湿式催化过氧化氢氧化处理环氧氯丙烷生产污水研究

doi:10.19965/j.cnki.iwt.2024-0920

摘要/Abstract

摘要：

环氧氯丙烷生产污水具有高有机物、高盐度和可生化性差等特点，处理难度较大，因此开发高效的处理工艺是该工业污水治理的迫切需求。高级氧化法在处理难降解有机物领域具有很大的优势，优化了过硫酸盐高级氧化工艺（SAOPs）、湿式催化过氧化氢氧化工艺（CWPO）处理环氧氯丙烷生产污水的工艺条件，对比了两种高级氧化工艺处理环氧氯丙烷废水的效果及出水水质，并利用全二维气相色谱-质谱（GC×GC-MS）从分子层面对CWPO处理过程中的有机污染物转化特性进行了探究。结果表明CWPO工艺处理环氧氯丙烷生产污水的最优条件为pH=9.0、反应温度70 ℃、Mn-Ce/Al₂O₃投加量20 g/L、m（H₂O₂）∶m（COD）=4∶1、H₂O₂分批次投加，此条件下反应80 min，TOC去除率达到86.00%，出水残余有机卤素质量浓度为52.3 mg/L、急性毒性值为60.33%，处理效果优于SAOPs。GC×GC-MS分析显示CWPO处理出水有机物种类明显减少，原水中主要有机污染物（酸类）大幅度降低，但可吸附有机卤素（AOX）较原水升高。根据原水及出水的主要氯代有机物，推测了CWPO处理出水中氯代副产物的生成途径，提出了减少或防止卤代副产物的调控措施，为环氧氯丙烷生产污水的高效处理、毒性控制及环境风险评估提供了理论依据和技术参考。

关键词: 环氧氯丙烷, 湿式催化过氧化氢氧化, 过硫酸盐高级氧化工艺, 急性毒性

Abstract:

Epichlorohydrin production wastewater is characterized by high organic content, high salinity, and poor biodegradability, making its treatment challenging. Thus developing efficient treatment processes is an urgent need. Advanced oxidation processes have great advantages in treating refractory organic compounds. This study optimized the process conditions of sulfate radical-based advanced oxidation processes (SAOPs) and catalytic wet peroxide oxidation (CWPO) for treating epichlorohydrin production wastewater. The treatment effects and effluent quality of the two advanced oxidation processes on epichlorohydrin production wastewater were compared, and the transformation characteristics of organic pollutants during the CWPO treatment process were analyzed at the molecular level using comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS). The results showed that the optimal conditions for the CWPO process in treating epichlorohydrin production wastewater were pH=9.0, reaction temperature of 70 ℃, Mn-Ce/Al₂O₃ dosage of 20 g/L, m(H₂O₂)∶m(COD)=4∶1, and batch addition of H₂O₂. Under these conditions, after 80 minutes of reaction, the TOC removal rate reached 86.00%, the residual organic halogen content was 52.3 mg/L, and the acute toxicity value was 60.33%. The treatment effect was better than that of SAOPs. GC×GC-MS analysis showed that the types of organic compounds in the CWPO effluent were significantly reduced, and the main organic pollutants (acids) in the raw water were greatly decreased, while the absorbable organic halogen (AOX) increased compared to the raw water. Based on the major chlorinated organic compounds identified in the raw water and effluent, the generation pathways of chlorinated by-products in the CWPO effluent were inferred. Control measures to reduce or prevent the formation of halogenated by-products were proposed. This study provides a theoretical basis and technical reference for the efficient treatment, toxicity control, and environmental risk assessment of epichlorohydrin production wastewater and related industrial effluents.

Key words: epichlorohydrin, catalytic wet hydrogen peroxide oxidation, sulfate radical-based advanced oxidation processes, acute toxicity

中图分类号:

X703

李海帆, 冯华良, 张召基. 湿式催化过氧化氢氧化处理环氧氯丙烷生产污水研究[J]. 工业水处理, 2025, 45(11): 140-150.

