WHEC 16 / 13-16 June 2006 Lyon France

Development of Membrane Technology for Highly-efficient Hydrogen Production

Isamu Yasuda a, Yoshinori Shirasaki b, Kazuto Kobayashi c, Hiroshi Nakajima d,
Toru Shimamori e, Tsuyoshi Sasaki f, Toshiki Kabutomori g, Misako Uchida h,
Hiroki Yoshizawa i, Motonori Nishida j and Yoichiro Shinpo k
a ,b

Tokyo Gas Co., Ltd. (1-16-25 Shibaura, Minato-ku, Tokyo, 105-0023 Japan,
a
iyasuda@tokyo-gas.co.jp, b whitey@tokyo-gas.co.jp)
c, d
Mitsubishi Heavy Industries, Ltd. (4-6-22 Kannon-Shinmachi, Nishi-ku, Hiroshima, 733-8553 Japan,
c
kazuto_kobayashi@mhi.co.jp, d hiroshi_nakajima@mhi.co.jp)
e
NGK Spark Plug Co., Ltd. (2808 Iwasaki, Komaki, 485-8510 Japan,
e
t-shimamori@mg.ngkntk.co.jp)
f, g
The Japan Steel Works, Ltd. (4 Chatsu-machi, Muroran, 051-8505 Japan,
f
tsuyoshi_sasaki@jsw.co.jp, g toshiki_kabutomori@jsw.co.jp)
h, i
Ishikawajima-Harima Heavy Industries Co., Ltd. (1 Shin-Nakaharacho, Isogo-ku,Yokohama
235-8501 Japan, h misako_uchida@ihi.co.jp, i hiroki_yoshizawa@ihi.co.jp)
j,
k Fukuda Metal Foil & Powder Co., Ltd. (20 Nakaomicho, Nishinoyama, Yamashina-ku, Kyoto,
607-8305 Japan, j mnishida@fukuda-kyoto.co.jp, k shinpo@fukuda-kyoto.co.jp)

ABSTRACT
A membrane reformer can perform steam reforming reaction and hydrogen separation processes
simultaneously, without shift converters and purification systems. The challenges to be pursued toward
commercialization of this technology are further improvement of the system efficiency and durability of the
membrane modules as well as significant cost reduction for manufacturing membrane modules. For this
purpose, a new 3-year project to develop membrane technologies for highly-efficient hydrogen production
has been launched under the NEDOs hydrogen program. For the system engineering, a 40 Nm3/h-class
membrane reformer with hydrogen production energy efficiency of 80% and the product hydrogen purity of
over 99.99% is going to be developed. For the membrane modules using palladium alloys, durability is going
to be improved to enable operation of the modules for 10,000 hours or more. A new type of module that has
palladium alloy film prepared on the surface of structured catalyst is going to be developed to reduce the
manufacturing cost and make a more compact reactor. For the membrane modules using non-palladium
alloys, three types of membrane materials will be developed to greatly reduce the module cost.
KEYWORDS : hydrogen production, membrane, steam reforming, separation

