The Generation of a Reduced Mechanism for Flame Inhibition by Phosphorus Containing Compounds Based on Path Flux Analysis Method

doi:10.1016/S1004-9541(13)60480-2

Chin.J.Chem.Eng. ›› 2013, Vol. 21 ›› Issue (4): 357-365.DOI: 10.1016/S1004-9541(13)60480-2

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The Generation of a Reduced Mechanism for Flame Inhibition by Phosphorus Containing Compounds Based on Path Flux Analysis Method

LI Shanling, JIANG Yong, QIU Rong

University of Science and Technology of China, State Key Laboratory of Fire Science, Hefei 230026, China

Received:2011-08-09 Revised:2012-01-20 Online:2013-04-26 Published:2013-04-28
Supported by:
Supported by the National Natural Science Foundation of China (51176181), the National Basic Research Program of China (2012CB719704), and the Research Fund for the Doctoral Program of Higher Education (20123402110047).

The Generation of a Reduced Mechanism for Flame Inhibition by Phosphorus Containing Compounds Based on Path Flux Analysis Method

李山岭, 蒋勇, 邱榕

University of Science and Technology of China, State Key Laboratory of Fire Science, Hefei 230026, China

通讯作者: JIANG Yong
基金资助:
Supported by the National Natural Science Foundation of China (51176181), the National Basic Research Program of China (2012CB719704), and the Research Fund for the Doctoral Program of Higher Education (20123402110047).

Abstract

Abstract: In order to analyze the complex chemical kinetic mechanism systematically and find out the redundant species and reactions, a numerical platform for mechanism analysis and simplification is established basing on Path Flux Analysis (PFA). It is used to reduce a detailed mechanism for flame inhibited by phosphorus containing compounds, a reduced mechanism with 65 species and 335 reactions is obtained. The detailed and reduced mechanism are both used to calculate the freely-propagating premix C₃H₈/air flame with different dimethyl methylphosphonate doped over a wide range of equivalence ratios. The concentration distributions of free radicals and major species are compared, and the results under two different mechanisms agree well. The laminar flame speed obtained by the two mechanisms also matches well, with the maximum relative error introduces as a small value of 1.7%. On the basis of the reduced mechanism validation, the correlativity analysis is conducted between flame speed and free radical concentrations, which can provide information for target species selection in the further mechanism reduction. By analyzing the species and reactions fluxes, the species and reaction paths which contribute the flame inhibition significantly are determined.

Key words: mechanism reduction, path flux analysis, phosphorus containing compounds, flame inhibition

摘要： In order to analyze the complex chemical kinetic mechanism systematically and find out the redundant species and reactions, a numerical platform for mechanism analysis and simplification is established basing on Path Flux Analysis (PFA). It is used to reduce a detailed mechanism for flame inhibited by phosphorus containing compounds, a reduced mechanism with 65 species and 335 reactions is obtained. The detailed and reduced mechanism are both used to calculate the freely-propagating premix C₃H₈/air flame with different dimethyl methylphosphonate doped over a wide range of equivalence ratios. The concentration distributions of free radicals and major species are compared, and the results under two different mechanisms agree well. The laminar flame speed obtained by the two mechanisms also matches well, with the maximum relative error introduces as a small value of 1.7%. On the basis of the reduced mechanism validation, the correlativity analysis is conducted between flame speed and free radical concentrations, which can provide information for target species selection in the further mechanism reduction. By analyzing the species and reactions fluxes, the species and reaction paths which contribute the flame inhibition significantly are determined.

关键词: mechanism reduction, path flux analysis, phosphorus containing compounds, flame inhibition

LI Shanling, JIANG Yong, QIU Rong . The Generation of a Reduced Mechanism for Flame Inhibition by Phosphorus Containing Compounds Based on Path Flux Analysis Method[J]. Chin.J.Chem.Eng., 2013, 21(4): 357-365.

李山岭, 蒋勇, 邱榕. The Generation of a Reduced Mechanism for Flame Inhibition by Phosphorus Containing Compounds Based on Path Flux Analysis Method[J]. Chinese Journal of Chemical Engineering, 2013, 21(4): 357-365.

References

1 Jayaweera, T.M., Melius, C.F., Pitz, W.J., “Flame inhibition by phosphorus-containing compounds over a range of equivalence ratios”, Combust. Flame, 140 (1-2), 103-115 (2005).

2 Tapscott, R.E., Sheinson, R.S., Babushok, V.I., Alternative Fire Suppressant Chemicals: A Research Review with Recommendations, Washington: Government Printing Office (2001).

3 Shmakov, A.G., Korobeinichev, O.P., Shvartsberg, V.M., Knyazkov, D.A., Bolshova, T.A., Rybitskaya, I.V., “Inhibition of premixed and nonpremixed flames with phosphorus-containing compounds”, Proc. Combust. Inst., 30 (2), 2345-2352 (2005).

4 Siow, H.E., Laurendeau, N.A., “Flame inhibition activity of phosphorus-containing compounds using laser-induced fluorescence measurements of hydroxyl”, Combust. Flame, 136 (1-2), 16-24 (2004).

