典型丙醚二级加氧产物的氢转移裂解反应理论研究  

Theoretical Study on the H-Transfer Reaction Combining with Dissociation for the Typical Intermediates of Secondary O2-Addition for Propyl Ethers

作　　者：刘猛 沈宇豪 颜应文[1] 田泽民 LIU Meng;SHEN Yuhao;YAN Yingwen;TIAN Zemin(School of Energy and Power,Nanjing University of Aeronautics and Astronautics,Nanjing 210016,China)

机构地区：[1]南京航空航天大学能源与动力学院,南京210016

出　　处：《新能源进展》2024年第5期580-587,共8页Advances in New and Renewable Energy

基　　金：江苏省自然科学青年基金项目(BK20200451)。

摘　　要：低温燃烧是一种有前景的高效清洁燃烧技术。其关键问题之一在于可靠地构建燃料低温氧化化学动力学机理。丙醚作为一种可再生清洁燃料,在低温燃烧方面有较高应用潜力,然而,其关键低温氧化反应的研究却十分缺乏。基于量子化学和过渡态理论,考虑物种的多重构象效应,计算三种典型的正丙醚/异丙醚二级过氧化物OOQOOH经过氢转移-裂解生成氢过氧化物醛酮类物质和OH基的反应势能面、热力学数据和反应速率常数。结果表明,多重构象效应对物种的焓、熵、定压比热容及速率常数有明显影响,计算时不可忽略。获得的热力学数据和反应速率常数可用于完善丙醚燃料低温氧化机理。Low-temperature combustion is a promising efficient and clean combustion technology.One of the key problems is constructing reliable chemical kinetic mechanism of low-temperature oxidation for practical fuels.Propyl ethers,a renewable clean fuel,have great potential in low-temperature combustion.However,there is a shortage of its low-temperature chemical kinetics studies.This work investigated three typical reactions of secondary O2-addition intermediates related to n-/iso-propyl ethers,denoting as OOQOOH,forming ketohydroperoxides plus OH,based on quantum chemistry and transition state theory.Potential energy surfaces,thermodynamic data and rate constants were obtained and refined using the multi-structure method.It was shown that the multi-structure torsional anharmonicity exerts notable influences on thermodynamic data and rate constants,which can be further used to improve the low-temperature chemical mechanism of propyl ethers.

关 键 词：二级加氧反应 势能面 丙醚 速率常数 量子化学 

分 类 号：TK421[动力工程及工程热物理—动力机械及工程]