HA驱动PM/PMS体系去除新污染物及膜污染控制

张超; 许岐斌; 王颖; 刘索; 赵纯

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中国环境科学 ›› 2025, Vol. 45 ›› Issue (6) : 3046-3053.

水污染与控制

HA驱动PM/PMS体系去除新污染物及膜污染控制

张超¹, 许岐斌¹, 王颖², 刘索¹, 赵纯¹

作者信息 +

HA driven PM/PMS system for removing emerging contaminants and controlling membrane fouling

ZHANG Chao¹, XU Qi-bin¹, WANG Ying², LIU Suo¹, ZHAO Chun¹

Author information +

文章历史 +

摘要

本研究采用腐殖酸(HA)驱动高锰酸钾/过一硫酸盐(PM/PMS+HA)体系的方法,研究小分子有机污染物的去除并探究膜污染控制效能的内容.结果表明,对于不同小分子有机物(阿特拉津(ATZ)、苯酚(Phenol)、双氯芬酸钠(DCF)、卡马西平(CBZ)、布洛芬(IBP)磺胺甲噁唑(SMX)),PM/PMS+HA体系去除效果良好,其一级动力学常数均高于18×10^-2min^-1,远高于单独超滤体系、PM体系和PM/PMS体系. 与此同时,PM/PMS+HA体系在膜污染缓解方面也表现良好. 采用HA作为膜污染物,15min内,PM/PMS+HA体系的出水比通量仅下降至0.919,远高于单独HA过滤时的0.393.同时,采用PM/PMS体系进行膜清洗时,膜通量恢复率达到98.51%.捕获试验以及紫外分光光度计的测定探究PM/PMS+HA体系的机理表明,PM/PMS+HA过滤过程中主要是体系中富电子特性的HA引发了复合氧化剂(PM-PMS)的分解.复合氧化剂的分解产生了活性氧(^•OH、SO₄^•-、¹O₂)以及活性锰(Mn(V)和Mn(VI)). 产生的活性氧和活性锰对污染物的氧化导致了新污染物的去除以及膜污染物分子量的降低,从而实现了新污染的去除和膜污染的控制.污染物驱动的PM/PMS体系实现了超滤膜与高级氧化技术的耦合.

Abstract

The study used humic acid (HA) to drive the potassium permanganate/persulfate (PM/PMS+HA) system to investigate the removal of small molecule organic pollutants and the effectiveness of membrane fouling control. The experimental results showed that the PM/PMS+HA system exhibited excellent removal performance for different small molecule organic compounds, including Atrazine (ATZ), Phenol (Phenol), Diclofenac Sodium (DCF), Carbamazepine (CBZ), Ibuprofen (IBP) and Sulfamethoxazole (SMX). The first-order kinetic constants of the PM/PMS+HA system were all higher than 18x10^-2min^-1, far higher than the PM/PMS system, PM system, and ultrafiltration system alone. At the same time, the PM/PMS system has a good membrane fouling alleviation effect. When HA was used as the pollutant, the effluent specific flux of the PM/PMS system only decreased to 0.919 within 15 minutes, much higher than the 0.393 obtained by HA filtration alone. Meanwhile, when using the PM/PMS system for membrane cleaning, the membrane flux recovery rate reached 98.51%. The mechanism of the PM/PMS+HA system was explored through capture experiments and measurements using a UV spectrophotometer. The experimental results indicate that during the filtration process of PM/PMS+HA, it is mainly the rich electronic HA in the system that triggers the decomposition of the composite oxidant (PM-PMS). The decompositionof composite oxidants produces reactive oxygen species (^•OH、SO₄^•-、¹O₂) and reactive manganese(Mn(V)and Mn(VI)). The generated reactive oxygen species and reactive manganese oxidize pollutants, leading to the removal of new pollutants and a decrease in the molecular weight of membrane pollutants, thereby achieving the removal of new pollutants and the control of membrane pollution. The PM/PMS system driven by pollutants has achieved the coupling of ultrafiltration membranes with advanced oxidation technology, providing new ideas for the removal of small molecule organic compounds and membrane fouling control in ultrafiltration technology.

