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Biodiesel Kinetics and Flame Chemistry

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Biodiesel Kinetics and Flame Chemistry Biodiesel Kinetics and Flame Chemistry Yiguang Ju, Princeton University On behalf of CEFRC: Biodiesel Thrust and Flame Chemistry Working Group Sept. 17-20, 2012, MACCCR Synergistic •High-pressure flames •Turbulent flames •Flame chemistry •Laminar flame speeds, •Droplet processes •Biodiesel kinetics 2D Research extinction and ignition, •Model reduction & pollutants Structure multi-scale modeling •Flow reactor experiments • DNS of HCCI/SACI combustion C. K. Law •Reactivity and species history • DNS data for model validation •H , CO, small HC chemistry • 2 High pressure turbulence/ •DME, small oxygenates chemistry interaction F. N. Egolfopoulos Y. Ju J. H. Chen F. L. Dryer •LES/PDF/ISAT turbulent •Mechanisms of butanols combustion •Automatic mechanism •Turbulence/chemistry S. B. Pope generation Three Thrusts W. H. Green Unite the Team •Low-T combustion engines H. Wang R. D. Reitz •HCCI and RCCI CFD modeling •Soot •Interface with DERC •Small HC chemistry consortium Alcohols Biodiesel •Transport properties N. Hansen •UQ methods E. A. Carter Foundation Fuels •Flame species by C. J. Sung •Ab initio methods D. G. Truhlar Synchrotron MS •Thermochemical kinetics •Burner-stabilized flames •Ester chemistry S. J. Klippenstein R. K. Hanson •Rapid compression machine •High-pressure ignition •Potential energy surfaces •Thermometry and species •Rate constants with tunneling •Shock tube/Laser •Potential energy surfaces diagnostics •Reaction rate constants •Ignition/Species histories •High pressure theories •Rate constants Motivation O Biodiesel: R2 R1 O • Produced from vegetable oils, animal fats, & waste materials • Energy density much higher than ethanol • 28 billion gallons of biodiesel produced in 2010 worldwide • Large molecules: C16-C18 with ester functional group • Different combustion chemistry/emissions from hydrocarbons • Large disparities in alkyl chain length and structures Biodiesel Trans-esterification Sooting Propensity of Diesel Surrogate and Large Ester Flames Diesel Biodiesel (Law, Princeton) Diesel surrogate: 70% n-C10H22 + 30% 1-methyl naphthalene Dagaut and coworkers (2010) Scientific Questions? How to address the knowledge gaps in kinetics of large, oxygenated fuel molecules? How can we use quantum chemistry and kinetic experiments to provide a better, predictive model? How to address the transport and chemistry interaction in flames? Research Objectives Advance the understanding of combustion kinetics of methyl esters Develop a validated kinetic methyl ester kinetic mechanism to model oxidation with quantum chemistry calculations Advance understanding of chemistry/transport interaction 1. Biodiesel Kinetics: Hypothesis O O O O O O O O Methyl Formate Methyl Acetate MethylMethyl PropanoatePopanoate Methyl Butanoate O O Methyl Decanoate Similarity between Small/Large Esters? Biodesel Methyl Butanoate Decomposition (C4+1) = + Alkane methyl stearate (C18+1) (C14) 1A. Small Methyl Ester Pyrolysis in Shock Tube Stanford University 1666K 1428K 1250K 1.0 2% Methyl Ester/Argon 0.8 1.5 atm, Yield at 1 ms 0.6 MB MP 0.4 Fractional Yield Fractional Yield 2 CO 0.2 MA 0.0 0.60 0.65 0.70 0.75 0.80 1000/T [K-1] The reactivity is strongly affected by the alkyl chain length 