Membrane Technology in the Chemical Industry. Edited by S. P. Nunes and K.-V.

Peinemann
Copyright © 2001 Wiley-VCH Verlag GmbH
ISBNs: 3-527-28485-0 (Hardcover); 3-527-60038-8 (Electronic)

6 Gas Separation with Membranes

6.1 Introduction
The separation of gas mixtures with membranes has emerged from being a laboratory
curiosity to becoming a rapidly growing, commercially viable alternative to traditional
methods of gas separation within the last two decades. Membrane gas separation has
become one of the most significant new unit operations to emerge in the chemical indu-
stry in the last 25 years [142]. The gas separation membrane module business for 2000
is estimated at $ 125 million with an annual growth rate of 8 %. Table 9 shows com-
mercial applications and some of the major suppliers of membrane gas separation units.
Tab. 9 shows established applications in the field of membrane gas separation. One
of the new and currently small applications as shown in Tab. 9 is natural gas dehydra-
tion. Problems related to this separation will be discussed in the last part of this chap-
ter (basic process design considerations). Besides the well-established applications
there are a number of emerging membrane gas separations. These are, for example, natu-
ral gas hydrocarbon dewpointing, olefin/paraffin separation and separation of hydro-
carbon isomeres. These will be addressed in the following material section. The pur-
pose of this chapter is to provide an overview of state of the art and emerging materials
for gas separation membranes, to give some key features of integral asymmetric and
composite membranes and finally to explain the influence of basic process parameters.

6.1.1 Materials and transport mechanisms

Organic polymers are the dominating materials for gas separation membranes. Many
polymers exhibit a sufficient gas selectivity and they can be easily processed into mem-
branes.
Palladium alloys are the only inorganic materials which are currently used for gas
separation (ultra-pure hydrogen generation) on a commercial scale. However, during
the last decade inorganic materials have been developed with exciting unmatched
selectivities for certain gas mixtures and some of the inorganic membranes described
in the scientific literature seem to be on the brink of commercialization. Table 10 shows
relevant membrane materials for gas separation.
40 Part I: Membrane Materials and Membrane Preparation

Tab. 9: Gas membrane applications and suppliers (adapted from “Economics of gas
separation membranes”, R.W. Spillman, in: Membranes separation technology. Princi-
ples and applications, Ed.: R.D. Noble, S.A. Stern, 1995, Elsevier Science.

Gas separation Application Suppliers

O2/N2 Nitrogen generation, A/G Technology
oxygen enrichment Permea (Air Products)
Generon (Messer)
IMS (Praxair)
Medal (DuPont, Air Liquide)
Aquilo (Parker Hannifin)
Ube

H2/Hydrocarbons Refinery hydrogen, Air Products

recovery Air Liquide
Praxair
H2/CO Syngas ratio adjustment as above
H2/N2 Ammonia purge gas as above
CO2/Hydrocarbon Acid gas treating, Kvaerner (Grace Membrane System)
enhanced oil recovery, Air Products
landfill gas upgrading Ube
H2S/hydrocarbon Sour gas treating as above
H2O/hydrocarbon Natural gas dehydration Kvaerner
Air Products
H2O/air Air dehydration Air Products
Ube
Hydrocarbons/air Pollution control, MTR, GMT, NKK
hydrocarbon recovery

Hydrocarbons from Organic solvent recovery, MTR, GMT, SIHI

process streams monomer recovery

Tab. 10: Materials for gas separating membranes.

Organic polymers Inorganic materials
Polysulfone, polyethersulfone Carbon molecular sieves
Celluloseacetate Nanoporous carbon
Polyimide, polyetherimide Zeolites
Polycarbonate (brominated) Ultramicroporous amorphous silicia
Polyphenyleneoxide Palladium alloys
Polymethylpentene Mixed conducting perovskites
Polydimethylsiloxane
Polyvinyltrimethylsilane
 6 Gas Separation with Membranes 41

6.1.2 Organic polymers

A number of excellent books and reviews have been published on the subject of poly-
meric gas separating membranes, which are recommended to the interested reader [143,
144, 145, 146, 147, 148, 149]. It is the purpose of this chapter to supply the reader with
a basic background which is important in the understanding of the transport mechanism
of gases through polymers, to introduce those polymers which are currently of com-
mercial importance and finally to give an outlook on interesting developments in this
field.

6.1.3 Background
The simplest model used to explain and predict gas permeation through non-porous
polymers is the solution-diffusion model. In this model it is assumed that the gas at the
high pressure side of the membrane dissolves in the polymer and diffuses down a con-
centration gradient to the low pressure side, where the gas is desorbed. It is further assu-
med that sorption and desorption at the interfaces is fast compared to the diffusion rate
in the polymer. The gas phase on the high and low pressure side is in equilibrium with
the polymer interface. The combination of Henry’s law (solubility) and Fick’s law (dif-
fusion) leads the to the equation

D ∗ S ∗ ∆p
J= (1)
l
which can be simplified to

P ∗ ∆p
J= (2)
l
where D is the diffusion coefficient of the gas in the polymer, S is the gas solubility, ∆p
is the pressure difference between the high and low pressure side, l is the membrane
thickness and P is the permeability coefficient1. As can be seen from (1) and (2) the per-
meability coefficient P is the product of D (a kinetic term) and S (a thermodynamic
term).

