Cobalt hydrocarbon synthesis catalysts

Khodakov A.Y., Chu W., and Fongarland P. 2007. Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels. Chem. Rev. 107 1692-744. 

Weller, S. E. 1947. Kinetics of carbiding and hydrocarbon synthesis with cobalt Fischer-Tropsch catalysts. J. Am. Chem. Soc. 69 2432-36. 

Lapidus, A., Krylova, A., Kazanskii, V., Borovkov, V., and Zaitsev, A. 1991. Hydrocarbon synthesis from carbon monoxide and hydrogen on impregnated cobalt catalysts. Part I. Physico-chemical properties of 10% cobalt/alumina and 10% cobalt/ silica. Appl. Catal. 73 65-81. 

Fischer-Tropsch (FT) process is used for the production of hydrocarbon fuels. The process uses synthesis gases CO and H2O. It is shown that cobalt/alumina-based catalysts are highly active for the synthesis. The process is also used to convert coal to substitute or synthetic natural gas (SNG). The use of Fe-based catalysts is also believed to be attractive due to their high FT activity. HRTEM has played a major role in the study of phase transformations in Fe Fischer-Tropsch during temperature programmed reduction (TPR) using both CO and H2 (Jin et al 2000, Shroff et al 1995). TiClj/MgC -based (Ziegler-Natta) catalysts are used for polymerization of alkenes (Kim et al 2000) and EM is used to study the polymerization (Oleshko et al 2002). 

The oxo reaction (31) is carried out in the liquid phase at high pressure using a cobalt catalyst. A mixture of aldehyde isomers is always produced, each isomer being one carbon number higher than the starting olefin. As a group the oxygenated products of the hydrocarbon synthesis (Fischer-Tropsch) process and the oxo process are primary compounds and thus (except, of course, the methyl and ethyl derivatives) differ fundamentally from the products based on alcohols made by the hydration of olefins, which are always secondary or tertiary in structure. 

Good evidence has been obtained that heterogeneous iron, ruthenium, cobalt, and nickel catalysts which convert synthesis gas to methane or higher alkanes (Fischer-Tropsch process) effect the initial dissociation of CO to a catalyst-bound carbide (8-13). The carbide is subsequently reduced by H2to a catalyst-bound methylidene, which under reaction conditions is either polymerized or further hydrogenated 13). This is essentially identical to the hydrocarbon synthesis mechanism advanced by Fischer and Tropsch in 1926 14). For these reactions, formyl intermediates seem all but excluded. 

The CO-hydrogenation reaction, or Fischer-Tropsch (F-T) synthesis reaction, has been thoroughly investigated since its discovery fn the 1920 s [1]. A range of catalysts has been shown to be active for hydrocarbon synthesis and iron [2] and cobalt [3] have found commercial applications in this field. A variety of reactors have been developed to optimize the synthesis reaction [4]. Variations of reactor conditions have been shown to maximize specific products from the broad range of products produced in the reaction [5). 

The hypothesis of formation of oxygenated compounds as intermediate products was rejected by Eidus on the basis of experiments on the conversion over cobalt of methyl and ethyl alcohols and formic acid which were found to form carbon monoxide and hydrogen in an intermediate step of the hydrocarbon synthesis (76). Methylene radicals are thought to be formed on nickel and cobalt catalysts (76) by hydrogenation of the unstable group CHOH formed by interaction of adsorbed carbon monoxide and hydrogen, while on iron catalysts methylene radicals are probably formed by hydrogenation of the carbide (78,81). Carbon dioxide was found to interact with the alkaline promoters on the surface of iron catalysts as little as 1 % potassium carbonate was found to occupy 30 to 40% of the active surface area. The alkali also promotes carbide formation and the synthesis reaction on iron (78). 

