VUV/UV/NaClO工艺降解百里香酚协同效应及活性物质贡献

doi:10.11949/0438-1157.20220060

化工学报 ›› 2022, Vol. 73 ›› Issue (5): 2233-2241.DOI: 10.11949/0438-1157.20220060

VUV/UV/NaClO工艺降解百里香酚协同效应及活性物质贡献

肖习羽^1,²(),李青松^2,⁴(),吴俊文^1,³(),李国新²,陈国元²

^1.汕头大学海洋灾害预警与防护广东省重点实验室，广东汕头 515063
^2.厦门理工学院水资源环境研究所，福建厦门 361024
^3.南方海洋科学与工程广东省实验室（广州），广东广州 511458
^4.厦门市水资源利用与保护重点实验室，福建厦门 361024

收稿日期:2022-01-12 修回日期:2022-03-26 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 李青松,吴俊文
作者简介:肖习羽(1995—)，女，硕士研究生，19xyxiao@stu.edu.cn
基金资助:
国家自然科学基金项目(51878582);广东省自然科学基金项目(2021A1515011886);南方海洋科学与工程广东省实验室(广州)重大专项团队项目(GML2019ZD0606);汕头大学科研启动基金项目(NTF18011);汕头市创新创业项目(201112176541391);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)

Synergistic effect of thymol degradation by VUV/UV/NaClO technique and its major contributor of active species

Xiyu XIAO^1,²(),Qingsong LI^2,⁴(),Junwen WU^1,³(),Guoxin LI²,Guoyuan CHEN²

^1.Guangdong Provincial Key Laboratory of Marine Disaster Prediction and Prevention, Shantou University, Shantou 515063, Guangdong, China
^2.Water Resource and Environment Institute, Xiamen University of Technology, Xiamen 361024, Fujian, China
^3.Southern Marine Science and Engineering Guangdong Laboratory, Guangzhou 511458, Guangdong, China
^4.Key Laboratory of Water Resources Utilization and Protection of Xiamen, Xiamen 361024, Fujian, China

Received:2022-01-12 Revised:2022-03-26 Online:2022-05-05 Published:2022-05-24
Contact: Qingsong LI,Junwen WU

摘要/Abstract

摘要：

采用VUV/UV/NaClO与UV/NaClO工艺降解百里香酚(Tml)，以协同因子(R)为评价指标，探究了NaClO浓度和pH对Tml去除及协同效应的影响；以硝基苯(NB)和苯甲酸(BA)为探针化合物，确定了不同工艺中HO·和Cl·的稳态浓度及其与Tml的二级反应速率常数；并对比了两种工艺中不同物质对Tml降解的贡献。结果表明，VUV/UV/NaClO与UV/NaClO工艺降解Tml均符合拟一级反应动力学，其一级动力学常数k_VUV/UV/Cl和k_UV/Cl分别为0.0113 s^-1和0.00479 s^-1，且均与NaClO浓度呈正相关；VUV/UV/NaClO和UV/NaClO工艺对Tml的降解具有显著的协同效应，相应的协同因子(R_VUV/UV/Cl、R_UV/Cl)随NaClO的浓度的增加及溶液pH的增大均先增加再降低；当NaClO浓度为0.3 mg·L^-1和pH=7时，R_VUV/UV/Cl和R_UV/Cl达到最大值，分别为1.9和2.1，对应的协同增效为90%和110%。VUV/UV/NaClO和UV/NaClO工艺中HO·的贡献率分别为42.7%和37.6%，Cl·的贡献率分别为42.4%和28.5%。两种工艺中HO·和Cl·均为主要贡献物质。

关键词: 百里香酚, VUV/UV/NaClO, 协同效应, 自由基, 贡献率

Abstract:

