Mini-review

Received: 29 April 2013 Revised: 11 June 2013 Accepted article published: 20 June 2013 Published online in Wiley Online Library: 24 July 2013

(wileyonlinelibrary.com) DOI 10.1002/jctb.4155

Membrane microreactors for catalytic reactions

Xiaoyao Tana and K. Lib∗

Abstract
Membrane microreactors (MMRs) combine the advantages of membrane separation and microreactors such as high area/volume
ratio, enhanced mass and/or heat transfer, improved catalytic efficiency without equilibrium limitation, good operational safety
and design flexibility. This article presents a short review of recent developments in MMRs and in particular highlights their
applications in catalytic processing. The structure and fabrication of MMRs, the incorporation of catalysts with membranes, the
flow characteristics as well as their applications in a variety of catalytic processes are presented. The prospects and challenges
of MMRs in catalytic processing are also presented and discussed.

c 2013 Society of Chemical Industry

Keywords: microreactor; membrane; hollow fibre; catalytic processing

INTRODUCTION avoided. Moreover, the selectivity and permeance of miniature

The membrane reactor is a device combining membrane-based membranes can be enhanced due to miniaturization compared
separation and a chemical reaction in a single unit. The integration with conventional membrane units.3 In recent years, considerable
of membranes in a catalytic reactor allows either selective removal research has been carried out on MMRs.4 – 7 This article provides
of one of the products from the reaction zone continuously, an interpretative review of recent advances and identifies trends
thus circumventing thermodynamic equilibrium, or alternatively for the future of MMRs especially for catalytic reactions.
dosing one of the reactants in a controlled manner so as to achieve
optimal axial concentration profiles.1 The selective product
removal may achieve supra-equilibrium conversions and improve CONFIGURATIONS AND FABRICATION OF
product purity, whereas the selective addition of a reactant may MMRs
enhance product selectivity and achieve improved temperature MMRs are characteristics of microchannels with anchored catalysts
control and safety by eliminating hot spots. In some cases, it is for reactions and miniature membranes to perform separation,
also helpful to prevent catalyst poisoning and deactivation by which are formed on porous ceramic or metal supports. Based on
removing undesirable byproducts from the reaction zone. the configuration and architecture of the reactor, MMRs can be
A microreactor is a minimized chemical reactor with a classified into two categories, i.e. the plate-type and the tubular
characteristic length of 1–1000 µm.2 The miniaturization of a type.
reactor offers numerous advantages such as high surface area per
unit volume, improved heat and mass transfer properties due to
the short transport distances, enhanced reaction performances (i.e. Plate-type MMRs
higher conversion, selectivity and yield), and better energy and In plate-type MMRs, the micro-channels with deposition of
material utilization with the result of more efficient production catalysts are fabricated on a porous silicon- or stainless steel
and less pollution. Other advantages include simpler process (i.e. SS 316L) plate, while the membrane layer is deposited on
optimization, rapid design implementation, easier scale-up the back of the plate to perform separation (membrane–catalyst
through replication and better safety. Rapid mass and heat transfer plate) as shown in Fig. 1(a). In some cases, the membrane layer,
rates obtained under a laminar flow regime makes microreactors an which also shows catalytic activities is deposited on the wall of the
excellent choice especially for fast or highly exothermic reaction microchannels for simultaneous reaction and separation (catalytic
systems, where external heat and mass transfer processes are membrane), as shown in Fig. 1(b). Both designs hold the promise
important. of many potential applications as MMRs, electrochemical cells and
A membrane microreactor (MMR) combines the advantages sensors.
of both the membrane reactor and the microreactor, leading
to greatly intensified production processes. It allows the reactor
∗
to work not only under optimum reaction conditions due to Correspondence to: K. Li, Department of Chemical Engineering and Technology,
Imperial College London, South Kensington, London SW7 2AZ, UK.
rapid mass and heat transfer rates but also at significantly E-mail: [email protected]
lower operating temperature and/or using less catalyst than in
conventional reactors. The miniaturization makes it possible to a The State Key Laboratory of Hollow Fibre Membrane Materials and Processes,
obtain a large membrane area in a small compact unit by simply Department of Chemical Engineering, Tianjin Polytechnic University, Tianjin
300387, China
assembling small membrane pieces. As a result, the problems that
plague large membrane units such as deformation and cracks due b DepartmentofChemicalEngineeringandTechnology,ImperialCollegeLondon,
1771

to accumulated stresses during processing and operation can be South Kensington, London SW7 2AZ, UK

J Chem Technol Biotechnol 2013; 88: 1771–1779 www.soci.org

c 2013 Society of Chemical Industry
 www.soci.org X Tan, K Li

Microchannels Catalyst Catalytic membrane

porous support

Membrane
(a) (b)

Figure 1. (a) Membrane–catalyst plate; (b) catalytic membrane plate.

