Fuel Processing Technology 71 2001. 157166 www.elsevier.

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FischerTropsch synthesis: current mechanism and futuristic needs

Burtron H. Davis )
Center for Applied Energy Research, Uniersity of Kentucky, 2540 Research Park Drie, Lexington, KY 40511-8410, USA

Abstract Mechanisms for the generation of hydrocarbon and oxygenate products from synthesis gas using the FischerTropsch synthesis are presented. The data generated to date indicate that, while there are similarities between iron and cobalt catalytic synthesis mechanisms, the details differ. For the iron catalyst, it is concluded that an oxygenate mechanism is more appropriate in light of todays data. While less mechanistic data for the cobalt catalyst are available, it appears that a surface carbide mechanism is a better choice. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: FischerTropsch synthesis; Reaction mechanism; Isotopic tracer studies

1. Introduction As the following shows, the description of a mechanism for a reaction as complex as the FischerTropsch synthesis is fraught with pitfalls. Unlike many reactions, the FischerTropsch synthesis converts two of the simplest compounds, H 2 and CO, into a complex array of products, consisting predominantly of alkenes and alkanes but also a variety of minor compounds, including a range of oxygenate compounds. In the following, we survey major mechanisms that have been introduced and in some cases revived again in a slightly modified form. The original carbide mechanism for the formation of hydrocarbon and oxygenate products with the FischerTropsch synthesis FTS. included the formation of the metal

Tel.: q 1-859-257-0251; fax: q 1-859-257-0302. E-mail address: davis@caer.uky.edu B.H. Davis..

0378-3820r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 8 - 3 8 2 0 0 1 . 0 0 1 4 4 - 8

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carbide followed by hydrogenation of the metal carbide to produce the various products w1x. It was eventually recognized that this mechanism was inconsistent with thermodynamic data for the formation of hydrocarbons by hydrogenation of the carbide at the temperatures used for the synthesis reaction w2,3x. The direct hydrogenation of the metal carbide was investigated by Kummer et al. w4x. These workers preformed iron carbide by the reaction of a reduced iron catalyst and radioactively labeled 14 CO. The fraction of methane that is 14 CH 4 when synthesis is effected with unlabeled CO is a measure of the contribution of direct hydrogenation of the preformed iron carbide to the synthesis. The data showed that carbide hydrogenation could be responsible for no more than 830% of the methane that is formed. These authors made a special effort to obtain data at low conversion levels that would represent the hydrogenation of only a percent of the total surface carbon; even under these conditions, direct hydrogenation was responsible for only a small fraction of the methane produced. In addition, the same conclusion applied for the higher carbon number compounds. This study led most investigators to abandon

Scheme 1.

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the formation and subsequent hydrogenation of a bulk metal carbide as an intermediate in the FTS mechanism. In the 1950s, the oxygenate enol. mechanism gained widespread acceptance w5,6x. This mechanism involves the chemisorption of CO which reacts with adsorbed hydrogen to form a species such as:

1.

This structure grows by a combination of condensation and water elimination steps using adjacent groups. This enol group can condense as depicted in Scheme 1 w7x.

Scheme 2.

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Scheme 3.

The results obtained by Emmett et al. w2,812x for their 14 C-tracer studies provided strong support for this mechanism. In these studies, a 14 C-labeled alcohol or alkene was added together with the synthesis gas and the distribution of the isotopically labeled

Scheme 4.

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products was determined. It was found that the added alkene or the alcohol was able to serve to initiate chain growth. Much of the work by Emmett et al. was conducted at atmospheric pressure. However, our later work w13x using medium pressure synthesis and slurry phase reaction conditions produced results that were in agreement with the conclusions of Emmett et al. In addition, our work showed that ethanol was incorporated 50100 times as rapidly as ethene when the two reactants were converted under the same reaction conditions w14x. An insertion mechanism involves the insertion of CO into a metalmethyl or metalmethylene carbon bond which is then hydrogenated to produce an alcohol or alkene; the alcohol or alcohol precursor can also eliminate oxygen to produce an alkene product. One form of this mechanism is shown in Scheme 2 w7,15x.

