Battin-Leclerc, F

Carstensen, Hans-Heinrich

De Bruycker, Ruben

Green, WH

Herbinet, O

Marin, Guy

Mershant, SS

Van Geem, Kevin

Vermeire, Florence

English

Ghent University Academic Bibliography

Laboratory for Chemical Technology, Ghent Universityhttp://www.lct.UGent.beExperimental and kinetic modeling study of the pyrolysis and oxidation of 1,5-hexadiene: The reactivity of allylic radicals and their role in the formation of aromaticsK. M. Van Geem, F. Vermeire, R. De Bruycker, H. Carstensen, G.B. Marin, O. Herbinet, F. Battin-Leclerc, S.S. Mershant, W.H. Green1SMARTCATS general meeting, Lisbon, 15/11/201610th International Conference on Chemical Kineticshttp://icck2017.engr.uic.edu/Chicago, USA 21st – 25th May 2017Local host: Ken Brezinsky (UIC)Program chair: Rob Tranter (ANL)Contact: icck2017@uic.eduSoot formation3SMARTCATS general meeting, Lisbon, 15/11/2016Model compound hexadiene for the role of allyl radicals in formation of aromaticsOutline of talkExperimental procedure - JSRKinetic model development – GenesysModel performanceROP/sensitivity analysisAromatics formation4SMARTCATS general meeting, Lisbon, 15/11/2016Experimental procedure5ϕ = 1.0, 2.0, ∞FV = 4.06 10-5 m³ s-1t = 2.0 sP = 1.07 barT = 500 K – 1100 KJet-stirred reactorAnalysis3 GC’s for online quantification: Carbosphere column and TCD detector PLOT-Q column and FID detector (proc. by methanizer) HP-5ms column and FID detector1 GC for on- or offline identification: PLOT-Q or HP-5ms column and quadrupole MSProcess conditionsSMARTCATS general meeting, Lisbon, 15/11/2016Kinetic model development6Kinetic and thermodynamic dataGenesys species and group additive value databases for HCs1,2Literature data or analogies for allylic HCs and oxygenatesLiterature QM data for key reactions3Propene oxidation mechanism4 and aromatics chemistry5,6SMARTCATS general meeting, Lisbon, 15/11/2016[1] M.K. Sabbe, M.F. Reyniers, M. Waroquier, G.B. Marin, Chemphyschem, 11 (2010) 195-210.[2] M.K. Sabbe, F. De Vleeschouwer, M.F. Reyniers, M. Waroquier, G.B. Marin, Journal of Physical Chemistry A, 112 (2008) 12235-12251.[3] A. Fridlyand, P.T. Lynch, R.S. Tranter, K. Brezinsky, Journal of Physical Chemistry A, 117 (2013) 4762-4776.[4] S.M. Burke, W. Metcalfe, O. Herbinet, F. Battin-Leclerc, F.M. Haas, J. Santner, F.L. Dryer, H.J. Curran, Combustion and Flame, 161 (2014) 2765-2784[5] O. Herbinet, B. Husson, M. Ferrari, P.A. Glaude, F. Battin-Leclerc, Proc. Combust. Inst., 34 (2013) 297-305.[6] S. Sharma, M.R. Harper, W.H. Green, Combustion and Flame, 157 (2010) 1331-1345.GenesysGeneration of reacting systemsGAV for thermodynamic data7Cd(-H)2Cd(-C)(-H)C(-Cd)(-C)(-H)2Benson’s group additivity method& Hydrogen bond increment methodHBIGAV database:Cp at different temperatures∆Hf°(298 K)S° (298 K)NASA polynomials(CHEMKIN format)SMARTCATS general meeting, Lisbon, 15/11/2016∆GAVs for Arrhenius parameters∆GAV databases implemented in Genesys H abstraction reactions addition/β-scission reactions8() = 	exp −	 = 	 +∆	 !"#$%(&#) = , +∆	()!"#$%(&#)∆GAV reference reactionSMARTCATS general meeting, Lisbon, 15/11/2016Model performance9ϕ=2.0No low temperature reactivityAcrolein, prop-2-en-1-ol and but-3-enyl-oxiran main oxygenated speciesQualitative agreement between model simulations and experimentsMain discrepancies for ethene and acetaldehyde for oxidationSMARTCATS general meeting, Lisbon, 15/11/2016Keto-enol tautomerization of ethenol and oxidation of 1-hydroxyl-ethyl radical main acetaldehyde formation pathwayReevaluation of OH addition to HXD to improve model performance Rate of production analysis HXD1030 % of ethene productionRevise allyl pathways to improve model performanceϕ=2.0800 K1000 KHO2• important in allyl radical consumptionAROMATICSBy intramolecular additionOHOHOHOSMARTCATS general meeting, Lisbon, 15/11/2016Sensitivity analysis11Lowest T: Primary 1,5-HXD decompositionHigher T: Secondarycombustion chemistryNormalized sensitivity coefficients for 1,5-hexadiene molefraction at ϕ=2.0Reactions that imply formationof allyl radicals have positivecoefficientsHO2• radicals main consumptionof allyl radicals, high sensitivityfor 1,5-HXD mole fractionSMARTCATS general meeting, Lisbon, 15/11/2016Aromatics formation12OOOHOO2HO2HO2R RHCH3HRRHO OHR RH CH31,3-cyclopentadiene and benzene starting from1,5-hexadienyl radicalSimilar pathways for formation of styrene and toluene1 22 main pathways for benzene formationSMARTCATS general meeting, Lisbon, 15/11/2016Conclusions13SMARTCATS general meeting, Lisbon, 15/11/2016Oxidation and pyrolysis experiments in jet-stirred reactorNew developed kinetic model with automatic kinetic model generation and literature reported QM calculationsQualitative good model performance1,5-hexadiene mole fraction sensitive to allyl radicalsMain aromatic formation pathways unraveled AcknowledgementsThis work was supported by thethe Institute for promotion ofInnovation through Science andTechnology in Flanders (IWT)through the SBO project“Bioleum“ and “ARBOREF“ andthe SMARTCATs STSM COSTAction CM1404.14SMARTCATS general meeting, Lisbon, 15/11/201615Thank youSMARTCATS general meeting, Lisbon, 15/11/2016

Unravelling the role of cyclopentadiene and hexadiene in the formation of aromatics

https://biblio.ugent.be/publication/8523977/file/8525221

Unravelling the role of cyclopentadiene and hexadiene in the formation of aromatics

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Ghent University Academic Bibliography