Modeling soot particles as stable radicals: a chemical kinetic study on formation and oxidation. Part I. Soot formation in ethylene laminar premixed and counterflow diffusion flames

Abstract

Based on recent theoretical and experimental evidences, this work proposes a detailed discrete sectional soot model considering particles and aggregates behaving as stable radicals, paving the way for the implementation of a game-changing assumption in soot kinetic models. The concentration of large closed-shell and open-shell polycyclic aromatic hydrocarbons (PAHs) levels out with the increase of their aromatic structure and, contrary to conventional assumptions in existing soot models, their reactivity approaches that of persistent radical species. These findings were implemented in the model here proposed to describe soot formation (Part I) and oxidation (Part II). While the number of lumped pseudo-species involved is significantly reduced compared to previous discrete sectional soot models since no distinction between the kinetics of closed-shell and open-shell particles is taken into account, the physical meaning and consistency with recent evidences improves together with model performances. Rate parameters of gas-phase reactions involving resonantly stabilized radical PAHs were used as a reference for soot particle kinetics. The model was validated against 65 target ethylene laminar premixed flames and counterflow diffusion flames, with a general good agreement between experimental data and numerical simulations at different pressures (P = 1–8 atm), maximum flame temperatures (Tmax∼1500–2400 K) and soot yields (fv∼0.01 to ∼170 ppm). Parity diagrams allow to identify systematic deviations of the present model from the experiments, while the comparison between all the flames included in the database highlights the relative contribution to soot formation and growth of the main reaction classes constituting the soot model, spotting analogies and peculiarities of the two flame configurations considered. Similar kinetic patterns characterize most of the flames within the database, independently of flame configuration and sooting tendency of the specific case. Large PAH condensation dominates the formation of the first soot nuclei, while the condensation of smaller PAHs up to four aromatic rings is primarily responsible for the growth of larger soot particles and aggregates. Finally, the contribution of the different fluid dynamics in premixed and counterflow flames to particle evolution, resulting in a higher hydrogenation level of soot particles in the latter, is discussed.