本文选取了华亭煤矿长焰煤为研究对象，构建了其平均分子结构模型。并使用反应力场分子动力学模拟研究了该煤分子燃烧过程中二氧化碳生成机理和燃烧机理，为国家实现煤炭的清洁利用和减少煤炭使用过程中的碳排放提供了一定贡献。

通过元素分析、¹³C-NMR和XPS对华亭长焰煤的元素质量占比、碳骨架信息、O和N元素赋存状态等结构信息进行了表征。其中芳香碳占52.52%，脂肪碳占37.92%，氧连接的脂肪碳占7%，羰基/羧基碳占2.55%。煤中的大部分氧原子以–COO（53%）的形式存在，而以C–O（29%）和C=O（18%）的形式则相对较少。在该煤样中，72%的N原子以吡咯形式存在，16%的N以吡啶形式存在。基于以上信息，通过ChemDraw构建出华亭长焰煤平均结构模型。使用Materials Studio中Forcite模块对其进行结构优化得到其能量较低的3D结构模型。使用MestReNova预测出该结构碳谱图并将其与实验谱图对比，将所建模型结构信息与实验结果对比，结果显示所构建的模型有较高的准确性，故选择所建模型作为研究对象进行反应力场分子动力学模拟。

了解煤燃烧过程中产生二氧化碳的机理对于降低碳排放至关重要。反应力场分子动力学模拟从原子水平角度研究了华亭煤燃烧产生CO₂的化学反应路径，得出了对应于四种CO₂生成途径的四种中间产物，分别是Rn–O、Rn–CHO、Rn–CO₂和C₂O₂。华亭煤燃烧过程中CO₂的产生始于煤分子中的的C–H键和C–C键在高温下的断裂，导致煤分子裂解生成碳链（Rn），进一步生成中间产物。中间产物可以通过含氧自由基的攻击或C–C键的断裂产生CO₂。Rn–O和Rn–CHO是产生CO的中间产物。使用M062X/6-311**泛函基组的密度泛函理论计算分析了乙炔的反应路线，该路线首先氧化成C₂O₂，然后通过·O攻击进一步氧化成CO₂。DFT计算结果证明了ReaxFF MD计算的精度，并表明高温和含氧自由基有利于CO₂生成过程。这些结果可以提高对煤燃烧过程中CO₂产生机理的理解。

模拟了所建分子结构模型在不同O₂浓度的气氛环境中燃烧过程，分析了长焰煤分子结构模型中官能团的微观反应行为。研究结果表明，煤分子的燃烧是氧化反应和裂解反应同时发生的。温度对于燃烧反应的微观作用机理主要是为化学键的断裂提供能量，并且为体系提供动能，提高原子的运动速率，加大原子碰撞概率，从而加速化学反应。而氧气浓度对于煤的燃烧反应的微观作用机理在于提供了促进反应发生的含氧自由基。在研究官能团反应机理过程中，煤上的羟基（–OH）发生脱氢反应，H原子脱离，其他的自由基攻击剩余的氧原子发生反应后形成碳氧化物或水。醚键（–O–）是较活跃的官能团，通常在模拟开始时就发生断裂。而且其反应规律为具有较低分子量且位于醚键一侧的烷基在模拟开始后不久就会发生断裂，随后剩余的氧原子被自由基攻击发生反应后形成碳氧化物或水。羰基（–CO）是较稳定的官能团，发生反应时间较慢，它们受到O₂或·O的攻击，发生反应形成碳氧化物。在大多数情况下，氢原子从羧基（–COOH）上解离出来，从剩余的一个碳原子和两个氧原子中生成CO₂。O₂的浓度对自由基、碳氧化物和水的产生有很强的影响。温度对化学键的断裂和化学反应的进行有很大的影响。自由基·OH、·HO₂在煤燃烧中起到促进作用。它们的数量随温度而变化，影响煤分子的燃烧过程。

In this paper, the long-flame coal of Huating Coal Mine is selected as the research object, and its average molecular structure model is constructed. And use the Reactive Force Field Molecular Dynamics simulation to study the CO₂ generation mechanism and combustion mechanism in the coal molecular combustion process and provide a certain contribution to the country’s clean utilization of coal and reduction of carbon emissions in the process of coal use.

