Chemical Reaction Engineering

Department of Chemical Engineering and Technology
Royal Institute of Technology

Stockholm 2002
TRITA-KET R 164
ISSN: 1104-3466
ISBN: 91-7283-391-2
ISRN KTH/KET/R-164-SE









Wall-related Lean Premixed Combustion
Modeled with Complex Chemistry





Johan Andrae



Dissertation







Abstract

Increased knowledge into the physics and chemistry controlling emissions
from flame-surface interactions should help in the design of combustion engines
featuring improved fuel economy and reduced emissions.
The overall aim of this work has been to obtain a fundamental understanding
of wall-related, premixed combustion using numerical modeling with detailed
chemical kinetics. This work has utilized CHEMKIN, one of the leading software
packages for modeling combustion kinetics.
The simple fuels hydrogen and methane as well as the more complex fuels
propane and gasified biomass have been used in the model. The main emphasis has
been on lean combustion, and the principal flow field studied is a laminar boundary
layer flow in two-dimensional channels. The assumption has been made that the wall
effects may at least in principle be the same for laminar and turbulent flames.
Different flame geometries have been investigated, including for example
autoignition flames (Papers I and II) and premixed flame fronts propagating toward a
wall (Papers III and IV). Analysis of the results has shown that the wall effects arising
due to the surface chemistry are strongly affected by changes in flame geometry.
When a wall material promoting catalytic combustion (Pt) is used, the homogeneous
reactions in the boundary layer are inhibited (Papers I, II and IV). This is explained by
a process whereby water produced by catalytic combustion increases the rate of the
third-body recombination reaction: H+O
2
+M ⇔ HO
2
+M. In addition, the water
produced at higher pressures increases the rate of the 2CH
3
(+M) ⇔ C
2
H
6
(+M)
reaction, giving rise to increased unburned hydrocarbon emissions (Paper IV).
The thermal coupling between the flame and the wall (the heat transfer and
development of the boundary layers) is significant in lean combustion. This leads to a
slower oxidation rate of the fuel than of the intermediate hydrocarbons (Paper III).
Finally in Paper V, a well-known problem in the combustion of gasified
biomass has been addressed, being the formation of fuel-NO
x
due to the presence of
NH
3
in the biogas. A hybrid catalytic gas-turbine combustor has been designed, which
can significantly reduce fuel-NO
x
formation.

Keywords: wall effects, premixed flames, flame quenching, numerical modeling,
CHEMKIN, boundary layer approximation, gasified biomass, fuel-NO
x
,
hybrid catalytic combustor.











The cover illustrates a chemically reacting boundary layer flow


Sammanfattning

En ökad förståelse av de fysiska och kemiska processer som kontrollerar
emissioner som uppstår vid väggnära förbränning kan bidra i utformningen av
förbränningsmotorer med bättre bränsleekonomi och minskade utsläpp.
Det huvudsakliga syftet med detta arbete har varit att få en grundläggande
förståelse för väggnära förbränning med hjälp av numerisk modellering med komplex
kemi. Arbetsverktyg har varit CHEMKIN, som är en av de ledande komersiella
programvarorna för modellering av kemiskt reagerande flöden.
Modellbränslen har varit relativt enkla gaser i form av vätgas och metan och
mera komplexa bränslen i form av propan och förgasad biomassa. Tyngdpunkten i
beräkningana ligger på mager förbränning och den huvudsakliga flödesgeometrin som
studeras är en tvådimensionell laminär gränskiktsströmning. Här görs antagandet att
den väggnära förbränningen sker med försumbar inverkan av turbulent strömning.
Olika typer av flamgeometrier behandlas i form av ’auto-ignition’ flammor
(artikel I och II) och förblandade flammor som propagerar mot en vägg (artikel III och
IV). När resultaten analyseras framgår det att de väggeffekter som ytkemin ger
upphov till starkt påverkas av ändring i flamgeometri. Då ett väggmaterial som ger
upphov till katalytisk förbränning (Pt) används, retarderas den homogena
förbränningen i gränsskiktet (artikel I, II och IV). Detta förklaras av att det vatten som
produceras genom den katalytiska förbränningen ökar hastigheten på tredjekropps-
reaktionen H+O
2
+M ⇔ HO
2
+M. Vid högre tryck ökar det katalytiskt bildade vattnet
också hastigetheten på reaktionen 2CH
3
(+M) ⇔ C
2
H
6
(+M), vilket ger upphov till
ökade utsläpp av kolväten (artikel IV).
Den termiska kopplingen mellan flamman och väggen, d v s värmeöverföring
och utvecklingen av gränskikten är betydande vid mager förbränning. Detta leder till
en långsammare oxidation av bränslet jämfört med intermediära kolväten (artikel III).
Slutligen i artikel V behandlas ett välkänt problem vid förbränning av förgasad
biomassa: bränsle-NO
x
bildningen p g a den ammoniak som finns i bränngasen. En
katalytisk hybridbrännkammere för tillämpning i gasturbiner designas där en
betydande minskning av bränsle-NO
x
uppnås.

Nyckelord: väggeffekter, förblandade flammor, flamutsläckning, numerisk
modellering, CHEMKIN, gränsskiktströmning, biogas, bränsle-
NO
x
, katalytisk hybridbrännkammare.






The work presented in this thesis is based on the following papers, referred to by their
Roman numerals. The papers are appended at the end of the thesis.


I. Andrae, J., and P. Björnbom, “Wall Effects of Laminar Hydrogen Flames over
Platinum and Inert Surfaces,” AIChE J., 46, 1454 (2000).

II. Andrae, J., P. Björnbom, and L. Edsberg, ”Numerical Studies of Wall Effects
with Laminar Methane Flames,” Combust. Flame, 128, 165 (2002).

III. Andrae, J., P. Björnbom, L. Edsberg, and L-E. Eriksson, ”A Numerical Study
of Sidewall Quenching with Propane/Air Flames,” Proc. Combust. Inst., 29, to
appear (2002).

IV. Andrae, J., P. Björnbom, L. Edsberg, and L-E. Eriksson, ”Kinetic and
Transport Effects of Pressurized Methane Flames in a Boundary Layer,”
submitted to Combust. Flame (2002).

V. Andrae, J., P. Björnbom, and P. Glarborg, ”A Design Concept to Reduce Fuel
NO
x
in Catalytic Combustion of Gasified Biomass,” submitted to AIChE J.
(2002).









Below are listed works presented at conferences and symposia not included in this
thesis.


1. Andrae, J., and P. Björnbom, ”Numerical Investigation of Wall Effects for
Laminar Hydrogen Flames over Platinum and Inert Surfaces,” Oral
Presentation, AIChE Annual Meeting, Dallas, Texas, USA, Oct. 31-Nov. 5
(1999).

2. Andrae, J., P. Björnbom, and L. Edsberg, ”Numerical Studies of Laminar
Methane Flames in a Boundary Layer,” Work in Progress Poster, Twenty-
Eighth International Symposium on Combustion, Edinburgh, Scotland, July 30-
Aug. 4 (2000).

3. Björnbom, P., J. Andrae, L. Edsberg, and D. Papadias, ”Modeling the Kinetics
of Catalytic Monolith Reactors,” Invited Plenar Lecture, Proceedings of the
Ninth International Symposium on Heterogeneous Catalysis, Eds. L. Petrov,
Ch. Bonev, and G. Kadinov, Varna, Bulgaria, Sept. 23-27, p. 3 (2000).

4. Andrae, J., P. Björnbom, and L. Edsberg, ”Modeling Wall Effects of Laminar
Methane Flames in a Boundary Layer,” Poster Presentation, AIChE Annual
Meeting, Los Angeles, California, USA, Nov. 12-17 (2000).

5. Andrae, J., P. Björnbom, and L. Edsberg, ”Numerical Studies of Wall Effects
of Laminar Methane Flames,” Proceedings of the First Biennial Meeting of the
Scandinavian-Nordic Section of the Combustion Institute, Gothenburg,
Sweden, April 18-20, p. 199 (2001).

6. Andrae, J., P. Björnbom, and P. Glarborg, ”Reduction of Fuel NO
x
in Catalytic
Combustion of Gasified Biomass,” Work in Progress Poster, Twenty-Ninth
International Symposium on Combustion, Sapporo, Japan, July 21-26 (2002).











To my family
































“There is no substitute for hard work.”

- Thomas Alva Edison (1847-1931)



Table of Contents

Nomenclature

1 Introduction 1
1.1 Lean combustion 1
1.2 Scope of this work 3

2 Fundamentals of Chemical Kinetics 6
2.1 Gas-phase chemistry: oxidation of hydrogen in air 6
2.1.1 Interpretation of the elementary reaction mechanism 10
2.2 Pressure-dependent reactions 11
2.3 Surface chemistry 13

3 Modeling of Near-wall Combustion 17
3.1 Near-wall turbulence 18
3.2 Laminar models 19
3.2.1 Mathematical description of a chemically-reacting
boundary layer flow 20
3.2.2 Boundary conditions 24

4 CHEMKIN Software 26
4.1 CHEMKIN architecture 26
4.2 The CRESLAF program 28
4.2.1 Numerical solutions using the differential/algebraic approach 29

5 Autoignition Flames (Papers I and II) 31
5.1 Hydrogen as fuel in the model (Paper I) 31
5.1.1 Inlet and boundary conditions 32
5.1.2 Results and discussion 33
5.2 Methane as fuel in the model (Paper II) 37
5.2.1 Inlet and boundary conditions 38
5.2.2 Results and discussion 40

6 Premixed Flame Fronts (Papers III and IV) 43
6.1 Quenching of premixed propane/air flames near an inert cold wall
(Paper III) 43
6.1.1 Inlet and boundary conditions 44
6.1.2 Fuel oxidation 46
6.1.3 Intermediate hydrocarbons 47
6.1.4 Conclusions 48
6.2 Pressurized methane flames using different wall materials (Paper IV) 48
6.2.1 Inlet and boundary conditions 49
6.2.2 Effect of flame-geometry 50


6.2.3 Effect of gas-phase chemistry 51
6.2.4 Effect of fuel/air ratio 52
6.2.5 Discussion 52

7 Reduction of Fuel-NO
x
in Catalytic Combustion of Gasified Biomass
(Paper V) 53
7.1 Gasified biomass 53
7.2 Primary methods for reducing NO
x
54
7.3 Catalytic combustion 54
7.4 The model 55
7.5 Lean primary λ 57
7.6 Rich primary λ 58
7.7 Discussion 60
7.8 Conclusion 61

8 Conclusions 62
8.1 Looking ahead 63

Acknowledgments 64

References 66


Nomenclature (cgs units)

i
A Pre-exponential factor in the rate constant of the i
th
reaction, unit
depends on reaction.
p
c Mixture specific heat capacity, erg/(g · K).
k
p
c Specific heat capacity of species k, erg/(g · K).
kj
D Multicomponent diffusion coefficient, cm
2
/s.
Mixture diffusion coefficient, cm
m k
D
,
2
/s.
T
k
D Thermal diffusion coefficient, g/(cm · s).
i
E Activation energy in the rate constant of the i
th
reaction, cal/mole.
g Acceleration of gravity, cm/s
2
.
o
k
H Standard state molar entropy of the k
th
species, erg/mole.
k
h Specific enthalpy, erg/g.
I Total number of reactions.
y
k
j Mass flux in the y direction, g/(cm
2
· s).
fi
k Forward rate constant of the i
th
reaction, unit depends on
reaction.
ri
k Reverse rate constant of the i
th
reaction, unit depends on reaction.
i
c
K Equilibrium constant in concentration units for the i
th
reaction,
unit depends on reaction.
i
p
K Equilibrium constant in pressure units for the i
th
reaction, unit
depends on reaction.
K Total number of species.
g
K Total number of gas-phase species.
s
K Total number of surface species.
f
s
K Number of first surface species.
l
s
K Number of last surface species.
[M] Concentration of third body, mole/cm
3
.
p Pressure, dyne/cm
2
.
atm
P Pressure of one standard atmosphere, dyne/cm
2
.
R Universal gas constant, erg/(mole · K).
c
R Universal gas constant in the same units as activation energy,
cal/(mole ·K).



k
s& Chemical production rate of species by surface reaction,
mole/(cm
2
·s).
o
k
S Standard state molar entropy of the kth species, erg/(mole·K).
T Temperature, K.
Temperature of the unburned gas, K.
u
T
Temperature at the wall, K.
w
T
Fluid velocity in the x direction, cm/s. u
Fluid velocity in the y direction, cm/s. v
x
k
V Diffusion velocity of species k in the axial direction, cm/s.
y
k
V Diffusion velocity of species k normal to wall, cm/s.
Molecular mass of species , g/mole.
k
W k
W Mean molecular weight of the mixture, g/mole.
x Distance along principal flow direction, cm.
k
X Mole fraction of species k.
y Cross-stream coordinate, cm.
k
Y Gas-phase species mass fractions.
k
X Gas-phase species mole fraction.
[ ]
k
X Molar concentration species k, mole/cm
3
.
k
Z Site fraction of species k.

Greek letters

ki
α Enhanced third-body efficiency of the k
th
species in the i
th
reaction.
i
β Temperature exponent in the rate constant of the i
th
reaction.
i
γ Sticking coefficient of the i
th
surface reaction.
λ Thermal conductivity, erg/(cm·sec·K).
k
σ Number of sites occupied by species k.
ki
ε Coverage parameter, cal/(mole · K).
ki
η Coverage parameter.
µ Viscosity, g/(cm·s).
ki
µ Coverage parameter.
ρ Mass density, g/cm
3
.
o
Γ Standard-state surface site density, mole/cm
2
.
Γ Surface site density, mole/cm
2
.




'
ki
υ Stoichiometric coefficient of the k
th
reactant species in the i
th

reaction.
' '
ki
υ Stoichiometric coefficient of the k
th
product species in the i
th

reaction.
k
ω& Chemical production rate of species k by gas-phase reaction,
mole/(cm
3
· s).
ψ Stream function, g/(cm · s).


1 erg = 10
-7
J
1 dyne/cm
2
= 10
-1
Pa





1 Introduction

Combustion of fossil fuels is the most important method of generating energy in
the world today. Other sources of energy such as solar, wind and nuclear energy still
account for less than 20% of total energy consumption. Fossil fuel combustion is used
for transportation, power generation, heating and process engineering. The combustion
of fossil fuels is expected to remain a key technology in the foreseeable future, while at
the same time world energy production is projected to increase by 60% over the next 20
years (EIA, 2000). It is widely known that combustion not only generates heat, which
can be converted into power, but also produces pollutants such as oxides of nitrogen
(NO
x
), soot, and unburned hydrocarbons (UHC). Increasingly stringent regulations are
forcing manufacturers of automobiles and power plants to reduce polluting emissions,
thereby reducing their negative impact on the environment. In addition, unavoidable
emissions of CO
2
are believed to contribute to global warming. Improving the
efficiency of the combustion process and thereby increasing fuel economy will reduce
these emissions. The use of renewable fuels (for example gasified biomass) will
eliminate the net emission of CO
2
into the atmosphere, but have other negative
environmental impacts that must be addressed, such as the formation of fuel-NO
x
.
Improvements in efficiency and decreases in pollutant formation in combustion systems
are only possible through improving our understanding of the fundamental processes
taking place during combustion.
The interaction between combustible gases and chamber walls is one of the
classic problems in combustion science (see von Kàrmàn & Millàn, 1953; Kurkov &
Mirsky, 1969; Ferguson & Keck, 1977; Westbrook Adamczyk & Lavoie, 1981; Hocks,
Peters & Adomeit, 1981; Blint & Bechtel, 1982; Wichman & Bruneaux, 1995).
Combustion is strongly influenced by the presence of walls, which can for example
cause flame fronts to quench. The effects of cool walls on unburned hydrocarbon
emissions in combustion engines has been studied for quite some time (see Daniel,
1956; Sloane & Schoene, 1983; Kiehne, Matthews & Wilson, 1986; Vlachos, Schmidt
& Aris, 1994b; Hasse, Bolling, Peters & Dwyer, 2000). Moreover, the flame has a
significant effect on the flow in the vicinity of the wall as well as on the heat flux to the
wall (Vosen, Greif & Westbrook, 1984; Lu, Ezekoye, Greif & Sawyer, 1990; Ezekoye,
Greif & Lee, 1992; Ezekoye & Greif, 1993; Popp & Baum, 1997).


1.1 Lean combustion

To reduce the fuel consumption in cars and thereby the emission of CO
2
, there is
a growing trend toward the increased use of lean combustion. However, the use of
excess air lowers the flame temperature, which increases the significance of the effects
of the combustor walls, for instance those of thermal quenching (Vlachos, Schmidt &
Aris, 1993; Vlachos, Schmidt & Aris, 1994a).
1
In a modern direct-injection spark-ignition (DISI) engine, the charge is stratified
near the spark plug, such that the flame initiated at the spark propagates through a
partially premixed heterogeneous mixture. This means that the charge is diluted in other
parts of the cylinder for an overall lean combustion. In the direct vicinity of the cold
wall flame, propagation is quenched due to radical depletion—radicals are required to
sustain the flame—in the cold near-wall zone by recombination reactions and by heat
losses. The radicals can also diffuse to the wall and be heterogeneously quenched. The
result is that some of the charge of fuel and oxidizer in each combustion cycle is left
unburned at the walls. This charge may be either transported from the viscous sublayer
to the main flow of the flame gases and be oxidized, or discharged into the exhaust
gases as residual hydrocarbon emissions.
An additional problem is that the treatment of the exhaust gas by catalytic
conversion does not work well because the molecules in the exhaust gas do not "add
up" as they do in the three-way-catalyst concept in traditional engines working with
stoichiometric fuel/air mixtures. Due to the air-excess, the oxygen consumes the
reduction matter—normally unburned hydrocarbons from the main flow—and there is
not enough to reduce all the NO
x
. Lean-burn engines therefore have difficulties
matching the output levels of three-way-catalyst engines, especially with regard to NO
x
.
The challenge for the automotive engineer is therefore how to modify the combustion
process where possible to find a catalyst that can selectively reduce NO
x
to N
2
in the
presence of some reduction matter (Heck & Farrauto, 1995).
Another engine concept featuring lean combustion is homogenous-charge-
compression-ignition, a hybrid between the spark-ignition engine and the diesel engine.
The charge is very lean (2 < λ < 7 where λ = 1/φ = [X
air
/X
fuel
/[X
air
/X
fuel
]
stoichiometric
is the
excess air ratio). which is too lean for spark ignition. Instead there is a spontaneous
autoignition due to compression. The lean and homogeneous charge keeps the
combustion temperature low, which leads to extremely low levels of NO
x
and
particulate emissions. On the other hand, the CO and hydrocarbon emissions can be
significant (Christensen, Johansson & Einewall, 1997; Christensen, Hultqvist &
Johansson, 1999).
The effect of the combustion chamber wall is also an important issue in lean-
burn gas-turbines used for energy production, for example the burnout of CO in a
cooled boundary layer flow (Correa, 1992). In contrast to the spark-ignition engine, the
wall temperature is several hundred degrees higher and the process is stationary. The
wall effects in such combustors can therefore be expected to differ from those in a lean-
burn spark-ignition engine (the effects of surface chemistry or adsorption are for
example not completely understood).




2
1.2 Scope of this work

Due to limitations in our current understanding, it is important to gain deeper
insight into the physics and chemistry controlling emissions resulting from flame-
surface interactions. This increased knowledge should help in the design of combustion
engines featuring improved fuel economy and reduced emissions. In this context,
mathematical simulations can play an important role in accelerating the understanding
of near-wall combustion. This is due to the complex nature of the wall effects in
combustion, including for example: compressible fluid flow coupled to convection,
diffusion and chemical reactions both in the gas-phase and on the surface (see Fig. 1.1).
In addition, it is difficult to perform measurements close to walls.



Transport of
momentum,
heat and
species
Stefan
velocity
Adsorption,
surface
reactions,
desorption
Gas-phase reactions
Diffusion, heat
conduction
Gas
Wall












Figure 1.1 Different processes that have to be modeled to understand near-wall
combustion.

The overall aim of this work has been to obtain a fundamental understanding of wall-
related premixed combustion by numerical modeling with detailed chemical kinetics.
The work utilized CHEMKIN®, a leading software package for modeling combustion
kinetics. The model used the simple fuels hydrogen and methane, and the more
complex fuels propane and gasified biomass. Emphasis has been on lean combustion
and the principal flow field is a laminar boundary layer flow in two-dimensional
channels. The assumption has been made that the wall effects may at least in principle
be the same for laminar and turbulent flows. Using laminar models instead of turbulent
ones for the gas-phase transport-equations strongly reduces the time needed for a single
computation, and at the same time enables the use of very detailed chemical reaction
mechanisms. There is usually a trade-off between the use of complex chemistry and
3
turbulence models (see Fig. 1.2). This is mainly due to the fact that resolution of the
small scales in turbulent flows demands far more grid points than does the analogues
laminar flow. Furthermore, unlike laminar flow solutions, the Navier-Stokes solution to
turbulent flows is itself time-dependent, and in any case, there is not a steady solution
(Warnatz, Maas & Dibble, 1996).




Chemistry complexity

3D-CFD simulation

F
l
o
w

m
o
d
e
l

c
o
m
p
l
e
x
i
t
y




2D laminar
model




Figure 1.2 Illustration of the usual trade-off between the use of complex chemistry and
flow model complexity.

The first part of this thesis treats the basic formalism of gas-phase and surface
kinetics, using the combustion of hydrogen as an example. The modeling of near-wall
combustion is then described together with the mathematical treatment of a chemically-
reacting boundary layer flow. Finally the software package CHEMKIN®, used to
accomplish a numerical solution for the reacting flow model is described, which
concludes this part of the thesis.
The second part of the thesis deals with autoignition flames. Uniform reactor
inlet conditions are specified, with temperatures above the autoignition temperature for
the specified stoichiometry. Premixed hydrogen-air flames have been modeled in Paper
I, and the fuel/air ratio, wall material, and carrier gas have all been varied in order to
determine the relative importance of the chemical wall-effects compared to the thermal
wall-effects in lean combustion. In Paper II methane has been used as the fuel in the
model, and the inlet conditions were changed somewhat from those used in Paper I. The
effects of changing fuel/air ratio, wall material and pressure have all been discussed.
The third part of the thesis deals with premixed flame fronts. The inlet
conditions vary strongly as a function of distance from the wall and a premixed flame
has been modeled that propagates towards a wall under the influence of a boundary
layer flow. In Paper III, propane has been used as the fuel in the model and the effects
of fuel/air ratio, pressure and wall temperature on the flame propagation and emissions
4
have all been discussed. Paper IV investigates the influences of different fuel/air ratios
and wall boundary conditions on the propagation of pressurized methane flames. A
comparison has been made between these results and those obtained in Paper II.
Finally in the last part of the thesis, Paper V treats a somewhat different but
nevertheless related area, namely combustion of gasified biomass in a hybrid catalytic
combustor for gas-turbine applications. Paper V discusses different operations of the
combustor for reducing Fuel-NO
x
, which is a major hurdle when using gasified biomass
as a fuel in combustion applications. To model the combustion in the gas-turbine
combustor, detailed homogenous and heterogeneous chemical kinetic schemes have had
to be used.
The author’s contribution to the above papers has been: (i) setting up the reacting
flow problems, (ii) performing the modeling and simulation work, and (iii) playing the
major role in reporting on the work and drafting the manuscripts. The other authors of
these papers have acted as academic advisors, involving for example providing
inspiration, ideas and as scientific reviewers of manuscripts.






















5
2 Fundamentals of Chemical Kinetics

This chapter deals with the basic formalism of gas-phase and surface kinetics. To
illustrate the detailed mechanisms of chemical kinetics that are used to describe
combustion processes, both the gas-phase and catalytic combustion of hydrogen have
been described in detail.

2.1 Gas-phase chemistry: oxidation of hydrogen in air

The net reaction or overall reaction for the combustion of a stoichiometric
mixture of hydrogen and air (an exothermic reaction with heat of combustion of -571.7
kJ/mole) is described by the equation:


2 H
2
(g) + O
2
(g) + 3.762 N
2
(g) → 2 H
2
O (g) + 3.762 N
2
(g). (2.1)


Often these overall reactions are bound by complicated rate laws, where the
reaction orders of the individual reactants may be: (i) non-integers, (ii) negative and
(iii) dependent on the time and reaction conditions. However, detailed investigations
show that water is not produced by one single collision between the three reacting
molecules; instead, the overall reaction is a consequence of a large number of
elementary reactions. Resolution of the elementary reactions can be a difficult and
time-consuming task. The formation of water for example, can be described by 38
elementary reactions (19 reversible reactions), as shown in Table 2.1. This mechanism
was used in Paper I. For the hydrocarbons, which are more complex than hydrogen,
hundreds or even thousands of elementary reactions are needed to describe their
combustion. The largest mechanisms are normally reduced, and the larger the number
of species used in these reduced mechanisms, the more exactly the chemistry can be
represented. Although the oxidation mechanism of hydrogen in air is a fairly simple
system compared to that of a hydrocarbon fuel, it does contain the chemistry of the
radicals H, O and OH that are very important in combustion processes.

A summary of the experimental techniques used for the determination of
elementary reactions can be found in Warnatz et al. (1996). Experiments are often
carried out in: (i) isothermal vessels filled with reactants, and the time behavior of the
concentrations is measured, or (ii) in flow reactors where the spatial profiles of the
concentrations provide information about their time behavior. Usually the reactive
species such as H and O have to be produced as reactants. This may be accomplished
thermally by using high temperatures (for example dissociation by heating in a shock
6
tube), or by a microwave discharge. High dilution with noble gases (He and Ar) slows
down the reaction of the reactive species with themselves.

Table 2.1 The gas-phase reaction mechanism for hydrogen-air.

No. Reaction A
a
β
a
E
a

[mol,cm,s] [-] [kJ/mol]
1. H+O
2
=O+OH 5.1×10
16
-0.82 69.1
2. H
2
+O=H+OH 1.8×10
10
1.00 37.0
3. H
2
+OH=H
2
O+H 1.2×10
9
1.30 15.2
4. OH+OH=H
2
O+O 6.0×10
8
1.30 0.0
5. H
2
+O
2
=OH+OH 1.7×10
13
0.00 200.0
6. H+OH+M=H
2
O+M* 7.5×10
23
-2.60 0.0
7. O
2
+M=O+O+M 1.9×10
11
0.50 400.1
8. H
2
+M=H+H+M** 2.2×10
12
0.50 387.7
9. H+O
2
+M=HO
2
+M*** 2.1×10
18
-1.00 0.0
10. H+O
2
+O
2
=HO
2
+O
2
6.7×10
19
-1.42 0.0
11. H+O
2
+N
2
=HO
2
+N
2
6.7×10
19
-1.42 0.0
12. HO
2
+H=H
2
+O
2
2.5×10
13
0.00 2.9
13. HO
2
+H=OH+OH 2.5×10
14
0.00 7.9
14. HO
2
+O=OH+O
2
4.8×10
13
0.00 4.2
15. HO
2
+OH=H
2
O+O
2
5.0×10
13
0.00 4.2
16. HO
2
+HO
2
=H
2
O
2
+O
2
2.0×10
12
0.00 0.0
17. H
2
O
2
+M=OH+OH+M 1.2×10
17
0.00 190.7
18. H
2
O
2
+H=HO
2
+H
2
1.7×10
12
0.00 15.7
19. H
2
O
2
+OH=H
2
O+HO
2
1.0×10
13
0.00 7.5
a
The rate constants are formulated with Equation 2.9.
Third-body enhancements factors:
* H
2
O /20.0/.

** H
2
O /6.0/ H/2.0/ H
2
/3.0/.

*** H
2
O /21.0/ H
2
/3.3/ O
2
/0.0/ N
2
/0.0/.

Source: Giovangigli & Smooke (1987).

The concentration measurement used should be sensitive and fast. Methods used
include mass spectroscopy, electron spin resonance, optical spectroscopic methods and
gas chromatography.

Using elementary reactions has many advantages: (i) the reaction order of elementary
reactions is always constant, and in particular is independent of time and the
experimental reaction conditions, and (ii) can be determined easily. All one has to do is
7
to look at the molecularity of the reaction. Only three possible values of the reaction
molecularity are observed, and these are described as follows.

Unimolecular reactions describe the rearrangement or dissociation of a molecule:

A → products. (2.2)

These have a first-order time behavior. When the initial concentration is doubled, the
reaction rate is also doubled.

Bimolecular reactions are the most common reaction type found (see Table 2.1). These
proceed according to the following reaction equations:

A + B → products, (2.3)

or

A + A → products. (2.4)

Bimolecular reactions always follow a second-order rate law. The doubling of the
concentration (doubling of the pressure) quadruples the reaction rate.

Trimolecular reactions are usually recombination reactions and obey a third-order law:

A + B + C → products, (2.5)



A + A + B → products, (2.6)

or

A + A + A → products. (2.7)


In general, the molecularity equals the order of the elementary reactions, and the
rate laws can be easily derived. For an elementary mechanism, the rate of formation
(mole/cm
3
· s) of a species k , is given by summation over the rate equations of all the
elementary reactions I as follows:


8
| | | | |
.
|

\
|
− − = ∏ ∏ ∑
= = =
' '
1
'
1 1
, , ,
) (
ki K
k
k ri
ki K
k
k fi
I
i
ki ki
k
X k X k
υ υ
υ υ ω& . (2.8)


In Equation 2.8, the superscript symbol
'
indicates forward stoichiometric coefficients
(
ki
υ ), while
'
indicates reverse stoichiometric coefficients for species
'
k in reaction .
The symbol | |
i
k
X (
k k
W Y / ) ρ = is the molar concentration of species k . This
expression can also be modified to take into account arbitrary reaction orders and third-
body reactions.

The temperature dependence of the rate constant ( ) in reaction i , is a synthesis of (i)
the theory of the Swedish chemist Arrhenius (Arrhenius, 1889), (ii) the collision theory
and (iii) the theory of activated complex:
f
k


) / ( T
c
R
i
E
i
i fi
e T A k

=
β
, (2.9)


where is the constant of proportionality between the concentrations of the reactants
and the rate at which they collide,
i
A
i
β is the temperature exponent, the activation
energy, the universal gas constant in the same units as the activation energy, and
i
E
c
R
f denotes that it is a forward reaction.

The reverse rate constants are determined by the forward rate constant and the
equilibrium constant:

i
c
fi
ri
K
k
k = . (2.10)


The equilibrium constants are calculated from the thermodynamic properties of the
species:



=
|
.
|

\
|

|
.
|

\
|
=
K
k
ki ki
atm
i
p
i
c
RT
P
K K
1
' ' '
υ υ
, (2.11)
9
|
.
|

\
| ∆


=
RT
H
R
S
K
o
i
o
i
i
p
exp , (2.12)


( )
R
S
R
S
o
k
K
k
ki ki
o
i

=
− =

1
' ' '
υ υ (2.13)
and

( ) ∑
=
− =
∆ K
k
o
k
ki ki
o
i
RT
H
RT
H
1
' ' '
υ υ , (2.14).


where refers to the change that occurs in passing completely from reactants to
products in the i

th
reaction. The standard state is defined as
atm
P

= 1 atm (Kee, Rupley,
Meeks & Miller, 1996). An alternative way is to explicitly state the reverse rate
coefficients.


2.1.1 Interpretation of the elementary reaction mechanism

The combustion of H
2
in air proceeds through a chained-branched explosion
when a fuel/air mixture within the flammability limits (the leanest or richest
concentrations that will self-support a flame) comes into contact with an ignition source
(Glassman, 1996). Chain-branched explosions are characterized by a period of ignition
delay, during which the radical pool (O, OH and H) builds up (Warnatz et al., 1996).
This means that during the first phase of the explosion, the temperature will not
increase much, because the energy released from the fuel and the oxidizer is stored in
the free radicals. The concentration of radicals therefore increases with time, and either
the fuel or the oxidizer concentration lowers. At a certain point in time, radical
recombination or chain-termination reactions become faster than chain-branching
reactions and the energy is finally released. The concentration of radicals decreases and
the temperature increases until the thermodynamic equilibrium of the system is finally
reached. Examples of different types of chain reactions in the reaction mechanism
outlined in Table 2.1 are:

• initiation (No. 5, forward reaction),
• chain-branching (No. 1, forward reaction),
• propagation (Nos. 2, 3 & 4 forward reactions), and
• termination (No. 8, backward reaction).
10
More free bonds are created than consumed in the chain-branching reaction and
the initiation reaction. However, in the initiation reaction the reactants contain no free
bonds. In the propagation reaction one free bond is consumed and one free bond is
created. In the termination reaction two free bonds are consumed, and the chain is
terminated due to a recombination of the two radicals.
In the recombination reactions, more energy is released by bonding two
molecules than the product molecule can carry, and a third species M is required that
can carry some of the energy. The third species M provides the energy required to split
the product back to reactants in the reverse reaction. In reaction Nos. 6, 7, 8, 9 and 17,
M denotes an unspecified molecule. The concentration of this third body is calculated
from the sum of concentrations of all the species in the gas times their factor of
effectiveness to carry the energy that is released or required, according to:

| | | | ∑
=
=
K
k
k ki
X M
1
α (2.15)

where
ki
α is the enhancement factor for species k in reaction . If all the species in the
mixture contribute equally as third bodies (
i
ki
α = 1), then the concentration of the third
body M equals the total concentration of the mixture.