The VUV/UV/NaClO and UV/NaClO processes were used to degrade thymol (Tml), and the synergistic factor (R) was used as the evaluation index to explore the effects of NaClO concentration and pH on Tml removal and synergistic effect. Meanwhile, using nitrobenzene (NB) and benzoic acid (BA) as probe compounds, the concentrations of HO· and Cl· in steady state, their contributions to Tml degradation, and their secondary reaction rates with Tml in two technologies were determined. The results show that the degradation of Tml using VUV/UV/NaClO and UV/NaClO technologies is in accord with the pseudo-primary reaction kinetics, and the first-level kinetic constants of k_VUV/UV/Cl and k_UV/Cl are determined to be 0.0113 s^-1 and 0.00479 s^-1, respectively, which is positively correlated with NaClO concentration. VUV/UV/NaClO and UV/NaClO processes had significant synergistic effects on the degradation of Tml, and the corresponding synergistic factors R_VUV/UV/Cl and R_UV/Cl showed an initial increase and then decrease with the increase of NaClO concentration and pH. The maximum R_VUV/UV/Cl and R_UV/Cl were determined to be 1.9 and 2.1 when the NaClO concentration and pH are 0.3 mg·L^-1 and 7, respectively, and the corresponding synergies were 90% and 110%. The contribution rates of HO· in the VUV/UV/NaClO and UV/NaClO processes were calculated to be 42.7% and 37.6%, respectively, while the contributions of Cl· were 42.4% and 28.5%, respectively. HO· and Cl· were the dominated contributors in the two processes.

Key words: thymol, VUV/UV/NaClO, synergistic effect, radical, contribution rate

中图分类号:

X 703

肖习羽, 李青松, 吴俊文, 李国新, 陈国元. VUV/UV/NaClO工艺降解百里香酚协同效应及活性物质贡献[J]. 化工学报, 2022, 73(5): 2233-2241.

Xiyu XIAO, Qingsong LI, Junwen WU, Guoxin LI, Guoyuan CHEN. Synergistic effect of thymol degradation by VUV/UV/NaClO technique and its major contributor of active species[J]. CIESC Journal, 2022, 73(5): 2233-2241.

图/表 8

图1 不同工艺中Tml的降解([Tml]0=3.33 μmol·L-1, [NaClO]0=0.3 mg·L-1, pH=7.0(±0.2))

Fig.1 Degradation of Tml in different processes

图2 NaClO对VUV/UV/NaClO和UV/NaClO降解Tml的k (a)和协同因子R (b)的影响([Tml]0=3.33 μmol·L-1, pH=7.0(±0.2))

Fig.2 Effect of NaClO concentration on the k (a) and R (b) during the Tml degradation by VUV/UV/NaClO and UV/NaClO

图3 pH对4种工艺降解Tml的k和去除率的影响([Tml]0=3.33 μmol·L-1, [NaClO]0=0.3 mg·L-1)

Fig.3 Effect of pH on the k and removal rate during the Tml degradation by four processes

图4 pH对VUV/UV/NaClO和UV/NaClO降解Tml k (a)和协同因子R (b)的影响([Tml]0=3.33 μmol·L–1, [NaClO]0=0.3 mg·L–1)

Fig.4 Effect of pH on the k (a) and R (b) during the Tml degradation by VUV/UV/NaClO and UV/NaClO

图5 不同工艺对NB和Tml的降解([NB]0=1.22 μmol·L-1, [Tml]0=3.33 μmol·L-1, [NaClO]0=0.3 mg·L-1, pH=7.0(±0.2))

Fig.5 Degradation of NB and Tml in different processes

图6 不同工艺对BA的降解([BA]0=1.23 μmol·L-1, [Tml]0=3.33 μmol·L-1, [NaClO]0=0.3 mg·L-1, pH=7.0(±0.2))

Fig.6 Degradation of BA by different processes

图7 VUV/UV/NaClO、UV/NaClO和NaClO对Tml的降解动力学([Tml]0=3.33 μmol·L–1, [NaClO]0=0.3 mg·L–1, pH=7.0(±0.2))

Fig.7 Kinetics of Tml degradation in VUV/UV/NaClO, UV/NaClO and NaClO

图8 VUV/UV/NaClO和UV/NaClO工艺中不同物质对Tml的降解的贡献([Tml]0=3.33 μmol·L-1, [NaClO]0=0.3 mg·L-1, pH=7.0(±0.2))

