Effect of synthesis conditions on performance of a hydrogen

selective nano-composite ceramic membrane

Mahdi Amanipour
a
, Aliakbar Safekordi
a
, Ensieh Ganji Babakhani
b,
*, Akbar Zamaniyan
b
,
Marzieh Heidari
a
a
Chemical Engineering and Petroleum Faculty, Sharif University of Technology, Azadi Avenue, Tehran, Iran
b
Gas department, Research Institute of Petroleum Industry, West Blvd. Azadi Sport Complex, Tehran 14665-137, Iran
a r t i c l e i n f o
Article history:
Received 21 April 2012
Received in revised form
7 July 2012
Accepted 20 July 2012
Available online 17 August 2012
Keywords:
Nano-composite membrane
Hydrogen
CVD method
Permeance ux
a b s t r a c t
A hydrogen-selective nano-composite ceramic membrane was prepared by depositing
a dense layer composed of SiO
2
and Al
2
O
3
on top of a graded multilayer substrate using co-
current chemical vapor deposition (CVD) method. The multilayer substrate was made by
dip-coating a macroporous a-alumina tubular support by a series of boehmite solutions to
get a graded structure. Using DLS analysis, it was concluded that decreasing hydrolysis
time and increasing acid concentration lead to smaller particle size of boehmite sols. XRD
analysis was carried out to investigate the structure of intermediate layer and an optimized
calcination temperature of 973 K was obtained. SEM images indicated the formation of
a graded membrane with a porous intermediate layer having a thickness of about 2 mm and
a dense top selective layer with a thickness of 80e100 nm. Permeation tests showed that H
2
permeance ux decreased from 5 10
5
mol m
2
s
1
Pa
1
for a fresh substrate to
6.30 10
7
mol m
2
s
1
Pa
1
after 6 h of deposition, but H
2
selectivity over N
2
increased
considerably from 5.6 to 203.
Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
Porous alumina-based ceramic membranes covered with
a selective layer synthesized by chemical vapor deposition
(CVD) or solegel methods have attracted great attention for
gas separation [1,2]. Because of their ability to separate small
gas molecules like hydrogen or helium, and their gas perme-
ation values larger than polymeric membranes, these kind of
membranes have great potential for applications in chemical,
petrochemical and energy industry where gas separation in
harsh conditions leads to increase in process efciency [1].
Silica membranes prepared by different methods like CVD
or solegel, deposited on mesoporous or macroporous supports
have been shown to be effective for H
2
permeation with good
selectivities [3e9]. OkuboandInoue [3,4] depositedsilica within
the pores of a kind of glass with 4 nm mean pore diameter,
using Tetraethylorthosilicate (TEOS) hydrolysis. Similarly, Wu
et al. [7] modied the pore size of g-alumina membranes by
counter current CVD of TEOS, and O
2
as a co-reagent. Oyama
and Lee [8,9] used CVDmethod to deposit silica on both porous
vycor glass andg-alumina supports withpore diameter of 4 nm
and obtained silica membranes with ultra-high selectivities of
hydrogen for temperatures less than 900 K.
Initial membranes which used macroporous supports had
very high permeances, but low selectivites. Hwang et al. [10]
carried out CVD of TEOS on a porous alumina tube with pore
size of about 100 nm and obtained a selectivity of 5.2 for H
2
/N
2
at 873 Kafter 32 h of deposition. Such lowselectivities indicate
* Corresponding author. Tel.: 98 21 48252398; fax: 98 21 44739716.
E-mail addresses: ganjie@ripi.ir, e_ganji@ripi.ir (E. Ganji Babakhani).
Available online at www.sciencedirect.com
j ournal homepage: www. el sevi er. com/ l ocat e/ he
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 7 ( 2 0 1 2 ) 1 5 3 5 9 e1 5 3 6 6
0360-3199/$ e see front matter Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2012.07.085
the presence of large pore defects. A good solution to this
problem is making a graded intermediate layer before addi-
tion of the top selective layer. Some works have been done
with g-alumina as intermediate layers [11e18]. Morooka et al.
[13,14] covered a macroporous a-alumina support which had
110e180 nm pore diameter with three layers of g-alumina
with mean pore diameter of about 8 nm. Using CVDmethod to
add silica layer to this modied support, they obtained
a membrane with selectivity for H
2
/N
2
of 100e1000 and a H
2
permeance of 10
8
e10
9
mol m
2
s
1
Pa
1
at 873 K.
