High-Temperature and High-Pressure Pyrolysis of Hexadecane: Molecular Dynamic Simulation Based on Reactive Force Field (ReaxFF).

As important products of heavy oil pyrolysis, heavier components such as gasoline and diesel supply the vast majority of energy demand through combustion, and lighter components such as ethylene and propylene are the main sources of industrial chemicals and plastic products. In this work, pyrolysis of hexadecane, as the model compound, was studied by reactive force field (ReaxFF) molecular simulation at high temperatures and high pressures. It was confirmed by unimolecular simulations that there exist eight different initial mechanisms all starting with C-C bond dissociation. The biradical mechanism was verified, through which the pyrolysis process can be accomplished within a shorter time. The enthalpy of reaction was calculated by the QM method, which was well consistent with ReaxFF calculation results. Multimolecular simulations showed that there is a strong dependency relationship between products distribution and temperature, as well as that between reaction rates and temperature. The optimal condition for ethylene formation in our work is 11.6 MPa and 2000 K, whereas it is best for hydrogen formation at conditions of 11.6 MPa and 3500 K. Kinetic analysis was performed with the activation energy of 113.03 kJ/mol and pre-exponential factor of 4.55 × 1012, and it is in good agreement with previous work.