Chemical Engineering Science 92 (2013) 4066

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Review

Recent advances on membranes and membrane reactors

for hydrogen production
Fausto Gallucci a,n, Ekain Fernandez b, Pablo Corengia b, Martin van Sint Annaland a
a

Multiphase Reactors Group, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, 5612 AZ Eindhoven,
The Netherlands
b
Tecnalia, Mikeletegi Pasealekua 2, 20009 Donostia, San Sebastian, Spain

H I G H L I G H T S
c
c
c
c

Recent advances in hydrogen selective membranes are presented.

Commercial membranes for hydrogen production are discussed.
An overview of the membrane reactor concepts is highlighted.
The application of membrane reactors to different feedstock is reported.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 22 October 2012
Received in revised form
17 December 2012
Accepted 6 January 2013
Available online 23 January 2013

Membranes and membrane reactors for pure hydrogen production are widely investigated not only
because of the important application areas of hydrogen, but especially because mechanically and
chemically stable membranes with high perm-selectivity towards hydrogen are available and are
continuously further improved in terms of stability and hydrogen ux. Membrane reactors are
(multiphase) reactors integrating catalytic reactions (generally reforming and water gas shift reactions
for hydrogen production) and separation through membranes in a single unit. This combination of
process steps results in a high degree of process integration/intensication, with accompanying
benets in terms of increased process or energy efciencies and reduced reactor or catalyst volume.
The aim of this review is to highlight recent advances in hydrogen selective membranes (from
palladium-based to silica and proton conductors) along with the advances for the different types of
membrane reactors available (from packed bed to uidized bed, from micro-reactors to bio-membrane
reactors). In addition, the application of membrane reactors for hydrogen production from different
feedstock is also discussed.
& 2013 Elsevier Ltd. All rights reserved.

Keywords:
Membrane reactor
Hydrogen production
Packed bed
Fluidization
Separations
Membranes

Contents
1.
2.

3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Hydrogen separation membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.1.
Membrane materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.2.
Membrane congurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.1.
Geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.2.
Unsupported and supported membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Dense metal membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.1.
General comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.2.
Progresses in commercialization of dense metal membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.1.
CRI/Criterion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.2.
ECN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

Corresponding author. Tel.: 31 40 247 3675; fax: 31 40 247 5833.

E-mail address: F.Gallucci@tue.nl (F. Gallucci).

0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.01.008

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

41

3.2.3.
Eltron Research, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.4.
Green Hydrotec . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.5.
Hy9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.6.
M&P . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.2.7.
MRT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.2.8.
Pall Corporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.2.9.
REB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.2.10. Tokyo Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.2.11. UTRC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4. Microporous membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.1.
Zeolite membranes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2.
Metalorganic framework membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.3.
Silica membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.4.
Carbon membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
5. Proton conducting membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.1.
Dense ceramic membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.1.1.
Perovskite-type membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.1.2.
Non-perovskite-type membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.2.
Cermet membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
6. Advances in membrane reactors for hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
6.1.
Packed bed membrane reactors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
6.2.
Fluidized bed membrane reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
6.3.
Membrane micro-reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
6.4.
Membrane bio-reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
7. Feedstock for hydrogen production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
7.1.
H2 production from methane in MR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
7.2.
H2 production from other hydrocarbons in MR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
7.3.
H2 production from biological related feedstock in MR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Web references . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

1. Introduction
It is widely accepted that the solution of the global warming
problem will be a combination of various contributions ranging
from carbon capture and sequestration (CCS) to improved carbon
efciency of fossil fuels, to large use of renewable energy sources
(in the long term). Among the various strategies proposed, CCS
seems to be a good candidate for CO2 emissions mitigation;
however, CCS has to be regarded as a mid-term solution as long
as the energy economy is based on fossil fuels: CCS will be used as
long as other technologies such as large-scale exploitation of
renewable sources and nuclear fusion are still under development. CCS consists of two challenging processes, viz. carbon
dioxide capture and its sequestration (mineralization or storage).
In this review only carbon capture is discussed, while sequestration (perhaps in off shore geological formations) is a process with
its own technological and societal challenges. Three main technological paths have been proposed for CCS from fossil-fuel red
power stations, namely the post-combustion capture, the precombustion decarbonization and the oxyfuel combustion route
(see Fig. 1).
This review focuses on separation and production of hydrogen
thus can be applied to the decarbonization route. Hydrogen from
fossil fuels can also be used to increase the efciency of the
system. An example of increased efciency is the conversion of
raw material into hydrogen and its use in fuel cells. In fact, for
example in automotive applications, electromotor combined with
hydrogen powered fuel cells shows an overall efciency (4055%)
signicantly higher than internal combustion engines (1330%).
Pt based catalyst are commonly used in polymer electrolyte
membrane (PEM) fuel cells, the performance of the catalyst

decrease dramatically if carbon monoxide (a main product of

most of the conversion technologies) or hydrogen sulde is
present. For this reason, the interest in the production of ultrapure hydrogen has strongly increased in the last years. It has been
demonstrated that by using pure hydrogen produced by membrane reactors in co-generation units the total efciency will be
increased by roughly 10% (Roses et al., 2010, 2011).
Traditionally, hydrogen is produced via steam reforming (SR)
of hydrocarbons such as methane, naphtha oil or methanol/
ethanol. But on industrial scale most of the hydrogen (more than
80%) is currently produced by SR of natural gas carried out in
large multi-tubular xed-bed reactors. In small-scale applications,
two other main alternatives are generally considered along with
SR: partial oxidation reactions, with a signicantly lower efciency than SR, and auto-thermal reforming, where the partial
oxidation (exothermic reaction) and SR (endothermic reaction)
are carried out in the same reactor.
The main drawbacks of conventional SR, partial oxidation and
auto-thermal conventional reactors are that all these reactions
are equilibrium limited and (even in case of complete fuel
conversion) produce a hydrogen rich gas mixture containing
carbon oxides and other by-products. Consequently, in order to
produce pure hydrogen, these chemical processes are carried out
in a number of reaction units (typically high temperature reformer, high and low temperature shift reactors) followed by
separation units (mostly pressure swing adsorption). The large
number of different process steps decreases the system efciency
and makes scale-down uneconomical. A typical reaction process
scheme is reported in Fig. 2.
Using this process, high hydrogen yields are achieved, but
costly high temperature heat exchangers and complex energy

42

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

the most promising and membrane separation is nowadays increasingly considered as a good candidate for substituting conventional
systems. The specic thermodynamic constrains limiting traditional
reactors can be circumvented by using innovative integrated systems,

integration among different process units are required to obtain

the hydrogen at the desired high purity.
Among different technologies related to production, separation and purication of H2, membrane technologies seem to be

N 2 , O2

Air
Post-Combustion
Capture

Coal
Gas
Biomass

Coal
Biomass

Pre-Combustion
Capture

Power &
Heat

CO2

Air/Steam

Gasification

Reforming
+ CO2
separation

Gas
Oil

Oxyfuel
Combustion

Coal
Gas
Biomass

CO2

CO2
separation

Power &
Heat

CO2
compression &
Dehydration

Air

Power &
Heat

CO2

O2
Air

Air separation

N2

Fig. 1. The three main CO2 capture routes (adapted from Metz et al., 2005).

Fig. 2. Conventional steam reforming reaction scheme. HT shift and LT shift are high and low temperature shift reactors, respectively.

Fig. 3. Membrane system and involved gas streams (Lu et al., 2007).

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

such as the so-called membrane reactors (MRs), engineering systems

in which both reaction and separation are carried out in the same
device (see Fig. 3).
In comparison to a conventional conguration in which a
reactor is combined with a downstream separation unit, the use
of membrane reactors can bring various potential advantages
such as reduced capital costs (due to the reduction in size of the
process unit), improved yields and selectivities (due to the
equilibrium shift effect) and reduced downstream separation
costs (separation is integrated).
The success of membrane reactors for hydrogen production
depends crucially on: (i) the advances in the membrane production methods for the production of thin membranes with high
hydrogen uxes and high hydrogen perm-selectivities; (ii) the
design of innovative reactor concepts which allow the integration
of separation and energy exchange, the reduction of mass and
heat transfer resistances and the simplication of the housing and
sealing of the membranes.
In this review we will rst discuss recent advances in (high
temperature) membranes to be applied in hydrogen production
units, categorized into dense metal membranes, microporous
membranes and proton conducting membranes. An overview of
the most permeable and selective membranes is given together
with a collection of commercial membranes for hydrogen production. Subsequently, recent developments in membrane reactors
design will be highlighted and the application of membrane
reactors for hydrogen production from different feedstock will
be discussed.

43

hydrogenation and dehydrogenation (Dittmeyer et al., 2001;

Gimeno et al., 2009), methane steam reforming (Matsumura and
Tong, 2008), and watergas shift (Bi et al., 2009).

2.1. Membrane materials

Regarding the type of materials, hydrogen separation membranes may be classied into the following categories: polymeric
membranes, porous membranes, dense metal membranes and
proton conducting membranes. Table 1 shows a comparison
between the different membrane types for hydrogen separation.
The most important parameters when comparing membranes are
the perm-selectivity, the ux and the temperature range at which
the membranes can be applied.
In order to obtain high purity hydrogen-permeate streams,
dense metal membranes (mainly palladium alloys) and dense
ceramic membranes are currently the most suitable materials
due to their high hydrogen selectivity. Pdalloys (mainly PdAg,
PdCu and PdXAu) are used to decrease the embrittlement
problem and to decrease the poisoning of the membrane when in
contact with H2S and other pollutants (such as CO). Microporous
ceramic membranes are promising materials for high purity
hydrogen production and separation. However, these membranes
separate hydrogen by size exclusion and thus selectivity is still
limited compared to more expensive dense inorganic membranes.
Nowadays, the selective layers are thin (for instance, Pd membranes are now produced with thicknesses in the order of 1 mm)
and therefore the cost of the selective layer is low or moderate
compared to the entire cost of the membrane.

2. Hydrogen separation membranes

Membranes are basically barriers that allow the ow of some
components of a feed gas mixture stream. The stream containing
the components that permeate through the membrane is called
permeate and the stream containing the retained components is
called retentate, as shown in Fig. 3. Membranes for hydrogen
separation should have the following characteristics:

1.
2.
3.
4.

High selectivity towards hydrogen.

High ux.
Low cost.
High mechanical and chemical stability.

There have been many applications of catalytic inorganic

membrane reactors for reactions involving hydrogen, such as

Fig. 4. Solutiondiffusion mechanism of hydrogen permeation through a dense

metal membrane (Yun and Oyama, 2011).

Table 1
Comparison of membrane types for hydrogen separation (Kluiters, 2004; Liu et al., 2010)
Membrane type

Polymeric

Microporous ceramic

Porous carbon

Dense metallic

Proton conducting
dense ceramic

Materials

Polymers: polyimide, cellulose

acetate, polysulfone, etc.
o 100
Low
Low

Silica, alumina, zirconia, titania, zeolites,

metal-organic frameworks (MOF)
200600
5139
60300

Carbon

Palladium alloys

500900
420
10200

300700
41000
60300

Perovskites (mainly
SrCeO3  d, BaCeO3  d)
600900
41000
680

Solution-diffusion

Molecular sieving

Solution-diffusion

Solution-diffusion

Swelling, compaction,
mechanical strength

Stability in H2O

Surface diffusion,
molecular sieving
Brittle, oxidizing

Stability in CO2

H2S

Low

Strong adsorbing
vapors, organics
Low

Phase transition
(causes
embrittlement)
H2S, HCl, CO
Moderate

Low

Temperature (1C)
H2 selectivity
H2 ux
(10  3 mol m  2
s  1) at DP 1 bar
Transport
mechanism
Stability issues

Poisoning issues

HCl, SOx, CO

Cost

Low

44

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

2.2. Membrane congurations

2.2.1. Geometry
Membrane geometries may be planar, tubular (that includes
tubes, capillaries and hollow bers), plate and frame and spiral
wound. Currently the most commonly used geometries for gas
separation are planar and tubular. The planar membranes are often
used in earlier laboratory research and development studies, while
for medium scale and industrial scale the tubular membranes are
the most preferred option (due to their higher surface area-tovolume ratio in comparison to planar membranes).

2.2.2. Unsupported and supported membranes

The membranes may be classied into unsupported and
supported membranes.
Unsupported membranes need to be thick self-standing lms
( 450 mm thick) in order to have a minimum mechanical stability.
The main drawback of these membranes is their low hydrogen
permeance. Moreover, in the case of using an expensive membrane material the cost of the whole membrane will be sharply
increased by increasing the membrane thickness. Thus there is a
threshold between membrane mechanical stability and membrane thickness (and thus ux and costs). For this reason it is
foreseen that the rst industrially available membranes will be
supported membranes.
Supported membranes consist of a thin selective lm deposited onto a support that provides mechanical stability. Thus, the
hydrogen permeance of the membrane will be higher so that less
membrane area is required and the whole membrane cost will be
lower than that for unsupported membranes. However, in the
total membrane cost, the cost of the support also becomes
important. Especially when very thin lm membranes are
selected, the support pore size should be much lower and the
surface much smoother, so that its cost will increase.
There are mainly two types of porous support materials:
metallic and ceramic.
Ceramic supports typically have better surface quality providing membranes with thinner selective layers. However, they are
more fragile. Currently, the ceramic supports that are commercially available are tubes and hollow bers. As an example, Inopor
produces and offers ceramic tubular supports of different ceramic
materials and pore sizes (http://www.inopor.com/). In general,
ceramic tubular supports consist of a porous ceramic substrate
processed by extrusion and a porous low roughness ceramic layer
deposited onto the support by, for example, solgel techniques.
On the other hand, hollow bers are usually prepared by spinning
(Li, 2007b).
Metallic supports are more robust than ceramic but the
commercial ones, mainly tubular, have lower surface qualities.
This is due to the fact that they are not used as membrane
supports but rather as particle lters. GKN (http://www.gkn-l
ters.de/), Mott (http://www.mottcorp.com/), and Pall (http://
www.pall.com) are known metallic support suppliers.
Some research groups are developing hollow ber supports
(both ceramics and metallic) in order to increase the surface area
to volume ratio and also improve the surface quality (LuitenOlieman et al., 2012).
In the case in which both the selective layer and the support
are metallic and the entire membrane is used at temperatures
above the Tamman temperature of one of the metallic parts, it is
necessary to position an inter-metallic diffusion barrier layer
between the metallic support and the metallic selective layer.
This is a common situation in dense metal composite membranes used for high temperature reforming reactions. In this case
the materials used as barrier layer are: ZrO2 (Tarditi et al., 2013;

Li et al., 2008a), YSZ (Sanz et al., 2011, Li et al., 2007a), TiO2

(Li et al., 2008b), CeO2 (Qiao et al., 2010) and Al2O3 (Dardas et al.,
2009). The typical deposition technologies used are: atmospheric
plasma spraying (APS) (Sanz et al., 2011; Huang and Dittmeyer,
2007), wet powder spraying (WPS) (Zhao et al., 2004) and powder
suspension suction (Chi et al., 2010).

