火区封闭是现阶段矿井煤火灾害防治的最后一道防线，但封闭后火区内的火灾往往难以得到有效控制。造成这一问题的重要原因之一是次生煤火灾害的存在，即原有高温热源向外传递能量所引发的不直接相连的煤体阴燃火灾。由于封闭火区环境的特殊性，次生煤火灾害往往处于原有火源产生的光与热以及空间内贫氧环境的综合作用下。本文在明确矿井封闭火区次生煤火灾害内涵及其主要特征的基础上，采用理论分析与物理实验相结合的方法，针对性地研究了封闭火区内光-热作用下煤体反应性参数变化，探究了贫氧状态下煤的氧化进程和机制，明确了煤氧化放热过程中的关键基团及其演变特征，并最终阐释了不同供风流速和引燃温度下煤体阴燃发生及蔓延规律。本文的主要创新成果如下：

（1）基于自建的煤光-热氧化装置，研究了封闭火区内高温热源光-热作用下松散煤体反应性参数变化。结果表明：光与热作用后，煤中自由基种类增多，对称性下降，反应速率加快；煤中芳香烃与脂肪烃的氧化被促进，含氧官能团尤其是−COO−的含量显著升高。热作用后煤的比表面积、孔体积下降而平均和最可几孔径显著增大，光作用后则无显著变化。光与热作用均会导致煤孔隙的贯通和分形维数的减小。热作用对煤反应性参数的变化起决定性作用，而光会增强热的作用效果。

（2）采用热重分析研究了原煤与光-热氧化煤在不同氧气浓度下的热反应特征，利用多组分叠加模型法确定了煤贫氧氧化过程热解与氧化反应竞争机制。结果表明：煤热解反应机制依次为水分蒸发→挥发分析出→半焦热解→半焦缩聚，氧化反应机制依次为水分蒸发→吸氧增重→挥发分析出与燃烧→半焦燃烧→焦炭燃烧。贫氧状态下煤倾向于遵循氧化反应机制。煤热解与氧化竞争的本质是煤氧反应能否提高体系内能以维持进一步的反应。煤氧化独立反应活化能和反应速率均随氧气浓度的降低而降低。反应速率dα/dt较活化能更加充分全面的体现了煤氧化动力学特征。贫氧限制了煤氧化反应的进行，但促进了焦炭的生成与燃烧。光-热氧化则促进了煤贫氧氧化过程中半焦和焦炭的燃烧过程。

（3）利用差示扫描量热和原位红外技术研究了煤贫氧氧化热效应及关键基团反应特征，结果表明：贫氧并未改煤氧化放热进程与微观基团反应特征，但会减小反应放热，导致反应整体向高温区移动。利用灰色关联分析确定了煤氧化关键基团演变特征，结果表明YM关键基团的变化趋势为−OH-1→−COO−→Ar−CH→Ar−CH （21%氧气浓度下），而经历光-热作用的VR-150则为−OH-1→−CH₃→−CH₃→Ar−CH （21%氧气浓度下）。任意氧气浓度下YM氧化的关键基团着遵循羟基→碳氧基团→脂肪烃化合物→芳香烃化合物的演化历程，而VR-150煤的关键基团演变特征则为羟基→脂肪烃化合物→脂肪烃化合物→芳香烃化合物。光-热作用会增强煤中脂肪烃的活性，导致其在低温氧化阶段起到关键作用。

（4）利用自建的煤体阴燃蔓延特性测试装置研究了煤体正/逆向阴燃反应特征，明确了煤阴燃反应机制及临界参数。结果表明：封闭火区内煤体正/逆向阴燃过程均会受到辐射加热温度和供风流速的影响。煤体逆向阴燃有向正向阴燃转变的趋势。随着供风流速和加热温度的增加，煤样阴燃由熄灭过渡为稳定蔓延并最终增强为有焰燃烧。煤体正/逆向阴燃过程均可分为未引燃，阴燃熄灭，阴燃维持（转变）和阴燃增强四种传播模式。辐射加热温度决定了阴燃反应发生与否，供风流速决定了正向阴燃能否稳定维持，而逆向阴燃向正向阴燃乃至有焰燃烧的转变则由加热温度和供风流速共同决定。正向阴燃稳定维持及有焰转变的临界供风流速分别为0.146 m/min和0.541 m/min（300.0 ℃加热下），稳定维持的临界加热温度为188.0℃（0.4 m/min供氧下）；逆向阴燃转变为正向阴燃及增强为有焰燃烧的临界供风流速分别为0.522 m/min和0.893 m/min（300.0 ℃加热下），转变为正向及有焰燃烧的临界加热温度分别186.1 ℃和212.0 ℃（1.0 m/min供氧下）。次生火灾的阴燃过程中产生的CO、CO₂、C₂H₄和C₂H₂的变化趋势与煤层整体温度相关，并相较于自然发火表现出较高的C₂H₄浓度。阴燃过程中C₂H₄/CO₂和CO/CO₂的变化趋势可用于判断煤阴燃进程。

本文的研究结果对封闭火区内次生煤火灾害的发生和蔓延机制以及封闭火区启封有着积极的意义。

Fire zone closure is the measure of last resort for coal fire disaster prevention and control in mines at this stage. However, fires in enclosed fire zones are often difficult to effectively control. One of the major causes of this problem is the existence of secondary coal fire disasters, i.e. the smoldering fire caused by the transfer of energy from the original high temperature heat source to non-directly connected coal seam. Due to the unique nature of the enclosed fire zone environment, secondary coal fire disasters are often under the combined effects of photo and heat generated by the original fire source and the oxygen-depleted environment in space.

