Low temperature-ethanol steam reforming over Ni-based catalysts supported on CeO2

  • Filomena Castaldo University of Salerno-Department of Industrial Engineering
  • Vincenzo Palma
  • Concetta Ruocco
  • Paolo Ciambelli
  • Gaetano Iaquaniello


Recent research has been focused on methods to produce hydrogen. There is growing interest in the properties ofhydrogen as an energy carrier and the prospects look good for hydrogen use in fuel cell applications, especially whenproduction processes involve clean, renewable sources.Although natural gas steam reforming is the most common way to obtain hydrogen, ethanol steam reforming (ESR)may reduce the dependence on fossil fuels and cut harmful emissions.The ESR reaction is promoted at high temperatures, being strongly endothermic, but in some cases it can be performedat low temperatures, using this process as a pre-reforming step before conventional methane steam reforming (MSR).The low temperature range could reduce: the thermal duty, costs and CO formation, making the produced hydrogencapable of being fed into a fuel cell.The performances of Ni-based catalysts for ethanol steam reforming in a low temperature range (LT-ESR) were evaluated.In particular, the activity of bimetallic samples, prepared by impregnation and coprecipitation, was monitoredin both diluted and concentrated feed stream conditions. By comparing bimetallic catalysts with monometallic onesprepared at dierent Pt or Ni loadings, it was possible to identify the most suitable sample. 3%wtPt / 10wt%Ni / CeO2obtained by impregnation achieved the highest performances in terms of both H2 yield and durability, allowing perfectagreement with thermodynamic data. However, during stability tests, reaction plugging phenomena occurred. By changingthe water-to-ethanol molar ratio from 3 to 6, a considerable increase in durability was observed. The investigationof exhaust catalysts through various characterization techniques was helpful for studying in detail possible sintering ordeactivation occurrence.

Author Biography

Filomena Castaldo, University of Salerno-Department of Industrial Engineering
Via casa rega 20, 83020, Domicella (AV), Italy


