炼化含盐污水处理全过程有机污染物降解特征

doi:10.16085/j.issn.1000-6613.2021-0905

摘要/Abstract

摘要：

某重质油炼化企业采用“物化单元（隔油+气浮）+曝气生物滤池（biofilter，BAF）+水解酸化（hydrolysis acidification，HA）+缺氧/好氧（anoxic/oxic，A/O）+好氧-膜生物反应器（oxic-membrane bioreactor，O-MBR）+催化臭氧氧化（catalytic ozonation，COP）”工艺处理含盐污水。本文采用GC-MS结合FT-ICR MS高等仪器的分析手段，对污水处理工艺全过程的有机污染物降解特征进行了深入研究。发现BAF单元主要去除的是小分子有机酸类、酯类和醛酮类等易降解化合物；HA单元基本未发挥降解作用；A/O单元能大幅度去除O₂类化合物，并能完全降解N₁O₂S₁类化合物；O-MBR单元未能完全降解的O₃S₁类和N₁O₃类化合物在COP单元被完全矿化；最终出水残留COD的构成主要是大分子饱和脂肪酸和高缩合度环烷酸类化合物。本文研究成果可为重质油炼化污水处理工艺的评价与优化提供依据。

关键词: 重质油, 含盐污水, 有机污染物, 降解特征, 傅里叶变换离子回旋共振高分辨质谱

Abstract:

The successive processes including physicochemical units (oil separation+air flotation)+biofilter (BAF)+hydrolysis acidification (HA)+anoxic/oxic (A/O)+oxic-membrane bioreactor (O-MBR)+catalytic ozonation (COP) were used to treat heavy oil refining saline wastewater. The organics degradation characteristics along treatment processes were comprehensively analyzed by GC-MS combined FT-ICR MS. Small molecular organic acids, esters, aldehydes and ketones were dominantly degraded by BAF. HA showed very weak degradation towards organics. Most O₂ species and all N₁O₂S₁ species were degraded by A/O. The O₃S₁ and N₁O₃ species, penetrated from O-MBR, were completely mineralized by COP. The residual COD in the final effluent mainly were macromolecular saturated fatty acid and naphthenic acid with high unsaturation degree. The results may guide the assessment and optimization of heavy oil refinery wastewater treatment plant.

Key words: heavy oil, saline wastewater, organics, degradation characteristics, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS)

中图分类号:

TE991

寇悦, 陈宇, 叶黄凡, 王庆宏, 陈春茂. 炼化含盐污水处理全过程有机污染物降解特征[J]. 化工进展, 2022, 41(4): 2202-2208.

KOU Yue, CHEN Yu, YE Huangfan, WANG Qinghong, CHEN Chunmao. Organics degradation characteristics along refining saline wastewater treatment processes[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 2202-2208.

