离子液体中杂质对1-己烯氢甲酰化反应的影响  

Effect of Impurities in Ionic Liquid on 1-Hexene Hydroformylation

作　　者：林棋[1] 娄本勇[1] 陈毅挺[1] 蒋维东[2] 陈华[2] 李贤均[2] 

机构地区：[1]闽江学院化学与化学工程系,福建福州350108 [2]绿色化学与技术教育部重点实验室四川大学化学学院,四川成都610064

出　　处：《石油化工》2009年第1期25-29,共5页Petrochemical Technology

基　　金：福建省自然科学基金项目(2008J0164);福州市科技项目(2007-Z-81);福建省青年人才创新基金项目(2008F3081)

摘　　要：利用无卤化物路线合成了离子液体1-丁基-3-甲基咪唑对甲苯磺酸盐([bmim][p-CH3C6H4SO3]),并作为水溶性铑膦络合物Rh-TPPTS(TPPTS为三(间-磺酸钠盐苯基)膦)催化1-己烯氢甲酰化反应的溶剂,通过添加一定量的杂质来模拟反应,研究了离子液体中可能存在的杂质对1-己烯氢甲酰化反应的影响。研究结果表明,离子液体中存在的杂质对1-己烯氢甲酰化反应均有不同程度的影响,其中卤化物杂质引起催化体系的反应活性和总醛(包括庚醛和2-甲基己醛)的选择性大幅度下降;对甲苯磺酸杂质对反应活性的影响不大,能很好地抑制1-己烯的加氢副反应,但加剧了1-己烯的异构化副反应,导致总醛的选择性降低;当溶剂中水的体积分数小于35%时,水对反应没有明显影响,只有当水的体积分数超过35%时,催化活性才明显降低。Ionic liquid, 1-n-butyl-3-methylimidazolium p-toluenesulfonate （ [ bmim ][ P- CH3C6H4SO3] ） was synthesized by non-halide route, and used as solvent in hydroformylation of 1-hexene catalyzed by water-soluble rhodium-phosphine complex Rh-TPPTS （ TPPTS ： mtriphenylphosphine trisulphonate sodium salt）. Some impurities, possibly brought in by ion exchange preparation of ionic liquid [ bmim] [p-CH3C6H4SO3 ] were added to simulate their effects on the hydroformylation. The presence of halides as impurities in ionic liquid plays a substantial negative role in 1-hexene hydroformylation, and the catalytic activity and selectivity to aldehydes including heptaldehyde and 2-methyl hexanal in 1-hexene hydroformylation drop strongly. The presence of p-toluenesulfonic acid in ionic liquid favorably inhibits the hydrogenation of 1-hexene but accelerates the isomerization of 1-hexene. The presence of water especially when its volume fraction is below 35 % shows only slight effect on hydroformylation of 1-hexene. When the volume fraction is more than 35% the activity of the catalytic system decreases apparently.

关 键 词：离子液体 杂质 1-己烯 氢甲酰化 水 卤化物 对甲苯磺酸 

分 类 号：TQ203.2[化学工程—有机化工]