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

石油炼制与化工 ›› 2021, Vol. 52 ›› Issue (2): 33-38.

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

刘静¹,肖之敏¹,洪学思²,周晓龙¹

1. 华东理工大学化工学院
2. 中国石化上海石油化工研究院

收稿日期:2020-09-07 修回日期:2020-11-04 出版日期:2021-02-12 发布日期:2021-01-19
通讯作者: 刘静 E-mail:liu_jing0814@126.com

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

Received:2020-09-07 Revised:2020-11-04 Online:2021-02-12 Published:2021-01-19

摘要/Abstract

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。

关键词: 乙醇, 磺酸树脂, 异丁烯叠合, 活化能, 吸附能

Abstract: 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.

Key words: ethanol, sulfonic acid resin, isobutene polymerization, activation energy, adsorption energy

刘静肖之敏洪学思周晓龙. 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[J]. 石油炼制与化工, 2021, 52(2): 33-38.

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