随着煤炭开采深度和强度的增大，煤矿自燃危险性越来越大，使得开采不易自燃的高变质无烟煤矿井，尤其是开采伴生黄铁矿无煤烟的矿井也多次发生自燃。本文主要围绕水与伴生黄铁矿影响煤自燃作用机制的关键科学问题，采用理论分析、实验研究和数学计算相结合的方法，以伴生黄铁矿无烟煤为研究对象，研究水与伴生黄铁矿对煤表面微观结构及其氧化动力学过程的协同作用机制，并通过主要活性基团与热动力学参数的关联性分析，确定参与氧化反应的关键活性基团，揭示水与伴生黄铁矿协同影响无烟煤氧化放热的作用机理。 （1）采用煤分子结构分析仪、真密度分析仪、XRD衍射仪和傅里叶红外光谱仪等，系统研究了无烟煤的孔隙结构、微晶结构、化学基团的分布特征，从结构变化角度确定了添加不同水分与黄铁矿含量煤的微观结构特征及其影响规律；利用原位漫反射红外光谱实验，研究了煤样氧化过程中7类活性基团的变化规律，掌握了水分与伴生黄铁矿促进煤结构中羟基、芳香烃生成的机制及其影响特征，揭示了水与伴生黄铁矿对煤化学基团中活性原子的协同作用机理。 （2）通过TG-DTG分析实验，研究了煤氧化过程的水分蒸发及脱附阶段、吸氧增重阶段的特征温度和质量变化特征。运用普适积分与微分相结合的方法，计算了多升温速率下煤样在吸氧增重阶段的表观活化能，掌握了煤氧化过程的表观活化能随水与伴生黄铁矿含量变化的阶段性变化特征，确定了最佳机理函数。得出了水与伴生黄铁矿协同作用下煤氧化过程的反应实质和机理均符合n=4 Avrami-Erofeev方程，表明水与伴生黄铁矿可以外在的影响煤的氧化进程，但并未从根本上改变反应实质。确定了当水分含量为10%~15%与黄铁矿含量为2%~4%协同存在时对氧化热失重贡献度最大，揭示了水分与黄铁矿协同作用影响无烟煤低温氧化的动力学机制。 （3）采用C80热分析实验，研究了水与伴生黄铁矿对无烟煤热效应的影响特征，掌握了煤样的总放热量及分阶段放热量等热效应参数，并计算出煤在快速放热阶段的热反应活化能为53.49~60.12 kJ/mol，揭示了水分与黄铁矿协同作用能够降低煤的热反应活化能。得出了水与伴生黄铁矿表现为协同作用时，存在一个对无烟煤促进放热贡献度最大的作用范围，黄铁矿为2%~4%与水分为10%~15%协同存在，此时所需的热反应活化能最小，对煤的热动力学进程有一定的推动作用。 （4）采用 Pearson 相关系数和灰色关联度相结合的方法，分析了水与伴生黄铁矿协同作用下煤的7类活性基团与热反应活化能的关联程度，得出关联度大小顺序为：芳核上Ⅳ类氢原子＞芳核上Ⅲ类氢原子＞游离羟基＞亚甲基＞芳香环C=C＞芳核上Ⅰ类氢原子＞分子内氢键，确定出促进煤氧化放热的关键活性基团（芳核上Ⅳ类氢原子、Ⅲ类氢原子和游离羟基）和起抑制作用的活性基团（芳香环C=C结构和脂肪烃的亚甲基），阐明了水与伴生黄铁矿协同作用使得动力学进程发生了改变，从微观动力学角度揭示了水与伴生黄铁矿协同促进了无烟煤的氧化放热动力学过程。 研究结果对进一步研究高硫无烟煤自然发火的预测与科学防控，具有重要的科学价值和实际指导意义。

With the increase of coal mining depth and strength, the danger of spontaneous combustion of coal mines is increasing, which makes mining coal mines that are not easy to spontaneously burn high-quality anthracite, and coal spontaneous combustion fires occur frequently, especially the non-steam associated with pyrite is more likely to occur self-ignition. This paper focuses on the key scientific issues of the mechanism of water-associated pyrite promoting coal spontaneous combustion. The combination of theoretical analysis, experimental research and mathematical calculation is used to study the associated pyrite anthracite. The synergistic mechanism of the mineral on the surface microstructure and its oxidative exothermic properties. The correlation between the main reactive groups and the thermodynamic parameters is used to determine the key reactive groups of the oxidation reaction, revealing the water-associated pyrite-induced coal. The mechanism of action of oxidative exotherm. (1) This article uses instruments such as coal molecular structure analyzer, true density analyzer, X-Ray Diffraction (XRD) and Fourier infrared spectrometer (FTIR). The pore structure, microcrystalline structure and chemical group distribution characteristics of anthracite coal were systematically studied. The microstructure characteristics and influence laws of coal with different water content and pyrite content were determined from the perspective of structural change. The in-situ diffuse reflectance infrared spectroscopy experiments were carried out to study the variation of seven reactive groups in the oxidation process of coal samples with different water and pyrite content. Mastered the mechanism of water and pyrite to promote the formation of hydroxyl and aromatic hydrocarbons in coal molecules and its influence law. The synergistic mechanism of water and associated pyrite on