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Review
H I G H L I G H T S
a r t i c l e i n f o a b s t r a c t
Article history: Membranes and membrane reactors for pure hydrogen production are widely investigated not only
Received 22 October 2012 because of the important application areas of hydrogen, but especially because mechanically and
Received in revised form chemically stable membranes with high perm-selectivity towards hydrogen are available and are
17 December 2012
continuously further improved in terms of stability and hydrogen flux. Membrane reactors are
Accepted 6 January 2013
Available online 23 January 2013
(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
Keywords: process steps results in a high degree of process integration/intensification, with accompanying
Membrane reactor benefits in terms of increased process or energy efficiencies and reduced reactor or catalyst volume.
Hydrogen production
The aim of this review is to highlight recent advances in hydrogen selective membranes (from
Packed bed
palladium-based to silica and proton conductors) along with the advances for the different types of
Fluidization
Separations membrane reactors available (from packed bed to fluidized bed, from micro-reactors to bio-membrane
Membranes reactors). In addition, the application of membrane reactors for hydrogen production from different
feedstock is also discussed.
& 2013 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2. Hydrogen separation membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.1. Membrane materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.2. Membrane configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.1. Geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.2. Unsupported and supported membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3. 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
n
Corresponding author. Tel.: þ31 40 247 3675; fax: þ31 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) 40–66 41
integration among different process units are required to obtain the most promising and membrane separation is nowadays increas-
the hydrogen at the desired high purity. ingly considered as a good candidate for substituting conventional
Among different technologies related to production, separa- systems. The specific thermodynamic constrains limiting traditional
tion and purification of H2, membrane technologies seem to be reactors can be circumvented by using innovative integrated systems,
N 2 , O2
Air
Post-Combustion Coal
Capture Power & CO2 CO2
Gas
Heat separation
Biomass
Coal CO2
Biomass Air/Steam
Reforming CO2
Pre-Combustion Power &
Gasification + CO2 compression &
Capture Heat
separation Dehydration
Gas
Air
Oil
Coal CO2
Power &
Gas Heat
Oxyfuel Biomass
Combustion O2
Air N2
Air separation
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) 40–66 43
such as the so-called membrane reactors (MRs), engineering systems hydrogenation and dehydrogenation (Dittmeyer et al., 2001;
in which both reaction and separation are carried out in the same Gimeno et al., 2009), methane steam reforming (Matsumura and
device (see Fig. 3). Tong, 2008), and water–gas shift (Bi et al., 2009).
In comparison to a conventional configuration in which a
reactor is combined with a downstream separation unit, the use
of membrane reactors can bring various potential advantages 2.1. Membrane materials
such as reduced capital costs (due to the reduction in size of the
process unit), improved yields and selectivities (due to the Regarding the type of materials, hydrogen separation mem-
equilibrium shift effect) and reduced downstream separation branes may be classified into the following categories: polymeric
costs (separation is integrated). membranes, porous membranes, dense metal membranes and
The success of membrane reactors for hydrogen production proton conducting membranes. Table 1 shows a comparison
depends crucially on: (i) the advances in the membrane produc- between the different membrane types for hydrogen separation.
tion methods for the production of thin membranes with high The most important parameters when comparing membranes are
hydrogen fluxes and high hydrogen perm-selectivities; (ii) the the perm-selectivity, the flux and the temperature range at which
design of innovative reactor concepts which allow the integration the membranes can be applied.
of separation and energy exchange, the reduction of mass and In order to obtain high purity hydrogen-permeate streams,
heat transfer resistances and the simplification of the housing and dense metal membranes (mainly palladium alloys) and dense
sealing of the membranes. ceramic membranes are currently the most suitable materials
In this review we will first discuss recent advances in (high due to their high hydrogen selectivity. Pd–alloys (mainly Pd–Ag,
temperature) membranes to be applied in hydrogen production Pd–Cu and Pd–X–Au) are used to decrease the embrittlement
units, categorized into dense metal membranes, microporous problem and to decrease the poisoning of the membrane when in
membranes and proton conducting membranes. An overview of contact with H2S and other pollutants (such as CO). Microporous
the most permeable and selective membranes is given together ceramic membranes are promising materials for high purity
with a collection of commercial membranes for hydrogen produc- hydrogen production and separation. However, these membranes
tion. Subsequently, recent developments in membrane reactors separate hydrogen by size exclusion and thus selectivity is still
design will be highlighted and the application of membrane limited compared to more expensive dense inorganic membranes.
reactors for hydrogen production from different feedstock will Nowadays, the selective layers are thin (for instance, Pd mem-
be discussed. branes 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
There have been many applications of catalytic inorganic Fig. 4. Solution–diffusion mechanism of hydrogen permeation through a dense
membrane reactors for reactions involving hydrogen, such as 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 Silica, alumina, zirconia, titania, zeolites, Carbon Palladium alloys Perovskites (mainly
acetate, polysulfone, etc. metal-organic frameworks (MOF) SrCeO3 d, BaCeO3 d)
Temperature (1C) o 100 200–600 500–900 300–700 600–900
H2 selectivity Low 5–139 4–20 41000 41000
H2 flux Low 60–300 10–200 60–300 6–80
(10 3 mol m 2
s 1) at DP ¼ 1 bar
Transport Solution-diffusion Molecular sieving Surface diffusion, Solution-diffusion Solution-diffusion
mechanism molecular sieving
Stability issues Swelling, compaction, Stability in H2O Brittle, oxidizing Phase transition Stability in CO2
mechanical strength (causes
embrittlement)
Poisoning issues HCl, SOx, CO Strong adsorbing H2S, HCl, CO H2S
vapors, organics
Cost Low Low Low Moderate Low
44 F. Gallucci et al. / Chemical Engineering Science 92 (2013) 40–66
2.2. Membrane configurations 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.,
2.2.1. Geometry 2009). The typical deposition technologies used are: atmospheric
Membrane geometries may be planar, tubular (that includes plasma spraying (APS) (Sanz et al., 2011; Huang and Dittmeyer,
tubes, capillaries and hollow fibers), plate and frame and spiral 2007), wet powder spraying (WPS) (Zhao et al., 2004) and powder
wound. Currently the most commonly used geometries for gas suspension suction (Chi et al., 2010).
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 3. Dense metal membranes
the most preferred option (due to their higher surface area-to-
volume ratio in comparison to planar membranes). 3.1. General comments
On the other hand, there is a group of metals called refractory Solubility of hydrogen is also important for binary alloys;
metals (e.g., vanadium, niobium, and tantalum) that have much Sonwane et al. (2006) have shown by using DFT calculations that
higher permeability at these lower temperatures in comparison to the maximum solubility for PdAg is found at 30% Ag while for
palladium. These metals are much cheaper and have greater PdAu the maximum is found at 20% Au. For PdAg (30% Ag) the
tolerances to high temperatures compared to palladium. Never- hydrogen solubility has been found to be 10 times higher than for
theless, producing membranes with only these metals (as pure pure Pd. Hao and Sholl (2011) also applied DFT to evaluate the
components) is hindered by the high embrittlement produced at permeability of amorphous metal membranes (such as ZrCu
room temperature in the presence of 6.9 barhydrogen. On the based membranes). The results in this case show that the
contrary, several alloys of these metals are also non-embrittling, permeability is not directly related to the solubility of hydrogen,
making them good candidates for hydrogen purification mem- giving guidelines also for the design of amorphous metal mem-
branes (Dolan, 2010; Dolan et al., 2011; Ishikawa et al., 2011; branes. DFT calculations have also been applied to evaluate the
Paglieri et al., 2011; Wolden et al., 2013). These metals are not effect of contaminants in the gas mixture on the hydrogen
normally used alone for hydrogen permeation also because of permeability (Ling and Sholl, 2009; Ozdogan and Wilcox, 2010;
poor surface properties (particularly formation of surface oxide Gallucci et al., 2007a,b); it has been found that CO affects the
layers) that reduce hydrogen transport. When palladium or permeation of hydrogen especially because there is a preferential
palladium alloys are applied over the surface of refractory alloys adsorption of CO molecules on the same sites (hollow and bridge)
(Makrides et al., 1967; Paglieri et al., 2009), forming metal–metal used by H2; moreover CO can jump between the two sites and
matrix membranes, the surface barriers are removed and hydro- this is why a small amount of CO is enough to deteriorate the
gen permeation follows the trend shown in Fig. 5. hydrogen permeability (Gallucci et al., 2007a,b). Ozdogan and
As the number of possible combinations of these metals is Wilcox showed that the adsorption of H2S on the surface of the
enormous, a modeling approach can help in identifying the most membrane depends on the metal used to alloy palladium. In
suitable combination of metals for producing hydrogen mem- particular they found a H2S binding tendency such as Cu o
branes. An interesting approach towards the definition of suitable PdoNb. This is why PdCu have are more resistant to H2S poisoning.