1B. Comparison of Premixed Flame Speeds of Small Methyl-Esters/Air (C1-C4: 1 atm) •Methyl formate has the highest reactivity Egolfopoulos et al. •Methyl propanoate is the second 1C. Comparison of Extinction Limits of Methyl Esters (C1-C10) Extinction limit vs. Transport weighted enthalpy (TWE) 500 Tf = 500 K, Tox = 298 K 400 [1/s] Methyl Formate E a Methyl Ethanoate 300 Methyl Propanoate Methyl Butanoate Methyl Pentanoate 200 Methyl Hexanoate Methyl Octanoate Methyl Decanoate 100 Extinction strain rateExtinction strain 0 0.5 1 1.5 2 Transport-Weighted Enthalpy [cal/cm3] •Uniqueness of small methyl esters: methyl formate & methyl propanoate •Similarity of large methyl esters 1D: BDEs (D298 ) (kcal/mol) in Biodiesel Methyl Butanoate (MB) MRSDCI /cc-pV∞Z // B3LYP Oyeyemi, V. B.; Pavone, M.; Keith, J. A.; Carter, E. A. CBS-QB3-Isodesmic* in preparation, (2012). * Osmont et al. J. Phys. Chem. A, 111, 3727 (2007) H O H H H 98.0 MB 92.9 96.8 98.6 98.9 94.2 98.7 101.1 H C O C C C C H 101.2 95.4 83.1 85.8 101.3 93.5 84.4 89.1 H H H H Seshadri et al. : 80.8 kcal/mol, 2009 • Weakest bonds: dissociated radicals are resonance stabilized. • C-C bonds are weaker than C-H bonds: alkyl fragments allow more structural relaxation than H. 1E. Kinetic Mechanism Development (Ester-MECH: C2-C11 methyl esters) H2/O 2 . MB: Ester functional group Dooley et al., 2008 . C1-C7: n-heptane model C -C 1 7 Curran et al., 2008, 2010 . H /O : PU hydrogen model MB Extension 2 2 C8-C10 Dievart et al., 34th Symposium on Combustion on Comb., 2012 Dievart et al. Combustion and Flame, 2012, Vol.159 , pp. 1795-1803. 1F. Model Validation: Ignition Delay Time Ignition delays from Hanson’s group (Aerosol Shock Tube, very lean mixtures, diluted in argon, ~7.5 atm) Present model in good agreement (35%), whereas literature models overestimate MD oxidation rate (50 to 80%) Present model, Seshadri et al’s model: Metathesis reactions: 95% Fuel Decomposition: 5% Seshadri et al’s model: Metathesis reactions: 55% Fuel Decomposition: 45% Bond dissociation energy affects strongly fuel decomposition pathway Model validation: JSR & Flame speeds methyl decanoate • high temperature kinetics • speciation profiles, flame speeds 70 3000 25000 2500 CO 60 20000 and ] -1 2000 CO 15000 50 2 Mole Fraction [ppm] Mole Fraction 1500 Mole Fraction [ppm] Fraction Mole 4 10000 H 40 2 1000 C 5000 Experimental data 500 30 Reduced model (529 species) Flame speed [cm.s MD and MD Reduced model (228 species) 0 0 Seshadri et al.'s model [14] 500 600 700 800 900 1000 1100 Luo et al's model [20] 20 Temperature [K] 0.6 0.8 1.0 1.2 1.4 1.6 Jet-Stirred reactor (Glaude et al., Equivalence Ratio C&F 157, 2010) Laminar Flame Speeds P = 1atm, τ = 1.5 s (Wang et al., C&F 158, 2011) P = 1atm, T = 403 K Glaude et al., CF, 2010. 14 Model comparison in diffusion flame: MD Model validation: Diffusion flame extinction 500 ] 1 - [s 400 E Methyl pentanoate Methyl hexanoate Methyl octanoate 300 Methyl decanoate Methyl formate Methyl ethanoate 200 Methyl propanoate Methyl butanoate 100 C2-C11 Extinction Strain rate, a rate, Strain Extinction esters 0 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 Fuel Mole Fraction, Xf Dievart et al., 34th symposium on combustion, 2012 Model validation: Species time history Methyl formate 3.0E-12 T = 1333 K 2.5E-12 P = 0.51 atm Xfuel = 239.1 ppm 3] 2.0E-12 - 1.5E-12 1.0E-12 [H] , [mol.cm , [H] 