炼化碱渣湿式氧化预处理过程DOM的化学转化特征

doi:10.11949/0438-1157.20230702

摘要/Abstract

摘要：

湿式氧化工艺(WAO)是炼化企业预处理高浓度碱渣的有效手段。基于3D-EEM、GC-MS以及Orbitrap MS组合分析，在分子水平上研究了碱渣中溶解性有机物(dissolved organic matter，DOM)在WAO过程的化学转化特征。研究发现：WAO过程主要发生加氧去氢(+1O-2H和+2O-2H)、加氧(+3O)以及脱烷基化(-C₂H₆)反应，芳香性DOM分子结构由高环(≥5环)向低环(3环/4环)转化；弱极性DOM由硫基苯甲醛、3，4-双(乙氧基甲基)噻吩等转化为硫酸盐、噻吩甲酸和硫醚等小分子化合物；强极性DOM则由具有较低不饱和度(DBE_wa 3.727)和O/C_wa(0.386)的O_2~4类和O₃S₁类化合物转化为具有较高不饱和度(DBE_wa 5.911)和O/C_wa(0.537)的O_5~9类和O_4~9S₁类化合物。WAO预处理后极性DOM种类由1792种增至4909种，水质的可生化性提升了35%。

关键词: 废水, 污染, 降解, 炼化碱渣, 湿式氧化, 溶解性有机物, 化学转化

Abstract:

Wet air oxidation (WAO) is an effective pretreatment process for high-concentration petrochemical spent caustics. In this study, an integrated analysis based on three-dimensional excitation-emission matrix fluorescence spectroscopy (3D-EEM), gas chromatography-mass spectrometry (GC-MS) and orbitrap mass spectrometry (Orbitrap MS) was established to investigate chemical conversion behaviors of petrochemical spent caustic along a WAO process at molecular level. Oxygen-dehydrogenation (+1O-2H and +2O-2H), oxygenation (+3O) and dealkylation (-C₂H₆) reactions happened in WAO process, resulting in a very significant change of DOM constituents. The molecular structures of fluorescent DOM converted from high ring number (≥5 rings) to low ring number (3 or 4 rings). Weak polar DOM, mainly thiobenzaldehyde and 3,4-bis(ethoxymethyl)-thiophene, is converted to sulfates, thiophenic acid and thioethers. The polar DOM, mainly O_2—4 and O₃S₁ species with low unsaturation (DBE_wa 3.727) and O/C_wa (0.386), is converted into O_5—9 and O_4—9S₁ species with high unsaturation (DBE_wa 5.911) and O/C_wa (0.537). Compound types of polar DOM increased from 1792 to 4909 by WAO pretreatment and the biodegradability of effluent improved by 35%.

Key words: waste water, pollution, degradation, petrochemical spent caustic, wet air oxidation, dissolved organic matter, chemical conversion

中图分类号:

TE 991

杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.

Baiyu YANG, Yue KOU, Juntao JIANG, Yali ZHAN, Qinghong WANG, Chunmao CHEN. Chemical conversion of dissolved organic matter in petrochemical spent caustic along a wet air oxidation pretreatment process[J]. CIESC Journal, 2023, 74(9): 3912-3920.

图/表 8

图1 WAO装置流程图

Fig.1 Flow diagram of WAO unit

表1 水质指标的测定方法与仪器

Table 1 Measurement methods and instruments for water quality indicators

项目	指标	测定方法与标准	仪器
DOM总量分析方法	SCOD	重铬酸钾法 HJ 828—2017	承德华通CTL-12化学需氧量速测仪
	SBOD₅	稀释与接种法 HJ 505—2009	美国HACH BODTrak Ⅱ生化需氧量测试仪
	DOC	燃烧氧化-非分散红外吸收法 HJ/T 104—2003	日本Shimadzu TOC-L CPH CN 200总有机碳测试仪
DOM组成表征方法	SUVA₂₅₄	测定样品在波长254 nm下的吸光度（UV₂₅₄），计算得到SUVA₂₅₄（UV₂₅₄×100/DOC）	日本Shimadzu UV-mini-1280UV-Vis紫外光谱仪
	3D-EEM荧光光谱	激发波长（λ_ex）和发射波长（λ_em）分别设置为200~550 nm和200~600 nm，步长为5 nm	法国Horiba Scientific Aqualog 3D-EEM荧光光谱仪
	GC-MS	样品利用二氯甲烷（色谱级，≥99.9%）液液萃取法进行富集，以超纯氦气为载气（1 ml/min），进样量为1.0 µl。离子源温度为250℃，四级杆温度为150℃	美国Agilent 7890B/GC-5977B/MSD GC-MS仪
	Orbitrap MS	样品DOM用固相萃取柱（美国Agilent，Bond Elut PPL）提取，并用甲醇（HPLC级，≥99.9%）洗脱浓缩^[12]。采用负离子电喷雾离子源模式，仪器的m/z检测范围设置为100~800 Da，相关操作参数同文献^[13]	美国ThermoFisher Scientific Orbitrap Fusion型Orbitrap MS仪