Scheme 5.

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) Hydrogenation and water elimination of the COH 2 surface species are assumed to be the rate controlling step. With the general availability of surface science instruments, it was found that CO adsorbs on single crystal metal surfaces to produce a surface covered with carbon, and little oxygen. This led to the conclusion that the CO chemisorbs and dissociates to adsorbed C and O. This step is followed by the rapid hydrogenation of adsorbed O to produce water. The hydrogenation of adsorbed carbon to form CH 2 is much slower. This mechanism may be viewed as a revival of the carbide theory but with the requirement that carbide formation is limited to the surface, or near surface, layer. Maitlis w16x has advanced this mechanism as the FischerTropschBradyPettitBiloenSachtler Mechanism and it is illustrated in Scheme 3 below. A more elaborate version of this mechanism has been provided by Dry w7x and is shown in Scheme 4. Dry considers the steps. involving the hydrogenation of surface C to be rate-limiting; the other reactions are assumed to be at equilibrium. A current view of the carbide carbene. theory is illustrated in Scheme 5. In the following, we consider characterization data and try to combine these with results from isotopic tracer studies in an attempt to provide a mechanism that more nearly applies under conditions amenable to industrial practice. The consideration will be limited to the lower severity conditions likely to be encountered in slurry phase synthesis with an iron catalyst. The conversion of 14 C labeled alcohols is consistent with the following reaction pathway:

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This reaction pathway allows for the direct formation of CO 2 and an alkane with one less carbon than the added alcohol, and is in agreement with the experimental results using 14 C labeled alcohols CH 3 CH 2 . 314 CH 2 OH and CH 3 CH 2 . 314 CH 2 CH 2 OH.. Furthermore, there is valid infrared data to support the type of structure as being formed on metal Fe and Co. surfaces. Thus, Blyholder et al. w17x offers the following mechanism for the reaction of CO, H 2 and C 2 H 4 on a cobalt catalyst:

A similar adsorption model has been proposed by Kolbel and Tillmetz w18x. A pathway similar to the above would account for the chain initiation by CO 2 as we have established w19x.

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The oxygenate mechanism is able to account for the initiation by CO 2 as well as requiring chain propagation to occur only by CO since it appears unreasonable to expect CO 2 to be adsorbed with the structure shown in the Blyholder model. The conversion pathway that the alcohol follows with the iron catalyst is not well defined. When an n-alcohol, the dominant alcohol product for each carbon number, is added to the feed gas it is expected to be dehydrated to the corresponding olefin. However, this is not the case. As shown above, the alcohol is converted directly to an alkane with one fewer carbon atoms in greater yield than to the same carbon number 1-alkene, and the CO 2 is formed directly rather than through the watergas shift reaction. Thus, we can eliminate the following as a major reaction pathway:

When the n-alcohol is converted over iron carbide or over Fe 3 O4 at atmospheric pressure in the absence of syngas, the alcohol undergoes two reactions w20x:

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and

Thus, the alcohol follows different reaction pathways in the presence and absence of syngas. It appears that the oxygen formed by dissociation of CO is needed to have the alcohol form CO 2 directly together with an alkane with one fewer carbon. In summary, there is clearly evidence for the participation of an oxygenate intermediate in the FischerTropsch synthesis using an iron catalyst. It is also clear that a carbide is the more active form of the iron catalyst. The intermediate leading to the 1-alkenes remains to be identified. On the other hand, the tracer studies with a cobalt catalyst are in agreement with a mechanism involving the carbene intermediate. Both CO 2 and alcohols behave as inert gases for the cobalt catalyst. The next step is to provide more conclusive data to show that the mechanism for the iron and cobalt catalysts are indeed different. If, as the data suggest, they are different then the objective is to define the catalyst properties responsible for the difference.

Acknowledgements This work was supported by U.S. DOE contract number DE-FC26-98FT40308 and the Commonwealth of Kentucky.

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