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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India


MEMBRANE SCIENCE AND TECHNOLOGY
BY
Prof. S. K. Gupta
Presentation on
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India

Membrane: Its allows some selected components to pass through it and


hence aids in separations.
Membranes physical phase: solid, Liquid & gas.
Membrane Types: Homogeneous, Heterogeneous, Symmetric &
Asymmetric Membranes.
Advantages:
1. Can work at room temp.
2. Less energy required. (Open Pan evaporator = 600 KWH/1000 kg water
5-7 effect evaporator = 37-53 KWH/1000 kg water
Reverse Osmosis membrane = 5-20 KWH/1000 kg water)
3. No phase change (except Pervaporation).
Introduction
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Disadvantages:
1. Purity is not achieved or if achieved it will be costly.
2. Completely dry products is not obtained. (Pressure Swing Adsorption
is used after membrane separation.)
3. Fouling of membrane takes place.
4. Concentration polarization takes place.
Low Concentration of Salt
High concentration of Salt
Negligible Concentration
of Salt
Feed
Reject
Permeate
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Membrane Materials:
1. Polymeric: Used up to 70
0
C Temp. range.
Cellulose Acetate (CA).

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.

Membrane material: Ceramic (Powder form), Metal, Polymer powder.

Pore size: 1-20 m.

Application: Micro filtration (Asymmetric Membrane).

Irregular Pore size. Porosity 10 % to 40 % .


Methods of Preparation

.............




:::::::::::::::::::::::::::::
::::::::::::::::::::::::::::
Pressurizing (also heating just
below the MP of Powder)
Plates 100-500 m
Fine Powder.

Binding Material may be used.


Also Lubricant is used.
Pressurizing (also heating just
below the MP of Powder)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2. Manufacturing technique: Stretching of polymer sheet.

Membrane material: Polymer sheet.

Pore size: 0.5-10 m.

Application: Micro filtration, Burn dressing, Artificial blood vessel.

Irregular pore size. Porosity 60 % to 70 % .


Stretch very slowly
(Bonds are broken)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
3. Manufacturing technique: Track Etched.

Membrane material: Polymer sheet.

Pore Size: 0.2-10 m.

Application: Micro filtration, Burn dressing, Artificial blood vessel.

Uniform pore size .


Nuclear source
Polymer sheet
First step: The bonds become weak from where
radiations pass.
Second step: Etching bath to wash out the weak
bonds & create pores.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
4. Manufacturing technique: Inversion technique.
Membrane material: Any Polymer.
Pore Size: 0.01-5 m.
Application: Micro filtration (MF), Ultra Filtration (UF), Reverse Osmosis
(RO).
Uniform pore size .
In first step:
Polymer + Solvent = Homogeneous solution (10 - 30 %wt Polymer)
Glass
support
Homogeneous
solution
In second step:
It can be done in 3 ways.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
a). Addition of Precipitants:

Precipitating agent: Mostly water , Air.


Polymer
Solvent Precipitate
A
B
C
Two phase
region
Homogeneous
region

Porous membranes are obtained


Phase inversion diagram
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
b). Solvent evaporation:
Solvent should be volatile.

Allow solvent to evaporate (for pore formation).


Polymer
Solvent Non-solvent
Phase inversion diagram
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
c). Thermally induced phase inversion:
Lower the temperature of homogeneous solution.

We get 2 separate phases.

From top remove solvent rich phase & polymer


(membrane) remains on glass plate.
T
1
T
Polymer + Solvent
Solvent rich
phase
Polymer rich
phase
Polymer Solvent
Phase inversion diagram
e.g.: Polypropylene membrane dissolved in N,N-bis-(2-hydroxyethyl)-
tolylamine.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Preparation of asymmetric membrane
1. Asymmetric membrane:
0.2 m Membrane thickness which
provides resistance
0.2 mm
Porous material
2. Composite membranes: (Most recent technique)
a). Coating on micro porous membrane.
b). Interfacial polymerization.
Polymer solution with
cross linking agent
For polymer
support
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
3. Integral asymmetric membrane:
Polymer + Solvent = Homogeneous solution (10 - 30 %wt Polymer).

