天然气净化厂废水处理过程中溶解性有机物的变化

doi:10.19965/j.cnki.iwt.2023-0887

摘要/Abstract

摘要：

溶解性有机物（DOM）是废水达标排放标准的重要考虑因素，综合分析废水中DOM的分子组成是对其高效去除的前提。以某天然气净化厂废水为研究对象，采用傅里叶变换离子回旋共振质谱法（FT-ICR MS）和三维荧光光谱（3D-EEMs）从分子层面深入分析氧化过程中DOM的荧光性质、分子组成、质荷比、分子转化。EEM结果表明，废水中主要以类腐殖质物质为主，其次为富里酸类物质。O₃/H₂O₂氧化降低了类腐殖质物质的荧光强度，但DOM降解受限于臭氧与富含电子有机物的反应特性；而O₃/H₂O₂-Fenton联合氧化能大幅降低总荧光强度，有效去除类腐殖质。FT-ICR MS结果表明，O₃/H₂O₂氧化去除了部分CHO类、CHON类DOM，但对CHOS类、CHONS类DOM的去除效果欠佳。多环芳烃和高度不饱和的化合物被臭氧降解为脂肪族类化合物，增加了CHO类DOM含氧量。O₃/H₂O₂-Fenton氧化对CHOS类、CHONS类DOM具有较好的去除效果，去除了大部分多酚化合物，生成具有含氧量更低和饱和度更高的DOM。同时，联合氧化极大地缓解了超滤膜污染，去除了大部分可逆污染和不可逆污染。

关键词: 溶解性有机物, 傅里叶变换离子回旋共振质谱分析, 三维荧光光谱分析, 分子特性

Abstract:

Dissolved organic matter (DOM) is a pivotal determinant for wastewater discharge compliance standards. A comprehensive analysis of the molecular composition of DOM is imperative for its efficient removal. In this study, wastewater from a natural gas purification plant was investigated. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and three-dimensional excitation-emission-matrix spectra (3D-EEMs) were employed to analyze the fluorescence properties, molecular composition, mass-to-charge ratio, and molecular transformations of DOM during the oxidation process at molecular level. The 3D-EEM results indicated wastewater was dominated by humic substances, followed by fulvic acid substances. O₃/H₂O₂ oxidation reduced the fluorescence intensity of humic substances, while DOM degradation was constrained by the reaction characteristics of ozone with electron-rich organic compounds. In contrast,the O₃/H₂O₂-Fenton combined oxidation significantly reduced the overall fluorescence intensity, and effectively removed humic-like substances. FT-ICR MS results revealed that O₃/H₂O₂ oxidation removed part of CHO and CHON type DOM, while the removal efficiency for CHOS and CHONS types was less pronounced. Polycyclic aromatic and highly unsaturated compounds were transformed into aliphatic compounds by ozone, with increase of the oxygen content of CHO type DOM. O₃/H₂O₂-Fenton oxidation exhibited superior removal efficiency for CHOS and CHONS type DOM, which almost eliminated polyphenolic compounds and generated DOM with lower oxygen content and higher saturation. Furthermore, the combined oxidation process significantly mitigated ultrafiltration membrane fouling with removing a substantial portion of reversible and irreversible fouling.

Key words: dissolved organic matter, fourier transform ion cyclotron resonance mass spectrometry analysis, three-dimensional fluorescence spectroscopy analysis, molecular properties

中图分类号:

X703.1

胡万金, 瞿杨, 吴雁, 刘文士, 王鑫, 王雪梅. 天然气净化厂废水处理过程中溶解性有机物的变化[J]. 工业水处理, 2024, 44(5): 164-170.

