水相耦合高级氧化法治理VOCs技术：机理、应用与挑战

doi:10.16085/j.issn.1000-6613.2025-0265

化工进展 ›› 2025, Vol. 44 ›› Issue (S1): 478-491.DOI: 10.16085/j.issn.1000-6613.2025-0265

• 资源与环境化工 • 上一篇

水相耦合高级氧化法治理VOCs技术：机理、应用与挑战

王伟豪¹^,²(), 吴贤豪¹, 周瑛², 冯向东¹, 胡达清¹(), 卢晗锋²()

^1.浙江浙能技术研究院有限公司，浙江省火力发电高效节能与污染物控制技术研究重点实验室，工业新水源技术浙江工程研究中心，浙江杭州 311100
^2.浙江工业大学化学工程学院，浙江杭州 310014

收稿日期:2025-02-24 修回日期:2025-06-09 出版日期:2025-10-25 发布日期:2025-11-24
通讯作者: 胡达清,卢晗锋
作者简介:王伟豪（1999—），男，硕士研究生，研究方向为大气污染控制技术。E-mail：1553412939@qq.com。
基金资助:
浙江浙能技术研究院科技研发项目(ZERD-KJ-2023-003);国家重点研发计划(2022YFC3702003);浙江省基础公益技术项目(LTGS24E080008)

Aqueous coupled advanced oxidation for VOCs treatment: Mechanism, applications and challenges

WANG Weihao¹^,²(), WU Xianhao¹, ZHOU Ying², FENG Xiangdong¹, HU Daqing¹(), LU Hanfeng²()

^1.Zhejiang Energy Technology R & D Institute Co. , Ltd. , Zhejiang Key Laboratory of Energy Conservation & Pollutant Control Technology for Thermal Power, Engineering Research Center for New Industrial Water Resources of Zhejiang Province, Hangzhou 311100, Zhejiang, China
^2.School of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2025-02-24 Revised:2025-06-09 Online:2025-10-25 Published:2025-11-24
Contact: HU Daqing, LU Hanfeng

摘要/Abstract

摘要：

传统气固相高温催化氧化法治理工业挥发性有机废气（VOCs）由于其安全性差、能耗过高、催化剂易失活而受到较大的应用阻碍。水相耦合高级氧化技术（AOPs）作为一种近些年来新兴的低温VOCs治理手段，因其具有安全性高、条件温和、成本低、适用性广等优点而广受关注。本文综述了一些常见高级氧化技术治理VOCs（如湿式-光催化氧化、Fenton反应、过硫酸盐氧化以及湿式-催化臭氧氧化）等方面的研究成果，系统分析了反应和吸收机理，以及反应条件在高级氧化技术净化中的影响，同时分析对比了各类AOPs技术的优缺点，发现该技术在未来工业化应用中的关键问题主要为氧化剂消耗、反应不连续、高效催化剂的研发等，通过本文期待能够对解决这些问题提供帮助。

关键词: 挥发性有机废气, 湿式-光催化氧化, Fenton反应, 过硫酸盐氧化, 湿式-臭氧催化氧化

Abstract:

The traditional gas-solid phase high-temperature catalytic oxidation method for the treatment of industrial organic waste gas (VOCs) is greatly hindered by its poor safety, high energy consumption and easy deactivation of catalysts. As an emerging low-temperature VOCs treatment method in recent years, aqueous phase-coupled advanced oxidation technology (AOPs) has attracted wide attention because of its advantages of high safety, mild conditions, low cost and wide applicability. In this paper, the research results of some common advanced oxidation technologies (AOPs) for the treatment of VOCs (such as wet-photocatalytic oxidation, Fenton reaction, persulfate oxidation, and wet-catalytic ozone oxidation) are summarized, the reaction and absorption mechanisms, as well as the influence of reaction conditions in the purification of advanced oxidation technologies, are systematically analyze, and the advantages and disadvantages of various AOPs technologies are analyzed and compared. In this article, we hope that the development of high-efficiency catalysts will help solve these problems.

Key words: volatile organic compounds (VOCs), wet-photocatalytic oxidation, Fenton reaction, persulfate-based oxidation, wet catalytic ozonation oxidation

中图分类号:

X511

王伟豪, 吴贤豪, 周瑛, 冯向东, 胡达清, 卢晗锋. 水相耦合高级氧化法治理VOCs技术：机理、应用与挑战[J]. 化工进展, 2025, 44(S1): 478-491.