Fig.8 Contribution of different species to Tml degradation in VUV/UV/NaClO and UV/NaClO processes

参考文献 48

1	Sui Q, Cao X Q, Lu S G, et al. Occurrence, sources and fate of pharmaceuticals and personal care products in the groundwater: a review[J]. Emerging Contaminants, 2015, 1(1): 14-24.
2	Schwab B W, Hayes E P, Fiori J M, et al. Human pharmaceuticals in US surface waters: a human health risk assessment[J]. Regulatory Toxicology and Pharmacology, 2005, 42(3): 296-312.
3	Ebele A J, Abou-Elwafa Abdallah M, Harrad S. Pharmaceuticals and personal care products (PPCPs) in the freshwater aquatic environment[J]. Emerging Contaminants, 2017, 3(1): 1-16.
4	张静, 冯岗, 袁旭超, 等. 百里香酚抑菌活性初探[J]. 中国农学通报, 2009, 25(21): 277-280.
	Zhang J, Feng G, Yuan X C, et al. Preliminary study on the antifungal activity of thymol[J]. Chinese Agricultural Science Bulletin, 2009, 25(21): 277-280.
5	Nakada N, Kiri K, Shinohara H, et al. Evaluation of pharmaceuticals and personal care products as water-soluble molecular markers of sewage[J]. Environmental Science & Technology, 2008, 42(17): 6347-6353.
6	梅雪冰, 隋倩, 张紫薇, 等. 不同特征污染源中指示性药物和个人护理品识别与筛选[J]. 中国环境科学, 2019, 39(3): 1173-1180.
	Mei X B, Sui Q, Zhang Z W, et al. Identification of indicator pharmaceutical and personal care products (PPCPs) in different emission sources[J]. China Environmental Science, 2019, 39(3): 1173-1180.
7	Esplugas S, Giménez J, Contreras S, et al. Comparison of different advanced oxidation processes for phenol degradation[J]. Water Research, 2002, 36(4): 1034-1042.
8	Couto C F, Lange L C, Amaral M C S. Occurrence, fate and removal of pharmaceutically active compounds (PhACs) in water and wastewater treatment plants—a review[J]. Journal of Water Process Engineering, 2019, 32: 100927.
9	闫子娇, 张有林, 于月英. 百里香挥发油成分分析及急性毒理学实验研究[J]. 食品工业科技, 2011, 32(2): 144-146.
	Yan Z J, Zhang Y L, Yu Y Y. Study of composition and emergency toxicology test of thymus[J]. Science and Technology of Food Industry, 2011, 32(2): 144-146.
10	张有林, 张润光, 钟玉. 百里香精油的化学成分、抑菌作用、抗氧化活性及毒理学特性[J]. 中国农业科学, 2011, 44(9): 1888-1897.
	Zhang Y L, Zhang R G, Zhong Y. Chemical component, antimicrobial effect, antioxidation activity and toxicological character of thyme essential oil[J]. Scientia Agricultura Sinica, 2011, 44(9): 1888-1897.
11	Bianchi C L, Pirola C, Ragaini V, et al. Mechanism and efficiency of atrazine degradation under combined oxidation processes[J]. Applied Catalysis B: Environmental, 2006, 64(1/2): 131-138.
12	Huang N, Wang T, Wang W L, et al. UV/chlorine as an advanced oxidation process for the degradation of benzalkonium chloride: synergistic effect, transformation products and toxicity evaluation[J]. Water Research, 2017, 114: 246-253.
13	Li S M, Ao X W, Li C, et al. Insight into PPCP degradation by UV/NH₂Cl and comparison with UV/NaClO: kinetics, reaction mechanism, and DBP formation[J]. Water Research, 2020, 182: 115967.
14	Liu Z, Xu B, Zhang T Y, et al. Formation of disinfection by-products in a UV-activated mixed chlorine/chloramine system[J]. Journal of Hazardous Materials, 2021, 407: 124373.
15	Gao Z C, Lin Y L, Xu B, et al. Effect of UV wavelength on humic acid degradation and disinfection by-product formation during the UV/chlorine process[J]. Water Research, 2019, 154: 199-209.
16	Juang L C, Tseng D H, Lee J F. Photolytic mechanism of monochlorobenzene in an aqueous UV/H₂O₂ system[J]. Chemosphere, 1998, 36(6): 1187-1199.
