Recent technological developments in Fischer-Tropsch catalysis

Fischer-Tropsch Synthesis is a promising, long-term, option for environmentally sound production of chemicals and fuels from coal. This paper focuses on catalyst and process developments which have occurred in the past decade. It features three important areas of FT catalysis: chemical modifications (additives, promoters, supports, pretreatments, and preparation methods), interception of intermediates (dual functionalism and secondary reactions), and limitation of chain growth by shape selectivity. Fundamental principles of catalyst design are emphasized. Conventional FT catalyst/process technology suffers from the following limitations: (1) limited selectivity for premium products (e.g. olefins, gasoline, and diesel fuel), (2) catalyst deactivation, (3) high capital cost, (4) heat removal, and (5) less than optimum thermal efficiency. Significant progress toward the solution of deactivation, heat removal, and thermal efficiency problems has been realized in the past two decades; with these innovations improvements in process economics of 30–40% are realizable. Of perhaps even greater significance is the progress made during the same period in the understanding of the relationship of catalyst structure to activity and selectivity properties which provides a scientific basis for catalyst design. Some of the key recent improvements in FT catalyst, reactor and process technology which could significantly impact the efficiency and economical production of fuels and chemicals from coal and natural gas are summarized.

[1]  A. Brenner,et al.  Catalysts of supported iron derived from molecular complexes containing one, two, and three iron atoms , 1979 .

[2]  Y. Chauvin,et al.  Catalytic synthesis of low molecular weight olefins from CO and H2 with Fe(CO)5, Fe3(CO)12, and [HFe3(CO)11]– supported on inorganic oxides , 1980 .

[3]  S. Ihm,et al.  METAL LOADING EFFECTS ON CO HYDROGENATION OF CO/Y ZEOLITE PREPARED BY ION-EXCHANGE AND CARBONYL COMPLEX IMPREGNATION , 1987 .

[4]  M. Dry Chemicals Produced in a Commercial Fischer-Tropsch Process , 1987 .

[5]  A. Miyamoto,et al.  Design of Fischer−Tropsch catalysts by pulse surface reaction rate analysis. II: Selective production of liquid fuel fraction on ruthenium/alumina catalyst promoted by rare earth oxides , 1988 .

[6]  A. Brenner Synthesis of highly dispersed catalysts of supported iron , 1979 .

[7]  C. H. Bartholomew,et al.  Cobalt-support interactions: their effects on adsorption and carbon monoxide hydrogenation activity and selectivity properties , 1985 .

[8]  J. Richardson Preparation variables in nickel catalysts , 1978 .

[9]  J. Dumesic,et al.  Surface, catalytic and magnetic properties of small iron particles: I. Preparation and characterization of samples , 1975 .

[10]  M. Rosen,et al.  MATHEMATICAL MODELING OF FISCHER- TROPSCH SLURRY BUBBLE COLUMN REACTORS , 1986 .

[11]  R. Anderson,et al.  The Fischer-Tropsch Synthesis , 1984 .

[12]  J. Gaube,et al.  Fischer-Tropsch-Synthese. Neuere Untersuchungen und Entwicklungen , 1983 .

[13]  N. B. Milestone,et al.  Carbon-Monoxide Hydrogenation Over Metal Loaded Aluminophosphates , 1989 .

[14]  J. L. Butler,et al.  Support and crystallite size effects in CO hydrogenation on nickel , 1980 .

[15]  J. G. Goodwin,et al.  Effect of preparation methods on the catalytic properties of zeolite-supported ruthenium in the Fischer-Tropsch synthesis , 1983 .

[16]  Joseph Haggin Fischer-Tropsch: new life for old technology: Helping to revive this venerable process is surge of research activity, mainly on mechanisms, catalysts, and reactor design , 1981 .

[17]  Alexis T. Bell,et al.  The kinetics and mechanism of carbon monoxide hydrogenation over alumina-supported ruthenium , 1981 .