On the other hand, hydrogen-selective silica materials are
hydrothermally unstable at moderate to high temperatures
[7,19e22]. Signicant work has been done to improve the
stability of silica membranes. Some researchers have tried to
prepare hydrophobic silica membranes by the incorporation of
methyl groups in the silica microstructure [21]. Another
approach involves exposing coated membranes to the humid
air for a few days and calcining them in the steam [22]. Oyama
et al. [23] foundthat preparingacompositelayer bysilicaandan
inorganic oxide like zirconia (ZrO
2
) gives rise to membrane
stabilitywithsuperior permeationproperties. Nomuraet al. [24]
reported an improvement of steam stability of a silica
membrane synthesized by counter diffusion CVD of TMOS and
O
2
fromopposite sides of the support. Althoughthis membrane
had a good selectivity for H
2
/N
2
of over 800 at 773 K, the per-
meancewas lowandintheorder of 2e710
8
mol m
2
s
1
Pa
1
.
Moreover, it is necessary to achieve a better understanding
of the effect of different synthesis parameters on membrane
performance. Although few attempts have been done to
systematically investigate the relation between these param-
eters and performance of the membrane [25,26], a clear
strategy should be presented in order to prepare membranes
withimprovedpermeationproperties andstability. Oyama and
Gu [25] worked on the effect of some parameters such as pep-
tizing agent on boehmite solutions, but they did not discuss
about some important factors like viscosity of sols, calcination
temperature and physical properties of the intermediate layer.
In this work, a nano-composite ceramic membrane has
been prepared by depositing a thin, hydrogen-selective layer
composed of silica (SiO
2
) and alumina (Al
2
O
3
) by co-current
CVD method on top of a graded mesoporous g-alumina
multilayer, which is supported by a macroporous a-alumina
tube. SEM and XRD analysis have been carried out to charac-
terize different layers of the membrane and effects of
synthesis conditions like changing the amount of peptizing
agent on membrane performance have been investigated
using DLS and viscometry analysis. Permeation tests were
performed at high temperatures in the range of 873e1073 K.
2. Materials and methods
2.1. Preparation of intermediate graded layer
The nano-composite membrane in this work was prepared by
depositing a very thin, dense layer composed of silica and
alumina on a macroporous alumina support which was
modied by a g-alumina graded multilayer. Fig. 1 shows the
schematic diagram of the consecutive steps that were carried
out to synthesize and characterize the membrane.
The intermediate multilayer was obtained from boehmite
(AlOOH) sols with different mean particle sizes. These sols
were prepared by carefully controlling the hydrolysis of
aluminum alkoxides and then peptization of the boehmite
precipitate with acid, as reported in literature [25]. The general
procedure is as follows: 0.1 mol of aluminum tri isopropilate
(Merck, >98%) was added to 150 ml of distilled water at 353 K
with high speed stirring and was maintained at this temper-
ature for 3e20 h to hydrolyze the alkoxide. This resulted in
formation of boehmite precipitate which was then heated to
363 K and was peptized with a quantity of nitric acid (Merck,
65%) with a molar ratio of H

/alkoxide in the range of 0.08e0.2.

The resulting solution was reuxed at 363 K for 18e20 h to get
a clear sol. A series of sols with median particle size in the
range of 50e700 nm were obtained depending on their
hydrolysis time and acid concentration.
