我国能源的特点是“缺油、少气、富煤”，煤炭一直以来都作为我国重要的一次能源。煤是生产油气和高附加值化学品的重要原料，其中富油煤最大的特点是富含较多热解可生成油气的富氢结构，焦油产率较高，近年来获得了人们的广泛关注。实现富油煤资源的低碳高附加值利用，将是支持实现碳达峰，碳中和战略目标的重要举措。煤中的小分子物质是以游离或镶嵌的形式赋存在煤大分子结构中并且分子量低于500的有机化合物，其对富油煤的化学及物理性质有着重要影响。本论文基于实验研究结果，构建了柴家沟富油煤分子模型，借助分子模拟手段进一步探究不同小分子对富油煤热解的作用机制，旨在从分子层面上揭示富油煤热解产物机理，为富油煤的清洁利用提供一定的理论依据和技术支持。

本文以柴家沟富油煤作为研究对象，采用了N-甲基吡咯烷酮-二硫化碳（NMP-CS₂）萃取和去离子水反萃取法分离了柴家沟富油煤中主要的小分子物质，采用正己烷、苯和四氢呋喃进行逐级萃取实现了不同类型小分子物质的组分分离，通过气相色谱质谱联用仪（GC/MS）分析了各级萃取物中小分子物质的组成，通过格金干馏仪研究了小分子物质萃取前后富油煤热解产物产率的变化。结果表明：NMP-CS₂混合溶剂对柴家沟富油煤样进行萃取的最大萃取率为18%。煤中小分子物质主要包含脂肪烃类（7.63%）、芳烃类（21.11%）和杂原子类（71.26%）。随着柴家沟富油煤中小分子物质的去除，柴家沟富油煤热解的半焦产率最高下降了16.18wt.%，焦油产率最高下降了3.39wt.%。证实了小分子物质对柴家沟富油煤热解的半焦及焦油产率有明显影响。

使用¹³C 固体核磁共振仪（¹³C NMR）、傅里叶红外光谱仪（FTIR）、X射线光电子能谱技术（XPS）、X射线衍射仪（XRD）、高分辨率透射电子显微镜（HRTEM）等设备，结合工业分析、元素分析的结果，构建了柴家沟富油煤的大分子结构模型，通过对比模拟的核磁谱图与实验谱图调整其大分子结构。结果表明：柴家沟富油煤结构中芳香碳含量为0.66，芳香结构单元主要以苯、萘、蒽、菲等芳香基团为主；脂肪结构单元主要以侧链、环烷烃等结构为主；氧原子主要以羰基，醚氧或羟基键，羧基结构为主，三种官能团在柴家沟煤中的比值约为4:11:3；氮的存在形式主要为吡咯型氮和吡啶型氮。最终构建了与实际特征相匹配的柴家沟富油煤大分子结构模型（分子式为C₁₈₀H₁₅₂O₂₄N₂，分子量为2724），为从分子层面上研究柴家沟富油煤热解奠定了基础。

使用Materials Studio 2020（MS）软件，结合柴家沟富油煤萃取及GC/MS结果分析，对柴家沟富油煤大分子空间结构模型进行分子模拟，构建并优化了含有不同种类小分子的5种煤晶胞模型。

使用Amsterdam Modeling Suite（AMS）软件对5种煤晶胞模型进行了基于反应力场（Reax FF）的分子动力学模拟。

结果表明，随着热解温度的升高，小分子物质使热解模拟中的总分子数有明显增加；含烷烃及芳烃小分子的煤模型热解轻质焦油C₅-C₁₃组分的生成及焦油组分二次裂解的温度都更低；在2400K下含芳烃小分子的煤模型在热解过程中产生了更多的羟基及羧基自由基，使得生成了较多的H₂O和CO₂分子。随着热解温度的升高，含烷烃小分子物质煤模型热解重质焦油C₁₄-C₄₀的最大产率提高为1800K下的37.23wt.%，焦炭C₄₀₊的产率在2200K的转变温度下达到最低的53.88wt.%；在2400K温度下，含烷烃小分子物质的煤模型热解生成了较多的CH₄及C₂H₄分子，含烷烃小分子物质煤模型热解程度最高，焦炭C₄₀₊产率为53.95wt.%。随着热解温度的升高，含杂原子小分子物质的煤模型热解产生的轻质焦油C₅-C₁₃产率在1800K下达到了5种煤模型中最高的18.8wt.%；在2400K温度下，含杂原子小分子物质煤模型热解产生的轻质焦油C₅-C₁₃组分分子数较高，C₅-C₁₃组分产率为5种模型中最高，达到了15.91wt.%。

The characteristics of my country's energy resources are "lack of oil, little gas and rich in coal". Coal has always been an important primary energy source in our country. Coal is an important raw material for the production of oil and gas and high value-added chemicals. The biggest feature of oil-rich coal is that it contains more hydrogen-rich structures that can be pyrolyzed to generate oil and gas. It has a high tar yield and has attracted widespread attention in recent years. Achieving low-carbon and high-value-added utilization of oil-rich coal resources will be an important measure to support the realization of the strategic goal of carbon peaking and carbon neutrality. Small molecular substances in coal are organic compounds with a molecular weight less than 500 that exist in the macromolecular structure of coal in free or embedded forms. They have an important impact on the chemical and physical properties of oil-rich coal. Based on the experimental research results, this paper constructed a molecular model of Chaijiagou oil-rich coal and used molecular simulation methods to further explore the mechanism of different small molecules on the pyrolysis of oil-rich coal, aiming to reveal the pyrolysis products of oil-rich coal at the molecular level. mechanism, providing certain theoretical basis and technical support for the clean utilization of oil-rich coal.