1. INTRODUCTION
One of the most promising pathways to produce hydrogen in the near- to mid-term future is on-site
hydrogen production from natural gas. It is critically important, however, to increase the energy efficiency in
production of hydrogen to make the option of FCV fueled by hydrogen from natural gas advantageous over
the other clean car and fuel options in view of overall energy efficiency and reduction of greenhouse gas
emissions on the well-to-wheel basis. An advanced concept of membrane reformer is expected to provide
the best solution to this issue.
A membrane reformer can perform steam reforming reaction and hydrogen separation processes
simultaneously, without shift converters and purification systems. In these few years, Tokyo Gas as a
member of The Japan Gas Association has successfully developed and operated a 40 Nm3/h-class
membrane reformer using pipeline natural gas as its feedstock and experimentally demonstrated its very
high efficiency of 76% and compact and simple system configuration 1). The challenges to be pursued in the
following development efforts were identified as further improvement of the system efficiency, durability of the
membrane modules and significant cost reduction for manufacturing membrane modules.
For this purpose, a new 3-year project to develop membrane technologies for highly-efficient hydrogen
production has been launched under the NEDOs hydrogen program. Efficient and powerful collaboration is
arranged among the competent companies and university laboratories who have key technologies and
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experiences in the fields of system engineering, membrane materials science, membrane and module
manufacturing, performance and mechanical reliability evaluation of membrane and modules, and process
analyses. For the system engineering, a 40 Nm3/h-class membrane reformer with hydrogen production
energy efficiency of 80% and the product hydrogen purity of 99.99% is going to be developed. For the
membrane modules using palladium alloys, durability is going to be improved to enable operation of the
modules for 10,000 hours or more. A new type of module that has palladium alloy film prepared on the
surface of structured catalyst is going to be developed to reduce the manufacturing cost and make a more
compact reactor. For the membrane modules using non-palladium alloys, three types of membrane materials
will be developed to greatly reduce the module cost. This paper presents the plans and the latest
achievements of these parallel developments.
2. PRINCIPLE AND FEATURES OF MEMBRANE REFORMER
The membrane reformer is a steam reformer equipped with hydrogen permeable membrane modules.
Most typically palladium alloys or other metallic alloys or ceramic materials in other cases, which allow only
hydrogen to pass through, are fabricated into membranes and used in the reformer for direct production of
high-purity hydrogen from natural gas with no help of shift converters and purification systems, as shown in
Figure 1. With the new concept of simultaneous generation and separation of hydrogen, the reactions can be
free from the limitation of chemical equilibrium, which gives higher reaction rates at lower reaction
temperatures. The typical operation temperature of 700 to 800C of the conventional reformers without insitu hydrogen separation can be reduced to 500 to 550C in the membrane reformer. Thus the membrane
reformer can be made compact and simple and requires less installation space than the conventional ones. It
offers great advantage of much higher efficiency in producing hydrogen than the conventional technologies.
Membrane module
(ex. Pd-based alloy)
Catalyst

Heat

Natural gas
with steam

Hydrogen

Figure 1. Principle of membrane reformer.

3. PRECEEDING R&D UNDER JAPANESE NATIONAL PROJECTS

Under a NEDOs project in FY 2000 to 2004, Tokyo Gas as a member of The Japan Gas Association has
successfully developed and operated a 40 Nm3/h-class membrane reformer system (Figure 2) using pipeline
natural gas as its feedstock and experimentally demonstrated its very high efficiency of 76% and compact
and simple system configuration 1). However, the total operation time of the system was limited to about
3,300 hours due to the insufficient durability of the membrane modules 2, 3). Mitsubishi Heavy Industries
under another NEDOs project worked with the concept of mobile hydrogen generator using a membrane
reformer and developed elemental technology for operating the membrane reformer with LPG feedstock. A
hydrogen separation module was continuously operated in connection with a pre-reformer and stable
hydrogen production was confirmed for about 3,000 hours 4). In parallel with the system engineering
technology developments, Japan Steel Works, Ishikawajima-Heavey Industries and Fukuda Metal Foil and
Powder under another NEDOs project worked on non-palladium metal membranes and manufacturing
modules using those membranes.

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Figure 2. External view of the 40 Nm3/h-class membrane reformer unit.

