油页岩及其干酪根官能团结构特性研究

发布时间：2018-02-28 22:06

本文关键词： 油页岩干酪根酸洗 FT-IR 13C-NMR　出处：《东北电力大学》2017年硕士论文　论文类型：学位论文

【摘要】：我国油页岩资源储备量较大,但石油资源匮乏,合理开发高品质的油页岩可在一定程度上缓解石油资源紧缺的状况。油页岩是一种具有无机矿物质骨架并含固体有机质的沉积岩。油页岩的工业价值及油气生成潜力,实质上取决于其内部所含分散有机显微组分的化学组成和结构特征。因此,深入研究油页岩化学组成及结构特征具有重要意义。目前,世界各国在研究油页岩的结构特性时,通常会采用酸洗去矿的方式来获取其主要油母质(干酪根),通过研究油母质来代替油页岩原样。但此过程也可能改变了油页岩的结构。本文从油页岩及干酪根官能团结构特征、酸洗去矿对油页岩结构影响及油页岩生烃特性三个方面进行了研究。通过先进的FTIR和13C-NMR测试技术对窑街、桦甸油页岩及其干酪根分别进行实验,并结合高斯分峰拟合和归一化法,获得油页岩和干酪根的化学组成和结构特性,同时分析了酸洗过程中油页岩及其干酪根中官能团和碳骨架结构的变化。结果表明,油页岩和干酪根中脂氢结构占主要部分,达55%以上,其中以又亚甲基为主,且多数以直链形式存在,脂环或支链较少。羟基氢键结构中主要以自缔合氢键和醚氢键为主,两者之和达65%以上。酸洗对油页岩的化学结构有一定影响。其中,对脂氢和羟基氢键影响较小,对含氧官能团和芳香结构影响较大。脂氢中除CH伸缩振动强度减少外,其他振动形式略有加强。另外,相比油页岩的脂氢结构,干酪根存在更多的支链,且酸洗过程提高了油页岩的生烃能力和反应活性。羟基氢键中,酸洗的过程会破坏羟基N氢键、羟基醚氢键和环氢键的结构。含氧官能团以C-OH为主,由高到低依次为C-O、O=C-O、C=O,酸洗后,由于受到水解、取代和离子交换的作用,变成了以C-OH、C-O为主。芳香结构中,由油页岩中以苯环三取代为主转变为干酪根中苯环二和三取代为主,且不仅减弱了芳环缩合程度,同时减少了缩合芳环量。对五种不同地区油页岩样品进行固体KBr压片红外吸收光谱分析,并通过曲线分峰拟合建立了干酪根中脂肪烃区域结构参数的定量分析方法,得到了油页岩的结构特征和生烃特性。结果表明:傅里叶红外光谱(FTIR)可以直接用来对油页岩进行生烃特性分析,而忽略矿物质对其影响,免去繁琐的制取干酪根的过程;油页岩脂肪族结构中CH3及次甲基含量相对较少;生烃能力越大的油页岩,其脂肪烃碳链越长(支化程度越低),生气潜力越大,芳烃含量越低,含氧官能团含量越高;此外,H/C分别与芳碳率(fa)、Hal/Har存在良好的线性关系,H/C越大,芳碳率(fa)越小,Hal/Har越大。
[Abstract]:China's oil shale resources reserves is large, but the lack of oil resources and the rational development of high-quality oil shale can alleviate the shortage of oil resources to a certain extent. The oil shale is a kind of inorganic mineral skeleton and sedimentary rocks containing solid organic matter. Industrial value and hydrocarbon generation potential of oil shale, essentially depends on in the interior of the containing dispersed macerals of chemical composition and structure characteristics. Therefore, it is important to further study the chemical composition and structure characteristics of oil shale. At present, all the countries in the world to study the structural properties of oil shale, usually by pickling to ore to obtain the main kerogen (Gan Laogen), by study on oil shale kerogen to replace the same. But this process may also change the structure of oil shale. The functional structure characteristics of oil shale and kerogen, pickling to impact on oil shale mine structure Three aspects of oil shale and hydrocarbon generation characteristics were studied. Through the advanced FTIR and 13C-NMR test technology of Yaojie, Huadian oil shale and kerogen test were carried out, and combined with the Gauss curve fitting and normalization method, obtain the chemical composition and structure characteristics of oil shale and kerogen, and analyzed in the process of pickling shale and kerogen functional group changes and carbon skeleton structure. The results show that the oil shale and kerogen in lipid hydrogen structure accounted for the major part, more than 55%, which is mainly to exist and the majority of methylene, straight chain, branched or alicyclic hydroxy less. Hydrogen bond structure mainly by hydrogen bonding and self association the two hydrogen bond based ether, and more than 65%. There is a certain effect of the chemical structure of oil shale pickling. Among them, little influence on lipid hydrogen and hydroxyl hydrogen bonds, a greater impact on the oxygen-containing groups and aromatic structures. In addition to lipid hydrogen CH To reduce the stretching vibration intensity, vibration and other forms are slightly strengthened. In addition, compared with the structure of hydrogen fat oil shale kerogen, more branched, improve the pickling process and oil shale hydrocarbon generation capacity and reaction activity. Hydroxyl hydrogen bond in the pickling process, will destroy the N hydroxyl hydrogen bond, hydrogen bond and hydrogen bond structure of hydroxyl ether ring the oxygen containing functional groups. Based on C-OH, from high to low was C-O, O=C-O, C=O, after pickling, due to hydrolysis, substitution and ion exchange, turned to C-OH, C-O. The aromatic structure, the oil shale in the three generation of benzene into benzene kerogen in two three and replaced, and not only weakened the degree of condensation of the aromatic ring, while reducing the amount of condensation of aromatic ring. Five kinds of oil shale samples from different regions were analyzed in solid KBr pellet infrared absorption spectrum, and the peak curve fitting to establish a dry area of aliphatic hydrocarbons in kerogen A method for quantitative analysis of domain structure parameters, the structure characteristics of oil shale and hydrocarbon generation characteristics. The results show that Fu Liye infrared spectroscopy (FTIR) can be directly used to analyze the hydrocarbon characteristics of oil shale, while neglecting the influence of minerals on the preparation process, from kerogen complex; CH3 and methylidyne were relatively small the oil shale oil shale in the aliphatic structure; hydrocarbon generation capacity is large, the aliphatic carbon chain is longer (branched lower level), angry more potential, the aromatics content is lower, the higher content of oxygen containing functional groups; in addition, H/C and aromatic carbon ratio (FA), there is a good linear relationship Hal/Har H/C, the greater the aromatic carbon rate (FA) is smaller, the greater the Hal/Har.

【学位授予单位】：东北电力大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TE662.3

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