UV/oxone降解水中甲氧苄啶的效能及模型评价

doi:10.16085/j.issn.1000-6613.2019-0239

摘要/Abstract

摘要：

研究采用UV、oxone、UV/oxone共3种工艺降解甲氧苄啶（TMP）的效果及动力学。采用响应面曲线法研究含有HCO₃ ^-、Cl^-、NO₃ ^-和pH四因素、三水平的水体条件下UV/oxone对TMP的降解效果及模型，并选用4种实际水源水体为水质背景来评价模型预测值与实际降解值的差别，最后比较了3种工艺的同等降解率条件下的降解效能。结果发现UV和oxone单独降解TMP时仅降解了5.5%和62.0%，而UV/oxone可达到93.2%，且降解过程符合拟一级反应动力学，动力学常数为0.1768min^-1。采用相对速率法可得到?SO₄ ^–与TMP的反应速率常数为2.07×10⁸L/(mol·s)。通过响应面曲线法得到UV/oxone降解TMP的回归方程式，对应的p值小于0.0001，拟合缺失项P不显著（0.9726>0.05），校正决定系数R ²=0.82＞0.8，说明该模型可信度高，采用实际水体进行模型验证后发现实际降解值基本符合模型预测值。降解率一定的条件下UV/oxone耗时最短，是一种高效、快速、可行的降解工艺。

关键词: 甲氧苄啶, UV/oxone, 响应面曲线法, 动力学, 效能评价

Abstract:

The efficiency and dynamics of degradation TMP with UV, oxone and UV/oxone processes were investigated in this study. The efficiency and model of four factors and three levels with response surface curve method were explored to investigate the effect of HCO₃ ^-、Cl^-、NO₃ ^- and pH on degradation TMP. Furthermore, four kinds of real source water were applied to evaluate the difference between the real degradation value and the modal predication value. Finally, the degradation efficiency of three processes were compared. The results showed that only 5.5% and 62% of TMP were degraded by UV and oxone alone. However, the degradation rate of UV/oxone process can reached 93.2%, which fitted the pseudo-first-order reaction equation, and the first-order reaction rate constant (K) was 0.1768min^-1. The second-order reaction rate constant of ?SO₄ ^– and TMP was 2.07×10⁸L/(mol·s) with relative rate method. The regression equations of UV/oxone degradation TMP with RSM was obtained, the corresponding p value was less than 0.0001, the lack of fit was not significant (0.9726 > 0.05), R ²= 0.82 > 0.8, which indicated that the model was reliable. The actual degradation value and the model prediction value were similar during actual water basic degraded. UV/oxone was a highly efficient, rapid and feasible degradation process under the same degradation rate.

Key words: trimethoprim, UV/oxone, RSM, dynamics, effectiveness evaluation

中图分类号:

X703

陈菊香,张梦文,杨静,高乃云. UV/oxone降解水中甲氧苄啶的效能及模型评价[J]. 化工进展, 2019, 38(11): 4825-4830.

Juxiang CHEN,Mengwen ZHANG,Jing YANG,Naiyun GAO. Degradation effect and model evaluation of trimethoprim by UV/oxone[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4825-4830.

