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Gas separation membrane

Applikasi
Year Researcher Membrane system
1850 Thomas Graham

1950 Van Amerongen

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

1996 Permea Propylene/ N2 separation


2000- Permea, Air liquid Generon Many process separation
Feed Retentate

Permeate
Fundamentals of Gas Permeation
Through Membranes
2.1: Gas Permeation Through Membranes

● two types of membrane that can be used for gas separation:

- porous

- nonporous.

● This section briefly discusses the theory of gas permeation through


porous and nonporous membranes which are the foundation of
present membrane science and technology.
2.1.1: Gas Permeation Through Porous Membranes
● Transport of gases through porous membranes can occur through five
mechanisms namely:
i) Poiseuille or viscous flow,
ii) Knudsen diffusion,
iii) slip flow,
iv) sieving action and
v) surface diffusion.
● The amount of Poiseuille flow and Knudsen diffusion that occurs
depends on both the pore size of the membrane and the mean free path
of the molecule.
● The mean free path l is defined as:

R0 T
λ= 1
22 πpNd m2

Where R0 is the universal gas constant, T the temperature, p is the


pressure of the permeating species, N is the Avogadro constant and the
molecular diameter.
● If the pore radius is much greater than the mean free path, then
Poiseuille flow prevails and the gas transport through membrane is given
as follows:
r 2 1 ⎛ pf + pp ⎞
Q= ⎜ ⎟ A p AΔp
8 R0 T Lη ⎝ 2 ⎠

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

where M is the molecular weight.

● 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.

● Slip flow may be somewhat separative but it is in evidence only when


viscous flow is also present and, therefore, is generally undesirable.

● Zeolites give a good example of sieving action where selectivity relates


to the size of the gas molecule. This mechanism is well known in
adsorption and reaction processes.
● Surface diffusion is caused by sorption of gases on the membrane
surface, and the diffusion of the sorbed gases through the
membranes pores.
● This mechanism may be the only means of separating gases with
identical molecular weights.

● At a given operating pressure and temperature, the extent of this


sorption depends on the chemical nature of the gas and that of the
membrane surface.
● In porous membranes, the most intensively studied gas separation
mechanism is Knudsen diffusion.

● In Knudsen diffusion, a membrane will be selective to the penetrant with


the lower molecular weight as follows:
follows

Selectivity = M B / MA (2.4)

● As a result, the level of Knudsen diffusion selectivity depends on the


difference in the molecular weights of the penetrants.

● Recently a nanoporous carbon membrane from pyrolised polyvinylidene


chloride with pore sizes in the range of 5 to 7 has been produced, and is
now considered to be close to commercial implementation
2.1.2: Gas Permeation Through Nonporous Membranes

● Gas permeation through nonporous membranes is generally controlled


by the solution-diffusion mechanism.

● According to Henry’s Law, the concentration C of the gas component at


the membrane surface is related to the partial pressure p of this
component in the gas phase by the following relationship:
relationship

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

Figure 2.1 Schematic diagram of the permeation process.


● Diffusion of a penetrant gas through nonporous polymer membranes is
normally described by Fick's first law:

⎛ dC ⎞
J = − D⎜ ⎟
⎝ dx ⎠
(2.6)

● where J is the permeation flux, D is the diffusion coefficient of the


permeant in the polymer and x is the coordinate direction of permeation
in the membrane.
● Under steady state conditions for a constant diffusion coefficient,
equation (2.6) can be integrated from the high to low pressure side of
the membrane denoted by point 0 and 1 respectively

C0 − C1
J=D
l (2.7)

where l is membrane thickness.

● It is more practical to express the rate of permeation in terms of the


penetrant gas pressures on both sides of the membrane, in equilibrium
with C0 and C1 respectively.
● Thus substituting equation (2.5) into equation (2.7) gives

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.

● The permeability coefficient for a particular component can therefore be


described as the product of solubility and diffusion coefficients.

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.

● The rate of gas permeation through a membrane is therefore described


in the form of a permeability coefficient, which depends on the nature of
the polymer and the penetrant gas.

● The permeability coefficient is independent of the thickness of the


membrane and is therefore a basic property of the polymeric material.
● For pure gas permeation applications, the selectivity is typically
considered as the ratio of the permeability coefficients of the fast
permeating component to the slower permeating component (PA/PB).

● For gas mixtures, the selectivity (aAB) is defined in terms of the


downstream (1) and upstream (0) mole fractions of components A and B:

⎛ 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)

● In the case of negligible downstream partial pressures, the selectivity


equals the ratio of the two permeability coefficients and is known as the
ideal selectivity which corresponds to that measured using pure gases
2.1.3: Gas Permeation Through Asymmetric Membranes

● Since thickness is subjective in such membranes, the following


expression is used to describe their permeation properties:

J = (Q/A) = (P/ℓ )(p0-p1) (2.12)

● where Q is the volumetric flow rate (STP) of gas through the membrane
and A is the membrane area.

● The pressure normalised flux, (P/ℓ ), is a practical parameter that


characterises the membrane in terms of permeability.