On the basis of the definition of secondary coal fire disasters in the closed fire zone and their main characteristics, this paper uses a combination of theoretical analysis and physical experiments to investigate the variations of coal reactivity parameters under the action of photo and heat in the closed fire zone, to explore the combustion process and combustion mechanism of coal in the oxygen-depleted state, to clarify the key groups in the exothermic process of coal combustion and their evolution laws, and finally the occurrence and spread of coal smoldering under different oxygen supply rate and ignition temperature are investigated. The main innovations of this paper are as follows:

Based on a self-built coal photo-thermal oxidation apparatus, the variation of the reactivity parameters of loose coals under the photo-thermal action from high temperature heat sources in the enclosed fire zone was investigated. The results show that after the interaction of photo and heat, the types of free radicals in coal increase, the symmetry decreases, and the reaction rate accelerates. The oxidation process of aromatic and aliphatic hydrocarbons in coal is promoted, and the content of oxygen-containing functional groups, especially −COO−, is significantly increased. The specific surface area and pore volume of the coal decrease while the average and most probable aperture increase significantly after thermal effects, while photo effects have less impact. Both photo and heat effects lead to penetration of pores and the reduction in the fractal dimension of the coal. Thermal effects have a decisive influence on the changes in coal reactivity parameters, while photo enhances thermal effects.

Thermogravimetric analysis was used to study the thermal reaction characteristics of raw coal and photo-thermally oxidized coal at different oxygen concentrations, and the multi-component superposition model was used to determine the competing reaction mechanisms of coal pyrolysis and oxidation under oxygen-depleted environment. The results show that the reaction mechanisms of coal pyrolysis are, in order, water evaporation → volatile separate out → semi-coke pyrolysis → semi-coke condensation, and the reaction mechanisms of oxidation are, in order, water evaporation → oxygen-absorption and mass-gain → volatile separate out and combustion → semi-coke combustion → coke combustion. Coal in the oxygen-depleted state tends to follow an oxidation reaction mechanism. The essence of coal pyrolysis competing with oxidation is the ability of the coal-oxygen reaction to raise within the system to sustain further reactions. The independent reaction activation energy and the reaction rate of coal oxidation decreases with decreasing oxygen concentration. The reaction rate dα/dt more fully characterizes the kinetics of coal oxidation than the activation energy. Oxygen depletion limits coal oxidation reactions, but promotes coke production and combustion. Photo-thermal oxidation facilitates the combustion of semi-coke and coke during the oxygen-depleted combustion of coal.

The thermal effects of oxygen-depleted coal oxidation and the reaction characteristics of key groups were investigated using differential scanning calorimetry and in situ infrared techniques. The results show oxygen depletion does not alter the exothermic process of coal combustion and the reaction characteristics of microscopic groups, but it does reduce the exotherm of the reaction and causes the overall reaction to move towards the high temperature region. The evolution of the key groups of coal oxidation was characterized using grey correlation analysis, which showed that the trend of the key groups of YM was −OH−1→−COO−→Ar−CH → Ar−CH (at 21% oxygen concentration), while VR-150 is −OH−1→−CH₃→−CH₃→Ar−CH (at 21% oxygen concentration). While YM combustion at arbitrary oxygen concentrations follows the microscopic reaction course of hydroxyl groups → carbon-oxygen group → aliphatic hydrocarbon compounds → aromatic hydrocarbon compounds, the evolution of key groups in the VR-150 coal sample is characterized by hydroxyl groups → aliphatic hydrocarbon compounds → aliphatic hydrocarbon compounds → aromatic hydrocarbon compounds. Photo-thermal oxidation enhances the activity of aliphatic hydrocarbons in coal, leading to their advancement in the low temperature oxidation phase.

A self-built test apparatus was used to investigate the characteristics of the forward/opposed smoldering of coal and to elucidate the mechanism of the smoldering reaction of coal and its critical combustion parameters. The results show that the forward/opposed smoldering of coal in the closed fire zone is influenced by the radiation heating temperature and oxygen supply rate, and there is a tendency for the opposed smoldering of coal to change to forward smoldering. As the oxygen supply rate and heating temperature increase, the opposed smoldering of the coal transitions from extinction to stable spreading and eventually increases to flaming combustion. The forward/opposed coal smoldering process can be divided into four modes of propagation: uninitiated, smoldering extinguished, smoldering maintained (transformed) and smoldering enhanced. The radiation heating temperature determines whether the smoldering reaction occurs or not, and the rate of oxygen supply determines whether the forward smoldering can be stably maintained. The transition from opposed to forward smoldering and even flamed combustion is determined by both the heating temperature and the oxygen supply rate. The critical oxygen supply rate for the stable maintenance of forward smoldering and flaming transformation is 0.146 m/min and 0.541 m/min (under 300.0 °C heating) respectively, and the critical heating temperature for smoldering maintained is 188.0 °C (under 0.4 m/min oxygen supply). The critical oxygen supply rate for the conversion of opposed smoldering to forward smoldering and enhancement to flamed combustion is 0.522 m/min and 0.893 m/min (at 300.0 °C heating), respectively, and the critical heating temperatures for conversion to forward smoldering and flamed combustion are 186.1 °C and 212.0 °C (at 1.0 m/min oxygen supply), respectively. The trends of CO, CO₂, C₂H₄ and C₂H₂ produced during the smoldering of secondary coal fires are correlated with the overall temperature of the coal seam, and shows a higher concentration of C₂H₄ compared to spontaneous combustion. Where the trends of C₂H₄/CO₂ and CO/CO₂ can be used to determine the smoldering of coal.

The research results of this article have positive significance for the occurrence and spread mechanism of secondary coal fire disasters in closed fire areas, as well as for the unsealing of closed fire areas.

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