芬顿氧化法对利福平制药废水中溶解性有机物的催化降解

doi:10.11949/0438-1157.20230044

摘要/Abstract

摘要：

采用芬顿技术(Fe²⁺/H₂O₂)处理实际抗生素(利福平)废水，探究溶液初始pH、反应时间、亚铁离子浓度和氧化剂浓度对降解效果的影响。采用同步荧光光谱结合二维相关光谱分析利福平废水中溶解性有机物(DOM)荧光组分的变化特性。结果表明，当pH为3、H₂O₂浓度为1.4 ml·L^-1、硫酸亚铁浓度为0.5 g·L^-1时反应180 min，废水COD降解率可达到73.29%，TOC降解率达到82.51%。利福平制药废水中类蛋白(PLF)、类富里酸(FLF)、类腐殖酸(HLF)和陆源类腐殖质(THLF)降解率分别可达到93%、90%、83%和65%左右。二维相关光谱分析表明，315 nm处类富里酸物质对Fenton氧化更为敏感，且能够优先被降解。BMG动力学模型对实验数据拟合最佳，其相关系数在0.99以上，且Peak₃₁₅的初始反应速率最快。自由基猝灭实验和EPR实验证实了反应过程中产生的·OH为氧化反应的主要活性物质。

关键词: 芬顿氧化法, 化学反应, 氧化, 利福平, 同步荧光, 动力学

Abstract:

In this study, Fenton technology (Fe²⁺/H₂O₂) was used to treat the actual antibiotic (rifampicin) wastewater, and the effects of initial pH of solution, reaction time, concentration of ferrous ions and oxidant on the degradation performance were explored. Synchronous fluorescence spectra (SFS) combined with two-dimensional correlation spectroscopy (2D-COS) was used to analyze the fluorescence characteristics of dissolved organic matter (DOM) in rifampicin wastewater. The results showed that when the pH was 3, the concentration of H₂O₂ was 1.4 ml·L^-1, and the concentration of ferrous sulfate was 0.5 g·L^-1, the degradation rate of COD and TOC in wastewater could reach 73.29% and 82.51% after reaction for 180 min. Meanwhile, the degradation rates of protein-like (PLF), fulvic-like (FLF), humic-like (HLF) and terrestrial humic-like fluorescence (THLF) in rifampicin pharmaceutical wastewater were about 93%, 90%, 83% and 65%, respectively. The result of 2D-COS analysis indicates that fulvic-like substances at 315 nm are more susceptible to the Fenton oxidation system, which can be preferentially degraded. BMG kinetic model has the best fitting effect on experimental data, and its correlation coefficient is above 0.99. The result also suggests the highest reaction rate for the degradation of fulvic-like substances at 315 nm. There is no distinct change in pH during the oxidation reaction. Free radical capture and EPR experiments confirmed that ·OH produced during the reaction was the main active substance.

Key words: Fenton oxidation, chemical reaction, oxidation, rifampicin, synchronous fluorescence, kinetics

中图分类号:

X 703

张全碧, 羊依金, 郭旭晶. 芬顿氧化法对利福平制药废水中溶解性有机物的催化降解[J]. 化工学报, 2023, 74(5): 2217-2227.

Quanbi ZHANG, Yijin YANG, Xujing GUO. Catalytic degradation of dissolved organic matter in rifampicin pharmaceutical wastewater by Fenton oxidation process[J]. CIESC Journal, 2023, 74(5): 2217-2227.

图/表 14

表1 水质指标参数

Table 1 Water quality parameters

名称	利福平/ (mg·L^-1)	pH	COD_Cr/ (mg·L^-1)	BOD₅/ (mg·L^-1)	SS/ (mg·L^-1)	色度
利福平废水	10~20	6.8	90.02	21.55	7.63	10倍

表2 降解实验设计

Table 2 Degradation experimental design

影响因素	实验设计
反应时间/min	10、20、30、60、120、180、240、300
pH	1、2、3、4、5、6、7
硫酸亚铁浓度/(g·L^-1)	0.2、0.3、0.4、0.5、0.6
H₂O₂浓度/(ml·L^-1)	0.8、1.1、1.4、1.7、2.0