modeling tools for this kind of study is given by the application of Ling and Sholl (2009) showed that any sulfide formation on the
density functional theory (DFT) calculations to predict the beha- membrane will decrease enormously the permeability of the
vior of binary or ternary alloys with pure hydrogen or with gas membrane especially due to the extremely slow diffusion of
mixtures. For example the group of Sholl published a series of H through the sulfide layer.
papers showing the potentiality of DFT in predicting the solubi- Regarding the experimental works on membranes, some of the
lity/diffusivity of hydrogen in different alloys, resulting in inter- most relevant current developments on dense metal membranes
esting guidelines for the future membrane production. In their for hydrogen production are presented afterwards.
works on PdCu based ternary alloys (Semidey-Flecha et al., 2010, Pd–Ag alloy membranes are usually prepared by electroless
Kamakoti and Sholl, 2003, 2006) the authors applied DFT to plating using a sequential deposition of the two metals. This
find an effective ternary additive to the PdCu alloy to retain the procedure gives the deposition of bi-layered metal films and
good poisoning resistance of the binary alloy while increasing the hence a high temperature and longer time is required for the
total permeability of the resulting membrane. It was found that complete inter-phase diffusion of two metals, in addition the
among different additives (such as Ni, Au, Ag, Rh, Pt) an addition precise control of Pd/Ag ratio in the membrane is difficult to
of Au or Ag can increase the permeability of the alloy of up to obtain.
5 times. They also found out that for this PdCuAg alloys, the At AIST-Japan, Pacheco Tanaka et al. (2005) developed a
increase of solubility due to the increase of Ag is more dominant method for the simultaneous plating of Pd-Ag with the desired
on the increase of permeability compared to the effect of composition of metals. This was achieved by the uniform deposi-
diffusivity. This means that for PdCu ternary alloys an additive tion of nano-particles of Pd nuclei on the surface of the substrate
that increases the solubility of hydrogen is to be preferred. and the careful control of the composition of the plating solution.
1e+0
1e-3 Al
1e-6 Be
1e-9 Co (eps)
Co (alfa)
1e-12
Permeability, mol/m s Pa1/2
Cu
1e-15 Ge
1e-18 Au
1e-21 Fe
Mo
1e-24
Ni
1e-27 Nb
1e-30 Pd
1e-33 Pt
1e-36 Si
Ta
1e-39
W
1e-42 V
1e-45 Ti
1e-48
0.0005 0.0010 0.0015 0.0020 0.0025 0.0030 0.0035 0.0040
1/T, 1/K
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) 40–66
Alloying of Pd and Ag was possible under lower temperature and around 1100 at 500 1C. The H2 flux achieved with a 2–3 mm thick
short heat treatment. The same group at AIST also prepared thin Pd–Au composite membrane was 0.62 mol m 2 s 1 at 500 1C. The
Pd–Au alloy membranes by electroless plating of Au on a Pd H2/N2 ideal selectivity was around 1400. Moreover cycling in
membrane; the amount of Au in the alloy was controlled by hydrogen between 250 and 450 1C had no significant effect on
adjusting the concentration of gold in the plating solution hydrogen and nitrogen permeation rates showing that mechan-
(Okazaki et al., 2008a). Okazaki and Pacheco Tanaka also studied ical stress caused by the differing thermal expansion of the joined
the effect of the substrate on the permeation of hydrogen at high materials is within the tolerance of the metal/ceramic composite
temperature, they demonstrated that at temperatures higher than membrane up to those temperatures (Shi et al., 2010).
650 1C alumina reacts with hydrogen and the Pd–Al alloy formed SINTEF (Norway) has developed a two-step technique for
decrease the permeation of hydrogen in that extent that at 850 1C manufacturing very thin defect free palladium-based hydrogen
no permeation occurs. On the other hand, YSZ is more stable and separation membranes. First, a defect-free Pd–alloy thin film is
can be used until 750 1C. (Okazaki et al., 2008b, 2009). The same prepared by PVD magnetron sputtering onto a silicon wafer
group in Japan, developed hydrogen permeable membrane of (surface with minimum roughness). In a second step, the film is
novel configuration (pore fill type membrane); in this configura- removed from the wafer and used as membrane. These films may
tion, palladium particles are filled in the nano-size pores of either be used as self-supported membrane or be integrated with
ceramic (g-Al2O3) layer located under the top surface (Pacheco various supports of different pore sizes and geometries. This
Tanaka et al., 2006). This ‘‘pore fill’’ configuration provides allows the preparation of thin ( 1–2 mm), high-flux membranes
advantages of improved toughness on handling since palladium supported on macroporous substrates avoiding all the mass
layer is not exposed on the surface. Moreover nano-size palla- transfer resistances given by microporous supports or problems
dium grains confined in the nanopore substantially suppress the with interdiffusion layers. It must be highlighted that according to
internal stress associated with a–b phase transition. This Pd the DFT calculations of Ling and Sholl, for membranes of 1 mm, the
membrane is tolerable below the critical temperature, where desorption resistance completely dominates the permeation at
fatal damage occurs for usual. Almost constant hydrogen permea- temperatures below 230 1C and it has an important contribution
tion and selectivity were maintained for more than 24 h at 50 1C at temperatures below 450 1C. Thus, at these temperatures
and 100 kPa pressure difference. At 300 1C and 4 bar of pressure smaller thicknesses will not improve the permeation flux of the
difference, the hydrogen permeance and H2/N2 ideal selectivity of membrane while will surely deteriorate the stability of the
this membrane were 1.3 10 6 mol m 2 s 1 Pa 1 and 41000, membrane.
respectively. Due to the difference of expansion coefficient In pure hydrogen, and at 400 1C and a H2 pressure difference of
between Pd and alumina, nanoporous alumina filled with Pd 25 bar, the H2 permeance and H2/N2 ideal selectivity were
has low stability at temperatures higher than 350–400 1C. To 1.46 10 2 mol m 2 s 1 Pa 0.5 and 2900. (Peters et al., 2011a).
overcome this problem, a membrane was prepared by filling In WGS conditions (57.5% H2, 18.7% CO2, 3.8% CO, 1.2% CH4 and
palladium into the nano pores of YSZ–g-Al2O3. The Pd–YSZ– 18.7% steam) SINTEF membranes have shown a H2 permeance of
Al2O3 composite membrane revealed excellent thermal stability 1.1 10 3 mol m 2 s 1 Pa 0.5 at 400 1C and 26 bar feed pres-
allowing long-term operation at elevated temperature (500 1C). sure. No membrane failure was detected operating the membrane
This has been attributed to improved fracture toughness of for more than 1 year using WGS and H2–N2 feed mixtures
YSZ–Al2O3 layer and matching of thermal expansion coefficient (Iaquaniello et al., 2011). SINTEF is also working in the develop-
between palladium and YSZ (Pacheco Tanaka et al., 2008). ment of Pd-based binary and ternary alloy membranes for H2
At 425 1C and 4 bar of pressure difference, the hydrogen per- separation (Peters et al., 2011b, 2012).
meance and H2/N2 ideal selectivity of this membrane were Research on self-supported membrane foils has been carried
1.6 10 6 mol m 2 s 1 Pa 1 and 300, respectively. out at Southwest Research Institute (SwRI). The institute used a
Various Pd alloys have been developed and tested as mem- magnetron sputtering technique to develop Pd–Au and Pd–Au–Pt
brane by the Colorado School of Mines (CSM). Supported mem- foils. SwRI tested Pd–Au–Pt (70–20–10%) foils at 400 1C, 12.7 bar
branes have been obtained with Pd–Au, Pd–Cu and Pd–Ru alloy with feed gas composition of 50% H2, 30% CO2, 19% H2O, and 1%
supported on commercial alumina and zirconia-coated porous CO (Coulter et al., 2012), and a H2 flux was approximately
stainless steel tubular substrates using an ELP technique (Roa 0.212 mol/m2/s. Currently, SwRI is developing amorphous
et al., 2009). The most promising result has been obtained by Zr-based alloys, specially focusing on Zr–Cu based ternary alloys.
using an alumina supported Pd–Au membrane. A H2 flux of The reason for the development of these alloys is that they
482 ml min 1 cm 2 (STP) and a H2/N2 ideal selectivity of 1000 showed good results (i.e., Zr30Cu60Ti10) in previous computational
at a temperature of 400 1C and a partial pressure difference of calculations predicting H2 flux through ternary alloys as functions
around 7 bar. On the other hand, a 2.3 mm thick Pd–Au membrane of operating temperature, H2 feed pressure, membrane thickness,
supported on zirconia-coated porous stainless steel achieved a H2 and trans-membrane pressure drop to advance testing (CO2
flux of 1.01 mol m 2 s 1 and a H2/N2 ideal selectivity of 82,000 at Handbook, 2011).
