碱催化过氧化氢体系降解四环素的作用规律与机制解析

doi:10.11949/0438-1157.20240268

化工学报

• •

碱催化过氧化氢体系降解四环素的作用规律与机制解析

寇梦瑶¹^,²(), 郑芳菲¹^,², 胥雯¹^,², 郭娜³, 廖兵¹^,²^,³()

^1.成都理工大学地质灾害防治与地质环境保护国家重点实验室，四川成都 610059
^2.成都理工大学生态环境学院，国家环境保护水土污染协同控制与联合修复重点实验室，四川成都 610059
^3.四川建筑职业技术学院，四川省城市污泥建材资源化利用工程研究中心，四川德阳 618000

收稿日期:2024-03-05 修回日期:2024-04-20 出版日期:2024-04-22
通讯作者: 廖兵
作者简介:寇梦瑶（2000—），女，硕士研究生，koumengyao10@163.com
基金资助:
国家自然科学基金项目(42007168);四川省自然科学基金面上项目(2023NSFSC0292)

Determination of tetracycline degradation by alkali-catalyzed hydrogen peroxide system: law of action and mechanism analysis

Mengyao KOU¹^,²(), Fangfei ZHENG¹^,², Wen XU¹^,², Na GUO³, Bing LIAO¹^,²^,³()

^1.State Key Laboratory of Geohazard Prevention and Geoenvironment Protection, Chengdu University of Technology, Chengdu 610059, Sichuan, China
^2.State Environmental Protection Key Laboratory of Synergetic Control and Joint Remediation for Soil & Water Pollution, College of Ecology and Environment, Chengdu University of Technology, Chengdu 610059, Sichuan, China
^3.Sichuan College of Architectural Technology, Sichuan Engineering Research Center for Resource Utilization of Municipal Sludge for BuildingMaterials, Deyang 618000, Sichuan, China

Received:2024-03-05 Revised:2024-04-20 Online:2024-04-22
Contact: Bing LIAO

摘要/Abstract

摘要：

在碱催化过氧化氢降解污染物时，不同的碱催化剂催化过氧化氢降解污染物的作用机制有所不同。研究选取了氢氧化钠、碳酸钠、碳酸氢钠、磷酸氢二钠作为不同的碱催化剂，以四环素作为目标污染物，探究碱催化过氧化氢体系降解四环素的作用规律与机制。考察了pH、四环素浓度、H₂O₂浓度、缓冲物质投加量、缓冲物质种类、预反应时间对四环素降解效果的影响。结果表明：pH对四环素降解效果影响最为显著，在pH为10.0~10.5时效果最佳，其余影响因素在本文研究的梯度范围内未产生显著影响。同时发现不同碱催化过氧化氢体系的pH在反应过程中的变化趋势不同，在其他体系中，随反应进行pH值不断降低，而在NaHCO₃-H₂O₂体系降解四环素的过程中，pH值不断升高，经过碳转换机制分析推测该现象是由HCO₄^-产生过程造成的。四环素的降解分为脱色与矿化两个过程：自由基淬灭实验证明其对四环素脱色过程贡献度不高。后CO₂通入实验证实HCO₄^-不氧化四环素，四环素脱色的主要作用物质是HO₂^-。通过对NaOH-H₂O₂体系与NaHCO₃-H₂O₂体系的TOC检测结果对比，发现NaOH-H₂O₂体系的矿化度高于NaHCO₃-H₂O₂体系，分析EPR电子顺磁共振实验发现NaOH-H₂O₂体系中·OH与O₂·^-信号高于NaHCO₃-H₂O₂体系，矿化过程中自由基是主要氧化物。

关键词: 四环素, 碳酸氢盐, 过氧化氢, 碱催化, 作用机制

Abstract:

