Methanol steam reforming; Effects of various metal oxides on the properties of a Cu-based catalyst

Document Type : Research Paper


1 Faculty of Chemistry and Chemical Engineering, Malek Ashtar University of Technology, Lavizan, P.O. Box 15875-1774, Tehran, Iran

2 malek ashtar university

3 Department of chemical technologies, Iranian Research Organization for Science & Technology (IROST), Tehran, Iran


Ternary Cu/ZnO/metal oxide catalysts are prepared through the co-precipitation method under strict control of parameters like pH, calcination conditions, and precipitation temperature in a systematic manner. The metal oxides applied in this study consist of Al2O3, ZrO2, La2O3 and Ce2O3. The distinction of this work in comparison with similar research is a comprehensive investigatation of the catalytic properties of metal oxides (including conversion, selectivity and stability) which have the potential for use in the methanol steam reforming process. The catalysts are characterized through XRD, SEM and BET. The prepared catalysts are applied in methanol steam reforming in a fixed bed reactor. A TGA analysis  performed for all four catalysts  determined that the Ce2O3 and ZrO2 metal oxide catalysts showed the best results in  terms of stability with a coke formation of 0.7wt% and 0.8wt%, respectively; and maximum surface area is related to Cu/ZnO/Ce2O3, which can result in excellent stability and Cu dispersion. Overall, the obtained results indicate that the ZrO2 metal oxide catalyst is the best candidate to be applied in methanol steam reforming due to its higher activity, selectivity and yield. The hydrogen selectivity and yield of Cu/ZnO/ZrO2 after 6 hours of experiment were 80.02% and 46.4%, respectively.


