UV/PMS、UV/PDS、UV/SPC工艺降解尼泊金甲酯

doi:10.11949/0438-1157.20221522

化工学报 ›› 2023, Vol. 74 ›› Issue (3): 1322-1331.DOI: 10.11949/0438-1157.20221522

UV/PMS、UV/PDS、UV/SPC工艺降解尼泊金甲酯

杨庆云¹^,²^,³(), 李青松¹^,⁴(), 陈泽铭¹, 邓靖³, 李玉瑛⁵(), 杨帆³, 陈国元¹, 李国新¹

^1.厦门理工学院水资源环境研究所，福建厦门 361024
^2.宁波市水务环境集团有限公司，浙江宁波 315046
^3.浙江工业大学土木工程学院，浙江杭州 310014
^4.厦门市水资源利用与保护重点实验室，福建厦门 361024
^5.五邑大学生物科技与大健康学院，广东江门 529000

收稿日期:2022-11-22 修回日期:2023-01-16 出版日期:2023-03-05 发布日期:2023-04-19
通讯作者: 李青松,李玉瑛
作者简介:杨庆云(1997—)，男，硕士研究生，251857181@qq.com
基金资助:
国家自然科学基金项目(51878582);福建省科技计划引导性资助项目(2021Y0041);福建省自然科学基金项目(2020J01256);福建省高校新世纪优秀人才支持计划项目(JA14227)

Degradation of methylparaben by UV/PMS, UV/PDS and UV/SPC process

Qingyun YANG¹^,²^,³(), Qingsong LI¹^,⁴(), Zeming CHEN¹, Jing DENG³, Yuying LI⁵(), Fan YANG³, Guoyuan CHEN¹, Guoxin LI¹

^1.Water Resource and Environment Institute, Xiamen University of Technology, Xiamen 361024, Fujian, China
^2.Ningbo Water Environment Group Co. , Ltd. , Ningbo 315046, Zhejiang, China
^3.College of Civil Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
^4.Key Laboratory of Water Resources Utilization and Protection of Xiamen City, Xiamen 361024, Fujian, China
^5.School of Biotechnology and Health, Wuyi University, Jiangmen 529000, Guangdong, China

Received:2022-11-22 Revised:2023-01-16 Online:2023-03-05 Published:2023-04-19
Contact: Qingsong LI, Yuying LI

摘要/Abstract

摘要：

采用UV/过一硫酸盐(PMS)、UV/过二硫酸盐(PDS)和UV/过碳酸盐(SPC)三种工艺降解尼泊金甲酯(MeP)，通过电子顺磁共振技术鉴定了三种工艺中存在的自由基，考察了氧化剂投加量、pH、阴离子、 $N H 4 +$ 和HA对MeP去除的影响，通过竞争动力学的方法测定了MeP与 $S O 4 -$ ·的二级反应速率常数及不同自由基对MeP去除的贡献，评估了不同氧化剂投加量下工艺的经济性，研究了不同工艺中有机物的矿化率和消毒副产物(DBPs)的生成。结果表明，三种氧化剂与UV联用都具有较好的协同效果，UV/PMS、UV/PDS和UV/SPC工艺降解MeP的拟一级动力学常数(k_obs)分别为0.1615、0.3868和0.0798 min^-1。 $S O 4 -$ ·与MeP的二级反应速率常数为1.37×10⁹ L·mol^-1·s^-1。三种工艺中k_obs都随氧化剂投加量的增加而增大，且UV/PDS工艺具有较好的经济效益。UV/PMS和UV/PDS工艺中k_obs值随着pH的升高略微增加，而UV/SPC工艺中k_obs则呈先上升后下降的趋势。三种工艺中 $N O 3 -$ 和 $H C O 3 -$ 对MeP的去除均有不同程度的促进作用，而 $N H 4 +$ 和HA则不同程度上抑制MeP的降解。Cl^-在UV/PDS工艺中对MeP的去除有抑制作用，而在UV/PMS和UV/SPC工艺中呈现双重作用。UV/PDS工艺对MeP的矿化率最高，但也生成了更多的消毒副产物。

关键词: 紫外, 高级氧化, 自由基, 动力学, 消毒副产物

Abstract:

The UV/PMS, UV/PDS和UV/SPC processes were employed to degrade MeP in aqueous solution. Different free radicals during the three processes were identified by electron paramagnetic resonance. The effects of different oxidant dosages, pH, anions, $N H 4 +$ and HA on MeP removal were investigated. The second-order rate constants of $S O 4 -$ · with MeP and contributions of different free radicals on MeP removal were determined by competitive kinetics, and the economics of different oxidant dosages were evaluated. The mineralization rate, DBPs formation and the alteration of acute toxicity during the degradation of MeP were investigated. The results showed that the three oxidants had good synergistic performances with UV, the pseudo-first-order kinetic rate constants of UV/PMS, UV/PDS and UV/SPC processes under experimental conditions were 0.1615, 0.3868 ^{and 0.0798 min^-1, respectively. The second-order rate constants of $S O 4 -$ · with MeP were determined to be 1.37×10⁹ L·mol^-1·s^-1. The k_obs of MeP during the three processes increased with the increasing of oxidant dosage and the economic benefit of UV/PDS was superior to the other two processes. The k_obs of UV/PMS and UV/PDS for MeP increased slightly with the increasing of pH, while the k_obs of UV/SPC for MeP had a tendency of increasing first and then decreasing. Among the three processes, $N O 3 -$ and $H C O 3 -$ promoted the k_obs of UV/PMS, UV/PDS and UV/SPC for MeP in varying degrees, while $N H 4 +$ and HA did the opposite. Cl^- had an inhibiting effect on UV/PDS process, but it had a dual effect on UV/PMS and UV/SPC processes. UV/PDS manifested the highest mineralization rate of MeP among the three processes, but also generated more disinfection by-products.}

Key words: UV, advanced oxidation, free radicals, kinetics, disinfection by-products

中图分类号:

X 703

杨庆云, 李青松, 陈泽铭, 邓靖, 李玉瑛, 杨帆, 陈国元, 李国新. UV/PMS、UV/PDS、UV/SPC工艺降解尼泊金甲酯[J]. 化工学报, 2023, 74(3): 1322-1331.

Qingyun YANG, Qingsong LI, Zeming CHEN, Jing DENG, Yuying LI, Fan YANG, Guoyuan CHEN, Guoxin LI. Degradation of methylparaben by UV/PMS, UV/PDS and UV/SPC process[J]. CIESC Journal, 2023, 74(3): 1322-1331.

图/表 9

图1 不同工艺中MeP的降解情况（a）；拟一级速率常数（kobs）（b）([MeP]=5 μmol·L-1, [PDS]= [PMS]=[SPC]=75 μmol·L-1, pH=7.0±0.2)

Fig.1 MeP degradation in different processes (a); Pseudo-first order rate constant (kobs) (b)

图2 加入自由基淬灭剂后不同工艺中MeP的降解（a）；DMPO-OH和DMPO-SO4的EPR谱图（b）([MeP]=5 μmol·L-1, [PDS]= [PMS]=[SPC]=75 μmol·L-1, [TBA]=[MeOH]=100 μmol·L-1, pH=7.0±0.2)

Fig.2 MeP degradation in different processes with free radical quencher (a); EPR spectra for DMPO-OH and DMPO-SO4 (b)

图3 MeP和BA在UV-LED/PDS/TBA工艺中的降解([MeP]0=[BA]0=5 μmol·L-1, [PDS]=75 μmol·L-1, [TBA]= 1 mmol·L-1, pH=7.0±0.2)

Fig.3 Degradation of MeP and BA in UV-LED/PDS/TBA process

图4 不同组分在UV/PDS、UV/PMS和UV/SPC工艺中降解MeP的贡献([MeP]0=5.0 μmol·L-1, [PDS]= [PMS]= [SPC]=75 μmol·L-1, pH=7.0±0.2)

Fig.4 Contributions of different species to degradation of MeP in UV/PDS, UV/PMS, and UV/SPC processes

图5 不同氧化剂投加量下MeP的降解（a）；不同摩尔投加比经济效益评估（b） ([MeP]0=5.0 μmol·L-1, pH=7.0±0.2)

Fig.5 MeP degradation in different processes under different oxidant dosages (a); Evaluation of economic benefit of different molar dosing ratios (b)

图6 初始pH对MeP在UV/PMS、UV/PDS和UV/SPC工艺中降解的影响([MeP]0=5 μmol·L-1, [PMS] =[PDS]= [SPC]=75 μmol·L-1)

Fig.6 Effects of initial pH on MeP degradation by UV/PMS, UV/PDS and UV/SPC treatments

图7 阴离子对MeP降解的影响([MeP]0=5 μmol·L-1, [PMS] =[PDS]= [SPC]=75 μmol·L-1, pH=7.0±0.2)

