As L y L y
L
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( ) ( ) ( )
( ) ( )
( )
( )
( ) ( )
( )
( ) ( ) ( )
1 1 1 2
3
4
, ,
1 ,
1
5
2
1
1 1 1 6
oB
ol oA h oA l oA
ih oh ol
ih iA oh oA ol oA
ol ol oA
ih oB
oA
oA h oA l oA
oA h oA l oA
AP
L y P x P y
L L L overall mass balance
L x L x L y
L L P
A
L P
P
From
y Px Py
and from
y P x P y
1
]
+
+
1
]
L
L
L
L
L
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( )
( )
( ) ( )
5 &6 ,
1
&
(4),
1
1 7
1
h l
oA
l
oA oA
h
l
ih iA oh oA ol oA
h
oh l ol
iA oA oA
ih h ih
l
iA oA
h
h l
l
iA
h
Adding weget
P P
y
P
x y
P
from
P
L x L y L y
P
L P L
x y y
L P L
P
x y
P
P P
P
x
P
+
+
+
+
1+
+
1
]
1
1+
+ 1
1
1 ]
1
]
L
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
7
7
ol
oA
ol
oA
If is known
Find from and Acanbecalculated as
L
A
P
If Ais known
L
Find from
A
P
and from canbecalculated
Pressure: 20 atm
Micro porous carbon
Coating from inside of 20 m
Zirconium oxide
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Membrane transport model:
( )
( )
( )
*
*
* *
*
*
:
:
m P
w
p
w
ps
m
s
s
ps p
p s
p
m
s
s
Permeability
v L P
L
P
Forothersolvents
L
v P
L L
P
L
L
v P
_
,
_
,
w
= Viscosity of water
L
P
*
= Standard permeability
= Standard permeability coefficient
Phone poulene membrane
Solvent
L
P
*
= 10
-12
Methanol 1.0
Acetone 1.0
n Heptane 0.7
Toluene 0.9
Dioxane 0.05
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Concentration polarization less than the limiting flux
( )
{
( ) ( )
( )
22 23
21 23
23
21
23
22
ln
22
ln
exp ,
1
1
1
v
obs
v P
s v s
Diffusionpart
Convectivepart
s
c c J
c c k
c
R and
c
c
R
c
FromKedem Katchelky Model
J L P
J W J c
c c
1442443
J
V
R
obs
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1 1
1 1
ln ln
1
ln
1
m
v
obs v
obs
m v
v
obs obs
P
R J
R J R
R R k
P J
J k
T R
+
_
_
+
,
,
_
+ +
,
J
V
T
obs
J
V
R
obs
J
V
1 - R
obs
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Pore Flow Model & Hindrance Transport Model for Ultra filtration:
r
P
Z = Z =
C
P
C
f
J
V
(m/s)
V = V
avg
( )
( )
0
1
. .
1
s
s c s d
s
s
P
s s
z z
f P
s
d c s s
s
d c s P
dC
N kVC k D
dz
dC
D diffusiontransport inbulk
dz
i e free fromhindrance
r
r
C C
Partitioncoefficient
C C
from
dC
k D kVC N
dz
dC
k D kVC VC
dz
L
N
s
= Flux of individual component i.e. solute
moving inside a pore
D
1
]
_
,
_
P
c v
c f P d
C
k J
kC C k D
_
,
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( ) ( )
( )
( ) ( )
( )
( )
( )
( ) ( )
( )
,1
1
ln
1 1
1
ln
1 1
1
ln
1
ln 1
1
, . .
1 1
ln
1
c
c v
d
c v
d
c v
d
v
d
d
m m
d
v
m
Let k
R
k J
R k D
R
k J
R k D
R
k J
R k D
R
J
R k D
k D
Let P ieP
k D
R J
R P
R
,
_
,
_
,
_
,
_
,
_
( )
1
exp
v
m
J
R P
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
( ) ( )
1
exp
1
1 1
, exp
1
v
m
v
m
J
R
F
R P
R F FR
F J
R where F
F P
]
1
1
]
Same as Spiegler Kedem model
But here reflection coefficient and permeability are depends on thickness and
hindrance factor
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Pervaporation
Pervaporation = Permeation + Evaporation
Vacuum is applied on permeate side and the permeate is removed in vapor form
]
? =
Mass transport within membrane and membrane selections:
1. Solvation of permeating molecules on a liquid side of the membrane
2. Diffusion of these molecules through the membrane
3. Evaporation from vapor side of the membrane
Anisotropic swelling: Nonlinear expression for solubility as well for diffusion
coefficient
Liq. Vapor
h
Swelling
Dry
1
]
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1. Downstream pressure is determining parameter in fixing the flux, where the
upstream pressure has very little effect
2. When temperature is raised, the fluxes increased following Arrhenius like
relationship
3. Because both solubility and diffusivity are functions of concentration of both
component of the binary mixture , a complex transport occurs. In general
the flux decreases when the mixture becomes poorer in A, where A is more
rapidly permeating species and loses its swelling properties, simultaneously
selectivity increases.
Calculation of temperature drop:
' '
,
' '
,
P A A
P B B
F
C A w
C B w
( F V )
" "
,
A B
V w w
,
,
, ,
& .