Equation 2.8 then changes to:

| | | | | | |
.
|

\
|
− − = ∏ ∏ ∑
= = =
' '
1
'
1 1
, , ,
) (
ki K
k
k ri
ki K
k
k fi
I
i
ki ki
k
X k X k M
υ υ
υ υ ω& . (2.16)


In reaction Nos. 6, 8 and 9 in Table 2.1, the enhancement factors for some molecules
differ from unity in the mixture. Clearly water has a strong third-body efficiency. As
shown in next section, an important feature of the third-body reactions is their pressure
dependence. At lower pressures, these reactions are relatively slow, but as the pressure
increases, they become increasingly important and compete with the two-body
reactions.

2.2 Pressure-dependent reactions

Under certain conditions, some reaction rate expressions depend on pressure as
well as temperature. An example of such a reaction is the recombination of methyl
11
radicals, which is part of all reaction mechanisms for hydrocarbons, and is shown
below:

2CH
3
(+ M) = C
2
H
6
(+M). (2.17)

This is a so-called third-body-recombination-fall-off reaction. At the high-pressure
limit, the reaction can be described as 2CH
3
= C
2
H
6
. At the low-pressure limit, a third
body is required to carry some amount of energy liberated in the recombination
reaction. When the reaction is at either limit, solely temperature-dependent rate-
expressions are applicable. However when the pressure and temperature are such that
the reaction falls between these limits, the rate expressions are more complicated. The
simplest approach is the model developed by Lindemann (1922). Arrhenius parameters
are required for both the high ( ) and the low ( ) pressure-limit cases:

k
o
k

) / exp( T R E T A k
c o
o
o o
− =
β
, (2.18)
and

) / exp( T R E T A k
c ∞

∞ ∞
− =
β
. (2.19)

The rate constant at any pressure is taken to be:


F
P
P
k k
r
r

+
=

1
, (2.20)


where the reduced pressure is given by



| |

=
k
M k
P
o
r
. (2.21)

The limiting behavior ( F = 1) becomes:

- high-pressure limit | → ∞ and | M

= k k , and
- low-pressure limit → 0 and |M| | | M k
o
k = .

12
The Lindemann model itself is a simplified model, and other approaches involve more
complex descriptions of F .
The reaction expressed in Equation 2.17 competes with other bimolecular steps,
such as 2CH
3
(+M) = C
2
H
5
+ H (+M). This reaction—which is endothermic—occurs
through the same energetically excited species C
2
H
6
* as the reaction expressed in
Equation 2.17:

2CH
3
→ C
2
H
6
* , (2.22)
C
2
H
6
* → 2CH
3
, (2.23)
C
2
H
6
* → C
2
H
5
+ H , (2.24)
and
C
2
H
6
* +M → C
2
H
6
+M . (2.25)

As the pressure increases, deactivating collisions between C
2
H
6
* and other molecules
cause the rate coefficient of C
2
H
6
formation to increase. At the same time, these
deactivating collisions preclude the dissociation of C
2
H
6
* into C
2
H
5
+ H.

2.3 Surface chemistry

The formalism of the surface chemistry is very similar to that of the gas-phase
reactions, via resolution into elementary reactions (Coltrin, Kee & Rupley, 1991;
Warnatz, 1992). The net chemical production rate of species by surface reaction (in
mole/cm
2
·s) is defined as:



| | | | |
.
|

\
|
− − = ∏ ∏ ∑
= = =
' '
1
'
1 1
, , ,
) (
ki K
k
k ri
ki K
k
k fi
I
i
ki ki k
X k X k s
υ υ
υ υ & , (2.26)


where I is the total number of elementary reversible (or irreversible) surface reactions.
For adsorbed species, the concentrations are given in moles/cm
2
by:


| |
k k k
Z X σ / Γ = , (2.27)

where is the site fraction of species
k
Z k , Γthe surface site density, and
k
σ the number
of sites occupied by species k . In the surface chemistry used in this thesis, the species
reside in only one surface phase.

13
The rate coefficients for adsorption, desorption and surface reactions can also depend
on surface coverage. This coverage dependence is taken into account by an additional
factor leading to the following rate expression for the rate coefficient of the forward
reaction k :
f



| |
| |
| |
|
|
.
|

\
| −
|
|
.
|

\
| −
= ∏
= T R
Z
Z
T R
E
T A k
c
k ki
ki
k
l
s
K
f
s
K k
k
Z
ki
c
i i
i fi
ε
u
η
β
exp 10 exp , (2.28)


where
ki
η ,
ki
u , and
ki
ε are the coverage parameters for species k in reaction i , and
is the site fraction. The product of Equation 2.28 covers only those surface species
that are specified as contributing to the coverage modification.
k
Z


Reverse rate constants can be determined from Equation 2.10 where:

( ) ∏
=
− −

=

− ∑
=
Γ
|
|
.
|

\
|
=
l
s
K
f
s
K k
ki ki
k
l
s
K
f
s
K k
ki ki
o
ki
g
K
k
ki
atm
i
p
i
c
T R
P
K K
)
' ' '
(
)
' ' '
(
)
'
1
' '
(
υ υ
υ υ
υ υ
σ . (2.29)


The thermodynamics of gas-phase reactions are well known. Utilizing Equation 2.10
and evaluating is the normal manner of describing reverse reaction rates when the
forward reaction rate is known. However for adsorbed species on a surface, the
thermodynamics are not well known. The reversible reactions can then be split into two
irreversible reactions, for example the adsorption or desorption of a species.
c
K

For some simple surface-reaction mechanisms, it is convenient to specify the adsorption
step in terms of a sticking coefficient. This is a common method for characterizing the
transfer of a molecule from the gas to the surface. The sticking coefficient is the
probability of a specific molecule hitting the surface and adsorbing onto it instead of
bouncing back into the gas phase, and is expressed as follows:


14
| |
| |
k
k
n
k fi
i
W
T R
X
X k
t bombardmen of rate
adsorption of rate
Π
Γ
= =
2
γ . (2.30)


The functional form of the sticking coefficient is taken to be:


| |
T
c
R
i
c
i
b
i i
e T a
/
, 1 max

= γ , (2.31)


where and are unitless, and the units of c are compatible with . The sticking
coefficient must lie between 0 and 1 to make physical sense. The expression for the
relation between the sticking coefficient and the rate constant becomes:
i
a
i
b
i c
R


k
n
i fi
W
RT
k
Π Γ
=
2
1
γ , (2.32)


where is the sum of the stoichiometric coefficients for the number of reactant
surface-species. The sticking coefficient can also depend on the surface coverage,
according to Equation 2.28. For large sticking coefficients—nearing 1—the velocity
distribution becomes skewed. Species whose random motion carries them close to the
surface have a high probability of staying there, which causes a non-Maxwellian
velocity distribution that in turn alters the net species flux near the surface. Motz and
Wise (1960) provided the following correction factor for the rate coefficient:
n


k
n
i
i
fi
W
RT
k
Π Γ
|
|
.
|

\
|

=
2
1
2 / 1 γ
γ
. (2.33)


Table 2.2 shows the surface mechanism for hydrogen oxidation on platinum used in
Paper I. The oxidation of H
2
on Pt is a well-studied phenomenon, both experimentally
and theoretically (Hellsing, Kasemo, Ljungstrom, Rosén & Wahnstrom, 1987;
Ljungstrom, Kasemo, Rosén, Wahnstrom & Fridell, 1989; Williams, Marks & Schmidt,
15
1992; Warnatz, Allendorf, Kee & Coltrin, 1994; Rinnemo, Deutschmann, Behrendt &
Kasemo, 1997; Aghalayam, Park & Vlachos, 2000a).

Table 2.2 The surface-reaction mechanism for hydrogen oxidation on Pt.

Reaction no. A
a
[cm,mol,s]
E
a
[kJ/mol]
1. H
2
+ Pt(s) = H
2
(s) 0.05
b
0.0
2. H
2
(s) + Pt(s) = H(s) + H(s) 7.50×10
22
15.6
3. O
2
+ Pt(s) = O
2
(s) 0.023
b
0.0
4. O
2
(s) + Pt(s) = O(s) + O(s) 2.50×10
24
0.0
5. H(s) + O(s) = OH(s) + Pt(s) 3.70×10
21
19.3
6. H(s) + OH(s) = H
2
O(s) + Pt(s) 3.70×10
21
0.0
7. OH(s) + OH(s) = H
2
O(s) + O(s) 3.70×10
24
100.5
8. H + Pt(s) = H(s) 1.00
b
0.0
9. O + Pt(s) = O(s) 1.00
b
0.0
10. H
2
O + Pt(s) = H
2
O(s) 0.75
b
0.0
11. OH + Pt(s) = OH(s) 1.00
b
0.0
12. H
2
O
2
+ 2Pt(s) = OH(s) + OH(s)
#
1.00
b
0.0
13. HO
2
+ 2Pt(s) = OH(s) + O(s)
#
1.00
b
0.0

Source: Warnatz et al. (1994).
Pt(s) denotes a free surface platinum site and X(s) is an adsorbed species.
All reactions are assumed to be reversible.
a
The rate constants are formulated with Equation 2.9.
b
The sticking coefficients are formulated with Equation 2.31.
Site density of the Pt-wall is = 2.71×10 Γ
-9
mole/cm
2

#
Reaction Nos. 12 and 13 have been added to the original mechanism.

The mechanism is based on laser-induced-fluorescence (LIF) measurements of
desorbed OH, and involves the following steps:

• dissociative adsorption of H
2
and O
2
(reaction Nos. 1-4),
• the adsorbed atoms collide while attached to the surface, forming first OH and
H
2
O in surface reactions (reaction Nos. 5-7), and
• finally desorption of H
2
O takes place (reaction No. 10).

The adsorption and desorption of radicals is accounted for in the remaining reactions.
The type of elementary gas-phase and surface-reaction mechanisms described in
this chapter can be very useful when coupled to reactive flow models for modeling the
coupling between homogeneous and heterogeneous combustion.

16
3 Modeling of Near-wall Combustion

Wall effects in combustion present a complicated problem for analysis since
many species and still more reactions are involved. The most complex situation is
encountered when chemical interactions are established between the gas and the wall,
such as in catalytic combustion. The simplest possible situation is that of a chemically-
inert wall, in which the coupling between the gas and the wall is mainly of a thermal
nature due to heat transfer, and of viscous shear due to momentum transfer. There are
no completely inert walls though, and the possibility of active radical destruction must
also be considered.
Factors that influence the wall effects include the temperature decrease across
the thermal boundary layer, and the destruction of radicals in the boundary layer, which
is more pronounced at lower temperatures. In turbulent combustion, additional
complexities such as the scale of the turbulence across the turbulent boundary layer and
the properties of the laminar sublayer may influence the flame-wall interaction. To
understand more about the wall effects, it is desirable to separate one of those factors
and to elucidate its relative importance.
In order to explain the quenching phenomenon, model calculations with rigorous
fluid mechanics and transport coefficients are required. It is inadequate however to use
global chemistry, as it does not account for the role of the radical pool (see Section 2.1),
and the intermediate hydrocarbons have been found to be significant during quenching
and must be accounted for in the kinetic model (Hocks et al., 1981; Kiehne et al., 1986;
Hasse et al., 2000). Although lean combustion of simpler hydrocarbons like methane
have limited pathways for forming intermediate hydrocarbons, detailed chemistry
schemes are needed to describe the interaction between transport and fuel oxidation in
the gas and on the surface. The results are further improved when the effect of thermal
diffusion (Soret effect) is considered (Popp & Baum, 1997). Thermal diffusion denotes
the diffusion of mass caused by temperature gradients.
Studies of maximum wall heat fluxes have shown that the following two generic
cases must be considered for laminar premixed flames (see Fig. 3.1).

• Stagnation or head-on quenching: when the premixed flame propagates towards
the wall, and where the flame stops at a certain distance from the wall.
• Sidewall quenching: when the premixed flame propagates along the wall. The
quenching distance is larger than for head-on quenching, and the wall heat flux
slightly lower.

Numerical modeling with complex chemistry has mostly used the stagnation
configuration in either the transient case of a flame freely propagating towards a wall
(Westbrook et al., 1981; Popp, Smooke & Baum, 1996; Popp & Baum, 1997; Hasse et
al., 2000) or the stationary case with head-on stagnation point flow (Vlachos et al.,
1993; Vlachos, Schmidt & Aris, 1994a; Bui, Vlachos & Westmoreland, 1996;
17
Egolfopoulos, Zhang & Zhang, 1997; Aghalayam, Bui & Vlachos, 1998; Forsth,
Gudmundson, Persson & Rosén, 1999).





a b
Flame zone







Flame zone

Wall Wall


Stagnation configuration Sidewall configuration

Figure 3.1 Typical flow configurations used to model near-wall combustion.


Furthermore, sidewall configuration has been dealt with by von Kármán and
Millán (1953) and Blint and Bechtel (1982), however not specifically using complex
chemistry. The emphasis in this thesis has therefore been placed on the sidewall
configuration.

3.1 Near-wall turbulence

Turbulent flows are characterized by a wide range of spatial and temporal scales.
The largest scales are given by the size of flow boundaries and by the flow velocity—
the integral length scale (l
o
). The smallest scales are at the level where turbulence is
dissipated by viscosity. At this so-called Kolmogorov length scale (l
k
), the time taken
for an eddy to rotate half a revolution is equal to the diffusion time across the diameter
(l
k
). The time scales for different chemical reactions can overlap with the turbulent time
scales.
Almost all practical flows in industry and the environment are turbulent. The
understanding and modeling of turbulent phenomena that occur near walls is a
formidable task. The treatment of near-wall turbulence for non-reacting flows is still a
difficult problem and quite often the limiting factor in making practical predictions.
Wall problems become even more critical in chemically-reacting flows. In practice,
18
very little is known about the effects of turbulence during flame-wall interaction. In
turbulent flows, the mixing between the fuel and the oxidant is drastically enhanced,
and in general the heat and mass transfer rates would be higher in a turbulent boundary
layer than in a laminar boundary layer. In order for computations with turbulent
reactive flows to be accurate, these must respect the smallest scales of length and time,
which often strain storage and computational efficiency past practical limits. In internal
combustion engines, the length scales of wall quenching are much smaller than those of
the turbulence (that is, the diffusion and molecular transport is in general faster than the
turbulent transport).


k
l

Figure 3.2 At the Kolmogorov length scale, the time taken for an eddy to rotate
half a revolution is equal to the diffusion across the diameter l .
k


The laminar sublayer is usually taken to be the region where eddies are completely
absent, however there is evidence that eddies do occasionally penetrate right up to the
surface. The situation is therefore highly complex, and any attempt to model the process
must involve simplifying assumptions.

3.2 Laminar models

Although the chemical reactions in both an internal combustion engine and a gas
turbine combustor take place in a turbulent flow field, there will always be a laminar
sublayer close to the wall, where the turbulence has died out and momentum transferred
due solely to viscous shear. This suggests that results obtained for laminar models are
also valid and can be compared with results obtained from turbulent models. As the
quench layer is usually within the laminar sublayer, and the quench distances in engines
can be well correlated to the distances obtained for laminar flame-quench calculations
(Ferguson & Keck, 1977), the use of laminar models has been generally accepted. In
this thesis, the numerical modeling work done on homogeneous premixed combustion
influenced by walls has been carried out exclusively using laminar models in the
sidewall configuration (see Fig. 3.1). The following section presents a description of the
19
mathematical treatment of a two-dimensional chemically-reacting boundary layer over
a flat wall.


3.2.1 Mathematical description of chemically-reacting boundary layer flow

Two-dimensional boundary layer flow is illustrated in Fig. 3.3. When modeling
a chemically-reacting boundary layer, fluid flow pattern, temperature and species fields
are calculated from conservation equations for mass, momentum, energy and species.
Reaction rates using factors such as the molecular weights, concentrations and
stoichiometries for specific species in all reactions are used in each species-
conservation equation to balance the mass transfer from one species to another.



y

Boundary layer




x

Wall

Figure 3.3 Two-dimensional boundary layer flow over a flat wall.


Elliptic approach (Navier-Stokes equations)
The laminar, multicomponent, chemically-reacting Navier-Stokes equations involve
few assumptions, and represent the most general approach. In a two-dimensional
Cartesian coordinate system, and at steady state, they can be expressed as follows (after
Bird, Stewart & Lightfoot, 2002).



Continuity:

0 =


+


y
v
x
u ρ ρ
. (3.1)


20
Axial momentum:


0
3
2
2
= +

|
|
.
|

\
|


+




|
|
.
|

\
|


+










+


+


g
x
v
y
u
y
y
v
x
u
x
u
x x
p
y
u
v
x
u
u
ρ u
u u ρ ρ
. (3.2)

Cross-flow momentum:



0
3
2
2 = +

|
|
.
|

\
|


+







|
|
.
|

\
|


+







+


+


g
y
v
x
u
y
v
y
y
u
x
v
x y
p
y
v
v
x
v
u
ρ u u
u ρ ρ
. (3.3)


Thermal energy:

k
k
g
K
k
k
y
k k
x
k k
g
K
k
k
p
p
W h
y
T
V Y
x
T
V Y c
y
T
y x
T
x y
p
v
x
p
u
y
T
v
x
T
u c
ω ρ ρ
λ λ ρ
& ∑ ∑
= =

|
|
.
|

\
|


+



|
|
.
|

\
|




+
|
|
.
|

\
|




+


+


=
|
|
.
|

\
|


+


1 1
. (3.4)


Species continuity:

g
k
k
y
k k
x
k k
k k
K k
W V Y
y
V Y
x y
Y
v
x
Y
u
, , , 1
0 ) ( ) (
=
= −


+


+


+


ω ρ ρ ρ ρ &
. (3.5)


21
State:

W
T R
p
ρ
= . (3.6)


For reactive walls, the variation of surface coverage—the fraction of surface
sites covered by species k —is calculated from the surface reaction rates according to
the following expression:


s
k
k
K k
s
dt
dZ
, , , , 1 =
Γ
=
&
. (3.7)

Equation 3.7 simply states that at steady state the surface composition does not change.
In some senses this could be considered a boundary condition (possibly complex) on
the gas-phase system, however because the surface composition is determined as a part
of the solution, Equation 3.7 should be considered to be a part of the system of
governing equations. All the variables are described in the Nomenclature section at the
beginning of the thesis.

Parabolic approach (Boundary layer approximation)
Pursuing solutions based on the Navier-Stokes equations for a propagating flame—fluid
flow equations coupled to the diffusion and energy equations with finite-rate
chemistry—is a formidable task, even for a two-dimensional stationary system.
Therefore it may be desirable to first undertake some simplifications of the fluid
mechanics. Prandtl first addressed the boundary layer approximations around 1904
(Prandtl, 1961) and these well-known approximations are still applied widely today in
fluid mechanics. Compared with an elliptical approach, the validity of the boundary
layer equations depends on the inlet velocity and the fuel/air ratio (Mantzaras, Appel &
Benz, 2000). As the flow rate in the channel increases (high Reynolds numbers) and the
fuel/air ratio (φ) decreases, the boundary layer approximations become increasingly
valid. Compared with the diffusive transport, under these conditions the convective
transport is dominant in the principal flow direction ( x). As a result, all the second
derivatives in the x direction are eliminated. It can be shown by order-of-magnitude
arguments that the cross-flow momentum equation is reduced to the simple statement
that there can be no pressure variation across the channel (Bird, Stewart & Lightfoot,
2002).

The governing equations are then be expressed as follows.

22
Continuity:

0 =


+


y
v
x
u ρ ρ
. (3.8)

Axial momentum:


0 = +


+
|
|
.
|

\
|







+


g
x
p
y
u
y y
u
v
x
u
u ρ u ρ ρ . (3.9)


Cross-flow momentum:

0 =


y
p
. (3.10)

Thermal energy:

0
1 1
= +


+
|
|
.
|

\
|







+


∑ ∑
= =
k
g
K
k
g
K
k
k
k
k
p
y
k k
p p
h W
y
T
c V Y
y
T
y y
T
c v
x
T
c u
ω ρ
λ ρ ρ
&
. (3.11)

Species continuity:

0 ) ( = −


+


+


k
k
y
k k
k k
W V Y
y y
Y
v
x
Y
u ω ρ ρ ρ &
. (3.12)
g
K k , , , 1 =

The state expressed by Equation 3.6, and the surface species conservation expressed by
Equation 3.7 have to be added to the system. In horizontal channels, the term g ρ in
Equation 3.9 can be omitted when the channel height is sufficiently small, as in this
thesis. The independent variables are denoted x and , and the dependent variables are
denoted
y
, , , , , ,
k
Y T v u p ρ and Z . The character of the equations changes from
k
23
elliptical to parabolic. This represents a huge simplification, leading to much more
efficient computational solution (Mantzaras et al., 2000; Raja, Kee, Deutschmann,
Warnatz & Schmidt, 2000).

The boundary layer approximations for the transport equations have been used
throughout this work. In Paper II, the validity of the boundary layer approximations for
the flame position was investigated. It was found that in most cases the effect of axial-
diffusive transport was small, although at lower pressures (higher flame velocities) and
higher concentrations, the parabolic approach should be used with caution.


3.2.2 Boundary conditions

Turning now to the energy equation, either the temperature (see Equation 3.13
below) or a zero heat flux (adiabatic) condition (see Equation 3.14) is specified at the
solid wall:

w
T T = (3.13)
or
0 =


y
T
. (3.14)

In addition, the axial velocity ( u) is assumed to be zero at the wall (the non-slip
condition). For chemically inert walls, the following zero-gradient Neumann boundary
condition is used for each species:

0 =


y
Y
k
. (3.15)

The boundary condition at the wall becomes relatively complex in the presence of
heterogeneous surface reactions. The convective and diffusive mass fluxes of gas-phase
species at the surface are balanced by the production (or depletion) rates of gas-phase
species by surface reactions, as represented in the following expression:


k k ky k
y
k
W s v V Y j & = + = ) ( ρ ,
g
K k , , , 1 = . (3.16)


In the above equation, the gas-phase diffusion velocity of species k in the direction
normal to the wall is given by:
24
y
T
T Y
D
y
X
D W
W X
V
k
T
k k
kj
g
K
j k
j
k
ky





= ∑

1 1
ρ
, (3.17)


when multicomponent transport is used, or by



y
T
T Y
D
y
X
X
D
V
k
T
k k
k
m k
ky





− =
1
,
ρ
(3.18)



when mixture-averaged transport is used. The velocity referred to as Stefan velocity,
which occurs when there is a net mass flux between the gas and the surface, is given by
the expression:



k
g
K
k
k
W s v ∑
=
=
1
1
&
ρ
. (3.19)


Equation 3.19 is obtained from Equation 3.16, and must satisfy the requirements that
the mass fractions total 1, and the diffusion fluxes total 0:

1
1
= ∑
=
g
K
k
k
Y (3.20)
and
0
1
= ∑
=
y
k
g
K
k
k
V Y ρ . (3.21)


Symmetry is used to specify the boundary conditions at the channel centerline in an
axisymmetric channel.





25
4 CHEMKIN Software

The software used in Papers I-V is called CHEMKIN®. This is on of the most
widely used software package for modeling combustion kinetics. CHEMKIN was
developed by Sandia National Laboratories in the early 1980s (Kee, Miller & Jefferson,
1980) and has had a noticeable impact on combustion research. CHEMKIN was
publicly available up until about 1994, when it was then licensed to Reaction Design,
who have continued its development. Today, the CHEMKIN Collection (Kee, Rupley,
Miller et al., 2000) is designed to analyze complex chemically-reacting processes in a
rigorous but flexible manner.

4.1 CHEMKIN architecture

CHEMKIN provides a structured approach to the computational modeling of
chemical kinetics and molecular transport in flowing systems. This means that
CHEMKIN handles complex chemistry and transport in a generic way, independent of
the particular type of reactive flow problem, and is able to disengage the generic
solution techniques from the actual physical model. This is illustrated in Fig. 4.1. The
upper rectangles shown in the figure contain the data that make the problem specific—
species identity, species properties, reaction path, and reaction rates. The CHEMKIN
software core utilities provide the interface between the problem-specific information
and the problem-independent “application”. The application represents the general
model, independently of which chemical species are included in a specific problem.
Typically the model description includes conservation equations for mass, momentum,
energy and species. Additional problem-specific information may also be input directly
by the user, including for example pressure, flow rate and concentration. One advantage
with this modular approach is that the software can benefit from the rapid advances in
computational mathematics and software.
The core utilities in the CHEMKIN Collection are: CHEMKIN-III (Kee et al.,
1996), SURFACE CHEMKIN-III (Coltrin, Kee, Rupley & Meeks, 1996) and the
TRANSPORT package (Kee, Dixon-Lewis, Warnatz, Coltrin, Miller & Moffat, 1986),
together with the CHEMKIN thermodynamic database (Kee, Rupley & Miller, 1990)
and TWOPNT mathematical software (Grcar, 1991). These core utilities contain a large
set of modular subroutines written in Fortran.
CHEMKIN-III was developed to assist the incorporation of complex gas-phase
chemical-reaction mechanisms into numerical simulations. This package calculates the
homogeneous reaction rates of the gas-phase species, as well as handles thermodynamic
data for the system needed to calculate reverse rate constants for the chemical reactions
(Kee et al., 1990). This package allows the user to specify the input required through a
high-level symbolic interpreter. This interpreter then passes the information on via an
application code. CHEMKIN’s utilization flexibility has developed significantly since
26
the original version, through for example the provision of new options for describing
the temperature and pressure dependence of a reaction.



TRANSPORT
SURFACE
CHEMKIN
Surface chemistry/
Thermochemistry input
Transport
properties
input
Gas-phase chemistry/
Thermochemistry input








CHEMKIN


Application
Input
APPLICATION





Problem-
independent
numerical software




POST-
PROCESSING




Figure 4.1 Illustration of the CHEMKIN modular approach to problem solving.

SURFACE CHEMKIN-III software has a similar user interface to CHEMKIN-
III, and is used to formulate the boundary conditions describing chemical reactions at
the surface. SURFACE CHEMKIN-III is designed to run in conjunction with
CHEMKIN-III, and execution of the CHEMKIN-III interpreter is required before the
SURFACE CHEMKIN-III interpreter can be run.
The TRANSPORT package provides information about the molecular diffusion.
This has the ability to calculate as a function of temperature, the binary diffusion
coefficients including thermal diffusion coefficients, thermal conductivities and
viscosities for every gas-phase species.

27
4.2 The CRESLAF program

The numerical solution for the two-dimensional chemically-reacting boundary
layer model presented in Equations 3.6 to 3.21 is accomplished using the CRESLAF
program (Coltrin, Kee & Miller, 1984; Coltrin, Kee & Miller, 1986; Coltrin, Moffat,
Kee & Rupley, 1993), which is a part of the CHEMKIN Collection. CRESLAF is
written as a subroutine and runs in conjunction with the CHEMKIN, SURFACE
CHEMKIN and TRANSPORT libraries. When CRESLAF executes, it reads the
linking-file information from the three preprocessors, and calls up appropriate
subroutine libraries from the preprocessors using these linking data. In CRESLAF, the
boundary layer equations are recast using von Mises transformation in a form in which
a stream function replaces the cross-flow ( ) coordinate as an independent variable
(Moore, 1964). The relationships between the physical coordinates (
y
x and ) and the
transformed coordinate (
y
ψ ) can be expressed as follows:



x y
v
x x
|
|
.
|

\
|



|
|
.
|

\
|


=
|
|
.
|

\
|


ψ
ρ
ψ
, (4.1)

and

x x
u
y
|
|
.
|

\
|


=
|
|
.
|

\
|


ψ
ρ , (4.2)


where the stream function is defined as



=
y
dy u
0
ρ ψ . (4.3)


The stream function variable represents the amount of mass going through a specified
physical domain. This transformation eliminates the mass continuity equation (Equation
3.8), replacing it with an integral, and the convective derivates in the direction
(normal to the wall) are eliminated. The equations transformed into planar coordinates
are listed below.
y


28
Axial momentum:
g
u
u u
x d
p d
x
u
u ρ
ψ
u ρ
ψ
ρ ρ +
|
|
.
|

\
|




= +


. (4.4)


Cross-flow momentum:

0 =


ψ
ρ
p
u . (4.5)

Thermal energy:


ψ
ρ ω
ψ
λ ρ
ψ
ρ ρ


− −
|
|
.
|

\
|




=


∑ ∑
= =
T
V Y c u h W
T
u u
x
T
c u
ky
g
K
k
k pk k k
g
K
k
k p
1
2
1
& . (4.6)


Species continuity:


( )
g
y
k k k k
k
K k V Y u W
x
Y
u , , , 1 , =


− =


ρ
ψ
ρ ω ρ & . (4.7)
The state expressed by Equation 3.6, and the surface species conservation expressed by
Equation 3.7 have to be added to the system.

4.2.1 Numerical solution using the differential/algebraic approach

Chemical kinetics provides the coupling between the concentrations of various
chemical species and the energy equation, through the heat of reaction. In many
combustion problems, the kinetic terms dictate the characteristic time and space in
which the numerical solution must be found. The widely differing scales of combustion
processes lead to the well-known stiffness problem when solving the species
concentration equations. To enable the inclusion of finite rate chemistry (reaction rates
that are not infinitely large), the boundary layer equations are expressed as a set of
differential/algebraic equations (DAEs) with the time-like direction represented by the
axial coordinate x. The finite-difference representation of the defining equations is
solved using the computer program called DASSL (Petzold, 1982).
29
The DAEs are written in the general form g(y, y’,t) = 0, where y and y’ represent
the components of the solution and their time derivatives, and t is time. As part of the
solution to the equations, a numerical Jacobian is formed, which is the partial derivative
of the residual g with respect to each component of the solution. A Jacobian is needed
because DASSL employs an implicit time-stepping method. Implicit methods are most
efficient for solving the stiff equations usually found in chemical kinetic problems.
Calculating the Jacobian is expensive and the most computationally-expensive aspect of
evaluating it is the calculation of the multicomponent transport properties. Holding the
transport properties fixed when calculating the numerical Jacobian can significantly
reduce the extent of computer time required to solve the set of DAEs. Although this
introduces some error into the Jacobian, DASSL requires only an approximate Jacobian
for the purpose of iterating to a converged solution. No error is introduced into the
solution by including this simplification in the Jacobian evaluation. However, the
computer time required by the model can be decreased by a factor of 10 or more
(Coltrin, Moffat, Kee & Rupley, 1993).

30
5 Autoignition Flames (Papers I and II)
The first flame geometry used in this study featured a uniform unburned mixture
of fuel and oxidizer at the inlet to the channel, having a temperature higher than the
crossover temperature. The crossover temperature is defined as the temperature at
which the effects of chain-branching reactions just balance that of chain-breaking
reactions. This leads to autoignition of the mixture at some point further downstream, as
illustrated in Fig. 5.1. This autoignition situation should have the following three
important applications:
• in the autoignition of an unburned fuel-oxidizer mixture at a cylinder wall
of an internal combustion engine which takes place before the ordinary
flame front has reached the cylinder wall—also referred to as knock;
• in catalytically-stabilized combustion (CST), including hydrogen-assisted
catalytically CST—in hydrogen-assisted CST the hydrogen can reduce
the catalyst light-off temperature, however hot-spots in the catalyst may
lead to an uncontrolled temperature rise and ignition in the gas-phase; and
• in homogeneous-charge-compression-ignition combustion (HCCI), for
which the combustion process is not totally explained, especially not
close to walls.

The fuels used in the model are hydrogen and methane, and the aim is to clarify the
relative importance of the thermal wall-effects compared to the chemical wall-effects.
Thermal effects are simply flame retardation or extinction, resulting from the transfer of
heat out of the flame region at a greater rate than the generation of heat by the
combustion process. Chemical effects occur when for example key reactive radical
intermediates in the combustion mechanism react with the walls, and are thereby
removed from their respective catalytic cycles, causing inhibition of the combustion.

5.1 Hydrogen as fuel in the model (Paper I)

Hydrogen was used as the fuel in the model in Paper I. Hydrogen is a non-
hydrocarbon, and as fewer reactions and species are involved than in hydrocarbon fuels,
the interpretation of the results is easier. On the other hand, as hydrogen has a higher
mass-diffusivity and burning velocity than hydrocarbon fuels, the results may not be
generalized. As mentioned in a Chapter 3, one reason for choosing the sidewall
configuration was that previous modeling studies using complex chemistry and
hydrogen as the fuel for the model had most commonly used the stagnation
configuration. By using different wall boundary conditions and gas-phase transport
parameters, issues were addressed such as which part of the wall effects—chemical or
thermal—was most important for a given set of conditions.
31

Figure 5.1 Representation of the autoignition geometry used in Papers I and II.
The lean unburnt fuel/air mixture is preheated above the
autoignition temperature leading to an autoignition flame
downstream in the axisymmetric channel.


5.1.1 Inlet and boundary conditions

Inlet conditions
An axisymmetric planar channel was considered, where = 1 cm in Fig. 5.1.
The pressure was atmospheric and two lean fuel/air ratios (φ) of 0.5 and 0.1 were used.
The inlet temperature was 975 K, which is above the crossover temperature for
autoignition at these stoichiometries, and the inlet velocity was 900 cm/s, which gave a
clear shape of the reaction zone after ignition. To elucidate the effects of heat and mass
transfer, the carrier gas N
y
2
was substituted with modified helium (He with the same heat
capacity as N
2
). This enhances heat and mass transfer rates due to the higher
conductivity and diffusivity of modified He compared to N
2
. Flat profiles of
temperature and species were used at the inlet, however the velocity boundary layer
thickness was 0.01 cm (within which the velocity profile was parabolic, in other words
fully developed). The velocity and thermal boundary layer then develops very rapidly
downstream of the channel and the velocity profile remains roughly parabolic, but due
to the expansion of the gas, the maximum velocity increases somewhat. The gas-phase
chemistry of hydrogen is described in Chapter 2.

