Fischer−Tropsch Kinetic Studies with Cobalt−Manganese Oxide Catalysts

An investigation was undertaken to establish the reaction mechanism for the Fischer−Tropsch reaction, in the presence of the water−gas shift reaction, over a cobalt−manganese oxide catalyst under conditions favoring the formation of gaseous, liquid, and solid (waxes) hydrocarbons (210−250 °C and 6−26 bar). A micro-fixed-bed reactor was used with a cobalt−manganese oxide catalyst prepared by a coprecipitation method. An integral reactor model involving both Fischer−Tropsch and water−gas shift reaction kinetics was used to describe the overall performance. Reaction rate equations based on Langmuir−Hinshelwood−Hougen−Watson models for the Fischer−Tropsch reaction (hydrocarbon forming) and empirical reaction rate equations for the water−gas shift reaction from the literature were tested. Different combinations of the reaction rate equation were evaluated with the aid of a nonlinear regression procedure. It was found that a reaction rate equation for the Fischer−Tropsch reaction based on the enolic theory perf...

[1]  M. Dry Advances in Fishcher-Tropsch Chemistry , 1976 .

[2]  Gilbert F. Froment,et al.  Kinetics of the Fischer-Tropsch reaction on a precipitated promoted iron catalyst. 2. Kinetic modeling , 1993 .

[3]  Bruce A. Finlayson,et al.  Packed bed reactor analysis by orthogonal collocation , 1971 .

[4]  C. Satterfield,et al.  Some kinetic design considerations in the Fischer-Tropsch synthesis on a reduced fused-magnetite catalyst , 1984 .

[5]  L. Young,et al.  Axial Dispersion in Nonisothermal Packed Bed Chemical Reactors , 1973 .

[6]  Bohdan W. Wojciechowski,et al.  Studies of the fischer-tropsch synthesis on a cobalt catalyst II. Kinetics of carbon monoxide conversion to methane and to higher hydrocarbons , 1989 .

[7]  R. Everson,et al.  Fischer–Tropsch studies with cobalt–manganese oxide catalysts: Synthesis performance in a fixed bed reactor , 1998 .

[8]  D. Mears,et al.  Diagnostic criteria for heat transport limitations in fixed bed reactors , 1971 .

[9]  G. Hutchings A comparative evaluation of cobalt chromium oxide, cobalt manganese oxide, and copper manganese oxide as catalysts for the water-gas shift reaction , 1992 .

[10]  Water-Gas Shift Reaction. Effect of Pressure on Rate over an Iron- Oxide-Chromium Oxide Catalyst. , 1950 .

[11]  D. Ollis,et al.  The chemistry and catalysis of the water gas shift reaction: 1. The kinetics over supported metal catalysts , 1981 .

[12]  C. Singh,et al.  Simulation of High-Temperature Water-Gas Shift Reactors , 1977 .

[13]  Claire A. Chanenchuk,et al.  The Fischer-Tropsch synthesis with a mechanical mixture of a cobalt catalyst and a copper-based water gas shift catalyst , 1991 .

[14]  Robert F. Blanks Fischer-Tropsch synthesis gas conversion reactor , 1992 .

[15]  G. Hutchings,et al.  Carbon monoxide hydrogenation using cobalt manganese oxide catalysts: initial catalyst optimization studies , 1988 .

[16]  J. Dennis,et al.  Derivative free analogues of the Levenberg-Marquardt and Gauss algorithms for nonlinear least squares approximation , 1971 .

[17]  D. Newsome The Water-Gas Shift Reaction , 1980 .

[18]  Douglas M. Ruthven,et al.  The activity of commercial water gas shift catalysts , 1969 .

[19]  W. Deckwer,et al.  Fischer-Tropsch synthesis in the slurry phase on Mn/Fe catalysts , 1982 .

[20]  W. Deckwer,et al.  Studies on the kinetics of Fischer-Tropsch synthesis in slurry phase , 1985 .

[21]  J. M. Moe Design of water-gas shift reactors , 1962 .

[22]  S. Oki,et al.  Identification of rate-controlling steps for the water-gas shift reaction over an iron oxide catalyst , 1973 .

[23]  M. Dry ADVANCES IN FISCHER-TROPSCH CHEMISTRY , 1977 .

[24]  A. Outi,et al.  Kinetics and mechanism of the fischer tropsch hydrocarbon synthesis on a cobalt on alumina catalyst , 1981 .

[25]  Enrique Iglesia,et al.  Selectivity Control and Catalyst Design in the Fischer-Tropsch Synthesis: Sites, Pellets, and Reactors , 1993 .

[26]  Reiji Mezaki,et al.  Mechanistic structure of the water-gas shift reaction in the vicinity of chemical equilibrium , 1973 .

[27]  Raymond C. Everson,et al.  The Fischer—Tropsch reaction with supported ruthenium catalysts: Modelling and evaluation of the reaction rate equation for a fixed bed reactor , 1996 .

[28]  G. Hutchings,et al.  CO hydrogenation using cobalt/manganese oxide catalysts. Comments on the mechanism of carbon–carbon bond formation , 1989 .

[29]  Hans Bohlbro,et al.  The kinetics of the water-gas conversion IV. Influence of alkali on the rate equation , 1964 .

[30]  C. Satterfield,et al.  Intrinsic kinetics of the Fischer-Tropsch synthesis on a cobalt catalyst , 1991 .

[31]  W.-D. Deckwer,et al.  Kinetics of the Fischer-Tropsch synthesis in the slurry phase on a potassium promoted iron catalyst , 1985 .

[32]  Dragomir B. Bukur,et al.  Reaction kinetics over iron catalysts used for the fischer‐tropsch synthesis , 1990 .

[33]  C. Bennett,et al.  Kinetics of the Fischer-Tropsch Reaction over Iron , 1979 .

[34]  The chemistry and catalysis of the water gas shift reaction: 1. The kinetics over supported metal catalysts , 1981 .

[35]  Kinetics of CO + H2Reaction over Co-Cu-Al2O3Catalyst , 1979 .