Author's Accepted Manuscript

Highly Stable Bilayer MFI Zeolite Membranes

for High Temperature Hydrogen Separation
Haibing Wang, Xueliang Dong, Y.S. Lin
PII: S0376-7388(13)00697-2
DOI: http://dx.doi.org/10.1016/j.memsci.2013.08.030
Reference: MEMSCI12358
To appear in: Journal of Membrane Science
Received date: 20 May 2013
Revised date: 20 August 2013
Accepted date: 22 August 2013
Cite this article as: Haibing Wang, Xueliang Dong, Y.S. Lin, Highly Stable
Bilayer MFI Zeolite Membranes for High Temperature Hydrogen Separation,
Journal of Membrane Science, http://dx.doi.org/10.1016/j.memsci.2013.08.030
This is a PDF file of an unedited manuscript that has been accepted for
publication. As a service to our customers we are providing this early version of
the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting galley proof before it is published in its final citable form.
Please note that during the production process errors may be discovered which
could affect the content, and all legal disclaimers that apply to the journal
pertain.
www.elsevier.com/locate/memsci
1

Highly Stable Bilayer MFI Zeolite Membranes for High Temperature Hydrogen Separation
Haibing Wang, Xueliang Dong and Y. S. Lin
*

School for Engineering of Matter, Transport and Energy,
Arizona State University
Tempe, Arizona 85287, USA

Abstract
Stable inorganic membranes perm-selective to hydrogen will find applications in a
number of important industrial processes including water gas shift reaction for hydrogen
production. This paper reports a highly stable bilayer MFI zeolite membrane with good hydrogen
separation characteristics. The membrane consists of a thin (2m) ZSM-5 layer on a thick (8m)
silicalite base layer supported on macroporous -alumina with a yttria stabilized zirconia
intermediate barrier layer. The zeolitic pores of the thin ZSM-5 layer were narrowed by catalytic
cracking deposition (CCD). At 500
o
C, the bilayer zeolite membrane exhibits H
2
permeance of
about 1.210
-7
molm
-2
s
-1
Pa
-1
, with H
2
to CO
2
, CO and H
2
O vapor selectivity respectively of
about 23, 28 and 180. The membrane shows slightly improved separation properties (H
2

permeance, H
2
/CO and H
2
/CO
2
selectivity) as the feed side pressure increases during the test of
separation of industrial relevant simulated gas mixture (25% H
2
: 25% CO: 25% H
2
O: 25% CO
2
,
with 400 ppm H
2
S) at 500
o
C for 24 days. Membrane reactor made of the bilayer zeolite
membrane shows stable performance under water gas shift reaction conditions (500
o
C,
H
2
O/CO=3, GHSV=60,000 h
-1
, with a ceria doped iron oxide catalyst) in terms of CO
conversion, H
2
recovery, and H
2
permeance and selectivity of the zeolite membrane. The
unprecedented thermal and chemical stability and good separation properties of the bilayer
zeolite membrane are related to its unique bilayer structure and synthesis methods.
Keywords: Microporous membranes, zeolite, stability, hydrogen separation, long-term stability;
water gas shift.
*
Corresponding author. Tel.: +1 480 965 7769; fax: +1 480 965 0037.
E-mail address: jerry.lin@asu.edu (Y.S. Lin).
2

Introduction
High temperature hydrogen-selective membranes can find applications in membrane
separators for separation of gas mixture containing hydrogen, or in membrane rectors to improve
conversion or selectivity of a chemical reaction involving hydrogen either as a reactant or a
product. One such an important application is membrane reactor for water gas shift (WGS)
reaction for hydrogen production. WGS is a key process in the more efficient integrated
gasification combined cycles (IGCC) technology that captures carbon dioxide before combustion
for electrical power generation [1]. The H
2
-selective membrane reactor is attractive over the
traditional reactor because in the former, purified hydrogen can be separated continuously from
the reactor, and a CO-conversion higher than the equilibrium CO-conversion can be obtained.
Such a membrane reactor offers potential to replace conventional WGS process consisting of
multiple reactors and separators. To match the properties of the catalysts used in WGS reaction,
the membrane reactor should be operated in 300-600
o
C. In this temperature range, the membrane
should exhibit high H
2
permeance, and is perm-selective for H
2
over other gases encountered in
WGS gas stream (such as CO
2
, CO, H
2
O). More importantly, the membrane should be stable at
high temperatures and in gas stream containing steam and impurities, in particular, H
2
S that is
found in reforming gas for WGS reaction.
Several different types of inorganic membranes, such as metallic (i.e. Pd/Pd-based alloy)
membranes [2-5], silica membranes [6-7], mixed proton and electron conducting ceramic
membranes [8-9], and zeolite membranes [10-11], have been studied as membrane reactors for
WGS reaction for hydrogen production. Dense metallic membranes exhibit extremely high H
2

permeance and selectivity over other gasses in 300-600
o
C. However, metallic membranes are
thermally and chemically unstable in some circumstances. The surface of the metallic membrane
can be poisoned upon exposure to a gas stream containing a trace amount of H
2
S. It has been
reported that the significant reduction in H
2
permeance through pure Pd membrane in the
presence of 54.8 ppm H
2
S was due to the blocking of surface sites (reversible) for H
2

dissociation and the formation of Pd
4
S (irreversible) resulting from the bulk sulfidation [12].
3

Although the bulk sulfidation of the Pd membrane in the presence of H

2
S was effectively
avoided by alloying with Au, hydrogen permeation reduction due to the surface side blocking
was still observed [12]. H
2
S concentration in the gas stream also affects greatly the hydrogen
permeation through Pd-Cu alloy membranes. Kulprathipanja et al. [13] observed that the
reduction in H
2
permeation flux through a Pd-Cu membrane was due to the site blocking for H
2

dissociation at low H
2
S concentration; while at high H
2
S concentration, the Pd-Cu membrane
failed due to the sulfidation of the Pd-Cu membrane and formation of micron sized pores. Gade
et al. [14] found that the Pd-Cu alloy membrane with a higher Cu content showed less H
2

permeation flux reduction when exposed to gases containing CO or H
2
S. Overall, although the
structural and chemical stability of Pd membranes can be improved by alloying Pd with some
other metals, such as Ag, Cu, Au, Ni and Fe, to fabricate metallic composite membranes,
significant property degradation was still observed in many situations when Pd alloy membranes
were exposed to H
2
S [13, 15], H
2
O [16, 17], and CO [18-19].

