Chemical Mechanism Reduction and Validation of Methyl Butanoate by Automatic Reduction Procedure

Methyl Butanoate의 상세 화학 반응 메커니즘 자동 축소화를 통한 기초 반응 메커니즘의 생성 및 검증

  • Received : 2015.11.13
  • Accepted : 2016.06.26
  • Published : 2016.09.30


In this study, skeletal mechanisms are produced by directed relation graph with specified threshold value and sensitivity analysis based on species database from the directed relation graph. Skeletal mechanism is optimized through the elimination of unimportant reaction steps by computational singular perturbation importance index. Reduction is performed for the detailed mechanism of methyl butanoate consisting of 264 species and 1219 elementary reactions. Validation shows acceptable agreement for auto-ignition delays in wide parametric ranges of pressure, temperature and equivalence ratio. Methyl butanoate has been proposed as a simple biodiesel surrogate although the alkyl chain consists of four carbon atoms. The resulting surrogate mechanism for n-heptane and MB consists of 76 species and 226 reaction steps including those for NOx.



  1. T. Turanyi, Reduction of large reaction mechanisms, New J. Chem., 14 (1990) 795-803.
  2. A.S. Tomlin, M.J. Pilling, T. Turanyi, J.H. Merkin and J. Brindley, Mecahanism reduction for the oscillatory oxidation of hydrogen: Sensitivity and quasi-steady-sate analyses, Combust. Flame, 91 (1992) 107-130.
  3. H. Wang and M. Frenklach, Detailed reduction of reaction mechanisms for flame modeling, Combust. Flame, 87 (1991) 365-370.
  4. T.F. Lu, Y. Ju and C.K. Law, A directed relation graph method for mechanism reduction, Proc. Combust. Inst., 30 (2005) 1333-1341.
  5. T.F. Lu, Y. Ju and C.K. Law, Linear time reduction of large kinetic mechanism with directed realtion graph: n-Heptane and iso-octane, Combust. Flame, 144 (2006) 24-36.
  6. T.F. Lu, Y. Ju and C.K. Law, Strategies for mechanism reduction for large hydrocarbons: n-heptane, Combust. Flame, 154 (2008) 153-163.
  7. N. Peters, Numerical Simulation of Combustion Phenomena, Lecture Notes in Physics. Springer, Berlin, 241 (1985) 90-109.
  8. N. Peters and R.J. Kee, The computation of stretched laminar methane-air diffusion flames using a reduced four-step mechanism, Combust. Flame, 68 (1987) 17-29.
  9. J.Y. Chen, A general procedure for constructing reduced reaction mechanisms with given independent relations, Combust. Sci. Technol., 57 (1988) 89-94.
  10. M.D. Smooke, Reduced kinetic mechanisms and asymptotic approximations for methan-air flames, Lecture Notes in Physics, Springer-Verlag, Berlin, 384 (1991) 1-28.
  11. A. Massias, D. Diamantis, E. Mastorakos and D. A. Goussis, An algorithm for the construction of global reduced mechanisms with CSP data, Combust. Flame, 117 (1999) 685-708.
  12. A. Massias, D. Diamantis, E. Mastorakos and D. A. Goussis, Global reduced mechanisms for methane and hydrogen combustion with nitric oxide formation constructed with CSP data, Combust. Theory Modelling, 3 (1999) 233-257.
  13. T.F. Lu, Y. Ju and C.K. Law, Complex CSP for chemistry reduction and analysis, Combust. Flame, 126 (2001) 1445-1455.
  14. U. Maas and S.B. Pope, Simplifying chemical kinetics: Intrinsic low-dimensional manifolds in composition space, Combust. Flame, 88 (1992) 239-264.
  15. E. M. Fisher W. J. Pitz, H. J Curran and C. K. Westbrook, Detailed chemical kinetic mechanisms for combustion of oxygenated fuels, Prog. Energy Combust. Sci., 28 (2000), 1579-1586.
  16. K. E. Niemeyer, Skeletal mechanism generation for surrogate fuels, Master Thesis, Case western Reserve University, 2010.
  17. R. J. Kee, F. M. Rupley and J. A. Miller, "Chemkin-II: A FORTRAN chemical Kinetics Package for the Analysis of Gas-Phase Chemical Kinetics," SAND89-8009, 1989.
  18. W. J. Pitz and C. J. Muller, Recent Progress in the development of diesel surrogate fuels, Prog. Energy Combust. Sci., 37 (2011), 330-350.
  19. J. L. Brakora, Y. Ra, R. D. Reitz, J. Mcfarlane and C. S. Daw, Development and validation of a reduced reaction mechanism for biodiesel-fueled engine simulation. SAE paper 2008-01-1378, 2008.
  20. B. AKih-Kumgeh and J. M. Bergthorson, Comparative study of methyl butanoate and n-heptane high temperature autoignition. Energy Fuels.24(4) (2010), 2439-48.