丁烯/丁醇异构体低温氧化Waddington反应机制理论研究  

A Systematic Theoretical Kinetics Analysis of Waddington Mechanism in Low-Temperature Oxidation of Butene and Butanol Isomers

作　　者：赵倩 李阳[2] Mani Sarathy 黄佐华[1] 张英佳[1] Zhao Qian;Li Yang;Mani Sarathy;Huang Zuohua;Zhang Yingjia(State Key Laboratory of Multiphase Flows in Power Engineering,Xi'an Jiaotong University,Xi'an 710049,China;Science and Technology on Combustion,Internal Flow and Thermostructure Laboratory,Northwestern Polytechnical University,Xi'an 710072,China;Clean Combustion Research Center,King Abdullah University of Science and Technology,Thuwal 23955,Saudi Arabia)

机构地区：[1]西安交通大学动力工程多相流国家重点实验室,西安710049 [2]西北工业大学燃烧、结构与内流场重点实验室,西安710072 [3]阿卜杜拉国王科技大学清洁燃烧研究中心,图沃23955,沙特阿拉伯

出　　处：《燃烧科学与技术》2022年第5期540-548,共9页Journal of Combustion Science and Technology

基　　金：陕西省杰出青年基金资助项目(2018JC-002).

摘　　要：Waddington机理是烯烃和醇类异构体低温氧化机理建模的重要组成部分.针对丁烯/丁醇异构体,系统研究了低温氧化过程的Waddington动力学机制.基于量子化学原理,对该反应机制下的反应速率常数和物种热力学性质进行计算.基于过渡态理论,结合RRKM/ME方法,获得目标体系温度-/压力依赖的速率系数.在统计热力学的基础上,计算了所有关键物种温度相关的内能、生成焓、熵和热容等热力学量.与文献结果比较发现,异丁烯(R4和R5体系)的动力学与热力学参数均与文献值吻合较好.该理论计算结果可直接用于丁烯和丁醇异构体低温氧化动力学模型构建.The Waddington mechanism is crucial for the low-temperature oxidation of both alkenes and alcohols.In this study,the Waddington mechanism in the oxidation of butene and butanol isomers was systematically investigated.Fundamental quantum chemical calculations were conducted for the rate constants and thermodynamic properties of the reactions and species in this mechanism.Temperature-and pressure-dependent rate constants were obtained based on the transition state theory,associated with the Rice Ramsperger Kassel Marcus and master equation theories.Temperature-dependent thermodynamic parameters(enthalpies of formation,entropy,and heat capacity)of all major species were also calculated based on the statistical thermodynamics.The comparative study reveals that the rate coefficients and thermodynamic parameters of isobutene(R4 and R5 reaction systems)show good agreement with the corresponding values obtained from the literature.All the calculated results can be directly used for developing the kinetic model of low-temperature oxidation of butene and butanol isomers.

关 键 词：Waddington机制 丁烯/丁醇异构体 从头算法 速率系数 热力学参数 

分 类 号：TK16[动力工程及工程热物理—热能工程]