In this study, PVA (polyvinyl alcohol, Biochemical,
M.W. 7200) was used as the binder. Proper solution was
prepared by adding 18 gr of PVAto 500 ml of water at 298 Kand
stirring for 30 min. The resulting solution is stable at ambient
temperature for at least one week. Viscosity of the sol
measured by a digital viscometer (Fungi lab, Alpha series) with
RPM of 30. A thin and uniform g-alumina multilayer was
prepared on a macroporous a-alumina support by dip-coating
Fig. 1 e Schematic of membrane preparation and
characterization steps.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 7 ( 2 0 1 2 ) 1 5 3 5 9 e1 5 3 6 6 15360
with a series of dilute boehmite solutions of different particle
sizes. Table 1 shows the synthesis parameters of three
boehmite sols with ascending median particle sizes used for
dip-coating process and denoted as A1, A2 and A3, respec-
tively. A commercial alumina membrane tube (GMITM
Corporation, i.d. 9 mm, o.d. 13 mm) with a nominal pore
sizeof 500nmwas usedas the support. Firstly, the tubewas cut
to a length of 5e6 cm, soaked in an ultra-sonic bath (BANDE-
LIN, Sonorex digital 10P) with 10% power for 15 min and dried
at ambient conditions for 24 h in order to clean the surface
pollution of the support. Each boehmite sol was diluted before
coating, by mixing with PVA solution in a 3 to 2 ratio to get
solutions with 1 Wt. % concentration of PVA. The resulting
solution was then stirred at 363 K for 3 h and the support was
dipped into this solution and was withdrawn after 10 s. The
coated support was then dried in ambient conditions for 24 h,
heated to 973 K in an electric furnace at a rate of 1 K min
1
and
was calcinedat this temperature for 2.5 h. This coating process
was carried out ve times by different solutions in the order of
decreasing sol particle size (A1, A1, A2, A3 and A3) to obtain
a graded structure intermediate layer.
2.2. Preparation of nano-composite dense layer
A composite silicaealumina membrane was synthesized
using the graded structure substrate to deposit a very thin
layer composed of SiO
2
and Al
2
O
3
by chemical vapor deposi-
tion (CVD) method. This process led to coat a composite layer
on the surface of the substrate by thermal decomposition of
tetraethyl orthosilicate (TEOS, Merck, >98%) and aluminum-
tri-sec-butoxide (ATSB, Merck, >98%) at high temperature.
The experimental setup is shown in Fig. 2. The CVD process
took place in a quartz tube in where silica and alumina were
deposited into the inner side of the support. Firstly, the
apparatus was heated to 873 K at a rate of 1 K min
1
in an inert
atmosphere, using two streams of argon on both sides of the
membrane module. After reaching to the desired tempera-
ture, valves were opened and two streams of argon as carrier
gas were passed through two bubblers lled with TEOS and
ATSB at 300 K and 393 K, respectively. These streams were
then mixed with argon dilution ow and were fed to the inner
side of the substrate. All streams were controlled carefully
using mass ow controllers. In general, the argon stream
passed through TEOS bubbler was xed at 13 ml min
1
and
CVD process was carried out on several substrates with
various amounts of ATSB carrier gas to produce a series of
selective composite membranes with different permeation
properties. The composition of the CVD layer was measured
using EDX (Philips, XL-30) analyzer with a 17 eV beam. The
results of the analysis are presented in Table 2.
XRD (Philips-XL10) analysis was used to recognize the
alumina phase of the intermediate layer and to determine the
proper calcination temperature of the membrane. Also, SEM
(Philips-XL30) analysis was used to investigate the
morphology of the synthesized nano-composite membrane.
Pore size of the formed layer was measured by mercury
porosimetery (Carlo Erba, 2000).
Permeation tests were carried out to investigate the effect
of preparation of dense top selective layer with a composite
structure. Gas permeation experiments were performed at
923e1073 K, using argon as the sweep gas on the inner side of
the membrane at atmospheric pressure and 50e200 ml min
1
ow rate. Single ows of H
2
and N
2
gases were passed indi-
vidually through the outer side of the membrane at about
160 kPa (Dp 60 kPa) and the ow rates of argon and perme-
ated gas through the membrane were measured using bubble
ow meter. The concentrations of gases were determined by
a gas chromatograph (GC, Agilent, 7890A) analyzer and
selectivity was dened as the H
2
/N
2
permeation ux.
3. Results and discussion
3.1. Effect of binder on sol viscosity
Using a sol with appropriate viscosity is important to prepare
the desired graded intermediate layer on the support. It has
been found that increasing viscosity of the sol results in
Table 1 e Synthesis parameters of boehmite sols used to
prepare the intermediate layer.
Sol no. Hydrolysis
time (h)
Molar ratio
of H

/alkoxide
Mean particle
size (nm)
A1 20 0.08 527
A2 10 0.2 148
A3 3 0.2 52
Fig. 2 e Schematic of CVD apparatus used for deposition of
the composite layer.
Table 2 e EDX analysis results from the surface of the
composite layer.
