Microreactors and membrane microreactors: fabrication and applications

Handbook of Membrane Reactors

Volumn 2, Issue , 2013, Pages 188-235

  Seelam, P K ^a   Huuhtanen, M ^a   Keiski, R L ^a  

^a UNIVERSITY OF OULU   (Finland)

Author keywords

Membrane microreactor; Microfabrication; Microfluidic device; Palladium micromembrane; Zeolite

Indexed keywords

MEMBRANE TECHNOLOGY; MICROFABRICATION; ZEOLITES;

MEMBRANE MICROREACTORS; MICRO-FLUIDIC DEVICES; MICRO-REACTOR; MICROMEMBRANES; MICROREACTOR DESIGN; OVERALL EFFICIENCY; PROCESS INDUSTRIES; PROCESS INTENSIFICATION;

CHEMICAL REACTORS;

EID: 84943223502     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1533/9780857097347.1.188     Document Type: Chapter

References (122)

1. Akbari M.H., Ardakani A.H.S., Tadbir M.A. A microreactor modeling, analysis and optimization for methane autothermal reforming in fuel cell applications. Chem Eng J 2011, 166:1116-1125.
2. Alfadhel K.A., Kothare M.V. Microfluidic modeling and simulation of flow in membrane microreactors. Chem Eng Sci 2005, 60:2911-2926.
3. Anastas P.T., Warner J.C. Green chemistry: Theory and practice 1998, Oxford University Press, New York, 30.
4. Aran H.C., Benito S.P., Luiten-Olieman M.W.J., Er S., Wessling M., Lefferts L., Benes N.E., Lammertink R.G.H. Carbon nanofibers in catalytic membrane microreactors. J Membrane Sci 2011, 381:244-250.
5. Athayde A.L., Baker R.W., Nguyen P. Metal composite membranes for hydrogen separation. J Membrane Sci 1994, 94:299-311.
6. Aubin J., Ferrando M., Jiricny V. Current methods for characterising mixing and flow in microchannels. Chem Eng Sci 2010, 65:2065-2093.
7. Bryden K.J., Ying J.Y. Nanostructured palladium membrane synthesis by Magnetron sputtering. Mater Sci Eng 1995, 204:140-145.
8. Bryden K.J., Ying J.Y. Nanostructured palladium-iron membranes for hydrogen separation and membrane hydrogenation reactions. J Membrane Sci 2002, 203:29-42.
9. Basile A., Pinacci P., Iulianelli A., Broglia M., Drago F., Liguori S., Longo T., Calabrò V. Ethanol steam reforming reaction in a porous stainless steel supported palladium membrane reactor. Int J Hydrogen Energy 2011, 36:2029-2037.
10. Casanovas A., Domínguez M., Ledesma C., Lopez E., Llorca J. Catalytic walls and micro-devices for generating hydrogen by low temperature steam reforming of ethanol. Catal Today 2009, 143:32-37.
11. Casanovas A., Saint-Gerons M., Griffon F., Llorca J. Autothermal generation of hydrogen from ethanol in a microreactor. Int J Hydrogen Energy 2008, 33:1827-1833.
12. Chau J.L.H., Leung A.Y.L., Yeung K.L. Zeolite micromembranes. Lab Chip 2003, 3:53-55.
13. Chen C., Gobina E. Ultra-thin palladium technologies enable future commercial deployment of PEM fuel cell systems. Membrane Technol. 2010, 3:6-13.
14. Chen Y., Zhang C., Wu R., Shi M. Methanol steam reforming in with constructal tree-shaped network. J Power Sources 2011, 196:6366-6373.
15. Chi Y.H., Yen P.S., Jeng M.S., Ko S.T., Lee T.C. Preparation of thin Pd membrane on porous stainless steel tubes modified by a two-step method. Int J Hydrogen Energ 2010, 35:6303-6310.
16. Coleman J.W., Garimella S. Characterization of two-phase flow patterns in small diameter round and rectangular tubes. Int J Heat Mass Transfer 1999, 42:2869-2881.
17. Colin R. Process Intensification and Green Chemistry. Green Chem 1999, 1:G15-G17.
18. Collins J.P., Way J.D. Preparation and characterization of a composite palladium-ceramic membrane. Ind Eng Chem 1993, 32:3006-3013.
19. Coronas J., Santamaria J. The use of zeolite films in small-scale and micro-scale applications. Chem Eng Sci 2004, 59:4879-4885.
