detailed studies on the oxidation of surrogate fuel ...n-propylbenzene oxidation modeling uic...
TRANSCRIPT
Kenneth Brezinsky
Department of Mechanical and Industrial Engineering
University of Illinois at Chicago
MULTI AGENCY COORDINATION COMMITTEE FOR COMBUSTION RESEARCH (MACCCR)
FUELS RESEARCH REVIEW
Argonne National Laboratory, Argonne, IL
September 21nd, 2011
2011 MURI AFOSR Annual Presentation
Generation of Comprehensive Surrogate Kinetic Models and Validation Databases for
Simulating Large Molecular Weight Hydrocarbon Fuels
Detailed Studies on the Oxidation of Surrogate Fuel
Components, Surrogate Mixtures and Real Fuels
Motivation
• Develop an experimental and kinetic modeling
validation database at high pressures and high
temperatures for
– Individual surrogate fuel components
• n-alkanes, iso-alkanes and aromatics
– Surrogate fuel component mixtures
– Jet A POSF 4658
Experimental Approach
• Provide high pressure experimental data and speciation data for
– Oxidation and pyrolysis of individual surrogate fuel components
• Iso-octane
• n-decane
• n-dodecane
• n-propylbenzene
• 1,3,5-trimethylbenzene
– Oxidation of 1st generation surrogate mixture
• iso-octane/decane/toluene
– Oxidation of 2nd generation surrogate mixture
• iso-octane/n-dodecane/n-propylbenzene/1,3,5-trimethylbenzene
– Oxidation of Jet A POSF 4658
• Comparison of speciation data between Jet A POSF 4658 and 1st
and 2nd generation surrogates
• Measurement of polycyclic aromatic hydrocarbons (PAHs), precursors to soot
Modeling Approach
• Testing published models against high pressure
experimental results of
– Iso-octane, decane, dodecane, and 1st generation surrogate
• Advanced detailed modeling of iso-octane, decane and
dodecane based on speciation data
• Develop models for oxidation and pyrolysis of alkylaromatics
– n-Propylbenzene and 1,3,5-trimethylbenzene
• Testing published soot models against the experimentally
measured PAHs
• Advanced detailed modeling of PAHs leading to soot
formation
High Pressure Single Pulse Shock Tube (HPST)
� HPST Operating Conditions
� Temperatures: 800-2500 K
Pressures: 15 – 1000 bar
Reaction times: 1.0 – 4.0 ms
� Single Pulse Shock Tube
heated to 100oC
�Analytical Setup� Stable species analyzed using the GCs
� TCD and FID x2 (used for quantification)
� MS (used only for identification)
� GC transfer lines heated to 150oC
� Common species found in the oxidation and pyrolysis experiments of all the three fuels
�Major intermediates:
� C1: CO, CO2, Methane (CH4),
� C2: Ethene (C2H4), Ethane (C2H6), Acetylene (C2H2),
� C4: Vinylacetylene (C4H4), Diacetylene (C4H2),
� C6: Triacetylene (C6H2), Benzene (C6H6),
� C7: Toluene (C6H5CH3), Benzaldehyde (C6H5CHO)
� C8: Styrene (C6H5C2H3)
New Set-Up: Direct connection between the HPST and the GC system
Average Carbon Recovery: 90% with the New Set-Up
800 1000 1200 1400 16000
20
40
60
80
100
120
Precarbon Total
Avg. P5 = 25 atm, φφφφ ~ 0.5
Avg. P5 = 50 atm, φφφφ ~ 0.5
Avg. P5 = 50 atm, φφφφ ~ 1.0
Avg. P5 = 25 atm, φφφφ ~ 2.0
Avg. P5 = 50 atm, φφφφ ~ 2.0
Carb
on
Re
co
ve
ry /
%
Temperature /K
800 1000 1200 1400 16000
20
40
60
80
100
120
PrecarbonTotal
Avg. P5 = 25 atm, φφφφ ~ 0.50
Avg. P5 = 50 atm, φφφφ ~ 0.50
Avg. P5 = 50 atm, φφφφ ~ 1.00
