アルコール燃料の燃焼排出物の 生成経路...アルコール燃料の燃焼排出物の...
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アルコール燃料の燃焼排出物の 生成経路
2011/12/5 1 第49回燃焼シンポジウム
防衛大学校応用化学科 安永健治
2011/12/5 2
Previous combustion studies of butanol isomers
n-Butanol Spark ignition engine
R. W. Rice, A. K. Sanyal, A. C. Elrod, J. Eng. Gas Power 113 (1991) 377-382 T. Wallner, S. A. Miers, S. McConnell, J. Eng. Gas Power 131 (2009) 32802-32809 G. L. Miller, J. L. Smith, J. P. Workman, Trans. ASAE 24 (1981) 538-540 M. Gautam, D. W. Martin, Proc. Inst, Mech. Eng. Part A 214 (2000) 165-182 M. Gautam, D. W. Martin, D. Carder, Proc. Inst, Mech. Eng. Part A 214 (2000) 497-511 Y. Yacoub, R. Bata, M. Gautam, Proc. Inst, Mech. Eng. Part 212 (1998) 363-379 F.N. Alasfour, Appl. Therm. Eng. 17 (1997) 537-549 F.N. Alasfour, Int. J. Energy Res. 21 (1997) 21-30 S. Szwaja, J. D. Naber, Fuel 89 (2010) 1573-1582
Compression ignition engine
G. L. Miller, J. L. Smith, J. P. Workman, Trans. ASAE 24 (1981) 538-540 M. Yao, H. Wang, Z. Zheng, Y. Yue, Fuel 89 (2010) 2191-2201 C. D. Rakopoulos, A. M. Diamaratos, E. G. Giakoumis, D. C. Rakopoulos, Energy 35 (2011) 5173-5184 F. Lujaji, L. Kristόf, A. Bereczky, M. Mbarawa, Fuel 90 (2011) 505-510. D. C. Rakopoulos, C. D. Rakopoulos, D. T. Hountalas, E. C. Kakaras, E. G. Giakoumis, R. G. Papagiannakis, Fuel 89 (2010) 2781-2790 D. C. Rakopoulos, C. D. Rakopoulos, E. G. Giakoumis, A. M. Diamaratos, D. C. Energ. Convers. Manage. 51 (2010) 1989-1997 O. Doģan, Fuel 90 (2011) 2467-2472. P. Saisirirat, F. Foucher, S. Chanchaona, C. Mounaïm-Rousselle, Energ. Fuel. 24 (2010) 5404–5409. P. Saisirirat, C. Togbé, S. Chanchaona ,F. Foucher, , C. Mounaïm-Rousselle, P. Dagaut, Proc. Combust. Inst. 33 (2010) 3007-3014. S. Lebedevas, G. Lebedeva, E. Sendzikiene, V. Makareviciene, Energ. Fuel. 24 (2010) 4503–4509. R.N. Mehta, M. Chakraborty, P. Mahanta, P.A. Parikh, Ind. Eng. Chem. Res 49 (2010) 7660–7665.
2011/12/5 第49回燃焼シンポジウム 3
iso-Butanol
Spark ignition engine
Compression ignition engine
F.N. Alasfour, Appl. Therm. Eng. 18 (1998) 245–256. F.N. Alasfour, Appl. Therm. Eng. 18 (1998) 609–618. F.N. Alasfour, Energ. Source. 21 (1999) 379–394.
M. Karabektas, M. Hosoz, Renew. Energ. 34 (2009) 1554–1559. M.I. Al-Hasan, M. Al-Momany, Transport 23 (2008) 306–310.
sec-Butanol and tert-Butanol
?????
OO
OO
OO
Previous combustion studies of butanol isomers
Gas analysis of oxidation of butanol isomers
2011/12/5 第49回燃焼シンポジウム 4
n-Butanol P. Dagaut, S.M. Sarathy, M.J. Thomson, Proc. Combust. Inst. 32 (2009) 229–237.
sec-Butanol, iso-Butanol C. Togbѐ, A. Mzѐ-Ahmed, P. Dagaut, Energ. Fuel. 24 (2010) 5244–5256.
Jet Stirred Reactor
Premixed laminar low pressure flame n-Butanol N. Hansen, M. R. Harper, W. H. Green, Phys Chem. Chem. Phys. 13 (2011) 20262-20274
P. Oßwald, H. Güldenberg, K. Kohse-Höinghaus, B. Yang, T. Yuan, F. Qi, Combust.
Flame 158 (1) (2011) 2-15.
sec-Butanol, iso-Butanol, tert-Butanol P. Oßwald, H. Güldenberg, K. Kohse-Höinghaus, B. Yang, T. Yuan, F. Qi, Combust.
Flame 158 (1) (2011) 2-15.
Flow reactor n-Butanol M.R. Harper, K.M. Van Geem, S.P. Pyl, G.B. Marin, W.H. Green, Combust. Flame
158 (2011) 16–41.
sec-Butanol K.M. Van Geem, S.P. Pyl, G.B. Marin, M.R. Harper, W.H. Green, Ind. & Eng. Chem.