20. Cui T., Fang J., Zheng A., Jones F., Reppond A. Fabrication of microreactors for dehydrogenation of cyclohexane to benzene. Sensor Actuator B Chem 2000, 71:228-231.
21. Cybulski A., Moulijn J.A. Structured catalysts and reactors 2006, CRC Press. 2nd.
22. Delsman E.R., Laarhoven B.J.P.F., De Croon M.H.J.M., Kramer G.J., Schouten J.C. Comparison between conventional fixed-bed and microreactor technology for a portable hydrogen production case. Chem Eng Res Des 2005, 83:1063-1075.
23. Deshpande K., Meldon J.H., Schmidt M.A., Jensen K.F. SOI-supported microdevice for hydrogen purification using palladium-silver membranes. J Microelectromech S 2010, 19:402-409.
24. Dittmeyer R., Höllein V., Daub K. Membrane reactors for hydrogenation and dehydrogenation processes based on supported palladium. Jmol Catal 2001, 173:135-184.
25. Doku G.N., Verboom W., Reinhoudt D.N., van den Berg V. On-microchip multiphase chemistry-a review of microreactor design principles and reagent contacting modes. Tetrahedron 2005, 61:2733-2742.
26. Domínguez M., Cristiano G., López E., Llorca J. Ethanol steam reforming over cobalt talc in a plate microreactor. Chem Eng J 2011, 176-177:280-285.
27. Ehrfeld W., Hessel V., Löwe H. Microreactors - New technology for modern chemistry 2000, Wiley-VCH, Weinheim.
28. Franz A., Jensen K.F., Schmidt M.A. 'Palladium based micromembranes for hydrogen separation and hydrogenation/dehydrogenation reactions', Ed. Ehrfeld W, Microreaction technology: industrial prospects 2000, 267-276.
29. Gavriilidis A., Angeli P., Cao E., Yeong K.K., Wan Y.S.S. Technology and applications of microengineered reactors. Trans IchemE, part A 2002, 80.
30. Gielens F.C., Knibbeler R.J.J., Duysinx P.F.J., Tong H.D., Vorstman M.A.G., Keurentjes J.T.F. Influence of steam and carbon dioxide on the hydrogen flux through thin Pd/Ag and Pd membranes. J Membrane Sci 2006, 279:176-185.
31. Gielens F.C., Tong H.D., van Rijn C.J.M., Vorstman M.A.G., Keurentjes J.T.F. High-flux palladium-silver alloy membranes fabricated by microsystem technology. Desalination 2002, 147:417-423.
32. Gielens F.C., Tong H.D., van Rijn C.J.M., Vorstman M.A.G., Keurentjes J.T.F. Microstystem technology for high-flux hydrogen separation membranes. J Membrane Sci 2004, 243:203-213.
33. Gokhale S.V., Tayal R.K., Jayaraman V.K., Kulkarni B.D. Microchannel reactors: Applications and use in process development. Int J Chem React Eng 2005, 3:R2.
34. Goltsov V.A. Hydrogen in metals, Questions of atomic sciences and engineering. Ser.: Atomic-Hydrogen Energetics 1977, 1(2):65.
35. Gorke O., Pfeifer P., Schubert K. Kinetic study of ethanol reforming in a microreactor. Appl Catal A Gen 2009, 360:232-241.
36. Goto S., Tagawa T., Assabumrungrat Sand, Praserthdam P. Simulation of membrane microreactor for fuel cell with methane feed. Catal Today 2003, 82:223-232.
37. Hessel V., Knobloch C., Löwe H. Review on patents in microreactor and micro process engineering. Recent Patents on Chemical Engineering 2008, 1:1-16.
38. Hessel V., Hardt S., Löwe H. Chemical micro process engineering: Fundamentals, modelling and reactions. Wiley-VCH Verlag GmbH 2005, 1-106.
39. Hessel V., Hardt S., Löwe H. Chemical micro process engineering: Fundamentals, modelling and reactions. Wiley-VCH Verlag GmbH 2005, 125-147.
40. Hessel V., Löwe H., Müller A., Kolb G. Chemical micro process engineering processing and plants 2005, 386-399. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
41. HolladayJ D., Hu J., King D.L., Wang Y. An overview of hydrogen production technologies. Catal Today 2009, 139:244-260.
