ReaxFF molecular dynamics study of N-containing PAHs formation in the pyrolysis of C2H4/NH3 mixtures

The reactive force field molecular dynamics (ReaxFF MD) simulations are performed to depict the whole process including fuel pyrolysis, the formation and growth of PAHs/NPAHs and soot formation in the pyrolysis of C₂H₄ and C₂H₄/NH₃ mixtures. NH₃ doping increases the concentration of H radicals through the decomposition of NH₃. These H radicals then promote the consumption of C₂H₄ by participating in H-abstraction reactions. The formation of C-N species (mainly HCN, H₂CN, C₂N, CH₃CN, NCCN, and HC₃N) removes the C atoms participating in the formation of PAHs and soot, thus inhibiting the formation of soot. And such inhibitory effect is strengthened with increasing temperature due to the promoted formation of C-N species. Most importantly, the structure, formation and evolution paths of N-containing PAHs (NPAHs) are identified based on the experimental and simulation results for the first time, revealing that N atoms in the NPAHs are almost always present in the carbon chains attached to the aromatic rings while barely enter the rings to form heterocyclic structure. The simulations further reveal that when the temperature is less than 2500 K, the first N-containing aromatic ring is formed through the reaction of phenyl with small C-N species (such as HCN and CN radicals), followed by the increase of new rings primarily via the HACA mechanism. At temperatures greater than 2500 K, the formation and growth of NPAHs are dominated by the continuous attachment of N-containing carbon chains and cyclic polycondensation-cyclization reactions. The identification of new C-N species especially NPAHs would help improve the kinetic mechanisms for ammonia blending combustion.