Modeling soot particles as stable radicals: a chemical kinetic study on formation and oxidation. Part II. Soot oxidation in flow reactors and laminar flames

Recent experimental and theoretical studies have shed light on the persistent radical behavior of large polycyclic aromatic hydrocarbons (PAHs) and soot particles. The first detailed soot model developed based on these findings is here proposed. While its good performances in predicting soot formation and growth when soot oxidation is negligible are presented in the companion paper of this work (Part I), the model is here validated against 45 cases of particle size distribution functions (PSDF) and soot volume fraction under oxidizing conditions. Notably, we show that by considering stable radical particles and aggregates it is possible to reproduce soot oxidation by O-2 in plug flow reactors under very diluted conditions, whereas existing models could not predict particle consumption in the absence of particle surface activating species. Therefore, this work paves the way for a different approach to soot modeling that could help to better interpret soot reactivity. Oxidation of soot produced from different fuels (ethylene, n-heptane, and toluene, i.e. leading to different particle graphitization) at different temperatures (950-1073 K) and O-2 concentrations (1000-10000 ppm) is successfully modeled adopting reference oxidation rates of gas-phase resonantly stabilized PAH radicals, featuring analogous reactivity compared to soot species, and by also accounting for different particle hydrogenation levels. Good model performances are also obtained in both rich and lean premixed ethylene flames (T-max similar to 1480-1510 K) and in two sets of counterflow ethylene soot formation/oxidation flames (SFO, T-max similar to 2560-2825 K), where OH radical becomes the dominant oxidizer. Finally, model limitations emerging in some of the cases considered are discussed through a sensitivity analysis and with references to other oxidation mechanisms proposed in the literature in order to highlight possible future improvement of the model predictive capability

Automated summary

Recent studies have provided new insights into the behavior of large polycyclic aromatic hydrocarbons (PAHs) and soot particles. In this work, a detailed model for soot based on these findings is proposed and validated against experimental data. The model successfully predicts soot formation and oxidation under various conditions, and offers a new approach to interpreting soot reactivity.