P = D∗S (3)

1 The permeability coefficient is most commonly given in Barrer, defined as 10-10 cm3cm/cm2s cm Hg
and named after R. M. Barrer. The correspondend SI unit is mol m/m2s Pa (1Barrer= 0.33x10-15mol
m/m2s Pa).
42 Part I: Membrane Materials and Membrane Preparation

The selectivity of a polymer to gas A relative to another gas B can be expressed in

terms of an ideal selectivity αAB defined by the relation
PA DA SA
α AB = = × (4)
PB DB SB
The ratio DA/DB can be viewed as mobility selectivity and the ratio SA/SB as solu-
bility selectivity. For a given gas pair mobility and solubility selectivity depend on the
chemical and physical properties of the polymeric material. Excellent reviews on rela-
tionships between polymer structure and transport properties of gases have been given
by Stern, Paul and Freeman [147, 150, 151]. Some general rules are useful for a first
understanding. The diffusion coefficient D always decreases with increasing size of the
molecule. The extent of this decrease is generally dependant on the flexibility of the
polymer backbone. The more rigid the polymer structure the higher the mobility sel-
ectivity will be for a given gas pair. The mobility selectivity is dominant for most glas-
sy polymers. Hence, the transport of smaller molecules is favored. On the other hand
the solubility of gases generally increases with molecular size, because the intermole-
cular forces between gas and polymer increase. Most rubbers show a low mobility sel-
ectivity due to their flexible polymer chain but their ability to separate gases is domi-
nated by their solubility selectivity. Thus large organic vapor molecules can permeate
much faster through some rubbers than smaller gases like oxygen or nitrogen. This is
depicted for silicone rubber in Fig. 14.

25
Solubility (cm3 (STP)/cm3 polymer bar)

60
Diffusion coefficient (10-6 cm2/s)

Pentane
Propane
Nitrogen
Methane

Butane
Oxygen

20 50

40
15
30
10
20
5 10

0 0
50 100 200 300
Critical volume (cm3/mol)

Fig.14: Diffusion and solubility coefficients of different gases in silicone rubber at 30°C [152, 153,
154] vs. the critical volume.
 6 Gas Separation with Membranes 43

It can be seen that the diffusion coefficient of the large pentane molecule is 3.6 times
smaller than the diffusion coefficient of oxygen. However, the solubility of pentane is
about 200 times larger than the solubility of oxygen. This solubility selectivity out-
numbers the reverse diffusion selectivity. As a result silicone rubber is much more per-
meable for pentane than for oxygen.
Contrary to rubbers glassy polymers usually show a preferred permeability to smal-
ler molecules. The mobility selectivity is much higher than the reverse solubility selec-
tivity. This is shown in Fig. 15 with the polyimide Matrimid (Ciba Geigy).

Solubility (10–3 cm3 (STP)/ cm3 cmHg)

1000 250
Diffusion coefficient (10–8 cm2/s)

100 200
He O2 CH4
10 H2 N2 C2H6
150
1
100
0.1

0.01 50

0.001 0
0 50 100 150 200
Critical volume
Fig. 15: Diffusion and solubility coefficients of different gases in Matrimid at 30°C vs. the critical
volume.

6.1.4 Polymers for commercial gas separation membranes

During the last two decades dozens of new polymers have been described in the litera-
ture, which have been developed for gas separation. The largest group among these are
probably polyimides [155]. In spite of these efforts less than 10 polymers are used for
industrial gas separations. Nearly all of these are technical polymers developed for total-
ly different applications. “Designer polymers” were either too expensive or their advan-
tage over commercial polymers were not sensational enough or they did not show the
expected performance in real applications. The latter is especially true for modified (flu-
orinated) polyimides. Some of the 6FDA-based polyimides showed tremendous sepa-
ration abilities in the laboratory but failed in real life due to plastizisation or physical
aging. Table 11 gives a list of polymers which are of practical importance for gas sepa-
ration.
44 Part I: Membrane Materials and Membrane Preparation

Tab. 11: Gas permeabilities of gas separation polymers.

Permeability at 30°C (Barrer*)

Polymer H2 N2 O2 CH4 CO2

Cellulose acetate 2.63 0.21 0.59 0.21 6.3
Ethyl cellulose 87 8.4 26.5 19 26.5
Polycarbonate, brominated 0.18 1.36 0.13 4.23
Polydimethylsiloxane 550 250 500 800 2700
Polymide (Matrimid) 28.1 0.32 2.13 0.25 10.7
Polymethylpentene 125 6.7 27 14.9 84.6
Polyphenyleneoxide 113 3.81 16.8 11 75.8
Polysulfone 14 0.25 1.4 0.25 5.6

* 1 Barrer = 10-10cm3 cm/cm2 s cmHg

Cellulose acetate, polysulfone and polyimides are by far the most important poly-
mers for gas separation membranes. When we look at the volume streams treated, the
old-fashioned cellulose acetate is probably still the dominating polymer. The company
Kvaerner Process Systems alone, which has acquired Grace Membrane Systems, has
sold or operates membrane plants with CA-membranes for carbon dioxide separation
for a total stream of more than 5 Mio m3 (STP)/day. The only polymer in Tab. 11, which
is especially designed for gas separation, is the brominated polycarbonate (tetra-
8

R CH3 R
R = Br O
O C O C
7 CH3
R R
2
PO / PN

R = Cl
6
2

5 R=H R = CH3

4
0 1 2 3 4 5 6 7
PO (Barrers)
2

Fig. 16: Selectivity vs. permeability for O2/N2 for various polycarbonates at 35°C and 1 bar. [156]
(reproduced by permission of Elsevier Scientific Publishers).
 6 Gas Separation with Membranes 45

bromopolycarbonate). It was shown by Paul and coworkers [156] that this relatively
simple modification led to an impressive increase in the oxygen/nitrogen separation fac-
tor without loss of permeability (see Fig. 16)

6.1.5 Ultra-high free volume polymers

Because the so-called ultra-high free volume polymers aroused much interest during
the last 10 years, they will be briefly described in this introductory chapter. The publi-
cation of the physical properties of poly (1-trimethylsilyl-1-propyne) (PTMSP) in 1983
[157] aroused much interest in the field of membrane research. Up to this time it has
been believed that the rubbery poly (dimethyl siloxane) has by far the highest gas per-
meability of all known polymers. Very surprisingly, the glassy PTMSP showed gas per-
meabilities more than 10 times higher than PDMS. This could be attributed to its very
high excess-free volume and the interconnectivity of the free volume elements. Since
then a number of high free volume polymers exhibiting extraordinaryly high gas per-
meabilities have been synthesized. Two of these are under extensive investigation and
are currently being studied for gas separation on a pilot scale. These are Du Pont’ s 2,2-
bistrifluoromethyl-4,5-difluoro-1,3-dioxole/tetrafluorethylene copolymer (Teflon AF
2400®) and poly (4-methyl-2-pentyne) (PMP). All three polymers PTMSP, PMP and
Teflon AF2400 are glassy with glass transition above 230°C and have a very high frac-
tional free volume (FFV). Figure 17 shows the chemical structure and fractional free
volume of these three polymers.

CH3 CH3
CF CF CF2 CF2
C C C C 0,9 0,1
n n O O
H3C Si CH3 H3C C CH3 C
F3C F3C
CH3 H

poly(1-trimethylsilyl-1-propyne) poly(4-methyl-2-pentyne) Teflon AF® 2400

PTMSP PMP

FFV: 29% FFV: 28% FFV: 37%

Fig. 17: Chemical structure and fractional free volume of PTMSP, PMP and Teflon AF24000.
46 Part I: Membrane Materials and Membrane Preparation

Table 12 shows the oxygen permeability and oxygen/nitrogen selectivity of PTMSP,

PMP and Teflon AF2400 in comparison with other polymers.

Tab. 12: Oxygen permeability and oxygen/nitrogen selectivity of high free volume poly-
mers in comparison with conventional polymers.

Polymer Oxygen permeability Oxygen/nitrogen

(Barrer) selectivity

PTMSP 9700 1.5

PMP 2700 2.0
Teflon AF2400 1300 1.7
PDMS 600 2.2
Polymethylpentene 37 4.2
Polyphenyleneoxide 17 4.4
Ethylcellulose 11 3.4
Polycarbonate 1.4 4.7

Although the PMP was already synthesized in 1982 [158], its high gas permeabili-
ties were first published 1996 by Pinnau et al. [159] at MTR, Menlo Park. MTR is cur-
rently evaluating the performance of PMP membranes for hydrocarbon separation. An
attractive application of membranes in this field is natural gas hydrocarbon dewpoin-
ting. This means the separation of higher hydrocarbons like butane present in natural
gas from methane. Table 13 shows the performance of PTMSP and PMP membranes
for the separation of a methane/butane mixture.

Tab. 13: Mixed gas permeation properties of PTMSP and PMP. Feed: 2 % butane in
methane, feed pressure: 10 bar, permeate pressure: atmospheric, temperature: 25 °C
From: I. Pinnau et al. In: Polymer membranes for gas and vapor separation, ACS Sym-
posium Series 733 (1999), 56–67.