图1 Fe2+/H2O2体系中不同实验条件下利福平的降解效果

Fig.1 Degradation effect of rifampicin by Fe2+/H2O2 systems at different experimental conditions

图2 Fe2+/H2O2体系中COD和TOC与时间的关系

Fig.2 Relationship between COD， TOC and time in Fe2+/H2O2 system

图3 同步荧光光谱图（Δλ=30 nm）

Fig.3 Synchronous fluorescence spectrogram (Δλ=30 nm)

图4 Fe2+/H2O2体系中荧光物质与时间关系

Fig.4 Relationship between fluorescent substance and time in Fe2+/H2O2 system

图5 同步相关谱图和异步相关谱图（白色为正，灰色为负）

Fig.5 Synchronous map and asynchronous map （the white regions represent positive correlations, whereas the grey regions represent negative correlations）

表3 各峰荧光强度与COD的相关关系

Table 3 Correlation between fluorescence intensity of each peak and COD

相关系数	Peak₂₇₅	Peak₃₁₅	Peak₃₆₅	Peak₄₀₀	Peak₄₆₀	Peak₄₇₃	Peak₅₀₀	Peak₅₆₇
R²	0.1967	0.4288	0.9084	0.9779	0.9111	0.8781	0.7801	0.5312

图6 COD降解动力学曲线[(a)~(c)]和TOC降解动力学曲线[(d)~(f)]

Fig.6 The degradation kinetics curve of COD [(a)—(c)] and TOC [(d)—(f)]

图7 荧光物质降解动力学曲线

Fig.7 The degradation kinetics curve of fluorescent substance

表4 荧光物质降解动力学拟合

Table 4 The degradation kinetics of fluorescent substance

各峰	1级		2级		BMG
各峰	k₁/min^-1	R²	k₂/(10^-6min^-1)	R²	1/b	1/m	R²
Peak₂₇₅	0.0047	0.1265	6.8503	0.2509	0.9095	1.5805	0.9991
Peak₃₁₅	0.0061	0.2880	2.5344	0.5008	0.9500	1.7687	0.9993
Peak₃₆₅	0.0052	0.3974	2.0935	0.6367	0.8925	0.5964	0.9996
Peak₄₀₀	0.0059	0.3954	1.6718	0.6847	0.9233	0.7703	0.9999
Peak₄₆₀	0.0056	0.3576	1.5457	0.6429	0.9217	0.8450	0.9999
Peak₄₇₃	0.0052	0.2348	2.7397	0.5437	0.9095	0.8013	0.9999
Peak₅₀₀	0.0038	0.3283	0.8610	0.5207	0.8389	0.5456	0.9999
Peak₅₆₇	0.0026	0.4143	0.7464	0.5401	0.6637	0.1770	0.9992

图8 反应中溶液pH、Fe2+和总铁浓度随时间的变化

Fig.8 Changes of pH, Fe2+, and total Fe over time in the reaction

图9 反应中H2O2浓度随时间的变化及其分解动力学

Fig.9 Changes of H2O2 concentration over time in the reaction and thermal decomposition kinetics

