Reaction mechanism and light gas conversion in pyrolysis and oxidation of dimethyl ether (DME): A ReaxFF molecular dynamics study

Abstract

To uncover the microscopic reaction mechanisms of dimethyl ether (DME) pyrolysis and oxidation, reactive molecular dynamics simulations were employed to investigate the reaction processes under various O2/DME ratios and impurity environments at 2200 K–3200 K. The results show that DME pyrolysis begins with a decomposition reaction of CH3OCH3 → CH3O + CH3, ultimately leading to the formation of CO, H2 and PAHs. The reaction pathways of DME oxidation contain light gas conversion and combustion. In fuel rich conditions, the oxidation produces mainly H2 and CO, while in fuel lean conditions, the oxidation products tend to be H2O and CO2. The carbon components of DME are completely converted into CO2 and CO regardless of O2 content. In the presence of impurities H2O or CO2, the oxidation reaction pathway is altered, causing consumption and transformation of these impurities into active radicals such as OH, further promoting the progress of the reaction. The top three light gases produced are hydrogen, methanol and methane, and increasing H2 production in the DME oxidation process can be achieved through both oxygen subtraction and water addition. The rate of formaldehyde generation during pyrolysis is higher than that during oxidation. However, a higher oxygen content leads to increased formaldehyde production.