CVD time (h) ATSB/TEOS molar ratio Si Wt.%
6 0.04 8.24
6 0.06 8.03
6 0.1 7.72
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 7 ( 2 0 1 2 ) 1 5 3 5 9 e1 5 3 6 6 15361
thicker layers, which leads to lower adhesion of the coating
and higher formation of cracks [27]. Also, use of binder has an
important effect on coating sol as it can decrease the brittle-
ness of the membrane and improves the mechanical strength;
prevent crack formation; increase adhesionof the coated layer
on the support; and change the sol viscosity [28,29].
As mentioned earlier, PVA was used as the binder in our
work. Fig. 3(a) and (b) show the light microscope (Bel
Photonics) images of the graded multilayer with 1 Wt. %
concentration of PVA which dried at ambient temperature for
24 h and then calcined at 973 K for 2 h. These images present
a smooth and homogeneous surface and show no formation
of cracks. Based on the present study, addition of PVA greater
than 1 Wt. % in sols increased the sol viscosity and led to
production of thicker and non-uniform membrane layers
which tended to crack formation during drying process.
Furthermore, high viscosity resulted in formation of aggre-
gates, thus leading to separable particles on the surface of the
support. Besides, the amount of PVA in sols had great inu-
ence on the membrane characteristic, especially pore size of
the membrane. Table 3 shows the effect of PVA on viscosity of
the sol and pore size of the membrane after calcined at 973 K.
Boehmite sol A1 was used for this experiment As shown in
Table 3, by increasing the amount of PVA, pore size of the
membrane was increased. Higher amount of PVA promoted
agglomeration of the boehmite particles, which after calci-
nation resulted in wider pore size [30]. The agglomeration
causes inhomogeneous growth of particles and void forma-
tion [31]. The viscosity of the sol was increased as the amount
of PVA in solution was changed from 0.8 Wt. % to 2 Wt. %,
which is in agreement with formation of aggregates in sol.
3.2. Effect of synthesis parameters on boehmite sol
properties
It has been shown that the formation of a thin, defect-free top
selective layer depends on preparation of a substrate with
uniform structure and with pore sizes smaller than 5 nm [32].
To obtain such substrate, it is important to prepare thin and
smooth intermediate layers with small and uniformpore sizes
by the use of dilute dipping solutions containing sol particles
with appropriate size. If the sol particles are too small
compared with mean pore size of the a-alumina support, they
penetrate into the pores, which gradually cause formation of
cracks on the surface of the support [33]. The use of sols with
large particle size can overcome the problem of penetration,
but if sol particles are too large, they can give rise to de-
ciencies. These large particles have large interstitial spaces,
and will not cover the surface uniformly leaving patches of
untreated surfaces [25]. A good solution is to use large particle
size and then successive deposition of particles of smaller size
on top. This strategy results in formation of a graded structure
multilayer with better lling of voids to obtain a smooth and
defect-free surface.
The preparation of boehmite sols fromalkoxide precursors
consists of several steps: rstly, the precursors are hydro-
lyzed, the alkoxides are removed and aluminum oxy
hydroxide precipitates are formed. Oyama and Gu. [25]
showed that the following reactions may occur during this
step:
Al(OR)
3
H
2
O /Al(OR)
2
(OH) R(OH), etc. (1)
2Al(OR)
2
(OH) H
2
O /2Al(OR)(OH) 2R(OH), etc. (2)
The second step is called peptization where precipitates
formed by hydrolysis are heated in acid in order to break up
the large precipitates and formsmaller particles. The acid also
causes particles to repel each other and allowthe formation of
stable suspensions by charging the surface of particles [25].
Preparation of a stable boehmite sols depends on many
synthesis parameters like hydrolysis time, acid type and acid
concentration [25]. Aluminum alkoxides must be heated
quickly above 353 K to prevent formation of bayerite (b-Al
(OH)
3
) which causes instability of the sols [34]. Also, acid type
has an inuence on the particle size of the sols. Acids that are
used for peptization step should have two important traits:
their anion should be noncomplexing with aluminum and
they should have sufcient strength to produce the required
charge effect at low concentrations [35].
