Chapter 4.
Hydrogen-Production Technologies Using
Amorphous Silica Membranes
Kazuki Akamatsu and Shin-ichi Nakao
Department of Environmental and Energy Chemistry, Faculty of Engineering, Kogakuin University, 2665-1 Nakano-machi, Hachioji,
Tokyo 192-0015, Japan.
Chapter Outline
1. Introduction
2. Pore-Size Control of Silica Membranes Prepared by
Chemical Vapor Deposition
3. Membrane Performance Under Hydrothermal
Conditions
4. Prediction of the Performance of Membrane Reactors
1. INTRODUCTION
The establishment of a hydrogen-based energy system for
efficiently producing and transporting high-purity
hydrogen is eagerly awaited. For example, hydrogen
production using natural energy or renewable energy has
attracted much attention, and, at the same time, organic
hydrides have become candidates for hydrogen carriers to
transport the produced hydrogen to the usage points [1e3].
In this system, it is necessary to develop a technology for
producing high-purity hydrogen from the organic hydrides.
In addition, hydrogen production by the decomposition of
hydrogen sulfide is also a promising technology in petro-
leum refineries, which has been proposed but is still not in
operation even after nearly 30 years [4,5]. Furthermore,
there remains room for technological improvements to
decrease the reaction temperature in the conventional
industrial hydrogen production system by steam reforming
of hydrocarbons [6,7]. In general, these reactions are
endothermic equilibrium reactions; so, the conversions are
limited by the thermodynamics. Therefore, these reactions
have to be conducted at higher temperatures to obtain
higher conversions. In addition, the produced hydrogen has
to be separated and purified from other gases for any
applications; thus, some separation and purification
processes as post-treatment have to be performed. As one
Handbook of Advanced Ceramics. http://dx.doi.org/10.1016/B978-0-12-385469-8.00018-6
Copyright Ó 2013 Elsevier Inc. All rights reserved.
331 5. Dehydrogenating Organic Hydrides 335
6. Decomposing Hydrogen Sulfide 337
332 7. Methane Steam Reforming 339
8. Summary 340
334 References 340
335
of the key technologies to solve these problems and to
achieve the establishment of a hydrogen-based energy
system, high-purity hydrogen production using membrane
reactors has gained much attention currently.
High-purity hydrogen-production technologies in
membrane reactors or catalytic membranes with hydrogen-
selective silica membranes have been studied for around
20 years. Figure 1 shows a conceptual illustration of
a membrane reactor. A membrane reactor is a system that
integrates “reaction” with catalysts and “separation” with
membranes. As reaction and separation occur simulta-
neously in a membrane reactor, an endothermic equilib-
rium reaction can be shifted forward beyond the
thermodynamic equilibrium by extracting one of the
generated components, hydrogen in this case, from
the reaction system using a membrane. This enables us to
achieve higher conversion at lower reaction temperature
than the conventional reactor temperature. In addition, it
also makes the hydrogen-production system compact
because it is not necessary to build additional separation
and purification processes for post-treatment. It is not an
exaggeration to say that the catalysts for producing
hydrogen and the membranes for extracting the produced
hydrogen determine the performance of the membrane
reactor.
331
332
FIGURE 1 A conceptual illustration of a membrane reactor for
producing high-purity hydrogen.
Three types of hydrogen-selective membranes are well
known: polymeric membranes based on polyimide [8e10],
metallic membranes such as palladium or its alloys
[11e13], and ceramic membranes such as amorphous
silica [14,15]. However, the polymeric membranes cannot
be used at high temperature where hydrogen-production
reactions are conducted. For example, hydrogen produc-
tion using such membrane reactors by dehydrogenating
organic chemical hydrides is supposed to be conducted at
500e600 K, and that by decomposing hydrogen sulfide or
steam reforming is at around 800e1000 K. Palladium or its
alloyed membranes have been extensively studied and
their hydrogen-selective performances are excellent
because of their unique hydrogen separation mechanism.
However, palladium is expensive, and it is apparent that its
total reserves are insufficient for such use. On the other
hand, ceramic membranes can be used even under such
high-temperature conditions and have a cost advantage.
