Fischer-Tropsch synthesis catalytic activity

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 catalytic partial oxidation of methane for the production of synthesis gas is an interesting alternative to steam reforming which is currently practiced in industry [1]. Significant research efforts have been exerted worldwide in recent years to develop a viable process based on the partial oxidation route [2-9]. This process would offer many advantages over steam reforming, namely (a) the formation of a suitable H2/CO ratio for use in the Fischer-Tropsch synthesis network, (b) the requirement of less energy input due to its exothermic nature, (c) high activity and selectivity for synthesis gas formation. 

Nurunnabi, M., Murata, K., Okabe, K., Inaba, M., and Takahara, I. 2008. Additive effect of Mn on catalytic activity of Ru/Al203 for Fischer-Tropsch synthesis. J. Jpn. Petrol. Inst. 51 252-53. 

Bian, G., Mochizuki, T., Fujishita, N., Nomoto, H., and Yamada, M. 2003. Activation and catalytic behavior of several Co/Si02 catalysts for Fischer-Tropsch synthesis. Energy Fuels 17 799-803. 

There has been considerable recent research interest in the activation of carbon monoxide en route to more complex organic molecules. Among the various reactions that have been investigated and/or newly discovered, the transition metal catalyzed reduction of CO to hydrocarbons (Fischer-Tropsch synthesis) has enjoyed particular attention (l- ). Whereas most of the successful efforts in this area have been directed toward the development of heterogeneous catalysts, there are relatively few homogeneous systems. Among these, two are based on clusters (10,11) and others are stoichiometric in metal (12-17). In this report we detail the synthesis and catalytic chemistry of polystyrene ( ) supported... 

Fischer-Tropsch synthesis making use of cobalt-based catalysts is a hotly persued scientific topic in the catalysis community since it offers an interesting and economically viable route for the conversion of e.g. natural gas to sulphur-free diesel fuels. As a result, major oil companies have recently announced to implement this technology and major investments are under way to build large Fischer-Tropsch plants based on cobalt-based catalysts in e.g. Qatar. Promoters have shown to be crucial to alter the catalytic properties of these catalyst systems in a positive way. For this reason, almost every chemical element of the periodic table has been evaluated in the open literature for its potential beneficial effects on the activity, selectivity and stability of supported cobalt nanoparticles. 

The catalytic activity for Fischer-Tropsch synthesis of the Fe-carbides (Fe2C and Fe7C3) produced by laser pyrolysis has been evaluated and compared to that of a precipitated iron oxide catalyst. Details of the results of these studies are the subject of chapter 19 of this book.35... 

The Rh(lll) surface is catalytically active for Fischer-Tropsch synthesis, but at pressures above one atmosphere (Castner, D. G. Blackadar, R. L. Somorjai, G. A., submitted to J. Catal.). 

According to the International Union of Pure and Applied Chemistry (IUPAC O)) the turnover frequency of a catalytic reac tion is defined as the number of molecules reacting per active site in unit time. The term active sites is applied to those sites for adsorption which are effective sites for a particular heterogeneous catalytic reaction. Because it is often impossible to measure the amount of active sites, some indirect method is needed to express the rate data in terms of turnover frequencies In some cases a realistic measure of the number of active sites may be the number of molecules of some compound that can be adsorbed on the catalyst. This measure is frequently used in the literature of the Fischer-Tropsch synthesis, where the amount of adsorption sites is determined by carbon monoxide adsorption on the reduced catalyst. However, it is questionable whether the number of adsorption sites on the reduced catalyst is really an indication of the number of sites on the catalyst active during the synthesis, because the metallic phase of the Fischer-Tropsch catalysts is often carbided or oxidized during the process. 

Activity. The catalytic activity of the Fe2oNi6oP20 alloys for the Fischer-Tropsch synthesis was analyzed and it was found that the amorphous alloy has the catalytic activity about three hundred times higher than the crystalline alloy ( 5,6). For Fe9o Zrio alloy, the catalytic activity of the amorphous and crystalline phases was analyzed for the same reaction at 248 and 255°C. 

H. Heinemann History of Industrial Catalysis. -J. C. R. Turner An Introduction to the Theory of Catalytic Reactors. - A. Ozaki, KAika Catalytic Activation of Dinitrogen. - M. E. Z)ry The Fischer-Tropsch Synthesis. - J. H. Sinfelt Catalytic of Hydrocarbons. 

The benefits of nonuniform activity distributions (site density) or diffusive properties (porosity, tortuosity) within pellets on the rate of catalytic reactions were first suggested theoretically by Kasaoka and Sakata (Ml). This proposal followed the pioneering experimental work of Maatman and Prater (142). Models of nonuniform catalyst pellets were later extended to more general pellet geometries and activity profiles (143), and applied to specific catalytic reactions, such as SO2 and naphthalene oxidation (144-146). Previous experimental and theoretical studies were recently discussed in an excellent review by Lee and Aris (147). Proposed applications in Fischer-Tropsch synthesis catalysis have also been recently reported (50-55,148), but the general concepts have been widely discussed and broadly applied in automotive exhaust and selective hydrogenation catalysis (142,147,149). 

In summary, cluster-derived catalysts have been widely used in various types of CO-based reactions such as Fischer-Tropsch synthesis, methanol synthesis, hydroformylation, carbonylation, and water-gas shift reactions. The catalytic performances of cluster-derived species are evaluated in terms of higher activities and selectivities for lower olefins and oxygenates in CO hydrogenation, compared with those of metal complexes in solution and conventional metal catalysts (Table XIII). 

Niobium oxide (niobia) is an active catalyst, and can be used as a support for metal nanoparticles or oxides, and it can serve as a promoter in some reactions ([43 5] and references therein). Catalytic applications of niobia include the Fischer-Tropsch synthesis, oxidative dehydrogenation of alkanes, and oxidative coupling of methane. Studies on high-surface-area niobium oxides are complicated by a high degree of complexity because several stable structures (NbO, NbO and Nb O ) exist and the resulting surfaces of high-surface-area niobium oxides are not simple truncations of bulk niobia structures. This is even more so for supported metal oxides when two-dimensional thin films of niobium oxide partially cover a support oxide (Al Oj, SiOj, ZrOj, TiOj, [43]). Nb Oj was also used as a support for V, Cr, Re, Mo, and W oxide overlayers [45, 46]. 

But how ubiquitous actually are alkalis in the promotion of reactions catalyzed at metal surfaces An examination of recent authoritative sources [6,7] shows that the majority of medium-to large-scale processes do not employ alkali promoters, even when one includes nonmetallic (i.e., metal oxide) catalysts. In a number of cases (e.g., steam reforming of naphtha) it seems clear that the role of alkali is simply to reduce the acidity of the oxide support. There are famous cases, of course, where the presence of alkali species on the catalytically active metal surface is critically important to the chemistry. Notable are ethene epoxidation (Ag-Cs), ammonia synthesis (Fe-K), acetoxylation of ethene to vinyl acetate (Pd, Pd/Au-K), and Fischer-Tropsch synthesis (Fe, Co, Ru-K). The first three are major industrial... 

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