發(fā)布時間：2018-09-13 06:10

【摘要】：煤炭、石油、天然氣等常規(guī)資源是我國主要的能源,為人們正常生產生活供應能量,但是目前它們的有效生產和合理利用面臨著許多問題,資源稟賦較低；能源是一個國家經濟發(fā)展的保障,經濟迅速地增長將要求能源供應也隨之增加,這就使得我國需要加快對非常規(guī)能源的研究力度。在我國目前的非常規(guī)油氣資源中,油頁巖的潛在儲量是最大的,加大對油頁巖的開發(fā)利用對緩解我國常規(guī)能源短缺問題有著重要作用。油頁巖含有的有機質是主要的生油母體,對油頁巖有機質基礎結構特性的研究是實現油頁巖高效利用的前提和基礎。油頁巖有機質是一種復雜的大分子聚合物,本文采用氧化降解的方法對其結構進行研究,即將大分子結構斷裂生成易檢測的小分子物質,而后根據小分子物質結構反演大分子物質結構。在本文的工作中,選擇依蘭縣油頁巖,將其進行堿-氧氧化,氧化產物通過高效液相色譜(HPLC)分析檢測,產物中發(fā)現有工業(yè)應用價值較高的十二種苯羧酸和小分子脂肪酸。為了進一步獲得較多苯羧酸和小分子脂肪酸,本文探索了反應溫度、壓力、時間、堿油頁巖比對氧化產物產率及分布的影響規(guī)律,在溫度220℃、O2初壓5 MPa、反應時間1 h、堿油巖比3/1的條件下,氧化油頁巖得到苯羧酸收率達到13.6%,小分子脂肪酸收率總和高達43.1%。油頁巖選擇性氧化得到高收率的苯羧酸和小分子酸不但為油頁巖的工業(yè)應用提供了新途徑,而且也為推測油頁巖母體結構提供了依據。在高溫高壓下氧化反應將油頁巖的有機質大分子斷裂的比較徹底,僅根據氧化產物推測油頁巖結構是不充分的。為獲得油頁巖更準確的結構信息,應該在不破壞油頁巖原有結構的基礎上,盡可能多的獲得它的結構信息。在這里,采用溶劑萃取油頁巖有機質和油頁巖理化特性表征的方法,通過對萃取物和依蘭縣油頁巖自身結構的分析表征,并結合前面的氧化實驗結果,最終進行油頁巖有機質基礎結構的反演。在這部分研究工作中,選取了NMP-CS2、環(huán)己酮-NMP、離子液體-NMP這三組萃取能力比較強的復合溶劑進行了萃取實驗,最終的萃取率分別達到7.32%、7.05%、22.7%。將萃取物和萃余物進行了紅外光譜、氣-質分析,得到萃取物中含有脂肪結構、芳香結構以及氧、硫等雜原子官能團。另外對依蘭縣油頁巖理化特性進行了研究,主要采用掃描電子顯微鏡(SEM)在不同放大倍數下得到油頁巖表面形態(tài)結構：呈現片狀,擁有緊密、平滑的薄紋層狀巖相結構,并且大小不規(guī)則；采用孔結構分析儀(BET)分析油頁巖的孔隙結構及比表面積的大�。嚎追植挤蔷鶆�,為片狀粒子堆積形成的狹縫孔,且脫灰前后的油頁巖孔面積分別為4.02 m2/g、8.70 m2/g,表明油頁巖脫灰后鑲嵌在無機礦物質中的有機質釋放出來,從而比表面積增大一倍多；采用X射線衍射光譜(XRD)對油頁巖脫灰前后的晶相結構及礦物質種類進行了分析研究：脫灰后的依蘭縣油頁巖屬于非晶態(tài)物質,并且得到該油頁巖中的礦物質主要為硅酸鹽,另外還含有少量的高嶺石、方解石、白云母等。為了使反演得到的油頁巖有機質基礎結構模型更加具有代表性,本文還進行了固體CP/MAS 13C核磁共振分析(NMR),積分計算得到依蘭油頁巖結構的十二種結構參數,其芳碳率為54%,脂碳率為41%。整合以上信息,本研究最終給出了依蘭縣油頁巖有機質的基礎結構模型。
[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.
【學位授予單位】：北京化工大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TE662.3

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本文編號：2240308