Page 183 - 《精细化工》2022年第4期

第 39 卷第 4 期 精 细 化 工 Vol.39, No.4
2022 年 4 月 FINE CHEMICALS Apr. 2022

水处理技术与环境保护
湿式催化氧化法处理高浓度高盐毒死蜱废水

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胡诗越，原金海 ，唐 倩，覃 余，慎琪琦，周 婧
（重庆科技学院 化学化工学院，重庆 401331）

摘要：以 γ-Al 2 O 3 为载体，通过超声浸渍法制备了 Mn-Ce/γ-Al 2 O 3 ，以其为催化剂采用湿式催化氧化法处理高浓
度高盐毒死蜱废水。通过 FTIR、XRD、SEM 对催化剂进行了表征。通过单因素实验探讨了反应温度、pH、催
化剂用量、氧化剂用量对化学需氧量（COD）去除率的影响。采用均匀设计法对湿式催化氧化实验条件进行了
优化，在进水 COD 质量浓度为 13550 mg/L 时，最优处理条件为反应温度 230 ℃，反应时间 2 h，进水 pH=7，
质量分数 30%过氧化氢 5.5 mL，Mn-Ce/γ-Al 2 O 3 用量 0.4 g。在该条件下，COD 去除率达到 90.63%；各因素影响
结果的主次顺序为：反应温度＞催化剂用量＞氧化剂用量＞pH＞反应时间。采用密度泛函理论（DFT）方法计
算了毒死蜱分子的量子化学参数，初步探讨了湿式催化氧化降解毒死蜱的可能机理。结果表明，γ-Al 2 O 3 上负载
了 MnO 2 、CeO 2 活性组分，Mn-Ce/γ-Al 2 O 3 能较好地促进 H 2 O 2 产生•OH。湿式催化氧化对废水 COD 的降解过程
符合准二级动力学方程。
关键词：湿式催化氧化；毒死蜱废水；工艺优化；催化剂；降解机理；水处理技术
中图分类号：X703 文献标识码：A 文章编号：1003-5214 (2022) 04-0819-09

Treatment of high-concentration and high-salt chlorpyrifos
wastewater by catalytic wet air oxidation

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HU Shiyue, YUAN Jinhai , TANG Qian, QIN Yu, SHEN Qiqi, ZHOU Jing
(School of Chemistry and Chemical Engineering, Chongqing University of Science & Technology, Chongqing 401331, China)

Abstract: Mn-Ce/γ-Al 2O 3 was prepared by ultrasonic impregnation method using γ-Al 2O 3 as carrier and
was used as catalyst to treat chlorpyrifos wastewater with high concentration and high salt by catalytic wet
air oxidation. The catalyst was characterized by FTIR, XRD and SEM. By single factor experiment, the
effects of reaction temperature, pH, catalyst dosage and oxidant dosage on chemical oxygen demand (COD)
removal rate were investigated. Uniform design method was used to optimize the experimental conditions
of catalytic wet air oxidation. When the mass concentration of influent COD was 13550 mg/L, the optimal
conditions of catalytic wet air oxidation were as follows: reaction temperature of 230 ℃, reaction time of 2
h, influent pH of 7, 30% mass fraction hydrogen peroxide of 5.5 mL, Mn-Ce/γ-Al 2O 3 catalyst dosage of 0.4
g. Under these conditions, COD removal rate reached 90.63%. The primary and secondary order of various
factors affecting the results was reaction temperature>amount of catalyst>amount of oxidant>pH>reaction
time. Quantum chemical parameters of chlorpyrifos molecule were calculated by density functional theory
method (DFT). Possible mechanism of catalytic wet air oxidation degradation of chlorpyrifos was
preliminarily discussed. The results showed that active components MnO 2 and CeO 2 were loaded on
γ-Al 2O 3. Mn-Ce/γ-Al 2O 3 could better promote H 2O 2 to produce •OH. The degradation process of wastewater
COD by catalystic wet air oxidation was in line with the quasi-second-order kinetic equation.
Key words: catalytic wet air oxidation; chlorpyrifos wastewater; process optimization; catalyst;
degradation mechanism; water treatment technology

收稿日期：2021-10-26; 定用日期：2021-12-28; DOI: 10.13550/j.jxhg. 20211099
基金项目：重庆市教委项目（KJQN201901512）；重庆市科技局自然科学基金项目（CSTC2020JCYJ-MSXMX0489）
作者简介：胡诗越（1997—），男，硕士生，E-mail：1357086774@qq.com。联系人：原金海（1978—），男，副教授，E-mail：
wenzhuyuan@126.com。