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Title: Oxidation and pyrolysis of methyl propyl ether

Abstract

Abstract 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 decompositionmore » and addition to 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.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1];  [4]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Univ. of Central Florida, Orlando, FL (United States). Center for Advanced Turbomachinery and Energy Research (CATER)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE
OSTI Identifier:
1837033
Alternate Identifier(s):
OSTI ID: 1786618
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
International Journal of Chemical Kinetics
Additional Journal Information:
Journal Volume: 53; Journal Issue: 8; Journal ID: ISSN 0538-8066
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; automatic mechanism generation; combustion; flow tube; ignition quality tester; methyl propyl ether; pyrolysis; rapid compression machine; shock tube

Citation Formats

Johnson, Matthew S., Nimlos, Mark R., Ninnemann, Erik, Laich, Andrew, Fioroni, Gina M., Kang, Dongil, Bu, Lintao, Ranasinghe, Duminda, Khanniche, Sarah, Goldsborough, S. Scott, Vasu, Subith S., and Green, William H. Oxidation and pyrolysis of methyl propyl ether. United States: N. p., 2021. Web. doi:10.1002/kin.21489.
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Johnson, Matthew S., Nimlos, Mark R., Ninnemann, Erik, Laich, Andrew, Fioroni, Gina M., Kang, Dongil, Bu, Lintao, Ranasinghe, Duminda, Khanniche, Sarah, Goldsborough, S. Scott, Vasu, Subith S., & Green, William H. Oxidation and pyrolysis of methyl propyl ether. United States. https://doi.org/10.1002/kin.21489
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Johnson, Matthew S., Nimlos, Mark R., Ninnemann, Erik, Laich, Andrew, Fioroni, Gina M., Kang, Dongil, Bu, Lintao, Ranasinghe, Duminda, Khanniche, Sarah, Goldsborough, S. Scott, Vasu, Subith S., and Green, William H. Mon . "Oxidation and pyrolysis of methyl propyl ether". United States. https://doi.org/10.1002/kin.21489. https://www.osti.gov/servlets/purl/1837033.
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@article{osti_1837033,
title = {Oxidation and pyrolysis of methyl propyl ether},
author = {Johnson, Matthew S. and Nimlos, Mark R. 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 Vasu, Subith S. and Green, William H.},
abstractNote = {Abstract 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 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},
journal = {International Journal of Chemical Kinetics},
number = 8,
volume = 53,
place = {United States},
year = {Mon May 17 00:00:00 EDT 2021},
month = {Mon May 17 00:00:00 EDT 2021}
}
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