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2 CEFRC2-3, 2014
Part 3: Chemical Kinetics, HCCI & SI Combustion
HCCI uses a hybrid combustion strategy. Premixed fuel and air is inducted,
but instead of igniting with a spark as in a SI engine, the high temperature from
compression causes the mixture to spontaneously react, like in a diesel engine.
Ignition occurs at slightly different times at different locations in the chamber.
One feature of HCCI combustion is how quickly the fuel is consumed.
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Part 3: Chemical Kinetics, HCCI & SI Combustion Curtis, 2014
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Part 3: Chemical Kinetics, HCCI & SI Combustion Daw, 2013
HCCI
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Part 3: Chemical Kinetics, HCCI & SI Combustion
Species conversion rate (Yi, species mass fraction, * local equilibrium solution)
dYi
Mallard-Le Chatelier propagating wave speed: ST D ~ Vpiston
dt
Glassman, 1996
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Part 3: Chemical Kinetics, HCCI & SI Combustion Halstead, 1977
R* R* + B
R* R* + Q Af04
R* + Q R* + B
B 2R*
R* termination
2R* termination
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Part 3: Chemical Kinetics, HCCI & SI Combustion
Turbulent mixing
Hot products with
Spark-ignition Cold reactants
t ~ k/e
burned
unburned ~ Lpiston / Vpiston
High turbulence
ST
- faster combustion
Diesel
Injected fuel with
entrained air
fuel air
t~ k/e
~ Lnozzle / Vnozzle
ST/SL
air
Matalon, 2011
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Part 3: Chemical Kinetics, HCCI & SI Combustion
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Part 3: Chemical Kinetics, HCCI & SI Combustion Williams, 1988
ei
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Part 3: Chemical Kinetics, HCCI & SI Combustion Law, 2006
h0f ,ii
13
T n 1.4 10 2
s
t cp
13
1.2 10
i 1
k 1 10
13 1.5
CH 4 OH
CH 3 H 2O
k 12
6 10
12
4 10
k AT b exp( E / RT )
0.5
12
2 10
d [CH 4 ] CH4 0 0
dt WCH4 T
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Part 3: Chemical Kinetics, HCCI & SI Combustion Reitz, 1981
0.6
Yi
i / 0.4
t
m
(1-U)
m=0.5
m+1
F(U)=U
0.3
T ns
h0f ,ii
Cold boundary 0.2
m=1.0
t i 1 cp difficulty 0.1
U
Consider single component system 0
0 0.2 0.4 0.6 0.8 1
T Tunburned U U
U 1.0
Tburned Tunburned
Example:
dU
F (U ) bU m 1 (1 U ) m
dt Ignition
1 1
For U Uo: mb t delay
U 0m U m
bt
So, time to reach, say, 5U0 : Uo
Ignition delay: b t 4 1
5mU 0m mb t Const. F (m, m;(1 m);U )
m 2 1
U
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Part 3: Chemical Kinetics, HCCI & SI Combustion Warnatz, 2006
Combustion chemistry models – CH4 (15 spec, 31 react.)
CH4+ 2 O2 = CO2 + 2 H2O
Methyl Reactions
Hydrogen-Oxygen Chain 13 CH3 + O CH2O + H
1 H + O2 OH +O 14 CH3+OH CH2O + H +H
2 H2 + O OH + H 15 CH3+OH CH2O + H2
High temperature
H2 O2 chemistry
Biodiesel surrogates
- Significant mechanism
reduction is required.