Dense proton conducting
perovskite membranes are highly perm-selective to hydrogen, but the membranes offer too low
hydrogen permeance in 300-600
o
C [20-21]. Besides, they are chemically unstable when exposed
to some gases such as CO
2
[22].
Microporous silica membranes prepared by sol-gel and chemical vapor deposition (CVD)
methods generally show good permeance and selectivity of H
2
over some larger gas molecules,
such as N
2
, CO, CO
2
, CH
4
[23]. These membranes are made of microporous silica of amorphous
structure with a pore size smaller than 0.5 nm, which allows small H
2
to permeate while
excluding bigger molecules. The small pore size gives inherently low permeability so
microporous silica membranes with thickness down to 30 nm should be prepared to obtain
sufficiently high H
2
permeance. For example, Oyama and co-workers [24-25] reported that a
silica-alumina composition membrane with a thickness of about 30-40 nm showed a hydrogen
permeance of 2-310
-7
molm
-2
s
-1
Pa
-1
at 600
o
C and a H
2
/CO
2
selectivity of 590. The main
problem with the amorphous microporous silica membranes is its hydrothermal instability [23].
H
2
permeance and selectivity of the microporous silica membranes drop when exposed to humid
4

gas stream at high temperatures due to changes in the membrane structure as a result of
continuous hydrolysis and condensation of the silica network.
Efforts to improve hydrothermal stability of amorphous microporous silica membranes
include doping with some metal (such as Co) in silica network [26-30], minimizing or
eliminating the surface hydroxyl groups of the as-prepared silica membranes by post-silylation
treatment [31-32], or preparing organic-silica hybrid microporous membranes using
Bis(triethoxysilyl) ethane (BTESE) as precursor [33]. These modified membranes exhibit an
improved hydrothermal stability, but separation performance is often compromised.
Furthermore, the modified membranes still do not exhibit the long-term hydrothermal stability
required for industrial application (most stability test was done within 100 hr). Although these
membranes show high selectivity for H
2
over CO
2
or CO, their H
2
/H
2
O selectivity is low (<40)
[30, 34], these undesired properties of microporous silica membranes are tied to their amorphous
structure of SiO
2
network, which is inherently unstable at high temperatures.
As discussed above, none of the inorganic membranes studied so far possesses all the
characteristics required for industrial applications such as in the membrane reactor for WGS.
Recent work conducted in our laboratory [35] and that of Dong and co-workers [10] on
crystalline microporous MFI type zeolite membranes show a new direction in developing
microporous membranes for industrial applications. Here we report for the first time that a
bilayer MFI zeolite membrane can offer high H
2
permeance, good selectivity for H
2
over CO,
CO
2
and H
2
O vapor, and excellent hydrothermal and chemical stability under industrially
relevant gas stream containing H
2
S up to 400 ppm. The bilayer MFI zeolite membrane consists
of a macroporous -alumina support, a macroporous yttria stabilized zirconia (YSZ)
intermediate barrier layer, and the zeolite bilayer including a relatively thick alumina-free MFI
(silicalite) layer and a thin alumina-containing MFI zeolite (ZSM-5) separation layer which is
modified by catalytic cracking deposition to narrow the zeolitic pores. It is the unique bilayer
membrane structure with the intermediate YSZ layer and specific synthesis methods that give the
unprecedented stability and separation properties for the zeolite membrane.
5

2. Experimental
2.1 Synthesis and characterization of ZSM-5/silicalite bilayer membrane
Macroporous -alumina support disks of about 20 mm in diameter and 2 mm in thickness
were prepared by the press and sintering method. The YSZ intermediate barrier layer was coated
on the -alumina porous supports by a dip-coating process, followed by calcination at 1000
o
C in
air. After that, a silicalite seed layer was coated on the YSZ coated alumina support by a
dip-coating and calcination process according to the procedure reported previously [35]. This
silicalite seed layer was then grown to a continuous silicalite layer by a templated secondary
growth method using a solution with a molar composition of 0.9 NaOH: 0.9 TPABr : 4 SiO
2
:
1000 H
2
O: 16 EtOH at 175
o
C for 8 h. The synthesized silicalite membrane was washed and dried,
then calcined at 500
o
C for 8 h in air to remove template. Subsequently, a thin ZSM-5 top layer
was synthesized on the silicalite layer at 180
o
C for 8 h using a template-free solution with a
composition of 5 g SiO
2
: 60 g H
2
O: 1.15 g NaOH: 0.65 g Al
2
(SO
4
)
3
18H
2
O. The synthesized
ZSM-5/silicalite bilayer membrane was then modified through catalytic cracking deposition
(CCD) of methyldiethoxysilane (MDES) precursor for zeolitic pore size reduction to enhance the
H
2
/CO
2
separation factor [35].
Briefly, for CCD modification process, MDES precursor kept at room temperature was
carried into the feed side (MFI zeolite layer side) of the zeolite membrane by an equimolar H
2

and CO
2
mixture gas. The MDES precursor molecules then adsorbed onto the active sites on the
inner surface of the zeolitic pore channels. At about 450
o
C, the adsorbed MDES molecules
decomposed and deposited as SiO
2
amorphous units for zeolitic pore size reduction to enhance
the H
2
/CO
2
separation factor.
The crystal structure of the modified MFI zeolite membranes was characterized before
and after long-term hydrothermal and chemical stability testing by X-ray diffraction (XRD)
(Bruker AXS-D8, Cu Ka radiation) with 2 from 5
o
to 45
o
at a step size of 0.015
o
. The
morphology and thickness of the MFI zeolite membranes were characterized using a scanning
electron microscopy (SEM, Philips, XL 30). The composition of the MFI zeolite membranes
6