Wall boundary conditions
The wall temperatures used were 600 and 400 K. To avoid numerical
difficulties, the wall temperature was set to equal the gas-phase temperature at the inlet
32
to the channel, and was then linearly ramped down to the wall temperature at x = 0.5
cm. The consequences of this were that in part of the reaction zones the wall
temperature varied. To investigate the heterogeneous effects, three different wall
materials were used: (i) an inert wall with no reactions, (ii) a wall facilitating the
recombination of intermediate species, and (iii) a wall promoting the catalytic
combustion of hydrogen. The catalytic mechanism is described in Chapter 2, and the
recombination mechanism is shown in Table 5.1.

Discretization
The mesh had 70 points in the transverse direction concentrated near the wall.
After comparison with 140 and 200 mesh points, this discretization of the grid was
found to provide satisfactory resolution. CRESLAF uses an adaptive method in the
axial direction. Consequently the axial resolution is automatically adapted to match a
given acceptable limit in the truncation error. The typical time needed for the CPU to
complete one calculation was approximately 3.5 min.

Table 5.1 Surface reaction mechanism on the recombination wall for hydrogen oxidation
(after Aghalayam et al., 1998).

Reaction No. A
a

[cm,mol,s]
E
a

[kJ/mol]
1. H + S → H(S) 1.0
b
0.0
2. 2 H(S) → H
2
+ 2 S 1×10
13
0.0
3. O + S → O(S) 1.0
b
0.0
4. 2 O(S) → O
2
+ 2 S 1×10
13
0.0
5. OH + S → OH(S) 1.0
b
0.0
6. 2 OH(S) → H
2
O + O(S) + S 1×10
13
0.0
7. 2 O(S) → O
2
+ 2 S 1×10
13
0.0
8. HO
2
+ 2(S) → OH(S) + O(S) 1.0
b
0.0
9. 2 OH(S) → H
2
O + O(S) + S 1×10
13
0.0
10. 2 O(S) → O
2
+ 2 S 1×10
13
0.0
11. H
2
O
2
+ 2(S) → 2 OH(S) 1.0
b
0.0
12. 2 OH(S) → H
2
O + O(S) + S 1×10
13
0.0
13. 2 O(S) → O
2
+ 2(S) 1×10
13
0.0
a
The rate constants are formulated with Equation 2.9.
b
The sticking coefficients are formulated with Equation 2.31.
S denotes a free surface site and e.g. H(S) is an adsorbed species.
Site density is Γ = 4.17×10
-7
moles/cm
2
.
5.1.2 Results and discussion
Table 5.2 presents a summary of the combinations of the wall materials and
carrier gases used in the calculations.
33
Table 5.2 Combinations of gas and surface mechanisms used in the calculations.

Carrier Gas
Surface mechanism Carrier Gas* Modified He**
Platinum (Table 2.2) PtN
2
PtHe
Recombination (Table 5.1) RrN
2
RrHe
Inert wall InN
2
InHe
* Abbreviations for the combinations e.g. PtN
2
= Pt wall-carrier gas N
2
.
** He with the same heat capacity as N
2


Contour plots of the fuel concentration ( ) and temperature (
2
H
X T ) for the
combinations of gas-phase materials and carrier gases in Table 5.2 are shown in Figs.
5.2-5.5.
























0.1 0.2 0.3 0.4
0.8
0.9
1
0.16
0.14
0.12
0.1
0.02
PtN2
h
e
i
g
h
t

y
,

c
m
0.1 0.2 0.3 0.4
0.8
0.9
1
0.16
0.14
0.1
0.08
0.02
PtHe
0.1 0.2 0.3 0.4
0.8
0.9
1
0.16
0.14
0.12
0.02
RrN2
h
e
i
g
h
t

y
,

c
m
0.1 0.2 0.3 0.4
0.8
0.9
1
0.16
0.14
0.1
0.02
RrHe
0.1 0.2 0.3 0.4
0.8
0.9
1
0.16
0.14
0.12
0.04
InN2
h
e
i
g
h
t

y
,

c
m
distance x, cm
0.1 0.2 0.3 0.4
0.8
0.9
1
0.16
0.14
0.1
0.02
InHe
distance x, cm
Figure 5.2 Contour of for the combustion systems in Table 5.2: φ = 0.5, T = 600
K, T = 975 K.
2
H
X
w
u
In these contour plots, y = 1 cm is at the wall. The boundary layers are emphasized
within the reaction zone and only a distance of 2-3 mm outward from the wall is shown.
The wall effects are the changes in the combustion process caused by the processes in
the boundary layer compared to an imaginary combustion process without any
34
boundary layer. The diagrams for the inert wall (InN
2
and InHe) give us information on
the extent of the wall effects due to heat transfer combined with viscous shear due to
momentum transfer.
Clearly, the Pt wall promotes catalytic combustion before the homogenous
ignition takes place. However after gas-phase ignition, the homogeneous reactions are
slowed down more by the Pt wall than the inert wall (see PtN
2
and PtHe in Fig. 5.2).
The Pt wall also slows down combustion more than the wall facilitating radical
recombination (which also has a significantly higher simulated site density than the Pt
wall). The Pt wall’s more significant quenching of the homogeneous combustion
reactions than the recombination wall has three causes:

1. the net adsorption of H radicals on the wall is higher using the Pt wall,
2. the depletion of H
2
in the boundary layer due to catalytic combustion results in
lower H-radical production, and
3. increased H-radical recombination in the boundary layer due to the third-body
effect caused by high concentrations of water—in the reaction
H+O
2
+M→HO
2
+M, where H
2
O acts as a third body.

























Figure 5.3 Contour of for the combustion systems in Table 5.2: φ = 0.1, T = 600
K, T = 975 K.
2
H
X
w
u
0.4 0.6 0.8 1
0.8
0.9
1
0.00404
0.0161
0.0321
0.0361
PtN2
h
e
i
g
h
t

y
,

c
m
0.4 0.6 0.8 1
0.8
0.9
1
0.00405
0.0121
0.0241
0.0322
0.0362 PtHe
0.4 0.6 0.8 1
0.8
0.9
1
0.00408
0.00813
0.0203
0.0365
RrN2
h
e
i
g
h
t

y
,

c
m
0.4 0.6 0.8 1
0.8
0.9
1
0.00408
0.0122
0.0243
0.0324
0.0364
RrHe
0.4 0.6 0.8 1
0.8
0.9
1
0.00408
0.00812
0.0122
0.0364
InN2
h
e
i
g
h
t

y
,

c
m
distance x, cm
0.4 0.6 0.8 1
0.8
0.9
1
0.00407
0.0122
0.0283
0.0364
InHe
distance x, cm
35
By interpretation of Fig. 5.2, together with a corresponding plot for the H radical ( ),
the third case is implied since:
H
X

1. the rate of H-radical adsorption is lower with the Pt wall than with the
recombination wall, and
2. the H-radical concentration is more depleted with the Pt wall than the
recombination wall, and more H
2
is left in the boundary layer.
















0.2 0.3 0.4 0.5 0.6
0.7
0.8
0.9
1
1.9e+003
1.71e+003
971
1.34e+003
PtN2
h
e
i
g
h
t

y
,

c
m
0.2 0.3 0.4 0.5 0.6
0.7
0.8
0.9
1
1.9e+003
1.71e+003
971
1.16e+003
PtHe
0.2 0.3 0.4 0.5 0.6
0.7
0.8
0.9
1
1.9e+003
1.72e+003
972
RrN2
h
e
i
g
h
t

y
,

c
m
0.2 0.3 0.4 0.5 0.6
0.7
0.8
0.9
1
1.9e+003
1.71e+003
785
970
RrHe
0.2 0.3 0.4 0.5 0.6
0.7
0.8
0.9
1
1.9e+003
1.71e+003
971
InN2
h
e
i
g
h
t

y
,

c
m
distance x, cm
0.2 0.3 0.4 0.5 0.6
0.7
0.8
0.9
1
1.9e+003
1.71e+003
970
InHe
distance x, cm
Figure 5.4 Contour of T (K) for the combustion systems in Table 5.2: φ = 0.5, T = 600
K, T = 975 K.
w
u


Vlachos (1996) and Bui et al. (1996) used the stagnation configuration, and observed
that homogeneous ignition of H
2
over a Pt wall was inhibited by the presence of water.
However in the sidewall configuration, the inhibition is expected to be stronger because
the concentration of water becomes greater and the water is affected by the boundary
layer flow. Obviously the boundary layers become thicker when changing carrier gas
from N
2
to modified He (see Fig. 5.4). However the same differences can be seen for
36
the three wall materials at φ = 0.5, implying that the chemical wall effects are most
significant in the richer combustion case.




























0.4 0.5 0.6 0.7 0.8
0.7
0.8
0.9
1
1.2e+003
1.14e+003
1.07e+003
935
PtN2
h
e
i
g
h
t

y
,

c
m
0.4 0.5 0.6 0.7 0.8
0.7
0.8
0.9
1
935
868
1e+003
1.07e+003
1.2e+003
PtHe
0.4 0.5 0.6 0.7 0.8
0.7
0.8
0.9
1
1.21e+003
939
1.01e+003
1.14e+003
RrN2 h
e
i
g
h
t

y
,

c
m
0.4 0.5 0.6 0.7 0.8
0.7
0.8
0.9
1
1e+003
1.07e+003
936
801
1.2e+003
RrHe
0.4 0.5 0.6 0.7 0.8
0.7
0.8
0.9
1
1.21e+003
1.14e+003
1.07e+003
939
InN2
h
e
i
g
h
t

y
,

c
m
distance x, cm
0.4 0.5 0.6 0.7 0.8
0.7
0.8
0.9
1
1.2e+003
936
1e+003
1.07e+003
869
InHe
distance x, cm
Figure 5.5 Contour of T (K) for the combustion systems in Table 5.2: φ = 0.1, T = 600
K, T = 975 K.
w
u

Reducing the fuel/air ratio to 0.1 reduces the observed differences between the wall
materials (see Fig. 5.3). At the same time, the boundary layers become thicker
compared with when φ = 0.5 (see Fig. 5.5), implying that the thermal wall effects are
the more significant. As expected, the overall wall effects are most significant in the
combination of the leaner combustion case with modified He as the carrier gas.
5.2 Methane as fuel in the model (Paper II)
In Paper II, the fuel used in the model was methane. Compared to hydrogen,
which is a strongly diffusionally-imbalanced fuel (Le ~ 0.3, where the Le number
measures the ratio of energy transport to mass transport), methane has a much lower
37
mass diffusivity and flame speed. Methane is a major constituent in natural gas and the
simplest of the hydrocarbons. Methane is an important fuel for modeling both
automotive and gas turbine applications. As in Paper I, different inlet conditions and
wall-boundary conditions were used in order to characterize the wall effects for the
autoignition flame.

5.2.1 Inlet and boundary conditions

Inlet conditions
The gas-phase chemistry describing methane oxidation in air is quite complex
and contains hundreds of reactions. In the work done here, the Gas Research Institute
Mechanism Version 1.2 with its corresponding thermodynamic and transport databases
(Frenklach, Wang, Goldenberg et el., 1995) were used. This mechanism has been
optimized at lean-to-stoichiometric fuel mixtures, over a wide range of pressures and
residence times. This mechanism represents one of the most recent and comprehensive
methane oxidation reaction mechanisms. There are two parallel oxidation paths in the
methane system: (1) via the oxidation of methyl radicals, and (2) via the oxidation of
ethane. For fuel-lean mixtures, the former path predominates; therefore a simplification
was made to only include this C
1
path in the calculations. Consequently, the reaction
CH
3
+ CH
3
+ M = C
2
H
6
+ M and all the third-body efficiencies for C
2
H
6
were removed
from the reaction mechanism (also known as the C
2
path of methane oxidation). The
reduced mechanism had 23 species (H
2
, H, O, O
2
, OH, H
2
O, HO
2
, H
2
O
2
, C, CH, CH
2
,
CH
2
(s), CH
3
, CH
4
, CO, CO
2
, HCO, CH
2
O, CH
2
OH, CH
3
O, CH
3
OH, Ar and N
2
) among
119 reversible reactions. Including only the C
1
path has the advantage that the CPU
time needed for the calculations can be reduced.

The conditions for the calculations were changed slightly from when hydrogen
was used as the fuel for the model. The channel was axisymmetric in planar
coordinates, but in Fig. 5.1 was set to 0.5 cm. By narrowing the channel, the effects
of heterogeneous reactions should become more significant. Two lean fuel/air ratios (φ)
of 0.4 and 0.2 were used, with an inlet velocity of 200 cm/s.
y

The inlet temperature was 1,200 K simulating an ignition source. A higher inlet
temperature was needed to cause the autoignition of methane than was the case with
hydrogen. In order to elucidate the influence of pressure on the wall effects, a pressure
of 10 atm was used in addition to atmospheric pressure. This increases concentrations,
mass-burning rates and enhances the rate of third-body reactions, but also in a better
way simulates the situation in a lean-burn combustion engine.

Wall boundary conditions
The wall temperatures used were 600 and 1,200 K, and the wall was isothermal.

38
The same types of wall materials were used in Paper II as in Paper I. The catalytic
combustion mechanism on Pt is considerably more complex than the corresponding one
for hydrogen. The mechanism shown in Table 5.3 developed by Deutschmann and co-
workers is the most frequently used mechanism published to date. In addition to
hydrogen, this mechanism also involves CO and methane adsorption and oxidation, and
has a complex surface-coverage-dependence on the activation energies for desorption
of adsorbed hydrogen and oxygen. The chemistry is therefore generally not as well
understood as that for hydrogen. However the situation has improved significantly in
recent years (Chou, Chen & Evans, 2000; Aghalayam, Park & Vlachos, 2000b;
Mhadeshwar, Aghalayam, Papavassiliou & Vlachos, 2002). The recombination
mechanism was the same as that used in Paper I (see Table 5.1). This would be a small
simplification, but removing the radicals H, OH and O would also slow down the
methane oxidation in the boundary layer, as they are important chain carriers.
0 1 2
0
0.1
0.2
0.3
0.4
1210
1400
1600
1800
2000
2020
(c)
axial dist., cm
r
a
d
.

d
i
s
t
.
,

c
m
0 0.1 0.2
0.25
0.3
0.35
0.4
0.45
1210
1400
1600
1800
2000
2040
(d)
axial dist., cm
0 0.1 0.2
0.25
0.3
0.35
0.4
0.45
1210
1300
1400
1500
1600
1620
(b)
0 1 2
0
0.1
0.2
0.3
0.4
1210
1300
1400
1500
1600
1620
(a)
r
a
d
.

d
i
s
t
,

c
m

Figure 5.6 Contour for T (K) for the Pt wall at = 1,200 K, where in (a) φ = 0.2, p =
1 atm, (b) φ = 0.2, p = 10 atm, (c) φ = 0.4, p = 1 atm, and (d) φ = 0.4, p =
10 atm.
w
T

Discretization
The mesh used had 70 points in the transverse direction concentrated near the
wall. In some of the calculations, more grid points were needed to resolve the wall-
boundary layer. Calculations were run on a Digital Alpha Unix machine, typically
requiring approximately 20 min of CPU time per calculation.

39
5.2.2 Results and discussion

Compared with hydrogen, when using methane there are no observed differences
between the wall materials at 600 K and 1 atm, implying that the wall effects are mainly
of a thermal nature due to heat transfer, and viscous shear due to momentum transfer.

Table 5.3 Surface reaction mechanism for methane oxidation on Pt.
Source: Deutschmann, Schmidt, Behrendt & Warnatz (1996).


A
a
β
a
E
a

[cm, mol,s] [-] [kJ/mol]
(1) H
2
+2Pt(s) →2H(s)* 0.046
b

(2) 2H(s) → H
2
+2Pt(s) 3.7×10
21
67.4-6⋅[Z
H
]
(3) H+Pt(s) → H(s) 1.0
b

(4) O
2
+2Pt(s) → 2O(s) 1.8×10
21
-0.5
(5) O
2
+2Pt(s) → 2O(s) 0.023
b

(6) 2O(s) → O
2
+2Pt(s) 1.8×10
21
213.2-60⋅[Z
O
]
(7) O+Pt(s) → O(s) 1.0
b

(8) H
2
O+Pt(s) → H
2
O(s) 0.75
b

(9) H
2
O(s) → H
2
O+Pt(s) 1.0×10
13
40.3
(10) OH+Pt(s) → OH(s) 1.0
b

(11) OH(s) → OH+Pt(s) 1.0×10
13
192.8
(12) H(s)+O(s) = OH(s)+Pt(s) 3.7×10
21
11.5
(13) H(s)+OH(s) = H
2
O(s)+Pt(s) 3.7×10
21
17.4
(14) 2OH(s) = H
2
O(s)+O(s) 3.7×10
21
48.2
(15) CO+Pt(s) → CO(s)** 0.84
b

(16) CO(s) → CO+Pt(s) 1.0×10
13
125.5
(17) CO
2
(s) → CO
2
+Pt(s) 1.0×10
13
20.5
(18) CO(s)+O(s) → CO
2
(s)+Pt(s) 3.7×10
21
105
(19) CH
4
+2Pt(s) → CH
3
(s)+H(s)*** 0.01
b

(20) CH
3
(s)+Pt(s) → CH
2
(s)+H(s) 3.7×10
21
20.0
(21) CH
2
(s)+Pt(s) → CH(s)+H(s) 3.7×10
21
20.0
(22) CH(s)+Pt(s) → C(s)+H(s) 3.7×10
21
20.0
(23) C(s)+O(s) → CO(s)+Pt(s) 3.7×10
21
62.8
(24) CO(s)+Pt(s) →C(s)+O(s) 1.0×10
18
184.0

a
The rate constants are formulated with Equation 2.9.
b
The sticking coefficients are formulated with Equation 2.31.
Pt(s) denotes a free surface platinum site and X(s) is an adsorbed species.
Site density of the Pt-wall is = 2.71×10 Γ
-9
mole/cm
2
.
Reaction (4) is equivalent to a sticking coefficient of 21 × T
-1

* Forward order in Pt(s) = 1.0
**Forward order in Pt(s) = 2.0
***Forward order in Pt(s) = 2.3

40
The chemical effects caused by the different wall materials are small but
significant at 1,200 K.
0 1 2
0
0.1
0.2
0.3
0.4
100
200
250
300
360
(c)
axial dist., cm
r
a
d
.

d
i
s
t
.
,

c
m
0 0.1 0.2
0.25
0.3
0.35
0.4
0.45
50
100
150
200
225
250
275
(b)
0 0.1 0.2
0.25
0.3
0.35
0.4
0.45
100
200
250
300
360
(d)
axial dist., cm
0 1 2
0
0.1
0.2
0.3
0.4
50
100
150
200
225
250
275
(a)
r
a
d
.

d
i
s
t
,

c
m


Figure 5.7 Contour for u (cm/s) for the Pt wall at T = 1,200 K, where in (a) φ = 0.2,
p = 1 atm, (b) φ = 0.2, p = 10 atm, (c) φ = 0.4, p = 1 atm, and (d) φ = 0.4,
p = 10 atm.
w


When the pressure is increased to 10 atm, the situation changes. The reaction zones
become thinner as a consequence of the higher inlet concentrations and burning rates.
Only one tenth of the boundary layer develops by the time the reactions are complete,
as can be seen by the contours in Figs. 5.6 and 5.7.


The increase in pressure does not alter the chemical wall-effects at the lower wall
temperature. However at the higher wall temperature, the changes in the chemical wall-
effects are significant, with the Pt wall slowing the homogeneous reactions more than
the recombination wall, and slowing them even more than the inert wall. These changes
take place according to the same mechanism presented in Paper I (see the contour in
Fig. 5.8).

41
The results obtained for the lower wall temperature correspond to the conditions in a
lean-burn spark-ignition engine, where thermal effects are more significant and
chemical wall-effects are less significant.

Recent work by Hultqvist, Christensen and Johansson (2000) supports the results
obtained in this paper at the higher wall temperature. The catalytic wall coating used by
Hultqvist and co-workers would, due to heat isolation and heat release, give rise to the
high wall temperature (1,200 K) used in Paper II. This implies that catalytic flame
quenching due to product inhibition would be responsible for the increased hydrocarbon
emissions they observed.
0 0.5 1
0.4
0.45
0.5
0.02
0.01
0.0005
Pt
r
a
d
.

d
i
s
t
.
,

c
m
0 0.5 1
0.4
0.45
0.5
Rec
r
a
d
.

d
i
s
t
.
,

c
m
0 0.5 1
0.4
0.45
0.5
In
axial dist., cm
r
a
d
.

d
i
s
t
.
,

c
m
0 0.1 0.2
0.4
0.45
0.5
0.02
0.01
0.0005
Pt
0 0.1 0.2
0.4
0.45
0.5
Rec
0 0.1 0.2
0.4
0.45
0.5
In
axial dist., cm


Figure 5.8 Contour for . φ = 0.2, p = 10 atm, where in the left column T = 600
K, and in the right column T = 1,200 K.
4
CH
X
w
w










42
6 Premixed Flame Fronts (Papers III and IV)

In combustion applications such as internal combustion engines operating with
homogeneous or stratified charges, unburned hydrocarbons are formed as a
consequence of local flame extinction. As mentioned in the Introduction, the effects of
a cooled wall can include the presence of a significant source of unburned hydrocarbons
in the form of quench layers (0.1-3.0 mm thick) being left at the wall in each
combustion cycle. This would be more pronounced in lean combustion as the flame is
weaker than under stoichiometric conditions. The results from Papers I and II support
the understanding that the thermal coupling between the flame and the wall is more
significant when the fuel/air ratio is decreased.

Another source of unburned hydrocarbons (UHCs) is the unburned gas that is forced
into crevices or narrow spaces connected to the combustion chamber. The spaces
between the piston, piston rings and the cylinder wall are the largest of these. The
trapped gas escapes the primary combustion process because the entrance to the
crevices is too narrow for the flame to enter. Finally UHCs are believed to originate
from the lubricating oil which leaves a film on the cylinder wall, piston and perhaps the
cylinder head. These oil layers can adsorb and desorb hydrocarbons (Heywood, 1988).

In Papers III and IV, the oxidation of a quench layer has been investigated using
propane and methane as fuels in the model. The flame geometry modeled was different
from that in the previous chapter (Papers I and II). Instead of uniform inlet conditions
for the temperature and species profiles, a premixed flame was placed close to the wall
(see Fig. 6.1). The inlet profiles for temperature, species and velocity vary strongly in
the direction normal to the wall. There is a boundary-layer flow between two parallel
plates located 2 cm apart, that provides an axisymmetric case in planar coordinates. The
stationary flame is closer to the wall at a more downstream position. If an observer was
able to travel with the flow, a flame propagating toward the wall would be seen. It is
assumed that a homogeneous charge is burned, meaning that the initial fuel/air ratio is
the same in the whole channel. This resembles the situation in conventional spark-
ignition engines, and HCCI engines. Modeling combustion with a stratified charge is
more complex than modeling a homogeneous charge and is not treated in this thesis.

6.1 Quenching of premixed propane/air flames near an inert cold wall
(Paper III)

In Paper III, the oxidation of a quench layer was investigated using propane as the fuel
in the model. To the best of the author’s knowledge, this was the first study in which
43
sidewall quenching was modeled with complex chemistry and using propane as the fuel
in the model.

Propane is an important combustion fuel (for example liquid petroleum gas) and is
often used in studies of oxidation processes in laboratory burners, internal combustion
engines, detonations, and many other environments. Unlike hydrocarbon fuels with
simpler structures—such as methane and ethane—the thermo-chemical and combustion
properties of propane are similar in many ways to those of more complex practical
fuels.






Figure 6.1 Geometry used in the two-dimensional flame calculations. The channel is
symmetric around the center plane.

6.1.1 Inlet and boundary conditions

Inlet conditions
Calculations were performed for pressures of 1 and 10 atm, wall temperatures of 400
and 600 K, and fuel/air ratios ranging from 0.4 to 1.0. The inlet velocity was 600 cm/s.
PREMIX (Kee, Grcar, Smooke & Miller, 1985), a part of the CHEMKIN Collection,
was used to produce a premixed laminar flame for a given combination of pressure,
temperature and fuel/air ratio, where the inlet temperature is the same as the wall
temperature. This flame was used as the inlet condition for the boundary-layer
44
calculation. The simulations were run on a grid of 60-80 nodes in the transverse
direction. The actual number of mesh points was determined from the inlet condition.
The intervals of time the CPU needed to complete a simulation varied with the inlet
conditions but were in the range of 50-80 min.

Boundary conditions
The wall temperature is held fixed at a constant temperature, and the axial velocity is
zero at the wall (non-slip wall condition). The wall is assumed to be chemically inert
for the low wall temperatures considered (400 K and 600 K). A test was conducted at
600 K and φ=1.0, where results for the recombination wall (Table 5.1) and an inert wall
were compared. No differences could be observed. This was not the case however in a
study by Popp, Smooke & Baum (1996), in which the stagnation configuration was
used. This is most likely related to the flame geometry. The effect of flame geometry
has been elaborated further in Paper IV.



0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
0,8 0,85 0,9 0,95 1
Distance from wall, cm (1cm=wall)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
1,E-08
1,E-07
1,E-06
1,E-05
1,E-04
1,E-03
1,E-02
1,E-01
M
o
l
e

f
r
a
c
t
i
o
n

C
3
H
8

(
-
)
0 cm
0.10
0.15
0.20
0.22
0.24
0.25



Figure 6.2 Transverse profiles for T (red) and (blue) along the channel: φ = 1.0,
p = 1 atm, and T = 400 K. The arrow shows the direction of the flame at
positions along the channel.
8 3
H C
X



45
6.1.2 Fuel oxidation

One major aim of this paper has been to examine the effect on thermal
quenching of the flame when the fuel/air ratio is changed from stoichiometric to lean.
As would be expected, the thermal coupling between the flame and the wall is small but
significant for stoichiometric and near-stoichiometric mixtures (see Fig. 6.2).
Stoichiometric and near-stoichiometric flames are very strong, and the thermal
boundary layer is relatively thin. Therefore the flame can consume the unburned fuel at
the wall within a short residence time. On the other hand, as the fuel/air ratio is
decreased to 0.6 or below, the thermal coupling between the flame and the wall
becomes very significant. These flames have thicker boundary layers and lower flame
temperatures. The residence time needed for burnout of the flame in the boundary layer
under these conditions is significantly increased and the fuel diffuses out from the wall
into the boundary layer (see Fig. 6.3). When the pressure is increased to 10 atm, the
quenching event is delayed as a result of the lower flame speed. Increasing the wall
temperature to 600 K drastically enhances the oxidation rate of the fuel in the boundary
layer.
0
200
400
600
800
1000
1200
1400
1600
0,30 0,50 0,70 0,90
Distance from wall, cm (1cm=wall)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
1,E-07
1,E-06
1,E-05
1,E-04
1,E-03
1,E-02
1,E-01
M
o
l
e

f
r
a
c
t
i
o
n

C
3
H
8

(
-
)
0 cm
5
6
7.5
10
15


Figure 6.3 Transverse profiles for T (red) and (blue) along the channel: φ = 0.5,
p = 1 atm, and T = 400 K. The arrow shows the direction of the flame at
positions along the channel.
8 3
H C
X


46
6.1.3 Intermediate hydrocarbons

A detailed kinetic model by Qin, Lissianski, Yang, Gardiner, Davis and Wang
(2000) has been used in order to determine the importance of the intermediate
hydrocarbons (IHCs) in relation to the fuel for the total hydrocarbon emissions when
the flame is quenched.




Figure 6.4 Transverse profiles for C
3
H
8
and intermediate hydrocarbons at the axial
distance 0.25 cm: φ = 1.0, p = 1 atm, and T = 400 K. The IHCs are the
dominant emissions for stoichiometric flames.
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
0,90 0,92 0,94 0,96 0,98 1,00
Distance from wall, cm (1cm=wall)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
1,E-08
1,E-07
1,E-06
1,E-05
1,E-04
1,E-03
1,E-02
M
o
l
e

f
r
a
c
t
i
o
n

C
3
H
8

a
n
d

I
H
C
s

(
-
)
T
C3H8
C3H6
CH2CO
pC3H4
CH2O
C2H4
C2H2
CH4
x=0.25 cm

The intermediate hydrocarbons (IHCs) result from the incomplete combustion of fuel
and air to CO
2
and water. Propane is a more complex fuel than for example methane,
and should therefore indicate the greater importance of the IHCs for the overall
emissions in quenching. Although the propane fuel (C
3
H
8
) is consumed, significant
numbers of intermediate species exist near the wall after quenching at a stoichiometric
fuel/air ratio (see Fig. 6.4). The intermediate IHCs have a much slower oxidation rate
than the fuel, and therefore persist longer in the laminar sublayer. These may be swept
subsequently from an engine cylinder as pollutants. These results are consistent with
those of an earlier work where propane was used as fuel in the model, but in the
stagnation configuration (Kiehne et al, 1986).
47

Figure 6.5 Transverse profiles of C
3
H
8
and intermediate hydrocarbons at the axial
distance 7.5 cm: φ = 0.5, p = 1 atm, and T = 400 K. Both the fuel and the
IHCs are important emissions.
0
200
400
600
800
1000
1200
1400
1600
0,7 0,8 0,9 1
Distance from wall, cm (1cm=wall)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
1,E-06
1,E-05
1,E-04
M
o
l
e

f
r
a
c
t
i
o
n

C
3
H
8

a
n
d

I
H
C
s

(
-
)
T
C3H8
C3H6
1-C4H8
CH2CO
pC3H4
aC3H4
CH2O
C2H4
C2H2
CH4
x=7.5 cm


When the fuel/air ratio is decreased the situation changes. Due to the excess of air, the
oxidation rate of the IHCs increases, but at the same time the oxidation of the fuel
significantly decreases (see Fig. 6.5). One obvious explanation for the overall slower
oxidation at φ = 0.5 is that the laminar flame speed decreases from ~ 60 cm/s at φ=1.0
(1 atm) to only ~ 12 cm/s. Therefore the unburnt fuel is of more importance to the
emissions in lean combustion.

6.1.4 Conclusions

In general, the results for the stoichiometric fuel/air ratio agree with previous
stagnation-configuration studies of flame quenching on cold walls. As a consequence,
this study supports the view that the effects observed are fairly general and independent
of flame geometry. In addition, Paper III has provided some new information on
quenching in lean combustion.

6.2 Pressurized methane flames using different wall materials (Paper IV)

The fuel used in the model in Paper IV is methane. The objective of Paper IV
was to characterize the kinetic and transport effects of the combustion in the boundary
layer, by using different pressures, fuel/air ratios and wall boundary conditions relevant
to lean premixed gas-turbine combustors and HCCI engines.
48
6.2.1 Inlet and boundary conditions

Inlet conditions
To model the gas-phase chemistry, the full GRI Mechanism Version 1.2 was
used (Frenklach et al., 1995). This consists of 32 species, where the species C
2
H, C
2
H
2
,
C
2
H
3
, C
2
H
4
, C
2
H
5
, C
2
H
6
, HCCO, CH
2
CO, and HCCOH have all been added—
compared with the reduced mechanism used in Paper II. The number of reversible
reactions increased to 177. The value of the unburned temperature was chosen to
represent a typical value for the inlet of a gas-turbine combustor after the compressor
stage and was set to 723 K. The inlet velocity into the channel was 600 cm/s.
Calculations were performed for pressures of 15 and 25 atm, and fuel/air ratios of 0.4,
0.5 and 0.6 were used. PREMIX was used to generate a premixed laminar flame for a
given combination of pressure, temperature and fuel/air ratio. This flame was used as
the inlet condition for the boundary-layer calculation. The simulations were run on a
grid of 80-125 nodes from the line of symmetry to the wall, leading to a CPU time
interval of 20-50 min.

Boundary conditions
The wall temperature was held fixed at a constant temperature of 1,200 K, and
the axial velocity was 0 at the wall. The same type of wall boundary conditions were
used as those in Paper II. However for the catalytic combustion of methane on Pt, the
mechanism of Chou et al. (2000) was used (similar to Deutschmann et al., 1996).
Compared with the original mechanism, the recombination mechanism included the
adsorption of CH
3
and CH
3
O. The site density of the reactive walls was 2.71 ⋅ 10
-9

mole/cm
2
.
1,E-08
1,E-07
1,E-06
1,E-05
1,E-04
1,E-03
1,E-02
1,E-01
0,80 0,85 0,90 0,95 1,00
Distance from wall, cm (1cm=wall)
C
H
4

m
o
l
e

f
r
a
c
t
i
o
n

(
-
)
0
0,01
0,03
0,05
0,1
0,2
0,33
0,35
0,345
0,34
0,3
Φ=0.5
p=25 atm
In

Figure 6.6 Transverse profiles for the CH
4
mole fraction at different axial positions along the
channel (cm): φ = 0.5, p = 25 atm (inert wall).
49
6.2.2 Effect of flame-geometry

It is interesting to compare the results obtained in Paper IV with those obtained
in Paper II. In regard to the chemical wall-effects, the essential differences between the
results of Papers II and IV, the recombination wall had a slowing effect compared to the
inert wall, while in Paper IV, there were no recombination-wall effects. This difference
may be explained by the different positions of the flames in these cases. In Paper II, the
flame was adjacent to the wall and radicals in the flame could easily diffuse to the wall
and recombine. The same would happen in the Pt wall case, which also exhibits
recombination on the wall combined with the release of water as a product of the
catalytic combustion (Forsth et al., 1999). However, for a premixed flame propagating
towards the wall there is a considerable distance between the flame and the wall
through the unburned fuel/air mixture that may provide strong resistance to diffusion of
the radicals to the wall. Therefore no recombination is observed on the wall, and it can
therefore be described as a short-range phenomenon.



