我国煤自然发火现象频发，造成了严重的资源浪费和环境污染。因此，研究高效、经济的煤自燃阻化剂十分重要。针对物理、化学阻化剂阻化效果单一，复合阻化剂制备复杂等问题。本论文制备物理阻化剂（膨胀型温敏水凝胶（HPMC-CS-EM））、优选化学阻化剂（褪黑素（MT）），完成了复合阻化剂（膨胀型温敏水凝胶协效褪黑素（HPMC-CS-EM/MT））的制备。采用实验测试和数学计算的方法，研究了复合阻化剂对煤氧化过程的阻化特性，揭示了HPMC-CS-EM/MT阻化煤自燃的微观作用过程。

首先，采用壳聚糖（CS）、羟丙基甲基纤维素（HPMC）和膨胀微球（EM）制备了膨胀型温敏水凝胶，系统研究了EM含量、HPMC黏度对HPMC-CS-EM的性能影响。EM含量为0.5%、HPMC黏度为50mPa•s的HPMC-CS-EM具有良好的流动性、在加热过程中不会出现分层现象且膨胀能力最强（1.33倍）。因此，最终选择A₅₀（HPMC:50 mPa•s、EM:0%）、B₅₀（HPMC: 50 mPa•s、EM:0.5%）作为复合阻化剂的物理阻化部分。

将A₅₀、B₅₀与褪黑素按照不同比例进行混合，完成了HPMC-CS-EM/MT阻化煤的制备。对原煤、单一阻化煤与复合阻化煤进行了顺磁共振波谱实验与热重实验，运用普适积分与微分相结合的方法，计算了多升温速率下煤样在初始失重阶段与缓慢氧化阶段的表观活化能，并采用Bagchi法确定了最概然机理函数。A₅₀与MT复配可延缓煤的氧化，但与单一阻化煤相比，协效作用不强。B₅₀与MT复配的阻化煤自由基浓度和种类增长趋势有明显的减缓，并且在B₅₀含量较多时，协效作用明显。阻化煤的最大失水速率温度（T₁）、着火温度点（T₃）与平均表观活化能均提高。综合自由基浓度、线宽、特征温度及平均表观活化能参数，对B₅₀:MT（1:1、3:1、5:1）复合阻化煤的阻化作用进行了评估，最终选择了B₅₀:MT(5:1)为最优阻化配比，该配比下煤样的T₁从88.6 ℃增加至100.1 ℃、干裂温度由205.74 ℃增加至229.8 ℃、T₃从346.0 ℃增加至358.2 ℃。两阶段的 平均活化能分别增加了49、115 kJ/mol。

利用原位漫反射红外光谱实验，研究了原煤、最佳阻化煤氧化过程中脂肪烃与含氧官能团的变化趋势，HPMC-CS-EM/MT可减少煤中甲基、亚甲基、羟基、羧基等的含量，提高较为稳定的醚键含量。同时结合阻化特性提出了HPMC-CS-EM/MT抑制煤氧化的作用过程，MT在内部捕获煤中羟基、脂过氧等自由基、降低脂肪烃、羟基等的含量、惰化了煤反应活性中心；HPMC-CS-EM则逐渐在相变、膨胀过程中析出水分、降低煤体的温度，并凝结覆盖在煤体表面隔氧，延长MT的作用时间、延缓煤氧化进程。最终通过内部惰化、外部隔氧降温的协同作用达到抑制煤自燃的效果，研究结果对高效绿色防控煤自燃具有重要的科学价值和实际指导意义。

Coal spontaneous combustion (CSC) occurs frequently in China, resulting in serious waste of resources and environmental pollution. Therefore, it's of importance to study efficient and economical coal self-ignition inhibitors. Aiming at the problems of single inhibition effect of physical or chemical inhibitors and complex preparation of composite inhibitors. This paper prepared a physical inhibitor (Intumescent Thermosensitive Hydrogel, HPMC-CS-EM), preferred chemical inhibitor (Melatonin, MT), the preparation of composite inhibitor (intumesent thermosensitive hydrogel co-acting melatonin, HPMC-CS-EM/MT) was completed. By means of experimental test and mathematical calculation, the characteristics of compound inhibitors on coal oxidation were studied, and the action process of HPMC-CS-EM/MT on CSC was revealed.

First, HPMC-CS-EM were prepared by using chitosan (CS), hydroxypropyl methylcellulose (HPMC) and expanded microspheres (EM). The effects of EM content and HPMC viscosity on HPMC-CS-EM were systematically studied. The HPMC-CS-EM that EM content of 0.5% and the HPMC viscosity of 50 mPa·s have good fluidity, no delamination during heating, and the highest expansion ability (1.33 times). Therefore, A₅₀ and B₅₀ were finally selected as the physical inhibition part of the composite inhibitor.

A₅₀, B₅₀ and MT were mixed in different proportions to complete the preparation of HPMC-CS-EM/MT inhibited coal. The paramagnetic resonance spectroscopy experiment and thermogravimetric experiment were carried out on the raw coal, single inhibited coal and composite inhibited coal. The method of combining universal integration and differential was used to calculate the initial weight loss and slow oxidation of coal samples under multiple heating rates. The apparent activation energies of the phases were determined, and the most probable mechanism function was determined by the Bagchi method. The combination of A₅₀ and MT was not strong compared with single inhibited coal. The growth trend of free radical concentration and species in the composite inhibiting coal compounded with B₅₀ and MT is obviously slowed down, and the synergistic effect is obvious when the content of B₅₀ is high. The maximum water loss rate temperature (T₁), the ignition temperature point (T₃) and the average apparent activation energy of the compound inhibited coal were all increased. Based on the parameters of free radical concentration, line width, characteristic temperature and average apparent activation energy, the inhibition effect of B₅₀:MT (1:1, 3:1, 5:1) composite inhibitory coal was evaluated, and the final choice was B₅₀:MT (5:1) is the optimal ratio of compound inhibitor. Under this ratio, the T₁, the dry cracking temperature and T₃ of coal samples increased from 88.6 ℃ to 100.1 ℃, 205.7 ℃ to 229.8 ℃, and 346.0 ℃ to 358.2 ℃, respectively. The average apparent activation energy in two stages increased 49 and 115 kJ/mol, respectively.

The change trend of aliphatic hydrocarbons and oxygen-containing functional groups in the oxidation process of raw coal and optimally inhibited coal was studied by in-situ diffuse reflectance infrared spectroscopy experiments. HPMC-CS-EM/MT can reduce the -CH₂, -CH₃, -OH, etc., increase the content of -C-O-. The process of HPMC-CS-EM/MT in inhibiting coal oxidation is proposed. MT internally captures free radicals, reduces the content of aliphatic hydrocarbons and hydroxyl groups, and inerts the coal reactive center; HPMC-CS-EM gradually separates out moisture in the process of phase change and expansion, lowers the temperature of the coal body, and condenses and covers the surface of the coal body to block oxygen, prolonging the action time of MT and delaying the process of coal oxidation. The research results have important scientific value and practical guiding significance for efficient and green prevention and control of coal spontaneous combustion.

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