In this study the effect of acid type on particle size of
boehmite sols was studied. Acetic acid (CH
3
COOH), nitric acid
(HNO
3
) and hydrochloric acid (HCl) were used with an H

/
alkoxide molar ratio of 0.08 and resulted boehmite sols were
analyzed using DLS (Dynamic Light Scattering, MALVERN,
nano-ZS) analysis. The analyzer was calibrated by a standard
latex solution with mean particle size of 65 nm and a value of
1.65 was used as the refractive index for boehmite sols. Fig. 4
shows the particle size distribution of these sols. It was found
that inorganic acids like nitric acid and hydrochloric acid give
smaller mean particle size (527 nm and 310 nm, respectively)
Fig. 3 e Light microscope images of the graded multilayer (3800): (a) dried at ambient temperature; (b) calcined at 973 K.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 7 ( 2 0 1 2 ) 1 5 3 5 9 e1 5 3 6 6 15362
compared to acetic acid (712 nm). Since the mean pore size of
the a-alumina support was 500 nm, HNO
3
seemed to be proper
and was used as the peptizing agent.
Nitric acid with various H

/alkoxide ratios in the range of

0.08e0.2 was used to investigate the effect of acid concentra-
tion on particle size of boehmite sols, and as shown in Fig. 5,
the amount of acid had considerable effect on the mean
particle size of the sols. As H

/alkoxide molar ratio increased

from 0.08 to 0.2, mean particle size of the resulting boehmite
sol decreased from about 1000 nm to less than 300 nm. This
result could be related to the fact that nitric acid causes
fracture of large agglomerates and results in formation of
smaller particles in sol.
3.3. Effect of calcination temperature on the membrane
phase structure
Calcination temperature of the intermediate layer has
a dominant effect on the microstructure of the membrane. If
the calcination temperature is low, boehmite (AlOOH) would
still exist in the membrane crystal structure, which is less
stable than gamma alumina (g-Al
2
O
3
). On the other hand,
calcination temperature should not be very high because the
tubular support used as the substrate cannot endure
temperatures higher than 1123 K and deformation occurs in
macroporous structure of the support. So, it is important to
nd an optimum temperature for calcination process. Fig. 6
shows three XRD patterns of the membrane calcined at
various temperatures. First pattern is obtained from analysis
of the support which shows only a-alumina peaks. The second
pattern presents a support which is coated with sols and
calcined at 923 K. This pattern indicates the existence of
boehmite in membrane structure and also a-alumina peaks
related to the support. Calcination process was carried out at
various ascending temperatures and as shown in third
pattern, at 973 K there is no boehmite remained in membrane
structure and all boehmite is changed into g-alumina phase.
Therefore, this temperature is chosen as an appropriate
temperature for calcination of intermediate layer.
3.4. Morphology of the membrane
Cross-sectional and surface images obtained from interme-
diate and top selective composite layers by SEM are shown in
Fig. 7. Fig. 7 (a) and (b) shows a porous g-alumina multilayer
with graded structure which is coated on the surface of
a macroporous a-alumina support. The support has a mean
pore size of around 500 nm which is in agreement with the
nominal value reported by the supplier. The thickness of the
intermediate multilayer is observed to be around 2 mm and
meanpore size to be less than 10 nm. As shownin Fig. 7 (c) and
(d), top selective composite layer deposited on top of inter-
mediate multilayer has a uniform, dense structure with
a thickness around 80e100 nm. These images indicate that gas
permeation follows different mechanisms through various
layers of the membrane because of a fundamental difference
Fig. 4 e Particle size distribution of boehmite sols peptized
with three different acids at a constant H
D
/alkoxide molar
ratio of 0.08.
Fig. 5 e Particle size distribution of boehmite sols peptized
with various molar ratios of nitric acid(R).
Fig. 6 e XRD patterns of a multilayer membrane calcined at
two different temperatures.
Table 3 e Effect of PVA on viscosity of boehmite sol A1
and pore size of the coated layer.
Amount of PVA in
sol (Wt. %)
Viscosity (cP) Pore size (nm)
0.8 1.97 14.10
0.9 2.19 15.47
1.0 2.35 16.21
1.4 3.14 27.15
1.7 4.05 36.39
2.0 4.95 44.11
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 7 ( 2 0 1 2 ) 1 5 3 5 9 e1 5 3 6 6 15363
in structure between the composite dense layer and the
porous substrate.