Soy biodiesel - Methyl:
- palmitate (C16:0)
- stearate (C18:0)
- oleate (C18:1)
CH4 - linoleate (C18:2)
- linolenate (C18:3)
C2 C4 C9
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Part 3: Chemical Kinetics, HCCI & SI Combustion Warnatz, 2006
800
600
400
200
0
555 580 605 630 655 680 705 730
Initial Temperature (K)
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Part 3: Chemical Kinetics, HCCI & SI Combustion Warnatz, 2006
Alkane fuel oxidation
Example: Propane Energy release
CO + OH CO2 + H
Smaller R HCO
High
CH3, C2H5,… Chain branching temperature >1200K
b-scission H + O2 OH + O reaction
+ O2
T, P
OO• H2O2
+ HO2•
• OOH O
+ + •OH
+ O2
O
OOH + •OH
HRR
Ethers/
• OO olefins
Degenerate
- •OH Branching Path
O O CAD
OH
• TDC
+ O +
HOO •
Aldehydes/ketones
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Part 3: Chemical Kinetics, HCCI & SI Combustion Patel, 2004
,7
3,4,5 7. C7H15O2 + O2= C7ket12 + OH
1,7 Time
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Part 3: Chemical Kinetics, HCCI & SI Combustion Ra, 2008
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Part 3: Chemical Kinetics, HCCI & SI Combustion Ra, 2011
Pre-exponential: A = k×Abase
0.01
Ignition delay sensitivity coefficient 600 700 800 900 1000 1100 1200 1300 1400
initial temperature [K]
(log10 tk1 log10 tk2 )
Sig (T ) 100 25
ignition delay sensitivity
gradient sensitivity
60
log10 tbase log10 (k1 k2 )
S gr (T ) dT dT 100 0
5
log10 (k1 k2 ) -10
-20
0
Positive Sgr: counter-clockwise rotation -30
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Part 3: Chemical Kinetics, HCCI & SI Combustion Ra, 2011
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Part 3: Chemical Kinetics, HCCI & SI Combustion Ra, 2008
ERC-MultiChem: PRF
41 species, 158 reactions base mechanism
Source mechanisms: LLNL n-heptane
100
(560 species; 2,539 reactions), isooctane
(857 species; 3,606 reactions), =1.0, 40 bar
10
Exp, iC8
1
0.1 Exp, PRF90
Exp, PRF80
Exp, PRF60
Exp, nC7
0.1 100 0.01
PRF
nC7H16/air 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6
MultiChem
10 Exp, Fieweger et al. (1997) 1000/initial temperature [1/K]
ignition delay [ms]
0.01
0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
1000/T [1/K] 1
0.1
n-dodecane n-heptane
n-alkane
n-octadecane n-tetradecane
iso-alkanes
heptamethyl nonane iso-octane 857 species 25 species
tetramethyl hexane 3586 reactions 51 reactions
Aromatics
naphthalene
mcymene
tetralin toluene
n-pentylbenzene
n-heptylbenzene
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Part 3: Chemical Kinetics, HCCI & SI Combustion Ra, 2011
8 Surrogate fuels: n-heptane,
Ignition delay validations - “MultiChem” iso-octane, tetradecane, cyclohexane,
Gauthier CNF 2004 Fieweger CNF 1997 toluene, decalin, ethanol, MB/D……
1000 10 100
Model Model
Experiment
Exp, Fieweger et al. (1997)
ignition delay [ms]
Experiment
100 Model
10
Propane 1 iC8H18
phi=1.0 0.1 nHeptane phi=1.0
1
Pin= 30 bar phi=1.0 0.1 Pini=40 bar
0.1
Pini=40 bar Fieweger CNF 1997
0.01
0.9 1 1.1 1.2 1.3 1.4 1.5 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 0.01
1000/T [1/K] 1000/T [1/K] 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
1000/T [1/K]
Model
1000 ERC-MultiChem
1000 1
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Part 3: Chemical Kinetics, HCCI & SI Combustion Amsden, 1997
Species
Momentum
combustion source terms
Energy
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Part 3: Chemical Kinetics, HCCI & SI Combustion Perini, 2014
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Part 3: Chemical Kinetics, HCCI & SI Combustion Perini, 2014
1
10
18 ignition delay calculations per
0
10
mech
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Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2009
Shi, 2012
Efficient chemistry solvers – cell clustering Perini, 2014
