固相化羰基铑膦配合物的制备及其催化加氢性能  

The Preparation of Anchored Heterogenized Rhodium Carbonyl Phosphino Complex and Its Catalytic Performance

作　　者：焦永杰[1] 赵继全[1] 何乐芹[1] 张月成[1] 刘艳华[1] 莒晓艳[1] 

机构地区：[1]河北工业大学化工学院,天津300130

出　　处：《化学反应工程与工艺》2006年第1期14-20,共7页Chemical Reaction Engineering and Technology

基　　金：河北省自然科学基金项目(200008)

摘　　要：以化学键连和溶胶-凝胶相结合的方法制备了带锚链固定的多相化羰基铑膦配合物催化剂。利用傅立叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)对催化剂进行了表征。考察了该催化剂对1-己烯催化加氢反应的催化性能,得出了1-己烯加氢反应的较佳反应条件为催化剂用量0.342 g(Rh 2.75×10-5mol),反应温度75℃,反应压力2.5 MPa,反应时间6 h,在此条件下1-己烯的转化率为99.0%,选择性为98.8%。电感耦合等离子体原子发射光谱(ICP)分析结果表明,催化剂在第1次使用中有7%的铑流失,随后使用中催化剂则基本不流失。该催化剂循环使用9次仍具有很高的催化活性。根据反应前后金属铑原子结合能及催化剂红外光谱的变化,得出该催化剂催化加氢反应的机理与均相催化剂一致。发现催化剂的活性与底物结构有关。The anchored heterogenized rhodium carbonyl phosphino complex catalyst was prepared by the combination of chemically anchoring and sol-gel methods, and it was characterized by fourier transform infrared spectrometer （FT-IR）, X-ray photoelectron spectrometry （XPS）. The catalytic performances of the catalyst for hydrogenation of 1-hexene were investigated. The optimized catalytic reaction conditions were obtained by the experiments, which were the catalyst loading amount 0.342 g（Rh 2.75×10^-5mol）, the reaction temparature 75 ℃ and pressure 2.5 MPa, and the reaction time 6 h. Conversion of 1-hexene was 99.0% and the selectivity was 98.8% under the optimal reaction conditions. Inductively coupled plasma spectrometry （ICP） results indicated that about 7% rhodium leached in the first run, but no leaching took place in the successive runs. Recycle test confirmed that the catalyst still had high activity in the 9th run. It was concluded that the catalytic mechanism was in agreement with that of the correspondent homogeneous catalyst by comparing the differences of the binding energy of rhodium and the IR spectra between fresh and used one. It was also found that the activity of the catalyst depends on the structure of the olefins.

关 键 词：羰基铑配合物 固相化催化剂 加氢 1-己烯 锚链固定 溶胶-凝胶 

分 类 号：TQ[化学工程]