Avg. P5 = 50 atm, φφφφ ~ 2.00
Avg. P5 = 50 atm, φφφφ ~ 2.00
Ca
rbo
n R
ec
ove
ry /%
Temperature /K
n-Propylbenzene m-Xylene 1,3,5-Trimethylbenzene
800 1000 1200 1400 1600 18000
20
40
60
80
100
120
Precarbon Total
Avg. P5 = 25 atm, φφφφ ~ 0.45
Avg. P5 = 50 atm, φφφφ ~ 0.45
Avg. P5 = 50 atm, φφφφ ~ 0.95
Avg. P5 = 25 atm, φφφφ ~ 1.76
Avg. P5 = 50 atm, φφφφ ~ 1.80
Ca
rbo
n R
eco
ve
ry (
%)
Temperature (K)
Carbon Totals and Measured Species
Minor intermediates: � C3:Allene (C3H4), Propyne (C3H4),
� C4:1,3-Butadiene (C4H6),
� C5:Cyclopentadiene (C5H6)
� C8:Phenylacetylene (C6H5C2H),
Species Specific to the Fuel
Bibenzyl Stilbene
n-Propylbenzene
m-xylene
1,3,5-Trimethylbenzene
1,2-Di-p-tolylethane Biphenylene2,2’-Dimethylbiphenyl
3,3’,5,5’-Tetramethylbibenzyl 2,4,6-Trimethylbiphenyl
1-Ethyl-3,5-dimethylbenzene 1-Ethenyl-3,5-dimethylbenzeneO
3,5-Dimethylbenzaldehyde
Om-Ethylbenzaldehyde
1-Ethynyl-4-methylbenzene
O
Benzofuran
1,3,5-Trimethylbenzene
Ethenylanthracene
Cyclopentaphenanthrene Fluoranthene Methylfluoranthene
1,3-Dimethylnaphthalene
3,6-Dimethylphenanthrene
2,3-Benzofluorene
9-Phenylanthracene
1,2-Benzanthracene Chrysene
Species Specific to the Fuel
n-Propylbenzene Oxidation Modeling
� UIC n-Propylbenzene Oxidation Model (CNF submission, in press)
� C0-C8 chemistry from Jet Fuel Surrogate Model1
� n-Propylbenzene oxidation chemistry
� Rate constants of oxidation reactions based on analogous reactions of propane2
and toluene3-7
� 26 reactions
� Polycyclic aromatic hydrocarbon chemistry (PAH)
� Rate constants estimated for formation of indene from fuel radicals(8 reactions)
� Reactions for formation of naphthalene, ethynylnaphthalene and anthracene
formation from Slavinskaya and Frank8 (61 reactions)
� Reactions for formation of diphenylmethane, benzofuran and fluorene from Ranzi9
(13 reactions)
1. S. Dooley, S. H. Won, M. Chaos, J. Heyne, Y. Ju, F. L. Dryer, K. Kumar, C. J. Sung, H. Wang, M. A. Oehschlaeger, R. J. Santoro and T. A. Litzinger, Combust. Flame, 157
(2010) 2333-2339.
2. W. Tsang, J. Phys. Chem. Ref. Data, 17 (1988) 887-951
3. D. L. Baulch, C. T. Bowman, C. J. Cobos, R. A. Cox, Th. Just, J. A. Kerr, M. J. Pilling, D. Stocker, J. Troe, W. Tsang, R. W. Walker, J. Warnatz, J. Phys. Chem. Ref. Data, 34
(2005) 757-1397
4. J. M. Nicovich, C. A. Gump and A. R. Ravishankara, J. Phys. Chem. 86 (1982) 1684-1690
5. S. S. Vasu, D. F. Davidson and R. K. Hanson, J. Propul. Power, 26 (2010) 280-287
6. M. A. Oehlschlaeger, D. F. Davidson, R. K. Hanson, Combust. Flame, 147 (2006) 195-208
7. R. Sivaramakrishnan, R. S. Tranter and K. Brezinsky, J. Phys. Chem. A, 110 (2006) 9388-9399
8. N. A. Slavinskaya and P. Frank, Combust. Flame 156 (2009) 1705 – 1722
9. E. Ranzi, High temperature mechanism (C1-C16), http://www.chem.polimi.it/CRECKModeling
n-Propylbenzene Oxidation Model Results
Analysis of the Simulation
� Model shows good agreement for the decay of the fuel, O2, CO and CO2
� Model shows good agreement for the formation of other major intermediates such as toluene and styrene
[ Symbols ] Experimental Data [ Lines] UIC n-Propylbenzene Oxidation Model
800 1000 1200 1400 1600
n-P
rop
ylb
en
ze
ne (
pp
m)
Temperature (K)
800 1000 1200 1400 1600
n-P
rop
ylb
en
zen
e (
pp
m)
Temperature (K)
