Fischer chain growth

The production of hydrocarbons using traditional Fischer-Tropsch catalysts is governed by chain growth or polymerization kinetics. The equation describing the production of hydrocarbons, commonly referred to as the Anderson-Schulz-Flory equation, is ... 

The readsorption and incorporation of reaction products such as 1-alkenes, alcohols, and aldehydes followed by subsequent chain growth is a remarkable property of Fischer-Tropsch (FT) synthesis. Therefore, a large number of co-feeding experiments are discussed in detail in order to contribute to the elucidation of the reaction mechanism. Great interest was focused on co-feeding CH2N2, which on the catalyst surface dissociates to CH2 and dinitrogen. Furthermore, interest was focused on the selectivity of branched hydrocarbons and on the promoter effect of alkali on product distribution. All these effects are discussed in detail on the basis... 

The carbon number distribution of Fischer-Tropsch products on both cobalt and iron catalysts can be clearly represented by superposition of two Anderson-Schulz-Flory (ASF) distributions characterized by two chain growth probabilities and the mass or molar fraction of products assigned to one of these distributions.7 10 In particular, this bimodal-type distribution is pronounced for iron catalysts promoted with alkali (e.g., K2C03). Comparing product distributions obtained on alkali-promoted and -unpromoted iron catalysts has shown that the distribution characterized by the lower growth probability a, is not affected by the promoter, while the growth probability a2 and the mass fraction f2 are considerably increased by addition of alkali.9 This is... 

In Fischer-Tropsch synthesis the readsorption and incorporation of 1-alkenes, alcohols, and aldehydes and their subsequent chain growth play an important role on product distribution. Therefore, it is very useful to study these reactions in the presence of co-fed 13C- or 14 C-labeled compounds in an effort to obtain data helpful to elucidate the reaction mechanism. It has been shown that co-feeding of CF12N2, which dissociates toward CF12 and N2 on the catalyst surface, has led to the sound interpretation that the bimodal carbon number distribution is caused by superposition of two incompatible mechanisms. The distribution characterized by the lower growth probability is assigned to the CH2 insertion mechanism. 

N. O. Elbashir and C. B. Roberts, Enhanced Incorporation of a-Olefins in the Fischer-Tropsch synthesis Chain-Growth Process over an Alumina-Supported Cobalt Catalyst in Near-Critical and Supercritical Hexane Media, Ind. Eng. Chem. Res., 2005, 44, 505-521. 

Fischer-Tropsch synthesis, 28 80, 97, 103, 30 166-168, 34 18, 37 147, 39 221-296 activation energy and kinetics, 39 276 added olefin reactions, 39 251-253 bed residence time effects on chain growth probability and product functionality, 39 246-250... 

A similar chain-growth mechanism was said to occur with the first molybdenum-sulfur-potassium based catalysts of table I (15). For such a chain-growth mechanism, the heavier the average molecular weight of alcohols, the greater the formation of heavy compounds and, more often than not, the lower the alcohols selectivity. Furthermore, in Fischer-Tropsch type catalysts (24,25) diffusion limitations, mostly due to the presence of liquid products condensed in the micro porosity, increase with the size of diffusing molecules. These molecules are capable of... 

A new mechanism to interpret alkene formation in Fischer-Tropsch synthesis has been presented 499-501 There is a general agreement that hydrocarbon formation proceeds according to the modified carbene mechanism. Specifically, CO decomposes to form surface carbide and then undergoes hydrogenation to form surface methine (=CH), methylene (=CH2), methyl and, finally, methane. Linear hydrocarbons are formed in a stepwise polymerization of methylene species. When chain growth is terminated by p-hydride elimination [Eq. (3.61)], 1-alkenes may be formed,502 which is also called the alkyl mechanism ... 

A new approach to develop a molecular mechanism for Fischer-Tropsch catalysis based on the use of [Fe2Co(CN)6] and [Fe(HCN)2]3 precursor complexes has been disclosed.509 The former produced mainly liquid aliphatic hydrocarbons, whereas the latter gave waxy aliphatic products. Results acquired by various techniques were interpreted to imply that chain growth proceeds via the insertion of CO into an established metal-carbon bond, that is, a C, catalytic insertion mechanism is operative. It follows that C2 insertion is an unlikely possibility. 

At the Mellon Institute he applied l4C tracers to examine the behavior of intermediates in Fischer-Tropsch synthesis over iron catalysts. By adding small amounts of radioactively labeled compounds to the CO/H2 synthesis gas mixtures, he was able to prove that some of these compounds (e.g., small alcohols) are involved in the initiation step of the chain growth process that leads to larger hydrocarbon products. It was during this era that his associates first placed a catalytic reactor into the carrier gas stream of a gas chromatograph and developed the microcatalytic pulse reactor, which is now a standard piece of equipment for mechanistic studies with labeled molecules. While at Mellon Institute Emmett began editing his comprehensive set of seven volumes called Catalysis, which he continued at Hopkins. 