Res., 49 (2010) 10399–10420.
Jet stirred reactor
2011/12/5 第49回燃焼シンポジウム 5
1(n)-butanol oxidation in a JSR at 10 atm, τ = 0.7 s and φ = 1. The initial fuel mole fraction was 0.1%.
Reaction Mechanism
Mani Sarathy, Stijn Vranckx, Kenji Yasunaga, Marco Mehl, Patrick Oßwald, Wayne K. Metcalfe, Charles K.
Westbrook, William J. Pitz, Katharina Kohse-Höinghaus, Ravi X. Fernandes, Henry J. Curran, Combustion and
Flame, accepted.
OO
CH3CH2CH2CHO
OO
CH3CH2CHCHOH
P. Dagaut, S.M. Sarathy, M.J. Thomson, Proc. Combust. Inst. 32 (2009) 229–237.
OO
CH3CHO
OO
CH2CHOH
2011/12/5 第49回燃焼シンポジウム 6
Experimental and predicted profiles for select species measured in stoichiometric 1(n)-butanol
flames by Hansen et al.
N. Hansen, M. R. W. H. Green, Phys Chem. Chem. Phys. 13 (2011) 20262-20274
n-Butanol, 42.8% O2, 50.0%Ar, f =1.0, p =15 Torr and v = 96.1 cm/s
Premixed laminar low pressure flame
Reaction Mechanism
Mani Sarathy, Stijn Vranckx, Kenji Yasunaga, Marco Mehl, Patrick Oßwald, Wayne K. Metcalfe, Charles K.
Westbrook, William J. Pitz, Katharina Kohse-Höinghaus, Ravi X. Fernandes, Henry J. Curran, Combustion and
Flame, accepted.
Premixed laminar low pressure flame
2011/12/5 第49回燃焼シンポジウム 7
P. Oßwald, H. Güldenberg, K. Kohse-Höinghaus, B. Yang, T. Yuan, F. Qi, Combust.
Flame 158 (1) (2011) 2-15.
Butanol, 58.1% O2, 25% Ar, f = 1.7, p = 30 Torr and v = 32.3 cm/s
Reaction Mechanism
Mani Sarathy, Stijn Vranckx, Kenji Yasunaga, Marco Mehl, Patrick Oßwald, Wayne K. Metcalfe, Charles K.
Westbrook, William J. Pitz, Katharina Kohse-Höinghaus, Ravi X. Fernandes, Henry J. Curran, Combustion and
Flame, accepted.
2011/12/5 第49回燃焼シンポジウム 8
P. Oßwald, H. Güldenberg, K. Kohse-Höinghaus, B. Yang, T. Yuan, F. Qi, Combust.
Flame 158 (1) (2011) 2-15.
Premixed laminar low pressure flame
Reaction Mechanism
Mani Sarathy, Stijn Vranckx, Kenji Yasunaga, Marco Mehl, Patrick Oßwald, Wayne K. Metcalfe, Charles K.
Westbrook, William J. Pitz, Katharina Kohse-Höinghaus, Ravi X. Fernandes, Henry J. Curran, Combustion and
Flame, accepted.
2011/12/5 第49回燃焼シンポジウム 9
Premixed laminar low pressure flame Reaction Path
2011/12/5 第49回燃焼シンポジウム 10
P. Oßwald, H. Güldenberg, K. Kohse-Höinghaus, B. Yang, T. Yuan, F. Qi, Combust.
Flame 158 (1) (2011) 2-15.
Premixed laminar low pressure flame
Reaction Mechanism
Mani Sarathy, Stijn Vranckx, Kenji Yasunaga, Marco Mehl, Patrick Oßwald, Wayne K. Metcalfe, Charles K.
Westbrook, William J. Pitz, Katharina Kohse-Höinghaus, Ravi X. Fernandes, Henry J. Curran, Combustion and
Flame, accepted.
2011/12/5 第49回燃焼シンポジウム 11
Premixed laminar low pressure flame Reaction Path
Flow Reactor
2011/12/5 第49回燃焼シンポジウム 12
Conversion and yield profiles for n-C4H9OH and n-butyraldehyde (C3H7CHO) in the
pyrolysis reactor at 1.7 atm.
920 960 1000 1040 10800
20
40
60
80
100
Tmax.
/ K
n-C
4H
9O
H c
on
vers
ion
(w
t %
)
920 960 1000 1040 10800.0
0.5
1.0
C3H
7C
HO
yie
ld (
w.t
. %
)
Tmax.
/ K
Reaction Mechanism
Mani Sarathy, Stijn Vranckx, Kenji Yasunaga, Marco Mehl, Patrick Oßwald, Wayne K. Metcalfe, Charles K.
Westbrook, William J. Pitz, Katharina Kohse-Höinghaus, Ravi X. Fernandes, Henry J. Curran, Combustion and
Flame, accepted.