When pollutants are degraded by alkali-catalyzed hydrogen peroxide system, different alkali catalysts have different mechanisms for catalyzing hydrogen peroxide to degrade pollutants. Sodium hydroxide, sodium carbonate, sodium bicarbonate, and disodium phosphate dodecahydrate were selected as different alkali catalysts in the study, and tetracycline was used as the target pollutant to investigate the law of action and mechanism of tetracycline degradation by alkali-catalyzed hydrogen peroxide system. The effects of pH, tetracycline concentration, H₂O₂ concentration, buffer substance dosage, buffer substance type and pre-reaction time on the degradation of tetracycline were investigated. The results showed that pH had the most significant effect on the degradation effect of tetracycline, with the best effect at pH 10.0-10.5, and the rest of the influencing factors did not produce significant effects within the gradient range studied in this paper. Meanwhile, it was found that the pH of different alkali-catalyzed hydrogen peroxide systems had different trends during the reaction process. In other systems, the pH value decreased continuously as the reaction proceeded, while the pH value increased continuously during the degradation of tetracycline in the NaHCO₃-H₂O₂ system, and it was speculated that this phenomenon was caused by the process of HCO₄^- production after the analysis of the carbon conversion mechanism. The degradation of tetracycline was divided into two processes, decolorization and mineralization: free radical quenching experiments proved that free radicals did not contribute much to the decolorization process of tetracycline. Post-CO₂ flux experiments confirmed that HCO₄^- does not oxidize tetracycline and that the main acting substance in tetracycline decolorization is HO₂^-. By comparing the TOC test results of NaOH-H₂O₂ system and NaHCO₃-H₂O₂ system, it was found that the mineralization degree of NaOH-H₂O₂ system was higher than that of NaHCO₃-H₂O₂ system, and the analysis of EPR electron paramagnetic resonance experiments revealed that the signals of ·OH and O₂·^- in the NaOH-H₂O₂ system were higher than that of the NaHCO₃-H₂O₂ system, and that mineralization process of free radicals are the main oxides.

Key words: tetracycline, bicarbonate, hydrogen peroxide, alkaline catalytic, mechanism of action

中图分类号:

X 52

寇梦瑶, 郑芳菲, 胥雯, 郭娜, 廖兵. 碱催化过氧化氢体系降解四环素的作用规律与机制解析[J]. 化工学报, DOI: 10.11949/0438-1157.20240268.

Mengyao KOU, Fangfei ZHENG, Wen XU, Na GUO, Bing LIAO. Determination of tetracycline degradation by alkali-catalyzed hydrogen peroxide system: law of action and mechanism analysis[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240268.

图/表 16

图1 四环素溶液的全波长扫描谱线

Fig.1 Full wavelength scanning spectral lines of tetracycline solution

图2 不同pH对四环素降解效果的影响

Fig.2 Effect of different pH on degradation of tetracycline

图3 不同四环素盐酸盐浓度下的降解曲线

Fig.3 Degradation curves of tetracycline hydrochloride at different concentrations

图4 不同过氧化氢浓度对四环素降解效果的影响（初始pH=12±0.3，不含缓冲物）

Fig.4 Effect of different hydrogen peroxide concentrations on degradation of tetracycline (Initial pH = 12±0.3 without buffer)

图5 不同缓冲物质投加量对四环素降解效果的影响

Fig.5 Effects of different amounts of buffer substances on degradation of tetracycline

图6 缓冲物质种类对降解效果的影响

Fig.6 Effect of buffer substances on degradation effect

图7 预反应时间对降解效果的影响

Fig.7 Effect of pre-reaction time on degradation effect

图8 碱催化体系中溶液的EPR谱图

Fig.8 EPR spectra of solution in alkali catalytic system

图9 自由基淬灭试验中四环素的降解情况

Fig.9 Degradation of tetracycline in free radical quenching test

图10 四环素去除过程中的TOC去除率

Fig.10 TOC removal rate in tetracycline removal

图11 对碱催化过氧化氢降解反应通入CO2的效果对比

Fig.11 Comparison of the effects of introducing CO2 into hydrogen peroxide degradation catalyzed by alkali

图12 NaHCO3-H2O2体系中可能存在的碳转化机制

Fig.12 Possible Carbon Conversion Mechanism in NaHCO3-H2O2 System

图13 NaHCO3-H2O2体系与NaHCO3体系的pH对比

Fig.13 Comparison of pH between NaHCO3-H2O2 System and NaHCO3 System

图14 四环素降解过程中可能的中间产物及降解途径

Fig.14 Possible intermediate products and degradation pathways in tetracycline degradation

图15 四环素分子结构图

Fig.15 Molecular structure diagram of tetracycline

图16 四环素降解前后的紫外全波长扫描

Fig.16 Ultraviolet full wavelength scanning before and after tetracycline degradation

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碱催化过氧化氢体系降解四环素的作用规律与机制解析

Determination of tetracycline degradation by alkali-catalyzed hydrogen peroxide system: law of action and mechanism analysis

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