Homogeneous solution put above glass plate & add precipitating agent.

The film is quenched in non solvent or in 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):

Good for RO.


3. Sponge structure (can be kept in dry condition):
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Factors that leads to different Asymmetric membrane:
1. The polymer & its concentration.
2. Solvent.
3. Precipitants.
4. Form of precipitants (vapor or liquid).
5. Temp. of precipitants.

High precipitation rate leads to Finger type.

Slow precipitation rate leads to sponge type.


Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1. Induced concentration gradient:

At surface concentration is minimum.


Under beneath concentration is higher.
A*
A
B
C
Polymer
Solvent Precipitants
2. Surface super saturation:
Initially mass transfer takes place at upper Thin layer but beneath
homogeneous solution.
The thin layer impart resistance and hence reduce mass transfer.
NS
NS
Solvent
P + S
Thin layer
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Inorganic membrane
Advantages of inorganic membrane:
1. Higher thermal stability.
1. Can be steam stabilized.
2. Allows higher pressure.
3. Resistance to chemical corrosion.
4. Resistance to microbial degradation.
5. Ability regenerate thermally.
Disadvantages:
1. Expensive (much more than polymer membrane).
2. Only micro filtration & Ultra filtration membranes
are available.
Micro porous = 5 nm to 50 m.
Nano porous & Ultra porous < 2 nm.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Manufacturing techniques
Manufacturing techniques:
1. Sol-gel process.
2. Chemical Vapor Deposition (CVD) modified membrane.
3. Leached hollow glass fibers.
4. Anodic oxidation.
Preparation of support:
Ceramic powder, Inorganic binding lubricant & water.
Paste is extruded in desired shape drying Sintering.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1. Sol-gel Process:
Alkoxide (metal salts,
metal organics)
May be acidic, basic, aqueous
media or in organic phase
Hydrolysis
Condensation
polymerization
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Acidic & Aqueous media:
Solvation of Metal ion:
M
Z+
+ n H
2
O M(OH
2
)
n
Z+
Solution of Metal ion
M(OH
2
)
n
Z+
M(OH)(OH
2
)
n-1
(Z-1)+
+ H
+

Monomer
Hydrolysis:
2 M(OH)(OH
2
)
n-1
(Z-1)+
M
2
(OH)
2
(OH
2
)
2n-4
2(Z-1)+
+ 2 H
2
O
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Basic & Organic media:
M(OH) + (OH)- MO- + H
2
O
MO- + n ROH M(OR)
n
+ -OH
M(OR)
n
+ H
2
O M(OR)
n-1
OH + ROH
M(OR)
n
+ M(OR)
n-1
OH M
2
O(OR)
2n-2
+ 2 ROH

Colloidal solution (destabilized by evaporation)
Glass
support
Gel
Drying 50
0
C
Sintering
Ceramic layer
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Fluxes

Multi component diffusing mixture:


1, 2, 3,......., n Components

1 2 3
, , ,........,
n
v v v v
ur uur ur uur
1 2 3
, , ,...........,
n

Velocities
Mass concentration (g/cm
3
)

These are not densities.


Molar concentration (gmol/cm
3
)
1 2 3
, , ,..........,
n
c c c c

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

Mass flux (Absolute) =

Molar flux (Absolute) =

Mass diffusion flux =

Molar diffusion flux =

Relation between absolute flux & diffusion flux:


1
*
1
n
i j i
i
j
n
i j i
i
j
n w n J
N x N J

+
+

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

Concentration difference only driving force

Chemical potential main driving force


Chemical potential
This equation gives better result
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
ln
ln
d RTd P
RTd f

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.

In Presence of Electric Field


( )
( )
*
*
* *
AB AB
A
A A A A
AB
A A A
AB
A
A A A A A
D D
J c c F
RT RT
D
c F
RT
D
J c F
RT




1
+
]
+
ur ur ur
ur
ur ur
Q
Z
A
= Charge
F = Faradays constant

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

In Presence of Thermal Gradient:


*
ln
T
AB
A
A A A
T
A
D
J c D T
RT
D

ur ur ur
Thermal Diffusion Coefficient
Thermal & Electrical effects are not significant
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Theory of Irreversible Thermodynamics
1 1
2 2
3 3
n n
J X
J X
J X
J X

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

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
1
0 0
0
1 1 2 2
1 11 1 12 2
2 21 1 22 2
[ ( )]
( )
n
i
i
i
x x
i
m i
x
i
i i i
J
dx J dx
J dx J
x
J J
J L L
J L L

+
+
+

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.