Wanjin HU, Yang QU, Yan WU, Wenshi LIU, Xing WANG, Xuemei WANG. Variations in dissolved organic matter during wastewater treatment in natural gas purification plants[J]. Industrial Water Treatment, 2024, 44(5): 164-170.

https://www.iwt.cn/CN/Y2024/V44/I5/164

图/表 7

表1 原水水质

Table 1 Raw water quality

指标	数值	指标	数值
pH	12.18	TDS	29 883 mg/L
硫化物	427.8 mg/L	TOC	285 mg/L
电导率	22.3 mS/cm	Cl^-	550.2 mg/L
COD	1 320 mg/L	SO₄ ^2-	10 508.6 mg/L
TSS	386 mg/L	Na⁺	22 524.4 mg/L

图1 不同氧化工艺对TOC的去除率注：F代表Fenton。

Fig.1 Removal rate of TOC by different oxidation processes

图2 氧化过程中的荧光强度变化

Fig.2 Fluorescence changes during oxidation process

图3 废水在处理过程中的质谱图

Fig. 3 Mass spectrum of wastewater during treatment process

图4 氧化过程中有机物的分类

Fig.4 Classification of organic compounds during oxidation process

图5 氧化过程中还原氧化特性的变化

Fig.5 Changes in reduction oxidation characteristics during oxidation process

图6 氧化前后超滤膜的扫描电镜图

Fig.6 Scanning electron microscopy images of ultrafiltration membranes before and after oxidation

