Hydrogenation of carbon monoxide on manganese oxide-supported ruthenium catalysts.

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• Activities of manganese oxide-supported ruthenium catalysts for CO hydrogenation and their hydrocarbon product distribution were studied to understand the effects of ruthenium origin, the method of catalyst preparation and reaction conditions. The reaction was carried out using a high pressure fixed bed flow reactor.Further, these catalysts were characterized by CO absorption and CO-TPR, and the correlation between desorption behavior of absorbed CO and catalytic behavior was also discussed.CO conversion and hydrocarbon product distribution were strongly affected by the dispersion of Ru metal supported on manganese oxide. The decrease of metal dispersion caused by calcination in air and Ru loading resulted in lower conversion of CO and richer yield of liquid hydrocarbon products, regardless of ruthenium origin, RuCl3, Ru(acac)3, or Ru3(CO)12.Not all CO conversions were, however, dependent on Ru dispersion. The RuCl3/MnO2 catalyst contributed only to the reaction for hydrogen reduction, and one without air-calcination showed low CO conversion in spite of high dispersion measured by CO adsorption. It was inferred that low activity was due to the chlorine residual in catalyst, as a result of XPS analysis on catalysts.The products were mainly normal hydrocarbons, and carbon chain-length distribution was found to comply with the rule of Schulz-Flory, which was not different from what is generally reported on CO hydrogenation products. On using RuCl3 supported on manganese oxide two characteristic behaviors were shown, compared with use of other metal oxides such as Al2O3. One was low productivity of methane, resulting in mainly liquid hydrocarbon products. The other was high selectivity for olefin. Since these characteristics were maintained up to high temperatures, chain growth probability was considered to be nearly constant for a wide range of temperatures.It is suggested that catalyst supported on manganese oxide has ability to retard successive hydrogenation.

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公益社団法人 石油学会 | 論文

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