类Fenton法处理含四环素废水研究现状及发展趋势

班福忱; 赵江浩

doi:10.13205/j.hjgc.202608011

类Fenton法处理含四环素废水研究现状及发展趋势

doi: 10.13205/j.hjgc.202608011

班福忱,
赵江浩^,

沈阳建筑大学市政与环境工程学院, 沈阳 110168

基金项目:

国家水体污染控制与治理科技重大专项（2018ZX07601001）；辽宁省高等学校创新人才支持计划项目（Z2219003）；辽宁省教育厅科技计划项目（LJZ2017017）；辽宁省自然科学基金资助项目（20170540744）

详细信息

作者简介:
班福忱（1976—），男，教授，主要研究方向为水污染控制理论与技术研究、污水处理与回用技术。banfc@163.com

通讯作者:
赵江浩（2000—），男，硕士研究生，主要研究方向为污水处理。13898822638@163.com

计量
- 文章访问数: 8
- HTML全文浏览量: 1
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2025-09-02

Progress and prospects in Fenton-like methods for tetracycline-containing wastewater treatment

BAN Fuchen,
ZHAO Jianghao^,

School of Municipal and Environmental Engineering, Shenyang Jianzhu University, Shenyang 110168, China

摘要

摘要: 四环素是一种难生物降解的有机污染物，对水环境构成严重威胁。类Fenton法因其氧化性强能够高效处理含四环素废水而受到广泛关注。类Fenton法通过活化H₂O₂产生羟基自由基（·OH），高效降解四环素，提高废水可生化性。综述了类Fenton法在四环素废水处理中的研究进展，系统总结了改进型Fenton法以及非均相Fenton法的反应原理、处理效果与技术特点。各类方法在优化条件下对四环素去除率可达90%以上。非均相Fenton法在拓宽pH适用范围、减少铁泥产量及催化剂回收利用方面展现出显著优势，是推动该技术实际应用的关键方向。最后对类Fenton法处理含四环素废水应用前景和发展方向进行展望。指出未来应聚焦新型催化剂开发、反应器优化、毒副产物控制及技术耦合，推动类Fenton法在实际工程中的应用。
- 四环素废水 /
- 类Fenton法 /
- 非均相催化 /
- Fenton氧化法 /
- 废水处理
Abstract: Tetracycline is a poorly biodegradable organic pollutant that poses a serious threat to the aquatic environment. The Fenton-like method has received much attention for its high efficiency in treating tetracycline-containing wastewater. It degrades tetracycline by generating hydroxyl radicals （·OH） through the activation of H₂O₂， thereby improving the biodegradability of wastewater. This review presents a comprehensive summary of recent advances in the application of Fenton-like methods and heterogeneous Fenton systems， detailing their reaction mechanisms， treatment efficiencies， and technical features. Under the optimized conditions， the removal rate of tetracycline by various methods can exceed 90%. Crucially， the heterogeneous Fenton method demonstrates superior applicability over a wider pH range， reduced iron sludge production， and excellent catalyst recyclability， representing the most promising strategy for practical implementation. Finally， this review outlines future perspectives， emphasizing the need for developing novel catalysts， optimizing reactor design， controlling toxic by-products， and integrating hybrid technologies to facilitate their practical application.
- tetracycline wastewater /
- Fenton-like method /
- heterogeneous catalysis /
- Fenton oxidation /
- wastewater treatment

HTML全文

参考文献(46)

