碳烟形成过程中燃料协同效应的实验和模型研究

The synergistic effect of fuels in soot formation means the enhancement of soot formation in combustion of a fuel mixture compared with the situations in combustion of individual fuels at the same experimental conditions. Investigations on this common phenomenon will help understand the soot formation mechanism and the combustion chemistry of practical transportation fuels with complex compositions, which are closely related to domestic demands in strategic fields such as energy conversion, environmental protection and transportation. Recognizing the limitations in literature work of synergistic effects, this project plans to perform investigations on this topic by using both advanced experimental technique and updated theoretical methods. For the experimental aspect, synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) will be applied to study the combustion of several binary fuel mixtures with synergistic effect and their individual components. Comprehensive chemical structures of their combustion in various reaction circumstances including the flow reactor pyrolysis and laminar premixed flame at various pressures will be measured to determine the influences of synergistic effect on concentrations of soot precursors. For the kinetic modeling aspect, quantum chemical calculations and rate constant calculations will be performed to provide rate constants of important elementary reactions, which will be used in the kinetic models of investigated fuels developed in this project. Validation of these models based on the experimental data will be performed to improve the accuracies of models. The development of kinetic models will increase our knowledge on the formation mechanism of benzene and PAH which is the controlling sub-mechanism of soot formation mechanism. For the mechanistic aspect, modeling analysis will be employed to understand the kinetic mechanisms leading to the synergistic effect and the roles of odd and even carbon routes in soot formation mechanism. The results are anticipated to promote the applied combustion researches involving soot formation mechanism and the combustion chemistry of practical transportation fuels with complex compositions.

碳烟形成过程中燃料的协同效应是指多种燃料组分混合后促进碳烟生成的现象。其研究有助于理解碳烟形成机理和复杂组分实用燃料燃烧反应动力学，事关我国能源、环境、运输等领域的重要需求。 针对前人协同效应研究中存在的局限性，拟在实验方面，利用先进的同步辐射真空紫外光电离质谱方法研究多种具有协同效应的二元混合燃料及其组分在变压力流动反应器热解和层流预混火焰中的微观燃烧化学结构，探索燃料协同效应对碳烟前驱体浓度的影响；在模型方面，对重要基元反应的速率常数进行理论计算，发展出准确性较高的燃烧反应动力学模型，增强对碳烟形成机理中的控制子机理- - 苯和多环芳烃形成机理的认识；在机理分析方面，揭示出引发燃料协同效应的反应动力学机制、以及奇数和偶数碳路径在碳烟形成机理中的作用，为涉及到碳烟形成机理和复杂组分实用燃料燃烧反应动力学的工程燃烧研究提供理论指导。

碳烟形成过程中燃料的协同效应是指多种燃料组分混合后促进碳烟生成的现象。其研究有助于理解碳烟形成机理和复杂组分实用燃料燃烧反应动力学，事关我国能源、环境、运输等领域的重要需求。.针对前人协同效应研究中存在的局限性，本项目结合实验探索和模型研究，系统地对多种具有协同效应的二元混合燃料及相关芳烃类、链烃类、环烃类和生物醇类组分进行了研究。在单组分燃烧研究中，基于同步辐射真空紫外光电离质谱（SVUV-PIMS）技术，对在不同压力和反应氛围下的微观燃烧结构进行了完备解析，特别是对多环芳烃（PAH）及其前驱体进行了深入的探测。发展了一系列单组分燃料的燃烧反应动力学模型，并完善了苯和PAH生成子机理，模型具有良好的预测能力。基于实验测量与模型分析，揭示了一系列燃料分子结构特征对于PAH前驱体及PAH生成的重要影响。在二元混合燃料研究中，通过设定不同的燃料掺混比例，得到了燃烧中间产物浓度随掺混比例的变化关系，发现了明显的燃料协同效应。通过实验研究和模型分析发现，二元混合燃料燃烧体系中形成燃料协同效应的主要原因包括自由基浓度的提高和不同类型前驱体的共同增强。前者通过加入较易分解的燃料组分，提高整个反应体系中的自由基浓度，激发较慢的芳烃和PAH生成反应，后者则对于特定的PAH，通过加强一种前驱体的生成，促进该PAH的大量生成，进而均引发了燃料协同效应。.本项目共发表论文17篇，其中SCI论文15篇，中文核心期刊论文2篇，包括国际权威燃烧学期刊Combustion and Flame 8篇、Proceedings of the Combustion Institute 3篇，发表于Physical Chemistry Chemical Physics的论文被选为当期封底论文。授权发明专利1项。研究成果获得国内外知名学者的高度评价，共被SCI引用80次，其中他引68次，在国内外学术会议上做大会特邀报告和邀请报告13次。获得2018年国家自然科学二等奖（第二完成人）、2017年亚太燃烧会议Young Investigator奖、及2015和2018年中国工程热物理学会燃烧学学术年会优秀论文奖。研究成果应用于我国多家航空和高超动力研发单位。