Several fabrication technologies are currently available for the adhesion and reasonable uniformity could be obtained. Cui et al.13
manufacture of plate-type microreactors and microseparators,8 used a different method to incorporate catalysts in the silicon
and the micro-electro-mechanical system (MEMS) is the most microchannels: 20 nm Ti was first sputtered and oxidized as the
popular one. It is a mature technology with existing production adhesion layer and catalyst carrier before a 20 nm thick Pt layer
infrastructure in the form of semiconductor foundries. This was sputtered as the catalyst. Ti oxidation using NaOH and H2 O2
fabrication method also allows other devices such as pressure proved to be a simple and very effective way to obtain catalyst
transducers, flow controllers and temperature control apparatus to carrier compared with anodic oxidation. It is noteworthy that in
be easily incorporated in the system to form micro-systems capable some cases the membrane itself may function as the catalyst for
of analyzing or synthesizing chemicals. However, there is a material the reactions, i.e. catalytic membrane, thus extra catalysts are not
restriction to silicon and design limitation to two dimensions. required.4,14
Another process called LIGA which includes the essential steps The incorporation of zeolites in MMRs as catalyst or membrane
of X-ray lithography using synchrotron radiation, electroplating with controlled particle size, crystal morphology, layer thickness
of metal to form the mold, injection molding of plastics, and (3–16 µm) and film orientation can be achieved by various
electroforming with the desired metal has been used for high strategies, i.e. zeolite powder coating, localized zeolite growth
aspect ratio micromachining. This process is relatively complex and etching of zeolite–silicon composite film.8 Among these
and requires sophisticated equipment. Other methods such as methods, the powder coating technique is relatively simple and
multi-lamination and direct-write ‘dip pen’ nanolithography (DPN) straightforward, and can easily be used to incorporate other
techniques are also becoming more popular because of increasing types of catalyst in addition to zeolites. The zeolite loading
maturity of the technology. DPN employs scanning tunneling and can be controlled by changing the concentration of zeolite in
atomic force microprobes to write patterns up to 30 nm line width. the slurry and through repeated coating of the microchannels.
One of the important issues in catalytic MMRs is the proper However, the coating adhesion is poor and the zeolites may be
incorporation of active catalysts within microchannels. Packing easily removed. Using chemical grafting and polymer adhesives
a powdered catalyst in the microchannels presents obvious can significantly improve powder adhesion, but they can also
difficulties in terms of pressure drop and flow distribution. interfere with the function of the catalyst and the operation of the
Therefore, the catalyst is usually deposited as a thin catalytic reactor. Comparatively, the zeolite film growth method is more
coating on the surface of the microchannels in MMRs. These advantageous since it yields a highly adherent catalytic layer, a
coatings should not only provide enough catalytic loads, but binder is not needed (meaning that the layer is 100% catalyst) and
also have high mechanical stability to withstand extremely severe the considerable experience gathered in the synthesis of zeolite
conditions in terms of temperature and mechanical shock and films allows regulation of film thickness and crystal orientation.15
good accessibility of the reactants to the catalyst (high external When the microchannels are coated with a 1–2 µm layer of zeolite,
surface/volume ratio in the coating). Ideally, the catalyst should almost all of the catalyst is available for reaction at a fraction
be an integral part of the MMR. For metal catalysts, the most of the pressure drop. In addition, the large surface to volume
direct approach is to deposit a thin layer of active metal (e.g. Pd, ratio provides excellent contact between reactants and catalyst,
Pt, Ag) using thermal deposition, chemical vapor deposition or thus minimizing bypass, and a better approach to matching
sputter coating methods. However, since the geometric surface of permeation and reaction rates. Figure 2 demonstrates the process
the microchannels is unable to provide sufficient specific surface for the preparation of a micro-scale zeolite membrane and catalyst
area for impregnating catalysts, which are necessary for most of on porous stainless steel plates through the local hydrothermal
the catalytic reactions, chemical treatments and deposition of thin synthesis method. The film thickness, crystal morphology and
catalytic coatings in most cases must be applied on the surface intergrowth can be controlled by modulating the seed population,
of the microchannel walls. In this case, a porous oxide layer is synthesis chemistry and hydrothermal treatment conditions.
formed by anodization or a suspension coating method (wash- A clear advantage of micro-scale zeolite membranes is the
coating technique), followed by impregnation with a solution higher probability of obtaining a defect-free interface, since this
of the metal precursor.9 – 12 The wash-coating process generally probability increases for smaller membrane areas. Furthermore,
includes the following four steps: (1) synthesis of the oxide powder micro-scale membranes are amenable to preparation methods
slurries containing binders such as acetic acid and acrylic acid; (2) that use high-throughput synthesis procedures.16
pre-treatment of the platelet support including cleaning and Iglesia et al.17 studied the preparation of MFI layers on
annealing; (3) coating deposition; and (4) drying and calcination microchannels by three different synthesis methods: hydrothermal
at elevated temperature. The binders in the slurry play important synthesis, seeded hydrothermal synthesis and steam assisted
roles in the properties of coatings like coating adhesion and crystallization. They found that the seeded hydrothermal method,
catalytic activity. By optimizing the slurry preparation parameters with careful control of gel dilution and temperature, was adequate
such as particle size, viscosity, solid loading and/or binder content, for controlling the thickness of the zeolite layer, resulting in well-
1772

porous oxide films at a desired thickness of 25 µm with good intergrown zeolite coatings on the channel surface. On the other

wileyonlinelibrary.com/jctb

c 2013 Society of Chemical Industry J Chem Technol Biotechnol 2013; 88: 1771–1779
Membrane microreactors for catalytic reactions www.soci.org

Fabricate microchannels
Prepare zeolite on porous metal plate
nanocrystal seeds

Clean multichannel plate

Recover and purify
nanocrystal seeds
Functionalize and seed
the backside of the
multichannel plate
Prepare zeolite
nanocrystal seeds
Hydrothermal regrowth
of zeolite membrane
Recover and purify
nanocrystal seeds
Coat zeolite catalyst into
microchannels

Remove organic template

by thermal calcination

Figure 2. Process flow diagram for the preparation of membrane-catalyst plate.

