直接氧化法制备2,5-二氯苯酚

doi:10.16085/j.issn.1000-6613.2018-1581

化工进展 ›› 2019, Vol. 38 ›› Issue (04): 1978-1983.DOI: 10.16085/j.issn.1000-6613.2018-1581

直接氧化法制备2,5-二氯苯酚

廖阳群^1,²(),张跃²(),严生虎^1,²,刘建武¹,马晓明^1,²,辜顺林¹,沈介发^1,²,陈代祥^1,²

1. 常州大学制药与生命科学学院，江苏常州 213164
2. 石油和化工行业连续流技术工程实验室，江苏常州 213164

收稿日期:2018-08-02 修回日期:2018-12-20 出版日期:2019-04-05 发布日期:2019-04-05
通讯作者: 张跃
作者简介:<named-content content-type="corresp-name">廖阳群</named-content>（1994—），女，硕士研究生，研究方向为流动化学和过程工程。E-mail：<email>1428542103@qq.com</email>。|张跃，研究员，工学博士，主要从事制药工程工艺学、化学工艺的优化研究工作。E-mail：<email>zyjs@cczu.edu.cn</email>

Preparation of 2,5-dichlorophenol by direct oxidation

Yangqun LIAO^1,²(),Yue ZHANG²(),Shenghu YAN^1,²,Jianwu LIU¹,Xiaoming MA^1,²,Shunlin GU¹,Jiefa SHEN^1,²,Daixiang CHEN^1,²

1. School of Pharmaceutical and Life Sciences, Changzhou University, Changzhou 213164, Jiangsu, China
2. Continuous Flow Engineering Laboratory of National Petroleum and Chemical Industry, Changzhou 213164, Jiangsu, China

Received:2018-08-02 Revised:2018-12-20 Online:2019-04-05 Published:2019-04-05
Contact: Yue ZHANG

摘要/Abstract

摘要：

2,5-二氯苯酚是重要的酚类化合物，工业上常用的2,5-二氯苯酚的制备方法大多存在生产流程长、污染严重等问题。针对这些问题，本文提出了以对二氯苯为原料、H₂O₂为氧化剂的直接氧化制备2,5-二氯苯酚的工艺，并对催化剂和溶剂进行初步筛选，探讨了不同催化体系对反应的影响，确定以铁粉作催化剂、乙酸为溶剂的反应体系下，通过对氧化剂用量、反应温度、反应时间、催化剂用量等工艺条件的考察，获得最佳工艺条件。实验结果表明，当工艺条件为n(对二氯苯)∶n(50%H₂O₂)∶n(Fe)=1∶3∶0.10、反应温度60℃、反应时间2.5h时，反应效果最佳；产物经GC-MS和¹HNMR分析确定为2,5-二氯苯酚，经气相色谱分析，2,5-二氯苯酚选择性达83.4%，收率达42.6%。

关键词: 直接氧化法, 过氧化氢, 对二氯苯, 2,5-二氯苯酚, 选择性

Abstract:

2,5-Dichlorophenol is an important phenolic compound. Regarding the preparation of 2,5-dichlorophenol, most of the preparation methods commonly used in the industry have problems such as long production process and serious pollution. The process of preparing 2,5-dichlorophenol by direct oxidation of dichlorobenzene as raw material and H₂O₂ as oxidant. The catalysts and solvents were initially screened to investigate the effects of different catalytic systems on the reaction. The process conditions of oxidant dosage, reaction temperature, reaction time and catalyst dosage were determined by using iron powder as catalyst and acetic acid as solvent. The experimental results showed that the best process conditions were n(p-dichlorobenzene)∶n(50% H₂O₂)∶n(Fe) = 1∶3∶0.10, the reaction temperature was 60℃ and the reaction time was 2.5h. The product was identified as 2,5-dichlorophenol by GC-MS and ¹H NMR analysis. The gas chromatographic analysis showed that the selectivity of 2,5-dichlorophenol was 83.4% and the yield of 2,5-dichlorophenol was 42.6%.

Key words: direct oxidation, hydrogen peroxide, p-dichlorobenzene, 2,5-dichlorophenol, selectivity

中图分类号:

TQ243.3

廖阳群, 张跃, 严生虎, 刘建武, 马晓明, 辜顺林, 沈介发, 陈代祥. 直接氧化法制备2,5-二氯苯酚[J]. 化工进展, 2019, 38(04): 1978-1983.

Yangqun LIAO, Yue ZHANG, Shenghu YAN, Jianwu LIU, Xiaoming MA, Shunlin GU, Jiefa SHEN, Daixiang CHEN. Preparation of 2,5-dichlorophenol by direct oxidation[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1978-1983.

图/表 8

图1 直接氧化法制备2,5-二氯苯酚的反应机理

图2 不同催化体系对反应的影响

图3 催化剂用量对反应的影响

图4 氧化剂摩尔比对反应的影响

图5 反应温度对反应的影响

图6 反应时间对反应的影响

图7 产物的GC-MS图

图8 产物的1H NMR图谱

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直接氧化法制备2,5-二氯苯酚

Preparation of 2,5-dichlorophenol by direct oxidation

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