Very little compaction Lower membrane life.


Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Membrane modules:
1. Flat sheet membrane:
Plate & frame module
Rectangular or Hexagonal
shape, 30-40 plates required
Spiral bound module
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Illustration of a spiral-wound module
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2. Tubular membrane:

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

j = 1 Bulk feed phase


j = 2 Interface between membrane & feed
j = 3 Bulk permeate phase
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Film Theory Model
Assumptions:

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

If membrane is perfect & doesnt allow any permeate, then


23
22
21
0
exp ( )
v
c
J c
A
c k

1

1
]
L
Equation (A) is not valid for laminar flow assumption
From (A) we can say higher flux will result in higher concentration
polarization

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

If we take some velocity then it doesnt


improve result thats why we take former
assumption that simplify the problem
30,000 ppm P > 30 atm
20,000 ppm P > 20 atm

Then we will design on 30,000 ppm P >


30 atm basis
(k)
permeable
& (k)
nonpermeable
values differ only
10%, so we can use same correlation for both
J = f / 2 = [k (Sc)
2/3
] / u

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

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
Kimura Sourirajan Model
Kimura Sourirajan Model also gives:
1
2
22 23
22 23
1
1
2
( )
( )
. ,
( )
,
0
s
N A P
N Bc
f c c
ie bc
bc c
Forpurewter
N AP
N P
N Bc

The value of A & B different


for SD Model & KM Model
N
1
P

A = Tan, we can find A


We cant find B because we cant measure C
22
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Kimura Sourirajan analysis:
1 22 23
2 22 23
22 23 1 2
21 23
2
23
22
2. { ( )}
3. ( )
4. exp
Find 'k'
1 1
ln ln (1
1. Find 'A' frompure water permeability data
)
1 1
obs v
obs
N A P bc c
N B c Bc c
c c N N
c c ck
R JR
R R k
cN
c
R
c


+
1

_

_
+

,
,

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)

Its 3 Parameter Model


1
1
0 0
1
0
0
[ ( )]
[ ( )]
Ma
Biological memb
ss Transfer only in x direction (Assume)
[ ( )]
ranes very near to equilibriu
[ ( )]
m
n
i
i
i
x x
n
i
m i
i
x
n
m ix i x
i
x
n
ix i x
i
J
dx J dx
J dx
J d

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)

ln ln ln ( For ideal solution =1)


ln(1 ) ln(1 ) ln(1 )
1
w s
m w w s s
w s
m w w s s w s
w w w w
s s s
x x x
s s s s
x x x x x x
J RT a V P J RT a V P
RT J a J a J V J V P
a x x
x x x
x x c x c x
c



1 1
+ + +
] ]
+ + +

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

For totally perfect membrane, = 1, i.e. completely reflect


For totally imperfect membrane, = 0, i.e. completely passes
Three parameters of
K-K Model
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Spiegler-Kedem Model (1965)
Its much better model
x=0 x=x
Consider infinitesimal small strip is in
thermodynamic equilibrium
( )
( )
( )
1
0 0
[ ( )]
( )
1
( )
n
i
i
i
v v
s v s
x x
v v
v v
v
v
v
J
dP d
J P Forasmall strip
dx dx
and
d
J W J c
dx
Forwholemembrane
dP d
J dx P dx
dx dx
J x P P
P
J P
x
dP d
P
dx dx



_


,
+

_


,

_


,


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

>

? For nearly perfect membrane (P and k also constant)


[ Pressure drop due to friction is very
small as compared to the applied P so we
can assume P as constant.
As k Q
0.8
For Turbulent flow
and k Q
0.3
For Laminar flow Thus
for smaller recovery say 20% we assume
k as constant If we
have analytical solution for 20% and the
recovery given in problem is 80% then
divide the model in 3 or more parts to
keep k constant]
For Plate & Frame and
Spiral wound module
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
x
23
x
22
x
21
x = 0
V
xf
, x
21f
At x = 0, V
x
= V
xf

x
21
= x
21f
For dilute solution, nearly 100 % salt rejecting
membrane C
22
C
23
C
22
N
1
> > N
2
( )
[ ]
( )
( )
1
11
2
21
1
x
x
dV
N
X
dx ch
N
dVX
dx

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

+
+

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
21
21 22
21 22
21 21
23
23
21
,
,
f
xf
f f
x
f xf
bcX
P
k
AP
c
B
AP
c
AP
x X
chV
X X
X X
X X
X V
X V
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

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
22 23
,
c c
as

0
21 23
c c

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

+
+
+

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( )
( )
( ) ( )
( )
( ) ( )
2 2
1 1
2
1 1 1 2
1
1
2 2
1 1
1
1 1 1 2 1 2
,
1
1
u u u
u
w u
i i
and
e du e du e du
u u u
e du
E u E u
u
e dw e du
L e
w u
L e E u E u E w E 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


+
+

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( )
( ) ( )
( )
( )
( )
( ) ( ) { }
( )
2 2
1 1
2 1
1 1
1
1
ln ln
1
ln
1
ln 1 ln 1 1 1
1
1
ln
1
V
V
V
L dV dV
V V
L V V V
L V V
L
L




+

+

+
+
+
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
+

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
23
21 f
X Bc
X

S
c
'
xf
V A

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
]

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
[ ]
( ) { }
2
1
23
23
1
1
1 1
1
1
1
1
I V L
I L
I L
I L
X L
L
X

+
+
+
+
+
+
+
+
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.

Additives are added to increase/decrease the solubility of any one species.

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

Here the transfer occurs through the pores


Big drops
Receiving phase
Feed Phase
Liquid Membrane
LM
LM
LM
LM
LM
LM
LM
Feed
Receiving Phase
Fiber
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Separation mechanism in Liquid membrane
S
A
Solubility rate of A
S
B
Solubility rate of B
Selectivity,
i i A A
ij
j j B B
D S D S
B
D S D S

A
B
LM Feed
1. Add additive to increase or decrease selectively of one of the components in
liquid membrane
A
A
B
B
LM (aq.)
A (Aromatic (org.))
NA
Additive N-methylpyrolidone Its increase solubility of A several folds
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2. Permeation with solute trapping mechanism

A + C D ( Instantaneous reaction)
Phenol + NaOH Sodium Phenolate ( Instantaneous reaction)
Thus Conc. of Phenol at receiving side becomes zero ( as Phenol is trapped
as Sodium Phenolate) Thus Conc. difference increases & thats why mass
transfer rate increases.
A
B
Aq.
Phenol
Org.
(Kerosene)
Cheaper
C
Aq.
Feed Side LM Receiving Side
NaOH
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
3. Carrier Mediated Transport:
(a) Facilitated Transport

If solubility of A in LM is very small & still we have to remove A from feed.

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

If reverse reaction is not possible or very-very small.


Carrier complex is very stable.
If carrier complex is photo sensitive then we use light energy.
AC + h A + C
AC
C
A
A
h
(d) Electro facilitation
AC AC
+
+ e
-
A + C
+
+ e
-

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:

It should be soluble in LM.


It Should form complex which is soluble in LM.
It should be insoluble in both external phases.
It should form complex easily.

Complex should be moderately stable.


Should be high mobility.

Commercially it is (LM) used for metal ions separation.


Carrier species for metal extraction:
1. Acidic:
(b) Hydroximes

Commercial carriers: LIX63, LIX65N, LIX64N, LIX70


LIX 63: CH
3
-(CH
2
)
3
-CH(C
2
H
5
)-CH(OH)-C(NOH)-CH(C
2
H
5
)-(CH
2
)
3
-CH
3
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
(b) B-diketones

Acetyl acetone, Benzyl acetone.


(2) Basic:
D2EHPA (Di-2-Ethylphosphoric Acid)
(3) Neutral:

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.

Strong surfactant difficulty in Demulsification.