hand, the steam assisted crystallization method allowed better inside the porous wall, while the separation is achieved by the
control of the location of the zeolite film and provided better porous hollow fibre itself or by the membrane formed on the outer
accessibility to the catalyst by maintaining the individuality of the surface of the hollow fibre, as shown in Fig. 5. Such catalytic hollow
zeolite crystals, but the synthesis time to obtain a zeolite layer was fibre membranes can be easily fabricated into MMRs, then called
as long as 8–16 days. In addition to MFI, other zeolites including hollow fibre membrane microreactors (HFMMRs).
TS-1, ZSM-5, MOR, ETS-10, BEA, LTA and FAU have been grown onto In the fabrication of HFMMRs, porous hollow fibre membranes
different supports such as ceramic monoliths, brass, molybdenum with asymmetric structures are first prepared through a phase-
and stainless steel microchannel reactors.18 – 22 Figure 3 shows inversion/sintering technique, which has been described in many
the CsX zeolite catalyst coating on the microchannels and the recent publications.26,27 The microstructure of the hollow fibres
NaA zeolite membrane grown on the back of the porous SS-316L can be tailored for different applications by modulation of
multichannel plate.23 the suspension composition and the spinning parameters.28,29
For the etching of zeolite composite film method, a highly Aran et al.6,16 developed porous Al2 O3 HFMMRs with various
oriented zeolite film is first grown on to the silicon wafer, which geometrical parameters for gas–liquid–solid (G-L-S) reactions.
can be achieved by seeding the wafer with colloidal zeolites The Pd–Al2 O3 catalyst was coated on the inner surface of
followed by hydrothermal synthesis. Etching is then performed the α-Al2 O3 hollow fibres (Fig. 5(a)) using the following steps:
to form microchannels.8 Using this fabrication methodology, the (1) aqueous γ -Al2 O3 suspension was prepared using PVA and
shape, morphology, quantity and individual locations of the zeolite acetic acid as the additives; (2) the suspension was introduced
catalysts can be precisely engineered to optimize the microreactor into the hollow fibre lumen and then emptied at a controlled
performance. filling/emptying speed; (3) the hollow fibre was dried and calcined
to form γ -Al2 O3 coatings; (4) the γ -Al2 O3 coated hollow fibre was
Tubular MMRs immersed into a Pd precursor solution followed by calcination
In tubular MMRs, the porous support for loading microchannels in O2 and subseqent reduction in H2 atmosphere. Perfluorinated
and separation membranes is of a tubular configuration. The octyltrichlorosilane (FOTS) was gas-deposited on the α-Al2 O3 layer
microchannels for fluid flow may be formed due to the small size of to make it hydrophobic so as to fit G-L-S reactions. In other work,25
the tube or distributed within the tube wall, while the separation Aran et al. fabricated a stainless steel HFMMR to improve the
membrane is usually coated on the outer surface of the tube. mechanical stability. Carbon nanofibres (CNFs) were grown by a
Yamamoto et al.24 constructed a simple MMR just by inserting chemical vapor deposition method inside the porous structure
a stainless-steel rod into a tubular membrane reactor to form of the stainless steel hollow fibres as catalyst support. Palladium
microchennals for dehydrogenation of cyclohexane to benzene, catalyst was then immobilized in the CNFs by the immersion-
as shown in Fig. 4. They investigated the effects of microchannel drying-calcination process. A dense polymer layer was coated on
size by varying the diameter of the stainless-steel rod and found the outer surface to serve as the membrane for gas separation, as
that the yield with the biggest rod was approximately two times shown in Fig. 5(b).
higher than that without any rods, which could be attributed to Recently, a novel Pd-MMR design based on asymmetric ceramic
the increase in the surface area per volume of the Pd membrane. hollow fibre membranes was developed by Li’s group for hydrogen
When the membrane tube is reduced in diameter to a certain production.30 – 32 As shown in Fig. 6(a), YSZ or Al2 O3 ceramic
level, i.e. ID < 1 mm, it becomes hollow fibre and the fibre lumen hollow fibre membranes with open finger-like pores on the inner
may take effects of microchannels on the fluid flow. The catalyst can surface side were fabricated by a modified phase inversion and
1773

be coated on the inner surface of the hollow fibre or impregnated sintering technique. A Pd/Ag membrane was deposited on the

J Chem Technol Biotechnol 2013; 88: 1771–1779

c 2013 Society of Chemical Industry wileyonlinelibrary.com/jctb
 www.soci.org X Tan, K Li

(a) (b)

10 µm

300 µm (c)

10 µm

Figure 3. SEM pictures of (a) top and cross-section views of a membrane–catalyst plate with (b) CsX catalysts coated on the microchannels and
(c) 6 µm thick NaA separation membrane.23

α-Al2O3 Stainless Porous

tube Wall
steel rod Liquid
Pd
Porous
membrane Glass coating wall
Catalyst
Liquid
Dense polymer
layer
Gas NFs
Gas
Catalyst
(a) (b)

Figure 5. Schematic diagram of the catalytic hollow fibre membrane

(a) with coated catalyst;6 and (b) with impregnated catalyst, respectively.25
+3H2 +3H2

to the low thermal conductivity. However, the mechanical stability

H2 H2
of single ceramic hollow fibre membranes is relatively low, limiting
maximum pressure differentials for driving mass transfer across
metal films and providing significant challenges to fabricating
mechanically stable membrane reactors.
Utilization of porous ceramic honeycomb monoliths could real-
ize large networks of microchannel membranes for gas separation
with superior mechanical stability. By increasing the thickness of
Figure 4. Microreactor with a Pd membrane for dehydrogenation of the membrane support to 500–1000 µm, limitations associated
cyclohexane to benzene.24
with mechanical stability can be effectively removed, while use
of high-porosity ceramic supports minimizes introduction of
outer surface of the hollow fibres by the electroless plating substantial mass transfer resistances (concentration polarization).
method for hydrogen separation. Catalysts such as 30%CuO/CeO2 Kim et al.33 fabricated Pd membranes within an extruded cordierite
for water–gas shift (WGS) or 10 wt% NiO/MgO– CeO2 for ethanol (2MgO-2Al2 O3 -5SiO2 ) honeycomb monolith for hydrogen purifica-
steam reforming (ESR) were impregnated in the finger pores tion. Washcoating with micropowder γ -Al2 O3 was first performed
by a sol–gel coating technique to form catalytic hollow fibre to realize cylindrical surfaces for subsequent deposition of palla-
membranes. As can be seen, the finger-like pores can be viewed as dium films. A second nanopowder γ -Al2 O3 layer washcoated to
microchannels with the diameters of around 10 µm although they provide a uniform surface for deposition of defect-free palladium
are not as regular as MEMS-manufactured ones. Each catalyst- films. Electroless plating under kinetic-limited conditions was
impregnated hollow fibre is actually a catalytic microreactor finally conducted to deposit thin (8 µm) defect-free palladium
made up of hundreds of microchannels (dp ∼10 µm) that are films with crystallite sizes of ∼2 µm. The resultant two-channel
perpendicularly distributed around the lumen of the fibre. This Pd-membrane system exhibited hydrogen flux of 1.0 − 5.5×10−3
catalytic HFMMR possesses advantages as an on-board hydrogen mol m−2 s−1 at 350◦ C and hydrogen-to-helium selectivities of
generator for vehicular applications due to its compact feature 40 − 360. They also presented a novel microreactor design strategy
and its ability to produce pure hydrogen for a fuel cell system. to employ resulting mini-channel membrane networks together
1774

Another advantage is that minimal heat losses can be realized due with precision-machined distributors capable of addressing each

wileyonlinelibrary.com/jctb

c 2013 Society of Chemical Industry J Chem Technol Biotechnol 2013; 88: 1771–1779
Membrane microreactors for catalytic reactions www.soci.org