42. Holladay J.D., Wang Y., Jones E. Review of developments in portable hydrogen production using micro reactor technology. Chem Rev 2004, 104:4767-4790.
43. Hou K., Hughes R. Preparation of thin and highly stable Pd/Ag composite membranes and simulative analysis of transfer resistance for hydrogen separation. J Membrane Sci 2003, 214:43-55.
44. Israni S.H., Nair B.K.R., Harold M.P. Hydrogen generation and purification in a composite Pd hollow fiber membrane reactor: Experiments and modeling. Catal Today 2009, 139:299-311.
45. Jayaraman V., LinY S. Synthesis and hydrogen permeation properties of ultrathin, palladium-silver alloy membranes. J Membrane Sci 1995, 104:251-262.
46. Jensen K.F. Microchemical systems: Status, challenges, and opportunities 1999, 45:2051-2054.
47. Jensen K.F. Microreaction engineering is small better?. Chem Eng Sci 2001, 56:293-303.
48. Jong J.D., Lammertink R.G.H., Wessling M. Membranes and microfluidics: a review. Lab Chip 2006, 6:1125-1139.
49. Karnik S.V., Hatalis M.K., Kothare M.V. Towards a palladium micro-membrane for the water gas shift reaction: Microfabrication approach and hydrogen purification results. J Microelectromech S 2003, 12:93-100.
50. Keurentjes J.T.F., Gielens F.C., Tong H.D., Rijn C.J.M., Vorstman M.A.G. High-flux palladium membranes based on microsystem technology. Ind Eng Chem Res 2004, 43:4768-4772.
51. Kim T., Kwon S. Catalyst preparation for fabrication of a MEMS fuel reformer. Chem Eng J 2006, 123:93-102.
52. Kim T.W. Studies of transport phenomena in hydrotalcite membranes and their use in direct methanol fuel cells 2008, PhD thesis, Faculty of the Graduate School University of Southern California.
53. Kim D., KelloggA Livaich E., Wilhite B.A. Towards an integrated ceramic micro-membrane network: Electroless-plated, palladium membranes in cordierite supports. J Membrane Sci 2009, 340:109-116.
54. Kiwi-Minsker L., Renken A. Microstructured reactors for catalytic reactions. Catal Today 2005, 110:2-14.
55. Kiwi-Minsker L., Wolfrath O., Renken A. Membrane reactor microstructured by filamentous catalyst. Chem Eng Sci 2002, 57:4947-4953.
56. Klemm E., Döring H., Geisselmann A., Schirrmeister S. Microstructured reactors in heterogeneous catalysis. Chem Eng Technol 2007, 30:1615-1621.
57. Kolb G., Hessel V. Micro-structured reactors for gas phase reactions. Chem Eng J 2004, 98:1-38.
58. Kwan S.M., Leung A.Y.L., Yeung K.L. Gas permeation and separation in ZSM-5 micromembranes. Sep Purif Technol 2010, 73:44-50.
59. Lai S.M., Martin-Aranda R., Yeung K.L. Knoevenagel condensation reaction in a membrane microreactor. Chem Commun 2003, 218-219.
60. Lau W.N., Yeung K.L., Zhang X.F., Martin-Arand R. Zeolite membrane microreactors and their performance. Stud Surf Sci Catal 2007, 170:1460-1465.
61. Levent M., Gunn D.J., El-Bousiffi M.A. Production of hydrogen-rich gases from steam reforming of methane in an automatic catalytic microreactor. Int J Hydrogen Energy 2003, 28:945-959.
62. Leung Y.L.A., Yeung K.L. Microfabricated ZSM-5 zeolite micromembranes. Chem Eng Sci 2004, 59:4809-4817.
63. Li A., Grace J.R., Lim C.J. Preparation of thin Pd-based composite membrane on planar metallic subst rate Part II. Preparation of membranes by electroless plating and characterization. J Membrane Sci 2007, 306:159-165.
64. Li A., Liang W., Hughes R. Characterization and permeation of palladium/ stainless steel composite membrane. J Membrane Sci 1998, 149:259-268.
65. Li Z.Y., Maeda H., Kusakabe K., Marooka S., Anzai H., Akiyama S. Preparation of palladium-silver alloy membranes for hydrogen separation by the spray pyrolysis method. J Membrane Sci 1993, 78:247-254.