Weak surfactant possibility of breakage of drops.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
4. Demulsification: No. of techniques are used.
a. Electrostatic demulsification
b. Heat treatment
c. Phase dilution
d. Shear forces
e. Adsorption of Kerosene
Kerosene (Oil)
Water
Demulsification
O/W Emulsion
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Important parameters: Membrane stability, Large interfacial area, Mass
transfer coefficient.
All important parameters are depend on different parameters: Concentration
of surfactant, Micro drop hold up, Temperature, Treatment ratio, RPM,
Internal reagent concentration.
Parameters Stability Mass transfer Interfacial area
Conc. of surfactant
+ + + + + +
Micro drop hold up
+ + + + + +
Temperature
+ + + + + + +
Treatment ratio
+ + + + + +
RPM
+ + + + + + + +
Internal reagent conc.
+ + + + +

+ Low, + + Moderate, + + + High


Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Surfactants: SPAN80, ECA4360J
Carrier species: LIX64N

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):

We use a micro porous support.


LM should be compatible with support.
Support material should not react with LM or with feed phase or receiving
phase.
LM should wet the micro porous membrane completely.

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

Thickness should also be small.


Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Permeable
species
Solvent
(LM)
Carrier Stripping
phase
Polymer
support
Pore
size
(m)
Porosit
y
Thickness
(Module)
Uranium in
ground water
n-Dodecane Cynex-272 [Bis-
(2,4,4)-trimethyl
pentyl phosphoric
acid]
HEDPA (1-
hydroxyethane
-1,1-
diphosphoric
acid)
Polypropyle
ne
0.02 38 25
(Flat sheet)

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:

Offers large interfacial area. ELM 3000 m


2
/m
3
, SLM 10,000 m
2
/m
3
Scalable.
Very high selectivity and fluxes.
The strip solution volume may be made smaller than the feed so that the
solution can be concentrated simultaneously.

Both extraction and stripping are carried out simultaneously.


Extraction
Scrubber
Stripper
Raffinate
Feed
Impurities
are removed
Scrubbing
solution
Strip liq.
Stripping solution
Solvent
Liq. Liq. Extraction
Raffinate Feed
Strip. Liq.
Stripping solution
Solvent
Liquid membrane
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Disadvantages:
ELM:
1. Membrane breakage due to agitation, poor membrane formation,
excessive internal drop size.
2. Requires emulsification.
SLM:
1. Solvent loss by evaporation or by pressure differences across the micro
porous membrane.
2. Carrier loss can occur due to irreversible side reaction.
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Gas separation using facilitated transport in LM:
1. O2/N2 Cobalt salen as a carrier.
2. CO2 Bicarbonate as a carrier.
3. H2S 1. Bicarbonate as a carrier.
2. Ion exchange membrane (cation exchange membrane),



Organic diamine cations as carriers.
4. Ethylene Propylene separation Ag
+
is used as carrier ethylene selectivity is
1000 time than propylene
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Mathematical modeling
Facilitated transport (ward 1970):
Assumptions:
1. Limited solubility of A.
2. C
A
o
(at x = 0) & C
A
L
(at x = L)

are known.
3. All the reactions are 1
st
order with respect to A, B & AB
4. B & AB dont leak through the membrane
C
T
(known) = C
B
+ C
AB
LM
A
AB
B
Feed Strip gas
A
A
C
A
o
X = 0
C
A
L
X = L
1
2
k
k
i
A B AB
C
t

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
Limiting cases:
1. Reaction equilibrium exists through out the membrane
2
2
1 2
0
0
0
2 1
0
0
0
.
( . )
,
0,
,
, &
A
A
A
A
A A
L
A A
L
A A
A
L
A A
A A
d C
A D
dx
dC
Constt
dx
C cx c Linearconc profile
Putting
at x C C
x LC C
C C
Weget c C c
L
C C
C x C
L


+

+
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.