.
v A
v B
v A v B
H Heat of vaporisation of A
H Heat of vaporisation of B
H H assume constt
but it changes with temp
1
1
]
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( )
( )
( )
( )
( )
' ' ' ' " "
, , , ,
" "
, ,
' ' ' '
, ,
"
, , ,
' ' ' '
, , ,
' ' " "
' '
, , , ,
,
'
,
1 & 1
, &
P A A P B B v A A v B B
v A A v B B
P A A P B B
v B v A v B A
P B P A P B A
B A B A
v A v B P A P B
v B
P B
F C w C w T V H w H w
H w H w
V
T
F
C w C w
H H H w
V
T
F
C C C w
w w w w
Let H H C C
H
V
T
F C
+ +
+
+
+
+
1
]
Q
By heat balance i.e. the amount of heat the liquid has lost = Heat gained in
vaporization
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
0
,
500
0.3
, 150
if component Biswaterthen
V
T
F
if Stagecut
then T C
Applications:
1. Homodialysis: Artificial kidney
2. Alchohol reduction in beer
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Q
out
, C
out
Q
in
, C
in
Q
in
, C
in
Q
out
, C
out
( )
' ' ' ' " " " "
' "
'
' ' "
:
,
:
.
in in out out out out in in
o
o
in out
o
in
in in out
m
Lost by feed side Gainedbydialysate
QC Q C Q C QC
Dialysates
M
D M Over all masstransfer
C C
Extractionratio
D M
E
Q
Q C C
Actual removal
Max amt that canremove
Feed side
Dialysate side
Counter current
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2
1
C
1S
C
1m
C
2m
C
2S
k
m
C1b
k k
l
dA
C
Q, C
C + dC
( )
( )
( )
( )
2
1 2
' "
0
' "
0
' ' " "
' "
' "
' "
' "
,
1 1 1 1
1 1
1 1
sm
im m
sm sm
s s m
m
o
o
D
N C C
l
kD kD
C C where k
l l
k k k k
dM k C C dA
QdC QdC
dC dC dM
Q Q
d C C dM
Q Q
1
1
]
+ +
_
,
_
,
&
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( )
( ) ( )
' "
0
' "
' "
' " ' "
' " ' "
' "
1 1
1 1
1 1
,
,
1 1
out
in
C
M
o
C
o
in out
o
in out
in out in out out in
in out in in out out
d C dM
Q Q
C C M
Q Q
C C
M
Q Q
Forcountercurrent
C C C C C C
Forco current
C C C C C C
d C
Q Q
,
_
&
0
' "
1 1
o
dM
k CdA
Q Q
_
,
_
,
Q
out
, C
out
Q
in
, C
in
Q
in
, C
in
Q
out
, C
out
Feed side
Dialysate side
Co current
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
0
' "
0
' "
0
0
0
ln
' '
" "
1 1
,
1 1
ln
ln
out
in
C
C
out in out
o
in
o
in out
out
in
o
in out
in out
d C
k dA
C Q Q
Integratingbothsides
d C
k A
C Q Q
C C C
k A
C
M
C C
M k A
C
C
M C k A
Q Q
Here flowratesareassumed
Q Q
,
_
,
_
0
'
T
tobesamethroughout
k A
N
Q
+
+
Z=0.25
Z=0.5
Z=1
Z=0.25
Z=0.5
Z=1
Counter current Co current
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Variations of dialysis:
Conventional process:
1. Packed column
2. Fluidized bed columns
3. Bubble column
4. Trickle bed reactors
5. Spray tower
6. Venturi scrubbers
Problem associated with conventional process:
1. Flooding, 2. Weeping, 3. Priming, 4. Foaming, 5. Entrainment, 6. Dumping
New applications
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1. Gas absorption & stripping:
Micro porous hydrophobic
membrane
gas Liq (aq.)
Immobilized face
P
g
P
aq
Pores
In this case water (aq.) will not go
in membrane pore
To avoid bubble formation through
liq P
aq
> P
g
But if P
aq
be too large then it break
through gas phase
P
aq
P
g
= P
r
< (2r cos ) / r
P
Micro porous hydrophilic
membrane
gas Liq (aq.)
Immobilized face
P
g
P
aq
Pores
In this case pore (membrane) will be
occupied by water
To liquid cant breakthrough the gas
P
g
> P
aq
To gas cant bubble through liquid
P
g
P
aq
= Pr < Breakthrough press.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Advantages:
1. The gas and liquid flow rates can be varied independently [i.e. there is no
problem of weeping, flooding etc.]
2. The gas/liquid interfacial area is known (a priority), since membrane area is
known
3. All membrane surface area is available for contacting even at very low flow
rates
4. Scale up is easier
5. Offer very high surface area
6. No moving parts required
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2. Membrane based Solvent Extraction:
Micro porous hydrophobic
membrane
Org Liq (aq.)
Immobilized face
P
org
P
aq
Pores
In this case organic compound not
water (aq.) inside membrane pore
P
aq
> P
org
P
aq
P
org
= P
r
< Break through
pressure
Micro porous hydrophilic
membrane
Org Liq (aq.)
Immobilized face
P
org
P
aq
Pores
In this case pore (membrane) will be
occupied by water
P
org
> P
aq
P
org
P
aq
= Pr < Breakthrough press.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Gas membrane: