Equipo 4 PDF

Ind. Eng. Chem. Res.
1999, 38, 3715-3737 3715
Membrane in a Reactor: A Functional Perspective

Kamalesh K. Sirkar,* Purushottam V. Shanbhag,† and A. Sarma Kovvali
Center for Membrane Technologies, Department of Chemical Engineering, Chemistry and Environmental
Science, New Jersey Institute of Technology, Newark, New Jersey 07102
Membrane reactors have found utility in a broad range of applications including biochemical,
chemical, environmental, and petrochemical systems. The variety of membrane separation
processes, the novel characteristics of membrane structures, and the geometrical advantages
offered by the membrane modules have been employed to enhance and assist reaction schemes
to attain higher performance levels compared to conventional approaches. In these, membranes
perform a wide variety of functions, often more than one function in a given context. An
understanding of these various membrane functions will be quite useful in future development
and commercialization of membrane reactors. This overview develops a functional perspective
for membranes in a variety of reaction processes. Various functions of the membranes in a reactor
can be categorized according to the essential role of the membranes. They can be employed to
introduce/separate/purify reactant(s) and products, to provide the surface for reactions, to provide
a structure for the reaction medium, or to retain specific catalysts. Within these broad contexts,
the membranes can be catalytic/noncatalytic, polymeric/inorganic, and ionic/nonionic and have
different physical/chemical structures and geometries. The functions of the membrane in a
reaction can be enhanced or increased also by the use of multiple membrane-based schemes.
This overview develops a perspective of each membrane function in a reactor to facilitate a better
appreciation of their role in the improvement of overall process performance.
1. Introduction gated in the literature is useful in the Introduction

before we present the functional perspective. Of the
Membrane reactors have been investigated since the many types of membrane separation processes and
1970s. The early investigations employed primarily membrane-based equilibrium separation processes avail-
polymeric membranes and enzymatic reactions. Later able for separation,10 membrane reactors have been
investigations show an abundance of petrochemically studied using the following: reverse osmosis (RO),
relevant systems and inorganic membranes. Whole cell nanofiltration (NF), ultrafiltration (UF), microfiltration
fermentation-based chemical and biochemical produc- (MF), electrodialysis (ED), liquid membranes (LM),
tions as well as degradation of pollutants biologically pervaporation (PV), gas permeation, vapor permeation,
or otherwise have also been studied in membrane molecular sieving, Knudsen diffusion (and molecular
reactors. Polymer membrane-based reactors have been
diffusion), gas membrane, membrane solvent extraction,
blessed with some commercial success. Much of this
and membrane gas absorption/stripping.
research has been discussed in a number of reviews.1-9
In these investigations a variety of membrane separa- An extraordinary variety of membranes have also
tion processes as well as membranes have been used. been used. Membranes are employed in gross physical
More importantly, the membrane inside the reactor has forms as flat films, hollow fibers, tubules, and tubes,
served a variety of functions. In some studies, the while their physical structures can be as follows: mi-
membrane has a single well-defined function. In others, croporous symmetric and asymmetric membranes, non-
the membrane allows two or more functions to be porous membranes, and composite membranes. Mem-
carried out. The variety of functions achievable via a branes can be of the polymeric variety or be inorganic
membrane in a reactor is very broad. An understanding in nature, which would include zeolitic, ceramic, and
of the breadth of the roles capable of being performed metallic membranes. Membranes can also conduct
by a membrane is likely to be quite useful in the future electrical charges and can be chosen from one of follow-
development of membrane reactors. This overview ing categories: ion-exchange membranes, bipolar mem-
proposes to develop a functional perspective of a membranes, mixed conducting membranes, proton-conduct-
brane(s) in a reactor. This perspective is developed by ing membranes, etc. In many cases, the membranes
employing a variety of contexts including different have catalysts incorporated in their porous structure or
membrane separation processes, different membranes, on the surfaces. The membranes in such cases are
chemical/electrochemical reactions, enzymatic processes, termed as catalytic membranes. Of course, the mem-
fermentations, catalyst immobilization/segregation, cata- brane can be catalytic by itself without the addition of
lytic membranes, integration of functions, etc. any catalyst materials from external sources. The term
A brief enumeration of different membrane separation catalytic membrane reactor sometimes includes the
processes and different classes of membranes investi- above cases as well as a catalytic reactor enclosed by a
membrane, which is noncatalytic.2
* To whom correspondence should be addressed. Tel.: (973) In the next section, we will first present a compact
596-8447. Fax: (973) 642-4854. E-mail: [email protected]. list of membrane functions in a reactor. Often, the
† Current address: Compact Membrane Systems, Inc., generic membrane function identified will affect the
Wilmington, DE 19804. reaction processes in different ways. Such effects on the
10.1021/ie990069j CCC: $18.00 © 1999 American Chemical Society
Published on Web 09/18/1999
3716 Ind. Eng. Chem. Res., Vol. 38, No. 10, 1999
Figure 2. Schematic of a recycle-based configuration of a coupled

reactor and membrane separator.
membrane in a given reactor is capable of all functions

identified in the figure. However, a given membrane
under appropriate circumstances can perform more than
one generic function. The introduction of another mem-
brane into the reactor can increase the number of
generic membrane functions in the reactor or achieve
the same generic membrane function vis-à-vis some
other species. Figure 1 also indicates other activities
concurrently taking place in the so-called nonreactor (or
permeate) side of the membrane as well as in the reactor
side of the membrane. A list of the generic membrane
functions performed by a membrane or two in a reactor
is provided next:
2.1. Separation of products from the reaction mixture
Figure 1. Schematic of possible functions of a membrane in a 2.2. Separation of a reactant from a mixed stream for
reactor. introduction into the reactor
2.3. Controlled addition of one reactant or two reac-
reaction will be identified. Each generic membrane tants
function will then be illustrated in a separate subsection 2.4. Nondispersive phase contacting (with reaction at
using examples from the literature. This illustrative the phase interface or in the bulk phases)
exposition will employ different membrane separation 2.5. Segregation of a catalyst (and cofactor) in a
processes, reaction-phase systems, and other distin- reactor
guishing features to elaborate briefly on particular 2.6. Immobilization of a catalyst in (or on) a mem-
membrane reactors. The goal is to develop a perspective brane
on the range and the utility of each membrane function 2.7. Membrane is the catalyst
in a membrane reactor rather than a review of all 2.8. Membrane is the reactor
investigations. Frequently, a membrane (or two mem- 2.9. Solid-electrolyte membrane supports the elec-
branes) incorporated in a reactor serves more than one trodes, conducts ions, and achieves the reactions on
desired function, only one of which may involve a its surfaces
membrane separation process where membrane flux 2.10. Transfer of heat
and selectivity are important. The development of such 2.11. Immobilizing the liquid reaction medium
a multifunctional perspective of membranes in a reactor
is an additional objective of this paper. Membranes in a reactor existing as membrane lami-
The reaction processes of interest in this paper may nates or physically separated membranes with a fluid
involve the production of a particular chemical or a phase between have also been studied. They can provide
biochemical product. Alternately, it may involve the particular combinations of the above functions some-
destruction of some organic species in a phase for the times with added and novel benefits;5,11 these novel
purpose of controlling environmental pollution. Reaction benefits include product separation and simultaneous
processes are sometimes employed to purify a particular concentration, separation of multiple products, reaction
fluid stream without destroying the undesirable species intensification, and physically containing the reaction
into simple compounds such as CO2, H2O, etc. (e.g., medium in multiphase reaction systems.
enzymatic resolution processes). Although such pro- Before proceeding further, it is necessary to point out
cesses are within the scope of this paper, our main focus that there are many studies where the membrane is
will be on those reactive processes where a particular physically located in a device external to the reactor
compound or two are produced by the reactions. We proper (structure). The reaction medium is then circu-
specifically exclude those processes where reactions are lated over the membrane and back to the reactor in a
used to enhance separation of a mixture. recycle mode (Figure 2). This configuration is frequently
employed in reaction processes based on enzymes and
2. Membrane Functions in a Reactor whole cells; it is also being proposed for organic syn-
theses. The reactor vessel in such case is sometimes
Figure 1 schematically identifies many of the major operated as a batch reactor or more frequently as a
generic functions performed by a membrane in a reactor. continuous stirred tank reactor (CSTR). In many cir-
One should not conclude from the figure that a given cumstances, the system behavior here can be considered
Ind. Eng. Chem. Res., Vol. 38, No. 10, 1999 3717
to be de facto equivalent to that with a membrane inside membrane reactor whereby the product H2 is withdrawn
a reactor. Therefore, such recycle membrane reactors through the palladium membrane to shift the reaction
will also be included in the following treatment: pri-
mary emphasis will however be on systems where a C2H5OH T CH3CHO + H2 (3a)
membrane (or two) is physically located in the reactor.
One must recognize the major advantages of these to the right showed that the deleterious effect of the side
different arrangements: reaction
(1) The mixing conditions and the flow velocities (and
therefore the extent of consequent concentration polar- C2H5OH + CH3CHO T CH3COOC2H5 + H2 (3b)
ization in membrane devices involving liquid-phase
systems) can be maintained at different levels in the can be drastically reduced, provided the reaction (3a)
reactor and the membrane separator if recycle mem- is shifted to the right via the Cu/SiO2-aq catalyst and
brane reactors are employed; conditions can be opti- H2 removal by the membrane.
mized for each. The reactor may require long residence (c) In consecutive catalytic reactions,
times whereas the membrane device may need a short AfB (4a)
residence time.
(2) Building a reactor with a membrane in it or using BfC (4b)
a membrane device as the reactor can sometimes be very
demanding on the membrane, especially for higher where B is the desired intermediate product, if the rate
temperature systems. The recycle membrane reactor constant for reaction 4b is significantly larger than the
allows the reactor and the membrane unit to operate rate constant for reaction 4a, it is difficult to achieve a
at two different temperatures by using heat exchangers high selectivity to B using a conventional packed bed,
in between. plug flow reactor. By using an inert sweep gas on the
(3) Recycle membrane reactors allow use of existing outside of a permeable tube having the catalysts and
equipment, namely, a separate reactor and a separate the reaction taking place inside the tube, the intermedi-
membrane device. ate product B may be selectively removed from the
(4) For fast reactions, the membrane in a reactor is reaction zone, leading to increased selectivity.14 Removal
likely to be a more desirable configuration. of the intermediate products (methanol/formaldehyde)
2.1. Separation of Products from the Reaction via a membrane in the partial oxidation of methane is
Mixture. Separation of products from the reaction an example; this strategy will prevent further oxidation
mixture is one of the most common functions of a of these products to CO and CO2.
membrane in a reactor. The separation may be purifica- (d) In fermentation processes, one of the products may
tion, enrichment, or concentration. Consider the follow- be inhibitory to the fermentation process. Removal of
ing elementary reversible reaction (see Figure 1): the product from the fermentation broth via a mem-
brane can substantially reduce product inhibition and
A+BTC+D (1) increase volumetric productivity of the fermentor.15,16
Further, one can use higher concentrations of the
where D is a product needed to be removed via the substrate in the feed (e.g., glucose for ethanol fermenta-
membrane to the permeate side. The separation process tion) since the product is being removed as it is being
employed may produce a permeate side stream where formed.17
the mole fraction of D is much higher than that in the The separation of a reaction product(s) (C or D or
reactor side. In the case of species D being H2 and a both) can be implemented using a variety of membrane
palladium membrane, pure H2 is obtained in the perme- processes. The nature of the membrane process is
ate side. The H2 partial pressure on the permeate side obviously influenced by the phase of the reaction
will be lower than the partial pressure of H2 on the feed medium exposed to the membrane and the desired
side. If species C also permeates to some extent through phase of the permeated product stream. Examples of
the membrane, the permeate stream is enriched in D such processes will be provided under two categories,
vis-à-vis the product species C: permeation of D leads namely, (1) liquid reaction medium/liquid feed phase
to partial purification of the product C in the reactor and (2) gaseous reactions/gaseous feed phase.
outlet stream. 2.1.1. Separation from a Liquid Reaction Mix-
Removal of D via the separation function of the ture. We will briefly mention and/or illustrate the use
membrane has the following effects on reaction (1) and of the following membrane separation processes for
the reactor performance: removing products from the liquid reaction medium:
(a) The equilibrium condition indicated in the revers- reverse osmosis, nanofiltration, ultrafiltration, pervapo-
ible reaction (1) is shifted to the right, i.e., leading to ration, gas membranes, electrodialysis, and liquid mem-
higher equilibrium conversion of A and B to C and D. branes.
(b) If there is an undesirable side reaction as shown 2.1.1.1. Reverse Osmosis. Vasudevan et al.18 have
below, described a membrane sandwich reactor in which the
Saccharomyces cerevisae (ATCC 4126) cells were ef-
B+DTE (2) fectively placed between an ultrafiltration (UF) mem-
brane and a reverse osmosis (RO) membrane; the
taking place in the reactor (see Figure 1), the separation reactor was fed with a solution of glucose at a high
of product D from the reaction mixture reduces the loss pressure from the UF membrane side and the product
of reactant B to the side reaction, increasing the solution was forced out through the RO membrane. The
selectivity of conversion to product C (or D) (modeled product solution concentration progressively increased
by Whu et al.12 for nanofiltration-aided liquid-phase in ethanol; the glucose in the feed solution was ef-
organic synthesis). An experimental study by Raich and fectively rejected by the RO membrane. The reactor
Foley13 of ethanol dehydrogenation in a palladium structure shown in Figure 3 has a microfiltration
Figure 3. Membrane “sandwich”: (1) UF membrane, (2) coarse

filter paper (>10 µm), (3) cell mass, (4) fine filter (0.2 µm,
microporous), and (5) RO membrane (reprinted from Vasudevan
et al.18 with permission).
Figure 5. Reactor performance as a function of enzyme concen-

tration and distance along the membrane for enzymatic reduction
j 0 ) 1 cm/s (reprinted with permission from
of starch to glucose; u
Closset et al.20 Copyright 1973, John Wiley & Sons, Inc.).
selectivity is achieved when the semibatch reactor is

externally coupled with a nanofiltration unit to remove
the solvent and the product D (in the manner of Figure
2). Operation as a continuous flow stirred tank reactor
as in Figure 2, coupled with a NF unit, could also
provide a way to increase the concentration of the
reactants in the reactor from a dilute feed if the
reactants are rejected by the NF membrane. In such a
case, separation of products by the NF unit may
facilitate conversion of the reactants.
2.1.1.3. Ultrafiltration. Cheryan and Mehaia6 have
provided a comprehensive review of enzyme-based and
whole-cell-based membrane bioreactors where ultrafil-
tration is often the predominant mode of membrane
separation. Many systems have been described. Some
examples are hydrolysis of proteins leading to modified
proteins with smaller molecular weights appearing in
the permeate; hydrolysis of carbohydrates, e.g., starch,
cellulose to produce lower molecular weight sugars;
hydrolysis of sugars, e.g., lactose. Perhaps the earliest
Figure 4. Selectivity with respect to the desired product C (SC) experimental study was carried out in a stirred tank
as a function of time. (SC, semibatch-coupled with membrane; SU,
semibatch-uncoupled; BU, batch-uncoupled) (reprinted from Whu reactor coupled to an ultrafiltration membrane cell for
et al.12 Copyright 1999, with permission from Elsevier Science). the hydrolytic breakdown of cellulose to the membrane
permeable product glucose using cellulase enzymes.19
membrane and a coarse filter paper on two sides of the The utility of a thin channel membrane reactor lined
yeast cells between the UF and the RO membrane to with UF membranes for the enzymatic reduction of
immobilize and provide physical protection in a high- starch to glucose is shown in Figure 5. The figure
pressure (up to 400 psig) environment. The membranes illustrates the lengthwise variation of the performance
in this reactor separate the product ethanol from the indicator fA of the plug flow membrane reactor defined
reactant glucose and effectively immobilize the biocata- by
lyst (whole cell).
2.1.1.2. Nanofiltration. Whu et al.12 have modeled fA )
the performance of a semibatch/batch reactor coupled (inlet flow of reactant ( flow of reactant
to an external nanofiltration (NF) unit for the synthesis
of the desired product C (a hydroxyester of MW ∼ 400) across the tube wall - flow of reactant
from reactants A (a diketone of MW ∼ 400) and B (an at a given axial distance)
alkoxide of MW ∼ 40-100) present in an organic (5)
inlet flow of reactant
synthesis solvent, methanol. The membrane removes
the low-molecular-weight product, D (MW ∼ 40-100) with that for a solid tube reactor; the membrane reactor
and the solvent which significantly improves the selec- has a much higher conversion for the cases analyzed
tivity if the reaction system consists of the reactions (1) where the enzyme is completely rejected.20
and A + D T E. Figure 4 illustrates the role of the 2.1.1.4. Pervaporation. The pervaporation (PV)
membrane in improving the selectivity of the reaction process is used to remove volatile reaction products from
for the product C. This figure shows that a much higher the reaction mixture; generally, a vacuum on the
Figure 6. Influence of the variation of the membrane area to the

solution volume ratio on the esterification rate of propionic acid
with 1-propanol. T ) 50 °C; 1 wt % catalyst; Noac/Noalc ) 1 (with
permission21).
no. 1 2 3 4
S/V (cm-1) 1 2 4 8
Figure 7. Schematic diagram showing the configuration and the
permeate side is employed to create the needed partial basic function of a bipolar membrane for water splitting (reprinted
from Strathmann.25 Copyright 1992, Kluwer Academic Publish-
pressure difference. The most common reaction system
ers).
studied for the application of pervaporation is an
esterification reaction between an alcohol and an acid membrane”-mediated selective transfer of volatile spe-
in the presence of a highly acidic catalyst (e.g., concen- cies has been used to remove volatile product species
trated sulfuric acid): from a reactor solution to that on the receiving side.
Twardowski and McGilvey24 have used a porous poly-
Cat-H+
R1COOH + R2OH {\} R1COOR2 + H2O v (6) (tetrafluoroethylene) (PTFE) membrane to transfer
acid alcohol ester product ClO2, from the reactant stream in a reactor to
the aqueous solution on the other side of the membrane
This reversible reaction in industrial processing is where it is ultimately used to bleach wood pulp, etc.
driven to high conversion by adding a large excess of Removal of the ClO2 from the reactor solution is
alcohol. Adding a poly(vinyl alcohol) (PVA)-based water- necessary to reduce the high partial pressure of ClO2
selective PV membrane to the esterification reactor inevitably occurring in the gas space of commercial ClO2
allows one to shift the equilibrium in reaction 6 to the generators which leads to localized decomposition of
right (thus reducing the need for excess alcohol beyond ClO2.
that needed for solubilization of the acid). Figure 6 2.1.1.6. Electrodialysis. In electrodialysis processes
illustrates how the conversion to the ester is increased using bipolar membranes, a solution of a salt, e.g., NaCl,
in a batch reactor with time as the ratio of the is converted to a pure solution of NaOH and another
membrane surface area (S) to the reaction volume (V) pure solution of HCl. This acid and base production is
is increased for the esterification reaction between carried out first by the production of H+ and OH- ions
propionic acid and 1-propanol studied by David et al.21 from water and their collection into separate aqueous
Note that in this case the equilibrium value of the solutions into which are fed the corresponding ions, viz.,
conversion in the absence of any product removal is 0.7; Cl- and Na+, respectively, via the electrodialysis pro-
the membrane allows a much higher conversion to be cess. The splitting of water into H+ and OH- ions in
attained much more rapidly. If the temperature of the separate aqueous solutions is carried out in a bipolar
esterification reaction is high, it will be necessary to ion-exchange membrane-based reactor shown in Figure
employ vapor permeation membranes to remove H2O 7.25 The thin space between a cation-exchange mem-
vapor. Another application of pervaporation studied22 brane and an anion-exchange membrane laminated
involved selective removal of alcohol from a fermenta- together and placed between a cathode and an anode is
tion broth in a recycle configuration using silicone filled with water. Any ions, e.g., Na+ and Cl-, in this
capillary membranes. Silicone (PDMS) is a highly water are quickly removed through the corresponding
biocompatible material. Further, some of the other ion-exchange membrane. This leads to deionized water
byproducts of fermentation (which can inhibit the in the space between the two laminated ion-exchange
fermentation if their concentrations build up in a recycle membranes. The resistance of the aqueous solution
system) like acetaldehyde, butanol, etc. are also easily becomes very high, which leads to H+ and OH- ions
removed. Removal of ethanol decreased product inhibi- participating in the transport of electrical charges
tion and increased fermentor productivity. through the membranes. In the water dissociation
2.1.1.5. Gas Membranes. A hydrophobic microporous equilibrium process,
or porous membrane having gas-filled pores and two
nonwetting aqueous solutions on two sides will allow H2O T H+ + OH- (7)
spontaneous transfer of volatile species from one solu-
tion to the other solution through the pore as long as As the ions H+ and OH- are removed through the
there is a partial pressure difference.23 Such a “gas cation-exchange membrane and anion-exchange mem-
Figure 8. Apparatus for the resolution of (R,S)-Phe-O-iPr-HCl with subtilisin, using a hollow fiber SLM module (reprinted with
permission from Ricks et al.26 Copyright 1992, American Chemical Society).
brane, respectively, more water is dissociated. Thus, 2.1.2.1. Liquid Membrane. One of the earliest
separation of products, H+ and OH-, through the studies by Ollis et al.27 involved acetaldehyde synthesis
membranes is essential to continue the water-splitting in a multiphase catalytic liquid membrane-based reac-
reaction. tor. The feed gaseous mixture of O2 and C2H4 as the
2.1.1.7. Liquid Membranes. Enantioselective hy- inner gas phase surrounded by an aqueous catalytic
drolysis of (R,S)-phenylalanine isopropyl esters by the liquid membrane layer was prepared by dispersing the
enzyme subtilisin Carlsberg in solution in a reactor was gas as bubbles into an aqueous liquid membrane
shown by Ricks et al.26 to selectively convert the (S)- reservoir containing the palladium-based catalyst PdCl2
ester to (S)-Phe-COO- while leaving the (R)-ester and the oxidizing agent CuCl2. The individual gas
essentially unchanged. Part of the enzymatic solution bubbles surrounded by the aqueous liquid membrane
was circulated on the shell side of a hollow fiber module layer then spontaneously rose through a solvent layer
in which a liquid membrane of N,N-diethyldodecana- kept above the aqueous catalyst reservoir. Any reaction
mide in dodecane is immobilized as a supported liquid product was extracted into the outer solvent layer. The
membrane in the pores of hydrophobic Celgard polypro- overall reaction and the continuous extraction of the
pylene hollow fibers. The (R)-ester is permeable through product acetaldehyde into a solvent phase (e.g., ethyl
this liquid membrane into an acidic strip solution where acetate, n-butanol, etc.) can be indicated by
it gets protonated and cannot partition back into the
feed phase. The (S)-Phe-COO- is essentially imperme- O2 (w) + C2H4 (w) f CH3CHO (w) f
able through the liquid membrane and is recovered from
CH3CHO (s) (9)
the feed solution. A part of the feed solution is recircu-
lated through the reactor and the membrane separator
in the recycle mode. If the (R)-ester accumulates in the The product acetaldehyde is recovered from the solvent
reaction media, it can inhibit the rate of conversion of in a separate flash drum, while the solvent phase is
the (S)-ester, which can also permeate through the recycled back to the reactor to form the outer continuous
membrane. The retention time of any ester fed to the solvent phase in the double-emulsion liquid membrane
reaction vessel is adjusted such that hydrolysis is employed in the reactor. The liquid membrane in this
essentially completed (12 min) before the solution is case allows not only product separation but also the
introduced in the membrane module in the recirculation segregation of the soluble catalyst in the aqueous
mode (Figure 8). This is an example of an unconverted membrane phase (function 2.6) in addition to being the
reactant being removed from the reaction mass as if it actual site where the reaction is taking place (function
were an inhibitory product. Further, a reaction (in this 2.8). The product separation here does not lead to a pure
case protonation) is carried out in the permeate phase product for which an additional step (flash) is necessary.
(Figure 1), 2.1.2.2. Knudsen Diffusion. Since the mid 1980s, a
large number of studies have been carried out using
D+FfG (8) reactants in the gas phase and an inorganic membrane
through which one or more of the gaseous products
to maintain a large driving force for the permeation of (usually H2) is withdrawn. The membranes used often
D. were microporous/mesoporous, e.g., γ-alumina, Vycor
2.1.2. Separation from a Gaseous Reaction Me- glass, etc., with or without a catalyst deposited in the
dium. The membrane processes employed include those pores. Tubular noncatalytic membranes were also used
using liquid membranes, Knudsen diffusion, gas per- packed with catalyst particles.
meation, molecular sieving, etc. We will briefly identify Sun and Khang28 have compared the performances
some typical examples to illustrate product removal by of a catalytic membrane reactor, an inert membrane
membranes in each case. reactor, and an ordinary reactor without any membrane
from 35% to 70%, moving the yield from 21% to 63%.13

In the catalytic dehydrogenation of propane using silica
membranes (having H2/N2 selectivity of 10-19, much
higher than Knudsen diffusion-based selectivity), a
propylene yield of 39.6% was obtained at 823 K com-
pared to a yield of 29.6% in a conventional packed-bed
reactor operated at the same flow rate.32 Catalytic
isobutane dehydrogenation in a dense silica membrane
reactor yielded somewhat higher isobutene yield and
selectivity than a conventional reactor.33
Catalytic decomposition of NH3 in a gas feed to N2
and H2 in a composite Pd-ceramic membrane reactor
achieved an NH3 conversion of over 94% at 873 K and
1618 kPa compared to 53% in a conventional reactor.34
A water-gas shift reaction carried out at 673 K in a
palladium membrane reactor enclosing an iron-chro-
mium oxide catalyst achieved higher CO conversion
Figure 9. Conversion vs temperature for high space-time than the equilibrium level due to selective removal of
operations with a Vycor glass membrane for cyclohexane dehy- H2.35 A metal membrane-based catalytic membrane
drogenation (reprinted with permission from Sun and Khang.28
Copyright 1988, American Chemical Society).
reactor for facilitating the water-gas shift reaction at
a temperature of 500 °C was run successfully and
for the dehydrogentation of cyclohexane: continuously for 6 months for the economical production
of H2 in a 0.4 ft2 plate-and-frame module.36 Recovery of
Pt H2 isotopes (tritium, deuterium) is being studied in Pd/
C6H12 {\} C6H6 + 3H2 (10) Ag-based membrane reactors from impurities present
in fusion reactor exhaust streams.37 Dixon et al.38 have
They employed a porous Vycor glass membrane tube modeled the performance of membrane reactors having
with and without a Pt catalyst in the pores (which mixed conducting O2 permeable ceramic membranes for
exhibited Knudsen flow for H2 and N2 but had surface the very high temperature reactions:
diffusion and other effects for C6H6 and C6H12). For the
noncatalytic membrane, catalyst particles were packed CO2 T CO + 1/2O2 (11a)
in the tube. Their simulation results shown in Figure 9
indicate that at high space-time operations the cata-
lytic membrane reactor is superior to the inert mem- NO2 T NO + 1/2O2 (11b)
brane reactor which performs better than a conventional
equilibrium-limited reactor without any selective sepa- Removal of O2 through the membrane resulted in
ration of products. Propane dehydrogenation studies in dramatic improvements in conversion over the non-
a packed-bed membrane reactor by Ziaka et al.29 membrane tubular reactors.
employed a 40 Å γ-Al2O3 membrane in a porous multi- Armor8 has provided a critical review of the needs in
layered alumina tube containing Pt/γ-Al2O3 catalyst many dehydrogenation membrane reactor applications.
particles; the membrane reactor at a residence time of The problem areas are: defects in metallic membranes
10 s provided 1.8 times higher propylene yield than the at higher temperatures, phase changes in metallic
corresponding equilibrium conversion. membranes causing catastrophic failure, leakage be-
Numerical studies30 of catalytic dehydrogenation of tween the membrane and device, low surface area per
ethylbenzene using microporous ceramic membranes unit volume of commonly used membranes, severe
possessing Knudsen diffusion behavior indicate only a mass-transfer limitations, very low feed flow rates
g5% increase in styrene yield over the thermodynamic resulting in high residence times, carbon deposition on
limit by a hybrid system, i.e., a fixed-bed reactor membrane pores and surfaces, no method (currently
followed by a membrane reactor. Numerical analysis by available) for repairing defective membranes in situ, and
Mohan and Govind31 of a cocurrent packed bed mem- the low turnover number of commercially available
brane reactor suggest among others, the use of a dehydrogenation catalysts. The approach adopted by
membrane with high permselectivity to achieve large Rezac et al.39 is of great interest in this respect. They
values of conversion; the loss of reactants to the perme- propose existing plug flow reactors and heat-exchange
ate side through a membrane with not-too-high a equipment to be used in series with an optimized higher-
selectivity is a serious concern. Hsieh1 has provided a temperature stable polyimide-ceramic composite H2
detailed review of the many investigations based on removal membrane module. Thus, C4H10 dehydrogena-
porous/mesoporous membranes. tion is carried out at 480 °C, the product mixture is
2.1.2.3. Gas Permeation/Molecular Sieving. A cooled to 180 °C, and H2 selectively permeated through
considerable number of membrane reactor studies with the polyimide-ceramic composite membrane (H2/C4H10
gas-phase reactions have employed denser membranes selectivity > 75). Unreacted C4H10 is passed on to the
with selectivities much higher than Knudsen diffusion second-stage reactor after heat exchange and so on. This
membranes; these membranes include metallic mem- resulted in a substantial increase in conversion and a
branes of Pd, molecular sieve membranes, and dense high selectivity for the production of n-C4H8; membrane
silica membranes among others.1 Catalytic dehydroge- poisoning is also substantially avoided.
nation of ethanol to acetaldehyde in a palladium mem- 2.2. Separation of a Reactant from a Mixed
brane reactor with H2 removal through the membrane Stream for Introduction into the Reactor. Figure
increased ethanol conversion from 60% to nearly 90% 1 identified a particular function of the membrane as
with a commensurate rise in selectivity to acetaldehyde “purify reactant A from species F before addition” to the
Figure 10. Two reactions coupled through a gas membrane; membrane-assisted synthesis (reprinted from Van Eikeren et al.44 with
permission).
reactor on the left-hand side. The effect of this separa- water (having high pH 9-11) are partitioned through
tion on the reaction system is generally quite different the silicone membrane into the biological reaction
from that of a reaction product from the reaction medium. Reactors operated over 3000 h show very high
mixture. The purification may lead to pure A being reductions of the pollutants without any form of pre-
introduced into the reactor; a direct effect of this is treatment, pH adjustment, or dilution of the wastewa-
prevention of dilution of the reaction mixture. It can also ter. The membrane essentially isolates the bioreactor
lead to rejection of a class of compounds by the mem- environment from the vagaries of the industrial waste-
brane while reactant species (one or a class) may be water properties as the pollutants get extracted out into
introduced by the membrane preferentially into the the bioreaction medium for degradation by the ap-
reactor from the feed stream; the species rejected can propriate microorganisms. Successful pilot plant studies
inhibit the reaction. An additional possibility involves have been conducted using this technique.
simultaneous operation of two different reactions on two 2.2.3. Purify Organic Compound from a Synthe-
sides of the membrane wherein the products of one sis Medium. To prepare a concentrated aqueous solu-
reaction feeds the other and vice versa; the latter could tion of diltiazem malate by reacting diltiazem (sparingly
be in a coupled mode as well (to be explained later). soluble in water) with malic acid, a liquid membrane
2.2.1. Pure O2 from Air. Mixed conducting dense was utilized to recover diltiazem from an aqueous
ceramic membranes (see sections 2.3 and 2.9 as well) reaction mixture containing diltiazem, NaCl, NaHCO3,
allow O2 transport from air to a lower O2 partial etc. A contained liquid membrane of decanol was
pressure side without allowing N2 to be transported utilized by Basu and Sirkar43 to extract diltiazem into
through the membrane. When such a membrane is used the reaction zone where it reacted with L-malic acid in
with air on one side and CH4 on the other side, partial water to form diltiazem malate (in solution). When a
oxidation of CH4 to syngas can be carried out at a high very high concentration of L-malic acid is maintained,
temperature (∼800 °C) without contaminating the reac- the aqueous concentration of diltiazem malate achieved
tion gas mixture with N2. Further, the need for an O2 could be 3 orders of magnitude higher than the very low
plant is eliminated,40 improving the economics consider- concentration of diltiazem in the feed solution. The
ably. When a similar dense ceramic membrane in a membrane not only facilitated production of a highly
solid-electrolyte-cell reactor (see section 2.9) is used, concentrated and purified solution of diltiazem malate
HCN is produced in a tubular reactor fed with a NH3 + but also avoided two steps of solvent extraction and back
CH4 mixture as O2 permeates through the membrane41 extraction which was very problematic due to the orders
as an anion O2- into the reaction zone; in this case air of magnitude difference in the two aqueous phase flow
is fed on the outside of the tubular reactor to produce rates, namely, the very high flow rate of a very dilute
oxygen throughout the reactor length (function 2.3). Had feed solution and the very concentrated reactor effluent
air been used directly, the auxiliary byproduct of H2 + having a low flow rate.
CO, a high-quality fuel stream, would have been diluted 2.2.4. Coupling of Two Chemical Reactions. In
with N2. enzymatic methods for the production of pure enanti-
2.2.2. Purify Organic Pollutants from Wastewa- omers from achiral precursors using, say, dehydroge-
ter for Biodegradation. Point-source industrial waste- nase enzymes, specialized and costly reagents, e.g.,
waters containing a variety of priority pollutants were nicotinamide cofactors (NAD+ or NADH), are required.
often considered recalcitrant from a biodegradation A process for efficient and continuous regeneration of
perspective. These industrial wastewaters are fre- these nicotinamide cofactors by a chemical reaction
quently released from organic synthesis and contain isolated from the main reaction by a membrane parti-
high salts, extreme pHs, and residual catalysts, all of tion is illustrated in Figure 10.44 The membrane em-
which are either singly or jointly very harmful to the ployed is a gas membrane (see 2.1.1.5) utilizing a
growth of microbial cultures used for biodegradation. microporous hydrophobic polypropylene membrane whose
Brookes and Livingston42 have employed a silicone pores (∼0.03 µm) are gas-filled. In the main reaction
capillary membrane-based device to extract organic compartment on the left side, D-lactic acid is produced
priority pollutants from these demanding wastewaters. in an aqueous solution by catalyzing the reduction of
The biological reaction medium is circulated between a pyruvic acid using D-lactic acid dehydrogenase. The
bioreactor and one side of this membrane device. On NAD+ produced by this reaction reacts with ethanol to
the other side of the silicone capillary membranes flows regenerate NADH required for the main reaction. In an
the wastewater. Priority organic pollutants, e.g., aniline, adjacent compartment, sodium borohydride reduction
4-chloroaniline, 3,4-dichloroaniline, etc., from the waste- of acetaldehyde leads to ethanol which, being volatile,
enters the main reaction chamber whereas acetaldehyde to study the oxidative dehydrogenation of C2H6 to C2H4
produced in the regeneration of NADH in the main at 600 °C. Air was introduced via permeation through-
reaction chamber enters the adjacent chamber (through out the length of the reactor from the outside of the tube.
the membrane). Thus, the membrane allows separation Controlling the ratio of C2H6 to O2 was found to be
of the volatile species from the rest of the nonvolatile crucial to selectivity (with respect to CO2, CO, etc.) and
reaction mixtures in both compartments and feeds each conversion. At low-to-moderate C2H6 to O2 feed ratios
volatile species at a controlled rate into the adjacent (<1.5), the C2H4 yield in the membrane reactor exceeded
reaction chamber (function 2.3). that in a cofeed plug flow reactor (PFR) operated under
A weaker coupling between two reactions on two sides the same conditions by a factor of 3. At higher feed ratios
of a membrane (see Figure 1 for A + B T C + D and D (g2.5) the PFR performed almost as well as the mem-
+ F f G where the membrane controls the addition of brane reactor. In the membrane reactor, the reactant
reactant D to the permeate side reaction) was explored feed ratio (C2H6:O2) near the inlet to the reactor was
numerically by Itoh and Govind.45 On the basis of earlier quite high; as a result, the selectivity was very high.
proposals by Gryaznov and Itoh, they modeled the Continuous but slow addition of O2 further down the
catalytic dehydrogenation of 1-butene to butadiene in reactor ensured high C2H6 conversion as well, in the
the main packed bed reactor. The permeate side was membrane reactor.
being continuously fed with O2 in air which oxidizes the Lu et al.48 have carried out a modeling study of the
permeated H2 to produce water and liberate heat by an performance of a tubular reactor for oxidative coupling
exothermic reaction. This reaction is surface-catalyzed of methane to yield C2 hydrocarbons. Methane was fed
by the palladium membrane used to remove hydrogen at the reactor inlet along with inerts. O2 was introduced
from the main reactor. The heat so generated is con- into the reactor at different feed points along the reactor
ducted through the palladium membrane to the main length; in another configuration O2 was introduced
endothermic dehydrogenation reaction. The membrane continuously along the length via an O2-permeable
has many functions: separate product of main reaction, membrane acting as the reactor wall. In terms of
H2 (function 2.1); provide purified reactant (H2) to maximum C2 hydrocarbon yield, the membrane reactor
second reaction (function 2.2); add reactant H2 to second performed the best, the distributed feed reactors came
reaction in a controlled way (function 2.3); supply heat next (the larger the number of feed points, the better
to main endothermic reaction (function 2.10) and thereby the performance), and the cofeed reactor (CH4 and O2
control both reactions; and catalyze the second reaction together) performed the worst.
(function 2.7). To produce synthesis gas from CH4 via partial oxida-
2.3. Controlled Addition of a Reactant or Two tion, Balachandran et al.40 employed CH4 feed through
Reactants. Control of the reaction pathway is a major a membrane tube packed with a Rh-based reforming
concern in reaction engineering. Partial oxidation reac- catalyst. Air was supplied on the outside of the dense
tions of hydrocarbons are especially relevant here. In ceramic tube made of a La-Sr-Fe-Co-Zr-O system;
particular cases, possibilities of thermal runaway and the mixed conducting ceramic membrane tube allowed
catalyst poisoning do exist. In biodegradation processes pure O2 to be introduced along the reactor length at 850
for toxic organics, microorganism growth may be af- °C. CH4 conversion efficiency was >98%, CO selectivity
fected by inhibition from the toxic organics unless their was 90%, and H2 produced was twice that of CO.
concentrations are controlled. In an aerobic wastewater Zaspalis et al.49,50 have experimentally studied the
treatment process, high O2 utilization with minimum dehydrogenation of methanol in a microporous γ-Al2O3
waste to the atmosphere requires controlled but efficient membrane with methanol fed from one side and O2 from
introduction of O2 to the system. In processes using the other (Figure 1, reactants A and B introduced into
reactants having limited half-lives, e.g., ozonation of the pore from opposite sides). This arrangement avoided
wastewater or for water purification, efficient and direct contact between the two streams (i.e., an alcohol
localized introduction of O3 at a controlled rate can lead and an oxidant), thereby minimizing undesirable gas-
to higher O3 utilization. Using a membrane to introduce phase reactions. Further, the inner surface areas of the
a reactant or two in a controlled fashion in the reactor membranes were used. Zaspalis et al.50 used silver
can facilitate achievement of the desired reaction condi- particles deposited on the γ-Al2O3 membrane pore
tions. A number of examples provided below will il- surfaces; CH3OH was fed from one side and O2 from
lustrate the role of a membrane in such processes. the other so that activation of the Ag catalyst occurred
2.3.1. Gas-Phase Reactions. Gas-phase reactions simultaneously with the methanol conversion to form-
where reactants are introduced into the reaction zone aldehyde. This opposed flow mode of feeding two reac-
by membranes at a controlled rate(s) (see Figure 1, tants must be carried out in a controlled manner so as
purify reactant A from species F before addition) can not to decrease the selectivity for the desired product.
involve three types of membranes: (1) inert porous 2.3.2. Gas-Liquid Reactions. Catalytic reactions
membranes which provide no selectivity; (2) microporous between gas and liquid phases pumped concurrently
membranes with some selectivity; (3) nonporous/dense down a bed of catalyst particles in conventional reactors
membranes having much higher selectivity. The first encounter mass-transport limitations due to intrapar-
two types of membranes may employ catalysts in the ticle mass-transfer resistance, liquid film resistance,
pores; the nonporous membrane can be inherently liquid maldistribution, channeling, etc., apart from hot
catalytic. All three types of membranes have been spots and undesirable side reactions. To overcome these
studied with O2 as one of the reactants introduced in a problems, Cini and Harold51 have studied hydrogenation
controlled manner for partial oxidation or oxidative of R-methylstyrene (diluted in mesitylene) to cumene
dehydrogenation reactions. in a porous (6 µm) tubular γ-Al2O3 membrane impreg-
Tonkovich et al.46,47 employed 50 Å γ-Al2O3 (effective nated with a Pd catalyst on the pore surface area. H2
layer) or 200 Å R-Al2O3 membrane tubes packed with a was supplied on one side of the porous membrane and
magnesium oxide catalyst doped with samarium oxide the liquid reactant flowed on the other side of the
membrane (Figure 1). The results demonstrated an

efficient supply of the volatile reactant, H2, which was
also the limiting reactant when compared with the
catalyst pellets conventionally used in a trickle-bed
reactor. There were no operational difficulties encoun-
tered in the membrane-based operation; further, the
rate increased by up to a factor of 20. From a study of
hydrogenation of nitrobenzene to produce aniline in a
tubular γ-Al2O3 membrane (50 Å pore size) having a Pt
catalyst deposited on the pore surfaces, Torres et al.52
have also concluded that catalytic membrane reactors
are efficient for three-phase reactions as a result of the
easy access of the gas to the catalytically active phase. Figure 11. Membrane as a phase separator/contactor for the
Biodegradation processes to destroy organic and reaction-extraction processes.
inorganic contaminants in air or water employ organ-
isms in a biofilm attached to a support. The efficient rate, the removal efficiency decreased since the limiting
supply of nutrients, e.g., O2 and pollutants, to the substrate shifted from carbon to O2. At this time, the
biofilm is demanding without incurring excessive power solvent loss in the exit gas also increased. For given
consumption and with minimum loss of O2 to the impeller speeds, the membrane can be designed to
atmosphere. Hydrophobic porous hollow fibers mem- control the rate of introduction of organic pollutants to
branes are especially useful. For example, Brindle et the biomass-containing medium.
al.53 have immobilized a biofilm on the fiber outer 2.4. Nondispersive Phase Contacting. In many
diameter. The shell side is fed with, say, the wastewater reactions, aqueous and organic phases are frequently
containing NH4+ which is oxidized by the nitrifying used together. One phase is dispersed as drops in the
biofilm into nitrite and then nitrate; the tube side is fed other phase followed by coalescence after the process is
with pure O2. Exceptionally high O2 utilization efficien- over. This can be problematic if there are tendencies
cies were achieved via efficient interfacial oxygen for emulsification. Microporous/porous membranes can
transfer to the biocatalyst in the biofilm, even at low be particularly useful here since the two immiscible
O2 supply rates. Parvatiyar et al.54 have demonstrated phases can be kept on two sides of the membrane with
efficient biodegradation of toluene in a hollow fiber their phase interfaces immobilized at the membrane
membrane-based biofilter: air containing toluene was pore mouths. Solvent extraction is conventionally used
fed on the lumen side of porous polysulfone hollow fibers to isolate and concentrate dilute organic products
on the outer surface of which the biofilm was im- obtained from whole cell-based fermentation processes.
mobilized. Nutrients were supplied via an aqueous If the fermentation suffers from product inhibition, then
extraction of the product(s) during fermentation in-
stream on the shell side. High conversion of toluene was
creases the fermentor productivity. However, solvent
achieved because of efficient contact of the biomass
dispersion can lead to a phase-level toxicity58 problem
catalyst with O2 and toluene through the membrane
for the whole cells. Nondispersive phase contacting
pores at controlled rates of supply of the reactants in
using microporous/porous membranes can resolve this
the gas phase.
problem.
Noncatalytic gas-liquid reactions are employed using In nondispersive phase contacting employing mi-
O3 to destroy pollutants and bacteria in water purifica- croporous/porous hydrophobic membranes, the organic
tion and wastewater treatment processes. Since O3 has phase wets the membrane pores; the aqueous phase is
a very low solubility in water, kla (volumetric mass- maintained outside the pores at a pressure equal to or
transfer coefficient) controls the mass-transfer rate of higher than that of the organic phase. As long as this
O3 and thereby the reaction rate. Further, O3 has a very excess pressure does not exceed a breakthrough pres-
limited half-life in a moist gaseous phase. Membrane- sure, the aqueous-organic interface remains immobi-
based nondispersive ozonation studied by Shanbhag et lized on the aqueous side of the membrane with each
al.55,56 provides a much higher value of kla (g5 times) phase flowing on a particular side of the membrane.59,60
compared to conventional dispersive bubble-based ozo- For hydrophilic microporous/porous membranes, the
nation, eliminating the possibility of gas-phase degrada- aqueous phase is inside the pores; the organic phase is
tion of the unstable O3 in bubbles and efficiently kept outside the pores at a pressure higher than that
bringing O3 in contact with the aqueous pollutants along of the aqueous phase (Figure 11).
the length of reactor. This technique has been employed in four types of
2.3.3. Liquid-Phase Reactions. Lee et al.57 carried reaction systems: fermentor-extractor; enzymatic fat
out simultaneous biodegradation of the pollutants tolu- splitting; phase transfer catalysis; extractive membrane
ene and p-xylene in a completely mixed and convention- bioreactor for enzymatic resolution of isomers. The
ally aerated bioreactor using the microorganism advantages of these techniques are: no dispersion and
Pseudomonas putida. Under aerobic conditions, the therefore no need for coalescence; no need for density
microorganisms utilize toluene and xylene as carbon difference between the two phases; known interfacial
sources. The pollutant species (toluene and p-xylene) area; modular systems leading to easy scale-up; mass-
were introduced into the reactor in a controlled manner transfer rates independent of interfacial tension; no
through silicone capillary membranes. The removal flooding and no loading, allowing widely different phase
efficiency of these species increased at the beginning flow rate ratios to be used. Further, the membrane may
with an increase in the transfer rate of the pollutant provide a very large interfacial area per unit reactor
mixture (increased by, for example, the impeller speed volume.
and not by the aeration rate or the circulation rate of Nondispersive phase contacting advantages are also
the solvents in the capillary); however, beyond a certain present in gas-liquid systems already discussed under
Figure 12. Bifunctional nature of hydrophobic membranes. Shown above is the end view of the hollow fiber membranes with biocatalyst
particles surrounding them. (a) The membrane can be used to supply gas throughout the reactor volume while at the same time removing
carbon dioxide and hydrogen. (b) When a solvent is passed through the membrane lumen under correct pressure conditions, solvent
extraction can provide integrated product recovery while removing carbon dioxide (reprinted with permission from Frank and Sirkar.61
Copyright 1986, John Wiley & Sons).
the category of gas-liquid reactions (section 2.3.2) for

the controlled addition of one or two reactants. To
achieve nondispersive operation, one has to maintain
the proper pressure in each phase. For example, for
hydrophobic microporous membranes, the aqueous phase
is usually outside the pores (which are gas-filled) and
maintained at a pressure23 higher than that of the gas.
For hydrophilic membranes, the aqueous or organic
phase is usually inside the pores and the outside gas
phase is at a higher pressure. Figure 13. Enzymatic fat splitting in a hollow fiber bioreactor
2.4.1. Fermentor-Extractor. In fermentation pro- (reprinted with permission from Hoq et al.63 Copyright 1985,
cesses for producing ethanol, acetone-butanol-ethanol American Oil Chemists’ Society).
(ABE), etc., microporous hydrophobic hollow fiber mem-
branes have been introduced into tubular reactors in are removed in the oil phase. The membrane allows
which whole cells are immobilized on appropriate sup- aqueous-organic phase immobilization, enzyme im-
ports on the shell side; through the bore of the hydro- mobilization, and localized product separation into the
phobic hollow fibers, O2 is supplied in ethanol fermen- appropriate phase. Molinari et al.64 have shown that
tation and N2 is supplied in ABE fermentation.15,61,62 this reactor was better than a conventional emulsion-
The gases supplied help the cells grow, maintain the based reactor: the specific enzymatic activity was
needed anaerobic condition, and remove gases such as higher, the specific rate was more constant with time,
CO2 and H2 produced by fermentation. When a sub- and the two products were separated after the reaction.
stantial concentration of the desired product has been 2.4.3. Phase Transfer Catalysis. Stanley and
achieved in the shell-side broth, an organic solvent, Quinn65 have studied the reaction of bromooctane in the
passed through the fiber lumen at a pressure lower than solvent chlorobenzene with aqueous iodide to form the
that in the broth, extracts the products (e.g., ethanol, displacement products, iodooctane in the solvent chlo-
ABE, etc.) nondispersively (Figure 12). This reduces robenzene and aqueous bromide. The phase transfer
product inhibition and can lead to considerably in- catalyst (PTC), tetrabutylammonium (TBA) ion, was
creased volumetric fermentor productivity.16 Other in- introduced as the bromide salt in the organic feed. The
hibitory side products, e.g., acetic acid, etc., are simul- aqueous feed was passed on one side of the microporous
taneously extracted out. Although the fermentation- hydrophobic flat membrane of poly(tetrafluoroethylene)
extraction process has not been commercialized yet, the (PTFE); the organic phase wetting the membrane pores
membrane-based solvent extraction technique is already was passed on the opposite side at a pressure lower than
being commercially employed in at least two large that of the aqueous phase. Conventional emulsification/
installations (one in Europe and the other in Japan). coalescence problems were avoided in this PTC-facili-
2.4.2. Enzymatic Fat Splitting. In enzymatic split- tated reaction. Further, since the membrane area
ting of olive oil using hydrophobic microporous mem- (therefore the aqueous-organic interfacial area) is
branes and the enzyme lipase immobilized at the known, operation of the reactor can be carried out with
aqueous-organic interface63 (Figure 13), olive oil flows greater flexibility.
on one side of the membrane and wets the pores; an 2.4.4. Extractive Membrane Bioreactor for En-
aqueous buffer solution flows on the other side at a zymatic Resolution. In a multiphase/extractive en-
higher pressure which immobilizes the aqueous-organic zyme membrane reactor66 used for the industrial pro-
interface. The enzyme Candida cylindracea lipase, duction of diltiazem chiral intermediate, an asymmetric
spontaneously adsorbed at the aqueous-organic inter- water-filled hydrophilic hollow fiber membrane of a
face of the microporous membrane, catalyzes the fol- copolymer of acrylonitrile having a 30000 MWCO (mo-
lowing hydrolysis reaction: lecular weight cutoff) skin on the fiber internal diameter
is employed. The enzyme is immobilized in the porous
enzyme substructure from the shell side via ultrafiltration
triglycerides + 3H2O {\} (function 2.6). The organic phase in which the enzyme
glycerine + 3 fatty acids (12) has limited solubility flows on the shell side at a higher
pressure, immobilizing the aqueous-organic interface
Glycerine is removed in the aqueous phase; fatty acids at the pore mouth, thus containing the enzyme in the
water-filled substructure bounded by the membrane and L-aspartate-β-decarboxylase in the second stage,
skin impermeable to the enzymes. If the enzyme activity
is reduced substantially, the enzyme can be flushed out L-aspartate-β-decarboxylase
L-aspartic acid 98
easily and fresh enzyme loaded in the absence of the L-alanine + CO2 (13b)
organic phase. The organic flow is then restarted.
Stereoselective enzymatic hydrolysis of the undesired
Some enzymatic synthesis reactions are carried out
isomer from a racemic mixture of glycidic esters and its
in hollow fiber ultrafiltration membrane devices in what
removal in an aqueous buffer is carried out continu- is called the “perfusion reactor” mode. The enzymes or
ously. Here, the membrane provides reversible im- the whole cells are packed on the shell side with the
mobilization of the hydrolytic enzymes in the pores of shell side ports being closed off; substrate-containing
the hydrophilic asymmetric hollow fiber, immobilization feed is pumped through the tube side. The substrate
of the aqueous-organic interface on the fiber outside diffuses through the membrane pores to the shell side
diameter, reaction product extraction, and a very large and reacts with the enzymes/whole cells, and the
aqueous-organic interfacial area. smaller molecular weight products diffuse back to the
2.5. Segregation of the Catalyst (and Cofactor) tube side and are carried away. The enzymes or whole
in a Reactor. A membrane incorporated in a catalytic cells may also be kept in the tube side with both ends
closed off: the substrate-containing solution will then
reaction system can perform, among others, a number
flow into and out of the shell side. This latter mode is
of functions related to the catalyst. If the catalyst is
not commonly used. A review of membrane bioreactors
mobile in the reaction fluid, the membrane can prevent wherein the membranes segregate enzymes/whole cells
its escape from the system. If the catalyst is to be is available in Cheryan and Mehaia.6
immobilized with easy access to the reactants and Some enzyme-based reactions, however, require low-
convenient exit for the products, a porous/microporous molecular-weight coenzymes or cofactors in addition to
membrane structure may have the catalyst immobilized the main enzyme to carry out the overall enzymatic
on/within its structure (function 2.6). Alternately, the reaction. Typical examples of such coenzymes are nico-
membrane material itself may act as the catalyst tinamide adenine dinucleotide (NAD+), the reduced
(function 2.7). We focus here on cases where the catalyst form of NAD+, viz., NADH, NADPH (the reduced form
is mobile in the reaction fluid. Examples of such of NAD phosphate), etc. Figure 10 shows one such
catalysts are enzymes (and cofactors where applicable), reaction where the D-lactate dehydrogenase enzyme
whole cells, and homogeneous catalysts (in organic needs NADH for the conversion of pyruvate to D-lactate.
synthesis). The segregation of particulate heterogeneous In the process, the oxidized form of NADH, viz., NAD+,
catalysts by filters is not under consideration. is produced. Unless this NADH is regenerated from
NAD+, one has to continuously supply NADH from
The production of organic compounds by synthesis in external sources. NADH is costly ($1000/mol). A number
organic solvents or an aqueous-organic biphasic reac- of strategies have been explored to solve this problem
tion medium is very common. Many use homogeneous (see Cheryan and Mehaia6).
catalysts whose molecular weights are considerable The strategy shown in Figure 10 is an important one,
(e.g., in the range of, say, 300-800). Very few mem- viz., an additional enzymatic reaction employing a
branes are capable of retaining such species while regenerating enzyme, in this case an alcohol dehydro-
allowing the organic solvent to pass at appreciable rates. genase, to regenerate the NADH from NAD+. However,
Nanofiltration membranes, just becoming available, this requires a cosubstrate (e.g., ethanol) and yields a
have the necessary solvent resistance and rejection coproduct (e.g., acetaldehyde). To design a continuous
behavior in a few cases. Whu et al.12 have identified process to retain the enzymes as well as the cofactors
in the system by a membrane as the substrates come
some of these capabilities including retaining the ho-
into the reaction chamber and the product and coprod-
mogeneous catalysts while passing the organic solvents.
uct leave the reaction chamber, one needs a very specific
More extensive use of such nanofiltration membranes membrane. Figure 10 provides a special example for
will allow their use in organic synthesis for, among volatile cosubstrate and coproduct. We consider here a
others, retaining the homogeneous catalysts. separate situation, but one more commonly encountered;
The use of membranes to segregate enzymes used as viz., enzymes have molecular weights > 40000 Da and
catalysts for biosynthesis or biocatalysis is practiced in the substrates are 5-12 carbon sugars; note that the
a wide scale. Primarily, ultrafiltration membranes hav- cofactor molecular weights are around 700 Da. Thus, if
ing molecular weight cutoffs in the range of 5000- we use too tight of a membrane, the substrate introduc-
100000 are used to retain the enzymes (molecular tion into the reaction zone will encounter considerable
weight range 10000-100000 Da) in the CSTR reactor resistance, although NAD+ and NADH will be retained
by the membrane.
as smaller products are removed with water through
To solve the problem, Nidetzky et al.69,70 have selected
the membrane (Figure 2). Originally suggested by a charged nanofiltration (NF) membrane having -ve
Michaels67 and implemented as early as 1970,19 this charges on the surface (as shown in Figure 14) that
technique is used commercially for the production of preferably retains the cofactors almost completely with-
amino acids. Jandel et al.68 have illustrated continuous out binding the enzymes or cofactors. However, the NF
production of L-alanine from fumaric acid in a two-stage membrane had a size exclusion (∼1 kD) slightly higher
membrane reactor using the enzyme aspartase in the than those molecules having the molecular mass of the
first stage, cofactor; this ensured higher substrate fluxes. The
charge of the NF membrane (-ve) in this case allows for
aspartase cofactor retention since both NAD and NADH carry
fumaric acid + NH3 {\} L-aspartic acid (13a) negative net charge at pH values greater than 3. This
the same side; product solution goes out through the

membrane skin (see Jones et al.73 for a brief introduc-
tion to the literature of hollow fiber enzymatic reactors
employing this method of immobilization). An example
of this type of immobilization in the context of aqueous-
organic enzymatic processing has been illustrated in
section 2.4.4. Technique (2) whereby the enzymes are
immobilized on the pressurized ultrafiltration mem-
brane surface where an adherent gel layer of concen-
trated enzymes are formed was suggested by Drioli and
Scardi.74
Lipase enzymes (e.g., C. cylindracea) are spontane-
ously adsorbed (technique (3)) on a hydrophobic mi-
Figure 14. The substrates and products flow through the croporous polypropylene membrane surface and are
nanofiltration (NF) membrane, whereas the enzyme and the
coenzyme stay within the enzyme reactor. The membrane used is utilized in aqueous-organic enzymatic processing (sec-
asymmetric with a supporting matrix of polyetherketone and tion 2.4.2). Enzymes can be covalently bound to hydro-
polyethersulfone with a thin-coated layer of sulfonated polysulfone. philic membranes by the cyanogen bromide procedure.
The fixed charge density is ∼1.5 mequiv g-1. NAD+, nicotinamide This technique has been known for a long time and has
adenine dinucleotide; NADH, reduced NAD+; UF, ultrafiltration been used, for example, for binding chymotrypsin to a
(reprinted with permission from Nidetzky et al.69 Copyright 1996, Millipore filter membrane by Matson and Quinn75 in
American Chemical Society).
their membrane reactor studies. Site-directed mutagen-
esis has been introduced into enzymes so that the active
process has been demonstrated for the conversion of site of the enzyme is away from the surfaces of mem-
fructose to mannitol by mannitol dehydrogenase69 (or branes such as hydrophobic poly(ether)sulfone; im-
xylose to xylitol by xylose reductase70) as the cosubstrate mobilized mutant enzymes on such membranes have
glucose was converted by the regenerating enzyme, much higher activity than randomly immobilized en-
glucose dehydrogenase, to glucono-δ-lactone (ultimately zymes for catalytic conversions.76 Finally, it is possible
converted to gluconic acid in a separate device). Pilot to incorporate particular enzymes into the organic
scale results show a TTN (total turnover number) of casting solution for polymeric membranes and then
coenzyme to be in the range of 75000-100000. prepare a membrane by the phase inversion process
This approach to cofactor retention or segregation by wherein the final membrane has the enzyme dispersed
the membrane appears to be considerably simpler than throughout the membrane structure.
the earlier strategy of binding the cofactors to a mac- Chopped microporous hydrophobic or hydrophilic hol-
romolecule, e.g., poly(ethylene glycol), dextran, etc., low fibers have been used to grow whole cells in the fiber
which allowed a regular UF membrane to retain the lumen and the fiber outside surface.77 Such chopped
cofactor within the reactor.71 (A similar strategy72 has hollow fibers with immobilized cells were later utilized
been pursued for the enantioselective addition of diethyl in a tubular fermentor to carry out yeast-based ethanol
zinc to benzaldehyde using a homogeneously soluble fermentation for an extended period. The chopped fibers
catalyst retained by a solvent-stable polyaramide UF of appropriate lengths provide adequate nutrients as
membrane within the reaction vessel; the R,R-diphenyl- well as O2 to the immobilized cell mass; such a biore-
1-prolinol used as the chiral ligand was coupled to a actor could also have continuous lengths of hydrophobic
copolymer made from 2-hydroxyethyl methacrylate and microporous hollow fibers for gas supply and removal
octadecyl methacrylate (96000 MW) and the solvent as well as for in situ product extraction by dispersion-
used was hexane.) However, the charged NF membrane- free solvent extraction.16
based retention of NAD+ is at this time somewhat lower, Nonbiological synthesis of most products involve
around 0.65-0.85. Optimization of the NF membrane chemical and thermal conditions too harsh for almost
vis-à-vis the cofactor retention is still needed unless the all of the current polymeric membranes available;
product happens to have a very high value so that a therefore, the membranes investigated are primarily
lower TTN (1000-5000) may be tolerated. inorganic in nature, either ceramic or metallic. The
2.6. Immobilization of a Catalyst in (or on) a catalysts are predominantly oxides and/or metals. Of
Membrane. Four basic types of catalysts are relevant: the numerous oxides and metals used as catalysts,
(a) enzymes and (b) whole cells for biocatalysis; (c) membrane reactor studies, where the membrane had
oxides and (d) metals for nonbiological synthesis. Bio- immobilized catalysts on/in it, have primarily used those
catalysts will be considered first since their immobiliza- employed for dehydrogenation reactions, viz., platinum,
tion in (or on) the membrane was explored much earlier. palladium, etc., on metal oxides such as alumina and
Five techniques have been studied in varying degrees. silica.1 Examples are a Pt-impregnated Vycor glass
They are (1) enzyme contained in the spongy fiber tube28 for cyclohexane dehydrogenation, Ag-modified 40
matrix; (2) enzyme immobilized on the membrane Å γ-Al2O3 membrane obtained via wet impregnation of
surface by gel polarization; (3) enzyme adsorbed on the AgNO3, and then calcination under a reduced atmo-
membrane surface; (4) enzyme immobilized in the sphere for dehydrogenation of methanol.50 For the Claus
membrane pore by covalent bonding; (5) enzyme im- reaction,
mobilized in the membrane during membrane formation
by the phase inversion process of membrane making.
Of these, technique (1) is used commercially. An 2H2S + SO2 T 3/8S8 + 2H2O (14)
enzyme solution is ultrafiltered from the spongy side
(porous substructure) of an asymmetric ultrafiltration 350-nm R-Al2O3 membrane pores were impregnated
membrane to the skin side; this introduces the enzymes with aluminum nitrate and urea solution in water,
in the spongy matrix. Feed solution is also supplied from dried, and calcined.78 For multiphase hydrogenation
studies, palladium was deposited on microporous γ-Al2O3

deposited on 6 µm R-Al2O3 by soaking the tube in an
aqueous solution of ammonium tetrachloropalladium,
drying it, and calcining it.51 For nitrobenzene hydroge-
nation, the platinum catalyst was deposited in a 50 Å
γ-Al2O3 membrane tube by ion exchange with H2PtCl6.52
Although the effect of catalyst distribution in a mem-
brane-enclosed catalytic reactor has been studied,79 no
studies have been made with a variation of catalyst
distribution in the catalytic membrane itself. Figure 15. Concentration profiles around a cation-exchange
Polymeric membrane-based studies involving the membrane. Example at the beginning of run no. 11. Catalyzing
distribution of nanosized clusters or micron-sized par- solution, 0.9 g of H2SO4 in 180 mL of methanol; reacting mixture,
ticles in porous or nonporous polymeric membranes has 25 g of oleic acid and 75 g of methanol (reprinted from Chemsed-
dine and Audinos.82 Copyright 1996, with permission from Elsevier
been carried out at GKSS (Geesthacht, Germany) by Science).
Fritsch;80 10% Pd on charcoal powder particles (40 µm)
were used as catalysts and dispersed in the casting (anions, e.g., HSO-4, do not get transported through the
solution for the preparation of porous polyetherimide cation-exchange membrane). The cation-exchange mem-
(PEI) membranes. Transfer hydrogenation of N-CBZ- brane also separates a reaction product, viz., water, from
L-phenylalanine to L-phenylalanine was successfully the reaction mixture. Water is transported from the
carried out at low temperatures. Hydrogenation of reaction mixture to the catalyzing mixture, thus achiev-
propene to propane was carried out by using a nonpo- ing equilibrium shift to the right in reaction 15 (section
rous membrane containing nanoclusters of Pd in a dense 2.1). If solid ion-exchange beads were used as the
poly(amide-imide) membrane. The mechanism of such catalyst, such a function would not have been possible
a membrane function has been described in section 2.8. in a continuous process.
Bellobono et al.81 have described the performance of The acid form of a Nafion membrane is also capable
microfiltration membranes formed with 30% TiO2 as of carrying out both functions.83 The acid form of the
well as some 6% of particular photocatalysts. The membrane prepared by boiling tubular Nafion mem-
monomer, prepolymer blend with the semiconductor branes in concentrated HNO3 and then in water was
TiO2 and the photcatalysts were photografted onto a found to catalyze the esterification of methanol or
perforated polyester support; the pore size of photosyn- n-butanol to methyl acetate or butyl acetate, respec-
thesized membranes were 2.5-4 µm. The membranes tively, with acetic acid. These membranes were also
were placed coaxially with a UV lamp in a stainless steel found to be effective in separating water from n-butanol
casing having a mirror-like surface for reflection. The (water/alcohol selectivity ∼ 8.0; water/acetic acid selec-
solutions processed permeated through the membrane; tivity ∼ 9.0). The Cs+ form of the Nafion membrane was
before entering the reactor, the wastewater solutions found to have a much higher selectivity for both water/
were saturated with O2 or O3. alcohol (∼71) and water/acetic acid (∼149). Simulta-
2.7. Membrane Is the Catalyst. Most catalytic neous catalysis and separation by a catalytically active
membrane reactors for higher temperature operations membrane can potentially increase the membrane flux
employ ceramic membranes in the pores/micropores of for the products produced and removed since the reac-
which catalysts were deposited. The base membranes, tions occur within the membrane compared to a passive
e.g., silica and alumina, are generally not catalysts for membrane over which the solution is passed after the
the reactions studied. There are, however, a number of reaction is completed.
membranes which are inherently catalytic for particular Palladium is known to be a catalyst for hydrogenation
reactions; no catalyst needs to be deposited on or in the and dehydrogenation reactions. A palladium membrane
membrane. Particular examples are cation-exchange is also infinitely selective for H2. Thus, for dehydroge-
membranes, Nafion membranes, palladium membranes, nation reactions, a palladium membrane simultaneously
and zeolite membranes. acts as a catalyst and allows the product H2 to be
Consider a cation-exchange membrane and an esteri- removed through the membrane and obtained in the
fication reaction (15) in which a carboxylic acid, R1- pure form (see section 2.1 for references). Zeolites are
COOH (e.g., oleic acid), reacts with an alcohol, R2OH well-known as catalysts. Thin zeolite membranes are
(e.g., methanol), under the influence of an acidic catalyst being developed for the selective transmission of species
providing a proton: preferentially adsorbed or smaller than the pore size.
A number of reactions have been studied.2
Cat-H+ 2.8. Membrane Is the Reactor. In a membrane
R1COOH + R2OH {\} R1COOR2 + H2O (15) reactor, catalysts are used frequently. The membrane
may physically segregate the catalyst in the reactor
In the schematic shown in Figure 15, CH3OH and H2- (function 2.5) or have the catalyst immobilized in the
SO4 are on one side of the membrane and the reactants, porous/microporous structure or on the membrane
viz., CH3OH and oleic acid, are on the other side of the surface (function 2.6). The membrane having the cata-
membrane.82 In this case protons are the counterions lyst immobilized in/on it functions almost in the same
in the cation-exchange membrane introduced from the way as a catalyst particle in a reactor does except
left-hand side of the membrane; naturally, a layer of separation of the product(s) (function 2.1) takes place,
protons appears on the other membrane surface exposed in addition, through the membrane to the permeate
to the reaction mixture of the alcohol and the acid. These side. All such configurations involve the bulk flow of the
protons catalyze the esterification reaction. No separate reaction mixture along the reactor length while diffusion
catalyst, e.g., H2SO4, p-toluenesulfonic acid, etc., is of the reactants/products takes place generally in a
required, eliminating the need for catalyst separation perpendicular direction to/from the porous/microporous
after reaction if homogeneous catalysts are employed catalyst.
When the bulk flow of a reaction mixture takes place

