甲苯常压催化氧化制苯甲酸及其它芳烃的氧化反应的研究

Study on Catalytic Oxidation of Toluene to Benzene Carbonic Acid and Other Aromatic Hydrocarbon

以２５％甲苯无水乙酸作反应液，钴、锰和铵的混合盐作催化剂，乙腈作促进剂，纯氧为氧化剂，在１１０℃±２℃下，常压反应１５ｈ，苯甲酸收率达８５％。用该催化剂体系氧化其它芳烃时，亦可获得类似结果。若芳烃侧链烷基Ｒ＝Ｃ１～Ｃ６时，首先起反应的是与苯环相邻的碳原子，伯碳由醛变为酸；仲碳由酮升温后断链变酸；叔碳或烯键则直接断键变为酸。

It was found that the optimized conditions of catalytic oxidation of toluene to benzene carbonic acid were that 25% toluene in non aqueous acetic acid as reaction medium, ammonia Co Mn complex salt as catalyst, acetonitrile as accelerator, pure oxygen as oxidizing agent at temperature 110℃±2℃ for 15h. The yield was about 85%. This catalytic system exhibited the same activity for other aromatic hydrocarbons. When alkyl group R=C 1～C 6 attached to benzene the carbon atom in aliphatic position reacted first, for primary carbon, aldehyde directly changed to acid, for secondary or tertiary carbons and olefen, they changed to acids after breaking C-C bonds at higher temperature.