Supported nickel catalysts for carbon dioxide reforming of methane in plug flow and membrane reactors

Abstract The catalytic production of synthesis gas through methane reforming using carbon dioxide was studied in a plug flow reactor and a membrane reactor at atmospheric pressure over nickel supported on MgO and La 2 O 3 . The Ni 0.03 Mg 0.97 O and the Ni/La 2 O 3 catalysts exhibited high activity and gave conversions of methane at equilibrium levels in the plug flow mode of operation. Incorporation of a Vycor glass membrane in the reactor resulted in higher conversions than obtained in an identical plug flow reactor operated without diluent. The catalysts had low to moderate surface areas and low uptakes of H 2 and CO at room temperature. X-ray diffraction showed that there was no discernable change between the catalysts before and after reaction. Elemental analysis showed that there was little carbon deposited on the Ni 0.03 Mg 0.97 O catalyst but there was slight coking on the Ni/La 2 O 3 catalyst.

[1]  J. Lunsford,et al.  Are the equilibrium concentrations of carbon monoxide and hydrogen exceeded during the oxidation of methane over a nickel/ytterbium oxide catalyst? , 1993 .

[2]  M. Poirier,et al.  Partial oxidation of methane over ruthenium catalysts , 1993 .

[3]  K. Tomishige,et al.  Noble metal promoted Ni0.03Mg0.97O solid solution catalysts for the reforming of CH4 with CO2 , 1996 .

[4]  L. Schmidt,et al.  Production of Olefins by Oxidative Dehydrogenation of Propane and Butane over Monoliths at Short Contact Times , 1994 .

[5]  J. Hochmuth.  Catalytic partial oxidation of methane over a monolith supported catalyst , 1992 .

[6]  Sunny C. Jiang,et al.  Temporary carbon barriers in the preparation of H2-permselective silica membranes , 1995 .

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

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

[9]  Kamalesh K. Sirkar,et al.  Chapter 11 Analysis and design of membrane permeators for gas separation , 1995 .

[10]  Malcolm L. H. Green,et al.  MOLYBDENUM AND TUNGSTEN CARBIDES AS CATALYSTS FOR THE CONVERSION OF METHANE TO SYNTHESIS GAS USING STOICHIOMETRIC FEEDSTOCKS , 1997 .

[11]  Sang-Eon Park,et al.  Catalytic activity and coke resistance in the carbon dioxide reforming of methane to synthesis gas over zeolite-supported Ni catalysts , 1996 .

[12]  Cocurrent membrane reactors vs. PFRs for shifting dehydrogenation equilibrium , 1997 .

[13]  V. Choudhary,et al.  Nonequilibrium Oxidative Conversion of Methane to CO and H2 with High Selectivity and Productivity over Ni/Al2O3 at Low Temperatures , 1993 .

[14]  A. Gadalla,et al.  The role of catalyst support on the activity of nickel for reforming methane with CO2 , 1988 .

[15]  Calvin H. Bartholomew,et al.  The stoichiometry of hydrogen and carbon monoxide chemisorption on alumina- and silica-supported nickel , 1980 .

[16]  S. Vlaev,et al.  Gas-Liquid Mass Transfer in Stirred Non-Newtonian Corn-Starch Dispersions , 1994 .

[17]  T. Sodesawa,et al.  Catalytic reactions of hydrocarbon with carbon dioxide over metallic catalysts , 1984 .

[18]  C. Au,et al.  Pulse studies of CH4 interaction with NiO/Al2O3 catalysts , 1994 .

[19]  Malcolm L. H. Green,et al.  Partial oxidation of methane to synthesis gas using carbon dioxide , 1991, Nature.

[20]  Heinz Heinemann,et al.  Partial oxidation of methane to syngas over Co/MgO catalysts. Is it low temperature? , 1993 .

[21]  M. Dokiya,et al.  Catalytic Decomposition of Hydrogen Sulfide , 1978 .

[22]  E. Barrett,et al.  (CONTRIBUTION FROM THE MULTIPLE FELLOWSHIP OF BAUGH AND SONS COMPANY, MELLOX INSTITUTE) The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms , 1951 .

[23]  L. L. V. Reijen,et al.  The Structure and Activity of Metal-on-Silica Catalysts , 1958 .

[24]  Talbot A. Chubb,et al.  Characteristics of CO2CH4 reforming-methanation cycle relevant to the solchem thermochemical power system , 1980 .

[25]  Jong‐Ho Kim,et al.  The reaction of CO2 with CH4 to synthesize H2 and CO over nickel-loaded Y-zeolites , 1994 .

[26]  H. Yokokawa,et al.  Possibility for effective production of hydrogen from hydrogen sulfide by means of a porous Vycor glass membrane , 1981 .