Among ceramic membranes, hydrogen-selective amor-
phous silica membranes have been studied for around
20 years. The silica membranes generally consist of porous
supports such as alumina on which amorphous silica as
separation layers is deposited. The preparation methods for
such silica layers are classified into two types: one is the
solegel method [16,17] and the other is the chemical vapor
deposition (CVD) method [18,19]. In the solegel method,
colloidal silica sol prepared by hydrolysis and condensa-
tion is coated onto the porous support, and silica
membranes are obtained after firing. In contrast, in the
CVD method, reaction between the silica precursor in
saturated vapor and oxygen or ozone takes place and the
silica is deposited into the pores of the substrate and onto
the porous substrate [20].
The performance of hydrogen-selective silica
membranes is evaluated in terms of the hydrogen per-
meance and the separation factors of hydrogen relative to
other gases that are to be separated. In both cases, larger
values are preferable. For the past 20 years, much effort
has been devoted to the development of hydrogen-
selective amorphous silica membranes and there are some
reports on excellent performances that matched palladium
or its alloyed membranes [21,22]. Unlike metallic
membranes, such as palladium, the separation mechanism
of the silica membranes is assumed to be a “molecular-
sieve,” which means that only the gas species with smaller
Handbook of Advanced Ceramics
size than the pore size of the membranes can permeate
through the membranes and that the other gas species
cannot. In the case of hydrogen-selective silica
membranes, amorphous silica networks are assumed to be
“pores” that small gas species such as hydrogen can
permeate through. At the same time, there exist a few
voids, where larger gas species such as nitrogen can
permeate through. On reviewing the articles on amorphous
silica membranes by many researchers, there are many
reports on successful separation of hydrogen from
nitrogen, which means that the pore size of the membrane
is distributed mainly around 0.3 nm.
When applied to membrane reactors for hydrogen
production, a larger hydrogen permeance contributes to
a larger equilibrium shift and a larger hydrogen separation
factor contributes to higher purity of the obtained hydrogen
in the permeate side, in general. Here, it should be noted
that the desirable pore size differs depending on the reac-
tion system. In other words, we should take into account the
sizes of the gas species that have to be separated from
hydrogen. To achieve a larger separation factor, the pore
size should be larger than hydrogen and at the same time
smaller than the gases that should be separated from
hydrogen. Furthermore, to achieve a larger hydrogen per-
meance, the pore size should be larger. Therefore,
a membrane whose pore size is just a little smaller than the
sizes of the gas species that should be separated from
hydrogen is preferable.
In this review, the strategy for developing silica
membranes appropriate for each hydrogen-production
system is discussed first, mainly from the viewpoint of
“pore-size control.” Then, examples of development of
membrane reactors with pore-size-controlled silica
membranes are presented: dehydrogenating organic
hydrides, decomposing hydrogen sulfide, and methane
steam reforming.
2. PORE-SIZE CONTROL OF SILICA
MEMBRANES PREPARED BY CHEMICAL
VAPOR DEPOSITION
As mentioned above, strict pore-size control is required for
each reaction system. For example, when applying the
dehydrogenation reaction of organic hydrides, the
produced hydrogen (kinetic diameter 0.289 nm) should be
separated from cyclohexane (kinetic diameter 0.60 nm) and
benzene (kinetic diameter 0.59 nm), or methylcyclohexane
(kinetic diameter 0.60 nm) and toluene (kinetic diameter
0.59 nm). Therefore, the pore size should be designed at
around 0.5e0.55 nm. On the other hand, when applying to
methane steam reforming, the produced hydrogen should
be separated from CO2 (kinetic diameter 0.33 nm), CO
(kinetic diameter 0.376 nm), or unreacted methane (kinetic
Chapter | 4.1 Hydrogen-Production Technologies Using Amorphous Silica Membranes
FIGURE 2 Single-component permeances through TMOS-, PTMS-, and
DMDPS-derived membranes at 573 K. (from [26]).
diameter 0.38 nm), which means that the pore size should
be designed at around 0.3 nm. However, there are few
successful reports on pore-size control of silica membranes
prepared by the CVD method because of the difficulty of
characterization in the subnanometer scale.
Among these, Sea et al. first reported successful pore-
size control using phenyl-substituted ethoxysilanes as
precursors [23e25]. They prepared silica membranes with
tetraethoxysilane, phenyltriethoxysilane, or diphenyldie-
thoxysilane. They showed that larger pores were con-
structed by using the phenyl-substituted ethoxysilanes as
precursors. In this way, the methodology of pore-size
control by changing the functional groups of the precursor
is considered reasonable, but the analysis of the reaction or
FIGURE 3 Arrhenius plots of single-component permeances through (a) TMOS-derived membrane, (b) PTMS-derived membrane, and (c) DMDPS-
derived membrane at 373e573 K. B, H2; ,, O2; >, N2; P, CF4; O, SF6. (from [26]).