3. Dense metal membranes

3.1. General comments
Dense metal membranes are commonly used for high purity
hydrogen production. The mechanism of hydrogen permeation
through dense metal membranes has been extensively studied. It
is well known that it generally follows a solutiondiffusion
mechanism. The steps involved in hydrogen transport from a
high to a low pressure gas region are the following (Lewis, 1967;
Fig. 4): (a) diffusion of molecular hydrogen to the surface of the
metal membrane, (b) reversible dissociative adsorption on the
metal surface, (c) dissolution of atomic hydrogen into the bulk
metal, (d) diffusion of atomic hydrogen through the bulk metal,
(e) association of hydrogen atom on the metal surface, (f) desorption
of molecular hydrogen from the surface, (g) diffusion of molecular
hydrogen away from the surface.
Common dense metal layer deposition technologies include
physical vapor deposition (PVD, including magnetron sputtering,
thermal evaporation or pulsed laser evaporation), chemical vapor
deposition (CVD or MOCVD), electroless plating (ELP), electroplating and diffusion welding (Iniotakis et al., 1987). Each technology has its strengths and weaknesses; therefore, there is a
trend of tailoring the deposition technology to the features of the
support in order to obtain a suitable composite membrane.
The most widely used preparation technology for dense metal
layers is ELP due to its ability of covering supports with complex
geometries, the simplicity of the required equipment and its low
cost (absence of electrodes or electrical source) (Mallory and
Hajdu, 1990).
On the other hand, PVD magnetron sputtering is a very
attractive deposition technology because it could provide thinner
uniform layers (down to only few nanometers), much lower than
the thickness achieved with the ELP technique, with a controlled
microstructure and composition across of these coatings. Other
important advantage of PVD versus ELP is its environmental
friendly operation, without producing waste liquids from chemical baths (Klette, 2005).
Among dense metal materials used for hydrogen purication,
developments in Pd and Pd alloys have been carried out for a long
time (Buxbaum, 1999; Grashoff et al., 1983; Holleck, 1970). The
most important problem associated with the use of pure Pd
membranes is the hydrogen embrittlement phenomenon. Operation with hydrogen at a temperature below 300 1C and a pressure
below 2 MPa, leads to the nucleation of the b-hydride phase from
the a-phase resulting in severe lattice strains. In this case a pure
palladium membrane becomes brittle after a few a2b cycles
(Hsieh, 1989).
Another important problem is the palladium surface poisoning, which can be more signicant for thin metal membranes, by
sulfur compounds (Edlund and Pledger, 1994), CO (Amandusson
et al., 2000), H2O (Li et al., 2000), chlorine, carbon, unsaturated
hydrocarbons, etc.. In order to avoid hydrogen embrittlement,
poisoning and reduce membrane cost, palladium can be alloyed
with other metallic elements such as Ag, Cu, Fe, Ni, Pt and Y
(Bryden and Ying, 2002; Qiao et al., 2010; Uemiya et al., 2007) or
the palladium grains can be used in nanometer sized (Pacheco
Tanaka et al., 2006).

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

On the other hand, there is a group of metals called refractory

metals (e.g., vanadium, niobium, and tantalum) that have much
higher permeability at these lower temperatures in comparison to
palladium. These metals are much cheaper and have greater
tolerances to high temperatures compared to palladium. Nevertheless, producing membranes with only these metals (as pure
components) is hindered by the high embrittlement produced at
room temperature in the presence of 6.9 barhydrogen. On the
contrary, several alloys of these metals are also non-embrittling,
making them good candidates for hydrogen purication membranes (Dolan, 2010; Dolan et al., 2011; Ishikawa et al., 2011;
Paglieri et al., 2011; Wolden et al., 2013). These metals are not
normally used alone for hydrogen permeation also because of
poor surface properties (particularly formation of surface oxide
layers) that reduce hydrogen transport. When palladium or
palladium alloys are applied over the surface of refractory alloys
(Makrides et al., 1967; Paglieri et al., 2009), forming metalmetal
matrix membranes, the surface barriers are removed and hydrogen permeation follows the trend shown in Fig. 5.
As the number of possible combinations of these metals is
enormous, a modeling approach can help in identifying the most
suitable combination of metals for producing hydrogen membranes. An interesting approach towards the denition of suitable
modeling tools for this kind of study is given by the application of
density functional theory (DFT) calculations to predict the behavior of binary or ternary alloys with pure hydrogen or with gas
mixtures. For example the group of Sholl published a series of
papers showing the potentiality of DFT in predicting the solubility/diffusivity of hydrogen in different alloys, resulting in interesting guidelines for the future membrane production. In their
works on PdCu based ternary alloys (Semidey-Flecha et al., 2010,
Kamakoti and Sholl, 2003, 2006) the authors applied DFT to
nd an effective ternary additive to the PdCu alloy to retain the
good poisoning resistance of the binary alloy while increasing the
total permeability of the resulting membrane. It was found that
among different additives (such as Ni, Au, Ag, Rh, Pt) an addition
of Au or Ag can increase the permeability of the alloy of up to
5 times. They also found out that for this PdCuAg alloys, the
increase of solubility due to the increase of Ag is more dominant
on the increase of permeability compared to the effect of
diffusivity. This means that for PdCu ternary alloys an additive
that increases the solubility of hydrogen is to be preferred.

Solubility of hydrogen is also important for binary alloys;

Sonwane et al. (2006) have shown by using DFT calculations that
the maximum solubility for PdAg is found at 30% Ag while for
PdAu the maximum is found at 20% Au. For PdAg (30% Ag) the
hydrogen solubility has been found to be 10 times higher than for
pure Pd. Hao and Sholl (2011) also applied DFT to evaluate the
permeability of amorphous metal membranes (such as ZrCu
based membranes). The results in this case show that the
permeability is not directly related to the solubility of hydrogen,
giving guidelines also for the design of amorphous metal membranes. DFT calculations have also been applied to evaluate the
effect of contaminants in the gas mixture on the hydrogen
permeability (Ling and Sholl, 2009; Ozdogan and Wilcox, 2010;
Gallucci et al., 2007a,b); it has been found that CO affects the
permeation of hydrogen especially because there is a preferential
adsorption of CO molecules on the same sites (hollow and bridge)
used by H2; moreover CO can jump between the two sites and
this is why a small amount of CO is enough to deteriorate the
hydrogen permeability (Gallucci et al., 2007a,b). Ozdogan and
Wilcox showed that the adsorption of H2S on the surface of the
membrane depends on the metal used to alloy palladium. In
particular they found a H2S binding tendency such as Cu o
PdoNb. This is why PdCu have are more resistant to H2S poisoning.
Ling and Sholl (2009) showed that any sulde formation on the
membrane will decrease enormously the permeability of the
membrane especially due to the extremely slow diffusion of
H through the sulde layer.
Regarding the experimental works on membranes, some of the
most relevant current developments on dense metal membranes
for hydrogen production are presented afterwards.
PdAg alloy membranes are usually prepared by electroless
plating using a sequential deposition of the two metals. This
procedure gives the deposition of bi-layered metal lms and
hence a high temperature and longer time is required for the
complete inter-phase diffusion of two metals, in addition the
precise control of Pd/Ag ratio in the membrane is difcult to
obtain.
At AIST-Japan, Pacheco Tanaka et al. (2005) developed a
method for the simultaneous plating of Pd-Ag with the desired
composition of metals. This was achieved by the uniform deposition of nano-particles of Pd nuclei on the surface of the substrate
and the careful control of the composition of the plating solution.

1e+0
1e-3

Al
Be
Co (eps)
Co (alfa)
Cu
Ge
Au
Fe
Mo
Ni
Nb
Pd
Pt
Si
Ta
W
V
Ti

1e-6
Permeability, mol/m s Pa1/2

1e-9
1e-12
1e-15
1e-18
1e-21
1e-24
1e-27
1e-30
1e-33
1e-36
1e-39
1e-42
1e-45
1e-48
0.0005

45

0.0010

0.0015

0.0020
0.0025
1/T, 1/K

0.0030

0.0035

0.0040

Fig. 5. Hydrogen permeability through several metals as a function of temperature (Basile et al., 2008).

46

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

Alloying of Pd and Ag was possible under lower temperature and

short heat treatment. The same group at AIST also prepared thin
PdAu alloy membranes by electroless plating of Au on a Pd
membrane; the amount of Au in the alloy was controlled by
adjusting the concentration of gold in the plating solution
(Okazaki et al., 2008a). Okazaki and Pacheco Tanaka also studied
the effect of the substrate on the permeation of hydrogen at high
temperature, they demonstrated that at temperatures higher than
650 1C alumina reacts with hydrogen and the PdAl alloy formed
decrease the permeation of hydrogen in that extent that at 850 1C
no permeation occurs. On the other hand, YSZ is more stable and
can be used until 750 1C. (Okazaki et al., 2008b, 2009). The same
group in Japan, developed hydrogen permeable membrane of
novel conguration (pore ll type membrane); in this conguration, palladium particles are lled in the nano-size pores of
ceramic (g-Al2O3) layer located under the top surface (Pacheco
Tanaka et al., 2006). This pore ll conguration provides
advantages of improved toughness on handling since palladium
layer is not exposed on the surface. Moreover nano-size palladium grains conned in the nanopore substantially suppress the
internal stress associated with ab phase transition. This Pd
membrane is tolerable below the critical temperature, where
fatal damage occurs for usual. Almost constant hydrogen permeation and selectivity were maintained for more than 24 h at 50 1C
and 100 kPa pressure difference. At 300 1C and 4 bar of pressure
difference, the hydrogen permeance and H2/N2 ideal selectivity of
this membrane were 1.3  10  6 mol m  2 s  1 Pa  1 and 41000,
respectively. Due to the difference of expansion coefcient
between Pd and alumina, nanoporous alumina lled with Pd
has low stability at temperatures higher than 350400 1C. To
overcome this problem, a membrane was prepared by lling
palladium into the nano pores of YSZg-Al2O3. The PdYSZ
Al2O3 composite membrane revealed excellent thermal stability
allowing long-term operation at elevated temperature (500 1C).
This has been attributed to improved fracture toughness of
YSZAl2O3 layer and matching of thermal expansion coefcient
between palladium and YSZ (Pacheco Tanaka et al., 2008).
At 425 1C and 4 bar of pressure difference, the hydrogen permeance and H2/N2 ideal selectivity of this membrane were
1.6  10  6 mol m  2 s  1 Pa  1 and 300, respectively.
Various Pd alloys have been developed and tested as membrane by the Colorado School of Mines (CSM). Supported membranes have been obtained with PdAu, PdCu and PdRu alloy
supported on commercial alumina and zirconia-coated porous
stainless steel tubular substrates using an ELP technique (Roa
et al., 2009). The most promising result has been obtained by
using an alumina supported PdAu membrane. A H2 ux of
482 ml min  1 cm  2 (STP) and a H2/N2 ideal selectivity of 1000
at a temperature of 400 1C and a partial pressure difference of
around 7 bar. On the other hand, a 2.3 mm thick PdAu membrane
supported on zirconia-coated porous stainless steel achieved a H2
ux of 1.01 mol m  2 s  1 and a H2/N2 ideal selectivity of 82,000 at
1.38 bar and 400 1C (Hatlevik et al., 2010). At these experimental
conditions no ux reduction was observed for this PdAu membrane for WGS mixture compared to a pure H2 feed gas. This
means that no CO adsorption on the membrane surface occurs at
these temperatures, which makes the membrane very attractive
for WGS reactions or pre-combustion CO2 capture plants.
A great research effort on novel membranes has been devoted
in China where the Dalian Institute of Chemical Physics (DICP) is
developing supported composite PdAu alloy membranes on
alumina substrates using ELP technique (Goldbach and Xu,
2011). Very thin membranes with high uxes have been produced
by DICP. They reported a remarkable H2 permeability of
1.3  10  8 mol m m  2 s  1 Pa  0.5 at 400 1C attained by a 5 mm
PdAu composite membrane. The H2/N2 ideal selectivity was

