Methane methanol synthesis

Steam reforming Carbon monoxide conversion Carbon monoxide methanization Methanol synthesis Oxo-synthesis... 

Thermal chlorination of methane was first put on an industrial scale by Hoechst in Germany in 1923. At that time, high pressure methanol synthesis from hydrogen and carbon monoxide provided a new source of methanol for production of methyl chloride by reaction with hydrogen chloride. Prior to 1914 attempts were made to estabHsh an industrial process for methanol by hydrolysis of methyl chloride obtained by chlorinating methane. 

The influence of Zn-deposition on Cu(lll) surfaces on methanol synthesis by hydrogenation of CO2 shows that Zn creates sites stabilizing the formate intermediate and thus promotes the hydrogenation process [2.44]. Further publications deal with methane oxidation by various layered rock-salt-type oxides [2.45], poisoning of vana-dia in VOx/Ti02 by K2O, leading to lower reduction capability of the vanadia, because of the formation of [2.46], and interaction of SO2 with Cu, CU2O, and CuO to show the temperature-dependence of SO2 absorption or sulfide formation [2.47]. 

As an alternate to LNG, natural gas can be chemically converted to methanol, chemical feedstocks (such as ethylene), gasoline, or diesel fuel. Most processes start with the conversion of methane to synthesis gas, a mixture of carbon monoxide and hydrogen. This can be done partial oxidation, an exothermic reaction ... 

Natural gas and crude oils are the main sources for hydrocarbon intermediates or secondary raw materials for the production of petrochemicals. From natural gas, ethane and LPG are recovered for use as intermediates in the production of olefins and diolefms. Important chemicals such as methanol and ammonia are also based on methane via synthesis gas. On the other hand, refinery gases from different crude oil processing schemes are important sources for olefins and LPG. Crude oil distillates and residues are precursors for olefins and aromatics via cracking and reforming processes. This chapter reviews the properties of the different hydrocarbon intermediates—paraffins, olefins, diolefms, and aromatics. Petroleum fractions and residues as mixtures of different hydrocarbon classes and hydrocarbon derivatives are discussed separately at the end of the chapter. 

The various processes involving carbon monoxide steam reforming, water-gas shift, methanation, and methanol synthesis illustrate the operation of thermodynamic constraints and some of their attendant economic consequences. 

Figure 8.4 Hypothetical reaction coordinate diagrams for CO hydrogenation on Pd and Ni the dissociation of CO is more difficult on Pd, making methanol synthesis more favorable than methane formation, which requires C-0 dissociation, and is the preferred pathway on Ni...

Fuel gas for gas turbines (IGCC) and as a replacement for natural gas or chemical substitute. Can be used as a feedstock to Fisher-Tropsch synthesis, methanation, methanol, and ammonia production. 

If the gasifier product stream is intended for downstream use as the feedstock for further upgrading such as methanation, methanol or Fischer Tropsch synthesis, very thorough desulphuri-sation is essential since the catalysts in these upgrading processes are highly sensitive to sulphur poisoning. The methanation catalysts normally cannot tolerate more than 0.05 ppm of sulphur in the feedstock. In addition to H2S sulphur values in the gasifier product it may contain COS, CS2, mercaptans and thiophenes. These are normally removed by activated carbon or zinc oxide filters ahead of the sensitive synthesis catalyst beds. 

Copper based catalysts have long been considered as the only effective methanol synthesis catalysts. However, Poutsma et al. (7) showed that palladium catalysts were active in methanol synthesis from CO-H. This latter metal had been previously considered as either almost inactive or active only for methane formation (8). Furthermore it is now known that both activity and selectivity can change drastically with the support. Vannice (9) observed that the methanation activity of a Pd/Al O was enhanced eighty and forty times compared to palladium black or Pd/SiO (or Pd/TiO ) respectively. The support effect on the selectivity was pointed out by many authors even at atmospheric pressure when the reaction temperature... 

Stage 3 shifts the source of hydrocarbon for transportation and chemicals to methane. Methane currently is reformed at elevated temperatures and pressures to synthesis gas. This mixture of hydrogen and carbon monoxide can then be converted via the well-known technologies of methanol synthesis and Fischer-Tropsch synthesis to eventually produce a variety of chemicals and fuels. In this stage, focus... 

If the product is a low- or medium-Btu gas, produced for direct combustion, the stream will probably be desulfurized for environmental reasons. In this instance, approximately 95% sulfur removal is typical of a reasonable level of purification - better than direct combustion of the coal by a factor of two, yet not requiring an excessive energy penalty. If the gaseous product is a synthesis gas, as in the production of methane, methanol, or Fishcher-Tropsch liquids, extreme desulfurization is required to protect the sulfur-sensitive downstream catalysts. 

When the gasified coal is to be used for synthesis of methane methanol, or hydrogen, part or all of it is subjected to the water-gas shift reaction, converting CO and water to CO2 and H2. Sulfur must be removed completely. The acid gases H2S and CO2 are first extracted from the gas before or after the shift conversion these acid gases may be processed in a second step in a Claus unit. The acid gas composition depends on each part of the sequence preceding the Claus unit. 

The current two-step industrial route for the synthesis of methanol, from coal or methane to synthesis gas and then from synthesis gas to methanol, has certain drawbacks. The economic viability of the whole process depends on the first step, which is highly endothermic. Thus a substantial amount of the carbon source is burned to provide the heat for the reaction. It would be highly desirable, therefore, to replace this technology with a technically simpler, single-step process. This could be the direct partial oxidation of methane to methanol, allowing an excellent way to utilize the vast natural-gas resources. Although various catalysts, some with reasonable selectivity, have been found to catalyze this reaction (see Sections 9.1.1 and 9.6.1), the very low methane conversion does not make this process economically feasible at present. 

Ammonia, Hydrogen, and Methanol Production The ammonia synthesis catalyst is metallic iron promoted with AljO,. K 0. MgO. and CaO. The hydrogen-producing (methane reforming) catalyst is supported nickel. The methanol synthesis catalyst is ZnO promoted with Cr Oj or Cu(l>—ZnO promoted with CrjOl or AUOi. The respective reactions are cited as follows. 

With the established success of heterogeneous catalysts in the hydrogenation of CO via methanol synthesis, methanation, and F-T synthesis, it is justifiable to question the interest in investigating these reactions under... 

Interaction of methane with steam on a nickel surface is the basis of the natural gas reforming process. The process is used as a source of hydrogen for ammonia production and methanol synthesis and, therefore, finds a large-scale industrial application. 

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