Enhanced ortho-selective t–butylation of phenol over sulfonic acid functionalized mesopore MTW zeolites

doi:10.1016/j.cjche.2023.02.014

Chinese Journal of Chemical Engineering ›› 2023, Vol. 60 ›› Issue (8): 1-7.DOI: 10.1016/j.cjche.2023.02.014

Enhanced ortho-selective t–butylation of phenol over sulfonic acid functionalized mesopore MTW zeolites

Baoyu Liu^1,2, Feng Xiong¹, Jianwen Zhang¹, Manna Wang¹, Yi Huang³, Yanxiong Fang^1,2, Jinxiang Dong^1,2

1. School of Chemical Engineering and Light Industry, Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, Guangzhou Key Laboratory of Clean Transportation Energy Chemistry, Guangdong University of Technology, Guangzhou 510006, China;
2. Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory (Rongjiang Laboratory), Jieyang 515200, China;
3. School of Engineering, Institute for Materials & Processes, The University of Edinburgh, Robert Stevenson Road, Edinburgh EH9 3FB, United Kingdom

Received:2022-11-11 Revised:2023-02-13 Online:2023-10-28 Published:2023-08-28
Contact: Baoyu Liu,E-mail:baoyu.liu@gdut.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (21978055, 22278090), Natural Science Foundation of Guangdong Province, China (2022A1515012088), the Science and Technology Planning Project of Guangdong Province, China (22A0505050073, 2022A0505030013), the Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, China (2021GDKLPRB10), and the “High-level Talents Program” of the Pearl River, China (2017GC010080).

Enhanced ortho-selective t–butylation of phenol over sulfonic acid functionalized mesopore MTW zeolites

Baoyu Liu^1,2, Feng Xiong¹, Jianwen Zhang¹, Manna Wang¹, Yi Huang³, Yanxiong Fang^1,2, Jinxiang Dong^1,2

1. School of Chemical Engineering and Light Industry, Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, Guangzhou Key Laboratory of Clean Transportation Energy Chemistry, Guangdong University of Technology, Guangzhou 510006, China;
2. Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory (Rongjiang Laboratory), Jieyang 515200, China;
3. School of Engineering, Institute for Materials & Processes, The University of Edinburgh, Robert Stevenson Road, Edinburgh EH9 3FB, United Kingdom

通讯作者: Baoyu Liu,E-mail:baoyu.liu@gdut.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (21978055, 22278090), Natural Science Foundation of Guangdong Province, China (2022A1515012088), the Science and Technology Planning Project of Guangdong Province, China (22A0505050073, 2022A0505030013), the Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, China (2021GDKLPRB10), and the “High-level Talents Program” of the Pearl River, China (2017GC010080).

Abstract

Abstract: Novel organo-inorganic hybrid materials (MTW-x-SO₃H) have been fabricated by immobilizing 3-mercaptopropyltriethoxysilane onto mesopore MTW zeolites, which is treated via a simple oxidation process with hydrogen peroxide as the oxidant to transform sulfhydryl group into sulfonic acid group. The organic sulfhydryl groups are covalently bonded to the external surface of MTW zeolites through the condensation between siloxane arising from organic fragments with silanol groups on the surface of MTW zeolites, the hybrids contain sulfonic acid group within the external surface of MTW zeolites and an opened mesoporous system in the matrix of MTW zeolites, which provide enough accessible Brønsted acid sites for the alkylation between phenol with tert-butyl alcohol. Through this methodology it’s possible to prepare multifunctional materials where the plenty of mesopores are benefit for the introduction of larger numbers of sulfonic acid groups that contributes to activity during reactions, resulting in high activity (>55%) of MTW-4-SO₃H and desired selectivity (>56%) of 2-TBP (2-tert-butyl phenol) in the alkylation between phenol with tert-butyl alcohol.

Key words: MTW Zeolites, Acidity, Catalysis, Alkylation

摘要： Novel organo-inorganic hybrid materials (MTW-x-SO₃H) have been fabricated by immobilizing 3-mercaptopropyltriethoxysilane onto mesopore MTW zeolites, which is treated via a simple oxidation process with hydrogen peroxide as the oxidant to transform sulfhydryl group into sulfonic acid group. The organic sulfhydryl groups are covalently bonded to the external surface of MTW zeolites through the condensation between siloxane arising from organic fragments with silanol groups on the surface of MTW zeolites, the hybrids contain sulfonic acid group within the external surface of MTW zeolites and an opened mesoporous system in the matrix of MTW zeolites, which provide enough accessible Brønsted acid sites for the alkylation between phenol with tert-butyl alcohol. Through this methodology it’s possible to prepare multifunctional materials where the plenty of mesopores are benefit for the introduction of larger numbers of sulfonic acid groups that contributes to activity during reactions, resulting in high activity (>55%) of MTW-4-SO₃H and desired selectivity (>56%) of 2-TBP (2-tert-butyl phenol) in the alkylation between phenol with tert-butyl alcohol.

关键词: MTW Zeolites, Acidity, Catalysis, Alkylation

Baoyu Liu, Feng Xiong, Jianwen Zhang, Manna Wang, Yi Huang, Yanxiong Fang, Jinxiang Dong. Enhanced ortho-selective t–butylation of phenol over sulfonic acid functionalized mesopore MTW zeolites[J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 1-7.

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Enhanced ortho-selective t–butylation of phenol over sulfonic acid functionalized mesopore MTW zeolites

Enhanced ortho-selective t–butylation of phenol over sulfonic acid functionalized mesopore MTW zeolites

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