The challenges to be pursued in the following development efforts were identified as further improvement
of the system efficiency, durability of the membrane modules and significant cost reduction for manufacturing
membrane modules. The three contractors who have been involved in development of non-palladium
metallic hydrogen permeable membranes independently reached the same conclusion that the biggest
technical issue is to realize both high permeability and resistance to brittleness in hydrogen-containing
atmospheres 5-7). Based on consideration of these technology development situations, a new project
Development of Membrane Technology for Highly-efficient Hydrogen Production was proposed and
awarded in FY2005 under NEDOs Development of Safety Utilization and Infrastructure of Hydrogen
Project. The new project is aimed at developing technologies for practical commercialization through further
improvement of efficiency and durability as well as cost reduction of the membrane reformer system.
4. R&D THEMES AND ORGANIZATION
The project has two parallel developments: the one is membrane reformer system engineering
development and the other is development of hydrogen permeable membrane materials and modules. The
system engineering development has 2 themes implemented by 2 contractors and the materials and
modules development has 5 themes implemented by 5 contractors and 6 subcontractors as listed in Table 1.
Table 1. R&D Themes and contractors under the Development of Membrane Technology
for Highly-efficient Hydrogen Production project.
Categories
System
engineering
development

Membrane
materials and
modules
development

Themes
Development of membrane reformer system
Study on durability of hydrogen separation membrane
Development of Membrane on catalyst module
Development
of
integrated
high-performance
hydrogen separation membrane
Development of hydrogen separation modules using
multi-phase alloy foils
Development of high-performance membranes using
metallic glasses and nano-crystalline materials
Testing
and
evaluation
of
high-performance
membrane materials

* Institutions in the parentheses are subcontractors.

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Contractors*
Tokyo Gas and Mitsubishi
Heavy Industries
Mitsubishi Heavy Industries
Tokyo Gas and NGK Spark
Plug (Gifu Univ.)
Ishikawajima-Harima Heavy
Industries
Japan Steel Works (Kitami
Institute of Technology)
Fukuda Metal Foil and
Powder (Tohoku Univ.)
Tokyo Gas (Tohoku Univ.,
Utsunomiya Univ., Nagoya
Univ.)

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5. TARGETS OF THE PROJECT
5.1 System engineering development
A 40 Nm3/h-class membrane reformer system is to be developed which meets the following specifications:
a) Overall efficiency: 80% HHV basis, at product hydrogen pressure of 0.03 MPa
( 75% HHV basis, at product hydrogen pressure of 0.74 MPa)
b) Hydrogen production capacity: 40 Nm3/h
c) Product hydrogen purity: 99.99%
5.2 Membrane materials and modules development
Membrane materials and modules are to be developed for both Pd-based and non-Pd materials which meet
the following specifications:
a) Hydrogen permeability: higher than double of Pd-based materials (hydrogen flux 30 cc/min/cm2)
b) Product hydrogen purity: 99.99%
c) Durability: Keep the permeability and purity specifications listed above even after the performance
tests specified in the following. As for Pd-based materials, the permeability should show no
degradation even after the performance tests.
d) Module cost: 50,000 JY per hydrogen production capability of 1 Nm3/h
The membranes and modules developed under the project should be evaluated in the following
performance test.
a) Sample size: such area as will give permeated hydrogen flow of 100 cc/min and should be
smaller than 50 mm x 400 mmL.
b) Operation temperature: 600C
c) Operation pressures for hydrogen permeability tests: 0.2 and 0.1 MPa at higher-pressure side and
permeate side, respectively.
d) Operation pressures for reforming tests: 0.9 and 0.1 MPa at process gas side and permeate side,
respectively.
e) Durability test pattern: 100 hours of continuous operation and shut-down, followed by 5 times of daily
start-up and shut-down operation cycles with 5 hours of soaking at a selected temperature (total
soaking time of 125 hours with 6 start-up and shut-down cycles).
6. PLANS AND PRESENT STATUS OF EACH R&D THEME
6.1 Development of Membrane Reformer System
A 40 Nm3/h-class membrane reformer system that can provide high overall efficiency of over 80% is to be
designed, manufactured and tested to prove its performance characteristics and finally to establish the
system engineering technology that can be commercialized to on-site hydrogen generators for hydrogen
refueling stations and other purposes. New hydrogen separation modules with improved durability will be
used, and the structure design for the reactor tube, which contains two modules to serve as the basic
building unit of the membrane reformer, will be modified. And then the structural design of the reactor will be
optimized before building and testing the system.
A process flow design has been completed to identify what improvements should be given to the system
components in order to achieve the overall efficiency of 80%. The 40 Nm3/h-class membrane reformer
system developed and operated under the foregoing project was disassembled and post-test analyses were
made to identify the possible reasons for the critical membrane failures. The findings from the post-test
analyses and the separate work for improvement of durability as will be described in the following subsection
(6.2) were feedbacked to manufacture new modules. A reactor tube containing the new modules using
membranes having less inclusions has been assembled and put into a durability test. The results have
shown that 40 Nm3/h of hydrogen can be produced when 112 reactor tubes are installed in the reactor and
operated at 550C, at process-gas and permeate pressures of 0.9 and 0.03 MPa, respectively and at natural
gas feed rate of 10.53 Nm3/h with the steam to carbon ratio of 2.9. CFD analyses have been carried out to
minimize the temperature distribution in the furnace in the reactor.
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6.2 Study on Durability of Hydrogen Separation Membrane

