Raney Ni高效催化氯酚类污染物还原脱氯降解

doi:10.16085/j.issn.1000-6613.2020-1520

化工进展 ›› 2021, Vol. 40 ›› Issue (7): 4003-4010.DOI: 10.16085/j.issn.1000-6613.2020-1520

Raney Ni高效催化氯酚类污染物还原脱氯降解

贾月娟¹(), 李晓涵², 马宣宣², 谢清明³, 刘莺², 刘苏静², 夏传海¹^,²()

^1.鲁东大学化学与材料科学学院，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.潍坊市知识产权保护中心，山东潍坊 261101

收稿日期:2020-08-03 修回日期:2020-11-13 出版日期:2021-07-06 发布日期:2021-07-19
通讯作者: 夏传海
作者简介:贾月娟（1995—），女，硕士研究生，研究方向为污染物控制。E-mail：jiayj1225@163.com。
基金资助:
国家自然科学基金(22006063);山东省自然科学基金青年项目(ZR2020QB145);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);中科院海岸带环境过程与生态修复重点实验室开放课题(2018KFJJ07)

Effective reductive dechlorination of chlorophenols over Raney Ni catalyst under mild conditions

JIA Yuejuan¹(), LI Xiaohan², MA Xuanxuan², XIE Qingming³, LIU Ying², LIU Sujing², XIA Chuanhai¹^,²()

^1.School of Chemistry and Materials Science, Ludong University, Yantai 264025, Shandong, China
^2.School of Resources and Environmental Engineering, Ludong University, Yantai 264025, Shandong, China
^3.Weifang Intellectual Property Protection Center, Weifang 261101, Shandong, China

Received:2020-08-03 Revised:2020-11-13 Online:2021-07-06 Published:2021-07-19
Contact: XIA Chuanhai

摘要/Abstract

摘要：

采用Raney Ni催化剂，选择50%乙醇-水（50/50，体积比）作为溶剂体系，考察了不同类型碱及其添加量对Raney Ni催化4-氯苯酚（4-CP）还原脱氯反应的影响。结果表明，强碱（NaOH和KOH）和Et₃N更有利于Raney Ni催化下还原脱氯反应的进行，而且当n(NaOH/Et₃N)∶n(4-CP)=1.1~2.2时，Raney Ni能够保持较高的催化活性，可以在30min内实现4-CP的彻底还原脱氯，并建立了Raney Ni-50%乙醇-水（50/50，体积比）-NaOH催化体系。将该体系应用于研究取代基对Raney Ni催化芳香氯代物还原脱氯的影响，研究表明，Raney Ni催化剂对4-CP和4-氯苯胺（4-CA）的还原脱氯具有较高的选择性。进一步将Raney Ni-50%乙醇-水（50/50，体积比）-1.5NaOH催化体系应用于高浓度氯酚工业危废的还原脱氯处理，发现在该催化体系中氯酚工业危废中的氯代有机污染物可以彻底还原脱氯，且催化剂可以至少重复使用5次。该催化体系可以有效、彻底地还原脱氯降解氯酚工业危废，对高浓度氯酚工业危废的还原脱氯降解具有良好的应用前景。

关键词: 废物处理, 氯酚, 催化, 还原脱氯, 降解, Raney Ni

Abstract:

The effects of different bases and their addition amount on the reductive dechlorination of 4-chlorophenol (4-CP) over Raney Ni in 50% ethanol-water (50/50, v/v) were studied. Compared to weak inorganic bases, strong inorganic bases (NaOH and KOH) and triethylamine (Et₃N) were more favorable to the Raney Ni-catalyzed reductive dechlorination reaction. Moreover, Raney Ni exhibited high catalytic activity when n(NaOH/Et₃N)∶n(4-CP) was 1.1—2.2, and the complete reductive dechlorination of 4-CP could be achieved within 30min. Based on the above studies, the catalytic system of Raney Ni-50% ethanol-water (50/50, v/v)-NaOH was developed, and applied to investigate the effects of different substituents on the reductive dechlorination of chlorinated aromatic compounds. The results showed that Raney Ni exhibited high selectivity for reductive dechlorination of 4-CP and 4-chloroaniline (4-CA). Furthermore, the catalytic system was applied to reductive dechlorination of industrial hazardous waste with high concentration chlorophenols. It was found that the chlorinated organic pollutants in industrial hazardous waste could be completely dechlorinated within 240min, and Raney Ni could be reused at least 5 times. Thus, the catalytic system showed excellent application potential for reductive dechlorination of industrial hazardous waste with high concentration chlorophenols because of its high efficiency and complete degradation ability.