表2 碱渣经WAO预处理前后综合污染指标变化

Table 2 Changes of comprehensive pollution indicators of spent caustics before and after WAO pretreatment

综合污染指标	预处理前	预处理后
DOC/(mg/L)	1147±7	947±4
SCOD/(mg/L)	9240±224	2060±12
SBOD₅/(mg/L)	2088±27	633±10
SBOD₅/SCOD	0.23±0.03	0.31±0.05
硫化物/(mg/L)	41701±601	35±2
$S O 4 2 -$ /(mg/L)	640±8	8561±93

表2 碱渣经WAO预处理前后综合污染指标变化

Table 2 Changes of comprehensive pollution indicators of spent caustics before and after WAO pretreatment

综合污染指标	预处理前	预处理后
DOC/(mg/L)	1147±7	947±4
SCOD/(mg/L)	9240±224	2060±12
SBOD₅/(mg/L)	2088±27	633±10
SBOD₅/SCOD	0.23±0.03	0.31±0.05
硫化物/(mg/L)	41701±601	35±2
$S O 4 2 -$ /(mg/L)	640±8	8561±93

图2 碱渣经WAO预处理前后的3D-EEM谱图

Fig.2 3D-EEM spectra of spent caustics before and after WAO pretreatment

图3 碱渣经WAO预处理前后的GC-MS结果

Fig.3 The GC-MS results of spent caustics before and after WAO pretreatment

表3 碱渣经WAO预处理前后的DOM分子类型及属性

Table 3 Molecular types and attributes of DOM of spent caustics before and after WAO pretreatment

项目		预处理前 DOM数量1792种	预处理后 DOM数量4909种
DOM类型	CHO/%	27.0	39.4
	CHOS/%	68.8	58.5
	CHON/%	4.1	1.9
	CHONS/%	0.1	0.1
分子属性	DBE_wa	3.727	5.911
	O/C_wa	0.386	0.537
	H/C_wa	1.536	1.099
	MW_wa/Da	282	278
	NOSC_wa	-0.626	0.091

图4 碱渣经WAO预处理前后的Orbitrap MS结果

Fig.4 The Orbitrap MS results of spent caustics before and after WAO pretreatment

图5 碱渣经WAO预处理前后的前体-产物对筛查结果

Fig.5 The screening results of precusor-product pairs among spent caustics before and after WAO pretreatment

