Part 3: Chemical Kinetics, HCCI & SI Combustion

Reciprocating Internal Combustion Engines

Prof. Rolf D. Reitz,

Engine Research Center,
University of Wisconsin-Madison
2014 Princeton-CEFRC
Summer Program on Combustion
Course Length: 15 hrs
(Mon.- Fri., June 23-27)

Copyright ©2014 by Rolf D. Reitz.

This material is not to be sold, reproduced or distributed without
prior written permission of the owner, Rolf D. Reitz.
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 Part 3: Chemical Kinetics, HCCI & SI Combustion

Short course outline:

Engine fundamentals and performance metrics, computer modeling supported
by in-depth understanding of fundamental engine processes and detailed
experiments in engine design optimization.
Day 1 (Engine fundamentals)
Part 1: IC Engine Review, 0, 1 and 3-D modeling
Part 2: Turbochargers, Engine Performance Metrics
Day 2 (Combustion Modeling)
Part 3: Chemical Kinetics, HCCI & SI Combustion
Part 4: Heat transfer, NOx and Soot Emissions
Day 3 (Spray Modeling)
Part 5: Atomization, Drop Breakup/Coalescence
Part 6: Drop Drag/Wall Impinge/Vaporization/Sprays
Day 4 (Engine Optimization)
Part 7: Diesel combustion and SI knock modeling
Part 8: Optimization and Low Temperature Combustion
Day 5 (Applications and the Future)
Part 9: Fuels, After-treatment and Controls
Part 10: Vehicle Applications, Future of IC Engines

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 Part 3: Chemical Kinetics, HCCI & SI Combustion

Modes of engine combustion http://www.erc.wisc.edu/combustion.php

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

Chemistry: importance of fuels

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Daw, 2013

New advanced combustion regimes

HCCI

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 Part 3: Chemical Kinetics, HCCI & SI Combustion

Basic combustion concepts – Spark Ignition (SI)

How can SI engines operate with engine speeds from 100 to 20,000 rev/min?
T Kinetic energy, k~Vpiston2
burned Integral length scale lI ~ Lpiston
x Turbulence! Kinetic energy dissipation rate,
e ~ Vpiston3/Lpiston
ST
fuel/air
Diffusivity, D ~ k2/e ~ Vpiston Lpiston

Because turbulent flame speed, ST, scales with rpm!

Characteristic Time Combustion (CTC) model Reitz & Bracco, 1983; Abraham, 1985

Species conversion rate (Yi, species mass fraction, * local equilibrium solution)

; tc ~ k/e ~ Lpiston / Vpiston

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

Basic combustion concepts – Diesel (CI)

Shell Ignition Model
Ignition Q
R* RH +O2  2R*
Delay
B R*  R* + P + Heat

R*  R* + B
R*  R* + Q Af04
R* + Q  R* + B

B  2R*

R*  termination

2R*  termination

Switch to Characteristic Time

Combustion model

Turbulence generated by fuel injection

tc ~ k/e ~ Lnozzle / Vnozzle
Kong, 1992

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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

Delayed ignition (PCCI)

- better mixing ST=0

Matalon, 2011

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 Part 3: Chemical Kinetics, HCCI & SI Combustion

Summary of combustion regimes

• Gasoline engine spark-ignition with flame propagation:
High turbulence for high flame speed  heat losses. Issues: NOx and UHC/CO,
knock (CR, fuels), throttling losses  low thermal efficiency TE ~25%
• Diesel engine with spray (diffusion) combustion:
Rich mixtures (soot) & high temperatures (NOx)  higher TE ~45%
• H/Premixed Charge Compression Ignition – LTC, chemistry controlled (CR):
Sensitive to fuel, poor combustion/load control, low NOx-soot  TE ~50%
spark-ignition
diesel
H/PCCI

