High-temperature pyrolysis of isoprenoid hydrocarbon p-menthane using ReaxFF molecular dynamics simulation

• High-temperature pyrolysis process simulation of p -menthane performed by Reactive Molecular Dynamic simulations. • Initiatial Consumption of p -menthane was mainly through ring-opening reactions. • Generation and consumption channels analysis of main intermediates. • Detailed reaction scheme with detected products including new short-lived radical intermediates. • Calculation of apparent activation energy and pre-exponential factor based on simulation results. The pyrolysis chemistry of p -menthane, a promising “drop-in” fuel of bio-derived isoprenoid hydrocarbon, has not been well understood especially under high temperatures. In this work, the pyrolysis of p -menthane is further investigated using molecular dynamics simulations with the reactive force-field interatomic potential (ReaxFF) under 2600 K. It is found that the scission of isopropyl and the ring-open reaction in the site adjacent to the isopropyl are two predominant initiations of p -menthane decomposition in our simulations. The main generation and consumption channels of important products, such as methane and ethylene, are also tracked by the straightforward scrutinize on simulation trajectories. In addition, a detailed reaction scheme of the high-temperature pyrolysis is proposed. The apparent activation energy calculated from our reactive molecular dynamics simulations in the temperature range from 2200 K to 3000 K is 232 kJ mol −1 , which is reasonably consistent with our experimental result of 225 ± 5 kJ mol −1 . In summary, the simulation results provided by ReaxFF are helpful to explain pyrolysis processes readily, which is the effective verification and extension of previous experimental studies.