Fig.7 Effects of inorganic anions on MeP degradation

图8 NH4+和HA对MeP降解的影响([MeP]0=5 μmol·L-1, [PMS]=[PDS]=[SPC]=75 μmol·L-1, pH=7.0±0.2)

Fig.8 Effects of NH4+ and HA on MeP degradation

图9 不同工艺降解MeP的矿化率和DBPs生成（[MeP]0=5 μmol·L-1, [PMS]=[PDS]=[SPC]=75 μmol·L-1, pH=7.0±0.2）

Fig.9 The mineralization and DBPs formation in different processes

参考文献 33

1	Yang Y, Ok Y S, Kim K H, et al. Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: a review[J]. Science of the Total Environment, 2017, 596/597: 303-320.
2	Sungur Ş. Pharmaceutical and personal care products in the environment: occurrence and impact on the functioning of the ecosystem[M]//Emerging Contaminants in the Environment. Amsterdam: Elsevier, 2022: 137-157.
3	Miklos D B, Remy C, Jekel M, et al. Evaluation of advanced oxidation processes for water and wastewater treatment—a critical review[J]. Water Research, 2018, 139: 118-131.
4	陈智锋. 典型杀生剂在受纳水环境与受纳土壤环境中的污染特征、环境行为及其生态风险研究[D]. 北京: 中国科学院大学, 2014.
	Chen Z F. Study on pollution characteristics, environmental behavior and ecological risks of typical biocides in receiving water environment and receiving soil environment[D]. Beijing: University of Chinese Academy of Sciences, 2014.
5	毛茜慧. 水中对羟基苯甲酸酯的污染调查及在化学预氧化法中的去除机理研究[D]. 合肥: 合肥工业大学, 2017.
	Mao Q H. Occurrence of parabens in aquatic environment and the degradation mechanism of the chemical pre-oxidation process[D]. Hefei: Hefei University of Technology, 2017.
6	Álvarez-Ruiz R, Picó Y, Alfarhan A H, et al. Dataset of pesticides, pharmaceuticals and personal care products occurrence in wetlands of Saudi Arabia[J]. Data Brief, 2020, 31: 105776.
7	Luis Malvar J, Luis Santos J, Martín J, et al. Occurrence of the main metabolites of pharmaceuticals and personal care products in sludge stabilization treatments[J]. Waste Management, 2020, 116: 22-30.
8	Zhang Y N, Zhao Y G, Maqbool F, et al. Removal of antibiotics pollutants in wastewater by UV-based advanced oxidation processes: influence of water matrix components, processes optimization and application: a review[J]. Journal of Water Process Engineering, 2022, 45: 102496.
9	Yao Z X, Wang M Q, Jia R B, et al. Comparison of UV-based advanced oxidation processes for the removal of different fractions of NOM from drinking water[J]. Journal of Environmental Sciences, 2023,126: 387-395.
10	Gao Y Q, Gao N Y, Chu W H, et al. UV-activated persulfate oxidation of sulfamethoxypyridazine: kinetics, degradation pathways and impact on DBP formation during subsequent chlorination[J]. Chemical Engineering Journal, 2019, 370: 706-715.
11	Wang Q F, Shao Y S, Gao N Y, et al. Impact of preoxidation of UV/persulfate on disinfection byproducts by chlorination of 2,4-di-tert-butylphenol[J]. Journal of Hazardous Materials, 2018, 358: 450-458.
12	Dong H Y, Qiang Z M, Hu J, et al. Degradation of chloramphenicol by UV/chlorine treatment: kinetics, mechanism and enhanced formation of halonitromethanes[J]. Water Research, 2017, 121: 178-185.
13	Carlson J C, Stefan M I, Parnis J M, et al. Direct UV photolysis of selected pharmaceuticals, personal care products and endocrine disruptors in aqueous solution[J]. Water Research, 2015, 84: 350-361.
14	Liu W S, Xiao K, Li j, et al. Efficient removal of organic contaminants in real shale gas flowback water using Fenton oxidation assisted by UV irradiation: feasibility study and process optimization[J]. Process Safety and Environmental Protection, 2022, 158: 687-697.
15	Fu Y Y, Wu G, Geng J J, et al. Kinetics and modeling of artificial sweeteners degradation in wastewater by the UV/persulfate process[J]. Water Research, 2019, 150: 12-20.
16	Xu M Y, Deng J, Cai A H, et al. Synergistic effects of UVC and oxidants (PS vs chlorine) on carbamazepine attenuation: mechanism, pathways, DBPs yield and toxicity assessment[J]. Chemical Engineering Journal, 2021, 413: 127533.