● The selectivity of a membrane to any two pure gases, i and j, is simply


the ratio of pressure-normalised fluxes, (P/ℓ )i/(P/ℓ )j.
2.2: Diffusion Theory of Small Molecules in Nonporous
Polymer Membranes

● The solution-diffusion mechanism of gas permeation through


nonporous membranes is usually considered as a macroscopic model,
and has been widely accepted as the method of generally evaluating
membrane performance.

● However, at a microscopic level, the phenomenon of gas diffusion in


nonporous membranes is more complex.
● The overall selectivity of a polymer membrane toward two different
penetrant gases A and B is typically expressed as the ratio of the
permeability coefficients:
P (A ) D (A ) S (A )
= ⋅
P ( B) D ( B) S ( B)
(2.13)

where the ratios of D(A)/D(B) and S(A)/S(B) are known respectively as


the diffusivity selectivity and solubility selectivity.

● In order to describe the mechanism of gas transport, numerous


theoretical models have been developed.
2.2.1: Diffusion Models for Rubbery Polymers

● Divided into two categories namely,

1) molecular models which analyse specific motion of penetrant


molecules and surrounding polymer chains relative to each other
and take into consideration the pertinent intermolecular forces
and

2) free volume models which attempt to elucidate the


relationship between the diffusion coefficient and the free volume
of the system, without direct consideration of molecular structure.
1) Molecular Models

● These models typically assume that fluctuating microcavities or holes


exist in the polymer matrix and that at equilibrium, a definite size
distribution of such holes is established on a time-average basis.

● A hole of sufficient size contains a dissolved penetrant molecule, which


can jump into a neighbouring hole once it acquires sufficient energy.

● Diffusion is achieved only when holes which have become vacant in


such a manner are occupied by other penetrant molecules.
● Molecular models which involve these characteristics largely follow
the Arrhenius behaviour of diffusion coefficients observed experimentally
as shown below:

D = Doexp (-Eapp/R0T) (2.14)

● where Eapp is the apparent energy of activation for diffusion, Do is a


constant, R0 is the universal gas constant and T is the absolute
temperature.

● A correlation is found between Eapp and the molecular diameter of the


penetrant, but no theoretical description for diffusion coefficient, D has
been made with molecular models .
i. The Model of Meares

● Meares proposed the first molecular model for diffusion in rubbery


polymers and found that the activation energy for diffusion correlates
linearly with the square of the penetrant diameter, but not with diameter
cubed.

● the diffusion step is not governed by the energy necessary to create a


hole that can accommodate a penetrant molecule, but instead by the
energy required to separate polymer chains so that a cylindrical void is
produced which allows the penetrant molecules to jump from one
equilibrium position to another.
● The phenomenological length, l, of the cylindrical void is the jump length,
which can be calculated from the expression proposed by Meares:
π 2
E d = σ Nλ(CED)
4
(2.15)

● where Ed is the actual activation energy for diffusion, s is the collision


diameter of the penetrant, CED is the cohesive energy density of the
polymer and N is Avogadro’s number.
ii. The Model of Brandt

● Brandt [39] considered polymer structure in order to also estimate the


actual activation energy for diffusion.

● 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).

Figure 2.3 (a): After Brandit

● The activation energy is proposed to consist of an intermolecular


contribution, Eb, due to the repulsion the bend chain experiences from its
neighbours, and an intramolecular contribution, Ei, due to the resistance
of the molecular chains to bending.
iii. The Model of DiBenedetto and Paul

● The molecular model of DiBenedetto and Paul assumed that a dissolved


gas molecule behaves as a three-dimensional harmonic oscillator within
a void formed by bundle of four parallel polymer segments.

● A diffusion jump is assumed to involve coordinated segmental rotations


and vibrations that produce a cylindrical void adjacent to the penetrant
molecule.

● In this case the activation energy is equivalent to the potential difference


between the normal dissolved state and the activated state in which the
void is present
● Figure 2.2 (b) schematically illustrates the diffusion process according to
DiBenedetto and Paul.
Paul

Figure 2.2 (b): After DiBenedetto and Paul


2) Free Volume Models

● relate mutual diffusion coefficients for a gas/polymer system to the free


volume or empty volume of the system, and thereby to the concentration
of the penetrant gas in the polymer.

● The total free volume was postulated to consist of two contributions:

a) vibrations in molecules that cannot be redistributed without a


large energy change and

b) discontinuous voids.

● Diffusion in such a liquid is not due to a thermal activation process, as it


is taken to be in the molecular models, but is assumed to result from a
redistribution of free volume voids caused by random fluctuations in
local density.
i. The Model of Fujita

● Fujita’s free volume model describes the strong concentration


dependence of organic vapours in some rubbery polymers but breaks
down for small penetrant molecules whose diffusion is largely
independent of their concentration.

● 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

● The diffusion mechanisms of gas molecules in glassy polymers are very


different to those in rubbery polymers.
polymers

● Diffusion through glassy polymers depends on both the glass transition


temperature Tg and the temperature of operation.

● Typically diffusion coefficients for light gases in glassy polymers are


found to be highly nonlinear functions of the penetrant concentration.

