【作者】 单亚飞；

【导师】 王继仁；

【作者基本信息】 辽宁工程技术大学 ， 安全技术与工程， 2006， 博士

【摘要】 煤是一种由多种化学键和官能团组成的大分子和低分子化合物组成的混合体。其中,煤中的低分子化合物是组成煤的重要物质,低分子化合物占煤中有机质的含量为10%～23%,甚至有占有机物总量40%的报导。煤中的低分子化合物在煤的自燃中起重要的作用,但没有人涉足本领域的研究。本论文首次应用量子化学理论从微观上系统地研究了煤有机质中低分子化合物的氧化自燃机理,应用密度泛函理论,B3LYP/6-3llG研究了低分子化合物氧化自燃过程中的反应物、中间体、过渡态和产物的整个反应历程,创立了煤中低分子化合物的氧化自燃机理理论,填补了煤自燃研究领域的空白。本研究对煤矿的开拓设计,安全生产,火灾综合防治、煤的综合利用以及想着科学的研究等方面都具有重要的意义和应用价值。主要研究内容和研究成果概括如下:应用量子化学密度泛函(DFT)理论计算方法,在B3LYP/6-31G计算水平上,对所构建煤中的低分子化学基本结构单元进行了优化,得到了分子构型参数和振动频率。根据分子轨道理论,煤中低分子化合物的氧化自燃反应发生在电荷密度较大的原子部位,计算得到了煤有机质中低分子化合物发生氧化自燃反应的活性点。根据煤分子的活性点,应用化学反应机理理论推测了煤氧化自燃生成水、一氧化碳、二氧化碳和甲烷的化学反应过程,采用量子化学密度泛函(DFT)理论在B3LYP/6-311G水平下对反应物、产物、中间体和过渡态分子进行几何优化,计算了反应各驻点的振动频率,并通过振动分析,确认所得的每一个过渡态的真实性。获得了零点振动能(ZPE),并在同一水平下进行了内禀更多还原

【Abstract】 Coal is a sort of mixture which composed of the bulky molecular compound and the low molecular compound. And the compound is composed of chemical bonds and functional groups. The low molecular compound is one of the most important components, and there are 10%²3%, even 40% reported, of the organic matter in coal be low molecular compound. It reacts important role during the spontaneous combustion of coal. The oxidation spontaneous combustion mechanism for the low molecular compound was studied by the quantum chemistry theory on the microscopic level for the first time, and the reaction process of the oxidation spontaneous combustion for the low molecular compound was studied at B3LYP/6-31G level by quantum chemical DFT method, and built the oxidation spontaneous combustion mechanism theory for the low molecular compound, which filled a gap in coal spontaneous combustion researching field. This researching is very important to mine development design, safety work, fire comprehensive control, coal comprehensive utilization. The main contents and achievements in this thesis include several aspects as follow:The vibration frequency and the parameters of molecule structure such as bond length, bond angle and dihedral angle can be gained while optimizing the basal chemical structure cell of coal molecule at B3LYP/6-31G level by quantum chemical DFT method. According to the molecule orbital theory, the oxidation spontaneous combustion reaction of the low molecular compound in coal takes place at the atoms which charge density is thick. And gained the active point at which the oxidation spontaneous combustion reaction of the low molecular compound in coal takes place.Based on the active constituent of the chemical reaction process about coal spontaneous combustion, which generates H₂O, CO, CO₂, CH₄ and C₂H₄, was deduced by chemical reaction mechanism theory. The geometry of reactants,更多还原