环氧树脂废盐有机污染物深度脱除效果及机理

doi:10.19965/j.cnki.iwt.2025-0133

摘要/Abstract

摘要：

以某企业环氧树脂生产过程中产生的有机污染废盐为研究对象，系统探究了多种高级氧化工艺对其深度处理过程中有机污染物的去除效果与反应机理。通过组合O₃、H₂O₂与UV构建系列高级氧化体系，开展污染物脱除与工艺参数优化，并综合运用竞争动力学和高分辨质谱技术，揭示了处理过程中活性物种贡献和分子水平转化特征。降解实验结果表明，UV/H₂O₂和UV/O₃工艺可使总有机碳（TOC）降至20 mg/L以下，O₃/H₂O₂工艺可使TOC降至10 mg/L以下。在活性物种贡献方面，竞争动力学结果显示，废盐中有机污染物与活性氯物种（Cl·、Cl₂ ^·-）的反应活性比·OH高1~2个数量级，且各体系中活性氯物种的稳态浓度均比·OH高2~3个数量级，导致其在污染物去除过程中的相对贡献比例最高。进出水高分辨质谱结果表明，3种工艺处理过程中大量类脂质和类蛋白物质被去除，少量芳香性化合物仍存留在出水中。

关键词: 环氧树脂废盐, 高级氧化, 活性物种贡献

Abstract:

Taking the organic-polluted waste salt generated in the production process of epoxy resin in a certain enterprise as the research object, the removal effect and reaction mechanism of various advanced oxidation processes on organic pollutants were systematically explored. By combining O₃, H₂O₂, and UV to construct a series of advanced oxidation systems, pollutant removal and process parameter optimization were carried out, and competitive kinetics and high-resolution mass spectrometry techniques were comprehensively applied to reveal the contribution of active species and molecular level transformation characteristics during the treatment process. The degradation experiment results showed that UV/H₂O₂ and UV/O₃ process could reduce TOC to below 20 mg/L, while O₃/H₂O₂ process could reduce TOC to below 10 mg/L. In terms of the contribution of active species, the competitive dynamics results showed that the reaction activity between organic pollutants and active chlorine species (Cl·, Cl₂ ^·-) in waste salt was 1-2 orders of magnitude higher than that of ·OH, and the steady-state concentration of active chlorine species in each system was 2-3 orders of magnitude higher than that of ·OH, resulting in the highest relative contribution ratio in the pollutant removal process. The results of high-resolution mass spectrometry showed that a significant proportion of lipid-like and protein-like substances were effectively removed by the three AOPs, while trace aromatic compounds persisted in the effluent.

Key words: epoxy resin waste salt, advanced oxidation processes, reactive species contribution

中图分类号:

孟娇, 宋玥言, 钟琳, 赵建树, 金青海, 徐飞, 何頔. 环氧树脂废盐有机污染物深度脱除效果及机理[J]. 工业水处理, 2026, 46(1): 51-59.

Jiao MENG, Yueyan SONG, Lin ZHONG, Jianshu ZHAO, Qinghai JIN, Fei XU, Di HE. Performance and mechanism of organic pollutants removal from epoxy resin waste salt[J]. Industrial Water Treatment, 2026, 46(1): 51-59.

https://www.iwt.cn/CN/Y2026/V46/I1/51

图/表 10

图1 工业废盐深度处理反应器

Fig.1 Advanced oxidation reactor of industrial waste salt

表1 废盐组分和配制溶液水质情况

Table 1 Parameters of waste salt and waste salt solution

废盐组分		废盐溶液
指标	数值	指标	数值
NaCl质量分数/%	97.9	Cl^-/（g·L^-1）	196
SO₄ ^2-质量分数/%	0.1	pH	11
水分质量分数/%	1.9	TOC/（mg·L^-1）	250
亚铁氰根	未检出	UV₂₅₄/cm^-1	0.167
TOC/（mg·L^-1）	320	SUV₂₅₄/（L·m^-1·mg^-1）	0.066 8

表2 各探针化合物与自由基的二级反应速率常数

Table 2 The second-order reaction rate constant of probe compounds with free radicals

探针化合物	$k O 3$ / （L·mol^-1·s^-1）	k _·OH/ （L·mol^-1·s^-1）	k _Cl·/ （L·mol^-1·s^-1）	k _Cl2·-/ （L·mol^-1·s^-1）
NB	0.09	3.9×10⁹	3.4×10⁸	<1.0×10⁵
BA	1.2	5.9×10⁹	1.4×10¹⁰	<2.0×10⁶
DMSO	8.2	7.0×10⁹	7.0×10⁹	1.2×10⁷
Phenol	1.0×10³	6.6×10⁹	1.1×10¹⁰	2.5×10⁸

表2 各探针化合物与自由基的二级反应速率常数

Table 2 The second-order reaction rate constant of probe compounds with free radicals

探针化合物	$k O 3$ / （L·mol^-1·s^-1）	k _·OH/ （L·mol^-1·s^-1）	k _Cl·/ （L·mol^-1·s^-1）	k _Cl2·-/ （L·mol^-1·s^-1）
NB	0.09	3.9×10⁹	3.4×10⁸	<1.0×10⁵
BA	1.2	5.9×10⁹	1.4×10¹⁰	<2.0×10⁶
DMSO	8.2	7.0×10⁹	7.0×10⁹	1.2×10⁷
Phenol	1.0×10³	6.6×10⁹	1.1×10¹⁰	2.5×10⁸

图2 不同工艺对废盐溶液有机物去除效果

Fig.2 Removal effect of organic matter from waste salt solution by different processes

图3 UV/H₂O₂工艺参数优化

Fig.3 Parameters optimization of UV/H₂O₂ process

图4 UV/O₃工艺参数优化

Fig.4 Parameters optimization of UV/O₃ process

图5 O₃/H₂O₂工艺参数优化

Fig.5 Parameters optimization of O₃/H₂O₂ process

图6 三体系自由基稳态浓度

Fig.6 Steady concentration of radicals in the three systems

图7 三体系自由基贡献比例

Fig.7 Contribution ratio of free radicals in the three systems

图8 进出水有机污染物类别占比

Fig.8 Proportion of organic pollutant categories in influent and effluent

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