through the membrane from one membrane surface to
the other, the membrane is the reactor. Generally, the
membrane in such a case will be porous/microporous to
reduce the pressure drop for practical flow rates. The
length of the pores/transport corridors is the reactor
length; the reactions may take place on the surfaces of
such macropores or there may be radial diffusion of
reactants into the micropores and products out of the
micropores into the main porous corridors where con-
vective motion occurs. The convective motion of the
reaction mixture through the membrane created by an
applied pressure drop across the membrane thickness
may involve Knudsen diffusion, Poiseuille flow, or a
Figure 16. Membrane and electrode assembly. The five regions
transitional regime for gaseous reaction mixtures. of the model are shown (not to scale) (adopted from refs 88 and
Such a reactor can have an exceptionally high value 89).
of reactor L/d for even thin membranes since d values
can be very small (from ∼0.2 µm to 4 nm). As a result, the shape of a thin disk of large diameter. A standard
extremely high conversions are possible, as shown by industrial reactor will have the shape of a long narrow
recent theoretical studies.84 Such a reactor can be tube.
identified as a pore flow through reactor (PFTR) since In an alternate strategy, Wu et al.87 had used a
each macropore that traverses the membrane thickness somewhat similar membrane as a reactor via interphase
is a reactor tube. Further, the mass-transfer resistance contacting. They employed PDMS membranes modified
encountered by the reactants to reach the catalytic sites appropriately and containing titanium silicalite zeolite
are significantly reduced because of the bulk flow as a catalyst. Oxyfunctionalization of n-hexane to a
through the membrane pores.85 Pina et al.85 have mixture of hexanol and hexanone was carried out by
experimentally demonstrated extremely efficient re- bringing in n-hexane and 30 wt % of an aqueous H2O2
moval of toluene and methyl ethyl ketone from air by solution: the silicone membrane acted as the reaction
low-temperature oxidation (100-320 °C) using a Pt/γ- medium and the reactor.
Al2O3 catalytic membrane operating under the Knudsen 2.9. Solid-Electrolyte Membrane Supports the
diffusion regime, supporting the earlier work by Pina Electrode, Conducts Ions, and Achieves the Reac-
et al.86 tions on the Surface. Solid electrolytes are solid-state
The membrane in this case does not possess appar- materials possessing ionic conductivity. The two ions
ently the separation capability characteristic of a mem- of the greatest relevance are H+ and O2-, although other
brane in a tubular reactor enclosed by a membrane. The ions, Cl-, F-, Ag+, etc., have been found to be conducted
membrane can still separate, for example, particles from as well. Solid polymer electrolytes such as perfluori-
a gas mixture as the gas mixture enters the membrane nated ionomer membranes (e.g., Nafion) allow transport
and is convected through the pores. One can have stacks of H+ ions in the presence of water and are often called
of disks of such membrane reactors with spaces between proton-exchange membranes. Solid solutions of oxides
the disks being used for product separation or reactant of di- or trivalent cations (e.g., Y2O3) in oxides of
addition or heat exchange. tetravalent metals such as ZrO2 can conduct O2- over
Fritsch80 deposited nanoclusters of catalysts such as a wide temperature range. Nonporous disks of such a
Pd, Pt/Ag, and Pd/Co in the size range of 1-3 nm in solid electrolyte can act as membranes for such ionic
polymeric membranes such as poly(amide-imide) and species and are quite useful for fuel cells and as O2-
poly(dimethylsiloxane) (PDMS). Reactions were carried conductors.
out in the flow through mode except that the mem- Consider a solid-polymer-electrolyte fuel cell: porous
branes were essentially nonporous. In this case, the graphite gas-diffusion electrodes hot pressed onto both
membrane treats every gas in the feed mixture accord- sides of a thin polymer membrane (e.g., Nafion) above
ing to the normal gas permeation selectivity displayed its glass transition temperature. This cell is fed with
in the polymeric membrane. For example, PDMS has a wet air on one side and wet H2 on the other side (derived
selectivity of 8.4 from pure gas measurements for C3H6 from the reforming of CH3OH in an adjacent reformer
(propene) over H2. Therefore, a feed gas ratio of at least and therefore contains CO2 also). The membrane and
8.4 for H2/C3H6 is required for complete conversion of the electrode assembly is schematically shown in Figure
C3H6 to C3H8. In fact, Fritsch80 has illustrated complete 16.88 The gas-diffusion electrode is made from porous
conversion of C3H6 to C3H8 using Pd cluster-containing graphite impregnated with a Pt catalyst. H2 gas diffuses
pore-free membranes of PDMS. The metallic catalytic through the porous electrode and is oxidized on Pt
nanoclusters were prepared during the polymeric mem- catalyst sites at the anode in a three-phase region
brane formation itself. (Figure 16) containing a polymer electrolyte, gaseous
Such thin membranes acting as the reactor are quite reactants, and a carbon matrix89
useful for fast exothermic reactions or for reactions
where one of the intermediates should be the main H2 T 2H+ + 2e- (16)
product. They possess very high catalyst surface area
per unit membrane area. However, the throughput per Protons transferred through the membrane react with
unit membrane area would be low. For example, Fritsch80 O2 at similar catalyst sites at the cathode to form water
has observed permeance values in the range of 1-3.2
× 10-6 cm3/cm2 s cmHg for PDMS membranes. The
reactor, therefore, has to have a large area and will have O2 + 4H+ + 4e- T 2H2O (17)
Thus, the membrane supports the electrodes on two

sides, transports H+, and achieves reactions on its
surfaces. The electrons in the external circuit obtained
from the chemical energy of the oxidation of H2 provide
the required current.
A solid ceramic proton conductor tube from a stron-
tium-ceria-ytterbia (SCY) perovskite of the form
SrCe0.95Yb0.05O3 has been employed with two porous
polycrystalline palladium films deposited on the two
sides of the ceramic tube to carry out NH3 synthesis at
atmospheric pressure.90 The two electrodes were con-
nected to an external galavanostat-potentiostat by
which the appropriate current was applied. At the
anode, gaseous H2 is converted to H+:
3H2 f 6H+ + 6e- (18)

Figure 17. Methane conversion to synthesis gas (Eltron Research
Inc., with permission91).
The protons are transported through the solid electro-
lyte to the cathode where the half-cell reaction
of the ceramic membranes. See Figure 17 from Eltron
+ -
N2 + 6H + 6e f 2NH3 (19) Research for CH4 conversion to synthesis gas.91 The
membrane in this case separates O2 from air through
takes place to complete the overall reaction the membrane, while supporting the catalyst for re-
forming CH4 and distributing O2 in a controlled fashion
N2 + 3H2 T 2NH3 (20) throughout the reactor. The study jointly sponsored by
DOE and Argonne National Laboratories40 used a
The reaction rate in this case was strictly controlled by rhodium-based partial oxidation catalyst inside the
the rate of H+ supply since H2 was the limiting reactant, mixed-conducting ceramic tube with O2 from the air
N2 being present in abundance. The membrane func- being present on the outside of the tube. Such arrange-
tions in this case again are quite similar to those in the ments also reduce the possibilities of an explosive
fuel cell example given earlier. At 570 °C and atmo- mixture.
spheric pressure, greater than 78% of the electrochemi- 2.10. Transfer of Heat. The most recent studies of
cally supplied H2 was converted into NH3. This rate membrane reactors have been in the context of the
exceeds that in a conventional catalytic reactor under petrochemical industry.8 They take place at higher
equivalent conditions of compositions, pressure, and temperatures (>200 °C) and there likely is a need for
temperature by 3 orders of magnitude. considerable heat transfer because the reaction may be
Using a yttria-stabilized zirconia-based (YSZ-based) exothermic or endothermic. Dehydrogenation reactions
conducting solid electrolyte which transports O2-, McK- studied frequently are endothermic. The membrane, if
enna et al.41 have studied the synthesis of HCN in a inert, is in a catalytic reactor, packed bed, or fluidized
solid-electrolyte-cell reactor. At the cathode, an O2- bed.92 Thus, the membrane may have to participate in
containing gas (containing N2) passes; adsorbed O2 gets heat transfer. Itoh and Govind45 have studied an en-
converted to O2- via dothermic dehydrogenation reaction on one side of a
palladium membrane coupled with an exothermic hy-
3
/2O2 + 6e- f 3O2- (21) drogen oxidation on the other side. Heat was transferred
from the oxidation reaction side to the dehydrogenation
which is then conducted to the anode surface. At the side through the membrane. They have concluded that
anode, a mixture of CH4 and NH3 is supplied, which heat transfer across the membrane leading to an
leads to the following reaction, adiabatic reactor resulted in a higher conversion than
what was possible under isothermal conditions.
CH4 + NH3 + 3O2- f HCN + 3H2O + 6e- (22) In actual practice, there will be one particular reaction
going on and heat is going to be supplied from a fired
producing HCN. In such a scheme, N2 in the air on the heater, molten salt baths, or thermal fluid jackets.
cathode side is rejected by the membrane. Therefore, the membrane is most likely going to be
For partial oxidation reactions using, for example, decoupled from the heat transfer process. A common
CH4, it is not necessary to apply a voltage. Instead, one configuration of some interest in a packed bed mem-
employs mixed conducting materials having both ionic brane reactor consists of multiple membrane tubes
and electronic conductivities. A gradient of O2 partial inside tubular catalyst beds, placed in turn, in another
pressure across the ceramic membrane induces a gradi- enclosure for heat exchange.7,92 Thermal expansion
ent of O2- in the same direction and electrons in the properties of the membrane tube, sealing at the header,
opposite direction. The mixed conducting membrane has and protection from abrasional damage from catalyst
a catalyst on the O2 side to facilitate the formation of particles are of much greater importance.8
O2-. The catalytic properties on the other surface of the 2.11. Immobilizing the Reaction Medium. Many
membrane allows CH4 to react in the manner of reactions are carried out in an organic solvent. These
include two-phase reactions, e.g., those encountered in
CH4 + O2- f CO + 2H2 + 2e- (23) phase transfer catalysis, gas-liquid reactions, etc. A
porous/microporous membrane can immobilize an ap-
generating the electrons which diffuse to the O2 side to propriate reaction medium in the pores. The two dif-
maintain charge neutrality in the ionic lattice structure ferent phases containing reactants can be brought to
Figure 18. Schematic diagrams for four configurations of a reactor where two membranes are separated by the reaction medium.
the two sides of the membrane. As long as the two feed 3. Functions of Multiple Membranes in a
phases are immiscible with the reaction medium, reac- Reactor
tants can partition into the reaction medium and react
and then the products can partition back into the Although more than two different types of membranes
flowing phases on opposite sides of the membrane. can be accommodated in a reactor, this section will
consider primarily the functions of only two membranes
Unfortunately, such a configuration, usually termed as
(different types or similar) in a reactor. There are cases
the supported liquid membrane (SLM), has limited
where two similar membranes carry out somewhat
stability93 because of a variety of reasons including a different functions or the same function vis-à-vis dif-
finite solubility of the reaction medium in the two ferent reactants/products. All such functional variations
different reactant-containing phases. Therefore, as dis- may be considered under two broad categories:
cussed in the next section, Guha and Sirkar,94 Chen et
al.,95 and Guha et al.11,96 have employed two different (1) Multiple membranes physically separated by the
hollow fiber membranes for bringing two reactant- reaction medium
containing streams into the membrane reactor while the (2) Multiple membranes existing as a laminate
reactants partitioned into the liquid reaction medium
contained (confined) in the shell side between the two We have already seen how many functions can be
sets of hollow fibers. implemented through a single membrane. In a practical
situation, only a few such functions (of all possible ones
Kim and Datta97 have used a porous support disk to appearing in Figure 1) are implemented via a given
immobilize a homogeneous catalyst in a high-boiling membrane. Obviously, when there is another mem-
organic solvent. However, they did not completely wet brane, the number of possible combinations increase
the pores so that the gas space was left in the pore. The greatly. Totally new functions may also become possible,
reaction was hydroformylation of ethylene to give pro- e.g., containing a reaction medium, separation of two
pionaldehyde. With an appropriate support membrane, product species, enrichment of product, and intensifica-
the capabilities of the reaction medium within the tion of a reaction. The particularity of a given chemical
membrane could be substantially enhanced. The only reaction will, however, limit the number of desired
issue is the lifetime of the reaction medium. functions. Thus, instead of considering all possible
combinations of functions possible in a two-membrane PFC medium. When one considers hydrophobic pollut-
reactor, we consider only particular cases that have been ants which are concentrated in the reaction medium by
studied experimentally and/or analyzed theoretically. extraction (section 2.2), one has now considerable
Under appropriate conditions, we briefly identify reac- process intensification. The thickness of the contained
tors having three or four membranes. First, we review PFC liquid layer is also important. By providing suf-
those systems where the reaction medium exists be- ficient thickness, one prevents O3 loss into water or the
tween two or more membranes. loss of a volatile organic pollutant into the gas phase.
3.1. Two or More Membranes Physically Sepa- It would be difficult to achieve it by immobilizing the
rated by the Reaction Medium. Of the many com- reaction medium in the pores of a single membrane,
binations possible, we will consider four types of systems since the required membrane thickness cannot be made
as illustrated in Figure 18. to order. Meanwhile, an extremely efficient pollutant
3.1.1. Homogeneous Catalytic Oxidation of Eth- destruction environment is created in the reaction
ylene. As shown in Figure 18a, the membrane reactor medium.
has two sets of microporous hydrophobic hollow fibers, This basic reactor configuration has been adopted by
one bringing in C2H4 (species A) while the other brings Shanbhag et al.99 to destroy volatile organic compounds
in O2 (species B). The catalytic reaction medium present (VOCs) from a gas phase via ozonation in a PFC liquid
on the shell side (in the manner of a hollow fiber- contained between three membranes in a reactor. One
contained liquid membrane of Majumdar et al.98) is an set of silicone capillaries in the reactor bring in a
aqueous solution of palladium chloride, cupric chloride, gaseous mixture of O3 in O2 which permeate into the
and cupric acetate. Chen et al.95 have studied the PFC phase on the shell side. Another set of silicone
oxidation of C2H4 to CH3CHO in such a system; the capillaries bring in the VOCs in air; the VOCs permeate
product CH3CHO can be removed through both gas through the silicone membrane and are dissolved in the
streams or through one of the gas streams. These PFC phase where they react with O3 and are destroyed.
investigators have shown that controlled and separate The nonvolatile reaction products are extracted into
introduction of C2H4 and O2 (function 2.3) through two water which flows through the bore of a third set of
separate membranes led to much better conversion porous Teflon capillaries in the reactor shell. The
compared to that achievable in a single hollow fiber volatile reaction products are removable through each
membrane-based reactor where both C2H4 and O2 were membrane. Use of silicone capillaries dramatically
simultaneously fed to the reactor in one gas stream. reduces the vapor-phase loss of PFC.
This two-membrane configuration may be replaced by 3.1.3. Efficient Mixing Membrane Reactor. In
a single porous membrane immobilizing the aqueous some biochemical processes, two reactants present in
reaction medium in the membrane pores; C2H4 and O2 two separate aqueous (say) solutions are to be mixed
may be separately introduced on two sides of the together. Direct mixing leads to further dilution of each
membrane. One has to be careful that the reaction reactant by the solvent present in the other incoming
medium properties remain unchanged with time. stream. However, if the scheme of Figure 18c suggested
3.1.2. Multiphase Ozonolysis of Organic Pollut- by Stanley and Quinn100 is adopted, then each mem-
ants. Figure 18b has two sets of hollow fibers: one set brane is used to introduce its own reactant, A and B,
of nonporous silicone capillaries through which gas B respectively, into the reaction liquid between the two
(in this case O3 in O2) is introduced into an organic inert membranes. Thus, the extent of dilution of species A
perfluorocarbon (PFC) reaction medium on the shell side as well as B is considerably reduced. One has to make
and another set of porous Teflon capillaries through sure, however, that the membrane for introduction of
which wastewater containing organic pollutants, e.g., A rejects species B and vice versa. The product P may
species A, flow. Pollutants are partitioned into the be permeable through both membranes. Here, each
contained liquid reaction medium at the aqueous- membrane carries out its own function of controlled
organic interface. The organic reaction medium concen- introduction of one reactant and rejection of the other.
trates the organic pollutants, especially the more hy- However, a combination of the two membranes achieves
drophobic ones, by extraction and allows O3 to react with a novel and important function, among others, i.e.,
these pollutants without the O3 being consumed by prevention of dilution of the two reactants.
nontargeted chemicals present in wastewater. 3.1.4. Partial Oxidation Process for Methane to
When first presented by Guha and Sirkar,94 the C2 Compounds. Oxidative coupling of methane in
system used two sets of microporous hydrophobic hollow membrane reactors is of considerable interest. Lu et al.48
fiber membranes instead of nonporous silicone capil- have made a numerical study for a cross-flow reactor
laries and porous Teflon capillaries. One could use just with a distributed feed of O2 and product removal. They
one set of microporous fibers and immobilize the reac- have modeled a number of reactor configurations. Their
tion medium in the pores. Both would lead to a high results show that distributed feed O2 could give rise to
loss, primarily by vaporization and also by solubilization much higher C2 yields than the cofeed reactor as long
of the perfluorocarbon (PFC) liquid which has a low but as the ratio of catalyst loading to initial methane flow
finite vapor pressure. The silicone membrane reduced rate was sufficiently high. On one hand, their calcula-
the vaporization-based loss of PFC liquid drastically. tions have further shown that although reactors with
Guha et al.11,96 have studied the system of Figure 18b optimally distributed O2 feed give much higher yield
using silicone capillaries and have demonstrated its than evenly distributed ones, the improvement is not
high efficiency in destroying most pollutants. The reac- significant. On the other hand, if a two-membrane
tion products partition back into the water phase and reactor is used (Figure 18d) where one membrane is
the gas phase on the two sides. This system avoids direct used for the O2 feed and the other for C2 product
ozonation of pollutants in wastewater where most of the removal, higher C2 yields could be obtained than that
O3 is wasted. Further, O3 has a very low solubility in in a single membrane reactor with distributed O2 feed.
water, whereas it has 14 times higher solubility in the However, if the membrane for C2 product removal is also
Figure 19. Different membrane laminate-based reactors.

