Methanol oxidation up to 100 atm in a supercritical pressure jet-stirred reactor

Methanol (CH3OH) has attracted considerable attention as a renewable fuel or fuel additive with low greenhouse gas emissions. Methanol oxidation was studied using a recently developed supercritical pressure jet-stirred reactor (SP-JSR) at pressures of 10 and 100 atm, at temperatures from 550 to 950 K, and at equiva-lence ratios of 0.1, 1.0, and 9.0 in experiments and simulations. The experimental results show that the onset temperature of CH3OH oxidation at 100 atm is around 700 K, which is more than 100 K lower than the onset at 10 atm and this trend cannot be predicted by the existing kinetics models. Furthermore, a negative temperature coefficient (NTC) behavior was clearly observed at 100 atm at fuel rich conditions for methanol for the first time. To understand the observed temperature shift in the reactivity and the NTC effect, we updated some key elementary reaction rates of relevance to high pressure CH3OH oxidation from the liter-ature and added some new low-temperature reaction pathways such as CH2O + HO2 = HOCH2O2 (RO2), RO2 + RO2 = HOCH2O (RO) + HOCH2O (RO) + O 2 , and CH3OH + RO2 = CH2OH + HOCH2O2H (ROOH). Although the model with these updates improves the prediction somewhat for the experimental data at 100 atm and reproduces well high-temperature ignition delay times and laminar flame speed data in the literature, discrepancies still exist for some aspects of the 100 atm low-temperature oxidation data. In addition, it was found that the pressure-dependent HO2 chemistry shifts to lower temperature as the pressure increases such that the NTC effect at fuel-lean conditions is suppressed. Therefore, as shown in the experi-ments, the NTC phenomenon was only observed at the fuel-rich condition where fuel radicals are abundantand the HO2 chemistry at high pressure is weakened by the lack of oxygen resulting in comparatively little HO2 formation.& COPY; 2022 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Automated summary

Methanol oxidation was studied in a supercritical pressure jet-stirred reactor. It was found that the onset temperature of methanol oxidation at 100 atm is lower than that at 10 atm and a negative temperature coefficient (NTC) behavior was observed at fuel-rich conditions. The kinetics models failed to predict these trends accurately. By updating elementary reaction rates and adding new reaction pathways, the model improved but discrepancies still exist.