around 1100 at 500 1C. The H2 ux achieved with a 23 mm thick

PdAu composite membrane was 0.62 mol m  2 s  1 at 500 1C. The
H2/N2 ideal selectivity was around 1400. Moreover cycling in
hydrogen between 250 and 450 1C had no signicant effect on
hydrogen and nitrogen permeation rates showing that mechanical stress caused by the differing thermal expansion of the joined
materials is within the tolerance of the metal/ceramic composite
membrane up to those temperatures (Shi et al., 2010).
SINTEF (Norway) has developed a two-step technique for
manufacturing very thin defect free palladium-based hydrogen
separation membranes. First, a defect-free Pdalloy thin lm is
prepared by PVD magnetron sputtering onto a silicon wafer
(surface with minimum roughness). In a second step, the lm is
removed from the wafer and used as membrane. These lms may
either be used as self-supported membrane or be integrated with
various supports of different pore sizes and geometries. This
allows the preparation of thin (  12 mm), high-ux membranes
supported on macroporous substrates avoiding all the mass
transfer resistances given by microporous supports or problems
with interdiffusion layers. It must be highlighted that according to
the DFT calculations of Ling and Sholl, for membranes of 1 mm, the
desorption resistance completely dominates the permeation at
temperatures below 230 1C and it has an important contribution
at temperatures below 450 1C. Thus, at these temperatures
smaller thicknesses will not improve the permeation ux of the
membrane while will surely deteriorate the stability of the
membrane.
In pure hydrogen, and at 400 1C and a H2 pressure difference of
25 bar, the H2 permeance and H2/N2 ideal selectivity were
1.46  10  2 mol m  2 s  1 Pa  0.5 and 2900. (Peters et al., 2011a).
In WGS conditions (57.5% H2, 18.7% CO2, 3.8% CO, 1.2% CH4 and
18.7% steam) SINTEF membranes have shown a H2 permeance of
1.1  10  3 mol m  2 s  1 Pa  0.5 at 400 1C and 26 bar feed pressure. No membrane failure was detected operating the membrane
for more than 1 year using WGS and H2N2 feed mixtures
(Iaquaniello et al., 2011). SINTEF is also working in the development of Pd-based binary and ternary alloy membranes for H2
separation (Peters et al., 2011b, 2012).
Research on self-supported membrane foils has been carried
out at Southwest Research Institute (SwRI). The institute used a
magnetron sputtering technique to develop PdAu and PdAuPt
foils. SwRI tested PdAuPt (702010%) foils at 400 1C, 12.7 bar
with feed gas composition of 50% H2, 30% CO2, 19% H2O, and 1%
CO (Coulter et al., 2012), and a H2 ux was approximately
0.212 mol/m2/s. Currently, SwRI is developing amorphous
Zr-based alloys, specially focusing on ZrCu based ternary alloys.
The reason for the development of these alloys is that they
showed good results (i.e., Zr30Cu60Ti10) in previous computational
calculations predicting H2 ux through ternary alloys as functions
of operating temperature, H2 feed pressure, membrane thickness,
and trans-membrane pressure drop to advance testing (CO2
Handbook, 2011).
Important advances on membrane preparation have been
achieved at the center for inorganic membranes of the Worcester
Polytechnic Institute (WPI). The group directed by Prof. Ma is
developing Pd-based membranes on tubular stainless steel or
alloy supports (such as, SS 316 L, Hastelloy and Inconel) by the
ELP technique. WPI achieved a H2 ux of 0.098 mol m  2 s  1 and a
H2/He selectivity of around 4500 at 450 1C and 1.03 bar DP with a
7 mm thick Pd membrane with an Inconel support shown in Fig. 6
(http://www.hydrogen.energy.gov/pdfs/progress09/ii_d_1_ma.
pdf). WPI is also developing supported molten metal membranes,
consisting of low-melting non-precious metals and its alloys (e.g.,
Sn, In, Ga, Bi) as supported thin lms (CO2 Handbook, 2011).
Moreover, WPI has also built an engineering-scale prototype
membrane with 8.8 mm thickness, 2 in. outer diameter, and 6 in.

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

47

Fig. 6. Pd/Inconel hydrogen separation membranes manufactured by WPI (http://

www.netl.doe.gov/publications/factsheets/project/Proj481.pdf).

length. WPI has demonstrated long-term membrane testing

with total test duration of 63 days at 450 1C, 1.03 bar DP,
0.303 mol m  2 s  1H2 ux, 99.99% purity. This ux is equivalent
to approximately 1.286 mol m  2 s  1 at 6.9 bar DP (Hydrogen
from Coal Program, 2010).
Currently, WPI is performing long-term tests with Pd-based
membranes under mixed gas streams (Guazzone et al., 2012;
Augustine et al., 2012).
3.2. Progresses in commercialization of dense metal membranes
There are different companies working on the commercialization of dense metal membranes for hydrogen separation/production. In the following, the main progresses achieved are presented.
Some of these commercial membranes have been successfully used
in uidized membrane reactors for methane steam reforming and
in membrane separators in a pilot plant for 20 m3/h hydrogen
production as described below.
3.2.1. CRI/Criterion
CRI/Criterion (a company owned by Shell) is in the process of
commercializing Pd and Pdalloy membranes on sintered porous
metal supports as published in a report (Shell Impact, 2010). CRI/
Criterion has produced membranes of this type as large as 2 in.
OD by 48 in. L, by welding two separate 24 in. L sections. The
support is polished with a robotized machine before the Pd
deposition. The H2 permeance of these membranes varies in a
range of 4070 Nm3 m  2 h  1 bar  0.5. Both hydrogen ux and
separation selectivity are stable at temperatures of 300500 1C
and differential pressures of 2642 bar. H2 purity of 499% has
been demonstrated for periods exceeding 4000 h in high temperature gas separations. In Fig. 7 some manufactured membranes are shown.
3.2.2. ECN
The Energy research Centre of the Netherlands (ECN) produces
and offers a line of hydrogen separation modules (Hysep) on a
pre-commercial basis for evaluation purposes as described in its
website (http://www.hysep.com/). There are three modules available: Hysep 108 (area of 0.04 m2), Hysep 308 (0.1 m2) and Hysep
1308 (0.5 m2) (Fig. 8). The Hysep modules use palladium composite membranes composed by a 39 mm thick palladium layer
deposited by ELP onto a porous ceramic alumina support. The
nominal capacity of the largest membrane module (Fig. 5) equals
3.56 Nm3 h  1, based on the obtained hydrogen ux applying
reformate with 33% H2, an inlet pressure of 25 bar and H2 outlet
pressure of 4 bar. Lifetimes of several thousands of hours have
been shown under different conditions and purities that can reach
the range from 99.5% to 99.995% depending on the initial
composition. ECN is also developing novel Pd alloy composite
membranes (e.g. PdAg, PdCu; Acha et al., 2011).

Fig. 7. High temperature Pd-based composite commercial hydrogen separation

membranes manufactured by CRI/Criterion (http://www.cricatalyst.com/).

Fig. 8. Hysep 1308 hydrogen separation module manufactured by ECN.

3.2.3. Eltron Research, Inc.

Eltron Research, Inc. has developed alloy-based membranes
and has developed a separator unit rated to produce 6.8 kg/day of
hydrogen (Hydrogen from Coal Program, 2010; CO2 Handbook,
2011). Eltrons best alloy membrane has demonstrated a H2 ux
rate of 809 mL min  1 cm  2 (STP) at 400 1C and 6.9 bar DP with
H2 pure gas feeding. Eltron has tested the membranes under WGS
feed stream conditions; tubular membranes were successfully
tested for greater than 300 h with a feed gas composition of 50%
H2, 29% CO2, 19% H2O, 1% CO, and 1% He.
3.2.4. Green Hydrotec
As shown on its website (www.grnhydrotec.com), Green
Hydrotech has developed Pd and PdCu membranes on porous
stainless steel tubes (Fig. 9) with an extremely high H2/N2 permselectivity ( 4100,000) and these membranes provide in situ
purication of hydrogen in a steam reformer for high purity
hydrogen (99.996 %).
3.2.5. Hy9
Hy9 is commercializing HPSTM hydrogen puriers based on
planar palladium alloy metal membranes (Fig. 10), as described
on its website (http://hy9.com/). Hy9s membrane puriers

48

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

Fig. 11. Pd alloy composite tubular membrane manufactured by Pall Corporation

(active surface area: 15 cm2).

patent-pending bonding technique has been developed to permanently attach membranes to support modules with a perfect,
hydrogen-tight seal.
For membranes thinner than 15 mm, MRT uses a proprietary
coating technique (Iaquaniello et al., 2011). MRT achieved a H2
ux of 95 N m3 m  2 h  1 with a 5 mm thick Pd membrane
supported on alumina-coated porous stainless steel tubular substrate at 550 1C and hydrogen pressure difference of 3.4 bar
(Li et al., 2007c).
Fig. 9. Pd-based composite membrane module manufactured by Green Hydrotech.

Fig. 10. HPS 689 hydrogen purier composed by PdCu alloy planar membrane.

tolerate a wide variety of feed stocks and gas mixtures, having

been successfully deployed with systems utilizing methanol,
natural gas, diesel, liqueed petroleum gas, ammonia borane,
and a variety of hydrides. The optimal operating temperature
conditions range from 300 to 350 1C and at inlet pressures from
3.4 to 17.2 barg depending on specic requirements.
3.2.6. M&P
Media and Process Technology, Inc. (M&P) (Liu et al., 2010) has
developed a Pd-based membrane module that is capable of
producing a H2 ow of 0.575 mol m  2 s  1 and H2/N2 selectivity
of over 1000. The Pd membrane composite membranes consist of
a  2 mm thick Pd layer deposited onto a porous ceramic support
with a H2 ux of 0.575 mol m  2 s  1 at 1.38 bar. Currently, tests
involving a WGS membrane reactor with this module are being
carried out.
3.2.7. MRT
Membrane Reactor Technologies (MRT) is developing a range
of hydrogen puriers to provide high-purity hydrogen and to
recover hydrogen from mixed gas streams, as described on its
website (http://www.membranereactor.com/).
MRT produces membranes either as rolled foils or as deposited
thin lms (815 mm).
While palladium-based foils of common compositions are
available commercially, MRT has developed its own alloy compositions for added performance and robustness. In addition, a

3.2.8. Pall Corporation

Pall Corporation produces and offers Pdalloy composite
tubular membranes on a pre-commercial basis (Fig. 11), as
published on its website (Pall.com). The support of this membrane is composed of YSZ inter-diffusion barrier layer deposited
onto a porous stainless steel tube. Pall has a couple of techniques
to deposit its 15 mm PdAu layer. Palls current membrane
ux performance and H2/Ar ideal selective are 295
354 mL min  1 cm  2 (STP) and 10,00020,000 at a temperature
of 400 1C and feed pressure of 1.38 barg (with permeate atmospheric) (CO2 Handbook, 2011, Pall.com, Damle, A. 2010). Development of a Pd-alloy composition tolerant up to 100 ppm H2S is
currently ongoing (Bredesen et al., 2011).
3.2.9. REB
REB Research and Consulting produces and offers metal
membranes made of 1.51.6 mm thick Pd-coated refractory metal
tubes (3/8 in. OD  0.007 in. wall) or palladiumsilver alloy tubes
(1/8 in. OD  0.003 in.), as described on its website (REBresearch.com). Palladiumsilver alloy membranes are available
plain, coated with palladium-grey, or coated with palladium
copper alloy.
The average membrane permeabilities of VTi based membranes
are
0.15 mol m m  2 s  1 Pa  0.5
at
600 1C
and
2 1
0.015 mol m m s Pa  0.5 at 300 1C. For VNb membranes,
the permeabilities are 0.2 mol m m  2 s  1 Pa  0.5 at 429 1C and
0.19 mol m m  2 s  1 Pa  0.5 at 340 1C (REBresearch.com, Buxbaum
2008). On the other hand, REB is developing metalmetal matrix
membranes which consist of a high permeable H2 metal layer
coated with Pdalloys on each side, with the aim of reducing
membrane cost and increasing durability. A H2 ux of
0.2 mol m  2 s  1 was achieved with a 0.5 mm PdCu coated on
each side of a high permeable metal membrane (B2) at 400 1C and
3.03 bar DP with feed gas mixture containing H2, CO, CO2, CH4
and H2S. These membranes have resisted poisoning from 50 h
with 100 ppm H2S. These novel membranes will be integrated
in a disc membrane reactor to be tested with coalgas
(CO2 Handbook, 2011).
REB membranes have also been successfully tested in uidized
bed membrane reactors for hydrogen production as discussed in
the following sections. The double membrane layer was able to

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

assure a high selectivity for long time under bubbling uidization

conditions (Roses et al.). It should also be highlighted that these
membranes have been successfully tested at temperatures up to
650 1C without deteriorating the perm-selectivity of the membranes which is probably the higher temperature used so fare for
Pd-based membranes and it is also the temperature window that
allow an effective integration of Pd membranes into methane
reformers (Gallucci et al., 2008a,b; Roses et al.).
3.2.10. Tokyo Gas
Tokyo Gas Co., Ltd. has been developing membrane reformers
(MRF) for hydrogen production with Mitsubishi Heavy Industries,
Ltd. since 1992. Recently, Tokyo Gas developed a MRF test system
with a hydrogen production of 40 Nm3/h, hydrogen purity of
99.99%, and hydrogen production efciency of 70% (Shirasaki
et al., 2009). The reformer has 112 reactor tubes, each of which
has two planar-type membrane modules composed of stainless
steel supports and PdY(Gd)Ag alloy lms of less than 20 mm
thick (Sakamoto et al., 1992). The longest operation time for this
membrane reformer was 3000 h. An interesting evolution of the
membrane modules introduced by Tokio Gas company is what
they called membrane-on-catalyst (MOC) module. This is a Pdbased membrane prepared on the porous surface of the tubular
structured catalyst that has catalytic activity for steam reforming
reaction. The important aspect to be taken into account when
preparing MOCs is the thermal expansion of the catalyst that has
to match with the membrane material, while also selecting a
proper porosity, mechanical strength and thermal conductivity of
the catalyst (Yasuda et al., 2006). This concept simplies enormously the membrane module design while also reducing the
mass transfer resistances otherwise affecting the packed bed
membrane modules used in their hydrogen generator.
3.2.11. UTRC
United Technologies Research Center (UTRC) is developing a
palladium copper (PdCu) trimetallic alloy hydrogen separator for
central H2 production from coal gasication-derived syngas (CO2
Handbook, 2011). UTRC has tested ve separators using PdCuTM
alloy which showed increased surface stability in bench-scale
tests (Hydrogen from Coal Program, 2010). UTRCs current membrane ux performance is approximately 0.230 mol m  2 s  1 at a
temperature of 400 1C and feed pressure of 6.9 bar). This membrane has also shown pressure capability up to 27.6 bar, sulfur
tolerance of 20 ppmv, CO tolerance and the production of at least
99.5% pure H2.
Three types of commercial membranes (MRT, ECN and one from
a not specied Japanese company) are being tested it a 20 m3/h
hydrogen production plant at Chieti (Italy) by Technimont-KT
(De Falco et al., 2011). Preliminary experimental tests have
conrmed the potential of membrane technology with an overall
conversion of approximately 57.3% was achieved at 600 1C, 26%
higher than what was achieved in a conventional reformer. This
conversion is expected to be even increased up to 62.8% by
doubling the membrane surface by a factor of two. Moreover, the
effect of operating temperature and gas mixture space velocity have
been evaluated over a period of 1000 h without detrimental effects
on the membranes performance.