1.38 bar and 400 1C (Hatlevik et al., 2010). At these experimental Important advances on membrane preparation have been
conditions no flux reduction was observed for this Pd–Au mem- achieved at the center for inorganic membranes of the Worcester
brane for WGS mixture compared to a pure H2 feed gas. This Polytechnic Institute (WPI). The group directed by Prof. Ma is
means that no CO adsorption on the membrane surface occurs at developing Pd-based membranes on tubular stainless steel or
these temperatures, which makes the membrane very attractive alloy supports (such as, SS 316 L, Hastelloy and Inconel) by the
for WGS reactions or pre-combustion CO2 capture plants. ELP technique. WPI achieved a H2 flux of 0.098 mol m 2 s 1 and a
A great research effort on novel membranes has been devoted H2/He selectivity of around 4500 at 450 1C and 1.03 bar DP with a
in China where the Dalian Institute of Chemical Physics (DICP) is 7 mm thick Pd membrane with an Inconel support shown in Fig. 6
developing supported composite Pd–Au alloy membranes on (http://www.hydrogen.energy.gov/pdfs/progress09/ii_d_1_ma.
alumina substrates using ELP technique (Goldbach and Xu, pdf). WPI is also developing supported molten metal membranes,
2011). Very thin membranes with high fluxes have been produced consisting of low-melting non-precious metals and its alloys (e.g.,
by DICP. They reported a remarkable H2 permeability of Sn, In, Ga, Bi) as supported thin films (CO2 Handbook, 2011).
1.3 10 8 mol m m 2 s 1 Pa 0.5 at 400 1C attained by a 5 mm Moreover, WPI has also built an engineering-scale prototype
Pd–Au composite membrane. The H2/N2 ideal selectivity was membrane with 8.8 mm thickness, 2 in. outer diameter, and 6 in.
F. Gallucci et al. / Chemical Engineering Science 92 (2013) 40–66 47
3.2.1. CRI/Criterion
CRI/Criterion (a company owned by Shell) is in the process of
commercializing Pd and Pd–alloy 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 Fig. 8. Hysep 1308 hydrogen separation module manufactured by ECN.
deposition. The H2 permeance of these membranes varies in a
range of 40–70 Nm3 m 2 h 1 bar 0.5. Both hydrogen flux and 3.2.3. Eltron Research, Inc.
separation selectivity are stable at temperatures of 300–500 1C Eltron Research, Inc. has developed alloy-based membranes
and differential pressures of 26–42 bar. H2 purity of 499% has and has developed a separator unit rated to produce 6.8 kg/day of
been demonstrated for periods exceeding 4000 h in high tem- hydrogen (Hydrogen from Coal Program, 2010; CO2 Handbook,
perature gas separations. In Fig. 7 some manufactured mem- 2011). Eltron’s best alloy membrane has demonstrated a H2 flux
branes are shown. 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
3.2.2. ECN feed stream conditions; tubular membranes were successfully
The Energy research Centre of the Netherlands (ECN) produces tested for greater than 300 h with a feed gas composition of 50%
and offers a line of hydrogen separation modules (Hysep) on a H2, 29% CO2, 19% H2O, 1% CO, and 1% He.
pre-commercial basis for evaluation purposes as described in its
website (http://www.hysep.com/). There are three modules avail-
3.2.4. Green Hydrotec
able: Hysep 108 (area of 0.04 m2), Hysep 308 (0.1 m2) and Hysep
As shown on its website (www.grnhydrotec.com), Green
1308 (0.5 m2) (Fig. 8). The Hysep modules use palladium compo-
Hydrotech has developed Pd and Pd–Cu membranes on porous
site membranes composed by a 3–9 mm thick palladium layer
stainless steel tubes (Fig. 9) with an extremely high H2/N2 perm-
deposited by ELP onto a porous ceramic alumina support. The
selectivity ( 4100,000) and these membranes provide in situ
nominal capacity of the largest membrane module (Fig. 5) equals
purification of hydrogen in a steam reformer for high purity
3.5–6 Nm3 h 1, based on the obtained hydrogen flux applying
hydrogen (99.996 þ%).
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 3.2.5. Hy9
the range from 99.5% to 99.995% depending on the initial Hy9 is commercializing HPSTM hydrogen purifiers based on
composition. ECN is also developing novel Pd alloy composite planar palladium alloy metal membranes (Fig. 10), as described
membranes (e.g. Pd–Ag, Pd–Cu; Acha et al., 2011). on its website (http://hy9.com/). Hy9’s membrane purifiers
48 F. Gallucci et al. / Chemical Engineering Science 92 (2013) 40–66
assure a high selectivity for long time under bubbling fluidization 4.1. Zeolite membranes
conditions (Roses et al.). It should also be highlighted that these
membranes have been successfully tested at temperatures up to Zeolites are microporous crystalline aluminosilicates with
650 1C without deteriorating the perm-selectivity of the mem- uniform molecular sized pores. The unique properties of zeolite
branes which is probably the higher temperature used so fare for membranes are: size and shape selective separation behavior
Pd-based membranes and it is also the temperature window that and thermal and chemical stabilities. Due to their crystallinity,
allow an effective integration of Pd membranes into methane zeolites have a well-defined pore size. The size of the channels is
reformers (Gallucci et al., 2008a,b; Roses et al.). typically 3–10 Å, in the range of molecular dimensions. Therefore,
the hydrogen permeation through zeolite membranes relies on
3.2.10. Tokyo Gas molecular sieve effect and/or competitive diffusion mechanisms
Tokyo Gas Co., Ltd. has been developing membrane reformers (Dong et al., 2000).
(MRF) for hydrogen production with Mitsubishi Heavy Industries, Regarding material and structure, the most extensively studied
Ltd. since 1992. Recently, Tokyo Gas developed a MRF test system zeolite membranes for hydrogen separation are mainly MFI (ZSM
with a hydrogen production of 40 Nm3/h, hydrogen purity of (Hong et al., 2005), silicate-1 (McLeary et al., 2006), LTA (NaA
99.99%, and hydrogen production efficiency of 70% (Shirasaki (Xu et al., 2000), DDR (Lin and Kanezashi, 2007) and CHA (SAPO-34
et al., 2009). The reformer has 112 reactor tubes, each of which (Hong et al., 2008).
has two planar-type membrane modules composed of stainless The most commonly used technologies for zeolite processing
steel supports and Pd–Y(Gd)–Ag alloy films of less than 20 mm are in situ hydrothermal synthesis (Coronas and Santamaria,
thick (Sakamoto et al., 1992). The longest operation time for this 2004), secondary (seeded) growth synthesis (Xomeritakis et al.,
membrane reformer was 3000 h. An interesting evolution of the 2000) and vapor phase transport synthesis (Chiang and Chao,
membrane modules introduced by Tokio Gas company is what 2001). Other various techniques have been applied, such as
they called membrane-on-catalyst (MOC) module. This is a Pd- conventional heating, microwave heating (Li et al., 2006), synth-
based membrane prepared on the porous surface of the tubular esis under centrifugal field (Tiscareño-Lechuga et al., 2003),
structured catalyst that has catalytic activity for steam reforming moved-synthesis (Richter et al., 2003). Often, pre-treatment of
reaction. The important aspect to be taken into account when supports (Berg et al., 2003) and post-treatment of membranes
preparing MOCs is the thermal expansion of the catalyst that has (Yan et al., 1997) (e.g. for pore size reduction and defects removal)
to match with the membrane material, while also selecting a are carried out to improve the quality of the as-synthesized
proper porosity, mechanical strength and thermal conductivity of membranes.
the catalyst (Yasuda et al., 2006). This concept simplifies enor- Some of the most relevant current developments on zeolite
mously the membrane module design while also reducing the membranes for hydrogen separation are presented below.
mass transfer resistances otherwise affecting the packed bed Lai et al. (Lai and Gavalas, 2000) developed ZSM-5 zeolite
membrane modules used in their hydrogen generator. membranes by hydrothermal synthesis using a template free gel
in order to avoid calcination step. The H2/N2 ideal selectivity and H2
3.2.11. UTRC permeance obtained were 109 and 1.2 10 7 mol m 2 s 1 Pa 1,
United Technologies Research Center (UTRC) is developing a respectively.