Pd/Ag membrane
(b)
H2 H2 H2
(a)

CO2 CO2 CO2

H2 H2 H2

H2 + CO2 H2 + CO2 H2 + CO2

Catalyst

CO2
C2H5OH+3H2O

Figure 6. Hollow fibre membrane reactor for hydrogen production.

individual channel as part of a thermally integrated portable hydrogen was obtained. For the ESR reaction, yttria stabilised zir-
reformer for high-purity hydrogen production. This technolgy conia (YSZ) hollow fibres were used as substrate for the deposition
would provide an inexpensive and rapid means of constructing of Pd/Ag membrane on the outer surface of the hollow fibre and
MMRs. impregnation of 10wt% NiO/MgO-CeO2 ESR catalyst inside the
hollow fibre. Results indicated that the flow rate of hydrogen pro-
duced in the hollow fibre MMR was three-fold higher than that in
APPLICATIONS OF MMRs the fixed-bed reactor and two-fold higher than that in the hollow
As mentioned above, MMRs benefit the fast and thermodynami- fibre microreactor despite less of the catalyst being used. During
cally limited reactions for which mass transfer limits the reaction the operation, high purity hydrogen was obtained at a yield of
processes to a large extent. Due to their compact nature and high more than 53% of the total hydrogen produced in the ESR reaction.
degree of control, the MMRs are especially suitable for portable A MEMS-based Pd-MMR was demonstrated for one-step
chemical processing. Table 1 summarizes typical applications of conversion of benzene to phenol by Ye et al.5 As shown in
MMRs for catalytic reactions. Fig. 7, the benzene and oxygen mixture and the hydrogen
feeds are introduced on oppoisite sides of the membrane. The
Pd-MMRs for the hydrogenation/dehydrogenation reactions active hydrogen species, which appear on the surface via the
The palladium-based membranes possess high hydrogen Pd membrane, can easily react with molecules of oxygen and
permeation fluxes and 100% hydrogen selectivity, and have form active species like HO* or HOO* radicals. Then the active
found considerable applications in a variety of dehydrogenation species attack benzene, and hydroxylation occurs readily to form
reactions.34 – 36 Applying microchannels in the membrane reactors phenol. No additional catalyst is needed since the Pd acts as both
can accelerate the thermodynamically limited dehydrogenation of catalyst and separator. Since the Pd-MMRs had a smaller dimension
cyclohexane to benzene leading to significantly improved yields.24 and a larger ratio of surface-to-volume compared with Pd-MRs, the
concentration of reactant gases is almost uniform on the surface of
C6 H12 ⇔ C6 H6 + 3H2 (1) the membrane, and as a result, active hydrogen species can be used
more effectively for hydroxylation of benzene on the Pd surface of
Significant interest in the development of portable systems the Pd-MMRs. Therefore, the Pd-MMRs can finish transformation
powered by polymeric proton exchange fuel cells (PEMFCs) drives of dominating reaction from oxidation to hydroxylation of the
the development of Pd-MMRs for hydrogen production, since benzene and achieve the largest yield of phenol at lower ratio
they can integrate fuel reforming and hydrogen purification of H2 /O2 . The phenol yield of 20% and benzene conversion of
within a single small device, and produce high purity 54% were obtained at 200◦ C. In addition, the products distribution
hydrogen with high hydrogen recovery.37,38 Wilhite et al.39 in the Pd-MMRs was very different from the Pd-MRs. Phenol
demonstrated a composite-catalytic micromembrane, comprised and dihydric phenols dominated products distribution in Pd-
of a palladium–silver micromembrane washcoated with reforming MMR, and the hydrogenation products of cyclohexane (C6 H12 )
catalyst (LaNi0.95 Co0.05 O3 ) to combine partial oxidation of and cyclohexanone (C6 H10 O) from benzene and phenol were not
methanol with hydrogen purification. A highest extracted detected in the Pd-MMR, while the hydrogenation products from
hydrogen yield of 32.4% was achieved at an oxygen-to-fuel feed benzene and phenol were main by-products in the Pd-MRs.
ratio of 0.43.
Recently, Garcı́a-Garcı́a et al. and Rahman et al. carried out
ethanol steam reforming (ESR) and water–gas shift (WGS) reaction Zeolite-MMRs for Knoevenagel condensation and selective
in catalytic hollow fibre Pd-MMRs.30 – 32 For the WGS reaction, oxidation reactions
asymmetric Al2 O3 hollow fibres produced by a phase-inversion Zeolite membranes have been applied for gas permeation and
and sintering technique were employed as a single substrate for separation, and liquid pervaporation. A clear advantage of micro-
coating the Pd membrane on the outer surface and impregna- scale zeolite membranes is the higher probability of obtaining a
tion of the 30%CuO/CeO2 catalyst in the porous fibre wall. The defect-free interface, since this probability increases for smaller
results indicated that the catalytic hollow fibre MMR performed membrane areas.40 In zeolite MMRs, the zeolites are incorporated
much better than the fixed-bed reactor and the catalytic hollow as catalyst for reaction and membrane for separation as well
fibre microreactor under the same conditions. A conversion of as structural material of the reactors. Reactions conducted
17% higher than the corresponding thermodynamic equilibrium in MMRs mainly include Knoevenagel condensation4,41,42 and
1775

conversion was achieved in the hollow fibre MMR and high purity selective oxidation reactions.43 Supra-equilibrium conversion may

J Chem Technol Biotechnol 2013; 88: 1771–1779

c 2013 Society of Chemical Industry wileyonlinelibrary.com/jctb
 www.soci.org X Tan, K Li