[27]  X. Verykios,et al.  Reforming of Methane with Carbon Dioxide to Synthesis Gas over Supported Rhodium Catalysts: I. Effects of Support and Metal Crystallite Size on Reaction Activity and Deactivation Characteristics , 1996 .

[28]  William J. Koros,et al.  Membrane-based gas separation , 1993 .

[29]  Sang-Eon Park,et al.  Catalytic reforming of methane with carbon dioxide over pentasil zeolite-supported nickel catalyst , 1994 .

[30]  E. Ruckenstein,et al.  Pulse-MS study of the partial oxidation of methane over Ni/La2O3 catalyst , 1995 .

[31]  David L. Trimm,et al.  The Formation and Removal of Coke from Nickel Catalyst , 1977 .

[32]  T. R. Hughes,et al.  Flow Adsorption Method for Catalyst Metal Surface Measurements , 1962 .

[33]  C. Lund,et al.  Defining conditions where the use of porous membrane reactors can be justified solely on the basis of improved yield , 1997 .

[34]  Masato Machida,et al.  Promotion of hydrogen permeation on metal-dispersed alumina membranes and its application to a membrane reactor for methane steam reforming , 1994 .

[35]  M. Bradford,et al.  Catalytic reforming of methane with carbon dioxide over nickel catalysts I. Catalyst characterization and activity , 1996 .

[36]  Michael Tsapatsis,et al.  Structure and aging characteristics of H2-permselective SiO2-Vycor membranes , 1994 .

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

[38]  Ivar M. Dahl,et al.  Carbon dioxide reforming of methane over lanthanum-modified catalysts in a fluidized-bed reactor , 1994 .

[39]  S. Goto,et al.  Carbon Dioxide Reforming of Methane on Supported Nickel Catalysts , 1994 .

[40]  F. Frusteri,et al.  Temperature-programmed reduction study of NiO–MgO interactions in magnesia-supported Ni catalysts and NiO–MgO physical mixture , 1990 .

[41]  T. Sodesawa,et al.  Catalytic reaction of methane with carbon dioxide , 1979 .

[42]  A. Cheetham,et al.  Catalytic conversion of methane to synthesis gas over europium iridate, Eu2Ir2O7: Anin situ study by x-ray diffraction and mass spectrometry , 1991 .

[43]  M. Bradford,et al.  Catalytic reforming of methane with carbon dioxide over nickel catalysts II. Reaction kinetics , 1996 .

[44]  W. Maier,et al.  CO2-Reforming of Methane on Supported Rh and Ir Catalysts , 1996 .

[45]  J. Richardson,et al.  Carbon dioxide reforming of methane with supported rhodium , 1990 .

[46]  P. W. Selwood.  The chemisorptive bonding of hydrogen on nickel , 1976 .

[47]  V. Choudhary,et al.  NiO/CaO‐Catalyzed Formation of Syngas by Coupled Exothermic Oxidative Conversion and Endothermic CO2 and Steam Reforming of Methane , 1994 .

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

[49]  C. Mirodatos,et al.  Deactivation of supported nickel catalysts during the reforming of methane by carbon dioxide , 1994 .

[50]  M. Sommer,et al.  Carbon dioxide reforming of methane on nickel catalysts , 1989 .

[51]  T. Tsotsis,et al.  The Enhancement of Reaction Yield Through the Use of High Temperature Membrane Reactors , 1993 .

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

[53]  S. Kitao,et al.  Gas Separation Performance of Thin Porous Silica Membrane Prepared by Sol-Gel and CVD Methods , 1992 .

[54]  J. Lunsford,et al.  Partial oxidation of methane to carbon monoxide and hydrogen over a Ni/Al2O3 catalyst , 1991 .

[55]  Gao Qing Lu,et al.  Carbon Dioxide Reforming of Methane To Produce Synthesis Gas over Metal-Supported Catalysts: State of the Art , 1996 .

[56]  K. Omata,et al.  Reduction of Carbon Dioxide by Methane with Ni-on-MgO-CaO Containing Catalysts , 1992 .

[57]  X. Verykios,et al.  Carbon dioxide reforming of methane to synthesis gas over Ni/La2O3 catalysts , 1996 .

[58]  F. Solymosi,et al.  Activation of CH4 and Its Reaction with CO2 over Supported Rh Catalysts , 1993 .

[59]  J. Armor,et al.  Catalysis with permselective inorganic membranes , 1989 .

[60]  J. Falconer,et al.  Chapter 14 Catalytic membrane reactors , 1995 .

[61]  V. Choudhary,et al.  Low-temperature selective oxidation of methane to carbon monoxide and hydrogen over cobalt-MgO catalysts , 1992 .

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