synthesized from solutions with different aluminum contents were analyzed by energy dispersive
X-ray spectroscopy (EDS).
2.2 Separation tests
The bilayer zeolite membrane disk was loaded in a stainless steel permeation cell with
zeolite membrane layer facing to the feed side, as shown in Figure 1 (without catalyst and glass
wool for separation tests). The membrane was sealed using soft graphite seals (Mercer Gasket &
Shim, NJ). In separation tests, the feed was equimolar H
2
/CO
2
mixture gas without or with H
2
O
vapor. The sweeping gas was helium. The gas flow rates on feed side were controlled by the
calibrated mass flow controllers (MKS Inc.), while the water flow rate was controlled by a
precisely calibrated liquid pump (LC-20AD, Shimadzu Corporation). The gas streams on feed
retentate and permeate sides passed through cold-traps (in the form of water-ice mixture) to
condense water vapor in the gas streams. After water condensation, the flow rates and
compositions of the gas streams were measured by a bubble flow meter and a gas chromatograph
(GC, Agilent, 6890 N), respectively. The permeate side pressure was kept at 1 atm during the
experiment. The helium sweeping gas flow rate on permeate side was 20 mlmin
-1
(STP) in the
separation tests. The temperature heating and cooling rates were 0.3
o
Cmin
-1
.
The H
2
, CO
2
permeance and the H
2
/CO
2
separation factor of the membrane were
measured from 500
o
C to 150
o
C using an equimolar H
2
/CO
2
mixture as the feed gas to study the
effect of temperature on gas permeation and separation properties of the modified membrane.
The effect of feed side pressure on the gas permeation and separation properties was also studied
by measuring the gas permeance and the H
2
/CO
2
separation factor from 1 to 6 atm at 500
o
C. The
flow rate of the equimolar H
2
/CO
2
mixture gas controlled was 80 mlmin
-1
.
The effect of water vapor on H
2
and CO
2
permeation through the modified MFI zeolite
membrane was studied by gradually increasing the water vapor partial pressure from 22.5 to
153.6 KPa in an equimolar H
2
/CO
2
mixture at 40 mlmin
-1
. The water vapor partial pressure in
the feed side was adjusted by changing the water feeding rate. The total pressure on feed side of
the membrane reactor was maintained at 2 atm during the water vapor permeation experiment.
7

The stainless steel gas tubes connecting the permeation cell and the water pump were heated up
to 200
o
C by the wrapped heating tape to vaporize the water.
2.3 Membrane stability tests under WGS reaction conditions
Membrane stability tests were conducted in the same membrane cell with the same
bilayer zeolite membrane disk, but with the feed side of the membrane packed with WGS
catalyst, as shown in Figure 1. About 0.2 g sieved cerium-doped iron oxide-based catalyst
(particle size 180-355 m) with a nominal composition of Fe
1.82
Ce
0.18
O
3
was used in each test.
The entrances of the gas inlet and outlet on feed side were covered with glass wools to prevent
the catalyst from getting into tubes and blocking them during the high temperature WGS reaction
process. The zeolite membrane reactor was then heated up to 200
o
C under helium inert gas at a
flow rate of 20 mlmin
-1
to clean the catalyst. After that, a process gas containing 33.3% CO:
25.0% CO
2
: 25.0% H
2
: 16.7% steam with a reduction factor of R=1.4 was fed into the membrane
reactor to activate the catalyst [36] at 400
o
C for 4 h. It has been reported that this optimized
activation process is able to reduce the hematitic iron oxide to magnetitic phase without over
reduction of the catalyst and the activated catalyst is very stable under high temperature WGS
reaction conditions [36].
The hydrothermal stability of the modified membrane reactor was tested for WGS
reaction with H
2
S free CO/H
2
O mixture gas (H
2
O/CO=3) as the feed. The feed flow rate was 100
mlmin
-1
(CO flow rate: 25 mlmin
-1
(STP), GHSV=60,000 h
-1
) at 2 atm. The sweeping gas was
helium at 20 mlmin
-1
(STP) and 1 atm. Long-term stability test was done at 500
o
C for 28 days.
During the long-term WGS reaction, the CO-conversion, H
2
recovery, H
2
permeance, and the
H
2
/CO
2
separation factor of the modified disk membrane reactor were measured. The
CO-conversion and H
2
recovery are calculated by the following equations, respectively.
in
CO
permeate
CO
rententate feed
CO
CO
F
F F
2 2
+
= (1)
rententate feed
H
permeate
H
permeate
H
H
F F
F
R
2 2
2
2
+
= (2)
8

where
rententate feed
CO
F
2
and
permeate
CO
F
2
are CO
2
flow rates in feed rententate and permeate side,
respectively;
in
CO
F is the flow rate of CO gas fed into the permeation cell;
rententate feed
H
F
2
and
permeate
H
F
2
are the H
2
flow rates in feed rententate and permeate sides, respectively.
After long-term hydrothermal stability testing, the membrane reactor was cooled down to
room temperature, and the WGS catalyst was removed. The membrane reactor was then sealed
and heated up again for the long-term chemical stability testing at 500
o
C under WGS reaction
conditions (without catalyst). The feed gas was the mixture of H
2
: CO
2
: CO: H
2
O=1:1:1:1, in the
presence of 400 ppm H
2
S. The feed gas and helium sweeping gas were respectively controlled at
80 mlmin
-1
and 20 mlmin
-1
. Initially, the stability testing was conducted under a feed side
pressure of 2 atm at 500
o
C for 12 days. The membrane was then kept under dry helium at the
same temperature for 8 days. After that, the feed side pressure was increased to 4 atm and further
tested under WGS reaction conditions for another 12 days. The helium sweep gas was
maintained at 1 atm in all the tests.
3. Results and Discussion
3.1 Separation Performance
Figure 2 shows a SEM cross-section of a ZSM-5/silicalite bilayer zeolite membrane
synthesized on an YSZ intermediate barrier (about 3 m thick) coated porous alumina support.
The YSZ intermediate layer is highly homogenous without any visible grain boundary. The
bilayer membrane consists of a thick (about 8 m) silicalite bottom layer and a thin (about 2 m)
ZSM-5 top layer. The silicalite base layer appears to have a less homogenous structure with
visible grain-boundary near the YSZ and silicalite interface (sililicate seed layer region) and a
more homogenous structure near the silicalite/ZSM-5 interface. The ZSM-5 layer is well
intergrown without visible grain-boundary. EDS analysis shows Si/Al ratio of about 17.8 for the
ZSM-5 layer and for the silicalite base layer.
H
2
permeance and H
2
/CO
2
selectivity for membranes at various preparation stages are
summarized in Table 1. As shown, the macroporous alumina and alumina/YSZ supports have
9