图/表 10

参考文献 18

1	郑虎 . 药物化学[M]. 4版. 北京: 人民出版社, 2000.
	ZHENG Hu . Pharmaceutical chemistry [M]. 4th ed. Beijing: People's Publishing House, 2000.
2	Qian SUI , WANG Bin , ZHAO Wentao , et al . Identification of priority pharmaceuticals in the water environment of China [J]. Chemosphere, 2012, 89(3): 280-286.
3	ZHANG Ruochun , YANG Yongkui , HUANG Ching-Hua , et al . UV/H₂O₂ and UV/PDS treatment of trimethoprim and sulfamethoxazole in synthetic human urine: transformation products and toxicity [J]. Environmental Science & Technology, 2016, 50(5): 2573-83.
4	古振川, 高乃云, 安娜, 等 . Cl^-/PMS体系降解甲氧苄啶的效能与机理[J]. 中国环境科学, 2018, 38(3): 977-984.
	GU Zhenchuan , GAO Naiyun , AN Na , et al . Efficiency and mechanism of trimethoprim degradationin Cl^-/PMS system [J]. China Environmental Science, 2018, 38(3): 977-984.
5	XIONG Yiying , MELCHING C S . Comparison of kinematic-wave and nonlinear reservoir routing of urban watershed runoff [J]. Journal of Hydrologic Engineering, 2005, 10(1): 39-49.
6	WONG M K , CHAN T C , CHAN W Y , et al . Dioxiranes generated in situ from pyruvates and oxone as environmentally friendly oxidizing agents for disinfection [J]. Environmental Science & Technology, 2006, 40(2): 625-630.
7	LIU Qun , ZHENG Zheng , YANG Xiaoying , et al . Effect of factors on decolorization of azo dye methyl orange by oxone/natural sunlight in aqueous solution [J]. Environmental Science and Pollution Research, 2012, 19: 577-584.
8	刘卫艳 . 一种新型过氧化物消毒剂在游泳池水消毒中的应用[J]. 中国消毒学杂志, 2016, 33(6): 533-536.
	LIU Weiyan . Application of potassium monopersulfate in swimming pool disinfection [J]. Chinese Journal of Disinfection, 2016, 33(6): 533-536.
9	WU Zihao , FANG Jingyun , XIANG Yingying , et al . Roles of reactive chlorine species in trimethoprim degradation in the UV/chlorine process: kinetics and transformation pathways [J]. Water Research, 2016, 104: 272-282.
10	BAEZA C , KNAPPE D R U . Transformation kinetics of biochemically active compounds in low-pressure UV photolysis and UV/H₂O₂ advanced oxidation processes [J]. Water Research, 2011, 45(15): 4531-4543.
11	古振川, 高乃云, 陈菊香, 等 . 单过硫酸氢钾复合粉降解水中甲氧苄啶的效能与机理[J]. 净水技术, 2018, 37(2): 17-23.
	GU Zhenchuan , GAO Naiyun , CHEN Juxiang , et al . Efficiency and mechanism of trimethoprim degradation by oxone in aqueous solution [J]. Water Purification Technology, 2018, 37(2): 17-23.
12	徐蕾, 袁瑞霞, 郭耀广, 等 . 氯离子对钴/单过氧硫酸盐体系降解2,4,6-三氯苯酚的影响[J]. 武汉大学学报(理学版), 2013, 59(1): 51-56.
	XU Lei , YUAN Ruixia , GUO Yaoguang , et al . Effects of chloride ions on degradation of 2,4,6-trichlorophenol by Co(Ⅱ)/peroxymonosulfate(Co/PMS) system [J]. Journal of Wuhan University (Natural Science Edition), 2013, 59(1): 51-56.
13	WANG Zhaohui , YUAN Ruixia , GUO Yaoguang , et al . Effects of chloride ions on bleaching of azo dyes by Co²⁺/oxone regent : kinetic analysis [J]. Journal of Hazardous Materials, 2011, 190(13): 1083-1087.
14	PI Yunqing , FENG Jinglan , SUN Jingyu , et al . Facile, effective, and environment-friendly degradation of sulfamonomethoxine in aqueous solution with the aid of a UV/oxone oxidative process [J]. Environmental Science and Pollution Research, 2013, 20(12): 8621-8628.
15	NETA P , HUIE R E , ROSS A B . Rate constants for reactions of inorganic radicals in aqueous solution [J]. Journal of Physical and Chemical Reference Data, 1988, 17(3): 1027-1284.
16	吴海, 牟玉静, 张晓山, 等 . 相对速率法测OH•自由基与几种低碳醇的反应速率常数[J]. 环境科学学报, 2001, 21(5): 525-529.
	WU Hai , MU Yujing , ZHANG Xiaoshan , et al . Rate constants for reactions of hydroxyl radicals with a series of alcohols by relative rate method [J]. Acta Scientiae Circumstantiae, 2001, 21(5): 525-529.
17	YUAN Wenjuan , CHENG Juan , HUANG Hexiang , et al . Optimization of cadmium biosorption by Shewanella putrefacie ns using a Box-Behnken design[J]. Ecotoxicology and Environmental Safety, 2019, 175: 138-147.
18	JAMES R B , KEITH G B , WILLIAM T , et al . Figures-of-Merit for the technical development and application of advanced oxidation technologies for both electric-and solar-driven systems (IUPAC technical report)[J]. Pure and Applied Chemistry, 2013, 73(4): 627-637.

