Fischer promoters

A useful catalyst for asymmetric aldol additions is prepared in situ from mono-0> 2,6-diisopropoxybenzoyl)tartaric acid and BH3 -THF complex in propionitrile solution at 0 C. Aldol reactions of ketone enol silyl ethers with aldehydes were promoted by 20 mol % of this catalyst solution. The relative stereochemistry of the major adducts was assigned as Fischer- /ir o, and predominant /i -face attack of enol ethers at the aldehyde carbonyl carbon atom was found with the (/ ,/ ) nantiomer of the tartaric acid catalyst (K. Furuta, 1991). 

Promoters. Many industrial catalysts contain promoters, commonly chemical promoters. A chemical promoter is used in a small amount and influences the surface chemistry. Alkali metals are often used as chemical promoters, for example, in ammonia synthesis catalysts, ethylene oxide catalysts, and Fischer-Tropsch catalysts (55). They may be used in as Httie as parts per million quantities. The mechanisms of their action are usually not well understood. In contrast, seldom-used textural promoters, also called stmctural promoters, are used in massive amounts and affect the physical properties of the catalyst. These are used in ammonia synthesis catalysts. 

Fischer-Tropsch ohgomerization of CO -1- H9 to make hydrocarbons and oxygenated compounds was originally catalyzed by cobalt, which forms the active carbonyl, but now iron promoted by potassium is favored. Dissociative chemisorption of CO has been observed in this process. 

Interestingly, the first report of a reaction of this type was reported by Fischer and Rudolph earlier the same year Friedlander reported his quinoline synthesis.Heating of acetylaniline (7) in the presence of zinc chloride promotes acyl migration to furnish 2-aminoacetophenone (8) and 4-aminoacetophenone (9). These two molecules combine to furnish flavanilin (10). ... 

Fischer Tropsch synthesis is catalyzed by a variety of transition metals such as iron, nickel, and cobalt. Iron is the preferred catalyst due to its higher activity and lower cost. Nickel produces large amounts of methane, while cobalt has a lower reaction rate and lower selectivity than iron. By comparing cobalt and iron catalysts, it was found that cobalt promotes more middle-distillate products. In FTS, cobalt produces... 

Alkali promoters are often used for altering the catalytic activity and selectivity in Fischer-Tropsch synthesis and the water-gas shift reaction, where C02 adsorption plays a significant role. Numerous studies have investigated the effect of alkalis on C02 adsorption and dissociation on Cu, Fe, Rh, Pd, A1 and Ag6,52 As expected, C02 always behaves as an electron acceptor. 

The fact that Fischer-Tropsch fuels contain neither sulfur nor aromatics may become a strong selling point for the process. Less sulfur in the fuel has, of course, a direct effect on the sulfur oxides in the emissions, and the newly developed exhaust purification systems for lean burning engines that can be introduced means that all emissions, including GO2 and NOx, will diminish. Aromatics promote particulate formation in the combustion of diesel fuels and are therefore undesirable. We discuss this further in Ghapter 10. 

An XPS Investigation of iron Fischer-Tropsch catalysts before and after exposure to realistic reaction conditions is reported. The iron catalyst used in the study was a moderate surface area (15M /g) iron powder with and without 0.6 wt.% K2CO3. Upon reduction, surface oxide on the fresh catalyst is converted to metallic iron and the K2CO3 promoter decomposes into a potassium-oxygen surface complex. Under reaction conditions, the iron catalyst is converted to iron carbide and surface carbon deposition occurs. The nature of this carbon deposit is highly dependent on reaction conditions and the presence of surface alkali. 

This XPS investigation of small iron Fischer-Tropsch catalysts before and after the pretreatment and exposure to synthesis gas has yielded the following information. Relatively mild reduction conditions (350 C, 2 atm, Hg) are sufficient to totally reduce surface oxide on iron to metallic iron. Upon exposure to synthesis gas, the metallic iron surface is converted to iron carbide. During this transformation, the catalytic response of the material increases and finally reaches steady state after the surface is fully carbided. The addition of a potassium promoter appears to accelerate the carbidation of the material and steady state reactivity is achieved somewhat earlier. In addition, the potassium promoter causes a build up on carbonaceous material on the surface of the catalysts which is best characterized as polymethylene. 

