煤层自燃对矿井安全生产构成巨大危害。富油煤以其独有的煤、油、气属性，在煤炭领域应用前景广阔，具有极高的战略价值。煤炭在较低氧环境中易煤自燃引发火灾，不仅危及矿井作业安全，还会导致生态环境破坏和能源损耗。本论文采用理论分析、实验研究相结合的方法，对陕北某矿富油煤的氧化过程气体生成、微观结构、热效应和动力学机理变化规律进行了研究，该研究成果为陕北某矿区富油煤自燃预警及煤层火灾防控提供了重要的理论依据和实践指导。主要内容如下：

利用高温程序升温实验，研究了在不同氧浓度环境下，室温至450℃升温过程中陕北某矿富油煤氧化过程气体产物变化规律。得到在富油煤氧化过程中，各气体产物的浓度、氧耗速率、一氧化碳生成速率、二氧化碳生成速率以及放热强度均呈现出随温度和氧气浓度上升而显著增加的趋势。在反应初期临界温度前，CO和CO₂气体缓慢增长，超过180℃后碳氧类气体含量迅速增长。而CH₄、C₂H₆和C₂H₄气体在升温初期浓度上升平缓，随后呈现快速增加趋势，最终在燃烧阶段达到最高浓度值。

采用同步热分析法对富油煤氧化过程的热效应特征进行系统分析，通过实验得到了不同升温速率和不同氧气浓度条件下氧化反应的特征温度点、放热峰强度以及总放热量等关键热力学参数的变化趋势。得到提高氧气浓度导致各特征温度参数向低温方向迁移，加速氧化反应进程；增大升温速率则使特征温度向高温区域转移。在相同升温速率下，随着氧气浓度的增加，煤样吸氧量增大，DSC曲线放热峰向低温区移动，峰值升高且放热总量增加；随着升温速率的提升，煤样放热峰向高温区域偏移且峰值强度增强。并采用KAS法和Satava-Sestak法对其受热分解及燃烧阶段进行动力学分析，得到随转化率的增大，表观活化能值呈现先上升后下降的变化规律。在不同氧气浓度气氛下，利用KAS法计算得到的富油煤受热分解及燃烧阶段活化能值与Satava-Sestak法得到的计算结果基本一致，随着氧气浓度的增加，活化能呈现逐步上升的趋势。而升温速度的加快，则会引起活化能出现先升高后降低的变化。

采用原位傅里叶变换红外光谱实验，研究了富油煤氧化过程微观结构演化特性，得到煤中官能团的含量由大到小排序依次为含氧官能团、芳香烃、脂肪烃。含氧官能团含量与氧气浓度呈现负相关关系；脂肪烃的相对含量随氧气浓度升高而先减后增；芳香烃的占比则先增后减。各活性基团的含量随氧浓度增加呈现先增后减的变化趋势，在氧气浓度条件达到9%左右时，基团含量均趋于稳定。甲基、亚甲基、C=C、C=O和C-O随着反应温度升高，吸收峰强度及含量随之增加，随着温度的上升，游离羟基和缔合氢键峰强度呈现先减弱后增强的变化规律。基于灰色关联度理论，定量分析富油煤氧化过程中微观活性官能团与气体生成及放热强度的关联性，随着氧气浓度升高，富油煤中各类官能团与耗氧量、氧化反应生成气体量及放热量之间的灰色关联系数总体呈现上升态势。富油煤氧化过程中产生的CO、CO₂、CH_4、C₂H₄、C₂H₆等气体与含氧官能团中的C=O伸缩振动基团表现出较强的关联性，从而证实了羰基具有较高的反应活性和易氧化性。在不同氧气浓度条件下，煤样放热量与气体生成量变化趋势一致，与放热量最为密切相关的官能团类型为碳碳和碳氧类的气体产物相关官能团。

Spontaneous Combustion of Coal Seams Poses Significant Hazards to Mine Safety Production.Rich-oil coal, with its unique coal-oil-gas properties, holds broad application prospects in the coal industry and carries high strategic value. Coal is prone to spontaneous combustion in low-oxygen environments, triggering fires that not only endanger mine operations but also lead to ecological damage and energy loss. This study employs a combination of theoretical analysis and experimental research to investigate the gas generation, microstructure, thermal effects, and kinetic mechanisms during the oxidation process of rich-oil coal from a mine in Northern Shaanxi. The findings provide crucial theoretical foundations and practical guidance for early warning of spontaneous combustion and fire prevention in rich-oil coal seams in this mining area. The main contents are as follows:

Using high-temperature programmed heating experiments, the variation patterns of gas products during the oxidation of rich-oil coal from room temperature to 450℃ under different oxygen concentrations were studied. The results indicate that during oxidation, the concentrations of gas products, oxygen consumption rate, CO generation rate, CO₂ generation rate, and heat release intensity all exhibit a significant increasing trend with rising temperature and oxygen concentration. Before the critical temperature in the early reaction stage, CO and CO₂ concentrations increase slowly, but beyond 180℃, carbon-oxygen gases grow rapidly. In contrast, CH₄, C₂H₄, and C₂H₆ show a gradual initial increase, followed by a sharp rise, peaking during the combustion phase.

Synchronous thermal analysis was employed to systematically examine the thermal characteristics of rich-oil coal oxidation. Key thermodynamic parameters including characteristic temperature points, exothermic peak intensity, and total heat release were obtained under varying heating rates and oxygen concentrations. The results demonstrate that higher oxygen concentrations shift characteristic temperatures toward lower values, accelerating oxidation, whereas increased heating rates shift them toward higher temperatures. Under the same heating rate, higher oxygen concentrations enhance oxygen absorption, causing the DSC curve’s exothermic peak to shift to lower temperatures with increased peak intensity and total heat release. Conversely, higher heating rates shift the exothermic peak toward higher temperatures while intensifying peak strength. Kinetic analysis using the KAS and Satava-Sestak methods revealed that the apparent activation energy first rises and then declines with increasing conversion rates. Under different oxygen concentrations, activation energy values calculated via the KAS method align closely with those from the Satava-Sestak method, showing a gradual increase with higher oxygen levels. Meanwhile, faster heating rates cause activation energy to first rise and then fall.

In-situ Fourier transform infrared spectroscopy (FTIR) was used to study the microstructural evolution of rich-oil coal during oxidation. The functional group content follows the order: oxygen-containing groups > aromatic hydrocarbons > aliphatic hydrocarbons. Oxygen-containing functional groups exhibit a negative correlation with oxygen concentration; aliphatic hydrocarbons initially decrease and then increase, while aromatic hydrocarbons show the opposite trend. Reactive group concentrations first rise and then decline with increasing oxygen levels, stabilizing at around 9% oxygen. The absorption peak intensities and contents of methyl, methylene, C=C, C=O, and C-O groups increase with rising temperature, whereas free hydroxyl and hydrogen-bonded hydroxyl groups first weaken and then strengthen. Based on grey correlation theory, a quantitative analysis was conducted to assess the relationship between reactive functional groups and gas generation heat release. As oxygen concentration increases, the grey correlation coefficients between functional groups and oxygen consumption, gas production, and heat release generally rise. Gases such as CO, CO₂, CH₄, C₂H₄, and C₂H₆ exhibit strong correlations with the C=O stretching vibration group, confirming the high reactivity and oxidizability of carbonyl groups. Under varying oxygen concentrations, the trends in heat release and gas generation align closely, with carbon-carbon and carbon-oxygen functional groups showing the strongest correlation with heat release.

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