WANG Weihao, WU Xianhao, ZHOU Ying, FENG Xiangdong, HU Daqing, LU Hanfeng. Aqueous coupled advanced oxidation for VOCs treatment: Mechanism, applications and challenges[J]. Chemical Industry and Engineering Progress, 2025, 44(S1): 478-491.

图/表 10

图1 PCO与WPCO降解VOCs性能[28]

图2 H2O2浓度、Fe2+浓度和pH对甲苯降解效率的影响[35-36]

图3 不同UV-Fenton工艺中甲苯的去除率、CO2的选择性以及365nm UV照射下铁离子的浓度分布[48]

图4 蛋黄壳Fe3O4@C催化剂的协同效应、传质和辛烷降解机理[55]

图5 电子和能量转移过程活化PMS和PDS[64]

图6 UV/PDS降解氯苯机理[66]

图7 PMS活化以及VOCs在CoS2/AC上深度氧化的可能机理[74]

图8 臭氧分子共振杂化式

图9 MnO x /AC对甲苯的WCO机理以及中试参数[91]

表1 水相耦合AOPs技术净化VOCs汇总

AOPs种类	体系	污染物	催化剂	ROS	去除率	参考文献
湿式-光催化氧化	真空紫外光（VUV）-H₂O	甲苯	—	·OH	83%	[29]
	F/TiO₂-WPCO	甲苯	F/TiO₂	·OH	约80%	[24]
	TiO₂-WPCO	甲苯	TiO₂（P25）	·OH	约60%	[28]
	TiO₂/g-C₃N₄-WPCO	异丙醇	TiO₂/g-C₃N₄	·OH	60%	[11]
Fenton反应	Fenton	甲苯	Fe²⁺	·OH	81%	[35]
	Fenton	苯	Fe²⁺	·OH	85%	[37]
	UV-Fenton	苯、乙苯、甲苯、二甲苯混合物（BETX）	Fe²⁺	·OH	84%~97%	[92]
	UV-Fenton	甲苯	Fe²⁺	·OH	92%	[36]
	UV-Fenton	甲苯	Fe²⁺	·OH	>90%	[46]
	UV-Fenton	甲苯	Fe²⁺	·OH	85.31%	[48]
	UV-Fenton	甲苯	Fe²⁺	·OH	80%	[47]
	FeS₂-Fenton	甲苯	FeS₂	·OH	95%	[52]
	Fe/ZSM-5-Fenton	甲苯	Fe/ZSM-5	·OH	>85%	[54]
	Fe₃O₄@C-Fenton	正辛烷	Fe₃O₄@C	·OH	84%	[55, 56]
	UV-AC-Fenton	正辛烷	AC、Fe²⁺	·OH	>80%	[93-94]
	SC_FeK-SiC/Fenton	甲硫醇	SC_FeK-SiC	·OH	约100%	[57]
	FeOCl/AC-Fenton	二氯乙烯	FeOCl/AC	·OH	86.5%	[95]
过硫酸盐氧化	UV-PMS	甲苯、乙酸乙酯	—	·SO $4 -$ 、·OH	98%、96%	[61]
	UV-PDS	氯苯	—	·SO $4 -$ 、·OH	97%	[66]
	UV-PDS-KMnO₄	甲苯	MnO _x	·SO $4 -$ 、·OH	>90%	[67]
	Fe²⁺/MoS₂-PMS	氯苯、甲苯、苯乙烯	Fe²⁺、MoS₂	·SO $4 -$ 、·OH	83%、84%、97%	[96]
	Co₃O₄/AC-PMS	甲苯	Co₃O₄/AC	·SO $4 -$ 、·OH	>90%	[69]
	MnCo _x /Kaolin-PMS	甲苯	MnCo _x /Kaolin	·SO $4 -$ 、·OH	98%	[72]
	CoS₂/AC-PMS	氯苯、甲苯、苯乙烯	CoS₂/AC	·SO $4 -$ 、·OH	>90%	[74]
	Co/NCNT-PMS	氯苯	Co/NCNT	·SO $4 -$ 、·OH	>90%	[70]
	Co/SBA-15-PMS	甲苯	Co/SBA-15	·SO $4 -$ 、·OH	95%	[97]
	Co/CN-PMS	甲苯	Co/CN	·SO $4 -$ 、·OH	>90%	[98]
	MWCNTs-PMS	苯乙烯	多壁碳纳米管（MWCNTs）	·SO $4 -$ 、·OH	98%	[99]
湿式-催化臭氧化	WMO	甲苯	—	·OH	97.08%	[81]
	H₂O₂-O₃	三氯乙烯	—	·OH	94%	[85]
	Ag/MnO₂-WCO	甲硫醇	Ag/MnO₂	·OH、·O $2 -$ 、¹O₂	97%	[90]
	MnO _x /AC-WCO	甲苯	MnO _x /AC	·OH、·O $2 -$	71.82%	[91]