49

4.1. Zeolite membranes

Zeolites are microporous crystalline aluminosilicates with
uniform molecular sized pores. The unique properties of zeolite
membranes are: size and shape selective separation behavior
and thermal and chemical stabilities. Due to their crystallinity,
zeolites have a well-dened pore size. The size of the channels is
in the range of molecular dimensions. Therefore,
typically 310 A,
the hydrogen permeation through zeolite membranes relies on
molecular sieve effect and/or competitive diffusion mechanisms
(Dong et al., 2000).
Regarding material and structure, the most extensively studied
zeolite membranes for hydrogen separation are mainly MFI (ZSM
(Hong et al., 2005), silicate-1 (McLeary et al., 2006), LTA (NaA
(Xu et al., 2000), DDR (Lin and Kanezashi, 2007) and CHA (SAPO-34
(Hong et al., 2008).
The most commonly used technologies for zeolite processing
are in situ hydrothermal synthesis (Coronas and Santamaria,
2004), secondary (seeded) growth synthesis (Xomeritakis et al.,
2000) and vapor phase transport synthesis (Chiang and Chao,
2001). Other various techniques have been applied, such as
conventional heating, microwave heating (Li et al., 2006), synth o-Lechuga et al., 2003),
esis under centrifugal eld (Tiscaren
moved-synthesis (Richter et al., 2003). Often, pre-treatment of
supports (Berg et al., 2003) and post-treatment of membranes
(Yan et al., 1997) (e.g. for pore size reduction and defects removal)
are carried out to improve the quality of the as-synthesized
membranes.
Some of the most relevant current developments on zeolite
membranes for hydrogen separation are presented below.
Lai et al. (Lai and Gavalas, 2000) developed ZSM-5 zeolite
membranes by hydrothermal synthesis using a template free gel
in order to avoid calcination step. The H2/N2 ideal selectivity and H2
permeance obtained were 109 and 1.2  10  7 mol m  2 s  1 Pa  1,
respectively.
Welk et al. (2004) from Sandia National Laboratories (SNL)
have studied the potential applications of zeolite membranes for
hydrogen separation from reforming streams. ZSM-5 membranes
were prepared by hydrothermal synthesis and the testing results
showed that the H2 purity was enriched from 76% to more than a
98% after a single pass through this membrane.
Tsapatsis and co-workers from University of Minnesota have
prepared 1 mm thick MCM-22/silica layer onto porous homemade
alumina support discs. The H2/N2 ideal selectivity and H2 permeance were 50 and 7  10  8 mol m  2 s  1 Pa  1 at 200 1C,
respectively (Choi and Tsapatsis, 2010). Besides, the same group
is developing membranes consisting of ex-foliated MCM-22 layers
onto commercial stainless steel tubular support to their later
integration in WGS reactors and integrated gasication combined
cycle plants (CO2 Handbook, 2011).
Recently, Zhang et al. (2012) from Nanjing University have
developed a MFI zeolite membrane on porous a-alumina porous
discs. The membrane was tested for the separation of H2/CO2
mixture containing 20 cm3 (STP)/min H2, 20 cm3 (STP)/min CO2
and 5 cm3 (STP)/min He under atmospheric pressure. The permeate side was swept by He stream with the ow rate of 30 cm3
(STP)/min. The H2/CO2 separation factor and the H2 permeance
were 42.6 and 2.82  10  7 mol/m2/s/Pa at 500 1C.

4. Microporous membranes

4.2. Metalorganic framework membranes

Microporous membranes are referred to as those with a pore

diameter smaller than 2 nm. Regarding the structure, the microporous membranes for H2 separation may be classied into
crystalline (zeolites and MOF) and amorphous (such as silica,
carbon, etc.).

Metalorganic frameworks are microporous crystalline hybrid

materials consisting of metal cations or cationic oxide clusters
that are linked by organic molecules. Pore size tailorability
combined with tunable sorption behavior provides promising
possibilities for the applications of MOFs as membranes for gas

50

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

separation applications. It is thought that MOF can solve problems that zeolites have for their industrial use, such as, longterm stability, T-cycling, regeneration and difcult housing
(Gascon and Kapteijn, 2010).
MOF are mechanically less stiff and brittle and have less
energy intensive synthesis conditions compared to zeolites (Tan
and Cheetham, 2011; Shah et al., 2012).
The zeolitic imidazolate frameworks (ZIFs) form a subfamily of
MOFs that are promising candidates as gas separation membranes
due to their thermal and chemical stability in combination with
(Shah et al., 2012).
their small pores (generally less than 5 A)
Other MOF materials that have been used for gas separation are
MOF-type (Yoo et al., 2009; Bux et al., 2009), HKUST-type
(Guerrero et al., 2010; Guo et al., 2009) and SIM-type (Aguado
et al., 2011a), among others.
The most commonly used technologies for MOF preparation
are in situ growth synthesis (Liu et al., 2010; Huang et al., 2010;
Guo et al., 2009), secondary (seeded) growth synthesis (Liu et al.,
2009; Ranjan and Tsapatsis, 2009; Yoo et al., 2009) and liquid
phase epitaxy (Shekhah et al., 2011). Besides, postsynthetic
modications of MOF membranes have been reported, for
instance, introducing side groups to give functionality to the
membranes (Huang and Caro, 2011; Aguado et al., 2011b).
Some of the most relevant current developments on MOF membranes for hydrogen separation are presented afterwards. Li and coworkers have prepared 2 mm thick ZIF-7 membrane deposited on an
asymmetric alumina disc by secondary (seeded) growth technique.
The H2 permeance and H2/N2 ideal selectivity of the membrane at
220 1C and at 1 atm were 4.55  10  8 mol m  2 s  1 Pa  1 and 20.7,
respectively (Li et al., 2010).
Recently, the same group in Hannover (Huang and Caro, 2011)
has prepared a 20 mm thick ZIF-90 membrane on a-Al2O3 porous
discs by solvothermal reaction. After synthesis the membrane has
been modied using ethanolamine and its H2 permeance has
slightly decreased from 2.5 to 2.1  10  7 mol m  2 s  1 Pa  1 and
the H2/N2 ideal selectivity has considerably increased from
around 7 to 17.5 at 200 1C and 1 atm.
(McCarthy et al. (2010) from Texas A&M University have
prepared a ZIF-8 membrane (20 mm thick) by in situ solvothermal
growth on a-Al2O3 support after its surface modication. The H2
permeance and H2/N2 ideal selectivity of the membrane at 25 1C
and at 1 atm were 1.73  10  7 mol m  2 s  1 Pa  1 and 11.6,
respectively.
The same group from Texas (Guerrero et al., 2010) has
prepared a 25 mm thick HKUST-1 membrane deposited on a
porous alumina support disc via secondary (i.e., seeded) growth
method, using thermal seeding in order to anchor HKUST-1 seed
crystals on the support. The H2 permeance and H2/N2 ideal
selectivity of the membrane at 190 1C and at 1 atm were
1.1  10  6 mol m  2 s  1 Pa  1 and 7.3, respectively.
Permeation data about other reported MOF membranes can be
found in the review prepared by Shah et al. (2012).
4.3. Silica membranes
Silica membranes are the most important representatives of
amorphous microporous membranes, because they can be more
easily prepared as ultra- or super-microporous thin layers in
comparison to other metal oxides (such as alumina, titania or
zirconia) and these can be used for molecular sieving applications.
The most widely used technologies for deposition of silica
layers on porous substrates are solgel (Tsuru, 2008) and CVD
(Nagano et al., 2008). Silica membranes with pore diameters less
than 1 nm can be prepared by CVD which provides high hydrogen
selectivity (molecular sieving) but, consequently, a lower permeability. Moreover, the CVD method requires substantial capital

investment and well dened and controlled deposition conditions. On the contrary, solgel derived membranes generally
achieve lower selectivities but higher permeabilities. These membranes are much easier to produce with the possibility of
controlling the pore size of the silica membranes, but the
prepared membranes still suffer of low reproducibility which
makes their industrial exploitation less attractive.
Akamatsu et al. (2008) prepared and tested silica membranes
via CVD technique. The test results showed an excellent H2
permeance at 600 1C of the order of 10  7 mol m  2 s  1 Pa  1,
and a high H2/N2 selectivity of over 1000.
Yoshino et al. (2005) reported silica membranes prepared by
solgel technique with a permeance at 600 1C of
7  10  7 mol m  2 s  1 Pa  1 and H2/N2 selectivity around 100.
This group (Yoshino et al., 2006) also fabricated a membrane
module with a membrane area of 0.05 m2.
The main problem of microporous silica membranes, as in the
case of titania and alumina, is that they are not stable at high
temperatures, especially in the presence of steam, leading to loss
of permeability. This is due to closure of pore channels by
densication which is catalyzed by humidity, particularly at high
temperatures (Lin, 2001). Furthermore, this phenomenon may
cause silica lm embrittlement with the subsequent loss in
separation properties.
In order to improve the stability of silica membranes, different
approaches have been proposed in the literature. The rst
approach used is the doping of silica with inorganic oxides (e.g.,
titania, zirconia and alumina) (Kanezashi and Asaeda, 2006;
Sekulic et al., 2002).
Kanezashi and Asaeda(2006) prepared Ni-doped silica membranes with a permeance of 4.6  10  6 m3 (STP) m  2 s  1 kPa  1
for H2 with a H2/N2 selectivity of 400 even after being kept in
steam (steam pressure: 90 kPa) at 500 1C for about 6 days. Tsuru
et al. (2011) prepared Co-doped silica membranes (approx. 50 nm
thick layer) with a H2 permeance of approximately 1.8 
10  7 mol m  2 s  1 Pa  1 and a H2/N2 selectivity of 730 even after
60 h of exposure to steam (steam: 300 kPa) at 500 1C. Doping of
metals into silica membranes has been investigated in order to
increase the hydrothermal stability at high temperatures and for
their possible application to membrane reactors, such as steam
reforming of methane (Battersby et al., 2009).
Another approach to obtain hydrothermal stable silica membranes is to incorporate methyl groups in the silica microstructure as proposed by Campaniello et al. (2004). Recently, hybrid
(organicinorganic) silica membranes are widely being studied
because the presence of organic groups in silica networks could
improve the hydrothermal stability of silica structures and help
controlling the pore size of the membrane (Duke et al., 2004).
Castricum et al. (2008) prepared hybrid silica membranes derived
by co-polymerization of methyltriethoxysilane and bis(triethoxysilyl)ethane with high hydrothermal stability. Kanezashi et al.
(2009) reported a hybrid silica membrane using BTESE as precursor with a high H2 permeance around 10  5 mol m  2 s  1 Pa  1
but low H2/N2 selectivity of around 10 at 200 1C.
4.4. Carbon membranes
Carbon membranes are promising candidates for hydrogen
separation due to their high separation performance and excellent
thermal and chemical resistance (Ismail and David, 2001; Koros
and Mahajan, 2000). Based on the pore size, carbon membranes
are generally divided in carbon molecular sieve membranes
(CMS) and selective surface ow (SSF) membranes. CMS membranes could allow the transport of small molecules through the
pores, avoiding the passage of larger molecules. Due to their small
pores, CMS membranes possess a high selectivity for separation of

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

gas mixtures containing small gas species. In this case, a precise

control of pore sizes near to molecular sieving size is required. SSF
membranes have pores larger than the dimensions of the molecules and thus the separation is based on the preferential
adsorption of some components in gas mixture followed by
surface diffusion in the carbon matrix (Seo et al., 2002). This
section will be focused on CMS membranes due to their properties for high H2 separation in comparison to SSF membranes.
CMS membranes are the result of the pyrolysis of polymeric
precursors under an inert or vacuum atmosphere. The most important parameters that would inuence the nal properties of CSM
membranes are: (i) type of polymeric precursors such as polyimides,
polyfurfuryl alcohol, phenolic resins, polyvinylidene chloride, polyacronitrile, cellulose derivates, and polyetherimide (Sau and Ismail,
2004); (ii) pyrolysis conditions (i.e., heating rate, atmosphere and
nal temperature) (Geiszler and Koros, 1996; Centeno et al., 2004);
and (iii) modications (i.e., pre- or post-treatment such as stabilization, activation or oxidation, and CVD) (Barsema et al., 2004; Lee
et al., 2008; Li et al., 2008c; Wang et al., 2002).
The most commonly used techniques for depositing CSM
layers onto supports may be dip coating (Hayashi et al., 1997),
ultrasonic deposition (Shiett and Foley, 2000), vapor deposition
(Wang et al., 2000), spin coating (Tseng et al., 2009), and spray
coating (Acharya and Foley, 1999).
Some of the most relevant current developments on carbon
membranes for hydrogen separation are presented afterwards.
Hosseini and Chung (2009) from National University of Singapore reported carbon membranes prepared from blends of PBI
and polyimides with a high H2/N2 selectivity of 460480 and H2
permeability of 60180 barrer (1 barrer1  10  10 cm3(STP)
cm cm  2 s  1 cm Hg  1). Campo et al. (2010) have developed
CMS membranes from cellophane paper with very interesting
hydrogen permeation properties: H2 permeability of 39.3 barrer,
H2/N2 and H2/CO2 selectivities of 1310 and 58.7, respectively

(Celo600 Sample). Grainger and Hagg

(2007) reported CMS from
cellulose base based precursors with a H2/N2 selectivity of 740
and H2 permeability of 1110 barrer at 90 1C and at a feed pressure
of 6 bar. Media and Process Technology, Inc. is commercializing
CSM composite membranes prepared by the pyrolysis of a PEI
precursor deposited onto a ceramic porous substrate (Abdollahi
et al., 2010; Sedigh et al., 2000).