active atoms in coal chemical groups were revealed. (2) Through TG-DTG analysis experiments, the characteristics of characteristic temperature and mass of water evaporation and desorption stage and oxygen absorption weight increase stage in coal oxidation process were studied. The apparent activation energy of the coal sample in the oxygen absorption and weight gain stage was calculated by the combination of universal integral and differential. The optimal mechanism function was determined by grasping the phased law of the apparent activation energy of coal oxidation process with the change of water and associated pyrite content. The essence and reaction mechanism of coal oxidation process under the action of water and associated pyrite are obtained, which are consistent with the n=4 Avrami-Erofeev equation, which indicates that water and associated pyrite can externally affect the oxidation process of coal samples, but the essence of the response has not been fundamentally changed. It is determined that the maximum moisture loss contribution is 10%~15%15% and the pyrite content is 2%~4%, revealing the dynamic mechanism of the synergistic effect of water and pyrite on the low temperature oxidation of anthracite. (3) The effect of water and associated pyrite on the thermal effect of anthracite was studied by C80 thermal analysis experiment. Master the thermal effect parameters such as the total heat release of the coal sample and the phased heat release, and calculate the thermal reaction activation energy of the coal sample. It is concluded that the synergistic effect of water and pyrite can reduce the thermal reaction activation energy of coal, which is 53.49~60.12kJ/mol in the rapid exothermic stage. When water and associated pyrite exhibit synergistic interaction, there is a range that contributes the most to the anthracite-promoting exotherm. When the pyrite content is 2%~4%, the moisture content is 10%~15%, which is required at this time. The thermal reaction activation energy is minimal and advances the thermodynamic progression of coal. (4) Based on the combination of Pearson correlation coefficient and grey correlation degree, the correlation degree between the seven reactive groups and the activation energy of the reaction under the synergistic action of water and associated pyrite was analyzed. The order of correlation was as follows: IV on the aromatic nucleus Hydrogen-like atoms>Type III hydrogen atoms in aromatic nucleus>Free hydroxyl group>Methylene group>Aromatic ring C=C>Type I hydrogen atom on the aromatic nucleus>Intermolecular association hydrogen bond, determine the key activity to promote coal oxidative exotherm a group (a type IV hydrogen atom on the aromatic nucleus, a type III hydrogen atom and a free hydroxyl group) and an inhibitory reactive group (an aromatic ring C=C structure and a methylene group of an aliphatic hydrocarbon). It is clarified that the synergistic action of water and associated pyrite makes the dynamic process change. From the perspective of microscopic dynamics, the oxidative exothermic kinetics of water and associated pyrite synergistically affecting anthracite are revealed.