参考文献 20

1	SELVAN K K， PANDA R C. Mathematical modeling，parametric estimation，and operational control for natural gas sweetening processes［J］. Chem Bio Eng Reviews，2018，5（1）：57-74． doi:10.1002/cben.201700009
2	ESMAEILI A， YOON T， ATSBHA T A，et al. Rate-based modeling and energy optimization of acid gas removal from natural gas stream using various amine solutions［J］. Process Safety and Environmental Protection，2023，177：643-663． doi:10.1016/j.psep.2023.07.030
3	李丽，严紫含，金艳，等. 天然气净化厂有机胺废水有机物降解工艺研究［J］. 天然气与石油，2022，40（2）：98-102． doi:10.3969/j.issn.1006-5539.2022.02.015
	LI Li， YAN Zihan， JIN Yan，et al. Study on degradation process of organic matter in organic amine wastewater from natural gas purification plant［J］. Natural Gas and Oil，2022，40（2）：98-102． doi:10.3969/j.issn.1006-5539.2022.02.015
4	肖芳，廖晓伟，范锐，等. 天然气净化厂高盐环胺废液处理工艺研究［J］. 天然气与石油，2023，41（4）：99-106． doi:10.3969/j.issn.1006-5539.2023.04.015
	XIAO Fang， LIAO Xiaowei， FAN Rui，et al. Study on treatment process of high-salinity cyclamine waste liquid in a natural gas purification plant［J］. Natural Gas and Oil，2023，41（4）：99-106． doi:10.3969/j.issn.1006-5539.2023.04.015
5	SHI Yufei， LI Shengnan， WANG Liye，et al. Compositional characteristics of dissolved organic matter in pharmaceutical wastewater effluent during ozonation［J］. The Science of the Total Environment，2021，778：146278． doi:10.1016/j.scitotenv.2021.146278
6	AFTAB B， SHIN H S，HUR J. Exploring the fate and oxidation behaviors of different organic constituents in landfill leachate upon Fenton oxidation processes using EEM-PARAFAC and 2D-COS-FTIR［J］. Journal of Hazardous Materials，2018，354：33-41． doi:10.1016/j.jhazmat.2018.04.059
7	LAVONEN E E， KOTHAWALA D N， TRANVIK L J，et al. Tracking changes in the optical properties and molecular composition of dissolved organic matter during drinking water production［J］. Water Research，2015，85：286-294． doi:10.1016/j.watres.2015.08.024
8	CARSTEA E M， BRIDGEMAN J， BAKER A，et al. Fluorescence spectroscopy for wastewater monitoring：A review［J］. Water Research，2016，95：205-219． doi:10.1016/j.watres.2016.03.021
9	YUAN Ziwen， HE Chen， SHI Quan，et al. Molecular insights into the transformation of dissolved organic matter in landfill leachate concentrate during biodegradation and coagulation processes using ESI FT-ICR MS［J］. Environmental Science & Technology，2017，51（14）：8110-8118． doi:10.1021/acs.est.7b02194
10	RUAN Mingqi， WU Fengchang， SUN Fuhong，et al. Molecular-level exploration of properties of dissolved organic matter in natural and engineered water systems：A critical review of FTICR-MS application［J］. Critical Reviews in Environmental Science and Technology，2023，53（16）：1534-1562． doi:10.1080/10643389.2022.2157167
11	GENG Chunxiang， CAO Na， XU Wei，et al. Molecular characterization of organics removed by a covalently bound inorganic-organic hybrid coagulant for advanced treatment of municipal sewage［J］. Environmental Science & Technology，2018，52（21）：12642-12648． doi:10.1021/acs.est.8b03306
12	LI Wen， LI Xuan， HAN Chunxiao，et al. A new view into three-dimensional excitation-emission matrix fluorescence spectroscopy for dissolved organic matter［J］. The Science of the Total Environment，2023，855：158963． doi:10.1016/j.scitotenv.2022.158963
13	CHEN Wen， WESTERHOFF P， LEENHEER J A，et al. Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter［J］. Environmental Science & Technology，2003，37（24）：5701-5710． doi:10.1021/es034354c
14	WANG Fan， HUANG Yuyu， ZHUO Xiaocun，et al. Molecular-level transformation characteristics of refractory organics in landfill leachate during ozonation treatment［J］. The Science of the Total Environment，2020，749：141558． doi:10.1016/j.scitotenv.2020.141558
15	郭送军，韦进毅，王晨路，等. 基于FT-ICR MS的蒸汽爆破预处理强化污泥厌氧消化的有机物分子解析［J］. 环境工程学报，2023，17（4）：1337-1345． doi:10.12030/j.cjee.202211173
	GUO Songjun， WEI Jinyi， WANG Chenlu，et al. Molecular analysis of organic compounds in anaerobic digestion of sludge enhanced by steam explosion pretreatment based on FT-ICR MS［J］. Chinese Journal of Environmental Engineering，2023，17（4）：1337-1345． doi:10.12030/j.cjee.202211173
16	何晨，何丁，陈春茂，等. 傅里叶变换离子回旋共振质谱在溶解性有机质组成分析中的应用［J］. 中国科学（地球科学），2022，52（12）：2323-2341． doi:10.1007/s11430-021-9954-0
	HE Chen， HE Ding， CHEN Chunmao，et al. Application of Fourier transform ion cyclotron resonance mass spectrometry in molecular characterization of dissolved organic matter［J］. Scientia Sinica（Terrae），2022，52（12）：2323-2341． doi:10.1007/s11430-021-9954-0
17	SEIDEL M， YAGER P L， WARD N D，et al. Molecular-level changes of dissolved organic matter along the Amazon River-to-ocean continuum［J］. Marine Chemistry，2015，177：218-231． doi:10.1016/j.marchem.2015.06.019
18	GU Zhepei， CHEN Weiming， HE Chen，et al. Molecular insights into the transformation of refractory organic matter in landfill leachate nanofiltration concentrates during a flocculation and O₃/H₂O₂ treatment［J］. Journal of Hazardous Materials，2022，435：128973． doi:10.1016/j.jhazmat.2022.128973
19	AGUILAR-ALARCÓN P， ZHEREBKER A， RUBEKINA A，et al ．Impact of ozone treatment on dissolved organic matter in land-based recirculating aquaculture systems studied by Fourier transform ion cyclotron resonance mass spectrometry［J］. The Science of the Total Environment，2022，843：157009． doi:10.1016/j.scitotenv.2022.157009
20	ZHANG Bingliang， SHAN Chao， WANG Shu，et al. Unveiling the transformation of dissolved organic matter during ozonation of municipal secondary effluent based on FT-ICR-MS and spectral analysis［J］. Water Research，2021，188：116484． doi:10.1016/j.watres.2020.116484

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