Methane and ethane are the two main components of natural gas and typically constitute more than 95% of it. In this study, a mixture of 90% CH4/10% C2H6 diluted in 99% Ar was studied at fuel lean (equiv. ratio = 0.5) conditions, for pressures around 1, 4, and 10 atm. Using laser absorption diagnostics, the time histories of CO and H2O were recorded between 1400 and 1800 K. Water is a final product from combustion, and its formation is a good marker of the completion of the combustion process. Carbon monoxide is an intermediate combustion species, a good marker of incomplete/inefficient combustion, as well as a regulated pollutant for the gas turbine industry. Measurements such as these species time histories are important for validating and assessing chemical kinetics models beyond just ignition delay times and laminar flame speeds. Time-history profiles for these two molecules were compared to a state-of-the-art detailed kinetics mechanism as well as to the well-established GRI 3.0 mechanism. Results show that the H2O profile is accurately reproduced by both models. However, discrepancies are observed for the CO profiles. Under the conditions of this study, the CO profiles typically increase rapidly after an induction time, reach a maximum, and then decrease. This maximum CO mole fraction is often largely over-predicted by the models, whereas the depletion rate of CO past this peak is often over-estimated for pressures above 1 atm.
Issue Section:
Gas Turbines: Combustion, Fuels, and Emissions
References
References
1.
de Vries
, J.
Petersen
, E. L.
2007
, “Autoignition of Methane-Based Fuel Blends Under Gas Turbine Conditions
,” Proc. Combust. Inst.
, 31
(2
), pp. 3163
–3171
.2.
Petersen
, E. L.
Hall
, J. M.
Smith
, S. D.
de Vries
, J.
Amadio
, A. R.
Crofton
, M. W.
2007
, “Ignition of Lean Methane-Based Fuel Blends at Gas Turbine Pressures
,” ASME J. Eng. Gas Turbines Power
, 129
(4
), pp. 937
–944
.3.
Cooke
, D. F.
Alan Williams
, A.
1975
, “Shock Tube Studies of Methane and Ethane Oxidation
,” Combust. Flame
, 24
, pp. 245
–256
.4.
Spadaccini
, L. J.
Colket
, M. B.
1994
, “Ignition Delay Characteristics of Methane Fuels
,” Prog. Energy Combust. Sci.
, 20
(5
), pp. 431
–460
.5.
Lamoureux
, N.
Paillard
, C.-E.
2003
, “Natural Gas Ignition Delay Times Behind Reflected Shock Waves: Application to Modelling and Safety
,” Shock Waves
, 13
(1
), pp. 57
–68
.6.
Herzler
, J.
Naumann
, C.
2009
, “Shock-Tube Study of the Ignition of Methane/Ethane/Hydrogen Mixtures With Hydrogen Contents From 0% to 100% at Different Pressures
,” Proc. Combust. Inst.
, 32
(1
), pp. 213
–220
.7.
Aul
, C. J.
Metcalfe
, W. K.
Burke
, S. M.
Curran
, H. J.
Petersen
, E. L.
2013
, “Ignition and Kinetic Modeling of Methane and Ethane Fuel Blends With Oxygen: A Design of Experiments Approach
,” Combust. Flame
, 160
(7
), pp. 1153
–1167
.8.
Ravi
, S.
Sikes
, T. G.
Morones
, A.
Keesee
, C. L.
Petersen
, E. L.
2015
, “Comparative Study on the Laminar Flame Speed Enhancement of Methane With Ethane and Ethylene Addition
,” Proc. Combust. Inst.
, 35
(1
), pp. 679
–686
.9.
Sivaramakrishnan
, R.
Brezinsky
, K.
Dayma
, G.
Dagaut
, P.
2007
, “High Pressure Effects on the Mutual Sensitization of the Oxidation of NO and CH4–C2H6 Blends
,” Phys. Chem. Chem. Phys.
, 9
(31
), pp. 4230
–4244
.10.
Rasmussen
, C. L.
Jakobsen
, J. G.
Glarborg
, P.
2008
, “Experimental Measurements and Kinetic Modeling of CH4/O2+- and CH4/C2H6/O2 Conversion at High Pressure
,” Int. J. Chem. Kinet.
, 40
(12
), pp. 778
–807
.11.
Mathieu
, O.
Mulvihill
, C.
Petersen
, E. L.
2017
, “Assessment of Modern Detailed Kinetics Mechanisms to Predict CO Formation From Methane Combustion Using Shock Tube/Laser Absorption Measurements
,” Fuel, in press.12.
Petersen
, E. L.
Rickard
, M. J. A.
Crofton
, M. W.
Abbey
, E. D.
Traum
, M. J.
Kalitan
, D. M.
