Pore Size Effects in Fischer Tropsch Synthesis over Cobalt-Supported Mesoporous Silicas

Abstract Pore size effects on Fischer Tropsch reaction rates and selectivities over cobalt catalysts were studied at atmospheric pressure using periodic (SBA-15 and MCM-41) and commercial mesoporous silicas as catalytic supports. The catalysts were characterized by nitrogen adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and oxygen titration. Fischer Tropsch reaction rates were found much higher on cobalt catalysts with the pore diameter exceeding 30 A than on the narrow pore catalysts. A larger diameter of catalyst pores also led to significantly higher C 5+ selectivities. The catalytic effects were interpreted in terms of different cobalt particle size and reducibility in the wide pore and narrow pore silicas. XRD and XPS showed that the size of supported cobalt species strongly depended on the pore size, increasing with increases in catalyst pore diameter. TGA and oxygen titration indicated higher extent of overall reduction of cobalt species in wide pore supports. Lower reducibility of small cobalt particles is likely to be one of the reasons responsible for the lower Fischer Tropsch reaction rates and higher methane selectivities on narrow pore cobalt catalysts.

[1]  A. Khodakov,et al.  Pore-Size Control of Cobalt Dispersion and Reducibility in Mesoporous Silicas , 2001 .

[2]  Hongwei Xiang,et al.  Effect of reaction conditions on the product distribution during Fischer–Tropsch synthesis over an industrial Fe-Mn catalyst , 2001 .

[3]  Wen-Hau Zhang,et al.  Synthesis and Characterization of Nanosized ZnS Confined in Ordered Mesoporous Silica , 2001 .

[4]  A. Kiennemann,et al.  Effect of Fischer–Tropsch synthesis on the microstructure of Fe–Co-based metal/spinel composite materials , 2001 .

[5]  Ryoo,et al.  TEM Studies of Platinum Nanowires Fabricated in Mesoporous Silica MCM-41 A part of this work was supported by CREST, Japan Science and Technology Cooperation. , 2000, Angewandte Chemie.

[6]  K. Fujimoto,et al.  The reaction performances and characterization of Fischer–Tropsch synthesis Co/SiO2 catalysts prepared from mixed cobalt salts , 2000 .

[7]  G. Stucky,et al.  Preparation of Noble Metal Nanowires Using Hexagonal Mesoporous Silica SBA-15 , 2000 .

[8]  T. Abe,et al.  Control of bandgap of iron oxide through its encapsulation into SiO2-based mesoporous materials , 2000 .

[9]  Dongyuan Zhao,et al.  Morphological Control of Highly Ordered Mesoporous Silica SBA-15 , 2000 .

[10]  C. H. Bartholomew,et al.  Reaction and deactivation kinetics for Fischer–Tropsch synthesis on unpromoted and potassium-promoted iron catalysts , 1999 .

[11]  J. Grimblot,et al.  Influence of the characteristics of γ-aluminas on the dispersion and the reducibility of supported cobalt catalysts , 1999 .

[12]  D. Zhao,et al.  Alumination and Ion Exchange of Mesoporous SBA-15 Molecular Sieves , 1999 .

[13]  Jinlin Li,et al.  The effect of boron on the catalyst reducibility and activity of Co/TiO2 Fischer–Tropsch catalysts , 1999 .

[14]  A. Kiennemann,et al.  Study on a cobalt silica catalyst during reduction and Fischer–Tropsch reaction: In situ EXAFS compared to XPS and XRD , 1998 .

[15]  Fredrickson,et al.  Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores , 1998, Science.

[16]  Synthesis and Characterization of MCM-41with Different Pore Size and Si/Al-ratio , 1998 .

[17]  D. Bazin,et al.  Reducibility of Cobalt Species in Silica-Supported Fischer–Tropsch Catalysts , 1997 .

[18]  A. Holmen,et al.  Study of Pt-promoted cobalt CO hydrogenation catalysts , 1995 .

[19]  S. Bessell Investigation of bifunctional zeolite supported cobalt Fischer-Tropsch catalysts , 1995 .

[20]  D. Mehandjiev,et al.  Active Surface of γ-Al2O3-Supported Co3O4 , 1994 .

[21]  Mark E. Davis,et al.  Studies on mesoporous materialsI. Synthesis and characterization of MCM-41 , 1993 .

[22]  J. S. Beck,et al.  Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism , 1992, Nature.

[23]  E. Iglesia,et al.  Fischer-Tropsch synthesis on cobalt and ruthenium. Metal dispersion and support effects on reaction rate and selectivity , 1992 .

[24]  D. Hercules,et al.  Effect of particle size on carbon monoxide hydrogenation activity of silica supported cobalt catalysts , 1990 .

[25]  D. Castner,et al.  X-ray absorption spectroscopy, x-ray photoelectron spectroscopy, and analytical electron microscopy studies of cobalt catalysts. 2. Hydrogen reduction properties , 1990 .

[26]  D. Castner,et al.  X-ray absorption spectroscopy, x-ray photoelectron spectroscopy, and analytical electron microscopy studies of cobalt catalysts. 1. Characterization of calcined catalysts , 1989 .

[27]  R. Prins,et al.  Characterization of supported cobalt and cobalt-rhodium catalysts . I . Temperature-programmed reduction ( TPR ) and oxidation ( TPO ) of Co---Rh / Al 2 O 3 , 2003 .

[28]  D. Koningsberger,et al.  Characterization of supported cobalt and cobalt-rhodium catalysts : III. Temperature-Programmed Reduction (TPR), Oxidation (TPO), and EXAFS of Co---Rh/SiO2 , 1986 .

[29]  R. W. Linton,et al.  X-ray photoelectron spectroscopy of thermally treated silica (SiO2) surfaces , 1985 .

[30]  C. H. Bartholomew,et al.  Structure sensitivity and its effects on product distribution in CO hydrogenation on cobalt/alumina , 1985 .

[31]  D. Vanhove,et al.  Hydrocarbon selectivity in fischer-tropsch synthesis in relation to textural properties of supported cobalt catalysts , 1984 .

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

[33]  J. Moulijn,et al.  Quantitative analysis of XPS intensities for supported catalysts , 1979 .

[34]  W. A. Dench,et al.  Quantitative electron spectroscopy of surfaces: A standard data base for electron inelastic mean free paths in solids , 1979 .

[35]  A. Heeres,et al.  The XPS spectra of the metathesis catalyst tungsten oxide on silica gel , 1978 .

[36]  C. H. Bartholomew Chemistry of nickel-alumina catalysts , 1976 .

[37]  D. Johnson,et al.  Studies of topochemical heterogeneous catalysis: 3. Catalysis of the reduction of metal oxides by hydrogen , 1974 .

[38]  S. J. Gregg,et al.  Adsorption Surface Area and Porosity , 1967 .

[39]  B. Cullity,et al.  Elements of X-ray diffraction , 1957 .

[40]  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 .

[41]  R. Anderson,et al.  Studies of the Fischer--Tropsch Synthesis. V. Activities and Surface Areas of Reduced and Carburized Cobalt Catalysts , 1949 .

[42]  E. Teller,et al.  On a Theory of the van der Waals Adsorption of Gases , 1940 .

[43]  Paul J. Flory,et al.  Molecular Size Distribution in Linear Condensation Polymers1 , 1936 .