油页岩中有机质的表征

发布时间：2018-04-15 04:01

本文选题：油页岩 + 结构表征　；参考：《北京化工大学》2015年硕士论文

【摘要】：油页岩是我国重要的替代能源之一,随着常规能源资源消耗的日益加大,油页岩等非常规能源资源的利用日益受到人们的重视。油页岩主要用于干馏炼油,然而我国油页岩炼油技术非常落后,仍沿用上世纪20-30年代的垂直筒式抚顺干馏炉,产能低、油收率低、油品质重。为了提高页岩油的收率和品质,众多研究者对油页岩中生油组分—一有机质进行了大量研究。我国关于油页岩有机质结构研究起步较晚,并且集中在对抚顺、茂名、桦甸油页岩的研究上,而关于依兰油页岩有机质结构的研究鲜有报道。本文采用FT-IR,13C NMR以及溶剂萃取法对依兰油页岩有机质的结构组成进行了研究,发现依兰油页岩有机质中芳香族化合物含量较高,芳碳率高达49%,主要为三环及三环以下的芳环结构,芳环取代度为0.46,并在其溶剂萃取物中检测到1-4环的芳香化合物；依兰油页岩有机质中脂肪碳含量为45%,主要为亚甲基和次甲基结构,且大部分以芳香结构间桥碳链形式存在,平均碳链长度为5-10个碳原子；同时含有16%的C-O、C-OH官能团以及羰基化合物。由于油页岩形成环境的不同,其成分、结构及颜色呈现不均一性。依兰和桦甸油页岩中均存在两种颜色不同、光泽度和密度等物理性质差异较大的油页岩,一种呈黑色,有沥青光泽,质轻,易破碎,为有机质富集的油页岩；另一种呈现为土灰色,密度大,质地坚硬,为矿物质富集的油页岩。本文对这两种不同富集形态油页岩的组成、结构进行研究,发现相同产地、不同富集形态油页岩结构组成差别较大,而不同产地、相同富集形态油页岩结构组成相近。灰色油页岩的H/C比(1.35)接近于沥青质,黑色油页岩的H/C比(0.86)接近于煤,灰色油页岩中挥发分含量(Vdaf)远高于黑色油页岩；依兰和桦甸黑色油页岩有机质碳骨架结构中芳香结构含量较高,其芳碳率分别为57%和58%；而灰色油页岩则含有较多的脂肪结构,其脂碳率分别为63%和62%。且灰色油页岩中脂链长度比黑色油页岩长。
[Abstract]:Oil shale is one of the important alternative energy sources in China. With the increasing consumption of conventional energy resources, the utilization of unconventional energy resources such as oil shale has been paid more and more attention.Oil shale is mainly used in retorting oil refining, however, the oil shale refining technology in China is very backward, and it still uses the vertical Fushun retort furnace in the 20-30 's of last century, with low production capacity, low oil yield and heavy oil quality.In order to improve the yield and quality of shale oil, many researchers have done a lot of research on the organic matter, an oil component in oil shale.The study on the organic matter structure of oil shale in China started late, and focused on Fushun, Maoming and Huadian oil shale, but there are few reports on the organic matter structure of Yilan oil shale.In this paper, the structure and composition of organic matter in Yilan oil shale were studied by FT-IRN 13C NMR and solvent extraction method. It was found that the aromatic compounds in the organic matter of Yilan oil shale were high, and the aromatic carbon content was as high as 49%.The degree of substitution of aromatic rings was 0.46, and 1-4 ring aromatic compounds were detected in their solvent extracts. The fatty carbon content in the organic matter of Yilan oil shale was 45, which mainly consisted of methylene and methylene groups, and most of them existed in the form of bridging carbon chains between aromatic structures.The average length of carbon chain is 5-10 carbon atoms, and it also contains 16% C-OO C-OH functional groups and carbonyl compounds.Because of the different formation environment of oil shale, its composition, structure and color show heterogeneity.There are two different colors in Yilan and Huadian oil shale, one is black oil shale, which has asphalt luster, light weight, easy to break, and is rich in organic matter.The other is a grayish, dense, hard, mineral-rich oil shale.In this paper, the composition and structure of the two kinds of oil shale with different enrichment forms are studied. It is found that the structural composition of the oil shale with the same origin and different enrichment forms is quite different, while the structural composition of the oil shale with the same enrichment form is similar in different producing areas.The H / C ratio of grey oil shale is close to that of asphaltene, the H / C ratio of black oil shale is 0.86), and the volatile content of grey oil shale is much higher than that of black oil shale.The content of aromatic structure in organic carbon framework of Yilan and Huadian black oil shale is high, and the aromatic carbon ratio is 57% and 58%, respectively, while the grey oil shale contains more fat structure, its lipide-carbon ratio is 63% and 62%, respectively.The length of lipid chain in grey oil shale is longer than that in black oil shale.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE662.3

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