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    煤的显微组分结构与直接液化反应性研究进展

    Research progress on the maceral structure of coal and its reactivity in direct liquefaction

    • 摘要: 我国低阶煤资源储量巨大,煤直接液化是实现低阶煤转化制备高端油品、缓解我国石油依赖的关键技术。煤中显微组分结构及其反应性是决定液化转化率、油品质量的主要因素,不同显微组分的芳香缩合程度、活性桥键数量以及含氧官能团总量的反应活性差异迥异。文章围绕煤中镜质体、惰质体和类脂体等显微组分,系统综述其结构特征与液化活性的内在关联,在此基础上重点讨论了不同显微组分液化转化效率以及液化过程中大分子共价键的断裂、自由基生成等机理,分析了不同显微组分之间在共液化过程中可能存在的交互作用机制。同时,从反应温度与停留时间、氢压与供氢溶剂、催化剂以及煤中矿物质等方面梳理了不同反应条件对显微组分液化的影响。提高温度可加速键断裂,但过高会加剧缩聚生焦;延长时间有助于提高转化率,但对油产率存在最优窗口;高氢压和优质供氢溶剂(如四氢萘)能有效稳定自由基,抑制其缩聚;而铁基催化剂等则通过促进氢转移和抑制结焦来提升液化效率;煤中矿物质在液化中发挥双重作用,黄铁矿通过生成磁黄铁矿催化相促进加氢,黏土矿物兼具强化传质与诱导缩聚的两面性,而碱金属与碱土金属的影响尚存争议。未来需借助先进实验研究手段与理论计算方法,深入揭示显微组分的结构差异-液化机理及以及工艺条件匹配机制,为液化原料的筛选与工况优化提供理论支撑。

       

      Abstract: China possesses enormous reserves of low-rank coal, and direct coal liquefaction is a key technology for converting low-rank coal into high-end oil products and alleviating the country's dependence on petroleum.The structure and reactivity of coal macerals are the primary factors determining liquefaction con-version efficiency and oil product quality. Different macerals exhibit markedly distinct reactivity in terms of the degree of aromatic condensation, the abundance of active bridge bonds, and the total content of oxygen-containing functional groups. Focusing on vitrinite, inertinite, and liptinite in coal, this paper systematically reviews the intrinsic relationship between their structural characteristics and liquefaction activity. On this basis, it highlights the liquefaction conversion efficiency of different macerals and the mechanisms of macromolecular covalent bond cleavage and free radical generation during liquefaction, and analyzes the possible interaction mechanisms among different macerals during co-liquefaction. Meanwhile, the effects of various reaction conditions on maceral liquefaction are examined, including reaction temperature and residence time, hydrogen pressure and hydrogen-donor solvents, catalysts, and mineral matter in coal. Increasing the temperature can accelerate bond cleavage, but excessively high temperatures intensify condensation and coke formation. Prolonging the residence time helps improve conversion, but there exists an optimal window for oil yield. High hydrogen pressure and high-quality hydrogen-donor solvents (e.g., tetralin) can effectively stabilize free radicals and inhibit their condensation. Iron-based catalysts enhance liquefaction efficiency by promoting hydrogen transfer and suppressing coking. Mineral matter in coal plays a dual role in liquefaction: pyrite promotes hydrogenation by generating the catalytic phase Fe???S, clay minerals exhibit a twofold nature of enhancing mass transfer while inducing condensation, and the influence of alkali and alkaline earth metals remains controversial. Future research should employ advanced experimental techniques and theoretical computational methods to deeply elucidate the relationship between structural differences of macerals, liquefaction mechanisms, and the matching of process conditions, thereby providing theoretical support for the selection of liquefaction feedstocks and the optimization of operating conditions.

       

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