紫外-高铁酸盐体系氧化降解水中的萘普生

doi:10.16085/j.issn.1000-6613.2022-0121

摘要/Abstract

摘要：

利用紫外线（UV）活化高铁酸盐[Fe(Ⅵ)]能显著提高萘普生（NPX）的降解率。本文考察了不同体系、 Fe(Ⅵ)投加量、溶液pH、磷酸盐、HCO $3 -$ 、Cl^-以及腐殖酸（HA）对NPX降解的影响，并通过自由基淬灭实验和中间价态铁鉴定实验确定了反应的主要活性物种。通过TOC去除率确定体系降解NPX的矿化程度并利用液相色谱质谱联用仪检测降解的中间产物，提出了可能的降解路径。结果表明，反应60min后，单独Fe(Ⅵ)几乎不能降解NPX，单独UV对NPX的降解率也不到26%，而UV-Fe(Ⅵ)体系对NPX的降解率高达82%，降解过程符合准一级动力学规律（R² $>$ 0.95），反应速率常数为0.0306min^-1，分别是单独UV和单独Fe(Ⅵ)降解速率的6.2倍和102倍。溶液初始pH对UV-Fe(Ⅵ)体系降解NPX有显著影响，酸性条件下有利于NPX的降解，主要是由于在不同pH下高铁酸盐和NPX的不同形态的双重作用。相同pH下，磷酸盐对NPX的降解有明显的抑制作用，主要是因为磷酸盐与Fe(Ⅵ)分解产物具有络合作用导致·O $2 -$ 减少。Cl^-和HA对NPX降解有不同程度的抑制作用，而HCO $3 -$ 对降解有促进作用，这是因为HCO $3 -$ 的加入使得溶液的pH升高从而增强了Fe(Ⅵ)的稳定性。较低的矿化率表明NPX的降解产物与其母体化合物相比难于在UV-Fe(Ⅵ)体系中去除。UV-Fe(Ⅵ)体系中的主要优势活性物种是·O $2 -$ ，NPX 与·O $2 -$ 主要通过电子转移机制发生脱羧反应，最终生成酸类、酮类和醚类物质。

关键词: 高铁酸盐, 紫外活化, 高级氧化, 自由基, 降解机理

Abstract:

The degradation rate of naproxen (NPX) can be significantly improved by activating ferrate under UV light. The effects of different process, Fe(Ⅵ) concentration, pH, phosphate, HCO $3 -$ , Cl^- and humic acid (HA) were investigated. The main active species of the reaction were determined by the free radical quenching experiment and the intermediate valence iron identification experiment. In addition, the mineralization degree of NPX was determined by TOC and the possible degradation paths were proposed on the basis of the intermediates detected by liquid chromatography-mass spectrometry analysis. The results showed that after 60min of reaction, Fe(Ⅵ) alone can hardly degrade NPX. The degradation rate of NPX by UV alone was less than 26%, while the degradation rate of NPX by UV-Fe(Ⅵ) process was as high as 82%. The degradation process conformed to the pseudo-first-order kinetic law (R²>0.95) with a reaction rate constant of 0.0306min^-1, which was 6.2 times and 102 times of the degradation rates of UV alone and Fe(Ⅵ) alone, respectively. The initial pH of the solution had a significant effect on the degradation of NPX in the UV-Fe(Ⅵ) process, and the degradation was favored under acidic conditions, mainly due to the dual effect of different forms of ferrate and NPX at different pH. At the same pH, phosphate had a significant inhibitory effect on the degradation of NPX, mainly because of the complexation of phosphate and the decomposition products of ferrate resulting in a decrease in ·O $2 -$ . In addition, Cl^- and HA had different degrees of inhibition on NPX degradation. However, HCO $3 -$ had a promoting effect on degradation, because the addition of HCO $3 -$ increased the pH of the solution and enhanced the stability of ferrate. The dominant active species in the UV-Fe(Ⅵ) process is ·O $2 -$ , which decarboxylates NPX mainly through electron transfer mechanism and finally generates acids, ketones and ethers.

Key words: ferrate, ultraviolet activation, advanced oxidation, free radicals, degradation mechanism

中图分类号:

X522

伊学农, 李京梅, 高玉琼. 紫外-高铁酸盐体系氧化降解水中的萘普生[J]. 化工进展, 2022, 41(8): 4562-4570.

YI Xuenong, LI Jingmei, GAO Yuqiong. Oxidative degradation of naproxen in water by UV-Fe(Ⅵ) process[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4562-4570.

