依兰县油页岩碱—氧氧化及其有机质结构的基础研究

发布时间：2018-09-13 06:10

【摘要】：煤炭、石油、天然气等常规资源是我国主要的能源,为人们正常生产生活供应能量,但是目前它们的有效生产和合理利用面临着许多问题,资源禀赋较低；能源是一个国家经济发展的保障,经济迅速地增长将要求能源供应也随之增加,这就使得我国需要加快对非常规能源的研究力度。在我国目前的非常规油气资源中,油页岩的潜在储量是最大的,加大对油页岩的开发利用对缓解我国常规能源短缺问题有着重要作用。油页岩含有的有机质是主要的生油母体,对油页岩有机质基础结构特性的研究是实现油页岩高效利用的前提和基础。油页岩有机质是一种复杂的大分子聚合物,本文采用氧化降解的方法对其结构进行研究,即将大分子结构断裂生成易检测的小分子物质,而后根据小分子物质结构反演大分子物质结构。在本文的工作中,选择依兰县油页岩,将其进行碱-氧氧化,氧化产物通过高效液相色谱(HPLC)分析检测,产物中发现有工业应用价值较高的十二种苯羧酸和小分子脂肪酸。为了进一步获得较多苯羧酸和小分子脂肪酸,本文探索了反应温度、压力、时间、碱油页岩比对氧化产物产率及分布的影响规律,在温度220℃、O2初压5 MPa、反应时间1 h、碱油岩比3/1的条件下,氧化油页岩得到苯羧酸收率达到13.6%,小分子脂肪酸收率总和高达43.1%。油页岩选择性氧化得到高收率的苯羧酸和小分子酸不但为油页岩的工业应用提供了新途径,而且也为推测油页岩母体结构提供了依据。在高温高压下氧化反应将油页岩的有机质大分子断裂的比较彻底,仅根据氧化产物推测油页岩结构是不充分的。为获得油页岩更准确的结构信息,应该在不破坏油页岩原有结构的基础上,尽可能多的获得它的结构信息。在这里,采用溶剂萃取油页岩有机质和油页岩理化特性表征的方法,通过对萃取物和依兰县油页岩自身结构的分析表征,并结合前面的氧化实验结果,最终进行油页岩有机质基础结构的反演。在这部分研究工作中,选取了NMP-CS2、环己酮-NMP、离子液体-NMP这三组萃取能力比较强的复合溶剂进行了萃取实验,最终的萃取率分别达到7.32%、7.05%、22.7%。将萃取物和萃余物进行了红外光谱、气-质分析,得到萃取物中含有脂肪结构、芳香结构以及氧、硫等杂原子官能团。另外对依兰县油页岩理化特性进行了研究,主要采用扫描电子显微镜(SEM)在不同放大倍数下得到油页岩表面形态结构：呈现片状,拥有紧密、平滑的薄纹层状岩相结构,并且大小不规则；采用孔结构分析仪(BET)分析油页岩的孔隙结构及比表面积的大小：孔分布非均匀,为片状粒子堆积形成的狭缝孔,且脱灰前后的油页岩孔面积分别为4.02 m2/g、8.70 m2/g,表明油页岩脱灰后镶嵌在无机矿物质中的有机质释放出来,从而比表面积增大一倍多；采用X射线衍射光谱(XRD)对油页岩脱灰前后的晶相结构及矿物质种类进行了分析研究：脱灰后的依兰县油页岩属于非晶态物质,并且得到该油页岩中的矿物质主要为硅酸盐,另外还含有少量的高岭石、方解石、白云母等。为了使反演得到的油页岩有机质基础结构模型更加具有代表性,本文还进行了固体CP/MAS 13C核磁共振分析(NMR),积分计算得到依兰油页岩结构的十二种结构参数,其芳碳率为54%,脂碳率为41%。整合以上信息,本研究最终给出了依兰县油页岩有机质的基础结构模型。
[Abstract]:Coal, petroleum, natural gas and other conventional resources are the main energy sources in China, which supply energy for people's normal production and life. But at present, their effective production and rational use are facing many problems, and their resource endowment is low; energy is the guarantee of a country's economic development, and the rapid economic growth will require the energy supply to increase accordingly. The potential reserves of oil shale are the largest among the unconventional oil and gas resources in our country at present, and the exploitation and utilization of oil shale plays an important role in alleviating the shortage of conventional energy in our country. Organic matter in oil shale is a kind of complex macromolecule polymer. In this paper, the structure of organic matter in oil shale is studied by oxidative degradation method, that is, breaking the macromolecule structure to form small molecule material which is easy to detect, and then inverting the large one according to the structure of small molecule material. In this paper, the oil shale of Yilan County was selected for alkali-oxygen oxidation, and the oxidation products were analyzed by high performance liquid chromatography (HPLC). Twelve kinds of phenylcarboxylic acids and small molecular fatty acids with high industrial value were found in the products. The effects of reaction temperature, pressure, time and alkali-oil shale ratio on the yield and distribution of oxidation products were investigated. The yield of phenylcarboxylic acid and small molecule fatty acid reached 13.6% and 43.1% respectively under the conditions of 220 C, O2 initial pressure 5 MPa, reaction time 1 h and alkali-oil-rock ratio 3/1. Benzocarboxylic acid and small molecule acid not only provide a new way for the industrial application of oil shale, but also provide a basis for speculating the parent structure of oil shale. Accurate structural information should be obtained as much as possible without destroying the original structure of oil shale. In this paper, the method of solvent extraction of organic matter and physical and chemical characteristics of oil shale is used to analyze and characterize the extracts and the structure of Yilan oil shale, combined with the previous oxidation experiments. In this part of work, three groups of complex solvents, NMP-CS2, cyclohexanone-NMP and ionic liquid-NMP, were selected to carry out the extraction experiments. The final extraction rates were 7.32%, 7.05% and 22.7% respectively. The extracts and residues were analyzed by infrared spectroscopy, gas-NMP and gas-NMP. In addition, the physicochemical properties of Yilan oil shale were studied. The surface morphology of oil shale was obtained by scanning electron microscopy (SEM) at different magnification. The oil shale was flaky, with compact and smooth lamellae. The pore structure and specific surface area of oil shale were analyzed by BET. The pore structure and specific surface area of oil shale were non-uniform, and the pore area of oil shale were 4.02 m2/g and 8.70 m2/g, respectively, which indicated that the oil shale was embedded in inorganic minerals after demineralization. The crystalline structure and mineral types of oil shale before and after deashing were studied by X-ray diffraction spectroscopy (XRD). The oil shale after deashing belongs to amorphous substance, and the mineral in the oil shale is mainly silicate and contains less. In order to make the inversion model more representative, the solid CP / MAS 13C NMR analysis (NMR) was carried out, and twelve structural parameters of the Yilan oil shale were calculated. The aromatic carbon rate was 54%, and the fatty carbon rate was 41%. Finally, the basic structure model of organic matter in oil shale of Yilan county is given.
【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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