微反应器一步法连续合成苯甲醚

doi:10.16085/j.issn.1000-6613.2022-0227

化工进展 ›› 2022, Vol. 41 ›› Issue (12): 6255-6260.DOI: 10.16085/j.issn.1000-6613.2022-0227

微反应器一步法连续合成苯甲醚

王德强¹(), 孙超¹, 王凯²(), 骆广生²

^1.潍坊科技学院，山东省海洋精细化工绿色化高值化工程技术研究中心，山东潍坊 262700
^2.清华大学化工系，化学工程联合国家重点实验室，北京 100084

收稿日期:2022-02-14 修回日期:2022-03-25 出版日期:2022-12-20 发布日期:2022-12-29
通讯作者: 王凯
作者简介:王德强（1973—），男，博士，讲师，研究方向为有机合成。E-mail：ciacwdq@163.com。
基金资助:
国家自然科学基金(21991104);山东省重大科技创新工程(2019JZZY020401)

One-step continuous synthesis of anisole in microreactor

WANG Deqiang¹(), SUN Chao¹, WANG Kai²(), LUO Guangsheng²

^1.Weifang University of Science and Technology, Shandong Peninsula Engineering Research Center of Comprehensive Brine Utilization, Weifang 262700, Shandong, China
^2.Department of Chemical Engineering, State Key Lab of Chemical Engineering, Tsinghua University, Beijing 100084, China

Received:2022-02-14 Revised:2022-03-25 Online:2022-12-20 Published:2022-12-29
Contact: WANG Kai

摘要/Abstract

摘要：

苯甲醚是一种重要的化工中间体，其工业生产主要以硫酸二甲酯和苯酚钠为原料，在搅拌釜中通过批次反应获得。该过程生产效率低、原料单耗高，同时存在硫酸二甲酯泄漏的安全隐患。本文提出了由微分散混合器和含有微小填料的静态混合器组合而成的微反应装置，以苯酚、氢氧化钠和硫酸二甲酯为反应原料，实施苯酚钠的形成和苯酚甲基化反应的耦合，实现反应过程的连续化和过程强化。实验考察了进料流量、物料配比、碱液浓度等关键因素对反应的影响，证明了微反应器内传递控制的反应机制。基于微混合器和静态混合元件的传质强化作用，在低于2min的反应时间内获得了98.5%的苯甲醚收率，硫酸二甲酯单耗较传统工艺降低10%，为工业化生产技术的升级换代提供研究基础。

关键词: 苯甲醚, 微反应系统, 连续合成, 反应强化

Abstract:

As an important chemical intermediate, anisole is mainly made by batch process using dimethyl sulfate and sodium phenol as raw materials in industry. However, neither the utilization rate of raw materials nor the production efficiency of anisole is satisfactory. Meanwhile, there are potential risks of dimethyl sulfate leakage during the production. In this paper, a microreactor system based on a microdispersion mixer and a static mixer was proposed, which employed phenol, sodium hydroxide, and dimethyl sulfate as the reactants, to implement the coupling of the formation of sodium phenate and the phenol methylation reaction and to realize the continuation and process intensification of the reaction process. The key influence factors such as feeding flow rate, molar ratio of phenol/dimethyl sulfate and concentration of sodium hydroxide were investigated, which demonstrated a transfer-controlled reaction mechanism within microreactor. Based on the mass transfer enhancement of micromixer and static mixer elements, up to 98.5% anisole yield was obtained in a reaction time less than 2min, and the consumption of dimethyl sulfate was reduced by 10% compared with the traditional reaction process, which provided the fundamental research for the upgrading of industrial production process.

Key words: phenylmethyl ether, microreactor system, continuous synthesis, reaction intensification

中图分类号:

TQ025.5

王德强, 孙超, 王凯, 骆广生. 微反应器一步法连续合成苯甲醚[J]. 化工进展, 2022, 41(12): 6255-6260.

WANG Deqiang, SUN Chao, WANG Kai, LUO Guangsheng. One-step continuous synthesis of anisole in microreactor[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6255-6260.

图/表 7

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Q_total/mL·min^-1	T_max/℃	t_r/min	Y_AN/%
8.4	82.6	7.4	90.3
24.1	100.3	2.6	95.2
39.3	105.5	1.6	96.7
56.1	109.0	1.1	98.1
56.1^①	93.3	1.8	87.2

Q_total/mL·min^-1	T_max/℃	t_r/min	Y_AN/%
8.4	82.6	7.4	90.3
24.1	100.3	2.6	95.2
39.3	105.5	1.6	96.7
56.1	109.0	1.1	98.1
56.1^①	93.3	1.8	87.2

w_NaOH/%	Q_NaOH/mL·min^-1	Q_org/mL·min^-1	T_max/℃	t_r/min	Y_AN/%
20	22.3	25.4	66.1	1.3	85.5
30	14.0	25.4	105.0	1.6	95.2
40	9.8	25.4	118.0	1.8	97.0

w_NaOH/%	Q_NaOH/mL·min^-1	Q_org/mL·min^-1	T_max/℃	t_r/min	Y_AN/%
20	22.3	25.4	66.1	1.3	85.5
30	14.0	25.4	105.0	1.6	95.2
40	9.8	25.4	118.0	1.8	97.0

编号	n_PhOH∶n_DMS∶n_NaOH	Y_AN/%	X_DMS/%
1	1.00∶1.00∶1.00	91.7	91.7
2	1.00∶1.05∶1.05	96.5	91.9
3	1.00∶1.10∶1.10	98.2	89.3
4	1.00∶1.15∶1.15	98.5	85.6
5	1.00∶1.15∶1.10	97.4	84.7
6	1.00∶1.15∶1.20	94.9	82.5
7	1.00∶1.20∶1.20	98.3	81.9

微反应器一步法连续合成苯甲醚

One-step continuous synthesis of anisole in microreactor

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