煤自燃是煤炭开采过程的主要灾害之一，煤火蔓延可能形成难以控制的大面积煤田火灾，在高温环境影响下火区周边煤体氧化反应性发生变化，进而对煤火灾害的蔓延、发展造成影响，然而目前煤田火区热损伤对煤氧化特性影响的研究较少。基于此，本文首先研究了煤热处理过程的反应动力学特征及气体生成规律，确定了模拟煤热损伤过程的研究条件并制备出不同温度热损伤煤样，测试分析了热损伤作用对煤氧化反应宏观特性与微观结构的影响，结合原位红外技术研究了煤氧化升温过程主要活性官能团的演变规律，通过灰色关联分析方法确定了影响热损伤煤氧化特性的关键活性基团，并采用量子化学方法研究了活性基团的氧化反应历程，揭示了热损伤对煤氧化特性的影响作用机制。主要研究成果如下：

采用热重分析仪与管式电阻炉，确定了终止温度、升温速率、终温保持时间对煤热处理过程的影响，得出温度是影响煤热处理过程的首要因素，随温度增大煤的热失重曲线呈现明显的阶段性特征，室温~100 ℃主要发生脱水干燥；100~200 ℃主要为脱气过程；200~400 ℃依次发生脱气、脱羧并初步开始热解；400~600 ℃进入快速热解阶段；600 ℃之后为缩聚反应阶段。升温速率越快微商热重曲线特征峰越窄、越尖锐，反应速率越快，升温速率越慢煤在特定温度下的剩余质量越小，反应程度越高。煤热处理过程气体产物浓度随终温保持时间动态变化，在保持时间达360 min后产物浓度可保持平稳，据此确定了模拟煤热损伤过程的反应条件。

采用管式电阻炉制备出不同温度热损伤煤样，通过程序升温实验系统与差示扫描量热仪，从热损伤煤氧化过程的温升特性、气体生成规律、热效应及氧化动力学等角度，分析了热损伤作用对煤氧化宏观特性的影响。发现100 ℃热损伤煤的交叉点温度降低，O₂浓度及CO、CO₂、CH₄、C₂H₆、C₂H₄等气体产物浓度变化早于原煤，煤样热平衡温度降低、反应前期吸热量减小、更早进入放热阶段，表明煤的自燃倾向增强；200 ℃、400 ℃、600 ℃热损伤煤样交叉点温度递增，气体浓度变化幅度减小，热平衡温度明显延后、热流曲线中由挥发性物质氧化造成的缓慢放热峰逐渐降低最后消失，煤的氧化反应性随热处理温度升高逐渐降低。通过改进的KAS法研究了热损伤煤氧化反应活化能的变化规律，发现100 ℃热损伤煤活化能低于原煤，200 ℃热损伤煤高于原煤，400 ℃、600 ℃热损伤煤的活化能在转化率0~0.45范围内高于原煤、而在转化率大于0.45以后低于原煤，表明该煤样低温阶段自燃倾向降低，但在高温阶段更易发生燃烧。

采用X射线衍射仪与傅里叶变换红外光谱仪分析了热损伤作用对煤微观结构的影响，结合原位红外技术研究了热损伤煤氧化活性基团的演变规律，发现随热处理温度升高煤中芳香层片间距减小，平均直径、平均堆砌高度及有效堆砌片数增大，微晶结构有序性增强。热损伤作用使煤中活性基团减少，随着热处理温度升高煤表面活性官能团中–OH、脂肪C–H、C–O、C=O的相对含量减少，而取代芳烃、芳环C=C等芳香族官能团相对含量增多，导致煤氧化反应性降低。热损伤煤氧化升温过程中活性官能团含量随温度的变化趋势与原煤一致，超过热解温度的热损伤作用使煤分子芳核更加稳定，官能团变化速率明显降低。

基于灰色关联分析方法计算了煤氧化过程宏观特性与微观活性基团吸收峰面积变化规律之间的关联度，确定了影响热流强度、放热量、碳氧化合物气体浓度的关键活性基团为C=O，影响碳氢化合物气体浓度的关键活性基团为脂肪C–H。采用量子化学方法对关键活性基团小分子模型化合物的氧化反应历程进行了模拟计算，结合理论分析与实验结果揭示了热损伤对煤氧化特性的影响作用机制。得出100 ℃热损伤作用使煤中水分蒸发，煤氧反应初期吸热量减少，水分对煤氧接触的阻碍降低，导致煤自燃倾向增强。200 ℃、400 ℃、600 ℃的热损伤作用使煤表面活性基团减少，煤分子结构有序性增加，氧气夺取活性基团氢原子的反应能垒增大、吸热量增大，延缓了煤氧化自由基链式反应，导致煤氧化反应性逐渐降低。

Spontaneous combustion of coal is one of the main disasters in the process of coal mining. The spread of coal fire may form a large-scale coalfield fire that is difficult to control. Under the influence of high temperature environment, the oxidation reactivity of coal around the fire area changes, which in turn affects the spread and development of coal fire disaster. However, there are few studies on the influence of thermal damage in coalfield fire area on coal oxidation characteristics. Based on this, firstly, the reaction kinetics characteristics and gas generation law of coal heat treatment process were studied, the experimental conditions for simulating coal thermal damage process were determined, and coal samples with different thermal damage degrees were prepared. The influence of thermal damage on the macro-characteristics and microstructure of coal oxidation reaction was tested and analyzed. The evolution law of main active functional groups in the process of coal oxidation heating was studied by in-situ infrared technology, and the key active groups affecting the oxidation characteristics of coal with thermal damage were determined by grey correlation analysis. The oxidation reaction process of active groups was studied by quantum chemistry method, revealing the mechanism of the influence of thermal damage on the oxidation characteristics of coal. The main research results are as follows.

