s p = 1 atm T u = 343 K n-butanol sec-bu


1 2 3 4 5 6 7 p = 1 atm T u = 343 K n-butanol n-propanol Methanol Ethanol p = 1 atm T u = 343 K n-butanol sec-butanol tert-butanol iso-butanol Oxidati...
Author:  Harjanti Budiman

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,cm/s

,cm/s

Methanol

n-Butanol

n-Butanol

n-Propanol

p = 1 atm Tu = 343 K

Equivalence Ratio, ϕ

sec-Butanol

Laminar flame speed,

Laminar flame speed,

Ethanol

tert-Butanol iso-Butanol

p = 1 atm Tu = 343 K

Equivalence Ratio, ϕ

• 

Oxidation of methanol represents an extreme case – formaldehyde (CH2O) produced directly from fuel consumption reactions.

• 

Branching reduces reactivity through the production of resonantly stable intermediates.

P.S. Veloo, Y.L Wang, F.N. Egolfopoulos, C.K. Westbrook, Combust. Flame 157 (2010) 1989–2004 P.S. Veloo, F.N. Egolfopoulos, "Flame Propagation of Butanol Isomers/Air Mixtures", Proc. Combust. Inst. (2010) doi:10.1016/j.proci.2010.06.163 P.S. Veloo, F.N. Egolfopoulos, "Studies of n-Propanol/Air, iso-Propanol/Air, and Propane/Air Premixed Flames”, submitted to Combustion and Flame (2010)

Laminar flame speed,

,cm/s

Model B1

Model B2 Model B4 Model B3

Model B5 p = 1 atm Tu = 343 K

Equivalence Ratio, ϕ Model B1: P.S. Veloo, Y.L Wang, F.N. Egolfopoulos, C.K. Westbrook, Combust. Flame 157 (2010) 1989–2004 Model B2: J.T. Moss, A.M. Berkowitz, M.A. Oehlschlaeger, J. Biet, V. Warth, P.A. Glaude, F. Battin-Leclerc, J. Phys. Chem. A 112 (2008) 10843–10855 Model B3: G. Black, H.J. Curran, S. Pichon, J.M. Simmie, V. Zhukov, Combust. Flame 157 (2010) 363–373 Model B4: S.M. Sarathy, M.J. Thomson, C. Togbé, P. Dagaut, F. Halter, C. Mounaim-Rousselle, Combust. Flame 156 (2009) 852–864 Model B5: M.R. Harper, K.M. Van Geem, S.P. Pyl, G.B. Marin, W.H. Green, Combust. Flame (2010) doi:10.1016/j.combustflame.2010.06.002

Model P2

n-Propanol Equivalence Ratio, ϕ

• 

p = 1 atm Tu = 343 K

Model P1

,cm/s Laminar flame speed,

Laminar flame speed,

,cm/s

Model P1

Model P2

iso-Propanol

p = 1 atm Tu = 343 K

Equivalence Ratio, ϕ

Model P2 superimposes the propanol chemistry by Curran and coworkers onto the USC Mech II H2/CO and C1-C4 for analytical purposes.

Model P1: M. V. Johnson, S.S. Goldsborough, E. Larkin, G. OMalley, Z. Serinyel, P. OToole, H.J. Curran, Energy Fuels 23 (12) (2009) 5886–5898 Model P2: P.S. Veloo, F.N. Egolfopoulos, "Studies of n-Propanol/Air, iso-Propanol/Air, and Propane/Air Premixed Flames”, submitted to Combustion and Flame (2010)

n-Butanol

n-Propanol

Ignition Temperature, Tign, K

Ignition Temperature, Tign, K

p = 1 atm Tu = 473 K Kglobal = 135 s-1

p = 1 atm Tu = 473 K Kglobal = 135 s-1 iso-Butanol

n-Butanol

Fuel Mole Fraction

sec-Butanol

Fuel Mole Fraction Non-Premixed Flame Ignition

• 

Trends previously noted are repeated in ignition data to a large extent.