参考文献 37

1	周彤, 邓德刚, 秦丽姣. 石油化工废碱液处理技术开发及工业应用[J]. 现代化工, 2019, 39(6): 187-189.
	Zhou T, Deng D G, Qin L J. Development and industrial application of treatment technology for spent caustic solution in petroleum and chemical industry[J]. Modern Chemical Industry, 2019, 39(6): 187-189.
2	中华人民共和国生态环境部. 国家危险废物名录(2021年版)[J]. 中华人民共和国国务院公报, 2021(4): 18-46.
	Ministry of Environment Protection of the People’s Republic of China. National list of hazardous wastes (2021 edition)[J]. Gazette of the State Council of the People’s Republic of China, 2021(4): 18-46.
3	Boucher V, Beaudon M, Ramirez P, et al. Comprehensive evaluation of non-catalytic wet air oxidation as a pretreatment to remove pharmaceuticals from hospital effluents[J]. Environmental Science: Water Research & Technology, 2021, 7(7): 1301-1314.
4	Ye H F, Yang B Y, Wang Q H, et al. Influences of integrated coagulation-ozonation pretreatment on the characteristics of dissolved organic pollutants (DOPs) of heavy oil electric desalting wastewaters[J]. Journal of Environmental Management, 2021, 300: 113756.
5	王国栋, 唐国建. 高效生物处理技术在碱渣废水处理中的应用[J]. 石油化工安全环保技术, 2017, 33(3): 54-61, 70.
	Wang G D, Tang G J. Application of high efficient biological treatment technology in treatment of alkaline wastewater[J]. Petrochemical Safety and Environmental Protection Technology, 2017, 33(3): 54-61, 70.
6	蓝春树. EM-BAF技术在乙烯废碱液处理中的应用[J]. 化工进展, 2009, 28(S2): 199-202.
	Lan C S. Application of EM-BAF technology in the treatment of ethylene waste lye[J]. Chemical Industry and Engineering Progress, 2009, 28(S2): 199-202.
7	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.
	He C, He D, Chen C M, et al. Application of Fourier transform ion cyclotron resonance mass spectrometry in composition analysis of dissolved organic matter[J]. Scientia Sinica (Terrae), 2022, 52(12): 2323-2341.
8	郝瑞霞, 曹可心, 赵钢, 等. 用紫外光谱参数表征污水中溶解性有机污染物[J]. 北京工业大学学报, 2006, 32(12): 1062-1066.
	Hao R X, Cao K X, Zhao G, et al. Ultraviolet absorption spectrum characterization approach for quantitative analysis of dissolved organic contaminants in sewage[J]. Journal of Beijing University of Technology, 2006, 32(12): 1062-1066.
9	Ye H F, Liu B D, Wang Q H, 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.
10	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 Z, Ji Y L, Zhang Y X, 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.
11	Peru K M, Thomas M J, Lozano D C P, et al. Characterization of oil sands naphthenic acids by negative-ion electrospray ionization mass spectrometry: influence of acidic versus basic transfer solvent[J]. Chemosphere, 2019, 222: 1017-1024.
12	Dittmar T, Koch B, Hertkorn N, et al. A simple and efficient method for the solid-phase extraction of dissolved organic matter (SPE-DOM) from seawater[J]. Limnology and Oceanography: Methods, 2008, 6(6): 230-235.
13	Kou Y, Jiang J T, Yang B Y, et al. Transformation of dissolved organic matter at a full-scale petrochemical wastewater treatment plant[J]. Journal of Environmental Management, 2023, 329: 117021.
14	朱大伟, 武道吉, 孙翠珍, 等. 三维荧光光谱(3D-EEM)技术在溶解性有机质(DOM)分析中的应用[J]. 净水技术, 2015, 34(1): 14-17, 28.
	Zhu D W, Wu D J, Sun C Z, et al. Application of three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectrum technology in analysis of dissolved organic matter(DOM)[J]. Water Purification Technology, 2015, 34(1): 14-17, 28.
15	孙青亮, 吴昌永, 胡翔, 等. 石化污水厂二级出水溶解性有机物分级解析研究[J]. 中国环境科学, 2012, 32(11): 2017-2022.
	Sun Q L, Wu C Y, Hu X, et al. Classification and analysis of dissolved organic matter in the effluent of a petrochemical wastewater treatment plant[J]. China Environmental Science, 2012, 32(11): 2017-2022.
16	Ye H F, Chen L, Kou Y, et al. Influences of coagulation pretreatment on the characteristics of crude oil electric desalting wastewaters[J]. Chemosphere, 2021, 264: 128531.
17	Liu Y N, Kujawinski E B. Chemical composition and potential environmental impacts of water-soluble polar crude oil components inferred from ESI FT-ICR MS[J]. PLoS One, 2015, 10(9): e0136376.