图10 EPR谱图和自由基猝灭实验结果

Fig.10 EPR spectrogram and free radical quenching experiment

参考文献 29

1	杨娜. 生化处理利福平抗生素制药废水的实验研究[D]. 沈阳: 东北大学, 2009.
	Yang N. Treatment of experimental study on biochemical rifampicin antibiotic wastewater[D]. Shenyang: Northeastern University, 2009.
2	Shafaati M, Miralinaghi M, Shirazi R H S M, et al. The use of chitosan/Fe₃O₄ grafted graphene oxide for effective adsorption of rifampicin from water samples[J]. Research on Chemical Intermediates, 2020, 46(12): 5231-5254.
3	Rodrigues-Silva F, Masceno G P, Panicio P P, et al. Removal of micropollutants by UASB reactor and post-treatment by Fenton and photo-Fenton: matrix effect and toxicity responses[J]. Environmental Research, 2022, 212: 113396.
4	迟春娟, 付月彪, 张嗣炯. 利福平废水的絮凝和生化处理研究[J]. 环境污染治理技术与设备, 2000(2): 17-20.
	Chi C J, Fu Y B, Zhang S J. Research of flocculant and biochemical treatment of rifampin wastewater[J]. Technigues and Equipments for Environmental Pollution Control, 2000(2): 17-20.
5	Kais H, Yeddou Mezenner N, Trari M. Biosorption of rifampicin from wastewater using cocoa shells product[J]. Separation Science and Technology, 2020, 55(11): 1984-1993.
6	Cai W L, Weng X L, Chen Z L. Highly efficient removal of antibiotic rifampicin from aqueous solution using green synthesis of recyclable nano-Fe₃O₄ [J]. Environmental Pollution, 2019, 247: 839-846.
7	许征宇, 陈洁, 余进. 高级氧化技术在污水处理中的应用及研究进展[J]. 中国资源综合利用, 2020, 38(10): 112-114.
	Xu Z Y, Chen J, Yu J. Application and research progress of advanced oxidation technology in sewage treatment[J]. China Resources Comprehensive Utilization, 2020, 38(10): 112-114.
8	Dang Thi Ngoc T, Thi H N, Nguyen Duc D, et al. Preparation and photocatalytic characterization of modified nano TiO₂/Nd/rice husk ash material for rifampicin removal in aqueous solution[J]. Journal of Analytical Methods in Chemistry, 2022, 2022: 2084906.
9	Duarte F D S, Melo A L M D S, Ferro A B, et al. Magnetic zinc oxide/manganese ferrite composite for photodegradation of the antibiotic rifampicin[J]. Materials, 2022, 15(22): 8185.
10	Ebratkhahan M, Zarei M, Zaier Akpinar I, et al. One-pot synthesis of graphene hydrogel/M (M: Cu, Co, Ni) nanocomposites as cathodes for electrochemical removal of rifampicin from polluted water[J]. Environmental Research, 2022, 214: 113789.
11	Liu L J, Xu Q Y, Owens G, et al. Fenton-oxidation of rifampicin via a green synthesized rGO@nFe/Pd nanocomposite[J]. Journal of Hazardous Materials, 2021, 402: 123544.
12	da Silva Duarte J L, Solano A M S, Arguelho M L P M, et al. Evaluation of treatment of effluents contaminated with rifampicin by Fenton, electrochemical and associated processes[J]. Journal of Water Process Engineering, 2018, 22: 250-257.
13	Yu H B, Song Y H, Tu X, et al. Assessing removal efficiency of dissolved organic matter in wastewater treatment using fluorescence excitation emission matrices with parallel factor analysis and second derivative synchronous fluorescence[J]. Bioresource Technology, 2013, 144: 595-601.
14	于本心, 张广彩, 孙迎雪. 应用二维相关同步荧光光谱研究市政污水中溶解性有机物组分[J]. 环境污染与防治, 2021, 43(6): 704-707.
	Yu B X, Zhang G C, Sun Y X. Applying tow-dimensional correlation synchronous fluorescence spectroscopy to study DOM fractions in municipal sewage[J]. Environmental Pollution & Control, 2021, 43(6): 704-707.
15	中华人民共和国环境保护部. 水质　化学需氧量的测定　重铬酸盐法: [S]. 北京: 中国环境出版社, 2017.
	Ministry of Environmental Protection of the People’s Republic of China. Water quality—Determination of the chemical oxygen demand—Dichromate method: [S]. Beijing: China Environmental Science Press, 2017.
