Rh/Ph_3PO催化剂体系的辛烯氢甲酰化反应性能考察和原位红外表征  

Hydroformylation of Octenes over Rh/Ph_3PO Catalytic System and its In-situ Infrared Characterization

作　　者：刘晔[1] 贺德华[1] 刘崇微[1] 王同恩[1] 刘金尧[1] 朱起明[1] 

机构地区：[1]清华大学一碳化工国家重点实验室,北京100084

出　　处：《分子催化》2000年第3期227-231,共5页Journal of Molecular Catalysis(China)

摘　　要：考察了反应温度、CO/H2 压力和 P/Rh比等因素 ,对 Rh/Ph3PO催化剂催化混合辛烯氢甲酰化反应活性的影响 ,优化出最佳反应条件 .并采用加热加压的原位红外表征方法 ,跟踪了在 1 -辛烯反应中 Rh/Ph3PO催化剂的活化、中间活性物种的产生和分解消失等瞬态变化情况 .实验结果表明 ,Rh/Ph3PO体系对产物异壬醛的收率明显优于 Rh/Ph3P催化剂 ;原位红外表征结果表明 ,催化反应活性物种 HRh( CO) x( Ph3PO) 4 - x( x=1～ 3)的产生、浓度以及其动态稳定性 ,是影响 Rh/Ph3PO催化剂反应性能的重要原因 ,并对 Rh/Ph3PO催化剂体系的辛烯氢甲酰化反应活性优于 Rh/Ph3P体系的原因进行了探讨 .Hydroformylation of mixed octenes over Rh/Ph 3PO catalyst was investigated in terms of reaction temperature, pressure of syngas and molar ratio of P/Rh to give the optimal reaction conditions for the yield of iso nonyl aldehydes (INA). Using an in situ infrared spectrometer, the activation of Rh/Ph 3PO and the formation (or decomposition) of catalytic species under the appointed temperatures were recorded. The obtained results indicate that the catalytic activity of Rh/Ph 3PO for the conversion of mixed octenes to INA is much higher than that of Rh/Ph 3P system, IR spectra show that the formation, concentration and stability of catalytic species of HRh(CO) x (Ph 3PO) 4 x ( x =1~3) affect the activities of Rh/P catalysts greatly, leading to the differences between the catalytic behaviors of Rh/Ph 3PO and Rh/Ph 3P systems.

关 键 词：辛烯 铑催化剂 氢甲酰化 原位红外 

分 类 号：O643.321[理学—物理化学] O643.364[理学—化学]