Polymer Permeability (Barrer) Mixed-gas selectivity Mixed-gas/pure gas

n-C4H10 CH4 n-C4H10/CH4 CH4 permeability ratio
PTMSP 53 500 1 800 30 0.1
PMP 7 500 530 14 0.2

Although the permeability and selectivity of PMP is significantly lower compared

to PTMSP , its performance for hydrocarbon separation is still superior to all other
known polymers. The advantage of PMP lies in its much better chemical stability. In
contrast to PTMSP it is not soluble in linear saturated hydrocarbons. With a mixed gas
 6 Gas Separation with Membranes 47

selectivity of butane over methane of 14, the PMP shows a much better performance
than poly (dimethyl-siloxane), for which a selectivity of about 5 has been determined
under similar conditions [160]. PMP has a poor pure gas selectivity for butane/metha-
ne separation, but in the presence of butane the methane permeability drops by a factor
of 5. This effect is well known for the gas permeation through nanoporous solids, the
condensable gas is selectively adsorbed on the pore walls, thus hindering the passage
of the smaller molecules. It is believed that in a similar way the extraordinarily high
excess free volume of the “super glassy” polymers can be occupied by condensable
gases.
It will be quite interesting to observe which class of polymers will finally be applied
for the attractive field of hydrocarbon dewpointing of natural gas. The superglasses like
PMP show the highest selectivities and fluxes. However, due to their double bonds their
chemical stability remains uncertain and they might be prone to physical aging, which
is the irreversible absorption of components with high boiling points. Rubbery poly-
mers like PDMS on the other hand are stable under natural gas conditions. However
they loose selectivity under high partial pressure of higher hydrocarbons.
The third polymer listed in figure 4 has a very different structure in comparison with
the polyacetylenes. The Teflon AF2400 is a perfluorinated random copolymer compo-
sed of 13 mol % tetrafluoroethylene and 87 mol % 2,2-bis(trifluoromethyl)-4,5-diflu-
oro-1,3-dioxole. Its extraordinarily high gas permeability was first described by Nem-
ser and Roman [161]. Composite membranes fabricated from this polymer are currently
being tested on a pilot scale by Compact Membrane Systems, Wilmington. An attrac-
tive application seems to be the production of oxygen-enriched or oxygen-depleted air
for mobile diesel engines [162] and the separation of supercritical carbondioxide [163].

6.1.6 Inorganic materials for gas separation membranes

The current market for inorganic membranes for gas separation is extremely small. One
of the few commercial applications are small scale palladium membrane systems to pro-
duce ultrapure hydrogen for specialized applications. They are marketed by Johnson
Matthey and Company. It is not believed that the market share of inorganic membra-
nes will increase significantly in the near future. The main obstacle is their high price
and some principle difficulties during reproducible large-scale production. On the other
hand fascinating research results have been published in the recent past such as a pro-
pene/propane mixed gas selectivity of more than 40 with carbon molecular sieve mem-
branes [164] or unmatched selectivities for carbondioxide/methane separation with
ceramic membranes [165]. The interested reader is referred to some good reviews on
inorganic membrane materials [166,167,168].
In this chapter three examples of inorganic membranes will be discussed, which
might find industrial applications in the future.
48 Part I: Membrane Materials and Membrane Preparation

6.2 Nanoporous carbon membranes

Nanoporous carbon membranes were one of the highlights in membrane development
for gas separation during the last decade. They can be produced by different methods.
The most advanced membranes of this kind have been produced by Air Products first
published 1993 [169]. Air Products called this membrane Selective Surface Flow
(SSF™) membrane.
It consists of a thin layer (2–3µm) of a nanoporous carbon matrix (5–7 Å pore dia-
meter) supported on the bore side of a macroporous (< 1µm pore diameter) alumina
tube. The membrane is produced by: (a) coating the bore side of the tubular support
with a thin uniform layer of a poly(vinylidene chloride-acrylate) terpolymer latex con-
taining small polymer beads in aqueous emulsion, (b) drying the coat under N2 at 50 ˚C,
(c) heating under a dry N2 purge to 600 ˚C for carbonizing the polymer, and (d) final-
ly passivating the nascent carbon film by heating in an oxidizing atmosphere at
200–300 ˚C. The resulting membranes have quite defined pores in the 5 to 8 Å range.
They are especially well suited for the separation of hydrogen/hydrocarbon mixtures.
The remarkable point is that they exhibit a preferred permeability for higher hydrocar-
bons over hydrogen. Table 14 gives some permeability data from the original paper.

Table 14: Gas separation properties of nanoporous carbon membrane.