permeable to other species as well as C2 products, low 3.2.1. Product Separation and Enrichment. Fig-
permeability of methane is critical to the achievement ure 19a illustrates a membrane laminate consisting of
of high C2 yield. One must recognize that the develop- a two-layer sandwich of a permselective membrane and
ment of such a membrane reactor structure at the a catalytic membrane.101 On the permselective side, a
higher temperatures needed is a formidable task. feed solution containing reactant R (e.g., an ester) and
3.2. Multiple Membranes in a Laminate. Here, we inerts flows. Reactant R partitions into the permselec-
consider a number of cases: tive membrane (e.g., an organic nonpolar liquid mem-
3.2.1. Product separation and enrichment brane, the feed solution being aqueous) and then
3.2.2. Separation of multiple products partitions into the aqueous environment of the catalytic
3.2.3. Supported liquid-phase catalytic membrane membrane where the reaction R f P leads to the
reactor-separator for homogeneous catalysis product P. The product P, in this case an acid, is rejected
by the nonpolar liquid membrane and therefore ac- Kim and Datta97 have suggested using a porous support
cumulates in the sweep aqueous liquid flowing on the disk to load the catalyst by evaporation of a volatile
other side. If the sweep liquid flow rate is much lower solvent in the catalyst solution impregnated into the
than that of the feed, it is possible to increase the pores. During the reaction, an essentially nonvolatile
concentration of P in the sweep stream to a very high solvent, dioctylphthalate, is used. To protect this solu-
value compared to the feed concentration of the reactant tion from being forced out, a second nonselective mem-
R. Thus, the membrane laminate allows simultaneous brane is used (Figure 19c) whereas the first membrane
separation of the product from the feed stream and its must be freely permeable to all the reactants but not
considerable enrichment in the product stream. Any the product. With a low flow rate of the sweep stream
inert in the feed, if it partitions through the liquid in contact with the second membrane, the product
membrane, will be present in the product stream at a concentration can be raised to a high level compared to
concentration lower than that in the feed. Matson and the feed concentration level (as in Figure 19a,b). Un-
Quinn101 have experimentally demonstrated this con- fortunately the membrane employed as the first mem-
cept by resolving a racemic aqueous mixture of a D,L- brane was a ultrafiltration-type membrane of 50 Å pore
ester where the L-ester was converted to the L-acid size; therefore, it had only a Knudsen diffusion-type
enzymatically in the catalytic membrane containing the selectivity (1.44) between ethylene and propionaldehyde.
enzyme chymotrypsin. The product stream was highly If a reaction
enriched in the L-acid.
3.2.2. Separation of Multiple Products. The con- AfBTC (26)
cept may be illustrated by considering the schematic of
Figure 19b. Reactant A in the feed solution is highly is desired to be carried out where C is the desired
permeable though the permselective membrane exposed product, then the schematic of Figure 19c can be
to the feed solution. On the other side of this membrane, employed, except that membrane 2 must also reject the
reactant A enters a catalytic membrane in an aqueous intermediate product B and be freely permeable to
environment and undergoes the following reaction: product C (but not to reactant A). This has been termed
as the “trapped intermediates” membrane bioreactor
AfB+C (24) since the intermediate B is trapped between the mem-
brane 1 and 2 and its increasing concentration forces
It so happens that product C is also very permeable the reaction in the direction of C.101 Contrast this
through the permselective membrane but product B is scheme with those of reactions 4a and 4b where the
rejected by this membrane. On one hand, if now the intermediate B is the desired product:14 the membrane
sweep solution on the other side of the catalytic mem- plays quite a different role for species B in these two
brane has a flow rate much lower than that of the feed, cases.
product B concentration will be very high in this sweep
stream. On the other hand, the concentration of C will 4. Concluding Remarks
be essentially the same in both solutions; however, most
of C will appear in the feed stream since its flow rate is A membrane in a reactor is capable of performing a
much higher. Thus, products B and C are effectively wide variety of useful functions. These capabilities can
separated; further, product B concentration is also much result in the performance levels of the membrane
higher than that of A. reactor and the process to be considerably higher than
those of a conventional reactor under similar operating
Matson and Quinn101 have demonstrated the utility
conditions. Membrane functions that are particularly
of this concept by carrying out the hydrolysis of N-
useful and unique in this regard are separation of
acetyl-L-tyrosine ethyl ester into the corresponding acid
product(s) from the reaction mixture, separation of a
(product B) and ethanol (product C); the catalytic
reactant from a mixed feed for introduction to the
membrane employs chymotrypsin covalently bound to
reactor, controlled addition of a reactant or two reac-
a Millipore filter to catalyze this hydrolysis. The perm-
tants, and a solid-electrolyte membrane acting as sup-
selective membrane was an immobilized liquid mem-
port for the electrodes, allowing the conduction of ions
brane of decanol through which alcohol, product C, as
and having reactions on its surfaces. When compared
well as the reactant ester are freely permeable.
with conventional reactors, there are additional unique
The bipolar ion-exchange membrane described in
functions, e.g., nondispersive phase contacting, segrega-
section 2.1.1.6 may also be considered as a membrane
tion of a catalyst (and cofactor) in a reactor, catalyst
laminate where a cation-exchange membrane and an
immobilization, etc., which impart considerable opera-
anion-exchange membrane have been joined together,
tional and economic advantages to devices in reaction
even though there is some space between them where
processes employing membrane(s). Simultaneous achieve-
water comes in from both sides. Further, under the
ment of a number of such functions by a membrane in
applied potential difference between the two electrodes
a reactor has made membrane reactors quite attractive.
(Figure 7), water dissociates in this space and two
Even when the membrane is located outside the reactor
products of the reaction, H+ and OH-, are effectively
and connected to it in a recycle mode, such coupled
separated by the two ion-exchange membranes.
reaction-separation processes provide considerable im-
3.2.3. Supported Liquid-Phase Catalytic Mem- provements in the overall reaction performance.
brane Reactor-Separator for Homogeneous Ca- Many investigations on membrane reactors have been
talysis. If instead of a covalently bound enzyme catalyst conducted in biochemical processing, petrochemical
in the membrane, a homogeneous catalyst is necessary, applications, and environmental pollution control. A few
say, for the hydroformylation of ethylene to form pro- processes employing polymeric membranes have been
pionaldehyde by the reaction commercialized. Utilizing more than one membrane in
a reactor imparts additional functional capabilities. For
H2 + CO + CH2dCH2 f CH3CH2CHO (25) effective large-scale utilization of the diverse functional
capabilities of a membrane in a reactor, considerable (17) Fournier, R. L. Mathematical Model of Microporous Hol-
research and development on membrane lifetime, avail- low-Fiber Membrane Extractive Fermentor. Biotechnol. Bioeng.
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(18) Vasudevan, M.; Matsuura, T.; Chotani, G. K.; Vieth, W.
membrane poisoning, and membrane cost are essential. R. Membrane Transport and Biocatalytic Reaction in an Im-
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higher temperature applications where the hurdles for 506, 345.
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Enzymatic Saccharification of Cellulose with Simultaneous Re-
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Ind. Eng. Chem. Res.

1999, 38, 3715-3737 3715

Membrane in a Reactor: A Functional Perspective

1. Introduction gated in the literature is useful in the Introduction

Figure 2. Schematic of a recycle-based configuration of a coupled

membrane in a given reactor is capable of all functions

Figure 3. Membrane “sandwich”: (1) UF membrane, (2) coarse

Figure 5. Reactor performance as a function of enzyme concen-

selectivity is achieved when the semibatch reactor is

Figure 6. Influence of the variation of the membrane area to the

from 35% to 70%, moving the yield from 21% to 63%.13

membrane (Figure 1). The results demonstrated an

the category of gas-liquid reactions (section 2.3.2) for

the same side; product solution goes out through the

studies, palladium was deposited on microporous γ-Al2O3

When the bulk flow of a reaction mixture takes place

Thus, the membrane supports the electrodes on two

3H2 f 6H+ + 6e- (18)

Figure 19. Different membrane laminate-based reactors.

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