Metallic Ni monolith–Ni/MgAl2O4 dual bed catalysts for the autothermal partial oxidation of methane to synthesis gas

Abstract A dual bed catalyst system consisting of a metallic Ni monolith catalyst in the front followed by a supported nickel catalyst Ni/MgAl 2 O 4 has been studied for the autothermal partial oxidation of methane to synthesis gas. The effects of bed configuration, reforming bed length, feed temperature and gas hourly space velocity on the reaction as well as the stability are investigated. The results show that the metallic Ni monolith in the front functions as the oxidation catalyst, which prevents the exposure of the reforming catalyst in the back to the very high temperature, while the supported Ni/MgAl 2 O 4 in the back functions as the reforming catalyst which further increases the methane conversion by 5%. A typical 5 mmNi monolith–5mmNi/MgAl 2 O 4 dual bed catalyst exhibits methane conversion and hydrogen and carbon monoxide selectivities of 85.3%, 91.5% and 93.0%, respectively, under autothermal conditions at a methane to oxygen molar ratio of 2.0 and gas hourly space velocity of 1.0 × 10 5  h −1 . The dual bed catalyst system is also very stable.

[1]  C. J. Bell,et al.  Effect of Relative Bed Lengths on a Platinum/Nickel Stratified Dual Bed Catalyst for the Catalytic Partial Oxidation of Methane at Millisecond Contact Times , 2007 .

[2]  Kenneth A. Williams,et al.  Spatial and temporal profiles in millisecond partial oxidation processes , 2006 .

[3]  T. Choudhary,et al.  Energy-efficient syngas production through catalytic oxy-methane reforming reactions. , 2008, Angewandte Chemie.

[4]  C. Leclerc,et al.  A dual catalyst bed for the autothermal partial oxidation of methane to synthesis gas , 2005 .

[5]  L. Schmidt,et al.  Production of Syngas by Direct Catalytic Oxidation of Methane , 1993, Science.

[6]  Yaquan Wang,et al.  Partial oxidation of methane to syngas over nickel monolithic catalysts , 2006 .

[7]  Kenneth A. Williams,et al.  Rapid lightoff of syngas production from methane: A transient product analysis , 2005 .

[8]  L. Schmidt,et al.  Comparison of monolith-supported metals for the direct oxidation of methane to syngas , 1994 .

[9]  Pio Forzatti,et al.  Catalytic partial oxidation of methane over a 4% Rh/α-Al2O3 catalyst Part II: Role of CO2 reforming , 2008 .

[10]  J. R. Engel,et al.  Catalytic partial oxidation of methane using RhSr- and Ni-substituted hexaaluminates , 2007 .

[11]  Malcolm L. H. Green,et al.  Partial oxidation of methane to synthesis gas , 1990 .

[12]  J. Yun,et al.  Inside Cover: Catalytic Asymmetric Boration of Acyclic α,β‐Unsaturated Esters and Nitriles (Angew. Chem. Int. Ed. 1/2008) , 2008 .

[13]  Götz Veser,et al.  A counter-current heat-exchange reactor for high temperature partial oxidation reactions: I. Experiments , 1999 .

[14]  Xiong Yin,et al.  Asymmetric Tubular Oxygen-Permeable Ceramic Membrane Reactor for Partial Oxidation of Methane , 2007 .

[15]  T. Rirksomboon,et al.  Methane partial oxidation over Ni/CeO2–ZrO2 mixed oxide solid solution catalysts , 2004 .

[16]  L. Schmidt,et al.  The Effect of Ceramic Supports on Partial Oxidation of Hydrocarbons over Noble Metal Coated Monoliths , 1998 .

[17]  S. Reyes,et al.  Evolution of Processes for Synthesis Gas Production: Recent Developments in an Old Technology , 2003 .

[18]  A. J. Murrell,et al.  Selective oxidation of methane to synthesis gas using transition metal catalysts , 1990, Nature.

[19]  Bingbing Li,et al.  Zirconia promoted metallic nickel catalysts for the partial oxidation of methane to synthesis gas , 2009 .

[20]  V. Choudhary,et al.  Oxidative Conversion of Methane to Syngas over Nickel Supported on Commercial Low Surface Area Porous Catalyst Carriers Precoated with Alkaline and Rare Earth Oxides , 1997 .

[21]  Enrique Iglesia,et al.  Structural requirements and reaction pathways in methane activation and chemical conversion catalyzed by rhodium , 2004 .

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

[23]  L. Lefferts,et al.  Dual catalyst bed concept for catalytic partial oxidation of methane to synthesis gas , 2004 .

[24]  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 .

[25]  Malcolm L. H. Green,et al.  Brief Overview of the Partial Oxidation of Methane to Synthesis Gas , 2003 .

[26]  Yutaek Seo,et al.  A highly effective and stable nano-sized Ni/MgO–Al2O3 catalyst for gas to liquids (GTL) process , 2008 .

[27]  D. Trimm,et al.  Alternative catalyst bed configurations for the autothermic conversion of methane to hydrogen , 1996 .

[28]  T. Choudhary,et al.  Methane reforming over a high temperature stable-NiCoMgOx supported on zirconia–hafnia catalyst , 2006 .

[29]  Yaquan Wang,et al.  Yttrium-stabilized zirconia-promoted metallic nickel catalysts for the partial oxidation of methane to hydrogen , 2009 .

[30]  L. Schmidt,et al.  Effects of H2O and CO2 addition in catalytic partial oxidation of methane on Rh , 2009 .

[31]  W. Li,et al.  Partial oxidation of methane to syngas over BaTi1 − xNixO3 catalysts , 2004 .

[32]  T. Choudhary,et al.  Partial oxidation of methane to syngas with or without simultaneous steam or CO2 reforming over a high-temperature stable-NiCoMgCeOx supported on zirconia–hafnia catalyst , 2006 .

[33]  G. Veser,et al.  Catalytic Partial Oxidation of Methane: Is a Distinction between Direct and Indirect Pathways Meaningful? , 2007 .

[34]  C. Leclerc,et al.  Metal oxides as combustion catalysts for a stratified, dual bed partial oxidation catalyst , 2007 .

[35]  Malcolm L. H. Green,et al.  Methane Oxyforming for Synthesis Gas Production , 2007 .

[36]  Gbmm Guy Marin,et al.  The Reaction Mechanism of the Partial Oxidation of Methane to Synthesis Gas: A Transient Kinetic Study over Rhodium and a Comparison with Platinum , 1997 .