过硫酸盐活化技术去除抗生素废水研究进展
Research Progress on Persulfate Activation Technology for Removing Antibiotic Wastewater
DOI: 10.12677/aep.2025.157115, PDF,   
作者: 王 杰, 查甫更, 付梦娇, 李 贺：安徽理工大学地球与环境学院，安徽 淮南
关键词: 过硫酸盐；四环素；高级氧化技术；自由基；Persulfate； Tetracycline； Advanced Oxidation Technology； Free Radical
摘要: 抗生素被广泛用于人类医疗、兽药及水产养殖领域，导致其大量残留在水中，对生态环境和人类健康构成严重威胁。基于硫酸根自由基的高级氧化技术因其快速高效、适用范围广等特点，已成为在抗生素废水处理的国内外研究热点。本文综述了过硫酸盐活化技术(热活化、光活化、超声活化、碳基材料活化及过渡金属离子活化)的研究进展与应用局限，并探讨了影响过硫酸盐活化的主要因素，评价了pH、常见无机阴离子以及有机物、催化剂浓度等对降解过程的影响，对该领域未来发展趋势进行展望。
Abstract: Antibiotics are widely used in human medical, veterinary, and aquaculture fields, resulting in their large residues in water, posing a serious threat to the ecological environment and human health. Advanced oxidation technology based on sulfate radical has become a hot research topic in antibiotic wastewater treatment both domestically and internationally due to its fast, efficient, and widely applicable characteristics. This article reviews the research progress and application limitations of persulfate activation technologies (thermal activation, photoactivation, ultrasonic activation, carbon based material activation, and transition metal ion activation), and explores the main factors affecting persulfate activation. The effects of pH, common inorganic anions, organic matter, catalyst concentration, etc. On the degradation process are evaluated, and the future development trends in this field are discussed.
文章引用：王杰, 查甫更, 付梦娇, 李贺. 过硫酸盐活化技术去除抗生素废水研究进展[J]. 环境保护前沿, 2025, 15(7): 1024-1032. https://doi.org/10.12677/aep.2025.157115

参考文献

[1] 吴文瞳, 张玲玲, 李子富, 等. 高级氧化技术降解抗生素及去除耐药性的研究进展[J]. 化工进展, 2021, 40(8): 4551-4561.
[2] 郑琴琴, 闵中芳, 李吉平, 等. 活化过硫酸盐高级氧化技术降解水中抗生素的研究进展[J]. 化工环保, 2021, 41(6): 678-687.
[3] 刘路明, 高志敏, 邓兆雄, 等. 过硫酸盐的活化及其在氧化降解水中抗生素的机理和应用[J]. 环境化学, 2022, 41(5): 1702-1717.
[4] Liu, B., Huang, B., Wang, Z., Tang, L., Ji, C., Zhao, C., et al. (2023) Homogeneous/Heterogeneous Metal-Catalyzed Persulfate Oxidation Technology for Organic Pollutants Elimination: A Review. Journal of Environmental Chemical Engineering, 11, Article ID: 109586. [Google Scholar] [CrossRef] 
[5] 李轶涵, 姜恬, 周旭, 等. 热活化过硫酸盐氧化降解水溶液中的抗生素卡巴多司和奥喹多司[J]. 环境科学学报, 2019, 39(11): 3821-3831.
[6] Ji, Y., Shi, Y., Dong, W., Wen, X., Jiang, M. and Lu, J. (2016) Thermo-Activated Persulfate Oxidation System for Tetracycline Antibiotics Degradation in Aqueous Solution. Chemical Engineering Journal, 298, 225-233. [Google Scholar] [CrossRef] 
[7] Lalas, K., Arvaniti, O.S., Zkeri, E., Nika, M., Thomaidis, N.S., Mantzavinos, D., et al. (2022) Thermally Activated Persulfate Oxidation of Ampicillin: Kinetics, Transformation Products and Ecotoxicity. Science of the Total Environment, 846, Article ID: 157378. [Google Scholar] [CrossRef] [PubMed]
[8] 杨梅. 热活化过硫酸盐降解四环素的机理及产物的生物毒性评价[D]. 重庆大学, 2020.
