Page 182 - 《精细化工》2020年 第10期

第 37 卷第 10 期 精 细 化 工 Vol.37, No.10
2020 年 10 月 FINE CHEMICALS Oct. 2020

水处理技术与环境保护
湿式催化氧化降解焦化废水

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马建超 ，郭精茂 ，任凯文 ，张晓朋 ，鲍卫仁 ，马清亮
（1. 太原理工大学 矿业工程学院，山西 太原 030024；2. 太原理工大学 煤科学与技术教育部和山西省
重点实验室，山西 太原 030024）
摘要：以 Cu(NO 3 ) 2 •3H 2 O 为原料，采用共沉淀法制备了 CuMgLa/Al 2 O 3 催化剂，TEM 和 N 2 吸附-脱附结果表明，
该催化剂具有介孔结构，主活性组分 CuO 的粒径约为 25 nm。以喹啉为降解目标污染物，考察了温度、催化
剂质量浓度等对湿式催化氧化降解喹啉效果的影响。结果表明，当喹啉模拟废水质量浓度为 1000 mg/L，催
化剂质量浓度为 0.2 g/L，反应温度为 240 ℃，O 2 分压为 0.53 MPa，反应 60 min 时，喹啉去除率接近 100.0%，
化学需氧量（COD）去除率达到 94.8%。通过 UV 光谱、LC-MS 分析喹啉降解生成的中间体，结合叔丁醇淬
灭实验，发现•OH 氧化在湿式催化氧化降解喹啉体系中起主导作用，推测了喹啉可能的降解路径。在最优工
艺条件下，COD 质量浓度为 7000 mg/L 的模拟焦化废水 COD 的去除率达 94.6%；而 COD 质量浓度为
4740.0 mg/L，NH 3 -N 质量浓度为 884.2 mg/L 的实际焦化废水 COD 去除率为 69.6%，NH 3 -N 去除率为 28.0%。
关键词：湿式催化氧化；喹啉；淬灭实验；降解路径；焦化废水；水处理技术
中图分类号：TQ630 文献标识码：A 文章编号：1003-5214 (2020) 10-2112-08

Catalytic wet oxidation degradation of coking wastewater

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MA Jianchao , GUO Jingmao , REN Kaiwen , ZHANG Xiaopeng ,
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BAO Weiren , MA Qingliang
（1. College of Mining Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China; 2. Key Laboratory
of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education and Shanxi Province, Taiyuan
030024, Shanxi, China）
Abstract: CuMgLa/Al 2O 3 was prepared from Cu(NO 3) 2 •3H 2O by coprecipitation method and characterized
by TEM and N 2 adsorption-desorption technique. The results showed that CuMgLa/Al 2 O 3 had a mesoporous
structure and the particle size of the main active component CuO was about 25 nm. The effects of
temperature and catalyst mass concentration on the degradation of quinoline by wet catalytic oxidation were
investigated. It was found that under the conditions of mass concentration of quinoline simulated
wastewater 1000 mg/L, catalyst mass concentration 0.2 g/L, reaction temperature 240 ℃, oxygen partial
pressure 0.53 MPa, reaction time 60 min, the removal rate of quinoline could reach about 100.0%, and the
removal rate of chemical oxygen demand (COD) could reach 94.8%. The quenching experiment of
tert-butanol revealed that •OH oxidation played a key role in quinoline degradation. The intermediate of
quinoline degradation were analyzed by LC-MS and UV spectra, and the possible degradation path of
quinoline was speculated. Meanwhile, under the optimal conditions, COD removal rate of 7000 mg/L mass
concentration of simulated coking wastewater could reach 94.6%. The removal rates of COD and NH 3-N
were 69.6% and 28.0% for the actual coking wastewater with COD and NH 3-N mass concentrations of
4740.0 and of 884.2 mg/L.
Key words: catalytic wet air oxidation; quinoline; quenching experiment; degradation process; coking
wastewater; water treatment technology

收稿日期：2020-07-27; 定用日期：2020-09-07; DOI: 10.13550/j.jxhg.20200692
基金项目：国家重点研发计划（2019YFC0408604-4）；山西省重点研发计划（社会发展领域）（201903D321053）；山西省自然科学基
金（201801D121273，201901D111110）；山西省留学回国人员科研项目（HGKY2019017）；山西省优秀青年学术带头人项目
作者简介：马建超（1980—），男，副教授，E-mail：majianchao@tyut.edu.cn。联系人：马清亮（1981—），男，讲师，E-mail：
maqingliang@tyut.edu.cn。