Abstract 1,1-Diethoxybutane is a promising next-generation biofuel and this work reports the first study for its pyrolysis chemistry. Pyrolysis of 1,1-diethoxybutane was investigated in a flow reactor at 0.04 and 1 atm using synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). A series of oxygenated and hydrocarbon products, including several radicals, were detected and their mole fractions were evaluated. A detailed kinetic model of 1,1-diethoxybutane, including 253 species and 1577 reactions, was developed and validated against the present experimental data. Modeling analyses including the rate of production analysis and sensitivity analysis were performed to reveal the crucial consumption pathways of 1,1-diethoxybutane, as well as the formation and consumption pathways of intermediates and products. The H-abstraction reactions of 1,1-diethoxybutane play a key role in fuel consumption. The intra-molecular elimination reactions and unimolecular C C or C O dissociation reactions of 1,1-diethoxybutane make minor contributions to fuel consumption. The sensitivity analysis also shows that the fuel consumption reactions have large sensitivities to 1,1-diethoxybutane. Further β-C C and β-C O scission reactions closely connect the consumption of six fuel radicals and the formation of most oxygenated products. The observation of high mole fractions of C1–C4 acids and aldehydes demonstrates the structural features of 1,1-diethoxybutane. Besides, several hydrocarbon products, such as C2–C4 alkenes, benzene and its precursors, were detected, some of which, such as propene, are also produced from the consumption reactions of fuel radicals. Besides, hydrocarbon products can also be produced from the combination reactions of small species, such as the combination reactions of C3 species to produce benzene and the combination reaction of allyl and methyl to produce 1-butene. The low benzene production ability of 1,1-diethoxybutane implies its low sooting tendency compared with fossil-derived transportation fuels.

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1,1-二乙氧基丁烷的热解化学探索：流动反应器和动力学模型研究

摘要 1,1-二乙氧基丁烷是一种很有前途的下一代生物燃料，这项工作报告了其热解化学的首次研究。使用同步加速器真空紫外光电离质谱 (SVUV-PIMS) 在流动反应器中在 0.04 和 1 个大气压下研究了 1,1-二乙氧基丁烷的热解。检测到一系列含氧和烃类产品，包括几个自由基，并评估了它们的摩尔分数。开发了 1,​​1-二乙氧基丁烷的详细动力学模型，包括 253 种物质和 1577 个反应，并根据目前的实验数据进行了验证。进行了包括产率分析和敏感性分析在内的建模分析，以揭示1,1-二乙氧基丁烷的关键消耗途径，以及中间体和产品的形成和消耗途径。1,1-二乙氧基丁烷的吸氢反应在燃料消耗中起关键作用。1,1-二乙氧基丁烷的分子内消除反应和单分子CC或CO解离反应对燃料消耗的贡献很小。敏感性分析还表明，燃料消耗反应对 1,1-二乙氧基丁烷具有很大的敏感性。进一步的 β-CC 和 β-CO 裂解反应将 6 个燃料自由基的消耗与大多数氧化产物的形成密切相关。观察到高摩尔分数的 C1-C4 酸和醛证明了 1,1-二乙氧基丁烷的结构特征。此外，还检测到了几种碳氢化合物产品，如 C2-C4 烯烃、苯及其前体，其中一些如丙烯也是由燃料自由基的消耗反应产生的。除了，烃类产品也可以由小物种的组合反应产生，例如C3物种的组合反应产生苯和烯丙基和甲基的组合反应产生1-丁烯。与化石衍生的运输燃料相比，1,1-二乙氧基丁烷的低苯生产能力意味着其低烟灰倾向。