Gas Pure gas permeability Mixed gas Mixed gas

(Barrer) permeability selectivity
H2 130 1.2 –
CH4 660 1.3 1.1
C2H6 850 7.7 5.1
C3H8 290 25 21
C4H10 155 110 94

41.0 % H2, 20.2 %CH4, 9.5 % C2H6, 9,4 % C3H8, 19.9 % C4H10
from: M.B. Rao, S. Sircar, J. Membrane Sci., 85 (1993)253

As can be seen from the table the pure gas selectivities of the nanoporous carbon
membrane are quite low, e.g. 1.19 for butane/hydrogen. However, for the mixture given
in Table 14 the butane/hydrogen selectivity increases to 94. The reason for this is that
the butane is selectively absorbed over hydrogen at the carbon pore wall and because
the pores are so small the pathway for hydrogen is blocked. This effect of selective sur-
face flow and pore blocking was first observed by Barrer and coworkers [170]. Due to
its unmatched selectivity the nanoporous carbon membrane looks very attractive for
hydrogen enrichment of refinery off-gases with low hydrogen content, e.g. FCC (flui-
dized catalytic cracker) off-gases. It is much more attractive than hydrogen selective
 6 Gas Separation with Membranes 49

membranes, because the hydrogen remains on the high-pressure side of the membrane
and can be fed into a pressure swing unit for further purification. The drawback of the
nanoporous carbon membrane is that water vapor and pentane and higher hydrocarbons
should be removed before the membrane separation because they absorb very strongly
in the membrane pores. Air Products SSF™-membrane is now being field-tested at dif-
ferent refinery sites [171].

6.3 Perovskite-type oxide membranes for oxygen

separation
It has been known for a long time that certain dense ceramic materials are good con-
ductors of oxygen at elevated temperatures. Oxygen transport through an ionic con-
ductor is a result of oxygen ionic conduction mechanisms that involve oxygen defects
such as lattice vacancies. One of the best known ceramic oxygen conductors is yttria-
doped zirconia, which is widely used in high temperature oxygen sensors. Oxygen is
transported through these materials as O2- ion. Hence, when oxygen permeates through
these materials there must be a flow of electrons in the opposite direction. Oxygen con-
ducting ceramics like doped zirconia are good oxygen conductors but poor electronic
conductors. The electronic conductivity of yttria stabilized zirconia is three to four
orders of magnitude lower than its ionic conductivity. The oxygen can be pumped
through the material by an external electrical field. However, a simple calculation reve-
als that this is not economic for oxygen separation due to the high electricity con-
sumption. The situation changes when the ceramic material is a good conductor for both
– oxygen ions and electrons. These materials are referred to as ionic-electronic mixed
conductors. With these a high oxygen flux can be obtained without an external electri-
cal field. Fig. 18 shows schematically the two types of oxygen ion transport membra-
nes.

electrically driven pressure driven

air high pressure air
O2 + 4e- 2O2- O2 + 4e- 2O2-

porous mixed
2O2- V e- 2O2- conductor
electrodes

low pressure oxygen

ion 2O2- O2 + 4e-
conductor 2O2- O2 + 4e-
oxygen
Fig. 18: Types of oxygen ion transport membranes.
50 Part I: Membrane Materials and Membrane Preparation

One of the first papers which stimulated large interest in this research was publis-
hed in 1985 by Teraoka et al. [172]. One of the figures of this pioneering paper is given
here (Fig. 19).

Oxygen Ion Transport Membranes

2.5
x=1.0

2.0 La1-x Srx Co0.4 Fe0.6 O3-δ

Oxygen flux (cm3(STP) min-1 cm-2)

1.5

1.0

x=0.8
0.5
x=0.4

0 x=0.0
700 800 900 1000 1100 1200
Temperatur (K)
Yamazoe et al., Chemistry Letters 1985, 1743
Fig. 19: Temperature dependence of the rate of oxygen permeation through perovskite membranes.

It may be deduced from Fig. 19 that, with a specific composition of the ceramic, an
oxygen flux of up to 2.4 cm3/min cm2 could be obtained at a oxygen partial pressure
difference across the membrane of 0.21 bar. The membrane thickness was 1mm. If one
uses these data to calculate the permeability a tremendous value of 2.5 million Barrer
is obtained. This is, of course, not totally correct because the oxygen flux through these
membranes is not direct proportional to the oxygen partial pressure difference and is
also not inversely proportional to the membrane thickness. At layers below 0.3 mm sur-
face reactions become rate limiting. But even 0.5 mm thick membranes exhibit an oxy-
gen flux at high temperatures which is orders of magnitude higher than the flux through
the best polymeric membranes. The promising prospect of these membranes is not in
the first place the production of oxygen, but their application in membrane reactors for
the partial oxidation of natural gas, which is schematically shown in Fig. 20.
 6 Gas Separation with Membranes 51

mixed conducting membrane

air O2- CH4

e-

O2+4e- 2O2- CH4+O2- CO+2H2+2e-

O2-

e-
partial CO + 2H2
N2 reduction oxidation
catalyst catalyst
Fig. 20: Ion transport membrane mediated partial oxidation of methane.

