Here, ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate constants for reactions on the C2H5O2 potential energy surface were adopted from the recent theoretical work of Klippenstein. In the present work, the internal H-abstraction in CH3CH2OO to form CH2CH2OOH was treated in detail. Modeling predictions were in good agreement with data from the present work as well as results at elevated pressure from literature. The experimental results and the modeling predictions do not support occurrence of NTC behavior in ethane oxidation. Even at the high-pressure conditions of the present work where the C2H5 + O2 reaction yields ethylperoxyl rather than C2H4 + HO2, the chain branching sequence CH3CH2OO → CH2CH2OOH → +O2 OOCH2CH2OOH → branching is not competitive, because the internal H-atom transfer in CH3CH2OO to CH2CH2OOH is too slow compared to thermal dissociation to C2H4 and HO2.
Hashemi, Hamid, Jacobsen, Jon G., Rasmussen, Christian T., Christensen, Jakob M., Glarborg, Peter, Gersen, Sander, van Essen, Martijn, Levinsky, Howard B., & Klippenstein, Stephen J. (2017). High-pressure oxidation of ethane. Combustion and Flame, 182(C). https://doi.org/10.1016/j.combustflame.2017.03.028
Hashemi, Hamid, Jacobsen, Jon G., Rasmussen, Christian T., et al., "High-pressure oxidation of ethane," Combustion and Flame 182, no. C (2017), https://doi.org/10.1016/j.combustflame.2017.03.028
@article{osti_1373395,
author = {Hashemi, Hamid and Jacobsen, Jon G. and Rasmussen, Christian T. and Christensen, Jakob M. and Glarborg, Peter and Gersen, Sander and van Essen, Martijn and Levinsky, Howard B. and Klippenstein, Stephen J.},
title = {High-pressure oxidation of ethane},
annote = {Here, ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate constants for reactions on the C2H5O2 potential energy surface were adopted from the recent theoretical work of Klippenstein. In the present work, the internal H-abstraction in CH3CH2OO to form CH2CH2OOH was treated in detail. Modeling predictions were in good agreement with data from the present work as well as results at elevated pressure from literature. The experimental results and the modeling predictions do not support occurrence of NTC behavior in ethane oxidation. Even at the high-pressure conditions of the present work where the C2H5 + O2 reaction yields ethylperoxyl rather than C2H4 + HO2, the chain branching sequence CH3CH2OO → CH2CH2OOH → +O2 OOCH2CH2OOH → branching is not competitive, because the internal H-atom transfer in CH3CH2OO to CH2CH2OOH is too slow compared to thermal dissociation to C2H4 and HO2.},
doi = {10.1016/j.combustflame.2017.03.028},
url = {https://www.osti.gov/biblio/1373395},
journal = {Combustion and Flame},
issn = {ISSN 0010-2180},
number = {C},
volume = {182},
place = {United States},
publisher = {Elsevier},
year = {2017},
month = {05}}
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division; European Graduate School (EGS); MAN Diesel and Turbo; European Union - Horizon 2020 Research and Innovation Programme
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1373395
Alternate ID(s):
OSTI ID: 1396740
Journal Information:
Combustion and Flame, Journal Name: Combustion and Flame Journal Issue: C Vol. 182; ISSN 0010-2180