推进化石燃料的清洁高效利用是碳达峰与碳中和目标的关键环节，为更好地理解燃烧过程，发展具有宽范围预测能力的燃烧反应动力学模型具有重要意义。燃烧反应动力学模型的发展涉及许多中间组分和基元反应，研究重要中间组分的燃烧反应动力学有助于理解复杂的燃烧网络。本文针对低温燃烧中间组分的烯醛和烯酮类分子和高温燃烧的多环芳烃中间组分，选取其中具有代表性的典型化合物，烯醛和烯酮类包括2-丁烯醛、异丁烯醛和丁烯酮，多环芳烃包括茚、萘、蒽和菲。实验方面，选取合适的实验装置和研究方法：对烯醛分子2-丁烯醛和异丁烯醛进行射流搅拌反应器氧化实验，对烯酮分子丁烯酮选取2,5-己二酮作为前驱体开展射流搅拌反应器氧化实验；在研究多环芳烃时采用掺混和取代基芳烃作为前驱体的实验方法，开展了甲苯掺混丙炔和丙二烯、邻亚硝基甲苯掺混乙炔和乙烯、氯甲基萘掺混丙炔和丙二烯的流动管热解实验。本文还使用到了电离能计算和动力学参数计算方法进行组分鉴定和模型参数计算。本文首先讨论低温氧化中间体2-丁烯醛和异丁烯醛分子中C=C双键和醛基对低温反应活性和污染物生成的影响。2-丁烯醛和异丁烯醛的低温反应活性都主要来自烯醛分子内C=C双键经历的OH加成反应。烯醛的共振稳定燃料自由基RCO与HO2的双分子反应是早期CO2形成的来源。不同烯醛生成的C3H5不同是反应活性差异的主要来源。本文利用2,5-己二酮作为丁烯酮的前驱体取得了良好效果，2,5-己二酮的分子结构使得丁烯酮是主要产物，对丁烯酮的OH和CH3加成解离反应产物乙醛和2-戊烯酮进行讨论，并对丁烯酮子机理参数修正提出参考意见。甲苯和丙炔/丙二烯在热解过程中分别生成苄基和炔丙基，在不同压力下对甲苯掺混丙炔和丙二烯的研究表明，掺混丙炔和丙二烯改变了苄基的消耗路径。掺混对茚和萘的生成表现出明显的协同效应，通过对茚和萘开展生成路径分析，茚和萘的生成还具有明显的压力依赖效应。进一步地，本文基于含取代基芳烃容易断键生成芳烃自由基的特点，使用邻亚硝基甲苯获取邻甲苯基，并与乙炔和乙烯反应，在实验中分别观察到了茚和茚满及其中间产物的生成。使用1-氯甲基萘和2-氯甲基萘掺混丙炔和丙二烯的热解实验中观察到了菲和蒽的生成。
Efficient and clean utilization of fossil fuels is a critical aspect of achieving carbon peak and carbon neutrality goals. Developing combustion reaction kinetics models with predictive capabilities is an essential tool for comprehending the combustion process. The development of combustion reaction kinetics models involves various intermediate species and elementary reactions. Conducting combustion reaction kinetics research on important intermediate species can facilitate a better understanding of complex combustion networks.This article focuses on representative intermediate species, specifically unsaturated aldehydes and ketones in the low-temperature region, and polycyclic aromatic hydrocarbons (PAHs) in the high-temperature region. The selected typical compounds include 2-butenal, methacrolein, and methyl vinyl ketone for unsaturated aldehydes and ketones, and indene, naphthalene, anthracene, and phenanthrene for PAHs. Regarding experimental approaches, suitable experimental apparatus and research methods were selected. For unsaturated aldehydes, oxidation experiments were conducted in a jet-stirred reactor for 2-butenal and methacrolein, while methyl vinyl ketone was oxidized in a jet-stirred reactor using 2,5-hexanedione as a precursor. In the case of PAHs, flow tube pyrolysis experiments were carried out using mixed and substituted aromatic hydrocarbons as precursors. This involved toluene mixed with propyne and propylene, o-nitrotoluene mixed with acetylene and ethylene, and chloromethyl naphthalene mixed with propyne and propylene.Based on experiments, this article discusses the effects of C=C double bonds and aldehyde groups on the low-temperature reaction activity and pollutant formation in the low-temperature oxidation intermediates of 2-butenal and methacrolein. The low-temperature reaction activity of both butenal compounds mainly comes from the OH addition reaction experienced by the C=C double bond within the unsaturated aldehyde molecule. The bimolecular reaction between the resonance-stabilized fuel radical RCO and HO2 is the source of early CO2 formation. The different C3H5 produced by different aldehydes are the main source of differences in reaction activity. This article achieved satisfactory results using 2,5-hexanedione as a precursor of methyl vinyl ketone. The double carbonyl structure of 2,5-hexanedione makes methyl vinyl ketone the main product, and the C=C double bond and carbonyl group within methyl vinyl ketone allow for OH addition dissociation reactions and CH3 addition dissociation reactions, respectively, which produce acetaldehyde and pentanone, respectively.This study investigates the pyrolysis of toluene and propyne/propylene, which result in benzyl and propargyl radicals, respectively. The effects of adding propyne and propylene to toluene at different pressures are explored. Results show that the addition of propyne and propylene has minimal impact on fuel consumption but alters the consumption pathways of benzyl radicals. Synergistic effects are observed for the generation of indene and naphthalene. Reaction pathway analysis reveals a clear pressure dependence for the formation of these PAHs. Furthermore, by utilizing the characteristic of aryl radicals easily forming upon bond cleavage of substituted aromatic hydrocarbons, the ortho-nitrotoluene was used to generate ortho-methyl toluene, which then reacted with ethyne and ethene to produce indene and indane as well as their intermediates. The pyrolysis of 1-chloromethylnaphthalene and 2-chloromethylnaphthalene with propyne and propylene resulted in the formation of anthracene and phenanthrene, respectively. The selection of propyne and propylene did not significantly affect the product distribution, but the position of the methyl group had a substantial impact.