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Williams, 1988

Premixed volumetric combustion & chemical kinetics

Species and energy conservation equations
i 
   ( i u )    [  D( i )]  ic  is
t 

Constant volume combustion – Well-Stirred-Reactor (WSR)

dYi Wi nr ''
  ( k ,i  k' ,i )k (Y , T ), i  1,..., ns
dt  k 1
 k' ,i  k'' ,i
ns
 Yi  ns
 Y  I specific internal energy
k (Y , T )   f ,k      b,k   i  chemical label
i 1  Wi  i 1  Wi 
nr reactions
; ns species
reactant/product
stoichiometric
coefficients
mass fraction
dT 1 ns
 ei (T ) dYi 
(Y , T )   
cv (Y , T ) i 1  Wi dt
(Y , T )  molecular weight
dt  ei species energy

ei
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 Part 3: Chemical Kinetics, HCCI & SI Combustion Law, 2006

Homogeneous charge: no spatial gradients

 Yi
 i / 
t A  1.6 107 (cm, mol , s), b  1.83, E  11.6(kJ / mol )

h0f ,ii
13

T n 1.4 10 2

 
s

t cp
13
1.2 10
i 1
k 1 10
13 1.5

Consider single overall reaction 12


8 10 CH4
k 1

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

 k[CH 4 ][OH ]  0 500 1000 1500 2000 2500

dt WCH4 T

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Reitz, 1981
0.6

HCCI: Ignition delay F (U ) m=0.25

0.5

 Yi
 i /  0.4

t

m
(1-U)
m=0.5

m+1
F(U)=U
0.3

T ns
h0f ,ii
  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

3 H2 + OH H2O + H 16c CH3 + H  CH4

4 H2O + O 2 OH 23 CH3 + H  CH2 + H2
Hydroperoxyl Formation and Consumption 28 CH3 + OH CH2 + H2O
5b H + O2 + M  HO2 + M Formaldehyde Reactions
6 HO2 + H  2 OH 17 CH2O + H CHO + H2
7 HO2 + H  H2 + O2 18 CH2O + OH CHO + H2O
8 HO2 + H  H2O + O Formyl Reactions
9 HO2 + OH  O2 + H2O 19 CHO + H CO + H2
Conversion of Carbon Monoxide to Carbon Dioxide 20 CHO + OH CO + H2O
End 10 CO + OH  CO2 + H 21 CHO + O2 CO + HO2
Methane Consumption 22 CHO + M CO + H + M
Start 11 CH4 + H  H2 + CH3 Initiation
H atom abstraction
12 CH4 + OH  H2O + CH3 Methylene Reactions
24 CH2 + O2  CO2 + H2
Methylidyne Reactions 25 CH2 + O2  CO + OH + H
27 CH + O2  CHO + O 26 CH2 +H  CH + H2
31 CH + OH  CH2O + H 29 CH2 + OH  CH2O + H
Conversion to products by sequential fragmentation by H abstraction 30 CH2 + OH  CH + H2O
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 Part 3: Chemical Kinetics, HCCI & SI Combustion Lu, 2009
Brakora, 2013
Chemical kinetic mechanisms for engine simulations
Requirements for mechanisms for practical engine simulations:
• Size can not be too large due to CPU time limitation ~ 100 species
• Capable of predicting auto-ignition delay time accurately
• Contain proper reactions for pollutant formation precursors

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

Hydrocarbon kinetics - NTC

Second Stage Ignition
H2O2 = OH + OH Acceleration by
1400
Q•OOH branching
1200

Induction Period (s)

O2
. 1000

800

600

400

200

0
555 580 605 630 655 680 705 730
Initial Temperature (K)

First Stage Ignition

Isomerization steps

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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

