综放开采的不断推广及煤炭自身氧化属性，造成采空区内存在不同程度的遗煤自燃现象，威胁着矿井的正常运转。阻化剂作为一种常规手段被广泛应用于井下煤自燃灾害治理，为达到抑制煤自燃的目的，本文选取适合的化学和物理阻化剂，化学阻化剂与煤中活性结构进行结合，物理阻化剂吸收煤中热量，减少煤氧吸附，实现对煤自燃的物化阻化。主要研究成果如下：

（1）将8 wt.%鞣花酸处理煤与8 wt.%柠檬酸处理煤进行煤自燃程序升温实验，对比得出目标抗氧化剂，鞣花酸的阻化效果优于柠檬酸。将8 wt.%碳酸氢钠处理煤与8 wt.%氯化镁处理煤进行煤自燃程序升温实验，得到碳酸氢钠的阻化效果优于氯化镁。

（2）将鞣花酸与下石节煤以2、4、6、8和10 wt.%的质量比均匀混合，分析鞣花酸处理煤在30~270 ℃内各个样品的活性官能团分布及热输运特性。发现鞣花酸处理煤中-CH₃、-CH₂、-OH和-C=O-的峰面积相较于原煤均减少，但C-O的峰面积增加；在相同煤温时，原煤的热扩散系数和导热系数高于鞣花酸处理煤，其比热容低于鞣花酸处理煤，且8 wt.% 鞣花酸对原煤低温氧化过程的热扩散系数、比热容和导热系数的平均抑制率分别为20.8、9.8和13.1 %；通过对煤自燃抑制效果的评价，确定最优质量比为8 wt.%。

（3）对原煤及鞣花酸-碳酸氢钠处理煤（复配比例为3:1、2:1、1:1、1:2、1:3）进行程序升温实验测试，初步得到单一阻化剂的阻化作用和阻化时间上低于鞣花酸-碳酸氢钠（1:1）阻化剂；五种复配比的鞣花酸-碳酸氢钠阻化剂均可显著降低煤氧化过程中的耗氧速率、CO浓度和CO产生率，具有较好的抑制煤自燃效果；复配比为1:1的鞣花酸-碳酸氢钠阻化剂的阻化效果最好，在170 ℃时的耗氧速率、CO浓度、CO产生率较原煤分别降低了67.3、60.9、87.2 %，在30~170 ℃对煤自燃的阻化率为60.9~86.9 %；相比于原煤，鞣花酸-碳酸氢钠（1:1）处理煤的最大放热强度减少了1132.89 J·cm^-3·s^-1，最小放热强度减少了466.25 J·cm^-3·s^-1。

（4）利用热分析仪对鞣花酸和碳酸氢钠在升温过程中的氧化过程进行分析，得出鞣花酸的最大质量损失率对应的温度为458.35 ℃，碳酸氢钠的最大质量损失率对应的温度为162.11 ℃。利用热重分析仪和差示扫描量热仪对下石节原煤及鞣花酸-碳酸氢钠（1:1）处理煤的煤自燃过程中热失重及热释放特性的变化进行研究。分析煤样的热失重曲线，发现处理煤的各特征温度相比于原煤向后推移。根据热释放曲线，与鞣花酸-碳酸氢钠（1:1）处理煤相比，原煤的最大释放热功率、全过程放热量及净放热量大，脱水脱附吸热量小。鞣花酸-碳酸氢钠（1:1）处理煤的燃烧特性参数低于原煤。鞣花酸-碳酸氢钠（1:1）处理煤在T₁-T₄阶段所需表观活化能比原煤多33.826 kJ mol^-1。

（5）基于煤氧复合及量子化学理论，掌握鞣花酸在常温下阻化煤自燃的阻化路径及化学反应所需能量。得到五种自由基的活性顺序为：RO·>·CH₂>ROO·>·CH₃>·OH，且电子主要分布在未成键的区域；鞣花酸含有的四个羟基的断键容易程度顺序为：O19-H26>O22-H28>O20-H25>O21-H27；H·与五种自由基可以快速结合，鞣花酸自由基同样具备活性，能与多数自由基自发成键。

With the continuous promotion of fully-mechanized caving mining and the oxidation properties of coal, there are different degrees of spontaneous combustion of residual coal in goaf, which threatens the safety of mine production and miners’ personal safety. As a conventional method, inhibitor is widely used in the treatment of underground coal spontaneous combustion disaster. In order to achieve the purpose of inhibiting coal spontaneous combustion, this paper selects suitable chemical and physical inhibitors. The chemical inhibitor is combined with the active structure in coal, and the physical inhibitor absorbs the heat in coal and reduces the adsorption of coal oxygen to realize the physical and chemical synergistic inhibition. The main research results are as follows:

(1) The temperature programmed experiment of coal spontaneous combustion was carried out on 8 wt.% ellagic acid treated coal and 8 wt.% citric acid treated coal. The target antioxidant was obtained by comparison, and the inhibition effect of ellagic acid was better than that of citric acid. The 8 wt.% sodium bicarbonate treated coal and 8 wt.% magnesium chloride treated coal were subjected to the temperature programmed experiment of coal spontaneous combustion, and the inhibition effect of sodium bicarbonate was better than that of magnesium chloride.

(2) The ellagic acid and Xiashijie coal were uniformly mixed at a mass ratio of 2, 4, 6, 8 and 10 wt.%. The distribution of active functional groups and heat transport characteristics of each sample of ellagic acid-treated coal at 30 to 270 ℃ were analyzed. The results showed that at the same coal temperature, the thermal diffusivity and thermal conductivity of raw coal are higher than those of EA-tc, and the specific heat capacity is lower than that of EA-tc. The average inhibition rates of 8 wt.% ellagic acid on the thermal diffusivity, specific heat capacity and thermal conductivity of raw coal during low temperature oxidation are 20.8, 9.8 and 13.1 %, respectively. Through the evaluation of the inhibition effect of coal spontaneous combustion, the optimal mass ratio was determined to be 8 wt.%.

(3) The temperature programmed experiment of raw coal and ellagic acid-sodium bicarbonate treated coal ( compound ratio of 3:1, 2:1, 1:1, 1:2, 1:3) was carried out. The inhibition effect and inhibition time of single inhibitor were lower than that of ellagic acid-sodium bicarbonate (1:1) inhibitor. The ellagic acid-sodium bicarbonate inhibitors of five compound ratios can significantly reduce the oxygen consumption rate, CO concentration and CO production rate in the process of coal oxidation, and have a good effect on inhibiting coal spontaneous combustion. The ellagic acid-sodium bicarbonate inhibitor with a compound ratio of 1:1 has the best inhibition effect. At 170 ℃, the oxygen consumption rate, CO concentration, and CO production rate are reduced by 67.3, 60.9, and 87.2 %, respectively, compared with the raw coal. And the inhibition rate of coal spontaneous combustion at 30 to 170 ℃ is at 60.9 to 86.9 % ; compared with raw coal, the maximum exothermic intensity of ellagic acid-sodium bicarbonate (1:1)-tc decreased by 1132.89 J·cm^-3·s^-1.

(4) The oxidation of ellagic acid and sodium bicarbonate during the heating process was analyzed by thermal analyzer. The temperature corresponding to the maximum mass loss rate of ellagic acid was 458.35 °C, and the temperature corresponding to the maximum mass loss rate of sodium bicarbonate was 162.11 °C. Thermogravimetric analyzer and differential scanning calorimeter were used to study the changes of thermal weight loss and heat release characteristics of Xiashijie raw coal and ellagic acid-sodium bicarbonate (1:1) treated coal during spontaneous combustion. According to the thermogravimetric curve of the coal sample, the characteristic temperatures of the treated coal move backward compared with the raw coal. According to Heat release curve, compared with ellagic acid-sodium bicarbonate (1:1)-tc, the maximum heat release power, whole process heat release and net heat release of raw coal are larger, and the heat absorption of dehydration and desorption is smaller. The flammability index and comprehensive combustion index of ellagic acid-sodium bicarbonate (1:1)-tc were significantly lower than those of raw coal. The apparent activation energy required by ellagic acid-sodium bicarbonate (1:1) treated coal at T₁ to T₄ was 33.826 kJ·mol^-1 higher than that of raw coal.

(5) Based on the theory of coal-oxygen composite and quantum chemistry, the inhibition path and the energy required for the chemical reaction of ellagic acid to inhibit the spontaneous combustion of coal at room temperature were mastered. The results show that the activity order of the five free radicals is RO·>·CH₂>ROO·>·CH₃>·OH, and the electrons are mainly distributed in the unbonded region. The order of the bond breaking ease of the four hydroxyl groups contained in ellagic acid is O19-H26>O22-H28>O20-H25>O21-H27; H· can be quickly combined with five free radicals, and ellagic acid free radicals also have activity and can spontaneously bond with most free radicals.

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