水源	HCO₃ ^-/mg·L^-1	Cl^-/mg·L^-1	NO₃ ^-/mg·L^-1	pH
超纯水	0	0	0	7.0±0.02
横山水库	134.0±8	63.1±0.4	0.07±0.02	7.6±0.21
锡东水厂	136.5±4	42.5±4.0	0.03±0.02	7.2±0.30
西氿水库	129.0±3	51.0±4.0	0.07±0.01	7.3±0.12

水源	HCO₃ ^-/mg·L^-1	Cl^-/mg·L^-1	NO₃ ^-/mg·L^-1	pH
超纯水	0	0	0	7.0±0.02
横山水库	134.0±8	63.1±0.4	0.07±0.02	7.6±0.21
锡东水厂	136.5±4	42.5±4.0	0.03±0.02	7.2±0.30
西氿水库	129.0±3	51.0±4.0	0.07±0.01	7.3±0.12

项目	Analysis of variance
项目	平方和	自由度	均方和	F值	p值	显著性
模型	627.08	14	44.79	10.23	<0.0001	显著
X ₁	3.45	1	3.45	0.79	0.3900
X ₂	4.25	1	4.25	0.97	0.3413
X ₃	21.60	1	21.60	4.93	0.0433
X ₄	110.72	1	110.72	25.29	0.0002
X ₁ X ₂	27.51	1	27.51	6.28	0.0251
X ₁ X ₃	4.67	1	4.67	1.07	0.3194
X ₁ X ₄	73.10	1	73.10	16.70	0.0011
X ₂ X ₃	129.05	1	129.05	29.48	<0.0001
X ₂ X ₄	18.97	1	18.97	4.33	0.0562
X ₃ X ₄	23.43	1	23.43	5.35	0.0364
X ₁ ²	2.64	1	2.64	0.60	0.4504
X ₂ ²	92.89	1	92.89	21.22	0.0004
X ₃ ²	1.47	1	1.47	0.34	0.5710
X ₄ ²	75.30	1	75.30	17.20	0.0010
残差	61.29	14	4.38
失拟项	22.44	10	2.24	0.23	0.9726	不显著
纯误差	38.86	4	9.71
总离差	688.38	28

项目	Analysis of variance
项目	平方和	自由度	均方和	F值	p值	显著性
模型	627.08	14	44.79	10.23	<0.0001	显著
X ₁	3.45	1	3.45	0.79	0.3900
X ₂	4.25	1	4.25	0.97	0.3413
X ₃	21.60	1	21.60	4.93	0.0433
X ₄	110.72	1	110.72	25.29	0.0002
X ₁ X ₂	27.51	1	27.51	6.28	0.0251
X ₁ X ₃	4.67	1	4.67	1.07	0.3194
X ₁ X ₄	73.10	1	73.10	16.70	0.0011
X ₂ X ₃	129.05	1	129.05	29.48	<0.0001
X ₂ X ₄	18.97	1	18.97	4.33	0.0562
X ₃ X ₄	23.43	1	23.43	5.35	0.0364
X ₁ ²	2.64	1	2.64	0.60	0.4504
X ₂ ²	92.89	1	92.89	21.22	0.0004
X ₃ ²	1.47	1	1.47	0.34	0.5710
X ₄ ²	75.30	1	75.30	17.20	0.0010
残差	61.29	14	4.38
失拟项	22.44	10	2.24	0.23	0.9726	不显著
纯误差	38.86	4	9.71
总离差	688.38	28

系统	P/kW	V/m³	k/min^-1	EE/O₁	M _W	cost₁	cost₂	EE/O₂	EE/O
UV/oxone	1.71×10^-5	1×10^-4	0.1768	16.11	614.76	0.003	0.03	0.05	16.16
UV	1.71×10^-5	1×10^-4	0.004	712.5	0	0	0	0	712.5
oxone	0	0	0.0664	0	614.76	0.012	0.12	0.20	0.20