锚链固定的多相化铑膦配合物氢甲酰化反应催化剂的制备及其催化性能

The Preparation of Anchored Heterogenized Rhodium Phosphine Complex Catalyst and Its Catalytic Performances in Hydroformylation of 1-Hexene

以溶胶-凝胶与锚链固定相结合的方法制备了新型多相化羰基铑膦配合物催化剂.利用FT-IR,XPS和ICP对催化剂进行了表征.考察了该催化剂对1-己烯氢甲酰化反应的催化性能,得到较佳的反应条件,即反应温度100℃、反应时间12h、催化剂用量为0.3382g(相当于金属铑含量为4.4×10-5mol)、反应压力5.0MPa.此时1-己烯的转化率为98.5%、醛的选择性92.4%、n/i比1.43.该催化剂循环使用7次仍具有较高的催化活性和选择性,表明该催化剂具有好的循环使用性能.XPS、ICP分析证明铑的部分流失主要是由于氢甲酰化反条件下CO取代膦配体所致.

A new anchored heterogenized rhodium carbonyl phosphino complex catalyst was prepared by the combination method of anchoring and sol-gel technique. The catalyst was characterized by FT-IR, XPS and ICP. The catalytic performances of the catalyst on hydroformylation of 1-hexene were studied and the optimized catalytic reaction conditions, which were the reaction temperature 100 ℃, pressure 5.0 MPa, reaction time 12h, and the cata- lyst loading amount 0.3382g （ Rh 4.4 10 ^-5 mol） were obtained. When the reaction was run at the optimized conditions, the conversion of 1-hexene reached 98.5% with an aldehyde selectivity of 92.4% and n/i of 1.43. The recycle tests confirmed that the catalyst remained higher activity in the seventh run, which indicated the catalyst had good recyclablity. The results of XPS and ICP analysis demonstrated that the leaching of Rh was mainly due to the replacement of phosphino ligand by CO in the hydroformylation conditions.