[9] Lin, C. and Ke, J. (2022) Degradation of Ofloxacin in Water Using Heat/s2o82-Process. 140, Article ID: 104542. [Google Scholar] [CrossRef] 
[10] 肖鹏飞, 姜思佳. 活化过硫酸盐氧化法修复有机污染土壤的研究进展[J]. 化工进展, 2018, 37(12): 4862-4873.
[11] Ji, Y., Fan, Y., Liu, K., Kong, D. and Lu, J. (2015) Thermo Activated Persulfate Oxidation of Antibiotic Sulfamethoxazole and Structurally Related Compounds. Water Research, 87, 1-9. [Google Scholar] [CrossRef] [PubMed]
[12] Dang, P., Xie, H., Gao, Y., Li, Y., Zhao, Y. and Yang, C. (2022) Ag/AgCl/BiO2−x Activated Persulfate to Degrade Rhodamine B under Visible Light. Journal of Materials Science: Materials in Electronics, 33, 5776-5789. [Google Scholar] [CrossRef] 
[13] Liu, Y., He, X., Fu, Y. and Dionysiou, D.D. (2016) Kinetics and Mechanism Investigation on the Destruction of Oxytetracycline by UV-254 Nm Activation of Persulfate. Journal of Hazardous Materials, 305, 229-239. [Google Scholar] [CrossRef] [PubMed]
[14] Ye, J., Liu, J., Ou, H. and Wang, L. (2016) Degradation of Ciprofloxacin by 280 Nm Ultraviolet-Activated Persulfate: Degradation Pathway and Intermediate Impact on Proteome of Escherichia coli. Chemosphere, 165, 311-319. [Google Scholar] [CrossRef] [PubMed]
[15] Zhang, T., Yang, Y., Gao, J., Li, X., Yu, H., Wang, N., et al. (2020) Synergistic Degradation of Chloramphenicol by Ultrasound-Enhanced Nanoscale Zero-Valent Iron/Persulfate Treatment. Separation and Purification Technology, 240, Article ID: 116575. [Google Scholar] [CrossRef] 
[16] Nasseri, S., Mahvi, A.H., Seyedsalehi, M., Yaghmaeian, K., Nabizadeh, R., Alimohammadi, M., et al. (2017) Degradation Kinetics of Tetracycline in Aqueous Solutions Using Peroxydisulfate Activated by Ultrasound Irradiation: Effect of Radical Scavenger and Water Matrix. Journal of Molecular Liquids, 241, 704-714. [Google Scholar] [CrossRef] 
[17] 魏红, 杨虹, 高扬, 等. 超声/K2S2O8体系降解水中左旋氧氟沙星的研究[J]. 西北农林科技大学学报(自然科学版), 2015, 43(3): 169-174.
[18] Li, N., Ye, J., Dai, H., Shao, P., Liang, L., Kong, L., et al. (2023) A Critical Review on Correlating Active Sites, Oxidative Species and Degradation Routes with Persulfate-Based Antibiotics Oxidation. Water Research, 235, Article ID: 119926. [Google Scholar] [CrossRef] [PubMed]
[19] Gao, Y., Wang, Q., Ji, G. and Li, A. (2022) Degradation of Antibiotic Pollutants by Persulfate Activated with Various Carbon Materials. Chemical Engineering Journal, 429, Article ID: 132387. [Google Scholar] [CrossRef] 
[20] Fang, G., Liu, C., Gao, J., Dionysiou, D.D. and Zhou, D. (2015) Manipulation of Persistent Free Radicals in Biochar to Activate Persulfate for Contaminant Degradation. Environmental Science & Technology, 49, 5645-5653. [Google Scholar] [CrossRef] [PubMed]
[21] 杨威, 王国相, 陈俊楠, 等. 稻壳生物炭/过硫酸盐降解水中四环素的研究[J]. 应用化工, 2024, 53(2): 341-345.
