Acta Phys. -Chim. Sin. ›› 2016, Vol. 32 ›› Issue (2): 453-464.doi: 10.3866/PKU.WHXB201512071

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Kinetic Calculation and Modeling Study of 1, 3-Butadiene Pyrolysis

Niao-Feng DU1,Hong-Bo NING2,Ze-Rong LI3,*(),Qi-Yi ZHANG2,*(),Xiang-Yuan LI2   

  1. 1 School of Aeronautics & Astronautics, Sichuan University, Chengdu 610065, P. R. China
    2 School of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China
    3 College of Chemistry, Sichuan University, Chengdu 610064, P. R. China
  • Received:2015-08-24 Published:2016-01-30
  • Contact: Ze-Rong LI,Qi-Yi ZHANG;
  • Supported by:
    the National Natural Science Foundation of China(91441114, 91441132)


1, 3-Butadiene is an important product in combustion and pyrolysis of hydrocarbon fuels and it is also an important precursor to formpolycyclic aromatic hydrocarbons (PAHs). Currently, a variety of experimental and mechanism studies have been performed on 1, 3-butadiene oxidation. However, few studies about pyrolysis mechanism of 1, 3-butadiene have been done. In this work, the optimization of the geometries and the vibrational frequencies for the reactants, products, and transition states of the relevant reactions in 1, 3-butadiene pyrolysis have been performed at the B3LYP/CBSB7 level. Their single point energies and the thermodynamic parameters are also calculated by using the composite CBS-QB3 method. The high-pressure limit rate constants for tight transition state reactions and barrierless reactions are obtained by transition state theory and variable reaction coordinate transition state theory, respectively. The calculated rate constants in this work are in good agreement with those available from literature. Furthermore, the mechanism of Hidaka et al. is updated with replacing the calculated rate constants of reactions in this work to simulate the shock tube experiment results of 1, 3-butadiene pyrolysisand the updated mechanism consists of 45 species and 224 reactions. It can be seen that the updated mechanism can improve the concentration profiles of the main products, ethylene, 1-butylene-3-acetylene, and benzene in 1, 3-butadiene pyrolysis. It can also provide reliable kinetic and thermodynamic parameters to further improve the core mechanism of C0-C4 species.

Key words: 1, 3-Butadiene, Pyrolysis mechanism, Rate constant, Kinetic simulation


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