无机矿物质对油页岩自加热干馏过程的影响

Effect of Minerals on Self-heating Retorting of Oil Shale

油页岩(OS)自加热干馏(SHR)是一种无需低温热载体、通过OS与含氧气体发生非燃烧放热反应而使干馏温度自发升高的干馏方式,大大降低了干馏过程所需的热量输入,但页岩油产率无明显损失。为探究OS所含无机矿物质对SHR过程特性的影响规律,本文首先采用HCl、HNO3或HF去除OS的碳酸盐、硅酸盐或硫铁矿,然后将经过不同酸去矿物化的OS用于SHR,结合TG、FT-IR、BET、XRD和GC-MS等表征技术,讨论了矿物质对SHR过程干馏峰值温度、半焦孔隙特征、页岩油的收率及组成的影响。研究结果表明:不同酸处理对SHR的峰值温度、半焦的性质以及油收率影响不同,碳酸盐对SHR有促进作用,硅酸盐有抑制作用,硫铁矿无明显作用。尽管不同的矿物质对SHR过程有上述不同的影响,但对所生成页岩油的组成没有明显的影响,本文所获得的所有页岩油均主要由饱和脂肪烃构成。

The oil shale （OS） self-heating retorting （SHR） can increase retorting temperature spontaneously without external heater by unburned exothermic reaction of OS with oxygen-containing gas, which can significantly simplify the retorting process. In this paper, HCI, HF or HNO3 was first used to remove the carbonate, silicate or pyrite in OS, and then obtained demineralized OSs were used as the feedstock of SHR for investigating effect of different minerals on SHR. By TG, FT-IR, BET, XRD and GC-MS techniques, the peak temperature of SHR, pore information of semi-coke and components of shale oil were analyzed. The results show that different demineralization of O S by different acids has different effect on the peak temperature of SHR process, the property of semi-coke and oil yield. Carbonate has promoting effect, silicate has inhibitory effect and pyrite has no obvious effect for SHR. However, different demineralization of OS by different acids cannot cause obvious change in the composition of prepared shale oil samples which all mainly consist of saturated aliphatic hydrocarbons.