average P5 = 50 atm
average P5 = 50 atm
800 1000 1200 1400 1600
O2
CO
CO2
Mo
le F
racti
on
(p
pm
)
Temperature (K)
800 1000 1200 1400 1600
O2
CO
CO2
Mo
le F
racti
on
(p
pm
)
Temperature (K)
800 1000 1200 1400 1600
Toluene
Styrene
Mo
le F
rac
tio
n (
pp
m)
Temperature (K)
800 1000 1200 1400 1600
Toluene
Styrene
Mo
le F
rac
tio
n (
pp
m)
Temperature (K)
n-Propylbenzene Oxidation Model Results
800 1000 1200 1400 1600 1800
Indene
Mo
le F
rac
tio
n (
pp
m)
Temperature (K)
800 1000 1200 1400 1600 1800
Fluorene
Mo
le F
racti
on
(p
pm
)
Temperature (K)
800 1000 1200 1400 1600 1800
Anthracene
Mo
le F
racti
on
(p
pm
)
Temperature (K)
800 1000 1200 1400 1600 1800
Diphenylmethane
Mo
le F
rac
tio
n (
pp
m)
Temperature (K)
800 1000 1200 1400 1600 1800
Naphthalene
Mo
le F
racti
on
(p
pm
)
Temperature (K)
Analysis of the Simulation
� Model shows good agreement with indene and bibenzyl profiles.
� The model shows satisfactory agreement with the profiles of most of the other two ringed and three ringed compounds
800 1000 1200 1400 1600
Bibenzyl
Mo
le F
racti
on
(p
pm
)
Temperature (K)
average P5 = 50 atm
[ Symbols ] Experimental Data [ Lines] UIC n-Propylbenzene Oxidation Model
� UIC 1,3,5-Trimethylbenzene Oxidation Model developed to predict
single ring aromatic hydrocarbons and aliphatic compounds from
fuel
� Rate constants of the oxidation reactions of 1,3,5-
trimethylbenzene based on analogous reactions of m-xylene9
� 41 reactions
� Thermochemical data of 1,3,5-trimethylbenzene and it’s
intermediates computed using group additivity and density
functional theory (B3LYP/6-31G(d))
� 12 species
1,3,5-Trimethylbenzene Oxidation Modeling
UIC 1,3,5-
Trimethylbenzene Model
UIC m-Xylene
Oxidation Model9
+Sequential oxidation reactions
of 1,3,5-trimethylbenzene
+Methyl side chain abstraction
reactions of 1,3,5-trimethylbenzene
9. S. Gudiyella, T. Malewicki, A. Comandini and K. Brezinsky, Combust. Flame, 158 (2011) 687 - 704
average P5 = 50 atm
average P5 = 50 atm
1,3,5-Trimethylbenzene Oxidation Model Results
Analysis of the Simulation
Models shows satisfactory agreement for the decay of the fuel, O2, CO and CO2
Model shows formation of toluene and benzene at higher temperatures when compared to experiments
Possibility of other pathways for the fuel decay
1000 1200 1400 1600
1,3
,5-T
rim
eth
ylb
en
ze
ne
(p
pm
)
Temperature (K)
1200 1350 1500 1650
1,3
,5-T
rim
eth
ylb
en
ze
ne
(p
pm
)
Temperature (K)
1000 1200 1400 1600
O2
CO
CO2
Mo
le F
rac
tio
n (
pp
m)
Temperature (K)
1200 1350 1500 1650
O2
CO
CO2
Mo
le F
racti
on
(p
pm
)
Temperature (K)
1000 1200 1400 1600
Benzene
Toluene
m-Xylene
Mo
le F
racti
on
(p
pm
)
Temperature (K)
1200 1350 1500 1650
Benzene
Toluene
m-Xylene
Mo
le F
racti
on
(p
pm
)
Temperature (K)
[ Symbols ] Experimental Data [ Lines] UIC 1,3,5-Trimethylbenzene Oxidation Model
1st and 2nd Generation Surrogates versus
Jet A POSF 4658
1000 1200 1400 1600 1800 1000 1200 1400 1600 1800
1000 1200 1400 1600 1800 1000 1200 1400 1600 1800
O2
Jet A 4658 1st Generation Surrogate 2nd Generation Surrogate
CO
CO2
Mo
le F
rac
tio
n /p
pm
CH4
Reflected Shock Temperature
Temperature Range
904-1760 K
Pressure Range
18-35 atm
1st and 2nd Generation Surrogates versus
Jet A POSF 4658
