The presence of ethane has been confirmed among the products of the catalytic decomposition of ethyl alcohol, and comparatively large amounts of carbon dioxide have been found to occur. The ethane produced has been shown to be due only in part, if at all, to the hydrogenation of ethylene, and may be explained by a decomposition of alcohol to acetaldehyde, water and ethane. In view of the small oil and acid production, the presence of carbon dioxide is inexplicable on the basis of accepted mechanisms.
A series of catalysts containing nickel and chromium has been prepared and their action on mixtures of ethyl alcohol and water studied. The most active catalysts are prepared by precipitation of the metals as hydroxides or in combination as nickel chromate. The activity of the catalysts depends very much on the nature of the treatment accorded them in preparation. The action of the nickel always predominates but it is more sensitive than chromium to vigorous treatment. The catalysts generally lose some of their activity with use, the nickel more so than the chromium, and the dehydrating efficiency of the catalyst may rise. Secondary reactions, with the production of carbon and complex organic liquids, usually occur, both of which result in carbon dioxide production.
Numerous experiments have been carried out on the decomposition of alcohol, alcohol and water, and alcohol and carbon dioxide mixtures over poly-component catalysts at temperatures up to 500 °C. Quantitative data on the gaseous and the liquid products were obtained. The properties of the poly-component catalysts, as evidenced by the simple primary and secondary reactions, have been shown to be qualitatively those of the single components.Methane can be produced in one or more of several secondary reactions, namely, the decomposition of acetaldehyde, the hydrogenation of carbon oxides and the decomposition of ethylene. Ethane can be produced in one or both of two reactions consisting of auto-oxidation and reduction of the alcohol, or the secondary hydrogenation of ethylene, confirming previous work. Carbon dioxide, in most cases, is formed as a result of the water-gas reaction and the decomposition of carbon monoxide. In other cases its origin is obscure. The results of certain experiments in which carbon dioxide and hydrogen were the major constituents of the off-gas cannot be explained in the same way. Reactions involving ketene decomposition and polymerization, and hydration of alcohol, have been suggested as possible explanations.
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