2005
, “A Facility for Gas-and Condensed-Phase Measurements Behind Shock Waves
,” Meas. Sci. Technol.
16
(9
), pp. 1716
–1729
.13.
Vivanco
, J. E.
2014
, “A New Shock-Tube Facility for the Study of High-Temperature Chemical Kinetics
,” Master's thesis, Texas A & M University, College Station, TX.14.
Rothman
, L. S.
Jacquemart
, D.
Barbe
, A.
Chris Benner
, D.
Birk
, M.
Brown
, L. R.
Carleer
, M. R.
Chackerian
, C.
, Jr.Chance
, K.
Coudert
, L. H.
Dana
, V.
2005
, “The HITRAN 2004 Molecular Spectroscopic Database
,” J. Quant. Spectrosc. Radiative Transfer
, 96
(2
), pp. 139
–204
.15.
Ren
, W.
Davidson
, D. F.
Hanson
, R. K.
Farooq
, A.
2012
, “CO Concentration and Temperature Sensor for Combustion Gases Using Quantum-Cascade Laser Absorption Near 4.7 μm
,” Appl. Phys. B: Lasers Opt.
, 107
(3
), pp. 1
–12
.16.
Li
, H.
Farooq
, A.
Jeffries
, J. B.
Hanson
, R. K.
2008
, “Diode Laser Measurements of Temperature-Dependent Collisional-Narrowing and Broadening Parameters of Ar-Perturbed H2O Transitions at 1391.7 and 1397.8 nm
,” J. Quant. Spectrosc. Radiative Transfer
, 109
(1
), pp. 132
–143
.17.
Mathieu
, O.
Mulvihill
, C.
Petersen
, E. L.
2017
, “Shock Tube Water Time-Histories and Ignition Delay Time Measurements for H2S Near Atmospheric Pressure
,” Proc. Combust. Inst.
36
(3
), pp. 4019
–4027
.18.
Reaction Design
, 2013
, “CHEMKIN-PRO 15131
,” Reaction Design, San Diego, CA.19.
Smith
, G. P.
Golden
, D. M.
Frenklach
, M.
Moriarty
, N. W.
Eiteneer
, B.
Goldenberg
, M.
Bowman
, C. T.
Hanson
, R. K.
Song
, S.
Gardiner
, W. C.
, Jr.Lissianski
, V. V.
Qin
, Z.
GRI-Mech
,” Gas Research Institute, Des Plaines, IL, accessed Aug. 19, 2017, http://www.me.berkeley.edu/gri_mech/20.
Kéromnès
, A.
Metcalfe
, W. K.
Heufer
, K. A.
Donohoe
, N.
Das
, A. K.
Sung
, C.-J.
Herzler
, J.
Naumann
, C.
Griebel
, P.
Mathieu
, O.
Krejci
, M. C.
Petersen
, E. L.
Pitz
, W. J.
Curran
, H. J.
2013
, “An Experimental and Detailed Chemical Kinetic Modeling Study of Hydrogen and Syngas Mixture Oxidation at Elevated Pressures
,” Combust. Flame
, 160
(6
), pp. 995
–1011
.21.
Metcalfe
, W. K.
Burke
, S. M.
Ahmed
, S. S.
Curran
, H. J.
2013
, “A Hierarchical and Comparative Kinetic Modeling Study of C1–C2 Hydrocarbon and Oxygenated Fuels
,” Int. J. Chem. Kinet.
, 45
(10
), pp. 638
–675
.22.
Burke
, S. M.
Burke
, U.
McDonagh
, R.
Mathieu
, O.
Osorio
, I.
Keesee
, C.
Morones
, A.
Petersen
, E. L.
Wang
, W.
DeVerter
, T. A.
Oehlschlaeger
, M. A.
Rhodes
, B.
Hanson
, R. K.
Davidson
, D. F.
Weber
, B. W.
Sung
, C.-J.
Santner
, J.
Ju
, Y.
Haas
, F. M.
Dryer
, F. L.
Volkov
, E. N.
Nilsson
, E. J. K.
Konnov
, A. A.
Alrefae
, M.
Khaled
, F.
Farooq
, A.
Dirrenberger
, P.
Glaude
, P.-A.
Battin-Leclerc
, F.
Curran
, H. J.
2015
, “An Experimental and Modeling Study of Propene Oxidation. Part 2: Ignition Delay Time and Flame Speed Measurements
,” Combust. Flame
, 162
(2
), pp. 296
–314
.23.
Burke
, S. M.
Metcalfe
, W.
Herbinet
, O.
Battin-Leclerc
, F.
Haas
, F. M.
Santner
, J.
Dryer
, F. L.
Curran
, H. J.