Thermodynamically
similar cells
(similar temperature,
equivalence ratio )
Chemkin Solver
Remap back
to cells
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Part 3: Chemical Kinetics, HCCI & SI Combustion Shi, 2012
2.5
Pressure (MPa)
2.0
1.5
1.0
Experiment
0.5
Simulation-Full Chemistry
0.0
Simulation-AMC + EDAC model
-50 -40 -30 -20 -10 0 10 20 30 40 50
Crank Angle
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Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2006
Post-flame Chemistry
• CO oxidation, H2-O2 reactions
• Pollutant formation mechanisms
Knocking Combustion
• Auto-ignition mechanisms
• Location / intensity
Spark Ignition Engine
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Part 3: Chemical Kinetics, HCCI & SI Combustion Law, 2014
A L
ST S L
A L
AT
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Part 3: Chemical Kinetics, HCCI & SI Combustion
Flamelets
lK lF
Ghandhi, 2012
lF
/c |
p T0
~ 20 mm
If lK Cm3l Cm3 0.1lF , local ST0 = 0
u S L Liang, 2007
0.60 methane
1,2,4-trimethylbenzene
m-xylene
0.55 1,3,5-trimethylbenzene
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Part 3: Chemical Kinetics, HCCI & SI Combustion Lutz, 1988
Rich
conditions
Acetylene
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Part 3: Chemical Kinetics, HCCI & SI Combustion Lutz, 1988
Importance of chemistry - Ethane
• Limited flux through slow methyl channels
– hydrogen abstraction leaves weaker secondary C-H2 bonds
• Greater flux through chain branching pathways, e.g.,
H + O2 OH + O
• Ignition delays are very sensitive to rates of H atom production
Acetylene
Olefin
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Part 3: Chemical Kinetics, HCCI & SI Combustion Wang, 2012
Diffusion: Turbulence models
(RANS - RNG k-e Production
P u i u j S ij
ui ui’ + Ui = ui Mean flow strain rate
t l = Ui t
t k/e
t
DT Cm k 2 / e
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Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007
Diffusion
G-Equation
Flame Φ≈1 CO2, H2O, CO, NO…
propagation
Burnt Gas
Diffusion
End Gas CH4, CO, H, H2 …
Φ>1
Auto-ignition
(detailed kinetics)
Fuel Droplets
ST from flame speed correlations
Burned gas: G>0 End-gas Flame Post-flame
Zone Front Zone
Unburned gas: G<0
~
G ~ ~ ~ ~
(v f vvertex ) G u ST0 G DT k G
t
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Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007
Cm 2 t tign
1/ 2
2
1/ 2
ST a b
2
l a b
2
l u l
1 1 exp 4 3 4 3 a4b3
2
Progress Term
Peters, 2000
3/ 2 Discrete Particle
u l
1/ 2
l
Stretch factor: I0 1 F 2 F u Ignition Kernel
15 l SL rK K (DPIK) model
(cm/sec)
2.18 0.8( 1) 20
b 0.16 0.22( 1) 15
L,ref
Reference State: 300K, 1bar 10
0
S
S L,0 Bm B2 ( m ) 2 5
Liang et al. : 0
SL,0 exp ( )2
0.0 0.5 1.0 1.5 2.0 2.5
Equivalence Ratio,
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Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007
CA = 10 ATDC CA = 20 ATDC
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Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007
Pressure (MPa)
Pressure (MPa)
0.0 0.0
-100 -50 0 50 100 -100 -50 0 50 100
o o
Crank Angle ( ATDC) Crank Angle ( ATDC)
2.5 2.5
EXPT EXPT
2.0 SIMU Pressure (MPa) 2.0 SIMU
Pressure (MPa)
1.0 1.0
0.5 0.5
0.0 0.0
-100 -50 0 50 100 -100 -50 0 50 100
o o
Crank Angle ( ATDC) Crank Angle ( ATDC)
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Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007
2.5
Pressure (MPa)
DI mode
PFI mode
1.5
2.0
dYi
Mallard-Le Chatelier propagating wave speed: ST D
dt
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Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007
Kinetics Controlled G-equation
Role of flame propagation
PFI case
Spark timing = -44 ATDC
Summary:
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