Zhang Xianming, Li Yanping, Hu Yufeng, Pang Jinglin, Wang Yunfei, Wu Zhen
Ordos Institute of Technology, Ordos 017000, Inner Mongolia, China.
State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing 102249, Beijing, China.
ACS Omega. 2019 Nov 6;4(21):19128-19135. doi: 10.1021/acsomega.9b02424. eCollection 2019 Nov 19.
Poly(oxymethylene) dimethyl ethers (PODME , = 2-6) are novel oxygenated compounds that can be used as promising candidates for new-generation fuels because of their excellent combustion performance. The oxidation of PODME ( = 2-6) is essential for the understanding of the combustion process. It is necessary to study the relationship between kinetic parameters and cetane number () of PODME ( = 2-6). In order to predict initiation step rate constants for the oxidation of PODME ( = 2-6), quantum mechanical calculations are performed using M06-2X/6-311G(d,p) and B3LYP/6-311G(d,p) methods. Structural, energetic, thermodynamics, and kinetics of the automatic ignition process are assessed. The kinetic model based on the conventional transition state theory is used to calculate the initiation step reaction rate constants at 1000 K. In both M06-2X/6-311G(d,p) and B3LYP/6-311G(d,p) methods, the calculated rate constants of the hydrogen abstraction process have an excellent correlation with the experimental of PODME ( = 2-6). Our methodology presented here can be used to simulate chemical kinetics for other fuel additives.
聚甲醛二甲醚（PODME，n = 2 - 6）是一类新型含氧化合物，因其优异的燃烧性能，有望成为新一代燃料的候选物。PODME（n = 2 - 6）的氧化对于理解燃烧过程至关重要。研究PODME（n = 2 - 6）的动力学参数与十六烷值（CN）之间的关系很有必要。为了预测PODME（n = 2 - 6）氧化的引发步骤速率常数，采用M06 - 2X/6 - 311G(d,p)和B3LYP/6 - 311G(d,p)方法进行量子力学计算。评估了自燃过程的结构、能量、热力学和动力学。基于传统过渡态理论的动力学模型用于计算1000 K下引发步骤的反应速率常数。在M06 - 2X/6 - 311G(d,p)和B3LYP/6 - 311G(d,p)两种方法中，计算得到的氢提取过程速率常数与PODME（n = 2 - 6）的实验十六烷值具有良好的相关性。本文提出的方法可用于模拟其他燃料添加剂的化学动力学。
