Direct production of p/m-cresol from catalytic methylation of phenol with methanol over MCM-22 zeolite: Acidity effect and reaction network

IF 4.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Molecular Catalysis Pub Date : 2025-03-27 DOI:10.1016/j.mcat.2025.115062
Minghui Liu , Huanling Zhang , Shipeng Song , Rong Fan , Mengqi Wang , Zhengchao Wang , Hao Yan , Guowei Wang , Xiang Feng , Chunyi Li , Chaohe Yang , Xiaolin Zhu
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Abstract

The methylation of phenol with methanol is an environment-friendly and simple method for cresol production. In this work, the direct and selective production of p/m-cresol from phenol methylation was realized over the MCM-22 zeolite catalyst by sensitive regulation of the reaction temperature. On the one hand, the effect of zeolite acidity was investigated by varying SiO2/Al2O3 ratio, and the strong Bronsted acid sites were indicated to be crucial for phenol methylation reaction. The MCM-22 zeolite with strong acidity and moderate porosity exhibited outstanding and stable catalytic performance with high phenol conversion (∼40 %), excellent cresol selectivity (>95 %) and flexible product composition (p-cresol/cresols ∼40 % or m-cresol/cresols ∼50 %). On the other hand, the reaction network of phenol methylation was refined. It was demonstrated that, in addition to the direct production of cresols from C-alkylation of phenol, the cresols could also be produced by the transalkylation between phenol and anisole yield from phenol O-alkylation. This work not only develops a novel eco-friendly p/m-cresol production method, but also deepens people's knowledge of the reaction mechanism of phenol methylation.

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MCM-22沸石上苯酚与甲醇催化甲基化直接生产p/m-甲酚:酸度效应和反应网络
甲醇甲基化苯酚是一种环保、简便的甲酚生产方法。在MCM-22沸石催化剂上,通过对反应温度的敏感调节,实现了苯酚甲基化直接选择性生产p/m-甲酚。一方面,研究了不同SiO2/Al2O3比对沸石酸性的影响,发现强Bronsted酸位点对苯酚甲基化反应至关重要。MCM-22分子筛具有强酸性和中等孔隙度,表现出优异而稳定的催化性能,苯酚转化率高(~ 40%),甲酚选择性好(> 95%),产物组成灵活(对甲酚/甲酚~ 40%或间甲酚/甲酚~ 50%)。另一方面,对苯酚甲基化反应网络进行了细化。结果表明,苯酚的c -烷基化反应除可直接生产甲酚外,苯酚与邻苯甲醚的烷基化反应也可直接生产甲酚。这项工作不仅开发了一种新的环保的p/m甲酚生产方法,而且加深了人们对苯酚甲基化反应机理的认识。
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来源期刊
Molecular Catalysis
Molecular Catalysis Chemical Engineering-Process Chemistry and Technology
CiteScore
6.90
自引率
10.90%
发文量
700
审稿时长
40 days
期刊介绍: Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods
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