Fuel: RH R Thermal decomposition Blue flame 1100K

+OH, H,… H2O2 OH + OH
+
n-C3H7• + O2
Internal H atom Negative
abstraction Chain propagation temperature 800
ROO QOOH
QO + OH coefficient ~900K
+O2
Olefin channel
OOQOOH
Internal H atom Chain branching
abstraction
HOOQ’O + OH Cool flames 800K
•CH2CH2CH2OOH HOOQ’OOH
Isomerization OQ’O + OH
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 Part 3: Chemical Kinetics, HCCI & SI Combustion Mehl, 2009
HCCI combustion kinetics
R• H Typical HCCI Combustion
Fast High Temperature Temperature and Heat Release Rate
- RH Combustion profiles
•
•

+ 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

Mechanism reduction – identify key reaction steps

ERC n-heptane mechanism

Burnout
stage
66
Temperature

1. n-C7H16 + OH= C7H15-2+ H2O

2. C7ket12 = C5H11CO + CH2O + OH

2nd
1st stage 3. H2O2 + M = OH + OH + M

stage 4. HO2 + HO2 = H 2O 2 + O2

5. CH4 + HO2= CH3 + H2O2

2
6. CO + OH= CO2 + H

,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

Reduced mechanisms: match shock tube and RCM data

First stage (t1), main ignition (t2=tig) delay

10
Expts: Fieweger, 1997

ignition delay [ms]

1

0.1 Cal, tig

Predicted ignition delay times Exp, tig
Cal, t1
validated against shock tube tests
Exp, t1
(data from Fieweger) 0.01
=1.0 and P=40 bar n-heptane/air 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
1000/initial temperature [1/K]

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Ra, 2011

Mechanism reduction methodology tetra-decane: ROO+O2 =R-keto+OH

10
Reduction of reaction pathways and species number A = k×Abase baseline
k=2
- combination of chemical lumping, graphical

ignition delay [ms]

k=0.5
reaction flow analysis and elimination methods 1

Reaction rate optimization

- ignition delay curve sensitivity analysis 0.1

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 )

gradient sensitivity coefficient

50
20
40

ignition sensitivity [%]

Ignition delay gradient sensitivity coefficient 15
30
20
d log10 tk1 d log10 tk2
 10 10

S gr (T )  dT dT 100 0
5
log10 (k1 k2 ) -10
-20
0
Positive Sgr: counter-clockwise rotation -30

Negative Sgr: clockwise rotation -5 -40

650 750 850 950 1050 1150 1250 1350 1450
initial temperature [K]

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Ra, 2011

Mechanism reduction – group reaction classes Ignition delay

sensitivity coefficient
No Reaction As Bs Cs Ar Br Cr effect
I RH  H  R  H 2O
II RH  OH  R  H 2O ●↓ ●↑ ●C τ1, p2, p3, τ 4
III RH  HO2  R  H 2O2 ○↓ ○↓ ○↓ τ 1, P2, P3, τ 4
IV RH  O2  R  HO2 ○↑ ○↓ ● P2, P3
V R  O2  ROO
VI-a ROO = QOOH ●↓ ●↓ ○C τ 1, P2
VI-b QOOH + O2 = OOQOOH ○↓ ●↓ P2, P3
VI-c OOQOOH = R-keto + OH ○↓ ●↓ P2, P3
VII R-keto = CH2O + R'CO + OH ●↓ ○C τ1
VIII R'CO = X1 + X2 + CO
IX R = S1 + S2 + S3 ●↑ ○ P2, P3, τ 4

Ignition delay gradient

Sensitivity of ignition delay curves of n-heptane oxidation
sensitivity coefficient
- solid circle, open circle and blank entry denote
dominant, mild and not significant influence, respectively.
- C indicates counter-clockwise rotation.
- Circle only indicates clockwise rotation.