Hydrocarbon distributions in the Fischer-Tropsch (FT) synthesis on Ru, Co, and Fe catalysts often do not obey simple Flory kinetics. Flory plots are curved and the chain growth parameter a increases with increasing carbon number until it reaches an asymptotic value. a-Olefin/n-paraffin ratios on all three types of catalysts decrease asymptotically to zero as carbon number increases. These data are consistent with diffusion-enhanced readsorption of a-olefins within catalyst particles. Diffusion limitations within liquid-filled catalyst particles slow down the removal of a-olefins. This increases the residence time and the fugacity of a-olefins within catalyst pores, enhances their probability of readsorption and chain initiation, and leads to the formation of heavier and more paraffinic products. Structural catalyst properties, such as pellet size, porosity, and site density, and the kinetics of readsorption, chain termination and growth, determine the extent of a-olefin readsorption within catalyst particles and control FT selectivity. 

It will be interesting to see whether further reports with more precise analytical data than those heretofore offered (89,90) will be forthcoming. Evidence ruling out the possibility of toluene formation by chain growth in Fischer-Tropsch synthesis followed by dehydrocyclization would also be necessary for a confirmation of the methylation of benzene as suggested by Eidus (89). 

This is the well-known Anderson-Flory-Schultz (ASF) distribution. Figure 5.4.4 shows how the Fischer-Tropsch product distribution depends on the chain-growth probability, a. 

Figure 5.4.4 Fischer-Tropsch product distributions in terms of interesting hydrocarbon fractions as a function of the chain-growth probability, a, as calculated with Equation (23). The insert shows a few ASF plots according to Equation (24).

Fischer-Tropsch Technology FTS can be carried out in several different reactor types fixed bed, fluidized bed, or slurry phase and at different temperatures. The high-temperature Fischer-Tropsch (HTFT) synthesis runs at 320°C-350°C, at which temperatures typically all products are in the gas phase [22], HTFT is operated in fluidized-bed reactors, with iron catalysts. Selectivities correspond to chain-growth probabilities in the range of 0.70-0.75 and are ideal for gasoline production, but olefins and oxygenates are formed as well and are used as chemicals. 

Low-temperature Fischer-Tropsch (LTFT) synthesis runs at temperatures between 200°C and 250°C [23-25]. The chain-growth probability at these conditions is much higher than for the HTFT, and as a consequence, the product distribution extends well into the liquid waxes. LTFT reactors are thus three-phase systems solid catalysts, gaseous reactants, and gaseous and liquid products. Both cobalt and iron... 

The Fischer-Tropsch reaction consists of an initiation step, a chain-growth step, and a termination step. However, the observed product distribution may reflect secondary reactions such as alkene insertion... 

In this review, we limit ourselves to the mechanisms of primary product formation, which are fimdamental to Fischer-Tropsch chemistry. Using new information mainly from computational studies, we focus on two coidlicting hypotheses regarding the key reaction steps that lead to chain growth. 

The first hypothesis of a Fischer-Tropsch mechanism, as formulated by Sachtler and Biloen, is illustrated in Scheme 1. This mechanism is characterized by an initial C—O bond cleavage and chain growth through addition of species. 

The authors conducted an experiment (now regarded as classical) in Fischer-Tropsch catalysis that supports this initiation mechanism (3,4). Using isotopes, they demonstrated that the carbon chain-growth reaction can occur from Ci species generated by the dissociation of CO. As shown below, this hypothesis implies that the rate of CO dissociation should be fast and should not control the overall Fischer-Tropsch reaction. 

The second proposed mechanism for the Fischer-Tropsch reaction is the Pichler-Schulz mechanism (2,16) (Scheme 2), which is characterized by chain growth by insertion of CO. This mechanism implies that the insertion step and subsequent dehydroxylation are fast compared with the chain-termination reaction. We emphasize that, according to this scenario, CO dissociation does not need to proceed rapidly. 

According to the Sachtler-Biloen mechanism, the Fischer-Tropsch reaction is initiated through CO adsorption followed by CO dissociation. Experimental evidence for the involvement of an oxygen-free intermediate exists it was observed that predeposited C is incorporated into the product during Fischer-Tropsch synthesis when CO was included in the feed gas (3). It is important to distinguish whether during the Fischer-Tropsch s)mthesis CO dissociation is strictly monomolecular or instead involves a reaction with Hads to produce an intermediate "HCO" formyl species that in a subsequent reaction decomposes to "CH" and Oads-Another question is how the rates of CO dissociation, chain growth, and termination depend on the catalyst surface structure. Thus, it is essential to know the relative values of the rate constants for these three elementary reactions. 

The equations that we consider in this section were deduced on the basis of the additional simplifying assumption that only one type of "Ci species is formed. In principle, hydrogenation of "Ci" species proceeds via consecutive surface reaction steps in which different "CH. " species are subsequently formed. In Section 3.3, we discuss the consequences of the presence of various "CH " species on the surface for the kinetics of the Fischer-Tropsch reaction. Considering this more complex scenario is relevant to understanding and calculation of the chain-growth parameter a. 

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