Main Subjects

[1] Sopian K., Daud W.R.W. "Challenges and future developments in proton exchange membrane fuel cells, Renew", Energy, 2006, 31 :719.
[2] Kamarudin S.K., Daud W.R.W., Yaakub Z., Misron Z., Anuar W, Yusuf N.A.N.N. "Synthesis and optimization of future hydrogen energy infrastructure planning in Peninsular Malaysia", Int. J. Hydrogen Energy, 2009, 34: 2077.
[3] Kamarudin S.K., Daud W.R.W., Som M.A., Takriff M.S., Mohammad A.W., Loke Y.K. "Design of a fuel processor unit for PEM fuel cell via shortcut design method", Chem. Eng. J., 2004, 104: 7.
[4] Perez-Hernandez R., Gutierrez-Martınez A., Palacios J., Vega-Hernandez M., Rodrıguez-Lugo V. "Hydrogen production by oxidative steam reforming of methanol over Ni/CeO2eZrO2 catalysts", Int. J. Hydrogen Energy, 2011, 36: 6601.
[5] Kamarudin S.K., Daud W.R.W., Som M.A., Takriff M.S., Mohammad A.W. "Technical design and economic evaluation of a PEM fuel cell system", J. Power Souces, 2006, 157: 641.
[6] McNicol B.D., Rand D.A.J., Williams K.R. Fuelcells for road transport purposes yes or no", J. Power Sources, 2001, 100: 47.
[7] Emonts B., Bogild Hansen J., Grube T., Hohlein B., Peters R., Schmidt H. "Operational experience with the fuel processing system for fuel cell drives", J. Power Sources, 2002, 106: 333.
[8] Lindstrom B., Pettersson L.J. "Steam reforming of methanol over copper-based monoliths: the effects of zirconia doping", J. Power Sources, 2002, 106: 264.
[9] Pettersson L.J., Westerholm R. "State of the art of multi-fuelreformer for fuel cell vehicles: problem identification andresearch needs", Int. J. Hydrogen Energy, 2001, 26 : 243.
[10] Lindstrom B., Pettersson L.J. "Deactivation of copper-based catalysts for fuel cell applications", Catal.Lett., 2001, 74 :27.
[11] Yong S.T., Ooi C.W., Chai S.P., Wub X.S. "Review of methanol reforming-Cu-based catalysts, surface reaction mechanisms, and reaction schemes", Int. J. Hydrogen Energy, 2013, 38: 1.
[12] Palo D.R., Dagle R.A., Holladay J.D. "Methanol steam reforming for hydrogen production", Chem. Rev., 2007, 107: 3992.
[13] Cubeiro M.L., Fierro J.L,G. "Selective production of hydrogen bypartial oxidation of methanol over ZnO-Supported palladium catalysts", J.Catal., 1998, 1: 150.
[14] Gunter M.M., Ressler T., Jentoft R.E., Bems B. "Redox behavior ofcopper oxide/zinc oxide catalysts in the steam reforming of methanol studied by in situ X-Ray diffraction and absorption Spectroscopy", J. Catal., 2001, 203: 133.
[15] Lindstrom B., Pettersson L.J. "Hydrogen generation by steam reforming of methanol over copper-based catalysts for fuel cell applications", Int. J. Hydrogen Energy 2001, 26: 923.
[16] Shen G.C., Fujita S., Matsumoto S., Takezawa N. "Steamreforming of methanol on binary Cu/ZnO catalysts: Effects ofpreparation condition upon precursors, surface-structure and catalytic activity", J. Mol. Catal. A: Chem., 1997, 124: 123.
[17] Lindstrom B., Pettersson L.J., Menon P.G. "Activity andcharacterization of Cu/Zn, Cu/Cr and Cu/Zr on γ-alumina formethanol reforming for fuel cell vehicles", Appl.Catal. A: Gen., 2002, 234: 111.
[18] Matter P.H., Ozkan U.S. "Effect of pretreatment conditions on Cu/Zn/Zr-based catalysts for the steam reforming of methanol to H2", J. Catal., 2005, 234: 463.
[19] Fuknaga T., Ryumon N., Ichikuni N., Shimazu S. "Characterizationof Cu-Mn-spinel catalyst for methanol steam reforming", Catal.Commun., 2009, 10: 1800.
[20] Zhang X.R., Shi P.F., Zhao J.X., Zhao M.Y., Liu C.T. "Productionof hydrogen for fuel cells by steam reforming of methanol on Cu/ZrO2/Al2O3 catalysts", Fuel Process. Technol., 2003, 83: 183.
[21] Huang G., Liaw B.J., Jhang C.J., Chen Y.Z. "Steam reforming ofmethanol over Cu/ZnO/CeO2/ZrO2/Al2O3 catalysts", Appl.Catal. A: Gen., 2009, 358: 7.
[22] Jones S.D., Hagelin-Weaver H.E. "Steam reforming of methanolover CeO2- and ZrO2-promoted Cu-ZnO catalysts supported onnanoparticle Al2O3", Appl.Catal. B: Environ., 2009, 90: 195.
[23] Matsumura Y., Ishibe H. "High temperature steam reforming of methanol over Cu/ZnO/ZrO2 catalysts", Appl.Catal. B: Environ., 2009, 91: 524.
[24] Udani P.P.C., Gunawardana P.V.D.S., Lee H.C., Kim D.H. "Steam reforming and oxidative steam reforming of methanol over CuO-CeO2 catalysts", Int. J. Hydrogen Energy, 2009, 34: 7648.
[25] Matter P.H., Braden D.J., Ozkan U.S. "Steam reforming of methanol to H2 over non-reduced Zr-containing CuO/ZnO catalysts", J. Catal., 2004, 223 :340.
[26] Agrell J., Birgersson H., Boutonnet M., Melian-Cabrer I., Navarro R.M., Fierro J.L.G. "Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and A12O3", J. Catal., 2003; 219 :389–403.
[27] Zhang X.R., Shi P.F. "Production of hydrogen by steam reformingof methanol on CeO2 promoted Cu/Al2O3 catalysts", J. Mol.Catal.A: Chem., 2003, 194: 99.
[28] Matsumura Y. "Stabilization of Cu/ZnO/ZrO2 catalyst for methanol steam reforming to hydrogen by co-precipitation on zirconia support", J. Power Sources, 2013, 238:109.