ReaxFF molecular dynamics simulations of n-eicosane reaction mechanisms during pyrolysis and combustion

Abstract

The pyrolysis and combustion mechanism of the hydrocarbon fuel has important scientific and practical significance. However, it is difficult to detect the whole intermediates and products using traditional methods, which brings trouble to the analysis of the reaction process. In this paper, the microscopic reaction mechanism and the main products of n-eicosane (C20H42) were simulated based on the reactive force field molecular dynamics (ReaxFF-MD). The effects of temperature (2000–3500 K) and oxygen on the initial decomposition, the distribution of main products, and the reactive pathways of C20H42 fuel were studied to determine its reaction mechanism. The initial decomposition of C20H42 was mainly initiated by small alkyl radicals in pyrolysis, and by the oxygen-containing radicals in combustion. The participation of oxygen had a greater effect on accelerating the decomposition reaction. The reactions involving oxygen of C20H42 initial decomposition accounted for 87.5% of the total reactions at 2000 K. Moreover, the detailed distribution and formation pathways of the main products of H2, C2H4, CH4, H2O, CO, and CO2 were depicted to construct the overall reaction mechanism of C20H42. •H radical formed from the composition of C2H4 was exactly consistent with the •H radical consumed by the generation of CH4 and H2 in the pyrolysis stage. The feasibility of the simulation method was verified by the result of thermal analysis. The results are helpful for further research on the reaction mechanism of hydrocarbon fuels.