Key technologies are to be developed to remove the oxide inclusions in the membrane that are penetrating
the membrane to the surface and will develop into origins for cracking of the membrane. By employing the
flux method and/or the cold crucible method, the oxide inclusions will be removed in molten alloys to such
levels as can avoid formation of critical cracks. The purification technology will be developed to reduce the
amount of impurities to less than 10 ppm in terms of weight and less than 625 /mm3 in terms of number of
impurity particles with a size of less than 4 microns. The effect of the purification will be confirmed by
improved creep resistance with creep life of over 10,000 hours at 550C.
The flux method using CaO-Al2O3 flux and a MgO crucible has been found to effectively reduce the
impurity content in the membrane from the initial 110 ppm to 74 ppm and the inclusions density to only about
1/9 of that before purification. The cold crucible method was also found effective to reduce the impurity
content to 30 ppm and the inclusion density to 20 to 40% of that before purification. A single-step purification
by the flux method was applied to prepare the new membrane modules for durability tests.
6.3 Development of Membrane On Catalyst Module
A new type of hydrogen separation module was proposed and developed. The new module, what we call
MOC (Membrane On Catalyst), was designed to have a membrane of palladium-based alloy prepared on the
surface of the tubular structured catalyst that has catalytic activity for steam reforming reaction, thermal
expansion matching with the membrane material, proper porosity, mechanical strength and thermal
conductivity. The best composition of the structured catalyst was identified in the composites of metallic Ni
and YSZ (Yttria-Stabilized Zirconia). A hydrogen separation module was manufactured by electroless plating
of Pd with thickness of 7 to 15 microns on the surface of porous sintered tube of Ni-YSZ with an approximate
size of 9 mm in diameter and 100 mm in length as shown in Figure 3. The hydrogen permeability
measurements have shown hydrogen flux of 25 to 35 cc/min at 550 to 600C, which is higher than the
permeability of the conventional modules using rolled Pd film. More details are presented in the separate
paper 8). The subcontractor Gifu Univ. is developing a technology to deposit Pd and Ag simultaneously by
electroplating in a supercritical CO2 solvent.
Membrane section

Connection pipe

Figure 3. Outlook of the MOC module (Size: 9 mm O.D. x 7 mm I.D. x 100 mm long).