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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

ignition delay [ms]

ERC n-heptane (29 species; 52 reactions)
iC8
10 PRF90
PRF 1 PRF80
MultiChem PRF60
Exp, Fieweger et al. (1997) nC7
ignition delay [ms]

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

=1.0, iC8H18/air, 40 bar

0.01
0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
1000/T [1/K]
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 Part 3: Chemical Kinetics, HCCI & SI Combustion Ra, 2011

Chemical class grouping: “MultiChem” skeletal mechanism

Physical property Chemistry LLNL Detailed ERC reduced
surrogates surrogates mechanism mechanism*
Cyclo alkanes
cyclohexane
cyclohexane
decalin

100 species, 348 reactions

MultiChem Mechanism
n-alkane

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

ignition delay [ms]

10

ignition delay [ms]

1

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]

10000 EXP (Bounaceur et al.)

10000 10
Bounaceur et al.
Experiment
Andrae et al.
ignition delay [micr-sec]

Model
1000 ERC-MultiChem

ignition delay [ms]

tig n [mic ro-s ]

1000 1

100 MCH Decalin

Phi=1.0 phi=1.0
100 0.1
10
Toluene Pini=40 bar
E xperiment
Model
1
10 0.01
0.55 0.6 0.65 0.7 0.75 0.8
0.8 0.9 1 1.1 1.2 1.3 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
1000/T [1/K]
1000/T [1/K ] 1000/T [1/K]
Bounaceur IJCK 2005; Andrae CNF 2005 Shen,Energy & Fuels, 2009

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Amsden, 1997

3-D CFD modeling

Solve conservation equations on (moving) numerical mesh
Mass

Species

Momentum
combustion source terms

Energy

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Perini, 2014

3-D CFD: Improved solver numerics

ERC PRF mechanism Jacobian structure LLNL n-heptane mech. Jacobian structure LLNL MD mechanism Jacobian structure

Sparse analytical Jacobian

formulation
Sparsity of hydrocarbon
fuel mechanisms increases
with size ns
non-zeroes: 860; sparsity: 62.7% non-zeroes: 3571; sparsity: 86.2% non-zeroes = 49763; sparsity: 99.7%

47 (62.7%) 160 (86.2%) 2878 (99.7%)

SpeedCHEM performance scaling

Y
2
i 10
 i /   ns
t 1
10 LLNL

time per evaluation [ms]

h i
nC7H16
T n 0 ERC
 
s
f ,i multichem
0
t i 1 cp 10 ERC
PRF
LLNL LLNL
-1 PRF MD
10
All functions and equations are evaluated in function, y' = f(y)
-2
matrix form 10 ERC Jacobian, J(y) = df(y)/dy
nC7H16 linear system solution
ODE system function, analytical Jacobian
-3
evaluation and linear system solution 10 1 2 3 4
10 10 10 10
achieve linear scaling with ns number of species, ns

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Perini, 2014

3-D CFD: Improved solver numerics

SpeedCHEM ignition delay time calculation scaling
9 reaction mechanisms tested
4
10

3 Direct dense Jacobian

10
SpeedCHEM, direct sparse
SpeedCHEM, Krylov
-ns = 29 to 7171
2
10 3
 ns -nr = 52 to 31669
CPU time [s]

1
10
18 ignition delay calculations per
0
10
mech

- phi = [0.5, 1.0, 2.0]

-1
10  ns
-2 - T0 = [650, 800, 1000] K
10
- p0 = [20, 50] bar
-3
10
1 2 3 4
- t = [0.1] s
10 10 10 10
number of species

Promising, efficient approach for practical engine simulations

1.Numerically exact solution (no mechanism reduction or manipulation).
2.Speed-up of more than three orders of magnitude at large sizes (ns>1000)
3.Even for modest sizes (~50-500 species), overall CPU time for chemistry is reduced
by 3-10 times in comparison with dense chemistry integrators
4.Preconditioned Krylov solution for future, very large mechanisms

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2009
Shi, 2012
Efficient chemistry solvers – cell clustering Perini, 2014

Group thermodynamically-similar cells to reduce the calling frequency to save

computer time - Adaptive Mechanism Clustering (AMC) scheme

Extended dynamic adaptive chemistry (EDAC) scheme

Dynamically determine the size of fuel chemical mechanism based on the
local and instantaneous thermal conditions of the cells

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

HCCI engine validation

ERC PRF mech. Full AMC AMC+EDAC

(39 sp, 141 rxn) 48.27 hrs. 3.99 hrs. 2.88 hrs.
3.0

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

29 29 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2006

SI engine combustion modeling

Flame propagation Models with Detailed Chemistry
Turbulent Flame Propagation
Spark plug • G-equation description of combustion
• Laminar and turbulent flame speeds
• Primary heat release calculation
• Flame quench due to mixture stratification

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

What is a turbulent flame?

