煤自燃灾害严重制约着煤炭资源的安全高效开采。煤氧化自燃过程由多种反应序列共同控制，不同反应机制对不同变质程度煤的自燃特征具有显著性差异。本文选取褐煤（HM）、长焰煤（CYM）、气煤（QM）、焦煤（JM）和无烟煤（WYM）为研究对象，开展煤氧化自燃过程的宏微观氧化特性研究，明确该过程涉及的平行反应，并揭示其竞相反应动力学机制。本研究对深入揭示煤自燃机理具有重要的理论意义。

利用热分析和程序升温实验，研究煤自燃过程吸放热、增失重和气体组分变化特性。煤样热量变化效应滞后于质量变化效应，CYM、QM和JM的阶段性热量和质量变化异于HM和WYM。基于TG-DTG曲线划分特征温度点，得出煤自燃过程包括脱水脱气、吸氧增重、受热分解、燃烧和燃尽五个阶段。特征阶段内CO和CH₄浓度随着温度升高而增加；CO₂、C₂H₄和C₂H₆浓度随着温度升高先增后减。随着煤变质程度增加，煤氧化自燃过程总产气量由70%~80%减少至30%~40%，其中挥发分被转化为固定碳，生成烷烯烃类气体的相对浓度减少，生成碳氧化物气体的相对浓度升高。

基于原位红外和电子顺磁共振实验，分析煤氧化自燃过程活性结构的变化规律。随温度升高，脂肪烃侧链逐渐被消耗，芳香环缩合程度加深，煤中赋存的持久性自由基逐渐累积，EPR曲线线形逐渐变窄，峰高整体呈现出增高趋势。各平行反应之间相互竞争，自由基浓度Ng、g因子值和线宽ΔH的曲线，随温度变化呈现出“波浪”形式的增减交替变化特征。HM中微观活性结构能快速生成含氧产物，并迅速分解产生气体或活性自由基。受热分解和吸氧增重阶段，羟基、脂肪烃和芳香烃结构含量占比整体减少，生成含氧官能团的反应序列占主导地位。

采用多峰高斯拟合方法，还原出煤自燃过程的五种平行反应序列，即脱水脱气、物理吸附O₂、氧化分解反应、气相燃烧反应和固相燃烧反应，其温度区间分别为30~204 °C、42~257 °C、136~590 °C、210~660 °C、260~642 °C。脱水脱气和物理吸附O₂在脱水脱气阶段发挥主要作用，氧化分解反应贯穿于煤自燃过程，并在吸氧增重和受热分解阶段占主导地位。

随煤的变质程度增加，氧化分解反应、气相燃烧反应和固相燃烧反应的活化能普遍增加。气相燃烧反应与氧化分解反应之间的竞争效应减弱，固相燃烧反应与气相燃烧反应之间的竞争效应先减弱后增强。氧化分解反应释放出热量，促进氧化分解反应向气相燃烧反应转变。氧化分解反应和气相燃烧反应共同作用，促进HM固相燃烧反应，抑制CYM、QM、JM和WYM固相燃烧反应。

The coal spontaneous combustion severely affects the safe and efficient exploitation of coal resources. The process of coal oxidation spontaneous combustion is controlled by multiple reaction sequences, with different reaction mechanisms exhibiting significant differences in the spontaneous combustion characteristics of coals at various degrees of metamorphism. The lignite (HM), long flame coal (CYM), gas coal (QM), coking coal (JM), and anthracite (WYM) were determined as the research objects, the macro-and micro-oxidation characteristics of their spontaneous combustion process were studied, including the parallel reactions involved, and the kinetic mechanism of the parallel reactions was revealed. This study holds significant theoretical implications in further elucidating the mechanism of coal spontaneous combustion.

The heat release (absorption), mass gain (loss), and gas composition changes during the coal spontaneous combustion have been investigated by thermal analysis and temperature program experiments. The heat change of coal lags behind the mass change. Where CYM, QM and JM are different from HM and WYM. The process of coal spontaneous combustion is divided into five stages: dehydration and degassing, oxygen gain, thermal decomposition, combustion and burnout, according to the characteristic temperature points divided by the TG-DTG curve. The concentrations of CO and CH₄ increase and the concentrations of CO₂, C₂H₄ and C₂H₆ firstly increase and then decrease with the increase of temperature in the characteristic stage. As the degree of metamorphism increases, the total gas yield from coal oxidation decreases from 70%~80% to 30%~40%. Among them, the volatile matter is converted into fixed carbon, resulting in a decrease in the relative concentration of alkene hydrocarbon gases and an increase in the relative concentration of carbon oxide gases.

The changes of the active structure of coal during oxidative spontaneous combustion were discussed by in-situ infrared and electron paramagnetic resonance experiments. During the oxidation process, the side chains of aliphatic hydrocarbons are gradually consumed, and the degree of aromatic ring condensation deepens. The persistent free radicals in coal accumulated gradually, the line shape of EPR curve narrowed gradually, and the peak height increased overall. The parallel reactions compete with each other, and the free radical concentration Ng, g factor value and line width ΔH curve show alternating changes in the form of "wave" with the change of temperature. The microscopic active structure in HM can quickly generate oxygen-containing products, and quickly decompose to produce gas or active free radicals. The proportion of hydroxyl, aliphatic and aromatic hydrocarbon structures decreased in thermal decomposition and weight gain stage, indicating that the reaction sequence of generating oxygen-containing functional groups dominated.

Five parallel reaction sequences of coal spontaneous combustion, dehydration and degassing, physical adsorption of O₂, oxidative decomposition, gas phase combustion and solid phase combustion, are defined by multi-modal Gaussian fitting method. Their temperature ranges are 30~204 °C, 42~257 °C, 136~590 °C, 210~660 °C, and 260~642 °C, respectively. Dehydration degassing and physical adsorption O₂ play a major role in the dehydration degassing stage, and the oxidation decomposition reaction runs through the process of coal spontaneous combustion, and plays a dominant role in the oxygen absorption weight gain and thermal decomposition stage.

With the increase of coal metamorphism, the activation energy of oxidation decomposition reaction, gas phase combustion reaction and solid phase combustion reaction generally increases. The competitive effect between gas phase combustion reaction and oxidation decomposition reaction is weakened, and the competitive effect between solid phase combustion reaction and gas phase combustion reaction is weakened first and then enhanced. The oxidative decomposition reaction releases heat, which promotes the transition from oxidative decomposition reaction to gas phase combustion reaction. The oxidation decomposition reaction and gas phase combustion reaction together promote the solid phase combustion reaction of the HM. However, they inhibit the solid phase combustion reaction of CYM, QM, JM and WYM.

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