66. McCool B., Xomeritakis G., Lin Y.S. Composition control and hydrogen permeation characteristics of sputter deposited palladium-silver membranes. J Membrane Sci 1999, 161:67-76.
67. McLeary E.E., Jansen J.C., Kapteijn F. Zeolite based films, membranes and membrane reactors: Progress and prospects. Micropor Mesopor Mat 2006, 90:198-220.
68. McLeod L.S., Degertekin F.L., Fedorov A.G. Determination of the rate-limiting mechanism for permeation of hydrogen through microfabricated palladium-silver alloy membranes. J Membrane Sci 2009, 341:225-232.
69. McMullen J.P., Jensen K.F. Integrated microreactors for reaction automation: New approaches to reaction development. Annu Rev Anal Chem 2010, 3:19-42.
70. Mills P.L., Quiram D.J., Ryley J.F. Microreactor technology and process miniaturization for catalytic reactions - A perspective on recent developments and emerging technologies. Chem Eng Sci 2007, 62:6992-7010.
71. Moulijn J.A., Stankiewicz A., Grievink J., Gorak A. Process intensification and process system engineering: a friendly symbiosis. Computer Aided Chem Eng 2006, 21:29-37.
72. Naddaf A., Bart H.J., Krätz L., Detemple P., Schmitt S., Hessel V., Faqir N. Microfabricated hydrogen sensitive membranes. Chem Eng Technol 2009, 32:103-113.
73. Nair B.K.R., Harold M.P. Pd encapsulated and nanopore hollow fiber membranes: Synthesis and permeation studies. J Membrane Sci 2007, 290:182-195.
74. O'Brien J., Hughes R., Hisek J. Pd-Ag membranes on porous alumina substrates by unbalanced magnetron sputtering. Surf Coat Tech 2001, 142:253-259.
75. Papautsky I., Ameel T., Frazier A.B. 'A review of laminar single-phase flow in microchannels', Proceeding of ASME International Mechanical Engineering Conference and Exposition, New York. Nov. 2001, 21-26.
76. Pattekar A.V., Kothare M.V. A microreactor for hydrogen production in micro fuel cell applications. J Microelectromech S 2004, 13:7-18.
77. 3 catalysts in a microchannel reactor. Chem Eng J 2011, 167:578-587.
78. PetersTA Stange M., Klette H., Bredesen R. High pressure performance of thin Pd-23%Ag/stainless steel composite membranes in water gas shift gas mixtures; influence of dilution, mass transfer and surface effects on the hydrogen flux. J Membrane Sci 2008, 316:119-127.
79. PetersT A., Stange M., Bredesen R. On the high pressure performance of thin supported Pd-23%Ag membranes-Evidence of ultrahigh hydrogen flux after air treatment. J Membrane Sci 2011, 378:28-34.
80. Pfahler J., Harley J., Bau H., Zemel J.N. Gas and liquid flow in small channels. Micromechanical Sensors, Actuators and Systems, ASME Winter Annual Meeting, Atlanta, GA 1991, 32:49-59.
81. Pina M.P., Mallada R., Arruebo M., Urbiztondo M., Navascués N., de la Iglesia O., Santamaria J. Zeolite films and membranes: Emerging applications. Micropor Mesopor Mat 2011, 144:19-27.
82. Plasynski S., Lang D., Tsapatsis M. 2008, (accessed on Jan 2012). http://www.netl.doe.gov/publications/factsheets/project/Proj306.pdf.
83. Rahman M.A., García-García F.R., Irfan Hatim M.D., Kingsbury B.F.K., Li K. 'Development of a catalytic hollow fibre membrane micro-reactor for high purity H2 production. J Membrane Sci 2011, 368:116-123.
84. Ratchananusorn W. Flow phenomena, heat and mass transfer in microchannel reactors, MSc. Thesis, Faculty of Technology, The Degree Program of Chemical Technology 2007, Lappeenranta University of Technology, Finland.
85. Roa F., Way J.D. Influence of alloy composition and membrane fabrication on the pressure dependence of the hydrogen flux of palladium-copper membranes. Ind Eng Chem Res 2003, 42:5827-5835.
