Electrochemical reduction of dechlorination of pentachloropyridine to 2,3,5,6-tetrachloropyridine over zinc-based catalyst: reaction mechanism and process optimization

doi:10.11949/j.issn.0438-1157.20151444

CIESC Journal ›› 2016, Vol. 67 ›› Issue (6): 2332-2339.DOI: 10.11949/j.issn.0438-1157.20151444

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Electrochemical reduction of dechlorination of pentachloropyridine to 2,3,5,6-tetrachloropyridine over zinc-based catalyst: reaction mechanism and process optimization

CHEN Zewei, WANG Yixiang, DING Xufen, XU Yinghua, MA Chun'an

State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China

Received:2015-09-14 Revised:2016-02-24 Online:2016-06-05 Published:2016-06-05
Supported by:
supported by the National Basic Research Program of China ( 2012CB722604 ) and the National Natural Science Foundation of China ( 21106133, 21576238 ).

锌催化电还原脱氯合成2,3,5,6-四氯吡啶:反应机理和工艺优化

陈泽伟, 王一想, 丁旭芬, 徐颖华, 马淳安

浙江工业大学化学工程学院, 绿色化学合成技术国家重点实验室培育基地, 浙江杭州 310032

通讯作者: 马淳安
基金资助:
国家重点基础研究发展计划项目(2012CB722604);国家自然科学基金项目(21106133,21576238)。

Abstract

Abstract:

The electrochemical dechlorination mechanism of pentachloropyridine (PCP) to 2,3,5,6-tetrachloropyridine (2,3,5,6-TCP) on stainless steel cathodes in an acetonitrile/water mixed solution containing ZnCl₂ was investigated by cyclic voltammetry and constant potential electrolysis methods. Moreover, an optimization of various operating conditions under constant potential electrolysis for the dechlorination process was performed in an H-cell. It showed that indirect electrochemical dechlorination using Zn/Zn²⁺ as the redox mediator is the main pathway of PCP to 2,3,5,6-TCP. The 0.08 mol·L^-1 PCP could be selectively dechlorinated to 2,3,5,6-TCP with 88.7% yield and 59.1% of current efficiency under optimum conditions (catholyte: an acetonitrile solution containing 0.025 mol·L^-1 HCl, 15%(vol) water, 0.2 mol·L^-1 sodium benzenesulfonate and 0.16 mol·L^-1 ZnCl₂, and 1.25 A·dm^-1 of current density).

Key words: pentachloropyridine, 2,3,5,6-tetrachloropyridine, zinc-catalyzed mechanism, electrochemical reductive dechlorination, process optimization

摘要：

采用循环伏安法和恒电位电解法,探讨了含有ZnCl₂的乙睛水混合溶液中五氯吡啶(PCP)在不锈钢阴极表面电还原脱氯生成2,3,5,6-四氯吡啶(2,3,5,6-TCP)的反应机理;采用恒电流电解法对该电还原脱氯过程的各种工艺条件进行了优化。结果表明:该体系中PCP电还原脱氯生成2,3,5,6-TCP主要遵循以Zn/Zn²⁺为氧化还原媒介的间接电还原机理;优化工艺条件下(阴极液含0.025mol·L^-1HCl+15%(体积分数)水+0.2mol·L^-1苯磺酸钠+0.16mol·L^-1ZnCl₂的乙腈溶液;电流密度为1.25A·dm^-2),0.08mol·L^-1PCP能高选择性地脱氯生成2,3,5,6-TCP,2,3,5,6-TCP的收率和电解电流效率分别可达88.7%和59.1%。

关键词: 五氯吡啶, 2,3,5,6-四氯吡啶, 锌催化机理, 电还原脱氯, 工艺优化

CLC Number:

TQ151.5

CHEN Zewei, WANG Yixiang, DING Xufen, XU Yinghua, MA Chun'an. Electrochemical reduction of dechlorination of pentachloropyridine to 2,3,5,6-tetrachloropyridine over zinc-based catalyst: reaction mechanism and process optimization[J]. CIESC Journal, 2016, 67(6): 2332-2339.

陈泽伟, 王一想, 丁旭芬, 徐颖华, 马淳安. 锌催化电还原脱氯合成2,3,5,6-四氯吡啶:反应机理和工艺优化[J]. 化工学报, 2016, 67(6): 2332-2339.

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Electrochemical reduction of dechlorination of pentachloropyridine to 2,3,5,6-tetrachloropyridine over zinc-based catalyst: reaction mechanism and process optimization

锌催化电还原脱氯合成2,3,5,6-四氯吡啶:反应机理和工艺优化

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