Homogeneous methanation

Hjertager, B. H., M. Bjorkhaug, and K. Fuhre. 1988b. Explosion propagation of non-homogeneous methane-air clouds inside an obstructed 50m vented vessel. J. Haz. Mat. 19 139-153. 

Modeling of Homogeneous Methane Combustion in Micro Channels... 

The above thermochemical values were used to fill the heterogeneous module of the kinetic scheme for the OCM reaction over a model Li/MgO catalyst with corresponding kinetic parameters (see Table III). In combination with a scheme of homogeneous methane oxidation, this set of reactions forms the desired micro-kinetic description. It allowed us to re-consider specific features of the OCM process and to obtain some unexpected results. 

Fig. 9. Methane oxidation in spatially distributed system effect of gas gap thickness on 0.i (time of reaching 10%-conversion) and relative efficiency of heterogeneous and homogeneous methane activation (Ifhom/ tot) (Sinev et al, 1997a, b).

Although most of known homogeneous reductions of carbon monoxide with hydrogen catalyzed by carbonyl complexes produce a mixture of oxygenated products, the iridium carbonyl species Ir4(CO)i2 has proved to catalyze the following homogeneous methanation reaction in toluene solutions. 

In addition to coal moisture, water is often added to the process as temperature-moderating steam or as liquid transport medium. Consequentiy, reactions such as a water-gas shift (4.9) or homogeneous methanation (4.10) may influence the final gas composition. 

Another method of manufacturing SiC by the decomposition of a gas mixture containing silane, propane, and hydrogen, and hydrogen chloride has been described (80). With such a mixture, it was possible to work at a relatively lower (1200°C) temperature and it was claimed that compact, homogeneous P SiC crystals were obtained. In a variation of this gas-phase synthesis theme, SiC has been produced from the reaction of SiCl and methane (81). SiC precipitates from 1000 to 3000°C. 

To 2 mmol of freshly prepared ethereal LiCu(C.H3), are added 154 mg (1 mmol) of ( — )-m-5-melhyl-2-cyclo-hexenyl acetate (3a). [a]25 —2.7 (c = 3, CHC1,), in a centrifuge tube at 0°C. The mixture is kept at 0 °C for 8 h after which 1 mL of water is added. Methane is evolved and a reddish precipitate forms. After centrifuging, the supernatant liquid is decanted and concentrated, and the product trims-4 is isolated by preparative GC. Isolated yields range from 30% and 40%. However, it was reported in a similar reaction that the yields range from 90% and 95% 5. Analysis by capillary GC shows the product to be 99.5% trans-4 and 0.5% t -4. Capillary GC of the starting 3a shows the acetate 3a to be homogeneous except for a trace ( — 1.0%) of the trans-isomers. 

For the first assumption, the value of Kw for the shift appears to be too high. It must be this high because it is necessary to make C02 appear while both C02 and CO are being consumed rapidly by methanation. The data may be tested to see if the indicated rate appears unreasonable from the standpoint of mass transfer to the gross catalyst surface. Regardless of the rate of diffusion in catalyst pores or the surface reaction rate, it is unlikely that the reaction can proceed more rapidly than material can reach the gross pill surface unless the reaction is a homogeneous one that is catalyzed by free radicals strewn from the catalyst into the gas stream. 

Thermal Decomposition. The therm decompn was studied betw 380 and 430° and found to be homogeneous and apparently 1st order. The products were complex and included nitric oxide, methane, carbon monoxide, and w plus small amts of ethane, ethylene, and nitrous oxide (Ref 23)... 

Jeffers PM, Ward LM, Woytowitch LM, et al. 1989. Homogenous hydrolysis rate constants for selected chlorinated methanes, ethanes, ethenes and propanes. Environmental Science and Technology 23 965-969. 

In situ infrared observations show that the primary species present during the reduction of NO by CH4 over Co-ZSM-5 are adsorbed NO 2 and CN. When O2 is present in the feed NO2 is formed by the homogeneous and catalyzed oxidation of NO. In the absence of O2, NO2 is presumed to be formed via the reaction 3 NO = NO2 + N2O. The CN species observed are produced via the reaction of methane with adsorbed NO2, and transient response studies suggest that CN species are precursors to N2 and CO2. A mechanism for the SCR of NO is proposed (see Figure 10). This mechanism explains the means by which NO2 is formed from adsorbed NO and the subsequent reaction sequence by which adsorbed NO2 reacts with CH4 and O2 to form CN species. N2 and CO or CO2 are believed to form via the reaction of CN with NO or NO2. CH3NO is presumed to be formed as a product of the reaction of CH4 with adsorbed NO2. The proposed mechanism explains the role of O2 in facilitating the reduction of NO by CH4 and the role of NO in facilitating the oxidation of CH4 by O2. 

It has been shown [90] that the homogeneous dissociation of methane is the only primary source of free radicals and it controls the rate of the overall process. This reaction is followed by a series of consecutive and parallel reactions with much lower activation energies. After the formation of acetylene (C2H2), a sequence of very fast reactions occurs, leading to the production of higher unsaturated and aromatic hydrocarbons and finally carbon ... 

Summary of literature data on methane decomposition catalysts and preferred temperature range. Catalysts 1 = nickel, 2 = iron, 3 = carbon, and 4 = other transition metals (Co, Pd, Pt, Cr, Ru, Mo, W). The dotted line arbitrarily separates heterogeneous (catalytic) and homogeneous (noncatalytic, gas phase) temperature regimes of the methane decomposition reaction. 

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