Experimental Study on Fractional Compositions of Residual Oil from Shale and Coal of China Using Grain-Based MSSV Pyrolysis
Experimental Study on Fractional Compositions of Residual Oil from Shale and Coal of China Using Grain-Based MSSV Pyrolysis
复制标题
基于颗粒的MSSV热解法研究中国页岩和煤残渣油的分组成实验研究
DOI：
10.1021/acs.energyfuels.5b02486
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发表时间：
2016-01-01
期刊：
影响因子：
5.3
通讯作者：
Lu, Jialan
中科院分区：
文献类型：
--
作者：
Liao, Lingling;Wang, Yunpeng;Lu, Jialan
为了更好地了解页岩和煤中残余油的组成和演化规律，采用基于颗粒的微型密闭容器(MSSV)全岩热解方法，研究了页岩、煤和煤质页岩样品中残余油的含量及其馏分组成及其在不同温度和成熟度下的变化。使用通过EasyRo(%)方法计算的当量Ro(%)，使用从渣油中提取的油量和C1至C5气体的产率来定义油、湿气和干气窗口。油窗定义为页岩为0.6-1.3%Ro，煤为0.5-1.2%；湿气窗为页岩为0.9-3.0%，煤为0.8-2.7%；干气窗为页岩为1.3-4.0%，煤为1.2-4.0%。煤炭显示出比页岩相对更宽的石油窗口，但与页岩的天然气窗口相似。最大剩余油含量分别为133.44 mg/g有机碳、69.84 mg/g海相页岩、10.03 mg/g煤和83.79 mg/g煤页岩。与天然残油相比，页岩的实验室残油含量要高得多，而煤中的残油由于其独特的结构而主要被保留。结果表明，在石油窗口中，海相和湖相页岩残油以饱和、芳烃、胶质为主，沥青质较少；煤残油以沥青质、芳烃、胶质为主，但饱和度较少。在干湿气窗口中，海相和湖相页岩残油主要由饱和油、芳烃和胶质组成，煤残油主要由沥青质和胶质组成。这些结果表明，海相页岩、湖相页岩和煤质页岩的剩余油含量较高，低成熟度时饱和烃和芳香烃的比例较高，显示出比煤更具页岩油气远景；而在高成熟度时，剩余油含量下降较快，但仍具有较高的裂解气潜力，可能成为页岩气的来源。煤中残油含量低，主要以芳烃、胶质和沥青质的形式存在，随着成熟度的增加，这些物质只能成为煤层气的来源。
For better understanding compositions and evolutions of residual oil of shale and coal, a grain-based microscale sealed vessel (MSSV) pyrolysis method to whole rock was used to investigate the residual oil contents and its fractional compositions from shale, coal, and coaly shale samples, as well as their variations at different temperatures and maturities. Quantities of extracted oil from residuals and yields of C1 to C5 gases were used to define oil, wet gas, and dry gas windows using equivalent Ro (%) calculated through EasyRo (%) method. Oil windows are defined as 0.6-1.3%Ro for shale and 0.5-1.2%Ro for coal; wet gas windows are 0.9-3.0%Ro for shale and 0.8-2.7%Ro for coal, and dry gas window are 1.3-4.0%Ro for shale and 1.2-4.0%Ro for coal, respectively. Coal shows relatively wider oil window than shale but similar gas window to shale. The maximum residual oil can reach 133.44 mg/g TOC, 69.84 mg/g TOC for marine and lacustrine shale, 10.03 mg/g TOC for coal, and 83.79 mg/g TOC for coaly shale, respectively. Comparing with natural residual oil, the laboratory residual oil of shale is much higher, while the residual oil in coal is mainly retained due to its unique structures. The results show that, in oil window, marine and lacustrine shale residual oil show mainly saturates, aromatics, resins but less asphaltenes, while coal residual oil are mainly asphaltenes, aromatics, resins but less saturates. In the wet and dry gas window, marine and lacustrine shale residual oil is mainly made up of saturates, aromatics, and resins, while coal residual oil is mainly made up of asphaltenes and resins. These results suggest that residual oil contents of marine shale, lacustrine shale, and coaly shale are higher with high proportions of saturated and aromatic hydrocarbons in low maturities which show high shale oil prospective than coal, while in high maturities the residual oil contents decrease quickly but still have higher potential for cracking gases which might become the source of shale gas. The residual oil in coal is low mainly in forms of aromatics, resins, and asphaltenes, which can only be the source of coal-bed methane as maturity increases.