16	国家环境保护总局. 水质　铁的测定　邻菲啰啉分光光度法(试行): [S]. 北京: 中国环境科学出版社, 2007.
	State Environmental Protection Administration. Water quality—Determination of iron—Phenanthroline spectrophotometry: [S]. Beijing: China Environmental Science Press, 2007.
17	黄燕, 杨永远, 杨湘智, 等. 钛盐光度法测定Fenton体系中过氧化氢浓度的试验研究[J]. 化工管理, 2020(15): 22-23.
	Huang Y, Yang Y Y, Yang X Z, et al. Experimental study on determination of hydrogen peroxide concentration in Fenton system by titanium salt spectrophotometry[J]. Chemical Enterprise Management, 2020(15): 22-23.
18	Tunç S, Duman O, Gürkan T. Monitoring the decolorization of acid orange 8 and acid red 44 from aqueous solution using Fenton’s reagents by online spectrophotometric method: effect of operation parameters and kinetic study[J]. Industrial & Engineering Chemistry Research, 2013, 52(4): 1414-1425.
19	吴锡峰, 杨恺. 芬顿氧化法对抗生素废水深度处理的实验研究[J]. 海峡科学, 2017(1): 19-21.
	Wu X F, Yang K. Experimental study on advanced treatment of antibiotic wastewater by Fenton oxidation[J]. Straits Science, 2017(1): 19-21.
20	赵云, 王丽萍, 何士龙, 等. Fenton试剂氧化对硝基酚中氧化还原电位的变化规律[J]. 环境污染与防治, 2011, 33(4): 58-61, 65.
	Zhao Y, Wang L P, He S L, et al. Variation of ORP during p-nitrophenol degradation by Fenton oxidation process[J]. Environmental Pollution & Control, 2011, 33(4): 58-61, 65.
21	徐祺琪, 陈维芳, 沈晓慧, 等. Fenton高级氧化技术去除水中有机污染物2-MIB的影响因素研究[J]. 水资源与水工程学报, 2014, 25(2): 158-161.
	Xu Q Q, Chen W F, Shen X H, et al. Study on factors affecting removal of organic pollutant 2-MIB in water by using Fenton advanced oxidation process[J]. Journal of Water Resources and Water Engineering, 2014, 25(2): 158-161.
22	郭旭晶, 彭涛, 王月, 等. 湖泊沉积物孔隙水溶解性有机质组成与光谱特性[J]. 环境化学, 2013, 32(1): 79-84.
	Guo X J, Peng T, Wang Y, et al. Study on the composition and spectral properties of dissolved organic matter extracted from lake sediment pore water in lake[J]. Environmental Chemistry, 2013, 32(1): 79-84.
23	Chen W, Habibul N, Liu X Y, et al. FTIR and synchronous fluorescence heterospectral two-dimensional correlation analyses on the binding characteristics of copper onto dissolved organic matter[J]. Environmental Science & Technology, 2015, 49(4): 2052-2058.
24	吴正龙. 腐殖质荧光及表面增强拉曼散射光谱分析[J]. 实验室研究与探索, 2011, 30(11): 227-230.
	Wu Z L. Fluorescence and SERS spectral analyses of humic substances[J]. Research and Exploration in Laboratory, 2011, 30(11): 227-230.
25	Hur J, Jung K Y, Jung Y M. Characterization of spectral responses of humic substances upon UV irradiation using two-dimensional correlation spectroscopy[J]. Water Research, 2011, 45(9): 2965-2974.
26	Weishaar J L, Aiken G R, Bergamaschi B A, et al. Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon[J]. Environmental Science & Technology, 2003, 37(20): 4702-4708.
27	宋凡浩, 栗婷婷, 张进, 等. 二维相关荧光光谱探究土壤富里酸亚组分的质子键合多相性[J]. 光谱学与光谱分析, 2019, 39(10): 3071-3077.
	Song F H, Li T T, Zhang J, et al. Proton binding heterogeneity in soil fulvic acid sub-fractions using two-dimensional correlation fluorescence spectrometry[J]. Spectroscopy and Spectral Analysis, 2019, 39(10): 3071-3077.
28	Noda I. Close-up view on the inner workings of two-dimensional correlation spectroscopy[J]. Vibrational Spectroscopy, 2012, 60: 146-153.
29	An S F, Zhang G H, Wang T W, et al. High-density ultra-small clusters and single-atom Fe sites embedded in graphitic carbon nitride (g-C₃N₄) for highly efficient catalytic advanced oxidation processes[J]. ACS Nano, 2018, 12(9): 9441-9450.

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