图/表 11

图1 三种体系对NPX的降解及反应动力学

图2 中间价态铁的鉴定实验

图3 自由基清除实验

图4 不同K2FeO4的投加量对NPX降解效果的影响

图5 有无磷酸盐缓冲液时pH对体系去除NPX的影响

图6 有无磷酸盐缓冲液时不同pH下NPX的降解速率

图7 不同水体基质及不同实际水体对体系降解NPX的影响

表1 不同实际水体水样水质参数

水样	pH	Cl^-/mg·L^-1	HCO $3 -$ /mg·L^-1	DOC/mg·L^-1
纯净水	7.00	0	0	≤0.02
天然水	7.53	6	143	6.19
自来水厂出厂水	7.66	10	137	4.31

表1 不同实际水体水样水质参数

水样	pH	Cl^-/mg·L^-1	HCO $3 -$ /mg·L^-1	DOC/mg·L^-1
纯净水	7.00	0	0	≤0.02
天然水	7.53	6	143	6.19
自来水厂出厂水	7.66	10	137	4.31

图8 不同Fe(Ⅵ)投加量下NPX的矿化程度

表2 UV-Fe(Ⅵ)体系降解NPX的中间产物

物质	m/z	名称
NPX	230	萘普生
P246	246	羟基萘普生
P134	134	羟基丁二酸
P184	184	2-甲氧基-6-萘乙烯
P200	200	2-甲氧基-6-萘乙酮
P186	186	2-甲氧基-6-乙基萘
P216	216	2-（6-羟基-2-萘基）丙酸
P202	202	2-（6-甲氧基-2-萘基）乙醇
P158	158	2-萘乙醚