1000 1200 1400 1600 1800 1000 1200 1400 1600 1800
1000 1200 1400 1600 1800 1000 1200 1400 1600 1800
C2H
2
Mo
le F
rac
tio
n /p
pm
C3H
6
Jet A 4658 1st Generation Surrogate 2nd Generation Surrogate
C4H
8C
6H
6
Reflected Shock Temperature /K
1st and 2nd Generation Surrogates Fuel Decay
Comparison with Single-Component Fuels
1000 1200 1400 1600 1800
Jet A POSF 4658
1st Generation Surrogate
2nd Generation Surrogate
Ca
rbo
n B
ala
nce
Reflected Shock Temperature /K
1000 1200 1400 1600
P = 21-33 atm
1st Generation Surrogate
n-Decane
iso-Octane
Toluene
Mo
le F
rac
tio
n /
pp
m
Reflected Shock Temperature /K
n-dodecane, n-decane, iso-octane, n-propylbenzene, and 1,3,5-
trimethylbenzene oxidation data
[ � � ] Surrogate Experimental Data [______
] Single Component Experimental Data (Line Connected Data)
n-Dodecane Experimental Data and Modeling
[ � � ] Experimental Data [_________
] C8-C16 n-Alkane Westbrook et al. Model* (Line Connected Data)
1000 1200 1400 1600
O2 | CO | CO
2
Mo
le F
rac
tio
n /
pp
m
Reflected Shock Temperature /K
1000 1200 1400 1600
CH4 | C
2H
4 | C
2H
2
Mo
le F
rac
tio
n /
pp
m
Reflected Shock Temperature /K
� Additional species not shown for this experimental data set
� ethane, propene, propadiene, propyne, 1-butene, 1,3-butadiene, 1-pentene, 1,3-pentadiene, benzene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene
* Westbrook, C. K., W. J. Pitz, O. Herbinet, H. J. Curran, and E. J. Silke, "A Detailed Chemical Kinetic Reaction
Mechanism for n-Alkane Hydrocarbons from n-Octane to n-Hexadecane," Combust. Flame 156 (1) (2009) 181-199
P5 avg = 50 atm
n-Decane Experimental Data and Modeling
[ � � ] Experimental Data [_________
] C8-C16 n-Alkane Westbrook et al. Model* (Line Connected Data)
� Additional species not shown for this experimental data set
� ethane, propene, propadiene, propyne, 1-butene, 1,3-butadiene, 1-pentene, 1,3-pentadiene, benzene, 1-hexene, 1-heptene, 1-octene, 1-nonene
* Westbrook, C. K., W. J. Pitz, O. Herbinet, H. J. Curran, and E. J. Silke, "A Detailed Chemical Kinetic Reaction
Mechanism for n-Alkane Hydrocarbons from n-Octane to n-Hexadecane," Combust. Flame 156 (1) (2009) 181-199
P5avg = 60 atm
1000 1100 1200 1300 1400 1500
O2 | CO | CO
2
Mo
le F
racti
on
/p
pm
Reflected Shock Temperature /K
1000 1100 1200 1300 1400 1500
CH4 | C
2H
4 | C
2H
2
Mo
le F
racti
on
/p
pm
Reflected Shock Temperature /K
1000 1200 1400 1600
CO2
CH4
C2H
4
C2H
6
C2H
2
C3H
6
aC3H
4
pC3H
4
C4H
8
Mo
le F
rac
tio
n /p
pm
Reflected Shock Temperature /K
O2 /10
iC8H
18
CO
P5avg = 54 atm
iso-Octane Experimental Data
[_________
] Line Connected Experimental Data
iso-Octane Modeling
� Original iso-Octane Sub-Model
� 1st Generation Surrogate Model by Dooley et al.1 with n-
decane2 reactions removed
� C0-C4 mechanism from Metcalfe et al.3
� iso-Octane (C5-iC8) reactions from Mehl et al.4
� Toluene reactions from Metcalfe et al.3
� Revised iso-Octane Sub-Model
� Additional C1-C2 reactions from Gudiyella et al.5
� Replaced iC7H14 reactions using Chaos et al.6
� Replaced key C0-C4 reaction in the base mechanism
1. Dooley, S., Won, S.H., Chaos, M., Heyne, J., Ju, Y.G., Dryer, F.L., Kumar, K., Sung, C.J., Wang, H.W., Oehlschlaeger, M.A.,
Santoro, R.J., Litzinger, T.A., Combust. Flame 157 (2010) 2333-2339.