After a particular conc. Of B any further addition doesnt increase the


mass transfer of A. This is due to change in viscosity. Because
diffusivity is a function of viscosity.
2. Slow chemical reaction
Approximation: As the reaction rates are small C
B
& C
AB
are constant.
1 2
2
1 2
2
0
& (1)
A B AB
A
A A B AB
kCC kC
dC
D kCC kC
dx

L
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
1 2 2
1 1 1
1 1 2 2
1 2 2
0
2 1 2 1
1
sinh cosh
, ,
cosh
,
sinh
&
A
B AB
L
A
A
AB
B B K
C kx kx
K K K
Where K k C K k C
KC K B kL
B KC K B
kL
K
k
D
1 1
+ +
] ]

1

]

1
]

Solving the above equation (1) by keeping C


B
& C
AB
constant we get
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Coupled transport:
[ ]
1
1
2 2 2
, &
k
k
Cu HX CuX H
Cu m HX HX H h

++ +
++ +
+ +
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

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
0 0
1
1 1 1
0
1
0
1 1
0
2
1
0
2
1 0
1
1 1 1
0
,
b
m m
b
m
m
m
m b
k m HX h k m HX h
m
D D
k HX h k HX h
k m HX h
D
J
D
k HX h
k HX
D
J
Thus P
D
m
HX h k mh
If HX Small Then

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.

Minimum two pairs are used.


Basically this process is used where salts are present.
+
+
+
+
+
+
1 Pair
Anion
Exchange
membrane
cation
Exchange
membrane
+
+
+
+
+
+
+
+
+
+
+ + +
+
+
+
+
+
Cathode
It collects cations
i.e. it is negatively
charged
It collects anions
i.e. it is positively
charged
Anode
Cations
Anions
Normal tendency
Concentrated brines
Lean in brines
NaCl Water solution
AEM AEM CEM CEM
(AEM)
(CEM)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Applications:
1. Production of potable water i.e. Desalination.
2. Waste water treatment.
3. Removal of salts & acids from pharmaceutical solution. Also used them for
food processing.
4. Removal of tartaric acid from wine.
5. Production of salt from sea water.
6. Water splitting using Bipolar membrane.
7. Membrane cell process for caustic soda production.
+
+
+
+
+
+
Bipolar membrane (BM)
H
2
O
H
2
O
H
+
,OH
-
Bipolar membranes:

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

If Electric Potential (EP) increases


then i increases & thus (t
+
- t
+

)
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

Diffusion is negligible & most of


transport is due to EP
In each pair of AEM & CEM, we need to find the local fluxes,
then integrate these fluxes
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2. Flow of anions through Cation Exchange Membrane (CEM)
CEM
Cathode
+
Anode
Anions
C
D,b
C
D,m
C
B,m
C
B,b
'
t t
+
+
>
3. Flow of cations through Anion Exchange Membrane (AEM)
Dilute side
Brine side
Cathode
+
Anode
Cations
C
D,b
C
D,m
C
B,m
C
B,b
Dilute side
Brine side
+
+
+
+
+
+
{
{
( )
'
'
0.04 & 0.5
in membrane
in solution
t t
t t
+
+
+
+
>

AEM
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
4. Flow of anions through Anion Exchange Membrane
Cathode
+
Anode
Anions
C
D,b
C
D,m
C
B,m
C
B,b
Dilute side
Brine side
+
+
+
+
+
+
AEM
'
t t
+
+
>
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Gas separation

Monsanto Composite Hollow Fibre


Different producers of membrane: Dow, DuPont, Air product, Union carbide.
Conditions for application:
1. Feed stream in the range of 4.2 10
3
to 57 10
6
m
3
/day
2. Moderate concentration of more permeable gas in the feed i.e. 10 to 85 %
3. Moderate high pressure i.e. 18 to 137 atm
4. Moderate temperature i.e. 0 to 65
0
C
5. Acceptability of moderate recovery i.e. less than 97 to 98 %.

