文献类型：期刊文献

中文题名：超(近)临界条件下醋酸甲酯水解过程研究

英文题名：Hydrolysis of Methyl Acetate Under Near- and Supercritical Conditions

作者：袁佩青[1];程振民[1];刘涛[1];袁渭康[1]

机构：[1]华东理工大学反应工程国家重点实验室,上海200237

年份：2003

卷号：24

期号：7

起止页码：1241

中文期刊名：高等学校化学学报

外文期刊名：Chemical Journal of Chinese Universities

收录：CSTPCD;;Scopus;北大核心:【北大核心2000】；CSCD:【CSCD2011_2012】；

基金：国家重点基础研究发展规划项目 (批准号 :G2 0 0 0 0 480 10 )资助

语种：中文

中文关键词：超临界;醋酸甲酯;水解;近临界;反应动力学

外文关键词：Methyl acetate; Supercritical; Near-critical; Hydrolysis

摘要：超 (近 )临界水作为优良的有机反应溶剂适合于针对酸碱催化类型有机反应绿色工艺的开发 .本课题以具备工业生产背景的醋酸甲酯水解作为研究体系 ,在一管式反应器中 ,将原料 (5 %质量分数 )置于体系的超 (近 )临界条件下 (5 2 3～ 6 73K,2 3～ 32 MPa)进行反应操作 .实验结果表明 ,在无外加酸性催化剂情况下 ,水解反应以接近 1的选择性 ,在 1 5 0～ 30 0 s内达到热力学平衡限制 ,同时在系统临界点附近 ,溶剂化作用对反应动力学影响显著 .根据 SN2反应机理对反应动力学方程进行了回归 .
Near- and supercritical water is an excellent medium for conducting chemical reactions, and is especially propitious to the development of environmentally benign techniques for acid/base catalyzed organic reactions. The work presented in this paper focuses on experimental investigation on noncatalytic hydrolysis for methyl acetate, trying to overcome high energy consumption and other defects of conventional ones. Hydrolysis of methyl acetate(5%) in this work was carried out in a tubular reactor under near- or supercritical conditions(523-673 K, 23-32 MPa), and characteristic of hydrolysis was investigated via combining various reaction conditions. The experimental results show that under the optimized operating condition conversion of methyl acetate achieves thermodynamic equilibrium within 150 to 300 s, the selectivity of which process closes to 1, with no acid catalyst added. Due to phase transition resulted from broad experimental range and singularity of supercritical zone, the influence of temperature and pressure on the reactivity takes on a complicated trend, transition-state theory and cluster theory were adopted to interpret experimental phenomena, also reaction kinetics was established based on S N2 mechanism. Conclusion drawn from this work indicates the promising prospect of applying near- and supercritical reaction technology to the industrial practice of hydrolysis of methyl acetate.