高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (12): 1900.

• 论文 • 上一篇    下一篇

固定床反应器中丙酮酸乙酯在Pt/γ-Al2O3催化剂上的不对称加氢反应

李晓红1, 尤欣2, 梁长海1, 张遂之1, 魏昭彬1, 李绪渊2, 李灿1   

  1. 1. 中国科学院大连化学物理研究所催化基础国家重点实验室, 大连 116023;
    2. 兰州大学化学系, 兰州 73000
  • 收稿日期:1999-12-03 出版日期:2000-12-24 发布日期:2000-12-24
  • 通讯作者: 李 灿(1960年生),男,研究员,博士生导师,从事物理化学、催化和表面光谱学研究.E-mail:canli@ms.dicp.ac.cn E-mail:canli@ms.dicp.ac.cn
  • 基金资助:

    国家自然科学基金(批准号:29625305)资助

Heterogeneous Asymmetric Hydrogenation of Ethyl Pyruvate on Chirally Modified Pt/Al2O3Catalyst with Fixed-bed Reactor

LI Xiao-Hong1, YOU Xin2, LIANG Chang-Hai1, ZHANG Sui-Zhi1, WEI Zhao-Bin1, LI Xu-Yuan2, LI Can1   

  1. 1. State Key Laboratoryof Catalysis, Dalian Instituteof Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;
    2. Department of Chemistry, Lanzhou University, Lanzhou 73000, China
  • Received:1999-12-03 Online:2000-12-24 Published:2000-12-24

摘要: 采用固定床反应器对辛可尼定修饰的Pt/γ-Al2O3催化剂上丙酮酸乙酯的多相不对称加氢体系进行了研究,同时用高压釜反应器进行了对比,分别取得60%和90%的e.e.值.在两种不同的反应器中,溶剂对反应结果的影响不同,在高压釜反应器中乙酸的效果好于乙醇,而在固定床反应器中则相反,推测在固定床反应器中催化表面反应机理与所用溶剂的介电常数或其极性有关.以CO探针分子对辛可尼定在催化剂表面的吸附行为进行了红外光谱研究,表明辛可尼定和金属铂主要通过大π键相互作用

关键词: Pt/&gamma, -Al2O3催化剂, 辛可尼定修饰, 固定床反应器, 丙酮酸乙酯, 多相不对称加氢

Abstract: The enantioselective hydrogenation of ethyl pyruvate on the cinchonidine modified Pt/Al2O3catalyst was investigated using a high pressure reaction system with a fixed bed reactor for the purpose to produce the chiral product without separating the catalyst from the reaction system.The reaction was also investigated in a batch reactor for comparison.About 60% e.e. and90% e.e. were obtained with the fixed bed reactor and the batch reactor respectively, demonstrating the possibility for the heterogeneous asymmetric hydrogenation in the fixed bed reactor.Some adsorbed chiral modifier, cinchonidine, can be slowly removed from the surface of Pt/Al2O3under the continuous flow reaction, as a result, the e.e. values drops with the reaction time in the fixed bed reactor.The enantio selectivity is higher in the fixed bed reactor, but lower in the batch reactor when ethanol was used as solvent than that when acetic acid as solvent.COwas used as molecular probe to characterize the adsorption of cinchonidine on the catalyst surface by IRspectroscopy.Ared shift observed in IRspectra of coadsorbed COwith cinchonidine suggests that the cinchonidine adsorption is mainly through the π interaction with platinum surface and donating electron to the platinum surface.

Key words: Pt/ γ-Al2O3catalyst, Cinchonidine modifier, Fixed bed reactor, Ethyl pyruvate, Heterogeneous asymmetric hydrogenation.

中图分类号: 

TrendMD: