Bridging the pressure and material gap in heterogeneous catalysis: cobalt Fischer-Tropsch catalysts from surface science to industrial application.

The Fischer-Tropsch (FT) process is the heart of many natural gas conversion processes as it enables the conversion of a mixture of CO and H(2) into valuable long-chain hydrocarbons. Here we report on the use of state-of-the-art surface science techniques to obtain information on the relationship between the surface atomic structure of model catalysts and their performance in the Fischer-Tropsch reaction. Cobalt single crystals and polycrystals were modified with non-reducible oxides as to resemble industrial catalysts. Reflection absorption infrared spectroscopy was used for examining the CO adsorption behaviour at room temperature as well as at 493 K at CO pressures spanning 10(-7) to 300 mbar on both (modified) Co single/polycrystals and an industrial catalyst. Polarization modulation was applied to cancel the CO gas phase absorption. Subsequently, they were subjected to reaction tests in the same apparatus at 1 bar and 493 K. This allowed us to close the material, pressure and instrument gap in the field of Fischer-Tropsch synthesis on cobalt-based catalysts.

[1]  A. Bell,et al.  Alumina and titania overlayers on rhodium: A comparison of the chemisorption catalytic properties , 1988 .

[2]  C. Nielsen,et al.  Infrared Study of CO Adsorbed on a Co/Re/γAl2O3-Based Fischer–Tropsch Catalyst , 2000 .

[3]  B. Weckhuysen,et al.  Combined EXAFS and STEM-EELS study of the electronic state and location of Mn as promoter in Co-based Fischer-Tropsch catalysts. , 2005, Physical chemistry chemical physics : PCCP.

[4]  J. Robbins,et al.  In-situ FT-IRAS study of the hydrogenation of CO on Ru(001). Potassium-promoted synthesis of formate , 1993 .

[5]  G. Beitel,et al.  A COMBINED IN-SITU PM-RAIRS AND KINETIC STUDY OF SINGLE-CRYSTAL COBALT CATALYSTS UNDER SYNTHESIS GAS AT PRESSURES UP TO 300 MBAR , 1997 .

[6]  C. Backx,et al.  Electron energy loss spectroscopy of ethylene on Ag(110) precovered with oxygen: energy dependence of the cross section , 1982 .

[7]  H. Oosterbeek,et al.  Chain Length Dependence of α-Olefin Readsorption in Fischer-Tropsch Synthesis , 1995 .

[8]  G. Hutchings,et al.  EFFECTS OF THIOPHENE AND SULFUR DIOXIDE ON CO ADSORPTION ON COBALT/SILICA CATALYSTS , 1997 .

[9]  G. Busca,et al.  Fourier-transform infrared study of the surface properties of cobalt oxides , 1990 .

[10]  K. Hayek,et al.  Vanadium oxide overlayers on rhodium: Influence of the reduction temperature on the composition and on the promoting effect in CO hydrogenation , 2002 .

[11]  J. Vaari,et al.  Growth and oxidation of Mg films on polycrystalline cobalt , 1992 .

[12]  J. Lahtinen,et al.  C, CO and CO2 hydrogenation on cobalt foil model catalysts: evidence for the need of CoO reduction , 1994 .

[13]  C. Peden,et al.  In-situ FT-IRAS study of the CO oxidation reaction over Ru(001): I. Evidence for an Eley-Rideal mechanism at high pressures? , 1991 .

[14]  C. Backx,et al.  Electron energy loss spectroscopy and its applications , 1980 .

[15]  Gert Jan Kramer,et al.  Fischer–Tropsch technology — from active site to commercial process , 1999 .

[16]  F. Hoffmann The kinetics of CO dissociation on Ru(001): Time-resolved vibrational spectroscopy at elevated pressures , 1989 .

[17]  M. C. Zonnevylle,et al.  The Fischer-Tropsch reaction on a cobalt (0001) single crystal , 1990 .

[18]  A. Zaitsev,et al.  Hydrocarbon synthesis from carbon monoxide and hydrogen on impregnated cobalt catalysts Part I. Physico-chemical properties of 10% cobalt/alumina and 10% cobalt/silica , 1991 .

[19]  B. Weckhuysen,et al.  In Situ X-ray Absorption of Co/Mn/TiO2 Catalysts for Fischer−Tropsch Synthesis , 2004 .

[20]  Freek Kapteijn,et al.  Cobalt particle size effects in the Fischer-Tropsch reaction studied with carbon nanofiber supported catalysts. , 2006, Journal of the American Chemical Society.

[21]  J. H. Merwe Theoretical considerations in growing uniform epilayers , 1993 .

[22]  B. Weckhuysen,et al.  Mn promotion effects in Co/TiO2 Fischer-Tropsch catalysts as investigated by XPS and STEM-EELS , 2005 .

[23]  R. Dziembaj,et al.  Active state of model cobalt foil catalyst studied by SEM, TPR/TPO, XPS and TG , 2001 .

[24]  M. Daturi,et al.  New types of polycarbonyls of Co+ formed after interaction of CO with Co–ZSM-5: An FTIR spectroscopic study , 2003 .

[25]  Y. Inoue,et al.  Infrared and X-ray photoelectron spectroscopy studies of carbon monoxide adsorbed on silica-supported cobalt catalysts , 1984 .

[26]  D. Goodman,et al.  The preparation and characterization of ultra-thin silicon dioxide films on a Mo(110) surface , 1993 .

[27]  A. Vehanen,et al.  Studies of Mg-O overlayers on Co(0001): growth mode and CO chemisorption properties , 1991 .

[28]  A. Ortega,et al.  The adsorption of CO on Pd(100) studied by IR reflection absorption spectroscopy , 1982 .

[29]  J. Vaari,et al.  Adsorption of CO on Mg-promoted Co(poly) , 1994 .

[30]  Gabor A. Somorjai,et al.  The enhancement of CO hydrogenation on rhodium by TiOx overlayers , 1987 .

[31]  J. H. Wilson,et al.  Non-ASF product distributions due to secondary reactions during Fischer-Tropsch synthesis , 1996 .

[32]  K. P. Jong,et al.  Investigation of promoter effects of manganese oxide on carbon nanofiber-supported cobalt catalysts for Fischer–Tropsch synthesis , 2006 .

[33]  Jon Wilson,et al.  Atomic-Scale Restructuring in High-Pressure Catalysis , 1995 .

[34]  P. Hollins The influence of surface defects on the infrared spectra of adsorbed species , 1992 .

[35]  C. Nielsen,et al.  Infrared study of CO adsorbed on Co/γ-Al2O3 based Fischer–Tropsch catalysts; semi-empirical calculations as a tool for vibrational assignments , 2000 .

[36]  J. Robbins,et al.  Time resolved ft-iras at high pressures: hydrogen assisted CO dissociation in the methanation reaction on Ru(001) , 1987 .

[37]  Hui-Chi Chiu,et al.  In situ FTIR Study of Cobalt Oxides for the Oxidation of Carbon Monoxide , 2003 .