palladium copper (Pd–Cu) trimetallic alloy hydrogen separator for Welk et al. (2004) from Sandia National Laboratories (SNL)
central H2 production from coal gasification-derived syngas (CO2 have studied the potential applications of zeolite membranes for
Handbook, 2011). UTRC has tested five separators using PdCuTM hydrogen separation from reforming streams. ZSM-5 membranes
alloy which showed increased surface stability in bench-scale were prepared by hydrothermal synthesis and the testing results
tests (Hydrogen from Coal Program, 2010). UTRC’s current mem- showed that the H2 purity was enriched from 76% to more than a
brane flux performance is approximately 0.230 mol m 2 s 1 at a 98% after a single pass through this membrane.
temperature of 400 1C and feed pressure of 6.9 bar). This mem- Tsapatsis and co-workers from University of Minnesota have
brane has also shown pressure capability up to 27.6 bar, sulfur prepared 1 mm thick MCM-22/silica layer onto porous homemade
tolerance of 20 ppmv, CO tolerance and the production of at least alumina support discs. The H2/N2 ideal selectivity and H2 per-
99.5% pure H2. meance were 50 and 7 10 8 mol m 2 s 1 Pa 1 at 200 1C,
Three types of commercial membranes (MRT, ECN and one from respectively (Choi and Tsapatsis, 2010). Besides, the same group
a not specified Japanese company) are being tested it a 20 m3/h is developing membranes consisting of ex-foliated MCM-22 layers
hydrogen production plant at Chieti (Italy) by Technimont-KT onto commercial stainless steel tubular support to their later
(De Falco et al., 2011). Preliminary experimental tests have integration in WGS reactors and integrated gasification combined
confirmed the potential of membrane technology with an overall cycle plants (CO2 Handbook, 2011).
conversion of approximately 57.3% was achieved at 600 1C, 26% Recently, Zhang et al. (2012) from Nanjing University have
higher than what was achieved in a conventional reformer. This developed a MFI zeolite membrane on porous a-alumina porous
conversion is expected to be even increased up to 62.8% by discs. The membrane was tested for the separation of H2/CO2
doubling the membrane surface by a factor of two. Moreover, the mixture containing 20 cm3 (STP)/min H2, 20 cm3 (STP)/min CO2
effect of operating temperature and gas mixture space velocity have and 5 cm3 (STP)/min He under atmospheric pressure. The perme-
been evaluated over a period of 1000 h without detrimental effects ate side was swept by He stream with the flow rate of 30 cm3
on the membranes performance. (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.
Microporous membranes are referred to as those with a pore Metal–organic frameworks are microporous crystalline hybrid
diameter smaller than 2 nm. Regarding the structure, the micro- materials consisting of metal cations or cationic oxide clusters
porous membranes for H2 separation may be classified into that are linked by organic molecules. Pore size tailorability
crystalline (zeolites and MOF) and amorphous (such as silica, combined with tunable sorption behavior provides promising
carbon, etc.). possibilities for the applications of MOFs as membranes for gas
50 F. Gallucci et al. / Chemical Engineering Science 92 (2013) 40–66
separation applications. It is thought that MOF can solve pro- investment and well defined and controlled deposition condi-
blems that zeolites have for their industrial use, such as, long- tions. On the contrary, sol–gel derived membranes generally
term stability, T-cycling, regeneration and difficult housing achieve lower selectivities but higher permeabilities. These mem-
(Gascon and Kapteijn, 2010). branes are much easier to produce with the possibility of
MOF are mechanically less stiff and brittle and have less controlling the pore size of the silica membranes, but the
energy intensive synthesis conditions compared to zeolites (Tan prepared membranes still suffer of low reproducibility which
and Cheetham, 2011; Shah et al., 2012). makes their industrial exploitation less attractive.
The zeolitic imidazolate frameworks (ZIFs) form a subfamily of Akamatsu et al. (2008) prepared and tested silica membranes
MOFs that are promising candidates as gas separation membranes via CVD technique. The test results showed an excellent H2
due to their thermal and chemical stability in combination with permeance at 600 1C of the order of 10 7 mol m 2 s 1 Pa 1,
their small pores (generally less than 5 Å) (Shah et al., 2012). and a high H2/N2 selectivity of over 1000.
Other MOF materials that have been used for gas separation are Yoshino et al. (2005) reported silica membranes prepared by
MOF-type (Yoo et al., 2009; Bux et al., 2009), HKUST-type sol–gel technique with a permeance at 600 1C of
(Guerrero et al., 2010; Guo et al., 2009) and SIM-type (Aguado 7 10 7 mol m 2 s 1 Pa 1 and H2/N2 selectivity around 100.
et al., 2011a), among others. This group (Yoshino et al., 2006) also fabricated a membrane
The most commonly used technologies for MOF preparation module with a membrane area of 0.05 m2.
are in situ growth synthesis (Liu et al., 2010; Huang et al., 2010; The main problem of microporous silica membranes, as in the
Guo et al., 2009), secondary (seeded) growth synthesis (Liu et al., case of titania and alumina, is that they are not stable at high
2009; Ranjan and Tsapatsis, 2009; Yoo et al., 2009) and liquid temperatures, especially in the presence of steam, leading to loss
phase epitaxy (Shekhah et al., 2011). Besides, postsynthetic of permeability. This is due to closure of pore channels by
modifications of MOF membranes have been reported, for densification which is catalyzed by humidity, particularly at high
instance, introducing side groups to give functionality to the temperatures (Lin, 2001). Furthermore, this phenomenon may
membranes (Huang and Caro, 2011; Aguado et al., 2011b). cause silica film embrittlement with the subsequent loss in
Some of the most relevant current developments on MOF mem- separation properties.
branes for hydrogen separation are presented afterwards. Li and co- In order to improve the stability of silica membranes, different
workers have prepared 2 mm thick ZIF-7 membrane deposited on an approaches have been proposed in the literature. The first
asymmetric alumina disc by secondary (seeded) growth technique. approach used is the doping of silica with inorganic oxides (e.g.,
The H2 permeance and H2/N2 ideal selectivity of the membrane at titania, zirconia and alumina) (Kanezashi and Asaeda, 2006;
220 1C and at 1 atm were 4.55 10 8 mol m 2 s 1 Pa 1 and 20.7, Sekulic et al., 2002).
respectively (Li et al., 2010). Kanezashi and Asaeda(2006) prepared Ni-doped silica mem-
Recently, the same group in Hannover (Huang and Caro, 2011) branes with a permeance of 4.6 10 6 m3 (STP) m 2 s 1 kPa 1
has prepared a 20 mm thick ZIF-90 membrane on a-Al2O3 porous for H2 with a H2/N2 selectivity of 400 even after being kept in
discs by solvothermal reaction. After synthesis the membrane has steam (steam pressure: 90 kPa) at 500 1C for about 6 days. Tsuru
been modified using ethanolamine and its H2 permeance has et al. (2011) prepared Co-doped silica membranes (approx. 50 nm
slightly decreased from 2.5 to 2.1 10 7 mol m 2 s 1 Pa 1 and thick layer) with a H2 permeance of approximately 1.8
the H2/N2 ideal selectivity has considerably increased from 10 7 mol m 2 s 1 Pa 1 and a H2/N2 selectivity of 730 even after
around 7 to 17.5 at 200 1C and 1 atm. 60 h of exposure to steam (steam: 300 kPa) at 500 1C. Doping of
(McCarthy et al. (2010) from Texas A&M University have metals into silica membranes has been investigated in order to
prepared a ZIF-8 membrane (20 mm thick) by in situ solvothermal increase the hydrothermal stability at high temperatures and for
growth on a-Al2O3 support after its surface modification. The H2 their possible application to membrane reactors, such as steam
permeance and H2/N2 ideal selectivity of the membrane at 25 1C reforming of methane (Battersby et al., 2009).
and at 1 atm were 1.73 10 7 mol m 2 s 1 Pa 1 and 11.6, Another approach to obtain hydrothermal stable silica mem-
respectively. branes is to incorporate methyl groups in the silica microstruc-
The same group from Texas (Guerrero et al., 2010) has ture as proposed by Campaniello et al. (2004). Recently, hybrid
prepared a 25 mm thick HKUST-1 membrane deposited on a (organic–inorganic) silica membranes are widely being studied
porous alumina support disc via secondary (i.e., seeded) growth because the presence of organic groups in silica networks could
method, using thermal seeding in order to anchor HKUST-1 seed improve the hydrothermal stability of silica structures and help
crystals on the support. The H2 permeance and H2/N2 ideal controlling the pore size of the membrane (Duke et al., 2004).
selectivity of the membrane at 190 1C and at 1 atm were Castricum et al. (2008) prepared hybrid silica membranes derived
1.1 10 6 mol m 2 s 1 Pa 1 and 7.3, respectively. by co-polymerization of methyltriethoxysilane and bis(triethox-
Permeation data about other reported MOF membranes can be ysilyl)ethane with high hydrothermal stability. Kanezashi et al.
