Abstract Huadian oil shale was subjected to step-wise acid treatment to remove inherent carbonate and silicate minerals. The original oil shale and its demineralization products (carbonate- and carbonate-silicate-free oil shale samples) were pyrolyzed in a fixed-bed pyrolyzer to determine the mineral matrix effect on product yield and characteristics of shale oil and gases. The shale oil yields of original, carbonate-free, and carbonate-silicate-free oil shale samples were 50.4 wt.%, 44.3 wt.%, and 50.3 wt.% (values on dry and mineral matter-free basis), respectively, which indicated that carbonates promote, while silicates suppress, shale oil production. Coking of aromatic compounds appeared to be the dominant mechanism accounting for the variation of the shale oil yield. Elimination of the carbonate minerals decreased the nitrogen- and oxygen-containing compounds of shale oil, while removal of silicates increased the oxygenated compounds. Both carbonate and silicate minerals decreased the atomic H/C ratio of shale oil. Silicates promoted the cracking and aromatization of aliphatic hydrocarbons, which increased the short-chain aliphatic hydrocarbons and aromatic hydrocarbons of shale oil, as well as C1–C4 hydrocarbons and H2 yields. On the contrary, carbonates suppressed the cracking of long chain aliphatic hydrocarbons.

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固有矿物基质对华电油页岩热解产物收率及表征的影响

摘要 对华电油页岩进行分步酸处理，去除固有的碳酸盐和硅酸盐矿物。将原始油页岩及其脱矿产物（无碳酸盐和无碳酸盐硅酸盐的油页岩样品）在固定床热解器中进行热解，以确定矿物基质对产品产量和页岩油气特性的影响。原始、无碳酸盐和无碳酸盐-硅酸盐油页岩样品的页岩油产率分别为 50.4 wt.%、44.3 wt.% 和 50.3 wt.%（基于干燥和无矿物质的值），这表明碳酸盐促进页岩油生产，而硅酸盐抑制页岩油生产。芳香族化合物的焦化似乎是导致页岩油产量变化的主要机制。碳酸盐矿物的去除减少了页岩油的含氮和含氧化合物，而硅酸盐的去除增加了含氧化合物。碳酸盐和硅酸盐矿物都降低了页岩油的原子 H/C 比。硅酸盐促进了脂肪烃的裂解和芳构化，从而增加了页岩油的短链脂肪烃和芳香烃，以及C1-C4烃和H2的产率。相反，碳酸盐抑制长链脂肪烃的裂解。增加了页岩油的短链脂肪烃和芳香烃，以及 C1-C4 烃和 H2 的产率。相反，碳酸盐抑制长链脂肪烃的裂解。增加了页岩油的短链脂肪烃和芳香烃，以及 C1-C4 烃和 H2 的产率。相反，碳酸盐抑制长链脂肪烃的裂解。