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生成経路 2011/12/5 第49回燃焼シンポジウム 1 防衛大学校応用化学科

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


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


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


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



Flame, accepted.




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



Flame, accepted.



Flame 158 (1) (2011) 2-15.


Reaction Mechanism



Flame, accepted.


Premixed laminar low pressure flame Reaction Path



Flame 158 (1) (2011) 2-15.


Reaction Mechanism



Flame, accepted.


Premixed laminar low pressure flame Reaction Path

Flow Reactor


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



Flame, accepted.

M.R. Harper, K.M. Van Geem, S.P. Pyl, G.B. Marin, W.H. Green, Combust. Flame

158 (2011) 16–41.


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



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.


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


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


Reaction path analysis for iso-C4H9OH pyrolysis. Shock conditions: 1.5% iso-C4H9OH

diluted in Ar, 1300 K, 1.9 atm, 20 % consumption

Summary


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

Documents

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 生成経路 2011/12/5 第49回燃焼シンポジウム 1 防衛大学校応用化学科

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生成経路 2011/12/5 第49回燃焼シンポジウム 1 防衛大学校応用化学科