[1]	LEICHTWEIS J，VIEIRA Y，WELTER N，et al. A review of the occurrence，disposal，determination，toxicity and remediation technologies of the tetracycline antibiotic[J]. Process Safety and Environmental Protection，2022，160：25-40.
[2]	XIE Y L. The study on tetracycline antibiotics wastewater treatment by UASB-A/O-Fenton combined processes[D]. Tianjin：Tianjin University of Technology，2015. 解永磊. UASB-A/O-Fenton组合工艺处理四环素类抗生素废水试验研究[D]. 天津：天津理工大学，2015.
[3]	WANG C Y，LI C. Research progress on the distribution and treatment technology of tetracycline antibiotics[J]. Applied Chemical Industry，2023，52（6）：1807-1812. 王超越，李超. 四环素类抗生素处理技术研究进展[J]. 应用化工，2023，52（6）：1807-1812.
[4]	LI N，HE X，YE J，et al. H₂O₂ activation and contaminants removal in heterogeneous Fenton-like systems[J]. Journal of Hazardous Materials，2023，458：131926.
[5]	JIANG Y，RAN J，MAO K，et al. Recent progress in Fenton/Fenton-like reactions for the removal of antibiotics in aqueous environments[J]. Ecotoxicology and Environmental Safety，2022，236：113464.
[6]	LI R P，LI Y F. Research and application progress of fenton oxidation for industrial wastewater treatment[J]. Liaoning Chemical Industry，2024，53（10）：1590-1593. 李瑞鹏，李亚峰. Fenton氧化法处理工业废水的研究及应用进展[J]. 辽宁化工，2024，53（10）：1590-1593.
[7]	ZHENG X. The study on degradation of tetracycline hydrochloride wastewater by Fenton and electro-Fenton reaction[D]. Chengdu：Southwest Jiaotong University，2021. 郑雪. Fenton及电-Fenton降解盐酸四环素生产废水的研究[D]. 成都：西南交通大学，2021.
[8]	CHEN Y P，ZHENG Y M. Research progress on the electro-Fenton-like cathode materials[J]. Industrial Water Treatment，2021，41（1）：11-17. 陈一萍，郑煜铭. 电（类）Fenton阴极材料的研究进展[J]. 工业水处理，2021，41（1）：11-17.
[9]	SOLTANI F，NAVIDJOUY N，KHORSANDI H，et al. A novel bio-electro-Fenton system with dual application for the catalytic degradation of tetracycline antibiotic in wastewater and bioelectricity generation[J]. RSC Advances，2021，11（44）：27160-27173.
[10]	FAN X，SHU Y，LI D，et al. Tetracycline hydrochloride degradation with simultaneous electricity generation by bio-electro-Fenton system configured with carbon-modified Fe，Co dual-metal cathode catalyst[J]. Chemical Engineering Journal，2024，500：156816.
[11]	ALIZADEH Z，JONOUSH Z A，RAZAEE A. Three-dimensional electro-Fenton system supplied with a nanocomposite of microbial cellulose/Fe₃O₄ for effective degradation of tetracycline[J]. Chemosphere，2023，317：137890.
[12]	YAO S R，HU J S. Condition analysis and optimization of tetracycline hydrochloride wastewater treatment by three-dimensional electrode method[J]. Liaoning Chemical Industry，2024，53（9）：1370-1374. 姚思如，胡俊生. 三维电极法处理盐酸四环素废水的条件分析及优化[J]. 辽宁化工，2024，53（9）：1370-1374.
[13]	BAI Y. Study on degradation of tetracycline in water by UV Fenton and activated persulfate[D]. Changchun：Jilin Jianzhu University，2023. 白岩. 紫外光芬顿及活化过硫酸盐降解水中四环素的研究[D]. 长春：吉林建筑大学，2023.
[14]	YUAN C X，FU M，CHEN Z B. Treatment of tetracycline hydrochloride in wastewater by ultrasonic enhanced H₂O₂[J]. Chinese Journal of Environmental Engineering，2021，15（4）：1219-1226. 袁晨曦，傅敏，陈正波. 超声强化H₂O₂处理废水中的盐酸四环素[J]. 环境工程学报，2021，15（4）：1219-1226.
[15]	MALAKOOTIAN M，ASADZADEH S N. Oxidative removal of tetracycline by sono Fenton-like oxidation process in aqueous media[J]. Desalination and Water Treatment，2020，193：392-401.
[16]	LÜ H，KUAI J，WANG R，et al. Synthesis of a novel hydrophobic CeO₂-BiOCl/CF composite cathode for efficient heterogeneous electro-Fenton degradation of tetracycline[J]. Catalysis Science& Technology，2025，15（2）：537-546.