[1] Zhai X, Ding S, Liu Z, Jin Y, Cheng Y. Catalytic performance of Ni catalysts for steam reforming of methane at high space velocity. Int J Hydrogen Energy 2011;36:482-489
[2] Wang C-H, Ho K-F , Chiou JYZ, Lee C-L, Yang S-Y, Yeh C-T, Wang C-B. Catal Commun 2011;12:854–858
[3] Roh H-S, Eum I-H, Jeong D-W. Low temperature steam reforming of methane over NieCe(1-x)Zr(x)O2 catalysts under severe conditions. Renew Energy (2012)42:212-216
[4] Xu J, Froment GF. Methane steam reforming: II. Diffusional Limitations and Reactor Simulation. Aiche J 1989;35:97-103
[5] Abashar MEE. Coupling of steam and dry reforming of methane in catalytic &uidized bed membrane reactors. Int J of Hydrogen Energy 2004;29:799-808
[6] Kim H-W, Kang K-M, Kwak H-Y, Kim JH. Preparation of supported Ni catalysts on various metal oxides with core/shell structures and their tests for the steam reforming of methane. Chemical Engineering Journal 2011;168:775–783
[7] Ryi S-K, Park J-S, Kim D-K, Kim T-H, Kim S-H. Methane steam reforming with a novel catalytic nickel membrane for effective hydrogen production. Journal of Membrane Science 2009; 339:189–194
[8] Udani PPC., Gunawardana PVDS, Lee HC, Kim DH. Steam reforming and oxidative steam reforming of methanol over CuO–CeO2 catalysts. Int J Hydrogen Energy 2009;34:7648-7655
[9] Basagiannis AC, Verykios XE. Catalytic steam reforming of acetic acid for hydrogen production. Int J Hydrogen Energy 2007;32(25):3343-3355
[10] Takeishi K, Suzuki H. Steam reforming of dimethyl ether. Appl Catal A Gen 2004;260(1):111-117
[11] Kwak BS, Kim J, Kang M. Hydrogen production from ethanol steam reforming over core-shell structured NixOy-, FexOy-, and CoxOy-Pd catalysts. Int J Hydrogen Energy 2010;35:11829-11843
[12] Demirbas A. Biofuels sources, biofuel policy, biofuel economy and global biofuel projections. Energy Conversion and Management 2008;49:21062116
[13] Li M, Li S, Zhang C, Wang S, Ma X, Gong J. Ethanol steam reforming over Ni/NixMg1LxO: Inhibition of surface nickel species diffusion into the bulk. Int J Hydrogen Energy 2011; 36:326-332
[14] Liguras DK, Goundani K, Verykios XE.Production of hydrogen for fuel cells by catalytic partial oxidation of ethanol over structured Ni catalysts. Journal of Power Sources 2004;130:30–37
[15] Vasudeva K, Mitra N, Umasankar P, Dhingra SC. Steam reforming of ethanol for hydrogen production: thermodynamic analysis. Int J Hydrogen Energy 21996; 21:13-18
[16] Alberton AL, Souza MMVM, Schmal M. Carbon formation and its influence on ethanol steam reforming over Ni/Al2O3 catalysts. Catalysis Today 2007;123:257–264
[17] Rossi CCRS, Alonso CG, Antunes OAC, Guirardello R., Cardozo-Filho L. Thermodynamic analysis of steam reforming of ethanol and glycerine for hydrogen production. Int J Hydrogen Energy 2009;34:323-332
[18] Erdohelyi A, Rasko J, Kecskes T, Toth M, Domok M, Baan K. Hydrogen formation in ethanol reforming on supported noble metal catalysts. Catal Today 2006;116:367-376
[19] Hernįndez L, Kafarov V. Thermodynamic evaluation of hydrogen production for fuel cells by using bio-ethanol steam reforming: Effect of carrier gas addition. J of Power Sources 2009; 192:195-199
[20] Silveira JL, Braga LB, de Souza ACC, Antunes JS, Zanzi R. The benefits of ethanol use for hydrogen production in urban transportation. Renewable and Sustainable Energy Reviews 2009;13:2525–2534
[21] Roh H-S, Platon A, Wang Y, King DL Catalyst deactivation and regeneration in low temperature ethanol steam reforming with Rh/CeO2–ZrO2 catalysts. Catalysis Letters 2006a;110:1–2, DOI: 10.1007/s10562-006-0082-2
[22] Roh H-S, Wang Y, King DL, Platon A, Chin Y-H. Low temperature and H2 selective catalysts for ethanol steam reforming. Catalysis Letters 2006b;108:1–2, DOI: 10.1007/s10562-006-0021-2
[23] Boyano A, Blanco-Marigorta AM, Morosuk T, Tsatsaronis G. Exergoenvironmental analysis of a steam methane reforming process for hydrogen production. Energy 2011;36:2202-2214
[24] Harrison DP; Peng Z. Low carbon monoxide hydrogen by sorption-enhanced reaction. Int. J. Chem. React. Eng 2003;1:A37.
[25] Aneggi E, Boaro M, de Leitenburg C, Dolcetti G, Trovarelli A. Insights into the redox properties of ceria-based oxides and their implications in catalysis. Journal of Alloys and Compounds 2006;408–412:1096–1102
[26] Song H, Ozkan US. Changing the Oxygen Mobility in Co/Ceria Catalysts by Ca Incorporation: Implications for Ethanol Steam Reforming. J. Phys. Chem. A 2010;114: 3796–3801
[27] Llorca J, Homs N, Sales J, de la Piscina RP. Efficient production of hydrogen over supported cobalt catalysts from ethanol steam reforming. Journal of Catalysis 2002;209:306-317