17	Yuan F, Hu C, Hu X X, et al. Degradation of selected pharmaceuticals in aqueous solution with UV and UV/H₂O₂ [J]. Water Research, 2009, 43(6): 1766-1774.
18	Yi Q Y, Ji J H, Shen B, et al. Singlet oxygen triggered by superoxide radicals in a molybdenum cocatalytic fenton reaction with enhanced REDOX activity in the environment[J]. Environmental Science & Technology, 2019, 53(16): 9725-9733.
19	Zoschke K, Börnick H, Worch E. Vacuum-UV radiation at 185 nm in water treatment—a review[J]. Water Research, 2014, 52: 131-145.
20	褚宏怡, 鲁金凤, 寇方航, 等. 过硫酸盐高级氧化技术的活化方法研究进展[J]. 供水技术, 2017, 11(4): 24-28.
	Chu H Y, Lu J F, Kou F H, et al. Research progress of the activation methods based on persulfate advanced oxidation technology[J]. Water Technology, 2017, 11(4): 24-28.
21	Lee Y, von Gunten U. Oxidative transformation of micropollutants during municipal wastewater treatment: comparison of kinetic aspects of selective (chlorine, chlorine dioxide, ferrate Ⅵ, and ozone) and non-selective oxidants (hydroxyl radical)[J]. Water Research, 2010, 44(2): 555-566.
22	Fang J Y, Fu Y, Shang C. The roles of reactive species in micropollutant degradation in the UV/free chlorine system[J]. Environmental Science & Technology, 2014, 48(3): 1859-1868.
23	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.
24	Gonzalez M G, Oliveros E, Wörner M, et al. Vacuum-ultraviolet photolysis of aqueous reaction systems[J]. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2004, 5(3): 225-246.
25	Buchanan W, Roddick F, Porter N, et al. Fractionation of UV and VUV pretreated natural organic matter from drinking water[J]. Environmental Science & Technology, 2005, 39(12): 4647-4654.
26	Chen J, Zhang P Y, Liu J. Photodegradation of perfluorooctanoic acid by 185 nm vacuum ultraviolet light[J]. Journal of Environmental Sciences, 2007, 19(4): 387-390.
27	Kim I, Tanaka H. Photodegradation characteristics of PPCPs in water with UV treatment[J]. Environment International, 2009, 35(5): 793-802.
28	Li W Z, Lu S G, Chen N, et al. Photo-degradation of clofibric acid by ultraviolet light irradiation at 185 nm[J]. Water Science and Technology, 2009, 60(11): 2983-2989.
29	Imoberdorf G, Mohseni M. Degradation of natural organic matter in surface water using vacuum-UV irradiation[J]. Journal of Hazardous Materials, 2011, 186(1): 240-246.
30	Li M K, Hao M Y, Yang L X, et al. Trace organic pollutant removal by VUV/UV/chlorine process: feasibility investigation for drinking water treatment on a mini-fluidic VUV/UV photoreaction system and a pilot photoreactor[J]. Environmental Science & Technology, 2018, 52(13): 7426-7433.
31	Xiang Y Y, Fang J Y, Shang C. Kinetics and pathways of ibuprofen degradation by the UV/chlorine advanced oxidation process[J]. Water Research, 2016, 90: 301-308.
32	Guo K H, Wu Z H, Shang C, et al. Radical chemistry and structural relationships of PPCP degradation by UV/chlorine treatment in simulated drinking water[J]. Environmental Science & Technology, 2017, 51(18): 10431-10439.
33	Bu L J, Zhou S Q, Zhu S M, et al. Insight into carbamazepine degradation by UV/monochloramine: reaction mechanism, oxidation products, and DBPs formation[J]. Water Research, 2018, 146: 288-297.
34	Yang L X, Zhang Z H. Degradation of six typical pesticides in water by VUV/UV/chlorine process: evaluation of the synergistic effect[J]. Water Research, 2019, 161: 439-447.
