煤炭在我国现阶段一次能源消费中占据主导地位，煤炭清洁高效转化是构建我国清洁低碳、安全高效的能源体系的重要组成部分。通过量子化学可获取试验方法难以测定的过渡态电子结构及几何构型等关键信息，从微观层面揭示煤炭热化学转化中有机分子释放、迁移及转化过程，为煤炭的清洁利用提供理论指导。概述了煤的结构与反应性研究中常用的量子化学计算方法的特点和作用，总结了基于密度泛函理论方法在煤燃烧污染物脱除、煤气化、煤热解及煤液化等热化学转化机理研究中的应用。重点探讨了煤燃烧中NOx及重金属污染物的脱除机理、煤焦气化反应的促进机制、煤热解中含氧官能团脱除机理及煤液化中的氢传递机理。目前基于密度泛函理论方法的研究能够有效揭示某种煤、某一方面的性质与其反应中所表现出的特征，但尚缺乏对煤分子结构系统全面的认知，随相关理论认识的进一步完善，将进一步发挥微观机理研究优势，为煤炭清洁转化利用技术的研究及应用提供借鉴。

Coal plays a leading role in  current China′s primary energy consumption. Clean and efficient conversion of coal is an important part of building a clean, low-carbon, safe and efficient energy system in China. The critical information of electronic structure and geometric configuration from transition states which is difficult to be measured by experimental methods can be investigated by quantum chemistry method. The molecular release, migration and transformation process of coal thermochemical conversion are revealed from the micro level to provide theoretical guidance for the clean utilization of coal. The characteristics and functions of density functional theory (DFT)-based methods in the study of coal structure and reactivity were investigated and the application of thermochemical conversion mechanism in coal combustion pollutant removal, gasification, pyrolysis and liquefaction was summarized. The removal mechanism of NOx and heavymetal pollutants in coal combustion, the promotion mechanism of coal char gasification reaction, the removal mechanism of oxygen-containing functional groups in coal pyrolysis and the hydrogen transfer mechanism in coal liquefaction were discussed. DFT methods can effectively reveal the properties of a certain aspect of coal and the characteristics shown in the reaction, but there is still a lack of comprehensive understanding of the molecular structure of coal. With the further improvement of relevant theoretical understanding, DFT methods will provide guidance for more clean utilization and conversion technology of coal through its advantages in micro-mechanism research.

0 引言

1 燃煤污染物脱除机理研究

   1.1 氮氧化物的脱除

   1.2 重金属污染物的转化及吸附脱除

2 煤气化微观机理研究

   2.1 不同气化剂的煤焦气化反应机理

   2.2 金属吸附及预氧化的促进机制

3 煤热解微观机理研究

   3.1 水分子表面吸附与催化热解的作用机理

   3.2 不同化学性质金属催化剂的作用机理

4 煤液化的微观机理研究

5 结语与展望