Professional Documents
Culture Documents
Applikasi
Year Researcher Membrane system
1850 Thomas Graham
1960-1970 Loeb and Sourirajan Spiral wound and hollow fiber modules for
reverse osmosis
1980 Permea Prism membrane for H2 separation
1982 Generon N2 /air separation system
1987 Ube, Medal, Generon O2/N2; H2/N2; H2/CH4 separation system
1988 MTR, GKSS Nitto Denko Vapor separation
1990 Separex, Cynara, GMS Cellulose acetate for CO2/CH4 separation
1994 Medal Polyimide membrane for CO2/CH4 separation
Permeate
Fundamentals of Gas Permeation
Through Membranes
2.1: Gas Permeation Through Membranes
- porous
- nonporous.
R0 T
λ= 1
22 πpNd m2
where r is the radius of pore, L the length of the capillary, the viscosity of
the gas, are the feed and permeate pressure respectively, the surface
porosity, A the membrane surface area and the pressure difference.
● if the pore radius is much smaller than the mean free path, Knudsen
diffusion will predominate and gas transport through membrane can be
expressed as follows:
1
8⎛ 1 ⎞2 r
Q= ⎜ ⎟ A p AΔp
3 ⎝ 2 πR0 TM ⎠ L
● The viscous flow regime involves a mass movement of the gas species
and hence this flow mechanism does not exhibit any separation. Viscous
flow is therefore avoided in gas separation membranes.
● The intermediate flow mechanism between Poiseuille and Knudsen flow
is called slip flow.
Selectivity = M B / MA (2.4)
C=Sp (2.5)
● where S the Henry’s law solubility constant for the particular polymer-
penetrant system and p, partial pressure
Membrane
High Pressure Side Low Pressure Side
C0
Feed
Permeate
C1
⎛ dC ⎞
J = − D⎜ ⎟
⎝ dx ⎠
(2.6)
C0 − C1
J=D
l (2.7)
J = DS
( p0 − p1 )
=P
( p0 − p1 )
l l (2.8)
● where p0 and p1 are the external partial pressures of the gas on the high
and low pressure sides of the membranes and P the permeability
coefficient.
P = DS (2.9)
● The solubility coefficient, S, is a thermodynamic parameter and gives a
measure of the amount of penetrant sorbed by the membrane under
equilibrium conditions whereas diffusion coefficient is a kinetic factor,
which describes the mobility of the penetrant in the polymer matrix.
⎛ X A1 ⎞ ⎛ X B0 ⎞
α AB =⎜ ⎟ ×⎜ ⎟ (2.10)
⎝ B1 ⎠ ⎝ A0 ⎠
X X
● This selectivity can also be expressed in terms of partial pressure
differences across the membrane:
α AB = ( PA PB ) ×
[ΔpA pA0 ]
[ΔpB pB0 ] (2.11)
● where Q is the volumetric flow rate (STP) of gas through the membrane
and A is the membrane area.
● In this model, the activated state in diffusion involves two polymer chains
which bend symmetrically in order to create or expand a passageway for
the penetrant molecule as shown in Figure 2.3 (a).
b) discontinuous voids.
● However, Stern and Frisch have extended the model to deal with the
permeation of light gases and binary gas mixtures.
2.2.2: Diffusion Models for Glassy Polymers
where:
cm3/g
V (Specific Volume) Vg
(volume of actual
glassy state)
Vg - Vl
(unrelaxed
volume)
Vl
(volume of densified glass)
T Tg
Temperature, oC
P = kDDD (2.17)
● The model was then modified and became known as the partial
immobilisation model.
● Under these conditions, the diffusive flux in glassy polymers can actually
be expressed in a general Fickian form:
dC D dC H
J = − DD − DH
dx dx (2.18)
⎛ FK ⎞
P = k D DD ⎜ 1 + ⎟
⎝ 1 + bp ⎠ (2.19)
● where:
● The Pace and Datyner model, included in Figure 2..2, is one of the most
recent and extends the understanding of diffusion on a molecular level.
● Unlike those previous, the Pace and Datyner model allows the
calculation of activation energy for diffusion without the use of any
adjustable parameters.
● However, they had to adopt a stochastic approach to estimate diffusion
coefficients. The equations they used are shown in Figure 2.4.
where
(
E d = f β , ρ , λ , d , ε * , ρ* )
b= average single bending modulus per unit length
r= the equilibrium chain separation,
l= the mean backbone element separation along the chain axis
d= the diameter of penetrant molecule
e* = the average Lennard-Jones energy parameter
r* = the average Lennard-Jones distance parameter.
Diffusion Coefficient 1 2
D= L v
6
where
L2 = mean-square jump displacement of penetrant molecule
v = frequency of chain openings that permit passage of penetrant
molecules