Figure 6.7 Transverse profiles for the CH
4
mole fraction at different axial positions along
the channel (cm): φ = 0.5, p = 25 atm (Pt wall).
1,E-08
1,E-07
1,E-06
1,E-05
1,E-04
1,E-03
1,E-02
1,E-01
0,80 0,85 0,90 0,95 1,00
Distance from wall, cm (1cm=wall)
C
H
4

m
o
l
e

f
r
a
c
t
i
o
n

(
-
)
0
0,01
0,03
0,05
0,1
0,2
0,3
0,35
0,37
0,4
0,43
0,45
0,46
0,465
Φ=0.5
p=25 atm
Pt


In contrast to recombination effects, catalytic flame quenching (Pt wall) is very
significant and illustrated for methane conversion in the boundary layer in Figs. 6.6-6.7.
The Pt wall provides significant slowing down of the boundary layer combustion
compared with the chemically-inert wall. The effect of generating water as a product
50
from the catalytic wall could therefore be said to be a long-range phenomenon,
independent of flame geometry. This could be applied to an HCCI engine with a
catalytic wall-coating in the combustion chamber. In Paper II, the increased fuel
emissions found by Hultqvist et al. (2000) were attributed to the third-body effect of
water on the radical recombination reaction: H+O
2
+M → HO
2
+M. The results of Paper
IV provide further support for this explanation, since in an HCCI engine, the situation
with a flame front separated from the wall by a thin layer of unburned gas would be
rather likely to occur.

6.2.3 Effect of gas-phase chemistry

At elevated pressures the effect of the fall-off/recombination reaction described
in Section 2.2 (2CH
3
(+M) → C
2
H
6
(+M)) would itself add to the formation of water by
catalytic combustion. This is illustrated in Figs. 6.8 and 6.9, where the formation of
ethane in the near-wall region is more significant with the Pt wall than the inert wall.
This would further explain the increased emissions of unburned hydrocarbons observed
when using a catalytic wall-coating, and concludes that the full GRI gas-phase
mechanism should be used when simulating higher pressures.


Figure 6.8 Transverse profiles for the C
2
H
6
mole fraction at different axial positions along
the channel (cm): φ = 0.5, p = 25 atm (inert wall).
1,E-09
1,E-08
1,E-07
1,E-06
1,E-05
1,E-04
1,E-03
0,8 0,85 0,9 0,95 1
Distance from wall, cm (1cm=wall)
C
2
H
6

m
o
l
e

f
r
a
c
t
i
o
n

(
-
)
Φ=0.5
p=25 atm
In
0
0,01
0,03
0,05
0,1
0,2
0,33
0,3
0,31
0,32
0,345


51
Dupont, Zhang & Williams (2001) anticipated the importance of homogeneous C
2

chemistry for explaining kinetic inhibiting effects from experimental results. However,
their results were not supported by calculations.

6.2.4 Effect of fuel/air ratio

The thermal coupling between the flame and the wall increases as the fuel/air
ratio decreases. This means that the rate of flame propagation in the boundary layer
decreases with the fuel/air ratio, which is in agreement with the findings in previous
papers.

6.2.5 Discussion

Another point that ought to be made about the results in Paper IV is that the
comparatively small variations in the system seen in both Papers II and IV led to rather
strong effects. This suggests that the wall effects are complicated and difficult to clarify
using ordinary flame experiments. Since variations in geometry on the submillimeter
scale may well cause dramatic changes, then when conducting these sorts of
experiments, submillimeter geometrical resolution is necessary.


Figure 6.9 Transverse profiles of the C
2
H
6
mole fraction at different axial positions along
the channel (cm): φ = 0.5, p = 25 atm (Pt wall).
1,E-09
1,E-08
1,E-07
1,E-06
1,E-05
1,E-04
1,E-03
0,8 0,85 0,9 0,95 1
Distance from wall, cm (1cm=wall)
C
2
H
6

m
o
l
e

f
r
a
c
t
i
o
n

(
-
)
Φ=0.5
p=25 atm
Pt
0,45
0,43
0,4
0,01
0
0,03
0,05
0,1
0,2
0,3
0,39
0,37
0,35


52
7 Reduction of Fuel-NO
x
in the Catalytic Combustion of Gasified
Biomass (Paper V)

The last paper in this series (Paper V) deals with the formation of fuel-NO
x
in the
catalytic combustion of gasified biomass in gas-turbine applications. The reactor
modeled was a hybrid type—where only part of the fuel is combusted catalytically in
the monolith and the rest in a homogeneous zone. The aim here has been to design the
hybrid combustor to minimize the formation of fuel-NO
x
. Similarly to the flame-wall
modeling described in Chapters 5 and 6, the complex chemistry has to be used in order
to understand the combustion and to design the combustor.

7.1 Gasified biomass

The potential problems of CO
2
emissions and the “greenhouse effect” associated
with it have made biomass (CO
2
neutral) an interesting alternative energy source, and
work is currently in progress to commercialize gasified biomass (biogas) produced from
partial oxidation/pyrolysis of biosolids as a primary fuel for combined heat-and-power
generation. The composition of biogas varies with both the method of gasification and
the composition of raw biomass material. The compositions shown in Table 7.1
therefore represent an attempt to summarize the distribution of the main components
from biomass using air as gasification medium.

Table 7.1 Composition of gasified biomass (mole-%).


Species Typical real
gasified biomass
Synthetic
gas*
Synthetic gas
mixed with
air (λ=2.5)
N
2

O
2

H
2

CO
CO
2

CH
4

H
2
O
NH
3

41-50
0
9-14
14-18
11-20
5-7
10-12
0.02-0.3
44.9
0
10.0
15.0
14.0
5.0
11.0
0.1
69.8
15.3
2.7
4.1
3.8
1.4
3.0
0.027
*Compositions used in the calculations

Biogas also contains C
2
-C
12
hydrocarbons, trace components (HCN, H
2
S and alkalis),
tars and aerosols. To simplify the modeling, these compounds have been omitted in this
study.

53
The N bond in the biomass that is converted to NH
3
during gasification is not entirely
but to a significant degree converted to NO
x
in the combustor, resulting in significant
pollutant emission. It is reasonable to assume here that future emission standards will
be more stringent for combustors fired with biogas. Therefore the combustor has to be
designed to lower NO
x
formation.


7.2 Primary methods for reducing NO
x


Primary measures used in the reduction of NO
x
emissions are re-burning of NO,
exhaust gas recirculation (EGR), and staged combustion.
Reburning is a chemically-complex process in which NO is abated using fuel as
reducing agent. The process involves partial oxidation of the reburning fuel under fuel-
rich conditions as well as reactions between hydrocarbon radicals and NO and
subsequent conversion of the intermediate nitrogenous species (Glarborg, Alzueta,
Dam-Johansen & Miller 1998).
In exhaust gas recirculation (EGR), exhaust gas is recirculated through the
combustion process where it acts as an inert gas and reduces the flame temperature,
lowering thermal NO
x
levels. A similar effect is achieved by the addition of water vapor
into the combustion zone. The EGR method reduces thermal NO
x
formation but is not
relevant to fuel-NO
x
formation from NH
3
.
When the combustion is rich, there is not enough oxygen available to oxidize
the N atoms. However the formation of other harmful substances such as HCN and NH
3

increases dramatically. Nevertheless, calculations have shown that a minimum of the
sum of total fixed nitrogen (NO + HXN + NH
3
) is achieved at stoichiometries between
60 and 80% theoretical air. This enables the minimizing of emissions of total fixed
nitrogen (TFN) by using staged combustion. The first stage is undertaken rich in order
to minimize the amount of NO
x
, and the second stage lean in order to lower the
temperature. The combustion is stoichiometric for the overall process and complete
burnout achieved.
To achieve ultra low NO
x
emissions through reburning, this must be
accompanied by secondary methods, such as selective non-catalytic reduction (SNCR)
or selective catalytic reduction (SCR). The use of stage combustion to minimize fuel-
NO
x
in gas-turbine combustion of biogas calls for innovative ideas in the design of the
gas-turbine combustor.

7.3 Catalytic combustion

One alternative to the above methods is to use high-temperature catalytic combustion.
This technique has received significant attention in relation to gas-turbine applications
because it is cost effective and it is possible to burn mixtures below the flammability
limits. This reduces the flame temperature and thermal NO
x
formation (Forzatti and
Groppi, 1999). While the catalytic combustion of natural gas has been developed for the
54
purpose of achieving ultra-low emission of NO
x
, the catalytic combustion of gasified
biomass may have other objectives. As biogas from air-blown gasifiers is a low
heating-value gas (~ 5 MJ/kg), catalytic combustion may be more attractive than
conventional combustion due to its higher combustion stability and safer ignition.

The aim of this work was to use for the first time, mathematical simulation with
detailed combustion kinetics to investigate the possibility of obtaining fuel-NO
x

reduction in a hybrid catalytic gas-turbine combustor. The approach adopted was to use
the potential reducing agents in the biogas to convert NO to N
2
in the homogeneous
zone. These agents are: (i) ammonia (NH
3
) that may react with NO under conditions
favorable to SNCR, or (ii) the fuel components, which may reduce NO in reburn-type
reactions.



Biogas (CH
4
, H
2
, CO, CO
2
, H
2
O, NH
3
, and N
2
)

Exhaust
753 K, 1.5 MPa
Bypass air
Monolith Homogeneous zone
T ~ 1573 K
Combustor











Compressor Turbine


Air, 1 atm


Figure 7.1 Principal design of the hybrid-catalytic gas-turbine combustor. To avoid
homogenous ignition of the biogas in the monolith, the predominant
channels have to be passive (blue color) compared to the active channels
(red).

7.4 The model

There are different designs of catalytic combustors, including fully-catalytic and
hybrid-catalytic combustors. Here a hybrid-catalytic gas-turbine combustor has been
modeled, featuring both active and passive channels in the monolith, so that only part of
55
the fuel is combusted catalytically (Dalla Betta, Schlatter, Yee, Loffler & Shoji, 1995;
Groppi, Belloni, Tronconi, & Forzatti, 1995). The hybrid gas-turbine combustor design
is illustrated in Fig. 7.1. The need for sophisticated catalyst materials for the catalyst
segment can be avoided due to the lower temperature reached in the active channels
using a catalytic coating. In addition, the use of biogas with its high H
2
content lowers
the light-off temperature for the catalyst in the active channels. This in turn enables the
combustor to run without a preburner. However to avoid homogeneous ignition in the
passive channels, the ratio of active to passive channels has to be adjusted; thereby
controlling the temperature profile.

The monolith has been modeled as a single two-dimensional channel using CRESLAF.
It has been assumed here that there is laminar flow, negligible heat dispersion and
uniform distribution of the gas properties at the inlet to the monolith. The subsequent
homogeneous zone has been modeled with SENKIN—part of the CHEMKIN
Collection (Lutz, Kee & Miller, 1988; Kee et al., 2000)—and the assumption made that
the homogeneous zone can be modeled with a plug-zone model. Perfect mixing after
the monolith may be a simplified hydrodynamic assumption, and have to be addressed
in forthcoming studies.

Inlet conditions
The pressure and velocity after the compressor were 1.5 MPa and 1 m/s respectively,
and the air and fuel were mixed to different λ-values, where λ denotes the excess air
ratio. The inlet temperature to the monolith was 753 K, which is a typical inlet
temperature for the catalytic section of hybrid combustors (Groppi et al., 1995). To
obtain a final gas temperature for the turbine of ~ 1573 K, the overall excess-air ratio
was 2.5. The gas-phase chemistry has been described with a detailed chemical-kinetic
model for hydrocarbon-ammonia-nitric-oxide interactions (Glarborg, Alzueta, Dam-
Johansen & Miller, 1998). This consists of 460 reversible reactions among 66 species.

Table 7.2 The reaction mechanism for NH
3
oxidation on Pt.

Reaction No. A
a
E
a

[mol,cm,s] [kJ/mol]
1. NH
3
+ 2 Pt(s) → NH
2
(s) + H(s) 0.1
b
0
2. NH
2
(s) + Pt(s) → NH(s) + H(s) 3.7×10
21
20
3. NH(s) + Pt(s) → N(s) + H(s) 3.7×10
21
20
4. N(s) + O(s) → NO(s) + Pt(s) 3.7×10
21
20
5. NO(s) → NO + Pt(s) * 1.0×10
13
20
Pt(s) denotes a free surface platinum site and X(s) is an adsorbed species.
a
The rate constants are formulated with Equation 2.9.
b
The sticking coefficient is formulated with Equation 2.31.
Site density of the Pt-wall is = 2.71×10 Γ
-9
mole/cm
2
.
* It is assumed that NH
3
is completely converted to NO.
56
Boundary conditions
The wall temperature profile in the non-adiabatic monolith has been constructed from
the corresponding adiabatic case, for example where 50% active channels would give a
50% adiabatic temperature rise in the monolith. The heterogeneous reactions in the
active channels in the monolith have been assumed to take place on a polycrystalline
Pt-surface (see Table 5.3). An NH
3
subset has been added to this mechanism (see Table
7.2). The NH
3
oxidation generating the product NO has been assumed to take place at
he same surface site as the oxidation of methane, CO and hydrogen. t

7.5 Lean primary λ

First the potential of a lean primary excess-air ratio of 2.5 was estimated. This results in
generating the adiabatic temperature to the turbine without the need for providing
additional air. The aim with a lean operation was to use the SNCR reactions to reduce
the formation of NO. These reactions are very temperature sensitive. The optimum
temperature decreases with an increasing concentration of combustibles (Alzueta,
Røjel, Kristensen, Glarborg & Dam-Johansen, 1997). However, when the combustibles
(from the passive channels) are oxidized, the adiabatic temperature rise is significant,
raising the temperature above the window for the SNCR reactions. Instead of reacting
with NO, the NH
3
is largely oxidized to NO.
Figure 7.2 NO and N
2
profiles as functions of residence time in the homogeneous zone
after the monolith: The inlet composition is taken from Table 7.3. A
significant amount of NO is formed by the oxidation of NH
3
before all
oxygen is consumed. The NO is subsequently reduced to N
2
.

57
0,0E+00
5,0E-05
1,0E-04
1,5E-04
2,0E-04
2,5E-04
3,0E-04
3,5E-04
4,0E-04
4,5E-04
0,00 0,20 0,40 0,60 0,80 1,00 1,20
Residence time (s)
N
O

M
o
l
e

f
r
a
c
t
i
o
n

(
-
)
0,6334
0,6335
0,6336
0,6337
0,6338
0,6339
N
2

M
o
l
e

f
r
a
c
t
i
o
n

(
-
)
N
2
NO
16 ppm
102 ppm
33 ppm
7.6 Rich primary λ

If the primary excess-air ratio is decreased to 0.8 the situation changes. The results from
the homogeneous zone after the monolith are shown in Fig. 7.2. The temperature rises
very rapidly in the main reaction zone, where all methane and NH
3
are consumed, and
then it has an almost constant value. First a significant amount of NO is formed from
the oxidation of NH
3
before all oxygen is consumed. The NO is subsequently reduced
to N
2
, and the reduction improves with longer residence times.


Table 7.3 Estimated composition (mole fractions) of the gas at the exit of the
monolith: primary λ=0.8, T
in
=753K, u
in
=1 m/s, length=1.5 cm, active
channels/passive channels=1/6.


Species
Active
channels
Passive
channels After mixing
N
2
0.638839 0.607006 0.612418
O
2
0.006020 0.096400 0.081035
H2 0.000004 0.053100 0.044074
CO 0.034000 0.080200 0.072346
CO
2
0.152000 0.075900 0.088837
CH
4
0.007600 0.026900 0.023619
H
2
O 0.161000 0.059900 0.077087
NH
3
0.000012 0.000537 0.000448
NO 0.000525 0.000000 0.000089
C
2
H
6
0.000000 0.000002 0.000002
H
2
O
2
0.000000 0.000024 0.000020
CH
2
O 0.000000 0.000031 0.000026


A reaction path analysis in the high temperature regime (>1900 K) reveals that there are
two major channels for consumption of NO in the absence of oxygen (see also Fig. 7.3):

I:
NO+H→N+OH (7.1)
and
N+NO→N
2
+O (7.2)

II:
NO+H+M→HNO+M, (7.3)
HNO+H→NH, (7.4)
NH+NO→N
2
O+H, (7.5)
58
and
N
2
O+M→N
2
+O . (7.6)


The reduction of NO is facilitated by the presence of the unburned fuel components CO
and H
2
, as they produce the H radical needed in the two channels (Glarborg, Kristensen,
Dam-Johansen, Alzueta, Millera & Bilbao, 2000).



CO+OH→CO
2
+H (7.7)
and
H
2
+OH→H
2
O+H . (7.8)



NNH


NH NH
2





N
2
O HNO


NO

N
2


N

+NO
+NO
+NO
+H
2
O, H
2

+NO
+NO
+H, +CO,
+M
+NO
+H +H
2
O, +H
2

+H
+H +NO
+NO
+NH
+H+M
+H+N
2

+OH,+H


Figure 7.3 Reaction flow analysis of the homogeneous plug-flow zone at fuel-rich
stoichiometries (T > 1900 K). The bold arrows indicate the main path for
the conversion of N in nitrogen compounds to molecular N
2
.


Bypass air is added downstream of the rich primary zone to burn out the remaining CO
and H
2
. The final reduction efficiency then reaches around 95% (see Figs. 7.1 and 7.4).


59
7.7 Discussion

The combustion chamber designs studied in Paper V have been simulated under
realistic conditions with respect to temperature and pressure for gas turbines. Practical
issues that must be addressed further for this design of the combustor include the use of
a wall material in the homogeneous zone that can stand the high resulting combustion
temperatures (> 1900 K), and avoiding formation of thermal NO when adding the
bypass air.
A primary λ of 0.8 gave a NO
x
reduction efficiency of 95%. However, even
higher reduction efficiencies may be achieved if an optimum primary λ can be found
that is rich enough to keep NO low and lean enough to avoid excessive HCN formation.

igure 7.4 Temperature, CO, H
2
, and NO profiles after the addition of air. Close to

he temperature in the homogeneous zone should be high enough for fast NO
mogeneous zone after the
monol
1370
1420
1470
1520
1570
0 0,001 0,002 0,003 0,004 0,005
Residence time (s)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
1,0E-07
1,0E-06
1,0E-05
1,0E-04
1,0E-03
1,0E-02
1,0E-01
M
o
l
e

f
r
a
c
t
i
o
n
s

(
-
)
NO
CO
H
2
T

F
13 ppm NO remains after combustion, which means an overall reduction
of 95% for a primary λ of 0.8.
T
reduction, but low enough to avoid thermal NO
x
production.
As can be seen in Fig. 7.2, the residence time in the ho
ith is fairly long. A long residence can be accomplished with a combustion
chamber of a tubular design (Perry’s, 1999). The work by Burch and Southward (2001)
indicates that catalytic materials such as Ir and Rh could selectively reduce the NO
through CO on the catalyst surface. Therefore, additional catalyst segments with these
catalysts located before the homogeneous zone would be worth testing. The idea would
60
be to already achieve a reduction of NO in the catalyst and thereby decrease the
residence time required in the subsequent homogeneous zone.

7.8 Conclusion
he conclusion that can be drawn from the paper is that it is possible to
signifi

T
cantly reduce the fuel-NO
x
formed due to the presence of ammonia in the
gasified biomass by staging the air rich-to-lean in a hybrid catalytic combustor. The
advantage with the hybrid-reactor concept is that only part of the fuel is catalytically-
converted in the monolith and thereby provides safe ignition of the low-heating value
gas. The use of passive channels in the monolith avoids homogeneous ignition in the
active channels. No reactants/reductants have to be added, as they are already part of
the incoming gas.























61
8 Conclusions

The work presented in this thesis is based on the assumption that all input data in
the form of mechanisms and kinetic and thermodynamic data have been well
established in previous experimental work. Given this to be true, mathematical
simulation should be a powerful method for increasing our understanding of the wall
effects in industrially-interesting combustion systems. The modeling work done in this
thesis has contributed to the understanding of flame quenching, a long-standing
practical combustion problem.
Detailed chemical kinetic models have been found to be very important in
explaining different kinetic and transport effects related to near-wall combustion.

• Catalytic flame quenching: the mechanism describing this phenomenon has been
outlined using hydrogen as the fuel in the model (Paper I). The same inhibition
(flame quenching) is also present when methane is used as fuel (Paper II),
however at a higher pressure and wall temperature. The complexity of the kinetic
mechanism used is important. In Paper IV, it was found that a catalytic wall in
addition to catalytic flame quenching also contributed to the formation of
unburned hydrocarbons, and this is more pronounced at higher pressures. To
account for this, a more detailed mechanism for the gas-phase methane oxidation
had to be used.

• Having a premixed flame as an inlet condition instead of uniform properties
(leading to autoignition) impacts on the chemical wall-effects. The wall
facilitating radical destruction produces no effects compared with a completely
inert wall, indicating that radical quenching by heterogeneous reactions is a
short-range effect. However changing the flame geometry does not affect
catalytic flame quenching, indicating that this is a long-range effect (Paper IV).

• For the first time, premixed propane/air flames have been modeled using
complex chemistry in a laminar boundary layer flow (Paper III). A distinction
can be made between strong stoichiometric flames and weaker flames (φ ≤ 0.6),
where the propagation in the boundary layer was significantly retarded.
Intermediate hydrocarbon emissions are more significant with stoichiometric
flames, while unburned fuel is more significant with leaner flames.

Another application of detailed kinetic modeling includes advances toward the
reduction of emissions of oxides of nitrogen (NO
x
) from combustors. In Paper V, it was
shown theoretically that fuel-NO
x
formation could be significantly reduced through a
new design of a hybrid catalytic gas-turbine combustor fueled with biogas.

62
The results presented in this thesis imply that laminar flow models accompanied
by complex chemistry models are a reasonable approximation to use to model near-wall
combustion phenomena.

8.1 Looking ahead

It would be very interesting to be able to confirm the results obtained in this
thesis using computational fluid dynamic (CFD) modeling, such as modeling turbulent
reactive boundary layers, which would address the relative importance of turbulence for
the wall effects. Software such as STAR-CD coupled to the CHEMKIN Collection
would be suitable for this purpose.
Another flame geometry that would be very interesting to study is stratified
charge combustion. The problem set-up used in this thesis with a homogeneous charge
would have to be changed somewhat to model the combustion of a stratified charge.
Radiation from the flame to the wall has not been included in the mathematical
model used in this thesis. However, radiation may influence the near-wall combustion
and could be a topic for further research.
Finally, the fuel-NO
x
reduction in the hybrid catalytic combustion of biogas
results obtained in Paper V could be further elaborated by both modeling and
experimental work.























63
Acknowledgments

Firstly I want to thank my supervisor at KTH, Professor Pehr Björnbom for his
invaluable supervision.

I am also very grateful to Associate Professor Lennart Edsberg from the
Department of Numerical Analysis and Computing Science, KTH, for the important
role he played in performing the calculations and post-processing the results. Moreover,
the inter-departmental diploma work was most fruitful.

I wish to thank Dr Lars-Erik Eriksson, Project Leader of the CeCoST Turbulent
Combustion project, for fruitful discussions leading to new insights into the near-wall
combustion problem that I could use in my research.

Thanks also to Professor Peter Glarborg from CHEC (the Combustion and
Harmful Emission Control research center), at the Technical University of Denmark,
for sharing his profound knowledge in the field of Chemical Kinetics, for his generous
co-operation in the Fuel-NO
x
paper, and for a really enjoyable time in Denmark in the
spring of 2002.

I wish to also thank Professor Marcus Aldén at the Center of Combustion
Science and Technology (CeCoST) for granting me the scholarship to visit DTU.

I wish to also thank the members of the reference group in the High-temperature
Catalytic-combustion Project (P910).

I wish to thank present and former colleagues at Chemical Reaction Engineering
and Chemical Technology at KTH.

Thanks also to everyone else in my department for assisting with all the practical
matters during the completion phase of this work, especially Britt-Mari Rydberg and
Monica Söderlund.

The financial support received from the Swedish Foundation for Strategic
Research, the Center for Combustion Science and Technology (CeCoST), the Center
for Environmental Science at KTH, and the Swedish Energy Agency is gratefully
acknowledged.

64
Last, but by no means least, I would like to thank my family, both in Sweden and
America, for their support and hope that they too enjoyed my research journey
culminating in the completion of this thesis.





































65
References

Aghalayam, P., P-A. Bui, and D.G. Vlachos, “The Role of Radical Wall Quenching in
Flame Stability and Wall Heat Flux: Hydrogen-Air Mixtures,” Combust. Theory and
Modeling, 2, 515 (1998).

Aghalayam P, Y.K. Park, and D.G Vlachos, “Construction and Optimization of
Complex Surface Reaction Mechanisms,” AIChE J., 46(10), 2017 (2000a).

Aghalayam, P., Y.K. Park, and D.G. Vlachos, “A Detailed Surface Reaction
Mechanism for CO Oxidation on Pt,” Proc. Combust. Inst., 28, 1331 (2000b).

Alzueta, M.U, H. Røjel, P.G. Kristensen, P. Glarborg, and K. Dam-Johansen,
”Laboratory Study of the CO/NH
3
/NO/O
2
System: Implications for Hybrid
Reburn/SNCR Strategies,” Energy & Fuels, 11, 716 (1997).

Arrhenius, S. ӆber die Reaktiongeschwindigkeit bei der Inversion von Rohrzucker
durch Säuren,” Z Phys Chem., 4, 226 (1889).

Bird, R.B., W.E. Stewart, and E.N. Lightfoot, Transport Phenomena, 2
nd
Ed., John
Wiley & Sons, New York (2002).

Blint, R.J., and J.H. Bechtel, “Flame-Wall Interface: Theory and Experiment,”
Combust. Sci. Tech., 27, 87 (1982).

Bui, P-A., D.G. Vlachos, and P.R Westmoreland, “Homogeneous Ignition of
Hydrogen-Air Mixtures over Platinum,” Proc. Combust. Inst., 26, 1763 (1996).

Burch, R., and B.W.L. Southward, “The Nature of the Active Metal Surface of
Catalysts for the Clean Combustion of Biogas Containing Ammonia,” J Catal., 198,
286 (2001).

Chou, C-P., J-Y. Chen, and G.H. Evans, “Numerical Studies of Methane Catalytic
Combustion Inside a Honeycomb Reactor Using Multistep Surface Reactions,” Comb.
Sci. Tech., 150, 27 (2000).

Christensen, M., B. Johansson, and P. Einewall “Homogenous Charge Compression
Ignition (HCCI) using Isooctane, Ethanol and Natural Gas,” Society of Automotive
Engineers, paper SAE 97-2874 (1997).

66
Christensen, M., A. Hultqvist, and B. Johansson, “Demonstrating the Multi Fuel
Capability of a Homogeneous Charge Compression Ignition Engine with Variable
Compression Ratio,” Society of Automotive Engineers, paper SAE 1999-01-3679
(1999).

Coltrin, M.E., R.J. Kee, and J.A. Miller, “A Mathematical Model of the Coupled Fluid
Mechanics and Chemical Kinetics in a Chemical Vapor Deposition Reactor,” J.
Electrochem. Soc., 131, 425 (1984).

Coltrin, M.E., R.J. Kee, and J.A. Miller, “A Mathematical Model of Silicon Chemical
Vapor Deposition – Further Refinements and the Effect of Thermal Diffusion,” J.
Electrochem. Soc., 133, 1206 (1986).

Coltrin, M.E., R.J. Kee, and F.M. Rupley, “Surface Chemkin: A General Formalism
and Software for Analyzing Heterogeneous Chemical Kinetics at a Gas-Surface
Interface,” Int. J. Chem. Kin., 23, 1111 (1991)

Coltrin, M.E., H.K. Moffat, R.J. Kee, and F.M. Rupley, ”CRESLAF (Version 4.0): A
Fortran Program for Modeling Laminar, Chemically Reacting, Boundary-Layer Flow
in Cylindrical or Planar Channels”, Sandia National Laboratories Report No.
SAND93-0478 (1993).

Coltrin, M. E., R. J. Kee, F. M. Rupley, and E. Meeks, ”SURFACE CHEMKIN-III: A
Software Package for the Analysis of Heterogeneous Chemical Kinetics at a Solid
Surface-Gas Phase Interface”, Sandia National Laboratories Report No. SAND96-
8217 (1996).

Correa, S. M., “CO Emissions in Lean Premixed Combustion,” J. Prop. Power, 8(6),
1144 (1992).

Dalla Betta, R.A., J.C. Schlatter, D.K. Yee, D.G. Loffler, T. Shoji, “Catalytic
Combustion Technology to Achieve Ultra Low NO
x
Emissions: Catalyst Design and
Performance Characteristics,” Catal Today, 26, 329 (1995).

Daniel, W. A., “Flame Quenching at the Walls of an Internal Combustion Engine,”
Proc. Combust. Inst., 6, 886 (1956).

Deutschmann, O., R. Schmidt, F. Behrendt, and J. Warnatz, ”Numerical Modeling of
Catalytic Ignition,” Proc. Combust. Inst., 26, 1747 (1996).

67
Dupont, V., S.H. Zhang, and A. Williams, “Experiments and Simulations of Methane
Oxidation on a Platinum Surface,” Chem. Eng. Sci., 56, 2659 (2001).

Egolfopoulos, F.N., H. Zhang, and Z. Zhang, “Wall effects on the Propagation and
Extinction of Steady, Strained, Laminar Premixed Flames,” Combust. Flame, 109,
237 (1997)

EIA, “International Energy Outlook 2000,” Energy Information Administration, U.S.
Department of Energy, Washington (2000).

Ezekoye, O., R. Greif, and D. Lee, “Increased Surface Temperature Effects on Wall
Heat Transfer During Unsteady Flame Quenching,” Proc. Combust. Inst., 24, 1465
(1992).

Ezekoye, O., and R. Greif, “A Comparison of One and Two Dimensional Flame
Quenching: Heat Transfer Results,” Trans. ASME: Heat Transfer in Fire and
Combustion Systems, 250, p. 11 (1993).

Ferguson, C.R., and J.C. Keck, “Laminar Flame Quenching and its Application to
Spark Ignition Engines,” Combust. Flame, 28, 197 (1977).

Forsth, M., F. Gudmundson F, J.L. Persson, and A. Rosèn, “The Influence of a
Catalytic Surface on the Gas-Phase Combustion of H
2
+O
2
,” Combust. Flame, 119,
144 (1999).

Forzatti, P. and Groppi, G., “Catalytic Combustion for the Production of Energy,”
Catal. Today, 54, 165 (1999).

Frenklach, M., H. Wang, M. Goldenberg, G.P. Smith, D.M. Golden, C.T. Bowman,
R.K. Hanson, W.C. Gardiner, V. Lissianski, GRI-Mech – An Optimized Detailed
Chemical Reaction Mechanism for Methane Combustion, Gas Research Institute
Report No. GRI-95/0058 (1995).

Giovangigli, V., and M.D. Smooke, “Extinction of Strained Premixed Flames with
Complex Chemistry,” Combust. Sci. Tech., 53, 23 (1987).

Glarborg, P., M.U. Alzueta, K. Dam-Johansen, and J.A. Miller, ”Kinetic Modeling of
Hydrocarbon/Nitric Oxide Interactions in a Flow Reactor,” Combust. Flame, 115, 1
(1998).

68
Glarborg, P., P.G. Kristensen, K. Dam-Johansen, M.U. Alzueta, A. Millera, and R.
Bilbao, ”Nitric Oxide Reduction by Non-Hydrocarbon Fuels. Implications for
Reburning with Gasification Gases,” Energy & Fuels, 14, 828 (2000).

Glassman, I., Combustion, 3
rd
Edition, Academic Press, San Diego (1996).

Grcar, J.F., “The Twopnt Program for Boundary Value Problems,” Sandia National
Laboratories Report No. SAND91-8230 (1991).

Groppi, G., A. Belloni, E. Tronconi, and P. Forzatti, “Analysis of Multidimensional
Models of Monolith Catalysts for Hybrid Combustors,” AIChE J., 41, 2250 (1995).

Hasse, C., M. Bolling, N. Peters, and H.A Dwyer, ”Quenching of Laminar Iso-Octane
Flames at Cold Walls,” Combust. Flame, 122, 117 (2000).

Heck, D.M., and R.J. Farrauto, Catalytic Air Pollution Control – Commercial
Technology, Van Nostrand Reinhold, New York, p. 192 (1995).

Hellsing, B., B. Kasemo, S. Ljungstrom, A. Rosén, and T. Wahnstrom, ”Kinetic Model
and Experimental Results for H
2
O and OH Production Rates on Pt,” Surf. Sci.,
189/190, 851 (1987).

