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Title: High-pressure oxidation of ethane

Abstract

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 C 2H 5O 2 potential energy surface were adopted from the recent theoretical work of Klippenstein. In the present work, the internal H-abstraction in CH 3CH 2OO to form CH 2CH 2OOH 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 C 2H 5 + O 2 reaction yields ethylperoxyl rather than C 2H 4 + HO 2, the chainmore » branching sequence CH 3CH 2OO → CH 2CH 2OOH → +O2 OOCH 2CH 2OOH → branching is not competitive, because the internal H-atom transfer in CH 3CH 2OO to CH 2CH 2OOH is too slow compared to thermal dissociation to C 2H 4 and HO 2.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [2];  [2];  [3];  [4]
  1. Technical Univ. of Denmark, Lyngby (Denmark)
  2. DNV-GL Oil & Gas, Groningen (The Netherlands)
  3. DNV-GL Oil & Gas, Groningen (The Netherlands); Univ. of Groningen, Groningen (The Netherlands)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
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; USDOE
OSTI Identifier:
1373395
Alternate Identifier(s):
OSTI ID: 1396740
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Combustion and Flame
Additional Journal Information:
Journal Volume: 182; Journal Issue: C; Journal ID: ISSN 0010-2180
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ethane; high pressure; ignition; reaction kinetics

Citation Formats

Hashemi, Hamid, Jacobsen, Jon G., Rasmussen, Christian T., Christensen, Jakob M., Glarborg, Peter, Gersen, Sander, van Essen, Martijn, Levinsky, Howard B., and Klippenstein, Stephen J.. High-pressure oxidation of ethane. United States: N. p., 2017. Web. doi:10.1016/j.combustflame.2017.03.028.
Hashemi, Hamid, Jacobsen, Jon G., Rasmussen, Christian T., Christensen, Jakob M., Glarborg, Peter, Gersen, Sander, van Essen, Martijn, Levinsky, Howard B., & Klippenstein, Stephen J.. High-pressure oxidation of ethane. United States. doi:10.1016/j.combustflame.2017.03.028.
Hashemi, Hamid, Jacobsen, Jon G., Rasmussen, Christian T., Christensen, Jakob M., Glarborg, Peter, Gersen, Sander, van Essen, Martijn, Levinsky, Howard B., and Klippenstein, Stephen J.. Tue . "High-pressure oxidation of ethane". United States. doi:10.1016/j.combustflame.2017.03.028. https://www.osti.gov/servlets/purl/1373395.
@article{osti_1373395,
title = {High-pressure oxidation of ethane},
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.},
abstractNote = {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},
journal = {Combustion and Flame},
number = C,
volume = 182,
place = {United States},
year = {Tue May 02 00:00:00 EDT 2017},
month = {Tue May 02 00:00:00 EDT 2017}
}

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