Table 1. Application examples of the MMRs

Reactor configuration Membrane Reaction Results Refs

Annular tube Pd/Al2 O3 Dehydrogenation of Yield increased by 200% 24

cyclohexane to benzene
Plate with coated catalyst Pd-Ag Partial oxidation of YH2 = 34.2% with improved 39
methanol to H2 conversion and selectivity
Hollow fibre with Pd/Al2 O3 Water–gas shift (WGS) 17% above the equilibrium 7,30
impregnated catalyst conversion
Hollow fibre with Pd-Ag/YSZ Ethanol steam reforming 53% H2 yield higher than 32
impregnated catalyst (ESR) that in ESR
Oxidized porous silicon plate Pd Hydroxylation of benzene to 20% phenol yield and 54% 5
with no catalyst phenol benzene conversion
Stainless steel plate with ZSM-5 and/or NaA Knoevenagel condensation Supra-equilibrium 4,23
coated zeolite catalyst zeolite conversion
Stainless steel plate with ZSM-5 zeolite Oxidation of aniline by H2 O2 Improved yield and 43
coated TS-1 catalyst to azoxybenzene selectivity
Hollow fibre with coated Pd Porous Al2 O3 Reduction of nitrite (NO2 − ) Drastically enhanced 6,16
catalyst by H2 in water performance
Hollow fibre with Porous stainless steel Reduction of nitrite (NO2 − ) Improved performance 25
impregnated Pd catalyst by H2 in water

reaction in MEMS-based stainless steel MMRs. The ZSM-5 and NaA

miniature membranes grown on the back of the multichannel
plate were used for selective membrane pervaporation of water
byproduct from the condensation reactions. A hybrid NaA-CsNaX
bilayer membrane catalyst film was coated on the microchannels
to further enhance the reaction conversions and selectivity. The
undesired reaction was suppressed by using catalyst film instead of
powder, because the smaller external catalyst surfaces in contact
with the solution prevented further product reaction. Supra-
equilibrium conversion and high product purity were obtained by
Figure 7. Working principle of the Pd membrane for direct hydroxylation selective removal of water during the reaction. Besides, the catalyst
of benzene. life was also prolonged by removing the water byproduct, which
is a poisoning substance for zeolite catalyst. The MMR consistently
be obtained in the former, while the latter displays improved performed better than the microreactor and the packed-bed
performance against catalyst deactivation. membrane reactor at comparable catalyst loading and residence
The Knoevenagel condensation reaction is an important C–C
time. The best reaction yield was obtained by locating the CsNaX
bond forming reaction commonly used for the production
catalyst immediately adjacent to the membrane because the
of fine chemical intermediates and pharmaceuticals. It
involves the condensation of methylene compounds (i.e. composite NaA–Faujasite micromembrane successfully combined
Z–CH2 –Z’ or Z–CHR–Z’) with ketones or aldehydes,4 which is the good catalytic properties of Cs–Faujasite for Knoevenagel
constrained by unfavorable thermodynamics. A typical example is condensation reaction and the excellent separation properties of
Knoevenagel condensation reaction between benzaldehyde and NaA membrane for water resulting in enhanced performance. An
ethyl cyanoacetate to produce ethyl 2-cyano-3-phenylacrylate. increase in microchannel height-to-width aspect ratio contacted a
larger volume of the reaction solution with the catalyst, resulting
in a proportional increase in the reaction conversion.
Wan et al.43 investigated the selective oxidation of aniline by
hydrogen peroxide to azoxybenzene in a multichannel MMR,
with or without water removal, employing TS-1 nanozeolite
as catalyst. The reaction was conducted at different residence
times and temperatures. A hydrophilic ZSM-5 membrane was
In addition to the condensation product (2-acetyl-3-
used to selectively remove water from the reaction mixture
phenylacrylic acid ethyl ester), numerous byproducts may also be
by membrane pervaporation. The results indicated that catalyst
produced from various competing side reactions. Selective water
removal by membrane pervaporation may significantly increase deactivation was reduced during the reaction. An improvement
the reaction conversion and suppress side reactions leading to in the product yield and selectivity towards azoxybenzene was
overall increase in product yield and purity. Furthermore, the also observed. Increasing temperature was beneficial for both
enormous surface area-to-volume ratio and the short diffusion yield and selectivity, but beyond 340 K, microreactor operation
distance facilitate the selective removal of water by-product and was ineffective due to bubble formation and hydrogen peroxide
1776

less catalyst deactivation. Yeung et al.23 investigated the above decomposition.

wileyonlinelibrary.com/jctb

c 2013 Society of Chemical Industry J Chem Technol Biotechnol 2013; 88: 1771–1779
Membrane microreactors for catalytic reactions www.soci.org

