煤炭资源是我国基础能源之一，在我国能源需求体系中占据重要地位。但是低变质程度的煤化学性质不稳定，易发生氧化自燃，对矿井安全生产带来极大的威胁。因此诸多阻化煤自燃的手段应用而生，改性水滑石因其层间阴离子热稳定性、可交换性以及层板组成元素的可调控性，被广泛应用于矿井煤自燃的防治工作中，但其无法根据煤自燃临界温度点进行定时阻化，且在矿井环境的影响下其阻化效率会降低。因此，本文选取改性水滑石为芯材，将其微胶囊化，研究微胶囊化改性水滑石对煤自燃的阻化性能。研究结果为进一步研制高效阻化材料提供了理论基础。

首先，采用共沉淀法制备出改性水滑石，通过X射线衍射实验、扫描电镜及能谱分析仪研究了La元素不同添加浓度对改性水滑石空间结构、微观形貌及性能的影响规律，发现随着La元素浓度增加，改性水滑石衍射峰附近出现少量杂峰，衍射峰的对称性及强度在不断降低，表明La元素的增高会对改性水滑石的空间结构造成破坏，并且改性水滑石外表面的纳米圆片状物质随La元素浓度的增加呈负相关，且逐渐凝结成团；通过热重分析实验研究了改性水滑石的阻化效果，发现La元素不同添加浓度的改性水滑石均能使原煤的临界温度点（T₁）滞后，活化能增大，其中LDHs-3使T₁推延程度最大（14.15℃），与原煤之间的活化能差值为10.50KJ/mol。因此，确定了LDHs-3为微胶囊化改性水滑石的芯材。

其次，基于材料的理化性质、相变温度点和阻化性能优选出聚乙二醇-碳酸氢钠的混合体为阻化微胶囊的壁材，以改性水滑石LDHs-3为芯材，采用微流体技术制备出微胶囊化改性水滑石。通过扫描电镜及能谱分析仪、激光粒度仪、紫外分光光度法研究了微胶囊化改性水滑石的微观形貌、粒度分布及升温过程中包覆率的变化情况，发现微胶囊化改性水滑石的粒度主要分布在5~13nm之间，且未出现粘结现象，在30~60℃温度区间内微胶囊化改性水滑石包覆率达87.5%；采用热重分析实验研究了微胶囊化改性水滑石的热稳定性，确定了微胶囊化改性水滑石热解过程的阶段性特征，即第一反应阶段（52~83.40℃）主要发生碳酸氢钠的分解反应及聚乙二醇的融解反应；第二反应阶段（83.40~247.64℃）主要以聚乙二醇的初步裂解反应及改性水滑石分子间层间水、-OH的脱除反应为主；第三反应阶段（247.64~323.43℃）主要以聚乙二醇完成裂解反应及改性水滑石分子结构中CO₃^2-的消除反应为主。因此，制备的微胶囊化改性水滑石具有较高的热稳定性及包覆率。

最后，利用程序升温实验研究了微胶囊化改性水滑石对煤自燃的阻化效果，发现向原煤中添加水滑石（LDHs-0）CO释放速率为原煤的61.1%，添加改性水滑石（LDHs-3）CO释放速率为原煤的51.1%，添加微胶囊化改性水滑石CO释放速率为原煤的33.7%，且向原煤中添加微胶囊化改性水滑石之后，阻化煤样与原煤之间活化能的差值达到最大（12.77kJ/mol），微胶囊化改性水滑石的阻化效果远高于改性水滑石（LDHs-0）、改性水滑石（LDHs-3）的阻化效果；发现向原煤中添加不同浓度的微胶囊化改性水滑石其阻化效果呈非线性变化，其中添加浓度为12.5%的微胶囊化改性水滑石在170℃的CO释放速率为原煤的31.5%，低于原煤在140℃的CO释放速率，在100℃时的阻化率达到最大，为81%。因此，微胶囊化改性水滑石对煤自燃具有较好的阻化效果，且微胶囊化改性水滑石与煤的最优配比浓度为12.5%。

关 键 词：煤自燃；微胶囊；改性水滑石；阻化性能；包覆率

As one of the basic energy sources in China, coal resource occupies an important position in the energy demand system.However, low metamorphic coals are chemically unstable and prone to oxidative spontaneous combustion, posing a significant threat to mine safety. As a result, a number of methods have been developed to prevent the spontaneous combustion of coal.Modified hydrotalcite is widely used in the prevention and control of coal spontaneous combustion in mines because of its interlayer anion thermal stability, exchangeability, and modifiability of laminate constituent elements. However, modified hydrotalcite cannot be timed to resist coal spontaneous combustion according to its critical temperature point, and its resisting efficiency decreases under the influence of mine environment. Therefore, in this paper, modified hydrotalcite was selected as the core material to be microencapsulated, so as to investigate the inhibition effect of microencapsulated modified hydrotalcites on coal spontaneous combustion. The results of the study provide a theoretical basis for the further development of efficient inhibition materials.

