随着煤开采强度和深度的增加，煤的赋存和开采条件愈加复杂，采空区煤自燃灾害的防控难度不断增大，注入高效安全的防控材料是控制采空区遗煤自燃的重要技术策略。本文基于凝胶泡沫防灭火材料的高效保水能力、出色成胶特性和优异的堆积渗流扩散特性，融合煤自燃防控新技术和纳米灭火新材料的优势特点，通过改性复合的方法制备一种新型纳米SiO2改性复合凝胶泡沫，提升材料的渗流扩散、覆盖阻化、固化堵漏等工艺性能。围绕纳米SiO2改性复合凝胶泡沫对煤自燃抑制作用，构建基于深度学习的材料配比预测优化模型，探究材料的优选与制备方法。开展改性复合凝胶泡沫材料的宏观抑制性能系列对比测试实验，搭建采空区模拟测试平台考察验证防煤自燃效果。结合现代测试分析技术手段，采用量子化学计算模拟方法，从分子反应的层面解析材料防煤自燃的微观机理，阐释纳米改性复合凝胶泡沫抑制煤自燃的作用机制。
获得了纳米SiO2改性复合凝胶泡沫材料的主要组分组成、关键组分改性及制备方法。结合防灭火材料阻化性能要求与现场生产环境的工艺需求，研究改性提效材料优选与配比优化策略，优选纳米SiO2颗粒、膨润土改性TBHQ抗氧化剂，实现物理化学阻化剂与凝胶泡沫的改性复合。采用插层嫁接的方法改性关键化学组分以提高材料的阻化性能和热稳定性，添加纳米SiO2颗粒增强凝胶泡沫网络骨架结构，提升了凝胶泡沫的整体阻化效能。膨润土改性TBHQ的化学改性策略，将抗氧化剂的失水率突变临界点从80℃提升至120℃，有效提升了材料的热稳定性。提出了一种基于深度卷积神经网络的材料浓度配比的预测优化方法。通过单因素实验法筛选出的单一组分最佳浓度，利用多因素响应面分析法获取关键组分的最优配比，基于深度卷积神经网络算法构建材料浓度配比预测优化CNN模型。将多因素条件下响应面分析因素组合的实验结果作为样本集，对比训练集和验证集的预测结果，评估模型的有效性与准确性。经过连续300次迭代训练得到优化后的材料浓度配比为：胶凝剂3.0%，交联剂0.2%wt，发泡剂0.2%wt，稳泡剂0.49%wt，纳米颗粒3.0%wt，阻化剂2.9%wt，预测优化的浓度配比与多因素响应面法优化结果的误差控制在[0.1%wt,1%wt]之间，从理论和实验两个维度预测优化所选材料配比的合理性。
研究阐释了纳米改性复合凝胶泡沫在抑制煤自燃过程中的宏观阻化性能与作用机制。通过应力黏度、封堵阻力、失水率等参数的对比测试，探究改性复合凝胶泡沫的流变扩散、封堵隔氧、热稳定性等宏观阻化性能，研究流变特性对煤体空间覆盖堆积性能的影响规律，揭示了材料封堵性能的时空变化对阻断煤自燃的作用机制。实验获得了长焰煤氧化反应阶段划分的特征温度点：53℃、145℃、231℃、268℃、408℃、562℃、767℃。改性复合强化了材料在低温氧化阶段的阻化性能，特别是在煤自燃吸氧增重阶段（T2-T4）展示出更加突出的阻化效果，特征点温度分别提高了6%、11%和26%。纳米改性复合凝胶泡沫流变行为表现是一种屈服假塑性流体，流变特性通过拟合本构方程τ=0.67+10.48γ0.38来描述，流变性质因泡沫化过程显著改变，屈服力从73.08Pa减少至0.67Pa，而稠度系数从157.86显著降低至10.48，固定的剪切速率下的黏度仅为普通凝胶的1/12。探讨纳米改性复合凝胶泡沫在封堵隔氧性能方面的有效性，添加2% wt 纳米改性复合凝胶泡沫的阻化煤样，漏风阻力能够显著提升至2.0kPa。开展纳米改性复合凝胶泡沫制防治遗煤自燃的采空区原位模拟验证实验，170℃时CO阻化率可达72.11%，阻化效果是普通凝胶泡沫的6倍、MgCl2浆液的3倍。
阐明了纳米SiO2改性复合凝胶泡沫防煤自燃宏观性能与抑制煤自燃微观机理之间的关系。运用电子自旋共振波谱ESR与原位红外光谱FTIR检测技术，对比阻化前后煤样活性基团分布演化规律，分析了材料阻断煤氧链式反应进程的作用机制。长焰煤的活性基团包括-CH3, -CH2、-COOH、-OH、-CH和Ar-C-O等，其中含氧官能团中占比最大，芳香烃结构的谱峰较为尖锐，改性复合凝胶泡沫在初期温度50℃~90℃范围对减缓自由基浓度增长的作用尤为显著。构建长焰煤分子简单模型化合物，开展活性基团的氧化链式反应传播路径的模拟分析，阐明活性基团反应路径和化学作用机制。发现长焰煤分子活性基团链式反应沿着直线型、交叉循环型路径进行，活化能小于40kJ/mol的脂肪烃-CH官能团率先发生反应，反复自我活化煤分子内其他官能团加速氧化反应。改性抗氧化剂通过氢离子消除自由基，中断煤氧复合反应的传播路径，通过羟基-OH与煤分子内部的-COO-等活性官能团之间的相互作用，遏制含氧官能团羧基-COO-引发的链式反应进程，膨润土释放的Na+和Ca2+与煤分子中的活性基团形成稳定的结构化合物，削弱基团的反应活性，降低煤氧复合反应的可能性。阐释了改性复合凝胶泡沫抑制煤自燃物理化学作用方式共同参与的协同作用机制，物理层面上空间覆盖和封堵隔氧的特性，化学层面上清除活性基团、形成稳定化合物的抗氧化特性，实现了协同阻止煤体自燃的效果。新材料的研制开发和阻化机理的研究，对我国煤炭绿色安全高效开采具有重要的现实意义。

With the increasing intensity and depth of coal seam mining, the conditions for coal seam occurrence and mining have become increasingly complex.The difficulty of preventing and controlling coal spontaneous combustion disasters in goaf has increased dramatically. Injecting efficient and safe prevention and control materials into goaf is an important technical strategy to control residual coal spontaneous combustion. This paper, based on the high water retention capacity, excellent gelation characteristics, and outstanding accumulation and seepage diffusion properties of gel foam fire extinguishing materials, integrates the advantages of new technologies for coal spontaneous combustion prevention and control and new nanomaterials for fire extinguishing. A new type of nano-SiO2 modified composite gel foam is prepared by modification and compounding methods to enhance the material’s seepage diffusion performance, persistent coverage and inhibition, and rapid solidification and plugging process performance. Focusing on the inhibitory effect of nano-SiO2 