Elemental analysis, ¹³C-NMR and XPS were used to characterize the structural information such as the mass ratio of elements, carbon skeleton information, and the occurrence state of O and N elements in Huating long-flame coal. Among them, aromatic carbons accounted for 52.52%, aliphatic carbons accounted for 37.92%, oxygen-linked aliphatic carbons accounted for 7%, and carbonyl/carboxyl carbons accounted for 2.55%. Most of the oxygen atoms in coal exist in the form of –COO (53%), and relatively few in the form of C–O (29%) and C=O (18%). In this coal sample, 72% of N atoms exist in the form of pyrrole, and 16% of N atoms exist in the form of pyridine. Based on the above information, the average structure model of Huating long-flame coal was constructed by ChemDraw. Use the Forcite module in Materials Studio to optimize its structure to obtain the 3D structure model with the lowest energy. Use MestReNova to predict the carbon spectrum of the structure and compare it with the experimental spectrum and compare the structural information of the built model with the experimental results. The results show that the built model has high accuracy, so the built model is selected as research object performs a reactive force field molecular dynamics simulation.

Understanding the mechanism of carbon dioxide generation during coal combustion is crucial to reducing carbon emissions. Reactive force field molecular dynamics simulations was used to study the chemical reaction pathways of CO₂ generated by Huating coal combustion at the atomic level, and obtain four intermediate products corresponding to the four CO₂ generation pathways, namely Rn–O, Rn–CHO, Rn–CO₂ and C₂O₂. The production of CO₂ in the combustion process of Huating coal begins with the breakage of C–H bonds and C–C bonds in coal molecules at high temperature, which leads to the cracking of coal molecules to generate carbon chains (Rn), and further generates intermediate products. Intermediates can generate CO₂ through the attack of oxygen-containing radicals or the cleavage of C–C bonds. Rn–O and Rn–CHO are intermediates during the production of CO. The reaction pathway of acetylene, which is first oxidized to C₂O₂ and then further oxidized to CO₂ by ·O attack, was analyzed using density functional theory calculations at the M062X/6-311** level. The DFT results demonstrate the accuracy of the ReaxFF MD calculations and show that high temperature and oxygen-containing radicals favor the CO₂ generation process. These results can improve the understanding of the mechanism of CO₂ generation during coal combustion.

The combustion process of the established molecular structure model in the atmosphere environment with different O₂ concentrations was simulated, and the microscopic reaction behavior of the functional groups in the long-flame coal molecular structure model was analyzed. The research results show that the combustion of coal molecules is the simultaneous occurrence of oxidation reaction and cracking reaction. The microscopic action mechanism of temperature on combustion reaction is mainly to provide energy for the breaking of chemical bonds, and provide kinetic energy for the system, increase the movement rate of atoms, increase the probability of atomic collisions, and thus accelerate chemical reactions. The microcosmic mechanism of the oxygen concentration on the combustion reaction of coal is to provide oxygen-containing free radicals that promote the reaction. In the process of studying the reaction mechanism of functional groups, the hydroxyl group (–OH) on the coal undergoes a dehydrogenation reaction, the H atoms are detached, and other free radicals attack the remaining oxygen atoms to form carbon oxides or water. Ether bonds (–O–) are the more reactive functional groups and usually break at the beginning of the simulation. Moreover, the reaction rule is that the alkyl group with a lower molecular weight and located on the side of the ether bond will break shortly after the simulation began, and then the remaining oxygen atoms will be attacked by free radicals and form carbon oxides or water. Carbonyl (–CO) is a relatively stable functional group with a slow reaction time. They are attacked by O₂ or ·O and react to form carbon oxides. In most cases, the hydrogen atom dissociates from the carboxyl group (–COOH), producing CO₂ from the remaining one carbon atom and two oxygen atoms. The concentration of O₂ has a strong effect on the production of free radicals, carbon oxides and water. Temperature has a great influence on the breaking of chemical bonds and the progress of chemical reactions. Free radicals ·OH, ·HO₂ play a role in promoting coal combustion. Their number varies with temperature, affecting the combustion process of coal molecules.

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