high permeance without selectivity of H

2
over CO
2
at 100
o
C. This is because the pore size of the
alumina and alumina/YSZ porous supports is very large, thus H
2
and CO
2
gases transported
through the supports via non-selective viscous flow mechanism. The H
2
permeance through the
YSZ/alumina support is smaller than that through the alumina support since the YSZ
intermediate layer contributed additional resistance for gas transport through the porous supports.
The permeance for the CCD modified bilayer zeolite membrane is less than 10% of that for the
supports, indicating that mass transport resistance is mainly contributed by the modified bilayer
zeolite membrane. It should be noted that for microporous MFI zeolite membrane with H
2
/CO
2

mixture feed, the H
2
/CO
2
selectivity increases with temperature and at 100
o
C the membrane is
CO
2
perm-selective [37].
Temperature dependence of the H
2
, CO
2
permeance and the H
2
/CO
2
separation factor of
the modified bilayer MFI zeolite membrane are shown in Figure 3. The increase of the H
2

permeance with temperature indicates that the H
2
permeation through the modified MFI zeolite
membrane with narrowed zeoitic pores follows an activated diffusion mechanism. The CO
2

permeance exhibits a slight decrease and then increase with temperature, showing a minima
point at approximate 300
o
C. The decrease of CO
2
permeance with the increase of temperature at
low temperature range (<300
o
C) was due to the fact that the adsorption affinity between CO
2

molecules and zeolitic pores is stronger at a lower temperature. At temperatures higher than
300
o
C, the adsorption affinity between CO
2
molecules and zeolitic pores is very weak. The
increase of CO
2
permeance with the temperature indicates that the CO
2
permeation through the
narrowed zeolitic pores follows an activated diffusion mechanism at high temperatures. The
H
2
/CO
2
separation factor of the modified membrane increases with increasing the temperature,
and then leveled off when the temperature attained 400
o
C. Therefore, a relatively high
temperature is beneficial for the H
2
/CO
2
separation. At 500
o
C, the H
2
/CO
2
separation factor
obtained was about 23.
It has been reported that the permeance of a non-adsorbing or weak adsorbing small gas
molecules through MFI zeolite membranes can be described by the following equation [37]:
10

) exp( )
8
(
5 . 0
RT
E
RT M z L
F
d
w

(3)
where F is the single gas permeance (molm
-2
s
-1
Pa
-1
), R is the gas constant (J mol
-1
K
-1
), L is
the thickness of the zeolite membrane layer (m), T is temperature (K),
d
E is the activation
energy for gas permeance through the MFI zeolite membrane (Jmol
-1
), is the ratio of the
membrane porosity to tortuosity,
w
M is the molecular weight of the permeating gas (gmol
-1
),
is about 1 nm for diffusion in a MFI-type zeolite, and z is the diffusion coordination number (4
for a MFI-type zeolite). Kanezashi et al. [37] observed that single gas permeance of H
2
and CO
2

through the MFI zeolite membrane was similar to the component gas permeance of a H
2
/CO
2

mixture gas at temperatures higher than 300
o
C because the adsorption affinity between H
2
, CO
2

gas molecules and MFI zeolitc pores is very weak at high temperatures. For this reason, equation
(3) can also be used to describe the H
2
and CO
2
gas permeance of the H
2
/CO
2
mixture through
the modified MFI zeolite membrane at temperatures higher than 300
o
C. Fitting the H
2
permeance
data shown in Figure 3 into the equation (3) gives that the activation energy for H
2
permeance
through the modified MFI zeolite membrane is 11.4 kJmol
-1
.
Figure 4 shows the effect of feed side pressure on H
2
, CO
2
permeance and H
2
/CO
2

separation factor of the modified MFI bilayer membrane at 500
o
C. The results show that the feed
side pressure has no obvious effect on the permeation and separation of H
2
and CO
2
mixture
through the modified MFI zeolite membrane at a high temperature. This is consistent with the
results reported by van de Graaf et al. [38] that helium and neon permeance through a MFI
zeolite membrane was pressure-independent. Poshusta et al. [39] reported that at low
temperatures, CO
2
permeation flux through a MFI zeolite membrane decreased as the pressure
on both sides of the membrane increased at a constant pressure drop across the membrane. This
can be well explained by the surface diffusion model because of the strong adsorption of CO
2

molecules on MFI zeolite membrane surface at low temperatures. However, at higher
temperatures, because the adsorption affinity between CO
2
molecules and MFI zeolitic pores is
11

