高铁酸盐耦合过氧乙酸深度处理水中甲硝唑的特性研究

doi:10.19965/j.cnki.iwt.2023-0344

摘要/Abstract

摘要：

甲硝唑（MNZ）是一种硝基咪唑类抗生素，在环境中易积累且代谢产物具有潜在的致癌、致突变性。研究了高铁酸盐/过氧乙酸〔Fe（Ⅵ）/PAA〕耦合技术深度处理水中MNZ的特性，模拟了MNZ在废水中的降解，并深入研究其反应机理。在Fe（Ⅵ）/PAA体系下，pH为8，Fe（Ⅵ）、PAA投加浓度分别为500、100 μmol/L，反应时间为60 min时MNZ的降解率可达94.85%，且降解过程遵循伪一级动力学。变量试验表明，MNZ的降解与Fe（Ⅵ）和PAA的投加量呈正相关，且在pH=8时达到最佳效果。水基质中的氯离子（Cl^-）和硝酸根离子（NO₃ ^-）对MNZ降解的影响较小，铵盐（NH₄ ⁺）能促进MNZ的降解，而碳酸氢根离子（HCO₃ ^-）和腐殖酸（HA）则抑制MNZ的降解。Fe（Ⅵ）/PAA体系对模拟医疗废水中MNZ降解与在超纯水中的降解效果相似，可以达到较好的去除效果。探针实验和猝灭实验表明，该体系的主要活性物种是Fe（Ⅳ）/Fe（Ⅴ），PAA溶液中的H₂O₂是Fe（Ⅵ）的主要活化剂，PAA对活性物种去除MNZ起加速作用。该结果有望为Fe（Ⅵ）/PAA体系应用于医疗废水中深度处理MNZ提供理论参考和数据支撑。

关键词: 甲硝唑, 高铁酸盐, 过氧乙酸, 降解动力学, 高级氧化

Abstract:

Metronidazole(MNZ), prone to accumulate in the environment, is a nitroimidazole antibiotic and its metabolites have potential carcinogenicity and mutagenicity. In this paper, the degradation characteristics of MNZ by coupled ferrate/peroxyacetic acid〔Fe(Ⅵ)/PAA〕technology, as well as the simulation of MNZ degradation and reaction mechanism, were investigated. When the dosages of Fe(Ⅵ) as 500 μmol/L and PAA as 100 μmol/L, the degradation of MNZ reached 94.85% at pH of 8 in 60 min, and the degradation process followed pseudo-first-order kinetics. Variable experiments showed that the degradation of MNZ was positively correlated with the dosage of Fe(Ⅵ) and PAA, and the best effect was achieved at pH=8. Chloride (Cl^-) and nitrate (NO₃ ^-) in the water matrix had little effect on the degradation of MNZ. Ammonium salt (NH₄ ⁺) could promote the degradation of MNZ,while bicarbonate (HCO₃ ^-) and humic acid (HA) inhibited the degradation. The removal of MNZ in simulated medical wastewater by Fe(Ⅳ)/PAA was similar to that in ultra-pure water, which could achieve better removal effect. Probe experiments and quenching experiments showed that PAA accelerated the removal of MNZ from active species. H₂O₂ coexisting with PAA was the main activator of Fe(Ⅵ) while the main active species of Fe(Ⅵ)/PAA system were Fe(V) and Fe(Ⅳ). The results were expected to provide theoretical reference and data support for the application of Fe(Ⅵ)/PAA system in the deep treatment of MNZ in medical wastewater.

Key words: metronidazole, ferrate(Ⅵ), peracetic acid, degradation kinetics, advanced oxidation processes

中图分类号:

X703.1

商伟伟, 杨焱, 沈芸, 赵世荣, 薛罡, 钱雅洁. 高铁酸盐耦合过氧乙酸深度处理水中甲硝唑的特性研究[J]. 工业水处理, 2024, 44(5): 111-119.

Weiwei SHANG, Yan YANG, Yun SHEN, Shirong ZHAO, Gang XUE, Yajie QIAN. Study on characteristics of ferrate coupled peracetic acid for advanced treatment of metronidazole in water[J]. Industrial Water Treatment, 2024, 44(5): 111-119.

https://www.iwt.cn/CN/Y2024/V44/I5/111

图/表 14

表1 各目标污染物测试参数

Table 1 Test parameters of target pollutants

目标污染物	流量/（mL·min^-1）	流动相（V _乙腈∶V _水）	进样量/μL	波长/nm	柱温/℃
MNZ	1	20∶80	10	316	35
PMSO	1	20∶80	60	230	35
PMSO₂	1	20∶80	60	268	35
BA	1	20∶80	100	257	35

图1 不同降解体系对MNZ的降解效果

Fig.1 The degradation effect of different system on MNZ

图2 Fe（Ⅵ）浓度对Fe（Ⅵ）/PAA体系中MNZ降解的影响

Fig.2 Effect of Fe（Ⅵ） concentration on MNZ degradation in Fe（Ⅵ）/PAA system

图3 PAA浓度对Fe（Ⅵ）/PAA体系中MNZ降解的影响

Fig.3 Effect of PAA concentration on MNZ degradation in Fe（Ⅵ）/PAA system

图4 pH对Fe（Ⅵ）/PAA体系中MNZ降解的影响

Fig.4 Effect of pH on MNZ degradation in Fe（Ⅵ）/PAA system

图5 Cl^-、HCO₃ ^-、NO₃ ^-、NH₄ ⁺和HA对Fe（Ⅵ）/PAA体系中MNZ降解的影响

Fig.5 Effects of chloride，bicarbonate，nitrate ammonium，and HA on MNZ removal by Fe（Ⅵ）/PAA

表2 模拟医院废水组分

Table 2 Components of simulated hospital wastewater

组分	NaCl	NH₄Cl	NaHCO₃	KCl	Na₂HPO₄	CaCl₂·2H₂O	尿素
浓度/（mmol·L^-1）	51.3	0.94	1.19	1.34	0.32	0.34	21

图6 MNZ在模拟医疗废水中的降解

Fig.6 MNZ degradation in simulated medical wastewater

图7 PMSO在UV/PAA系统中的降解

Fig.7 Degradation of PMSO by UV/PAA

图8 PMSO和PMSO₂在Fe（Ⅵ）/PAA系统中的浓度变化

Fig.8 Changes of PMSO and PMSO₂ concentrations in Fe（Ⅵ）/PAA system

图9 BA在UV/PAA系统中的降解

Fig.9 Degradation of BA by UV/PAA

图10 BA在Fe（Ⅵ）/PAA系统中的降解

Fig.10 Degradation of BA by Fe（Ⅵ）/PAA

图11 PAA和/或H₂O₂存在的情况下Fe（Ⅵ）的降解

Fig.11 Degradation of Fe（Ⅵ） in the presence of PAA and/or H₂O₂

图12 PAA和H₂O₂对Fe（Ⅵ）/HSO₃ ^-体系去除MNZ和PMSO的影响

Fig.12 Impacts of PAA and H₂O₂ on MNZ and PMSO removal by the Fe（Ⅵ）/HSO₃ ^- system

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