某炼化污水处理厂水中可溶有机物的转化规律研究

doi:10.19965/j.cnki.iwt.2021-0446

摘要/Abstract

摘要：

利用三维荧光和高分辨质谱等手段分析某炼油化工企业炼化废水处理厂不同来源污水（炼油废水、酸性废水、化工废水）可溶有机质（DOM）的分子组成。结果表明，炼油废水DOM浓度低且极性化合物以含氧类化合物为主；酸性废水、化工废水DOM浓度较高，检测到高丰度的表面活性剂及其衍生物为主的聚合物类等多氧含硫类化合物。对不同来源废水在水解酸化、生化和臭氧催化氧化单元工艺中的DOM变化规律进行研究，发现分子缩合度较低的化合物及多氧含硫类化合物在水解酸化工艺中能得到有效降解；生化处理后86%的DOM得到降解，其中分子缩合度低，在荧光光谱中显示类酪氨酸类特征的化合物在生化单元中得到有效去除；臭氧催化氧化工艺对类腐殖酸具有良好去除效果。此外研究发现，废水经生化单元处理，其DOM去除效率、荧光基团及极性化合物变化规律不受进水水质影响；类色氨酸类和多氧含硫类化合物等难降解有机物，是影响废水可生化性能及处理达标的关键因素。

关键词: 炼化废水, 可溶有机质, 组成特征, 转化规律

Abstract:

The molecular components of dissolved organic matter（DOM） in sewage source（refining，acid and chemical wastewater）from a wastewater treatment plant in a refining⁃chemical integration plant was characterized by three⁃dimensional fluorescence excitation⁃emission matrix and Fourier transform ion cyclotron resonance mass spectrometry. It was found that the refining wastewater had low content of dissolved organic carbon（DOC） and CHO compounds（containing carbon，hydrogen，and oxygen atoms in the molecules）were the major polar substances；while the chemical wastewater and acid wastewater had high DOC and showed high abundance of polymer⁃based oxygen⁃containing sulfur compounds（CHOS）. The transformation of these compounds during the process of hydrolytic acidification，aerobic contact oxidation，and ozone catalytic oxidation were investigated. It was observed that the aliphatic and unsaturated phenolic CHOS compounds could be effectively degraded in the hydrolysis acidification process. After biochemical treatment，86% of organic matter was reduced. Among them，the molecular condensation degree was low，and the compounds showing tyrosine⁃like characteristics in the fluorescence spectrum could be effectively removed in the biochemical unit. Ozone catalytic oxidation unit had a good performance on the reduction of humic⁃like compounds. Moreover，in the process of biochemical unit，the results showed that the removal efficiency of DOC，fluorophores，and polar compounds were little affected by the characteristic of the incoming water. The major factors that influence the biodegradability were the refractory organics mainly consisting of tryptophan⁃like，multiple⁃oxygen⁃atom CHOS compounds.

Key words: refinery wastewater, dissolved organic matter, composition characteristics, transformation

中图分类号:

TE992.2

吴百春, 李玉果, 聂凡, 何晨, 史权. 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.

Baichun WU, Yuguo LI, Fan NIE, Chen HE, Quan SHI. 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.

https://www.iwt.cn/CN/Y2022/V42/I1/133

图/表 14

图1 某石化企业综合污水处理厂工艺流程图及采样点

Fig. 1 Process flow chart and sampling points of a comprehensive sewage treatment plant in a petrochemical enterprise

表1 不同废水水质特征及有机组成对比

Table 1 Comparison table of water quality characteristics and organic composition of different wastewaters

分析方法与参数		7^#炼油废水	1^#酸性废水	2^#化工污水
原水DOC/（mg·L^-1）		45.2	256.1	27.6
原水COD/（mg·L^-1）		250	1 076	104
原水氨氮/（mg·L^-1）		17.5	6.9	2
DCM相石油四组分质量分数/%	饱和烃	45.22	9.95	37.04
	芳香烃	12.17	2.94	18.54
	胶质	33.04	80.32	34.86
	沥青质	5.22	2.26	5.56
3D-EEM 荧光基团*	DCM相	B1、T2	B1、B2	B1、T2
3D-EEM 荧光基团*	水相	B1、B2	T1、T2	B1、B2
水相FT-ICR MS 极性化合物数量	O _x	1 619	67	912
	O _x S	1 119	178	1 086
	N _x O _x	828	24	281
	NOS	275	16	36
	总	3 841	285	2 315
	丰度较高	O₆~O₇	O₅S₁~O₇S₁	O₈S₁~O₉S₁