333
the mechanism of micropore formation has hardly been
discussed.
Ohta et al. employed phenyl-substituted methoxysilanes
to prepare amorphous silica membranes by the CVD
method. Tetramethoxysilane (TMOS), phenyltrimethoxy-
silane (PTMS), and dimethoxydiphenylsilane (DMDPS)
were used as precursors [26]. The precursors contain zero,
one, and two phenyl groups in one molecule, respectively. In
the study, it was expected that the existence of the phenyl
groups would result in a looser silica network, and larger
pores would be built. After optimization of membrane
preparation conditions for each precursor, the permeation
characteristics through their membranes were compared.
Figure 2 shows the permeation results at 573 K of H2, O2, N2,
CF4, and SF6 through the TMOS-, PTMS-, and DMDPS-
derived membranes prepared at 873 K. In every gas species,
the permeance was highest through the DMDPS-derived
membrane, followed by the PTMS-derived membrane, and
then the TMOS-derived membrane. This order coincided
with the number of phenyl groups in the precursor. In
addition, it is noteworthy that hydrogen permeance through
the DMDPS-derived membrane was as high as 1
106 mol
m2 s1 Pa1 and this value matches that through palladium
or its alloyed membranes. Figure 3(a)e(c) show the
temperature dependence of permeation for H2, O2, N2, CF4,
and SF6 through the TMOS-, PTMS-, or DMDPS-derived
membranes. As for hydrogen permeation, the activation
energy through the TMOS-derived membrane was 19 kJ
mol1, while it decreased to 11 kJ mol1 in the case of the
PTMS-derived membrane and finally it became 0.8 kJ
mol1 in the case of the DMDPS-derived membrane. These
results also indicate that the pore size of the silica membrane
increased as the number of phenyl groups in the precursor
molecule increased.
To deposit an amorphous silica layer, the silica precursors
are assumed to form silanones, and then they have to undergo
oligomerization reactions. Quantum chemical calculations
334
were conducted to investigate whether steric hindrance
because of the bulky group would occur when using
precursors such as PTMS or DMDPS containing the phenyl
group. If this is the case, it is clear that pore-size control can
be achieved by changing the chemical structure of the
precursors. In this study, bond energies of the silica sources
were estimated by quantum chemical calculations with the
CBS-QB3 method available in Gaussian 03. The results
showed a strong tendency for gas-phase conversion of TMOS
and PTMS to dimethoxysilanone, (MeO)2Si]O, and
DMDPS to methoxyphenylsilanone, Ph(MeO)Si]O, tran-
sient intermediates that are assumed to be major precursors
of amorphous silica. This result was, of course, just based on
the bonding energy, not based on the kinetic viewpoint.
Therefore, it can be speculated that the PTMS-derived
membrane was produced from the intermediates of dime-
thoxysilanone including a small amount of methox-
yphenylsilanone, and that the DMDPS-derived membrane
was mainly from methoxyphenylsilanone. This can explain
the result that the PTMS-derived membrane has somewhat
larger micropores than the TMOS-derived membrane and the
DMDPS-derived membrane has much larger micropores
than the TMOS membrane. Indeed, the ratio of methox-
yphenylsilanone to dimethoxysilanone is not clearly under-
stood; however, the phenyl group of the precursors probably
resulted in enlargement of pore sizes in the silica membranes.
3. MEMBRANE PERFORMANCE UNDER
HYDROTHERMAL CONDITIONS
If we wish to apply appropriate silica membranes to
a membrane reactor for hydrogen production, especially for
the steam-reforming reaction, a severe problem remains
unsolved. Silica membranes are not hydrothermally stable.
Exposure to moisture leads to deterioration of the
membrane performance, in general. It is often pointed out
that this is because of the “densification” of the silica.
Essentially, the structure of the silica membrane would
change by rearrangement of siloxane bonds or dehydration
of silanol groups into siloxane groups under hydrothermal
conditions. However, this is just an assumption at this stage
and more detailed studies are necessary.
To avoid this deterioration under hydrothermal condi-
tions, several types of metal-doped silica membranes have
been investigated. Among them, nickel-doped silica
membranes prepared by the solegel method were shown to
maintain both high hydrogen permeance and high hydrogen
selectivity after exposure to steam at 873 K [27].
