【摘要】：面對石油需求的與日俱增和動蕩的國際局勢,提高石油自給比例,降低對外依存度,對國家發(fā)展意義重大。油頁巖作為一種非常規(guī)能源,其干餾能產(chǎn)生類似石油原油的頁巖油,經(jīng)過分離、改善油品后有望作為汽油、柴油等的替代油,所以開發(fā)利用油頁巖對緩解我國石油緊張局勢意義重大。油頁巖中含有大量的礦物質(zhì),對油頁巖的熱分解有影響,但其中的黃鐵礦在干餾過程中會產(chǎn)生H2S等含硫氣體污染環(huán)境和腐蝕設備。因此有必要探究內(nèi)在礦物質(zhì)和黃鐵礦對油頁巖熱解中的影響作用,為清潔高效利用頁巖油提供理論指導。通過對油頁巖原樣和脫灰后的干酪根在不同溫度下進行固定床熱解實驗,并借助FTIR、GC-MS等分析手段對不同溫度下的產(chǎn)物產(chǎn)率、半焦化學結構和頁巖油組成特性進行了分析,獲得了油頁巖熱解的基本特性及自身礦物質(zhì)對熱解過程的影響。結果表明隨著溫度的升高,油頁巖轉(zhuǎn)化率不斷升高,干酪跟最佳產(chǎn)油率溫度為490℃,礦物質(zhì)存在時該溫度提高到520℃,并促進了頁巖油的生成。礦物質(zhì)對脂肪族長鏈和甲基側(cè)鏈的斷裂、環(huán)狀結構的生成、氧的脫除有促進作用,對干酪跟高溫下的芳構化有抑制作用,同時能抑制其他來源的氧轉(zhuǎn)化成羧基。頁巖油中以脂肪烴為主要成分,礦物質(zhì)促進了脂肪烴的生成,對烯烴的生成起抑制作用,礦物質(zhì)存在的情況下頁巖油中的PAC通過脂肪烴氣相裂解反應生成,頁巖油中硫含量也降低。通過對干酪添加黃鐵礦和單質(zhì)硫進行熱解實驗,并借助FTIR、GC-MS等分析手段分析了干酪根有無添加劑熱解時不同溫度下的產(chǎn)物產(chǎn)率、半焦化學結構和頁巖油組成特性。結果表明外加黃鐵礦和單質(zhì)硫不利于頁巖油的生成。黃鐵礦在低溫下對氣態(tài)烴類的生成起到了促進作用,單質(zhì)硫促進油母質(zhì)大分子的解聚和裂解,同時促進了頁巖油和小分子的氣態(tài)產(chǎn)物生成,這與黃鐵礦的催化作用不同。黃鐵礦和單質(zhì)硫的存在抑制了芳構化進程。加入黃鐵礦時PACs主要通過脂肪烴氣相裂解反應生成的,加入單質(zhì)硫時PACs主要通過Diels-Alder型反應生成。黃鐵礦和單質(zhì)硫在促進自由基形成過程中的作用機理相同。
[Abstract]:In the face of the increasing oil demand and volatile international situation, it is of great significance for the development of the country to increase the proportion of oil self-sufficiency and reduce the degree of dependence on foreign countries. As an unconventional energy, oil shale can produce shale oil similar to petroleum and crude oil. After separation and improvement of oil products, it is expected to be used as an alternative oil for gasoline, diesel and so on. Therefore, the development and utilization of oil shale is of great significance to ease the oil tension in China. Oil shale contains a large number of minerals, which has an impact on the thermal decomposition of oil shale, but pyrite in the process of dry distillation will produce H _ 2S and other sulfur-containing gases to pollute the environment and corrode equipment. Therefore, it is necessary to explore the influence of internal minerals and pyrite on the pyrolysis of oil shale, and to provide theoretical guidance for clean and efficient utilization of shale oil. The fixed bed pyrolysis experiments of kerogen after oil shale and deashing were carried out at different temperatures, and the product yield, semi-coke chemical structure and shale oil composition at different temperatures were analyzed by means of FTIR,GC-MS. The basic characteristics of oil shale pyrolysis and the effect of its own minerals on the pyrolysis process were obtained. The results show that with the increase of temperature, the conversion of oil shale increases, the temperature of cheese and the optimum oil production rate is 490 鈩，

本文編號：2507350