高铁酸钾强化铁锰氧化膜过滤去除水中双酚A及机理

doi:10.16085/j.issn.1000-6613.2024-1002

摘要/Abstract

摘要：

目前双酚A（BPA）已被发现存在于多种水环境中，严重影响饮水安全。为了解决这一问题，本文提出了一种高铁酸钾（K₂FeO₄）强化铁锰氧化膜（MeO _x ）去除水中BPA的新技术。研究了K₂FeO₄强化过滤对BPA的去除效果以及影响因素，探究了长期运行实验中BPA去除效果的持续稳定性，并深入分析了K₂FeO₄强化铁锰氧化膜过滤去除BPA的微观作用机理。在中试系统进水中投加0.02mg/L的K₂FeO₄，可将BPA的去除效率由原来的20%提高至约70%。在BPA的长期去除实验中，氧化膜活性降低后可向进水中投加1.0mg/L的Mn²⁺恢复其活性，从而维持中试系统对于BPA的有效去除。pH在6.54~8.52范围内，对于BPA的去除影响较小，NH $4 +$ 浓度的增加会导致BPA的去除效率明显下降。在去除BPA的过程中，BPA中的苯环分解生成􀰶CH₂CH(OH)􀰹 _n 和CH₃CH₂CHO，且K₂FeO₄将铁锰氧化物膜中的Mn和MnO氧化为高价MnO₂和Mn₂O₃，有助于提高氧化膜活性。本文将为有效去除水中BPA提供新的思路。

关键词: 高铁酸钾, 强化过滤, 铁锰氧化膜, 双酚A

Abstract:

At present, bisphenol A (BPA) has been found to exist in a variety of water environments, seriously affecting the safety of drinking water. In order to solve this problem, a new technology for removing BPA from water by using potassium ferrate (K₂FeO₄) to strengthen iron manganese oxide film (MeO _x ) was proposed. The removal effect and influencing factors of BPA by K₂FeO₄ enhanced filtration were studied, the sustained stability of BPA removal effect in long-term operation experiments was explored, and the microscopic mechanism of BPA removal by K₂FeO₄ enhanced MeO _x filtration was analyzed. Adding 0.02mg/L K₂FeO₄ in the influent increased the removal efficiency of BPA from 20% to about 70% in a pilot-scale filter system. In the long-term removal experiment of BPA, after the activity of the oxidation film decreased, the dosage of 1.0mg/L Mn²⁺ in the influent was used to gradually restore the activity of the oxide film, thus maintaining the effective removal of BPA. The pH in the range of 6.54 to 8.52 had less effect on the removal of BPA. The increase in the concentration of NH $4 +$ would lead to a decrease in the removal efficiency of BPA. The benzene ring in BPA decomposed to form 􀰶CH₂CH(OH)􀰹 _n and CH₃CH₂CHO during the removal process of BPA, and that K₂FeO₄ oxidized Mn and MnO in the oxide film to high-valent MnO₂ and Mn₂O₃, which helped to improve the activity of MeO _x . The study would provide a new idea for the effective removal of BPA from water.

Key words: potassium ferrate, enhanced filtration, iron manganese oxide film (MeO _x ), bisphenol A

中图分类号:

TU991.2

曹曼曼, 郭英明, 曹袁圆, 张宇宏, 张哲凯. 高铁酸钾强化铁锰氧化膜过滤去除水中双酚A及机理[J]. 化工进展, 2025, 44(7): 4274-4281.

CAO Manman, GUO Yingming, CAO Yuanyuan, ZHANG Yuhong, ZHANG Zhekai. Study on the removal of bisphenol A from water by potassium ferrate-enhanced MeO _x and its mechanism[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 4274-4281.

图/表 8

表1 原水水质指标

水质指标	数值	地下水质量标准（GB/T 14848—2017）
氨氮/mg·L^-1	0.08±0.02	≤0.50
BPA/mg·L^-1	0	≤0.01
锰/mg·L^-1	0.01±0.00	≤0.10
铁/mg·L^-1	0.05±0.01	≤0.30
水温/℃	15.20±6.00	—
pH	7.80±0.30	6.50~8.50
溶解氧/mg·L^-1	6.80±0.20	—
浊度	1.45±0.55	≤3.00

图1 水中K2FeO4对铁锰氧化膜去除BPA的影响滤柱A—原始滤料+未投加K2FeO4；滤柱B—负载铁锰氧化膜的滤料+未投加K2FeO4；滤柱C—原始滤料+投加0.01mg/L K2FeO4；滤柱D—负载铁锰氧化膜的滤料+投加0.01mg/LK2FeO4

图2 K2FeO4强化铁锰氧化膜去除BPA的浓度变化

图3 水质条件对BPA沿程浓度的影响

图4 滤料形态及SEM微观表征

图5 不同阶段的XPS能谱

图6 原始滤料、第30天和第45天滤料表面氧化膜的XRD能谱

图7 水中BPA去除机理

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