The mixed conducting membrane eliminates the cryogenic air separation plant and
it forms a safety barrier between the natural gas and air. The membrane becomes more
productive in a configuration like this, because the slow oxygen desorption at the per-
meate side is enhanced by the chemical reaction. The big challenge for the future is the
economic scale up of membrane production and the gas tight potting for temperatures
above 700 ˚C.
The perovskite type ceramic membranes have attracted much attention from major
chemical and petrochemical companies in the USA. Companies currently involved in
the development of the mixed conducting ceramic membranes include AirProducts, Pra-
xair, BP and Amoco. Many believe that the mixed conducting membrane technology
will represent a major breakthrough in industrial application of inorganic membranes.

6.4 Mixed matrix membranes

Molecular sieves such as zeolites or carbon molecular sieves show a much higher selec-
tivity for many gas mixtures than polymeric membranes due to their very defined
pore sizes. For example it can be calculated from reported sorption and diffusivity data
that zeolite 4A has an O2-permeability of 0.77 Barrer and an O2/N2 selectivity of appro-
ximately 37 at 35°C [173]. The preparation of defect-free zeolite layers on a large scale
is extremely difficult and it seems doubtful that this will ever be achieved at a compe-
titive price. However, the combination of the superior gas selectivities of molecular
sieves with the processibility of polymeric membranes have attracted many researchers.
52 Part I: Membrane Materials and Membrane Preparation

The hybrid membranes consisting of inorganic molecular sieves and polymers are often
referred to as mixed matrix membranes [174].
It was believed for a long time that the incorporation of a molecular sieve in a poly-
mer matrix does not change the polymer selectivity under steady state conditions. Hen-
nepe, from the university of Twente, proved for the first time that the incorporation of
silicalite in PDMS increased the ethanol/water selectivity significantly under steady
state conditions [175] in pervaporation experiments. Later it was shown by Jia et al.
[176] that using the same approach (silicalite in PDMS) the gas selectivity could be also
changed due to a molecular sieving effect. However, the effects were too small to be of
any interest for practical applications. One of the fundamental questions of this concept
is how the permeability of the polymer should match with the molecular sieve per-
meability. Koros proposed to use the following equation for an ideal modelling of the
mixed matrix permeability:

( Pd + 2 Pc − 2φ ( Pc − Pd )
Peff = Pc
( Pd + 2 Pc + φ ( Pc − Pd )
where Peff is the effective permeability, φ is the volume fraction of the dispersed phase,
and the subscripts d and c refer to the dispersed and continuous phases, respectively.
This equation was first derived by Maxwell to calculate the electric conductivity of a
metal in which small spheres of a second metal are dispersed [177]. If this equation is
used to calculate the selectivity of a mixed matrix membrane we obtain

α c (1 / Pc1 + 2 / Pd1 − 2φ (1 / Pd1 − 1 / Pc1 )(α c / Pc1 + 2 / Pd 2 + φ (1 / Pd 2 − α c / Pc1 ))

α eff =
(1 / Pc1 + 2 / Pd1 + φ (1 / Pd1 − 1 / Pc1 )(α c / Pc1 + 2 / Pd 2 − 2φ (1 / Pd 2 − α c / Pc1 ))

where αc is the selectivity of the continuous phase (the polymer) and the indices 1 and
2 refer to gas 1 and 2.
This equation looks complex at first sight but it allows the plotting of the selectivi-
ty of a mixed matrix membrane versus the polymer permeability, when the other para-
meters are fixed. An example is given in Fig. 21. In this example a 4A zeolite with an
estimated O2/N2 selectivity of 37 and an O2 permeability of 0.77 Barrer has been disper-
sed in polymer matrix with a O2/N2 selectivity of 7. The volume fraction of the zeolite
is 0.60. The plot reveals that a maximum selectivity of the mixed matrix membrane is
obtained in this case, when the polymer permeability is slightly higher than the zeolite
permeability. When the polymer permeability becomes too high the selectivity of the
mixed matrix membrane approaches the polymer selectivity. Hence the above equati-
on gives a theoretical estimation of the selectivity of a mixed matrix membrane and it
gives an idea of how the permeability of molecular sieve and polymer should match.
The practical challenge is to improve the compatibility between inorganic molecular
sieves and glassy polymers in order to eliminate gas diffusion pathways at the interface
between polymer and zeolite. Once this problem is solved using nano-sized zeolite
crystals the mixed matrix membranes might become an attractive alternative to poly-
meric membranes for commercial gas separation.
 6 Gas Separation with Membranes 53

Selectivity of MMC membrane vs. polymer permeability

19

P 1z :0.77
17 α z : 37
αp : 7
15 d: 0.60
selectivity

13

11

5
0.001 0.01 0.1 1 10 100 1000
polymer permeability
Fig. 21: Selectivity of a mixed matrix membrane vs. polymer permeability, zeolite O2/N2 selectivity
37, zeolite oxygen permeability 0.77 Barrer, polymer selectivity 7, zeolite volume fraction 0.60.