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

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
( )
( )
( )
,
,
. ,
,
hi
li
hi
li
hi li i
i i i hi li
i i
i hi li
i i i
i
i hi li
c
i i i
c
i
i
i hi li
c
i i
c
i
hi li
Let k k k
J Dk P P
Dk
J P P
P kD Permeability
P
J P P
AsJ Ddc
if Disnotconstt then
J Dc c
Ddc
WhereD
c c

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
( )
( )
( )
( )
( )
'
,
,
,
hi hi hi
li li li
hi li i
i
i i
hi li
i
i hi hi li li
i
i hi hi li li
i
i hi li
i
hi hi li li
i
hi li
c k P
if Henry slawis applicable
c k P
if k k k
Then P Dk
if k k
Then J D k P k P
D
J k P k P
P
As J P P
D k P k P
P
P P

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
As temperature increases the permeability is also increased & reverse
behavior is also observed

Cohen & Turnbull (Fujita) Free volume theory


P
i
P
i
P
hi
T
P
l
P
h
P
h
>> P
l
Henrys law is
applicable
( ) ( )
( )
( )
( )
*
0
2
*
exp
f
f f s s
h
f
D ART
V
V V V T T P P
P C T k P
V


_



,
+ +
+
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:

Gas permeation unit: Stage cut (), Temperature


(T), Permeability (P
i
), Flow pattern
Stage cut (): Amount of feed that is allowed to
permeate through membrane
Feed
Un permeate
stream
Permeate stream
Membrane
Low pressure side
high pressure side
Membrane properties:
1. A high permeability towards a specific component to be separated from a gas
mixture and high selectivity for this component relative to other components in
mixture.
P
i
= k
i
D
i
Separation will be if
(a) k
i
s are different and D
i
s are same
(b) D
i
s are different and k
i
s are same
(c) K
i
s as well as D
i
s are different most desirable condition
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
2. Chemical inertness and physically stable
3. Absence of pinholes or other mechanical defects.

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

Driving force is different every


where
3. Co current flow
4. Counter current flow
Highest efficiency
Feed
Compositions are different every where
Un permeated stream
Permeate stream
Compositions are different every where
Un permeated stream
Permeate stream
Feed
Permeate stream
Feed Un permeated stream
Cross flow pattern
Co current flow Counter current flow
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
For fully mixed flow (solved by Weller (1950)):

A B two component system


P
OA
Permeability of A, P
OB
Permeability of B

= 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

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
Ultrafiltration
Applications:
1. Metal finishing: Electro paint, Oil/Water emulsions, Spray paint
2. Dairy: Whey protein, Protein in milk
3. Pharmaceutical: Recovery of enzymes, vaccines, plasma proteins, antibiotics,
pyrogens, membrane reactions
4. Food: separation of potato starch, egg white, gelatins, juice classification
5. Textile: Removal of dyes, sizing chemicals
6. Pulp & paper: Removal of lignin compounds
7. Chemicals: Waste polymer, waste latex
8. Leather working: Tannery waste
9. Sewage treatment
10. Water (treatment) purification: Removal of bacteria, pretreatment for RO
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Concentration polymerization:

Membrane is semi permeable


Solute is retained at membrane surface
Gel formation on membrane surface
takes place
Gel layer
Work as RO
P
J
V
Limiting flux
Membrane fouling:
If module is operated at high fluxes, some of the
particles go inside the membrane and the
membrane gets permanently damaged
Commercial membrane:
Polyamide, polysulfone: phase inversion technique
Limited P
H
range
Temperature 80
0
C to 90
0
C
J
V
Time (hr)
5 hr 20 hr
P = fixed
Due to membrane fouling
Concentration polarization
Membrane fouling
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Carbosep membranes:

Tubular membranes made of micro porous carbon


MW: 20,000
P
H
: 0 to 14
T: Can be used till 120
0
C

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

= Diffusion coefficient in free solution


k
c
& k
d
are convective & diffusive transport
correction facto i.e. hindrance factor
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) [ ]
( )
( )
0
0
0
0
0
1
ln
ln
ln
1 1
1
ln
s
z
s
z
s
z
s
z
C
s
c s P d C
C
c s P
C
c d
c s P
z c
c s P d
z
c P P c
c f P d
v
P P
f f
c
dC V
dz
kC C k D
V
kC C z
k k D
k C C
kV
k C C k D
kC C kV
kC C k D
J V where porosityinmembrane
C C
R R
C C
k

