Abstract
The numerical simulation of practical combustion devices such as engines and gas turbines requires the coupling of descriptions of complex physical flows with complex chemistry in order to accurately predict phenomena such as ignition and flame propagation. For three-dimensional simulations, this becomes computationally challenging where interactions between large numbers of chemical species are involved. Historically therefore, such simulations used highly simplified descriptions of chemistry, which limited the applicability of the models. More recently, however, a range of techniques for reducing the size of chemical schemes have been developed, where the resulting reduced schemes can be shown to have accuracies which are almost as good as much larger comprehensive mechanisms. Such techniques will be described in this chapter. Skeletal reduction techniques are first introduced which aim to identify redundant species and reactions within a mechanism over wide ranges of conditions. Approaches based on sensitivity analysis, optimization and direct relation graphs are introduced. Lumping techniques are then discussed which exploit similarities between the structure and reactivity of species in describing lumped components, which can represent the sum of several isomers of a particular hydrocarbon species for example. Both approaches can lead to a substantial reduction in the size of chemical mechanisms (numbers of species and reactions) without having a significant impact on model accuracy. They are combined in the chemistry-guided reduction approach, which is shown to generate reduced chemical schemes which are small enough be used within simulations of ignition behaviour in a homogeneous charge compression ignition (HCCI) engine.
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Ahmed SS, Mauss F, Zeuch T (2009) The generation of a compact n-heptane toluene reaction mechanism using the chemistry guided reduction (CGR) technique. Zeitschrift Fur Physikalische Chemie-Int J Res Phys Chem Chem Phys 223(4–5):551–563
Androulakis IP (2000) Kinetic mechanism reduction based on an integer programming approach. AIChE J 46:361–371
Banerjee I, Ierapetritou MG (2003) Development of an adaptive chemistry model considering micromixing effects. Chem Eng Sci 58(20):4537–4555
Banerjee I, Ierapetritou MG (2006) An adaptive reduction scheme to model reactive flow. Combust Flame 144:619–633
Battin-Leclerc F, Glaude PA, Warth V et al (2000) Computer tools for modelling the chemical phenomena related to combustion. Chem Eng Sci 55(15):2883–2893
Bhattacharjee B, Schwer DA, Barton PI et al (2003) Optimally-reduced kinetic models: reaction elimination in large-scale kinetic mechanisms. Combust Flame 135:191–208
Börger I, Merkel A, Lachmann J et al (1992) An extended kinetic model and its reduction by sensitivity analysis for the methanol/oxygen gas-phase thermolysis. Acta Chim Hung 129:855–864
Bounaceur R, Warth V, Glaude PA et al (1996) Chemical lumping of mechanisms generated by computer—application to the modeling of normal-butane oxidation. J Chim Phys Phys-Chim Biol 93:1472–1491
Edwards K, Edgar TF, Manousiouthakis VI (1998) Kinetic model reduction using genetic algorithms. Comp Chem Eng 22:239–246
Edwards K, Edgar TF, Manousiouthakis VI (2000) Reaction mechanism simplification using mixed-integer nonlinear programming. Comput Chem Eng 24(1):67–79
Elliott L, Ingham DB, Kyne AG et al (2004) Genetic algorithms for optimization of chemical kinetics reaction mechanisms. Prog Energy Combust Sci 30:297–328
Elliott L, Ingham DB, Kyne AG et al (2005) Reaction mechanism reduction and optimization using genetic algorithms. Ing Eng Chem Res 44(4):658–667
Fournet R, Warth V, Glaude PA et al (2000) Automatic reduction of detailed mechanisms of combustion of alkanes by chemical lumping. Int J Chem Kinet 32:36–51
Grana R, Frassoldati A, Cuoci A et al (2012a) A wide range kinetic modeling study of pyrolysis and oxidation of methyl butanoate and methyl decanoate. Note I: Lumped kinetic model of methyl butanoate and small methyl esters. Energy 43(1):124–139
Grana R, Frassoldati A, Saggese C et al (2012b) A wide range kinetic modeling study of pyrolysis and oxidation of methyl butanoate and methyl decanoate—note II: lumped kinetic model of decomposition and combustion of methyl esters up to methyl decanoate. Combust Flame 159(7):2280–2294