51

hopping between oxide ions (Grotthuss mechanism). As for the

oxygen conductors, sufciently high temperatures are required
for high proton conductivity.
The general formula of perovskite-type oxides is AB1  x
MxO3  d, where the A element is taken from the group consisting
of (Ca, Sr, B); the B element is taken from the group consisting of
be Ce, Tb, Zr, Tl; M element is taken from the group consisting of
Ti, Cr, Mn, Co, Ni, Co, Al, Y, Ga; x is less than the upper limit of
solid solution formation range (usually less than 0.2) and d is the
oxygen deciency per unit cell.
The most extensively studied high temperature perovskitetype oxides are SrCeO3 (Higuchi et al., 2004; Song et al., 2002),
BaCeO3 (Guan et al., 1997; Ma et al., 1998) and BaZrO3 (Tetsuo
et al., 2002). These perovskites have high protonic conductivity
but their electronic conductivity is poor. In order to improve the
latter conductivity it is common to dope these perovskites with
cations, such as Y (Sammes et al. 2004), Eu (Song et al., 2003) and
Gd (Shima and Haile, 1998).
The common methods for perovskite power synthesis are sol
gel (Selvaraj et al., 1991), spray drying (Varma et al., 1994),
hydrothermal synthesis (Zheng et al., 1997) and combustion of
polymerized complexes (Liu et al., 2002). On the other hand,
typical methods for perovskite lm deposition onto ceramic or
metal supports are CVD (Ngamou and Bahlawane, 2009), EVD
(Pal and Singhal, 1990) and PVD (Ma et al., 2008).
Some of the most relevant current developments on
perovskite-type membranes for hydrogen separation are presented afterwards.
Yuan et al. (2010) have prepared SrCe0.75Zr0.20Tm0.05O3 d
membranes with a H2 permeation ux up to 0.042 mL min  1 cm  2
at H2 partial pressure of 0.4 atm and at a temperature of 900 1C. The
Zr doping can increase mechanical stability of the membrane and
the resistance to reduction.
Yazdi et al. (2009) have developed BaCe1  xYxO3  d lms by DC
magnetron sputtering at room temperature. Ceramatec (Paglieri
and Way, 2002, CO2 Handbook, 2011) is producing a prototype
membrane for hydrogen separation from coal-derived syngas
using perovskite-type membranes. The pevoskite used is a mixture of barium cerate (BaCeO3) and ceria, where the former is
proton conductor and the latter is electron conductor. The preliminary tests showed a perfect H2 separation (100%) from H2/CO2
mixture.

5. Proton conducting membranes

Proton conducting membranes can be classied into two
groups: dense ceramic membranes and composite ceramic metal
(cermet) membranes. Both have their advantages and disadvantages in terms of membrane ux, perm-selectivity and stability. In
the following section both types of membranes are discussed.
5.1. Dense ceramic membranes
Dense ceramic membranes can recover a very high purity H2
stream due to a proton transport mechanism, but they have to
operate at temperatures as high as 900 1C. The hydrogen ux
through these membranes is proportional to the ambipolar
protonicelectronic conductivity. It is necessary to have high
values for protonic and electronic conductivities to obtain a high
hydrogen ux. The dense ceramic membranes may be classied
into two sub-categories: perovskite-type and non-perovskitetype membranes.
5.1.1. Perovskite-type membranes
The protons are embedded in perovskites in the electron cloud
of an oxygen ion, forming hydroxide defects. They migrate by

5.1.2. Non-perovskite-type membranes

The non-perovskite-type membranes used for hydrogen
separation are mainly doped rare earth metal oxides and
uorite-structured metal oxides. There are lots of different doped
rare earth metal oxides that may be interesting for hydrogen
separation, such as, Tb2O3, Ln2Ti2O7 and Er2Ti2O7.
Haugsrud and Norby (2006) prepared a 10 mm thick lm of
acceptor-doped LaNbO4 (i.e. La0.99Ca0.01NbO4) that has a H2 ux of
0.1 mL (STP) cm  2 min  1 at a temperature of 1000 1C and a
difference in pressure of 10 bar. This group also reported that
Ln6WO12 membranes have sufcient mixed electronproton conductivity at intermediate temperatures (Haugsrud, 2007).
Escolastico et al. (2011) have developed Nd5LaWO12 membranes and the results showed that the addition of La to Nd6WO12
increases the hydrogen ux from 0.03 to 0.05 mL min  1 cm  2 at
1000 1C and difference pressure of 0.5 bar.
Among uorite-structured metal oxides CeO2, YSZ and Y2O3
are the most used.
Nigara et al. (2003) have reported hydrogen permeation through
doped CeO2 and YSZ (Nigara et al., 2004) membranes, but unfortunately H2 permeabilities of these membranes are very low. Serra
et al. (2005) studied H2 permeation through commercial alumina

52

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

tubes obtaining as a result a H2 ux of 4  10  8 mol s  1 m  2 at

1400 1C.
5.2. Cermet membranes
Cermet membranes consist of a combination of a ceramic
phase and a metallic phase. The former is a pure proton conductor, while the latter is a highly electron conductor. Combining
these two phases together may provide high H2 permeation
because both proton and electron conductivities become high,
resulting in high hydrogen permeation.
Due to the hydrogen transport by both metals and oxides,
mainly three different combinations with respect to functional
properties of both phases can be realized: (1) a metal with low
hydrogen conductivity in combination with a highly proton
conductive oxide, (ii) a metal or an alloy with high hydrogen
permeability (i.e., Pd, Pd/Ag, Pd/Cu, Nb, Ta, V) combined with a
ceramic of low hydrogen permeability and (3) a combination
where both the metallic and ceramic phases conduct hydrogen.
Some of the most relevant current developments on cermet
membranes for hydrogen separation are presented in the following.
Balachandran et al. (2006) from Argonne National Laboratory (ANL)
developed Pd/YSZ composite membranes and the highest H2 ux
was  20.0 cm3 (STP) min  1 cm  2 for a  22 mm thick membrane
at 900 1C using 100% H2 as feed gas. Recently, Zhu et al. (2011) have
developed a 30 mm thick NiBZCY (Ba(Zr0.1Ce0.7Y0.2)O3 d) cermet
layer onto ceramic support that exhibited a maximum H2 ux of
2.4  10  7 mol cm  2 s  1 at 900 1C using 80% H2/N2 (with 3% of
H2O) as feed gas and dry high purity argon as sweep gas.
Park et al. (2011) have developed a 0.5 mm thick Ta/YSZ membrane and the highest H2 ux obtained was 1.2 ml min  1 cm  2 at
300 1C using 100% H2 as the feed gas and Ar as the sweep gas.
Jeon et al. (2011a) have developed a 0.5 mm cermet membrane composed of Pd embedded in proton conducting ceramic
matrix (CaZr0.9Y0.1O3  d) and its H2 ux was around 2.3 cm3
(STP) min  1 cm  2 at 900 1C. This group also has developed
PdGDC (Ce0.8Gd0.2O2  d) cermet membranes for high sulfur
resistance and no sharp drop in hydrogen permeation ux was
observed using feed gases with 220 ppm H2S (Jeon et al., 2011b).
The best performances of membranes investigated in the
various research organizations are summarized in Table 2.
Besides, membranes on the way to commercialization commented before are shown in Table 3. It is shown that relatively high
uxes with good perm-selectivities can be now achieved with
hydrogen membranes which make this technology closer to the
real market.

6. Advances in membrane reactors for hydrogen production

The application of membrane reactors for dehydrogenation
reactions has been rst proposed to the scientic community by
Prof. Gryaznov in the late 60s (see for example Gryaznov et al.,
1970). Removing hydrogen through a thick membrane resulted in
a shift of the equilibrium reaction towards the product of interest.
Membrane reactors in dehydrogenation reactions were a scientic curiosity until around 1996 with few papers published per
year. With the increasing interest into hydrogen as a possible
clean energy carrier, the scientic attention towards membrane
reactors as high efcient hydrogen production systems sharply
increased in the last years (Fig. 12). Probably the echo produced
by the two books The Hydrogen Economy (Rifkin, 2002;
National Academy of Engineering, 2004) was also reected in
the great increase of number of papers in the last 5 years.
However, our research will focus on the progresses on membrane
reactors in the last 10 years. Accordingly with the increase of

number of papers, the patents awarded on hydrogen production

in membrane reactors also increased with time and in the last years
this number is increasing rapidly. In fact, most of the patents have
been awarded in the last 10 years (Gallucci et al., 2009).
Different types of membrane reactors for hydrogen production
have been proposed in the literature. Most of the previous work
has been performed in packed bed membrane reactors (PBMR);
however, there is an increasing interest in novel congurations
such as uidized bed membrane reactors (FBMR) and micromembrane reactors (MMR) especially because better heat management and decreased mass transfer limitations can be obtained
in these reactor congurations. In the following, these reactor
congurations, along with membrane bio-reactors (MBR) and
catalytic membrane reactors (CMR) for hydrogen production will
be discussed in detail.
6.1. Packed bed membrane reactors
The packed bed membrane reactor conguration is the rst
and most studied conguration for hydrogen production in
membrane reactors. This is because, the rst studies on membrane reactors focussed on the effect of the hydrogen permeation
through membranes on the reaction system. Thus it was straightforward to compare two packed bed reactors (avoiding the
complication of complex uid dynamics such as in uidized
bed) in one of which a membrane was used.
In the following table the main investigators working with
PBMR for hydrogen production are summarized (source Scopus):
The different authors showed that the concept of Pd-based
membrane reactor can be used to carry out and intensify different
dehydrogenation reactions such as reforming of methane and
different alcohols. In particular, packed bed membrane reactors
have been used for producing hydrogen via reforming of methane
(Gallucci et al., 2006; Matsumura and Tong, 2008), reforming of
alcohols (Kikuchi et al., 2008; Tosti et al., 2009), autothermal
reforming (Simakov and Sheintuch, 2009), partial oxidation of
methane (Tan and Li, 2009), etc. The results of these studies are
interesting to show that indeed the Pd membranes are not
poisoned by the different alcohols and the products of the
reactions such as CO2 or higher hydrocarbons. The only poisoning
can be due to the presence of H2S as said above or CO (if low
temperature o300 1C is used).
In a packed bed membrane reactor the catalyst is conned in
xed bed conguration and in contact with a perm-selective
membrane. The most used packed bed conguration is the
tubular one where the catalyst may be packed either in the
membrane tube (Fig. 13a) or in the shell side (Fig. 13b), while the
permeation stream is collected in the other side of the membrane
(in case of hydrogen selective membranes) or one reactant is feed
on the other side of the membrane (in case of oxygen selective
membrane Jin et al., 2000).
For multi-tubular membrane reactor congurations the catalyst in tube conguration can be preferred especially for construction reasons and for the extent of bed-to-wall mass and heat
transfer limitations which can be very detrimental when the
catalyst is positioned in shell conguration.
Often, a sweep gas can be used in the permeation side of the
membrane in order to keep the permeation hydrogen partial
pressure as low as possible for minimizing the membrane area
required for the hydrogen separation. This practice is for example
very useful if hydrogen for ammonia plant is being produced, in
which case an amount of nitrogen can be used for sweeping the
permeation side producing a synthesis stream (N2/H2 1/3)
ready for the nal reaction step. If a sweep gas is used in the
permeation side then a packed bed membrane reactor can be
used in both co-current and counter current modes. Using a

Table 2
Permeation data of different hydrogen separation membranes reported in the literature.
Membrane material

Preparation method

Selective
layer
thickness
(mm)

T (1C)

Permeance
H2 [10  8
(mol/m2 s Pa)]a

Permeability
H2 [10  13
(mol m/m2 s Pa)]

Ideal
selectivity

Sulfur
tolerance
(ppm)

Durability
(h)

AIST (Pacheco Tanaka et al., 2006)

AIST (Pacheco Tanaka et al., 2008)
CSM (Hatlevik et al., 2010)
DICP (Goldbach and Xu, 2011)
SINTEF (Peters et al., 2011a)b
SwRI (Coulter et al., 2012)b
WPI (Ma, 2009)
CALTECH (Li et al., 2000)
SNL (Welk et al., 2004)

Pd/Al2O3
Pd/YSZ
PdAu/YSZ/PSS
PdAu/Al2O3
PdAg/PSS
PdAuPt
Pd/Inconel
ZSM-5/Al2O3
ZSM-5/Al2O3

Pore lling
Pore lling
ELP
ELP
PVD-MS
PVD-MS
ELP
Hydrothermal synthesis
Hydrothermal synthesis

5
5
2.3
23
2.8
25
7
67
 10

300
425
400
500
400
400
450
150
25

170
210
710
620
1,500
54
96
12
68

160
160
420
130
67
7.8
68

2000

 2,200

Nanjing University (Zhang et al., 2012)

Liebniz University Hannover (Li et al., 2010)
Liebniz University Hannover (Huang and
Caro, 2011)
Texas A&M University (McCarthy et al.,
2010)
Texas A&M University (Guerrero et al.,
2010)
University of Minnesota (Choi and
Tsapatsis, 2010)
The University of Tokyo (Akamatsu et al.,
2008)
Noritake Company (Yoshino et al., 2005)
Hiroshima University (Kanezashi and
Asaeda, 2006)
Hiroshima University (Tsuru et al., 2011)
Hiroshima University (Kanezashi et al.,
2009)
National University of Singapore (Hosseini
and Chung, 2009)
University of Porto (Campo et al., 2010)

NTNU (Grainger and Hagg,

2007)

