Study on combustion mechanism of methanol/nitromethane based on reactive molecular dynamics simulation

Oxygenated fuels and nitro fuels are effective strategies for addressing incomplete combustion by increasing the oxygen-fuel ratio. A computational approach based on reactive molecular dynamics simulations reveals oxidation mechanisms of temperature-induced effects on a mixed fuel of methanol and nitromethane. The method enables the demonstration of the initial reaction scheme of a binary fuel mixture, even for complicated interplay and coupling reactions. The results showed that the first reaction step of nitromethane was homolysis in poor-oxygen conditions, mainly via CH3NO2 → CH3 + NO2 (Net flux = 183, ratio = 92.89%). Methanol undergoes dehydrogenation reaction with the assistance of active radicals (OH, HO2, CH3, NO, and NO2), and the participation rates of these active groups are 60%, 17.14%, 8.57%, 7.62%, and 6.67%, respectively. The decomposition of nitromethane provided NO2 and CH3 radicals and significantly increased the amount of OH and NO via a reaction of NO2 + H → HNO2 → OH + NO. By fragment analysis, the main C1 intermediates are formed by pyrolysis of methanol/nitromethane such as formaldehyde, hydroxymethyl radical, and formyl radical. The CH3OH and CH2O are relatively stable, and the dehydrogenation is mainly highly active groups such as OH and NO. In contrast, the dehydrogenation of CH2OH and CHO free radicals is completed by self-cleavage or with the help of O2, NO2, etc. Our findings shed light on the oxidation behaviors of methanol/nitromethane mixed fuel in combustion.