Besides this, the silica membranes prepared by CVD
using TMOS and oxygen at higher temperature were
shown to keep both high hydrogen permeance and high
hydrogen selectivity under humid conditions. For
example, TMOS-derived membranes prepared at 773 K
Handbook of Advanced Ceramics
are damaged simply by exposure to air at room tempera-
ture. In contrast, membranes prepared at 873 K are stable
even under 76 kPa of steam vapor at 773 K for 82 h, as
shown in Figure 4 [28]. This is one of the target conditions
for applying to membrane reactors for methane steam
reforming. Actually, the TMOS-derived membranes were
tested at higher temperatures than the preparation
temperature, such as 973 K, or 1073 K [29]. The perme-
ation tests revealed that hydrogen permeance decreased
slightly at such higher temperatures above the fabrication
temperature under dry conditions; however, once the
membrane was subjected to higher temperatures, hydrogen
permeance did not change even when it was exposed to
high temperature again. On the other hand, in humid
conditions, a slight deterioration of hydrogen permeance
was observed at such higher temperatures. Recently,
hexamethyldisiloxane (HMDS) was employed as a silica
precursor and its performance under hydrothermal condi-
tions was investigated [30]. The membrane exhibited the
same degree of H2/N2 selectivity under hydrothermal
conditions as the TMOS-derived membrane, and addi-
tionally it showed much higher permeance for hydrogen
than the TMOS-derived membrane.
In view of these results, the HMDS-derived membranes
and the TMOS-derived membranes for use in membrane
reactors to deal with reaction systems containing H2O have
to be prepared at a higher temperature than the application
temperature. However, the reason why these membranes
prepared at higher temperature are stable under hydro-
thermal conditions is not clear at this stage, even though the
microporous structure of the membranes is assumed to be
exerting some influence.
FIGURE 4 Steam post-treatment for the silica membrane prepared at
873 K. (from [28]).
Chapter | 4.1 Hydrogen-Production Technologies Using Amorphous Silica Membranes 335

4. PREDICTION OF THE PERFORMANCE

OF MEMBRANE REACTORS
Prediction of the performance of a membrane reactor is
one of the most important points. To do this, the simplest
1-D model is constructed just by considering perme-
ations through the membrane and reactions. In other
words, mass balance is just applied to reaction and
permeation. However, hydrogen-production reactions are
endothermic, in general. Therefore, the method of heat
supply for the enthalpy of the reactions is very important
for the development of membrane reactors. In addition,
these enthalpy changes are relatively large in most cases;
so, it is often pointed out that the large enthalpy changes
result in inhomogeneous temperature distribution profiles
in the reactors. Furthermore, these models cannot be
used to discuss 3-D complicated configurations of the
membrane reactors. There are some reports on the
prediction of the performance of membrane reactors
using computational fluid dynamics to consider heat
profiles in the membrane reactors, which is one of the
crucial factors for determining the reactivity [31]. Such
detailed analysis of the temperature profiles enables us to
design membrane reactors where heat supply can be
achieved effectively.

FIGURE 5 Relationship between the reaction temperature and cyclo-

5. DEHYDROGENATING ORGANIC
HYDRIDES
Organic hydrides are one of the promising candidates for
hydrogen carriers because of their high storage capacities
and easy handling. Representative examples of organic
hydrides are as follows:
C6 H12 % 3H2 þ C6 H6 ðCyclohexane  Benzene systemÞ;
C6 H11  CH3 % 3H2 þ C6 H5  CH3
ðMethylcyclohexane  Toluene systemÞ;
C10 H18 % 5H2 þ C10 H8 ðDecalin  Naphthalene systemÞ:
According to thermodynamics, these reactions should be
conducted at 473e573 K. For palladium or its alloyed
membrane, hydrogen brittleness emerges as a problem in
this temperature range. Therefore, a ceramic membrane is
preferred. From the viewpoint of equilibrium conversions,
the dehydrogenation of decalin occurs easily, followed by
methylcyclohexane, then cyclohexane. In addition,
hydrogen-storage efficiency is the highest in the case of
decalin, and meets the target of the US Department of Energy
hydrogen plan. However, in the decalinenaphthalene reac-
tion system, naphthalene is in the solid state at ordinary
temperatures and pressures, which is not desirable.