very weak, a pressure-independent CO

2
permeation behavior was observed. Similar permeation
behavior of CO
2
and CH
4
through silicalite membranes was also reported by Algieri et al [40].
Figure 5 shows the H
2
O, H
2
and CO
2
permeance through the modified MFI zeolite
membrane at different water vapor partial pressures (P
H2O
=22.5-153.6 kPa) at 500
o
C. It is
obvious that both H
2
and CO
2
permeance decreased slightly as the water vapor partial pressure in
the H
2
/CO
2
/H
2
O ternary gas system increased. However, the suppression effect of water vapor
on H
2
and CO
2
permeation through the modified MFI zeolite membrane was much smaller than
that through the unmodified MFI zeolite membrane reported previously [41]. As shown in Figure
5, water vapor permeance through the modified MFI zeolite membrane is approximately
independent of its partial pressure in the H
2
/CO
2
/H
2
O ternary gas system. The average water
vapor permeance was measured to be 7.210
-10
molm
-2
s
-1
Pa
-1
, which is much lower than that
through the unmodified MFI zeolite membrane [41]. Figure 5 also shows that the highest H
2
/H
2
O
selectivity is 180, with the average of around 175, for the modified zeolite membrane. This is
highest H
2
/H
2
O vapor selectivity for microporous inorganic membranes.
Although H
2
O has a smaller kinetic diameter than that of CO
2
molecule, the H
2
/H
2
O
selectivity was much higher than the H
2
/CO
2
selectivity. A reason is that the membrane
synthesized in this study has a unique bilayer structure, i.e. a ZSM-5 top thin layer and a
hydrophobic silicalite bottom thick layer. The hydrophobic silicalite layer significantly limited
water vapor permeation through the membrane. Another possible reason is that there is a
stronger adsorption affinity between H
2
O molecules and the ZSM-5 zeolite, thus, the low H
2
O
permeance the membrane may also stem from the surface adsorption of H
2
O molecules on the
ZSM-5 zeolite.
3.2 Long-term hydrothermal and chemical stability
Figure 6(a) shows the CO-conversion and hydrogen recovery during WGS reaction in a
bilayer MFI zeolite membrane reactor (with the WGS catalyst packed in the feed side). WGS
reaction was conducted at 500
o
C, H
2
O/CO=3 and GHSV=60,000 h
-1
for 28 days. The
CO-conversion in the membrane reactor increases first and then maintains at about 84%. The
12

initial enhancement of CO-conversion may be caused by the fact that WGS catalyst has not been
fully activated by the process gas. During the first 22 days of WGS reaction, no obvious
change in hydrogen recovery was observed. From the 23
th
day, the hydrogen recovery increased
slightly from 22% to about 23.2%. The stable CO-conversion and H
2
recovery during the
long-term WGS reaction in the modified MFI zeolite membrane reactor indicates that both the
modified bilayer MFI zeolite membrane reactor and the WGS catalyst are extremely stable under
WGS reaction environment.
The H
2
/CO
2
separation factor and H
2
permeance through the modified membrane reactor
during the long-term WGS reaction were also measured and the results are shown in Figure 6(b).
Similar to the hydrogen recovery, the H
2
permeance of the membrane reactor was approximately
constant for the first 23 days, and then increased slightly. The H
2
/CO
2
separation factor of the
modified membrane reactor shows a slightly decrease from 22.4 to 21.7 over 28 days of WGS
reactions. As shown in Figure 6(b), the H
2
permeance of the modified membrane reactor under
WGS reaction conditions is about 1.0410
-7
molm
-2
s
-1
Pa
-1
which is lower than that of the
as-modified membrane (1.2810
-7
molm
-2
s
-1
Pa
-1
).

This is because water vapor has some
suppression effect on hydrogen and carbon dioxide permeation through the MFI zeolite
membrane as also observed in our previous study [41].
The long-term hydrothermal stability of the modified MFI zeolite membranes is much
better than that of silica membranes which usually undergo severe densification through
hydrolysis of Si-O-Si linkages and formation of Si-OH hydroxyl groups upon exposure to water
vapor at high temperatures. The high hydrothermal stability of the modified MFI zeolite
membranes is attributed to the highly crystallized structure without silanol groups on the zeolite
membrane surface. Although some hydrophilic SiO
2
amorphous units are deposited into zeolitic
pores for pore size reduction through CCD modification, water vapor could hardly diffuse
through these narrowed zeolitic pores, thus the interaction between deposited amorphous SiO
2

units and water vapor is reduced and the stability is significantly improved.
The reformed gas used as the feed gas for WGS reaction for hydrogen production usually
13

contains a very small amount of H

2
S (in ppm level). In order to examine the long-term chemical
stability of the modified MFI zeolite membrane under WGS reactions conditions in the presence
of 400 ppm H
2
S, H
2
permeance, H
2
/CO
2
and H
2
/CO separation factors of the membrane were
measured and the results are shown in Figure 7. Although the H
2
permeance fluctuates during the
long-term stability study, it is generally stable over the 12 days of testing at a feed side pressure
of 2 atm. The fluctuation of H
2
permeance may be caused by the strong adsorption affinity of
H
2
S on zeolite. When the feed side pressure increases to 4 atm, H
2
permeance increases initially
and then maintains at a constant. The H
2
/CO
2
separation factor of the modified membrane is very
stable during the long-term stability testing under WGS reaction conditions in the presence of
400 ppm H
2
S. A slight increase in H
2
/CO
2
separation factor is observed as the feed side pressure
increases from 2 to 4 atm. As mentioned previously, H
2
S also has stronger adsorption affinity on
zeolite, which has some effect on other gas permeation through the membrane. The strong
adsorption of H
2
S on zeolite might affect CO and CO
2
adsorption on zeolite and slightly
decrease their permeance through the modified membrane. As a result, a slight increase in
H
2
/CO
2
and H
2
/CO separation factor was observed as the feed side pressure increased from 2 to
4 atm. These results demonstrate that the modified MFI zeolite membrane is highly stable upon
exposure to 400 ppm H
2
S in the presence of water vapor at high temperature. Considering that
the modified MFI zeolite membrane also exhibits high H
2
/CO
2
separation factor and significant
H
2
permeance, it is an excellent membrane reactor candidate for high temperature WGS reaction
for hydrogen separation.
Figure 8 compares the SEM surface micrograph of the membrane after long-term
hydrothermal and chemical stability testing to that of the fresh membrane. As can be seen from
Figure 8(b), some small dots or fiber-like structures are observed on the surface of the MFI
zeolite membrane experienced long-term hydrothermal and chemical stability testing. These may
be the residuals of the WGS catalyst, and ceramic wool that was used to cover the inlet and
outlet on the feed side of the membrane reactor to prevent catalyst from getting into these
entrances. The zeolite crystals underneath the small dots or fiber-like structures are still in very
14