This paper takes Chaijiagou oil-rich coal as the research object. N-Methylpyrrolidone-Carbon disulfide (NMP-CS₂) extraction and deionized water back-extraction methods are used to separate the main small molecular substances in Chaijiagou oil-rich coal. n-hexane, benzene and tetrahydrofuran are used to carry out step-by-step The extraction achieved the component separation of different types of small molecule substances. The composition of small molecule substances in the extracts at all levels was tested by Gas Chromatograph Mass Spectrometer (GC/MS). The changes in the pyrolysis products of oil-rich coal before and after the extraction of small molecule substances were studied by the Gray-King carbonization apparatus. The results show that the maximum extraction rate of NMP-CS₂ mixed solvent for oil-rich coal samples from Chaijiagou is 18%. Small molecular substances in coal mainly include aliphatic hydrocarbons (7.63%), aromatic hydrocarbons (21.11%) and heteroatoms (71.26%). With the removal of small molecular substances in Chaijiagou oil-rich coal, the semi-coke yield of Chaijiagou oil-rich coal pyrolysis dropped by up to 16.18wt.%, and the tar yield dropped by up to 3.39wt.%. It was confirmed that small molecular substances have a significant impact on the semi-coke and tar yields of Chaijiagou oil-rich coal pyrolysis.

Using ¹³C solid-state nuclear magnetic resonance (¹³C NMR), Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), high-resolution transmission electron microscope (HRTEM) and other equipment, Combining the results of industrial analysis and elemental analysis, a macromolecular structure model of Chaijiagou oil-rich coal was constructed, and its macromolecular structure was adjusted by comparing the simulated NMR spectrum with the experimental spectrum. The results show that the aromatic carbon content in the structure of Chaijiagou oil-rich coal is 0.66. The aromatic structural units are mainly composed of benzene, naphthalene, anthracene, phenanthrene and other aromatic groups; the fatty structural units are mainly composed of side chains, cycloalkanes and other structures; Oxygen atoms are mainly carbonyl, ether oxygen or hydroxyl bonds, and carboxyl structures. The ratio of the three functional groups in Chaijiagou coal is about 4:11:3; nitrogen mainly exists in the form of pyrrole nitrogen and pyridine nitrogen. Finally, a macromolecular structure model of Chaijiagou oil-rich coal was constructed that matched the actual characteristics (molecular formula is C₁₈₀H₁₅₂O₂₄N₂, molecular weight is 2724), which laid the foundation for studying the pyrolysis of Chaijiagou oil-rich coal at the molecular level.

Using Materials Studio 2020 (MS) software, combined with Chaijiagou oil-rich coal extraction and GC/MS result analysis, molecular simulation was performed on the macromolecular spatial structure model of Chaijiagou oil-rich coal, five coal unit cell models containing different types of small molecules were constructed and optimized.

Molecular dynamics simulations based on reaction force field (Reax FF) were performed on five coal unit cell models using Amsterdam Modeling Suite (AMS) software.

The results show that with the increase of pyrolysis temperature, the total number of molecules in the pyrolysis simulation increased significantly due to small molecules; the generation of C₅-C₁₃ components of light tar and the secondary cracking temperature of tar components in the pyrolysis of coal models containing alkane and aromatic small molecules are lower; at 2400K, the coal model containing aromatic small molecules produced more hydroxyl and carboxyl radicals during the pyrolysis process, resulting in the generation of more H₂O and CO₂ molecules. With the increase of pyrolysis temperature, the maximum yield of heavy tar C₁₄-C₄₀ in the pyrolysis of coal models containing alkane small molecules increased to 37.23wt.% at 1800K, and the yield of coke C₄₀₊ reached the lowest 53.88wt.% at the transition temperature of 2200K; at 2400K, the pyrolysis of coal models containing alkane small molecules generated more CH₄ and C₂H₄ molecules, and the pyrolysis degree of coal models containing alkane small molecules was the highest, with a coke C₄₀₊ yield of 53.95wt.%. With the increase of pyrolysis temperature, the yield of light tar C₅-C₁₃ produced by pyrolysis of coal model containing heteroatom small molecules reached 18.8wt.%, the highest among the five coal models at 1800K; at 2400K, the molecular number of light tar C₅-C₁₃ component produced by pyrolysis of coal model containing heteroatom small molecules was higher, and the yield of C₅-C₁₃ component was the highest among the five models, reaching 15.91wt.%.

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