modified composite gel foam on coal spontaneous combustion, a material ratio prediction optimization model based on deep learning is constructed to explore the material selection and preparation methods. A series of comparative tests on the macroscopic inhibitory performance of the modified composite gel foam materials are carried out, and a goaf simulation testing platform is built to examine and verify the effect of preventing coal spontaneous combustion. Quantum chemical simulation calculation methods are used in conjunction with modern testing and analysis techniques to analyze the microscopic mechanism of the material’s prevention of coal spontaneous combustion from the molecular reaction level, elucidating the action mechanism of nano-modified composite gel foam in inhibiting coal spontaneous combustion.
The main component composition, key component modification, and preparation methods of nano-SiO2 modified composite gel foam materials have been obtained. Combining the requirements of fire extinguishing material inhibition performance and the process needs of the on-site production environment, the material selection and ratio optimization strategies for the modification and efficiency improvement of the modified composite gel foam are studied to realize the modification and compounding of physical and chemical inhibitors with gel foam, with the selection of Nano-SiO2 particles and bentonite-modified TBHQ antioxidants. The key chemical components are modified by intercalation grafting to improve the material’s inhibition performance and thermal stability, and nano-SiO2 particles are added to enhance the network skeleton structure of the gel foam, improving the inhibition efficiency of the gel foam. The chemical modification strategy of bentonite-modified TBHQ shifts the critical point of the antioxidant’s dehydration rate from 80°C to 120°C, effectively enhancing the material’s thermal stability.
A prediction optimization method for the concentration ratio of nano-modified composite gel foam materials based on deep convolutional neural networks is proposed. The single component type and optimal concentration are screened out by the single-factor experimental method, and the optimal ratio of six components is obtained using the multifactorial response surface analysis method. A prediction optimization CNN model is constructed based on the deep convolutional neural network algorithm. The experimental results of the response surface analysis factor combinations under multifactorial conditions are used as the sample set. The prediction results of the training set and validation set are compared to evaluate the model’s effectiveness and accuracy. After 300 consecutive iterations of training, the optimized material concentration ratio is obtained: coagulant 3.0%, cross-linking agent 0.2%wt, foaming agent 0.2%wt, foam stabilizer 0.49%wt, nano-particles 3.0%wt, inhibitor 2.9%wt. The prediction-optimized concentration ratio has an error range of [0.1%wt,1%wt] compared to the optimization results of the multifactorial response surface method, predicting the rationality of the selected material ratio from both theoretical and experimental dimensions.