● This is due to the presence of intersegmental packing defects that are


frozen into the structure as the polymer is cooled through its glass
transition.
● in rubbery polymers, diffusion coefficients for light gases are generally
independent of concentration but may occasionally slightly increase with
increasing concentration.

i. The Dual-Mode Sorption Model

● The most useful and widely accepted phenomenological description of


the dependence of diffusion coefficient, solubility and permeability
coefficient on penetrant concentration or feed stream pressure in glassy
polymers is provided by the dual-mode sorption model, particularly its
partial immobilisation version developed by Paul and Koros.
● This model postulates that a gas dissolved in a glassy polymer consists
of two distinct molecular populations:

a) molecules dissolved in the polymer matrix by a normal dissolution


process, which follows the form of Henry’s Law, similar to that above Tg

b) molecules dissolved in a limited number of fixed pre-existing


microvoids, or at fixed sites in the polymer matrix as described by
Langmuir isotherms.

● The second population is unique to glassy polymers and its prevalence


is correlated with the abrupt change in slope of the specific free volume
versus temperature curve as the glass transition temperature is
traversed as depicted in Figure 2.3.
● The overall solubility isotherm in the dual-mode sorption model is given
by the following equation:

C = CD + CH = kDp + C’Hbp/ (1 + bp) (2.16)

where:

- CD is the concentration of molecules dissolved by the normal


dissolution process and known as Henry’s law isotherm,

- CH is the concentration of molecules dissolved in microcavities


known as the Langmuir isotherm,

- p is the penetrant pressure,

- b is the hole affinity constant and

- C’H is the hole saturation constant, which is measure of the sorption


capacity of the unrelaxed volume.
Glass Rubber

cm3/g
V (Specific Volume) Vg
(volume of actual
glassy state)

Vg - Vl
(unrelaxed
volume)

Vl
(volume of densified glass)

T Tg
Temperature, oC

Figure 2.3 Schematic representation of the relationship


between temperature and specific free volume.
● The first term represents the Henry’s law sorption of normally diffusible
species, while the second term represents sorption in holes
characterised by affinity and saturation constants b and C’H respectively.

● the mean permeability is given by the product of Henry’s law constant


and the diffusivity of the mobile fraction of the sorbed molecules:

P = kDDD (2.17)

● However, more recently, it has been recognised that the penetrant


molecules sorbed in the Langmuir mode may not necessarily be
completely immobilised.

● 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)

● where J is the diffusive flux and the coefficients DD and DH characterise


diffusion due to local concentration gradients in the Henry’s law and
Langmuir mode isotherms respectively.
● When the downstream pressure is maintained at approximately zero, the
permeabilities can be expressed as follows:

⎛ FK ⎞
P = k D DD ⎜ 1 + ⎟
⎝ 1 + bp ⎠ (2.19)

● where:

- K = C’Hb/kD is a ratio characteristic of the relative amounts of gas


sorbed in the two modes and

- the diffusivity ratio F = DH/DD is a measure of the degree of


immobilisation.
2.2.3: Models for Diffusion in both Rubbery and Glassy Polymers

● two models which are applicable to diffusion of small molecules in glassy


as well as rubbery polymers namely,

i) the model of Pace and Datyner and

ii) the model of Vrentas and Duda.

i) The Model of Pace and Datyner

● Pace and Datyner proposed a detailed molecular model which


incorporates the features of the Brandt model and the DiBenedetto and
Paul model.
● They assumed that the penetrant molecule can move through the matrix
of an amorphous polymer in two distinct ways:

a) along the axis of a tube formed by four adjacent parallel chains


(DiBenedetto and Paul model) and

b) perpendicular to this axis, when two polymer chains separate


sufficiently to allow passage of the molecule (Brandt model).

● 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.

● The expression for diffusion coefficient contains only one adjustable


parameter namely, the mean-square jump distance of the diffusing
penetrant molecules which must be solved at 0 K.
Energy of Activation for Diffusion

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

Figure 2.4 Parameters in expressions for energy of activation for diffusion


and the diffusion coefficient from the theory of Pace and Datyner.
ii) The Model of Vrentas and Duda

● Vrentas and Duda proposed a free volume model to describe the


diffusion of small molecules in both rubbery and glassy polymers.

● The model describes the temperature dependence of the diffusion


coefficient but requires values for a number of parameters even for
binary systems.

● This model is particularly applicable to penetrants with high solubilities,


e.g., organic vapours and liquids, which can plasticise the polymer.

● However its validity has not been sufficiently tested.


● Recently, rigorous computational techniques have been applied to gas
transport in polymers such as the molecular dynamic simulation
technique for rubbery polymers and the Monte-Carlo simulation
technique for both rubbers and glasses.

● In addition to molecular dynamic and Monte-Carlo simulations,


development of new experimental techniques for determining the free
volume distribution in polymers have evolved recently.

● These techniques include positron annihilation lifetime spectroscopy


(PALS) and the use of photochromic and fluorescent probes [32].

● It would be most interesting if such experimental data was to be


compared with the information determined from the molecular dynamic
simulations.

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