Abstract：The occurrence of membrane fouling and the poor retention effect of small molecular organic pollutants have been important factors limiting the development of ultrafiltration technology. This study realized the mitigation of membrane fouling and the removal of small molecular organic pollutants (SMOP) in the ultrafiltration process by coupling advanced oxidation technology. Cross-linked polypyrrole carbon nanotubes were deposited on the surface of polyvinylidene fluoride (PVDF) membrane by spraying, and the crosslinked polypyrrole carbon nanotubes composite ultrafiltration membrane (CP/PVDF) with excellent conductivity was obtained. The performance of fouling mitigation (HA as the simulated pollutant) and removing small molecular organic pollutants was compared when peroxymonosulfate (PMS) and peroxodisulfate (PDS) were used as oxidants respectively. The results showed that the E-PS-CP/PVDF system had high removal ratios for three different small molecular organic pollutants, carbamazepine (CBZ), diclofenac sodium (DCF) and sulfamethoxazole (SMX), and its first-order kinetic constants were higher than 15×10-2min-1, much higher than that of the ultrafiltration system alone (the highest was 0.072×10-2min-1). E-PS-CP/PVDF system had obvious membrane pollution mitigation effect.When using PMS and PDS as electrolytes, the normalized membrane flux only decreased to 0.93and 0.84 within 60min, respectively. The applied electric field and the oxidation of oxidizing hydroxyl radicals on HA changed the interaction of pollutants on the membrane surface and reduced the deposition of HA on the membranes. In addition, the fouling mitigation mechanism of E-PS-CP/PVDF system to alleviate membrane fouling was explored through quenching experiments. The results of mechanism experiments showed that the main reason for alleviating membrane fouling in E-PS-CP/PVDF system was the ·OH, SO4·-and 1O2 generated by the cathodic activation of PS, and PMS had better performance as oxidant than PDS. Therefore, E-PS-CP/PVDF system can alleviate membrane pollution and remove small molecular organic pollutants during ultrafiltration, and has a good application prospect in the field of actual water treatment.
朱烨,朱秀荣,金鑫,等.改性陶瓷膜催化PMS氧化的二级出水处理特性[J]. 中国环境科学, 2023,43(4):1706-1715. Zhu Y, Zhu X R, Jin X, et al. Removal and fouling mitigation performance of carbon-based catalyst modified ceramic membrane with in-situ peroxymonosulfate activation [J]. China Environmental Science, 2023,43(4):1706-1715.
[2]
Kang G D, Cao Y M. Application and modification of poly(vinylidene fluoride) (PVDF) membranes-A review [J]. Journal of Membrane Science, 2014,463(1):145-165.
[3]
Kim S, Chu K H, Al-Hamadani Y A J, et al. Removal of contaminants of emerging concern by membranes in water and wastewater:A review [J]. Chemical Engineering Journal, 2018,335:896-914.
[4]
Khan A, Liao Z, 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.
[5]
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.
[6]
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.
[7]
Wang S, Tian J, 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.
[8]
Wu H, Xu X, Shi L, et al. Manganese oxide integrated catalytic ceramic membrane for degradation of organic pollutants using sulfate radicals [J]. Water Research, 2019,167:115110.
[9]
Li N, Lu X, He M, et al. Catalytic membrane-based oxidation-filtration systems for organic wastewater purification:a review [J]. Journal of Hazardous Materials, 2021,414:125478.
[10]
Cheng X, Li P, Zhu X, 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.
[11]
苏冰琴,温宇涛,林昱廷,等.改性活性炭纤维活化过硫酸盐深度处理焦化废水及降解吡啶[J]. 中国环境科学, 2023,43(2):576-591. Su B Q, Wen Y T, Lin Y T, et al. Advanced treatment of coking wastewater and degradation of pyridine using modified activated carbon fiber activating peroxymonosulfate [J]. China Environmental Science, 2023,43(2):576-591.
[12]
Lee Y C, Li Y, Chen M J, et al. Efficient decomposition of perfluorooctanic acid by persulfate with iron-modified activated carbon [J]. Water Research, 2020,174:115618.
[13]
Zhang Y, Zhang B T, Teng Y, et al. Heterogeneous activation of persulfate by carbon nanofiber supported Fe3O4@carbon composites for efficient ibuprofen degradation [J]. Journal of Hazardous Materials, 2021,401:123428.
[14]
晋墩尚,谢松辰,李志霞,等.膜蒸馏用抗污染PVDF复合膜的制备与研究[J]. 膜科学与技术, 2022,42(5):129-138. Jin D S, Xie S C, Li Z X, et al. Preparation and study of anti-fouling PVDF composite membrane for membrane distillation [J]. Membrane Science and Technology (Chinese), 2022,42(5):129-138.
[15]
王新艳,张伟政,李海峰,等.g-C3N4改性PVDF-CTFE混合基质超滤膜的制备与性能[J]. 膜科学与技术, 2023,43(1):99-108. Wang X Y, Zhang W Z, Li H F, et al. Preparation and properties of PVDF-CTFE/g-C3N4 composite microporpous membrane [J]. Membrane Science and Technology (Chinese), 2023,43(1):99-108.
[16]
Bairagi S, Ali W. Investigating the role of carbon nanotubes (CNTs) in piezoelectric performance of PVDF/KNN based flexible electrospun nanogenerator [J]. Soft Matter, 2020,16:4876-4886.