6.4 Development of Integrated High-performance Hydrogen Separation Membrane

Membrane materials showing high hydrogen permeability have problems of cracking due to large volume
changes and the resulting strains in hydrogen incorporation and evolution. The reason for the cracking is
considered to be strain concentrations caused by the volume changes and fatigue. This theme is aimed at
developing hydrogen separation membranes with both high durability and high hydrogen permeability by
integrating a metal mesh structural support and non-Pd membrane materials such as V-base alloys to form a
composite foil. Substantial cost reduction can be expected by using less costly non-Pd membrane materials.
An integrated foil of a Ni mesh and a powder mixture of vanadium with 10 wt% of Ni was prepared by rolling.
The foil of 55 microns thick with thin Pd plating on both surface showed high hydrogen permeability of 5 x 108
mol H2/m/s/Pa0.5 at 400C and the hydrogen permeation flux of 15 cc/min/cm2 which is comparable to the
conventional Pd-alloy foils. Tasks to be followed are improvement of gas tightness of the integrated
membrane, reduction of the membrane thickness, optimization of Pd coating condition to avoid degradation
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of hydrogen permeability and verification of mechanical integrity and durability of the foil under practical
operating conditions.
6.5 Development of Hydrogen Separation Modules Using Multi-phase Alloy Foils
Multi-phase alloy membranes are to be developed in which one phase covers hydrogen permeability and
the other phase covers resistance against hydrogen brittleness. Kitami Institute of Technology (KITEC) has
been working on such a concept and found that Nb-Ti-Co alloys are good candidate materials for it. Under
this theme, KITEC will develop membrane materials with high permeability by optimizing the composition and
microstructure of the alloys. Japan Steel Works will develop thin membranes and modules manufacturing
processes using the materials developed by KITEC.
A foil of Nb52Ti25Co23 was manufactured by arc melting and cold rolling followed by annealing at 1000C for
10 hours. It was found that islands of hydrogen permeable (Nb, Ti) phase are distributed in the matrix of
(Nb, Ti)+CoTi and the shape and orientation of the (Nb, Ti) phase affects the hydrogen permeability of the
multi-phase alloy foils. Cold rolling decreases the hydrogen permeability, but the subsequent annealing at
1000C changes the shape of the hydrogen permeating phase and as a result increases the permeability.
The 30 microns thick foil of Nb52Ti25Co23 showed hydrogen permeation flux of 18 cc/min/cm2 at 400C.
6.6 Development of High-performance Membranes Using Metallic Glasses and Nano-crystalline
Materials
New membrane materials with high hydrogen permeability are to be developed based on non-Pd metallic
glasses and nano-crystalline materials, which is expected to greatly reduce the membrane cost. New
materials will be developed by balancing the hydrogen permeability and durability and applicability to the
selected manufacturing process. Processing technology to prepare thin foils will also be developed by
considering materials properties, mass productivity and potential for cost reduction. Hydrogen permeability,
selectivity and durability will be evaluated and the results will be feedbacked to materials design and
processing technology development.
Membranes of Ni25Nb40Zr30Co5 alloy with thickness of 5, 10 and 20 microns were deposited on porous
alumina support disks by multi-target sputtering. The alloy was found to be amorphous and have higher
crystallization temperature than the alloys prepared by melt-spinning. But it had many micro cracks and was
not gastight enough for permeability experiments. To prepare a composite of nano-crystalline Nb dispersed in
the matrix of metallic glass, 7 wt% of Nb powder was melt together with Cu60Zr30Ti10 alloy and quenched on a
cold roll. The resulting alloy foil was found to be composed of single-phase amorphous alloy and its
hydrogen permeability was only 1 x 10-8 mol H2/m/s/Pa0.5 at 450C. The subcontractor Tohoku Univ. is also
working on Nb-rich Ni-Nb-Zr alloy glasses, focusing on developing optimum compositions and bonding and
shaping under a super-cooled melt condition.
6.7 Testing and Evaluation of High-performance Membrane Materials
Performance evaluation is to be carried out with reference to the project targets already described in 5.2 for
well-developed Pd alloys and non-Pd materials that are developed under this project, and the results are
feedbacked to improve the material properties. Data of mechanical properties such as elastic constant and
bending strength and creep rupture strength are to be measured in detail and used for evaluation of
mechanical reliability of the membranes. For evaluation of applicability of various membrane materials and
modules from wide viewpoints, the subcontractors Tohoku Univ., Nagoya Univ. and Utsunomiya Univ. are
working on surface reaction mechanism, non-Pd alloy design for having both high hydrogen permeability and
resistance to hydrogen brittleness, and high-pressure and low-temperature hydrogen production system
using a membrane reactor, respectively.
The common performance tests as described in 5.2 were performed for 20 microns thick foil samples of PdTb, Pd-Ag, Pd-Ag-Au and Pd-Cu alloys which showed hydrogen permeation flux of 35, 24, 18 and 9
cc/min/cm2 at 600C for the former 3 alloys and at 450C for Pd-Cu alloy. All these alloys were found to show
stable permeability and no leakage over the whole test period including 6 start-up and shut-down cycles. The
thermal expansion coefficient was measured between 50C and 600C in N2 atmosphere for Pd-Ag, Pd-Ag6/7