found in the review prepared by Shah et al. (2012). (2009) reported a hybrid silica membrane using BTESE as pre-
cursor with a high H2 permeance around 10 5 mol m 2 s 1 Pa 1
4.3. Silica membranes but low H2/N2 selectivity of around 10 at 200 1C.
Silica membranes are the most important representatives of 4.4. Carbon membranes
amorphous microporous membranes, because they can be more
easily prepared as ultra- or super-microporous thin layers in Carbon membranes are promising candidates for hydrogen
comparison to other metal oxides (such as alumina, titania or separation due to their high separation performance and excellent
zirconia) and these can be used for molecular sieving applications. thermal and chemical resistance (Ismail and David, 2001; Koros
The most widely used technologies for deposition of silica and Mahajan, 2000). Based on the pore size, carbon membranes
layers on porous substrates are sol–gel (Tsuru, 2008) and CVD are generally divided in carbon molecular sieve membranes
(Nagano et al., 2008). Silica membranes with pore diameters less (CMS) and selective surface flow (SSF) membranes. CMS mem-
than 1 nm can be prepared by CVD which provides high hydrogen branes could allow the transport of small molecules through the
selectivity (molecular sieving) but, consequently, a lower perme- pores, avoiding the passage of larger molecules. Due to their small
ability. Moreover, the CVD method requires substantial capital pores, CMS membranes possess a high selectivity for separation of
F. Gallucci et al. / Chemical Engineering Science 92 (2013) 40–66 51
gas mixtures containing small gas species. In this case, a precise hopping between oxide ions (Grotthuss mechanism). As for the
control of pore sizes near to molecular sieving size is required. SSF oxygen conductors, sufficiently high temperatures are required
membranes have pores larger than the dimensions of the mole- for high proton conductivity.
cules and thus the separation is based on the preferential The general formula of perovskite-type oxides is AB1 x
adsorption of some components in gas mixture followed by MxO3 d, where the A element is taken from the group consisting
surface diffusion in the carbon matrix (Seo et al., 2002). This of (Ca, Sr, B); the B element is taken from the group consisting of
section will be focused on CMS membranes due to their proper- be Ce, Tb, Zr, Tl; M element is taken from the group consisting of
ties for high H2 separation in comparison to SSF membranes. Ti, Cr, Mn, Co, Ni, Co, Al, Y, Ga; x is less than the upper limit of
CMS membranes are the result of the pyrolysis of polymeric solid solution formation range (usually less than 0.2) and d is the
precursors under an inert or vacuum atmosphere. The most impor- oxygen deficiency per unit cell.
tant parameters that would influence the final properties of CSM The most extensively studied high temperature perovskite-
membranes are: (i) type of polymeric precursors such as polyimides, type oxides are SrCeO3 (Higuchi et al., 2004; Song et al., 2002),
polyfurfuryl alcohol, phenolic resins, polyvinylidene chloride, poly- BaCeO3 (Guan et al., 1997; Ma et al., 1998) and BaZrO3 (Tetsuo
acronitrile, cellulose derivates, and polyetherimide (Saufi and Ismail, et al., 2002). These perovskites have high protonic conductivity
2004); (ii) pyrolysis conditions (i.e., heating rate, atmosphere and but their electronic conductivity is poor. In order to improve the
final temperature) (Geiszler and Koros, 1996; Centeno et al., 2004); latter conductivity it is common to dope these perovskites with
and (iii) modifications (i.e., pre- or post-treatment such as stabiliza- cations, such as Y (Sammes et al. 2004), Eu (Song et al., 2003) and
tion, activation or oxidation, and CVD) (Barsema et al., 2004; Lee Gd (Shima and Haile, 1998).
et al., 2008; Li et al., 2008c; Wang et al., 2002). The common methods for perovskite power synthesis are sol–
The most commonly used techniques for depositing CSM gel (Selvaraj et al., 1991), spray drying (Varma et al., 1994),
layers onto supports may be dip coating (Hayashi et al., 1997), hydrothermal synthesis (Zheng et al., 1997) and combustion of
ultrasonic deposition (Shiflett and Foley, 2000), vapor deposition polymerized complexes (Liu et al., 2002). On the other hand,
(Wang et al., 2000), spin coating (Tseng et al., 2009), and spray typical methods for perovskite film deposition onto ceramic or
coating (Acharya and Foley, 1999). metal supports are CVD (Ngamou and Bahlawane, 2009), EVD
Some of the most relevant current developments on carbon (Pal and Singhal, 1990) and PVD (Ma et al., 2008).
membranes for hydrogen separation are presented afterwards. Some of the most relevant current developments on
Hosseini and Chung (2009) from National University of Singa- perovskite-type membranes for hydrogen separation are pre-
pore reported carbon membranes prepared from blends of PBI sented afterwards.
and polyimides with a high H2/N2 selectivity of 460–480 and H2 Yuan et al. (2010) have prepared SrCe0.75Zr0.20Tm0.05O3 d
permeability of 60–180 barrer (1 barrer¼1 10 10 cm3(STP) membranes with a H2 permeation flux up to 0.042 mL min 1 cm 2
cm cm 2 s 1 cm Hg 1). Campo et al. (2010) have developed at H2 partial pressure of 0.4 atm and at a temperature of 900 1C. The
CMS membranes from cellophane paper with very interesting Zr doping can increase mechanical stability of the membrane and
hydrogen permeation properties: H2 permeability of 39.3 barrer, the resistance to reduction.
H2/N2 and H2/CO2 selectivities of 1310 and 58.7, respectively Yazdi et al. (2009) have developed BaCe1 xYxO3 d films by DC
(Celo600 Sample). Grainger and Hägg (2007) reported CMS from magnetron sputtering at room temperature. Ceramatec (Paglieri
cellulose base based precursors with a H2/N2 selectivity of 740 and Way, 2002, CO2 Handbook, 2011) is producing a prototype
and H2 permeability of 1110 barrer at 90 1C and at a feed pressure membrane for hydrogen separation from coal-derived syngas
of 6 bar. Media and Process Technology, Inc. is commercializing using perovskite-type membranes. The pevoskite used is a mix-
CSM composite membranes prepared by the pyrolysis of a PEI ture of barium cerate (BaCeO3) and ceria, where the former is
precursor deposited onto a ceramic porous substrate (Abdollahi proton conductor and the latter is electron conductor. The pre-
et al., 2010; Sedigh et al., 2000). liminary tests showed a perfect H2 separation (100%) from H2/CO2
mixture.
tubes obtaining as a result a H2 flux of 4 10 8 mol s 1 m 2 at number of papers, the patents awarded on hydrogen production
1400 1C. in membrane reactors also increased with time and in the last years
this number is increasing rapidly. In fact, most of the patents have
5.2. Cermet membranes been awarded in the last 10 years (Gallucci et al., 2009).
Different types of membrane reactors for hydrogen production
Cermet membranes consist of a combination of a ceramic have been proposed in the literature. Most of the previous work
phase and a metallic phase. The former is a pure proton con- has been performed in packed bed membrane reactors (PBMR);
ductor, while the latter is a highly electron conductor. Combining however, there is an increasing interest in novel configurations
these two phases together may provide high H2 permeation such as fluidized bed membrane reactors (FBMR) and micro-
because both proton and electron conductivities become high, membrane reactors (MMR) especially because better heat man-
resulting in high hydrogen permeation. agement and decreased mass transfer limitations can be obtained
Due to the hydrogen transport by both metals and oxides, in these reactor configurations. In the following, these reactor
mainly three different combinations with respect to functional configurations, along with membrane bio-reactors (MBR) and
properties of both phases can be realized: (1) a metal with low catalytic membrane reactors (CMR) for hydrogen production will
hydrogen conductivity in combination with a highly proton be discussed in detail.