Catalytic MMRs for G-L-S reactions the flow in the microchannels of MMRs is predominantly
MMRs can be applied for heterogeneously catalyzed gas-liquid- laminar. Secondary ‘molecular’ effects can be significant as the
solid (G-L-S) reactions. Catalysts are incorporated with the characteristic length decreases to the point where the properties
membrane by coating on the membrane surface or depositing like density, temperature and velocity are not continuous functions
inside the membrane wall. In operation, the gas and liquid phases of position, and the fluid–surface interaction becomes more
are introduced into the reaction zone from opposite sides of important than the fluid–fluid interactions. At this moment, the
the membrane and meet precisely on the catalyst layer. Such continuum assumptions for the normal reactors are no longer valid
MMR systems exhibit many advantages such as: (1) the gas, and a velocity slip at boundaries has to be implemented to describe
liquid and solid phases can be independently controlled during the fluid flows. Furthermore, the selective permeation of a fluid
the process and the gas–liquid interface is well-defined and component through the membrane also influence significantly
stabilized by the membrane; (2) the gaseous reactant is distributed the overall velocity field in the MMRs. Therefore, the flow in MMRs
homogeneously along the full reactor length, which makes the is far more complicated than that in macro-scale reactors.
reactors advantageous for processes with low gaseous reactant The departure of the flow in microchannels from the continuum
solubility or high gas consumption, preventing possible depletion assumption can be measured by the Knudsen number, i.e. the
of this reactant in the reactor; (3) mass transfer limitations in the ratio fo the mean free path λ to the hydraulic diameter hD of the
liquid phase (reactant diffusion from bulk to the catalytic wall) can microchannel.44
be overcome by miniaturizing the characteristic dimension of the
reactor channels. √
Aran et al.6,16,25 used porous Al2 O3 and stainless steel hollow λ 3ν π MW / (2RT)
Kn = = (5)
fibre MMRs for the removal of nitrite (NO2 − ) from water by the hD 2hD
catalytic hydrogenation reaction over Pd catalysts, where the
aqueous solution of NO2 − was pumped into the lumen while the
gaseous hydrogen reactant was delivered to the shell side of the where MW is the average molecular weight of the fluid, R is the
reactor. The nitrite comes in direct contact with hydrogen in the universal gas constant, T is the absolute temperature, and ν is the
catalytic regions to form nitrogen. kinematic viscosity.
Pd It is generally agreed that the continuum assumption holds only
2NO− −→ N2 + 2OH− + 2H2 O
2 + 3H2 − (3) with Kn ≤10−3 and the flow can be described by the application of
the Navier–Stokes equations with their customarily used no-slip
Pd boundary conditions, i.e. the velocity at the wall is zero, whereas the
2NO− −→ 2NH4+ + 4OH−
2 + 6H2 − (4) behavior of the fluid for Kn ≥10 has to be described with molecular
level modeling. For most microchannel systems, Kn is less than 0.1
In the porous α-Al2 O3 hollow fibre MMR a Pd-γ -Al2 O3 catalyst
and the fluid flow is in the slip regime (10−3 ≤Kn ≤0.1).45 In this
layer was coated on the inner surface of the fibres,6,16 as shown
case, the fluid flow still can be described using the continuum
in Fig. 5(a). In order to realize liquid flow inside the intrinsically
conservative equations, but slip boundary conditions must be
hydrophilic porous reactor channel and to obtain a stabilized
incorportated since velocity slip and temperature jump may occur
gas–liquid–solid interface, the α-Al2 O3 hollow fibre support
at the microchannel surfaces.46
was hydrophobized through the treatment with a fluorinated
Computational modeling and simulation are important tools
alkyl trichlorosilane (FOTS), whereas the Pd-γ -Al2 O3 catalyst
layer remained hydrophilic. Experimental results showed that for studying the flow and reaction behavior of MMRs. Alfadhel
the performance of the reactor could be drastically enhanced and Kothanre44 set up a mathematical model to describe
by tuning the surface properties, and remained high even at low isothermal microfluidic steady flow in a silicon MMR employing
partial pressures of hydrogen due to the high transfer efficiency. As the Navier–Stokes equations with first-order tangential velocity
the thickness of the catalyst support layer was increased, the NO-2 slip at the walls to account for high Knudsen number and fluid
reaction rate per Pd-catalyst decreased indicating internal mass permeation drift velocity boundary conditions for fluid permeation
transfer limitations. Reducing the inner diameter of the reactor through the membrane. The effect of fluid permeation through
and also integration of slug flow enhanced the performance the membrane and the Knudsen number on the velocity profile
by improving its external mass transfer. In the stainless steel and pressure drop were evaluated. An analytical solution of
HFMMR,25 carbon nanofibres (CNFs) were grown inside the hollow the velocity profiles in MMRs, incorporating both slip and fluid
fibres as the support for Pd catalyst as shown in Fig. 5(b). The permeation at the boundary was derived. The general pressure
outer surface of the porous hollow fibre was covered with a dense gradient formula derived in this work is in agreement with results
gas permeable polymeric coating in order to stabilize the G-L-S from published literature for the limiting cases of no slip (Kn → 0)
interface. Results proved high nitrite reduction performance of the and no permeation. Jani et al.47 provided a 2D CFD model using
reactors, even without the presence of palladium or additional the continuum conservative equations with a normal parabolic
hydrogen supply. In addition to the high surface area and velocity profile (no-slip boundary condition) to study the mass
mechanical strength, the intrinsic reducing properties and catalytic transport and heterogeneously catalyzed reactions in a porous
activity of the reactors make them very suitable for hydrogenation hollow fibre MMR. Boundary conditions were derived which
reactions. represent the reactant concentration at the microreactor inner wall
as a function of catalytic layer properties to obtain an optimized
reactor geometry. An optimum in conversion was found for varying
FLUID FLOW IN MMRs the catalytic membrane layer thickness. Simulation results also
Microreactors have a small characteristic length (or hydraulic indicated that reactor miniaturisation significantly improves the
1777

diameter) which makes Reynolds number (Re) very small, hence mass transfer and reaction performances in the MMRs.48

J Chem Technol Biotechnol 2013; 88: 1771–1779

c 2013 Society of Chemical Industry wileyonlinelibrary.com/jctb
 www.soci.org X Tan, K Li