good integrity, indicating that MFI zeolite crystals had very limited adverse interaction with
water vapor during the long-term stability testing. Compared to the fresh membrane, the surface
of the membrane after the long-term stability appears to contain less faceted crystals with smaller
grains fused together. This might suggest some sintering effect on the MFI zeolite when operated
at high temperatures, which could have improved the separation performance of the membrane
as observed.
EDS elemental composition analysis on the surface of the membrane after long-term
stability testing shows the presence of only Al, Si, Na and O on the membrane surface, as shown
in Figure 8(c). The Si/Al ratio on the membrane surface is 18.6, which is very similar to that of
the as-synthesized membrane (17.8). Considering the accuracy of EDS analysis, this result also
indicates that there was no elemental diffusion between alumina support and the zeolite
membrane layer during the long-term stability testing at 500
o
C. Figure 9 shows the XRD patterns
of the membrane before and after long-term stability testing. The two XRD patterns are
essentially identical in both peak position and peak broadness. These indicate the crystal
structure of the MFI zeolite layer remains unchanged. The XRD pattern is also consistent with
the SEM micrographs of the membrane experienced long-term stability testing, which shows that
the MFI zeolite crystals were still integrity after long-term stability testing.
The excellent thermal and chemical stability of the bilayer MFI zeolite membrane is due
to the intrinsic stability and hydrophobicity of highly siliceous MFI zeolite [42]. The use of YSZ
intermediate barrier layer effectively prevents diffusion of aluminum from the support into the
MFI zeolite layer in operation at high temperature, ensuring a low or zero aluminum content in
the MFI zeolite layer for extended period of time [43]. To ensure good separation performance,
the MFI zeolite membranes should have minimum or no defects as well as intercrystalline gaps.
This was achieved by the synthesis methods used in this work. However, even for a perfect MFI
zeolite membrane, zeolitic pores of MFI zeolite are not sufficiently small to provide good
diffusion-controlled selectivity for H
2
over CO
2
and CO [35]. Therefore, zeolitic pore size of the
MFI zeolite membrane was reduced by the catalytic cracking deposition (CCD) selectively on
15

the MFI zeolite framework [35]. However, it is important to control the deposition in a small
region along the membrane thickness direction. The bilayer structure with a thick base silicalite
layer (to control membrane quality) and a thin ZSM-5 layer (for CCD to narrow pore size)
ensure effective reduction of the zeolitic pores in a narrow region along gas permeation direction.
In this way, the modification resulted in substantial improvement in selectivity with minimum
reduction in hydrogen permeance.
4. Conclusions
The bilayer MFI zeolite membrane consisting of a thin (2m) ZSM-5 layer on a thick
(8m) silicalite supported on macroporous -alumina with a yttria stabilized zirconia
intermediate barrier layer was prepared by a multiple step synthesis method. The zeolitic pores of
the thin ZSM-5 layer were narrowed by catalytic cracking deposition (CCD). At 500
o
C, the
bilayer zeolite membrane exhibited H
2
permeance of about 1.210
-7
molm
-2
s
-1
Pa
-1
and H
2
to
CO
2
, CO and H
2
O vapor selectivity respectively of about 23, 28 and 180. The separation
properties of the membranes have a weak dependence on feed pressure and water vapor pressure
at high temperatures. The bilayer MFI zeolite membrane is highly stable at 500
o
C for at least 24
days under industrially relevant conditions for water gas shift reaction (equimolar mixture of CO,
CO
2
, H
2
and H
2
O plus 400 ppm H
2
S).
Acknowledgement
The authors would like to acknowledge the support of the U. S. Department of Energy
(DE-PS36-03GO93007) for this project. We would also like to acknowledge Prof. Panagiotis
Smirniotis at University of Cincinnati for providing the catalyst used for water gas shift reaction
in this work.



16

References
[1] G. Q. Lu,

J. C. D. da Costa, M. Duke, S. Giessler, R. Socolow, R. H. Williams, T.
Kreutz, Inorganic membranes for hydrogen production and purification: A critical
review and perspective, J. Coll. Interf. Sci. 314 (2007) 589603.
[2] S. Tosti, A. Basile, G. Chiappetta, C. Rizzello, V. Violante, Pd-Ag membrane reactors
for water gas shift reaction, Chem. Eng. J. 93 (2003) 2330.
[3] Y. Bi, H. Xu, W. Li, A. Goldbach, Water-gas shift reaction in a Pd membrane reactor
over Pt/Ce
0.6
Zr
0.4
O
2
catalyst, Int. J. Hydrogen Energy. 34 (2009) 29652971.
[4] A. Basile, A. Criscuoli, F. Santella, E. Drioli, Membrane reactor for water gas shift
reaction, Gas Sep. Purif. 10 (1996) 243254.
[5] A. S. Augustine, Y. H. Ma, N. K. Kazantzis, High pressure palladium membrane reactor
for the high temperature water-gas shift reaction, Int. J. Hydrogen Energy. 36 (2011)
53505360.
[6] S. Giessler, L. Jordan, J. C. D. da Costa, G. Q. Lu, Performance of hydrophobic and
hydrophilic silica membrane reactors for the water gas shift reaction, Sep. Purif.
Technol. 32 (2003) 255264
[7] S. Battersby, S. Smart, B. Ladewig, S. Liu, M. C. Duke, V. Rudolph, J. C. D. da Costa,
Hydrothermal stability of cobalt silica membranes in a water gas shift membrane reactor,
Sep. Purif. Technol. 66 (2009) 299305.
[8] P. S. Maiya, T. J. Anderson, R. L. Mieville, J. T. Dusek, J. J. Picciolo, U. Balachandran,
Maximizing H
2
production by combined partial oxidation of CH
4
and water gas shift
reaction, Appl. Catal. A: Gen. 196 (2000) 6572.
[9] J. Li, H. Yoon, T. K. Oh, E. D. Wachsman, Stability of SrCe
1-x
Zr
x
O
3-
under water gas
shift reaction conditions, J. Electrochem. Soc. 157 (2010) B383B387.
[10] Z. Tang, S. J. Kim, G. K. Reddy, J. Dong, P. Smirniotis, Modified zeolite membrane
reactor for high temperature water gas shift reaction, J. Membr. Sci. 354 (2010)
114122.
17

