文献类型：期刊文献

中文题名：钛酸四丁酯催化合成柠檬酸三辛酯动力学

英文题名：Kinetics of synthesis of trioctyl citrate catalyzed by tetrabutyl titanate

作者：马进荣[1];许志美[1];奚桢浩[1];赵玲[1]

机构：[1]华东理工大学化学工程联合国家重点实验室,上海200237

年份：2016

卷号：45

期号：7

起止页码：828

中文期刊名：石油化工

外文期刊名：Petrochemical Technology

收录：CSTPCD;;Scopus;北大核心:【北大核心2014】；CSCD:【CSCD2015_2016】；

语种：中文

中文关键词：柠檬酸三辛酯;钛酸四丁酯;酯化;反应动力学

外文关键词：trioctyl citrate; tetrabutyl titanate; esterification; kinetics;

摘要：以柠檬酸和异辛醇为原料、以钛酸四丁酯为催化剂，合成了柠檬酸三辛酯。采用HPLC，1H NMR，LC-MS等技术对柠檬酸酯化反应产物进行表征。表征结果显示，酯化过程的副产物为异辛醚柠檬酸三辛酯。采用Benson基团贡献法对反应体系的焓变、熵变、平衡常数进行计算的结果表明，酯化过程可视为不可逆。建立了包含3步酯化反应及副反应的表观动力学模型，利用140～170℃下的实验数据对模型参数进行拟合。模拟结果表明，生成单酯和双酯两步反应的活化能均低于第三步酯化反应，副反应活化能略高于第三步酯化反应。动力学模型计算值与实验值吻合良好，验证了模型的正确性。
The kinetics of the esterification of citric acid with 2-ethylhexanol in the presence of tetrabutyl titanate as the catalyst was investigated. The esterification process might be regarded as irreversible through the calculation of the enthalpy change,entropy change and equilibrium constants by means of Benson group contribution method. The products of the esterification process including three esterification reactions and a side reaction were characterized by means of LC-MS and 1H NMR. A kinetic model was established based on the reaction mechanism. The kinetic parameters, k and Ea,were obtained by fitting the experimental data in the temperature range of 140-170 ℃. The results showed that the calculated values agreed well with experimental data,and the activation energies estimated for both the first and the second step reactions were lower than that of the third step reaction, which was a little lower than that of the side reaction.