Haifan LI, Hualiang FENG, Zhaoji ZHANG. Study on treatment of epichlorohydrin production wastewater by catalytic wet hydrogen peroxide oxidation[J]. Industrial Water Treatment, 2025, 45(11): 140-150.

https://www.iwt.cn/CN/Y2025/V45/I11/140

图/表 15

表1 环氧氯丙烷生产污水水质

Table 1 Water quality of epichlorohydrin production wastewater

指标	数值
温度/℃	70~80
pH	10.67±0.02
电导率/（mS·cm^-1）	173.63±0.40
COD_Cr/（mg·L^-1）	6 070.00±86.60
TOC/（mg·L^-1）	1 027.50±2.12
NH₄ ⁺-N/（mg·L^-1）	ND
NO₂ ^--N/（mg·L^-1）	ND
NO₃ ^--N/（mg·L^-1）	ND
TN/（mg·L^-1）	ND
TP/（mg·L^-1）	ND
TDS/（mg·L^-1）	206.27±0.19
Cl^-/（g·L^-1）	112.68±1.56
Ca²⁺/（g·L^-1）	68.53±0.26

表2 试剂及材料

Table 2 Reagents and materials

分子式	名称	规格	品牌
Na₂S₂O₈	过硫酸钠	分析纯	国药集团化学试剂
FeSO₄·7H₂O	七水合硫酸亚铁	分析纯	国药集团化学试剂
H₂O₂	过氧化氢	分析纯	西陇科学
H₂SO₄	硫酸	分析纯	西陇科学
NaOH	氢氧化钠	分析纯	国药集团化学试剂
Mn/AC	锰负载活性炭催化剂	4~8 mm球状	平顶山市炭诺环保材料
Mn-Ti/AC	锰钛双金属负载活性炭催化剂	4~8 mm球状	平顶山市炭诺环保材料
Mn-Ce/Al₂O₃	锰铈双金属负载氧化铝催化剂	4~8 mm球状	平顶山市炭诺环保材料
Fe/AC	铁负载活性炭催化剂	4~8 mm球状	平顶山市炭诺环保材料

图1 不同催化剂对TOC的去除效果

Fig.1 Evaluation of TOC removal by different catalysts

图2 不同催化剂的吸附性能评价

Fig.2 Evaluation of adsorption performance of different catalysts

图3 不同催化剂的XRD谱图

Fig.3 XRD patterns of different catalysts

图4 pH、温度、催化剂投加量和m（H₂O₂）∶m（COD）对CWPO矿化效果的影响

Fig. 4 Effects of pH，temperatrue，catalyst dosage， and m（H₂O₂）∶m（COD） on the mineralization efficiency of CWPO

图5 H₂O₂投加方式对矿化效果的影响

Fig.5 Effects of H₂O₂ dosing method on mineralization efficiency

图6 不同影响因素对SAOPs工艺矿化效果的影响

Fig.6 Effects of different factors on the mineralization efficiency of SAOPs

图7 不同高级氧化工艺出水水质特征

Fig.7 Water quality characteristics of effluent treated by different advanced oxidation processes

图8 急性毒性与水质指标相关性分析

Fig.8 Correlation analysis between acute toxicity and water quality parameters

图9 原水与CWPO出水的各类有机物对比

Fig.9 Comparison of various organic compounds in raw water and CWPO effluent

图10 原水及出水主要有机酸的峰面积和峰面积占比

Fig. 10 Peak area and peak area proportion of major organic acids in raw and treated water

表3 环氧氯丙烷生产污水中主要氯代有机物

Table 3 The primary chlorinated organic compounds in wastewater from epichlorohydrin production

组分	峰面积	峰面积占比/%	结构式
3-氯-1-丙醇	349 643 680	1.77
2，3-二氯-1-丙醇	32 407 734	0.16

表4 CWPO出水中主要氯代有机物

Table 4 The primary chlorinated organic substances in the effluent of CWPO

组分	峰面积	峰面积占比/%
1，3-二氯丙醇	499 572 256	17.25
三氯丙酮	36 134 972	1.25
1，1，3，3-四氯丙酮	14 221 909	0.49
2，3-二氯-1-丙醇	12 915 817	0.45
2，2-二氯丙烷	7 106 751.5	0.25