Heywood, J.B., Internal Combustion Engine Fundamentals, McGraw-Hill (1988).

Hocks, W., N. Peters, and G. Adomeit, ”Flame Quenching in Front of a Cold Wall
under Two-Step Kinetics,” Combust. Flame, 41, 157 (1981).

Hultqvist, A., M. Christensen, and B. Johansson, “The Application of Ceramic and
Catalytic Coatings to Reduce the Unburned Hydrocarbon Emissions from a
Homogeneous Charge Compression Ignition Engine,” Society of Automotive
Engineers, Paper SAE 2000-01-1833 (2000).

Kee, R.J., J. A. Miller, and T. H. Jefferson, "Chemkin: A General-Purpose, Problem-
Independent, Transportable, Fortran Chemical Kinetics Code Package" Sandia
National Laboratories Report No. SAND80-8003 (1980).

Kee, R.J., J.F. Grcar, M.D. Smooke, and J.A Miller, “A Fortran Program for Modeling
Steady Laminar One-Dimensional Premixed Flames,” Sandia National Laboratories
Report No. SAND85-8240 (1985).
69
Kee, R.J, G. Dixon-Lewis, J.Warnatz, M.E. Coltrin, J.A. Miller, and H.K. Moffat, “A
Fortran Computer Code Package for the Evaluation of Gas-Phase Multicomponent
Transport Properties,” Sandia National Laboratories Report No. SAND86-8246
(1986).

Kee, R.J., F.M. Rupley, and J.A. Miller, “The CHEMKIN Thermodynamic Data Base,”
Sandia National Laboratories Report No. SAND87-8215B (1990).

Kee, R.J., F.M. Rupley, E. Meeks, and J.A. Miller, ”CHEMKIN-III: A Fortran
Chemical Kinetics Package for the Analysis of Gas-Phase Chemical and Plasma
Kinetics”, Sandia National Laboratories Report No. SAND96-8216 (1996).

Kee, R.J., F.M Rupley, J.A. Miller, M.E. Coltrin, J.F.Grcar, E. Meeks, H.K. Moffat,
A.E. Lutz, G. Dixon-Lewis, M.D. Smooke, J. Warnatz, G.H. Evans, R.S. Larson, R.E.
Mitchell, L.R. Petzold, W.C. Reynolds, M. Caracotsios, W.E. Stewart, P. Glarborg, C.
Wang, and O. Adigun, CHEMKIN Collection, Release 3.6, Reaction Design, Inc., San
Diego (2000).

Kiehne, T.M, R.D. Matthews, and D.E. Wilson, “The Significance of Intermediate
Hydrocarbons During Wall Quench of Propane Flames,” Proc. Combust. Inst., 21,
481 (1986).

Kurkov, A.P., and W. Mirsky, “An Analysis of the Mechanism of Flame Extinction by
a Cold Wall,” Proc. Combust. Inst., 12, 615 (1969).

Lindemann, F.A., ”The Radiation Theory of Chemical Action,” Trans. Farad. Soc., 17,
598 (1922).

Ljungstrom, S., B. Kasemo, A. Rosén, T. Wahnstrom, and E. Fridell, “An Experimental
Study of the Kinetics of OH and H
2
O Formation on Pt in H
2
+ O
2
Reaction,” Surf.
Sci., 216, 63 (1989).

Lu, J.H., O. Exekoye, R. Greif, and F. Sawyer, “Unsteady Heat Transfer during Side
Wall Quenching of a Laminar Flame,” Proc. Combust. Inst., 23, 441 (1990).

Lutz, A.E., R. J. Kee, and J. A. Miller, "SENKIN: A Fortran Program for Predicting
Homogeneous Gas Phase Chemical Kinetics with Sensitivity Analysis," Sandia
National Laboratories Report 87-8248 (1988).
70
Mantzaras, J., C. Appel, and P. Benz, “Catalytic Combustion of Methane/Air Mixtures
over Platinum: Homogeneous Ignition Distances in Channel Flow Configurations,”
Proc. Combust. Inst., 28, 1349 (2000).

Mhadeshwar, A.B., P. Aghalayam, V. Papavassiliou, and D.G. Vlachos, ”Surface
Reaction Mechanism Development for Platinum Catalyzed Oxidation of Methane,”
Proc. Combust. Inst., 29, to appear (2002).

Moore, F.K., Theory of Laminar Flows, High Speed Aerodynamics and Jet Propulsion,
Vol IV, Princeton University Press, Princeton, NJ (1964).

Motz, H. and H. Wise, “Diffusion and Heterogeneous Reaction. III. Atom
Recombination at a Catalytic Boundary,” J. Chem. Phys., 32, 1893 (1960).

Perry's Chemical Engineers' Handbook, Gas Turbines, McGraw-Hill, New York,
Section 29, pp. 29-40 (1999).

Petzold, L.R., “A Description of DASSL,” Sandia National Laboratories Report No.
SAND82-8637 (1982).

Popp, P., M.D. Smooke, and M. Baum, “Heterogeneous/Homogeneous Reaction and
Transport Coupling During Flame-Wall Interaction,” Proc. Combust. Inst., 26, 2693
(1996).

Popp, P., and M. Baum, “Analysis of Wall Heat Fluxes, Reaction Mechanisms and
Unburnt Hydrocarbons during the Head-On Quenching of a Laminar Methane
Flame,” Combust. Flame, 108, 327 (1997).

Prandtl, L., Gesammelte Abhandlungen, 2, p. 575, Springer-Verlag, Berlin (1961).

Raja, L.L., R.J. Kee, O. Deutschmann, J. Warnatz, and L.D. Schmidt, ”A Critical
Evaluation of Navier-Stokes, Boundary-Layer, and Plug-Flow Models of the Flow
and Chemistry in a Catalytic-Combustion Monolith,” Catal. Today, 59, 47 (2000).

Rinnemo, M., O. Deutschmann, F. Behrendt, and B. Kasemo, ”Experimental and
Numerical Investigation of the Catalytic Ignition of Hydrogen and Oxygen on
Platinum,” Combust. Flame, 111, 312 (1997).



71
Qin, Z., V. Lissianski, H. Yang, W.C. Gardiner, Jr., S.G. Davis, and H. Wang,
“Combustion Chemistry of Propane: A Case Study of Detailed Reaction Mechanism
Optimization,” Proc. Combust. Inst., 28, 1663 (2000).

Sloane, T.M., and A.Y. Schoene, “Computational Studies of End-Wall Flame
Quenching at Low Pressure: The Effects of Heterogeneous Radical Recombination
and Crevices,” Combust. Flame, 49, 109 (1983).

Vlachos, D.G., L.D. Schmidt, and R. Aris, “Ignition and Extinction of Flames Near
Surfaces: Combustion of H
2
in Air,” Combust. Flame, 95, 313 (1993).

Vlachos, D.G., L.D. Schmidt, and R. Aris, “Ignition and Extinction of Flames Near
Surfaces: Combustion of CH
4
in Air,” AIChE J., 40(6), 1005 (1994a).

Vlachos, D.G., L.D. Schmidt, and R. Aris, “Products in Methane Combustion Near
Surfaces,” AIChE J., 40(6), 1018 (1994b).

Vlachos, D.G., “Homogeneous-Heterogeneous Oxidation Reactions over Platinum and
Inert Surfaces,” Chem. Eng. Sci., 51, 2429 (1996).

Von Kàrmàn, T., and G. Millàn, “Thermal Theory of a Laminar Flame Front Near a
Cold Wall,” Proc. Combust. Inst., 4, 173 (1953).

Vosen, S. R., R. Greif, and C. K. Westbrook, “Unsteady Heat Transfer During Laminar
Flame Quenching,” Proc. Combust. Inst., 20, 75 (1984).

Warnatz, J., “Resolution of Gas-Phase and Surface Combustion Chemistry Into
Elementary Reactions,” Invited Lecture, Proc. Combust. Inst., 24, 553 (1992).

Warnatz, J., M. D. Allendorf, R. J. Kee, and M. E. Coltrin, “A Model of Elementary
Chemistry and Fluid Mechanics in the Combustion of Hydrogen on Platinum
Surfaces,” Combust. Flame, 96, 393 (1994).

Warnatz, J., U. Maas, and R.W. Dibble, Combustion-Physical and Chemical
Fundamentals, Modeling and Simulation, Experiments, Pollutant Formation, Springer
Verlag, Heidelberg, Germany (1996).

Westbrook, C. K., A. A. Adamczyk, G. A. Lavoie, “A Numerical Study of Laminar
Flame Wall Quenching,” Combust. Flame, 40, 81 (1981).

72
Wichman, I.S., and G. Bruneaux, “Head-On Quenching of a Premixed Flame by a Cold
Wall,” Combust. Flame, 103, 296 (1995).

Williams, W. R., C. M. Marks, and L. D. Schmidt, “Steps in the Reaction H
2
+ O
2
=
H
2
O on Pt – OH Desorption at High Temperatures,” J. Phys. Chem., 96, 5922 (1992).


73

Abstract Increased knowledge into the physics and chemistry controlling emissions from flame-surface interactions should help in the design of combustion engines featuring improved fuel economy and reduced emissions. The overall aim of this work has been to obtain a fundamental understanding of wall-related, premixed combustion using numerical modeling with detailed chemical kinetics. This work has utilized CHEMKIN, one of the leading software packages for modeling combustion kinetics. The simple fuels hydrogen and methane as well as the more complex fuels propane and gasified biomass have been used in the model. The main emphasis has been on lean combustion, and the principal flow field studied is a laminar boundary layer flow in two-dimensional channels. The assumption has been made that the wall effects may at least in principle be the same for laminar and turbulent flames. Different flame geometries have been investigated, including for example autoignition flames (Papers I and II) and premixed flame fronts propagating toward a wall (Papers III and IV). Analysis of the results has shown that the wall effects arising due to the surface chemistry are strongly affected by changes in flame geometry. When a wall material promoting catalytic combustion (Pt) is used, the homogeneous reactions in the boundary layer are inhibited (Papers I, II and IV). This is explained by a process whereby water produced by catalytic combustion increases the rate of the third-body recombination reaction: H+O2+M ⇔ HO2+M. In addition, the water produced at higher pressures increases the rate of the 2CH3(+M) ⇔ C2H6(+M) reaction, giving rise to increased unburned hydrocarbon emissions (Paper IV). The thermal coupling between the flame and the wall (the heat transfer and development of the boundary layers) is significant in lean combustion. This leads to a slower oxidation rate of the fuel than of the intermediate hydrocarbons (Paper III). Finally in Paper V, a well-known problem in the combustion of gasified biomass has been addressed, being the formation of fuel-NOx due to the presence of NH3 in the biogas. A hybrid catalytic gas-turbine combustor has been designed, which can significantly reduce fuel-NOx formation. Keywords: wall effects, premixed flames, flame quenching, numerical modeling, CHEMKIN, boundary layer approximation, gasified biomass, fuel-NOx, hybrid catalytic combustor.

The cover illustrates a chemically reacting boundary layer flow

Den termiska kopplingen mellan flamman och väggen. Olika typer av flamgeometrier behandlas i form av ’auto-ignition’ flammor (artikel I och II) och förblandade flammor som propagerar mot en vägg (artikel III och IV). som är en av de ledande komersiella programvarorna för modellering av kemiskt reagerande flöden. Tyngdpunkten i beräkningana ligger på mager förbränning och den huvudsakliga flödesgeometrin som studeras är en tvådimensionell laminär gränskiktsströmning. Nyckelord: väggeffekter. Vid högre tryck ökar det katalytiskt bildade vattnet också hastigetheten på reaktionen 2CH3(+M) ⇔ C2H6(+M). Slutligen i artikel V behandlas ett välkänt problem vid förbränning av förgasad biomassa: bränsle-NOx bildningen p g a den ammoniak som finns i bränngasen. Här görs antagandet att den väggnära förbränningen sker med försumbar inverkan av turbulent strömning. bränsleNOx. . II och IV). retarderas den homogena förbränningen i gränsskiktet (artikel I. Detta leder till en långsammare oxidation av bränslet jämfört med intermediära kolväten (artikel III). Det huvudsakliga syftet med detta arbete har varit att få en grundläggande förståelse för väggnära förbränning med hjälp av numerisk modellering med komplex kemi.Sammanfattning En ökad förståelse av de fysiska och kemiska processer som kontrollerar emissioner som uppstår vid väggnära förbränning kan bidra i utformningen av förbränningsmotorer med bättre bränsleekonomi och minskade utsläpp. förblandade flammor. katalytisk hybridbrännkammare. gränsskiktströmning. numerisk modellering. vilket ger upphov till ökade utsläpp av kolväten (artikel IV). CHEMKIN. d v s värmeöverföring och utvecklingen av gränskikten är betydande vid mager förbränning. Arbetsverktyg har varit CHEMKIN. Då ett väggmaterial som ger upphov till katalytisk förbränning (Pt) används. Modellbränslen har varit relativt enkla gaser i form av vätgas och metan och mera komplexa bränslen i form av propan och förgasad biomassa. flamutsläckning. Detta förklaras av att det vatten som produceras genom den katalytiska förbränningen ökar hastigheten på tredjekroppsreaktionen H+O2+M ⇔ HO2+M. En katalytisk hybridbrännkammere för tillämpning i gasturbiner designas där en betydande minskning av bränsle-NOx uppnås. biogas. När resultaten analyseras framgår det att de väggeffekter som ytkemin ger upphov till starkt påverkas av ändring i flamgeometri.

.

”A Design Concept to Reduce Fuel NOx in Catalytic Combustion of Gasified Biomass. 29.. ”Kinetic and Transport Effects of Pressurized Methane Flames in a Boundary Layer. Glarborg. L. and L-E. I..” submitted to AIChE J.The work presented in this thesis is based on the following papers. Andrae. Inst. Flame. J. “Wall Effects of Laminar Hydrogen Flames over Platinum and Inert Surfaces. J. P.” AIChE J. P. Andrae. J.” Proc. referred to by their Roman numerals. Björnbom. 1454 (2000). P.. and P. 128. L. and L-E. Eriksson.. Björnbom. (2002). Björnbom. 165 (2002). Björnbom. Edsberg.. Andrae. J. Flame (2002). Combust. II. Edsberg. ”Numerical Studies of Wall Effects with Laminar Methane Flames. Edsberg. Andrae. ”A Numerical Study of Sidewall Quenching with Propane/Air Flames.” submitted to Combust.. and P. IV. . and L. J. P. 46. Björnbom..” Combust. to appear (2002). Andrae. Eriksson. V. The papers are appended at the end of the thesis. III.

J. J. 5. P. Andrae. Björnbom.” Work in Progress Poster. and P. Edsberg. TwentyEighth International Symposium on Combustion. April 18-20. Dallas. Gothenburg. Andrae. 6. .. Andrae. Björnbom. and G. Kadinov. ”Modeling Wall Effects of Laminar Methane Flames in a Boundary Layer.” Proceedings of the First Biennial Meeting of the Scandinavian-Nordic Section of the Combustion Institute. Andrae. Bulgaria. Bonev. J.” Poster Presentation. 5 (1999).. 199 (2001). Edsberg. ”Numerical Studies of Wall Effects of Laminar Methane Flames. and D.Below are listed works presented at conferences and symposia not included in this thesis. Björnbom. p.. Edsberg. and P. P. 4. Andrae. Texas.” Invited Plenar Lecture. P. AIChE Annual Meeting. P. J. Los Angeles.. Nov. ”Reduction of Fuel NOx in Catalytic Combustion of Gasified Biomass. J.” Work in Progress Poster. USA. July 30Aug. Edinburgh. L. California. Sept. AIChE Annual Meeting. Eds. 31-Nov. ”Modeling the Kinetics of Catalytic Monolith Reactors. L. Oct. Ch. and L. Papadias. Edsberg. J. and L. Björnbom.” Oral Presentation. Björnbom. USA. ”Numerical Investigation of Wall Effects for Laminar Hydrogen Flames over Platinum and Inert Surfaces. Twenty-Ninth International Symposium on Combustion. Sweden. and L. July 21-26 (2002). 12-17 (2000). Japan. 3.. ”Numerical Studies of Laminar Methane Flames in a Boundary Layer. Sapporo.. Björnbom. Andrae. 2. 23-27. Scotland. Glarborg. 4 (2000). 3 (2000). Petrov. Proceedings of the Ninth International Symposium on Heterogeneous Catalysis. Varna. P. 1. p.

” .To my family “There is no substitute for hard work.Thomas Alva Edison (1847-1931) .

.

4 Conclusions 6.1 Inlet and boundary conditions 5.1 Quenching of premixed propane/air flames near an inert cold wall (Paper III) 6.1 Hydrogen as fuel in the model (Paper I) 5.2 The CRESLAF program 4.1 Mathematical description of a chemically-reacting boundary layer flow 3.2.1 Interpretation of the elementary reaction mechanism 2.2 Results and discussion 6 Premixed Flame Fronts (Papers III and IV) 6.2 Effect of flame-geometry 1 1 3 6 6 10 11 13 17 18 19 20 24 26 26 28 29 31 31 32 33 37 38 40 43 43 44 46 47 48 48 49 50 .1 Inlet and boundary conditions 5.2 Scope of this work 2 Fundamentals of Chemical Kinetics 2.2.1 Near-wall turbulence 3.1.2.1 Inlet and boundary conditions 6.1 CHEMKIN architecture 4.1 Numerical solutions using the differential/algebraic approach 5 Autoignition Flames (Papers I and II) 5.2 Methane as fuel in the model (Paper II) 5.1.1.3 Surface chemistry 3 Modeling of Near-wall Combustion 3.1 Gas-phase chemistry: oxidation of hydrogen in air 2.2.2.2 Results and discussion 5.2 Boundary conditions 4 CHEMKIN Software 4.1 Lean combustion 1.2 Laminar models 3.3 Intermediate hydrocarbons 6.1.2 Pressurized methane flames using different wall materials (Paper IV) 6.1.1.1 Inlet and boundary conditions 6.Table of Contents Nomenclature 1 Introduction 1.2.1.2 Pressure-dependent reactions 2.2 Fuel oxidation 6.2.

6.5 Discussion 7 Reduction of Fuel-NOx in Catalytic Combustion of Gasified Biomass (Paper V) 7.4 The model 7.8 Conclusion 8 Conclusions 8.1 Gasified biomass 7.5 Lean primary λ 7.7 Discussion 7.3 Catalytic combustion 7.6 Rich primary λ 7.3 Effect of gas-phase chemistry 6.2 Primary methods for reducing NOx 7.2.4 Effect of fuel/air ratio 6.2.1 Looking ahead Acknowledgments References 51 52 52 53 53 54 54 55 57 58 60 61 62 63 64 66 .2.

cal/mole. Pressure of one standard atmosphere. Total number of species. Specific enthalpy. Specific heat capacity of species k. Standard state molar entropy of the kth species. Multicomponent diffusion coefficient. cm2/s. unit depends on reaction. erg/(g · K). Equilibrium constant in concentration units for the ith reaction. Reverse rate constant of the ith reaction. unit depends on reaction. cal/(mole ·K). cm2/s. Mixture specific heat capacity. unit depends on reaction.Nomenclature (cgs units) Ai cp Pre-exponential factor in the rate constant of the ith reaction. mole/cm3. Total number of surface species. Mixture diffusion coefficient. unit depends on reaction. c pk Dkj Dk . Number of first surface species. Thermal diffusion coefficient. cm/s2. unit depends on reaction. dyne/cm2. Forward rate constant of the ith reaction. Mass flux in the y direction. Pressure. Concentration of third body. erg/(mole · K). Universal gas constant. Acceleration of gravity. g/(cm2 · s). Equilibrium constant in pressure units for the ith reaction.m DkT Ei g H ko hk I jk y k fi k ri K ci K pi K Kg Ks K sf K sl [M ] p Patm R Rc . Total number of reactions. erg/mole. Number of last surface species. Activation energy in the rate constant of the ith reaction. erg/(g · K). Universal gas constant in the same units as activation energy. g/(cm · s). Total number of gas-phase species. erg/g. dyne/cm2.

Coverage parameter. g/cm3. Coverage parameter. cal/(mole · K). Molecular mass of species k . α ki βi γi λ σk ε ki ηki µ µ ki ρ Γo Γ Enhanced third-body efficiency of the kth species in the ith reaction. erg/(mole·K). g/mole. K. K. K. mole/cm2. mole/cm3. Surface site density. cm/s. erg/(cm·sec·K). Fluid velocity in the y direction. Temperature. Diffusion velocity of species k in the axial direction. Cross-stream coordinate. cm/s. Gas-phase species mass fractions. mole/(cm2 ·s). Fluid velocity in the x direction. Number of sites occupied by species k. Site fraction of species k. Coverage parameter. Mean molecular weight of the mixture. Distance along principal flow direction. Temperature exponent in the rate constant of the ith reaction. cm. . Mass density. Temperature at the wall. g/(cm·s). mole/cm2. Diffusion velocity of species k normal to wall. g/mole. Molar concentration species k. Mole fraction of species k. Temperature of the unburned gas. cm. Viscosity. Standard-state surface site density. cm/s.& sk S ko T Tu Tw u v Vk x Vk y Wk W x Xk y Yk Xk [X k ] Zk Greek letters Chemical production rate of species by surface reaction. Gas-phase species mole fraction. cm/s. Thermal conductivity. Standard state molar entropy of the kth species. Sticking coefficient of the ith surface reaction.

' υ ki '' υ ki Stoichiometric coefficient of the kth reactant species in the ith reaction. mole/(cm3 · s). Chemical production rate of species k by gas-phase reaction. & ωk ψ 1 erg = 10-7 J 1 dyne/cm2 = 10-1 Pa . Stream function. g/(cm · s). Stoichiometric coefficient of the kth product species in the ith reaction.

.

Schmidt & Aris. but also produces pollutants such as oxides of nitrogen (NOx). wind and nuclear energy still account for less than 20% of total energy consumption. 1. power generation. 1990. However. 1986. for instance those of thermal quenching (Vlachos. which increases the significance of the effects of the combustor walls. Schmidt & Aris. 1969.1 Lean combustion To reduce the fuel consumption in cars and thereby the emission of CO2. Ezekoye & Greif. while at the same time world energy production is projected to increase by 60% over the next 20 years (EIA. 1953. Greif & Westbrook. Lu. Other sources of energy such as solar. the use of excess air lowers the flame temperature. 1982. 1984. the flame has a significant effect on the flow in the vicinity of the wall as well as on the heat flux to the wall (Vosen. 1981. Wichman & Bruneaux. 1956. Matthews & Wilson. Peters & Dwyer. 1995). The use of renewable fuels (for example gasified biomass) will eliminate the net emission of CO2 into the atmosphere. Popp & Baum. Ezekoye. Kiehne. 2000). 1994a). The combustion of fossil fuels is expected to remain a key technology in the foreseeable future. soot. Hasse. Combustion is strongly influenced by the presence of walls. thereby reducing their negative impact on the environment. Hocks. Blint & Bechtel. Bolling. 1977. 1983. Ferguson & Keck. Sloane & Schoene. Improvements in efficiency and decreases in pollutant formation in combustion systems are only possible through improving our understanding of the fundamental processes taking place during combustion. Schmidt & Aris. Vlachos. Ezekoye. Greif & Lee. The interaction between combustible gases and chamber walls is one of the classic problems in combustion science (see von Kàrmàn & Millàn. Improving the efficiency of the combustion process and thereby increasing fuel economy will reduce these emissions. Vlachos. 1997). which can for example cause flame fronts to quench. Increasingly stringent regulations are forcing manufacturers of automobiles and power plants to reduce polluting emissions. 1992. 1994b. 2000). which can be converted into power. The effects of cool walls on unburned hydrocarbon emissions in combustion engines has been studied for quite some time (see Daniel. Moreover. but have other negative environmental impacts that must be addressed. unavoidable emissions of CO2 are believed to contribute to global warming. such as the formation of fuel-NOx. 1 . Fossil fuel combustion is used for transportation. Peters & Adomeit. and unburned hydrocarbons (UHC). Kurkov & Mirsky. 1981. Greif & Sawyer. Westbrook Adamczyk & Lavoie. heating and process engineering. In addition.1 Introduction Combustion of fossil fuels is the most important method of generating energy in the world today. 1993. It is widely known that combustion not only generates heat. there is a growing trend toward the increased use of lean combustion. 1993.

This charge may be either transported from the viscous sublayer to the main flow of the flame gases and be oxidized. 2 . Lean-burn engines therefore have difficulties matching the output levels of three-way-catalyst engines. or discharged into the exhaust gases as residual hydrocarbon emissions. for example the burnout of CO in a cooled boundary layer flow (Correa.In a modern direct-injection spark-ignition (DISI) engine. The challenge for the automotive engineer is therefore how to modify the combustion process where possible to find a catalyst that can selectively reduce NOx to N2 in the presence of some reduction matter (Heck & Farrauto. 1999). Instead there is a spontaneous autoignition due to compression. the oxygen consumes the reduction matter—normally unburned hydrocarbons from the main flow—and there is not enough to reduce all the NOx. which is too lean for spark ignition. 1997. especially with regard to NOx. Hultqvist & Johansson. This means that the charge is diluted in other parts of the cylinder for an overall lean combustion. the wall temperature is several hundred degrees higher and the process is stationary. Johansson & Einewall. 1995). The charge is very lean (2 < λ < 7 where λ = 1/φ = [Xair/Xfuel/[Xair/Xfuel]stoichiometric is the excess air ratio). In contrast to the spark-ignition engine. The wall effects in such combustors can therefore be expected to differ from those in a leanburn spark-ignition engine (the effects of surface chemistry or adsorption are for example not completely understood). the charge is stratified near the spark plug. the CO and hydrocarbon emissions can be significant (Christensen. which leads to extremely low levels of NOx and particulate emissions. An additional problem is that the treatment of the exhaust gas by catalytic conversion does not work well because the molecules in the exhaust gas do not "add up" as they do in the three-way-catalyst concept in traditional engines working with stoichiometric fuel/air mixtures. On the other hand. The lean and homogeneous charge keeps the combustion temperature low. The effect of the combustion chamber wall is also an important issue in leanburn gas-turbines used for energy production. a hybrid between the spark-ignition engine and the diesel engine. Due to the air-excess. Christensen. such that the flame initiated at the spark propagates through a partially premixed heterogeneous mixture. 1992). The result is that some of the charge of fuel and oxidizer in each combustion cycle is left unburned at the walls. propagation is quenched due to radical depletion—radicals are required to sustain the flame—in the cold near-wall zone by recombination reactions and by heat losses. The radicals can also diffuse to the wall and be heterogeneously quenched. Another engine concept featuring lean combustion is homogenous-chargecompression-ignition. In the direct vicinity of the cold wall flame.

diffusion and chemical reactions both in the gas-phase and on the surface (see Fig. This is due to the complex nature of the wall effects in combustion. and the more complex fuels propane and gasified biomass. Transport of momentum. This increased knowledge should help in the design of combustion engines featuring improved fuel economy and reduced emissions. The model used the simple fuels hydrogen and methane. In addition.1. Emphasis has been on lean combustion and the principal flow field is a laminar boundary layer flow in two-dimensional channels. it is difficult to perform measurements close to walls. a leading software package for modeling combustion kinetics. Using laminar models instead of turbulent ones for the gas-phase transport-equations strongly reduces the time needed for a single computation. surface reactions.1). and at the same time enables the use of very detailed chemical reaction mechanisms. The overall aim of this work has been to obtain a fundamental understanding of wallrelated premixed combustion by numerical modeling with detailed chemical kinetics. In this context. including for example: compressible fluid flow coupled to convection. 1. heat and Gas-phase reactions species Adsorption. heat conduction Stefan velocity Wall Figure 1. The work utilized CHEMKIN. mathematical simulations can play an important role in accelerating the understanding of near-wall combustion.2 Scope of this work Due to limitations in our current understanding. The assumption has been made that the wall effects may at least in principle be the same for laminar and turbulent flows.1 Different processes that have to be modeled to understand near-wall combustion. desorption Gas Diffusion. it is important to gain deeper insight into the physics and chemistry controlling emissions resulting from flamesurface interactions. There is usually a trade-off between the use of complex chemistry and 3 .

and in any case. there is not a steady solution (Warnatz. unlike laminar flow solutions. The modeling of near-wall combustion is then described together with the mathematical treatment of a chemicallyreacting boundary layer flow. 1996). In Paper III. using the combustion of hydrogen as an example. which concludes this part of the thesis. propane has been used as the fuel in the model and the effects of fuel/air ratio. Furthermore. wall material. with temperatures above the autoignition temperature for the specified stoichiometry. and carrier gas have all been varied in order to determine the relative importance of the chemical wall-effects compared to the thermal wall-effects in lean combustion. The effects of changing fuel/air ratio. The second part of the thesis deals with autoignition flames. wall material and pressure have all been discussed. and the fuel/air ratio. The third part of the thesis deals with premixed flame fronts. pressure and wall temperature on the flame propagation and emissions 4 . 1.2 Illustration of the usual trade-off between the use of complex chemistry and flow model complexity. Premixed hydrogen-air flames have been modeled in Paper I. Finally the software package CHEMKIN®. In Paper II methane has been used as the fuel in the model. used to accomplish a numerical solution for the reacting flow model is described. and the inlet conditions were changed somewhat from those used in Paper I. Uniform reactor inlet conditions are specified. Maas & Dibble.turbulence models (see Fig. The first part of this thesis treats the basic formalism of gas-phase and surface kinetics. the Navier-Stokes solution to turbulent flows is itself time-dependent. The inlet conditions vary strongly as a function of distance from the wall and a premixed flame has been modeled that propagates towards a wall under the influence of a boundary layer flow. This is mainly due to the fact that resolution of the small scales in turbulent flows demands far more grid points than does the analogues laminar flow. Flow model complexity 3D-CFD simulation 2D laminar model Chemistry complexity Figure 1.2).

A comparison has been made between these results and those obtained in Paper II. which is a major hurdle when using gasified biomass as a fuel in combustion applications. and (iii) playing the major role in reporting on the work and drafting the manuscripts. detailed homogenous and heterogeneous chemical kinetic schemes have had to be used. Paper IV investigates the influences of different fuel/air ratios and wall boundary conditions on the propagation of pressurized methane flames. involving for example providing inspiration. ideas and as scientific reviewers of manuscripts. Paper V treats a somewhat different but nevertheless related area. The author’s contribution to the above papers has been: (i) setting up the reacting flow problems. Paper V discusses different operations of the combustor for reducing Fuel-NOx. 5 . The other authors of these papers have acted as academic advisors. namely combustion of gasified biomass in a hybrid catalytic combustor for gas-turbine applications.have all been discussed. Finally in the last part of the thesis. To model the combustion in the gas-turbine combustor. (ii) performing the modeling and simulation work.

762 N2 (g). To illustrate the detailed mechanisms of chemical kinetics that are used to describe combustion processes. The largest mechanisms are normally reduced. (1996). This mechanism was used in Paper I. This may be accomplished thermally by using high temperatures (for example dissociation by heating in a shock 6 .7 kJ/mole) is described by the equation: 2 H2 (g) + O2 (g) + 3.762 N2 (g) → 2 H2O (g) + 3. (2. Usually the reactive species such as H and O have to be produced as reactants. instead. For the hydrocarbons. can be described by 38 elementary reactions (19 reversible reactions).2 Fundamentals of Chemical Kinetics This chapter deals with the basic formalism of gas-phase and surface kinetics. or (ii) in flow reactors where the spatial profiles of the concentrations provide information about their time behavior. The formation of water for example.1) Often these overall reactions are bound by complicated rate laws. the more exactly the chemistry can be represented.1. O and OH that are very important in combustion processes. it does contain the chemistry of the radicals H. A summary of the experimental techniques used for the determination of elementary reactions can be found in Warnatz et al. and the larger the number of species used in these reduced mechanisms. (ii) negative and (iii) dependent on the time and reaction conditions. Resolution of the elementary reactions can be a difficult and time-consuming task. as shown in Table 2. where the reaction orders of the individual reactants may be: (i) non-integers. However. hundreds or even thousands of elementary reactions are needed to describe their combustion. 2. which are more complex than hydrogen. both the gas-phase and catalytic combustion of hydrogen have been described in detail. detailed investigations show that water is not produced by one single collision between the three reacting molecules. Experiments are often carried out in: (i) isothermal vessels filled with reactants. Although the oxidation mechanism of hydrogen in air is a fairly simple system compared to that of a hydrocarbon fuel. the overall reaction is a consequence of a large number of elementary reactions. and the time behavior of the concentrations is measured.1 Gas-phase chemistry: oxidation of hydrogen in air The net reaction or overall reaction for the combustion of a stoichiometric mixture of hydrogen and air (an exothermic reaction with heat of combustion of -571.

