汽提净化水回用原油电脱盐过程的溶解性有机物转移特征

doi:10.16085/j.issn.1000-6613.2023-0559

摘要/Abstract

摘要：

汽提净化水回用原油电脱盐是炼化企业重要的节水措施。本研究基于气相色谱-质谱和静电场轨道阱高分辨质谱组合分析，从微观层次上探究了汽提净化水回用电脱盐过程的溶解性有机物转移特征。电脱盐过程中，汽提净化水有13种芳香胺类、34种含氮杂环类、13种中长链烷基酚类和1种醚类化合物转移到油相，对油品品质影响轻微，对油品收率有所促进，同时可将电脱盐污水的有机负荷总量降低约50%。原油中的8种环烷酸类、7种含氧杂环类、3种短链烷基酚类、504种低不饱和度的O₂、O₄、O₃S₁和N₁O₃类以及186种高不饱和度的O₄S₁和N₁O₂类化合物转移到水相，使得电脱盐污水的有机污染组成更为复杂，急性生物毒性更强。本研究对于掌握高浓度点源污水的水质特性、提高炼化企业污水管控水平具有指导意义。

关键词: 汽提净化水, 原油电脱盐, 溶解性有机物, 转移特征, 静电场轨道阱高分辨质谱

Abstract:

The reusing of stripping purified water (SPW) in crude oil electric desalting process (EDP) is an efficient water-saving measure for petroleum refineries. In this study, a comprehensive analysis based on gas chromatography-mass spectrometry (GC-MS) and orbitrap mass spectrometry (Orbitrap MS) was established, and the transfer behaviors of dissolved organic matter (DOM) along SPW reusing crude oil EDP were investigated at the micro-level. During EDP, 13 types of aromatic amines, 34 types of nitrogen-containing heterocycles, 13 types of medium-/long-chain alkylphenols and 1 type of ether in SPW were transferred into oil phase. The quality of crude oil was not deteriorated while the yield slightly increased, and the total organic load in electric desalting wastewater (EDW) reduced by 50%. Simultaneously, 8 types of naphthenic acids, 7 types of oxygen-containing heterocycles, 3 types of short-chain alkylphenols, 504 types of O₂, O₄, O₃S₁, N₁O₃ species with low unsaturation and 186 types of O₄S₁, N₁O₂ species with high unsaturation originally in crude oil were transferred into water phase, increasing the complexity of DOM constituents and acute bio-toxicity of EDW. The results enhanced insights to highly polluted point-source wastewaters and improved the management of petroleum refineries.

Key words: stripping purified water, crude oil electric desalting, dissolved organic matter, transfer behaviors, orbitrap mass spectrometry

中图分类号:

TE991

张瑞, 寇悦, 孙鹤, 王辰予, 李琢宇, 王庆宏, 陈春茂. 汽提净化水回用原油电脱盐过程的溶解性有机物转移特征[J]. 化工进展, 2024, 43(4): 2153-2160.

ZHANG Rui, KOU Yue, SUN He, WANG Chenyu, LI Zhuoyu, WANG Qinghong, CHEN Chunmao. Transfer behaviors of dissolved organic matter along stripping purified water reusing crude oil electric desalting process[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 2153-2160.

图/表 6

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基础水质指标	测定方法与标准	仪器名称与型号
溶解性COD（SCOD）	重铬酸钾法 HJ 828—2017	承德华通CTL-12化学需氧量速测仪
溶解性BOD₅（SBOD₅）	稀释与接种法 HJ 505—2009	美国HACH BODTrak Ⅱ生化需氧量测试仪
溶解性有机碳（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
总溶解性氮（total dissolved nitrogen, TDN）	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
石油类	红外分光光度法 HJ 637—2012	北京华夏科创OIL480红外测油仪
极性油	红外分光光度法 HJ 637—2012	北京华夏科创OIL480红外测油仪
半数效应浓度（median effect concentration, EC₅₀）	发光细菌法 GB/T 15441—1995	英国Modern Water实验室Microtox LX生物毒性仪

基础水质指标	测定方法与标准	仪器名称与型号
溶解性COD（SCOD）	重铬酸钾法 HJ 828—2017	承德华通CTL-12化学需氧量速测仪
溶解性BOD₅（SBOD₅）	稀释与接种法 HJ 505—2009	美国HACH BODTrak Ⅱ生化需氧量测试仪
溶解性有机碳（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
总溶解性氮（total dissolved nitrogen, TDN）	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
石油类	红外分光光度法 HJ 637—2012	北京华夏科创OIL480红外测油仪
极性油	红外分光光度法 HJ 637—2012	北京华夏科创OIL480红外测油仪
半数效应浓度（median effect concentration, EC₅₀）	发光细菌法 GB/T 15441—1995	英国Modern Water实验室Microtox LX生物毒性仪

基础水质指标	汽提净化水	电脱盐污水
SCOD/mg·L^-1	3217	3518
SBOD₅/mg·L^-1	1787	1152
DOC/mg·L^-1	1545	848
极性油/mg·L^-1	312	238
石油类/mg·L^-1	24	40
TDN/mg·L^-1	194	145
DON/mg·L^-1	167	101
SBOD₅/SCOD	0.56	0.33
EC₅₀（体积分数）/%	7.33	0.38

基础水质指标	汽提净化水	电脱盐污水
SCOD/mg·L^-1	3217	3518
SBOD₅/mg·L^-1	1787	1152
DOC/mg·L^-1	1545	848
极性油/mg·L^-1	312	238
石油类/mg·L^-1	24	40
TDN/mg·L^-1	194	145
DON/mg·L^-1	167	101
SBOD₅/SCOD	0.56	0.33
EC₅₀（体积分数）/%	7.33	0.38

样品	DOM类型	DBE_wa	O/C_wa	特有DOM数量	相对丰度/%
汽提净化水	总计	2.45	0.24	71	100
	O _x	4.35	0.23	18	1.66
	O _x S _x	2.33	0.24	13	95.01
	N _x O _x	6.64	0.29	21	2.08
	N _x O _x S _x	2.09	0.17	19	1.25
电脱盐污水	总计	4.10	0.21	1784	100
	O _x	4.94	0.19	569	41.63
	O _x S _x	2.68	0.24	605	50.99
	N _x O _x	9.36	0.12	407	6.91
	N _x O _x S _x	6.81	0.39	203	0.47