By using thermogravimetric analyzer and tube resistance furnace, the effects of termination temperature, heating rate and final temperature holding time on the coal heat treatment process were determined, and the experimental conditions for simulating the coal thermal damage process were defined. It is concluded that temperature is the primary factor affecting the heat treatment process of coal. As the temperature increases, the thermal weight loss curve of coal shows obvious stage characteristics. Dehydration and drying mainly occurs between room temperature and 100 ℃. Degassing occurs mainly between 100 ℃ and 200 ℃. Degassing, decarboxylation and preliminary pyrolysis occur at 200 ℃ and 400 ℃. The rapid pyrolysis stage occurs between 400 ℃ and 600 ℃. After 600 ℃ is the polycondensation reaction stage. The faster the heating rate, the narrower and sharper the characteristic peak of the differential thermogravimetric curve, and the faster the reaction rate. The slower the heating rate, the smaller the remaining mass of coal at a specific temperature, and the higher the degree of reaction. During the coal thermal treatment process, the gas product concentration changes dynamically with the final temperature holding time, and the product concentration can remain stable after the holding time reaches 360 minutes. Accordingly, the reaction conditions for simulating the thermal damage process of coal were determined.

Coal samples with different degrees of thermal damage were prepared using a tubular resistance furnace. The temperature rise characteristics, gas generation rules, thermal effects and oxidation kinetics of the oxidation process of thermally damaged coal were analyzed through a programmed temperature rise experimental system and a differential scanning calorimeter. The influence of thermal damage on the macroscopic characteristics of coal oxidation was studied. It was found that the crossing-point temperature of thermally damaged coal at 100 ℃ decreased, and the concentration of O₂ and gaseous products such as CO, CO₂, CH₄, C₂H₆, and C₂H₄ changed earlier than that of raw coal. The thermal equilibrium temperature decreased, the heat absorption in the early stage of reaction decreased, and it entered the exothermic stage earlier, indicating that the spontaneous combustion tendency of coal increased. The crossing-point temperature of thermally damaged coal samples at 200 ℃, 400 ℃, and 600 ℃ increases gradually, the change amplitude of gas concentration decreases, the thermal equilibrium temperature is significantly delayed, and the slow exothermic peak caused by the oxidation of volatile substances in the heat flow curve gradually decreases and finally disappears, indicating that the oxidation reactivity of coal gradually decreases as the heat treatment temperature increases. The variation pattern of the activation energy of thermally damaged coal oxidation reaction was studied through the improved KAS method. It was found that the activation energy of thermally damaged coal at 100 ℃ was lower than that of raw coal, that of thermally damaged coal at 200 ℃ was higher than that of raw coal, and that of heat damaged coal at 400 ℃ and 600 ℃ was higher than that of raw coal in the conversion rate range of 0 to 0.45, but lower than that of raw coal after the conversion rate was greater than 0.45, indicating that the spontaneous combustion tendency of the coal sample decreased at low temperature stage, but it was more prone to burn at high temperature stage.

X-ray diffractometer and Fourier transform infrared spectrometer were used to analyze the influence of thermal damage on the microstructure of coal, and the evolution law of oxidative active groups in thermal damaged coal was studied by combining with in-situ infrared technology. It is found that with the increase of heat treatment temperature, the spacing of aromatic lamellae in coal decreases, the average diameter, average stacking height and effective stacking number increase, and the order of coal microcrystal structure increases. Thermal damage reduces the active groups in coal. As the heat treatment temperature increases, the relative contents of –OH, aliphatic C–H, C–O, and C=O in the active functional groups on the coal surface decrease, while the relative contents of aromatic functional groups such as substituted aromatics and aromatic ring C=C increase, resulting in a decrease in coal oxidation reactivity. The trend of the change of the active functional group content with temperature during the oxidation heating process of thermal damaged coal is consistent with that of the original coal. The thermal damage effect exceeding the pyrolysis temperature makes the aromatic nucleus of the coal molecule more stable, and the rate of functional group change is significantly reduced.

Based on the method of grey correlation analysis, the correlation coefficient between the macroscopic characteristics of coal oxidation process and the variation law of absorption peak area of microscopic active groups is calculated. It is determined that the key active group affecting heat flux intensity, heat release and hydrocarbon gas concentration is C=O, and the key active group affecting hydrocarbon gas concentration is aliphatic C–H. Quantum chemical methods were used to simulate and calculate the oxidation reaction process of small molecule model compounds with key active groups, revealing the mechanism of the influence of thermal damage on coal oxidation characteristics. It was concluded that the thermal damage at 100 ℃ evaporates the water in the coal, reduces the heat absorption in the early stage of the coal-oxygen reaction, and reduces the hindrance of water to coal-oxygen contact, resulting in an enhanced tendency of coal to spontaneously ignite. Thermal damage at 200 ℃, 400 ℃, and 600 ℃ reduces the active groups on the coal surface, increases the order of the coal molecular structure, increases the reaction energy barrier and heat absorption for oxygen to take away the hydrogen atoms of the active groups, and delays the Coal oxidation radical chain reaction leads to the gradual decrease of coal oxidation reactivity.

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