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

Partial pressure on permeate side should be as low as possible


Liquid
Vacuum
Pervaporation
(Permeate)
Liquid
Carrier gas + Pervaporation
Liquid Permeate
Carrier gas (N2, He etc. ) to reduce mole fraction i.e. ultimately partial pressure
Condense
Pervaporation
Mole fraction of water in
liquid form
M
o
l
e

f
r
a
c
t
i
o
n

o
f

w
a
t
e
r

i
n

v
a
p
o
r

f
o
r
m
Water Dioxane mixture
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Advantages:
1. No additive is required
2. Low energy demands, because only permeating component needs to be
evaporated
3. Closed loop operations are possible, as small volume of permeate needs to be
recycled
4. Lower capital cost as compared to distillation
Membrane:
1. Polyvinyl Alcohol (PVA) Hydrophilic membrane
Water >> MeOH > EtOH >> Other organic components absorbing power
2. Silicone composite Hydrophobic (Organophilic)
MeOH > EtOH > Aldehydes > Ketones >> Water
3. Modified Cellulose Esters Use for separation of two organic compounds
Aromatics > Paraffins
Olefins > Paraffins
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Diens > Olefins
n Paraffins > Branched Paraffins
Low MW Paraffins > High MW Paraffins
Potential Applications:
1. Mixtures that are difficult to separate by conventional techniques such as
azeotropic mixtures
2. Separation of heat sensitive products such as in food industries
3. Elimination of traces of impurities
4. Enrichment of organic pollutants for quantitative defection
5. Drying of natural gas obtained from offshore
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
"
"
'
'
'
"
1 1
A
B
A B
A
B
A B
w
Feed
w
w Pervaporate
w
should be Or

]
? =
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

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
Anisotropic swelling occurs in case of pervaporation
[ ]
( )
( )
( )
' "
' "
' "
. ,
,
V
V
V
V
d
J D
dx
Fraction of penetrant within the membrane
J D
h
if D Constt sp
p p
J Ds
h
p p
J P
h
Where P Permeability

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( ) ( )
( )
( ) ( )
( )
( ) ( )
( )
( ) ( )
'
"
0
' "
' ' " "
' ' ' " " "
0 exp
0 0
0 exp
0
exp exp
0
exp exp
, &
h
V
V
V
D D g
D at
J dx D g d
D
J g g
gh
D
J gs p gs p
gh
where s p s p


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

Thus, we have to put a heat exchanger say after T=20


0
C i.e. we need inter
stage heater
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
Dialysis
It is a membrane process in which compounds having different molecular
weight are separated through membrane
Driving force is concentration gradient

Fluxes are very small

Advantages (used when):


1. Concentration polarization phenomena is high
2. The external forces are damaging to the fluid being treated

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

Department of Chemical Engineering


Indian Institute of Technology-Delhi, New Delhi 110 016, India
( ) ( )
( ) ( )
( ) ( )
'
"
'
,
1 exp 1
1
1 exp 1
1 exp 1
o
T
T
T
Q
Z
Q
OnceMknown
D
Find E
Q
N Z
E Forco current
Z
N Z
E Forcountercurrent
Z N Z

+

+



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:

In spite of normal membranes, charged membranes are used


1. Donnan dialysis
CEM
Cu
++
Feed
Conc. H
2
SO
4
Stripping side
2
' '
" "
2
4
7 6
10 1
10 10
Cu H
Cu
H
a a
Ratio of activities
a a
++ +
+
_



,
_


,
2. Ion exchange dialysis
Cu
++
2H
+
Feed
CuSO
4
, H
2
SO
4
H
+
Cu
++
4
SO

H
+
4
SO

Weak type anion exchange
i.e. only H
+
not other cation can pass
Prevents cation to pass through
Weak type AEM
H
2
SO
4
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India

New applications of micro porous membranes:


1. Gas absorption and stripping
2. Membrane based solvent extraction
3. Membrane distillation

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:

Pores are filled with membrane


Liq1(aq)
Liq2(aq)
Hydrophobic
Osmotic distillation:

Driving force = Osmotic pressure (This


is finally related to concentration)
Pw
1
> Pw
2
Hydrophobic
Pw
1
Pw
2
Low osmotic
solution (aq)
High osmotic
solution (aq)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India
3. Membrane distillation:

Here temperature is driving force


Pw
1
Pw
2
Hot solution
(more salt)
Cold solution
(less salt)
Department of Chemical Engineering
Indian Institute of Technology-Delhi, New Delhi 110 016, India

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