焦化废水生物出水中可溶解性有机物的分子识别

doi:10.16085/j.issn.1000-6613.2022-1868

化工进展 ›› 2023, Vol. 42 ›› Issue (9): 4984-4993.DOI: 10.16085/j.issn.1000-6613.2022-1868

焦化废水生物出水中可溶解性有机物的分子识别

王琦¹^,²^,³(), 寇丽红¹^,²^,³, 王冠宇¹^,²^,³, 王吉坤¹^,²^,³, 刘敏¹^,²^,³, 李兰廷¹^,²^,³, 王昊¹^,²^,³

^1.煤炭科学技术研究院有限公司，北京 100013
^2.煤炭资源高效开采与洁净利用国家重点实验室，北京 100013
^3.国家能源煤炭高效利用与节能减排技术装备重点实验室，北京 100013

收稿日期:2022-10-09 修回日期:2022-11-16 出版日期:2023-09-15 发布日期:2023-09-28
通讯作者: 王琦
作者简介:王琦（1994—），男，硕士，助理研究员，研究方向为煤化工废水处理。E-mail：abaliangshu@163.com。
基金资助:
政府间国际科技创新合作重点专项(2019YFE0103300);中国煤炭科工集团有限公司科技创新创业资金专项(2019-ZD004)

Molecular recognition of dissolved organic matter in bio-treated effluent of coking wastewater

WANG Qi¹^,²^,³(), KOU Lihong¹^,²^,³, WANG Guanyu¹^,²^,³, WANG Jikun¹^,²^,³, LIU Min¹^,²^,³, LI Lanting¹^,²^,³, WANG Hao¹^,²^,³

^1.China Coal Research Institute, Beijing 100013, China
^2.State Key Laboratory of Coal Mining and Clean Utilization, Beijing 100013, China
^3.National Energy Technology ＆ Equipment Laboratory of Coal Utilization and Emission Control, Beijing 100013, China

Received:2022-10-09 Revised:2022-11-16 Online:2023-09-15 Published:2023-09-28
Contact: WANG Qi

摘要/Abstract

摘要：

焦化废水中可溶解性有机物成分复杂、难生化降解。为从分子层次揭示焦化废水生物出水中可溶解性有机化合物的组成，首先使用二氯甲烷作为萃取剂，通过液液萃取将河北迁安宏奥工贸焦化厂的焦化废水生物出水分离成有机相和萃余相；对有机相进行四组分分离，根据四组分极性的不同，对极性较弱的饱和分和芳香分采用气相色谱-质谱联用仪（GC/MS）分析，对极性较强的胶质和沥青质采用傅里叶变换离子回旋共振质谱结合电喷雾电离源（ESI FT-ICR MS）分析；对极性强的萃余相用固相萃取法得到SPE洗脱物，并进行ESI FT-ICR MS分析。结果表明：饱和分中共检测到120种化合物，焦化废水经生物处理后的难溶解有机物主要为一些分子质量较大的正构烷烃和链烷烃；芳香分中检测到34种化合物，主要检测到较高含量的醇类、酯类和酚类化合物，其中酚类主要是苯酚的烷基取代物；胶质、沥青质和SPE洗脱物分别检测到N _x 、N₁O _x 、N₂O _x 、O _x 和O _x S₁ 5类主要碱性有机物和非碱性有机物，胶质和沥青质中的化合物类型分布相似，且沥青质中的化合物更加丰富，SPE洗脱物的化合物类型分布与胶质和沥青质差别较大。根据碳数分布和DBE值，分别得到了主要化合物分子的结构，为焦化废水深度处理工艺的优化和改进提供了理论依据。

关键词: 焦化废水, 生物出水, 可溶解性有机物, 分子识别

Abstract:

The composition of soluble organic compounds in coking wastewater is complex and difficult to be biodegraded. In order to reveal the composition of soluble organic compounds in the biological effluent of coking wastewater from the molecular level, dichloromethane was first used as the extractant to separate the biological effluent of coking wastewater from Hebei Qian’an Hong’ao Industry and Trade Coking Plant into organic phase and raffinate phase through liquid-liquid extraction. The organic phase was separated into four components. According to the different polarity of the four components, the saturated and aromatic components with weak polarity were analyzed by GC/MS, and the resin and asphaltene with strong polarity were analyzed by Fourier transform ion cyclotron resonance mass spectrometry combined with electric spray ionization source (ESI FT-ICR MS).The SPE eluate was obtained from the strongly polar raffinate by solid phase extraction and analyzed by ESI FT-ICR MS. The results showed that one hundred and twenty kinds of compounds were detected in the saturated fraction, and the insoluble organics in the coking wastewater after biological treatment were mainly n-alkanes and alkanes with higher molecular weight. Thirty-four compounds were detected in the aromatic fraction, mainly alcohols, esters and phenols with high content, of which phenols were mainly alkyl substitutes of phenol. The resin, asphaltene and SPE eluate detected five main types of alkaline and non alkaline organics, including N _x, N₁O _x, N₂O _x, O _x_{and O _x S₁, respectively. The distribution of compound types in resins and asphaltenes was similar, and the compounds in asphaltenes were more abundant. The distribution of compound types in SPE eluates was quite different from those in resins and asphaltenes. According to the carbon number distribution and DBE value, the molecular structures of the main compounds were obtained, which provided a theoretical basis for the optimization and improvement of the coking wastewater advanced treatment process.}

Key words: coking wastewater, bio-treated effluent, dissolved organic matter, molecular recognition

中图分类号:

X703

王琦, 寇丽红, 王冠宇, 王吉坤, 刘敏, 李兰廷, 王昊. 焦化废水生物出水中可溶解性有机物的分子识别[J]. 化工进展, 2023, 42(9): 4984-4993.

WANG Qi, KOU Lihong, WANG Guanyu, WANG Jikun, LIU Min, LI Lanting, WANG Hao. Molecular recognition of dissolved organic matter in bio-treated effluent of coking wastewater[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4984-4993.

图/表 13

参考文献 22

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化合物种类	数量	质量分数/%	有机物组成（按质量分数排序）
正构烷烃	20	36.95	二十烷、十八烷、3-甲基-十九烷、二十二烷、十六烷、二十四烷、二十七烷、8-庚基-十五烷、二十九烷、二十六烷、2,6,10,14-四甲基-十七烷、 3-甲基-十七烷、11-丁基-二十二烷等
链烷烃	58	42.69
环烷烃	10	6.74
烯烃	3	2.18
含氧化合物	24	6.18
含硫化合物	0	0
其他	5	3.26
汇总	120	100

化合物种类	数量	质量分数/%	有机物组成（按质量分数排序）
正构烷烃	20	36.95	二十烷、十八烷、3-甲基-十九烷、二十二烷、十六烷、二十四烷、二十七烷、8-庚基-十五烷、二十九烷、二十六烷、2,6,10,14-四甲基-十七烷、 3-甲基-十七烷、11-丁基-二十二烷等
链烷烃	58	42.69
环烷烃	10	6.74
烯烃	3	2.18
含氧化合物	24	6.18
含硫化合物	0	0
其他	5	3.26
汇总	120	100

化合物种类	数量	质量分数/%	有机物组成（按质量分数排序）
醇类化合物	3	22.31	2,4-双(1,1-二甲基乙基)-苯酚、2,2'-亚乙撑双（4,6-二叔丁基苯酚）、1,2-苯二甲酸二异辛酯、 4,5,7-三（1,1-二甲基乙基）-3,4-二氢-1,4-环氧萘-1(2H)-甲醇等
酯类化合物	6	20.33
醛类化合物	1	4.33
酸类化合物	3	7.32
酚类化合物	3	37.48
其他	18	8.23
汇总	34	100

化合物种类	数量	质量分数/%	有机物组成（按质量分数排序）
醇类化合物	3	22.31	2,4-双(1,1-二甲基乙基)-苯酚、2,2'-亚乙撑双（4,6-二叔丁基苯酚）、1,2-苯二甲酸二异辛酯、 4,5,7-三（1,1-二甲基乙基）-3,4-二氢-1,4-环氧萘-1(2H)-甲醇等
酯类化合物	6	20.33
醛类化合物	1	4.33
酸类化合物	3	7.32
酚类化合物	3	37.48
其他	18	8.23
汇总	34	100

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焦化废水生物出水中可溶解性有机物的分子识别

Molecular recognition of dissolved organic matter in bio-treated effluent of coking wastewater

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