6.5 Process design

In this chapter some fundamental equations are given, which allow a first design of a
one stage membrane separation unit. Questions to be answered are: what is the maxi-
mum enrichment, which can be achieved with a membrane of a given selectivity? How
is the separation performance influenced by feed and permeate pressure? It will be
explained why for some applications a high selective membrane will be outperformed
by a membrane with a lower selectivity.
For the following we look at a simple gas separation unit with two components,
which is illustrated in Fig. 22.
One parameter, which does of course determine the gas enrichment, is the membra-
ne selectivity α, which is a membrane property and defined here as α = P2/P1with P2
and P1 as permeability coefficients for gas 2 and 1. Equally important are two process
parameters the stage cut θ and the pressure ratio φ. The stage cut is defined as ratio per-
meate flow/feed flow and the pressure ratio is the ratio of total feed pressure to total
permeate pressure. For the sake of simplicity we start with a stage cut close to zero, i.e.
there is no concentration difference between feed and retentate. The maximum enrich-
ment of the faster component 2 can now determined easily. For the maximum enrich-
ment the maximum driving force is needed, i.e. the permeate pressure can be neglec-
ted when compared to the feed pressure. The flux of component 1 is proportional to its
54 Part I: Membrane Materials and Membrane Preparation

Schematic view of binary gas mixture separation

Feed Retentate

pressure p'
composition c1', c2'
pressure p''
composition c1'', c2''

Permeate Membrane selectivity α = P2

P1
permeate flow
stage cut θ = feed flow
p'
pressure ratio φ = p''

Fig. 22: Model gas separation unit with two components.

volume fraction on the feed side, for component 2 we have, as an additional factor the
membrane selectivity.

J1 = const. × c1′ = const. × (1 − c2′ )

J2 = const. × α × c2′
The concentration of component 2 on the permeate side must be equal to the flux J2
of component 2 divided by the total flux J1 + J2. Combining equations 1 and 2 then yields

c2′ × α
c2′′ =
1 + c2′ (α − 1) (3)

This simple equation gives the maximum possible enrichment of one gas of a two
component mixture when separated by a membrane with a selectivity of a. The equati-
on becomes more complex when the permeate pressure cannot be neglected [178]. Fol-
lowing the simple solution-diffusion model the gas fluxes for gas 1 and 2 through the
membrane are

P1 ( p1′ − p1′′)
J1 = (4)
l
and

P2 ( p2′ − p2′′)
J2 = (5)
l
 6 Gas Separation with Membranes 55

where P1 and P2 are the permeabilities of component s 1 and 2, l is the membrane

thickness, and p1',p2'' and p1'', p2'' are the partial pressures of the two gases in the feed
and permeate streams, respectively. The total gas pressure is equal to the sum of the par-
tial pressures, i.e.

p′ = p1′ + p2′ (6)

p′′ = p1′′+ p2′′ (7)
with
c2′ = p2′ / p′ c2′′ = p2′′ / p′′ (8)

and
J1 / J2 = c1′′/(1 − c1′′) = (1 − c2′′) / c2′′ (9)

Combining equations (4–9) then yields the expression

 1 1  1 1  4c2′α 

c2′′ = 0.5φ c2′ + + −  c2′ + + −
φ α − 1 φ (α − 1) 
(10)
 φ α −1 

Equation 10 gives the concentration of the faster permeating gas in the permeate stre-
am as a function of the membranes selectivity and the pressure ratio across the mem-
brane. It breaks down into two limiting cases. At high driving forces when the pressu-
re ratio is much higher than selectivity (φ>>α) equation 10 reduces to equation 3. We
call this a selectivity controlled region, because the enrichment is now independent of
the pressure ratio. When on the other hand, the pressure ratio becomes much smaller
than the selectivity (φ<<α), equation 10 reduces to

c2′′ = c2′φ (11)

The enrichment is now independent of the membranes selectivity. Hence, this is the
pressure ratio limited region. There is, of course, an intermediate region between these
two limiting cases where both the presure ratio and the membrane selectivity affect the
degree of separation. This is illustrated in Fig. 23, in which the calculated permeate con-
centration is plotted versus pressure ratio for a membrane with a selectivity of 200.
For numerous technical applications the pressure ratio does not exceed 10 or 20. An
example is the separation of organic vapors, where a typical pressure ratio is about 10.
Fig. 24 shows a plot of permeate concentration versus selectivity at a pressure ratio of
10. The plot reveals that an incrase of the selectivity above 40 does not increase the
enrichment significantly. The highest permeate concentration achievable in this exam-
ple is 5 % as predicted by equation 11.
The process might not only not benefit from a high selective membrane, but a too
selective membrane might even be a disadvantage. This will be demonstrated with a
56 Part I: Membrane Materials and Membrane Preparation

60

50

40
Permeate conc. (%)

30

20

10

0
1 10 100 1000 10000
Pressure ratio
Fig. 23: Calculated permeate concentration for a membrane with a selectivity of 200 as a function
of pressure ratio. The feed concentration is 0.5 %.