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 6.1. Packed bed membrane reactors
ceramic of low hydrogen permeability and (3) a combination
where both the metallic and ceramic phases conduct hydrogen. The packed bed membrane reactor configuration is the first
Some of the most relevant current developments on cermet and most studied configuration for hydrogen production in
membranes for hydrogen separation are presented in the following. membrane reactors. This is because, the first studies on mem-
Balachandran et al. (2006) from Argonne National Laboratory (ANL) brane reactors focussed on the effect of the hydrogen permeation
developed Pd/YSZ composite membranes and the highest H2 flux through membranes on the reaction system. Thus it was straight-
was 20.0 cm3 (STP) min 1 cm 2 for a 22 mm thick membrane forward to compare two packed bed reactors (avoiding the
at 900 1C using 100% H2 as feed gas. Recently, Zhu et al. (2011) have complication of complex fluid dynamics such as in fluidized
developed a 30 mm thick Ni–BZCY (Ba(Zr0.1Ce0.7Y0.2)O3 d) cermet bed) in one of which a membrane was used.
layer onto ceramic support that exhibited a maximum H2 flux of In the following table the main investigators working with
2.4 10 7 mol cm 2 s 1 at 900 1C using 80% H2/N2 (with 3% of PBMR for hydrogen production are summarized (source Scopus):
H2O) as feed gas and dry high purity argon as sweep gas. The different authors showed that the concept of Pd-based
Park et al. (2011) have developed a 0.5 mm thick Ta/YSZ mem- membrane reactor can be used to carry out and intensify different
brane and the highest H2 flux obtained was 1.2 ml min 1 cm 2 at dehydrogenation reactions such as reforming of methane and
300 1C using 100% H2 as the feed gas and Ar as the sweep gas. different alcohols. In particular, packed bed membrane reactors
Jeon et al. (2011a) have developed a 0.5 mm cermet mem- have been used for producing hydrogen via reforming of methane
brane composed of Pd embedded in proton conducting ceramic (Gallucci et al., 2006; Matsumura and Tong, 2008), reforming of
matrix (CaZr0.9Y0.1O3 d) and its H2 flux was around 2.3 cm3 alcohols (Kikuchi et al., 2008; Tosti et al., 2009), autothermal
(STP) min 1 cm 2 at 900 1C. This group also has developed reforming (Simakov and Sheintuch, 2009), partial oxidation of
Pd–GDC (Ce0.8Gd0.2O2 d) cermet membranes for high sulfur methane (Tan and Li, 2009), etc. The results of these studies are
resistance and no sharp drop in hydrogen permeation flux was interesting to show that indeed the Pd membranes are not
observed using feed gases with 220 ppm H2S (Jeon et al., 2011b). poisoned by the different alcohols and the products of the
The best performances of membranes investigated in the reactions such as CO2 or higher hydrocarbons. The only poisoning
various research organizations are summarized in Table 2. can be due to the presence of H2S as said above or CO (if low
Besides, membranes on the way to commercialization commen- temperature o300 1C is used).
ted before are shown in Table 3. It is shown that relatively high In a packed bed membrane reactor the catalyst is confined in
fluxes with good perm-selectivities can be now achieved with fixed bed configuration and in contact with a perm-selective
hydrogen membranes which make this technology closer to the membrane. The most used packed bed configuration is the
real market. 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
6. Advances in membrane reactors for hydrogen production (in case of hydrogen selective membranes) or one reactant is feed
on the other side of the membrane (in case of oxygen selective
The application of membrane reactors for dehydrogenation membrane Jin et al., 2000).
reactions has been first proposed to the scientific community by For multi-tubular membrane reactor configurations the cata-
Prof. Gryaznov in the late 60s (see for example Gryaznov et al., lyst in tube configuration can be preferred especially for con-
1970). Removing hydrogen through a thick membrane resulted in struction reasons and for the extent of bed-to-wall mass and heat
a shift of the equilibrium reaction towards the product of interest. transfer limitations which can be very detrimental when the
Membrane reactors in dehydrogenation reactions were a scien- catalyst is positioned in shell configuration.
tific curiosity until around 1996 with few papers published per Often, a sweep gas can be used in the permeation side of the
year. With the increasing interest into hydrogen as a possible membrane in order to keep the permeation hydrogen partial
clean energy carrier, the scientific attention towards membrane pressure as low as possible for minimizing the membrane area
reactors as high efficient hydrogen production systems sharply required for the hydrogen separation. This practice is for example
increased in the last years (Fig. 12). Probably the echo produced very useful if hydrogen for ammonia plant is being produced, in
by the two books ‘‘The Hydrogen Economy’’ (Rifkin, 2002; which case an amount of nitrogen can be used for sweeping the
National Academy of Engineering, 2004) was also reflected in permeation side producing a synthesis stream (N2/H2 ¼1/3)
the great increase of number of papers in the last 5 years. ready for the final reaction step. If a sweep gas is used in the
However, our research will focus on the progresses on membrane permeation side then a packed bed membrane reactor can be
reactors in the last 10 years. Accordingly with the increase of used in both co-current and counter current modes. Using a
Table 2
Permeation data of different hydrogen separation membranes reported in the literature.
Institute Membrane material Preparation method Selective T (1C) Permeance Permeability Ideal Sulfur Durability
layer H2 [10 8 H2 [10 13 selectivity tolerance (h)
thickness (mol/m2 s Pa)]a (mol m/m2 s Pa)] (ppm)
(mm)
AIST (Pacheco Tanaka et al., 2006) Pd/Al2O3 Pore filling 5 300 170 – 4 1,000 (H2/N2) – –
AIST (Pacheco Tanaka et al., 2008) Pd/YSZ Pore filling 5 425 210 – 300 (H2/N2)
CSM (Hatlevik et al., 2010) Pd–Au/YSZ/PSS ELP 2.3 400 710 160 82,000 (H2/N2) – –
DICP (Goldbach and Xu, 2011) Pd–Au/Al2O3 ELP 2–3 500 620 160 1400 (H2/N2) – –
SINTEF (Peters et al., 2011a)b Pd–Ag/PSS PVD-MS 2.8 400 1,500 420 2900 (H2/N2) – 2000
SwRI (Coulter et al., 2012)b Pd–Au–Pt PVD-MS 25 400 54 130 – – –
WPI (Ma, 2009) Pd/Inconel ELP 7 450 96 67 4,500 (H2/He) – 2,200
CALTECH (Li et al., 2000) ZSM-5/Al2O3 Hydrothermal synthesis 6–7 150 12 7.8 109 (H2/N2) – –
SNL (Welk et al., 2004) ZSM-5/Al2O3 Hydrothermal synthesis 10 25 68 68 16.6 (H2/CO2, CO, – –
CH4)
Nanjing University (Zhang et al., 2012) MFI/Al2O3 Hydrothermal synthesis – 500 28 – 42.6 (H2/CO2) – –
a
Permeance values have been calculated for a H2 partial pressure of 1 bar.
b
Self-supported membranes.
53
54 F. Gallucci et al. / Chemical Engineering Science 92 (2013) 40–66
Table 3
Major investigators on packed bed membrane reactors
Fig. 13. Membrane reactor catalyst in tube (A) and catalyst in shell
(B) configurations.
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 fiber membrane reactors (source Scopus)
Table 5
Major investigators on fluidized bed membrane reactors (Scopus has been used for
the search).
Indeed, Roy et al. (1999) first demonstrated that autothermal a single two-side planar membrane panel consists of two Pd–Ag
operation could be achieved by directly adding oxygen to a foils mounted on a porous stainless steel base using proprietary
fluidized bed reformer to provide all the required heat via partial MRT sealing and protection techniques.
oxidation reaction. The extension of this work to a membrane A scheme of the membrane reactor used is reported in Fig. 18
fluidized bed reactor has been performed by the same group few (Mahecha-Botero et al., 2008):
years later. In particular, the previous experiences with autothermal Based on their experience in the fluidized bed, the authors
fluidized beds and membrane fluidized beds have been condensed suggest that the flux through membranes computed by Sieverts’
in a modeling paper by Grace et al. (2001). The model chosen by equation must be multiplied by an effectiveness factor for
Grace was an equilibrium model and this selection was made based membranes immersed in fluidized-bed reactors. The authors
on the previous experience on modeling and experiments on suggested that this effectiveness factor could possibly be due fine
fluidized bed membrane reactors which suggested that the overall dust generated in the bed or to other mass transfer resistances.
composition of each species at each position inside the bed was They demonstrated that by using ATR catalyst the effectiveness
found to be mainly controlled by two factors: (i) the quantity of factor could be higher than the case of reforming catalyst and
hydrogen which had permeated through the membranes (depend- could in principle be higher than 0.9 (as high as 0.98 according
ing on the difference in hydrogen partial pressure and membrane with Chen et al., 2007).
characteristics); (ii) chemical equilibrium at the given temperature The experiments show that the maximum temperature differ-
and overall pressure on the reactor side (depending on the very ence along the reactor where membranes are immersed is always
high catalytic activity for methane reforming). lower that 20 1C (Mahecha-Botero et al., 2008), which results in a
The model was applied in order to investigate the influence of higher membrane lifetime and avoids formation of pinholes.
various parameters on the performance of FBMR with oxygen All these works confirm that the autothermal reforming of
addition. Although the results showed that autothermal operation methane is possible in a fluidized bed membrane reactor with
can be achieved by using approximately 0.3 O2/CH4 feed ratio, the oxygen (or air) addition without hot spot formation.