As mentioned in Section 2, the DMDPS-derived
membrane is favorable for membrane reactors to
hexane conversion for three reactors: a blind tube, a TMOS-derived
membrane, and a DMDPS-derived membrane. The pressure in the reactor
was 1 atm. (from [32]).
dehydrogenate cyclohexane or methylcyclohexane
because of its larger pore size. Figure 5 shows the rela-
tionships between the reaction temperature and the
conversion of cyclohexane at 0.1 MPa when a nonporous
tube, a TMOS-derived membrane, or a DMDPS-derived
membrane was used [32]. The reactor with a nonporous
tube would act as a packed-bed reactor because there is no
extraction of hydrogen. In using the nonporous tube, the
conversions agreed well with the equilibrium values at all
temperature conditions. On the other hand, in using the
TMOS-derived membrane, the conversions were above the
equilibrium values. When the DMDPS-derived membrane
was used, the conversions were much higher than those
when the TMOS-derived membrane was used. It should be
noted that this order coincides with the order of hydrogen
permeance. This means that larger hydrogen permeance
resulted in larger equilibrium shifts, and this can also be
explained by using the simple reactor model, as described
in Section 4. Figure 6 shows the relationships between the
reaction temperature and the conversion of methyl-
cyclohexane at 0.1 MPa when a nonporous tube or
a DMDPS-derived membrane was used [33]. In the case of
the methylcyclohexaneetoluene system, a similar
336
FIGURE 6 Relationships between reaction temperature and methyl-
cyclohexane conversion for the packed-bed reactor and the DMDPS-
derived membrane reactor. (from [33]).
tendency was observed. Figure 7 shows the relationships
between the reaction pressure and the conversion of
methylcyclohexane at 533 K when a nonporous tube or
a DMDPS-derived membrane was used. This dehydroge-
nation reaction generates 3 mol of H2 and 1 mol of toluene
from 1 mol of methylcyclohexane. Therefore, higher
pressure is unfavorable to achieve higher conversion from
the viewpoint of thermodynamics. On the other hand,
extraction of hydrogen in a membrane reactor, which
results in an equilibrium shift, is effective when there is
a larger partial pressure difference in hydrogen. Thus,
higher pressure is favorable to achieve higher conversion
from the viewpoint of the driving force of permeation in
membrane reactors. In the case of using a nonporous tube,
conversion of methylcyclohexane decreased as reaction
pressure increased. This is because there is no hydrogen
extraction in this case, and the dehydrogenation reaction in
this reactor was subject only to thermodynamics. When
using the DMDPS-derived membrane, the conversion of
methylcyclohexane exceeded the equilibrium value, and
the conversion was virtually constant at pressures ranging
from 0.1 to 0.25 MPa. Its value was as high as 0.99. This
means that the unfavorable effect of thermodynamics was
completely compensated by the larger hydrogen extraction
because of the higher pressure.
Handbook of Advanced Ceramics
FIGURE 7 Relationships between reaction pressure and methyl-
cyclohexane conversion for the packed-bed reactor and the DMDPS-
derived membrane reactor. (from [33]).
Actually, these experiments were conducted using carrier
gas and sweep gas to demonstrate the effectiveness of the
membrane reactor with hydrogen-selective silica membranes.
However, these operations with carrier gas and sweep gas are
not realistic for practical use because the hydrogen should be
produced with high purity. If the hydrogen is produced using
carrier gas and sweep gas, the produced hydrogen will
contain a lot of carrier gas and sweep gas and some post-
treatment to purify the hydrogen would be required.
Therefore, the neat organic hydride should be supplied in
a pressurized condition, and the membrane reactors should be
operated without carrier gas or sweep gas. This operation can
produce high-purity hydrogen at atmospheric pressure, and it
can be directly supplied to any application, for example, to
fuel cells. Figure 8 shows an example of such an operation.
