污水处理厂臭氧处理单元中溶解性有机质的转化特性

doi:10.19965/j.cnki.iwt.2024-0438

摘要/Abstract

摘要：

臭氧氧化常作为污水处理厂深度处理单元用于难降解有机物的去除，但由于污水成分复杂，目前对臭氧处理过程中溶解性有机质（DOM）的转化特性仍缺乏足够认知。采用紫外-可见吸收光谱、三维荧光光谱和傅里叶变换离子回旋共振质谱（FT-ICR-MS）解析4个不同污水处理厂二级出水中DOM在臭氧处理过程中的转化特性。结果表明，臭氧氧化可有效去除DOM中的芳香物质以及类色氨酸、类富里酸、溶解性微生物产物和类腐殖酸等荧光组分，但其矿化效率有限，且其对化工产业污水和印染污水中COD的去除率较低。污水处理厂二级出水中DOM的分子组成主要为CHO、CHON和CHOS类物质，其物质类别主要为高度不饱和类物质及酚类物质、脂肪类物质和多酚类物质。经臭氧处理后，部分CHOS类物质会被氧化为CHO类物质，同时高度不饱和类物质及酚类物质、多酚类物质会转化为饱和类物质。臭氧处理后反应产物的氧原子数明显增加，难降解有机物的分子质量主要分布在150~600 u，不饱和双键数（DBE）主要为3~11。此外，质量差异分析和统计学分析发现综合污水、化工产业污水和电子产业污水中三羟基化反应（+3O）发生的最多，而印染污水中脱环丙基（-C₃H₄）的反应发生最多。

关键词: 臭氧氧化, 溶解性有机质, 分子转化, 傅里叶变换离子回旋共振质谱

Abstract:

Ozonation is often used as an advanced treatment unit for the removal of refractory organic matters in wastewater treatment plants. However, due to the complex composition of wastewater, the transformation characteristics of dissolved organic matter(DOM) in ozone treatment are still not well understood. UV-vis spectrometry, three-dimensional fluorescence spectrometry and Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR-MS) were used to analyze the transformation characteristics of DOM during ozone treatment of secondary effluent from four different wastewater treatment plants. The results showed that ozonation could effectively remove aromatic compounds and fluorescent components such as tryptophan-like, fulvic acid-like, dissolved microbial products and humic acid-like in DOM. However, the mineralization effect was poor, and the COD removal rates of chemical industry wastewater and printing and dyeing wastewater were relatively low. The molecular composition of DOM in secondary effluent from the wastewater treatment plants was mainly composed of CHO, CHON and CHOS substances, and its compound categories were mainly highly unsaturated and phenolic substances, fatty substances and polyphenolic substances. After ozone treatment, some CHOS substances could be oxidized and converted into CHO substances, while highly unsaturated and phenolic substances and polyphenols could be converted into saturated substances. The number of oxygen atoms of the products increased significantly, and the molecular weight of resistants was mainly 150-600 u, and the double bond equivalents(DBE) was mainly 3-11. In addition, the mass difference analysis and statistical analysis showed that largest number of trihydroxylation(+3O) reaction occurred in synthetic wastewater, chemical industrial wastewater and electronic wastewater, but the number of decyclopropyl reaction (-C₃H₄) in printing and dyeing wastewater was the largest.

Key words: ozonation, dissolved organic matter, molecular transformation, Fourier transform ion cyclotron resonance mass spectrometry

中图分类号:

X703.1

张万里, 程方奎, 朱敬林. 污水处理厂臭氧处理单元中溶解性有机质的转化特性[J]. 工业水处理, 2025, 45(6): 150-158.

Wanli ZHANG, Fangkui CHENG, Jinglin ZHU. Transformation characteristics of dissolved organic matter in ozone treatment unit of wastewater plants[J]. Industrial Water Treatment, 2025, 45(6): 150-158.

https://www.iwt.cn/CN/Y2025/V45/I6/150

图/表 9

表1 污水处理厂二级出水水质

Table 1 Water quality of secondary effluent from wastewater treatment plants

样品	pH	电导率/ （μS·cm^-1）	UV₂₅₄/ cm^-1	TOC/ （mg·L^-1）	COD/ （mg·L^-1）	Cl^-/ （mg·L^-1）	SO₄ ^2-/ （mg·L^-1）	NO₃ ^-/ （mg·L^-1）	Ca²⁺/ （mg·L^-1）	Mg²⁺/ （mg·L^-1）
S1	7.33	0.16	0.15	5.82	28.5	52.9	462.2	3.39	55.16	11.30
S2	8.11	2.82	0.29	18.18	44.0	162.0	108.3	0.14	29.17	7.96
S3	7.40	2.32	0.03	2.21	19.5	80.4	389.7	0.55	61.14	5.04
S4	6.87	2.91	0.57	14.27	64.0	155.5	164.6	4.18	35.71	15.63

图1 臭氧处理过程中不同污水COD的变化

Fig.1 COD variation in different wastewater during ozone treatment

图2 臭氧处理前后不同废水中DOM的三维荧光光谱

Fig.2 Three-dimensional fluorescence spectra in different wastewater before and after ozone treatment

图3 臭氧处理前后不同样品中DOM的Van Krevelen图 n代表样品的分子式总数；区域1中为饱和类物质，区域2中为脂肪类物质，区域3中为高度不饱和类物质及酚类物质，区域4中为多酚类物质，区域5中为稠环多环芳烃。

Fig.3 Van Krevelen diagrams of DOM in different samples before and after ozone treatment

图4 臭氧处理前后不同污水中DOM的相对丰度（S5、S6、S7、S8分别为S1、S2、S3、S4经臭氧处理后的样品）

Fig.4 The relative abundance of DOM in different wastewater before and after ozone treatment（S5，S6，S7，and S8 are samples of S1，S2，S3，and S4 treated with ozone，respectively）

图5 不同污水在臭氧处理过程中前体物和反应产物中O _x 类物质的数量分布

Fig.5 Number distribution of O _x species of precursors and products in different wastewater during ozone treatment

图6 臭氧处理过程中不同污水中DOM的分子转化 ①区域代表不饱和的氧化态物质，②区域代表不饱和的还原态物质，③区域代表饱和的还原态物质，④区域代表饱和的氧化态物质；（a）、（b）、（c）、（d）分别为S1、S2、S3、S4经臭氧处理后前体物和难降解物质的分子分布；（e）、（f）、（g）、（h）分别为S1、S2、S3、S4经臭氧处理后反应产物和难降解物质的分子分布。

Fig.6 Molecular transformation of DOM in different wastewater during ozone treatment

图7 不同污水在臭氧处理中难降解物质的分布图（a）、（b）、（c）、（d）分别为S1、S2、S3、S4在臭氧处理中难降解物质的分布图；坐标轴上方的柱状图是难降解物质对应分子质量的数量分布图，坐标轴右边的柱状图是难降解物质对应DBE的数量分布图。

Fig.7 Distribution diagrams of resistants in different wastewater during ozone treatment

图8 不同污水在臭氧处理过程中可能的前体物-反应产物对数量分布

Fig.8 Number distribution of possible precursor-product pairs during ozone treatment of different wastewater

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