[22] Chen, X., Oh, W. and Lim, T. (2018) Graphene-and CNTs-Based Carbocatalysts in Persulfates Activation: Material Design and Catalytic Mechanisms. Chemical Engineering Journal, 354, 941-976. [Google Scholar] [CrossRef] 
[23] Su, H., Dou, X., Xu, D., Feng, L., Liu, Y., Du, Z., et al. (2022) Fe0-Loaded Superfine Powdered Activated Carbon Prepared by Ball Milling for Synergistic Adsorption and Persulfate Activation to Remove Aqueous Carbamazepine. Chemosphere, 293, Article ID: 133665. [Google Scholar] [CrossRef] [PubMed]
[24] Forouzesh, M., Ebadi, A. and Aghaeinejad-Meybodi, A. (2019) Degradation of Metronidazole Antibiotic in Aqueous Medium Using Activated Carbon as a Persulfate Activator. Separation and Purification Technology, 210, 145-151. [Google Scholar] [CrossRef] 
[25] Zhao, Q., Mao, Q., Zhou, Y., Wei, J., Liu, X., Yang, J., et al. (2017) Metal-Free Carbon Materials-Catalyzed Sulfate Radical-Based Advanced Oxidation Processes: A Review on Heterogeneous Catalysts and Applications. Chemosphere, 189, 224-238. [Google Scholar] [CrossRef] [PubMed]
[26] Kang, J., Duan, X., Zhou, L., Sun, H., Tadé, M.O. and Wang, S. (2016) Carbocatalytic Activation of Persulfate for Removal of Antibiotics in Water Solutions. Chemical Engineering Journal, 288, 399-405. [Google Scholar] [CrossRef] 
[27] Wang, X., Zhang, X., Zhang, D., Chen, W., Sun, Y., Zuo, W., et al. (2021) Heterogeneous Activation of Persulfate by Iron/Graphene Oxide-MCM for Removing Levofloxacin Hydrochloride in Water. Desalination and Water Treatment, 239, 228-240. [Google Scholar] [CrossRef] 
[28] Ahn, Y. and Yun, E. (2019) Heterogeneous Metals and Metal-Free Carbon Materials for Oxidative Degradation through Persulfate Activation: A Review of Heterogeneous Catalytic Activation of Persulfate Related to Oxidation Mechanism. Korean Journal of Chemical Engineering, 36, 1767-1779. [Google Scholar] [CrossRef] 
[29] Shang, Y., Chen, C., Zhang, P., Yue, Q., Li, Y., Gao, B., et al. (2019) Removal of Sulfamethoxazole from Water via Activation of Persulfate by Fe3C@NCNTs Including Mechanism of Radical and Nonradical Process. Chemical Engineering Journal, 375, Article ID: 122004. [Google Scholar] [CrossRef] 
[30] Duan, X., Ao, Z., Sun, H., Zhou, L., Wang, G. and Wang, S. (2015) Insights into N-Doping in Single-Walled Carbon Nanotubes for Enhanced Activation of Superoxides: A Mechanistic Study. Chemical Communications, 51, 15249-15252. [Google Scholar] [CrossRef] [PubMed]
[31] 陈一萍, 夏管商, 郑朝洪, 等. CNTs/PMS高级氧化体系去除水中的环丙沙星[J]. 化工进展, 2019, 38(4): 2037-2045.
[32] 赵齐灵, 余圣品, 李佳乐, 等. 过渡金属活化过硫酸盐去除水中抗生素研究进展[J]. 生态毒理学报, 2024, 19(4): 156-165.
[33] 张玉平. 典型过渡金属离子活化过硫酸盐氧化水中磺胺甲噁唑的研究[D]: [硕士学位论文]. 哈尔滨: 哈尔滨工程大学, 2014.