表1 水相耦合AOPs技术净化VOCs汇总

AOPs种类	体系	污染物	催化剂	ROS	去除率	参考文献
湿式-光催化氧化	真空紫外光（VUV）-H₂O	甲苯	—	·OH	83%	[29]
	F/TiO₂-WPCO	甲苯	F/TiO₂	·OH	约80%	[24]
	TiO₂-WPCO	甲苯	TiO₂（P25）	·OH	约60%	[28]
	TiO₂/g-C₃N₄-WPCO	异丙醇	TiO₂/g-C₃N₄	·OH	60%	[11]
Fenton反应	Fenton	甲苯	Fe²⁺	·OH	81%	[35]
	Fenton	苯	Fe²⁺	·OH	85%	[37]
	UV-Fenton	苯、乙苯、甲苯、二甲苯混合物（BETX）	Fe²⁺	·OH	84%~97%	[92]
	UV-Fenton	甲苯	Fe²⁺	·OH	92%	[36]
	UV-Fenton	甲苯	Fe²⁺	·OH	>90%	[46]
	UV-Fenton	甲苯	Fe²⁺	·OH	85.31%	[48]
	UV-Fenton	甲苯	Fe²⁺	·OH	80%	[47]
	FeS₂-Fenton	甲苯	FeS₂	·OH	95%	[52]
	Fe/ZSM-5-Fenton	甲苯	Fe/ZSM-5	·OH	>85%	[54]
	Fe₃O₄@C-Fenton	正辛烷	Fe₃O₄@C	·OH	84%	[55, 56]
	UV-AC-Fenton	正辛烷	AC、Fe²⁺	·OH	>80%	[93-94]
	SC_FeK-SiC/Fenton	甲硫醇	SC_FeK-SiC	·OH	约100%	[57]
	FeOCl/AC-Fenton	二氯乙烯	FeOCl/AC	·OH	86.5%	[95]
过硫酸盐氧化	UV-PMS	甲苯、乙酸乙酯	—	·SO $4 -$ 、·OH	98%、96%	[61]
	UV-PDS	氯苯	—	·SO $4 -$ 、·OH	97%	[66]
	UV-PDS-KMnO₄	甲苯	MnO _x	·SO $4 -$ 、·OH	>90%	[67]
	Fe²⁺/MoS₂-PMS	氯苯、甲苯、苯乙烯	Fe²⁺、MoS₂	·SO $4 -$ 、·OH	83%、84%、97%	[96]
	Co₃O₄/AC-PMS	甲苯	Co₃O₄/AC	·SO $4 -$ 、·OH	>90%	[69]
	MnCo _x /Kaolin-PMS	甲苯	MnCo _x /Kaolin	·SO $4 -$ 、·OH	98%	[72]
	CoS₂/AC-PMS	氯苯、甲苯、苯乙烯	CoS₂/AC	·SO $4 -$ 、·OH	>90%	[74]
	Co/NCNT-PMS	氯苯	Co/NCNT	·SO $4 -$ 、·OH	>90%	[70]
	Co/SBA-15-PMS	甲苯	Co/SBA-15	·SO $4 -$ 、·OH	95%	[97]
	Co/CN-PMS	甲苯	Co/CN	·SO $4 -$ 、·OH	>90%	[98]
	MWCNTs-PMS	苯乙烯	多壁碳纳米管（MWCNTs）	·SO $4 -$ 、·OH	98%	[99]
湿式-催化臭氧化	WMO	甲苯	—	·OH	97.08%	[81]
	H₂O₂-O₃	三氯乙烯	—	·OH	94%	[85]
	Ag/MnO₂-WCO	甲硫醇	Ag/MnO₂	·OH、·O $2 -$ 、¹O₂	97%	[90]
	MnO _x /AC-WCO	甲苯	MnO _x /AC	·OH、·O $2 -$	71.82%	[91]

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水相耦合高级氧化法治理VOCs技术：机理、应用与挑战

Aqueous coupled advanced oxidation for VOCs treatment: Mechanism, applications and challenges

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