2014
, “An Experimental and Modeling Study of Propene Oxidation—Part 1: Speciation Measurements in Jet-Stirred and Flow Reactors
,” Combust. Flame
, 161
(11
), pp. 2765
–2784
.24.
Li
, Y.
Zhou
, C.-W.
Somers
, K. P.
Zhang
, K.
Curran
, H. J.
2017
, “The Oxidation of 2-Butene: A High Pressure Ignition Delay, Kinetic Modeling Study and Reactivity Comparison With Isobutene and 1-Butene
,” Proc. Combust. Inst.
, 36
(1
), pp. 403
–411
.25.
Zhou
, C.-W.
Li
, Y.
O'Connor
, E.
Somers
, K. P.
Thion
, S.
Keesee
, C.
Mathieu
, O.
Petersen
, E. L.
DeVerter
, T. A.
Oehlschlaeger
, M. A.
Kukkadapu
, G.
Sung
, C.-J.
Alrefae
, M.
Khaled
, F.
Farooq
, A.
Dirrenberger
, P.
Glaude
, P.-A.
Battin-Leclerc
, F.
Santner
, J.
Ju
, Y.
Held
, T.
Haas
, F. M.
Dryer
, F. L.
Curran
, H. J.
2016
, “A Comprehensive Experimental and Modeling Study of Isobutene Oxidation
,” Combust. Flame
, 167
, pp. 353
–379
.26.
Nilsson
, E. J. K.
Konnov
, A. A.
2016
, “Role of HOCO Chemistry in Syngas Combustion
,” Energy Fuels
, 30
(3
), pp. 2443
–2457
.27.
Weston
, R. E.
, Jr.Nguyen
, T. L.
Stanton
, J. F.
Barker
, J. R.
2013
, “O + CO Reaction Rates and H/D Kinetic Isotope Effects: Master Equation Models With Ab Initio SCTST Rate Constants
,” J. Phys. Chem. A
, 117
(5
), pp. 821
–835
.28.
Nguyen
, T. L.
Xue
, B. C.
Weston
, R. E.
, Jr.Barker
, J. R.
Stanton
, J. F.
2012
, “Reaction of HO With CO: Tunneling is Indeed Important
,” J. Phys. Chem. Lett.
, 3
(11
), pp. 1549
–1553
.29.
Yu
, H.-G.
Muckerman
, J. T.
2006
, “Quantum Molecular Dynamics Study of the Reaction of O2 With HOCO
,” J. Phys. Chem. A
, 110
(16
), pp. 5312
–5316
.30.
Yu
, H.-G.
Muckerman
, J. T.
Francisco
, J. S.
2005
, “Direct Ab Initio Dynamics Study of the OH + HOCO Reaction
,” J. Phys. Chem. A
, 109
(23
), pp. 5230
–5236
.31.
Yu
, H.-G.
Poggi
, G.
Francisco
, J. S.
Muckerman
, J. T.
2008
, “Energetics and Molecular Dynamics of the Reaction of HOCO With HO2 Radicals
,” J. Chem. Phys.
, 129
(21
), p. 214307
.32.
Yu
, H.-G.
Francisco
, J. S.
2008
, “Energetics and Kinetics of the Reaction of HOCO With Hydrogen Atoms
,” J. Chem. Phys.
, 128
(24
), p. 244315
.33.
Yu
, H.-G.
Muckerman
, J. T.
Francisco
, J. S.
2007
, “Quantum Force Molecular Dynamics Study of the Reaction of O Atoms With HOCO
,” J. Chem. Phys.
, 127
(9
), p. 094302
.34.
Yu
, H.-G.
Francisco
, J. S.
2009
, “Theoretical Study of the Reaction of CH3 With HOCO Radicals
,” J. Phys. Chem. A
, 113
(16
), pp. 3844
–3849
.35.
Petersen
, E. L.
1998
, “A Shock Tube and Diagnostics for Chemistry Measurements at Elevated Pressures With Application to Methane Ignition
,” Ph.D. thesis, Stanford University, Stanford, CA.36.
Li
, J.
Zhao
, Z. W.
Kazakov
, A.
Chaos
, M.
Dryer
, F. L.
Scire
, J. J.
2007
, “A Comprehensive Kinetic Mechanism for CO, CH2O, and CH3OH Combustion
,” Int. J. Chem. Kinet.
39
(3
), pp. 109
–136
.37.
Krasnoperov
, L. N.
Chesnokov
, E. N.
Stark
, H.
Ravishankara
, A. R.
2004
, “Unimolecular Dissociation of Formyl Radical, HCO → H + CO, Studied Over 1-100 Bar Pressure Range
,” J. Phys. Chem. A
, 108
(52
), pp. 11526
–11536
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