Methane, formation

The processes that have been developed for the production of synthetic natural gas are often configured to produce as much methane in the gasification step as possible thereby minimizing the need for a methanation step. In addition, methane formation is highly exothermic which contributes to process efficiency by the production of heat in the gasifier, where the heat can be used for the endothermic steam—carbon reaction to produce carbon monoxide and hydrogen. 

Hackstein et al ° have suggested that there may be a phylogenetic basis for the occurrence of significant methane formation in the gut of animals. It was argued that this refiected the presence of a methanogen receptor in the gut of animals which support large populations of these bacteria, since the production of... 

At the temperatures used in coal gasification 870°C), methane formation also occurs by hydrogenation of carbon ... 

Kinetics. Extensive studies of the kinetics of methane synthesis were reported by White and co-workers (10,11, 12, 13, 14, 15). They studied the reaction between CO and hydrogen over a reduced nickel catalyst on kieselguhr at 1 atm and 300°-350°C (10). They correlated the rate of methane formation by the equation ... 

The kinetic expression was derived by Akers and White (10) who assumed that the rate-controlling factor in methane formation was the reaction between the adsorbed reactants to form adsorbed products. However, the observed temperature-dependence of the rate was small, which indicates a low activation energy, and diffusion was probably rate-controlling for the catalyst used. 

It is highly active but easily poisoned by sulfur and not particularly selective to methane. Oddly enough, carbon monoxide appears to inhibit the rate of methane formation. 

It is obvious that one can use the basic ideas concerning the effect of alkali promoters on hydrogen and CO chemisorption (section 2.5.1) to explain their effect on the catalytic activity and selectivity of the CO hydrogenation reaction. For typical methanation catalysts, such as Ni, where the selectivity to CH4 can be as high as 95% or higher (at 500 to 550 K), the modification of the catalyst by alkali metals increases the rate of heavier hydrocarbon production and decreases the rate of methane formation.128 Promotion in this way makes the alkali promoted nickel surface to behave like an unpromoted iron surface for this catalytic action. The same behavior has been observed in model studies of the methanation reaction on Ni single crystals.129... 

The influence of electronegative additives on the CO hydrogenation reaction corresponds mainly to a reduction in the overall catalyst activity.131 This is shown for example in Fig. 2.42 which compares the steady-state methanation activities of Ni, Co, Fe and Ru catalysts relative to their fresh, unpoisoned activities as a function of gas phase H2S concentration. The distribution of the reaction products is also affected, leading to an increase in the relative amount of higher unsaturated hydrocarbons at the expense of methane formation.6 Model kinetic studies of the effect of sulfur on the methanation reaction on Ni(lOO)132,135 and Ru(OOl)133,134 at near atmospheric pressure attribute this behavior to the inhibition effect of sulfur to the dissociative adsorption rate of hydrogen but also to the drastic decrease in the... 

The relative rate of coke versus methane formation then follows from... 

Tec and rn decrease when the carbon adsorption energy increases. Volcano-type behavior of the selectivity to coke formation is found when the activation energy of C-C bond formation decreases faster with increasing metal-carbon bond energy than with the rate of methane formation. Equation (1.16b) indicates that the rate of the nonselective C-C bond forming reaction is slow when Oc is high and when the metal-carbon bond is so strong that methane formation exceeds the carbon-carbon bond formation. The other extreme is the case of very slow CO dissociation, where 0c is so small that the rate of C-C bond formation is minimized. 

A new, heat-stable, coenzyme concerned with methyl group transfer has been isolated from Methanobacterium. The coenzyme, which is involved in transmethylation reactions prior to methane formation by the organism, contains phosphorus and has a u.v. absorption at 260 nm, suggesting that it may be a nucleotide. 

Methanation Studies. Turnover frequencies for methane formation were... 

Methanatlon Studies. Because the most effective way to determine the existence of true bimetallic clusters having mixed metal surface sites Is to use a demanding catalytic reaction as a surface probe, the rate of the CO methanatlon reaction was studied over each series of supported bimetallic clusters. Turnover frequencies for methane formation are shown In Fig. 2. Pt, Ir and Rh are all poor CO methanatlon catalysts In comparison with Ru which Is, of course, an excellent methanatlon catalyst. Pt and Ir are completely inactive for methanatlon In the 493-498K temperature range, while Rh shows only moderate activity. 

Figure 2. The dependence of the reaction rate for methane formation on surface composition.

Ermler U, W Grabarse, S Shima, M Goubeaud, RK Thauer (1997) Crystal structure of methyl-coenzyme M reductase the key enzyme of biological methane formation. Science 278 1457-1462. 

Hippe H, D Caspari, K Fiebig, G Gottschalk (1979) Utilization of trimethylamine and other N-methyl compounds for growth and methane formation by Methanosarcina barkeri. Proc Natl Acad Sci USA 76 494-498. 

The dependence of methane formation on methyl coverage is shown in fig. 3. The yield of methane increases as the coverage increases. At coverages below 0.05 ML, little meAane is formed. Nearly all of the methyl groups decompose. At saturation coverage, about 0.14 ML of the methyl groups form methane, and roughly 0.27 ML decompose... 

Ruthenium is a known active catalyst for the hydrogenation of carbon monoxide to hydrocarbons (the Fischer-Tropsch synthesis). It was shown that on rathenized electrodes, methane can form in the electroreduction of carbon dioxide as weU. At temperatures of 45 to 80°C in acidihed solutions of Na2S04 (pH 3 to 4), faradaic yields for methane formation up to 40% were reported. On a molybdenium electrode in a similar solution, a yield of 50% for methanol formation was observed, but the yield dropped sharply during electrolysis, due to progressive poisoning of the electrode. 

The broken-line curves at the top of Figure 1 represent the tendencies for surface decarburization of steels while they are in contact with hydrogen. The solid-line curves represent the tendencies for steels to decarburize internally with resultant Assuring and cracking created by methane formation. 

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