[11] S. J. Kim, Z. Xu, G. K. Reddy, P. Smirniotis, J. Dong, Effect of pressure on

high-temperature water gas shift reaction in microporous zeolite membrane reactor, Ind.
Eng. Chem. Res. 51 (2012) 13641375.
[12] C.-H. Chen, Y. H. Ma, The effect of H2S on the performance of Pd and Pd/Cu
composite membrane, J. Membr. Sci., 362 (2010) 535544.
[13] A. Kulprathipanja, G. O. Alptekin, J. L. Falconer, J. D. Way, Pd and Pd-Cu membranes:
inhibition of H
2
permeation by H
2
S, J. Membr. Sci. 254 (2005) 4962.
[14] S. K. Gade, S. J. DeVoss, K. E. Coulter, S. N. Paglieri, G. O. Alptekin, J. D. Way,
Palladium-gold alloy membranes in mixed gas streams with hydrogen sulfide: Effect of
alloy content and fabrication technique, J. Membr. Sci., 378 (2011) 35 41.
[15] C. P. OBrien, B. H. Howard, J. B. Miller, B. D. Morreale, A. J. Gellman, Inhibition of
hydrogen transport through Pd and Pd
47
Cu
53
membranes by H
2
S at 350
o
C, J. Membr.
Sci. 349 (2010) 380384.
[16] J. Catalano, M. G. Baschetti, G. C. Sarti, Influence of water vapor on hydrogen
permeation through 2.5 m Pd-Ag membranes, Int. J. Hydrogen Energy 36 (2011)
86588673.
[17] H. Gao, Y. S. Lin, Y. Li, B. Zhang, Chemical stability and its improvement of
palladium-based metallic membranes, Ind. Eng. Chem. Res. 43 (2004) 69206930.
[18] T. B. Flanagan, D. Wang, K. Shanahan, The effect of CO on hydrogen permeation
through Pd and through internally oxidized and un-oxidized Pd alloy membranes, Sep.
Purif. Technol. 79 (2011) 385392.
[19] B. Arstad, H. Venvik, H. Klette, J.C. Walmsley, W.M. Tucho, R. Holmestad, A.
Holmen, R. Bredesen, Studies of self-supported 1.6 m Pd/23 wt.% Ag membranes
during and after hydrogen production in a catalytic membrane reactor, Catal. Today 118
(2006) 6372.
18

[20] X. Qi and Y. S. Lin, Electrical conduction and hydrogen permeation through mixed
proton-electron conducting strontium cerate membranes, Solid State Ionics 130 (2000)
149156.
[21] S. Cheng, V. K. Gupta, Y. S. Lin, Synthesis and Hydrogen Permeation Properties of
Thin Proton-Conducting Ceramic

Membranes, Solid State Ionics 176 (2005) 26532662.
[22] J. Kniep and Y. S. Lin, Oxygen- and Hydrogen-Permeable Dense Ceramic Membranes,
in Solid State Electrochemistry I, Fundamentals, Materials and Their Applications, Ed.
V. V. Kharton, Springer, Chapter 10, pp.467500, 2011.
[23] Y. S. Lin, I. Kumakiri, B. N. Nair, H. Alsyouri, Microporous Inorganic Membranes, Sep.
Purif. Methods 32 (2002) 229379.
[24] Y. Gu, P. Hacarlioglu, S. T. Oyama, Hydrothermally stable silica-alumina composite
membranes for hydrogen separation, J. Membr. Sci. 310 (2008) 2837.
[25] Y. Gu, S. T. Oyama, Permeation properties and hydrothermal stability of silica-titania
membranes supported on porous alumina substrates, J. Membr. Sci. 345 (2009)
267275.
[26] M. Nomura, K. Ono, S. Gopalakrishinan, T. Sugawara, S. I. Nakao, Preparation of a
stable silica membrane by a counter diffusion chemical vapor deposition method, J.
Membr. Sci. 251 (2005) 151158.
[27] V. Boffa, D. H. A. Blank, J. E. ten Elshof, Hydrothermally stability of microporous
silica and niobia-silica membranes, J. Membr. Sci. 319 (2008) 256263.
[28] K. Akamatsu, M. Nakane, T. Sugawara, S. I. Nakao, Performance under thermal and
hydrothermal condition of amorphous silica membrane prepared by chemical vapor
deposition, AIChE J. 55 (2009) 21972200.
[29] S. Battersby, T. Tasaki, S. Smart, B. Ladewig, S. Liu, M. Duke, V. Rudolph, J. C. D. da
Costa, Performance of cobalt silica membranes in gas mixture separation, J. Membr. Sci.
329 (2009) 9198.
19

[30] T. Tsuru, R. Igi, M. Kanezashi, T. Yoshioka, Permeation properties of hydrogen and

