研究煤氧化过程的微观机理是控制和预防煤自然发火的重要方法。本文通过理论分析、实验研究和统计计算三种手段相结合的方法，对淮南矿区6个煤矿的典型煤样在氧化自燃过程的微观特征和宏观特性，以及两者之间的关联性进行了详细的分析，研究了在高温氧化过程中，煤分子中官能团变化规律及氧化气体产物的动力学特性，为淮南煤自燃灾害的早期预测预报提供了指导，并对在自燃过程中采取科学的防治措施提供了重要的理论依据。 采用元素分析、工业分析、比表面积及孔径分布分析、导热特性、XRD微晶结构参数分析、红外光谱分析等测试技术，分析了淮南煤的物理化学结构特性，掌握了煤样的煤质组成以及内部结构特征。结果表明淮南煤质的特点为低灰分、较高挥发分；比表面积较小，孔径以中孔为主，常温状态下较难发生氧化；煤样的热扩散系数随着温度的升高不断减小，比热容和导热系数随着温度的升高不断增大；微晶结构中芳香环缩合程度中等，层片结构较为有序，煤中主要含有高岭石、地开石、方解石、石英和菱铁矿等矿物成分；煤样表面分子结构中官能团种类相似但数量不同，均能检测到羟基、脂肪烃、芳香烃、含氧官能团。通过原位漫反射傅里叶红外光谱分析了煤氧化过程中微观结构特征及其变化规律，对四类官能团中的21种基团随温度变化的特性进行分析发现，羟基在升温反应过程中不断减少，脂肪烃先增大后减小，芳香烃中Ar-CH基团比较稳定，呈现先增大后减小的现象，而C=C基团一直缓慢减少，含氧官能团在燃点温度之前不断增大，直至燃点温度之后含量才有所减少。 通过西安科技大学自主研发的高温程序升温实验系统，测试了在升温至500℃过程中的淮南煤氧化释放的气体产物变化规律，并根据指标气体增长率分析法测算出五个特征温度点，将整个氧化升温过程分为四个阶段，分别是临界温度阶段、干裂-活性-增速温度阶段、增速-燃点温度阶段和燃烧阶段。实验证明，在临界温度阶段，CO和CO2气体缓慢增长，超过该温度阶段直至增速-燃点温度阶段，碳氧类气体含量迅速增长，燃烧温度阶段气体浓度有所下降，继而由于稳定官能团的断裂，继续上涨。CH4、 C2H6和 C2H4气体在干裂-活性-增速温度阶段之前均增长缓慢，之后才开始急剧增长，到燃烧温度阶段达到峰值。利用高温程序升温实验数据，采用两种不同的动力学方法，对四个不同阶段的动力学特性进行计算研究，反应所需活化能随温度阶段的递进先降低后增大，燃烧阶段所需活化能大于增速-燃点温度阶段。此外，通过差示扫描法对氧化过程中的放热性进行了计算。 通过分析微观特性与宏观表征，选取灰色关联性分析中的相对关联度分析，对淮南煤氧化升温的四个温度阶段中氧化释放的气体和放热量与14种不同活性基团之间的关联度大小进行统计分析，推断出影响各个阶段气体和热量释放的主要官能团，分析发现，前三阶段中，羰基是影响宏观气体释放和热量产生的主要官能团，脂肪烃和芳环结构是燃烧阶段中产生气体和热量的主要官能团，且C=C结构在燃烧阶段才开始大量参与反应，释放气体产物。

Study on the microscopic mechanism of coal oxidation is the essence of controlling and preventing coal spontaneous combustion. This thesis combined three method of theory analysis, experimental analysis and statistical calculation to study the macro characteristics and micro characteristics and the relationship between them of 6 medium rank of coal in Huainan, China, show the regulation changes in functional groups of coal molecule and the kinetic characteristics of gas productions during oxidation. It provides an important theoretical basis for scientific prevention and control measures. To adopted experiments of elemental analysis, proximate analysis, BET specific surface area and pore size distribution analysis, thermal conductivity analysis, X ray diffraction (XRD) microcrystalline structure parameter analysis, and Fourier transform infrared spectrometer (FTIR) analysis to study the physical and chemical characteristics, and mastered the composition of coal samples and the characteristics of the functional groups in Huainan coal samples. The experimental results show that the characteristics of Huainan coal quality is low ash, high volatile and low sulfur. The specific surface of coal is small, the pore size is mainly of the medium pore and macro pore, which is difficult to oxidize under the normal temperature. Thermal conductivity is decreased by the temperature raised, and thermal diffusivity and specific heat capacity are increased while the temperature raised. The degree of condensation of aromatic rings in the microcrystalline structure of coal is moderate, and the structure of the lamellae is orderly. The mineral composition of coal mainly contains kaolinite, calcite, quartz and siderite. The functional groups of different coal samples were detected hydroxyl, a aliphatic hydrocarbon, aromatic hydrocarbons and oxygen-containing groups with similar kinds but different amounts. The characteristics of microstructure and its variation during coal oxidation were analyzed by in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The characteristics of the 21 groups in the four kinds of functional groups were analyzed. The results showed in the process of heating, the hydroxyl group decreased, the aliphatic hydrocarbon increased at first and then decreased, Ar-CH group increased at first and then decreased, and finally increased, the C=C group had been slowly reduce, oxygen-containing groups increased before the ignition temperature, and on the contrary after it. Based on the high temperature-programmed experimental system, which was independently research and developed by Xi’an University of Science and Technology, to test the gas productions during the heating temperature to 500℃. Moreover, to calculate the characteristic temperatures by growth rate method of indicate gas. Additionally, to divided the whole oxidation process into four stages: a critical temperature stage, a crack-active-speedup temperature stage, a speedup-ignition temperature stage, and an ignition temperature stage. The results proved that CO and CO2 increased slowly in critical temperature stage, beyond this stage till speedup-ignition temperature stage the content of carbon-oxygen gas increased rapidly, and the gas concentration in the ignition temperature decreased, and then continued to rise due to the rupture of stable functional groups. CH4, C2H6 and C2H4 gases increased gradual before crack-active-speedup temperature stage, and then sharply increased till the peak point in ignition temperature stage. According to the data of high temperature-programmed experimental system, two different dynamic methods were used to calculate the dynamic characteristics of the four stages. The reaction activation energy decreased at first and then increased with the temperature raised, the ignition temperature stage of the required activation energy is higher than the speedup-ignition temperature stage. In addition, the heat release coefficient was calculated by differential scanning analysis. To analyze the relationship of micro and macro characteristics, grey correlation analysis was chosen to statistically analyze the correlation between the amount of gas, heat release and 14 different active groups in the four stages. The main functional groups that affect the release of gas and heat in each stage were deduced. In the first three stages, carbonyl was the main functional groups which effect gas release and heat generation. Aliphatic hydrocarbon and aromatic ring structure were the main functional groups effect gas and heat release in the ignition temperature stage, and aromatic ring structure began to participate in reaction until the ignition temperature stage.