油页岩是一种非传统一次能源，其有机质结构与煤类似。油页岩中矿物质含量较高是其无法高效利用的主要原因之一，超临界液化法作为一种热处理新方法广泛应用于煤、生物质的利用和结构研究中，目前在油页岩中利用较少。对抚顺油页岩进行HCl、HF逐级酸洗处理，采用高温高压间歇式反应釜以乙醇为溶剂对油页岩原样及脱矿页岩进行超临界液化试验，探究内在碳酸盐、硅酸盐对液化产物特性的影响。XRF和XRD结果表明，抚顺油页岩内在矿物质以硅铝酸盐为主。液化温度升高对页岩油收率有促进作用，360 ℃下原样及2种脱矿油页岩制得页岩油收率均达到最高，其中原样、脱碳酸盐样品和脱碳酸-硅酸盐样品油收率分别为53.8%、56.9%和42.8%，较300 ℃下的样品收率分别提高33.4%、37.8%和29.3%。碳酸盐中的碱金属、碱土金属阳离子抑制烷烃生成。硅酸盐通过酸性位点促进烃类向低碳数富集。碳酸盐和硅酸盐对酯化反应分别具有促进和抑制作用。超临界液化过程发生干酪根结构中含氧弱键及脂肪结构C—C键的断裂。这2类键断裂形成小分子的形式共同作为页岩油的有机来源。

Oil shale is a kind of non-traditional primary energy with organic matter structure similar to that of coal. High mineral content in oil shale is one of the main reasons why it can not be used efficiently. As a new method of heat treatment, supercritical liquefaction is widely used in the research of coal and biomass utilization and structure, but it is less utilized in oil shale. Fushun oil shale was treated by HCl and HF acid elution to obtain demineralized oil shale.Supercritical liquefaction experiments of crude oil shale and demineralized oil shale were carried out in a high temperature and high pressure batch reactor with ethanol as solvent to explore the effects of internal carbonate and silicate on the characteristics of liquefaction products. XRF and XRD results show that the minerals in Fushun oil shale are mainly silica-aluminates. The increase of liquefaction temperature has a promoting effect on the shale oil yield. At 360 ℃, the yields of shale oil prepared by the original sample and demineralized oil shale reaches the highest value. The yields of shale oil from original sample, decarbonate sample and desilicate sample are 53.8%, 56.9% and 42.8% at 360 ℃, respectively, which are increased by 33.4%, 37.8% and 29.3% than those of 300 ℃. Alkali metal and alkaline earth metal cations in carbonate inhibit the formation of alkanes. Silicate promotes the formation of low carbon number hydrocarbon through acid sites. Carbonate promotes the formation of ethyl fatty acid, whereas silicate has the opposite effect. The oxygen-containing weak bond and C—C bond of fat structure are broken during supercritical liquefaction. These two types of broken bonds form small molecules as organic sources of shale oil.

0 引言

1 试验

   1.1 试验原料

   1.2 样品制备方法

   1.3 超临界液化试验

   1.4 产物表征

2 结果与讨论

   2.1 油页岩矿物质组成特征

   2.2 温度对页岩油收率的影响

   2.3 页岩油GC-MS分析

   2.4 页岩油的FTIR分析

3 结论