不粘煤广泛分布于我国西部地区，其变质程度较低，在开采过程中自燃危险性较高。本文采用理论分析和实验研究相结合的方法，选取陕北矿区不粘煤为研究对象，开展了二氧化碳对其氧化自燃过程中动力学特征及官能团活性的抑制作用等方面的研究，研究结果对煤自燃灾害防治工作具有积极意义。

利用TG及DSC方法进行二氧化碳抑制条件下不粘煤氧化自燃过程表征及动力学特征研究，采用两系列混合气体（二氧化碳-空气；二氧化碳-氮气-氧气）进行三种不同升温速率的热分析实验，以此为基础进行动力学参数计算。研究结果表明，二氧化碳-空气气氛下，二氧化碳浓度的提高使得TG-DTG曲线向高温区域偏移、特征温度点升高、活性氧化阶段氧化反应量降低，增长吸热与放热阶段历程，起到延缓煤自燃进程的作用。二氧化碳-氮气-氧气气氛下，消除氧浓度降低的影响因素，发现二氧化碳气体能有效降低解吸附量、延后特征温度点，但对临界温度T₂在浓度达到60%后抑制效果下降，解吸附阶段内吸热量随二氧化碳浓度上升逐级递增，但在浓度达到60%后增量微弱，活性氧化阶段内的特征温度点与二氧化碳浓度呈正比，放热量随二氧化碳浓度增大持续降低。

基于FWO和KAS等转化率法，得出二氧化碳对空气的分压越大，样品在解吸附和活性氧化阶段的活化能均越大。规避氧浓度降低带来的影响，发现解吸附阶段内二氧化碳气体对活化能的提高效果在60%浓度达到峰值；活性氧化阶段内活化能与二氧化碳浓度呈正相关。研究结果表明，60%是二氧化碳气体抑制煤样解吸附阶段氧化自燃的临界浓度值，活性氧化阶段的抑制效果随二氧化碳浓度增大而增强。

通过傅里叶原位红外光谱实验对混合气体下煤氧化自燃过程中官能团变化进行研究，首先结合TG实验数据分析了官能团随特征温度的主要变化趋势，随后对不同气氛下煤分子中官能团变化趋势进行对比，发现不同二氧化碳浓度下，官能团活性具有显著差异性。二氧化碳-空气气氛下，二氧化碳浓度为60%时，羟基、脂肪烃、芳香烃、含氧官能团在解吸附阶段的反应活性最低，活性氧化阶段内则是二氧化碳浓度越大反应强度越弱；二氧化碳-氮气-氧气气氛下的实验数据进一步表明，氧浓度不变时，60%二氧化碳在低温阶段的抑制作用最显著，80%二氧化碳则是在活性氧化阶段对反应强度表现出突出的抑制作用。

Non-stick coal is widely distributed in the western regions of China, and it has a low degree of metamorphism, which makes it highly susceptible to spontaneous combustion during mining. This paper uses a combination of theoretical analysis and experimental research, selecting non-stick coal from the Shaanxi North mining area as the research object. The study explores the effects of carbon dioxide on the kinetic characteristics and functional group activity during the oxidation and spontaneous combustion process of coal, which has significant implications for the prevention and control of coal spontaneous combustion disasters.

Utilizing thermogravimetric (TG) and differential scanning calorimetry (DSC) methods, this research characterizes the oxidation and spontaneous combustion process of non-stick coal under carbon dioxide suppression conditions and investigates its kinetic features using two series of gas mixtures (carbon dioxide-air; carbon dioxide-nitrogen-oxygen) at three different heating rates to calculate kinetic parameters. The results show that under a carbon dioxide-air atmosphere, increasing carbon dioxide concentration shifts the TG-DTG curves to higher temperature regions, raises characteristic temperature points, and decreases the amount of oxidation reactions in the active oxidation stage, thereby extending the endothermic and exothermic stages and delaying the coal's spontaneous combustion process. Under a carbon dioxide-nitrogen-oxygen atmosphere, eliminating the effects of reduced oxygen concentration, carbon dioxide effectively lowers the desorption amount and delays characteristic temperature points, but its inhibition effect on the critical temperature T₂ decreases after reaching a concentration of 60%. The desorption stage's endothermic capacity increases with rising carbon dioxide concentration, but the increment becomes negligible after reaching 60%, and the characteristic temperature points in the active oxidation stage are directly proportional to the carbon dioxide concentration, with the heat release continuously decreasing as the carbon dioxide concentration increases.

Based on conversion rate methods like the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS), it is found that the greater the partial pressure of carbon dioxide in the air, the higher the activation energy during the desorption and active oxidation stages. Avoiding the impact of reduced oxygen concentration, it is found that the enhancing effect of carbon dioxide on activation energy reaches a peak at a 60% concentration during the desorption stage; in the active oxidation stage, the activation energy is directly proportional to the carbon dioxide concentration. The results indicate that 60% is the critical concentration of carbon dioxide for inhibiting coal oxidation and spontaneous combustion during the desorption stage, and the inhibition effect on the active oxidation stage increases with the carbon dioxide concentration.

In-situ Fourier-transform infrared spectroscopy experiments on the coal oxidation and spontaneous combustion process under mixed gas conditions first analyze the main trends in functional group changes according to TG data. Subsequent comparisons of functional group trends in coal molecules under different atmospheres reveal significant differences in functional group activity at different carbon dioxide concentrations. Under a carbon dioxide-air atmosphere, when the carbon dioxide concentration is 60%, the reactivity of hydroxyl, aliphatic hydrocarbon, aromatic hydrocarbon, and oxygen-containing functional groups is the lowest during the desorption stage, and the reaction intensity weakens as the carbon dioxide concentration increases during the active oxidation stage. Further experimental data under a carbon dioxide-nitrogen-oxygen atmosphere show that at a constant oxygen concentration, 60% carbon dioxide has the most significant inhibitory effect at low temperatures, while 80% carbon dioxide exhibits a pronounced inhibitory effect on reaction intensity during the active oxidation stage.

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