interaction between the different parameters is quite complex. It has be pointed out that feeding air directly in the reactors
For instance, in methane reformers an important parameter is the brings two drawbacks: (i) the exhaust gas mainly consists of
steam/carbon ratio. However, when feeding also oxygen, the nitrogen and CO2, if CO2 capture is required the separation is
steam becomes also a product of the oxidation reaction and this difficult (and costly); (ii) in each case nitrogen dilutes the amount
makes the prediction of the reactor behavior a bit more compli- of hydrogen in the reactor, reducing the driving force for hydro-
cated. Furthermore, an important conclusion of the work is that gen permeation through the membranes and resulting in higher
oxygen addition reduces the coke formation and consequently the membrane area required in the reactor. For these reasons, feeding
catalyst deactivation. oxygen in the fluidized bed membrane reactor for achieving
Based on this paper and on various other papers dealing with autothermal reforming is more appropriate. However, an air
both theoretical and experimental works, recently the same group separation unit (a costly process) outside the reactor is required
presented the experimental findings of pre-commercial mem- to produce the oxygen for the autothermal reforming.
brane reactor prototypes for both methane reforming and ATR This problem can be circumvented by using novel reactor config-
(with air addition) (Chen et al., 2007; Mahecha-Botero et al., urations proposed by Kuipers and co-workers (Patil et al., 2005, 2007;
2008). The authors used optimized plane membranes, where Gallucci et al., 2008a, b). In particular two configurations have been
Fig. 18. Reactor configuration 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) 40–66
proposed to achieve the autothermal methane reforming: the two in both sections can be controlled independently by selecting the
configurations are called methane combustion configuration and proper ratio of CH4/H2O fed at the oxidation and reforming/shift
hydrogen combustion configuration. sections, while maintaining overall autothermal operation with
The methane combustion configuration is sketched in Fig. 19 optimal energy efficiency.
and consists of two sections (Patil et al., 2005). Hydrogen perm- In Fig. 20, the hydrogen combustion configuration is shown,
selective membranes are integrated in a fluidized reforming/shift where the energy for steam reforming is delivered via burning
top section where ultra-pure H2 is extracted and the energy part of the produced hydrogen (Gallucci et al., 2008a). This
required for the steam reforming is supplied via in situ methane configuration consists of only one fluidized bed section, where
oxidation in a separate fluidized bottom section, where oxygen is two types of hydrogen perm-selective membranes are incorpo-
selectively fed to the methane/steam feed via oxygen perm- rated: dead-end Pd-based membranes to recover ultra-pure H2 by
selective membranes. Two different sections are required because applying a vacuum on the permeate side (similar to the ones used
metallic Pd-based membranes for selective H2 extraction can only in the methane combustion configuration) and U-shaped Pd-
be operated below typically 700 1C because of membrane stabi- based membranes with oxidative sweeping, by feeding air to
lity, while acceptable O2 fluxes through available perovskite-type the permeate side to burn the permeated hydrogen.
O2 perm-selective membranes can only be realized above The hydrogen combustion configuration has the clear advan-
900–1000 1C. In this case the air separation is achieved in situ tage that only one section is required, circumventing the need for
resulting in lower costs and in intrinsic CO2 capture. a (costly) high temperature bottom section. On the other hand, in
In the oxidation section, CH4 is partially oxidized in order to the methane combustion configuration steam is produced in situ,
achieve the high temperatures required for O2 permeation which enhances the CO conversion. Moreover, in the hydrogen
through the perovskite membranes and to simultaneously pre- combustion configuration, part of the expensive Pd-based mem-
heat part of the CH4/steam feed. branes are used to burn part of the produced hydrogen, while for
The preheated feed is mixed with additional CH4 and steam the methane combustion configuration further development of
and fed to the reforming/shift section, where CH4 is completely oxygen perm-selective membranes (esp. the mechanical and
converted to CO, CO2 and H2 because of the selective H2 extrac- chemical stability) is essential.
tion through the Pd membranes which shifts the methane steam Patil et al. (2005) and Gallucci et al., 2008a,b demonstrated
reforming. H2 extraction can be achieved by using dead-end Pd from both experimental and theoretical point of view that
membranes and applying a vacuum on the permeate side. Alter- autothermal reforming can be achieved in both reactor
natively, a sweep gas (such as H2O) could be used, but the configuration.
decrease in membrane area due to the increased driving force Moreover, applying detailed models to both packed bed and
should outweigh the additional costs for separating H2 from the fluidized bed membrane reactors Gallucci et al. (2010b) demon-
sweep gas. Overall autothermal operation can be achieved by strated that for methane reforming the fluidized bed membrane
tuning the overall CH4, O2 and steam fed to the reactor. The reactor requires half membrane area compared to the packed bed
distinct advantage of this reactor concept is that the temperatures membrane reactors where external mass transfer limitations are
prevailing.
Detailed modeling of fluidized bed membrane reactors is hin-
dered by the fact that the hydrodynamics correlations present in
the literature are based on experiments carried out in fluidized bed
without membranes. As it is well accepted that the presence of and
permeation through membranes influence the hydrodynamics of
Fig. 19. Methane combustion configuration for pure hydrogen production through Fig. 20. Hydrogen combustion configuration for pure hydrogen production
autothermal reforming of methane. through autothermal reforming of methane.
F. Gallucci et al. / Chemical Engineering Science 92 (2013) 40–66 59
environmental friendly. In addition, exploitation of such pro- presented. Most of the hydrogen is produced by methane reform-
cesses would lead to utilization of renewable resources. ing, for this reason also a great part of the literature on MRs deals
Das and Veziroglu (2001, 2008) reviewed the biological pro- with hydrogen production via reforming of methane in mem-
cesses for hydrogen production which, according to the authors, brane reactors. However, great attention is devoted to hydrogen
can be summarized as: production from other hydrocarbons, and even more on hydrogen
production from renewable sources such as bio-ethanol and bio-
methanol.
Biophotolysis of water using algae and cyanobacteria.
Photodecomposition of organic compounds by photo-synthetic 7.1. H2 production from methane in MR
bacteria.
Fermentative hydrogen production from organic compounds Methane steam reforming has been used for hydrogen produc-
Hybrid systems using photosynthetic and fermentative bacteria. tion since long time, and it is the industrially most exploited
reaction system for hydrogen production. Optimized catalysts for
The advances in research related to these processes can be such a reaction commercially exist (mostly Ni based catalysts)
found in Das and Veziroglu (2008). and the catalytic activity is so high that the equilibrium conver-
Different biological hydrogen production processes can be sion is easily achieved in these reactors.
effectively carried out in membrane bio-reactors. In most of the Since the methane steam reforming is an equilibrium system,
cases the membrane is not immersed in the reactor where the application of hydrogen selective membranes inside the
hydrogen production takes place but rather used outside the reactor help to circumvent the equilibrium limitation while
reactor as a retention (of feedstock) media. The membrane should simultaneously produce a pure hydrogen stream. The membrane
be able to separate the fluids (water and gases) from bacteria and reactor system needs thus milder reaction conditions with respect
unconverted feedstock. to a conventional reactor and a downstream separation system is
The membranes used are thus typical (polymeric) membranes not required. There are different papers in the literature showing
already commercially applied for water treatments like hollow that the application of Pd-based membranes to the methane
fibers for ultra filtration and so on. steam reforming leads to a methane conversion well above the
Examples of such a membrane bio-reactor for hydrogen bio- equilibrium limitation (see for example Gallucci et al., 2004;
production are reported by few authors in the recent literature Ferreira-Aparicio et al., 2005; Chen et al., 2008). The extent of
(see Jeong et al., 2007; Lee et al., 2007; Oh et al., 2004). the increase of conversion and amount of hydrogen production is
Lee and co-workers used a membrane bio-reactor consisting of a related to the surface of membrane installed per unit of volu-
hollow fiber MF commercial module connected downstream to a metric feed flow rate (Gallucci et al., 2008b). The higher is the
CSTR reactor. The CSTR is the typical reactor where the fermentative membrane area installed the higher is the conversion and the
hydrogen production takes place; easy to design and operate, the pure hydrogen production rate.
only drawbacks of the CSTR for such a process is the low cell The advances in hydrogen production by methane reforming
retention resulting in low hydrogen yield. Connecting the micro- in membrane reactors are basically related to: (i) the design of a
filtration module (on the market for a wide range of water treat- suitable reactor to decrease the mass transfer limitations; (ii) heat
ments) to the CSTR, the liquid effluent is filtered out in the hollow supply to the reactor; (iii) combining the steam reforming with
fiber module and the cells are recycled inside the reactor, circum- other reactions to optimize the system.