[17]
Ma Z, Zhang S, Chen G, 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.
[18]
Song H, Shao J, He Y, 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.
[19]
Liu J, Tian C, Xiong J, et al. Polypyrrole blending modification for PVDF conductive membrane preparing and fouling mitigation [J]. Journal of Colloid and Interface Science, 2017,494:124-129.
[20]
Yan Z, Liu B, Qu F, 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.
[21]
Liang C, Huang C F, Mohanty N, et al. A rapid spectrophotometric determination of persulfate anion in ISCO [J]. Chemosphere, 2008, 73(9):1540-1543.
[22]
王虹,邵亚楠,于迪,等.MXene/C电催化膜制备及对水中盐酸四环素降解性能研究[J]. 膜科学与技术, 2022,42(6):151-158. Wang H, Shao Y N, Yu D, et al. Preparation of MXene/C electrocatalytic membrane and study on degradation performance of tetracycline hydrochloride in water [J]. Membrane Science and Technology (Chinese), 2022,42(6):151-158.
[23]
Kadam A N, Chowdhury S R, Bathula C, et al. A novel reduction approach for fabrication of transparent conducting fluorine and tin doped indium oxide thin film with low sheet resistance [J]. Ceramics International, 2022,48(19Pt.2):29307-29313.
[24]
Yan L, Li Y S, Xiang C B, et al. Effect of nano-sized Al2O3-particle addition on PVDF ultrafiltration membrane performance [J]. Journal of Membrane Science, 2006,276(1/2):162-167.
[25]
Zhang X, Wang Y, You Y T, et al. Preparation, performance and adsorption activity of TiO2 nanoparticles entrapped PVDF hybrid membranes [J]. Applied Surface Science, 2012,263:660-665.
[26]
Li Z, Li X, Li Y, et al. Efficient removal of micropollutants from low-conductance surface water using an electrochemical Janus ceramic membrane filtration system [J]. Water Research, 2022,220:118627.
[27]
Weng Y H, Chaung-Hsieh L H, Lee H H, et al. Removal of arsenic and humic substances (HSS) by electro-ultrafiltration (EUF) [J]. Journal of Hazardous Materials, 2005,122(1):171-176.
[28]
Wang T, Wang Z, Wang P, et al. An integration of photo-Fenton and membrane process for water treatment by a PVDF@CuFe2O4 catalytic membrane [J]. Journal of Membrane Science, 2019,572:419-427.
[29]
Li M, Jin Y T, Cao D Y, et al. Efficient decomposition of perfluorooctane sulfonate by electrochemical activation of peroxymonosulfate in aqueous solution:efficacy, reaction mechanism, active sites, and application potential [J]. Water Research, 2022,221:118778.
[30]
Zhang L, Ma H, Huang X, et al. Fast and efficient inactivation of antibiotic resistant Escherichia coli by iron electrode-activated sodium peroxydisulfate in a galvanic cell [J]. Chemical Engineering Journal, 2019,355:150-158.
[31]
Og W. Infrared characteristic group frequencies:Tables and charts [J]. Journal of Molecular Structure, 1995,372(s2/3):285.
[32]
Solum M S, Pugmire R J, Jagtoyen M, et al. Evolution of carbon structure in chemically activated wood [J]. Carbon, 1995,33(9):1247-1254.
[33]
Chen C, Xie M, Kong L, et al. Mn3O4 nanodots loaded g-C3N4 nanosheets for catalytic membrane degradation of organic contaminants [J]. Journal of Hazardous Materials, 2020,390:122146.
[34]
Lu Z, Lin T, Chen W, et al. Influence of KMnO4 preoxidation on ultrafiltration performance and membrane material characteristics [J]. Journal of Membrane Science, 2015,486:49-58.
[35]
Duan X, Sun H, Kang J, et al. Insights into heterogeneous catalysis of persulfate activation on dimensional-structured nanocarbons [J]. Acs Catalysis, 2015,5(8):4629-4636.
[36]
Zhu J, Chen C, Li Y, et al. Rapid degradation of aniline by peroxydisulfate activated with copper-nickel binary oxysulfide [J]. Separation and Purification Technology, 2019,209:1007-1015.
[37]
Hua L C, Huang C, Huang C. Insights on free radical oxidation and in-situ coagulation in PMS/Fe(Ⅱ) process for the removal of algogenic organic matter precursors [J]. Chemical Engineering Journal, 2022,446:136986.
[38]
Xu Q, Liu Y, Wang Y, et al. Synergistic oxidation-filtration process of electroactive peroxydisulfate with a cathodic composite CNT-PPy/PVDF ultrafiltration membrane [J]. Water Research, 2022,210:117971-.
[39]
Zhou C, Liang Y, Xia W, et al. Single atom Mn anchored on N-doped porous carbon derived from spirulina for catalyzed peroxymonosulfate to degradation of emerging organic pollutants [J]. Journal of Hazardous Materials, 2023,441:129871.
[40]
Xu Q B, Song Y Q, Wang Y, et al. Integrated electric fied with persufate in cathodic ultrafltration membrane process:Comparison between peroxydisulfate and peroxymonosulfate [J]. ACS ES&T Engineering, 2023,DOI:10.1021/acsestengg.3c00294.
