Deactivation of Ni catalysts during methane autothermal reforming with CO2 and O2 in a fluidized-bed reactor

A series of different-sized Ni catalysts (4.5–45.0 nm) were prepared and used for methane autothermal reforming with CO2 and O2 in a fluidized-bed reactor. It was found that the activity and stability of Ni catalysts depend strongly on the particle size and the operating space velocity. Small sized Ni is more active and stable at space velocity <54,000 h−1. Characterizations disclosed that methane decomposition rate decreases with the enlarging Ni particle size, and some of the surface carbons (derived from methane decomposition) are inactive in CO2 atmosphere. As the methane decomposition rate slows on larger Ni particles and at higher space velocity to ensure complete conversion of the oxygen, surface Ni will be gradually oxidized by remaining O2, leading to Ni deactivation.

[1]  M. Che,et al.  Control of Dispersion of Ni2+ Ions via Chelate Ligands in the Preparation of Ni/SiO2 Materials. A XAFS Study , 1998 .

[2]  T. Yashima,et al.  Carbon deposition on meso-porous Al2O3 supported Ni catalysts in methane reforming with CO2 , 2005 .

[3]  S. Neophytides,et al.  Dissociative adsorption of CH4 on NiAu/YSZ: The nature of adsorbed carbonaceous species and the inhibition of graphitic C formation , 2006 .

[4]  V. Choudhary,et al.  High-temperature stable and highly active/selective supported NiCoMgCeOx catalyst suitable for autothermal reforming of methane to syngas , 2005 .

[5]  J. Nørskov,et al.  Steam Reforming and Graphite Formation on Ni Catalysts , 2002 .

[6]  Johannes A. Lercher,et al.  Methane autothermal reforming with and without ethane over mono- and bimetal catalysts prepared from hydrotalcite precursors , 2005 .

[7]  F. M. Dautzenberg,et al.  Hydrogen production by coupled catalytic partial oxidation and steam methane reforming at elevated pressure and temperature , 2007 .

[8]  Jens R. Rostrup-Nielsen,et al.  Theoretical Studies of Stability and Reactivity of CHx Species on Ni(111) , 2000 .

[9]  K. Kunimori,et al.  Effect of Ni Loading on Catalyst Bed Temperature in Oxidative Steam Reforming of Methane over α-Al2O3-Supported Ni Catalysts , 2005 .

[10]  M. Schmal,et al.  Combination of carbon dioxide reforming and partial oxidation of methane over supported platinum catalysts , 2003 .

[11]  T. Yashima,et al.  Meso-porous Ni/Mg/Al catalysts for methane reforming with CO2 , 2004 .

[12]  Kenji Maruyama,et al.  Temperature profiles of alumina-supported noble metal catalysts in autothermal reforming of methane , 2004 .

[13]  Y. Matsuo,et al.  Autothermal CO2 reforming of methane over NiO–MgO solid solution catalysts under pressurized condition: Effect of fluidized bed reactor and its promoting mechanism , 2000 .

[14]  Chunshan Song,et al.  Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios , 2004 .

[15]  T. Yashima,et al.  Surface properties of a coke-free Sn doped nickel catalyst for the CO2 reforming of methane , 2004 .

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

[17]  T. Yashima,et al.  Small Amounts of Rh-Promoted Ni Catalysts for Methane Reforming with CO2 , 2003 .

[18]  Z. Hou,et al.  Syngas production from reforming of methane with CO2 and O2 over Ni/SrO–SiO2 catalysts in a fluidized bed reactor , 2004 .

[19]  K. Tomishige Syngas production from methane reforming with CO2/H2O and O2 over NiO–MgO solid solution catalyst in fluidized bed reactors , 2004 .

[20]  F. Mondragón,et al.  CO2 reforming of CH4 over La–Ni based perovskite precursors , 2006 .

[21]  Q. Jing,et al.  Combined Carbon Dioxide Reforming and Partial Oxidation of Methane to Syngas over Ni−La2O3/SiO2 Catalysts in a Fluidized-Bed Reactor , 2005 .