WHEC 16 / 13-16 June 2006 Lyon France

Au, Pd-30Cu, Pd-40Cu, Pd-45Cu and Pd-Tb alloys which gave 14.5, 14.5, 14.9, 15.0, 15.9 and 14.2 x 10-6K-1,
respectively. FEM analyses have also been made to simulate the stress distribution in the membrane for
several sets of membrane-support geometries, the results of which will be used for structural design of
modules that can offer good mechanical integrity and reliability. The subcontractor Tohoku Univ. has been
studying the effect of coexisting gases on hydrogen permeability and developed an emprical formulation of
surface reaction rate, which is presented in the separate paper 9). The subcontractor Nagoya Univ. has
developed a unique small punch test to obtain stress vs. strain data of membrane samples under in-situ
hydrogen permeation. The preliminary results have clearly shown brittle fracture behavior in membranes
having high hydrogen permeability such as Nb foil with Pd coating on the surface. The subcontractor
Utsunomiya Univ. has been assembling a lab-scale high-pressure membrane reactor to study hydrogen
production at low temperatures. Taking gasification of wood biomass with the presence of super-critical
water followed by hydrogen production in a membrane reactor as a model reaction, reaction kinetics at
around 400C and process gas pressure of 1 MPa will be investigated.
REFERENCES
1. I. Yasuda, Y. Shirasaki, T. Asakura, H. Ishikawa, H. Shinkai and R. Yamaguchi, Abstracts of 6th
International Conference on Catalysis in Membrane Reactors, Lahnstein, July 2004, p. 91.
2. Y. Shirasaki, T. Tsuneki, T. Mori, H. Furuta and I. Yasuda, presented at World Hydrogen Technologies
Convention 2005, Singapore, October 2005.
3. I. Yasuda, T. Tsuneki and Y. Shirasaki, Abstracts of 7th International Conference on Catalysis in
Membrane Reactors, Cetraro, September 2005, p. 138.
4. K. Kobayashi, NEDO FY2004 Report of Development of Safety Utilization and Infrastructure of
Hydrogen Project (available only in Japanese), p. 98.
5. T. Sasaki, NEDO Post Project Review Committee Report of Research and Development of Polymer
Electrolyte Fuel Cell Systems Project (available only in Japanese), p. 49, 2005.
6. M. Nishida, ibid., p. 53, 2005.
7. M. Uchida, ibid., p. 57, 2005.
8. I. Yasuda, T. Tsuneki, Y. Shirasaki, T. Shimamori, H. Shigaki and H. Tanaka, to be presented at the 16th
World Hydrogen Eneergy Conference, Lyon, June 2006.
9. A. Unemoto, A. Kaimai, T. Otake, K. Yashiro, T. Kawada, J. Mizusaki, T. Tsuneki and I. Yasuda, to be
presented at the 16th World Hydrogen Eneergy Conference, Lyon, June 2006.
ACKNOWLEDGEMENT
This work was supported by the New Energy and Technology Development Organization (NEDO). The
authors would like to thank their financial and technical supports.

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