碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化 试剂的烷基酚、烷氧基酚及其混合物的烷基化转化

张少华 王泽 林伟刚 宋文立 李松庚

doi:10.12034/j.issn.1009-606X.217162

过程工程学报 >

2017 , Vol. 17 >Issue 6: 1239 - 1248

DOI: https://doi.org/10.12034/j.issn.1009-606X.217162

过程与工艺

碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化试剂的烷基酚、烷氧基酚及其混合物的烷基化转化

张少华王泽林伟刚宋文立李松庚

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1. 中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190；2. 中国科学院大学化学与化工学院，北京，100049； 3. 丹麦技术大学化学和生化工程系，林格比丹麦 DK-2800

收稿日期: 2017-03-06

修回日期: 2017-04-11

网络出版日期: 2017-12-05

基金资助

国家自然科学基金面上项目：原位供氢条件下生物质水热转化制备液体燃料基础研究;油页岩高效油气炼制与过程节能科学基础973项目

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Alkylation of Alkylphenol, Alkoxyphenol and Their Mixture with Methanol under the Catalysis of Alkali and Alkaline-earth Salts Modified Activated Alumina

Shaohua ZHANG Ze WANG Weigang LIN Wenli SONG Songgeng LI

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1. State Key Lab of Multi-phase Complex Systems, Inst. Process Eng., Chinese Academy of Sciences, Beijing 100190, China; 2. School of Chemistry and Chemical Engeering, University of Chinese Academy of Sciences, Beijing 100049, China; 3. Department of Chemical and Biochemical Engineering, Technical University of Denmark, Denmark Lyngby DK-2800

Received date: 2017-03-06

Revised date: 2017-04-11

Online published: 2017-12-05

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摘要

以甲醇为烷基化试剂，考察了碱金属(A)及碱土金属盐(AE)改性的活性氧化铝(AA)催化剂对烷基酚、烷氧基酚及其二元及五元混合体系的烷基化转化反应的影响规律. 结果表明，碱金属盐改性的活性Al2O3 (A/AA)可显著促进苯酚及甲基苯酚的O-烷基化转化，尤其是以Cs2CO3/AA为催化剂时，苯酚转化率最高可达90.4%(?)，且O-烷基化产物苯甲醚的选择性为96.1%(area). 相同反应条件下，邻甲氧基苯酚的转化率和产物的选择性均不理想，调节反应温度、空速及Cs负载量仍不能有效改善. 混合酚混合物体系的烷基化转化过程中存在非常显著的协同效应，烷基酚的转化受到严重抑制而烷氧基酚的转化得到显著促进，且C-烷基化产物显著增加.

关键词： 烷基化; 烷基酚; 烷氧基酚; 催化; 碱金属

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张少华王泽林伟刚宋文立李松庚 . 碱金属盐及碱土金属盐改性的活性氧化铝催化作用下以甲醇为烷基化试剂的烷基酚、烷氧基酚及其混合物的烷基化转化[J]. 过程工程学报, 2017 , 17(6) : 1239 -1248 . DOI: 10.12034/j.issn.1009-606X.217162

Abstract

Using methanol as the alkylation reagent, the alkylations of alkylphenol, alkoxyphenol, and their binary and five-component mixtures were investigated, under the catalysis of alkali (A) and alkaline-earth (AE) salts modified activated alumina (AA). The results showed that phenol and methylphenol can high efficiently be converted to O-alkylation products over A/AA. Specifically, under the catalysis of Cs2CO3/AA, the conversion rate of phenol reached to the highest value of 90.4%(?) with high anisole selectivity of 96.1%(area). However, under the same reaction conditions, neither the conversion rate nor the product selectivity is satisfactory for the alkylation of methoxyphenol, and the adjustment of the reaction temperature, the space velocity, or the Cs loading amount cannot make the results better. There exists a strong synergistic effect for the co-alkylation of the alkylphenol/alkoxyphenol mixture, under this effect, the conversion of alkylphenol is inhibited, while the conversion of alkoxyphenol is promoted, with remarkably enhanced selectivity to C-alkylation products.

Key words： alkylation; alkylphenol; alkoxyphenol; catalysis; alkali metal

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