基于FT-ICR MS表征煤焦化废水处理过程有机物分子组成变化  

Molecular Characterization of Dissolved Organic Matter in Coal Coking Wastewater by FT-ICR MS

作　　者：马超[1] 吴建勋 倪洪星 房治 王威 高源 史权[2] MA Chao;WU Jian-xun;NI Hong-xing;FANG Zhi;WANG Wei;GAO Yuan;SHI Quan(School of Earth System Science,Tianjin University,Tianjin 300072,China;State Key Laboratory of Heavy Oil,China University of Petroleum,Beijing 102249,China;Sinochem Asset Management Co.,Ltd.,Beijing 100045,China;State Key Laboratory of Environmental and Biological Analysis,Hong Kong Baptist University,Hong Kong 999077,China)

机构地区：[1]天津大学地球系统科学学院,天津300072 [2]中国石油大学(北京)重质油国家重点实验室,北京102249 [3]中化资产管理有限公司,北京100045 [4]香港浸会大学环境与生物分析国家重点实验室,中国香港999077

出　　处：《质谱学报》2023年第3期387-396,I0003,共11页Journal of Chinese Mass Spectrometry Society

摘　　要：有效去除水溶性有机质(DOM)是废水处理的一项重要内容,但DOM分子组成及其在处理过程中的变化规律并不明确。本文以一整套煤焦化废水为研究对象,通过液-液萃取和固相萃取分离得到不同极性的水相有机质组分,使用傅里叶变换离子回旋共振质谱(FT-ICR MS)对所得的有机质进行分子层次表征。油相和水相有机质的水溶性总有机碳(TOC)比例基本一致,随着处理过程的进行,废水的“油性”越来越弱,能溶解在二氯甲烷中的有机质越来越少,最后所剩的主要是一些难以降解的腐殖质类物质;而水相有机质具有极其复杂的分子组成,在单一质谱图中共鉴定出70余种不同种类的化合物,这些化合物,尤其是O_(4)S_(1)类化合物,虽然在废水处理过程中有很好的去除效果,但在最终出水中仍有残留。Efficient removal of dissolved organic matter(DOM) is an important task for wastewater treatment.However,the molecular composition of DOM and its transformation during the treatment are still unclear.In this paper,the organic components in the stream of a coal coking wastewater treatment process were studied.The wastewater was extracted by dichloromethane(CH_(2)Cl_(2)),the extract was named as 'oil phase'.Then the raffinate was extracted by solid-phase extraction,the extract was named as 'water phase'.The ratios of total organic carbon contents(TOC) in the oil and water phase samples were generally consistent during the treatment process.The extracted DOM was characterized by Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS).Eight class species were as assigned from the mass spectra,namely N_(1)O_(1-7),N_(2)O_(1-6),N_(1)O_5,N_(1)O_(2-6)S_(1),N_(2)O_(3-5)S_(1),O_(2-8),O_(2-6)S_(1),O_(4-5)S_(2).The class categories which contain multiple oxygen atoms(O_(x)) and both multiple oxygen and sulfur atoms(O_(x)S_(y)) were dominant in the oil phase.The relative abundance of each species was decreased sharply after the first aerobic biological process,which was consistent with the TOC rapid decline in the sample.O_(2-8) compounds existed in all wastewater samples and dominated in the final sample,indicating that these compounds were the most stubborn pollutants which were difficult to remove in all treatment processes.It is speculated that these compounds may come from some humic-acids which have complex structure and multiple oxygen atoms naturally existing in natural water.The composition of O_(3) class species showed two patterns among the wastewater treatment process,compounds with high double bond equivalent(DBE) were dominant in the first four processes,while a proliferation of low DBE components was observed in the last three samples.It indicated that those low DBE components were generated by the oxidation of other substances,such as O_(1) and O_(2) species.The water phase organic matter had an

关 键 词：煤焦化废水 水溶性有机质 傅里叶变换离子回旋共振质谱(FT-ICR MS) 

分 类 号：O657.63[理学—分析化学]