water vapor through porous silica membrane at high temperatures, AIChE J. 57 (2011)
618629.
[31] H. Verweij, Y. S. Lin, and J. Dong, Microporous silica and zeolite membranes for
hydrogen purification, MRS Bull. 31 (2006) 756764.
[32] J. Dong, Y. S. Lin, M. Kanezashi, Z. Tang, Microporous inorganic membranes for high
temperature hydrogen purification, J. Appl. Phys. 104 (2008) 12130117.
[33] M. Kanezashi, K. Yada, T. Yomohisa, T. Tsuru, Organic-inorganic hybrid silica
membranes with controlled silica network size: preparation and gas permeation
characteristics, J. Membr. Sci. 348 (2010) 310318.
[34] B. K. Sea, M. Watanabe, K. Kusakabe, S. Morooka, S. S. Kim, Formation of hydrogen
permselective silica membrane for elevated temperature hydrogen recovery from a
mixture containing steam, Gas Sep. Purif. 10 (1996) 187195.
[35] H. Wang, Y. S. Lin, Synthesis and modification of ZSM-5/silicalite bilayer membrane
with improved hydrogen separation performance, J. Membr. Sci. 396 (2012) 128137.
[36] A. Khan, P. Chen, P. Boolchand, P. G. Smirniotis, Modified nano-crystalline ferrite for
high temperature WGS membrane reactor applications, J. Catal. 253 (2008) 91104.
[37] M. Kanezashi, Y. S. Lin, Gas Permeation and Diffusion Characteristics of MFI-type
Zeolite Membranes at High Temperatures, J. Phys. Chem. C 113 (2009) 37673774.
[38] J. M. van de Graaf, F. Kapteijn, J. A. Moulijn, Permeation of weakly adsorbing
components through a silicalite-1 membrane, Chem. Eng. Sci. 54 (1999) 10811092.
[39] J. C. Poshusta, R. D. Noble, J. L. Falconer, Temperature and pressure effects on CO
2

and CH
4
permeation through MFI zeolite membranes, J. Membr. Sci. 160 (1999)
115125.
[40] C. Algieri, P. Bernardo, G. Golemme, G. Barbieri, E. Drioli, Permeation properties of a
thin silicalite-1 (MFI) membrane, J. Membr. Sci. 222 (2003) 181190.
20

[41] H. Wang, Y. S. Lin, Effects of water vapor on gas permeation and separation properties
of MFI zeolite membranes at high temperature, AIChE J. 58 (2012) 153162.
[42] S. G. Deng and Y. S. Lin, Sulfur dioxide sorption properties and thermal stability of
hydrophobic zeolites, Ind. Eng. Chem. Res. 34 (1995) 40634070.
[43] M. Kanezashi, J. OBrien, Y. S. Lin, Thermal stability improvement of MFI-type zeolite
membranes: Effect of YSZ intermediate layer, Mesopor. Micropor. Mater. 103 (2007)
302308.
21

Figure 1: Schematic of membrane cell for testing separation performance of zeolite
membrane disk with gas mixture feed under water gas shift reaction conditions (with a catalyst)

22

Figure 2: A cross-section microstructure of the silicalite/ZSM-5 bilayer membrane.
23

Figure 3: Effect of temperature on the gas permeation and separation properties of the
modified bilayer membrane (total pressure on feed side: 1 atm, with 50:50 H
2
/CO
2
feed, feed gas
flow rate: 40 mlmin
-1
(STP), sweeping helium flow rate: 20 mlmin
-1
(STP))
24

Figure 4: Effect of feed side pressure on the gas permeation and separation properties of
the modified bilayer membrane (at 500
o
C, with 50:50 H
2
/CO
2
feed, total feed gas flow rate: 80
mlmin
-1
(STP), sweeping helium flow rate and pressure are 40 mlmin
-1
(STP) and 1 atm,
respectively).

25

Figure 5: Water vapor permeation through the bilayer MFI zeolite membrane (total
pressure of the H
2
/CO
2
/H
2
O mixture gas as the feed was 2 atm (~200 kPa), water vapor pressure
increased from 22.5 to153.6 kPa, equimolar H
2
/CO
2
flow rate: 40 mlmin
-1
(STP), H
2
/CO
2
,
operation temperature: 500
o
C, helium sweeping: 20 mlmin
-1
(STP)).

F
factor (b)
zeolite m
sweeping

Figure 6: CO
) versus tim
membrane (to
g: 20 mlmin
O-conversion
e on stream
otal feed gas
n
-1
(STP), pe
n and H
2
rec
for water ga
flow rate: 1
rmeate side
26

covery (a), a
as shift (WG
00 mlmin
-1
pressure: 1 a
and H
2
perm
GS) reaction
(STP), feed
atm)
meace and H
in the modi
d side pressu


H
2
/CO
2
separ
ified bilayer
ure: 2 atm, he
ration
r MFI
elium

F
reaction
presence
flow rate

Figure 7: lon
conditions
of 400 ppm
e: 20 mlmin
-
ng-term stab
(gas compo
m H
2
S at 500
-1
(STP), per
bility of the
osition on f
0
o
C, total ga
rmeate side p
27

e modified b
feed side: H
as flow rate:
pressure: 1at
bilayer mem
H
2
: CO
2
: H
2
80 mlmin
-1
tm).
mbrane under
2
O: CO = 1
1
(STP), swee
r water gas
1:1:1:1, with
eping helium

shift
h the
m gas

FFigure 8: SE EM microgrraph of the
28

fresh membbrane (a), an



nd SEM miccrograph (b)) and
29

EDS spectrum (c) of the surface of the membrane after long-term hydrothermal and chemical
stability.

Figure 9: XRD spectra of the modified membrane before and after long-term
hydrothermal and chemical stability testing.

Table 1: Hydrogen permeance and H

2
/CO
2
selectivity for the membranes at
various preparation stages
Membrane stage
H
2
permenace
(mol/m
2
.s.Pa)
H
2
/CO
2

separation factor
Porous alumina support 1.7410
-6
, @100
o
C 1.02
Alumina supported coated with
YSZ intermediate layer
1.3610
-6
, @100
o
C 1.04
Alumina/YSZ/bi-layer zeolite
membrane (as CCD modified)
35

1.2810
-7
, @450
o
C 25.3

30

Highlights:
Highly Stable Bilayer MFI Zeolite Membranes for High Temperature Hydrogen Separation
Haibing Wang, Xueliang Dong and Y. S. Lin
*

School for Engineering of Matter, Transport and Energy,
Arizona State University
Tempe, Arizona 85287, USA

The modified bilayer membrane showed high H
2
selectivity over CO, CO
2
and H
2
O.
The modified bilayer membrane showed excellent long-term hydrothermal stability for
WGS reaction.
[44] The modified bilayer membrane demonstrated unprecedented chemical stability in the
presence of 400ppm H
2
S.

Graphical