MFI/Al2O3
ZIF-7/Al2O3
ZIF-90/Al2O3

2
20

500
220
200

28
4.5
21

0.9
42

ZIF-8/Al2O3

Hydrothermal synthesis
Secondary (seeded) growth
In situ growth (modied after synthesis
with ethanoldiamine)
In situ growth (support surface modied)

4 1,000 (H2/N2)
300 (H2/N2)
82,000 (H2/N2)
1400 (H2/N2)
2900 (H2/N2)

 4,500 (H2/He)
109 (H2/N2)
16.6 (H2/CO2, CO,
CH4)
42.6 (H2/CO2)
20.7 (H2/N2)
17.5 (H2/N2)

20

25

17

42.5

11.6 (H2/N2)

HKUST-1/Al2O3

Secondary (seeded) growth

25

190

110

275

7.3 (H2/N2)

(MCM-22)-SiO2/Al2O3

Layer-by-layer deposition

1

200

0.7

 50 (H2/N2)

SiO2/Al2O3

CVD

600

1014

4 1,000 (H2/N2)

Total

SiO2/Al2O3
NiSiO2/Al2O3

Sol-gel
Solgel

0.02
0.3

600
500

70
20

0.14
0.6

100 (H2/N2)
400 (H2/N2)

144

Solgel
Solgel

0.05
0.5

500
200

18
1,000

0.09
50

730 (H2/N2)
10 (H2/N2)

60

Pyrolisis

35

0.20.27

460480 (H2/N2)

Pyrolisis
Pyrolisis

9.22

29.5
90

0.14

0.13
3.7

1,310 (H2/N2)
740 (H2/N2)

350

Liquid citrate method

900

0.64

Pressing

10

1000

0.22

0.22

Solgel

0.63

PdYSZ
Ni-BZCY/ceramic

Pressing
Pressing

 22
30

900
1000
900
900

150
2.9

330
8.7

TaYSZ

Pressing

500

300

8.9

450

PdCZY

Pressing

500

900

7.8

390

PdGDC

Pressing

282

900

19

540

220

CoSiO2
Hybrid silica (BTESE as
precursor)
Carbon (from PBI and
polyimide blends)
Carbon (from cellophane)
Carbon (from cellulosebased precursors)
South China University of Technology (Yuan SrCe0.75Zr0.20Tm0.05O3-d
et al., 2010)
University of Oslo (Haugsrud and Norby,
La0.99Ca0.01NbO4
2006)
ITQ- UPV (Escolastico et al., 2011)
Nd5LaWO12
ANL (Balachandran et al., 2006)
University of Science and Technology of
China (Zhu et al., 2011)
Korea Institute of Energy Research (Park
et al., 2011)
Chonnam National University (Jeon et al.,
2011a)
Chonnam National University (Jeon et al.,
2011b)
a
b

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

Institute

Permeance values have been calculated for a H2 partial pressure of 1 bar.

Self-supported membranes.
53

54

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

Table 3
Major investigators on packed bed membrane reactors
Investigator
name

Institution

Number
of papers

Basile A.
Tosti S.
Rahimpour,
M.R
Itoh N.
Lombardo
E.A.
Nomura N.

Institute on Membrane Technology (Italy)

ENEA (Italy)
Sharaz University (Iran)

35
29
27

Utsunomiya University (Japan)

Instituto de Investigaciones en Catalisis y
Petroqumica (Argentina)
University of Tokyo (Japan)

12
11
7

Fig. 13. Membrane reactor

(B) congurations.

Fig. 12. Number of papers on hydrogen production in membrane reactors per

year. Database Scopus (www.scopus.com). Keywords membrane reactor and
hydrogen production11 December 2012

counter-current mode leads to completely different partial pressure proles in reaction and permeation sides with respect to the
co-current mode (independently on the reaction system considered) (Gallucci et al., 2008c).
Although the tube in tube conguration is quite useful to work
in lab scale and for proof of principle of membrane reactors, for
industrial scale some other congurations need to be used in
order to increase the membrane area per volume of vessel used.
In fact, the amount of hydrogen produced is directly related to the
amount of membrane area installed in the reactor. Starting for the
tube in tube conguration, a straightforward way to increase the
membrane area in packed bed is the tube in shell conguration
(Buxbaum, 2002; Tosti et al., 2008). An example of multi-tube
membrane housing has been patented by Buxbaum (2002) and
reported in Fig. 14. In this case the catalyst is loaded in the shell
side of the reactor while the membrane tubes are connected to a
collector for the pure hydrogen. In particular, in the gure the
possibility to use a catalyst in a separate chamber is shown. In
case of reforming reactions, this chamber acts as a pre-reforming
zone where the greatest temperature proles are concentrated. In
this way the membranes will work at an almost constant
temperature.
The second way to increase the membrane area per volume of
reactor is adopting the hollow ber conguration. For example, in
case of perovskite membranes the membrane ux is generally
quite low and the hollow ber conguration is quite interesting.
The main investigators of hollow ber membrane reactors are
summarized in Table 4.

catalyst

in tube

(A)

and

catalyst in shell

These studies conrmed that the membrane preparation procedure can be also intensied to produce hollow ber membranes
with similar selectivities of the planar or tubular membranes.
Kleinert et al. (2006) studied for example POM in a hollow
ber membrane reactor. The perovskite membranes used by the
authors were produced from Ba(Co,Fe,Zr)O3  d (BCFZ) powder via
phase inversion spinning technique. A tube in tube conguration
has been used while the catalyst was packed in the shell side of
the reactor.
In their paper the authors show that the membrane was able
to give quite interesting results with a methane conversion of 82%
and a CO selectivity of 83%. Moreover the membrane was quite
stable under the reactive conditions investigated. Finally, the
combination of steam reforming and POM was studied by feeding
steam along with methane in order to suppress the carbon
formation. Even in these conditions the membrane reactor
showed good stability.
The membrane area required for the separation can be reduced
by increasing the membrane uxes (by keeping the same high
perm-selectivity). As already described above, membrane uxes can
be increased by decreasing the separation thickness (ultra thin
membranes). For example, for Pd-based membranes, defect free
separation layers as thin as 12 mm are now commonly produced in
laboratory (Mejdell et al., 2009a). The thinner is the separation
layer, the highest is the hydrogen ux through the membrane, the
lowest should be the membrane area required for a given hydrogen
recovery. However, the production of thin membranes brought
under the spotlight one of the disadvantages of xed bed membrane reactors: the inuence of bed-to-wall mass transfer limitations on the membrane area required. Briey, as long as the
hydrogen ux through the membrane is a limiting step, the effect
of external mass transfer limitations such as the limitations to
hydrogen transport between the bulk of the catalytic bed (where
hydrogen is produced) and the membrane wall (where hydrogen is
recovered) can be neglected. However, by increasing the membrane
ux, the external mass transfer limitations became limiting and
determine the extent of membrane area. An example of the increase

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

55

Fig. 14. Membrane housing (A), catalyst distribution (B) and membrane connectors (C) for a multitube membrane reactor (Buxbaum, 2002).

Table 4
Major investigators on hollow ber membrane reactors (source Scopus)
Investigator
name

Institution

Number
of papers

Tan, X. (Xiaoyao)
Haginaka, J. (Jun)
Li, K. (Kang)

Caro, J. (Jurgen)
Schiestel, T. (Thomas)

Shandong University of Technology, China

Mukogawa Women University, Japan
Imperial College London, UK
University of Hannover, Germany
Grenzachen

Fraunhofer-Institut fur
und Bioverfahrenstechnik, Germany

4
4
4
4
4

of extent of mass transfer limitations in membrane reactors was

given by Tiemersma et al. (2006) and reported in Fig. 15. In their
paper the authors claimed that with the membrane available in
2006 the effect of mass transfer limitations was quite limited.
However, by increasing their experimental membrane ux
(increase foreseen in a couple of years of membrane developments)
the external mass transfer limitation could become a limiting step
(as indicated in the gure).
The conclusions drawn by Tiemersma were really appropriated and were completely conrmed by the work carried out
at SINTEF by Bredesen and co-workers (see for example Peters
et al., 2008).
As indicated in Fig. 16, it is evident that the extent of bed-towall mass transfer limitations (also known as concentration
polarization) is the limiting factor for the permeation of hydrogen
through the membrane and thus it determines the amount of
membrane area required for a given hydrogen recovery. These
results have been also conrmed for self-supported membranes
via detailed modeling by Caravella et al. (2009).
A second important limitation of packed bed (membrane
reactors) is due to the pressure drop along the reactor, which
dictates the dimension of catalyst particle diameter to be used in
the reactor. To decrease the pressure drop large particles need to
be used and this reects in the extent of intra-particle mass
transfer limitations. The increase of intra-particle mass transfer
limitations lowers the local hydrogen partial pressure in the
reaction side and, consequently, it lowers the driving force for
hydrogen permeation through the membrane resulting in
increased membrane area required for a given conversion/
recovery.
Finally, the reactions for hydrogen production are often quite
endothermic (reforming reactions) or exothermic (CPO, etc.). The
temperature control is thus quite important because a decrease of

Fig. 15. Relative H2 weight fraction proles at changing membrane permeability.

Reproduced from Tiemersma et al. (2006) with permission of Elsevier.

temperature on the membrane surface leads to a decrease of

hydrogen ux through the membrane while an increase of
temperature could result in crack on the membrane surface with
consequent decrease of perm-selectivity (and thus deteriorating
the membrane reactor performances). The heat management and
temperature control in packed bed membrane reactors are quite
difcult and temperature proles along the membrane length are
difcult to avoid in such a reactor.
The combination of these drawbacks has driven the research
towards new reactor concepts such as micro-membrane reactors
or uidized bed membrane reactors as it is discussed in the
following sections.
6.2. Fluidized bed membrane reactors
A typical uidized membrane reactor (or membrane assisted
uidized bed MAFBR) for hydrogen production consists of a
bundle of hydrogen-selective membranes immersed in a catalytic
bed operated in the bubbling or turbulent regime. The use of
uidized bed membrane reactors reduces the bed-to-wall mass
transfer limitations, but also allows operating the reactor at a
virtually isothermal condition (due to the movement of catalyst).
This possibility can be used for operating the autothermal

56

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

Table 5
Major investigators on uidized bed membrane reactors (Scopus has been used for
the search).
Investigator
name

Institution

Number of
papers

Grace, J.R. (John)

The University of
British Columbia, Canada
Misr University for Science and
Technology, Egypt
Eindhoven University,
The Netherlands
Shiraz University, Iran

15

Elnashaie, S.S.E.H.
(Said)
Van Sint Annaland, M.
(Martin)
Rahimpour, M.R.
(Mohammad)
Abashar, M.E.E.
(Mohamed)

King Saud University,

Saudi Arabia

15
10
10
6

Fig. 16. Hydrogen pressure drops due to depletion, concentration polarization,

transport in the palladium membrane and porous support compared to the total
hydrogen partial pressure drop. Reprinted from Peters et al. (2008) with permission of Elsevier.

reforming of hydrocarbons inside the membrane reactor. In fact,

as indicated by Tiemersma et al. (2006), the autothermal reforming of methane in a packed bed membrane reactor is quite
difcult due to the hot-spot at the reactor inlet which can melt
down the membrane. This problem is completely circumvented in
uidized bed membrane reactors. In this case both autothermal
reforming and hydrogen recovery can be performed in a single
reactor.
According to Deshmukh et al. (2007) the main advantages of
the MAFBR can be listed as:

 Negligible pressure drop, which allows using small particle sizes

resulting in no internal mass and heat transfer limitations.

 (Virtual) isothermal operation.

 Flexibility in membrane and heat transfer surface area and
arrangement of the membrane bundles.

 Improved uidization behavior as a result of:

Compartmentalization, i.e. reduced axial gas backmixing.
Reduced average bubble size due to enhanced bubble
breakage, resulting in improved bubble to emulsion
mass transfer.
Different research groups applied membrane assisted uidized
bed for different reaction systems (mostly involving hydrogen) as
indicated in Table 5.
Even though Rahimpour et al. (2008, 2009, 2010) often used
uidized bed membrane reactor for distributive hydrogen feeding
in methanol reactors, most of the literature has focused on pure
hydrogen production through Pd-based membranes (see among
other Adris et al., 1991; Prasad and Elnashaie, 2002; Chen et al.,
2003a; Khademi et al., 2009) and on autothermal reforming
reactions (see for example Grace et al., 2001; Prasad and
Elnashaie, 2003; Patil et al., 2005; Gallucci, 2010a). It is important
to stress here how the experimental works on membrane assisted
uidized beds have also demonstrated as the Pd-based membranes can maintain their perm-selectivity even when operated in
uidized beds, thus when in contact with moving catalyst
particles.
A typical Pd-based membrane assisted uidized bed has been
proposed by Adris and co-workers and is reported in Fig. 17.
With this reactor the bed-to-wall mass transfer limitations can
be circumvented, while the heat required for the reforming

Fig. 17. Schematic representation of a uidized bed membrane reactor for

selective removal of hydrogen. After Adris et al. (1994).

reactions (often endothermic equilibrium reaction) is supplied

through heat exchange surfaces inserted in the reactor system. In
fact, uidized bed reactors present higher heat exchange coefcients compared to xed bed reactors.
However, beside the high heat exchange coefcients, uidized
beds are also suitable for isothermal operations even if a highly
exothermic reaction is occurring. This has been demonstrated for
example by Deshmukh et al. (2005a, b), who carried out oxidative
dehydrogenation of methanol in lab scale membrane uidized
bed reactors. The authors found virtually isothermal conditions
even for very high methanol feed concentrations.
This important aspect of uidized bed reactors make it
possible to operate autothermal reforming of methane (and other
hydrocarbons) by feeding oxygen directly in the membrane
reactor preventing the formation of hotspots and subsequent
damage of the membranes.

