黄铁矿对龙口油页岩热解的影响
发布时间：2019-06-28 13:56
【摘要】：面对石油需求的与日俱增和动荡的国际局势,提高石油自给比例,降低对外依存度,对国家发展意义重大。油页岩作为一种非常规能源,其干馏能产生类似石油原油的页岩油,经过分离、改善油品后有望作为汽油、柴油等的替代油,所以开发利用油页岩对缓解我国石油紧张局势意义重大。油页岩中含有大量的矿物质,对油页岩的热分解有影响,但其中的黄铁矿在干馏过程中会产生H2S等含硫气体污染环境和腐蚀设备。因此有必要探究内在矿物质和黄铁矿对油页岩热解中的影响作用,为清洁高效利用页岩油提供理论指导。通过对油页岩原样和脱灰后的干酪根在不同温度下进行固定床热解实验,并借助FTIR、GC-MS等分析手段对不同温度下的产物产率、半焦化学结构和页岩油组成特性进行了分析,获得了油页岩热解的基本特性及自身矿物质对热解过程的影响。结果表明随着温度的升高,油页岩转化率不断升高,干酪跟最佳产油率温度为490℃,矿物质存在时该温度提高到520℃,并促进了页岩油的生成。矿物质对脂肪族长链和甲基侧链的断裂、环状结构的生成、氧的脱除有促进作用,对干酪跟高温下的芳构化有抑制作用,同时能抑制其他来源的氧转化成羧基。页岩油中以脂肪烃为主要成分,矿物质促进了脂肪烃的生成,对烯烃的生成起抑制作用,矿物质存在的情况下页岩油中的PAC通过脂肪烃气相裂解反应生成,页岩油中硫含量也降低。通过对干酪添加黄铁矿和单质硫进行热解实验,并借助FTIR、GC-MS等分析手段分析了干酪根有无添加剂热解时不同温度下的产物产率、半焦化学结构和页岩油组成特性。结果表明外加黄铁矿和单质硫不利于页岩油的生成。黄铁矿在低温下对气态烃类的生成起到了促进作用,单质硫促进油母质大分子的解聚和裂解,同时促进了页岩油和小分子的气态产物生成,这与黄铁矿的催化作用不同。黄铁矿和单质硫的存在抑制了芳构化进程。加入黄铁矿时PACs主要通过脂肪烃气相裂解反应生成的,加入单质硫时PACs主要通过Diels-Alder型反应生成。黄铁矿和单质硫在促进自由基形成过程中的作用机理相同。
[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，
本文编号：2507350
[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，
本文编号：2507350
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