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

Wang, Ziyu; Zhao, Hao; Yan, Chao; Lin, Ying; Lele, Aditya D.; Xu, Wenbin; Rotavera, Brandon; Jasper, Ahren W.; Klippenstein, Stephen J.; Ju, Yiguang

doi:10.1016/j.proci.2022.07.068

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

Journal Article · Wed Sep 07 00:00:00 EDT 2022 · Proceedings of the Combustion Institute

DOI:https://doi.org/10.1016/j.proci.2022.07.068· OSTI ID:2375487

^[1]; ^[1]; Yan, Chao ^[1]; ^[1]; ^[1]; Xu, Wenbin ^[1]; ^[2]; Jasper, Ahren W. ^[3]; Klippenstein, Stephen J. ^[3]; Ju, Yiguang ^[1]

Princeton Univ., NJ (United States)
Univ. of Georgia, Athens, GA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

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 equivalence ratios of 0.1, 1.0, and 9.0 in experiments and simulations. Here, 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 literature and added some new low-temperature reaction pathways such as CH₂O + HO₂ = HOCH₂O₂ (RO₂), RO₂ + RO₂ = HOCH₂O (RO) + HOCH₂O (RO) + O₂, 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 experiments, the NTC phenomenon was only observed at the fuel-rich condition where fuel radicals are abundant and the HO₂ chemistry at high pressure is weakened by the lack of oxygen resulting in comparatively little HO₂ formation.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); US Army Research Office (ARO)

Grant/Contract Number:: AC02-06CH11357; SC0021135

OSTI ID:: 2375487

Alternate ID(s):: OSTI ID: 1984158

Journal Information:: Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 39; ISSN 1540-7489

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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