35	Watts M J, Linden K G. Chlorine photolysis and subsequent OH radical production during UV treatment of chlorinated water[J]. Water Research, 2007, 41(13): 2871-2878.
36	Li M K, Qiang Z M, Hou P, et al. VUV/UV/chlorine as an enhanced advanced oxidation process for organic pollutant removal from water: assessment with a novel mini-fluidic VUV/UV photoreaction system (MVPS)[J]. Environmental Science & Technology, 2016, 50(11): 5849-5856.
37	Cai W W, Peng T, Zhang J N, et al. Degradation of climbazole by UV/chlorine process: kinetics, transformation pathway and toxicity evaluation[J]. Chemosphere, 2019, 219: 243-249.
38	Yang L X, Li M K, Li W T, et al. A green method to determine VUV (185 nm) fluence rate based on hydrogen peroxide production in aqueous solution[J]. Photochemistry and Photobiology, 2018, 94(4): 821-824.
39	Deborde M, von Gunten U. Reactions of chlorine with inorganic and organic compounds during water treatment—kinetics and mechanisms: a critical review[J]. Water Research, 2008, 42(1/2): 13-51.
40	Wang D, Bolton J R, Hofmann R. Medium pressure UV combined with chlorine advanced oxidation for trichloroethylene destruction in a model water[J]. Water Research, 2012, 46(15): 4677-4686.
41	Collivignarelli C, Sorlini S. AOPs with ozone and UV radiation in drinking water: contaminants removal and effects on disinfection byproducts formation[J]. Water Science and Technology: a Journal of the International Association on Water Pollution Research, 2004, 49(4): 51-56.
42	李博强, 马晓雁, 李青松, 等. UV-LED/NaClO工艺对水中对乙酰氨基酚的降解[J]. 中国环境科学, 2019, 39(11): 4681-4688.
	Li B Q, Ma X Y, Li Q S, et al. Degradation of acetaminophen in aqueous by UV-LED/NaClO process[J]. China Environmental Science, 2019, 39(11): 4681-4688.
43	Han M Q, Mohseni M. Impact of organic and inorganic carbon on the formation of nitrite during the VUV photolysis of nitrate containing water[J]. Water Research, 2020, 168: 115169.
44	Chen B Y, Huang Y X, Zhang Q, et al. Formation of nitrite and hydrogen peroxide in water during the vacuum ultraviolet irradiation process: impacts of pH, dissolved oxygen, and nitrate concentration[J]. Environmental Science & Technology, 2021, 55(3): 1682-1689.
45	Dao Y H, Tran H N, Tran-Lam T T, et al. Degradation of paracetamol by an UV/chlorine advanced oxidation process: influencing factors, factorial design, and intermediates identification[J]. International Journal of Environmental Research and Public Health, 2018, 15(12): 2637.
46	Kutschera K, Börnick H, Worch E. Photoinitiated oxidation of geosmin and 2-methylisoborneol by irradiation with 254 nm and 185 nm UV light[J]. Water Research, 2009, 43(8): 2224-2232.
47	Kong Q Q, Lei X, Zhang X R, et al. The role of chlorine oxide radical (ClO•) in the degradation of polychoro-1, 3-butadienes in UV/chlorine treatment: kinetics and mechanisms[J]. Water Research, 2020, 183: 116056.
48	Yang B, Kookana R S, Williams M, et al. Removal of carbamazepine in aqueous solutions through solar photolysis of free available chlorine[J]. Water Research, 2016, 100: 413-420.

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VUV/UV/NaClO工艺降解百里香酚协同效应及活性物质贡献

Synergistic effect of thymol degradation by VUV/UV/NaClO technique and its major contributor of active species

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