煤的热解是煤热化学转化过程研究的基础，低温热解后出现煤自燃的可能性增大，热解过程中温度及能量的传递与内部结构演化息息相关。基于固体物理学研究可知，非金属固体物质热传导的主要热载流子是声子。因此，探究煤中声子微观特性以及原子团振动规律，有助于揭示出煤在热解过程中内部热量传递特性，对煤自燃防治及煤炭利用效率的提升提供理论基础。

本文基于实验测试和理论计算，构建了煤样的分子结构模型，计算得到了静态以及不同温度下（300、500、700、900 K）下的声子感温特性。通过红外光谱和拉曼光谱实验分析了不同温度下煤中不同原子团的振动规律。最后，采用激光导热实验，测试了低温下煤样的热物性参数变化规律，分析了声子、原子团振动以及热物性参数之间的关系，揭示煤样热解过程中的热传导特性。主要研究成果如下：

煤样的结构分子式为C₁₈₉H₁₂₇O₂₃N₃S，其中，C、H、N、O和S的元素质量分数分别为79.86%、4.49%、1.49%、13.02%和1.14%。芳香碳、脂肪碳和羰基碳占比分别为59.64%、34.46%和5.90%，萘分子占比最大，最低能量构型的煤晶胞的密度为1.15 g/cm³，最低能量为1686.97 kcal/mol。

理论计算结果表明，煤分子中的声子态密度在低频区间明显高于高频区间，不同原子的振动频率与原子质量有关，C原子和H原子分别是声子总态密度和高频区间声子态密度的主要贡献者。温度升高，声子总态密度峰值向不同频率区域扩散移动，导致不同原子结构表现出不同的热传导特性。其中，羧基碳原子、羰基碳原子及羟基碳原子的声子态密度变化对应的温度分别为700 K、900 K和500 K。

红外光谱和拉曼光谱实验研究反映出不同原子团的振动规律及演化规律。芳香烃结构、脂肪烃结构整体呈现下降的趋势，700 K后降速增快；含氧官能团及羟基波峰整体呈现先升后降的趋势，转折温度为700 K。煤中D峰和G峰拉曼振动模式在温度升至600 K后发生明显变化，表现为W_D和W_G减小，两峰半宽高均降低，A_D/A_G比值先降后增，A_S/A_G比值快速减小。对比发现500~700 K是各种原子团结构的振动强度变化的温度区间，与声子表现出的感温特性密切相关。

在低温（300~570 K）热解过程中，比热容和导热系数逐渐升高，热扩散系数持续降低。相关性分析表明，煤样在低温热解的热传导特性与内部结构演化相关性较高，其中煤中的含氧官能团和芳香结构对热解的影响最大。此外，不同结构的拉曼振动模式强度、芳香结构数量以及原子间振动强度的加强，促进能量扩散，导热能力增强。

The process of coal pyrolysis serves as the fundamental basis for all thermochemical transformation processes.  The occurrence of coal spontaneous combustion is more likely following low temperature pyrolysis, and the temperature and energy transfer during the pyrolysis process are closely intertwined with internal structural evolution. The investigation of solid-state physics reveals that phonons serve as the primary conduits for thermal conduction in nonmetallic solid materials. Therefore, investigating the microscopic phonon characteristics in coal and the vibration law of atomic group is crucial for unveiling the internal heat transfer behavior during pyrolysis, the study offers a theoretical foundation for the prevention of coal spontaneous combustion and the enhancement of coal utilization efficiency.

The present study constructs a molecular structure model of coal samples based on experimental tests and theoretical calculations. Then, the properties of phonons at static state and various temperatures (300, 500, 700, 900 K) are calculated. The vibrational characteristics of diverse molecular structures in coal at different temperatures were analyzed through experiments utilizing Infrared and Raman spectroscopy. Finally, the thermal and physical properties of coal samples at low temperatures were examined through laser heat conduction experiments. The relationship between phonon vibrations, atomic group, and parameters related to thermal and physical properties was analyzed in order to elucidate the heat conduction characteristics of coal samples during pyrolysis. The primary tasks and research accomplishments are outlined as follows:

The macromolecular structure formula of the coal sample is C₁₈₉H₁₂₇O₂₃N₃S, with elemental mass fractions of 79.86% for carbon (C), 4.49% for hydrogen (H), 1.49% for nitrogen (N), 13.02% for oxygen (O), and 1.14% for sulfur (S). The proportions of aromatic carbon, fatty carbon, and carbonyl carbon were 59.64%, 34.46%, and 5.90% respectively, with naphthalene being the predominant aromatic structure. The unit cell of coal with the lowest energy configuration has a density of 1.15 g/cm³ and its minimum energy is 1686.97 kcal/mol.

The results show that the density of phonon states in the low frequency region is obviously higher than that in the high frequency region.  The vibration frequencies of different atoms are determined by their respective atomic masses.  Specifically, the C atom and H atom play key roles in contributing to the overall state density of phonons and the density of phonon states in the high frequency region, respectively. The increase in temperature leads to the diffusion of the peak of the total state density of phonons across different frequency regions, resulting in variations in different atomic structures showing different heat conduction characteristics. Among them, the temperatures at which the phonon state densities of carboxyl carbon atoms, carbonyl carbon atoms, and hydroxyl carbon atoms change are 700 K, 900 K, and 500 K respectively. The subsequent calculation reveals a continuous increase in the heat capacity of phonons up to 800 K, followed by a deceleration under both static and various dynamic simulation temperatures.

The experimental results of Infrared and Raman spectroscopy provide insights into the vibrational intensity and evolution of diverse atomic structures. The overall trend observed among them was a decrease in the structure of aromatic hydrocarbons and aliphatic hydrocarbons, with an increased deceleration rate after reaching 700 K. However, the peak of oxygen-containing functional groups and hydroxyl groups exhibited an initial increase followed by a subsequent decrease, with the corresponding transition temperature occurring at 700 K. The Raman vibrational modes of the D-peak and G-peak in coal undergo significant changes upon heating to 600K, indicating a decrease in W_D and W_G, as well as a reduction in both peak half-width and height. Additionally, the A_D/A_G ratio initially decreases before increasing again, while the A_S/A_G ratio experiences a rapid decline. The region of 500~700K is identified as the range where the vibration intensity of various atomic structures undergoes significant changes, aligning closely with the temperature-sensing characteristics exhibited by phonons.

 During the pyrolysis process at low temperature (300~570K), there is a gradual increase in specific heat and thermal conductivity, while the thermal diffusion coefficient exhibits a continuous decrease with decreasing speed at higher temperatures. The correlation analysis reveals a strong association between the thermal conductivity characteristics of coal sample pyrolysis within the low temperature and structural evolution, with the oxygen-containing functional groups and aromatic structures in coal exerting the greatest influence.  Furthermore, an increase in the intensity of Raman vibration modes for different structures, along with a rise in the number of aromatic ring structures, enhances interatomic vibration intensification and promotes energy diffusion, thereby leading to an elevation in both thermal diffusion coefficient and thermal conductivity.

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