图2 3种废水DCM萃取有机相（上）及水相（下）可溶有机质的3D-EEM

Fig. 2 3D-EEM of dissolved organic matter in organic phase and aqueous phase of three wastewaters

图3 3种废水水相鉴定化合物种类的相对丰度图

Fig. 3 Relative abundance of the identified compounds in the aqueous phase for the wastewaters

表2 高浓度污水处理工艺基础数据

Table 2 Bulk properties of high⁃concentration wastewater treatment process

样品	3^#高浓度进水	4^#水解酸化	5^# 3/4 生化出水	6^#臭氧催化氧化
COD/（mg·L^-1）	1 151	564	83	57
氨氮/（mg·L^-1）	40.9	26.5	14.2	8
总DOC/（mg·L^-1）	174.2	178.2	25.3	17.3
DCM相DOC占比/%	31.26	28.86	9.56	7.98
水相DOC占比/%	5.70	9.71	24.67	27.62
DOC总收率/%	36.96	38.57	34.23	35.60

图4 高浓度处理工艺水相可溶有机质的3D-EEM

Fig. 4 3D-EEM spectra of aqueous phase DOM from the high⁃concentration wastewater treatment process

图5 高浓度处理工艺DCM相可溶有机质的3D-EEM

Fig. 5 3D-EEM spectra of organic phase DOM from the high⁃concentration wastewater treatment process

图6 高浓度处理工艺水相DOM中所鉴定化合物的杂原子相对丰度

Fig. 6 Relative abundance of identified compounds in aqueous phase of the wastewaters from the high⁃concentration wastewater treatment process

图7 高浓度处理工艺流程CHO和CHOS类化合物的VK图（a）水解酸化；（b）生化；（c）臭氧催化氧化处理前后

Fig. 7 van Krevelen diagrams of removed and newly formed CHO and CHOS formulas in the aqueous phase of high⁃concentration wastewater treatment process

表3 高浓度处理工艺极性化合物在水处理过程中种类和数量的变化

Table 3 Variations in the types and quantities of polar compounds in high⁃concentration treatment processes

种类	高浓度进水	水解酸化出水	3/4生化出水	臭氧催化氧化出水
O _x	647	1 498	1 987	1 320
N _x O _x	63	208	707	419
O _x S₁	857	691	987	1 217
NOS	98	50	176	166
总计	1 665	2 447	3 857	3 122

表4 低浓度污水处理工艺生化处理前后DOC、COD、氨氮质量浓度变化

Table 4 Changes of DOC，COD and NH₃-N before and afterbiochemical treatment of low⁃concentration sewage treatment process

水样来源	DOC/（mg·L^-1）	COD/（mg·L^-1）	氨氮/（mg·L^-1）
1/2生化前	55.3	236	37
1/2生化后	9.6	37	1.7

图8 高、低浓度污水处理工艺生化单元出水可溶有机质的3D-EEM图

Fig. 8 3D-EEM of dissolved organic matter in effluent of biochemical unit of high and low concentration wastewater treatment process

图9 高、低浓度处理工艺生化出水可溶有机质的杂原子丰度图

Fig. 9 Relative abundance of assigned compound classes in the aqueous phase DOM from biochemical treatment processes

图10 高、低浓度污水处理工艺生化处理过程CHO、CHOS类的生成和去除的VK图（a）高浓度处理工艺3/4生化；（b）低浓度处理工艺1/2生化

Fig. 10 van Krevelen diagrams of removed and newly formed CHO and CHOS formulas in the biochemical treatment process of high and low concentration wastewater treatment routes

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