M.R. Harper, K.M. Van Geem, S.P. Pyl, G.B. Marin, W.H. Green, Combust. Flame
158 (2011) 16–41.
2011/12/5 第49回燃焼シンポジウム 13
Flow Reactor
960 980 1000 1020 10400
20
40
60
80
100
T
max./ K
sec-C
4H
9O
H c
on
vers
ion
(w
t %
)
960 980 1000 1020 10400
2
4
6
8
10
12
14
16
C
H3C
OC
H3 (
wt
%)
Tmax.
/ K
Conversion and yield profiles for sec-C4H9OH and acetone in the pyrolysis reactor at 1.7
atm measured by Van Geem et al.
Reaction Mechanism
Mani Sarathy, Stijn Vranckx, Kenji Yasunaga, Marco Mehl, Patrick Oßwald, Wayne K. Metcalfe, Charles K.
Westbrook, William J. Pitz, Katharina Kohse-Höinghaus, Ravi X. Fernandes, Henry J. Curran, Combustion and
Flame, accepted.
K.M. Van Geem, S.P. Pyl, G.B. Marin, M.R. Harper, W.H. Green, Ind. & Eng. Chem.
Res., 49 (2010) 10399–10420.
2011/12/5 第49回燃焼シンポジウム 14
0
50
100
150
n-C4H
9OH
C2H
4
C /
C0 (
%)
0
20
40
C2H
2
C2H
6
C /
C0 (
%)
1000 1100 1200 1300 1400 15000
30
60
CO
CH4
C3H
6
T5 / K
1000 1100 1200 1300 1400 15000
10
20
C3H
4-A
C4H
8-1
CH3CHO
C /
C0 (
%)
C /
C0 (
%)
T5 / K
0
50
100sec-C
4H
9OH
CH3CHO
CO
0
30
60 C2H
4
CH3COCH
3
C3H
6
C /
C0 (
%)
C /
C0 (
%)
1000 1100 1200 1300 1400 15000
30
60C
2H
5CHO
C3H
4-A
CH4
C2H
6
C2H
2
T5 / K
1000 1100 1200 1300 1400 15000
3
6
9C
/ C
0 (
%)
C
/ C
0 (
%)
T5 / K
Shock tube
Normalized species concentration profiles for the pyrolysis of 1.5% n-C4H9OH
diluted in Ar, effective heating time = 2.6−3.0 ms, lines simulation.
Normalized species concentration profiles for the pyrolysis of 1.5% sec-C4H9OH
in Ar, effective heating time = 2.6−3.0 ms, lines simulation.
OO
CH3CHO
OO
CH2CHOH
OO
CH3COCH3
OOiC3H5OH
OO
C2H5CHO
OO
CH3CHCHOH
n-Butanol
OO
sec-Butanol
Shock tube
2011/12/5 第49回燃焼シンポジウム 15
0
50
100
C /
C0 (
%)
iso-C4H
9OH
CO
C3H
4-A
0
30
60
C2H
5CHO
CH3CHO
C /
C0 (
%)
C3H
6
C2H
4
iC4H
8
1000 1100 1200 1300 1400 15000
20
40
60 CH4
C2H
6
C2H
2
T5 / K
1000 1100 1200 1300 1400 15000
5
10
15
C /
C0 (
%)
C /
C0 (
%)
T5 / K
0
50
100
C /
C0 (
%)
t-C4H
9OH
i-C4H
8
CO
0
30
60
C /
C0 (
%)
CH3COCH
3
C3H
6
CH4
C2H
6
C2H
2
1000 1100 1200 1300 1400 15000
20
C2H
4
C3H
4-A
C3H
4-P
T5 / K
1000 1100 1200 1300 1400 15000
10
20
30
C /
C0 (
%)
C /
C0 (
%)
T5 / K
Shock tube
Shock tube
Normalized species concentration profiles for the pyrolysis of 1.5% iso-C4H9OH
diluted in Ar, effective heating time = 2.6−3.0 ms, lines simulation.
Normalized species concentration profiles for the pyrolysis of 1.0% tert-C4H9OH
in Ar, effective heating time = 1.5 − 1.7 ms, lines simulation.
OO
iso-Butanol
OO
tert-Butanol
Reaction path analysis
2011/12/5 第49回燃焼シンポジウム 16
Reaction path analysis for iso-C4H9OH pyrolysis. Shock conditions: 1.5% iso-C4H9OH
diluted in Ar, 1300 K, 1.9 atm, 20 % consumption
Summary
2011/12/5 第49回燃焼シンポジウム 17
Keto-enol tautomerization
OO
CH3CHO
OO
CH2CHOH
Hydrogen addition and methyl elimination
OO
CH3CHCHOH OO
CH2CHOH
H
+ CH3
Chemically-activated H-atom (HO2 radical and formic acid) assisted tautomerization reaction
OO
CH3CHO
OO
CH2CHOH
H + H +
Further reactions