3.5. Permeation properties of nano-composite membrane
In this part, performance of the prepared membrane with and
without the top selective composite layer was studied and the
results are shown in Fig. 8. The composite membrane used for
permeation tests was synthesized by 6 h deposition of silica
and alumina with constant ATSB/TEOS molar ratio of 0.1. The
high-temperature gas permeation results show that perme-
ation values of 5.0 10
5
mol m
2
s
1
Pa
1
for H
2
and
9.0 10
6
mol m
2
s
1
Pa
1
for N
2
were obtained at 1073 K,
using a support coated with a gamma alumina graded multi-
layer (Fig. 8(a)). These values indicate an H
2
/N
2
selectivity of
about 5.6, which is not high enough and should be improved.
The overall transport properties of this substrate were
controlled mainly by the transport properties of intermediate
layer [32]. This is due to the larger diffusion resistance
imposed by small pores of the g-alumina multilayer compared
to those of larger pores of the a-alumina support. Knudsen
diffusion is the dominant transport mechanism in this
multilayer substrate, because this mechanism mostly takes
place through porous materials when the mean pore size is
much smaller than the mean free path of gas molecules [36].
The results conrm that permeation is proportional to the
inverse square root of the temperature which is well in
agreement with Knudsen diffusion relations.
After deposition of silica and alumina composite layer by
CVD method, H
2
selectivity increased considerably, although
there was a large decrease in permeation uxes. Fig. 8(b)
shows gas permeance of H
2
and N
2
at a temperature range of
923e1073 K. Permeation values of 9.0 10
7
mol m
2
s
1
Pa
1
and 1.3 10
8
mol m
2
s
1
Pa
1
were obtained at 1073 K after
6 h of deposition for H
2
and N
2
, respectively. These values
resulted ina H
2
/N
2
selectivity of 203, whichwas about 36 times
more than that obtained before CVD and is quite acceptable
compared to the works reported in the literature [10]. The
Fig. 7 e SEM images of the nano-composite membrane: (a) cross-sectional image of the graded intermediate multilayer,
(b) surface image of the porous multilayer, (c) cross-sectional image of the nal composite membrane, (d) surface image of
the top selective silicaealumina dense layer.
Fig. 8 e Gas permeation of membrane at different
temperatures: (a) permeation in graded multilayer without
dense layer; (b) permeation in nano-composite membrane.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 7 ( 2 0 1 2 ) 1 5 3 5 9 e1 5 3 6 6 15364
increase of permeance by temperature indicates an activated
diffusion transport mechanism through dense layer. This can
be explained by a theory based on a mechanism based on
jumps betweensolubility sites [25]. Briey, the permeating gas
molecules move in solubility sites and jump randomly from
site to site. These sites in composite membrane have a size of
around 0.3 nm [25], which is larger than kinetic diameter of
most gases and can explain high H
2
selectivity over N
2
in
dense layer.
4. Conclusions
Anano-composite ceramic membrane witha graded structure
was successfully synthesized to purify hydrogen at high
operating temperatures. This membrane was prepared by
depositing a dual element thin layer composed of SiO
2
and
Al
2
O
3
on top of a graded substrate by co-current CVD method.
The graded substrate was synthesized by dip-coating the
macroporous a-alumina support with three different size
controlled boehmite sols using solegel method. Boehmite sols
of different particle size in the range of 50e700 nm were ob-
tained by carefully hydrolysis of aluminum tri isopropilate
followed by peptization with nitric acid. It was found that the
hydrolysis time and acid concentration would affect sol
particle size, so that longer hydrolysis time and lower acid
concentration gave larger particle size which was supposed to
be related to the formation of larger agglomerates in sols. SEM
images obtained from cross section of the membrane indi-
cated formation of a multilayer structure with an interme-
diate thickness of about 2.5 mm and a top selective layer of
80e100 nm. Permeation tests showed a reduction in gas per-
meance values after 6 h of CVD, but H
2
/N
2
selectivity increased
from 5.6 to a high value of 203. This happens because gas
permeation mechanism changes from Knudsen diffusion in
intermediate layer to an activated mechanism of hopping
between solubility sites in dense top layer.
Acknowledgment
The authors would like to thank SUNA (Renewable Energy
Organization of Iran) as the nancial supporter of this study.
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