预氧化卸荷破碎煤体的热行为特性与微观结构特征

Thermal behavior characteristics and microstructural features of pre-oxidized and unloaded crushed coal

  • 摘要: 随着煤层采掘深度不断增加,煤体初始承载应力与环境温度逐步升高,致使深井开采面临着更为突出的煤火灾害风险。为了探究不同初始载荷—卸荷破碎过程及承压—卸荷—预氧化过程对破碎煤微观孔隙、官能团结构的损伤规律及其对氧化释热特性的影响,采用低温氮气吸附、同步热分析及原位漫反射红外光谱等试验手段,系统研究了卸荷破碎煤体的微观结构特征与氧化自燃特性。结果表明:在承压—卸荷破碎过程中,煤体卸荷破碎分形维数随初载应力增大而提高,承压—卸荷引发煤体骨架伸缩与化学键断裂,活性官能团含量上升,降低了煤氧复合起始温度并加快反应速率,增强了煤体低温氧化产热倾向;在承压—卸荷—预氧化过程中,预氧化处理后卸荷破碎煤的分形维数增大,初次高温氧化过程中出现了煤粒二次黏附效应。初载低应力与120 ℃初次氧化会促进微孔和介孔衍生,预氧化温度过高会破坏孔隙结构。120 ℃初载高应力组与180 ℃初载低应力组煤样的低温特征温度低、反应需热量少、反应速率快,表现出较强的氧化倾向。随着预氧化温度升高,卸荷破碎煤中的—COOH、—CHO、—OH结构含量升高,甲基簇结构含量先升高后降低;120 ℃的预氧化主导了卸荷破碎煤内部活性甲基簇结构的大量累积,180 ℃的预氧化主导了卸荷破碎煤内部—CH2、—OH的消耗和—CH3、—CHO的生成累积。初载低应力的预氧化卸荷破碎煤中的官能团水平与承载应力呈正相关,8~16 MPa为预氧化卸荷破碎煤微观结构与氧化特性改变的关键初载应力节点。初始应力升高会造成卸荷破碎煤微观结构损伤,使其自燃倾向性增强;初载静应力—卸荷过程与预氧化过程对煤氧化特性的改变具有协同作用,过高的初始应力与预氧化温度协同作用反而会降低遗留破碎煤的自燃风险;揭示了承压卸荷与高温预氧化对采空区遗煤的复合作用机制。研究结果可为深部煤层安全开采及采空区遗煤复采回收等工程实践提供理论参考。

     

    Abstract: With the increasing depth of coal seam mining, the initial load-bearing stress and ambient temperature of the coal body are gradually increased, leading to increasingly prominent coal fire disaster risks in deep shaft mining. To investigate the damage caused by different initial load-unloading crushing processes and pressure-unloading-pre-oxidation processes on the microstructure of crushed coal, as well as the influences imposed by these processes on oxidative heat release characteristics, the microstructural and oxidative spontaneous combustion characteristics of unloaded crushed coal were systematically studied by means of experiments such as low-temperature nitrogen gas adsorption, simultaneous thermal analysis, and in-situ diffuse reflectance infrared spectroscopy. The results indicate that in the load-bearing-unloading crushing process, the fractal dimension of the unloaded crushed coal is increased with the increase of initial load stress; the expansion of the coal body skeleton and the breakage of chemical bonds are triggered by load-bearing-unloading, and the content of reactive functional groups is increased, by which the starting temperature of coal-oxygen composite is reduced, the reaction rate is accelerated, and the low-temperature oxidative heat generation tendency of the coal is strengthened. In the load-bearing-unloading-pre-oxidation process, the fractal dimension of the unloaded crushed coal is increased with the increase of pre-oxidation degree, and the initial high-temperature oxidation and oxidative heat production tendencies of the coal body are enhanced; in the pressure-unloading-pre-oxidation process, the fractal dimension of the unloaded crushed coal after pre-oxidation treatment is increased, and a secondary adhesion effect of coal particles is exhibited during the initial high-temperature oxidation process. It is found that the development of micropores and mesopores can be promoted by initial low stress and initial oxidation at 120 ℃, whereas the pore structure is destroyed by excessively high pre-oxidation temperatures. Specifically, lower low-temperature oxidation starting temperatures, lower reaction heat requirements, and faster reaction rates are exhibited by coal samples in the 120 ℃ initial high-stress group and the 180 ℃ initial low-stress group, indicating a stronger oxidation tendency. With the increase of pre-oxidation temperature, the contents of —COOH, —CHO, and —OH in the unloaded crushed coal are increased, while the content of methyl cluster structures is initially increased and then decreased; the accumulation of reactive methyl clusters inside the unloaded crushed coal is dominated by pre-oxidation at 120 ℃, while the depletion of —CH2 and —OH, as well as the formation of —CH3 and —CHO inside the unloaded crushed coal, are dominated by pre-oxidation at 180 ℃. A positive correlation is exhibited between the level of functional groups in the pre-oxidized unloaded crushed coal with low initial stress and the bearing stress, and the range of 8−16 MPa is identified as the critical initial stress interval for changes in microstructure and oxidation characteristics. Microstructural damage is caused to the unloaded crushed coal by elevated initial stress, by which its spontaneous combustion tendency is enhanced; a synergistic effect is exerted by the initial static stress-unloading process and the pre-oxidation process on the changes in coal oxidation characteristics, while the spontaneous combustion risk of the leftover crushed coal is reduced by the synergistic effect of excessively high initial stress and pre-oxidation temperature. A composite mechanism of the combined effect of bearing stress unloading and high-temperature pre-oxidation on the leftover coal in the mining area is revealed, and theoretical references can be provided by the results of this study for the safe mining of deep coal seams and the engineering practice of re-mining and recycling of the leftover coal in goafs.

     

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