导出引用

张超, 许岐斌, 王颖, 刘索, 赵纯. HA驱动PM/PMS体系去除新污染物及膜污染控制[J]. 中国环境科学. 2025, 45(6): 3046-3053

ZHANG Chao, XU Qi-bin, WANG Ying, LIU Suo, ZHAO Chun. HA driven PM/PMS system for removing emerging contaminants and controlling membrane fouling[J]. China Environmental Science. 2025, 45(6): 3046-3053

中图分类号： X703.1

参考文献

[1] Yang J X, Bai L M, Zhao J, et al. Cobalt oxide decorated activated carbon/peroxymonosulfate pretreatment for ultrafiltration membrane fouling control in secondary effluent treatment: Insights into interfacial interaction and fouling model transformation [J]. Separation and Purification Technology, 2023,316:123820.
[2] Yue X R, Ji X, Xu H Y, et al. Performance investigation on GO-TiO₂/PVDF composite ultrafiltration membrane for slightly polluted ground water treatment [J]. Energy, 2023,273:127215.
[3] Zhang J J, Zhou Y F, Fang Y Z, et al. Chalcopyrite functionalized ceramic membrane for micropollutants removal and membrane fouling control via peroxymonosulfate activation: The synergy of nanoconfinement effect and interface interaction [J]. Journal of Colloid and Interface Science, 2024,658:714-727.
[4] Huang X J, Chen K Y, Zhang Z Q, et al. Continuation of a cleaning process: Application of MNBs-coagulation process to mitigate ultrafiltration membrane fouling [J]. Water Research, 2024,250: 121032.
[5] Ma Y X, Zhao K, Wang D D, et al. MnFe₂O₄ composited polyvinylidene fluoride catalytic ultrafiltration membrane via peroxymonosulfate activation for humic acid treatment: exploration of synergistic mechanisms [J]. Separation and Purification Technology, 2024,332:125708.
[6] 刘寅,许岐斌,宋子恒,等.CP/PVDF膜电活化PS降解新污染物及缓解膜污染[J]. 中国环境科学, 2023,43(11):5757-5764.Liu Y, Xu Q B, Song Z H, et al. Degradation emerging contaminants and mitigation membrane fouling by electrochemical activation of persulfateg [J]. China Environmental Science, 2023,43(11):5757- 5764.
[7] Tang S Y, Fu W Y, Song T T, et al. In-Situ H₂O₂ cleaning for fouling control of manganese-doped ceramic membrane through confined catalytic oxidation inside membrane [J]. Membranes, 2022,12(1):21.
[8] Giannakis S, Lin K-Y A, Ghanbari F. A review of the recent advances on the treatment of industrial wastewaters by sulfate radical-based advanced oxidation processes (SR-AOPs) [J]. Chemical Engineering Journal, 2021,406:127083.
[9] Khan A, Liao Z W, Liu Y, et al. Synergistic degradation of phenols using peroxymonosulfate activated by CuO-Co₃O₄@MnO₂ nanocatalyst [J]. Journal of Hazardous Materials, 2017,329:262-271.
[10] Liu Z, Zhao C, Wang P, et al. Removal of carbamazepine in water by electro-activated carbon fiber-peroxydisulfate: comparison, optimization, recycle, and mechanism study [J]. Chemical Engineering Journal, 2018,343:28-36.
[11] 郑璐,成小翔,谷统翰,等.过硫酸盐高级氧化在膜法组合工艺中的研究进展[J]. 中国给水排水, 2022,38(6):33-37.Zheng L, Cheng X X, Gu T H, et al. Research progress of persulfate- based advanced oxidation in membrane combination processes [J]. China Water & Wastewater, 2022,38(6):33–37.
[12] Wang S X, Tian J Y, Wang Q, et al. Development of CuO coated ceramic hollow fiber membrane for peroxymonosulfate activation: a highly efficient singlet oxygen-dominated oxidation process for bisphenol a degradation [J]. Applied Catalysis B: Environmental, 2019, 256:117783.
[13] Wu H, Xu X Y, Shi L, et al. Manganese oxide integrated catalytic ceramic membrane for degradation of organic pollutants using sulfate radicals [J]. Water Research, 2019,167:115110.
[14] Cheng X X, Li P J, Zhu X W, et al. Role of different dimensional carbon nanoparticles in catalytic oxidation of organic pollutants and alleviating membrane fouling during ultrafiltration of surface water [J]. Separation and Purification Technology, 2021,270:118804.
[15] Li N, Lu X K, He M T, et al. Catalytic membrane-based oxidation- filtration systems for organic wastewater purification: a review [J]. Journal of Hazardous Materials, 2021,414:125478.
[16] Sun M, Zucker I, Davenport D M, et al. Reactive, self-cleaning ultrafiltration membrane functionalized with iron oxychloride nanocatalysts [J]. Environmental Science & Technology, 2018,52(15): 8674-8683.
[17] Shi Y F, Xiao S Z, Qian Y J, et al. Revisiting the synergistic oxidation of peracetic acid and permanganate(Ⅶ) towards micropollutants: the enhanced electron transfer mechanism of reactive manganese species [J]. Water Research, 2024,262:122105.