图11 CWPO处理过程中可能存在的氯代有机物生成途径

Fig. 11 Possible formation pathways of chlorinated organic compounds during CWPO

参考文献 38

[1]	张新合，卢兴玉，谭化平，等. 环氧氯丙烷皂化废水处理工艺研究［J］. 广东化工，2015，42（13）：202-203．
	ZHANG Xinhe， LU Xingyu， TAN Huaping，et al. Study on the processing technology of epoxy chloropropane saponification wastewater［J］. Guangdong Chemical Industry，2015，42（13）：202-203．
[2]	GUO Shijun， SHARMA S， ISSAKHOV A，et al. Evaluation of the safety of high-salt wastewater treatment in coal chemical industry based on the AHP fuzzy method［J］. Journal of Chemistry，2021，2021（1）：7107058． doi:10.1155/2021/7107058
[3]	李慧. 电渗析-生物处理环氧氯丙烷生产过程废水研究［D］. 天津：天津大学，2014．
	LI Hui. Study on electrodialysis-biological treatment of wastewater from epichlorohydrin production process［D］. Tianjin：Tianjin University，2014．
[4]	WANG Ling， CUI Youwei. Simultaneous treatment of epichlorohydrin wastewater and polyhydroxyalkanoate recovery by halophilic aerobic granular sludge highly enriched by Halomonas sp［J］. Bioresource Technology，2024，391：129951． doi:10.1016/j.biortech.2023.129951
[5]	ZHENG Xiaoxian， NIU Xiaojun， ZHANG Dongqing，et al. Metal-based catalysts for persulfate and peroxymonosulfate activation in heterogeneous ways：A review［J］. Chemical Engineering Journal，2022，429：132323． doi:10.1016/j.cej.2021.132323
[6]	ANJORIN E O， ALFRED D M O， SOTUNDE B，et al. Overview of the mechanism of degradation of pharmaceuticals by persulfate/peroxysulfate catalysts［J］. ChemBioEng Reviews，2024，11（4）：e202300079． doi:10.1002/cben.202300079
[7]	帅晓丹. 甘油法环氧氯丙烷高盐废水处理技术研究［D］. 上海：华东理工大学，2014．
	SHUAI Xiaodan. Study on treatment technology of high salt wastewater from epichlorohydrin by glycerol method［D］. Shanghai：East China University of Science and Technology，2014．
[8]	苏尚伟，高俊斌，慕朝，等. 富含表面羟基的活性炭制备及其在电催化氧化垃圾渗滤液中的应用［J］. 环境污染与防治，2024，46（8）：1128-1132．
	SU Shangwei， GAO Junbin， MU Zhao，et al. Preparation of an activated carbon rich in surface hydroxyl and its application in the electrocatalytic oxidation of landfill leachate［J］. Environmental Pollution & Control，2024，46（8）：1128-1132．
[9]	RHADFI T， PIQUEMAL J Y， SICARD L，et al. Polyol-made Mn₃O₄ nanocrystals as efficient Fenton-like catalysts［J］. Applied Catalysis A：General，2010，386（1/2）：132-139． doi:10.1016/j.apcata.2010.07.044
[10]	HUSSAIN S， ANEGGI E，GOI D. Catalytic activity of metals in heterogeneous Fenton-like oxidation of wastewater contaminants：A review［J］. Environmental Chemistry Letters，2021，19（3）：2405-2424． doi:10.1007/s10311-021-01185-z
[11]	MAMONTOV E， EGAMI T， BREZNY R，et al. Lattice defects and oxygen storage capacity of nanocrystalline ceria and ceria-zirconia［J］. The Journal of Physical Chemistry B，2000，104（47）：11110-11116． doi:10.1021/jp0023011
[12]	BOKARE A D， CHOI W. Review of iron-free Fenton-like systems for activating H₂O₂ in advanced oxidation processes［J］. Journal of Hazardous Materials，2014，275：121-135． doi:10.1016/j.jhazmat.2014.04.054
[13]	ZHENG Yanxia， YANG Lixi， HUANG Chuxin，et al. Catalytic activation of peroxodisulfate using shape-controlled cerium-manganese composite oxide for phenol degradation：Kinetics and degradation pathway investigation［J］. Journal of Rare Earths，2024，42（8）：1514-1523． doi:10.1016/j.jre.2023.10.008
[14]	ZHAO Lele， ZHANG Zhiping， LI Yushi，et al. Synthesis of CeaMnO _x hollow microsphere with hierarchical structure and its excellent catalytic performance for toluene combustion［J］. Applied Catalysis B：Environmental，2019，245：502-512． doi:10.1016/j.apcatb.2019.01.005
[15]	QI Fei， XU Bingbing， CHEN Zhonglin，et al. Influence of aluminum oxides surface properties on catalyzed ozonation of 2，4，6-trichloroanisole［J］. Separation and Purification Technology，2009，66（2）：405-410． doi:10.1016/j.seppur.2009.01.013
[16]	HOU B， LIU J， TANG J，et al. Heterogeneous Fenton oxidation of aniline aerofloat catalyzed by Fe/Mn binary oxides supported on activated carbon：Performance and mechanism［J］. Journal of Environmental Chemical Engineering，2025，13（1）：115126. doi:10.1016/j.jece.2024.115126
[17]	GOSU V， SIKARWAR P， SUBBARAMAIAH V. Mineralization of pyridine by CWPO process using nFe⁰/GAC catalyst［J］. Journal of Environmental Chemical Engineering，2018，6（1）：1000-1007． doi:10.1016/j.jece.2018.01.017
[18]	HE Guangjun， ZHONG Dengjie， XU Yunlan，et al. Pyrite/H₂O₂/hydroxylamine system for efficient decolorization of rhodamine B［J］. Water Science and Technology，2021，83（9）：2218-2231． doi:10.2166/wst.2021.135
[19]	刘宇程，杨冰，李沁蔓，等. Cl^-和pH对高级氧化工艺去除含盐废水中有机物的影响及机理［J］. 环境工程学报，2021，15（5）：1487-1499．
	LIU Yucheng， YANG Bing， LI Qinman，et al. Effects and mechanism of Cl^- and pH on organic matter removal in saltcontaining wastewater treatment by advanced oxidation processes［J］. Chinese Journal of Environmental Engineering，2021，15（5）：1487-1499．
[20]	WANG Jianlong， WANG Shizong. Activation of persulfate （PS） and peroxymonosulfate （PMS） and application for the degradation of emerging contaminants［J］. Chemical Engineering Journal，2018，334：1502-1517． doi:10.1016/j.cej.2017.11.059
[21]	ARVANITI O S， IOANNIDI A A， MANTZAVINOS D，et al. Heat-activated persulfate for the degradation of micropollutants in water：A comprehensive review and future perspectives［J］. Journal of Environmental Management，2022，318：115568． doi:10.1016/j.jenvman.2022.115568
[22]	ANTONIOU M G， DE LA CRUZ A A， DIONYSIOU D D. Degradation of microcystin-LR using sulfate radicals generated through photolysis，thermolysis and e^- transfer mechanisms［J］. Applied Catalysis B：Environmental，2010，96（3/4）：290-298． doi:10.1016/j.apcatb.2010.02.013
[23]	ZHAO Qingxia， MAO Qiming， ZHOU Yaoyu，et al. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes：A review on heterogeneous catalysts and applications［J］. Chemosphere，2017，189：224-238． doi:10.1016/j.chemosphere.2017.09.042
[24]	HUO Jiajie， TESSONNIER J P， SHANKS B H. Improving hydrothermal stability of supported metal catalysts for biomass conversions：A review［J］. ACS Catalysis，2021，11（9）：5248-5270． doi:10.1021/acscatal.1c00197
[25]	张丽. 高级氧化技术处理垃圾渗滤液的实验究［D］. 北京：北京工业大学，2014． doi:10.1016/j.biortech.2013.05.006
	ZHANG Li. Experimental study on treatment of landfill leachate by advanced oxidation technology［D］. Beijing：Beijing University of Technology，2014． doi:10.1016/j.biortech.2013.05.006
[26]	ZOU L， WANG Y， HUANG C，et al. Meta-cresol degradation by persulfate through UV/O₃ synergistic activation：Contribution of free radicals and degradation pathway［J］. Science of the Total Environment， 2021， 754： 142219. doi:10.1016/j.scitotenv.2020.142219