venting the cell washout problem. The authors applied the Mass transfer limitations can be decreased by applying a
membrane bio-reactor to hydrogen production from different sub- reasonable design such as micro-reactors and fluidized bed as
strates (fructose, sucrose and glucose) and in each case it has been described above. The heat required by the reactor can be achieve
demonstrated that the hydrogen yield in the membrane reactor is by feeding air (or oxygen) directly in the reactor to obtain the
much higher than the corresponding hydrogen yield of a single CSTR. autothermal reforming, but in this case a fluidized bed reactor is
A similar approach to a glucose based hydrogen bio- more suitable in order to avoid hot spots (Chen et al., 2007;
production has been applied by Oh et al. (2004), where a cross- Mahecha-Botero et al., 2008; Abashar et al., 2008). Also oxygen
flow membrane module has been used to retain the hydrogen feeding through membranes has been proposed and discussed
production bacteria to be re-circulated in the anaerobic reactor. above (Patil et al., 2007; Gallucci et al., 2008a), or heat supply by
Also the authors found out that the hydrogen production rate can burning part of the hydrogen recovered (Gallucci et al., 2008b)
be increased by 25% by using a membrane bio-reactor instead of a can be used.
single anaerobic reactor. Since methane reforming in membrane reactors is carried out
Finally Jeong et al. (2007) applied a commercial hollow fiber at lower temperatures ( o600 1C) with respect conventional
module connected to an acid fermentation reactor for hydrogen systems ( 4900 1C), the heat supply in MR is somehow simpler
production from waste activated sludge. Also in this case the and other heat sources can be used. For instance, Giaconia et al.
membrane separation busted the system to a higher hydrogen (2008) and De Falco et al. (2010) used a system in which the heat
production compared to a system without membrane separation. required by the methane reforming is supplied via molten salts
From these examples it is clear as a membrane reactor can produced via concentrated solar power. The molten salts have a
help the biological production of hydrogen from renewable temperature of 550 1C and can be successfully used to supply the
sources. Of course the typical problems of such a membrane heat to the membrane reformer, in a tubes-in-shell configuration.
system (caking, aging) already well known in water treatment Also thermally coupled reactors have been proposed for heat
processes have to be taken into account when designing the supply, where an exothermic reaction takes place in a chamber of
membrane bio-reactor. 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).
7. Feedstock for hydrogen production In this case along with the ratio between the methane reforming
rate and permeation rate already discussed, another important
In the following section a brief review on the advances parameter to be carefully controlled is the ratio between the
on hydrogen production in MRs from different feedstock is oxidation reaction taking place in a chamber and the steam
F. Gallucci et al. / Chemical Engineering Science 92 (2013) 40–66 61
reforming reaction rate. This ratio, in a thermally coupled reactor, with H2-selective membranes, higher hydrogen yield is obtained
defines the temperature profiles inside the membrane reformer. while pure hydrogen stream is also directly available for fuel cells
Concerning the possibility to couple the steam reforming with applications. Of course, all the aspects already discussed for
other reactions the two most interesting applications are the so- methane reforming in membrane reactors (heat supply, mass
called steam dry reforming, where steam reforming and dry transfer limitations, and so on) also read for reforming of higher
reforming of methane are coupled in the reaction zone of the hydrocarbons, while the positive aspect to be taken into account
membrane reactor (see e.g. Abashar, 2004) and the steam reform- is that higher hydrocarbons are generally liquid and easier to
ing coupled with the methanation reaction, where the methana- transport and with higher energy density compared to methane.
tion takes place in the permeation side of the membrane reactor On the other hand, often higher hydrocarbon are reformed not
(see Mori et al., 2008). Dry reforming of methane is a significant directly to syngas, but rather dehydrogenated to more valuable
process since reformates methane with a greenhouse gas (CO2) products. Few examples are: ethane to ethylene (Wang et al.,
into syngas. For this reason it attracted much attention in the last 2003), cyclohexane to benzene, system which is seen as an
years, and also in membrane reactors (Paturzo et al., 2003; interesting hydrogen carrier (Itoh et al., 2003), isobutane to
Gallucci et al., 2008d). isobutene (Liang and Hughes, 2005). In any of these processes,
In his interesting theoretical work Abashar (2004) proposed to hydrogen is ‘‘simply’’ a by-product, while its withdrawn will
develop a dual functional fluidized bed membrane reactor to increase the conversion towards the product of interest, while
couple the steam reforming with the dry reforming of methane, at the same time producing a pure stream of hydrogen available
where the high amount of carbon dioxide produced by the steam for PEM fuel cells and other applications.
reforming is used to produce syngas via dry reforming. Also for
this specific application, the membrane reactor shows a higher
performance compared with traditional reactor. The membrane 7.3. H2 production from biological related feedstock in MR
reactor configuration (in terms of flow configuration, mixed
catalysts and so on) can be optimized with the model proposed A biological route for hydrogen production is highly desirable
by Abashar. since from one side the fossil fuels (such as NG) are limited and
The second interesting application is proposed by Mori et al. not renewable, while from the other side the biological route
(2008), who suggest to use a methanator in the shell side of the often do not produce additional CO2 emission into atmosphere. In
membrane reactor to convert traces of CO (which are surely a previous section, the direct hydrogen production from biological
present in the permeation stream of the reactor when the feedstock has been introduced and the application of membrane
membrane is not completely hydrogen perm-selective), to reactors to enhance the hydrogen yield has been highlighted.
methane which is not armful for the fuel cell catalyst. Although the direct bio-hydrogen production is a promising
The study of Mori, shows that even when the Pd-based route, a more realistic route for hydrogen production from bio-
membrane presents some defects (due to membrane aging or mass related feedstock is via reforming intermediate products (or
membrane production method), the system is able to produce bio-products) of bio-mass transformation. In this case, reforming
pure hydrogen ( 499.8%) while maintaining the CO concentration of alcohols (methanol, ethanol) and acetic acid produced from
well below 10 ppm, thus a hydrogen stream suitable for PEM fuel biomass has been greatly investigated in literature. Methanol,
cell applications. ethanol and acetic acid can be converted (via steam reforming) to
a mixture of hydrogen, carbon oxides and other products like
7.2. H2 production from other hydrocarbons in MR methane, ethane, etc.).
The reforming of the feedstock is generally an equilibrium
The recent literature presents also works related to the system, involving also WGS reaction, although the overall system
production of hydrogen for higher hydrocarbons in membrane requires much lower temperatures compared with the reforming
reactors. The production of hydrogen from other hydrocarbons of natural gas (Kikuchi et al., 2008; Lin and Chang 2004).
than methane is studied from two points of view: (i) the higher Methanol has been widely studied, also because methanol
hydrocarbon is considered a feedstock for hydrogen production itself can be considered as an energy carrier much easier to
and (ii) hydrogen is a byproduct of a reaction involving a higher handle than hydrogen (Gallucci et al., 2007a,b). The permeation
hydrocarbon. through hydrogen selective membranes results in shifting the
As far as the higher hydrocarbon is used as direct feedstock for reaction equilibrium (as for the methane reforming) while produ-
hydrogen, the typical reaction system occurring is based on the cing CO-free hydrogen stream directly available for PEM fuel cells.
following reactions (see for example Chen et al., 2003b, 2006; Many authors (not reported in this review) reported the positive
Damle, 2008, 2009): effect of membranes in enhancing the methanol conversion. An
interesting application has been proposed by Fu and Wu (2007)
CnHm þnH2O-nCOþ(nþm/2)H2 who adopted a double jacketed membrane reactor to obtain the
autothermal reforming of methanol. The methanol reforming
COþ3H23CH4 þH2O
takes place in the shell between the membrane tube and the
COþH2O3CO2 þ H2 second jacket, the hydrogen permeates through the membrane
and is recovered as CO-free stream. The unconverted reactants
Basically, the higher hydrocarbon is easily converted to CO and and the unrecovered hydrogen are converted in the second jacket
hydrogen at moderate temperatures, through an irreversible with air producing the heat which is supplied to the reforming
reaction. Two successive equilibrium reactions (methanation system through the jacket wall. In this way, complete conversion
and WGS) follow the reforming. Being the temperature of the of methanol and complete recovery of hydrogen are not required,
reactor between 450 and 550 1C, the methanation is more shifted and autothermal operation can be achieved. The reforming/
towards the products, while the WGS is more shifted towards the oxidation ratio can be adjusted by tuning the air flow in the
reactants, corresponding to a lower hydrogen production. By second jacket.
using a membrane reactor, hydrogen is withdrawn during the Ethanol reforming in hydrogen selective membrane reactors
reforming, which results in suppressing the methanation reaction has been studied by Lin et al. (2004, 2008), Tosti et al. (2009),
and promoting the WGS. Thus, by using the membrane reactor Gallucci et al. (2010a), and others.
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