The polymers were converted to supported catalysts corresponding to homogeneous complexes of cobalt, rhodium and titanium. The cobalt catalyst exhibited no reactivity in a Fischer-Tropsch reaction, but was effective in promoting hydroformylation, as was a rhodium analog. A polymer bound titanocene catalyst maintained as much as a 40-fold activity over homogeneous titanocene in hydrogenations. The enhanced activity indicated better site isolation even without crosslinking. 

Jacobs G., Ji Y., Davis B.H., Cronauer D., Kropf J., and Marshall C.L. 2007. Fischer-Tropsch synthesis Temperature programmed EXAFS/XANES investigation of the influence of support type, cobalt loading and noble metal promoter addition to the reduction behaviour of cobalt oxide particles. Appl. Catal. A Gen. 333 179-91. 

Jacobs G., Das T.K., Zhang Y., Li J., Racoillet G., Davis B.H. 2002. Fischer-Tropsch synthesis Support, loading and promoter effects on the reducibility of cobalt catalysts. Appl. Catal. A Gen. 233 263-81. 

Morales F., de Smit E., de Groot F.M.F., Visser T., and Weckhuysen B.M. 2007. Effects of manganese oxide promoter on the CO and H2 adsorption properties of titania-supported cobalt Fischer-Tropsch catalysts. J. Catal. 246 91-99. 

Girardon J.-S., Quinet E., Constant-Griboval A., Chemavskii P.A., Gengembre L., and Khodakov A.Y. 2007. Cobalt dispersion, reducibility and surface sites in promoted silica-supported Fischer-Tropsch catalysts. J. Catal. 248 143-57. 

Soled S.L., Iglesia E., and Fiato R.A. 1992. Copper-promoted cobalt manganese spinel catalyst and method for making the catalyst for Fischer-Tropsch synthesis. U.S. Patent 5162284. 

Concerning the Fischer-Tropsch synthesis, carbon nanomaterials have already been successfully employed as catalyst support media on a laboratory scale. The main attention in literature has been paid so far to subjects such as the comparison of functionalization techniques,9-11 the influence of promoters on the catalytic performance,1 12 and the investigations of metal particle size effects7,8 as well as of metal-support interactions.14,15 However, research was focused on one nanomaterial type only in each of these studies. Yu et al.16 compared the performance of two different kinds of nanofibers (herringbones and platelets) in the Fischer-Tropsch synthesis. A direct comparison between nanotubes and nanofibers as catalyst support media has not yet been an issue of discussion in Fischer-Tropsch investigations. In addition, a comparison with commercially used FT catalysts has up to now not been published. 

Bezemer, G. L., Radstake, P. B., Falke, U., Oosterbeek, H., Kuipers, H. P. C. E., van Dillen, A., and de Jong, K. P. 2006. Investigation of promoter effects of manganese oxide on carbon nanofiber-supported cobalt catalysts for Fischer-Tropsch synthesis. Journal of Catalysis 237 152-61. 

Li, J.L., Jacobs, G., Das, T.K., and Davis, B.H. 2002. Fischer-Tropsch synthesis Effect of water on the catalytic properties of a ruthenium promoted Co/Ti02 catalyst. Appl. Catal. 233 255-62. 

Vada, S., Hoff, A., Adnane, E., Schanke, D., and Holmen, A. 1995. Fischer-Tropsch synthesis on supported cobalt catalysts promoted by platinum and rhenium. Topics Catal. 2 155-62. 

Schulz, H., Claeys, M., and Harms, S. 1997. Effect of water partial pressure on steady state Fischer-Tropsch activity and selectivity of a promoted cobalt catalyst. Stud. Surf. Sci. Catal. 107 193-200. 

Tavasoli, A., Malek Abbaslou, R. M., and Dalai, A. K. 2008. Deactivation behavior of ruthenium promoted Co/a-Al203 catalysts in Fischer-Tropsch synthesis. Appl. Catal. A 346 58-64. 

Morales, F., and Weckhuysen, B. M. 2006. Promotion effects in Co-based Fischer-Tropsch catalysis. Catalysis 19 1 10. 

Wesner, D. A., Linden, G., and Bonzel, H. P. 1986. Alkali promotion on cobalt Surface analysis of the effects of potassium on carbon monoxide adsorption and Fischer-Tropsch reaction. Appl. Surf. Sci. 26 335-56. 

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