【摘要】：面對(duì)石油需求的與日俱增和動(dòng)蕩的國(guó)際局勢(shì),提高石油自給比例,降低對(duì)外依存度,對(duì)國(guó)家發(fā)展意義重大。油頁(yè)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(yè)巖油,經(jīng)過(guò)分離、改善油品后有望作為汽油、柴油等的替代油,所以開(kāi)發(fā)利用油頁(yè)巖對(duì)緩解我國(guó)石油緊張局勢(shì)意義重大。油頁(yè)巖中含有大量的礦物質(zhì),對(duì)油頁(yè)巖的熱分解有影響,但其中的黃鐵礦在干餾過(guò)程中會(huì)產(chǎn)生H2S等含硫氣體污染環(huán)境和腐蝕設(shè)備。因此有必要探究?jī)?nèi)在礦物質(zhì)和黃鐵礦對(duì)油頁(yè)巖熱解中的影響作用,為清潔高效利用頁(yè)巖油提供理論指導(dǎo)。通過(guò)對(duì)油頁(yè)巖原樣和脫灰后的干酪根在不同溫度下進(jìn)行固定床熱解實(shí)驗(yàn),并借助FTIR、GC-MS等分析手段對(duì)不同溫度下的產(chǎn)物產(chǎn)率、半焦化學(xué)結(jié)構(gòu)和頁(yè)巖油組成特性進(jìn)行了分析,獲得了油頁(yè)巖熱解的基本特性及自身礦物質(zhì)對(duì)熱解過(guò)程的影響。結(jié)果表明隨著溫度的升高,油頁(yè)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(shí)該溫度提高到520℃,并促進(jìn)了頁(yè)巖油的生成。礦物質(zhì)對(duì)脂肪族長(zhǎng)鏈和甲基側(cè)鏈的斷裂、環(huán)狀結(jié)構(gòu)的生成、氧的脫除有促進(jìn)作用,對(duì)干酪跟高溫下的芳構(gòu)化有抑制作用,同時(shí)能抑制其他來(lái)源的氧轉(zhuǎn)化成羧基。頁(yè)巖油中以脂肪烴為主要成分,礦物質(zhì)促進(jìn)了脂肪烴的生成,對(duì)烯烴的生成起抑制作用,礦物質(zhì)存在的情況下頁(yè)巖油中的PAC通過(guò)脂肪烴氣相裂解反應(yīng)生成,頁(yè)巖油中硫含量也降低。通過(guò)對(duì)干酪添加黃鐵礦和單質(zhì)硫進(jìn)行熱解實(shí)驗(yàn),并借助FTIR、GC-MS等分析手段分析了干酪根有無(wú)添加劑熱解時(shí)不同溫度下的產(chǎn)物產(chǎn)率、半焦化學(xué)結(jié)構(gòu)和頁(yè)巖油組成特性。結(jié)果表明外加黃鐵礦和單質(zhì)硫不利于頁(yè)巖油的生成。黃鐵礦在低溫下對(duì)氣態(tài)烴類的生成起到了促進(jìn)作用,單質(zhì)硫促進(jìn)油母質(zhì)大分子的解聚和裂解,同時(shí)促進(jìn)了頁(yè)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(gòu)化進(jìn)程。加入黃鐵礦時(shí)PACs主要通過(guò)脂肪烴氣相裂解反應(yīng)生成的,加入單質(zhì)硫時(shí)PACs主要通過(guò)Diels-Alder型反應(yīng)生成。黃鐵礦和單質(zhì)硫在促進(jìn)自由基形成過(guò)程中的作用機(jī)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(hào)：2507350