Catalytic degradation of dissolved organic matter in rifampicin pharmaceutical wastewater by Fenton oxidation process

doi:10.11949/0438-1157.20230044

Abstract

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

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

CLC Number:

X 703

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.

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.

Figures/Tables 14

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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

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

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

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

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