Sulfur poisoning is a key problem in hydrocarbon synthesis from coal-derived synthesis gas. The most important hydrocarbon synthesis reactions include methanation, Fischer-Tropsch synthesis, and methanol synthesis, which occur typically on nickel, iron, or cobalt, and ZnO-Cu catalysts, respectively. Madon and Shaw (2) reviewed much of the early work dealing with effects of sulfur in Fischer-Tropsch synthesis. Only the most important conclusions of their review will be summarized here. 

BIFUNCTIONAL COBALT-ZSM-5 CATALYST FOR THE SYNTHESIS OF HYDROCARBONS FROM THE PRODUCTS OF BIOMASS GASIFICATION... 

The Co-MgO-ZSM-5 catalyst was prepared as a physical mixture of cobalt hydroxycarbonate, MgO and NaZSM-5. It was found to be active in the hydrocarbon synthesis from the products of biomass gasification. The addition of CO2 caused a decrease of the growth factor while that of N an increase. ... 

Cobalt, nickel, and iron catalysts combined with all types of promoters were tested. The investigations, which are valuable contributions to the research work on hydrocarbon synthesis, confirmed the observations of Fischer and his co-workers. 

The optimum conditions of pressure and temperature for hydrocarbon synthesis on nickel, cobalt, iron, and ruthenium are close to the conditions at which formation of carbonyls and carbonyl hydrogen compounds can be detected. Pressure requirements for the catalytic synthesis and for carbonyl formation appear to be closely parallel in the case of metallic catalysts. 

Other Syntheses Related to the Fischer-Tropsch Process Comparatively little is yet known of some synthetic reactions which obviously resemble the Fischer-Tropsch process very closely, but they are worth brief mention because they are also likely to be controlled by geometrical factors. The Oxo synthesis (15) of aldehydes by the interaction of ethylene or other olefins with carbon monoxide and hydrogen is carried out in contact with cobalt catalysts at temperatures in the range 110-150°, and under a pressure of 100-200 atmospheres. Cyclic olefins react similarly for example, cyclohexene gives hexahydrobenzaldehyde. There can be little doubt that a two-point adsorption of the hydrocarbon must take place and that the adsorbed molecule then reacts with carbon monoxide and hydrogen the difference between this process and that responsible for the normal hydrocarbon synthesis is that adsorbed carbon monoxide survives as such under the less drastic temperature conditions which are employed. Owing to the fact that a variety of isomeric aldehydes are produced, this system deserves further detailed study on geometrical lines. 

The first of these new cobalt catalysts were made in 1986 by coprecipitation techniques using aqueous solutions with ammonium bicarbonate as the precipitant in a similar way to the methods used for methanol synthesis catalysts. The new catalysts were immediately found to be very active and selective catalysts for the conversion of syngas into hydrocarbons. A particularly attractive feature was their low methane make and tolerance of CO2 The CO2 tolerance was ascribed to the interplay between the support and the cobalt phase both in the oxidized and reduced forms. The general belief is that the support stabilizes the cobalt phase such that the catalyst can be operated at the higher temperatures, required to maintain activity despite competitive adsorption by CO2, without any loss in stability. Other investigators e.g. Shell have used similar strategies [2]. 

For the synthesis of higher hydrocarbons by Fischer-Tropsch, cobalt and iron are the most used metals. Under the form of trivalent cations, they have close ionic radii, which allow their crystallization in an ABO3 structure with La in the A sites. The final goal is the formation after reduction (partial or total) of an efficient catalyst for hydrocarbons synthesis. The most simple combination is to synthesize mixed La(Co cFei )03 perovskites. Bedel et al. [36] studied the preparation, by a sol-gel-like method, of these perovskites over the whole range of... 

The reaction is done with a metal catalyst. Catalysts based upon iron or cobalt have been used commercially for hydrocarbon synthesis [5], The mechanism involves adsorption of hydrogen and carbon monoxide on the metal surface [6]. The Fischer-Tropsch process enables natural gas to be converted to liquid synthetic fuel. First, the natural gas is oxidized to syn gas which is then converted by the Fischer-Tropsch process to the liquid hydrocarbon mixture, which is useful as fuel. 

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