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电催化膜反应器耦合臭氧技术处理印染废水反渗透浓缩液及Na2SO4资源化利用

作者：王若晗¹，²，杜明辉¹，²，王虹¹，²，李建新¹，²

单位： 1. 天津工业大学材料科学与工程学院，天津 300387； 2. 天津工业大学先进分离膜材料全国重点实验室，天津 300387

关键词：印染废水；反渗透浓缩液；电催化膜反应器；臭氧氧化； Na2SO4回收

DOI号： 10.16159/j.cnki.issn1007-8924.2025.03.013

分类号： TQ028

出版年,卷(期):页码： 2025,45(3):127-135

摘要：

含高盐和难降解有机物的印染废水反渗透（Reverse Osmosis，RO）浓缩液的有效处理是一项巨大的挑战。本文利用自制的多通道导电炭膜作为阴极，石墨板为辅助阳极，构建电催化膜反应耦合O3体系（ECMR-O3）处理工业印染废水RO浓缩液。结果表明，ECMR-O3对RO浓缩液COD去除率达93.75%，出口COD质量浓度降低为48.15 mg/L，达到《纺织染整工业回用水水质标准》(FZ/T 01107 2011)(COD质量浓度<50 mg/L）。Na2SO4回用成本分析表明，处理每吨印染废水RO浓缩液可以回收28.1 kg Na2SO4，具有客观的经济效益。借助电子自旋共振（ESR）证实了·OH是ECMRO3产生协同效应的关键活性物种，借助紫外可见光谱图（UV-Vis）和三维荧光光谱（3DEEM）深入阐明降解机制，为印染废水RO浓缩液高效处理提供了一种有效途径。

The effective treatment of Reverse osmosis (RO) concentrate in dyeing wastewater with high salts and refractory organics is a great challenge. In this study, an electrocatalytic membrane reactor coupled with O3 system (ECMR-O3) was constructed using multi-channel conductive carbon membrane as cathode and graphite plate as auxiliary anode. Further, the ECMR is employed for the treatment of the RO concentrate from dyeing wastewater. The results show that the COD removal rate of RO concentrate by ECMR coupled with O3 reached 93.75%, and the COD mass concentration is reduced to 48.15 mg/L, which meets the “Water Quality Standard for Reuse of Textile Dyeing and Finishing Wastewater” (FZ/T 01107 2011) (COD mass concentration< 50 mg/L). The cost analysis of Na2SO4 recovery shows that 28.1 kg Na2SO4 can be recovered from each ton of dyeing wastewater RO concentrate treated, which has objective economic benefits. Further, electron spin-resonance (ESR) spectroscopy confirmed that ·OH is the key active species for the synergistic effect of ECMR-O3. UV-Vis and 3D-excitation-emission matrix (EEM) spectra clarified the degradation mechanism deeply. In summary, this study provides an effective way for the efficient treatment of RO concentrate from dyeing wastewater.

基金项目：

国家重点研发计划项目 (2020YFA0211003)