AT
ST

A L

Ensemble of thin (laminar) flamelets,

interacting with the flow turbulence.

Due to increased surface area, turbulent

flame “brush” propagates at enhanced velocity

ST  S L
A L

AT

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 Part 3: Chemical Kinetics, HCCI & SI Combustion

Turbulent flame structure Combustion regime diagram

Kolmogorov/Batchelor Peters, 2000
length scales:
1/ 4 Quenched broken
 3  reaction zones
lK     Re3/ 4 lI
e  lK  l Engine flames

Flamelets
lK  lF
Ghandhi, 2012

Laminar flame thickness:

lF 
  /c |
p T0
~ 20 mm
If lK  Cm3l  Cm3 0.1lF , local ST0 = 0
u S L Liang, 2007

It is not possible to resolve a turbulent flame on a practical engine simulation grid

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 Part 3: Chemical Kinetics, HCCI & SI Combustion Reitz, 1981

Laminar flame speed: balance between reaction and diffusion

 Yi  2Yi
 D 2  i / 
t x dY
~
ST = DT i - Mallard, Le Chatelier
T  T 2 N
 D 2   h0f ,ii /  c p
dt
t  x i 1
Consider the single component system:
U  2U T  Tunburned
 D 2  F (U ) with U  and F (U )  bU
m 1
(1  U )m
t x Tburned  Tunburned
Admits a traveling wave solution
1.0 
mS
( x  St )
U ( x  St )  [1/(1  e D
)]1/ m
where U S
Db D D(m  1)
S and  
m 1 mS b m2 0
x
33 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Farrell, 2005

Laminar flame speed

C-C-OH
C-C-C C=C-C methanol
0.90
1-pentene ethanol
propene
1-butene
0.85 1-heptene benzene
1-hexene
1-octene
ethane
n-heptane anisole
0.80 3-heptene
cyclohexane
Peak Burning Velocity (m/s)

cyclopentane 2-butene 2-pentene ethylbenzene i-propylbenzene

n-hexane
cyclopentene
n-butane
0.75 propane t-butylbenzene
n-pentane n-propylbenzene
methylcyclopentane
2-methyl-2-butene
0.70 2-methyl-1-butene MTBE
iso-octane toluene
iso-octene
iso-pentane
0.65
iso-butane

neopentane o,p xylene

0.60 methane
1,2,4-trimethylbenzene
m-xylene

0.55 1,3,5-trimethylbenzene

Paraffins Olefins Aromatics Oxygenates

34 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Lutz, 1988

Importance of chemistry - Methane

Flux analysis: oxidation proceeds through methyl
– slow path, high activation energy due to tight C-H3 bonds

Rich
conditions

Acetylene

35 CEFRC2-3, 2014
 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

Ignition delay Ethane < Ignition delay Methane

36 CEFRC2-3, 2014
 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

k = 3ui2/2 Reynolds stresses

t l = Ui t
t  k/e
t

~ turbulent/mean flow time scale

DT  Cm k 2 / e
37 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007

Ignition and level set (G-equation) models

Partially Premixed Flame (DI Engine)
Discrete particle
ignition model
Φ<1
O2, O, NO …

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 
38 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007

Turbulent flame speed correlations

  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

SL  I0   t   2b1 lF  2b1 lF  Sl lF  

     

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

Turbulence stretch Curvature

k
Characteristic Timescale: t 
e
k1.5
Transition criterion: rk  Cm1  l I  Cm1  0.16 rk
e
~
G   ~ u 0 ~ ~ ~ Fan, 2000
 (v f  vvertex )  G  ST G  DT k G
t 
39 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007

Laminar flame speed correlations

Power Law (Metghalchi & Keck, 1982):
 b 30
T   p
S L  S L,0     1  2.1Ydil  Metghalchi et al.
 T0   p0  25 Present
Liang et study
al.

