Unraveling the carbene chemistry of oxymethylene ethers: Experimental investigation and kinetic modeling of the high-temperature pyrolysis of OME-2

Oxymethylene ethers (OMEs) form an interesting family of synthetic compounds to replace fossil fuels. This alternative liquid energy carrier can contribute to a circular carbon economy when produced via car-bon capture and utilization technology using renewable electricity. Despite the potential to reduce green-house gas and particulate matter emissions and their ideal ignition characteristics, little is known about the thermal decomposition behavior of OMEs. In this work, new insights are obtained in the pyrolysis chemistry of oxymethylene ether-2 (OME-2) and the role of carbenes by performing experiments at high temperatures (> 850 K) in a tubular quartz reactor. The used continuous bench-scale pyrolysis unit has a dedicated on-line analysis section including comprehensive two-dimensional gas chromatography (GC x GC) coupled with flame ionization detection (FID) and mass spectroscopy (MS) to identify and quantify the full product spectrum over the complete temperature range. The reactor temperature was varied be-tween 850 and 1150 K at a fixed pressure of 0.15 MPa and residence times of 400 to 850 ms. The major products are dimethoxymethane, formaldehyde, methyl formate, methane, CO2, CO and H 2 . Minor inter-mediate compounds comprise dimethyl ether, formic anhydride, formic acid, methoxymethyl formate and methoxymethanol. The yields of compounds with carbon-carbon bonds are low since no such bonds orig-inally occur in OME-2. Precursors of aromatic compounds and soot particles are absent in the reactor ef-fluent. The experimental results are simulated with a new first principles-based kinetic model for pyrolysis and combustion of OME-2. This model can predict the experimental trends of major products on average within the experimental uncertainty margin of & PLUSMN; 10% relative for major product species. A reaction pathway and sensitivity analysis are presented to highlight the importance of the carbenes for initiation of the radical chemistry under pyrolysis conditions. & COPY; 2022 The Combustion Institute. Published by Elsevier Inc. All rights reserved.