Exploring flow reactor pyrolysis of branched OMEs: Insights into multi-sidechain effects on pyrolysis chemistry of CH3OCH3-n(OCH3)n (n = 1–3)

Oxymethylene ethers (OMEs) have received great attention due to their carbon-neutral nature and advantageous properties as alternative transportation fuels or fuel additives. Previous studies focused on the combustion of linear OMEs with the chemical formula of CH 3 O(CH 2 O) m CH 3 ( m ≥ 0), while a deep understanding of the combustion of branched OMEs with the chemical formula of CH 3 OCH 3- n (OCH 3 ) n (0 ≤ n ≤ 3) is still absent. In this work, the flow reactor pyrolysis of dimethoxymethane (DMM, n = 1), trimethoxymethane (TMM, n = 2), and tetramethoxymethane (TeMM, n = 3) is investigated using gas chromatography, with special attention given to the multi-sidechain effects on the pyrolysis chemistry. A pyrolysis model of branched OMEs is developed and validated against the new pyrolysis data. Modeling analysis is performed to provide insights into the pyrolysis chemistry of the three branched OMEs and the multi-sidechain effects. Unimolecular decomposition and H-abstraction reactions are found to be two major types of fuel decomposition pathways, with the former dominating TMM decomposition, the latter dominating DMM decomposition, and both contributing almost equally to TeMM decomposition. Sensitivity analysis shows that C O bond dissociation is the most sensitive reaction to fuel decomposition in DMM pyrolysis, while methanol elimination is the most sensitive reaction in TMM and TeMM pyrolysis. Among the three fuels, DMM has the lowest pyrolysis reactivity and produces the least abundant methanol. In contrast, TMM is observed with the highest pyrolysis reactivity and produces the most abundant methanol. Theoretical calculations reveal that TMM and DMM have the lowest and highest energy barriers of methanol elimination reactions, which determines the order of their pyrolysis reactivities and methanol formation trends. As a result, DMM pyrolysis occurs at higher temperature regions where the C O bond dissociation and H-abstraction reactions are preferred, while TMM pyrolysis occurs at lower temperature region where methanol elimination dominates.