Abstract:

Oil samples, obtained by retorting Huadian oil shale at five different final temperatures, were divided, according to boiling point, into light oil (<300℃) and heavy oil (>300℃). The light oil was analyzed using GC-MS and their components classified to find the regular pattern that is variation of oil chemical composition with final retorting temperature. ¹H and ¹³C nuclear magnetic resonance spectroscopy was employed to analyze the chemical structure of the compounds in the heavy oil. The results show that the majority of Huadian light shale oil is aliphatic series compounds. Among of them, n-alkanes, α-alkenes, n-alkanals and n-alcohols are of homology and all come from alkyl radicals. With the increase of final retorting temperature, length of carbon chains in light oil is shorter and there is more n-aliphatic hydrocarbons in heavy oil, because long chain aliphatic compounds were decomposed and the side chains in branched alkanes broken, while more aromatic ring condensation reactions took place which results in more aromatic rings formation in both light oil and heavy oil as well as increase of condensational degree in light oil.

Key words: shale oil, pyrolysis, GC-MS, NMR, hydrocarbons, chemical structure

摘要：

通过控制桦甸油页岩干馏终温,得到5个不同终温下页岩油样品,对各页岩油样按沸点300℃进行切割,其中轻质油馏分(<300℃)进行GC-MS检测,对产物分类统计,分析页岩油组成成分随干馏终温变化规律;重质油馏分(>300℃)进行了¹H和¹³C核磁共振波谱分析,对谱图积分获得其氢、碳分布情况,研究了干馏终温对页岩油化学结构的影响。结果显示,轻质油组成中脂肪族化合物占绝大部分,其中正构烷烃、α-烯烃和正构醛、醇三者具有同源性,均由烷基自由基生成。随着干馏终温的升高,长链烷烃分解,支链烷烃侧链断裂,使轻质油脂肪烃碳链长度变短,重质油直链脂肪烃增多,页岩油发生更多的芳环缩合反应导致轻质油与重质油芳香环数量均增多,同时轻质油中芳环缩合程度加深。

关键词: 页岩油, 热解, 气相色谱质谱, 核磁共振, 碳氢化合物, 化学结构