Fischer product distribution

Finally, it has been reported that carbon electrodes modified with thin polymeric films of polypyridyl metal complexes containing a dispersion of metal particles (Rh° or Pd°) can be used as electrocatalyst for reduction of C02 to hydrocarbons in MeCN. Apparently CH4 is the dominant reduction product (up to 18% of faradaic efficiency).123,124 It should be noted that the product distribution is reminiscent of a Fischer-Tropsch process since C2, C3, and C4 hydrocarbons are also formed. 

Huang, X. W., Elbashir N. O., and Roberts, C. B. 2004. Supercritical solvent effects on hydrocarbon product distributions from Fischer-Tropsch synthesis over an alumina-supported cobalt catalyst. Industrial Engineering Chemistry Research 43 6369-81. 

Temperature-programmed reduction combined with x-ray absorption fine-structure (XAFS) spectroscopy provided clear evidence that the doping of Fischer-Tropsch synthesis catalysts with Cu and alkali (e.g., K) promotes the carburization rate relative to the undoped catalyst. Since XAFS provides information about the local atomic environment, it can be a powerful tool to aid in catalyst characterization. While XAFS should probably not be used exclusively to characterize the types of iron carbide present in catalysts, it may be, as this example shows, a useful complement to verify results from Mossbauer spectroscopy and other temperature-programmed methods. The EXAFS results suggest that either the Hagg or s-carbides were formed during the reduction process over the cementite form. There appears to be a correlation between the a-value of the product distribution and the carburization rate. 

The TPR-XAFS technique confirmed that doping Fischer-Tropsch synthesis catalysts with Cu and alkali (e.g., K) remarkably promotes the carburization rate relative to the undoped catalyst. The EXAFS results suggest that either the Hagg or e-carbides were formed during the reduction process over the cementite form. A correlation is observed between the a-value of the product distribution and the carburization rate. 

In this chapter a two a selectivity model is proposed that is based on the premise that the total product distribution from an Fe-low-temperature Fischer-Tropsch (LIFT) process is a combination of two separate product spectrums that are produced on two different surfaces of the catalyst. A carbide surface is proposed for the production of hydrocarbons (including n- and iso-paraffins and internal olefins), and an oxide surface is proposed for the production of light hydrocarbons (including n-paraffins, 1-olefins, and oxygenates) and the water-gas shift (WGS) reaction. This model was tested against a number of Fe-catalyzed FT runs with full selectivity data available and with catalyst age up to 1,000 h. In all cases the experimental observations could be justified in terms of the model proposed. 

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. 

Zhan, X., Davis, B. H. 2002. Assessment of internal diffusion limitation on Fischer-Tropsch product distribution. Applied Catalysis A General 236 149-61. 

Donnelly, T.J., Yates, I.C., Satterfield, C.N. 1988. Analysis and prediction of product distributions of the Fischer-Tropsch synthesis. Energy Fuels 2 734. 

Schulz, H., Claeys, M. 1999. Kinetic modelling of Fischer-Tropsch product distributions. Appl. Catal. A 186 91. 

Kuipers, E.W., Scheper, C., Wilson, J.H., Vinkenburg, I.H., and Oosterbeek, H. 1996. Non-ASF product distributions due to secondary reactions during Fischer-Tropsch synthesis. J. Catal. 158 288-300. 

Iron-based catalysts have been used in all the plants constructed after the war, because (a) iron is considerably cheaper than cobalt, (b) iron systems are generally more stable, and (c) greater flexibility with regard to product distribution can be attained. With the exception of the SASOL complex, which will be dealt with in Section I,B, the only Fischer-Tropsch plant of any appreciable size constructed in the West since the... 

Table I. Product Distribution using CpCo(C0)2 5 as a Fischer-Tropsch Catalyst...

The product distribution frcm the Fischer-Tropsch reaction on 5 is shown in Table I. It is similar but not identical to that obtained over other cobalt catalysts (18-21,48, 49). The relatively low amount of methane production (73 mol T when compared with other metals and the abnormally low amount of ethane are typical (6). The distribution of hydrocarbons over other cobalt catalysts has been found to fit the Schulz-Flory equation [indicative of a polymerization-type process (6)]. The Schulz-Flory equation in logarithmic form is... 

X. Huang, N. O. Elbashir and C. B. Roberts, Supercritical Solvent Effects on Hydrocarbon Product Distributions from Fischer-Tropsch synthesis over an Alumina-Supported Cobalt Catalyst, Ind. Eng. Chem. Res., 2004, 43, 6369-6381. 

More recently the flash photolysis of diethyl mercury has been re-investigated by Fischer and Mains92. At 1.54 torr and 24 °C the major products are butane (36 %), ethylene (32 %), ethane (22 %), propane (6 %) and hydrogen (4 %). Only traces of methane were detected. The addition of perfluorodimethylcyclo-butane vapour did not alter the extent of photolysis, but the butane yield increased approximately 25 % while the yield of ethylene, ethane, hydrogen and propane all decreased. The change in product distribution occurred as the inert gas pres-... 

Fischer-Tropsch synthesis, 30 178, 191 -Hj conversion, product distribution, 38 336-337, 340-341... 

The Mills-Nixon hypothesis that small ring annelation on benzene would induce bond fixation (bond alternation) by trapping out one Kekul6 tautomer is a casualty of early twentieth century structural chemistry. Due to a lack of direct methods for analyzing molecular structure, structural postulates of that time were often supported by an analysis of product distributions. An experimental observable such as product selectivity or isomer count was correlated to an unobservable structural feature derived on the basis of a chemical model. Classical successes of this method are van t Hoff s proof of the tetrahedral carbon atom and Fischer s proof for the configuration of sugars. In the case of Mills and Nixon, however, the paradigm broke down. 

Metal molybdates421 and cobalt-thoria-kieselguhr422 also catalyze the formation of hydrocarbons. It is believed, however, that methanol is simply a source of synthesis gas via dissociation and the actual reaction leading to hydrocarbon formation is a Fischer-Tropsch reaction. Alumina is a selective dehydration catalyst, yielding dimethyl ether at 300-350°C, but small quantities of methane and C2 hydrocarbons423 424 are formed above 350°C. Heteropoly acids and salts exhibit high activity in the conversion of methanol and dimethyl ether.425-428 Acidity was found to determine activity,427 130 while hydrocarbon product distribution was affected by several experimental variables.428-432... 

Ruthenium is known to catalyze a number of reactions, including the Fischer-Tropsch synthesis of hydrocarbons (7) and the polymerization of ethylene (2). The higher metal dispersions and the shape selectivity that a zeolite provides has led to the study of ruthenium containing zeolites as catalytic materials (3). A number of factors affect the product distribution in Fischer-Tropsch chemistry when zeolites containing ruthenium are used as the catalyst, including the location of the metal (4) and the method of introducing ruthenium into the zeolite (3). 

Non-Flory Product Distributions in Fischer— Tropsch Synthesis Catalyzed by Ruthenium, Cobalt, and Iron... 

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).

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... 

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