[28] Aupretre F, Descorme C, Duprez D, Casanave D, Uzio D. Ethanol steam reforming over MgxNi1−xAl2O3 spinel oxide-supported h catalysts. Journal of Catalysis 2005;233:464 477
[29] Basagiannis AC, Panagiotopoulou P, Verykios X. Low Temperature Steam Reforming of Ethanol Over Supported Noble Metal Catalysts. Topics in Catalysis 2008;51: 2–12 DOI 10.1007/s11244-008-9130-z
[30] Yamazaki T, Naoko K, Katoh M, Hirose T, Saito H, Yoshikawa T, Mamoru W. Behavior of steam reforming reaction for bio-ethanol over Pt/ZrO2. catalysts. Applied Catalysis B: Environmental 2010;99: 81–88
[31] Fatsikostas AN, Kondarides DI, Verykios XE. Production of hydrogen for fuel cells by reformation of biomass-derived ethanol. Catalysis Today 2002;75:145-155.
[32] Sun J, Qiu X, Wu F, Zhu W. H2 from steam reforming of ethanol at low temperature over Ni/Y2O3, Ni/La2O3 and Ni/Al2O3 catalysts for fuelcell application. International Journal of Hydrogen Energy 2005;30: 437-445
[33] Benito M, Padilla R, Sanz JL, Daza L. Thermodynamic analysis and performance of a 1kW bioethanol processor for a PEMFC operation. Journal of Power Sources 2007;169:123–130
[34] Mariño F, Baronetti G, Jobbagy M, Laborde M. Cu-Ni-K/-Al2O3 supported catalysts for ethanol steam reforming. Formation of hydrotalcitetype compounds as a result of metal–support interaction. Appl Catal A Gen 2003;238:41–54
[35] Furtado AC, Gonc C, Alonso CG, Cantao MP, Fernandes-Machado N.R.C. Bimetallic catalysts performance during ethanol steam reforming: Influence of support materials. International Journal of Hydrogen Energy 2009;34:7189-7196
[36] Vizcaino AJ, Carrero A, Calles JA. Ethanol steam reforming on Mg- and Ca-modified Cu–Ni/SBA-15 catalysts. Catalysis Today 2009;146:63–70
[37] Men Y, Kolb G, Zapf R, Hessel V, Loewe H. Ethanol steam reforming in a microchannel reactor. Process Safety and Environmental Protection 2007;85(B5):413-418
[38] Ruggiero A. PhD Thesis. University of Salerno 2009
[39] Banach B, Machocki A, Rybak P, Denis A, Grzegorczyk W, Gac W. Selective production of hydrogen by steam reforming of bio-ethanol. Catalysis Today 2011;176:28– 35
[40] Ciambelli P, Palma V, Ruggiero A. Low temperature catalytic steam reforming of ethanol. 1. The effect of the support on the activity and stability of Pt catalysts. Applied Catalysis B: Environmental 2010; 96:18–27
[41] Heracleous E, Leeb AF, Wilson K,.Lemonidou AA. Investigation of Ni-based alumina-supported catalysts for the oxidative dehydrogenation of ethane to ethylene: structural characterization and reactivity studies. Journal of Catalysis 2005;231:159–171
[42] Das D, Veziroglu TN. Hydrogen Production by Biological Processes: A Survey of Literature. International Journal of Hydrogen Energy 2001;26:13-28
[43] Jacobs G, Keogh RA, Davis BH. Steam reforming of ethanol over Pt/ceria with co-fed hydrogen. Journal of Catalysis 2007;245:326-337.
[44] Paryjczak T, Rynkowski J, Karski S. Thermoprogrammed reduction of cobalt oxide. Journal of Chromatography A 1980;188:254-256
[45] de Leitenburg C, Trovarelli A, Kasˇpar J. A temperatureprogrammed
and transient kinetic study of CO2 activation and methanation over CeO2 supported noble metals. J Mol Catal 1977;166:98–107
[46] Lin SS-Y, Daimon H, Ha SY. Co/CeO2-ZrO2 catalysts prepared by impregnation and coprecipitation for ethanol steam reforming. Appl Catal A 2009;366:252–261
[47] McCabe RW, Wong C, Woo HS. The passivating oxidation of platinum. J Catal 1988;114:354–367
[48] Galetti AE, Gomez MF, Arrua LA, Abello MC. Ethanol steam reforming over Ni/ZnAl2O4-CeO2. Influence of calcination atmosphere and nature of catalytic precursor. Applied Catalysis A: General 2011;408:78– 86
[49] Wang W, Wang Y. Steam reforming of ethanol to hydrogen over nickel metal catalysts. Int. J. Energy Res. 2010;34:1285–1290
How to Cite
CASTALDO, Filomena et al. Low temperature-ethanol steam reforming over Ni-based catalysts supported on CeO2. Journal of Power Technologies, [S.l.], v. 95, n. 1, p. 54--66, mar. 2015. ISSN 2083-4195. Available at: <https://papers.itc.pw.edu.pl/index.php/JPT/article/view/441>. Date accessed: 25 apr. 2024.
Renewable and Sustainable Energy


bimetallic catalysts; bio-ethanol; hydrogen; steam reforming

Most read articles by the same author(s)

Obs.: This plugin requires at least one statistics/report plugin to be enabled. If your statistics plugins provide more than one metric then please also select a main metric on the admin's site settings page and/or on the journal manager's settings pages.