H2+O=H+OH 1.1 The gas-phase reaction mechanism for hydrogen-air. *** H2O /21.8×10 0.5×10 0.0 0. H+O2+N2=HO2+N2 13 2. Using elementary reactions has many advantages: (i) the reaction order of elementary reactions is always constant. HO2+H=OH+OH 2.1 37.0×10 0.2 0. H+O2+M=HO2+M*** 2.2 4.0 0.30 13 1.00 17 0. H2+O2=OH+OH 23 6.0/.7×10 0.00 18. H+O2+O2=HO2+O2 6. H2O2+H=HO2+H2 13 19.5×10 0.8×10 1. H2+M=H+H+M** 18 -1. electron spin resonance.0 200.3/ O2 /0.50 8.30 3.5 The concentration measurement used should be sensitive and fast. Methods used include mass spectroscopy.1×10 -0. HO2+H=H2+O2 14 13.9.00 a The rate constants are formulated with Equation 2.2×10 0.9 4.5×10 -2. No.00 5. All one has to do is 7 . Reaction Ea [kJ/mol] 69. optical spectroscopic methods and gas chromatography. HO2+HO2=H2O2+O2 2. Third-body enhancements factors: * H2O /20.0×10 0.0 190.00 9.2×10 1.7 0. HO2+OH=H2O+O2 12 16.00 9 1.0/ H2 /3.7×10 -1. HO2+O=OH+O2 13 5.42 11. H2+OH=H2O+H 8 4. Source: Giovangigli & Smooke (1987). H+OH+M=H2O+M* 7.0/ N2 /0.2×10 12 1. O2+M=O+O+M 1. H2O2+OH=H2O+HO2 1.9 7.0 0.1×10 19 10.0/.00 14.2 0. Table 2.0 15.50 12 2.00 13 4.0/ H/2.1 387. H2O2+M=OH+OH+M 1.tube).0×10 0.00 17. and (ii) can be determined easily.7 7.82 10 2.s] [-] 16 1. H+O2=O+OH 5.0×10 1.7 15. OH+OH=H2O+O 6.7×10 -1.0 2. High dilution with noble gases (He and Ar) slows down the reaction of the reactive species with themselves.0 400. or by a microwave discharge.60 11 7. Aa βa [mol.cm.00 15.0/.42 19 6. ** H2O /6.0/ H2 /3. and in particular is independent of time and the experimental reaction conditions.00 12.7×10 0.9×10 0.

to look at the molecularity of the reaction. Only three possible values of the reaction molecularity are observed, and these are described as follows. Unimolecular reactions describe the rearrangement or dissociation of a molecule: A → products. (2.2)

These have a first-order time behavior. When the initial concentration is doubled, the reaction rate is also doubled. Bimolecular reactions are the most common reaction type found (see Table 2.1). These proceed according to the following reaction equations: A + B → products, or A + A → products. (2.4) (2.3)

Bimolecular reactions always follow a second-order rate law. The doubling of the concentration (doubling of the pressure) quadruples the reaction rate. Trimolecular reactions are usually recombination reactions and obey a third-order law: A + B + C → products, (2.5)

A + A + B → products, or A + A + A → products.

(2.6)

(2.7)

In general, the molecularity equals the order of the elementary reactions, and the rate laws can be easily derived. For an elementary mechanism, the rate of formation (mole/cm3 · s) of a species k , is given by summation over the rate equations of all the elementary reactions I as follows:

8

' '' υki υki  K  K & ω k = ∑ (υ − υ ) k fi ∏ [ X k ] − k ri ∏ [ X k ]  . i =1 k =1  k =1  I ,, ki , ki

(2.8)

In Equation 2.8, the superscript symbol ' indicates forward stoichiometric coefficients (υ ki ), while '' indicates reverse stoichiometric coefficients for species k in reaction i . The symbol [ X k ] (= Yk ρ / Wk ) is the molar concentration of species k . This expression can also be modified to take into account arbitrary reaction orders and thirdbody reactions. The temperature dependence of the rate constant ( k f ) in reaction i , is a synthesis of (i) the theory of the Swedish chemist Arrhenius (Arrhenius, 1889), (ii) the collision theory and (iii) the theory of activated complex:

k fi = Ai T βi e ( − Ei / RcT ) ,

(2.9)

where Ai is the constant of proportionality between the concentrations of the reactants and the rate at which they collide,

β i is the temperature exponent, Ei the activation

energy, Rc the universal gas constant in the same units as the activation energy, and f denotes that it is a forward reaction. The reverse rate constants are determined by the forward rate constant and the equilibrium constant:

k ri =

k fi K ci

.

(2.10)

The equilibrium constants are calculated from the thermodynamic properties of the species:
K

P  K ci = K p  atm  k =1 i  RT 
9

'' '   ∑  υki −υki   

,

(2.11)

 ∆ Sio ∆ H io  K pi = exp −  R RT  
o ∆ Sio K '' ' Sk = ∑ (υki − υki ) k =1 R R

,

(2.12)

(2.13)

and

H ko ∆ H io K '' ' = ∑ (υ ki − υ ki ) k =1 RT RT

,

(2.14).

where ∆ refers to the change that occurs in passing completely from reactants to products in the ith reaction. The standard state is defined as Patm = 1 atm (Kee, Rupley, Meeks & Miller, 1996). An alternative way is to explicitly state the reverse rate coefficients.
2.1.1 Interpretation of the elementary reaction mechanism

The combustion of H2 in air proceeds through a chained-branched explosion when a fuel/air mixture within the flammability limits (the leanest or richest concentrations that will self-support a flame) comes into contact with an ignition source (Glassman, 1996). Chain-branched explosions are characterized by a period of ignition delay, during which the radical pool (O, OH and H) builds up (Warnatz et al., 1996). This means that during the first phase of the explosion, the temperature will not increase much, because the energy released from the fuel and the oxidizer is stored in the free radicals. The concentration of radicals therefore increases with time, and either the fuel or the oxidizer concentration lowers. At a certain point in time, radical recombination or chain-termination reactions become faster than chain-branching reactions and the energy is finally released. The concentration of radicals decreases and the temperature increases until the thermodynamic equilibrium of the system is finally reached. Examples of different types of chain reactions in the reaction mechanism outlined in Table 2.1 are: • • • • initiation (No. 5, forward reaction), chain-branching (No. 1, forward reaction), propagation (Nos. 2, 3 & 4 forward reactions), and termination (No. 8, backward reaction). 10

More free bonds are created than consumed in the chain-branching reaction and the initiation reaction. However, in the initiation reaction the reactants contain no free bonds. In the propagation reaction one free bond is consumed and one free bond is created. In the termination reaction two free bonds are consumed, and the chain is terminated due to a recombination of the two radicals. In the recombination reactions, more energy is released by bonding two molecules than the product molecule can carry, and a third species M is required that can carry some of the energy. The third species M provides the energy required to split the product back to reactants in the reverse reaction. In reaction Nos. 6, 7, 8, 9 and 17, M denotes an unspecified molecule. The concentration of this third body is calculated from the sum of concentrations of all the species in the gas times their factor of effectiveness to carry the energy that is released or required, according to:

[M ] = k∑1α ki [X k ] =
K

(2.15)

α ki is the enhancement factor for species k in reaction i . If all the species in the mixture contribute equally as third bodies (α ki = 1), then the concentration of the third
where body M equals the total concentration of the mixture. Equation 2.8 then changes to:
' '' υki υ ki  K  K ∏ [X ] ∏ [X ]  . & − k ri ω k = (υ − υ ) [M ]  k fi k k i =1 k =1  k =1 

I

,, ki

, ki

(2.16)

In reaction Nos. 6, 8 and 9 in Table 2.1, the enhancement factors for some molecules differ from unity in the mixture. Clearly water has a strong third-body efficiency. As shown in next section, an important feature of the third-body reactions is their pressure dependence. At lower pressures, these reactions are relatively slow, but as the pressure increases, they become increasingly important and compete with the two-body reactions.

2.2 Pressure-dependent reactions
Under certain conditions, some reaction rate expressions depend on pressure as well as temperature. An example of such a reaction is the recombination of methyl

11

At the high-pressure limit. a third body is required to carry some amount of energy liberated in the recombination reaction. k∞ (2. However when the pressure and temperature are such that the reaction falls between these limits. .radicals. Arrhenius parameters are required for both the high ( k∞ ) and the low ( ko ) pressure-limit cases: ko = AoT βo exp(− Eo / RcT ) .18) k∞ = A∞T β∞ exp(− E∞ / RcT ) .high-pressure limit [M ] → ∞ and k = k∞ . The rate constant at any pressure is taken to be: (2. and 12 . and is shown below: 2CH3 (+ M) = C2H6 (+M). the reaction can be described as 2CH3 = C2H6. the rate expressions are more complicated. The simplest approach is the model developed by Lindemann (1922). (2.19)  P  k = k∞  r  F . When the reaction is at either limit.20) Pr = ko [M ] . which is part of all reaction mechanisms for hydrocarbons. and (2.21) The limiting behavior ( F = 1) becomes: . solely temperature-dependent rateexpressions are applicable.low-pressure limit [M ] → 0 and k = ko [M ] . 1 + Pr  where the reduced pressure is given by (2. At the low-pressure limit.17) This is a so-called third-body-recombination-fall-off reaction.

i =1 k =1  k =1  I . such as 2CH3 (+M) = C2H5 + H (+M).26) where I is the total number of elementary reversible (or irreversible) surface reactions. the concentrations are given in moles/cm2 by: [X k ] = Z k Γ / σ k . 1991.24) (2. 1992).17 competes with other bimolecular steps. (2. C2H6* +M → C2H6 +M .23) (2. ki (2.3 Surface chemistry The formalism of the surface chemistry is very similar to that of the gas-phase reactions. At the same time. For adsorbed species. 13 . and σ k the number of sites occupied by species k . Kee & Rupley. In the surface chemistry used in this thesis. via resolution into elementary reactions (Coltrin. (2.. the species reside in only one surface phase.25) and As the pressure increases.The Lindemann model itself is a simplified model. 2. and other approaches involve more complex descriptions of F .22) (2.17: 2CH3 → C2H6* . ki . Γ the surface site density. Warnatz. deactivating collisions between C2H6* and other molecules cause the rate coefficient of C2H6 formation to increase. This reaction—which is endothermic—occurs through the same energetically excited species C2H6* as the reaction expressed in Equation 2. The net chemical production rate of species by surface reaction (in mole/cm2·s) is defined as: ' '' υ ki υ ki  K  K & sk = ∑ (υ − υ ) k fi ∏ [ X k ] − k ri ∏ [ X k ]  . C2H6* → C2H5 + H .27) where Z k is the site fraction of species k . The reaction expressed in Equation 2. these deactivating collisions preclude the dissociation of C2H6* into C2H5 + H. C2H6* → 2CH3 .

29) The thermodynamics of gas-phase reactions are well known. k fi = AiT exp  R T k = K f  RT   c  s   c βi (2.28) where ηki . However for adsorbed species on a surface. and Z k is the site fraction. µ ki . This coverage dependence is taken into account by an additional factor leading to the following rate expression for the rate coefficient of the forward reaction k f :  − Ei  K sl  − ε [Z ]  η [Z ]  ∏ 10 ki k [Z k ]µ ki exp ki k  .28 covers only those surface species that are specified as contributing to the coverage modification.The rate coefficients for adsorption. f '' ' (2. and is expressed as follows: 14 . and ε ki are the coverage parameters for species k in reaction i . For some simple surface-reaction mechanisms. This is a common method for characterizing the transfer of a molecule from the gas to the surface.10 where: Kg '' ' ∑ (υ ki −υki ) k =1 l Ks '' ' ∑ (υ ki −υ ki ) f k =Ks P  K ci = K pi  atm   RT    (Γ ) o l Ks ∏ k =Ks σ k−(υki −υki ) . for example the adsorption or desorption of a species. The reversible reactions can then be split into two irreversible reactions. The sticking coefficient is the probability of a specific molecule hitting the surface and adsorbing onto it instead of bouncing back into the gas phase. the thermodynamics are not well known. The product of Equation 2. desorption and surface reactions can also depend on surface coverage.10 and evaluating K c is the normal manner of describing reverse reaction rates when the forward reaction rate is known. Utilizing Equation 2. it is convenient to specify the adsorption step in terms of a sticking coefficient. Reverse rate constants can be determined from Equation 2.

Williams. Marks & Schmidt. 15 . Species whose random motion carries them close to the surface have a high probability of staying there. 2Π Wk (2. which causes a non-Maxwellian velocity distribution that in turn alters the net species flux near the surface. The sticking coefficient can also depend on the surface coverage. The expression for the relation between the sticking coefficient and the rate constant becomes: k fi = γ i 1 Γn RT . Ljungstrom. aiT bi e − ci / RcT ].31) where ai and bi are unitless. (2. 2Π Wk (2.30) The functional form of the sticking coefficient is taken to be: γ i = max[1. The sticking coefficient must lie between 0 and 1 to make physical sense. Ljungstrom. Kasemo. according to Equation 2. both experimentally and theoretically (Hellsing. 1987. For large sticking coefficients—nearing 1—the velocity distribution becomes skewed.32) where n is the sum of the stoichiometric coefficients for the number of reactant surface-species. Wahnstrom & Fridell. (2.33) Table 2. and the units of ci are compatible with Rc . Rosén & Wahnstrom.28.2 shows the surface mechanism for hydrogen oxidation on platinum used in Paper I. Rosén. Motz and Wise (1960) provided the following correction factor for the rate coefficient:  γi  1 k fi =    1 − γ / 2  Γn i   RT . Kasemo.rate of adsorption = γi = rate of bombardmen t k fi [ X k ] Γ n [X k ] RT 2 Π Wk . 1989. The oxidation of H2 on Pt is a well-studied phenomenon.

5-7). • the adsorbed atoms collide while attached to the surface.1992.70×1024 1.75b 1. H(s) + OH(s) = H2O(s) + Pt(s) 7.71×10-9 mole/cm2 # Reaction Nos.0 0.05b 7. H2(s) + Pt(s) = H(s) + H(s) 3.50×1024 3.00b 1. O + Pt(s) = O(s) 10. OH + Pt(s) = OH(s) 12.00b 1.2 The surface-reaction mechanism for hydrogen oxidation on Pt. H + Pt(s) = H(s) 9. Aghalayam.5 0. H2O2 + 2Pt(s) = OH(s) + OH(s)# 13.023b 2. Park & Vlachos. H2 + Pt(s) = H2(s) 2.00b Ea [kJ/mol] 0. All reactions are assumed to be reversible. Kee & Coltrin.mol.31. O2(s) + Pt(s) = O(s) + O(s) 5. (1994).s] 0.0 0.0 0. H2O + Pt(s) = H2O(s) 11.70×1021 3.0 100.0 0. Allendorf. Warnatz. O2 + Pt(s) = O2(s) 4. 2000a).0 Source: Warnatz et al. 10). 1994. 1997.00b 0.0 0. Rinnemo. Deutschmann. forming first OH and H2O in surface reactions (reaction Nos. The adsorption and desorption of radicals is accounted for in the remaining reactions. and • finally desorption of H2O takes place (reaction No.9. H(s) + O(s) = OH(s) + Pt(s) 6. OH(s) + OH(s) = H2O(s) + O(s) 8.00b 1.3 0.6 0. Behrendt & Kasemo.70×1021 3. HO2 + 2Pt(s) = OH(s) + O(s)# Aa [cm. The type of elementary gas-phase and surface-reaction mechanisms described in this chapter can be very useful when coupled to reactive flow models for modeling the coupling between homogeneous and heterogeneous combustion. Table 2. Site density of the Pt-wall is Γ = 2. 1-4). 16 . a The rate constants are formulated with Equation 2.50×1022 0. The mechanism is based on laser-induced-fluorescence (LIF) measurements of desorbed OH. Reaction no. b The sticking coefficients are formulated with Equation 2.0 15. 12 and 13 have been added to the original mechanism.0 0. and involves the following steps: • dissociative adsorption of H2 and O2 (reaction Nos. 1.0 19. Pt(s) denotes a free surface platinum site and X(s) is an adsorbed species.

1). 1993. Vlachos. it is desirable to separate one of those factors and to elucidate its relative importance. It is inadequate however to use global chemistry.. Hasse et al. To understand more about the wall effects. 2000) or the stationary case with head-on stagnation point flow (Vlachos et al. 17 . and the destruction of radicals in the boundary layer. and the intermediate hydrocarbons have been found to be significant during quenching and must be accounted for in the kinetic model (Hocks et al. as it does not account for the role of the radical pool (see Section 2. Vlachos & Westmoreland.1). The results are further improved when the effect of thermal diffusion (Soret effect) is considered (Popp & Baum. 1997. and where the flame stops at a certain distance from the wall. Although lean combustion of simpler hydrocarbons like methane have limited pathways for forming intermediate hydrocarbons. 1996. and the possibility of active radical destruction must also be considered.. 1997).. There are no completely inert walls though. detailed chemistry schemes are needed to describe the interaction between transport and fuel oxidation in the gas and on the surface. In turbulent combustion. in which the coupling between the gas and the wall is mainly of a thermal nature due to heat transfer. 1981. Bui. 1986. Factors that influence the wall effects include the temperature decrease across the thermal boundary layer. and of viscous shear due to momentum transfer. Numerical modeling with complex chemistry has mostly used the stagnation configuration in either the transient case of a flame freely propagating towards a wall (Westbrook et al. Smooke & Baum. such as in catalytic combustion.3 Modeling of Near-wall Combustion Wall effects in combustion present a complicated problem for analysis since many species and still more reactions are involved. Schmidt & Aris. 1996. Kiehne et al. and the wall heat flux slightly lower. Studies of maximum wall heat fluxes have shown that the following two generic cases must be considered for laminar premixed flames (see Fig. additional complexities such as the scale of the turbulence across the turbulent boundary layer and the properties of the laminar sublayer may influence the flame-wall interaction. which is more pronounced at lower temperatures.. The simplest possible situation is that of a chemicallyinert wall.. 3. Popp. The most complex situation is encountered when chemical interactions are established between the gas and the wall. Popp & Baum. 2000). In order to explain the quenching phenomenon. Thermal diffusion denotes the diffusion of mass caused by temperature gradients. 1994a.. 1981. Hasse et al. • Stagnation or head-on quenching: when the premixed flame propagates towards the wall. The quenching distance is larger than for head-on quenching. model calculations with rigorous fluid mechanics and transport coefficients are required. • Sidewall quenching: when the premixed flame propagates along the wall.

1998. Aghalayam. Almost all practical flows in industry and the environment are turbulent. 3. Bui & Vlachos. Gudmundson.1 Typical flow configurations used to model near-wall combustion. sidewall configuration has been dealt with by von Kármán and Millán (1953) and Blint and Bechtel (1982). however not specifically using complex chemistry. The largest scales are given by the size of flow boundaries and by the flow velocity— the integral length scale (lo). Persson & Rosén. The emphasis in this thesis has therefore been placed on the sidewall configuration. At this so-called Kolmogorov length scale (lk). Forsth. Wall problems become even more critical in chemically-reacting flows. The time scales for different chemical reactions can overlap with the turbulent time scales. The understanding and modeling of turbulent phenomena that occur near walls is a formidable task.Egolfopoulos. The smallest scales are at the level where turbulence is dissipated by viscosity. Zhang & Zhang. In practice.1 Near-wall turbulence Turbulent flows are characterized by a wide range of spatial and temporal scales. the time taken for an eddy to rotate half a revolution is equal to the diffusion time across the diameter (lk). a Flame zone b Flame zone Wall Stagnation configuration Wall Sidewall configuration Figure 3. 1997. 1999). The treatment of near-wall turbulence for non-reacting flows is still a difficult problem and quite often the limiting factor in making practical predictions. 18 . Furthermore.

the use of laminar models has been generally accepted.1).very little is known about the effects of turbulence during flame-wall interaction. In order for computations with turbulent reactive flows to be accurate. the diffusion and molecular transport is in general faster than the turbulent transport). In turbulent flows. and any attempt to model the process must involve simplifying assumptions. there will always be a laminar sublayer close to the wall. The laminar sublayer is usually taken to be the region where eddies are completely absent. the mixing between the fuel and the oxidant is drastically enhanced. however there is evidence that eddies do occasionally penetrate right up to the surface.2 Laminar models Although the chemical reactions in both an internal combustion engine and a gas turbine combustor take place in a turbulent flow field. where the turbulence has died out and momentum transferred due solely to viscous shear. The situation is therefore highly complex. This suggests that results obtained for laminar models are also valid and can be compared with results obtained from turbulent models. In internal combustion engines. As the quench layer is usually within the laminar sublayer.2 At the Kolmogorov length scale. 1977). 3. the length scales of wall quenching are much smaller than those of the turbulence (that is. The following section presents a description of the 19 . and the quench distances in engines can be well correlated to the distances obtained for laminar flame-quench calculations (Ferguson & Keck. 3. which often strain storage and computational efficiency past practical limits. the time taken for an eddy to rotate half a revolution is equal to the diffusion across the diameter l k . these must respect the smallest scales of length and time. lk Figure 3. In this thesis. and in general the heat and mass transfer rates would be higher in a turbulent boundary layer than in a laminar boundary layer. the numerical modeling work done on homogeneous premixed combustion influenced by walls has been carried out exclusively using laminar models in the sidewall configuration (see Fig.

Continuity: ∂ ρu ∂ ρ v + = 0. Elliptic approach (Navier-Stokes equations) The laminar. 3. In a two-dimensional Cartesian coordinate system. y Boundary layer x Wall Figure 3. fluid flow pattern. energy and species. temperature and species fields are calculated from conservation equations for mass.1) 20 .3 Two-dimensional boundary layer flow over a flat wall. 2002). momentum. and at steady state.mathematical treatment of a two-dimensional chemically-reacting boundary layer over a flat wall. Stewart & Lightfoot.2.1 Mathematical description of chemically-reacting boundary layer flow Two-dimensional boundary layer flow is illustrated in Fig. they can be expressed as follows (after Bird. 3. ∂x ∂y (3. Reaction rates using factors such as the molecular weights. When modeling a chemically-reacting boundary layer. chemically-reacting Navier-Stokes equations involve few assumptions. and represent the most general approach. multicomponent. concentrations and stoichiometries for specific species in all reactions are used in each speciesconservation equation to balance the mass transfer from one species to another.3.

k = 1.4) Species continuity: ρu ∂ ∂Yk ∂Y ∂ & + ρ v k + ( ρ YkVk x ) + ( ρYkVk y ) − ω k Wk = 0 ∂y ∂x ∂ y ∂x .2) ∂   ∂u ∂v   µ  +   + ρg = 0 ∂y   ∂y ∂x    Cross-flow momentum: ρu ∂v ∂v ∂p ∂   ∂v ∂u  + ρv + −  µ  +  ∂x ∂y ∂y ∂x   ∂x ∂y    ∂  ∂v 2  ∂u ∂v  − 2 µ − µ  +  + ρg = 0 ∂y  ∂y 3  ∂x ∂y    Thermal energy: .5) 21 . (3.Axial momentum: ρu − ∂u ∂u ∂p ∂  ∂u 2  ∂u ∂v  + ρv + − 2µ − µ  +  ∂x ∂ y ∂ x ∂ x  ∂x 3  ∂x ∂y    .3) ρ cp  u  − Kg  ∂T ∂T  ∂p ∂ p ∂  ∂T  ∂  ∂T  + λ  +v =u +v + λ ∂x ∂y  ∂x ∂ y ∂ x  ∂x  ∂ y  ∂ y        Kg  ∂T ∂T  &  − ∑ hk ω k Wk + ρYkVk y c p k  ρYkVk x  k =1 ∂x ∂ y  k =1   ∑ . . (3. . K g (3. (3.

The governing equations are then be expressed as follows. all the second derivatives in the x direction are eliminated. (3. the variation of surface coverage—the fraction of surface sites covered by species k —is calculated from the surface reaction rates according to the following expression: & dZ k s k = dt Γ k = 1. Parabolic approach (Boundary layer approximation) Pursuing solutions based on the Navier-Stokes equations for a propagating flame—fluid flow equations coupled to the diffusion and energy equations with finite-rate chemistry—is a formidable task. .7 should be considered to be a part of the system of governing equations. the boundary layer approximations become increasingly valid. (3.7) Equation 3. It can be shown by order-of-magnitude arguments that the cross-flow momentum equation is reduced to the simple statement that there can be no pressure variation across the channel (Bird. Compared with an elliptical approach. Appel & Benz. even for a two-dimensional stationary system. As the flow rate in the channel increases (high Reynolds numbers) and the fuel/air ratio (φ) decreases. . Stewart & Lightfoot. As a result. All the variables are described in the Nomenclature section at the beginning of the thesis. Therefore it may be desirable to first undertake some simplifications of the fluid mechanics. 22 . 2000).State: p= ρ RT W . 1961) and these well-known approximations are still applied widely today in fluid mechanics. Prandtl first addressed the boundary layer approximations around 1904 (Prandtl. 2002). however because the surface composition is determined as a part of the solution.7 simply states that at steady state the surface composition does not change. Equation 3. In some senses this could be considered a boundary condition (possibly complex) on the gas-phase system. under these conditions the convective transport is dominant in the principal flow direction ( x ).6) For reactive walls. K s . . the validity of the boundary layer equations depends on the inlet velocity and the fuel/air ratio (Mantzaras. Compared with the diffusive transport.

9) Cross-flow momentum: ∂p = 0. − µ + ρv ∂ y ∂ y  ∂ y  ∂x ∂x   (3. The independent variables are denoted x and y . u . and the dependent variables are denoted p. and Z k .6. as in this thesis.7 have to be added to the system.10) ∂T ∂T ∂  ∂T   + ρ vc p − λ ∂x ∂y ∂y  ∂y  . . K g . Yk . and the surface species conservation expressed by Equation 3.9 can be omitted when the channel height is sufficiently small.11) Species continuity: ρu ∂Y ∂ ∂Yk & + ρv k + ( ρ YkVk y ) − ω k Wk = 0 ∂x ∂y ∂y k = 1. (3. The character of the equations changes from 23 . T .12) The state expressed by Equation 3. .8) ρu ∂u ∂  ∂u  ∂ p ∂u + + ρg = 0. v. ρ . ∂y Thermal energy: (3. the term ρ g in Equation 3. In horizontal channels. ∂x ∂y Axial momentum: (3.Continuity: ∂ ρu ∂ ρ v + = 0.  Kg ∂T K g & + ∑ ρ YkVk y c pk + ∑ ω k Wk hk = 0 k =1 ∂ y k =1 ρ uc p (3.

2000). Raja. Deutschmann.15) The boundary condition at the wall becomes relatively complex in the presence of heterogeneous surface reactions.elliptical to parabolic.13 below) or a zero heat flux (adiabatic) condition (see Equation 3. 2000.16) In the above equation. Warnatz & Schmidt.2 Boundary conditions Turning now to the energy equation. The convective and diffusive mass fluxes of gas-phase species at the surface are balanced by the production (or depletion) rates of gas-phase species by surface reactions. . .2. For chemically inert walls. 3. In Paper II.. ∂y In addition. Kee. (3. ∂y (3.13) (3. It was found that in most cases the effect of axialdiffusive transport was small. as represented in the following expression: & jk y = ρ Yk (Vky + v) = sk Wk . the following zero-gradient Neumann boundary condition is used for each species: ∂Yk = 0. the axial velocity ( u ) is assumed to be zero at the wall (the non-slip condition). the parabolic approach should be used with caution. k = 1. although at lower pressures (higher flame velocities) and higher concentrations. This represents a huge simplification. either the temperature (see Equation 3.14) ∂T = 0. leading to much more efficient computational solution (Mantzaras et al.14) is specified at the solid wall: T = Tw or (3. the gas-phase diffusion velocity of species k in the direction normal to the wall is given by: 24 . K g . the validity of the boundary layer approximations for the flame position was investigated. The boundary layer approximations for the transport equations have been used throughout this work.

and the diffusion fluxes total 0: Kg k =1 ∑ Yk =1 = 0. ∑ W j Dkj k≠ j ∂ y ρ Yk T ∂ y Kg (3. or by Dk . 25 .m ∂ X k DkT 1 ∂T − Vky = − X k ∂ y ρ Yk T ∂ y (3. (3.19) Equation 3. The velocity referred to as Stefan velocity.1 Vky = X kW ∂ X k DkT 1 ∂T − .21) Symmetry is used to specify the boundary conditions at the channel centerline in an axisymmetric channel.17) when multicomponent transport is used. is given by the expression: v= 1 Kg ρ k =1 ∑ & s kWk .19 is obtained from Equation 3. and must satisfy the requirements that the mass fractions total 1.16. (3.18) when mixture-averaged transport is used.20) and Kg k =1 ∑ ρ YkVk y (3. which occurs when there is a net mass flux between the gas and the surface.

independent of the particular type of reactive flow problem. together with the CHEMKIN thermodynamic database (Kee. This package calculates the homogeneous reaction rates of the gas-phase species. 4. These core utilities contain a large set of modular subroutines written in Fortran.1. 1990). Coltrin.. and reaction rates. energy and species. Today. flow rate and concentration. Typically the model description includes conservation equations for mass. This is illustrated in Fig. Miller & Moffat. the CHEMKIN Collection (Kee. independently of which chemical species are included in a specific problem. CHEMKIN’s utilization flexibility has developed significantly since 26 . The CHEMKIN software core utilities provide the interface between the problem-specific information and the problem-independent “application”. Miller et al. 1980) and has had a noticeable impact on combustion research. Dixon-Lewis. momentum. CHEMKIN-III was developed to assist the incorporation of complex gas-phase chemical-reaction mechanisms into numerical simulations. 1996) and the TRANSPORT package (Kee. as well as handles thermodynamic data for the system needed to calculate reverse rate constants for the chemical reactions (Kee et al. 1996). This is on of the most widely used software package for modeling combustion kinetics. SURFACE CHEMKIN-III (Coltrin. CHEMKIN was developed by Sandia National Laboratories in the early 1980s (Kee. species properties. including for example pressure. The application represents the general model.4 CHEMKIN Software The software used in Papers I-V is called CHEMKIN.. who have continued its development. Rupley & Meeks. 1986). and is able to disengage the generic solution techniques from the actual physical model.. 1990) and TWOPNT mathematical software (Grcar. 4. This package allows the user to specify the input required through a high-level symbolic interpreter. This interpreter then passes the information on via an application code. Warnatz. Additional problem-specific information may also be input directly by the user. reaction path. 2000) is designed to analyze complex chemically-reacting processes in a rigorous but flexible manner. Miller & Jefferson. Kee. One advantage with this modular approach is that the software can benefit from the rapid advances in computational mathematics and software.1 CHEMKIN architecture CHEMKIN provides a structured approach to the computational modeling of chemical kinetics and molecular transport in flowing systems. The upper rectangles shown in the figure contain the data that make the problem specific— species identity. when it was then licensed to Reaction Design. 1991). CHEMKIN was publicly available up until about 1994. The core utilities in the CHEMKIN Collection are: CHEMKIN-III (Kee et al. Rupley & Miller. Rupley. This means that CHEMKIN handles complex chemistry and transport in a generic way.

1 Illustration of the CHEMKIN modular approach to problem solving. This has the ability to calculate as a function of temperature. and execution of the CHEMKIN-III interpreter is required before the SURFACE CHEMKIN-III interpreter can be run. The TRANSPORT package provides information about the molecular diffusion. 27 . Gas-phase chemistry/ Thermochemistry input Surface chemistry/ Thermochemistry input Transport properties input CHEMKIN SURFACE CHEMKIN TRANSPORT Application Input APPLICATION Problemindependent numerical software POSTPROCESSING Figure 4. SURFACE CHEMKIN-III is designed to run in conjunction with CHEMKIN-III. and is used to formulate the boundary conditions describing chemical reactions at the surface. thermal conductivities and viscosities for every gas-phase species. SURFACE CHEMKIN-III software has a similar user interface to CHEMKINIII. the binary diffusion coefficients including thermal diffusion coefficients. through for example the provision of new options for describing the temperature and pressure dependence of a reaction.the original version.

replacing it with an integral.  x (4. (4. CRESLAF is written as a subroutine and runs in conjunction with the CHEMKIN.21 is accomplished using the CRESLAF program (Coltrin.1) ∂  ∂   = ρ u  ∂y   ∂ψ  x  where the stream function is defined as   . The equations transformed into planar coordinates are listed below. Kee & Miller. 1984. which is a part of the CHEMKIN Collection. This transformation eliminates the mass continuity equation (Equation 3. Coltrin. 1964). Moffat. Coltrin.2 The CRESLAF program The numerical solution for the two-dimensional chemically-reacting boundary layer model presented in Equations 3. When CRESLAF executes. 1993). Kee & Miller.6 to 3. it reads the linking-file information from the three preprocessors.3) The stream function variable represents the amount of mass going through a specified physical domain. the boundary layer equations are recast using von Mises transformation in a form in which a stream function replaces the cross-flow ( y ) coordinate as an independent variable (Moore. 1986.  x (4. The relationships between the physical coordinates ( x and y ) and the transformed coordinate (ψ ) can be expressed as follows:  ∂   ∂   ∂   =   − ρ v  ∂x   ∂x   ∂ψ   y  ψ  and   . and calls up appropriate subroutine libraries from the preprocessors using these linking data.2) ψ = ∫0y ρ u dy . 28 .4. and the convective derivates in the y direction (normal to the wall) are eliminated.8). SURFACE CHEMKIN and TRANSPORT libraries. In CRESLAF. Kee & Rupley.

