酸洗脱矿下富油煤热解过程中官能团演化的同步原位红外研究

In-situ synchrotron ftir study on functional group evolution during pyrolysis of tar-rich coal de-mineralized by acid washing

  • 摘要: 富油煤是一种重要的煤基油气资源,其热解制油工艺是富油煤高效利用的重要方向之一。煤中的固有矿物可通过影响热解过程中官能团的迁移释放进而改变热解产物特性,而酸洗脱矿是一种有效去除煤中固有矿物的手段。因此,探明固有矿物(酸洗脱矿)对富油煤热解过程中官能团演化的影响机理,是明晰富油煤热解过程与机理的关键科学问题。利用合肥国家同步辐射实验室原位红外光谱技术,原位表征富油煤及其酸洗煤热解过程中(50~500 ℃)官能团的迁移释放,并量化分析样品原位红外光谱中脂肪族官能团(32002800 cm‒1)和芳香族官能团(17501400 cm‒1)的吸收峰,结合热重实验(TG),揭示固有矿物对富油煤热解过程中官能团演化的影响。研究结果表明:酸洗脱矿后的富油煤在原位红外光谱检测中会去除了Si—O吸收峰的影响,显现出更多的有机官能团特征峰。针对32002800 cm‒1波段内脂肪族官能团,矿物质的脱除极大地加快了富油煤热解过程中甲基(—CH3)和亚甲基(—CH2—)的断裂,而使脂肪侧链裂解生烃反应可在更低的温度下进行。针对17501400 cm‒1波段内芳香族官能团,酸洗处理会为富油煤中引入更多含氧官能团和共轭结构,促进芳构化反应和芳香化合物的缩合反应。富油煤中矿物质对热解反应有抑制作用,酸洗脱矿可提高热解反应活性,热解质量总损失高出原煤9.7 %质量分数,且热解起始温度比原煤低了150 ℃左右。该研究有助于深化对富油煤热解过程中官能团的迁移演化以及固有矿物对其影响机理的理解,为富油煤热解技术的发展提供坚实的理论基础。

     

    Abstract: Tar-rich coal is a significant coal-based resource for oil and gas, and its pyrolysis for oil production is a crucial direction for its efficient utilization. Inherent minerals in coal can alter the characteristics of pyrolysis products by affecting the migration and release of functional groups during pyrolysis. Acid washing is an effective method for removing these inherent minerals. Understanding the influence mechanism of inherent minerals (removed via acid washing) on the evolution of functional groups during the pyrolysis of tar-rich coal is a key scientific issue in elucidating the pyrolysis process and mechanism of tar-rich coal. Using in-situ infrared spectroscopy technology at the National Synchrotron Radiation Laboratory in Hefei, in-situ characterization was performed on the migration and release of functional groups during the pyrolysis of tar-rich coal and its acid-washed variant (0‒500℃). The absorption peaks of aliphatic (32002800 cm‒1) and aromatic (17501400 cm‒1) functional groups in the in-situ infrared spectra were quantitatively analyzed, and combined with thermogravimetric (TG) experiments, to reveal the impact of inherent minerals on the evolution of functional groups during the pyrolysis of tar-rich coal. The study results indicate that after acid washing, the influence of the Si—O absorption peak is removed in the in-situ infrared spectra of tar-rich coal, revealing more characteristic peaks of organic functional groups. In the 32002800 cm−1 range, the removal of minerals significantly accelerates the cleavage of methyl (—CH3) and methylene (—CH2—) groups during pyrolysis, allowing the cracking of aliphatic side chains to produce hydrocarbons at lower temperatures. For the aromatic functional groups in the 17501400 cm‒1 range, acid washing introduces more oxygen-containing functional groups and conjugated structures into the tar-rich coal, promoting aromatization and the condensation of aromatic compounds. Compared to the raw tar-rich coal, the mass loss of acid-washed coal during pyrolysis is 9.7% higher, and the initial pyrolysis temperature is approximately 150 °C lower. The research enhances the understanding of functional group migration and evolution during the pyrolysis of tar-rich coal and the influence mechanism of inherent minerals. It provides a solid theoretical foundation for the development of tar-rich coal pyrolysis technology.

     

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