图/表 5

图1 HORSW有机负荷总量在处理全过程中的降解特征

图2 基于GC-MS分析的HORSW处理工艺全过程污染物的降解特征

图3 HORSW处理工艺全过程极性污染物的二维Van Krevelen程序图

图4 O2~4类、O3S1类、N1O3类和N1O2S1类在HORSW处理工艺全过程的降解特征

图5 HORSW处理工艺全过程O2-4类DBE与碳数对应关系

参考文献 27

1	夏瑜, 何绪文, 徐恒, 等. 典型电脱盐废水预处理技术及其应用[J]. 化工环保, 2020, 40(1): 1-6.
	XIA Yu, HE Xuwen, XU Heng, et al. Typical pretreatment technologies of electric desalination effluents and their application[J]. Environmental Protection of Chemical Industry, 2020, 40(1): 1-6.
2	李长刚, 郎旭东, 郭绍辉, 等. 三种典型原油炼制企业点源污水氮污染物形态分布及排放特征[J]. 石油科学通报, 2019, 4(2): 204-212.
	LI Changgang, LANG Xudong, GUO Shaohui, et al. Morphological distribution and discharge characteristics of nitrogen pollutants in point source wastewater from three typical crude oil refining enterprises[J]. Petroleum Science Bulletin, 2019, 4(2): 204-212.
3	PINZÓN-ESPINOSA A, KANDA R. Naphthenic acids are key contributors to toxicity of heavy oil refining effluents[J]. Science of the Total Environment, 2020, 729: 138119.
4	龚朝兵, 肖立光, 钟震, 等. 采用臭氧-内循环曝气生物滤池工艺处理高酸重质原油含盐污水[J]. 石化技术与应用, 2015, 33(5): 437-440.
	GONG Chaobing, XIAO Liguang, ZHONG Zhen, et al. Treatment of saline wastewater from high acid heavy crude oil by ozonizing-biological aerated filter combined process[J]. Petrochemical Technology & Application, 2015, 33(5): 437-440.
5	王晓猛, 张黎明, 姚亮, 等. 电脱盐污水除油设施在常减压蒸馏装置中的应用[J]. 炼油技术与工程, 2013, 43(7): 36-39.
	WANG Xiaomeng, ZHANG Liming, YAO Liang, et al. Application of oil removal facility for electric desalting wastewater in atmospheric-vacuum distillation units[J]. Petroleum Refinery Engineering, 2013, 43(7): 36-39.
6	薛建良, 赵东风, 李石, 等. 炼化企业含盐废水处理的研究进展[J]. 工业水处理, 2011, 31(7): 22-26.
	XUE Jianliang, ZHAO Dongfeng, LI Shi, et al. Study on brine wastewater treatment in refineries[J]. Industrial Water Treatment, 2011, 31(7): 22-26.
7	李凌波, 齐敏, 申开莲, 等. 气相色谱-质谱法表征炼油厂外排废水中的有机组分[J]. 中国环境监测, 2000, 16(2): 32-36.
	LI Lingbo, QI Min, SHEN Kailian, et al. Characterization of organic components in wastewater discharged from refinery by gas chromatography-mass spectrometry[J]. Environmental Monitoring in China, 2000, 16(2): 32-36.
8	栗则, 季远玲, 张宇曦, 等. GC-MS解析炼化污水中挥发性有机物组成和变化[J]. 化工进展, 2018, 37(10): 4053-4059.
	LI Ze, JI Yuanling, ZHANG Yuxi, et al. Application of GC-MS for the determination of volatile organic compounds in refinery wastewater treatment process[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 4053-4059.
9	BARROW M P, WITT M, HEADLEY J V, et al. Athabasca oil sands process water: characterization by atmospheric pressure photoionization and electrospray ionization fourier transform ion cyclotron resonance mass spectrometry[J]. Analytical Chemistry, 2010, 82(9): 3727-3735.
10	QIAN K N, RODGERS R P, HENDRICKSON C L, et al. Reading chemical fine print: resolution and identification of 3000 nitrogen-containing aromatic compounds from a single electrospray ionization Fourier transform ion cyclotron resonance mass spectrum of heavy petroleum crude oil[J]. Energy & Fuels, 2001, 15(2): 492-498.
11	BARROW M P, PERU K M, FAHLMAN B, et al. Beyond naphthenic acids: environmental screening of water from natural sources and the Athabasca oil sands industry using atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry[J]. Journal of the American Society for Mass Spectrometry, 2015, 26(9): 1508-1521.
12	YE Huangfan, LIU Baodong, WANG Qinghong, et al. Comprehensive chemical analysis and characterization of heavy oil electric desalting wastewaters in petroleum refineries[J]. Science of the Total Environment, 2020, 724: 138117.
13	YE Huangfan, CHEN Lin, KOU Yue, et al. Influences of coagulation pretreatment on the characteristics of crude oil electric desalting wastewaters[J]. Chemosphere, 2020, 264: 128531.
14	FANG Zhi, LI Lijie, JIANG Bin, et al. Molecular composition and transformation of dissolved organic matter (DOM) in coal gasification wastewater[J]. Energy & Fuels, 2019, 33(4): 3003-3011.
15	KASPRZYK-HORDERN B, ZIÓŁEK M, NAWROCKI J. Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment[J]. Applied Catalysis B: Environmental, 2003, 46(4): 639-669.
16	WANG Jianlong, CHEN Hai. Catalytic ozonation for water and wastewater treatment: recent advances and perspective[J]. Science of the Total Environment, 2020, 704: 135249.
17	ZHANG Lei, ZHANG Yanyan, GAMAL EL-DIN M. Integrated mild ozonation with biofiltration can effectively enhance the removal of naphthenic acids from hydrocarbon-contaminated water[J]. Science of the Total Environment, 2019, 678: 197-206.
18	LI Yongyong, FANG Zhi, HE Chen, et al. Molecular characterization and transformation of dissolved organic matter in refinery wastewater from water treatment processes: characterization by fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels, 2015, 29(11): 6956-6963.
19	LI Y Y, XU C M, Chung K H, et al. Molecular characterization of dissolved organic matter and its subfractions in refinery process water by Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels, 2015, 29(5): 2923-2930.
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.
21	GONSIOR M, ZWARTJES M, COOPER W J, et al. Molecular characterization of effluent organic matter identified by ultrahigh resolution mass spectrometry[J]. Water Research, 2011, 45(9): 2943-2953.
22	FÓNAGY O, SZABÓ-BÁRDOS E, HORVÁTH O, et al. Application of ozonation and silveration for heterogeneous photocatalytic degradation of an aromatic surfactant[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2018, 366: 152-161.
23	ZHENG Fang, WANG Jie, XIAO Rui, et al. Dissolved organic nitrogen in wastewater treatment processes: transformation, biosynthesis and ecological impacts[J]. Environmental Pollution, 2021, 273: 116436.
24	JIA Xiaoqiang, JIN Dayao, LI Chen, et al. Characterization and analysis of petrochemical wastewater through particle size distribution, biodegradability, and chemical composition[J]. Chinese Journal of Chemical Engineering, 2019, 27(2): 444-451.
25	KUSIC H, KOPRIVANAC N, BOZIC A L. Minimization of organic pollutant content in aqueous solution by means of AOPs: UV- and ozone-based technologies[J]. Chemical Engineering Journal, 2006, 123(3): 127-137.
26	VAIOPOULOU E, MISITI T M, PAVLOSTATHIS S G. Removal and toxicity reduction of naphthenic acids by ozonation and combined ozonation-aerobic biodegradation[J]. Bioresource Technology, 2015, 179: 339-347.
27	AFZAL A, CHELME-AYALA P, DRZEWICZ P, et al. Effects of ozone and ozone/hydrogen peroxide on the degradation of model and real oil-sands-process-affected-water naphthenic acids[J]. Ozone Science & Engineering, 2015, 37(1): 45-54.

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