正丙醇低压热解的实验和模型研究

本文利用同步辐射真空紫外光电离质谱技术研究了正丙醇在1.333 kPa和1000～1400 K下的流动反应器热解实验,鉴定了包括自由基、烯醇等活泼物种在内的20余种热解物种,测量了这些热解物种的摩尔分数随热解温度的变化曲线。构建了一个包含142个物种和1149步反应的正丙醇热解反应动力学模型,并利用本文实验结果对模型进行了验证,结果显示本模型对实验结果具有良好的预测性。基于生成速率分析和敏感性分析,揭示了正丙醇分解和关键热解产物生成中的关键路径。并通过与异丙醇低压热解结果的对比,分析了丙醇热解中的燃料同分异构体效应。     

2,5-二甲基四氢呋喃低压热解实验和动力学模型研究

2,5-二甲基四氢呋喃是一种非常有应用潜力的生物质燃料。本文利用同步辐射真空紫外光电离质谱(SVUVPIMS)技术,研究了2,5-二甲基四氢呋喃在压力为3990 Pa、温度从948到1198 K条件下的流动管热解反应。实验探测到了包括自由基和稳定产物在内的四十余种物种,基于实验结果,提出了一个由265个物种和1490个反应组成的动力学模型,并利用实验结果进行了验证;通过生成速率(ROP)分析,得到了燃料的初级解离过程和主要热解产物的生成路径。     

1,3-丁二烯掺混丙炔热解中芳烃生成的协同效应理论研究

A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation.A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments.The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments,as well as the synergistic effect between 1,3-butadiene and propyne on the formation of a series of aromatic hydrocarbons.Based on the rate of production and sensitivity analyses,key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved.The synergistic effect results from the interaction between 1,3-butadiene and propyne.The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons.Besides,the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously,which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene.