Effect of Promotion with Sn on Supported Pt Catalysts for CO2Reforming of CH4

The reforming of CH4with CO2(dry reforming) was studied at 800°C over SiO2and ZrO2supported Pt–Sn catalysts. Several preparation methods were investigated. It was found that the Pt/ZrO2catalyst had much higher activity and stability than the Pt/SiO2catalyst due to the ability of the ZrO2to promote CO2dissociation. On this catalyst, the decomposition of CH4and the dissociation of CO2occur via two independent pathways. The long-term activity of the catalyst is dependent upon the balance between the rate of CH4decomposition and the rate of cleaning of carbonaceous deposits. The co-impregnation of Sn and Pt on the ZrO2results in lower activity and stability than the monometallic catalysts. Depending on the reaction conditions, disruption of the Pt–Sn alloys may occur, causing deposition of tin oxide that inhibits the role of the ZrO2. Special preparation methods can result in the controlled placement of Sn on the Pt particle, minimizing the promoter–support interaction. These catalysts exhibit higher activity and stability than the monometallic catalyst under severely deactivating conditions, 800°C, and a 3 : 1 ratio of CH4: CO2. It is possible to deposit Sn onto Pt/ZrO2catalysts in a manner which reduces carbon deposition without inhibiting the beneficial role of the support.

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

[2]  F. Solymosi,et al.  Catalytic reaction of CH4 with CO2 over alumina-supported Pt metals , 1991 .

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

[4]  J. Dumesic,et al.  L-zeolite-supported platinum and platinum/tin catalysts for isobutane dehydrogenation , 1995 .

[5]  J. Lapszewicz,et al.  Study of mixed steam and CO2 reforming of CH4 to syngas on MgO-supported metals , 1994 .

[6]  J. H. Edwards,et al.  The chemistry of methane reforming with carbon dioxide and its current and potential applications , 1995 .

[7]  J. Lercher,et al.  Problem of coke formation on Ni/ZrO2 catalysts during the carbon dioxide reforming of methane , 1994 .

[8]  C. Mirodatos,et al.  Methane reforming reaction with carbon dioxide over Ni/SiO2 Catalyst. I. Deactivation studies , 1996 .

[9]  X. Verykios,et al.  Reforming of methane with carbon dioxide to synthesis gas over supported Rh catalysts , 1994 .

[10]  Julian R.H. Ross,et al.  The catalytic conversion of natural gas to useful products , 1996 .

[11]  D. Resasco,et al.  Isobutane Dehydrogenation on Pt–Sn/SiO2Catalysts: Effect of Preparation Variables and Regeneration Treatments , 1997 .

[12]  Julian R.H. Ross,et al.  TAP Investigations of the CO2 Reforming of CH4 over Pt/ZrO2 , 1997 .

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

[14]  N. Ostrovskii,et al.  Propane dehydrogenation over Pt-Sn catalysts , 1992 .

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

[16]  L. Schmidt,et al.  Microstructures of Pt-Sn and Rh-Sn particles on SiO2☆ , 1991 .

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

[18]  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 .

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

[20]  W. Sachtler,et al.  Potential of zeolite supported rhodium catalysts for the CO2 reforming of CH4 , 1997 .

[21]  O. Krylov,et al.  Heterogeneous catalytic reactions of carbon dioxide , 1995 .

[22]  M. Bradford,et al.  CO2Reforming of CH4over Supported Pt Catalysts , 1998 .

[23]  Daniel E. Resasco,et al.  Effects of promoters and supports on coke formation on Pt catalysts during CH4 reforming with CO2 , 1997 .

[24]  A. Holmen,et al.  Propane dehydrogenation over supported platinum catalysts: effect of tin as a promoter , 1995 .

[25]  J. Bitter,et al.  The state of Zirconia Suported Platinum Catalysts for CO2/CH4 Reforming , 1997 .

[26]  J. R. Rostrup-Nielsen,et al.  Aspects of CO2-reforming of Methane , 1994 .

[27]  H. Verbeek,et al.  The study of the alloys of platinum and tin by chemisorption , 1976 .

[28]  D. Hercules,et al.  Infrared and carbon dioxide chemisorption study of Mo/ZrO2 catalysts , 1995 .

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

[30]  P. Ross.  Trends in the bonding of CO to the surfaces of Pt3M alloys (M=Ti, Co, and Sn) , 1992 .