[27]	程澳，陈丹，任兰天，等. 蘑菇渣和稻秸堆肥中不同分子量水溶性有机物含量分布和光谱特征［J］. 光谱学与光谱分析，2024，44（5）：1330-1337．
	CHENG Ao， CHEN Dan， REN Lantian，et al. The distributions and spectral characteristics of molecular weight-fractionated dissolved organic matter derived from mushroom residue and rice straw compost［J］. Spectroscopy and Spectral Analysis，2024，44（5）：1330-1337．
[28]	BLUM K M， ANDERSSON P L， RENMAN G，et al. Non-target screening and prioritization of potentially persistent，bioaccumulating and toxic domestic wastewater contaminants and their removal in on-site and large-scale sewage treatment plants［J］. Science of the Total Environment，2017，575：265-275． doi:10.1016/j.scitotenv.2016.09.135
[29]	胡兴，刘易，杜泽学. 3-氯丙烯直接合成环氧氯丙烷催化剂研究进展［J］. 化工进展，2024，43（）：325-334．
	HU Xing， LIU Yi， DU Zexue. Research progress of catalysts for direct synthesis of epichlorohydrin in 3-chloropropene［J］. Chemical Industry and Engineering Progress，2024，43（S1）：325-334．
[30]	SANTACESARIA E， TESSER R， DI SERIO M，et al. New process for producing epichlorohydrin via glycerol chlorination［J］. Industrial & Engineering Chemistry Research，2010，49（3）：964-970． doi:10.1021/ie900650x
[31]	VITIELLO R， RUSSO V， TURCO R，et al. Glycerol chlorination in a gas-liquid semibatch reactor：New catalysts for chlorohydrin production［J］. Chinese Journal of Catalysis，2014，35（5）：663-669． doi:10.1016/s1872-2067(14)60069-3
[32]	MUNOZ M， DE PEDRO Z M， CASAS J A，et al. Combining efficiently catalytic hydrodechlorination and wet peroxide oxidation （HDC-CWPO） for the abatement of organochlorinated water pollutants［J］. Applied Catalysis B：Environmental，2014，150：197-203． doi:10.1016/j.apcatb.2013.12.029
[33]	PÉREZ-MOYA M， GRAELLS M， DEL VALLE L J，et al. Fenton and photo-Fenton degradation of 2-chlorophenol：Multivariate analysis and toxicity monitoring［J］. Catalysis Today，2007，124（3/4）：163-171． doi:10.1016/j.cattod.2007.03.034
[34]	JIANG Jingyi， ZHANG Xiangru. A smart strategy for controlling disinfection byproducts by reversing the sequence of activated carbon adsorption and chlorine disinfection［J］. Science Bulletin，2018，63（18）：1167-1169． doi:10.1016/j.scib.2018.07.022
[35]	XU Guofang， ZHAO Siyan， CHEN Chen，et al. Dehalogenation of polybrominated diphenyl ethers and polychlorinated biphenyls catalyzed by a reductive dehalogenase in Dehalococcoides mccartyi strain MB［J］. Environmental Science & Technology，2022，56（7）：4039-4049．
[36]	XU Jiang， CHEN Chaohuang， HU Xiaohong，et al. Particle-scale understanding of arsenic interactions with sulfidized nanoscale zerovalent iron and their impacts on dehalogenation reactivity［J］. Environmental Science & Technology，2023，57（51）：21917-21926． doi:10.1021/acs.est.3c08635
[37]	MENG Di， ZHU Qian， WEI Yan，et al. Light-driven activation of carbon-halogen bonds by readily available amines for photocatalytic hydrodehalogenation［J］. Chinese Journal of Catalysis，2020，41（10）：1474-1479． doi:10.1016/s1872-2067(20)63582-3
[38]	GUO Yun， LI Yang， WANG Zhiwei. Electrocatalytic hydro-dehalogenation of halogenated organic pollutants from wastewater：A critical review［J］. Water Research，2023，234：119810． doi:10.1016/j.watres.2023.119810

选择文件类型/文献管理软件名称

选择包含的内容