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

doi:10.11949/0438-1157.20250151

Abstract

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

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

CLC Number:

X 52

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.

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.

Figures/Tables 11

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

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

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

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

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

Fig.6 Changes in the solution during the reaction

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

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

Fig.9 TOC changes during the reaction

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

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

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