文献类型：期刊文献

中文题名：茂金属催化乙酸与丁醇酯化反应

英文题名：Esterification of Acetic Acid with n-Butanol Catalyzed by Metallocenes

作者：许胜[1];李洪彬[2];林秋宁[1];曾繁花[1];沈洁[1];闫修维[1];米普科[1]

机构：[1]华东理工大学化学与分子工程学院化学系,上海200237;[2]上海交通大学化学与化工学院,上海200240

年份：2009

卷号：30

期号：4

起止页码：365

中文期刊名：催化学报

收录：CSTPCD;;Scopus;北大核心:【北大核心2008】；CSCD:【CSCD2011_2012】；

基金：中国石油天然气公司资助项目(06-04A-02-01-02)

语种：中文

中文关键词：茂金属;负载型催化剂;乙酸;丁醇;酯化反应

外文关键词：metallocene;supported catalyst;acetic acid;n-butanol;esterification

摘要：以二茂铁、二茂钛、二茂锆和取代茂锆为催化剂用于催化酯化合成乙酸丁酯,探讨了不同茂金属、反应时间和催化剂用量对反应性能的影响.结果表明,低含量的茂金属就可高效催化酯化反应.当催化剂为二茂钛,其含量为0.049%(摩尔比)时,反应30 min产物乙酸丁酯的分离收率达到90%,纯度达到98%.以400目不同温度活化的硅胶为载体,考察了负载二茂锆催化剂的性能.当硅胶在400 oC焙烧4.0 h,负载二茂锆催化剂用量为Zr/丁醇=0.487%(摩尔比),反应后乙酸丁酯收率为90.6%,TOF=318 h-1.该反应的产物后处理不需要用水洗涤,无废水排出,催化剂易回收利用,是一个绿色的反应过程.
Efficient esterification of acetic acid with n-butanol has been achieved using metallocenes as the catalyst,and the ester can be produced with a high yield.The effect of several factors such as reaction time,molar ratio of catalyst/alcohol,and different metallocenes on the yield has been investigated.The results of homogeneous catalytic reaction show that Cp2Fe,Cp2TiCl2,Cp2ZrCl2,and [o-MeOC6H4C（Et）2Cp]2ZrCl2 are effective catalysts for aliphatic acid esterification at a very low catalyst/alcohol molar ratio.When Cp2TiCl2 was used as the catalyst at a molar ratio of Ti/n-butanol equal to 0.049%,90% yield was gained after 30 min.Silica gel（400 mesh） was used as the support to load metallocenes.The supported Cp2ZrCl2 catalyst exhibits high activity as that of Cp2ZrCl2 under optimum experimental conditions（calcination temperature = 400 oC,calcination time = 4.0 h,the molar ratio of Zr/butanol = 0.487%,reaction time = 45 min） with the ester yield of 90.6%.The use of supported metallocenes as the catalysts results in a cleaner process for esterification without wastewater produced.Moreover,the catalyst is easy to recycle.