超临界二氧化碳和水复合溶剂中铑膦配合物催化丙烯氢甲酰化反应  

Hydroformylation of Propylene in the Mixture of Supercritical Carbon Dioxide and Water Catalyzed by Rhodium Phosphine Complex

作　　者：曹维良[1] 王宏斌[1] 高希信[1] 张建军[1] 张敬畅[1] 

机构地区：[1]北京化工大学现代催化研究所,北京100029

出　　处：《催化学报》2004年第7期556-560,共5页

基　　金：国家自然科学基金 ( 2 0 0 760 0 4);教育部博士学科点基金 ( 2 0 0 0 0 0 10 0 5 )资助项目

摘　　要：以乙酰丙酮羰基铑为催化剂母体 ,以水溶性三苯基膦三间磺酸钠 (TPPTS)为配体 ,在超临界CO2 和水复合溶剂中成功地实现了超临界条件下的均相丙烯氢甲酰化反应 .最佳反应条件为 :温度 5 5℃ ,铑的浓度 1 5 μg/ml,P/Rh摩尔比 1 8.在压力为 1 2 0～ 1 4 0MPa下反应 6h后 ,产物正丁醛 /异丁醛摩尔比可达 4 3～ 4 5 ,丁醛的时空收率达 1 90 1～ 2 0 5 3g/ (g·h) .反应过程中体系处于超临界状态 ,反应结束后分为水、油两相 ,铑催化剂溶于水相 ,产物处于油相 ,油相中铑的含量仅为 1 0ng/ml,基本上消除了铑的流失 ,实现了催化剂与产物的有效分离 ,便于催化剂的回收和循环使用 .与相同反应条件下的水 有机两相氢甲酰化反应相比 ,超临界CO2The homogeneous hydroformylation of propylene in the mixture solvent of supercritical CO 2 and H 2O using the rhodium phosphine complex catalyst prepared with Rh(acac)(CO) 2 and water soluble ligand TPPTS was firstly carried out. The influence factors such as reaction temperature, rhodium concentration and molar ratio of phosphine to rhodium (P/Rh) were investigated and the optimized reaction conditions were suggested. Under the optimal conditions of temperature of 55 ℃, Rh concentration of 15 μg/ml, P/Rh molar ratio of 18, pressure of 12 0～14 0 MPa and reaction time of 6 h, the turnover frequency reached 190 1～205 3 g/(g·h) and the n butylaldehyde to i butylaldehyde molar ratio was 4 3～4 5. The reaction was performed homogenously in a supercritical phase, and after the reaction the water phase was automatically separated from the organic phase. The rhodium phosphine complex catalyst in the water phase could be reused in the next run, and therefore the loss of rhodium could be basically eliminated. Compared with the conventional hydroformylation, the hydroformylation of propylene in supercritical CO 2 and water shows higher reaction rate and selectivity.

关 键 词：超临界二氧化碳 丙烯 氢甲酰化 三苯基膦三间磺酸钠 铑配合物 

分 类 号：O643[理学—物理化学]