The ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1–20 bar 600–1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non-monotonic variation in conversion and product distribution is observed in the flow-tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to O2 at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.
Nimlos, Mark R., et al. "Oxidation and Pyrolysis of Methyl Propyl Ether." International Journal of Chemical Kinetics, vol. 53, no. 8, May. 2021. https://doi.org/10.1002/kin.21489
Nimlos, Mark R., Johnson, Matthew S., Ninnemann, Erik, Laich, Andrew, Fioroni, Gina M., Kang, Dongil, Bu, Lintao, Ranasinghe, Duminda, Khanniche, Sarah, Goldsborough, S. Scott, Vasu, Subith S., & Green, William H. (2021). Oxidation and Pyrolysis of Methyl Propyl Ether. International Journal of Chemical Kinetics, 53(8). https://doi.org/10.1002/kin.21489
Nimlos, Mark R., Johnson, Matthew S., Ninnemann, Erik, et al., "Oxidation and Pyrolysis of Methyl Propyl Ether," International Journal of Chemical Kinetics 53, no. 8 (2021), https://doi.org/10.1002/kin.21489
@article{osti_1785328,
author = {Nimlos, Mark R. and Johnson, Matthew S. and Ninnemann, Erik and Laich, Andrew and Fioroni, Gina M. and Kang, Dongil and Bu, Lintao and Ranasinghe, Duminda and Khanniche, Sarah and Goldsborough, S. Scott and others},
title = {Oxidation and Pyrolysis of Methyl Propyl Ether},
annote = {The ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1–20 bar 600–1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non-monotonic variation in conversion and product distribution is observed in the flow-tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to O2 at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.},
doi = {10.1002/kin.21489},
url = {https://www.osti.gov/biblio/1785328},
journal = {International Journal of Chemical Kinetics},
number = {8},
volume = {53},
place = {United States},
year = {2021},
month = {05}}
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); Co-Optimization of Fuels & Engines (Co-Optima) Project