17	Yue L C, Cheng J, Hua J J, et al. A sodium percarbonate/ultraviolet system generated free radicals for degrading capsaicin to alleviate inhibition of methane production during anaerobic digestion of lipids and food waste[J].Science of the Total Environment, 2021, 761: 143269.
18	Wang Q F, Shao Y S, Gao N Y, et al. Degradation kinetics and mechanism of 2,4-di-tert-butylphenol with UV/persulfate[J]. Chemical Engineering Journal, 2016, 304: 201-208.
19	邓靖, 杨庆云, 陈民杰, 等. UV-LED/NaClO工艺降解尼泊金甲酯:不同活性物种的作用[J]. 化工学报, 2022, 73(9): 4113-4121.
	Deng J, Yang Q Y, Chen M J, et al. Degradation of methylparaben by UV-LED/NaClO process: the role of different active species[J]. CIESC Journal, 2022, 73(9): 4113-4121.
20	Golshan M, Kakavandi B, Ahmadi M, et al. Photocatalytic activation of peroxymonosulfate by TiO₂ anchored on cupper ferrite (TiO₂@CuFe₂O₄) into 2,4-D degradation: process feasibility, mechanism and pathway[J]. Journal of Hazardous Materials, 2018, 359: 325-337.
21	Liu Y Q, He X X, Duan X D, et al. Significant role of UV and carbonate radical on the degradation of oxytetracycline in UV-AOPs: kinetics and mechanism[J]. Water Research, 2016, 95: 195-204.
22	付永胜,史鸿乐,刘义青,等. UV/H₂O₂光化学降解水中的三氯生[J]. 中国环境科学, 2018, 38(2): 616-626.
	Fu Y S, Shi H L Liu Y Q, et al. Photochemical degradation of triclosan by UV/H₂O₂ in water[J]. China Environmental Science, 2018, 38(2): 616-626.
23	Kalsoom U, Ashraf S S, Meetani M A, et al. Degradation and kinetics of H₂O₂ assisted photochemical oxidation of Remazol Turquoise Blue[J]. Chemical Engineering Journal, 2012, 200/201/202: 373-379.
24	Liu W, Li Y Y, Liu F Y, et al. Visible-light-driven photocatalytic degradation of diclofenac by carbon quantum dots modified porous g-C₃N₄: mechanisms, degradation pathway and DFT calculation[J].Water Research, 2019, 151: 8-19.
25	Lian L S, Yao B, Hou S D, et al. Kinetic study of hydroxyl and sulfate radical-mediated oxidation of pharmaceuticals in wastewater effluents[J]. Environmental Science & Technology, 2017, 51(5): 2954-2962.
26	Wojnárovits L, Tóth T, Takács E. Rate constants of carbonate radical anion reactions with molecules of environmental interest in aqueous solution: a review[J]. Science of the Total Environment, 2020, 717: 137219.
27	Wang W L, Wu Q Y, Huang N, et al. Synergistic effect between UV and chlorine (UV/chlorine) on the degradation of carbamazepine: influence factors and radical species[J]. Water Research, 2016, 98: 190-198.
28	Xiong R H, Lu Z J, Tang Q, et al. UV-LED/chlorine degradation of propranolol in water: degradation pathway and product toxicity[J]. Chemosphere, 2020, 248: 125957.
29	Yao H, Pei J, Wang H, et al. Effect of Fe(Ⅱ/Ⅲ) on tetracycline degradation under UV/VUV irradiation[J]. Chemical Engineering Journal, 2017, 308: 193-201.
30	Wang Y, Li H Y, Yi P, et al. Degradation of clofibric acid by UV, O₃ and UV/O₃ processes: performance comparison and degradation pathways[J]. Journal of Hazardous Materials, 2019, 379: 120771.
31	Coha M, Farinelli G, Tiraferri A, et al. Advanced oxidation processes in the removal of organic substances from produced water: potential, configurations, and research needs[J]. Chemical Engineering Journal, 2021, 414: 128668.
32	Gao Z C, Lin Y L, Xu B, et al. Degradation of acrylamide by the UV/chlorine advanced oxidation process[J]. Chemosphere, 2017, 187: 268-276.
33	Ding S K, Deng Y, Bond T, et al. Disinfection byproduct formation during drinking water treatment and distribution: a review of unintended effects of engineering agents and materials[J]. Water Research, 2019, 160: 313-329.

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UV/PMS、UV/PDS、UV/SPC工艺降解尼泊金甲酯

Degradation of methylparaben by UV/PMS, UV/PDS and UV/SPC process

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