Hydrodesulfurization of Dibenzothiophene Catalyzed by Supported Metal Carbonyl Complexes.

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  • ISHIHARA Atsushi
    Dept. of Chemical Engineering, Faculty of Technology, Tokyo University of Agriculture and Technology
  • QIAN Weihua
    Dept. of Chemical Engineering, Faculty of Technology, Tokyo University of Agriculture and Technology
  • KABE Toshiaki
    Dept. of Chemical Engineering, Faculty of Technology, Tokyo University of Agriculture and Technology

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  • 担持金属カルボニル錯体を用いたジベンゾチオフェンの水素化脱硫反応

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Abstract

Hydrodesulfurization (HDS) of dibenzothiophene (DBT) catalyzed by supported anionic molybdenum and ruthenium carbonyl complexes is described, specifically the catalytic activity and the product selectivity. A Mo(CO)6-NEt3-EtSH/Al2O3 system activated by H2 or H2S shows the highest catalytic activity among catalysts derived from supported-metal carbonyls and conventional molybdena-alumina. Investigation of the effects of supports found the yields of HDS products decreased in the order, SiO2-Al2O3>Al2O3>TiO2=Active carbon>SiO2>NaY zeolite=HZSM-5>HY zeolite.<br>The effects of addition of alkali metal hydroxide on the catalytic activity and product selectivity of sulfided alumina-supported ruthenium carbonyls in HDS of DBT were described. Addition of an alkali metal hydroxide to catalysts derived from alumina-supported Ru3(CO)12 remarkably increased the conversion of DBT. The Ru3(CO)12 must be supported on alumina so that the reaction with the alkali metal hydroxide will form an anionic ruthenium hydride complex [HRu3(CO)11]-, which is essential to obtain the high catalytic activity. Cesium was the most effective of the alkali metals. The conversion of DBT reaches the maximum at Cs/Ru=2. Further addition of cesium decreased the activity. Biphenyl was produced selectively in this system.<br>The involvement of cesium was elucidated by tracing the behavior of 35S on the alumina-supported ruthenium carbonyls-cesium hydroxide systems in HDS of [35S]DBT. The amount of labile sulfur was estimated from the amount of 35S accommodated on the catalyst. The rate constant of [35S]H2S release was estimated from the first order plot of the decreasing radioactivity of product [35S]H2S. The results obtained indicated that the dispersion of ruthenium species was significantly high. Cesium probably promotes the C-S bond scission of DBT and increases the activity by stabilizing the Ru-S bonds of ruthenium sulfide.

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