主管：中华人民共和国应急管理部
主办：应急管理部天津消防研究所
ISSN 1009-0029  CN 12-1311/TU
消防科学与技术

消防科学与技术 ›› 2020, Vol. 39 ›› Issue (11): 1482-1485.

• • 上一篇    下一篇

基于改进ReaxFF 力场的全氟己酮热分解机理研究

谷伟，彭章娥   

  1. 上海应用技术大学城市建设与安全工程学院，上海201418
  • 出版日期:2020-11-15 发布日期:2020-11-15
  • 通讯作者: 彭章娥（1970-），女，上海应用技术大学城市建设与安全工程学院副教授，硕士生导师。
  • 作者简介:谷伟（1995-），男，江苏盐城人，上海应用技术大学城市建设与安全工程学院硕士研究生，主要从事环境安全与污染物控制研究，上海市奉贤区海泉路100号，201418。
  • 基金资助:
    国家自然科学基金重大研究计划培育项目（91952102）

Study on thermal decomposition mechanism of perfluorohexanone based on improved ReaxFF force field

GU Wei, PENG Zhang-e   

  1. School of Urban Construction and Safety Engineering,Shanghai Institute of Technology, Shanghai 201418，China
  • Online:2020-11-15 Published:2020-11-15

摘要： 采用基于密度泛函的紧束缚模型（DFTB）和改进的反作用力场（ReaxFF）对全氟己酮的热分解机理进行反应分子动力学仿真研究，分析了热分解的初始反应路径、微观反应过程以及体系内气体的生成机理，探讨了温度对全氟己酮热分解的影响，建立了以仿真数据为基础的一级动力学方程并对热分解过程进行一级动力学评估。结果表明，全氟己酮热分解的起始反应为：全氟己酮→全氟异戊烷+一氧化碳，全氟己酮热分解的主要产物为一氧化碳、四氟甲烷、六氟丙烯、全氟异丁烯、十氟丁烷、全氟异戊烷及大量活性基团。经一级动力学评估得到指前因子和表观活化能分别为5.021 7×1014 s-1和1 771.96 kJ/mol。

关键词: 全氟己酮, ReaxFF, DFTB, 热分解机理

Abstract:

A molecular dynamics simulation study on the thermal decomposition mechanism of perfluorohexanone using the tight functional model based on density functional model (DFTB) and the improved reaction force field (ReaxFF) was condcted. The initial reaction path of thermal decomposition,the microscopic reaction process and the gas generation mechanism in the system was analyzed. The effect of temperature on the thermal decomposition of perfluorohexanone was discussed.The first-order kinetic equation based on simulation data was established and the first-order kinetic evaluation of the thermal decomposition process was carried out. The results showed that the initial reaction of thermal decomposition of perfluorohexanone is: perfluorohexanone → perfluoroisopentane + carbon monoxide. The main products of thermal decomposition of perfluorohexanone are carbon monoxide, tetrafluoromethane, hexafluoropropylene,perfluoroisobutylene, decafluorobutane, perfluoroisopentane and a large number of active groups. The firstorder kinetic evaluation showed that the pre- finger factor and the apparent activation energy were 5.0217×1014 s-1 and 1 771.96 kJ/mol, respectively.

Key words:

perfluorohexanone; ReaxFF, DFTB, thermal decomposition mechanism