图9 UV-Fe(Ⅵ)体系降解NPX的路径

参考文献 36

1	CARBALLA M, OMIL F, LEMA J M. Removal of cosmetic ingredients and pharmaceuticals in sewage primary treatment[J]. Water Research, 2005, 39: 4790-4796.
2	SHARMA V K. Potassium ferrate( Ⅵ ): an environmentally friendly oxidant[J]. Advances in Environmental Research, 2002, 6: 143-156.
3	吕婧, 封莉, 张立秋. 不同活性炭对水中微量药物萘普生的吸附规律研究[J]. 环境科学学报, 2012, 32(10): 2443-2449.
	LYU J, FENG L, ZHANG L Q. Adsorption of trace naproxen in water by different activated carbons[J]. Acta Scientiae Circumstantiae, 2012, 32(10): 2443-2449.
4	SHARMA V K, ZBORIL R, VARMA R S. Ferrates: greener oxidants with multimodal action in water treatment technologies[J]. Accounts of Chemical Research, 2015, 48(2): 82-191.
5	FENG M B, JINADATHA C, MCDONALD T J. Accelerated oxidation of organic contaminants by ferrate(Ⅵ): the overlooked role of reducing additives[J]. Environmental Science & Technology, 2018, 52(19): 11319-11327.
6	MANOLI K, NAKHLA G, RAY A K, et al. Enhanced oxidative transformation of organic contaminants by activation of ferrate( Ⅵ ): possible involvement of Fe^Ⅴ/Fe^Ⅳ species[J]. Chemical Engineering Journal, 2017, 307: 513-517.
7	FENG M, CIZMAS L, WANG Z Y, et al. Activation of ferrate(Ⅵ) by ammonia in oxidation of flumequine: kinetics, transformation products, and antibacterial activity assessment[J]. Chemical Engineering Journal, 2017, 323: 584-591.
8	BZDYRA B M, SPELLMAN JR C D, ANDREU I, et al. Sulfite activation changes character of ferrate resultant particles[J]. Chemical Engineering Journal, 2020, 393: 124771.
9	GONG H, CHU W, XU K H, et al. Efficient degradation, mineralization and toxicity reduction of sulfamethoxazole under photo-activation of peroxymonosulfate by ferrate( Ⅵ )[J]. Chemical Engineering Journal, 2020, 389: 124084.
10	CHU W H, LI D M, GAO N Y, et al. The control of emerging haloacetamide DBP precursors with UV/persulfate treatment[J]. Water Research, 2015, 72: 340-348.
11	SHADA A, CHEN J, QU R J, et al. Degradation of sulfadimethoxine in phosphate buffer solution by UV alone, UV/PMS and UV/H₂O₂: kinetics, degradation products, and reaction pathways[J]. Chemical Engineering Journal, 2020, 398: 125357.
12	CHEN Y Q, XIONG Y, WANG Z P, et al. UV/ferrate(Ⅵ) oxidation of profenofos: efficiency and mechanism[J]. Desalination and Water Treatment, 2015, 55(2): 506-513.
13	ASLANI H, NASSERI S, NABIZADEH R, et al. Haloacetic acids degradation by an efficient Ferrate/UV process: byproduct analysis, kinetic study, and application of response surface methodology for modeling and optimization[J]. Journal of Environmental Management, 2017, 203: 218-228.
14	VANESSA J, PEREIRA, HOWARD S, et al. UV degradation kinetics and modeling of pharmaceutical compounds in laboratory grade and surface water via direct and indirect photolysis at 254nm[J]. Environmental Science & Technology, 2007, 41: 1682-1688.
15	WU S H, LI H R, LI X, et al. Performances and mechanisms of efficient degradation of atrazine using peroxymonosulfate and ferrate as oxidants[J]. Chemical Engineering Journal, 2018, 353: 533-541.
16	FENG M B, SHARMA V K. Enhanced oxidation of antibiotics by ferrate(Ⅵ)-sulfur(Ⅳ) system: elucidating multi-oxidant mechanism[J]. Chemical Engineering Journal, 2018, 341: 137-145.
17	ZOSCHKE K, BORNICK H, WORCH E. Vacuum-UV radiation at 185nm in water treatment: a review[J]. Water Research, 2014, 52: 131-145.
18	SHARMA V K. Ferrate( Ⅵ ) and ferrate( Ⅴ ) oxidation of organic compounds: kinetics and mechanism[J]. Coordination Chemistry Reviews, 2013, 257: 495-510.
19	LI H C, SHAN C, PAN B C. Fe( Ⅲ )-doped g-C₃N₄ mediated peroxymonosulfate activation for selective degradation of phenolic compounds via high-valent iron oxo species[J]. Environmental Science & Technology, 2018, 52: 2197-2205.
20	LI Y, WU Y L, DONG W B. Trace catechin enhanced degradation of organic pollutants with activated peroxymonosulfate: comprehensive identification of working oxidizing species[J]. Chemical Engineering Journal, 2022, 429: 132408.
21	SHAO B B, DONG H Y, SUN B, et al. Role of ferrate(Ⅳ) and ferrate(Ⅴ) in activating ferrate(Ⅵ) by calcium sulfite for enhanced oxidation of organic contaminants[J]. Environmental Science & Technology, 2019, 53: 894-902.
22	GAO Y Q, ZHANG J, LI C, et al. Comparative evaluation of metoprolol degradation by UV/chlorine and UV/H₂O₂ processes[J]. Chemosphere, 2020, 243: 125325.
23	WANG Z, JIANG J, PANG S Y, et al. Is sulfate radical really generated from peroxydisulfate activated by iron(Ⅱ) for environmental decontamination[J]. Environmental Science & Technology, 2018, 52: 11276-11284.
24	袁光明, 皮若冰, 吴钊成, 等. 高铁酸盐-亚硫酸盐体系氧化降解水中污染物阿特拉津[J]. 化工进展, 2020, 39(9): 3794-3800.
	YUAN G M, PI R B, WU Z C, et al. Oxidative degradation of atrazine in water by ferrate-sulfite system[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3794-3800.
25	LAI X J, NING X A, ZHANG Y P, et al. Treatment of simulated textile sludge using the Fenton/Cl^- system: the roles of chlorine radicals and superoxide anions on PAHs removal[J]. Environmental Research, 2021, 197: 110997.
26	方智煌, 刘祥, 余阳, 等. 高铁酸盐对水中H₂受体拮抗剂的降解特性[J]. 化工进展, 2021, 40(8): 4647-4655.
	FANG Z H, LIU X, YU Y, et al. Performance and properties of H₂ receptor antagonist degradation by ferrate[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4647-4655.
27	WU S H, LIU H Y, LIN Y, et al. Insights into mechanisms of UV/ferrate oxidation for degradation of phenolic pollutants: role of superoxide radicals[J]. Chemosphere, 2020, 244: 125490.
28	GU D, GUO C S, HOU S, et al. Kinetic and mechanistic investigation on the decomposition of ketamine by UV-254nm activated persulfate[J]. Chemical Engineering Journal, 2019, 370: 19-26.
29	WANG S L, WU J F, LU X Q, et al. Removal of acetaminophen in the Fe²⁺/persulfate system: kinetic model and degradation pathways[J]. Chemical Engineering Journal, 2019, 358: 1091-1100.
30	KRALCHEVSKA R P, PRUCE R, KOLARIK J, et al. Remarkable efficiency of phosphate removal: ferrate(Ⅵ)-induced in situ sorption on core-shell nanoparticles[J]. Water Research, 2016,103: 83-91.
31	WANG J L, WANG S Z. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants[J]. Chemical Engineering Journal, 2018, 334: 1502-1517.
32	CHI H Z, HE X, ZHANG J Q, et al. Hydroxylamine enhanced degradation of naproxen in Cu²⁺ activated peroxymonosulfate system at acidic condition: efficiency, mechanisms and pathway[J]. Chemical Engineering Journal, 2019, 361: 764-772.
33	JALLOULI N, ELGHNIJI K, HENTATI O, et al. UV and solar photo-degradation of naproxen: TiO₂ catalyst effect, reaction kinetics, products identification and toxicity assessment[J]. Journal of Hazardous Materials, 2016, 304: 329-336.
34	JIMENEZ-SALCEDO M, MONGE M, TENA M T. The photocatalytic degradation of naproxen with g-C₃N₄ and visible light: identification of primary by-products and mechanism in tap water and ultrapure water[J]. Journal of Environmental Chemical Engineering, 2022, 10: 106964.
35	KANAKARAJU D, MOTTI C A, GLASS B D, et al. TiO₂ photocatalysis of naproxen: effect of the water matrix, anions and diclofenac on degradation rates[J]. Chemosphere, 2015, 139: 579-588.
36	LUO S, GAO L W, WEI Z S, et al. Kinetic and mechanistic aspects of hydroxyl radical-mediated degradation of naproxen and reaction intermediates[J]. Water Research, 2018, 137: 233-241.

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