基于GC×GC-TOF MS的煤液化产物油分子组成结构表征  

Molecular composition and structure characterization of coal liquefaction product oil based on GC×GC-TOF MS

作　　者：李奕菲 苏沿霏 尹甜[2] 姜浩强 许志明[1] 张霖宙 史权[1] 徐春明[1] LI Yifei;SU Yanfei;YIN Tian;JIANG Haoqiang;XU Zhiming;ZHANG Linzhou;SHI Quan;XU Chunming(State Key Laboratory of Heavy Oil Processing,Petroleum Molecular Engineering Center(PMEC),China University of Petroleum,Beijing 102249,China;China Shenhua Coal to Liquid and Chemical Co.,Ltd.,Beijing 100010,China;Ordos Coal to Oil Branch,China Shenhua Coal to Liquid and Chemical Co.,Ltd.,Ordos 017209,Inner Mongolia,China)

机构地区：[1]中国石油大学(北京)重质油全国重点实验室石油分子工程中心,北京102249 [2]中国神华煤制油化工有限公司,北京100010 [3]中国神华煤制油化工有限公司鄂尔多斯煤制油分公司,内蒙古鄂尔多斯017209

出　　处：《化工学报》2025年第2期543-553,F0001,共12页CIESC Journal

基　　金：国家自然科学基金项目(22222815);国家能源集团科技项目(GJNY-23-23)。

摘　　要：煤直接液化产物分子组成复杂,探究产物的详细分子组成对煤制油工艺的优化具有重要意义。建立了煤液化油及其加氢过程产物的全二维气相色谱-飞行时间质谱/氢火焰离子化检测器(GC×GC-TOF MS/FID)分子层次的组成和结构定性定量表征方法,揭示了煤液化加氢反应规律。GC×GC-TOF MS液化油分子组成表征技术通过分子极性在二维上的差异初步解决了一维色谱中多个化合物因保留时间相近共逸出的问题。煤液化油加氢后环烷烃含量增加,芳烃含量减少。在循环溶剂中主要通过三环、四环芳烃分子不同程度的氢化分子起到溶氢供氢的作用。另外,针对煤直接液化石脑油和柴油也建立了GC×GC-TOF MS/FID烃族组成表征,与直馏加氢汽柴油的族组成含量相比,煤直接液化产物中含有较多的环烷烃化合物。The molecular composition of the direct coal liquefaction products is complex.It is of great significance to explore the detailed molecular composition of the direct coal liquefaction products for the optimization of the coal-to-oil process.Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry/hydrogen flame ionization detector(GC×GC-TOF MS/FID)method was established for the qualitative and quantitative characterization of composition and structure of coal liquefaction oil and its hydrogenation process products at the molecular level,which revealed the hydrogenation reaction law of coal liquefaction.The molecular composition characterization technology of GC×GC-TOF MS liquefied oil preliminarily solved the problem that multiple compounds co-escape in one-dimensional chromatography due to the same retention time through the difference of molecular polarity in two dimensions.After hydrogenation of coal liquefaction oil,the content of cycloalkanes increases and the content of aromatics decreases.In the circulating solvent,the hydrogen dissolving and supplying hydrogen is mainly achieved through the hydrogenation of three-ring and four-ring aromatic molecules to varying degrees.In addition,the GC×GC-TOF MS/FID characterization technology of hydrocarbon group composition was also established for direct coal liquefaction naphtha and diesel.Compared with the group composition content of straight-run hydrogenated diesel and gasoline,the direct coal liquefaction products diesel and gasoline contain more monocyclic,bicyclic and tricyclic alkanes.

关 键 词：煤制油 加氢 化学分析 GC×GC-TOF MS 分子工程 定性定量 

分 类 号：TE622[石油与天然气工程—油气加工工程]