催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (1): 31-35.DOI: 10.1016/S1872-2067(10)60156-8

• 研究快讯 • 上一篇    下一篇

P/Rh 比对 PPh3-Rh/SiO2 催化剂上丙烯氢甲酰化反应的影响

严丽 1,2, 丁云杰 1,2, 刘佳 1,2, 朱何俊 1,2, 林励吾 1,2   

  1. 1中国科学院大连化学物理研究所, 辽宁大连 116023; 2中国科学院大连化学物理研究所洁净能源国家实验室, 辽宁大连 116023
  • 收稿日期:2010-09-17 修回日期:2010-11-09 出版日期:2011-01-13 发布日期:2014-05-22

Influence of Phosphine Concentration on Propylene Hydroformylation over the PPh3-Rh/SiO2 Catalyst

YAN Li1,2, DING Yunjie1,2,*, LIU Jia1,2, ZHU Hejun1,2, LIN Liwu1,2   

  1. 1Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China; 2Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
  • Received:2010-09-17 Revised:2010-11-09 Online:2011-01-13 Published:2014-05-22

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摘要： 研究了 P/Rh 比对 PPh3-Rh/SiO2 催化剂上丙烯氢甲酰化反应性能的影响. 结果表明, 当 P/Rh 比为 15 时, 丙烯氢甲酰化反应性能最好, 丙烯转化率为 25.9%, 产物丁醛正异比为 14, 转换频率为 241 h-1. PPh3-Rh/SiO2 催化剂的固体 31P 核磁共振结果表明, 在合成气气氛下, 物理吸附的 PPh3 能够溢流到 Rh/SiO2 表面形成化学吸附的 PPh3, 从而促进了具有氢甲酰化活性的铑膦络合物的形成. Wilkinson 催化平衡理论也很好地解释了本实验结果.

关键词: 三苯基膦, 铑, 二氧化硅, 膦铑比, 丙烯, 氢甲酰化, 核磁共振

Abstract: The effect of triphenyl phosphine concentration in the novel PPh3-Rh/SiO2 catalyst for propylene hydroformylation was studied and found an optimum P/Rh ratio of 15, a butyraldehyde n#/em/em# ratio of 14, a butyraldehyde TOF of 241 h-1, and high catalytic stability for PPh3-Rh/SiO2. Solid-state 31P NMR shows that in an atmosphere of syngas the physically adsorbed PPh3 migrates onto the surface of Rh/SiO2 where it chemically adsorbs and then promotes the in situ formation of carbonyl phosphine complexes.

Key words: triphenyl phosphine, rhodium, silica, phosphine/rhodium ratio, propylene, hydroformylation, nuclear magnetic resonance