Granata S, Faravelli T, Ranzi E (2003) A wide range kinetic modeling study of the pyrolysis and combustion of naphthenes. Combust Flame 132(3):533–544
Gupta GK, Hecht ES, Zhu H et al (2006) Gas-phase reactions of methane and natural gas with air and steam in non-catalytic regions of a solid-oxide fuel cell. J Pow Sources 156:434–447
He KY, Androulakis IP, Ierapetritou MG (2010a) Incorporation of detailed chemical mechanisms in reactive flow simulations using element-flux analysis. Ing Eng Chem Res 49:10471–10478
He KY, Androulakis IP, Ierapetritou MG (2010b) Multi-element flux analysis for the incorporation of detailed kinetic mechanisms in reactive simulations. Energy Fuels 24:309–317
He KY, Androulakis IP, Ierapetritou MG (2010c) On-the-fly reduction of kinetic mechanisms using element flux analysis. Chem Eng Sci 65(3):1173–1184
He KY, Ierapetritou MG, Androulakis IP (2010d) Integration of on-the-fly kinetic reduction with multidimensional CFD. AIChE J 56(5):1305–1314
He KY, Androulakis IP, Ierapetritou MG (2011) Numerical investigation of homogeneous charge compression ignition (HCCI) combustion with detailed chemical kinetics using on-the-fly reduction. Energy Fuels 25(8):3369–3376
Huang H, Fairweather M, Griffiths JF et al (2005) A systematic lumping approach for the reduction of comprehensive kinetic models. Proc Combust Inst 30:1309–1316
Hughes KJ, Fairweather M, Griffiths JF et al (2009) The application of the QSSA via reaction lumping for the reduction of complex hydrocarbon oxidation mechanisms. Proc Combust Inst 32:543–551
Jiang Y, Qiu R (2009) Reduction of large kinetic mechanisms of hydrocarbon fuels with directed relation graph. Acta Phys Chim Sin 25(5):1019–1025
Kelley AP, Liu W, Xin YX et al (2011) Laminarflame speeds, non-premixed stagnation ignition, and reduced mechanisms in the oxidation of iso-octane. Proc Combust Inst 33:501–508
KINALC (2013) CHEMKIN based program for KInetic aNALysis. http://garfield.chem.elte.hu/Combustion/kinalc.htm
Li G, Rabitz H (1989) A general analysis of exact lumping in chemical kinetics. Chem Eng Sci 44(6):1413–1430
Li G, Tomlin AS, Rabitz H et al (1993) Determination of approximate lumping schemes by a singular perturbation method. J Chem Phys 99:3562–3574
Li G, Tomlin AS, Rabitz H et al (1994a) A general analysis of approximate nonlinear lumping in chemical kinetics. I. Unconstrained lumping. J Chem Phys 101:1172–1187
Li G, Tomlin AS, Rabitz H et al (1994b) A general analysis of approximate nonlinear lumping in chemical kinetics. II. Constrained lumping. J Chem Phys 101:1188–1201
Liang L, Stevens JG, Raman S et al (2009) The use of dynamic adaptive chemistry in combustion simulation of gasoline surrogate fuels. Combust Flame 156:1493–1502
Lu T, Law C (2006a) Linear time reduction of large kinetic mechanisms with directed relation graph: n-heptane and iso-octane. Combust Flame 144:24–36
Lu T, Law CK (2006b) On the applicability of directed relation graphs to the reduction of reaction mechanisms. Combust Flame 146:472–483
Lu T, Law CK (2005) A directed relation graph method for mechanism reduction. Proc Comb Inst 30:1333–1341
Luo ZY, Lu TF, Liu JW (2011) A reduced mechanism for ethylene/methane mixtures with excessive NO enrichment. Combust Flame 158(7):1245–1254
Luo ZY, Lu TF, Maciaszek MJ et al (2010a) A reduced mechanism for high-temperature oxidation of biodiesel surrogates. Energy Fuels 24:6283–6293
Luo ZY, Lu TF, Som S et al (2010b) Numerical study on combustion characteristics of biodiesel using a new reduced mechanism for methyl decanoate as surrogate. Proc Am Soc Mech Eng, New York, pp 837–884
Lv Y, Wang ZH, Zhou JH et al (2009) Reduced mechanism for hybrid NOx control process. Energy Fuels 23:5920–5928
Nagy T, Turányi T (2009) Reduction of very large reaction mechanisms using methods based on simulation error minimization. Combust Flame 156:417–428
Naik CV, Puduppakkam KV, Modak A et al (2010) Validated F-T fuel surrogate model for simulation of jet-engine combustion. Proc Am Soc Mech Eng, New York, Paper No GT2010–23709
