Evaluation of the performance of Ni/La 2 O 3 catalyst prepared from LaNiO 3 perovskite-type oxides for the production of hydrogen through steam reforming and oxidative steam reforming of ethanol Sania M. de Lima a,1 , Adriana M. da Silva a , Lı ´dia O.O. da Costa a , Jose ´ M. Assaf b , Gary Jacobs c , Burtron H. Davis c , Lisiane V. Mattos a,2 , Fa ´ bio B. Noronha a, * a Instituto Nacional de Tecnologia - INT, Av. Venezuela 82, CEP 20081-312, Rio de Janeiro, Brazil b Universidade Federal de Sa˜o Carlos - UFSCar, Laborato ´rio de Cata ´lise, Via Washington Luiz, Km 235, CEP 13565-905, Sa ˜o Carlos, Brazil c Center for Applied Energy Research, The University of Kentucky, 2540 Research Park Drive, Lexington, KY 40511, USA 1. Introduction The development of new processes for the production of chemicals and fuels from biomass requires new catalysts tailored to convert these feedstocks with high conversion rates, selectiv- ities, and stabilities. Hydrogen emerges as an energy carrier with high potential and if produced from renewable sources, may contribute to the sustainable production of energy, as it can be directly converted electrochemically in PEM fuel cells to produce electricity for use in transportation applications and portable power devices. Hydrogen can be produced through the steam reforming of biomass-derived liquids such as bioethanol, a water and ethanol mixture that may be obtained by biomass fermenta- tion [1–3]. However, there are currently no viable commercial catalysts for bio-ethanol steam reforming. Different catalysts, including metal oxides [4–7], mixed metal oxides [8–10], supported base metals (Ni, Co, Cu) [11–20] and supported noble metals (Pd, Pt, Rh, Ru, Ir) [21–30], have been extensively studied for the steam reforming (SR), partial oxidation (POX) and oxidative steam reforming (OSR) of ethanol. In spite of their lower activity relative to supported metal catalysts, metal oxides are capable of producing hydrogen free of CO as well as carbon deposits, depending on the reaction conditions used [19,26]. However, a wide range of undesirable by-products (e.g., ethene, acetaldehyde and acetone) is formed during steam reforming of ethanol over metal oxides in compari- son with supported metal catalysts, depending on the metal oxide properties. Supported metal catalysts are more active and selective to hydrogen than metal oxides but they undergo significant losses in activity with time on stream (TOS) [6,29]. Catalyst deactivation during ethanol conversion reactions may be associated with:  metal particle sintering;  metal oxidation (mainly for Co- and Ni-based catalysts);  carbon deposition, including both filamentous carbon and amorphous carbon covering the metallic particle and the support. The type of carbon formed and the mechanism of catalyst deactivation depends on the nature of the metal employed. Applied Catalysis A: General 377 (2010) 181–190 ARTICLE INFO Article history: Received 8 October 2009 Received in revised form 15 January 2010 Accepted 26 January 2010 Available online 2 February 2010 Keywords: Perovskite-type oxides Hydrogen production Ethanol steam reforming Ethanol oxidative steam reforming Deactivation mechanism Nickel catalyst ABSTRACT This paper studies the performance of LaNiO 3 perovskite-type oxide precursor as a catalyst for both steam reforming and oxidative steam reforming of ethanol. According to results of temperature- programmed desorption of adsorbed ethanol and by carrying out diffuse reflectance infrared Fourier transform spectroscopy analyses of ethanol steam reforming, ethanol decomposes to dehydrogenated species like acetaldehyde and acetyl, which at moderate temperatures, convert to acetate by the addition of hydroxyl groups. Demethanation of acetate occurs at higher temperatures, leading to a steady state coverage of carbonate. Catalyst deactivation occurs from the deposition of carbon on the surface of the catalyst. Both thermogravimetric and scanning electron microscopy analyses of postreaction samples indicate that lower reaction temperatures and lower H 2 O/EtOH ratios favor the deposition of filamentous carbon. However, less carbon formation occurs when the H 2 O/EtOH ratio is increased. Increasing reaction temperature or including O 2 in the feed suppresses filamentous carbon formation. ß 2010 Elsevier B.V. All rights reserved. * Corresponding author. Tel.: +55 21 2123 1177; fax: +55 21 2123 1051. E-mail address: fabio.bellot@int.gov.br (F.B. Noronha). 1 Present Address: Universidade Estadual do Oeste do Parana ´ - Unioeste, Campus de Toledo, Rua da Faculdade, 645, Jd. La Salle, CEP 85903-000, Toledo - Brazil. 2 Present Address: Universidade Federal Fluminense, Rua Passo da Pa ´ tria, 156, Nitero ´ i, RJ CEP 24210-240, Brazil. Contents lists available at ScienceDirect Applied Catalysis A: General journal homepage: www.elsevier.com/locate/apcata 0926-860X/$ – see front matter ß 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2010.01.036