[17]	YU Q S，WEI Z Q，ZHAO J W，et al. Experimental and theoretical study of the photo-Fenton and photoelectrochemical properties of Ni doped FeOCl[J]. Journal of Alloys and Compounds，2024，1005：176158.
[18]	KARACA M，KARACA C，EROGLU Z，et al. Usage of MnFe₂O₄-rGO Nanocomposite as efficient Fenton catalyst for Tetracycline removal by heterogeneous sono Fenton process：characterizations，catalytic performance assessment，and mechanism[J]. Materials Chemistry and Physics，2023，309：128379.
[19]	WANG F，WANG Z，ZHAO Y，et al. Performance of traditional and emerging water-treatment technologies in the removal of tetracycline antibiotics[J]. Catalysts，2024，14（4）：269.
[20]	BEFENZI H，EZZARIAI A，MECHICHI T，et al. Degradation of antibiotics by homogeneous and heterogeneous Fenton processes：A review[J]. Journal of Hazardous Materials Advances，2025，17：100522.
[21]	WANG Q，WANG L，WANG J，et al. Methods and prospects for enhancing heterogeneous Fenton catalytic activity[J]. ChemistrySelect，2025，10（1）：e202404183.
[22]	WANG R，LIU X H，WANG Y，et al. Research progress of Fenton oxidation treatment refractory organic wastewater[J]. Industrial Water Treatment，2022，42（5）：58-66. 王锐，刘宪华，王勇，等. Fenton氧化处理难降解有机废水研究进展[J]. 工业水处理，2022，42（5）：58-66.
[23]	CHEN J Y，YI Y Q，FANG Z Q，et al. A study of four iron-based materials for heterogeneous Fenton degradation of tetracycline[J]. Journal of South China Normal University（Natural Science Edition），2019，51（1）：49-55. 陈俊毅，易云强，方战强，等. 4种常用铁基材料非均相芬顿降解四环素的研究[J]. 华南师范大学学报（自然科学版），2019，51（1）：49-55.
[24]	MASHAYEKH-SALEHI A，AKBARMOJENI K，ROUDBARI A，et al. Use of mine waste for H₂O₂-assisted heterogeneous Fenton-like degradation of tetracycline by natural pyrite nanoparticles：Catalyst characterization，degradation mechanism，operational parameters and cytotoxicity assessment[J]. Journal of Cleaner Production，2021，291：125235.
[25]	CHEN Y，YANG Y，WANG D，et al. Removal of tetracycline from water by a magnetically modified activated carbon-non-homogeneous Fenton system[J]. Journal of Nanjing University（Natural Science），2023，59（5）：865-876. 陈玉，杨英，王娣，等. 磁改性活性炭-非均相类Fenton体系去除水中四环素[J]. 南京大学学报（自然科学），2023，59（5）：865-876.
[26]	ZHONG W，PENG Q，LIU K，et al. Building Cu⁰/CuFe₂O₄ framework to efficiently degrade tetracycline and improve utilization of H₂O₂ in Fenton-like system[J]. Chemical Engineering Journal，2023，474：145522.
[27]	QIN H D，XIAO R，WU S Z，et al. Heterogeneous Fenton degradation of tetracycline in water catalyzed by magnetic MnFe₂O₄ nanorods[J]. Acta Scientiae Circumstantiae，2020，40（11）：3913-3921. 秦航道，肖榕，吴思展，等. MnFe₂O₄磁性纳米棒非均相Fenton催化降解水中四环素的研究[J]. 环境科学学报，2020，40（11）：3913-3921.
[28]	ZHU T T，SU Z X，ZHAO T H，et al. Treatment of antibiotic wastewater enhanced by zero-valent iron and its coupling technology[J]. Chemical Industry and Engineering Progress，2022，41（8）：4513-4529. 朱婷婷，苏仲弦，赵天杭，等. 零价铁及其耦合技术强化抗生素废水的处理[J]. 化工进展，2022，41（8）：4513-4529.
[29]	SUN Y，XIA L，WANG J，et al. Activation of H₂O₂ via sulfide-modified nanoscale zero-valent iron for tetracycline removal：Performance and mechanism[J]. Separation and Purification Technology，2024，330：125238.
[30]	WEI S，ZHANG L，DU G，et al. Mechanistic study of tetracycline removal and degradation in water using nCo@nZVI composite materials within a Fenton system[J]. Research on Chemical Intermediates，2025，51（3）：1555-1582.
[31]	ZHU Y，XIE Q，DENG F，et al. The differences in heterogeneous Fenton catalytic performance and mechanism of various iron minerals and their influencing factors：a review[J]. Separation and Purification Technology，2023，325：124702.
