The rate-controlled constrained-equilibrium method (RCCE) has been further developed to model the combustion process of ethanol air mixtures. The RCCE is a reduction technique based on local maximization of entropy or minimization of a relevant free energy at any time during the nonequilibrium evolution of the system subject to a set of kinetic constraints. An important part of RCCE calculation is determination of a set of constraints that can guide the nonequilibrium mixture to the final stable equilibrium state. In this study, 16 constraints have been developed to model the nonequilibrium ethanol combustion process. The method requires solution of 16 differential equations for the corresponding constraint potentials. Ignition delay calculations of ethanol oxidizer mixtures using RCCE have been compared to those of detailed chemical kinetics using 37 species and 235 reactions. Agreement between the two models is very good. In addition, ignition delay of C2H5OH/O2/Ar mixtures using RCCE has been compared with the experimental measurements in the shock tube and excellent agreement has been reached validating the RCCE calculation.
Issue Section:
Fuel Combustion
Keywords:
Fuel combustion
Topics:
Combustion,
Equilibrium (Physics),
Ethanol,
Fuels,
Ignition delay,
Modeling,
Shock tubes,
Temperature,
Water,
Pressure
References
1.
Nicolas
, G.
, Janbozorgi
, M.
, and Metghalchi
, H.
, 2014
, “Constrained-Equilibrium Modeling of Methane Oxidation in Air
,” ASME J. Energy Resour. Technol.
, 136
(3
), p. 032205
.2.
Keck
, J. C.
, and Gillespie
, D.
, 1971
, “Rate-Controlled Partial-Equilibrium Method for Treating Reacting Gas Mixtures
,” Combust. Flame
, 17
(2
), pp. 237
–241
.3.
Keck
, J. C.
, 1990
, “Rate-Controled Constrained-Equilbrium Theory of Chemical Reactions in Complex Systems
,” Prog. Energy Combust. Sci.
, 16
(2
), pp. 125
–154
.4.
Janbozorgi
, M.
, Ugarte
, S.
, Metghalchi
, M.
, and Keck
, J. C.
, 2009
, “Combustion Modeling of Mono-Carbon Fuels Using the Rate-Controlled Constrained-Equilibrium Method
,” Combust. Flame
, 156
(10
), pp. 1871
–1885
.5.
Law
, R.
, Metghalchi
, M.
, and Keck
, J. C.
, 1989
, “Rate-Controlled Constrained Equilibrium Calculation of Ignition Delay Times in Hydrogen-Oxygen Mixtures
,” Symp. (Int.) Combust.
, 22
(1
), pp. 1705
–1713
.6.
Bishnu
, P.
, Hamiroune
, D.
, Metghalchi
, M.
, and Keck
, J. C.
, 1997
, “Constrained-Equilibrium Calculations for Chemical Systems Subject to Generalized Linear Constraints Using the NASA and STANJAN Equilibrium Programs
,” Combust. Theory Model.
, 1
(3
), pp. 295
–312
.7.
Hamiroune
, D.
, Bishnu
, P.
, Metghalchi
, M.
, and Keck
, J. C.
, 1998
, “Rate-Controlled Constrained-Equilibrium Method Using Constraint Potentials
,” Combust. Theory Model.
, 2
(1
), pp. 81
–94
.8.
Ugarte
, S.
, Gao
, Y.
, and Metghalchi
, M.
, 2005
, “Application of the Maximum Entropy Principle in the Analysis of a Non-Equilibrium Chemically Reacting Mixture
,” Int. J. Thermodyn.
, 8
(1
), pp. 43
–53
.9.
Janbozorgi
, M.
, Gao
, Y.
, Metghalchi
, M.
, and Keck
, J. C.
, 2006
, “Rate-Controlled Constrained-Equilibrium Calculations of Ethanol-Oxygen Mixture
,” ASME
Paper No. IMECE2006-15667.10.
Nicolas
, G.
, 2012
, “The Rate-Controlled Constrained-Equilibrium Modeling of C1–C2/O2/Diluent Mixtures
,” Ph.D. thesis, Department of Mechanical and Industrial Engineering, Northeastern University, Boston, MA.11.
Bishnu
, P. S.
, Hamiroune
, D.
, and Metghalchi
, M.
, 2001
, “Development of Constrained Equilibrium Codes and Their Applications in Non-Equilibrium Thermodynamics
,” ASME J. Energy Resour. Technol.
, 123
(3
), pp. 214
–220
.12.
Janbozorgi
, M.
, and Metghalchi
, M.
