超细SiO_2负载型水溶性铑膦配合物催化剂研究

Study on Ultrafine SiO_2 Supported Water-soluble Phosphine-Rh Complex Catalysts

用超细 Si O2 负载水溶性铑膦配合物 ,并研究其对 1-己烯氢甲酰化的催化性能 .实验结果表明 ,粒径为10～ 2 0 nm的超细 Si O2 负载水溶性铑膦配合物所表现的催化活性比颗粒 Si O2 负载型催化剂高 3倍多 ,且可在较宽的含水量范围内保持高反应活性 .当膦铑摩尔比为 5 0 ,超细 Si O2 负载型催化剂含水量为 2 5 %～ 5 5 % (质量分数 )、烯铑摩尔比为 2 5 0 0、反应温度 373K和 CO/H2 (1/1,体积比 )压力 4.0 MPa的反应条件下 ,其 1-己烯氢甲酰化的反应转化数为 45 0 h- 1 ,产物醛的选择性为 10 0 % ,醛的 n/i比值达 3.

In this work an ultrafine SiO\-2 supported water\|soluble phosphine\|Rh complexes catalyst (ultrafine\|SiO\-2\|SAPC) has been developed for hydroformylation of 1\|hexene. The experimental results show that the ultrafine\|SiO\-2\|SAPC catalyst prepared by using SiO\-2 powder with particle sizes of 10~20 nm exhibits remarkably higher activity as compared to the reported granular SiO\-2\|SAPC catalyst and can maintain high activity with in wider range of water contents. An average TOF of a 450 h -1 run of 1\|hexene hydroformylation, where the selectivity to aldehyde is 100% and aldehyde n/i ratio is about 3.2, is obtained on the ultrafine\|SiO\-2\|SAPC containing 25%~55% of water under P/Rh(molar ratio)=50, 1\|hexene/\{Rh(molar ratio)=\}2 500, reaction temperature 373 K, and CO/H\-2 (1/1, volume ratio) pressure 4.0 MPa.