2. Westbrook, C.K., Pitz, W.J., Herbinet, O., Curran, H.J., Silke, E.J., Combust. Flame 156 (2009) 181-199.
3. Metcalfe, W.K., Dooley, S., Dryer, F.L., Proceedings Combustion Institute (2010).
4. Mehl, M., Curran, H.J., Pitz, W.J., Westbrook, C.K., in: European Combustion Meeting, Vienna, Austria, 2009.
5. Gudiyella, S., Brezinsky, K., (Submitted to Combustion and Flame) (2011).
6. Chaos, M., Kazakov, A., Zhao, Z.W., Dryer, F.L., Int. J. Chem. Kinet. 39 (2007) 399-414.
iso-Octane Pyrolysis Modeling
P5avg = 60 atm
1000 1200 1400 1600 1800 1000 1200 1400 1600 1800 1000 1200 1400 1600 1800
1000 1200 1400 1600 1800 1000 1200 1400 1600 1800 1000 1200 1400 1600 1800
Experimental Data Original Sub-Model Revised Sub-Model
CH4
Mo
le F
rac
tio
n /p
pm
C2H
2C
4H
8
C6H
6C
4H
6
Reflected Shock Temperature /K
C7H
14
[ ______ _ _ _ _ ] Line Connected Modeling Data
Extended Analytical Setup (GCxGC)DURIP funded instrument
� Extended analytical setup� LECO GCxGC system
� 2 x FID detectors
� Agilent 7890A system
� 1 x FID, 1 x TCD
Analytical Capabilities
� GCxGC 2-D chromatogram of JP-8 obtained at UIC
1std
imen
sio
n r
ete
nti
on
tim
e /s
DURIP Funded GCxGC LECO System
Experiments Summary
Fuel Φ Avg. Pressure /atm Temperature /K
n-propylbenzene 0.5-2.0, ∞ 25-50 910-1678
1,3,5-trimethylbenzene 0.5-2.0, ∞ 25-50 845-1663
iso-octane 0.5-2.0, ∞ 25-50 837-1672
n-decane 0.5-2.0, ∞ 50 984-1718
n-dodecane 0.5-2.0, ∞ 25-58 867-1739
1st Gen. surrogate 1.0 & > 1 25 & 50 875-1749
2nd Gen. surrogate 1.0 25 & 50 910-1760
Jet A POSF 4658 <1.0 25 901-1750
Experiments Summary
• Speciation data obtained for all the fuels
• Jet A 4658 and 1st and 2nd generation surrogates
– Similar reactivity (O2, CO, CO2) between the
surrogates and the real fuel
– Similar small species (C1-C3) concentrations
• Polycyclic aromatic species up to 5 rings quantified
in alkylaromatic experiments
– Common two ringed and three ringed polycyclic
aromatic hydrocarbons identified for all fuels
– Formation of 4 ringed and 5 ringed aromatic
hydrocarbons dependent on fuel structure
Modeling Summary
• Tested the published model against the
– Oxidation data of decane and dodecane
• Revised the model for oxidation of iso-octane
• Importance of pyrolytic chemistry for n-alkane and iso-
alkane components
• Developed chemical kinetic models for
– Oxidation of n-propylbenzene and 1,3,5-
trimethylbenzene
Future Work
� Experiments
� Lean and rich oxidation experiments of the 1st and 2nd
Generation Surrogate (n-dodecane/iso-octane/1,3,5-
trimethylbenzene/n-propylbenzene) at 25 and 50 atm
� Jet A POSF 4658, JP-8 oxidation experiments
� Modeling
� 1,3,5-Trimethylbenzene Oxidation Model:
� Additional steps: intermediate formation
� Include the polycyclic aromatic hydrocarbon chemistry
� Refinement and validation of the n-decane/n-
dodecane sub-model and contribute to development
of the 2nd generation surrogate model
Acknowledgements
� AFOSR, financial sponsor through MURI FA9550-07-1-
0515, PI: Professor F.L. Dryer
� AFOSR DURIP, Dr. J. Tishkoff
� HPST Laboratory Students - Soumya Gudiyella, Tom
Malewicki, Andrea Comandini, Alex Fridlyand