开发一种功能化定向阻化不同变质程度煤的绿色高效阻化剂，对提高预防煤自燃火 灾的经济性、高效性、环保性、科学性具有非常重要的现实意义。本论文采用理论分析、 实验测试、量子化学模拟相结合的方法，以优选的 4 种阴离子与 6 种阳离构成的四类（咪 唑类、吡啶类、吡咯烷、季鏻类）24 种离子液体阻化的褐煤为研究对象，研究离子液体 中阴阳离子对煤微观结构的影响规律，确定阻化煤样官能团氧化过程的阶段性演变特征 及演化机理，掌握离子液体抑制煤分子表面官能团活性的微观机理，并得到阻化煤样氧 化过程的热动力学响应机制，对揭示煤自燃阻化机理及煤自燃的主动预防具有重要理论 和实际指导意义。 采用 XRD 技术、XPS 技术、FTIR 技术，系统表征了煤样的微晶结构、碳氧氮硫四 种元素的赋存特征、官能团分布特征及 FTIR 结构参数变化规律。结果表明：褐煤灰分 较多，自燃倾向性较高，存在较多的元素依次是 O、C、Si 和 Al。含有的醇羟基最多， 其次为酚羟基，游离的羟基数量最少。阴离子的酸性越强，阳离子主环结构相连的链越 长，对煤体的煤微晶结构层片直径 La 的破坏能力越大，对 C=O 和 COO 官能团的破坏 程度越加明显，脱硫能力也越强。离子液体在对煤微观结构影响的过程中，阴阳离子都 能起作用，但阴离子起着较为关键的主导作用。 采用原位漫反射技术，实时测定了阻化煤样氧化过程中官能团的变化规律，揭示了 氧化过程中官能团转化和生成的演化机制。煤分子表面官能团的演化呈现阶段性变化， 在各个阶段内都表现出良好的线性转化关系。羟基、脂肪烃、含氧官能团、芳香烃在氧 化的各阶段拥有独立的转化机制，离子液体阻化剂难以改变官能团的反应路径。离子液 体阻化剂难以改变煤样官能团向另一通道的转换，但可以影响转化过程中能量的变化， 官能团在各自反应通道转化的过程中，需要克服更高的能量完成转化及反应。此外，依 据官能团演化过程克服能量的大小，确定了功能化定向抑制煤 9 种官能团氧化活性的离 子液体阻化剂配比。 利用高斯量子化学理论，对离子液体抑制煤表面分子官能团活性的微观作用机理进 行了深入研究。首先通过 Molclus 和 Gaussian 软件优化得到[BMIM][BF4]离子液体与煤 分子表面五种关键官能团（甲基、亚甲基、羟基、醚键、羧基）作用体结构模型。然后 分析作用体的电荷转移、分子表面静电势、轨道相互作用等特性，最后通过绘制 RDG 和 IGM 实现了弱相互作用的可视化研究。结果表明，所有构象体系均呈现强的稳定性， 作用体的稳定性为：[BMIM][BF4]-OH>[BMIM][BF4]-CH3>[BMIM][BF4]-COOH>[BMI M][BF4]-O->[BMIM][BF4]-CH2-。[BMIM][BF4]离子液体与煤分子官能团形成的体系内主 要是范德华作用，对于羟基还存在弱的氢键。对范德华力起主要作用的是离子液体 [BMIM][BF4]中的阴离子[BF4] -，与阳离子[BMIM]+形成的原子对对作用力的贡献也有， 但相对较少。 通过 STA 实验，研究了阻化煤样氧化过程中的热力学特性，探讨了煤样氧化放热 过程的热动力学响应机制，考察了煤样氧化过程中离子液体阻化剂的定向阻化性能。实 验证明离子液体阻化剂能够抑制煤的氧化，表现为煤样临界温度、干裂温度、着火点温 度上升，吸热量和初始放热量降低。阻化煤样氧化过程需要的能量增加，热动力学机理 发生变化，表明离子液体阻化剂能够从本质上影响煤的氧化反应。煤体在氧化放热的过 程中表观活化能与指前因子拥有良好的正相关的补偿关系。从煤热释放表观活化能的角 度掌握了离子液体的阻化效率，所选的离子液体阻化剂能够有效的抑制煤的氧化进程。

It is of great practical significance to develop a green and highly efficient ionic liquids (ILs) inhibitor for inhibiting spontaneous combustion of coals of metamorphic grade, which is very important for improving the economy, high efficiency, environmental protection and science of preventing spontaneous coal combustion fires. Using a combination of theoretical analysis, experimental tests, and quantum chemical simulations, the 24 ILs (Imidazoles, pyridines, pyrrolidines, and quaternary phosphoniums) inhibited lignite composed of preferably 4 anions and 6 cations were taken as the study object in this paper. The effect law of anions and cationsfrom ILs on the microstructure of coal is studied. The stage evolution characteristics and evolution mechanism of functional groups for inhibition coal samples on oxidation process were mastered. The microscopic mechanism of inerting the activity for functional groups on the surface of coal molecules by ILs was grasped. In addition, the thermodynamic response mechanism of the oxidation process of inhibition coal samples was revealed. The results of the study have the enormous theoretical and practical guidances to reveal the inhibiting mechanism and the active prevention of coal spontaneous combustion. (1) To systematically characterized the microcrystalline structure of the coal samples, the assignment characteristics of the four elements of carbon, oxygen, nitrogen and sulfur, the distribution characteristics of the functional groups, and the changes of the structural parameters, the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier Transform infrared spectroscopy (FTIR) were conducted in this paper. The results show that lignite has more ash and higher propensity to spontaneous combustion, and the elements present in higher amounts as order are O, C, Si and Al. Next, lignite also contains the most alcoholic hydroxyl groups, followed by phenolic hydroxyl groups, and the least number of free hydroxyl groups. The stronger the acidity of the anion, the longer the chain connected to the main ring structure of the cation, the greater the ability to destroy the coal microcrystalline structure lamellae diameter La of the coal body, the more obvious the destruction of C=O and COO functional groups, and the