Methane from thermal decomposition

The volatile matter is the portion of coal which, when the coal is heated in the absence of air under prescribed conditions, is liberated as gases and vapors. Volatile matter does not exist by itself in coal, except for a httle absorbed methane, but res lilts from thermal decomposition of the coal substance. 

Monoamino-1,3,5-triazines 36 are formed by heating guanidines with A -formylformimidamide (35) in dimethylformamide. Amidinc 35 is itself derived from tris(formylamino)methane by thermal decomposition in dimethylformamide.440... 

Synthesis gas is obtained either from methane reforming or from coal gasification (see Coal conversion processes). Telescoping the methanol carbonylation into an esterification scheme furnishes methyl acetate directly. Thermal decomposition of methyl acetate yields carbon and acetic anhydride,... 

The thermal decomposition of diazo(phenylsulfonyl)methane 223 under a nitrogen atmosphere generates phenylsulfonylcarbene which is trapped by olefin such as cyclohexene to give norcaranes 224 and 225 (equation 138)132. No cycloheptatriene derivative is isolated from the thermolysis of223 in benzene133. In contrast, intramolecular insertion of sulfonylcarbenes into a benzene ring is observed in the thermolysis of 226 (equation 139)134. 

The steam reforming of natural gas process is the most economic near-term process among the conventional processes. On the other hand, the steam reforming natural gas process consists of reacting methane with steam to produce CO and H2. The CO is further reacted or shifted with steam to form additional hydrogen and CO2. The CO2 is then removed from the gas mixture to produce a clean stream of hydrogen. Normally the CO2 is vented into the atmosphere. For decarbonization, the CO2 must be sequestered[l,2]. The alternative method for hydrogen production with sequestration of carbon is the thermal decomposition of methane. 

It has been generally accepted that the thermal decomposition of paraffinic hydrocarbons proceeds via a free radical chain mechanism [2], In order to explain the different product distributions obtained in terms of experimental conditions (temperature, pressure), two mechanisms were proposed. The first one was by Kossiakoff and Rice [3], This R-K model comes from the studies of low molecular weight alkanes at high temperature (> 600 °C) and atmospheric pressure. In these conditions, the unimolecular reactions are favoured. The alkyl radicals undergo successive decomposition by [3-scission, the main primary products are methane, ethane and 1-alkenes [4], The second one was proposed by Fabuss, Smith and Satterfield [5]. It is adapted to low temperature (< 450 °C) but high pressure (> 100 bar). In this case, the bimolecular reactions are favoured (radical addition, hydrogen abstraction). Thus, an equimolar distribution ofn-alkanes and 1-alkenes is obtained. 

At Brookhaven National Laboratory in the 1980s, a two-step process was described for the coproduction of hydrogen and carbon, with methane being the intermediate see Steinberg.107108 In the first step, carbonaceous material is hydrogasified to methane with a subsequent thermal decomposition of the methane to hydrogen and carbon. In the process, water is also formed from the oxygen present in the fuel. A typical overall conversion of biomass, as reported by Milne et al.,5 would be... 

Fig. 6.1 (a) TEM image and (b) Raman spectrum of graphene prepared by the thermal decomposition of methane (70 seem), (c) FESEM image and (d) Raman spectrum of graphene obtained by benzene (argon passed through benzene with flow rate of 200 seem) at 1000 °C on a nickel sheet (from [8]). 

Recently Lee et al (Ref 3) re-examined the behavior of PETN under 10 to 50 kbars of external pressure. They also find a reduction in decomposition rate with increasing applied pressure. HMX behaves similarly to PETN. TNT whose explosion products contain a high proportion of solid carbon, as expected from LeChatelier s Principle, shows little pressure effect on its thermal decomposition. Nitro-methane, however, appears to decompose more rapidly under an external pressure of 50 kbars than 10 kbars. This effect is not completely understood but Lee et al suggest that high pressure may favor the formation of the thermally less stable aci form of Nitromethane ... 

Recently, several new processes for methane thermal decomposition were reported in the literature. In one report, the authors proposed a methane decomposition reactor consisting of a molten metal bath.8 Methane bubbles through molten tin or copper bath at high temperatures (900°C and higher). The advantages of this system are efficient heat transfer to a methane gas stream and ease of carbon separation from the liquid metal surface by density difference. In... 

There have been attempts to use catalysts in order to reduce the maximum temperature of thermal decomposition of methane. In the 1960s, Universal Oil Products Co. developed the HYPROd process for continuous production of hydrogen by catalytic decomposition of a gaseous hydrocarbon streams.15 Methane decomposition was carried out in a fluidized bed catalytic reactor from 815 to 1093°C. Supported Ni, Fe and Co catalysts (preferably Ni/Al203) were used in the process. The coked catalyst was continuously removed from the reactor to the regeneration section where carbon was burned off by air, and the regenerated catalyst returned to the reactor. Unfortunately, the system with two fluidized beds and the solids-circulation system was too complex and expensive and could not compete with the SR process. 

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