刘海超,陈华,黎耀忠,程溥明,李贤均.负载水溶性铑-膦配合物催化1-己烯氢甲酰化反应的研究[J].分子催化,1994,(1):
负载水溶性铑-膦配合物催化1-己烯氢甲酰化反应的研究
1-Hexene Hydroformylation on Supported Aqueous-Phase Catalyst of Rhodium Complex
  
DOI:
中文关键词:  铑-膦配合物,1-己烯,烯烃氢甲酰化
英文关键词:Rhodium-phosphine complex,1-Hexene, Olefin hydroformylation.,
基金项目:石油化工总公司及石油化工研究院资助
刘海超  陈华  黎耀忠  程溥明  李贤均
四川大学化学系络合催化研究室
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中文摘要:
      将水溶性铑-膦配合物Rhci(CO)(TPPTS)_2(TPPTS:P-(m-C_6H_4SO_3Na)_3)负载于扩孔硅胶上,制成负载水相催化剂(SAPC),在高压反应釜中研究其催化1-己烯氢甲酰化的性能。结果表明,催化剂的水含量对其活性影响很大,在一较窄的水含量范围内(25—35wt%),催化剂活性急剧增大,且存在一极大值,表现出水膜催化剂的特性。反应温度、总压和CO/H_2分压、Rh/P比的影响,与使用烃溶性能。三苯膦络合催化剂时有类似规律,溶剂的影响不明显,实验证明,SAPC具有良好催化活性,SiO_2上负载的铑配合物不会被原料和产物洗提而造成流失,有利于催化剂的稳定和重复使用。
英文摘要:
      The supported aqueous-phase catalyst(SAPC) has been prepared by impregnating water-soluble organometallic complex RhCl(CO)(TPPTS)_2 (TPPTS is the trisodium salt of tri(m-sulfophenyl)phosphine)onto a hydrophilic SiO_2 with high surface area and narrow pore volume distribution.The 1-hexene hydroformylation on SAPC has been carried out in an autoclave. The effects of the process, parameters such as the Rh/phosphine ratio, temperature, total and partial pressure of H_2/CO,solvent as well as the rhodium and water content of SAPC are studied. The results indicate that the water content of the catalyst can strongly influence the catalytic activity. A maximum of activity is observed when the water content of SAPC is in the range of about25-3 5 wt%. The formation of the water film with a suitable depth on the SiO_2 surface is the key factor for the molecular dispersion and migration of the rhodium complexes in the water film. The hydroformylation of olefin occurs on the inter face of two immiscible phases consisted of water and organic layers. The SAPC is an active immobilized homogeneous catalyst. The rhodium complexes do not leach into the product.
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