, 2009
, “Rate-Controlled Constrained-Equilibrium Theory Applied to Expansion of Combustion Products in the Power Stroke of an Internal Combustion Engine
,” Int. J. Thermodyn.
, 12
(1
), pp. 44
–50
.13.
Beretta
, G. P.
, Keck
, J. C.
, Janbozorgi
, M.
, and Metghalchi
, M.
, 2012
, “The Rate-Controlled Constrained-Equilibrium Approach to Far-From-Local Equilibrium Thermodynamics
,” Entropy
, 14
(2
), pp. 92
–130
.14.
Janbozorgi
, M.
, and Metghalchi
, M.
, 2012
, “Rate-Controlled Constrained-Equilibrium Modeling of H/O Reacting Nozzle Flow
,” AIAA J. Propul. Power
, 28
(4
), pp. 677
–684
.15.
Nicolas
, G.
, and Metghalchi
, M.
, 2015
, “Comparison Between RCCE and Shock Tube Ignition Delay Time at Low Temperatures
,” ASME J. Energy Resour. Technol.
, 137
(6
), p. 062203
.16.
Janbozorgi
, M.
, Sheikhi
, M. R.
, and Metghalchi
, M.
, 2013
, “Principle of Detailed Balance and the Second Law of Thermodynamics in Chemical Kinetics
,” ASME J. Energy Resour. Technol.
, 135
(4
), p. 041901
.17.
Li
, J.
, 2004
, “Experimental and Numerical Studies of Ethanol Chemical Kinetics
,” Ph.D. thesis, Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ, p. MAE 3122-T.18.
Smith
, S. R.
, Gordon Smith
, S. R.
, and Gordon
, A. S.
, 1956
, “Studies of Diffusion Flames. II. Diffusion Flames of Some Simple Alcohols
,” J. Phys. Chem.
, 60
(8
), pp. 1059
–1062
.19.
Lieb
, D. F.
, and Roblee
, L. H. S.
, Jr., 1970
, “Radioisotopic Tracer Study of Carbon Formation in Ethanol/Air Diffusion Flames
,” Combust. Flame
, 14
(3
), pp. 285
–296
.20.
Bansal
, K. M.
, and Freeman
, G. R.
, 1968
, “Free-Radical Chain Reactions in Radiation-Sensitized Pyrolysis of Ethanol Vapor
,” J. Am. Chem. Soc.
, 90
(26
), pp. 7190
–7196
.21.
Brown
, J.
, and Tipper
, C. F. H.
, 1969
, “Cool Flame Combustion of Ethanol
,” Proc. R. Soc. London, Ser. A
, 312
(1510
), pp. 399
–407
.22.
Borisov
, A. A.
, Zamanskii
, V. M.
, Konnov
, A. A.
, Lisyanskii
, V. V.
, Rusakov
, S. A.
, and Skachkov
, G. I.
, 1992
, “High-Temperature Ethanol Ignition
,” Soviet J. Chem. Phys.
, 9
, pp. 2527
–2537
.23.
Natarajan
, K.
, and Bhaskaran
, K. A.
, 1981
, “An Experimental and Analytical Investigation of High Temperature Ignition of Ethanol. Shock Tube And Waves
,” 13th International Symposium on Shock Waves
, Niagara Falls, NY, July 6–9, pp. 834
–842
.24.
Curran
, H. J.
, Dunphy
, M. P.
, Simmie
, J. M.
, Westbrook
, C. K.
, and Pitz
, W. J.
, 1992
, “Shock Tube Ignition of Ethanol, Isobutene and MTBE: Experiments and Modeling
,” Proc. Combust. Inst.
, 24
(1
), pp. 769
–776
.25.
Dunphy
, M.
, and Simmie
, J.
, 1991
, “High-Temperature Oxidation of Ethanol. Part 1—Ignition Delays in Shock Waves
,” J. Chem. Soc. Faraday Trans.
, 87
(11
), pp. 1691
–1696
.26.
Norton
, T. S.
, and Dryer
, F. L.
, 1992
, “An Experimental and Modeling Study of Ethanol Oxidation Kinetics in an Atmospheric Pressure Flow Reactor
,” Int. J. Chem. Kinetics
, 24
(4
), pp. 319
–344
.27.
Egolfopoulos
, F. N.
, Du
, D. X.
, and Law
, C. K.
, 1992
, “A Study on Ethanol Oxidation Kinetics in Laminar Premixed Flames, Flow Reactors, and Shock Tubes
,” Symp. (Int.) Combust.
, 24
(1
), pp. 833
–841
.28.
Li
, J.