[34] Nie, W., Mao, Q., Ding, Y., Hu, Y. and Tang, H. (2019) Highly Efficient Catalysis of Chalcopyrite with Surface Bonded Ferrous Species for Activation of Peroxymonosulfate toward Degradation of Bisphenol A: A Mechanism Study. Journal of Hazardous Materials, 364, 59-68. [Google Scholar] [CrossRef] [PubMed]
[35] Luo, T., Wan, J., Ma, Y., Wang, Y. and Wan, Y. (2019) Sulfamethoxazole Degradation by an Fe(II)-Activated Persulfate Process: Insight into the Reactive Sites, Product Identification and Degradation Pathways. Environmental Science: Processes & Impacts, 21, 1560-1569. [Google Scholar] [CrossRef] [PubMed]
[36] Liang, C. and Su, H. (2009) Identification of Sulfate and Hydroxyl Radicals in Thermally Activated Persulfate. Industrial & Engineering Chemistry Research, 48, 5558-5562. [Google Scholar] [CrossRef] 
[37] Ghanbari, F. and Moradi, M. (2017) Application of Peroxymonosulfate and Its Activation Methods for Degradation of Environmental Organic Pollutants: Review. Chemical Engineering Journal, 310, 41-62. [Google Scholar] [CrossRef] 
[38] Zhao, Y., Song, M., Cao, Q., Sun, P., Chen, Y. and Meng, F. (2020) The Superoxide Radicals’ Production via Persulfate Activated with CuFe2O4@Biochar Composites to Promote the Redox Pairs Cycling for Efficient Degradation of O-Nitrochlorobenzene in Soil. Journal of Hazardous Materials, 400, Article ID: 122887. [Google Scholar] [CrossRef] [PubMed]
[39] Hu, Q., Cao, J., Yang, Z., Xiong, W., Xu, Z., Song, P., et al. (2021) Fabrication of Fe-Doped Cobalt Zeolitic Imidazolate Framework Derived from CO(OH)2 for Degradation of Tetracycline via Peroxymonosulfate Activation. Separation and Purification Technology, 259, Article 118059. [Google Scholar] [CrossRef] 
[40] Liang, C., Wang, Z. and Bruell, C.J. (2007) Influence of pH on Persulfate Oxidation of TCE at Ambient Temperatures. Chemosphere, 66, 106-113. [Google Scholar] [CrossRef] [PubMed]
[41] Nie, M., Yan, C., Li, M., Wang, X., Bi, W. and Dong, W. (2015) Degradation of Chloramphenicol by Persulfate Activated by Fe2+ and Zerovalent Iron. Chemical Engineering Journal, 279, 507-515. [Google Scholar] [CrossRef] 
[42] Lu, J., Zhou, Y. and Zhou, Y. (2021) Efficiently Activate Peroxymonosulfate by Fe3O4@MoS2 for Rapid Degradation of Sulfonamides. Chemical Engineering Journal, 422, Article ID: 130126. [Google Scholar] [CrossRef] 
[43] He, J., Tang, J., Zhang, Z., Wang, L., Liu, Q. and Liu, X. (2021) Magnetic Ball-Milled FeS@Biochar as Persulfate Activator for Degradation of Tetracycline. Chemical Engineering Journal, 404, Article ID: 126997. [Google Scholar] [CrossRef] 
[44] Wang, J. and Wang, S. (2018) Activation of Persulfate (PS) and Peroxymonosulfate (PMS) and Application for the Degradation of Emerging Contaminants. Chemical Engineering Journal, 334, 1502-1517. [Google Scholar] [CrossRef] 
[45] Chen, C., Sun, H., Zhang, S. and Su, X. (2023) Non-Metal Activated Peroxydisulfate by Straw Biochar for Tetracycline Hydrochloride Oxidative Degradation: Catalytic Activity and Mechanism. Environmental Science and Pollution Research, 30, 50815-50828. [Google Scholar] [CrossRef] [PubMed]
[46] Pan, Y., Zhang, Y., Zhou, M., Cai, J., Li, X. and Tian, Y. (2018) Synergistic Degradation of Antibiotic Sulfamethazine by Novel Pre-Magnetized FeO/PS Process Enhanced by Ultrasound. Chemical Engineering Journal, 354, 777-789. [Google Scholar] [CrossRef]