有机胺对Pd/C催化氯酚加氢脱氯反应的影响

doi:10.16085/j.issn.1000-6613.2022-0198

化工进展 ›› 2022, Vol. 41 ›› Issue (11): 6185-6194.DOI: 10.16085/j.issn.1000-6613.2022-0198

有机胺对Pd/C催化氯酚加氢脱氯反应的影响

马云波¹(), 王彦斐², 李鹏², 刘欢³, 武海洋², 苏衡¹, 马宣宣², 夏传海¹^,²()

^1.鲁东大学滨海生态高等研究院，山东烟台 264025
^2.鲁东大学资源与环境工程学院，山东烟台 264025
^3.中国石油大学（北京）化学工程与环境学院，北京 102249

收稿日期:2022-02-06 修回日期:2022-04-21 出版日期:2022-11-25 发布日期:2022-11-28
通讯作者: 夏传海
作者简介:马云波（1997—），男，硕士研究生，研究方向为污染物控制。E-mail：mayunbo1016@163.com。
基金资助:
山东省自然科学基金(ZR2020QB145);国家自然科学基金(21976076);固体废弃物资源化利用福建省高校工程研究中心开放基金(LYGF-201803)

Effect of organic amines on catalytic hydrodechlorination of chlorophenols over Pd/C catalyst

MA Yunbo¹(), WANG Yanfei², LI Peng², LIU Huan³, WU Haiyang², SU Heng¹, MA Xuanxuan², XIA Chuanhai¹^,²()

^1.The Institute for Advanced study of Coastal Ecology, Ludong University, Yantai 264025, Shandong, China
^2.School of Resources and Environmental Engineering, Ludong University, Yantai 264025, Shandong, China
^3.College of Chemical Engineering and Environment, China University of Petroleum, Beijing 102249, China

Received:2022-02-06 Revised:2022-04-21 Online:2022-11-25 Published:2022-11-28
Contact: XIA Chuanhai

摘要/Abstract

摘要：

采用Pd/C催化剂，选择不同的溶剂体系，首先分别比较了有机碱Et₃N以及无机强碱NaOH对Pd/C催化2,4-二氯苯酚（2,4-DCP）加氢脱氯反应的影响。结果表明，醇类溶剂中，Et₃N作为质子吸收剂，2,4-DCP能够在Pd/C催化下高效彻底加氢脱氯。并通过SEM、XRD和XPS等表征分析，发现Et₃N能够中和加氢反应产生的HCl，生成三乙胺盐酸盐（Et₃N·HCl），从而消除HCl对催化剂的毒化作用，同时避免了因Et₃N·HCl在催化剂表面的沉积而引发的催化剂失活的问题。进一步研究了不同类型的有机胺对甲醇中Pd/C催化2,4-DCP加氢脱氯反应速率和反应选择性的影响。研究表明，短链有机胺（伯胺、仲胺和叔胺）更有利于Pd/C催化2,4-DCP加氢脱氯反应的进行。在此基础上建立一种新型Pd/C-甲醇-短链有机胺催化体系，可以高效、彻底地实现对多氯代苯酚类污染物的加氢脱氯降解，为实现温和条件下高浓度多氯代苯酚类污染物的环境友好无害化处理提供新的思路和方法。

关键词: 2,4-二氯苯酚, 催化, 加氢, 降解, 有机胺

Abstract:

The effects of organic base triethylamine (Et₃N) and inorganic base NaOH on the liquid-phase hydrodechlorination (HDC) of 2,4-chlorophenol (2,4-DCP) over Pd/C catalyst in different solvent systems were studied. The results showed that efficient HDC of 2,‍4-DCP could be achieved in methanol and ethanol with Et₃N as the proton scavenger. Meanwhile, the reaction mechanism was studied through catalyst characterization (SEM, XRD, and XPS). It was found that the byproduct HCl could be efficiently eliminated by generating Et₃N·HCl with Et₃N in methanol, which prevented the catalyst poisoning caused by HCl. Moreover, the high solubility of Et₃N·HCl in methanol prevented inorganic salts from depositing on the surface of catalyst and thereby avoided the decline in the activity and stability of the catalyst. Furthermore, the effects of different types of organic amines on the HDC rate and the selectivity of 2,4-DCP over Pd/C catalyst in methanol were investigated. Compared to long-chain organic amines, short-chain organic amines (primary amines, secondary amines, and tertiary amines) were more favorable. Based on these studies, a novel Pd/C-methanol-short-chain organic amine catalytic system was established for the efficient HDC of pollutants containing high concentration polychlorinated phenols. Thus, this study provided a vital guidance for realizing the environmentally friendly and harmless HDC treatment of the pollutants with high concentration polychlorinated phenols under mild conditions.

Key words: 2,4-dichlorophenol (2,4-DCP), catalysis, hydrogenation, degradation, organic amine

中图分类号:

X592

马云波, 王彦斐, 李鹏, 刘欢, 武海洋, 苏衡, 马宣宣, 夏传海. 有机胺对Pd/C催化氯酚加氢脱氯反应的影响[J]. 化工进展, 2022, 41(11): 6185-6194.

MA Yunbo, WANG Yanfei, LI Peng, LIU Huan, WU Haiyang, SU Heng, MA Xuanxuan, XIA Chuanhai. Effect of organic amines on catalytic hydrodechlorination of chlorophenols over Pd/C catalyst[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 6185-6194.

图/表 10

图1 NaOH和Et3N存在下不同溶剂中Pd/C催化2,4-DCP加氢脱氯反应性

图2 使用前后Pd/C的扫描电镜（SEM）图及能量色散X射线光谱（EDX）图

图3 使用前后Pd/C催化剂的XRD图及XPS图

图4 不同碳链长度的叔胺对甲醇中Pd/C催化2,4-DCP加氢脱氯反应的影响

图5 不同碳链长度的伯胺对甲醇中Pd/C催化2,4-DCP加氢脱氯反应的影响

图6 不同数目取代基的有机胺对甲醇中Pd/C催化2,4-DCP加氢脱氯反应的影响

图7 有机胺对Pd/C催化2,4-DCP加氢脱氯反应过程的影响

图8 不同有机胺对2-CP和4-CP混合溶液在Pd/C催化下的加氢脱氯反应的影响

图9 Pd/C催化2,4-DCP加氢脱氯反应过程

图10 甲醇中三乙胺作质子吸收剂Pd/C催化2,4-DCP加氢脱氯的重复利用

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有机胺对Pd/C催化氯酚加氢脱氯反应的影响

Effect of organic amines on catalytic hydrodechlorination of chlorophenols over Pd/C catalyst

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