[18] Yang Y, Li J X, Wang H, et al. An electrocatalytic membrane reactor with self-cleaning function for industrial wastewater treatment [J]. Angewandte Chemie International Edition, 2011,50(9):2148-2150.
[19] Yuan W, Zydney A L. Humic acid fouling during ultrafiltration [J]. Environmental Science & Technology, 2000,34(23):5043-5050.
[20] Lin T, Lu Z J, Chen W. Interaction mechanisms of humic acid combined with calcium ions on membrane fouling at different conditions in an ultrafiltration system [J]. Desalination, 2015,357:26- 35.
[21] Ma Z B, Zhang S, Chen G H, et al. Superhydrophilic and oleophobic membrane functionalized with heterogeneously tailored two- dimensional layered double hydroxide nanosheets for antifouling [J]. Journal of Membrane Science, 2019,577:165-175.
[22] Song H C, Shao J H, He Y L, et al. Natural organic matter removal and flux decline with PEG–TiO₂-doped PVDF membranes by integration of ultrafiltration with photocatalysis [J]. Journal of Membrane Science, 2012,405-406:48-56.
[23] Yan Z S, Liu B, Qu F S, et al. Control of ultrafiltration membrane fouling caused by algal extracellular organic matter (EOM) using enhanced Al coagulation with permanganate [J]. Separation and Purification Technology, 2017,172:51-58.
[24] Zhu Y H, Zhao C, Liang J L, et al. Rapid removal of diclofenac in aqueous solution by soluble Mn(III)_(aq)generated in a novel electro-activated carbon fiber-permanganate (E-ACF-PM) process [J]. Water Research, 2019,165:114975.
[25] Miao R, Feng Y Y, Wang Y P, et al. Exploring the influence mechanism of ozonation on protein fouling of ultrafiltration membranes as a result of the interfacial interaction of foulants at the membrane surface [J]. Science of The Total Environment, 2021,785: 147340.
[26] Weis A, Bird M R, Nyström M, et al. The influence of morphology, hydrophobicity and charge upon the long-term performance of ultrafiltration membranes fouled with spent sulphite liquor [J]. Desalination, 2005,175(1):73-85.
[27] Fu X Y, Maruyama T, Sotani T, et al. Effect of surface morphology on membrane fouling by humic acid with the use of cellulose acetate butyrate hollow fiber membranes [J]. Journal of Membrane Science, 2008,320(1):483-491.
[28] Lu Z J, Lin T, Chen W, et al. Influence of KMnO₄preoxidation on ultrafiltration performance and membrane material characteristics [J]. Journal of Membrane Science, 2015,486:49-58.
[29] You Y, Shi Z K, Li Y H, et al. Magnetic cobalt ferrite biochar composite as peroxymonosulfate activator for removal of lomefloxacin hydrochloride [J]. Separation and Purification Technology, 2021,272: 118889.
[30] Bu Z Y, Hou M H, Li Z H, et al. Fe³⁺/Fe²⁺ cycle promoted peroxymonosulfate activation with addition of boron for sulfamethazine degradation: efficiency and the role of boron [J]. Separation and Purification Technology, 2022,298:121596.
[31] Moan J, Wold E. Detection of singlet oxygen production by ESR [J]. Nature, 1979,279(5712):450-451.
[32] Cui J X, Zhang L Y, Xi B D, et al. Chemical oxidation of benzene and trichloroethylene by a combination of peroxymonosulfate and permanganate linked by in-situ generated colloidal/amorphous MnO₂ [J]. Chemical Engineering Journal, 2017,313:815-825.
[33] Chen J, Rao D D, Dong H Y, et al. The role of active manganese species and free radicals in permanganate/bisulfite process [J]. Journal of Hazardous Materials, 2020,388:121735.
[34] Simandi L I, Jaky M, Schelly Z A. Short-lived manganate(VI) and manganate(V) intermediates in the permanganate oxidation of sulfite ion [J]. Journal of the American Chemical Society, 1984,106(22): 6866-6867.
[35] Wang L, Jiang J, Pang S Y, et al. Further insights into the combination of permanganate and peroxymonosulfate as an advanced oxidation process for destruction of aqueous organic contaminants [J]. Chemosphere, 2019,228:602-610.
[36] Yang J F, He M, Wu T F, et al. Sulfadiazine oxidation by permanganate: Kinetics, mechanistic investigation and toxicity evaluation [J]. Chemical Engineering Journal, 2018,349:56-65.
[37] Li C, Wang Z B, Li A, et al. Superior performance of catalytic ozonation on molecular-level transformation of effluent organic matter and self-cleaning property in catalytic ozonation membrane reactor [J]. Applied Catalysis B: Environmental, 2023,338:123076.
[38] Zhu C Q, Zhao S F, Fan Z W, et al. Confinement of CoP nanoparticles in nitrogen-doped yolk-shell porous carbon polyhedron for ultrafast catalytic oxidation [J]. Advanced Functional Materials, 2020,30(49): 2003947.