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Title: An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures

Abstract

The oxidation of syngas mixtures was investigated experimentally and simulated with an updated chemical kinetic model. Ignition delay times for H2/CO/O2/N2/Ar mixtures have been measured using two rapid compression machines and shock tubes at pressures from 1 to 70 bar, over a temperature range of 914–2220 K and at equivalence ratios from 0.1 to 4.0. Results show a strong dependence of ignition times on temperature and pressure at the end of the compression; ignition delays decrease with increasing temperature, pressure, and equivalence ratio. The reactivity of the syngas mixtures was found to be governed by hydrogen chemistry for CO concentrations lower than 50% in the fuel mixture. For higher CO concentrations, an inhibiting effect of CO was observed. Flame speeds were measured in helium for syngas mixtures with a high CO content and at elevated pressures of 5 and 10 atm using the spherically expanding flame method. A detailed chemical kinetic mechanism for hydrogen and H2/CO (syngas) mixtures has been updated, rate constants have been adjusted to reflect new experimental information obtained at high pressures and new rate constant values recently published in the literature. Experimental results for ignition delay times and flame speeds have been compared with predictions usingmore » our newly revised chemical kinetic mechanism, and good agreement was observed. In the mechanism validation, particular emphasis is placed on predicting experimental data at high pressures (up to 70 bar) and intermediate- to high-temperature conditions, particularly important for applications in internal combustion engines and gas turbines. The reaction sequence H2 + HO˙2 ↔ H˙+H2O2 followed by H2O2(+M) ↔ O˙H+O˙H(+M) was found to play a key role in hydrogen ignition under high-pressure and intermediate-temperature conditions. The rate constant for H2+HO˙2 showed strong sensitivity to high-pressure ignition times and has considerable uncertainty, based on literature values. As a result, a rate constant for this reaction is recommended based on available literature values and on our mechanism validation.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [3];  [4];  [4];  [4];  [5];  [5];  [5];  [6];  [1]
  1. National Univ. of Ireland, Galway (Ireland)
  2. Case Western Reserve Univ., Cleveland, OH (United States); Univ. of Connecticut, Storrs, CT (United States)
  3. Univ. of Connecticut, Storrs, CT (United States)
  4. German Aerospace Center (DLR), Stuttgart (Germany)
  5. Texas A & M Univ., College Station, TX (United States)
  6. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1342998
Report Number(s):
LLNL-JRNL-588374
Journal ID: ISSN 0010-2180
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Combustion and Flame
Additional Journal Information:
Journal Volume: 160; Journal Issue: 6; Journal ID: ISSN 0010-2180
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; hydrogen; syngas; kinetic mechanism; ignition delay times; flame speed

Citation Formats

Keromnes, Alan, Metcalfe, Wayne K., Heufer, Karl A., Donohoe, Nicola, Das, Apurba K., Sung, Chih -Jen, Herzler, Jurgen, Naumann, Clemens, Griebel, Peter, Mathieu, Olivier, Krejci, Michael C., Petersen, Eric L., Pitz, William J., and Curran, Henry J. An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures. United States: N. p., 2013. Web. doi:10.1016/j.combustflame.2013.01.001.
Keromnes, Alan, Metcalfe, Wayne K., Heufer, Karl A., Donohoe, Nicola, Das, Apurba K., Sung, Chih -Jen, Herzler, Jurgen, Naumann, Clemens, Griebel, Peter, Mathieu, Olivier, Krejci, Michael C., Petersen, Eric L., Pitz, William J., & Curran, Henry J. An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures. United States. doi:10.1016/j.combustflame.2013.01.001.
Keromnes, Alan, Metcalfe, Wayne K., Heufer, Karl A., Donohoe, Nicola, Das, Apurba K., Sung, Chih -Jen, Herzler, Jurgen, Naumann, Clemens, Griebel, Peter, Mathieu, Olivier, Krejci, Michael C., Petersen, Eric L., Pitz, William J., and Curran, Henry J. Tue . "An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures". United States. doi:10.1016/j.combustflame.2013.01.001. https://www.osti.gov/servlets/purl/1342998.
@article{osti_1342998,
title = {An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures},
author = {Keromnes, Alan and Metcalfe, Wayne K. and Heufer, Karl A. and Donohoe, Nicola and Das, Apurba K. and Sung, Chih -Jen and Herzler, Jurgen and Naumann, Clemens and Griebel, Peter and Mathieu, Olivier and Krejci, Michael C. and Petersen, Eric L. and Pitz, William J. and Curran, Henry J.},
abstractNote = {The oxidation of syngas mixtures was investigated experimentally and simulated with an updated chemical kinetic model. Ignition delay times for H2/CO/O2/N2/Ar mixtures have been measured using two rapid compression machines and shock tubes at pressures from 1 to 70 bar, over a temperature range of 914–2220 K and at equivalence ratios from 0.1 to 4.0. Results show a strong dependence of ignition times on temperature and pressure at the end of the compression; ignition delays decrease with increasing temperature, pressure, and equivalence ratio. The reactivity of the syngas mixtures was found to be governed by hydrogen chemistry for CO concentrations lower than 50% in the fuel mixture. For higher CO concentrations, an inhibiting effect of CO was observed. Flame speeds were measured in helium for syngas mixtures with a high CO content and at elevated pressures of 5 and 10 atm using the spherically expanding flame method. A detailed chemical kinetic mechanism for hydrogen and H2/CO (syngas) mixtures has been updated, rate constants have been adjusted to reflect new experimental information obtained at high pressures and new rate constant values recently published in the literature. Experimental results for ignition delay times and flame speeds have been compared with predictions using our newly revised chemical kinetic mechanism, and good agreement was observed. In the mechanism validation, particular emphasis is placed on predicting experimental data at high pressures (up to 70 bar) and intermediate- to high-temperature conditions, particularly important for applications in internal combustion engines and gas turbines. The reaction sequence H2 + HO˙2 ↔ H˙+H2O2 followed by H2O2(+M) ↔ O˙H+O˙H(+M) was found to play a key role in hydrogen ignition under high-pressure and intermediate-temperature conditions. The rate constant for H2+HO˙2 showed strong sensitivity to high-pressure ignition times and has considerable uncertainty, based on literature values. As a result, a rate constant for this reaction is recommended based on available literature values and on our mechanism validation.},
doi = {10.1016/j.combustflame.2013.01.001},
journal = {Combustion and Flame},
number = 6,
volume = 160,
place = {United States},
year = {2013},
month = {3}
}

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