• 

Branching again leads to lower reactivity, i.e. larger ignition temperature

High-Temperature Air Tign

Non-Premixed Flame Fuel + N 2

C3 Alcohols – Major intermediates (e.g.) C

C

OH

C

O

H C

OH C

C

C

C

O

Propionaldehyde

C

C

C

C

C

C

Propene

Acetone

C

C4 Alcohols – Major intermediates (e.g.) C

C

C

OH

C

H

OH C

C

C

C

C

C

C C

C H

O O

Butyraldehyde

C

C

C C

Butanone

C

C

C

O

iso-Butyraldehyde

C C

C

C C OH C C C

C C OH

C

C C

1-Butene

C

C

C C

2-Butene

C

C

C

iso-Butene

O

O C C

Laminar flame speed,

,cm/s

Butanone

C

C

C

Acetone

Butanone

Acetone

p = 1 atm Tu = 343 K

C

Model K1

C

C C

Equivalence Ratio, ϕ

• 

O

Butyraldehyde ,cm/s

C

Laminar flame speed,

C

H

H C

C

O

Propionaldehyde Propionaldehyde

Butyraldehyde

p = 1 atm Tu = 343 K

Equivalence Ratio, ϕ

Preliminary results indicate that the aldehydes are more reactive than their equivalent ketones

Model K1: Z. Serinyel, G. Black, H. J. Curran, J. M. Simmie, Combust. Sci. Technol. 182 (2010) 574–587

C

Methyl decanoate

Model MB1 Model MB4

Model MB3 Model MB2 Experimental

Equivalence Ratio, ϕ

,cm/s

Tu = 403 K

Laminar flame speed,

Laminar flame speed,

,cm/s

Methyl butanoate

Tu = 403 K

Model MD1

Experimental

Equivalence Ratio, ϕ

Experimental: Y.L. Wang, Q. Feng, F.N. Egolfopoulos, T.T. Tsotsis, “Studies of C4 and C10 Methyl Ester Flames”, submitted for “Combustion and Flame” (2010) Model MB1 : E.M. Fisher, W.J. Pitz, H.J. Curran, C.K. Westbrook, Proc. Combust. Inst. 28 (2000) 1579-1586. Model MB2 : S. Gail, M.J. Thomson, S.M. Sarathy, S.A. Syed, P. Dagaut, P. Dievart, A.J. Marchese, F.L. Dryer, Proc. Combust. Inst. 31 (2007) 305-311. Model MB3 : S. Dooley, H.J. Curran, J.M. Simmie, Combust. Flame 153 (2008) 2-32. Model MB4 : L.K. Huynh, K.C. Lin, A Violi, J. Phys. Chem. A 112 (2008) 13470-13480. Model MD1 : K. Seshadri, T. Lu, O. Herbinet, S. Humer, U. Niemann, W.J. Pitz, R. Seiser, C.K. Law, Proc. Combust. Inst. 32 (2009) 1067-1074.

Methyl decanoate

Methyl crotonate ,cm/s

Tu = 403 K

n-butane Methyl crotonate Methyl butanoate

Equivalence Ratio, ϕ

Laminar flame speed,

Laminar flame speed,

,cm/s

Methyl butanoate

Tu = 403 K

n-Decane Methyl decanoate

Equivalence Ratio, ϕ

• 

Presence of the methyl ester group lowers overall reactivity, especially on the lean side. Effect diminishes as carbon chain length increases

• 

Double bond in unsaturated methyl ester increases overall reactivity, with the effect mainly being through higher temperatures

Y.L. Wang, Q. Feng, F.N. Egolfopoulos, T.T. Tsotsis, “Studies of C4 & C10 Methyl Ester Flames”, submitted for “Combustion and Flame” (2010)