The co-precipitation method was adopted to prepare the modified hydrotalcites. The effects of different additive concentrations of La element on the spatial structure, microscopic morphology and properties of the modified hydrotalcite were investigated by X-ray diffraction experiments, scanning electron microscopy and energy spectrum analyzer. It was found that as the concentration of La element increased, a small amount of spurious peaks appeared near the diffraction peaks of modified hydrotalcite, and the symmetry and intensity of diffraction peaks were decreasing, indicating that the increase of La element would cause damage to the spatial structure of modified hydrotalcite. Moreover, the nano-cylinders on the outer surface of the modified hydrotalcite showed a negative correlation with the increase of La element concentration, and gradually agglomerated into clusters. The inhibition effect of modified hydrotalcite was investigated by thermogravimetric analysis experiments. It was found that all the modified hydrotalcites with different additive concentrations of La elements could hinder the critical temperature point (T₁) of the original coal and increase the activation energy, among which LDHs-3 caused the greatest degree of deferral of T₁ (14.15°C) and the activation energy difference between it and the original coal was 10.50 KJ/mol. Therefore, LDHs-3 was identified as the core material of the microencapsulated modified hydrotalcite.

Based on the physicochemical properties, phase transition temperature point and inhibition properties of the material, the polyethylene glycol-sodium bicarbonate blend was preferably selected as the wall material for the inhibition microencapsulation. The microfluidic technique was adopted to prepare microencapsulated modified hydrotalcites using modified hydrotalcite LDHs-3 as the core material. The microscopic morphology, particle size distribution and the change of encapsulation rate during the warming process of microencapsulated modified hydrotalcite were investigated by scanning electron microscopy and energy spectrum analyzer, laser particle size meter and UV spectrophotometry. It was found that the particle size distribution of microencapsulated modified hydrotalcite was mainly between 5 and 13 nm, without bonding phenomenon, and the microencapsulated modified hydrotalcite coverage rate reached 87.5% in the temperature interval of 30-60°C. The thermal stability of microencapsulated modified hydrotalcite was investigated by thermogravimetric analysis experiments. The stage characteristics of the microencapsulated modified hydrotalcite pyrolysis process were determined, namely, the first reaction stage (52~83.40℃), in which the decomposition reaction of sodium bicarbonate and the melting reaction of polyethylene glycol mainly occurred; the second reaction stage (83.40~247.64℃) was mainly dominated by the preliminary cleavage reaction of polyethylene glycol and the removal reaction of interlayer water and -OH between modified hydrotalcite molecules; the third reaction stage (247.64~323.43℃) is mainly based on the completion of the cleavage reaction of polyethylene glycol and the elimination of CO₃^2- from the molecular structure of modified hydrotalcite. Therefore, the prepared microencapsulated modified hydrotalcite has high thermal stability and encapsulation rate.

The inhibition effect of microencapsulated modified hydrotalcites on coal spontaneous combustion was investigated by a programmed warming experiment. It was found that the CO release rate by adding hydrotalcite (LDHs-0) to the raw coal was 61.1% of that of the raw coal, the CO release rate by adding modified hydrotalcite (LDHs-3) was 51.1% of that of the raw coal, and the CO release rate by adding microencapsulated modified hydrotalcite was 33.7% of that of the raw coal. And after adding microencapsulated modified hydrotalcite to the raw coal, the difference of activation energy between the inhibited coal sample and the raw coal reached the maximum value (12.77 kJ/mol), and the inhibition effect of microencapsulated modified hydrotalcite was much higher than that of modified hydrotalcite (LDHs-0) and modified hydrotalcite (LDHs-3). It was found that the inhibition effect of adding different concentrations of microencapsulated modified hydrotalcite to the raw coal showed a nonlinear variation, in which the CO release rate of microencapsulated modified hydrotalcite added at a concentration of 12.5% was 31.5% of that of the raw coal at 170°C, which was lower than that of the raw coal at 140°C, and the inhibition rate reached the maximum at 100°C, which was 81%. Therefore, the microencapsulated modified hydrotalcite has a better inhibition effect on coal spontaneous combustion, and the optimal ratio concentration of microencapsulated modified hydrotalcite to coal is 12.5%.

Key words: Coal spontaneous combustion; Microencapsulation; Modified hydrotalcite; Inhibition performance; Encapsulation rate

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