86. Rong B.G., Kolehmainen E., Turunen L. Methodology of conceptual process synthesis for process intensification. Computer Aided Chem Eng 2008, 25:283-288.
87. Sanders J.P.M., Clark J.H., Harmsen G.J., Heeres H.J., Heijnen J.J., Kersten S.R.A., van Swaaij W.P.M., Moulijn J.A. Process intensification in the future production of base chemicals from biomass. Chem Eng Process: Process Intensification 2011, 51:117-136.
88. Schiewe B., Staudt-Bickel C., Vuin A., Wegner G. Membrane-based gas separation of e thylene/ethylene oxide mixtures for product enrichment in microreactor technology. ChemPhysChem 2001, 2:211-218.
89. Seelam P.K., Liguori S., Iulianelli A., Pinacci P., Drago F., Calabrò V., Huuhtanen M., Keiski R., Piemonte V., Tosti S., De Falco M., Basile A. Hydrogen production from bio-ethanol steam reforming reaction in a Pd/PSS membrane reactor. Catal Today 2012, 193:42-48.
90. Su C., Jin T., Kuraoka K., Matsumura Y., Yazawa T. Thin palladium film supported on SiO2-modified porous stainless steel for a high-hydrogen-flux membrane. Ind Eng Chem Res 2005, 44:3053-3058.
91. 3 hollow fiber by electroless plating: High permeance and selectivity. J Membrane Sci 2006, 284:110-119.
92. Tadbir M.A., Akbari M.H. Methanol steam reforming in a planar wash coated microreactor integrated with a micro-combustor. Int J Hydrogen Energy 2011, 36:12822-12832.
93. Takahashi T., Tanaka S., Chang K.S., Esashi M. 'In-situ chemical vapor deposition of alumina catalyst bed on a suspended membrane microreactor', Solid-State Sensors, Actuators and Microsystems, TRANSDUCERS '05. The 13th. International Conference 2005, 1:899-903.
94. Tong H.D., Berenschot J.W.E., De Boer M.J., Gardeniers J.G.E., Wensink H., Jansen H.V., Nijdam W., Elwenspoek M.C., Gielens F.C., van Rijn C.J.M. Microfabrication of palladium-silver alloy membranes for hydrogen separation. J Microelectromech S 2003, 12:622-629.
95. Tong H.D. Microfabricated palladium-based membranes for hydrogen separation. PhD thesis, Transducers Science and Technology of the MESA+ Research Institute at the University of Twente, Enschede, Netherlands 2004.
96. Tong H.D., Gielens F.C., Gardeniers J.G.E., Jansen H.V., Berenschot J.W., de Boer M.J., de Boer J.H., van Rijn C.J.M., Elwenspoek M.C. Microsieve supporting palladium-silver alloy membrane and application to hydrogen separation. J Microelectromech S 2005, 14(1):113-124.
97. Tong J., Suda H., Haraya K., Matsumura Y. A novel method for the preparation of thin dense Pd membrane on macroporous stainless steel tube filter. J Membrane Sci 2005, 260:10-18.
98. Tong J., Matsumura Y., Suda H., Haraya K. Thin and dense Pd/CeO2/ MPSS composite membrane for hydrogen separation and steam reforming of methane. Sep Purif Technol 2005, 46:1-10.
99. Tong J., Matsumura Y. Pure hydrogen production by methane steam reforming with hydrogen-permeable membrane reactor. Catal Today 2006, 111:147-152.
100. Tong J., Su L., Kashima Y., Shirai R., Suda H., Matsumura Y. Simultaneously depositing Pd-Ag thin membrane on asymmetric porous stainless steel tube and application to produce hydrogen from steam reforming of methane. Ind Eng Chem Res 2006, 45:648-655.
101. Tonomura O., Noda M., Kano M., Hasebe S. Optimal design approach for microreactors with uniform residence time distribution,. The 10th Asian Pacific Confederation of Chemical Engineering (APCChE), 4B-07, Kitakyushu, Japan Oct. 2004, 17-21.
102. Tonomura O., Noda M., Kano M., Hasebe S. Thermo-fluid design approach to microreactors with uniform temperature and residence time distribution. AIChE Annual Meeting 2004, 2004:430d.