(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, 

For iso-octane,   26.9   -0.134   3.86   1.146

40 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007

Validation - PFI/DI gasoline engines

Bore × Stroke 89 mm × 79.5 mm Based on MIT PRF Mechanism
Compression Ratio 12 : 1
(25 species, 51 reactions)
Engine Speed 1500 rev/min Model constants: Cm1=2.0, Cm2=1.0
PFI Mode (Fixed in all cases)
Spark timings (ATDC) -44, -40, -36, -32
MAP (kPa) 65
DI Mode (Spark timing sweeps)
Spark timings (ATDC) -32, -28, -24, -20
MAP (kPa) 75
End of Injection (ATDC) - 72
DI Mode (Manifold-Absolute-Pressure sweeps)
MAP (kPa) 75, 80, 90, 100
Spark timing (ATDC) - 33
End of Injection (ATDC) - 68
DI Mode (End-Of-Injection sweeps)
End of Injection (ATDC) -76, -72, -68, -64
MAP (kPa) 75 DI Configuration
Spark timing (ATDC) - 32
41 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007

Validation - PFI engine operation

Spark Timing = 40 BTDC

CA = -20 ATDC CA = -5 ATDC

CA = 10 ATDC CA = 20 ATDC

Evolution of the G=0 surface

Evolution of Temperature

42 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007

Validation - PFI engine operation

2.5 2.5
EXPT EXPT
2.0 SIMU 2.0 SIMU Spark Timing
-44, -40, -36,

Pressure (MPa)
Pressure (MPa)

PFI mode PFI mode

O O
-32 ATDC -36 ATDC
1.5 1.5
-32 ATDC
1.0 1.0
Engine Speed
1500 rev/min
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)
2.5 2.5
EXPT EXPT
2.0 SIMU Pressure (MPa) 2.0 SIMU
Pressure (MPa)

PFI mode PFI mode

O O
1.5 -40 ATDC 1.5 -44 ATDC

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)

43 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007

Role of flame propagation

Explore Kinetics-Controlled Formulation for Turbulent Flame Propagation:
After ignition kernel stage, each cell is modeled as a WSR, detailed chemistry is
applied. “Flame propagation” is controlled by heat conduction and auto-ignition.
2.5 3.5
EXPT
EXPT
3.0 G-equation
2.0 G-equation
Kinetics only
Kinetics only
Pressure (MPa)

2.5

Pressure (MPa)
DI mode
PFI mode
1.5
2.0

1.5 Spark timing

1.0 Spark timing
-32 ATDC
-44 ATDC
1.0
0.5
Transition from kernel to G-eqn 0.5 Transition from kernel
-20 ATDC to G-eqn at -20 ATDC
0.0 0.0
-80 -60 -40 -20 0 20 40 60 80 -80 -60 -40 -20 0 20 40 60 80
o o
Crank Angle ( ATDC) Crank Angle ( ATDC)

dYi
Mallard-Le Chatelier propagating wave speed: ST  D
dt
44 CEFRC2-3, 2014
 Part 3: Chemical Kinetics, HCCI & SI Combustion Liang, 2007
Kinetics Controlled G-equation
Role of flame propagation
PFI case
Spark timing = -44 ATDC

Summary:

Auto-ignition chemistry alone is

NOT sufficient to properly model
flame propagation.
Turbulence enhancing effect on
flame propagation speed in SI
engines CANNOT be neglected.

45 CEFRC2-3, 2014