CONCLUSIONS AND CHALLENGES ACKNOWLEDGEMENTS

MMR represents a promising technology for chemical processing The authors gratefully acknowledge research funding from the
in the case that external mass and heat transfer limitations cannot Natural Science Foundation of China (No. 20676073, 21176187),
be ignored. It exhibits great potential for process intensification Tianjin Natural Science Foundation (11JCZDJC23400) and the
by integrating multiple process streams within one compact unit Royal Academy of Engineering Research Exchanges with China
for mass and heat transfer applications, thus is especially suitable and India Scheme.
for portable applications.49,50 Although considerable progress has
been made in recent years in this field, there are still many
challenges to be faced by the MMRs:
REFERENCES
1 Deshmukh SARK, Heinrich S, Mörl L, van Sint Annaland M and Kuipers
JAM, Membrane assisted fluidized bed reactors: potentials and
(1) Design and fabrication of commercially viable MMRs require hurdles. Chem Eng Sci 62:416–436 (2007).
low-cost and standardised fabrication techniques. The 2 Mills PL, Quiram DJ and Ryley JF, Microreactor technology and
fabrication of microchemical systems remains extremely process miniaturization for catalytic reactions – a perspective on
difficult, nonstandard, and based on customized designs recent developments and emerging technologies. Chem Eng Sci
that use microfabrication techniques borrowed from the 62:6992–7010 (2007).
3 Leung AYL and Yeung KL, Microfabricated ZSM-5 zeolite
microelectronics industries. Alternative fabrication methods micromembranes. Chem Eng Sci 59:4809–4817 (2004).
amenable to mass production such as casting or stamping 4 Lau WN, Yeung KL and Martin-Aranda R, Knoevenagel condensation
must be developed to reduce their cost and increase reaction between benzaldehyde and ethyl acetoacetate inmi-
their productivity. In addition, strategies for precise and croreactor and membrane microreactor. Micropor Mesopor Mater
115:156–163 (2008).
selective incorporation of active elements such as catalyst, 5 Ye S-Y, Hamakawa S, Tanaka S, Sato K, Esashi M and Mizukami F, A
membrane, adsorbent, contactor and sensors must be one-step conversion of benzene to phenol using MEMS-based Pd
established. Using the phase inversion–sintering technique membrane microreactors. Chem Eng J 155:829–837 (2009).
enables simplification of the fabrication process and reduction 6 Aran HC, Chinthaginjala JK, Groote R, Roelofs T, Lefferts L, Wessling M
of the costs of hollow fibre type MMRs significantly, but it still and Lammertink RGH, Porous ceramic mesoreactors: a new approach
for gas–liquid contacting in multiphase microreaction technology.
has to be improved so that the morphology and microstructure Chem Eng J 169:239–246 (2011).
of the hollow fibre membranes can be controlled. 7 Garcı́a-Garcı́a FR, Kingsbury BFK, Rahman MA and Li K, Asymmetric
(2) Highly resistant materials are requred to fabricate microchan- ceramic hollow fibres applied in heterogeneous catalytic gas phase
nel structures that are stable under reaction conditions and reactions. Catal Today 193:20–30 (2012).
8 Wan YSS, Chau JLH, Gavriilidis A and Yeung KL, Design and fabrication
to reduce cost. Substitution of stainless steel for silicon is of zeolite-based microreactors and membrane microseparators.
one step toward cost reduction, but this is currently offset by Micropor Mesopor Mater 42:157–175 (2001).
the cost of micromachining and fabrication. Ceramics such 9 Conant T, Karim A and Datye A, Coating of steam reforming catalysts in
as cordierite, mullite (3Al2 O3 –2SiO2 ), alumina (Al2 O3 ), etc. are non-porous multi-channeled microreactors. Catal Today 125:11–15
ideal to reduce heat losses due to low thermal conductivity, (2007).
10 Conant T, Karim A, Rogers S, Samms S, Randolph G and Datye A,
but the brittleness especially under harsh reaction environ- Wall coating behavior of catalyst slurries in non-porous ceramic
ments limits their practical application. Utilization of porous microstructures. Chem Eng Sci 61:5678–5685 (2006).
ceramic monoliths to realize large networks of microchannel 11 Men Y, Gnaser H, Zapf R, Hessel V and Ziegler C, Parallel screening
membranes is a promising way to obtain superior mechanical of Cu/CeO2 /γ -Al2 O3 catalysts for steam reforming of methanol in a
10-channel micro-structured reactor. Catal Comm 5:671–675 (2004).
stability. 12 Stefanescu A, van Veen AC, Mirodatos C, Beziat JC and Duval-Brunel
(3) Better materials need to be developed to address problems E, Wall coating optimization for microchannel reactors. Catal Today
of membrane stability, and to reach the ultimate goal of 125:16–23 (2007).
high permeation rate combined with high permselectivity. 13 Cui T, Fang J, Zheng A, Jones F and Reppond A, Fabrication of
Although inorganic membranes can be used in the high microreactors for dehydrogenation of cyclohexane to benzene.
Sensor Actuat B - Chem 71:228–231 (2000).
temperature and chemically harsh environments, their long- 14 Caro J, Catalysis in micro-structured membrane reactors with nano-
term stability under technical conditions has to be improved designed membranes. Chinese J Catal 29:1169–1177 (2008).
significantly. Using a Pd membrane made by CVD or a Pd–Ag 15 Kwan SM, Leung AYL and Yeung KL, Gas permeation and separation in
alloyed membrane made by sputtering is capable of improving ZSM-5 micromembranes. Sep Purif Technol 73:44–50 (2010).
16 Aran HC, Klooster H, Jani JM, Wessling M, Lefferts L and Lammertink
the stability of Pd-MMRs for hydrogen production. On the other RGH, Influence of geometrical and operational parameters on the
hand, the layered and delaminated porous materials such as performance of porous catalytic membrane reactors. Chem Eng J
zeolites, silicates, titanosilicates and MOFs can be promising 207/208:814–821 (2012).
membrane and catalyst candidates used in MMRs due to their 17 Iglesia O, Sebastián V, Mallada R, Nikolaidis G, Coronas J, Kolb G, Zapf R,
Hessel V and Santamarı́a J, Preparation of Pt/ZSM-5 films on stainless
high aspect ratios.51 – 54 steel microreactors. Catal Today 125:2–10 (2007).
(4) The theory and fundamental physical understanding of 18 Sebastián V, de la Iglesia O, Mallada R, Casado L, Kolb G, Hessel V
microchemical systems remains an area of ongoing research. and Santamarı́a J, Preparation of zeolite films as catalytic coatings
Computational modeling and simulation are important tools on microreactor channels. Micropor Mesopor Mater 115:147–155
(2008).
for the design and operation of microreactors. But adequate
19 Zamaro JM and MiróE, Confined growth of thin mordenite films into
models involve many physical parameters that can only be microreactor channels. Catal Commun 10:1574–1576 (2009).
found experimentally and thus are classically complicated 20 Mies MJM, Rebrov EV, Jansen JC, de Croon MHJM and Schouten JC,
because of the coupling of heat, mass, and momentum transfer Method for the in situ preparation of a single layer of zeolite Beta
in confined geometries. Moreover, the match of membrane crystals on a molybdenum substrate for microreactor applications. J
Catal 247:328–338 (2007).
permeability with the catalytic activity, which determines the 21 Pina MP, Mallada R, Arruebo M, Urbiztondo M, Navascués N, de la
performances of membrane reactors, needs a deep theoretical Iglesia O and Santamaria J, Zeolite films and membranes Emerging
1778

investigation. applications. Micropor Mesopor Mater 144:19–27 (2011).

wileyonlinelibrary.com/jctb

c 2013 Society of Chemical Industry J Chem Technol Biotechnol 2013; 88: 1771–1779
Membrane microreactors for catalytic reactions www.soci.org