, Zhao
, Z.
, Kazakov
, A.
, Chaos
, M.
, and Dryer
, F. L.
, 2007
, “A Comprehensive Kinetic Mechanism for CO, CH2O, CH3OH Combustion
,” Int. J. Chem. Kinetics
, 39
(3
), pp. 109
–136
.29.
Li
, J.
, Kazakov
, A.
, Chaos
, M.
, and Dryer
, F. L.
, 2007
, “Chemical Kinetics of Ethanol Oxidation
,” 5th U.S. Combustion Meeting
, San Diego, CA, Mar. 25–28, Paper No. C-26.30.
Li
, J.
, Zhao
, Z.
, Kazakov
, A.
, and Dryer
, F. L.
, 2004
, “An Updated Comprehensive Kinetic Model of Hydrogen Combustion
,” Int. J. Chem. Kinetics
, 36
(10
), pp. 566
–575
.31.
Held
, T. J.
, 1993
, “The Oxidation of Methanol, Isobutene and Methyl Tertiary-Butyl Ether
,” Ph.D. thesis, Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ.32.
Wang
, H.
, Laskin
, A.
, Djurisic
, Z. M.
, Law
, C. K.
, Davis
, S. G.
, and Zhu
, D. L.
, 1999
, “A Comprehensive Mechanism of C2Hx and C3Hx Fuel Combustion
,” Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Raleigh, NC, Oct. 10–13, pp. 129
–132
.33.
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.
, and Qin
, Z.
, “Overview of GRI-Mech
,” Gas Research Institute, Chicago, IL, http://www.me.berkeley.edu/gri_mech/34.
Marinov
, N. M.
, 1999
, “A Detailed Chemical Kinetic Model for High Temperature Ethanol Oxidation
,” Int. J. Chem. Kinetics
, 31
(3
), pp. 183
–220
.35.
Kee
, R. J.
, Rupley
, F. M.
, and Miller
, J. A.
, 1987
, “The Chemkin Thermodynamic Data Base
,” Sandia National Laboratories, Albuquerque, NM, Report No. SAND87-8215.36.
Burcat
, A.
, 2007
, “Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion
,” online database, http://burcat.technion.ac.il/dir/37.
Ruscic
, B.
, Pinzon
, R. E.
, Morton
, M. L.
, Srinivasan
, N. K.
, Su
, M.-C.
, Sutherland
, J. W.
, and Michael
, J. V.
, 2006
, “Active Thermochemical Tables: Accurate Enthalpy of Formation of Hydroperoxyl Radical, HO2
,” J. Phys. Chem., A
, 110
(21
), pp. 6592
–6601
.38.
Li
, J.
, Kazakov
, A.
, and Dryer
, F. L.
, 2001
, “Ethanol Pyrolysis Experiments in a Variable Pressure Flow Reactor
,” Int. J. Chem. Kinetics
, 33
(12
), pp. 859
–867
.39.
Li
, J.
, Kazakov
, A.
, and Dryer
, F. L.
, 2004
, “Experimental and Numerical Studies of Ethanol Decomposition Reactions
,” J. Phys. Chem. A
, 108
(38
), pp. 7671
–7680
.40.
Haas
, F. M.
, Chaos
, M.
, and Dryer
, F. L.
, 2009
, “Low and Intermediate Temperature Oxidation of Ethanol and Ethanol–PRF Blends: An Experimental and Modeling Study
,” Combust. Flame
, 156
(12
), pp. 2346
–2350
.41.
Dunphy
, M. P.
, Patterson
, P. M.
, and Simmie
, J. M.
, 1991
, “High-Temperature Oxidation of Ethanol. Part II Kinetic Modeling
,” J. Chem. Soc. Faraday Trans.
, 87
(16
), pp. 2549
–2559
.42.
Reynolds
, W. C.
, 1986
, STANJAN Program, Stanford University, Stanford, CA, ME270, HO#7.43.
Wang
, B. L.
, Olivier
, H.
, and Gronig
, H.
, 2003
, “Ignition of Shock-Heated H2-Air-Steam Mixtures
,” Combust. Flame
, 133
, pp. 93
–106
.44.
Yu
, C. L.
, Frenklach
, M.
, Masten
, D. A.
, Hanson
, R. K.
, and Bowman
, C. T.
, 1994
, “Reexamination of Shock-Tube Measurements of the Rate Coefficient of H + O2 → OH + O
,” J. Phys. Chem.
, 98
(17
), pp. 4770
–4771
.Copyright © 2016 by ASME
You do not currently have access to this content.
