<p>煤自燃及其诱导的次生灾害对煤矿安全生产构成严重威胁，但由于煤分子结构复杂，煤自燃机理的研究一直面临巨大挑战。为此，本论文从煤的分子结构入手，以超声萃取技术为手段，将煤中的活性基团从煤大分子体系中剥离出来，在系统研究各个活性基团氧化反应特性的基础上，探究煤自燃的微观反应机理，为煤自燃化学靶向阻化材料的研究提供理论支撑。研究结果对进一步揭示煤自然发火的本质、完善煤自燃理论和开发煤自燃高效阻化技术，具有重要的科学和实际指导意义。</p> <p>利用核磁共振波谱仪获取煤样的碳骨架结构信息，本论文所选YM和WYM分子分别主要以萘为和菲为核心结构，两种煤样的表面基团包括羟基、碳氧基团、脂肪族基团和芳香族基团。采用Gaussian 16软件构建出了以萘为核心，以羟基、羰基、乙基和苯环为侧链的四种YM基团稳定结构模型；以菲为核心，以羟基、羰基、甲基和苯环为侧链的四种WYM基团稳定结构模型。最终，采用约化密度梯度（RDG）分析方法，明确了萃取剂分子与煤分子表面活性基团间的弱相互作用，优选出了分别针对-OH基团、碳氧基团、碳氧基团和芳香族基团的四种优势萃取剂乙二胺、N-甲基吡咯烷酮、石油醚和甲苯。</p> <p>采用优势萃取剂对YM和WYM进行了超声辅助下的溶剂萃取，将煤中的复杂结构单元化、离散化，进而结合傅里叶红外光谱、电子顺磁共振波谱和原位红外光谱技术确定了煤自燃过程中的主要活性基团，并揭示了其演变规律。结果显示低温下YM以小分子自由基为主，而WYM则以大分子自由基为主。低温氧化阶段，缔合羟基在100℃前快速下降，醇羟基则在300~350℃快速下降；-C-O-呈现先增后降后增加的变化趋势，而&minus;C=O和-COO基团在250~300℃前基本保持稳定，之后则快速上升；脂肪烃和碳氧基团的演变存在明显的递进关系，脂肪烃会被氧化为碳氧基团。</p> <p>采用TG/DSC测试进一步探究萃取前后煤样的氧化特性。结果显示萃取后煤样的TG曲线整体向高温区域移动，-OH和碳氧基团的减少使得煤样在300℃之前的放热量减少，而脂肪族与芳香族基团的减少使得煤在燃烧阶段放热减少，-OH是低温氧化过程最为关键的一个含氧活性基团。</p> <p>&nbsp;</p> <p>采用量子化学计算软件模拟计算了活性基团的电子密度、静电势、前线轨道分布等特征，进而结合TG/DSC、FTIR、ESR和TG-MS等测试，揭示了煤氧化反应活性基团的演变分子动力学特性，提出了羟基链式自促进煤自燃机理，阐释了煤自燃过程中主要指标气体的生成规律。研究表明，煤样中含氧基团的煤氧复合活性位点位于基团的氢原子处，侧链的活性位点则优先位于-CH₂-中的氢原子处，苯环侧链中无活性位点。煤在低温氧化过程中，其分子表面活性基团首先经历氧夺氢的过程，形成&middot;OOH自由基，进而分解为可持续引发一系列链式复合反应的关键自由基&middot;OH，逐步将脂肪族侧链转化为羰基和羧基。羰基断裂分解是低温氧化过程中CO的主要来源，而CO₂则来自于羰基氧化后生成的羧基的断裂。</p>

<p>The spontaneous combustion of coal and its induced secondary disasters pose a significant threat to coal mine safety production. However, due to the complex molecular structure of coal, the study of the mechanism underlying coal spontaneous combustion has long been confronted with formidable challenges. Hence, the ultrasonic extraction technique&nbsp;was employed to separate active functional groups from the complex macromolecular system of coal according to organic chemical reactions in this paper. Based on systematically studying the oxidization reaction characteristics of each active functional group, investigates the microscopic reaction mechanism of coal spontaneous combustion, so as to provide theoretical support for the study of coal spontaneous combustion chemical targeting inhibition materials. The results of the study are of great scientific and practical significance for further revealing the nature of coal spontaneous ignition, improving the theory of coal spontaneous ignition and developing the high efficiency inhibition technology of coal spontaneous ignition.</p> <p>The Nuclear Magnetic Resonance (NMR) spectroscopy was employed to obtain the semi-quantitative structural information of the carbon skeleton, and naphthalene was the core structure of YM sample, while phenanthrene was that of the WYM sample. The surface functional groups of both coal samples include hydroxyl (-OH), carbonyl groups, aliphatic groups, and aromatic groups. Gaussian 16 software was used to construct stable structure models of active functional groups for four types of YM with naphthalene as the core and hydroxyl, carbonyl ethyl and phenyl rings as side chains; and for four types of WYM, with phenanthrene as the core and hydroxyl, carbonyl, methyl and phenyl rings as side chains. Finally, the Reduced Density Gradient (RDG) analysis method was used to clarify the weak interactions between organic solvent molecules and surface active groups of coal molecules, and the four dominant extractants ethylenediamine, NMP, petroleum ether and toluene targeting the -OH group, carbon-oxygen group, carbon-oxygen group, and aromatic group, respectively, were preferentially selected.