乙醇为抑制剂时磺酸树脂催化异丁烯叠合反应的理论研究  

THEORETICAL STUDY ON ISOBUTENE POLYMERIZATION OVER SULFONIC ACID RESIN IN PRESENCE OF ETHANOL

作　　者：刘静 肖之敏 洪学思 周晓龙[1] Liu Jing;Xiao Zhimin;Hong Xuesi;Zhou Xiaolong(East China University of Science and Technology,School of Chemical Engineering,Shanghai 200237;SINOPEC Shanghai Research Institute of Petrochemical Technology)

机构地区：[1]华东理工大学化工学院,上海200237 [2]中国石化上海石油化工研究院

出　　处：《石油炼制与化工》2021年第2期33-38,共6页Petroleum Processing and Petrochemicals

摘　　要：基于密度泛函理论,采用B3LYP/6-31G(d,p)计算方法对乙醇为抑制剂、磺酸树脂为催化剂的异丁烯叠合反应体系进行理论研究。乙醇与异丁烯的醚化反应及异丁烯叠合反应的活化能分别为62.8 kJ/mol和167.8 kJ/mol,与异丁烯叠合反应相比,醚化反应的反应能垒较低,反应会优先发生。乙醇在苯磺酸上的物理吸附能为-71.3 kJ/mol,异丁烯在苯磺酸上的物理吸附能为-44.8 kJ/mol,物理吸附态的异丁烯容易被磺酸基上的H质子化形成烷氧基中间体,烷氧态化学吸附的吸附能为-80.2 kJ/mol。通过对比乙醇和异丁烯在苯磺酸上的吸附及两个反应的活化能,分析了乙醇在异丁烯叠合反应体系中的作用机理。The polymerization of isobutene over sulfonic acid resin in the presence of ethanol was studied using DFT theory and B3LYP/6-31G(d,p)algorithm method.The activation energies of the etherification reaction of ethanol and isobutylene and the polymerization reaction of isobutylene are 62.8 kJ/mol and 167.8 kJ/mol,respectively.Compared with the polymerization reaction of isobutylene,the reaction energy barrier of the etherification reaction is lower and the reaction will take place preferentially.The physical adsorption energy of ethanol on benzenesulfonic acid is-71.3 kJ/mol,and the physical adsorption energy of isobutylene on benzenesulfonic acid is-44.8 kJ/mol.The physically adsorbed isobutylene is easily protonated by the H of the sulfonic acid group to form alkoxy intermediate with chemical adsorption energy of-80.2 kJ/mol.Finally,the mechanism of ethanol in the isobutene polymerization system was analyzed.

关 键 词：乙醇 磺酸树脂 异丁烯叠合 活化能 吸附能 

分 类 号：TE624.81[石油与天然气工程—油气加工工程]