プロピレンのアリル型酸化に対する酸化亜鉛の触媒活性

概要

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The catalytic oxidation of propylene over zinc oxide and the reduction of zinc oxide with propylene were studied at 450-580℃, and the active site for allylic oxidation to 1.5-hexadiene was discussed. Various zinc oxide catalysts were more or less active for 1.5-hexadiene formation, and their activities and sslectivities varied considerably with the preparation condition and the history. The oxidation conditions resulting in full conversion of gaseous oxygen caused the gradual increase of activity for 1.5-hexadiene formation. In the reduction of zinc oxide with propylene, the amount of carbon dioxide formed by complete oxidation decreased monotonously with reduction time, while that of 1,5-hexadiene increased at first and then decreased through maximum. This fact means that active sites for allylic oxidation should be produced by the reduction of zinc oxide surface. From these results, it may be reasonably proposed that surface Zn2+ ion whose coordination sites are highly unsaturated by lack of surface oxygen may act as the active center for allylic oxidation to 1,5-hexadiene. On the other hand, complete oxidation would take place at Zn2+ site associated with many oxygen ions.
長崎大学工学部,Faculty of Engineering, Nagasaki Universityの論文