[32]	WANG H，CHEN T，CHEN D，et al. Sulfurized oolitic hematite as a heterogeneous Fenton-like catalyst for tetracycline antibiotic degradation[J]. Applied Catalysis B：Environmental，2020，260：118203.
[33]	KUANG J，GUO H J，SI Q，et al. Highly dispersed natural Goethite/Fe₃O₄ heterogeneous Fenton-like catalyst for efficient tetracycline degradation：rapid accumulation of hydroxyl radicals by Fe-O-Si bonds[J]. Journal of Cleaner Production，2023，420：138262.
[34]	YANG H Y，ZHENG X. Application and research progress of advanced oxidation process for degradation of organic pollutants[J]. Technology of Water Treatment，2021，47（12）：13-18. 杨鹤云，郑兴. 高级氧化法降解有机污染物的应用及研究进展[J]. 水处理技术，2021，47（12）：13-18.
[35]	LI M X，SHENG G Y，HE A F. Progress of metal catalysts for Fenton reaction at a wide range of pH[J]. Industrial Water Treatment，2021，41（2）：20-25. 李孟宣，盛光遥，何岸飞. 金属催化剂在宽泛pH进行Fenton反应的进展[J]. 工业水处理，2021，41（2）：20-25.
[36]	HE Z，XU X，WANG B，et al. Evaluation of iron-loaded granular activated carbon used as heterogeneous Fenton catalyst for degradation of tetracycline[J]. Journal of Environmental Management，2022，322：116077.
[37]	WANG S，CUI C，ZHANG K，et al. Heterogeneous Fenton system driven by magnetic graphene-like biochar for degrading tetracycline[J]. Journal of Environmental Chemical Engineering，2024，12（6）：114559.
[38]	WU Z，GU Y，XIN S，et al. Cu_xNi_yCo-LDH nanosheets on graphene oxide：an efficient and stable Fenton-like catalyst for dual-mechanism degradation of tetracycline[J]. Chemical Engineering Journal，2022，434：134574.
[39]	GU Y Y，WU Z，SHEN Y，et al. Efficient Fenton-like degradation of tetracycline by stalactite-like CuCo-LDO/CN catalysts：the overlooked contribution of dissolved oxygen[J]. Chemosphere，2023，338：139540.
[40]	GAO K J，YANG Z Y，ZHONG H H，et al. Research progress and prospects of three-dimensional electro-fenton technology in the treatment of refractory organic wastewater[J]. Technology of Water Treatment，2025，51（2）：29-36. 高康健，杨紫怡，钟海红，等. 三维电芬顿技术在难降解有机废水处理中的研究进展[J]. 水处理技术，2025，51（2）：29-36.
[41]	QI X J，WEI F H，FAN J W. Research progress on treatment of antibiotics and their resistance genes by advanced oxidation technologies[J]. Industrial Water Treatment，2022，42（12）：55-64. 戚徐健，魏凡皓，樊佳炜. 高级氧化技术处理抗生素及其抗性基因的研究进展[J]. 工业水处理，2022，42（12）：55-64.
[42]	LI W，YIN J，YOU X M，et al. Research progress on degradation of organic matter in water by ultrasonic technology[J]. Technology of Water Treatment，2025，51（2）：22-28. 李伟，殷进，尤兴萌，等. 超声技术降解水中有机物研究进展[J]. 水处理技术，2025，51（2）：22-28.
[43]	GAO W Y，ZHAO X，ZHOU X L，et al. Strategies research progress and enlightenment of enhancing the heterogeneous Fenton catalytic reactivity：a critical review[J]. Progress in Chemistry，2022，34（5）：1191-1202. 高文艳，赵玄，周曦琳，等. 提高非均相芬顿催化活性策略、研究进展及启示[J]. 化学进展，2022，34（5）：1191-1202.
[44]	XU Z，SUN S，GAO M，et al. Degradation of tetracyclines via calcium peroxide activation by ultrasonic：roles of reactive species，oxidation mechanism and toxicity evaluation[J]. Chemosphere，2023，334：139033.
[45]	WANG C，QU G，WANG T，et al. Removal of tetracycline antibiotics from wastewater by pulsed corona discharge plasma coupled with natural soil particles[J]. Chemical Engineering Journal，2018，346：159-170.
[46]	CHEN S，TANG L，FENG H，et al. Carbon felt cathodes for electro-Fenton process to remove tetracycline via synergistic adsorption and degradation[J]. Science of the Total Environment，2019，670：921-931.