29 . .2. K g . ∂x ∂ψ ( ) (4.  k =1 k =1 ∂ψ  (4.7) The state expressed by Equation 3.5) ρ uc p ∂T ∂ = ρu ∂x ∂ψ  ∂T  ρ uλ  ∂ψ  Kg  Kg ∂T &  − ∑ ω kWk hk − ρ 2u ∑ c pkYkVky . In many combustion problems. The widely differing scales of combustion processes lead to the well-known stiffness problem when solving the species concentration equations. 4. ∂ψ (4.6) Species continuity: ρu ∂Yk ∂ & = Wk ω k − ρ u ρYkVk y .6. To enable the inclusion of finite rate chemistry (reaction rates that are not infinitely large). the boundary layer equations are expressed as a set of differential/algebraic equations (DAEs) with the time-like direction represented by the axial coordinate x . through the heat of reaction.7 have to be added to the system.Axial momentum: ρu ∂u d p ∂ + = ρu ∂x d x ∂ψ  ∂u   ρ uµ  + ρg . the kinetic terms dictate the characteristic time and space in which the numerical solution must be found.4) Cross-flow momentum: ρu Thermal energy: ∂p = 0. and the surface species conservation expressed by Equation 3. .  ∂ψ    (4. 1982). k = 1.1 Numerical solution using the differential/algebraic approach Chemical kinetics provides the coupling between the concentrations of various chemical species and the energy equation. The finite-difference representation of the defining equations is solved using the computer program called DASSL (Petzold.

the computer time required by the model can be decreased by a factor of 10 or more (Coltrin. As part of the solution to the equations. where y and y’ represent the components of the solution and their time derivatives. and t is time. Calculating the Jacobian is expensive and the most computationally-expensive aspect of evaluating it is the calculation of the multicomponent transport properties. However. Kee & Rupley.t) = 0. Implicit methods are most efficient for solving the stiff equations usually found in chemical kinetic problems. which is the partial derivative of the residual g with respect to each component of the solution. 30 .The DAEs are written in the general form g(y. A Jacobian is needed because DASSL employs an implicit time-stepping method. y’. Holding the transport properties fixed when calculating the numerical Jacobian can significantly reduce the extent of computer time required to solve the set of DAEs. 1993). a numerical Jacobian is formed. Although this introduces some error into the Jacobian. DASSL requires only an approximate Jacobian for the purpose of iterating to a converged solution. Moffat. No error is introduced into the solution by including this simplification in the Jacobian evaluation.

This leads to autoignition of the mixture at some point further downstream. and as fewer reactions and species are involved than in hydrocarbon fuels. Thermal effects are simply flame retardation or extinction. 31 . On the other hand. As mentioned in a Chapter 3. issues were addressed such as which part of the wall effects—chemical or thermal—was most important for a given set of conditions. Hydrogen is a nonhydrocarbon. causing inhibition of the combustion. and the aim is to clarify the relative importance of the thermal wall-effects compared to the chemical wall-effects. one reason for choosing the sidewall configuration was that previous modeling studies using complex chemistry and hydrogen as the fuel for the model had most commonly used the stagnation configuration. The crossover temperature is defined as the temperature at which the effects of chain-branching reactions just balance that of chain-breaking reactions.1. and are thereby removed from their respective catalytic cycles. for which the combustion process is not totally explained.5 Autoignition Flames (Papers I and II) The first flame geometry used in this study featured a uniform unburned mixture of fuel and oxidizer at the inlet to the channel. 5. This autoignition situation should have the following three important applications: • in the autoignition of an unburned fuel-oxidizer mixture at a cylinder wall of an internal combustion engine which takes place before the ordinary flame front has reached the cylinder wall—also referred to as knock. having a temperature higher than the crossover temperature. especially not close to walls. the interpretation of the results is easier. Chemical effects occur when for example key reactive radical intermediates in the combustion mechanism react with the walls. resulting from the transfer of heat out of the flame region at a greater rate than the generation of heat by the combustion process. however hot-spots in the catalyst may lead to an uncontrolled temperature rise and ignition in the gas-phase. • in catalytically-stabilized combustion (CST). the results may not be generalized. By using different wall boundary conditions and gas-phase transport parameters. 5. including hydrogen-assisted catalytically CST—in hydrogen-assisted CST the hydrogen can reduce the catalyst light-off temperature. as illustrated in Fig.1 Hydrogen as fuel in the model (Paper I) Hydrogen was used as the fuel in the model in Paper I. and • in homogeneous-charge-compression-ignition combustion (HCCI). as hydrogen has a higher mass-diffusivity and burning velocity than hydrocarbon fuels. The fuels used in the model are hydrogen and methane.

which is above the crossover temperature for autoignition at these stoichiometries. where y = 1 cm in Fig. To avoid numerical difficulties. The inlet temperature was 975 K. 5. in other words fully developed).1 Inlet and boundary conditions Inlet conditions An axisymmetric planar channel was considered.1 Representation of the autoignition geometry used in Papers I and II. the maximum velocity increases somewhat. Flat profiles of temperature and species were used at the inlet. 5. To elucidate the effects of heat and mass transfer. the carrier gas N2 was substituted with modified helium (He with the same heat capacity as N2). which gave a clear shape of the reaction zone after ignition. This enhances heat and mass transfer rates due to the higher conductivity and diffusivity of modified He compared to N2.1 were used. Wall boundary conditions The wall temperatures used were 600 and 400 K. the wall temperature was set to equal the gas-phase temperature at the inlet 32 . and the inlet velocity was 900 cm/s.5 and 0. The pressure was atmospheric and two lean fuel/air ratios (φ) of 0.01 cm (within which the velocity profile was parabolic. but due to the expansion of the gas. The velocity and thermal boundary layer then develops very rapidly downstream of the channel and the velocity profile remains roughly parabolic.1. The gas-phase chemistry of hydrogen is described in Chapter 2.Figure 5. however the velocity boundary layer thickness was 0.1. The lean unburnt fuel/air mixture is preheated above the autoignition temperature leading to an autoignition flame downstream in the axisymmetric channel.

2 OH(S) → H2O + O(S) + S 1×10 13 0. 2 OH(S) → H2O + O(S) + S 1×10 13 0. (ii) a wall facilitating the recombination of intermediate species.0 12.mol.s] [kJ/mol] 1. and was then linearly ramped down to the wall temperature at x = 0.0 1. After comparison with 140 and 200 mesh points. Reaction No. 2 O(S) → O2 + 2 S 1×10 1. 1998). 5. Table 5. this discretization of the grid was found to provide satisfactory resolution.5 min. and (iii) a wall promoting the catalytic combustion of hydrogen.0 13.0 3. HO2 + 2(S) → OH(S) + O(S) 13 0.0b 0.5 cm.g.0 7. H + S → H(S) 0. 2 O(S) → O2 + 2 S 1×10 b 0.0 0. 2 O(S) → O2 + 2(S) 1×10 a The rate constants are formulated with Equation 2.0 2. S denotes a free surface site and e.2 presents a summary of the combinations of the wall materials and carrier gases used in the calculations. The consequences of this were that in part of the reaction zones the wall temperature varied. and the recombination mechanism is shown in Table 5. The typical time needed for the CPU to complete one calculation was approximately 3. Aa Ea [cm. To investigate the heterogeneous effects. O + S → O(S) 13 0. OH + S → OH(S) 13 0.0 1. 2 H(S) → H2 + 2 S 1×1013 b 1.. 33 .to the channel.17×10-7 moles/cm2. Discretization The mesh had 70 points in the transverse direction concentrated near the wall.31.0 6.2 Results and discussion Table 5.1.0 10.0 4. Consequently the axial resolution is automatically adapted to match a given acceptable limit in the truncation error.0 5.0b 0. The catalytic mechanism is described in Chapter 2.0 0.1. H2O2 + 2(S) → 2 OH(S) 13 0. 2 OH(S) → H2O + O(S) + S 1×10 13 0.0 11. CRESLAF uses an adaptive method in the axial direction.9. three different wall materials were used: (i) an inert wall with no reactions.0 8. b The sticking coefficients are formulated with Equation 2. 2 O(S) → O2 + 2 S 1×10 b 1.0 9. Site density is Γ = 4. H(S) is an adsorbed species.1 Surface reaction mechanism on the recombination wall for hydrogen oxidation (after Aghalayam et al.

8 0.2-5.9 0. 1 height y. ** He with the same heat capacity as N2 Contour plots of the fuel concentration ( X H 2 ) and temperature ( T ) for the combinations of gas-phase materials and carrier gases in Table 5.14 0.02 0.8 0.4 0.8 0.8 0.2 0.2 Combinations of gas and surface mechanisms used in the calculations.14 0. cm 0.4 0. cm .2 0.4 0. Carrier Gas Surface mechanism Carrier Gas* Modified He** Platinum (Table 2.Table 5.14 1 0.5.g.04 0.12 0.1 1 0.8 0. The boundary layers are emphasized within the reaction zone and only a distance of 2-3 mm outward from the wall is shown.02 0.1 1 height y.2 0.9 0.3 distance x.2 0. cm 0.14 0.2 0.12 0.9 0.3 0.16 0.1 0.2: φ = 0.1) RrN2 RrHe Inert wall InN2 InHe * Abbreviations for the combinations e.3 distance x. The wall effects are the changes in the combustion process caused by the processes in the boundary layer compared to an imaginary combustion process without any 34 height y.4 0.02 0.12 0. PtN2 = Pt wall-carrier gas N2. Tu = 975 K. cm 0. 5.9 PtN2 0. y = 1 cm is at the wall.02 0.16 0.3 0. cm 0. Tw = 600 K.1 1 0. In these contour plots.3 0.2 0.2) PtN2 PtHe Recombination (Table 5.8 0.16 0.9 RrN2 0.02 0.4 0.1 0.1 0.1 0.14 0.1 0.16 0.3 0.9 InN2 0.1 1 RrHe 0.16 0.16 PtHe 0.4 Figure 5.5.08 0.14 0.2 are shown in Figs.2 Contour of X H 2 for the combustion systems in Table 5.1 InHe 0.

where H2O acts as a third body.0122 1 0.8 0.6 0.6 0. The diagrams for the inert wall (InN2 and InHe) give us information on the extent of the wall effects due to heat transfer combined with viscous shear due to momentum transfer.8 0.4 1 height y. 35 .00812 0.00405 PtHe 0.0364 RrHe 0.0361 0. the homogeneous reactions are slowed down more by the Pt wall than the inert wall (see PtN2 and PtHe in Fig. and 3.00408 0.8 0.0203 0.9 0.0161 0.8 0.2).9 0.0364 0. 5. The Pt wall’s more significant quenching of the homogeneous combustion reactions than the recombination wall has three causes: 1.0322 0.4 1 0.0283 0.0243 0.4 1 0.8 0.9 0.0324 0. Tu = 975 K.6 0. cm 1 0. Clearly.2: φ = 0.4 0.8 distance x.0321 0.0365 RrN2 0. However after gas-phase ignition.6 0.0122 1 0.9 0. 2.9 0.0241 0. Tw = 600 K. cm 1 Figure 5.6 0.3 Contour of X H 2 for the combustion systems in Table 5. the depletion of H2 in the boundary layer due to catalytic combustion results in lower H-radical production. cm 0.00404 PtN2 0.1. the net adsorption of H radicals on the wall is higher using the Pt wall. 1 height y.boundary layer.4 1 height y.8 distance x.0121 0.8 0.0122 0.4 0.9 0. cm 1 0.0364 0.00407 InHe InN2 0.00408 0. cm 0.6 0.00813 0.8 0.0362 0. The Pt wall also slows down combustion more than the wall facilitating radical recombination (which also has a significantly higher simulated site density than the Pt wall). increased H-radical recombination in the boundary layer due to the third-body effect caused by high concentrations of water—in the reaction H+O2+M→HO2+M.8 0. the Pt wall promotes catalytic combustion before the homogenous ignition takes place.00408 1 0.8 0.8 1 0.

9e+003 Figure 5.7 0.2 0. Obviously the boundary layers become thicker when changing carrier gas from N2 to modified He (see Fig.3 785 1.9e+003 RrN2 0. and 2. However in the sidewall configuration.2 1 0.71e+003 1.5 distance x.71e+003 1.8 InHe 0. and more H2 is left in the boundary layer.4 Contour of T (K) for the combustion systems in Table 5.7 0.6 0. 5. the H-radical concentration is more depleted with the Pt wall than the recombination wall.3 0.5 0.5 0.5 0.7 0.4 971 1.72e+003 1. 1 height y.2. cm 0.2 0.9 970 0. cm 0.7 0.4 0.4 971 1.4).2 1 height y.6 1. cm 0.9e+003 0.71e+003 1.4 0.9e+003 PtHe 0. Tu = 975 K.By interpretation of Fig.8 0.9 0.4 0.6 1 0.9e+003 PtN2 0.3 972 1.9 0.71e+003 1.3 971 1. (1996) used the stagnation configuration.8 0.8 0.3 970 0.16e+003 1.2 1 height y. 5. the rate of H-radical adsorption is lower with the Pt wall than with the recombination wall.5. Vlachos (1996) and Bui et al. However the same differences can be seen for 36 .6 0.7 0.8 0. together with a corresponding plot for the H radical ( X H ). the third case is implied since: 1.2 1 0.7 0.9 0.6 0.71e+003 1.3 0.9 0.2: φ = 0. and observed that homogeneous ignition of H2 over a Pt wall was inhibited by the presence of water.5 0.9e+003 InN2 0.5 distance x. Tw = 600 K. the inhibition is expected to be stronger because the concentration of water becomes greater and the water is affected by the boundary layer flow.6 0.9 0. cm 0.34e+003 1.4 0. cm 0.8 RrHe 0.

8 1.9 0.4 1 0.4 0.6 0.7 0.7 0. the fuel used in the model was methane.8 Figure 5.1 reduces the observed differences between the wall materials (see Fig.9 0.6 869 0. Reducing the fuel/air ratio to 0.5 Contour of T (K) for the combustion systems in Table 5. cm 0.8 1.5 0.7 0.7 distance x. Tu = 975 K.3).21e+003 1.7 0.8 0.5 1 939 0.9 RrN2 1. where the Le number measures the ratio of energy transport to mass transport).6 0.3.2 Methane as fuel in the model (Paper II) In Paper II.7 0.6 0.9 0. implying that the thermal wall effects are the more significant.8 0. implying that the chemical wall effects are most significant in the richer combustion case.8 0.07e+003 1. the boundary layers become thicker compared with when φ = 0.5 0.4 0. cm 0.5 0.8 1.2: φ = 0.14e+003 0.07e+003 1e+003 InHe 0.5 1 939 0.6 801 0.4 0.6 0.2e+003 1e+003 RrHe 0. methane has a much lower 37 .1.21e+003 1.7 0.07e+003 height y.9 935 868 1e+003 1.7 0.5 936 0. 1 height y.2e+003 1.07e+003 InN2 0. Tw = 600 K. which is a strongly diffusionally-imbalanced fuel (Le ~ 0.8 1.14e+003 1.01e+003 height y. cm 0.07e+003 1. the overall wall effects are most significant in the combination of the leaner combustion case with modified He as the carrier gas.4 1 0.8 1.2e+003 1.2e+003 PtHe 0.the three wall materials at φ = 0.5 (see Fig. 5.7 0.14e+003 PtN2 0. 5.5).9 936 0. Compared to hydrogen. At the same time.8 0.8 0.7 0. cm 0.7 distance x. 5.8 1. As expected. cm 935 1 0.5.4 0.7 0.

and (2) via the oxidation of ethane. therefore a simplification was made to only include this C1 path in the calculations. CO. different inlet conditions and wall-boundary conditions were used in order to characterize the wall effects for the autoignition flame. but y in Fig. H2O. CO2. HCO. This mechanism has been optimized at lean-to-stoichiometric fuel mixtures. Methane is an important fuel for modeling both automotive and gas turbine applications. the Gas Research Institute Mechanism Version 1. HO2. CH3O. For fuel-lean mixtures. CH3OH. Including only the C1 path has the advantage that the CPU time needed for the calculations can be reduced. H.5 cm. This mechanism represents one of the most recent and comprehensive methane oxidation reaction mechanisms. mass-burning rates and enhances the rate of third-body reactions. CH. In order to elucidate the influence of pressure on the wall effects. Methane is a major constituent in natural gas and the simplest of the hydrocarbons. CH4. The reduced mechanism had 23 species (H2. Wall boundary conditions The wall temperatures used were 600 and 1. In the work done here. the former path predominates. CH2.mass diffusivity and flame speed.200 K. Two lean fuel/air ratios (φ) of 0. By narrowing the channel.200 K simulating an ignition source. OH.2 with its corresponding thermodynamic and transport databases (Frenklach. and the wall was isothermal. Consequently. a pressure of 10 atm was used in addition to atmospheric pressure. 1995) were used. CH2O. the effects of heterogeneous reactions should become more significant. H2O2. over a wide range of pressures and residence times. This increases concentrations. CH2 (s). but also in a better way simulates the situation in a lean-burn combustion engine. CH2OH. CH3. O.1 Inlet and boundary conditions Inlet conditions The gas-phase chemistry describing methane oxidation in air is quite complex and contains hundreds of reactions. As in Paper I. the reaction CH3 + CH3 + M = C2H6 + M and all the third-body efficiencies for C2H6 were removed from the reaction mechanism (also known as the C2 path of methane oxidation). The channel was axisymmetric in planar coordinates. There are two parallel oxidation paths in the methane system: (1) via the oxidation of methyl radicals. 5.2. C. 38 . 5.2 were used.4 and 0. A higher inlet temperature was needed to cause the autoignition of methane than was the case with hydrogen. Ar and N2) among 119 reversible reactions.. with an inlet velocity of 200 cm/s. The conditions for the calculations were changed slightly from when hydrogen was used as the fuel for the model. Wang.1 was set to 0. The inlet temperature was 1. O2. Goldenberg et el.

(c) φ = 0. cm 0.3 2 0.3 (d) 1210 2040 0.35 0.4 1210 0. p = 10 atm. Discretization The mesh used had 70 points in the transverse direction concentrated near the wall. Aghalayam. In addition to hydrogen. but removing the radicals H. 2000b. This would be a small simplification.3 0. Chen & Evans. dist. cm 2 0.1 0 0 (c) 2000 1400 1600 1800 0. 2002).2 1600 2000 1800 rad..1 0 0 1400 1500 1600 1620 0.4 0.25 0 Figure 5..1 0. as they are important chain carriers.1 1400 1600 0. cm 2020 1 axial dist. more grid points were needed to resolve the wallboundary layer.45 1210 0. OH and O would also slow down the methane oxidation in the boundary layer.6 Contour for T (K) for the Pt wall at Tw = 1.4.The same types of wall materials were used in Paper II as in Paper I.3 0.4 0.4. In some of the calculations.2 0. Mhadeshwar. typically requiring approximately 20 min of CPU time per calculation.2 axial dist. dist.2. 39 . (b) φ = 0. p = 1 atm. 1300 1210 13001400 1500 1620 rad. The mechanism shown in Table 5. and (d) φ = 0.. The chemistry is therefore generally not as well understood as that for hydrogen. Calculations were run on a Digital Alpha Unix machine. Aghalayam. and has a complex surface-coverage-dependence on the activation energies for desorption of adsorbed hydrogen and oxygen.200 K. Papavassiliou & Vlachos. this mechanism also involves CO and methane adsorption and oxidation.45 0. However the situation has improved significantly in recent years (Chou. Park & Vlachos.35 0.1).2 0. 2000. The catalytic combustion mechanism on Pt is considerably more complex than the corresponding one for hydrogen.4 0. The recombination mechanism was the same as that used in Paper I (see Table 5. where in (a) φ = 0. p = 10 atm.2.3 developed by Deutschmann and coworkers is the most frequently used mechanism published to date. p = 1 atm. cm 0.25 0 (b) (a) 1 0.

0×1013 3. Reaction (4) is equivalent to a sticking coefficient of 21 × T-1 * Forward order in Pt(s) = 1.5 213.3 b 40 .0 20.0b 0.0 (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) a H2+2Pt(s) →2H(s)* 2H(s) → H2+2Pt(s) H+Pt(s) → H(s) O2+2Pt(s) → 2O(s) O2+2Pt(s) → 2O(s) 2O(s) → O2+2Pt(s) O+Pt(s) → O(s) H2O+Pt(s) → H2O(s) H2O(s) → H2O+Pt(s) OH+Pt(s) → OH(s) OH(s) → OH+Pt(s) H(s)+O(s) = OH(s)+Pt(s) H(s)+OH(s) = H2O(s)+Pt(s) 2OH(s) = H2O(s)+O(s) CO+Pt(s) → CO(s)** CO(s) → CO+Pt(s) CO2(s) → CO2+Pt(s) CO(s)+O(s) → CO2(s)+Pt(s) CH4+2Pt(s) → CH3(s)+H(s)*** CH3(s)+Pt(s) → CH2(s)+H(s) CH2(s)+Pt(s) → CH(s)+H(s) CH(s)+Pt(s) → C(s)+H(s) C(s)+O(s) → CO(s)+Pt(s) CO(s)+Pt(s) →C(s)+O(s) The rate constants are formulated with Equation 2. implying that the wall effects are mainly of a thermal nature due to heat transfer.3 192.8×1021 1.7×1021 1.7×1021 3.0 ***Forward order in Pt(s) = 2.8 184.01b 3.0×1013 3. Pt(s) denotes a free surface platinum site and X(s) is an adsorbed species.4 48.s] 0. The sticking coefficients are formulated with Equation 2.0 **Forward order in Pt(s) = 2.0×1018 βa [-] Ea [kJ/mol] 67.84b 1.0b 1. Table 5.7×1021 0. Site density of the Pt-wall is Γ = 2.5.0b 1.71×10-9 mole/cm2.7×1021 3.0×1013 1.7×1021 0.7×1021 1. when using methane there are no observed differences between the wall materials at 600 K and 1 atm. Source: Deutschmann.7×1021 3.2 Results and discussion Compared with hydrogen.0×1013 1.5 17.7×1021 3.0 20.3 Surface reaction mechanism for methane oxidation on Pt. and viscous shear due to momentum transfer.5 20. Schmidt.9. Aa [cm.023b 1.2.2-60⋅[ZO] 40.5 105 20.2 125.7×1021 3.75b 1. Behrendt & Warnatz (1996).0 62. mol.8 11.4-6⋅[ZH] -0.046b 3.8×1021 0.31.

4 0. 41 . dist.4 200 0. p = 1 atm. the situation changes.35 0. When the pressure is increased to 10 atm.2.4 0. Only one tenth of the boundary layer develops by the time the reactions are complete. 5.3 0.35 (c) 2 0. and slowing them even more than the inert wall.. (b) φ = 0.3 0. (c) φ = 0. p = 10 atm. cm 2 50 150 100 0. 50 100 275 (a) 1 100 rad.8).4.1 0 0 300 250 360 1 axial dist.The chemical effects caused by the different wall materials are small but significant at 1.1 0 0 250 225 Figure 5.4.200 K. and (d) φ = 0. as can be seen by the contours in Figs. p = 10 atm..45 200 0..200 K.2 0. cm 0. where in (a) φ = 0. cm 0.6 and 5.3 0.7. dist.3 0.2 250 rad.2. with the Pt wall slowing the homogeneous reactions more than the recombination wall. The reaction zones become thinner as a consequence of the higher inlet concentrations and burning rates.25 0 (d) 300 250 0. cm 0. The increase in pressure does not alter the chemical wall-effects at the lower wall temperature. 5.4 150 200 0.45 200 0. However at the higher wall temperature.2 axial dist.1 100 360 225 0. These changes take place according to the same mechanism presented in Paper I (see the contour in Fig. the changes in the chemical walleffects are significant.1 0. p = 1 atm.7 Contour for u (cm/s) for the Pt wall at Tw = 1.25 0 275 (b) 0.2 0.

due to heat isolation and heat release.4 0 0. and in the right column Tw = 1.5 0.8 Contour for X CH .5 1 0. cm 0. dist. p = 10 atm.. give rise to the high wall temperature (1.0005 0..5 0. Christensen and Johansson (2000) supports the results obtained in this paper at the higher wall temperature. rad.45 0.01 0.02 0.45 0.2 Figure 5.4 0 0. This implies that catalytic flame quenching due to product inhibition would be responsible for the increased hydrocarbon emissions they observed. dist.The results obtained for the lower wall temperature correspond to the conditions in a lean-burn spark-ignition engine.200 K) used in Paper II.5 0.5 0.4 0 In 0. Recent work by Hultqvist.45 0.200 K.1 0.5 0.0005 Pt 0. where thermal effects are more significant and chemical wall-effects are less significant.2.2 axial dist. cm 1 Rec 0. cm Rec 0.4 0 In 0. where in the left column Tw = 600 4 K. φ = 0. cm rad.1 0.5 0. rad.01 Pt 0.. dist.4 0 0.5 axial dist.1 0.2 0.4 0 0.02 0.45 0..5 1 0. cm 42 .45 0.45 0.. The catalytic wall coating used by Hultqvist and co-workers would.

These oil layers can adsorb and desorb hydrocarbons (Heywood.1-3. that provides an axisymmetric case in planar coordinates. Instead of uniform inlet conditions for the temperature and species profiles. The trapped gas escapes the primary combustion process because the entrance to the crevices is too narrow for the flame to enter. There is a boundary-layer flow between two parallel plates located 2 cm apart. species and velocity vary strongly in the direction normal to the wall. The stationary flame is closer to the wall at a more downstream position. 6. This would be more pronounced in lean combustion as the flame is weaker than under stoichiometric conditions. It is assumed that a homogeneous charge is burned. If an observer was able to travel with the flow.0 mm thick) being left at the wall in each combustion cycle. 1988). As mentioned in the Introduction. and HCCI engines. Finally UHCs are believed to originate from the lubricating oil which leaves a film on the cylinder wall. The flame geometry modeled was different from that in the previous chapter (Papers I and II).6 Premixed Flame Fronts (Papers III and IV) In combustion applications such as internal combustion engines operating with homogeneous or stratified charges. The inlet profiles for temperature. Another source of unburned hydrocarbons (UHCs) is the unburned gas that is forced into crevices or narrow spaces connected to the combustion chamber. This resembles the situation in conventional sparkignition engines. the effects of a cooled wall can include the presence of a significant source of unburned hydrocarbons in the form of quench layers (0. a flame propagating toward the wall would be seen. the oxidation of a quench layer was investigated using propane as the fuel in the model. meaning that the initial fuel/air ratio is the same in the whole channel. this was the first study in which 43 . piston and perhaps the cylinder head.1). To the best of the author’s knowledge. The spaces between the piston. Modeling combustion with a stratified charge is more complex than modeling a homogeneous charge and is not treated in this thesis. The results from Papers I and II support the understanding that the thermal coupling between the flame and the wall is more significant when the fuel/air ratio is decreased. the oxidation of a quench layer has been investigated using propane and methane as fuels in the model. piston rings and the cylinder wall are the largest of these. 6. unburned hydrocarbons are formed as a consequence of local flame extinction. a premixed flame was placed close to the wall (see Fig.1 Quenching of premixed propane/air flames near an inert cold wall (Paper III) In Paper III. In Papers III and IV.

sidewall quenching was modeled with complex chemistry and using propane as the fuel in the model. wall temperatures of 400 and 600 K. internal combustion engines. a part of the CHEMKIN Collection.4 to 1. Grcar. The channel is symmetric around the center plane.1. This flame was used as the inlet condition for the boundary-layer 44 . Figure 6. PREMIX (Kee. Unlike hydrocarbon fuels with simpler structures—such as methane and ethane—the thermo-chemical and combustion properties of propane are similar in many ways to those of more complex practical fuels. where the inlet temperature is the same as the wall temperature.1 Inlet and boundary conditions Inlet conditions Calculations were performed for pressures of 1 and 10 atm. and fuel/air ratios ranging from 0. and many other environments.1 Geometry used in the two-dimensional flame calculations. 6. temperature and fuel/air ratio. detonations. Propane is an important combustion fuel (for example liquid petroleum gas) and is often used in studies of oxidation processes in laboratory burners. 1985).0. Smooke & Miller. was used to produce a premixed laminar flame for a given combination of pressure. The inlet velocity was 600 cm/s.

in which the stagnation configuration was used. Smooke & Baum (1996).25 1.E-01 1.95 Distance from wall. p = 1 atm.1) and an inert wall were compared. where results for the recombination wall (Table 5.E-06 1. The intervals of time the CPU needed to complete a simulation varied with the inlet conditions but were in the range of 50-80 min.20 0.E-04 1. 45 .15 0.22 0.E-03 1. This is most likely related to the flame geometry. This was not the case however in a study by Popp. A test was conducted at 600 K and φ=1.24 0.E-02 1. The simulations were run on a grid of 60-80 nodes in the transverse direction. No differences could be observed.2 Transverse profiles for T (red) and X C3H8 (blue) along the channel: φ = 1. The effect of flame geometry has been elaborated further in Paper IV. Boundary conditions The wall temperature is held fixed at a constant temperature.E-07 1.85 0. cm (1cm=wall) 1 0 cm 0.10 0.0. and T = 400 K. and the axial velocity is zero at the wall (non-slip wall condition). 2400 2200 2000 1800 Temperature (K) 1600 1400 1200 1000 800 600 400 200 0 0.8 0.E-05 1.E-08 Mole fraction C3H8 (-) Figure 6.0. The wall is assumed to be chemically inert for the low wall temperatures considered (400 K and 600 K).9 0. The arrow shows the direction of the flame at positions along the channel. The actual number of mesh points was determined from the inlet condition.calculation.

the thermal coupling between the flame and the wall becomes very significant. as the fuel/air ratio is decreased to 0. The arrow shows the direction of the flame at positions along the channel. Stoichiometric and near-stoichiometric flames are very strong.E-03 1.50 0. the quenching event is delayed as a result of the lower flame speed. As would be expected.2).6.30 0 cm 5 6 7.E-02 1.3). On the other hand. Increasing the wall temperature to 600 K drastically enhances the oxidation rate of the fuel in the boundary layer.6 or below. Therefore the flame can consume the unburned fuel at the wall within a short residence time.5. When the pressure is increased to 10 atm. the thermal coupling between the flame and the wall is small but significant for stoichiometric and near-stoichiometric mixtures (see Fig. 6.3 Transverse profiles for T (red) and X C3H8 (blue) along the channel: φ = 0. cm (1cm=wall) Mole fraction C3H8 (-) Figure 6. These flames have thicker boundary layers and lower flame temperatures. 1600 1400 Temperature (K) 1200 1000 800 600 400 200 0 0.5 10 15 1.E-04 1.1.E-01 1. 6. The residence time needed for burnout of the flame in the boundary layer under these conditions is significantly increased and the fuel diffuses out from the wall into the boundary layer (see Fig.70 0. p = 1 atm.E-06 1.E-05 1.90 Distance from wall. and T = 400 K.E-07 0. 46 .2 Fuel oxidation One major aim of this paper has been to examine the effect on thermal quenching of the flame when the fuel/air ratio is changed from stoichiometric to lean. and the thermal boundary layer is relatively thin.

Gardiner. These may be swept subsequently from an engine cylinder as pollutants. Davis and Wang (2000) has been used in order to determine the importance of the intermediate hydrocarbons (IHCs) in relation to the fuel for the total hydrocarbon emissions when the flame is quenched. These results are consistent with those of an earlier work where propane was used as fuel in the model. The intermediate hydrocarbons (IHCs) result from the incomplete combustion of fuel and air to CO2 and water.E-03 1.E-04 1.98 Distance from wall. 6. and therefore persist longer in the laminar sublayer.4). The IHCs are the dominant emissions for stoichiometric flames.E-08 1.96 0. Yang.0. p = 1 atm. Although the propane fuel (C3H8) is consumed.3 Intermediate hydrocarbons A detailed kinetic model by Qin.E-02 1.00 Mole fraction C3H8 and IHCs (-) Figure 6. but in the stagnation configuration (Kiehne et al. significant numbers of intermediate species exist near the wall after quenching at a stoichiometric fuel/air ratio (see Fig.90 0.E-06 1. 2400 2200 2000 1800 Temperature (K) 1600 1400 1200 1000 800 600 400 200 0 0. Lissianski. cm (1cm=wall) T C3H8 C3H6 CH2CO pC3H4 CH2O C2H4 C2H2 CH4 x=0.E-05 1.92 0.6. and T = 400 K.E-07 1.94 0. 47 .1.25 cm 1. 1986). The intermediate IHCs have a much slower oxidation rate than the fuel. Propane is a more complex fuel than for example methane.4 Transverse profiles for C3H8 and intermediate hydrocarbons at the axial distance 0. and should therefore indicate the greater importance of the IHCs for the overall emissions in quenching.25 cm: φ = 1.