[18]  J. Phillips,et al.  Production of supported metal catalysts by the decomposition of metal carbonyls (review) , 1984 .

[19]  A. Bell,et al.  Analysis of the design of bubble-column reactors for Fischer-Tropsch synthesis , 1985 .

[20]  R. Snel,et al.  Metal carbonyl clusters in the catalytic hydrogenation of carbon monoxide , 1985 .

[21]  M. Vannice,et al.  The preparation, characterization, and use of supported potassium-Group VIII metal complexes as catalysts for CO hydrogenation , 1980 .

[22]  S. Suib,et al.  Preparation of highly dispersed cobalt clusters in zeolites via microwave discharge methods , 1986 .

[23]  Effect of liquid composition on the slurry Fischer-Tropsch synthesis. 1. Rate of reaction , 1985 .

[24]  J. C. Hoogendoorn,et al.  Technology of the Fischer-Tropsch Process , 1981 .

[25]  W. Garwood,et al.  Advances in Fischer-Tropsch chemistry , 1979 .

[26]  J. Basset,et al.  Selective formation of propene from CO + H2 or C2H4 with Fe3(CO)12 supported on inorganic oxides. mechanistic implication in Fischer–Tropsch synthesis , 1980 .

[27]  Alexis T. Bell,et al.  Effects of mass transfer on the performance of slurry reactors used for fischer-tropsch synthesis , 1983 .

[28]  G. Bond,et al.  Catalysis, science and technology , 1983 .

[29]  C. H. Bartholomew,et al.  Physical properties and Fischer-Tropsch activities of Co/Al2O3 catalysts prepared from the decomposition of Co4(CO)12 , 1989 .

[30]  C. H. Bartholomew,et al.  Effects of support and dispersion on the CO hydrogenation activity/selectivity properties of cobalt , 1984 .

[31]  F. Rodríguez-Reinoso,et al.  Hydrogenation of CO on carbon-supported iron catalysts prepared from iron penta-carbonyl , 1986 .

[32]  C. H. Bartholomew,et al.  Effects of preparation, dispersion, and extent of reduction on activity/selectivity properties of iron/alumina CO hydrogenation catalysts , 1989 .

[33]  J. Falbe New Syntheses with Carbon Monoxide , 1980 .

[34]  J. Richardson,et al.  Fischer-Tropsch selectivity of Ni/Al2O3 catalysts , 1986 .

[35]  A. Bell,et al.  A theoretical model for the performance of bubble-column reactors used for Fischer-Tropsch synthesis , 1985 .

[36]  M. Vannice,et al.  Carbon-supported FeMn and KFeMn clusters for the synthesis of C2C4 olefins from CO and H2: I. Chemisorption and catalytic behavior , 1987 .

[37]  C. H. Bartholomew,et al.  Dispersed cobalt-containing zeolite Fischer-Tropsch catalysts , 1987 .

[38]  C. H. Bartholomew Preparation of a well dispersed platinum-iron alloy on carbon , 1972 .

[39]  J. A. Cusumano,et al.  A Technological Perspective for Catalytic Processes Based on Synthesis Gas , 1981 .

[40]  R. Snel Catalytic hydrogenation of carbon monoxide to alkenes over partially degraded iron complexes: I. Unsupported Iron Catalysts , 1988 .

[41]  C. Chang,et al.  Synthesis gas conversion to aromatic hydrocarbons , 1979 .

[42]  J. Zwart,et al.  Fischer-tropsch synthesis using zeolite-supported iron catalysts derived from iron carbonyl complexes , 1987 .

[43]  J. Dumesic,et al.  Surface, catalytic and magnetic properties of small iron particles: II. Structure sensitivity of ammonia synthesis , 1975 .

[44]  C. H. Bartholomew,et al.  Effects of crystallite size and support on the carbon monoxide hydrogenation activity/selectivity properties of iron/carbon , 1986 .