stronger the desulfurization ability. The anion plays a more critical and dominant role on the effect of ILs in the process on the coal microstructure. (2) The changes pattern of functional groups during the oxidation of inhibited coal samples were determined by in situ diffuse reflection technique (In Situ FTIR), and the evolution mechanism of conversion and generation of functional groups during oxidation was revealed. The evolution of the functional groups in the coals showed stage changes, and showed good linear transformation relationships within each stage. Hydroxyl groups, aliphatic hydrocarbons, oxygenated functional groups, and aromatic hydrocarbons possess independent conversion mechanisms at each stage of oxidation, and ILs hadrly to inhibit to change the reaction paths of functional groups. It is difficult for ILs to influence the conversion of functional groups of coal samples to another channel, but they can influence the energy of the conversion process, and the functional groups need to overcome higher energy to complete the conversion and reaction in the process of overcoming the conversion of the reaction channel. In addition, based on the magnitude of the energy overcome during the evolution of functional groups, theoretical ILs ratios were established for inhibiting the activity of nine functional groups. (3) The reaction mechanism of ILs inhibiting the activity of molecular functional groups on the coal surface had been thoroughly investigated using Gaussian quantum chemical theory based on the density functional theory (DFT). Firstly, the structural models of the ILs ([BMIM][BF4]) with five functional groups (methyl, methylene, hydroxyl, ether bond, carboxyl) interactors were optimized by Molclus and Gaussian software. Then the charge transfer, molecular surface electrostatic potential, and orbital interactions were analyzed, and finally the visualization of the weak interactions was realized by drawing RDG. The results showed that all conformational systems showed strong stability. The stability of the formed interactors follows the order as: [BMIM][BF4]-OH > [BMIM][BF4]-CH3 > [BMIM][BF4]-COOH > [BMIM][BF4]-O- > [BMIM][BF4]-CH2-. [BMIM][BF4] with coal molecules within the functional group system is mainly van der Waals interaction, for the hydroxyl group also exists weak hydrogen bonding. The main contribution to van der Waals forces is the anion [BF4] - in the [BMIM][BF4], and the contribution of the cation [BMIM]+ to the atomic pair is also present, but relatively small. (4) The thermodynamic characteristic parameters of the oxidation process of the inhibited coal sample were investigated, the thermodynamic response mechanism of the exothermic process of coal sample oxidation was explored, and the inhibiting performance of the ILs inhibitor in the oxidation process of coal sample was examined by conducted the DSC/DTA-TG (STA) experiments based on the heating rates of 5、10、15、20 ℃/min. It was demonstrated that the ILs inhibitor could inhibit the oxidation of coal, which showed that the critical temperature, dry cracking temperature, and ignition point temperature of coal samples increased, and the heat absorption and initial heat release decreased. The energy required for the oxidation process of the inhibited coal sample increases and the thermodynamic mechanism of the oxidation process changes, indicating that the ILs inhibitor can essentially affect the oxidation reaction of coal. The apparent activation energy of the coal body in the process of oxidation exotherm possesses a good positive compensation relationship with the pre-exponential factor. The inhibiting efficiency of ILs is grasped from the perspective of the apparent activation energy of coal heat release, and the selected ILs can effectively inhibit the oxidation process of coal.