盐酸羟胺强化芬顿体系在近中性条件下去除2，4-DCP的性能及机理研究

doi:10.11949/0438-1157.20250151

化工学报 ›› 2025, Vol. 76 ›› Issue (8): 4273-4283.DOI: 10.11949/0438-1157.20250151

盐酸羟胺强化芬顿体系在近中性条件下去除2，4-DCP的性能及机理研究

廖兵¹^,²^,³(), 祝鑫宇¹^,², 黄倩倩¹^,², 胥雯¹^,², 寇梦瑶¹^,², 郭娜³

^1.成都理工大学地质灾害防治与地质环境保护全国重点实验室，四川成都 610059
^2.成都理工大学生态环境学院，生态环境部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:2025-02-18 修回日期:2025-05-08 出版日期:2025-08-25 发布日期:2025-09-17
通讯作者: 廖兵
作者简介:廖兵（1989—)，男，博士，副教授，liaobing17@cdut.edu.cn
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)

Performance and mechanism of enhanced Fenton system by hydroxylamine hydrochloride for removal of 2, 4-DCP under near-neutral conditions

Bing LIAO¹^,²^,³(), Xinyu ZHU¹^,², Qianqian HUANG¹^,², Wen XU¹^,², Mengyao KOU¹^,², Na GUO³

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

Received:2025-02-18 Revised:2025-05-08 Online:2025-08-25 Published:2025-09-17
Contact: Bing LIAO

摘要/Abstract

摘要：

针对传统芬顿体系中低pH和低活性铁含量等问题，通过向Fenton体系加入碳酸氢盐，与H₂O₂反应生成HCO $4 -$ ，再经盐酸羟胺（HAH）还原提升活性铁含量，可实现近中性条件下对2,4-二氯苯酚（2,4-DCP）的高效降解。结果表明，HAH强化 $H C O 3 -$ 改良Fenton体系在pH约为6.46的条件下，Fe²⁺、NaHCO₃、H₂O₂与HAH的浓度分别为4、10、10和0.5 mmol·L^-1时，反应60 min后，2,4-DCP可被完全降解。高浓度的 $N O 3 -$ 、Cl^-和共存有机质会对2,4-DCP的降解产生抑制作用。反应体系中HAH的引入促进了Fe²⁺和Fe³⁺的循环，提高体系的催化能力，降低Fe²⁺的用量。通过自由基淬灭实验和EPR检测验证了在反应过程中主要参与的自由基是HO^·，¹O₂和 $O 2 · -$ 的贡献很小。且毒性评估结果显示，在降解过程中产生的大多有机中间体的毒性相较于 2,4-DCP明显降低。

关键词: 芬顿, 碳酸氢盐, 过氧化氢, 盐酸羟胺, 碳氢化合物, 活化作用

Abstract:

To address the limitations of traditional Fenton systems, such as the requirement for low pH conditions and the limited availability of active iron, this study proposes a modified approach by incorporating bicarbonate into the Fenton system. The bicarbonate reacts with H₂O₂ to generate HCO $4 -$ , which is further enhanced by HAH to achieve efficient degradation of 2,4-DCP under the near-neutral conditions. The results show that HAH enhanced HCO $3 -$ modified Fenton system under the condition of pH about 6.46, when the concentrations of Fe²⁺, NaHCO₃, H₂O₂ and HAH are 4, 10, 10 and 0.5 mmol·L^-1, 2,4-DCP can be completely degraded after 60 minutes of reaction. However, the degradation efficiency was found to be inhibited by high concentrations of $N O 3 -$ , Cl^- and coexisting organic matter. The introduction of HAH into the reaction system facilitated the redox cycling of Fe²⁺ and Fe³⁺, thereby enhancing the catalytic efficiency of the system, and reducing the required dosage of Fe²⁺. Free radical quenching experiments and EPR detection experiments confirmed that HO^· were the primary reactive species involved in the degradation process, while the contributions of ¹O₂ and $O 2 · -$ were relatively minor. Toxicity assessment results indicate that most of the organic intermediates generated during the degradation process have significantly reduced toxicity compared to 2,4-DCP.

Key words: Fenton, bicarbonate, hydrogen peroxide, hydroxylamine hydrochloride, hydrocarbons, activation

中图分类号:

X 52

廖兵, 祝鑫宇, 黄倩倩, 胥雯, 寇梦瑶, 郭娜. 盐酸羟胺强化芬顿体系在近中性条件下去除2，4-DCP的性能及机理研究[J]. 化工学报, 2025, 76(8): 4273-4283.

Bing LIAO, Xinyu ZHU, Qianqian HUANG, Wen XU, Mengyao KOU, Na GUO. Performance and mechanism of enhanced Fenton system by hydroxylamine hydrochloride for removal of 2, 4-DCP under near-neutral conditions[J]. CIESC Journal, 2025, 76(8): 4273-4283.

图/表 11

图1 不同Fe²⁺、NaHCO₃和H₂O₂浓度对2,4-二氯苯酚去除率及反应前后pH的影响

Fig.1 Effect of different Fe2+, NaHCO3 and H2O2 concentration ratios on the removal of 2,4-DCP and pH before and after reaction

图2 HAH浓度对反应前后2,4-DCP降解和pH的影响

Fig.2 Effect of HAH concentration on the degradation of 2,4-DCP and pH before and after reaction

图3 2,4-DCP初始浓度对反应前后降解和pH的影响

Fig.3 Effect of initial concentration of 2,4-DCP on degradation and pH before and after reaction

图4 不同Cl-、NO3-浓度对反应前后2,4-DCP降解和pH的影响

Fig.4 Effects of different Cl-, NO3- concentrations on the degradation of 2,4-DCP and pH before and after reaction

图5 不同有机质浓度对反应前后2,4-DCP降解和pH的影响

Fig.5 Effects of different organic matter concentrations on the degradation of 2,4-DCP and pH before and after reaction

图6 反应过程中溶液的变化

Fig.6 Changes in the solution during the reaction

图7 自由基淬灭实验以及反应过程中的p-HBA浓度

Fig.7 Free radical quenching assay and p-HBA concentration during the reaction

图8 BMPO- HO·、TEMP-1O2的EPR谱图以及DMPO作为捕获剂获得的EPR谱图

Fig.8 EPR mapping of BMPO- HO·, TEMP-1O2 and EPR profiles obtained with DMPO as trapping agent

图9 反应过程中的 TOC 变化

Fig.9 TOC changes during the reaction

图10 2,4-DCP 降解反应机理和可能途径

Fig.10 2,4-DCP degradation reaction mechanism and possible pathways

图11 反应系统中产生的有机中间体的急性毒性

Fig.11 Acute toxicity of organic intermediates produced in the reaction system

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盐酸羟胺强化芬顿体系在近中性条件下去除2，4-DCP的性能及机理研究

Performance and mechanism of enhanced Fenton system by hydroxylamine hydrochloride for removal of 2, 4-DCP under near-neutral conditions

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