本文關鍵詞： 油頁巖 干酪根 酸洗 FT-IR 13C-NMR　出處：《東北電力大學》2017年碩士論文　論文類型：學位論文

【摘要】：我國油頁巖資源儲備量較大,但石油資源匱乏,合理開發(fā)高品質的油頁巖可在一定程度上緩解石油資源緊缺的狀況。油頁巖是一種具有無機礦物質骨架并含固體有機質的沉積巖。油頁巖的工業(yè)價值及油氣生成潛力,實質上取決于其內部所含分散有機顯微組分的化學組成和結構特征。因此,深入研究油頁巖化學組成及結構特征具有重要意義。目前,世界各國在研究油頁巖的結構特性時,通常會采用酸洗去礦的方式來獲取其主要油母質(干酪根),通過研究油母質來代替油頁巖原樣。但此過程也可能改變了油頁巖的結構。本文從油頁巖及干酪根官能團結構特征、酸洗去礦對油頁巖結構影響及油頁巖生烴特性三個方面進行了研究。通過先進的FTIR和13C-NMR測試技術對窯街、樺甸油頁巖及其干酪根分別進行實驗,并結合高斯分峰擬合和歸一化法,獲得油頁巖和干酪根的化學組成和結構特性,同時分析了酸洗過程中油頁巖及其干酪根中官能團和碳骨架結構的變化。結果表明,油頁巖和干酪根中脂氫結構占主要部分,達55%以上,其中以又亞甲基為主,且多數以直鏈形式存在,脂環(huán)或支鏈較少。羥基氫鍵結構中主要以自締合氫鍵和醚氫鍵為主,兩者之和達65%以上。酸洗對油頁巖的化學結構有一定影響。其中,對脂氫和羥基氫鍵影響較小,對含氧官能團和芳香結構影響較大。脂氫中除CH伸縮振動強度減少外,其他振動形式略有加強。另外,相比油頁巖的脂氫結構,干酪根存在更多的支鏈,且酸洗過程提高了油頁巖的生烴能力和反應活性。羥基氫鍵中,酸洗的過程會破壞羥基N氫鍵、羥基醚氫鍵和環(huán)氫鍵的結構。含氧官能團以C-OH為主,由高到低依次為C-O、O=C-O、C=O,酸洗后,由于受到水解、取代和離子交換的作用,變成了以C-OH、C-O為主。芳香結構中,由油頁巖中以苯環(huán)三取代為主轉變?yōu)楦衫腋斜江h(huán)二和三取代為主,且不僅減弱了芳環(huán)縮合程度,同時減少了縮合芳環(huán)量。對五種不同地區(qū)油頁巖樣品進行固體KBr壓片紅外吸收光譜分析,并通過曲線分峰擬合建立了干酪根中脂肪烴區(qū)域結構參數的定量分析方法,得到了油頁巖的結構特征和生烴特性。結果表明:傅里葉紅外光譜(FTIR)可以直接用來對油頁巖進行生烴特性分析,而忽略礦物質對其影響,免去繁瑣的制取干酪根的過程;油頁巖脂肪族結構中CH3及次甲基含量相對較少;生烴能力越大的油頁巖,其脂肪烴碳鏈越長(支化程度越低),生氣潛力越大,芳烴含量越低,含氧官能團含量越高;此外,H/C分別與芳碳率(fa)、Hal/Har存在良好的線性關系,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.

【學位授予單位】：東北電力大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TE662.3

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本文編號：1549148