Niemeyer KE, Sung CJ, Raju MP (2010) Skeletal mechanism generation for surrogate fuels using directed relation graph with error propagation and sensitivity analysis. Combust Flame 157(9):1760–1770
Pepiot-Desjardins P, Pitsch H (2008) An efficient error-propagation-based reduction method for large chemical kinetic mechanisms. Combust Flame 154:67–81
Pepiot P, Pitsch H (2005) Systematic reduction of large chemical mechanisms. In: 4th joint meeting of the U.S. Sections of the Combustion Institute, Philadelphia
Ranzi E, Dente M, Goldaniga A et al (2001) Lumping procedures in detailed kinetic modeling of gasification, pyrolysis, partial oxidation and combustion of hydrocarbon mixtures. Prog Energy Combust Sci 27(1):99–139
Ranzi E, Faravelli T, Gaffuri P et al (1995) Low-temperature combustion: automatic generation of primary oxidation reactions and lumping procedures. Combust Flame 102:179–192
Ranzi E, Faravelli T, Gaffuri P et al (1997) A wide-range modeling study of iso-octane oxidation. Combust Flame 108(1–2):24–42
Ranzi E, Frassoldati A, Granata S et al (2005) Wide-range kinetic modeling study of the pyrolysis, partial oxidation, and combustion of heavy n-alkanes. Ing Eng Chem Res 44(14):5170–5183
Schwer DA, Lu P, Green WH (2003) An adaptive chemistry approach to modeling complex kinetics in reacting flows. Combust Flame 133:451–465
Seshadri K, Lu TF, Herbinet O et al (2009) Experimental and kinetic modeling study of extinction and ignition of methyl decanoate in laminar non-premixed flows. Proc Combust Inst 32:1067–1074
Shi Y, Ge HW, Brakora JL et al (2010a) Automatic chemistry mechanism reduction of hydrocarbon fuels for HCCI engines based on DRGEP and PCA methods with error control. Energy Fuels 24:1646–1654
Shi Y, Liang L, Ge HW et al (2010b) Acceleration of the chemistry solver for modeling DI engine combustion using dynamic adaptive chemistry (DAC) schemes. Combust Theor Modell 14(1):69–89
Soyhan H, Mauss F, Sorusbay C (2002) Chemical kinetic modeling of combustion in internal combustion engines using reduced chemistry. Combust Sci Tech 174:73–91
Tomlin AS, Li GY, Rabitz H et al (1994) A general-analysis of approximate nonlinear lumping in chemical-kinetics. 2 constrained lumping. J Chem Phys 101(2):1188–1201
Tomlin AS, Pilling MJ, Turányi T et al (1992) Mechanism reduction for the oscillatory oxidation of hydrogen: sensitivity and quasi-steady-state analyses. Combust Flame 91:107–130
Turányi T (1990a) KINAL—A program package for kinetic analysis of reaction mechanisms. Comput Chem 14(3):253–254
Turányi T (1990b) Reduction of large reaction mechanisms. New J Chem 14:795–803
Turányi T (1990c) Sensitivity analysis of complex kinetic systems. Tools and applications. J Math Chem 5:203–248
Turányi T, Bérces T, Vajda S (1989) Reaction rate analysis of complex kinetic systems. Int J Chem Kinet 21:83–99
Wei J, Kuo JCW (1969) A lumping analysis in monomolecular reaction systems. Ind Eng Chem Fundam 8:114–123
Zeuch T, Moréac G, Ahmed SS et al (2008) A comprehensive skeletal mechanism for the oxidation of n-heptane generated by chemistry-guided reduction. Combust Flame 155:651–674
Zheng XL, Lu TF, Law CK (2007) Experimental counterflow ignition temperatures and reaction mechanisms of 1,3-butadiene. Proc Combust Inst 31:367–375
Zsély IG, Nagy T, Simmie JM et al (2011) Reduction of a detailed kinetic model for the ignition of methane/propane mixtures at gas turbine conditions using simulation error minimization methods. Combust Flame 158:1469–1479
Zsély IG, Turányi T (2001) Investigation and reduction of two methane combustion mechanisms. Arch Combust 21:173–177
Zsély IG, Turányi T (2003) The influence of thermal coupling and diffusion on the importance of reactions: The case study of hydrogen-air combustion. Phys Chem Chem Phys 5:3622–3631
Acknowledgments
TT acknowledges the financial support of OTKA grants K84054 and NN100523. AST acknowledges the financial support of EPSRC through grants GR/R76172/01(P) and GR/R39597/01.
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Tomlin, A.S., Turányi, T. (2013). Mechanism Reduction to Skeletal Form and Species Lumping. In: Battin-Leclerc, F., Simmie, J., Blurock, E. (eds) Cleaner Combustion. Green Energy and Technology. Springer, London. https://doi.org/10.1007/978-1-4471-5307-8_17
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