</p> <p>The dominant extractants were used for solvent extraction of YM and WYM under ultrasound assistance to unitize and discretize the complex structures in coal, and then the main reactive groups in the spontaneous combustion process of coal were identified and their evolution patterns were revealed by combining Fourier infrared spectroscopy, electron paramagnetic resonance spectroscopy and in situ infrared spectroscopy techniques. The results show that YM is dominated by small molecular radicals at low temperatures, while WYM is dominated by large molecular radicals. In the low-temperature oxidation stage, the conjugated hydroxyl group decreases rapidly before 100℃, while the alcohol hydroxyl group decreases rapidly at 300~350℃; -C-O- shows a tendency of increasing, then decreasing, and then increasing, while -C=O and -COO groups remain basically stable before 250~300℃, and then increase rapidly; there is an obvious progressive relationship between the evolution of aliphatic hydrocarbons and carbon-oxygen groups The aliphatic hydrocarbons are oxidized to carbon-oxygen groups.</p> <p>The oxidation characteristics of the coal samples before and after extraction were further investigated by TG/DSC test. The results showed that the TG curves of the extracted coal samples shifted to the high-temperature region, and the reduction of -OH and carbon-oxygen groups led to the decrease of the exothermic amount of the coal samples before 300℃, while the reduction of aliphatic and aromatic groups led to the decrease of the exothermic amount of the coal in the combustion stage, and -OH is the most critical oxygen-containing reactive group in low-temperature oxidization process.</p> <p>The electron density, electrostatic potential, and front-line orbital distribution of the reactive group were simulated by quantum chemical calculation software, and then combined with TG/DSC, FTIR, ESR and TG-MS tests to reveal the molecular dynamics of the evolution of the reactive group in the coal oxidation reaction, and to elucidate the generation of the main indicator gases in the process of spontaneous combustion of coal. It was shown that the active sites of coal-oxygen complexes of oxygen-containing groups in the coal samples were located at the hydrogen atoms of the groups, while the active sites of the side chains were preferentially located at the hydrogen atoms in -CH₂-, and there were no active sites in the benzene ring side chains. During the low-temperature oxidation of coal, the active groups on its molecular surface first undergo the process of oxygen-robbing for hydrogen, forming -OOH radicals, which then decompose into -OH, the key radical that can sustainably trigger a series of chain complex reactions, and gradually transform the aliphatic side chains into carbonyl and carboxyl groups. Carbonyl group breakage and decomposition is the main source of CO in the low-temperature oxidation process, while CO₂&nbsp;comes from the breakage of the carboxyl group generated by the oxidation of the carbonyl group.</p>

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