Methyl decanoate

Tu = 403 K Tu = 403 K

Model MB1 Model MB4

Model MB3 Experimental Model MB2

Fuel to N2 mass ratio, mF/mN2

Extinction strain rate, Kext, s-1

Extinction strain rate, Kext, s-1

Methyl butanoate

Model MD1

Experimental

Fuel to N2 mass ratio, mF/mN2

Experimental: Y.L. Wang, Q. Feng, F.N. Egolfopoulos, T.T. Tsotsis, “Studies of C4 and C10 Methyl Ester Flames”, submitted for “Combustion and Flame” (2010) Model MB1 : E.M. Fisher, W.J. Pitz, H.J. Curran, C.K. Westbrook, Proc. Combust. Inst. 28 (2000) 1579-1586. Model MB2 : S. Gail, M.J. Thomson, S.M. Sarathy, S.A. Syed, P. Dagaut, P. Dievart, A.J. Marchese, F.L. Dryer, Proc. Combust. Inst. 31 (2007) 305-311. Model MB3 : S. Dooley, H.J. Curran, J.M. Simmie, Combust. Flame 153 (2008) 2-32. Model MB4 : L.K. Huynh, K.C. Lin, A Violi, J. Phys. Chem. A 112 (2008) 13470-13480. Model MD1 : K. Seshadri, T. Lu, O. Herbinet, S. Humer, U. Niemann, W.J. Pitz, R. Seiser, C.K. Law, Proc. Combust. Inst. 32 (2009) 1067-1074.

Models MB3, MB4

Model MB2

Model MB1 New estimate*

Temperature, K

Extinction strain rate, Kext, s-1

Binary diffusion coefficient, cm2/s

Methyl butanoate – N2

Tu = 403 K

Model MB4 Model MB3

Using newly estimated values of DMB-N2

Experimental

Fuel to N2 mass ratio, mF/mN2

* Estimated using the Tee-Gotoh-Steward correlations of corresponding states (I&EC Fundam. 5 (1996) 356-363).

• 

Using newly estimated values of DMB-N2 resulted in >50% reduction in the computed Kext’s, underlining the importance of using consistent and accurate sets of L-J parameters in the transport databases.

Model MB1 : Model MB2 : Model MB3 : Model MB4 :

E.M. Fisher, W.J. Pitz, H.J. Curran, C.K. Westbrook, Proc. Combust. Inst. 28 (2000) 1579-1586. S. Gail, M.J. Thomson, S.M. Sarathy, S.A. Syed, P. Dagaut, P. Dievart, A.J. Marchese, F.L. Dryer, Proc. Combust. Inst. 31 (2007). S. Dooley, H.J. Curran, J.M. Simmie, Combust. Flame 153 (2008) 2-32. L.K. Huynh, K.C. Lin, A Violi, J. Phys. Chem. A 112 (2008) 13470-13480.

Tu = 333 K Φ = 0.8

Ethyl propanoate Ethyl formate

Ethyl acetate

Methyl formate Methyl acetate Methyl propanoate

Strain rate, K, s-1

•  • 

Ethyl formate Reference flame speed, Su,ref,cm/s

Reference flame speed, Su,ref,cm/s

Methyl formate Methyl acetate Methyl propanoate

Ethyl acetate

Ethyl propanoate

Tu = 333 K Φ= 1.2

Ethyl propanoate Ethyl formate Ethyl acetate

Methyl formate Methyl acetate Methyl propanoate

Strain rate, K, s-1

Ethyl ester flames propagate faster than their methyl counterparts Methyl or ethyl acetates propagate slower than formate and propanoates flames

p = 1 atm Tu = 403 K Kglobal = 30 s-1 Methyl crotonate Methyl butanoate

n-Hexane

Methyl Crotonate + Ar n-Pentane + Ar

n-Pentane n-Butane Propane

Methyl Butanoate

n-Butane + Ar

ϕ = 0.8, Tu= 333 K, Kglobal = 168 s-1

n-butane/air > methyl butanoate/air

ϕ = 1.2, Tu = 333 K, Kglobal = 168 s-1

n-butane/air > methyl butanoate/air

Same flame temperature:

Same flame temperature:

n-butane/air ~ methyl butanoate/air

n-butane/air > methyl butanoate/air

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