Key words: waste treatment, chlorophenol, catalysis, reductive dechlorination, degradation, Raney Ni

中图分类号:

X592

贾月娟, 李晓涵, 马宣宣, 谢清明, 刘莺, 刘苏静, 夏传海. Raney Ni高效催化氯酚类污染物还原脱氯降解[J]. 化工进展, 2021, 40(7): 4003-4010.

JIA Yuejuan, LI Xiaohan, MA Xuanxuan, XIE Qingming, LIU Ying, LIU Sujing, XIA Chuanhai. Effective reductive dechlorination of chlorophenols over Raney Ni catalyst under mild conditions[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 4003-4010.

图/表 10

参考文献 11

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催化剂性质	表征值
Ni质量分数/%	90
Al质量分数/%	≤7
Mo质量分数/%	3
pH	8~11
平均粒径/μm	50
活性（以H₂产量计）/mL·min^-1·g^-1	≥5

催化剂性质	表征值
Ni质量分数/%	90
Al质量分数/%	≤7
Mo质量分数/%	3
pH	8~11
平均粒径/μm	50
活性（以H₂产量计）/mL·min^-1·g^-1	≥5

序号	保留时间/min	化合物	主要离子（m/z）	质量浓度/g·kg^-1	质量分数/%
1	3.23	PA	151，137，93	1.23	0.32
2	4.12	2-CPA	185，127，92，79	26.37	5.64
3	4.38	2，6-DCPA	219，161，127，91	46.74	8.43
4	4.77	4-CPA	185，127，92，79	21.98	4.70
5	5.56	苯酚	93，79	N.D.	0
6	6.69	2，4-DCPA	219，161，127，91	64.77	11.68
7	7.52	TriCP	195，161，125，91	11.79	2.38
8	7.89	2-CP	127，91，65	3.53	1.10
9	8.78	4-CP	127，91，65	N.D.	0
10	9.98	2，6-DCP	161，125，91	73.60	17.99
11	11.88	2，4-DCP	161，125，91	154.37	37.75
12	13.83	2，4，6-TCP	195，161，123，91	24.15	4.87
13	15.04	TetraCPA	287，253，195，161	38.66	5.14

序号	保留时间/min	化合物	主要离子（m/z）	质量浓度/g·kg^-1	质量分数/%
1	3.23	PA	151，137，93	1.23	0.32
2	4.12	2-CPA	185，127，92，79	26.37	5.64
3	4.38	2，6-DCPA	219，161，127，91	46.74	8.43
4	4.77	4-CPA	185，127，92，79	21.98	4.70
5	5.56	苯酚	93，79	N.D.	0
6	6.69	2，4-DCPA	219，161，127，91	64.77	11.68
7	7.52	TriCP	195，161，125，91	11.79	2.38
8	7.89	2-CP	127，91，65	3.53	1.10
9	8.78	4-CP	127，91，65	N.D.	0
10	9.98	2，6-DCP	161，125，91	73.60	17.99
11	11.88	2，4-DCP	161，125，91	154.37	37.75
12	13.83	2，4，6-TCP	195，161，123，91	24.15	4.87
13	15.04	TetraCPA	287，253，195，161	38.66	5.14

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Raney Ni高效催化氯酚类污染物还原脱氯降解

Effective reductive dechlorination of chlorophenols over Raney Ni catalyst under mild conditions

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t/min	流动相A/%	流动相B/%	流动相C/%
0	55	5	40
7	35	15	50
12	20	15	65
25	20	15	65
26	55	5	40
32	55	5	40

t/min	流动相A/%	流动相B/%	流动相C/%
0	55	5	40
7	35	15	50
12	20	15	65
25	20	15	65
26	55	5	40
32	55	5	40