The time course for cyclohexane conversion measured by gas
chromatography, reaction pressure, hydrogen purity,
production rate of H2, and permeance of H2 before and after
each day’s run is shown [34]. For the first day’s run, the
conversion and hydrogen purity were around 0.8 and 99.9%,
respectively, and these values were stable for 6 h. In addition,
this performance was also reproduced for the second, third,
seventh, and eleventh day’s runs. Mass-spectrometric
measurement of the gas on the permeate side, diluted with
nitrogen, showed that a small amount of benzene and
cyclohexane was obtained. The concentrations of benzene
and cyclohexane in the permeate gas were estimated to be
0.118% and 0.043%, respectively. Consequently, hydrogen
with high purity at 1 atm was stably obtained in the permeate
side during this test. Actually, it was reported that the
permeate gas produced by the membrane reactor was directly
Chapter | 4.1 Hydrogen-Production Technologies Using Amorphous Silica Membranes 337

FIGURE 8 Production of hydrogen from cyclohexane using the membrane reactor with DMDPS-derived membrane. Time course of conversion,
reaction pressure, hydrogen purity, hydrogen production rate, and hydrogen permeance through the DMDPS-derived membrane are shown. After each
day’s operation, the reactor was cooled to room temperature overnight and restarted again when the experiment was continued. Hydrogen permeance
through the DMDPS-derived membrane was measured before and after the hydrogen production test. (from [34]).

supplied to a commercial fuel cell, and stable electric power
generation with output greater than 4 V was successfully
observed. In Figure 9, results in the methylcyclohex-
aneetoluene system are also shown [33]. For the first day’s
run, the conversion and hydrogen purity were around 0.8 and
99.95%, respectively. The performance of the membrane
reactor was stable during the period of operation.
The application of membrane reactors with high-
performance hydrogen-selective amorphous silica
membranes to dehydrogenation of organic hydrides is one
of the successful examples of hydrogen production.
6. DECOMPOSING HYDROGEN SULFIDE
Hydrogen sulfide is produced as a by-product of purifi-
cation processes in petroleum refineries that remove
sulfur by using an enormous amount of hydrogen, or it
can be present in natural gas. For removing this, the
conventional industrial treatment method is the Claus
process. This process turns hydrogen sulfide into water
and sulfur, which results in the consumption of a large
amount of hydrogen. If hydrogen sulfide could be
decomposed to sulfur and hydrogen as shown below, this
hydrogen could be reused for the removal of more sulfur,
or used for other purposes:
nH2 S % nH2 þ Sn ðn ¼ 1  8Þ:
A membrane reactor to decompose hydrogen sulfide for
producing hydrogen can achieve the goal. In addition,
the equilibrium conversion for this decomposition
reaction is extremely low, and, for example, the
conversion cannot exceed 20% below 1200 K. This also
makes membrane reactors superior to conventional
reactors. Actually, the application of membrane reactors
with hydrogen-selective membranes has been proposed
for no less than 30 years; however, no membrane reactor
for decomposing hydrogen sulfide has ever been
developed successfully.
338 Handbook of Advanced Ceramics

FIGURE 9 Course of the production of hydrogen from methylcyclohexane in the membrane reactor with the DMDPS-derived membrane. Changes in
methylcyclohexane conversion, reaction pressure, hydrogen purity, production rate of hydrogen, and hydrogen permeance for the DMDPS-derived
membrane during the dehydrogenation of methylcyclohexane are shown. (from [33]).

The kinetic diameter of hydrogen sulfide is almost
the same as that of nitrogen. In addition, it was proved
that the membrane reactor should be operated above
873 K to obtain higher conversion. Therefore, the use of
TMOS-derived membranes for developing membrane
reactors is preferable because these membranes can
stably separate H2/N2 at such higher temperatures.
Figure 10 shows the relationship between the residence
time and conversion achieved by a membrane reactor
with a TMOS-derived membrane at 873 K [35]. The
equilibrium conversion at this reaction condition was
only 7.8%. On the other hand, the membrane reactor
exceeded equilibrium values at every residence time
from 1 s to 7 s. The achieved conversion increased with
the residence time, and it reached as high as 69% at
a residence time of 7 s in the experimental conditions.
This is of course because the TMOS-derived membrane
had both sufficient permselectivity for hydrogen/
hydrogen sulfide and a large permeance for hydrogen.
This effect of hydrogen-selective extraction resulted in
the shift of the equilibrium conversion. Figure 11 shows
the hydrogen permeance before and after the decom-
position reaction test. The hydrogen permeance changed
only slightly: at 873 K, it changed from 1.4
107 mol
m2 s1 Pa1 to 1.0
107 mol m2 s1 Pa1. This
shows that the excellent performance of the membrane
Chapter | 4.1 Hydrogen-Production Technologies Using Amorphous Silica Membranes
FIGURE 10 Conversion of hydrogen sulfide as a function of the resi-
dence time in our membrane reactor at 873 K. (from [35]).
reactor is based on the high tolerance of the TMOS-
derived membrane to sulfur-containing atmospheres and
to the high temperature. Indeed, at this stage, no long-
term durability test has been conducted yet. Therefore,
the durability of the hydrogen-selective membrane or
the membrane reactor under such a crude condition
should be studied in detail.