18	Shao L M, Deng Y T, Qiu J J, et al. DOM chemodiversity pierced performance of each tandem unit along a full-scale “MBR+NF” process for mature landfill leachate treatment[J]. Water Research, 2021, 195: 117000.
19	Hou C Y, Chen L, Dong Y W, et al. Unraveling dissolved organic matter in drinking water through integrated ozonation/ceramic membrane and biological activated carbon process using FT-ICR MS[J]. Water Research, 2022, 222: 118881.
20	宋健健. 百万吨级乙烯装置配套含硫废碱液处理新技术[J]. 石油炼制与化工, 2023, 54(3): 96-100.
	Song J J. New treatment process of sulfur-containing spent caustic waste water from ethylene plant[J]. Petroleum Processing and Petrochemicals, 2023, 54(3): 96-100.
21	杨长生. 电化学氧化处理特殊点源含油污水实验[J]. 油气田环境保护, 2021, 31(4): 32-36.
	Yang C S. Experiment on electrochemical oxidation treatment of special point source oily wastewater[J]. Environmental Protection of Oil & Gas Fields, 2021, 31(4): 32-36.
22	张洪涛, 杨旭, 李志, 等. 煤焦制气装置处理炼化废碱渣的新途径[J]. 中外能源, 2023, 28(6): 89-93.
	Zhang H T, Yang X, Li Z, et al. A new method for treating refinery waste alkali residue in coal and coke gasification plant[J]. Sino-Global Energy, 2023, 28(6): 89-93.
23	Kasuga I, Yuthawong V, Kurisu F, et al. Molecular-level comparison of dissolved organic matter in 11 major lakes in Japan by Orbitrap mass spectrometry[J]. Water Supply, 2020, 20(4): 1271-1280.
24	Zhang B L, Wang X N, Fang Z Y, et al. Unravelling molecular transformation of dissolved effluent organic matter in UV/ H₂O₂, UV/persulfate, and UV/chlorine processes based on FT-ICR-MS analysis[J]. Water Research, 2021, 199: 117158.
25	Patra D, Mishra A. Total synchronous-fluorescence scan spectra of petroleum products[J]. Analytical and Bioanalytical Chemistry, 2002, 373(4): 304-309.
26	Patra D, Lakshmi Sireesha K, Mishra A K. Characterization and investigation of polycyclic aromatic compounds present in petrol, diesel, kerosene and 2T oil using excitation emission matrix fluorescence[J]. Indian Journal of Chemistry, Section A. Inorganic, Physical, Theoretical & Analytical, 2001, 40A(4): 374-379.
27	Chen W, 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.
28	吴静, 曹知平, 谢超波, 等. 石化废水的三维荧光光谱特征[J]. 光谱学与光谱分析, 2011, 31(9): 2437-2441.
	Wu J, Cao Z P, Xie C B, et al. 3-D fluorescence properties of petrochemical wastewater[J]. Spectroscopy and Spectral Analysis, 2011, 31(9): 2437-2441.
29	Christensen J H, Hansen A B, Mortensen J, et al. Characterization and matching of oil samples using fluorescence spectroscopy and parallel factor analysis[J]. Analytical Chemistry, 2005, 77(7): 2210-2217.
30	Zhang B L, Shan C, Wang S, 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.
31	Maqbool T, Sun M M, Chen L, et al. Exploring the fate of dissolved organic matter at the molecular level in the reactive electrochemical ceramic membrane system using fluorescence spectroscopy and FT-ICR MS[J]. Water Research, 2022, 210: 117979.
32	吴百春, 李玉果, 聂凡, 等. 某炼化污水处理厂水中可溶有机物的转化规律研究[J]. 工业水处理, 2022, 42(1): 133-142.
	Wu B C, Li Y G, Nie F, et al. Study on the evolution of dissolved organic compounds in the water from a petrochemical wastewater treatment plant[J]. Industrial Water Treatment, 2022, 42(1): 133-142.
33	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.
34	刘彩风, 胡海冬, 廖可薇, 等. 污水处理厂中溶解性有机硫的浓度分布和分子转化特征[J]. 环境科学学报, 2022, 42(6): 12-23.
	Liu C F, Hu H D, Liao K W, et al. Concentration and molecular transformation of dissolved organic sulfur in the wastewater treatment plant[J]. Acta Scientiae Circumstantiae, 2022, 42(6): 12-23.
35	Frank R A, Fischer K, Kavanagh R, et al. Effect of carboxylic acid content on the acute toxicity of oil sands naphthenic acids[J]. Environmental Science & Technology, 2009, 43(2): 266-271.
36	任丽敏. 原油中含硫化合物的分子组成分析方法及应用[D]. 北京:中国石油大学(北京). 2019.
	Ren L M. Molecular characterization of sulfur-containing compounds in crude oils: methodology and application[D]. Beijing: China University of Petroleum, 2019.
37	Hübner U, von Gunten U, Jekel M. Evaluation of the persistence of transformation products from ozonation of trace organic compounds—a critical review[J]. Water Research, 2015, 68: 150-170.

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