22 Chau JLH, Wan YSS, Gavriilidis A and Yeung KL, Incorporating zeolites 39 Wilhite BA, Weiss SE, Ying JY, Schmidt MA and Jensen KF, High-purity
in microchemical systems. Chem Eng J 88:187–200 (2002). hydrogen generation in a microfabricated 23wt% Ag-Pd membrane
23 Yeung KL, Zhang X, Lau WN and Martin-Aranda R, Experiments and device integrated with 8:1 LaNi095 Co005 O3 /Al2 O3 catalyst. Adv Mater
modeling of membrane microreactors. Catal Today 110:26–37 18:1701–1704 (2006).
(2005). 40 Coronas J and Santamaria J, The use of zeolite films in small-scale and
24 Yamamoto S, Hanaoka T, Hamakawa S, Sato K and Mizukami F, micro-scale applications. Chem Eng Sci 59:4879–4885 (2004).
Application of a microchannel to catalytic dehydrogenation of 41 Lai SM, Ng CP, Martin-Aranda R and Yeung KL, Knoevenagel
cyclohexane on Pd membrane. Catal Today 118:2–6 (2006). condensation reaction in zeolite membrane microreactor. Micropor
25 Aran HC, Pacheco Benito S, Luiten-Olieman MWJ, Er S, Wessling M, Mesopor Mater 66:239–252 (2003).
Lefferts L, Benes NE and Lammertink RGH, Carbon nanofibres in 42 Lau WN, Yeung KL, Zhang XF and Martin-Aranda R, Zeolite
catalytic membrane microreactors. J Membr Sci 381:244–250 (2011). membrane microreactors and their performance. Stud Surf Sci Catal
26 Tan, X, Liu S and Li K, Preparation and characterization of inorganic 170:1460–1465 (2007).
hollow fibre membranes. J Membr Sci 188:87–95 (2001). 43 Wan YSS, Yeung KL and Gavriilidis A, TS-1 oxidation of aniline to
27 Li K, Ceramic hollow fibre membranes and their applications, in azoxybenzene in a microstructured reactor. Appl Catal A: Gen
Comprehensive Membrane Science and Engineering, ed by Drioli E 281:285–293 (2005).
and Giorno L. Oxford Academic Press, 253–273 (2010). 44 Alfadhel KA and Kothare MV, Microfluidic modeling and simulation
28 Kingsbury BFK and Li K, A morphological study of ceramic hollow fibre of flow in membrane microreactors. Chem Eng Sci 60:2911–2926
membranes. J Membr Sci 328:134–140 (2009). (2005).
29 Tan X, Liu N, Meng B and Liu S, Morphology control of perovskite 45 Alfadhel KA and Kothare MV, Modeling of multicomponent
hollow fibre membranes for oxygen separation using different bore concentration profiles in membrane microreactors. Ind Eng Chem
fluids. J Membr Sci 378:308–318 (2011). Res 44:9794–9804 (2005).
30 Garcı́a-Garcı́a FR, Rahman MA, Kingsbury BFK and Li K, A novel catalytic 46 Jie D, Diao X, Cheong KB and Yong LK, Navier–Stokes simulations of
membrane microreactor for COx free H2 production. Catal Comm gas flow in microdevices. J Micromech Microeng 10:372–379 (2000).
12:161–164 (2010). 47 Jani JM, Aran HC, Wessling M and Lammertink RGH, Modeling of
31 Rahman MA, Garcı́a-Garcı́a FR and Li K, Development of a catalytic gas–liquid reactions in porous membrane microreactors. J Membr
hollow fibre membrane microreactor as a microreformer unit for Sci 419–420:57–64 (2012).
automotive application. J Membr Sci 390/391:68–75 (2012). 48 Chasanis P, Kenig EY, Hessel V and Sehmitt S, Modelling and simulation
32 Rahman MA, Garcı́a-Garcı́a FR, Irfan Hatim MD, Kingsbury BFK and Li of a membrane microreactor using computational fluid dynamics.
K, Development of a catalytic hollow fibre membrane micro-reactor Computer Aided Chem Eng 25:751–756 (2008).
for high purity H2 production. J Membr Sci 368:116–123 (2011). 49 Gallucci F, Fernandez E, Corengia P and van S M Annaland, Recent
33 Kim D, Kellogg A, Livaich E and Wilhite BA, Towards an integrated advances on membranes and membrane reactors for hydrogen
ceramic micro-membrane network: electroless-plated palladium production. Chem Eng Sci 92:40–66 (2013).
membranes in cordierite supports. J Membr Sci 340:109–116 (2009). 50 Kolb G, Review: microstructured reactors for distributed and renewable
34 Ma YH, Mardilovich IP and Engwall EE, Thin composite palladium and production of fuels and electrical energy. Chem Eng Process 65:1–44
palladium/alloy membranes for hydrogen separation. Ann NY Acad (2013).
Sci 984:346–360 (2003). 51 Corma A, Fornes V, Pergher SB, Maesen TLM and Buglass JG,
35 Tosti S, Overview of Pd-based membranes for producing pure Delaminated zeolite precursors as selective acidic catalysts. Nature
hydrogen and state of art at ENEA laboratories. Int J Hydrogen 396:353–356 (1998).
Energy 35:12650–12659 (2010). 52 Sun Y, Zhang F, Du X, Liu X, Chu G, Zhang S and Jin Y, Synthesis of novel
36 Bredesen R, Peters TA, Stange M, Vicinanza N and Venvik HJ, alumino-titanosilicates with JDF-L1 structure. Mater Lett 97:31–33
Palladium-based membranes in hydrogen production, in Membrane (2013).
Engineering for the Treatment of Gases, volume 2: Gas-separation 53 Farrusseng D, Aguado S and Pinel C, Metal-organic frameworks:
Problems Combined with Membrane Reactors, ed by Drioli E and oOpportunities for catalysis. Angew Chem Int Edn 48:7502–7513
Barbieri G. RSC Publishing, 40–86 (2011). (2009).
37 Shah K, Ouyang X and Besser RS, Microreaction for microfuel 54 Zacher D, Shekhah O, Woll C and Fischer RA, Thin films of metal-organic
processing: challenges and prospects. Chem Eng Technol frameworks. Chem Soc Rev 38:1418–1429 (2009).
28:303–313 (2005).
38 Moharana MK, Peel NR, Khandekar S and Kunzru D, Distributed
hydrogen production from ethanol in a microfuel processor: issues
and challenges. Renew Sust Energ Rev 15:524–533 (2011).

1779

J Chem Technol Biotechnol 2013; 88: 1771–1779

c 2013 Society of Chemical Industry wileyonlinelibrary.com/jctb