The macro-action mechanism of nano-modified composite gel foam in inhibiting the process of coal spontaneous combustion is elucidated. Through comparative tests of parameters such as stress viscosity, plugging resistance, and dehydration rate, the rheological dispersion performance, plugging and oxygen-blocking ability, inhibition effect, and thermal stability of the modified composite gel foam are explored. The influence of the material’s rheological properties on the spatial coverage and accumulation performance of the coal body is studied, revealing the mechanics of the temporal and spatial changes in plugging performance on blocking coal spontaneous combustion. The characteristic temperature points of the oxidation reaction stages of long-flame coal are obtained: 53°C, 145°C, 231°C, 268°C, 408°C, 562°C, 767°C. The modified composite enhances the inhibition performance during the low-temperature oxidation stage, especially during the coal spontaneous combustion oxygen absorption weight gain stage (T2-T4), showing more prominent inhibition effects, with the characteristic point temperatures increasing by 6%, 11%, and 26%, respectively. It is revealed that the rheological behavior of nano-modified composite gel foam is a yield pseudoplastic fluid, and its rheological properties can be described by fitting the constitutive equation τ=0.67+10.48γ0.38. The rheological properties change significantly due to the foaming process, with the yield strength reducing from 73.08Pa to 0.67Pa, and the consistency coefficient significantly lowering from 157.86 to 10.48. The viscosity under a fixed shear rate is only 1/12 of that of ordinary gel. The effectiveness of nano-modified composite gel foam in plugging and oxygen-blocking performance is discussed. The wind leakage resistance of the coal sample with 2% wt nano-modified composite gel foam added can be significantly increased to 2.0kPa. An in-situ simulation experiment of nano-modified composite gel foam for preventing and treating residual coal spontaneous combustion in goaf areas is carried out. At 170°C, the CO inhibition rate can reach 72.11%, which is six times that of ordinary gel foam and three times that of MgCl2 slurry.
The relationship between the macroscopic performance of nano-SiO2 modified composite gel foam in preventing coal spontaneous combustion and the microscopic mechanism of inhibiting coal spontaneous combustion is clarified. Using electron spin resonance (ESR) and fourier transform infrared spectroscopy (FTIR) detection techniques, the distribution changes of active groups in coal samples before and after inhibition are compared and analyzed, and the mechanism of action in blocking the coal oxygen chain reaction process is analyzed. The active groups of long-flame coal include -CH3, -CH2, -COOH, -OH, -CH, and Ar-C-O, among which oxygen-containing functional groups have the largest proportion, and the spectral peaks of aromatic structures are relatively sharp. The modified composite gel foam has a particularly significant effect on slowing the increase in free radical concentration in the initial temperature range of 50°C to 90°C. It is found that the chain reactions of active groups in long-flame coal molecules proceed along linear and cross-cyclic paths. The fatty hydrocarbon -CH functional groups with activation energy less than 40kJ/mol react first, repeatedly self-activating other functional groups within the coal molecules to accelerate the oxidation reaction. The oxidation chain reaction propagation path of active groups is simulated and analyzed using model compound experiments combined with quantum chemical calculation simulations, clarifying the reaction path and chemical mechanism of active groups. The modified antioxidant interrupts the propagation path of the coal oxygen composite reaction by removing free radicals with hydrogen ions. Through the interaction between the hydroxyl -OH and the -COO- and other active functional groups inside the coal molecule, the chain reaction process initiated by the carboxyl -COO- containing oxygen functional groups is inhibited. The Na+ and Ca2+ ions released by bentonite form stable structural compounds with the active groups in the coal molecules, eliminating the reactivity of the active groups and reducing the possibility of coal oxidation reactions. The synergistic action mechanism of the modified composite gel foam in inhibiting coal spontaneous combustion is elucidated, involving the physical characteristics of spatial coverage and oxygen-blocking on the physical level, and the antioxidant characteristics of clearing active groups and forming stable compounds on the chemical level, achieving the synergistic effect of preventing coal body spontaneous combustion. The research results provide data and experience for the precise prevention and control of coal spontaneous combustion disasters and have significant practical significance for the green, safe, and efficient mining of China’s coal.

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