5 Korobeinichev, O.P., Shvartsberg, V.M., Shmakov, A.G., Bolshovaa, T.A., Jayaweera, T.M., Melius, C.F., Pitz, W.J., Westbrook, C.K., “Flame inhibition by phosphorus-containing compounds in lean and rich propane flames”, Proc. Combust. Inst., 30 (2), 2353-2360 (2005).

6 Macdonald, M.A., Jayaweera, T.M., Fisher, E.M., “Variation of chemically active and inert flame suppression effectiveness with stoichiometric mixture fraction”, In: 27th International Symposium on Combustion. Pittsburgh, 2749-2756 (1998).

7 Jeng, R.J., Shau, S.M., Lin, J.J., “Flame retardant epoxy polymers based on all phosphorus containing components”, Eur. Polym. J., 38 (4), 683-693 (2002).

8 Korobeinichev, O.P., Shvartsberg, V.M., Chernov, A.A., Mokrushin,V., “Hydrogen-oxygen flame doped with trimethyl phosphate, its structure and trimethyl phosphate destruction chemistry”, In: 26th International Symposium on Combustion, Naples, Italy, 1035-1042 (1996).

9 Korobeinichev, O.P., Shvartsberg, V.M., Chernov, A.A., “The destruction chemistry of organophosphorus compounds in flames II: Structure of a hydrogen-oxygen flame doped with trimethyl phosphate”, Combust. Flame, 118 (4), 727-732 (1999).

10 Werner, J.H., Cool, T.A., “Kinetic model for the decomposition of DMMP in a hydrogen/oxygen flame”, Combusti. Flame, 117 (1-2), 78-98 (1999).

11 Werner, J.H, Cool, T.A., “Flame sampling photoionization mass spectrometry of CH₃PO₂ and CH₃OPO₂”, Chem. Phys. Lett., 275 (3-4), 278-282 (1997).

12 Lu, T.F., Law, C.K., “On the applicability of directed relation graphs to the reduction of reaction mechanisms”, Combust. Flame, 146 (3), 472-483 (2006).

13 Maas, U., Popeb, S.B., “Simplifying chemical kinetics: Intrinsic low-dimensional manifolds in composition space”, Combust. Flame, 88 (3-4), 239-264 (1992).

14 Lam, S.H., Goussis, D.A., “The CSP method for simplifying kinetics”, Int. J. Chem. Kinet., 26 (4), 461-486 (1994).

15 Lam, S.H., Goussis, D.A., “Understanding complex chemical kinetics with computational singular perturbation”, In: 22nd Symposium on Combustion, Seattle, 931-941 (1989).

16 Wang, B.B., Jiang, Y., Qiu, R. “Application of CSP to the reduction of a complex combustion reaction system”, Acta Phys. Chim. Sin., 24 (12), 2221-2228 (2008).

17 Turanyi, T., Tomlin, A.S., Pilling, M.J., “On the error of the quasi-steady-state approximation”, J. Phys. Chem., 97 (1), 163-172 (1993).

18 Rabitz, H., Kramer, M., Dacol, D., “Sensitivity analysis in chemical kinetics”, Rev. Phys. Chem., 34 (2), 419-461 (1983).

19 Turányi, T., “Sensitivity analysis in chemical kinetics (editorial)”, Int. J. Chem. Kinet., 40 (11), 685-686 (2008).

20 Turányi, T., “Sensitivity analysis of complex kinetic systems tools and applications”, J. Math. Chem., 5 (3), 203-248 (1990).

21 Lu, T.F., Law, C.K, “A directed relation graph method for mechanism reduction”, Proc. Combust. Inst., 30 (1), 1333-1341 (2005)

22 Vajda, S., Valko, P., Turányi, T., “Principal component analysis of kinetic models”, Int. J. Chem. Kinet., 17 (1), 55-81 (1985).

23 Brown, N.J., Koszykowski, M.L., “Mechanism reduction via principal component analysis”, Int. J. Chem. Kinet., 29 (6), 393-414 (1997).

24 Sun, W.T., Chen, Z., Gou, X.L., “A path flux analysis method for the reduction of detailed chemical kinetic mechanisms”, Combust. Flame, 157 (7), 1298-1307 (2010).

25 Jiang, Y., Qiu, R., “Reduction of large kinetic mechanisms of hydrocarbon fuels with directed relation graph”, Acta Phys. Chim. Sin., 25 (5), 1010-1025 (2009).

26 Chen, W.T., Jiang, Y., Qiu, R., “Effects of CO addition on the lean premixed CH₄/air flame”, Acta Phys. Chim. Sin., 26 (6), 1481-1487 (2010).

27 Twarowski, A., “The influence of phosphorus oxides and acids on the rate of H OH recombination”, Combust. Flame, 95 (1-2), 91-107 (1993).

The Generation of a Reduced Mechanism for Flame Inhibition by Phosphorus Containing Compounds Based on Path Flux Analysis Method

The Generation of a Reduced Mechanism for Flame Inhibition by Phosphorus Containing Compounds Based on Path Flux Analysis Method

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