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

Indeed, Roy et al. (1999) rst demonstrated that autothermal

operation could be achieved by directly adding oxygen to a
uidized bed reformer to provide all the required heat via partial
oxidation reaction. The extension of this work to a membrane
uidized bed reactor has been performed by the same group few
years later. In particular, the previous experiences with autothermal
uidized beds and membrane uidized beds have been condensed
in a modeling paper by Grace et al. (2001). The model chosen by
Grace was an equilibrium model and this selection was made based
on the previous experience on modeling and experiments on
uidized bed membrane reactors which suggested that the overall
composition of each species at each position inside the bed was
found to be mainly controlled by two factors: (i) the quantity of
hydrogen which had permeated through the membranes (depending on the difference in hydrogen partial pressure and membrane
characteristics); (ii) chemical equilibrium at the given temperature
and overall pressure on the reactor side (depending on the very
high catalytic activity for methane reforming).
The model was applied in order to investigate the inuence of
various parameters on the performance of FBMR with oxygen
addition. Although the results showed that autothermal operation
can be achieved by using approximately 0.3 O2/CH4 feed ratio, the
interaction between the different parameters is quite complex.
For instance, in methane reformers an important parameter is the
steam/carbon ratio. However, when feeding also oxygen, the
steam becomes also a product of the oxidation reaction and this
makes the prediction of the reactor behavior a bit more complicated. Furthermore, an important conclusion of the work is that
oxygen addition reduces the coke formation and consequently the
catalyst deactivation.
Based on this paper and on various other papers dealing with
both theoretical and experimental works, recently the same group
presented the experimental ndings of pre-commercial membrane reactor prototypes for both methane reforming and ATR
(with air addition) (Chen et al., 2007; Mahecha-Botero et al.,
2008). The authors used optimized plane membranes, where

57

a single two-side planar membrane panel consists of two PdAg

foils mounted on a porous stainless steel base using proprietary
MRT sealing and protection techniques.
A scheme of the membrane reactor used is reported in Fig. 18
(Mahecha-Botero et al., 2008):
Based on their experience in the uidized bed, the authors
suggest that the ux through membranes computed by Sieverts
equation must be multiplied by an effectiveness factor for
membranes immersed in uidized-bed reactors. The authors
suggested that this effectiveness factor could possibly be due ne
dust generated in the bed or to other mass transfer resistances.
They demonstrated that by using ATR catalyst the effectiveness
factor could be higher than the case of reforming catalyst and
could in principle be higher than 0.9 (as high as 0.98 according
with Chen et al., 2007).
The experiments show that the maximum temperature difference along the reactor where membranes are immersed is always
lower that 20 1C (Mahecha-Botero et al., 2008), which results in a
higher membrane lifetime and avoids formation of pinholes.
All these works conrm that the autothermal reforming of
methane is possible in a uidized bed membrane reactor with
oxygen (or air) addition without hot spot formation.
It has be pointed out that feeding air directly in the reactors
brings two drawbacks: (i) the exhaust gas mainly consists of
nitrogen and CO2, if CO2 capture is required the separation is
difcult (and costly); (ii) in each case nitrogen dilutes the amount
of hydrogen in the reactor, reducing the driving force for hydrogen permeation through the membranes and resulting in higher
membrane area required in the reactor. For these reasons, feeding
oxygen in the uidized bed membrane reactor for achieving
autothermal reforming is more appropriate. However, an air
separation unit (a costly process) outside the reactor is required
to produce the oxygen for the autothermal reforming.
This problem can be circumvented by using novel reactor congurations proposed by Kuipers and co-workers (Patil et al., 2005, 2007;
Gallucci et al., 2008a, b). In particular two congurations have been

Fig. 18. Reactor conguration and Pd-based plane membrane details used by Grace group. (Mahecha-Botero et al., 2008) Reprinted with permission of Elsevier.

58

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

proposed to achieve the autothermal methane reforming: the two

congurations are called methane combustion conguration and
hydrogen combustion conguration.
The methane combustion conguration is sketched in Fig. 19
and consists of two sections (Patil et al., 2005). Hydrogen permselective membranes are integrated in a uidized reforming/shift
top section where ultra-pure H2 is extracted and the energy
required for the steam reforming is supplied via in situ methane
oxidation in a separate uidized bottom section, where oxygen is
selectively fed to the methane/steam feed via oxygen permselective membranes. Two different sections are required because
metallic Pd-based membranes for selective H2 extraction can only
be operated below typically 700 1C because of membrane stability, while acceptable O2 uxes through available perovskite-type
O2 perm-selective membranes can only be realized above
9001000 1C. In this case the air separation is achieved in situ
resulting in lower costs and in intrinsic CO2 capture.
In the oxidation section, CH4 is partially oxidized in order to
achieve the high temperatures required for O2 permeation
through the perovskite membranes and to simultaneously preheat part of the CH4/steam feed.
The preheated feed is mixed with additional CH4 and steam
and fed to the reforming/shift section, where CH4 is completely
converted to CO, CO2 and H2 because of the selective H2 extraction through the Pd membranes which shifts the methane steam
reforming. H2 extraction can be achieved by using dead-end Pd
membranes and applying a vacuum on the permeate side. Alternatively, a sweep gas (such as H2O) could be used, but the
decrease in membrane area due to the increased driving force
should outweigh the additional costs for separating H2 from the
sweep gas. Overall autothermal operation can be achieved by
tuning the overall CH4, O2 and steam fed to the reactor. The
distinct advantage of this reactor concept is that the temperatures

in both sections can be controlled independently by selecting the

proper ratio of CH4/H2O fed at the oxidation and reforming/shift
sections, while maintaining overall autothermal operation with
optimal energy efciency.
In Fig. 20, the hydrogen combustion conguration is shown,
where the energy for steam reforming is delivered via burning
part of the produced hydrogen (Gallucci et al., 2008a). This
conguration consists of only one uidized bed section, where
two types of hydrogen perm-selective membranes are incorporated: dead-end Pd-based membranes to recover ultra-pure H2 by
applying a vacuum on the permeate side (similar to the ones used
in the methane combustion conguration) and U-shaped Pdbased membranes with oxidative sweeping, by feeding air to
the permeate side to burn the permeated hydrogen.
The hydrogen combustion conguration has the clear advantage that only one section is required, circumventing the need for
a (costly) high temperature bottom section. On the other hand, in
the methane combustion conguration steam is produced in situ,
which enhances the CO conversion. Moreover, in the hydrogen
combustion conguration, part of the expensive Pd-based membranes are used to burn part of the produced hydrogen, while for
the methane combustion conguration further development of
oxygen perm-selective membranes (esp. the mechanical and
chemical stability) is essential.
Patil et al. (2005) and Gallucci et al., 2008a,b demonstrated
from both experimental and theoretical point of view that
autothermal reforming can be achieved in both reactor
conguration.
Moreover, applying detailed models to both packed bed and
uidized bed membrane reactors Gallucci et al. (2010b) demonstrated that for methane reforming the uidized bed membrane
reactor requires half membrane area compared to the packed bed
membrane reactors where external mass transfer limitations are
prevailing.
Detailed modeling of uidized bed membrane reactors is hindered by the fact that the hydrodynamics correlations present in
the literature are based on experiments carried out in uidized bed
without membranes. As it is well accepted that the presence of and
permeation through membranes inuence the hydrodynamics of

Fig. 19. Methane combustion conguration for pure hydrogen production through
autothermal reforming of methane.

Fig. 20. Hydrogen combustion conguration for pure hydrogen production

through autothermal reforming of methane.

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

the uidized bed, no detailed correlation to describe this multiphase reactor system are yet been proposed.
De Jong et al. (2011) presented for the rst a detailed study on
the inuence of permeation through vertical membranes on the
hydrodynamics of uidized bed membrane reactors. Through a
non-invasive experimental technique (particle image velocimetry
coupled with digital image analysis PIV-DIA) the authors studied
the hydrodynamics of a pseudo-2D uidized bed. It has been
demonstrated that, perhaps counter-intuitively, the extraction of
gas through the membranes may result in an increase of the
average bubble size, whereas the addition of gas via the porous
walls may result in a decrease of the average bubble size. Detailed
coupled PIV-DIA experiments have elucidated that these results
can be explained by the occurrence of densied zones near the
membranes and induced enhanced bubble coalescence in the
centre in case of gas extraction, and gas by-passing along the
walls in case of gas addition. It is clear that the detailed description of the effect of membrane on the characteristic of the
uidized bed is required to avoid under- or overestimation of
mass transfer and thus performance of the reactor.
6.3. Membrane micro-reactors
Micro-structured (membrane) reactors are quite interesting
due to their: (i) improved mass and heat transfer owing to the
reduction of the scale length in the micro-channels; (ii) removal
of mass transfer limitations (concentration polarization); (iii) high
degree of process intensication by integrating different process
steps in a small scale devise.
Although there is a great interest in micro-reactors, the
application of membrane micro-reactors is still limited. An interesting work is being carried out by Bredesen and co-workers
(Mejdell et al., 2009a,b,c) using thin, high selective and high
permeable Pd-based membranes produced via magnetron spattering
technique.
In particular, by comparing the performance of the same
membrane in different congurations, the authors showed that
in tubular conguration the extent of concentration polarization
is the limiting step for the hydrogen permeation (as also indicated
above), while with the same membrane used in micro-channel
conguration the concentration polarization effect can be completely neglected (Mejdell et al., 2009b). The micro-channel
reactor conguration proposed by Bredesen and co-workers is
depicted in Fig. 21 (Mejdell et al., 2009a).
The reactor consists of s micro-channels 13 mm long and a
section 1 mm  1 mm, while the membranes used are selfsupported Pd-based membrane thinner than 3 mm. It has been
shown that in this conguration a 1.4 mm thick membrane can
withstand a differential pressure 4470 kPa.
In another work (Mejdell et al., 2009c) the authors studied the
inuence of CO and CO2 (components always present in reforming reactions) on the permeation of hydrogen. Although concentration polarization is not a problem, at low temperatures CO
preferentially absorbs on the Pd surface (as found for all kind of
congurations) depleting the hydrogen permeation rate.
Other studies on membrane micro-reactors were carried out
for integrating different process steps in one micro-devise
for portable hydrogen production for fuel cells applications
(see for example Gervasio et al., 2005; Kim et al., 2009; Kudo
et al., 2009).
In their work, Gervasio and co-workers designed and operated
a membrane micro-reactor for generating pure hydrogen at
ambient temperature. The system can generate hydrogen for a
small fuel cell system. The interesting idea is based on the
efciency of the macro-reactor system (integrating feeding, reaction and hydrogen separation) coupled with an efcient hydrogen

59

Fig. 21. Sketch of the micro-channel reactor conguration used by Bredesen for
Pd-based membrane tests (Mejdell et al., 2009a). Reprinted with permission of
Elsevier.

carrier. The carrier is a liquid aqueous alkaline borohydride

solution which reacts (completely) at room temperature over a
Ru-based catalyst packed in the micro-reactor. One wall of the
reactor is made of a celgar membrane which is impermeable for
the liquid solution but permeable for gaseous hydrogen.
Another integration study has been carried out by Kim and coworkers who prepared integrated catalytic structured minichannel networks covered by a Pd-based membrane for hydrogen
recovery. This rst step work leads to a hydrogen separator made
of defect free Pd-layer. However, this is a step further towards the
use of such a system as integrated micro-reformer and separator.
A same approach has been used by Karnik and co-workers who
successfully produced Pd-based membrane via micro-fabrication
and used it for hydrogen separation. The authors were able to
design and fabricate a micro-reactor that was used for hydrogen
separation; however, the support (or a part of it) for the micromembrane is made of copper which is also active catalyst for
WGS reaction. The reactor can be thus used for on-board hydrogen production for micro-fuel cells application.
A different approach is used by Kudo et al. (2009) where the
micro-reactor applied consists of an array of up to 15 stages and
the membrane is used as a catalytic membrane in order to achieve
hydrogen production through methanol reforming reaction. The
particular gas proles in the micro-channels due to the laminar
ow are responsible, according to the authors, to the higher
methanol conversion and higher hydrogen yield compared to a
traditional tubular reactor system.
Finally, Alfadhel and Kothare (2005) modeled a membrane
micro-reactor for WGS reaction with a simplied (1D, isothermal)
model, suggesting the limitation of the simple model in simulating a membrane micro-reactor.
As above mentioned, membrane micro-reactors are very interesting systems to be studied in case external mass transfer
limitations could not be ignored (such as for high ux Pd-based
membranes) and when different steps need to be coupled
(coupling exothermic and endothermic reaction is an example).
However, more research is required before being able to design an
optimum membrane micro-reactor.
6.4. Membrane bio-reactors
As already mentioned above, most of the hydrogen is nowadays produced via high temperature reforming of fossil fuels
(especially natural gas). The rest of hydrogen is produced by
water splitting. It is clear that both the processes (thermal or
electrical) are energy intensive and sometimes (when using fossil
fuels) not environment friendly. For this reason, a great attention
is devoted to biological processes for hydrogen production, which
are low temperature processes (often ambient condition) and

60

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

environmental friendly. In addition, exploitation of such processes would lead to utilization of renewable resources.
Das and Veziroglu (2001, 2008) reviewed the biological processes for hydrogen production which, according to the authors,
can be summarized as:

 Biophotolysis of water using algae and cyanobacteria.

 Photodecomposition of organic compounds by photo-synthetic



bacteria.
Fermentative hydrogen production from organic compounds
Hybrid systems using photosynthetic and fermentative bacteria.

