CuBr2-吡啶离子液体催化甲醇液相一步氧化生成甲缩醛  

One-step Oxidation of Liquid Methanol to Dimethoxymethane with CuBr2-Pyridine Ionic Liquids as Catalyst

作　　者：赵凌峰 翟刚[2] 邓志勇[1] 张华[2] 王公应[1,2,3] ZHAO Ling-feng;ZHAI Gang;DENG Zhl-yong;ZHANG Hua;WANG Gong-ying(Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences,Chengdu 610041,Sichuan,China;Chengdu Organic Chemicals Co.,Ltd.,Chinese Academy of Sciences,Chengdu 610041,Sichuan,China;University of Chinese Academy of Sciences,Beijing 10049,China)

机构地区：[1]中国科学院成都有机化学研究所,四川成都610041 [2]中国科学院成都有机化学有限公司,四川成都610041 [3]中国科学院大学,北京100049

出　　处：《精细化工》2018年第9期1542-1547,共6页Fine Chemicals

基　　金：四川省杰出青年基金培育计划(2016JQ0062);成都市科技惠民计划(2016-HM01-00091-SF)~~

摘　　要：考察了以CuBr2与具有不同烷基支链和阴离子类型的吡啶离子液体组成的催化剂体系对甲醇一步液相氧化合成甲缩醛（DMM）的催化性能，发现CuBr2-N乙基吡啶溴盐催化性能最好。考察了不同催化剂组成、催化剂浓度、反应温度、氧气压力、反应时间对甲醇一步液相氧化合成甲缩醛反应的影响。得到的最佳反应条件为：n（CuBr2）觑（Ⅳ-乙基吡啶溴盐）=1．0、催化剂质量浓度为40g／L、反应温度130。C、氧气压力3MPa和反应时间4h，在该条件下甲醇转化率达到26．1％，DMM选择性达到95．0％。CuBr2．Ⅳ．乙基吡啶溴盐重复使用9次后，甲醇转化率为22．2％，DMM选择性为91．2％，催化活性仍然保持稳定。CuBr2-pyridine ionic liquids with different alkyl side chain and anion were used as catalyst for one-step liquid-phase synthesis of dimethoxymethane （DMM） by oxidation of methanol. And it was found that CuBr2-N-ethylpyridinium bromide exhibited the best catalytic activity. The effects of catalyst composition, catalyst concentration, reaction temperature, oxygen pressure and reaction time on the reaction were investigated. The results showed that methanol conversion of 26.1% could be obtained with a DMM selectivity of 95.0% under the optimum conditions： n（N-ethylpyridinium bromide）/n（CuBr2）=l.0, catalyst mass concentration of 40 g/L, reaction temperature of 130 ℃, oxygen pressure of 3.0 MPa and reaction time of 4 h. CuBr2-N-ethylpyridinium bromide could keep excellent activity and stability after being reused nine times, and methanol conversion and DMM selectivity could reach 22.2% and 91.2%, respectively.

关 键 词：甲醇 氧化 甲缩醛 吡啶离子液体 催化技术 

分 类 号：TQ314[化学工程—高聚物工业]