Ni, Co and bimetallic Ni–Co catalysts for the dry reforming of methane

Abstract Alumina supported Ni, Co and bimetallic Ni–Co catalysts (with 9 wt.% nominal metal content) have been prepared, characterized and tested for the dry reforming of methane. For catalysts characterization the following techniques have been used: Atomic Absorption Spectroscopy (ICP-AES), Transmission Electron Microscopy (TEM), Temperature Programmed Reduction (TPR-H2) and Temperature Programmed Oxidation (TPO). The dry reforming of methane was carried out at 973 K using a mixture CH4:CO2 (1:1). Among the catalysts studied, those with the highest cobalt content (Co(9) and NiCo(1–8)) are the most active and stable, but they produce a large amount of carbon. The higher activity exhibited by cobalt rich catalysts is related with the higher activity of this metal for methane decomposition, while their remarkable stability seems to be due to the presence of large particles involved in long-term conversion, because they produce non-deactivating carbon deposits.

[1]  M. Goldwasser,et al.  New Co-Ni catalyst systems used for methane dry reforming based on supported catalysts over an INT-MM1 mesoporous material and a perovskite-like oxide precursor LaCo0.4Ni0.6O3 , 2005 .

[2]  M. Illán-Gómez,et al.  Effect of potassium content in the activity of K-promoted Ni/Al2O3 catalysts for the dry reforming of methane , 2006 .

[3]  F. Frusteri,et al.  Alkali promotion of Ni/MgO catalysts , 1999 .

[4]  A. Dalai,et al.  Effects of metal content on activity and stability of Ni-Co bimetallic catalysts for CO2 reforming of CH4 , 2008 .

[5]  Peng Wang,et al.  Autothermal reforming of CH4 over supported Ni catalysts prepared from Mg–Al hydrotalcite-like anionic clay , 2004 .

[6]  M. Illán-Gómez,et al.  Nickel catalyst activation in the carbon dioxide reforming of methane: Effect of pretreatments , 2009 .

[7]  R. Baker,et al.  Catalytic growth of carbon filaments , 1989 .

[8]  Gen-hui Xu,et al.  Non-thermal plasma approaches in CO2 utilization , 1999 .

[9]  E. Tanabe,et al.  Formation of highly concentrated hydrogen through methane decomposition over Pd-based alloy catalysts , 2006 .

[10]  N. Nichio,et al.  Role of chromium in the stability of Ni/Al2O3 catalysts for natural gas reforming , 2000 .

[11]  Kevin J. Smith,et al.  A kinetic model of CH4 decomposition and filamentous carbon formation on supported Co catalysts , 2005 .

[12]  Jens R. Rostrup-Nielsen,et al.  CO2-Reforming of Methane over Transition Metals , 1993 .

[13]  G. Ertl,et al.  Catalytic oxidation of CO on Pt(111): The influence of surface defects and composition on the reaction dynamics , 1984 .

[14]  Yun Hang Hu,et al.  Role of support in CO2 reforming of CH4 to syngas over Ni catalysts , 1996 .

[15]  Jin-Hong Kim,et al.  Effect of metal particle size on coking during CO2 reforming of CH4 over Ni–alumina aerogel catalysts , 2000 .

[16]  K. Takanabe,et al.  Influence of the reduction temperature on catalytic activity of Co/TiO2 (anatase-type) for high pressure dry reforming of methane , 2003 .

[17]  K. L. Tan,et al.  CO2 Reforming of Methane to Synthesis Gas over Sol–Gel-made Ni/γ-Al2O3 Catalysts from Organometallic Precursors , 2000 .

[18]  V. Gunaseelan Anaerobic digestion of biomass for methane production: A review , 1997 .

[19]  Toshiaki Mori,et al.  Intermediate hydrocarbon species for the CO2-CH4 reaction on supported Ni catalysts , 1994 .

[20]  M. Illán-Gómez,et al.  Catalytic activity and characterization of Ni/Al2O3 and NiK/Al2O3 catalysts for CO2 methane reforming , 2004 .

[21]  M. Bradford,et al.  CO2 Reforming of CH4 , 1999 .

[22]  A. Dalai,et al.  Development of stable bimetallic catalysts for carbon dioxide reforming of methane , 2007 .

[23]  J. Santamaría,et al.  Deactivation by coking and poisoning of spinel-type Ni catalysts , 1997 .

[24]  E. Ruckenstein,et al.  Carbon dioxide reforming of methane over nickel alkaline earth metal oxide catalysts , 1995 .

[25]  K. Takanabe,et al.  Modification of Co/TiO2 for dry reforming of methane at 2 MPa by Pt, Ru or Ni , 2004 .

[26]  T. Horiuchi,et al.  Highly hydrogen-deficient hydrocarbon species for the CO2-reforming of CH4 on Co/Al2O3 catalyst , 1995 .

[27]  Huaiyong Zhu,et al.  New nickel catalysts supported on highly porous alumina intercalated laponite for methane reforming with CO2 , 2001 .

[28]  K. Takanabe,et al.  Titania-supported cobalt and nickel bimetallic catalysts for carbon dioxide reforming of methane , 2005 .

[29]  M. Beller,et al.  Facile catalytic coupling of aryl bromides with terminal alkynes by phospha-palladacycles , 1996 .

[30]  E. Ruckenstein,et al.  Carbon Deposition and Catalytic Deactivation during CO2 Reforming of CH4 over Co/γ-Al2O3 Catalysts , 2002 .

[31]  A. Lemonidou,et al.  Carbon dioxide reforming of methane over 5 wt.% nickel calcium aluminate catalysts – effect of preparation method , 1998 .

[32]  Tetsuya Shishido,et al.  Preparation of egg-shell type Ni-loaded catalyst by adopting “Memory Effect” of Mg–Al hydrotalcite and its application for CH4 reforming , 2004 .