FIGURE 11 Arrhenius plots for hydrogen permeation through the
TMOS-derived membrane before and after the decomposition reaction test.
(from [35]).
339
7. METHANE STEAM REFORMING
Steam reforming of hydrocarbons is one of the best-
established methods for industrial hydrogen production.
Among them, the methane steam-reforming reaction has
been used conventionally in large-scale hydrogen
plants. This can be divided into the following two
reactions:
CH4 þ H2 O % 3H2 þ CO;
CO þ H2 O % H2 þ CO2 :
The steam-reforming reaction is generally performed at
around 1150 K because of the endothermic character of the
first reaction, so the reaction temperature should be
decreased to more moderate conditions. For this purpose,
membrane reactors with hydrogen-selective membranes
are promising. Another issue for applying silica membranes
to the membrane reactors for steam reforming is the char-
acteristics of steam durability of the membranes, as
described in Section 3. Therefore, a membrane with steam
stability is desirable.
Figure 12 shows the relationship between the reaction
pressures and the conversions of methane at 773 K when
a TMOS-derived membrane or an HMDS-derived
membrane was used [30]. Just as with the reaction for
dehydrogenating organic hydrides, a higher pressure is
not preferable from the viewpoint of thermodynamic
equilibrium. On the other hand, a membrane reactor
FIGURE 12 The relationship between the pressure in the reaction side
and the conversion of methane in the two membrane reactors with the
TMOS- and HMDS-derived silica membranes. The S/C ratio was 3, the
feed rate of methane was 5.0
106 mol s1, and the reaction temperature
was 773 K. (from [30]).
340
FIGURE 13 Continuous production of H2 in the membrane reactor with
the HMDS-derived silica membrane and Ni catalyst. The S/C ratio was 2.5,
the feed rate of methane was 1.0
106 mol s1, and the reaction
temperature was 773 K. (from [30]).
using the TMOS-derived membrane showed an equilib-
rium shift at every pressure condition because of
hydrogen extraction. Furthermore, in the case of
a membrane reactor using the HMDS-derived membrane,
the conversion was much higher than that in the case of
the TMOS-derived membrane. The order of the equilib-
rium shifts also coincided with the order of hydrogen
permeance.
To study the stability of the membrane reactor with the
HMDS-derived membrane, which showed a larger equi-
librium shift, continuous operation of the membrane
reactor was conducted to produce H2 for 30 h. The pressure
on the reaction side was just 0.1 MPa, and the S/C ratio was
only 2.5. The time course of the conversion of methane is
shown in Figure 13 [30]. A methane conversion as high as
0.8 was obtained, and this equilibrium shift was stable for
30 h. No sudden decrease in the performance of the
membrane reactor was observed. This result showed that
the HMDS-derived membrane stably extracted the H2 and,
at the same time, the catalyst also worked stably for this
period of time.
8. SUMMARY
In this review, efficient high-purity hydrogen-production
technology using membrane reactors was described as
one of the promising technologies using ceramic
membranes, in particular, using hydrogen-selective
amorphous silica membranes. The membrane reactors
Handbook of Advanced Ceramics
consisting of amorphous silica membranes for hydrogen
separation and catalysts for hydrogen production can
extract hydrogen as soon as produced, which results in
favorable equilibrium shifts when applied to equilibrium
reactions such as dehydrogenation of organic hydrides,
decomposition of hydrogen sulfide, or steam reforming of
hydrocarbons. In addition, this efficient system also
makes it possible to achieve higher conversions under
lower reaction temperature conditions, compared with
conventional reactors. To develop such membrane reac-
tors, a high-performance hydrogen-selective membrane
that can be used in the reaction atmospheres is one of the
key factors, and silica membranes can meet this condi-
tion. Today, fundamental reports on developing
membrane reactors with ceramic membranes are
increasing in number. However, the study of long-term
durability has been scarcely discussed. In addition, the
technology to develop larger-size reactors, especially for
large-area membranes, should also be developed for
practical use. Consistent approaches to these issues will
help “Hydrogen Production Technologies Using Ceramic
Membranes” edge closer to practical use.
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