5.0E-13 17 0.0E+00 0.E+00 5.E-04 1.E-03 2.E-03 2.E-03 Time [s] H abstraction reactions by OH and H: Methyl Formate Large deviations between the rate constants calculated by the Carter’s group (J. Phys. Chem. A, 2012) and the previous estimates or calculations. CH3OCHO + OH = CH3OCO + H2O CH3OCHO + H = CH3OCO + H2 1.0E+13 1.0E+13 ] ] 1 1 - - .s .s 3 - 3 1.0E+12 1.0E+12 - 1.0E+11 1.0E+11 Ting Tan (Carter) Ting Tan (Carter) Good and Francisco Good and Francisco Current Model 1.0E+10 1.0E+10 Current Model Akih-Kumgeh Szilagyi et al. (2004) Peukert et al. (Argonne) Rate constant [mol cm Rate constant [mol cm constant[mol Rate Peukert et al. 1.0E+09 1.0E+09 300 800 1300 1800 300 500 700 900 1100 1300 1500 1700 1900 Temperature [K] Temperature [K] Good and Francisco, J. Phys. Chem. A, 2002, Vol. 106, pp. 1733-1738 Peukert et al., Combustion and Flame, 2012, Vol. 159, pp. 2312-2323 Akih-Kumgeh and Bergthorson, Comb. Flame, 2011, Vol. 158, pp. 1037-1058 Szilagyi et al., J. Phys. Chem, 2004, Vol. 118, pp. 479-492 Methyl-Ester Radical Decomposition Reactions (Collaborative work : Carter, Klippenstein and Ju) Decomposition of small methyl ester radicals such as CH3OCO (and C2H5OCO) are key reactions. Literature: only high pressure limit rate constant with low level PES is available (e.g. BH&HLYP/CC-PVTZ). Present method: MRACPF/CBS//CASPT2/CC-PVTZ method on PES and VARIFLEX for pressure dependence 1.0E+13 CH3OCO = CH3 + CO2 ] 1 - 1.0E+11 1.0E+09 HPL 1.0E+07 100 atm Rate constant [s constant Rate 10 atm 1.0E+05 1 atm HPL Huynh and Violi 1.0E+03 0.3 0.8 1.3 1.8 1000/T [K] L.K. Huynh, A. Violi. J. Org. Chem. 72 (2008) 94-101. Collaborative structure of the Biodiesel Yang, Raghu, Ju, Carter Klippenstein Hanson group • Thermochemistry •Rate constants •Rate constants MX+ OH H, Cp, S CH3OCO X=F,A,P,B •Rate constants C2H5OCO MF, ME, MP… MF+X , ME+X, MP+X… Decomposition •Speciation time (OH, H, CH3, HO2) history Ester-MECH C2-C11 Esters Egolfopoulos, Ju, Law Dryer, Hansen and Ju •Flame speeds •Speciation experiments Sung and Hanson •Flame structure (Flow tube, flames) •Extinction •Ignition delay •Emissions (Shock tube, RCM) 20 Summary: OH + Methyl Esters Products 1429K 1250K 1111K 1000K 909K 833K Methyl Ester + OH = Products ] -1 s -1 1E13 mol 3 [cm MButanoate MPropanoate MFormate Methyl Ester + OH Methyl k MAcetate 1E12 Lines: Modified SAR (SAR x 0.75) 0.7 0.8 0.9 1.0 1.1 1.2 1000/T [1/K] • Data agree within 25% with Structure Activity Relationship (SAR) estimated rate constants ( the same rate used in the current model). 21 Methyl Formate Decomposition Kinetics Summary Arrhenius Plot k1: MF → CO + CH3OH 22 Wide T range Low data scatter Repeatable ±25% Advanced diagnostics- high pressure reactors at low and intermediate temperatures MBMS/mid-IR with flow reactor/jet stirred reactor 120 2500 100 In air, 60 Torr, 293 K CH4 2000 80 O [ppm] H2O 1500 2 60 1000 40 20 500 Measured H Measured Measured CH4Measured [ppm] 0 0 0 500 1000 1500 Calibration mole fraction [ppm] Multipath-IR H2O2 Measurements, DME/O2/He JSR (2 sec, 1 atm (0.02/0.1/0.88) 4000 3500 MBMS Modeling 3000 2500 Herriott cell 2000 reflections 1500 concentration (ppm) 2 O 1000 2 H Mixing 500 H2O2 0 500 550 600 650 700 750 Temperature (K) Preheated air Preheated HO ? High pressure, high temperature chamber temperature high pressure, High 2 Fuel 2.
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