复合型质子酸性离子液体协同催化异丁烯齐聚反应

doi:10.7523/j.issn.2095-6134.2020.05.004

中国科学院大学学报 ›› 2020, Vol. 37 ›› Issue (5): 599-605.DOI: 10.7523/j.issn.2095-6134.2020.05.004

复合型质子酸性离子液体协同催化异丁烯齐聚反应

余晓佳^1,2, 刘莹², 王慧², 吴幼青¹, 郭艳秋²

1. 华东理工大学资源与环境工程学院, 上海 200237;
2. 中国科学院过程工程研究所绿色过程与工程重点实验室, 多相复杂系统国家重点实验室, 北京 100190

收稿日期:2019-03-21 修回日期:2019-05-13 发布日期:2020-09-15
通讯作者: 刘莹, 吴幼青
基金资助:
国家自然科学基金（21576264，21776285和21306098）资助

Oligomerization of isobutene catalyzed by combined proton acidic ionic liquids

YU Xiaojia^1,2, LIU Ying², WANG Hui², WU Youqing¹, GUO Yanqiu²

1. School of Resources and Environment Engineering, East China University of Science and Technology, Shanghai 200237, China;
2. CAS Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2019-03-21 Revised:2019-05-13 Published:2020-09-15
Supported by:

摘要/Abstract

摘要： 合成1-（4-磺酸丁基）-3-甲基咪唑三氟甲磺酸盐（[NNS][CF₃SO₃]）和1-（4-磺酸丁基）-3-甲基咪唑硫酸氢盐（[NNS][HSO₄]）两种质子酸性的咪唑基离子液体，应用于催化异丁烯齐聚反应，深入研究离子液体种类及反应条件、两种离子液体的复配摩尔比和搅拌方式对催化活性、二聚体C₈⁼产品的选择性和催化剂循环稳定性的影响，并利用核磁探讨反应进程。结果表明：在催化剂用量5 mmol、温度100℃、反应时间3 h、两种离子液体复配摩尔比1：1时，催化活性和二聚产物C₈⁼的选择性最高，异丁烯的转化率最高达84%，C₈⁼选择性为77%；改进搅拌方式后，催化剂循环稳定性得到明显提高，稳定循环达6次，异丁烯转化率保持在70%以上，C₈⁼选择性高达90%以上。

关键词: 齐聚, 异丁烯, 质子酸性离子液体, 高选择性二聚

Abstract: Two proton acidic imidazolium-based ionic liquids(ILs) of 1-(4-sulfobutyl)-3-methylimidazolium trifluoromethanesulfonate ([NNS][CF₃SO₃]) and 1-(4-sulfobutyl)-3-methylimidazolium hydrosulfate ([NNS][HSO₄])， were synthesized and applied in the oligomerization of isobutene. Some important parameters, including the types of ionic liquids, amount of catalysts, the reaction temperature, the reaction time, molar ratios of two ILs, stirring method and speeds, were screened. The optimized reaction conditions were determined as follows, 5 mmol of catalyst, 100 ℃, 3 h, and molar ratio of 1：1 for the two ILs. Under these conditions, the catalytic activity of the complexed ILs reached the highest with conversion rate of 84% for isobutene and selectivity of 77% for C₈⁼. The complex ILs could be recycled six times without obvious loss of catalytic activities, and conversion rate of isobutene remained 70% with above 90% selectivity of C₈⁼. The reaction was monitored on NMR and the formation process was further determined.

Key words: oligomerization, isobutene, proton acidic ionic liquid, highly selective dimerization

中图分类号:

TQ211
O69

余晓佳, 刘莹, 王慧, 吴幼青, 郭艳秋. 复合型质子酸性离子液体协同催化异丁烯齐聚反应[J]. 中国科学院大学学报, 2020, 37(5): 599-605.

YU Xiaojia, LIU Ying, WANG Hui, WU Youqing, GUO Yanqiu. Oligomerization of isobutene catalyzed by combined proton acidic ionic liquids[J]. , 2020, 37(5): 599-605.

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复合型质子酸性离子液体协同催化异丁烯齐聚反应

Oligomerization of isobutene catalyzed by combined proton acidic ionic liquids

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