The advances in research related to these processes can be

found in Das and Veziroglu (2008).
Different biological hydrogen production processes can be
effectively carried out in membrane bio-reactors. In most of the
cases the membrane is not immersed in the reactor where
hydrogen production takes place but rather used outside the
reactor as a retention (of feedstock) media. The membrane should
be able to separate the uids (water and gases) from bacteria and
unconverted feedstock.
The membranes used are thus typical (polymeric) membranes
already commercially applied for water treatments like hollow
bers for ultra ltration and so on.
Examples of such a membrane bio-reactor for hydrogen bioproduction are reported by few authors in the recent literature
(see Jeong et al., 2007; Lee et al., 2007; Oh et al., 2004).
Lee and co-workers used a membrane bio-reactor consisting of a
hollow ber MF commercial module connected downstream to a
CSTR reactor. The CSTR is the typical reactor where the fermentative
hydrogen production takes place; easy to design and operate, the
only drawbacks of the CSTR for such a process is the low cell
retention resulting in low hydrogen yield. Connecting the microltration module (on the market for a wide range of water treatments) to the CSTR, the liquid efuent is ltered out in the hollow
ber module and the cells are recycled inside the reactor, circumventing the cell washout problem. The authors applied the
membrane bio-reactor to hydrogen production from different substrates (fructose, sucrose and glucose) and in each case it has been
demonstrated that the hydrogen yield in the membrane reactor is
much higher than the corresponding hydrogen yield of a single CSTR.
A similar approach to a glucose based hydrogen bioproduction has been applied by Oh et al. (2004), where a crossow membrane module has been used to retain the hydrogen
production bacteria to be re-circulated in the anaerobic reactor.
Also the authors found out that the hydrogen production rate can
be increased by 25% by using a membrane bio-reactor instead of a
single anaerobic reactor.
Finally Jeong et al. (2007) applied a commercial hollow ber
module connected to an acid fermentation reactor for hydrogen
production from waste activated sludge. Also in this case the
membrane separation busted the system to a higher hydrogen
production compared to a system without membrane separation.
From these examples it is clear as a membrane reactor can
help the biological production of hydrogen from renewable
sources. Of course the typical problems of such a membrane
system (caking, aging) already well known in water treatment
processes have to be taken into account when designing the
membrane bio-reactor.

7. Feedstock for hydrogen production

In the following section a brief review on the advances
on hydrogen production in MRs from different feedstock is

presented. Most of the hydrogen is produced by methane reforming, for this reason also a great part of the literature on MRs deals
with hydrogen production via reforming of methane in membrane reactors. However, great attention is devoted to hydrogen
production from other hydrocarbons, and even more on hydrogen
production from renewable sources such as bio-ethanol and biomethanol.
7.1. H2 production from methane in MR
Methane steam reforming has been used for hydrogen production since long time, and it is the industrially most exploited
reaction system for hydrogen production. Optimized catalysts for
such a reaction commercially exist (mostly Ni based catalysts)
and the catalytic activity is so high that the equilibrium conversion is easily achieved in these reactors.
Since the methane steam reforming is an equilibrium system,
the application of hydrogen selective membranes inside the
reactor help to circumvent the equilibrium limitation while
simultaneously produce a pure hydrogen stream. The membrane
reactor system needs thus milder reaction conditions with respect
to a conventional reactor and a downstream separation system is
not required. There are different papers in the literature showing
that the application of Pd-based membranes to the methane
steam reforming leads to a methane conversion well above the
equilibrium limitation (see for example Gallucci et al., 2004;
Ferreira-Aparicio et al., 2005; Chen et al., 2008). The extent of
the increase of conversion and amount of hydrogen production is
related to the surface of membrane installed per unit of volumetric feed ow rate (Gallucci et al., 2008b). The higher is the
membrane area installed the higher is the conversion and the
pure hydrogen production rate.
The advances in hydrogen production by methane reforming
in membrane reactors are basically related to: (i) the design of a
suitable reactor to decrease the mass transfer limitations; (ii) heat
supply to the reactor; (iii) combining the steam reforming with
other reactions to optimize the system.
Mass transfer limitations can be decreased by applying a
reasonable design such as micro-reactors and uidized bed as
described above. The heat required by the reactor can be achieve
by feeding air (or oxygen) directly in the reactor to obtain the
autothermal reforming, but in this case a uidized bed reactor is
more suitable in order to avoid hot spots (Chen et al., 2007;
Mahecha-Botero et al., 2008; Abashar et al., 2008). Also oxygen
feeding through membranes has been proposed and discussed
above (Patil et al., 2007; Gallucci et al., 2008a), or heat supply by
burning part of the hydrogen recovered (Gallucci et al., 2008b)
can be used.
Since methane reforming in membrane reactors is carried out
at lower temperatures ( o600 1C) with respect conventional
systems ( 4900 1C), the heat supply in MR is somehow simpler
and other heat sources can be used. For instance, Giaconia et al.
(2008) and De Falco et al. (2010) used a system in which the heat
required by the methane reforming is supplied via molten salts
produced via concentrated solar power. The molten salts have a
temperature of 550 1C and can be successfully used to supply the
heat to the membrane reformer, in a tubes-in-shell conguration.
Also thermally coupled reactors have been proposed for heat
supply, where an exothermic reaction takes place in a chamber of
the reactor while the membrane reformer is the other chamber of
the reactor and the heat is supplied via the wall dividing the two
chambers (Patel and Sunol, 2007; Simakov and Sheintuch, 2009).
In this case along with the ratio between the methane reforming
rate and permeation rate already discussed, another important
parameter to be carefully controlled is the ratio between the
oxidation reaction taking place in a chamber and the steam

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

reforming reaction rate. This ratio, in a thermally coupled reactor,

denes the temperature proles inside the membrane reformer.
Concerning the possibility to couple the steam reforming with
other reactions the two most interesting applications are the socalled steam dry reforming, where steam reforming and dry
reforming of methane are coupled in the reaction zone of the
membrane reactor (see e.g. Abashar, 2004) and the steam reforming coupled with the methanation reaction, where the methanation takes place in the permeation side of the membrane reactor
(see Mori et al., 2008). Dry reforming of methane is a signicant
process since reformates methane with a greenhouse gas (CO2)
into syngas. For this reason it attracted much attention in the last
years, and also in membrane reactors (Paturzo et al., 2003;
Gallucci et al., 2008d).
In his interesting theoretical work Abashar (2004) proposed to
develop a dual functional uidized bed membrane reactor to
couple the steam reforming with the dry reforming of methane,
where the high amount of carbon dioxide produced by the steam
reforming is used to produce syngas via dry reforming. Also for
this specic application, the membrane reactor shows a higher
performance compared with traditional reactor. The membrane
reactor conguration (in terms of ow conguration, mixed
catalysts and so on) can be optimized with the model proposed
by Abashar.
The second interesting application is proposed by Mori et al.
(2008), who suggest to use a methanator in the shell side of the
membrane reactor to convert traces of CO (which are surely
present in the permeation stream of the reactor when the
membrane is not completely hydrogen perm-selective), to
methane which is not armful for the fuel cell catalyst.
The study of Mori, shows that even when the Pd-based
membrane presents some defects (due to membrane aging or
membrane production method), the system is able to produce
pure hydrogen ( 499.8%) while maintaining the CO concentration
well below 10 ppm, thus a hydrogen stream suitable for PEM fuel
cell applications.
7.2. H2 production from other hydrocarbons in MR
The recent literature presents also works related to the
production of hydrogen for higher hydrocarbons in membrane
reactors. The production of hydrogen from other hydrocarbons
than methane is studied from two points of view: (i) the higher
hydrocarbon is considered a feedstock for hydrogen production
and (ii) hydrogen is a byproduct of a reaction involving a higher
hydrocarbon.
As far as the higher hydrocarbon is used as direct feedstock for
hydrogen, the typical reaction system occurring is based on the
following reactions (see for example Chen et al., 2003b, 2006;
Damle, 2008, 2009):
CnHm nH2O-nCO(nm/2)H2
CO3H23CH4 H2O
COH2O3CO2 H2
Basically, the higher hydrocarbon is easily converted to CO and
hydrogen at moderate temperatures, through an irreversible
reaction. Two successive equilibrium reactions (methanation
and WGS) follow the reforming. Being the temperature of the
reactor between 450 and 550 1C, the methanation is more shifted
towards the products, while the WGS is more shifted towards the
reactants, corresponding to a lower hydrogen production. By
using a membrane reactor, hydrogen is withdrawn during the
reforming, which results in suppressing the methanation reaction
and promoting the WGS. Thus, by using the membrane reactor

61

with H2-selective membranes, higher hydrogen yield is obtained

while pure hydrogen stream is also directly available for fuel cells
applications. Of course, all the aspects already discussed for
methane reforming in membrane reactors (heat supply, mass
transfer limitations, and so on) also read for reforming of higher
hydrocarbons, while the positive aspect to be taken into account
is that higher hydrocarbons are generally liquid and easier to
transport and with higher energy density compared to methane.
On the other hand, often higher hydrocarbon are reformed not
directly to syngas, but rather dehydrogenated to more valuable
products. Few examples are: ethane to ethylene (Wang et al.,
2003), cyclohexane to benzene, system which is seen as an
interesting hydrogen carrier (Itoh et al., 2003), isobutane to
isobutene (Liang and Hughes, 2005). In any of these processes,
hydrogen is simply a by-product, while its withdrawn will
increase the conversion towards the product of interest, while
at the same time producing a pure stream of hydrogen available
for PEM fuel cells and other applications.

7.3. H2 production from biological related feedstock in MR

A biological route for hydrogen production is highly desirable
since from one side the fossil fuels (such as NG) are limited and
not renewable, while from the other side the biological route
often do not produce additional CO2 emission into atmosphere. In
a previous section, the direct hydrogen production from biological
feedstock has been introduced and the application of membrane
reactors to enhance the hydrogen yield has been highlighted.
Although the direct bio-hydrogen production is a promising
route, a more realistic route for hydrogen production from biomass related feedstock is via reforming intermediate products (or
bio-products) of bio-mass transformation. In this case, reforming
of alcohols (methanol, ethanol) and acetic acid produced from
biomass has been greatly investigated in literature. Methanol,
ethanol and acetic acid can be converted (via steam reforming) to
a mixture of hydrogen, carbon oxides and other products like
methane, ethane, etc.).
The reforming of the feedstock is generally an equilibrium
system, involving also WGS reaction, although the overall system
requires much lower temperatures compared with the reforming
of natural gas (Kikuchi et al., 2008; Lin and Chang 2004).
Methanol has been widely studied, also because methanol
itself can be considered as an energy carrier much easier to
handle than hydrogen (Gallucci et al., 2007a,b). The permeation
through hydrogen selective membranes results in shifting the
reaction equilibrium (as for the methane reforming) while producing CO-free hydrogen stream directly available for PEM fuel cells.
Many authors (not reported in this review) reported the positive
effect of membranes in enhancing the methanol conversion. An
interesting application has been proposed by Fu and Wu (2007)
who adopted a double jacketed membrane reactor to obtain the
autothermal reforming of methanol. The methanol reforming
takes place in the shell between the membrane tube and the
second jacket, the hydrogen permeates through the membrane
and is recovered as CO-free stream. The unconverted reactants
and the unrecovered hydrogen are converted in the second jacket
with air producing the heat which is supplied to the reforming
system through the jacket wall. In this way, complete conversion
of methanol and complete recovery of hydrogen are not required,
and autothermal operation can be achieved. The reforming/
oxidation ratio can be adjusted by tuning the air ow in the
second jacket.
Ethanol reforming in hydrogen selective membrane reactors
has been studied by Lin et al. (2004, 2008), Tosti et al. (2009),
Gallucci et al. (2010a), and others.

62

F. Gallucci et al. / Chemical Engineering Science 92 (2013) 4066

The application of hydrogen selective membranes inside the

reactor during ethanol reforming suppresses the formation of
methane (helping its reforming to hydrogen) resulting in an
increased conversion of ethanol and a pure hydrogen stream
generation. The heat required by the reforming reaction can be
supplied either feeding oxygen inside the reaction system (Lin,
2001) or by burning part of the hydrogen recovered (Gallucci
et al. (2010a)). In the rst case an air separation unit is required,
while in the second case up to 15% of the hydrogen produced is
lost to supply the heat through a Pd membrane.
Another way to produce hydrogen in membrane reactor is by
reforming of acetic acid as indicated by Basile et al. (2008). Since
methane is a main product of the reforming reaction, by applying
a mixture of catalysts (to be optimized) and a membrane reactor
(recovering hydrogen) the methane formation can be decreased
and the hydrogen yield can be enhanced.
Finally, a big attention on the reforming of bio-oils to produce
syngas or hydrogen has been paid in the recent literature;
however, the application of membranes in such a system has
not been yet exploited.

8. Conclusions
In this review, an extensive overview of the most suitable
membrane materials for hydrogen separation is presented.
Depending on the operating conditions and feed gas composition,
a wide variety of membrane materials can be selected for
hydrogen separation. The most widely studied membranes for
hydrogen separation are dense metal membranes and among
these membranes the Pd-based membranes are the closest to the
market. Extensive experimental study as well as DFT-based
calculations have shown that the permeability of the Pd-based
membranes can be enhanced by alloying the Pd in binary or
ternary alloys. This can improve the permeability but also the
stability of the membrane against poisoning of CO and or H2S.
Some examples of the progress in commercialization of these
membranes are shown. On the other hand, microporous and
proton conducting are also promising ones for high purity
hydrogen purication.
Membranes can be integrated in membrane reactors with different embodiments. The easiest and most studied reactor type is the
packed bed membrane reactor conguration. However, with the
production of very thin and highly permeable membranes the extent
of mass transfer limitations (concentration polarization) prevailing in
packed bed membrane reactor make this conguration not suitable
for hydrogen production. Industrial type of reactors for pure hydrogen production will most likely be based on uidized bed conguration and/or micro-structured reactors. In both cases the mass
transfer limitations within the catalysts bed are circumvented and
the membrane area required is thus minimized. Membranes and
membrane reactors discussed in this review can easily be applied to
different fuels (from gas fossil fuels to bio-derived fuels). Experimental data especially on packed bed membrane reactors with
different fuels also indicated that the membrane performances are
not deteriorated by the presence of alcohols or bio-derived fuels.
Based on the results and the state of the art on membrane reactors
the rst membrane reactors operated at larger scale will be probably
based on natural gas reforming and on bio-ethanol reforming.

Acknowledgments
The research leading to these results has received funding
from the European Union Seventh Framework Programme
(FP7/2007-2013) under Grant agreement No. 262840 (DEMCAMER).

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