103. Uemiya S., Kude Y., Asugino K., Sato N., Matsuda T., Kikuchi E. A palladium/porous glass composite membrane for hydrogen separation. Chem Lett 1988, 17:1687-1690.
104. Van Gerven T., Stankiewicz A. Structure, energy, synergy, time -The fundamentals of process intensification. Ind Eng Chem Res 2009, 48:2465-2474.
105. Waelchli S., Rohr P.R.V. Two-phase flow characteristics in gas-liquid microreactors. Int J Multiphas Flow 2006, 32:791-806.
106. Watts P., Haswell S.J. The application of micro reactors for organic synthesis. Chem Soc Rev 2005, 34:235-246.
107. Wan Y.S.S., Chau J.L.H., Gavriilidis A., Yeung K.L. Design and fabrication of zeolite-based microreactors and membrane microseparators. Micropor Mesopor Mater 2001, 42:157-175.
108. Wang D., Tong J., Xu H., Matsumura Y. Preparation of palladium membrane over porous stainless steel tube modified with zirconium oxide. Catal Today 2004, 93-95:689-693.
109. Wang J., Liu G., Xiong Y., Huang X., Guo Y., Tian Y. Fabrication of ceramic microcomponents and microreactor for the steam reforming of ethanol. Microsystem Technol 2008, 14:1245-1249.
110. Wilhite B.A., Schmidt M.A., Jensen K.F. Palladium-based micromembranes for hydrogen separation: Device performance and chemical stability. Ind Eng Chem Res 2004, 43:7083-7091.
111. Wilhite B.A., Weiss S.E., Ying J.Y., Schmidt M.A., Jensen K.F. High-purity hydrogen generation in a microfabricated 23wt% Ag-Pd membrane device integrated with 8:1 LaNi0.95Co0.05°3/Al203 catalyst. Adv Mater 2006, 18:1701-1704.
112. Wolfrath O., Kiwi-Minsker L., Renken A. Novel Membrane Reactor with Filamentous Catalytic Bed for Propane Dehydrogenation. Ind Eng Chem Res 2001, 40:5234-5239.
113. Xomeitakis G., Lin Y.S. Fabrication of thin metallic membranes by MOCVD and sputtering. J Membrane Sci 1996, 133:217-230.
114. Yamamoto S., Hanaoka T., Hamakawa S., Sato K., Mizukami F. Application of a microchannel to catalytic dehydrogenation of cyclohexane on Pd membrane. Catal Today 2006, 118:2-6.
115. Yan S., Maeda H., Kusakabe K., Morooka S. Thin palladium membrane formed in support pores by metal-organic chemical vapor deposition method and application to hydrogen separation. Ind Eng Chem Res 1994, 33:616-622.
116. Ye S.Y., Tanaka S., Esashi M., Hamakawa S., Hanaoka T., Mizukami F. Thin palladium membrane microreactor with porous silicon support and their application in hydrogenation reaction',Solid-State Sensors, Actuators and Microsystems, 2005. Digest of Technical Papers. Transducers '05. The 13th International Conference, 2 2005, 2078-2082.
117. Ye S.Y., Tanaka S., Esashi M., Hamakawa S., Hanaoka T., Mizukami F. MEMS-based thin palladium membrane microreactors. Proc SPIE 2006, 6032:603207.
118. Yepes D., Cornaglia L.M., Irusta S., Lombardo E.A. Different oxides used as diffusion barriers in composite hydrogen permeable membranes. J Membrane Sci 2006, 274:92.
119. Yeung K.L., Zhang X., Lau W.N., Martin-Aranda R. Experiments and modeling of membrane microreactors. Catal Today 2005, 110:26-37.
120. Zhang X., Stefanick S., Villani F.J. Application of Microreactor technology in Process Development. Org Proc Res Dev 2004, 8:455-460.
121. Zhang Y., Gwak J., Murakoshi Y., Ikehara T., Maeda R., Nishimura C. Hydrogen permeation characteristics of thin Pd membrane prepared by microfabrication technology. J Membrane Sci 2006, 277:203-209.
122. Zhou W., Tang Y., Pan M., Wei X., Chen H., Xiang J. A performance study of methanol steam reforming microreactor with porous copper fibre sintered felt as catalyst support for fuel cells. Int J Hydrogen Energy 2009, 4:9745-9753.