5
Permeate conc. (%)

0
0 10 20 30 40 50

Selectivity
Fig. 24: calculated permeate concentration versus membrane selectivity for a pressure ratio of 10,
feed concentration 0.5 %.
 6 Gas Separation with Membranes 57

simple model calculation concerning natural gas dehydration. Natural gas dehydration
is one of the emerging applications of membrane-based gas separation. The permeati-
on of water vapor through polymers has one peculiarity. When plotting gas permeabi-
lity versus selectivity for different polymers a general tendency exists: the more selec-
tive a polymer is the lower is its permeability, as shown in the famous Robeson plots
[179]. Fig. 25 displays a plot of water vapor/nitrogen selectivity versus water permea-
bility for a number of polymers. The afore-mentioned tendency does not hold here. On
the contrary, many very selective polymers also have a very high permeability1. Nume-
rous polymers are available with water vapor selectivities of 5000 and more.

1 000 000 Polyvinyl-

Cellulose alcohol
100 000
water vapor/nitrogen selectivity

10 000 PVC

Ethylcellulose
1 000

100 Polypropylene PDMS

Polyethylene
10

1 Teflon
1 10 100 1 000 10 000 100 000
water vapor permeability
Fig. 25: H2O/N2-selectivity versus permeability for various polymers.

For the following calculation a two component water vapor/methane mixture has
been assumed with 0.2 % water vapor. The membrane unit shall reduce this water con-
tent by one order of magnitude; i.e. the retentate water concentration has been set to
0.02 %. The simple equation 10 cannot be applied, the equations first derived by Wel-
ler and Steiner [180] have been used for the calculation of methane loss and the equa-
tion of Saltonstall [181] for calculation of membrane area. The methane loss is simply
defined by methane permeate stream divided by methane feed stream times 100. In
Fig. 26 the methane loss is plotted versus membrane selectivity for two different pres-
sure ratios.
The figure reveals that the methane loss is smaller at the higher pressure ratio. For
the pressure ratio of 80 methane loss starts at 5 % for a selectivity of 100 and drops to

1 When looking at the permeabilities in Fig. 25 one has to keep in mind, that the water vapor per-
meability often strongly depends on its vapor pressure. Most permeability data have been genera-
ted near saturation pressure.
58 Part I: Membrane Materials and Membrane Preparation

5
methane loss (%)

pressure ratio 80
3

1
pressure ratio 1000

0
100 1000 10000
water vapor/methane selectivity
Fig. 26: Methane loss versus selectivity for pressure ratios 80 and 1000, volume fraction of
methane in feed 0.2 %.

2,75 % for a selectivity of 5000. But even with a very selective membrane it is never
smaller than 2,7 %. At the high pressure ratio of 1000 the methane loss drops to a favor-
able 0.17 %. However, a pressure ratio of 1000 is quite unrealistic. Additional com-
pression of the feed is out of question. The permeate pressure could be reduced by va-
cuum pumps; but this idea is not liked by the gas companies because of cost and safety
concerns. If a membrane dehydration system is operated at a pressure ratio of 80, the
difference between methane loss from a membrane with a selectivity of 500 (3.2 % met-
hane loss) and a membrane with a selectivity of 5000 (2.75 % methane loss) is quite
small. Hence, as far as methane loss is concerned there is a small benefit in using the
high-selective membrane. The picture changes when the required membrane area is
taken into account, which is demonstrated in Fig. 27. Membrane area has been calcu-
lated for a feed stream of 1000 m3 (STP)/h, the water vapor flux through the membra-
ne has been fixed at 1.1 10-2cm3/cm2 s cmHg. Membrane selectivity was adjusted by
variation of methane flux.
As the figure shows, the membrane area required increases strongly with selectivi-
ty. There is an 8 x increase of membrane area for a selectivity of 500 and 5000. This
example illustrates that it is not always a good strategy to look for the most selective
membrane but that a less selective membrane may do a better job.
 6 Gas Separation with Membranes 59

100

80
membrane area (m2)

60 pressure ratio 80

40

20

pressure ratio 1 000

0
100 1 000 10 000
water vapor/methane selectivity
Fig. 27: Membrane area versus selectivity at pressure ratios of 80 and 1000, water vapor flux fixed
at 1.1 10-2cm3/cm2 s cmHg, water vapor feed concentration 0.2 %, retentate concentration 0.02 %,
feed pressure 8 MPa.

Acknowledgements:
The electron micrographs were kindly supplied by Michael Schossig-Tiedemann,
GKSS-Forschungszentrum Geesthacht.

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