作者简介：

王若晗（2001-），女，山东济南人，硕士研究生，主要研究方向为膜法水处理

参考文献：

[1]Ma D S, Yi H, Cui L, et al. Critical review of advanced oxidation processes in organic wastewater treatment[J]. Chemosphere, 2021, 275: 130104.
[2]周姝岑, 芦婉蒙, 李攀. 微纳米气泡臭氧氧化处理印染废水产生的RO浓水[J]. 中国给水排水, 2022, 38(9): 88-93.
[3]Shi J X，Huang W P，Han H J, et al. Review on treatment technology of salt wastewater in coal chemical industry of China[J]. Desalination, 2020, 493: 114640.
[4]李忠华,常娜,陈董根,等. 基于纳滤技术的印染废水中碳酸钠和硫酸钠高效分离及回用染布研究[J].膜科学与技术,2025,45（1）: 129-136，145.
[5]Li X, Wang Y J, Yuan S, et al. Degradation of the anti-inflammatory drug ibuprofen by electro-peroxone process[J]. Water Res, 2014, 63: 81-93.
[6]Xia G S, Wang H J, Zhan J H, et al. Evaluation of the stability of polyacrylonitrile-based carbon fiber electrode for hydrogen peroxide production and phenol mineralization during electro-peroxone process[J]. Chem Eng J, 2020, 396: 125291.
[7]Acero J L, Benitez F J, Real F J, et al. Removal of emerging contaminants from secondary effluents by micellar-enhanced ultrafiltration[J]. Sep Purif Technol, 2017, 181: 123-131.
[8]Petrucci N, Sardini S. Severe neurotoxic reaction associated with oral ingestion of low-dose diethyltoluamide-containing insect repellent in a child[J]. Pediatr Emerg Care, 2000, 16(5): 341-342.
[9]Li K L, Zhang Y, Xu L L, et al. Mass transfer and interfacial reaction mechanisms in a novel electro-catalytic membrane contactor for wastewater treatment by O3[J]. Appl Catal, 2020, 264:118512.
[10]Yang Y, Wang H, Li J, et al. Novel functionalized nano-TiO2 loading electrocatalytic membrane for oily wastewater treatment[J]. Environ Sci Technol, 2012, 46(12): 6815-6821.
[11]Yang Y, Li J X, Wang H, et al. An electrocatalytic membrane reactor with self‐cleaning function for industrial wastewater treatment[J]. Angew Chem Int Ed, 2011, 9(50): 2148-2150.
[12]Du M H, Malefetse T J, Mamba B, et al. Recent advances in electrochemical membrane reactor based on cathodic carbon membrane for wastewater treatment: Design, materials, application and mechanism[J]. Sep Purif Technol, 2024,360: 131133.
[13]Pan Z L, Yu F P, Li L, et al. Low-cost electrochemical filtration carbon membrane prepared from coal via self-bonding[J]. Chem Eng J, 2020, 385: 123928.
[14]Dong J W, Du M H, Wang H, et al. A carbon membrane-aerated electrochemical reactor for efficient electrosynthesis of H2O2[J]. Chem Eng J, 2025,505: 159609.
[15]Yin X, Li W, Zhu H W, et al. Electrochemical treatment of municipal reverse osmosis concentrates by a TiO2-BNTs/SnO2-Sb reactive electrochemical membrane[J]. Sep Purif Technol, 2024, 331: 125726.
[16]Song Y Q, Zhao C, Wang T, et al. Simultaneously promoted reactive manganese species and hydroxyl radical generation by electro-permanganate with low additive ozone[J]. Water Res, 2021, 189: 116623.
[17]Liu H, Vecitis C D. Reactive transport mechanism for organic oxidation during electrochemical filtration: mass-transfer, physical adsorption, and electron-transfer[J]. J Phys Chem C, 2012, 116(1): 374-383.
[18]Yang W Q, Yang S H, Sun W, et al. Nanostructured palladium-silver coated nickel foam cathode for magnesium-hydrogen peroxide fuel cells[J]. Electrochim Acta, 2006, 52(1): 9-14.
[19]Yang Q, Li M Y, Wang J W, et al. Synergistic electro-catalytic oxidation of ibuprofen in electro-peroxone system with flow-through carbon nanotube membrane cathode[J]. Chem Eng J, 2022, 435(2):135180.
[20]Liaw S S, Justo O R, Perez V H, et al. Ozonation of pyrolytic aqueous phase: Changes in the content of phenolic compounds and color[J]. Chem Eng Technol, 2016, 39(10), 1828-1834.
[21]Gao J, Shi N, Guo X B, et al. Electrochemically selective ammonia extraction from nitrate by coupling electron-and phase-transfer reactions at a three-phase interface[J]. Environ Sci Technol, 2021, 55(15): 10684-10694.
[22]Zhang Q, Wang L, Chen B Y, et al. Understanding and modeling the formation and transformation of hydrogen peroxide in water irradiated by 254 nm ultraviolet (UV) and 185 nm vacuum UV (VUV): Effects of pH and oxygen[J]. Chemosphere, 2020, 244: 125483.
[23]Zhang K, Duan Y X, Graham N, et al. Efficient electrochemical generation of active chlorine to mediate urea and ammonia oxidation in a hierarchically porous-Ru/RuO2-based flow reactor[J]. J Hazard Mater, 2023, 444: 130327.
[24]Qu C, Lu S F, Liang D W, et al. Simultaneous electro-oxidation and in situ electro-peroxone process for the degradation of refractory organics in wastewater[J]. J Hazard Mater, 2019, 364: 468-474.
[25]Li X Y, Sun S B, Zhang X, et al. Combined electro-catazone/electro-peroxone process for rapid and effective Rhodamine B degradation[J]. Sep Purif Technol, 2017, 178: 189-192.
[26]Chen M, Pan S, Zhang C, et al. Electrochemical oxidation of reverse osmosis concentrates using enhanced TiO2-NTA/SnO2-Sb anodes with/without PbO2 layer[J]. Chem Eng J, 2020, 399: 125756.
[27]Li W T, Xu Z X, Li Y, et al. Characterization of fluorescent-dissolved organic matter and identification of specific fluorophores in textile effluents[J]. Environ Sci Pollut 2015, 22: 4183-4189.
[28]Wu Q, Li W T, Yu W H, et al. Removal of fluorescent dissolved organic matter in biologically treated textile wastewater by ozonation-biological aerated filter[J]. J Taiwan Inst Chem Eng, 2016, 59: 359-364.
[29]高占先.有机化学(第三版)[M]//北京：高等教育出版社, 2018: 347.

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