E-05 1. cm (1cm=wall) x=7. this study supports the view that the effects observed are fairly general and independent of flame geometry. and T = 400 K.E-04 Mole fraction C3H8 and IHCs (-) 1.5.9 1 Distance from wall.5 is that the laminar flame speed decreases from ~ 60 cm/s at φ=1.2 Pressurized methane flames using different wall materials (Paper IV) The fuel used in the model in Paper IV is methane.1.E-06 Figure 6. As a consequence. fuel/air ratios and wall boundary conditions relevant to lean premixed gas-turbine combustors and HCCI engines.4 Conclusions In general.8 0.0 (1 atm) to only ~ 12 cm/s. When the fuel/air ratio is decreased the situation changes. 6. Both the fuel and the IHCs are important emissions. by using different pressures. In addition. Therefore the unburnt fuel is of more importance to the emissions in lean combustion.5). 6.7 0. Paper III has provided some new information on quenching in lean combustion. One obvious explanation for the overall slower oxidation at φ = 0. p = 1 atm. 6.5 Transverse profiles of C3H8 and intermediate hydrocarbons at the axial distance 7. the results for the stoichiometric fuel/air ratio agree with previous stagnation-configuration studies of flame quenching on cold walls. the oxidation rate of the IHCs increases.1600 1400 1200 Temperature (K) 1000 800 600 400 200 0 0.5 cm: φ = 0. 48 .5 cm T C3H8 C3H6 1-C4H8 CH2CO pC3H4 aC3H4 CH2O C2H4 C2H2 CH4 1. but at the same time the oxidation of the fuel significantly decreases (see Fig. Due to the excess of air. The objective of Paper IV was to characterize the kinetic and transport effects of the combustion in the boundary layer.

cm (1cm=wall) Figure 6.2.00 0. the full GRI Mechanism Version 1. leading to a CPU time interval of 20-50 min.05 0.4.2 0. the recombination mechanism included the adsorption of CH3 and CH3O. 0.E-03 1.80 Φ=0. This consists of 32 species.E-01 1. C2H6.6.5 and 0. C2H4. where the species C2H.90 0. p = 25 atm (inert wall).E-06 1.3 0 0.1 0.E-02 CH4 mole fraction (-) 1.1 Inlet and boundary conditions Inlet conditions To model the gas-phase chemistry.5. and the axial velocity was 0 at the wall. and HCCOH have all been added— compared with the reduced mechanism used in Paper II. However for the catalytic combustion of methane on Pt. 1996).34 0. The inlet velocity into the channel was 600 cm/s.35 1..95 Distance from wall. PREMIX was used to generate a premixed laminar flame for a given combination of pressure. C2H5.33 0.E-05 1.200 K. CH2CO. 49 .345 0. Boundary conditions The wall temperature was held fixed at a constant temperature of 1.5 p=25 atm In 0. The number of reversible reactions increased to 177. The site density of the reactive walls was 2. This flame was used as the inlet condition for the boundary-layer calculation. Calculations were performed for pressures of 15 and 25 atm. C2H3.E-07 1.6 were used. HCCO.E-04 1. 1. 1995).71 ⋅ 10-9 mole/cm2.E-08 0.2 was used (Frenklach et al. temperature and fuel/air ratio. Compared with the original mechanism.. C2H2. The simulations were run on a grid of 80-125 nodes from the line of symmetry to the wall. (2000) was used (similar to Deutschmann et al. The value of the unburned temperature was chosen to represent a typical value for the inlet of a gas-turbine combustor after the compressor stage and was set to 723 K.01 0.03 0. The same type of wall boundary conditions were used as those in Paper II. and fuel/air ratios of 0.6 Transverse profiles for the CH4 mole fraction at different axial positions along the channel (cm): φ = 0.85 0. the mechanism of Chou et al.

E-08 0. This difference may be explained by the different positions of the flames in these cases.E-06 1.37 0. the essential differences between the results of Papers II and IV..43 0.03 0 0.E-04 1. However.46 0.2. Therefore no recombination is observed on the wall.7 Transverse profiles for the CH4 mole fraction at different axial positions along the channel (cm): φ = 0. which also exhibits recombination on the wall combined with the release of water as a product of the catalytic combustion (Forsth et al.7. In regard to the chemical wall-effects. catalytic flame quenching (Pt wall) is very significant and illustrated for methane conversion in the boundary layer in Figs.5 p=25 atm Pt 0. cm (1cm=wall) 1.45 0.E-02 CH4 mole fraction (-) 1. 1999). the flame was adjacent to the wall and radicals in the flame could easily diffuse to the wall and recombine.80 Φ=0.00 Figure 6.5.E-07 1.95 Distance from wall.E-01 1. while in Paper IV.35 0. for a premixed flame propagating towards the wall there is a considerable distance between the flame and the wall through the unburned fuel/air mixture that may provide strong resistance to diffusion of the radicals to the wall.6. and it can therefore be described as a short-range phenomenon.3 0. the recombination wall had a slowing effect compared to the inert wall.2 Effect of flame-geometry It is interesting to compare the results obtained in Paper IV with those obtained in Paper II.465 0.E-05 1. 6.E-03 1.1 0. The same would happen in the Pt wall case.6-6.90 0. p = 25 atm (Pt wall).85 0. The Pt wall provides significant slowing down of the boundary layer combustion compared with the chemically-inert wall.05 0.4 0. there were no recombination-wall effects.01 0. In contrast to recombination effects. The effect of generating water as a product 50 . In Paper II.2 0. 1.

8 Transverse profiles for the C2H6 mole fraction at different axial positions along the channel (cm): φ = 0. In Paper II.8 0. cm (1cm=wall) 0 0.E-04 C2H6 mole fraction (-) 1. 6.E-06 1.95 1 Distance from wall. since in an HCCI engine.E-08 0.2.from the catalytic wall could therefore be said to be a long-range phenomenon. The results of Paper IV provide further support for this explanation.3 0.9 0.8 and 6.2 0. (2000) were attributed to the third-body effect of water on the radical recombination reaction: H+O2+M → HO2+M.33 Figure 6. This could be applied to an HCCI engine with a catalytic wall-coating in the combustion chamber.01 0.5 p=25 atm In 0. This would further explain the increased emissions of unburned hydrocarbons observed when using a catalytic wall-coating.E-07 1.32 0.5. and concludes that the full GRI gas-phase mechanism should be used when simulating higher pressures. 6.2 (2CH3 (+M) → C2H6 (+M)) would itself add to the formation of water by catalytic combustion. This is illustrated in Figs.1 0.05 0. independent of flame geometry.9.85 0.E-05 1.E-09 0. the situation with a flame front separated from the wall by a thin layer of unburned gas would be rather likely to occur. p = 25 atm (inert wall). 51 .31 0. where the formation of ethane in the near-wall region is more significant with the Pt wall than the inert wall.E-03 1.03 Φ=0. the increased fuel emissions found by Hultqvist et al.3 Effect of gas-phase chemistry At elevated pressures the effect of the fall-off/recombination reaction described in Section 2.345 1. 1.

2. Since variations in geometry on the submillimeter scale may well cause dramatic changes.2. 1.E-03 1.4 0.39 0. 6. This suggests that the wall effects are complicated and difficult to clarify using ordinary flame experiments. However.45 1.E-06 Φ=0.03 0.8 0.2 0. This means that the rate of flame propagation in the boundary layer decreases with the fuel/air ratio. cm (1cm=wall) Figure 6.9 Transverse profiles of the C2H6 mole fraction at different axial positions along the channel (cm): φ = 0. Zhang & Williams (2001) anticipated the importance of homogeneous C2 chemistry for explaining kinetic inhibiting effects from experimental results. 52 .5.37 0. which is in agreement with the findings in previous papers.05 0.01 0.43 0.9 0.E-07 0 1. then when conducting these sorts of experiments.E-04 C2H6 mole fraction (-) 1. 6.5 p=25 atm Pt 0.5 Discussion Another point that ought to be made about the results in Paper IV is that the comparatively small variations in the system seen in both Papers II and IV led to rather strong effects.95 1 Distance from wall.85 0.4 Effect of fuel/air ratio The thermal coupling between the flame and the wall increases as the fuel/air ratio decreases. their results were not supported by calculations. submillimeter geometrical resolution is necessary.E-09 0.Dupont.35 0.E-05 1. p = 25 atm (Pt wall).3 0.1 0.E-08 1.

and work is currently in progress to commercialize gasified biomass (biogas) produced from partial oxidation/pyrolysis of biosolids as a primary fuel for combined heat-and-power generation. 7. H2S and alkalis). trace components (HCN. To simplify the modeling.0 5.027 41-50 N2 0 O2 9-14 H2 14-18 CO 11-20 CO2 5-7 CH4 10-12 H2O 0.7 Reduction of Fuel-NOx in the Catalytic Combustion of Gasified Biomass (Paper V) The last paper in this series (Paper V) deals with the formation of fuel-NOx in the catalytic combustion of gasified biomass in gas-turbine applications.3 2. the complex chemistry has to be used in order to understand the combustion and to design the combustor. Table 7. Similarly to the flame-wall modeling described in Chapters 5 and 6.5) 69.1 Composition of gasified biomass (mole-%). The composition of biogas varies with both the method of gasification and the composition of raw biomass material.1 3. 53 . The aim here has been to design the hybrid combustor to minimize the formation of fuel-NOx. tars and aerosols.0 0.1 Gasified biomass The potential problems of CO2 emissions and the “greenhouse effect” associated with it have made biomass (CO2 neutral) an interesting alternative energy source.02-0. The reactor modeled was a hybrid type—where only part of the fuel is combusted catalytically in the monolith and the rest in a homogeneous zone.8 1.7 4.0 11. The compositions shown in Table 7.0 0.0 15.9 0 10.8 15. these compounds have been omitted in this study. Species Typical real gasified biomass Synthetic gas* 44.1 therefore represent an attempt to summarize the distribution of the main components from biomass using air as gasification medium.0 14.3 NH3 *Compositions used in the calculations Biogas also contains C2-C12 hydrocarbons.4 3.1 Synthetic gas mixed with air (λ=2.

and the second stage lean in order to lower the temperature. 7. exhaust gas recirculation (EGR). there is not enough oxygen available to oxidize the N atoms. lowering thermal NOx levels. Nevertheless. It is reasonable to assume here that future emission standards will be more stringent for combustors fired with biogas. this must be accompanied by secondary methods. However the formation of other harmful substances such as HCN and NH3 increases dramatically. calculations have shown that a minimum of the sum of total fixed nitrogen (NO + HXN + NH3) is achieved at stoichiometries between 60 and 80% theoretical air. A similar effect is achieved by the addition of water vapor into the combustion zone. This technique has received significant attention in relation to gas-turbine applications because it is cost effective and it is possible to burn mixtures below the flammability limits. While the catalytic combustion of natural gas has been developed for the 54 . Reburning is a chemically-complex process in which NO is abated using fuel as reducing agent. The use of stage combustion to minimize fuelNOx in gas-turbine combustion of biogas calls for innovative ideas in the design of the gas-turbine combustor. In exhaust gas recirculation (EGR).The N bond in the biomass that is converted to NH3 during gasification is not entirely but to a significant degree converted to NOx in the combustor. The EGR method reduces thermal NOx formation but is not relevant to fuel-NOx formation from NH3. The first stage is undertaken rich in order to minimize the amount of NOx. Dam-Johansen & Miller 1998). 1999). This reduces the flame temperature and thermal NOx formation (Forzatti and Groppi. Therefore the combustor has to be designed to lower NOx formation. The process involves partial oxidation of the reburning fuel under fuelrich conditions as well as reactions between hydrocarbon radicals and NO and subsequent conversion of the intermediate nitrogenous species (Glarborg. such as selective non-catalytic reduction (SNCR) or selective catalytic reduction (SCR). and staged combustion. Alzueta. resulting in significant pollutant emission.2 Primary methods for reducing NOx Primary measures used in the reduction of NOx emissions are re-burning of NO. The combustion is stoichiometric for the overall process and complete burnout achieved. To achieve ultra low NOx emissions through reburning. When the combustion is rich. This enables the minimizing of emissions of total fixed nitrogen (TFN) by using staged combustion. 7. exhaust gas is recirculated through the combustion process where it acts as an inert gas and reduces the flame temperature.3 Catalytic combustion One alternative to the above methods is to use high-temperature catalytic combustion.

1 Principal design of the hybrid-catalytic gas-turbine combustor.5 MPa Combustor Bypass air Exhaust Compressor Turbine Air. 1. so that only part of 55 . Here a hybrid-catalytic gas-turbine combustor has been modeled. As biogas from air-blown gasifiers is a low heating-value gas (~ 5 MJ/kg). Biogas (CH4. H2. mathematical simulation with detailed combustion kinetics to investigate the possibility of obtaining fuel-NOx reduction in a hybrid catalytic gas-turbine combustor. CO. which may reduce NO in reburn-type reactions. CO2. NH3. These agents are: (i) ammonia (NH3) that may react with NO under conditions favorable to SNCR. the predominant channels have to be passive (blue color) compared to the active channels (red). the catalytic combustion of gasified biomass may have other objectives. 7. catalytic combustion may be more attractive than conventional combustion due to its higher combustion stability and safer ignition. including fully-catalytic and hybrid-catalytic combustors. and N2) Monolith Homogeneous zone T ~ 1573 K 753 K. The aim of this work was to use for the first time. The approach adopted was to use the potential reducing agents in the biogas to convert NO to N2 in the homogeneous zone. H2O.purpose of achieving ultra-low emission of NOx. To avoid homogenous ignition of the biogas in the monolith. featuring both active and passive channels in the monolith. 1 atm Figure 7. or (ii) the fuel components.4 The model There are different designs of catalytic combustors.

5. & Forzatti. Kee & Miller. which is a typical inlet temperature for the catalytic section of hybrid combustors (Groppi et al. Tronconi. 7. 2000)—and the assumption made that the homogeneous zone can be modeled with a plug-zone model.31. NH2(s) + Pt(s) → NH(s) + H(s) 3. the overall excess-air ratio was 2. Aa Ea [mol. 56 . where λ denotes the excess air ratio. To obtain a final gas temperature for the turbine of ~ 1573 K. Belloni. The gas-phase chemistry has been described with a detailed chemical-kinetic model for hydrocarbon-ammonia-nitric-oxide interactions (Glarborg. 1995). NH(s) + Pt(s) → N(s) + H(s) 21 3. It has been assumed here that there is laminar flow. thereby controlling the temperature profile. Perfect mixing after the monolith may be a simplified hydrodynamic assumption.7×10 20 4. Loffler & Shoji... Kee et al.s] [kJ/mol] 0 0. the use of biogas with its high H2 content lowers the light-off temperature for the catalyst in the active channels. b The sticking coefficient is formulated with Equation 2.1b 1. The need for sophisticated catalyst materials for the catalyst segment can be avoided due to the lower temperature reached in the active channels using a catalytic coating. Alzueta. The subsequent homogeneous zone has been modeled with SENKIN—part of the CHEMKIN Collection (Lutz. In addition. 1988. and the air and fuel were mixed to different λ-values.7×1021 20 3.9. Groppi.cm. Schlatter. 1995). * It is assumed that NH3 is completely converted to NO.0×1013 20 5.7×1021 20 3. The inlet temperature to the monolith was 753 K. N(s) + O(s) → NO(s) + Pt(s) 1. a The rate constants are formulated with Equation 2. Yee. However to avoid homogeneous ignition in the passive channels.5 MPa and 1 m/s respectively.2 The reaction mechanism for NH3 oxidation on Pt. and have to be addressed in forthcoming studies. Reaction No. The hybrid gas-turbine combustor design is illustrated in Fig. negligible heat dispersion and uniform distribution of the gas properties at the inlet to the monolith. The monolith has been modeled as a single two-dimensional channel using CRESLAF. DamJohansen & Miller. NO(s) → NO + Pt(s) * Pt(s) denotes a free surface platinum site and X(s) is an adsorbed species. This consists of 460 reversible reactions among 66 species.71×10-9 mole/cm2. 1998). 1995. NH3 + 2 Pt(s) → NH2(s) + H(s) 2.the fuel is combusted catalytically (Dalla Betta.1. Inlet conditions The pressure and velocity after the compressor were 1. Table 7. Site density of the Pt-wall is Γ = 2. This in turn enables the combustor to run without a preburner. the ratio of active to passive channels has to be adjusted.

5E-04 4.Boundary conditions The wall temperature profile in the non-adiabatic monolith has been constructed from the corresponding adiabatic case.6334 1.6335 Residence time (s) Figure 7.6337 NO 0. A significant amount of NO is formed by the oxidation of NH3 before all oxygen is consumed. for example where 50% active channels would give a 50% adiabatic temperature rise in the monolith.2).3). Kristensen.6336 16 ppm 0.20 102 ppm 33 ppm N2 0.0E+00 0. when the combustibles (from the passive channels) are oxidized.0E-04 3.5E-04 1.00 0.5 Lean primary λ First the potential of a lean primary excess-air ratio of 2. 1997).0E-04 1. The heterogeneous reactions in the active channels in the monolith have been assumed to take place on a polycrystalline Pt-surface (see Table 5.5E-04 2. 7.40 0.6339 0.5E-04 NO Mole fraction (-) 3. This results in generating the adiabatic temperature to the turbine without the need for providing additional air. raising the temperature above the window for the SNCR reactions.0E-05 0.0E-04 2. The optimum temperature decreases with an increasing concentration of combustibles (Alzueta. Instead of reacting with NO. the NH3 is largely oxidized to NO. An NH3 subset has been added to this mechanism (see Table 7. the adiabatic temperature rise is significant.6338 N2 Mole fraction (-) 0. The NH3 oxidation generating the product NO has been assumed to take place at the same surface site as the oxidation of methane.80 1.0E-04 5. The NO is subsequently reduced to N2. CO and hydrogen.20 0. Glarborg & Dam-Johansen. These reactions are very temperature sensitive.00 0. Røjel.2 NO and N2 profiles as functions of residence time in the homogeneous zone after the monolith: The inlet composition is taken from Table 7. However. 57 .60 0. The aim with a lean operation was to use the SNCR reactions to reduce the formation of NO.5 was estimated. 4.3.

8 the situation changes.5 cm.000000 0.7.034000 0.000537 0.000002 0. and the reduction improves with longer residence times.000012 0.023619 0. The results from the homogeneous zone after the monolith are shown in Fig.161000 0.088837 0.8.000089 0.000000 0. The temperature rises very rapidly in the main reaction zone.607006 0.000020 0.6 Rich primary λ If the primary excess-air ratio is decreased to 0.1) .026900 0.080200 0. length=1.096400 0. 58 (7. HNO+H→NH.3 Estimated composition (mole fractions) of the gas at the exit of the monolith: primary λ=0.007600 0. active channels/passive channels=1/6.3) (7.4) (7.059900 0.072346 0.2) (7. 7.000026 A reaction path analysis in the high temperature regime (>1900 K) reveals that there are two major channels for consumption of NO in the absence of oxygen (see also Fig.000000 0. The NO is subsequently reduced to N2. Tin=753K.077087 0. First a significant amount of NO is formed from the oxidation of NH3 before all oxygen is consumed.044074 0.000004 0. NH+NO→N2O+H.000448 0. where all methane and NH3 are consumed.000000 Passive channels 0. Table 7. 7.053100 0.3): I: NO+H→N+OH and N+NO→N2+O II: NO+H+M→HNO+M. uin=1 m/s.081035 0.000031 Species N2 O2 H2 CO CO2 CH4 H2O NH3 NO C2H6 H2O2 CH2O After mixing 0.006020 0.075900 0. and then it has an almost constant value.612418 0. Active channels 0.000024 0.152000 0.2.000525 0.000002 0.638839 0.5) (7.

Millera & Bilbao.7) (7.6) The reduction of NO is facilitated by the presence of the unburned fuel components CO and H2. Bypass air is added downstream of the rich primary zone to burn out the remaining CO and H2. The bold arrows indicate the main path for the conversion of N in nitrogen compounds to molecular N2. as they produce the H radical needed in the two channels (Glarborg. Alzueta. 59 . 7. 2000). +M +NO NO +H +NH +H2O. Dam-Johansen.3 Reaction flow analysis of the homogeneous plug-flow zone at fuel-rich stoichiometries ( T > 1900 K). The final reduction efficiency then reaches around 95% (see Figs.8) NNH +NO +NO NH +H +NO +H2O. +H2 N2 N +NO Figure 7.4).+H N2O +NO HNO +H. H2 NH2 +NO +NO +H +H+M +H+N2 +OH. and CO+OH→CO2+H H2+OH→H2O+H .1 and 7. (7. Kristensen. +CO.and N2O+M→N2+O . (7.

A long residence can be accomplished with a combustion chamber of a tubular design (Perry’s. and avoiding formation of thermal NO when adding the bypass air.8. Therefore.4 Temperature. additional catalyst segments with these catalysts located before the homogeneous zone would be worth testing.0E-06 H2 1370 0 0.7. H2. The idea would 60 . 1. The work by Burch and Southward (2001) indicates that catalytic materials such as Ir and Rh could selectively reduce the NO through CO on the catalyst surface.7 Discussion The combustion chamber designs studied in Paper V have been simulated under realistic conditions with respect to temperature and pressure for gas turbines. which means an overall reduction of 95% for a primary λ of 0.0E-04 1.0E-02 1. However.005 Mole fractions (-) CO 1470 Figure 7. The temperature in the homogeneous zone should be high enough for fast NO reduction. Close to 13 ppm NO remains after combustion.2.002 0. Practical issues that must be addressed further for this design of the combustor include the use of a wall material in the homogeneous zone that can stand the high resulting combustion temperatures (> 1900 K).0E-07 0. 7. As can be seen in Fig. 1999).003 0. CO.001 0.0E-01 1570 T Temperature (K) 1520 1. and NO profiles after the addition of air. the residence time in the homogeneous zone after the monolith is fairly long.0E-03 NO 1. A primary λ of 0. even higher reduction efficiencies may be achieved if an optimum primary λ can be found that is rich enough to keep NO low and lean enough to avoid excessive HCN formation.8 gave a NOx reduction efficiency of 95%.0E-05 1420 1.004 Residence time (s) 1. but low enough to avoid thermal NOx production.

8 Conclusion The conclusion that can be drawn from the paper is that it is possible to significantly reduce the fuel-NOx formed due to the presence of ammonia in the gasified biomass by staging the air rich-to-lean in a hybrid catalytic combustor.be to already achieve a reduction of NO in the catalyst and thereby decrease the residence time required in the subsequent homogeneous zone. 7. No reactants/reductants have to be added. The advantage with the hybrid-reactor concept is that only part of the fuel is catalyticallyconverted in the monolith and thereby provides safe ignition of the low-heating value gas. 61 . The use of passive channels in the monolith avoids homogeneous ignition in the active channels. as they are already part of the incoming gas.

it was found that a catalytic wall in addition to catalytic flame quenching also contributed to the formation of unburned hydrocarbons. however at a higher pressure and wall temperature. a more detailed mechanism for the gas-phase methane oxidation had to be used. • For the first time. Given this to be true. and this is more pronounced at higher pressures. Intermediate hydrocarbon emissions are more significant with stoichiometric flames.6). Detailed chemical kinetic models have been found to be very important in explaining different kinetic and transport effects related to near-wall combustion. However changing the flame geometry does not affect catalytic flame quenching. premixed propane/air flames have been modeled using complex chemistry in a laminar boundary layer flow (Paper III). a long-standing practical combustion problem. indicating that radical quenching by heterogeneous reactions is a short-range effect. • Catalytic flame quenching: the mechanism describing this phenomenon has been outlined using hydrogen as the fuel in the model (Paper I). 62 . The modeling work done in this thesis has contributed to the understanding of flame quenching. To account for this. indicating that this is a long-range effect (Paper IV). Another application of detailed kinetic modeling includes advances toward the reduction of emissions of oxides of nitrogen (NOx) from combustors. The wall facilitating radical destruction produces no effects compared with a completely inert wall. where the propagation in the boundary layer was significantly retarded.8 Conclusions The work presented in this thesis is based on the assumption that all input data in the form of mechanisms and kinetic and thermodynamic data have been well established in previous experimental work. A distinction can be made between strong stoichiometric flames and weaker flames (φ ≤ 0. In Paper IV. it was shown theoretically that fuel-NOx formation could be significantly reduced through a new design of a hybrid catalytic gas-turbine combustor fueled with biogas. • Having a premixed flame as an inlet condition instead of uniform properties (leading to autoignition) impacts on the chemical wall-effects. The same inhibition (flame quenching) is also present when methane is used as fuel (Paper II). The complexity of the kinetic mechanism used is important. mathematical simulation should be a powerful method for increasing our understanding of the wall effects in industrially-interesting combustion systems. In Paper V. while unburned fuel is more significant with leaner flames.

such as modeling turbulent reactive boundary layers. the fuel-NOx reduction in the hybrid catalytic combustion of biogas results obtained in Paper V could be further elaborated by both modeling and experimental work. Another flame geometry that would be very interesting to study is stratified charge combustion. Software such as STAR-CD coupled to the CHEMKIN Collection would be suitable for this purpose. Radiation from the flame to the wall has not been included in the mathematical model used in this thesis.1 Looking ahead It would be very interesting to be able to confirm the results obtained in this thesis using computational fluid dynamic (CFD) modeling. The problem set-up used in this thesis with a homogeneous charge would have to be changed somewhat to model the combustion of a stratified charge. However. Finally. which would address the relative importance of turbulence for the wall effects. radiation may influence the near-wall combustion and could be a topic for further research. 63 .The results presented in this thesis imply that laminar flow models accompanied by complex chemistry models are a reasonable approximation to use to model near-wall combustion phenomena. 8.

Project Leader of the CeCoST Turbulent Combustion project. for fruitful discussions leading to new insights into the near-wall combustion problem that I could use in my research. and the Swedish Energy Agency is gratefully acknowledged. and for a really enjoyable time in Denmark in the spring of 2002. especially Britt-Mari Rydberg and Monica Söderlund. KTH. at the Technical University of Denmark. the inter-departmental diploma work was most fruitful. for sharing his profound knowledge in the field of Chemical Kinetics. I wish to thank Dr Lars-Erik Eriksson. I wish to also thank Professor Marcus Aldén at the Center of Combustion Science and Technology (CeCoST) for granting me the scholarship to visit DTU. Thanks also to everyone else in my department for assisting with all the practical matters during the completion phase of this work. Professor Pehr Björnbom for his invaluable supervision. I am also very grateful to Associate Professor Lennart Edsberg from the Department of Numerical Analysis and Computing Science. the Center for Environmental Science at KTH. the Center for Combustion Science and Technology (CeCoST). Moreover. I wish to also thank the members of the reference group in the High-temperature Catalytic-combustion Project (P910).Acknowledgments Firstly I want to thank my supervisor at KTH. I wish to thank present and former colleagues at Chemical Reaction Engineering and Chemical Technology at KTH. The financial support received from the Swedish Foundation for Strategic Research. for the important role he played in performing the calculations and post-processing the results. Thanks also to Professor Peter Glarborg from CHEC (the Combustion and Harmful Emission Control research center). 64 . for his generous co-operation in the Fuel-NOx paper.

both in Sweden and America. 65 .Last. for their support and hope that they too enjoyed my research journey culminating in the completion of this thesis. but by no means least. I would like to thank my family.

150. Røjel. P.R Westmoreland. Dam-Johansen.E.” Proc. Johansson. Arrhenius. Vlachos. 2017 (2000a). and B. Glarborg.” Proc. 26. and D. 2nd Ed.” J Catal. Southward. 286 (2001). Einewall “Homogenous Charge Compression Ignition (HCCI) using Isooctane. Aghalayam. John Wiley & Sons. New York (2002). Y. R. Alzueta.. P.W. R. 198. P. 46(10). W.G.H. and P. Bird.. Inst.L.” AIChE J. 2. Aghalayam P.. Lightfoot. 226 (1889).” Society of Automotive Engineers. 4. Inst..References Aghalayam. 1331 (2000b).H. Park.G Vlachos.. ”Laboratory Study of the CO/NH3/NO/O2 System: Implications for Hybrid Reburn/SNCR Strategies. and P. P-A. S. 28. and D.” Comb. B... and K.. D. 1763 (1996). 11.” Z Phys Chem. M. Kristensen.” Energy & Fuels. 515 (1998). J-Y. Combust. Sci. Vlachos.. Y.J. “Construction and Optimization of Complex Surface Reaction Mechanisms.. 27. Chou. Transport Phenomena.B. Theory and Modeling.. and G. Combust. “A Detailed Surface Reaction Mechanism for CO Oxidation on Pt. Tech. Stewart. Vlachos. and E.” Combust. Sci. C-P.. “The Nature of the Active Metal Surface of Catalysts for the Clean Combustion of Biogas Containing Ammonia. H.G. Bechtel. Evans.. R. and J. “The Role of Radical Wall Quenching in Flame Stability and Wall Heat Flux: Hydrogen-Air Mixtures. 27 (2000).K. Chen. Burch.. Bui. M. P-A. 66 . 716 (1997). Tech.N. ”Über die Reaktiongeschwindigkeit bei der Inversion von Rohrzucker durch Säuren. Park. “Numerical Studies of Methane Catalytic Combustion Inside a Honeycomb Reactor Using Multistep Surface Reactions. Blint.. and D. Bui. paper SAE 97-2874 (1997).K. Ethanol and Natural Gas.U. P..G.” Combust. “Flame-Wall Interface: Theory and Experiment. 87 (1982). “Homogeneous Ignition of Hydrogen-Air Mixtures over Platinum. Christensen.G.

Boundary-Layer Flow in Cylindrical or Planar Channels”. Prop. Hultqvist.E. Kee. R.G. 67 .A. and J. M. Schmidt. Miller. Dalla Betta. A. Moffat. 425 (1984).J. R. Electrochem. 133. and B.” Catal Today. M. J.J. F. “Demonstrating the Multi Fuel Capability of a Homogeneous Charge Compression Ignition Engine with Variable Compression Ratio. “Flame Quenching at the Walls of an Internal Combustion Engine. M. “CO Emissions in Lean Premixed Combustion.. Power... ”Numerical Modeling of Catalytic Ignition. H.K. M.M. ”CRESLAF (Version 4. paper SAE 1999-01-3679 (1999). 1747 (1996). Inst.. Chemically Reacting. Combust. Loffler. 26. 26. Sandia National Laboratories Report No.J.. O. Kee. “A Mathematical Model of the Coupled Fluid Mechanics and Chemical Kinetics in a Chemical Vapor Deposition Reactor. Warnatz. S. Johansson.. ”SURFACE CHEMKIN-III: A Software Package for the Analysis of Heterogeneous Chemical Kinetics at a Solid Surface-Gas Phase Interface”.. Coltrin. 1144 (1992).” Proc. Rupley. R.K. Behrendt. and J..” J. Inst. 329 (1995). 23. 8(6). Correa. SAND968217 (1996). Yee.. W. Kee. Chem. and E.” Int.0): A Fortran Program for Modeling Laminar. Coltrin. Soc. M. “Catalytic Combustion Technology to Achieve Ultra Low NOx Emissions: Catalyst Design and Performance Characteristics.M.. M. R. Coltrin.. and J. D. Sandia National Laboratories Report No. “Surface Chemkin: A General Formalism and Software for Analyzing Heterogeneous Chemical Kinetics at a Gas-Surface Interface. T. Schlatter.Christensen. Shoji. Kee. F. R. 1111 (1991) Coltrin..E. Kin. and F. Miller. SAND93-0478 (1993). Combust. Electrochem.. 1206 (1986). Deutschmann.E.” J.J. and F.A. 131. Soc. A. “A Mathematical Model of Silicon Chemical Vapor Deposition – Further Refinements and the Effect of Thermal Diffusion. R. Coltrin. D. R. J. M.” Proc. Meeks. Daniel. Rupley. 6.. J.” Society of Automotive Engineers. Rupley.A.E. 886 (1956). E.C.” J.. M. Kee.

M. Ezekoye. S.. Tech. Eng. Alzueta. U. Flame.” Catal. and J.” Trans. 2659 (2001). Flame. p.” Combust.U.. Forsth. Sci. 28. Combust. “Extinction of Strained Premixed Flames with Complex Chemistry.Dupont.K. Greif.T. Gardiner. GRI-Mech – An Optimized Detailed Chemical Reaction Mechanism for Methane Combustion. Giovangigli. C.M. and Z. “Catalytic Combustion for the Production of Energy. Goldenberg. and D. 115. Glarborg. and M. Persson. 144 (1999). “A Comparison of One and Two Dimensional Flame Quenching: Heat Transfer Results. Lissianski. O. and J.H. H. Flame. 11 (1993). Smooke. D.” Chem.D. Department of Energy. “Increased Surface Temperature Effects on Wall Heat Transfer During Unsteady Flame Quenching. and A. 68 . “Wall effects on the Propagation and Extinction of Steady. P. 197 (1977). ”Kinetic Modeling of Hydrocarbon/Nitric Oxide Interactions in a Flow Reactor. H. Strained. Sci. Bowman. Laminar Premixed Flames. 23 (1987). and A.C. 54.. V. 119. Hanson. 237 (1997) EIA.A.. 24. Ezekoye. Egolfopoulos. C. 109. M. Keck.. Washington (2000). Gas Research Institute Report No.N. “International Energy Outlook 2000.. R. K..” Energy Information Administration.” Proc. 165 (1999). Wang. M. Lee. Williams.C. ASME: Heat Transfer in Fire and Combustion Systems.. 53. Zhang. Dam-Johansen. Rosèn. Today. J. 1465 (1992). P. G.L. O. Forzatti.S. G. 1 (1998). 250. R.R. Ferguson. GRI-95/0058 (1995). Greif. F. Golden. Gudmundson F. Zhang. 56. “The Influence of a Catalytic Surface on the Gas-Phase Combustion of H2+O2. Inst.. Zhang..” Combust.” Combust. W. Smith.” Combust. Flame.. Miller. “Experiments and Simulations of Methane Oxidation on a Platinum Surface. and Groppi. M. and R.. F.. Frenklach. “Laminar Flame Quenching and its Application to Spark Ignition Engines.P.” Combust. V. V.

Ljungstrom. “The Application of Ceramic and Catalytic Coatings to Reduce the Unburned Hydrocarbon Emissions from a Homogeneous Charge Compression Ignition Engine..J. H.” Sandia National Laboratories Report No. M. Glassman. SAND80-8003 (1980). ”Flame Quenching in Front of a Cold Wall under Two-Step Kinetics. Internal Combustion Engine Fundamentals. and P.M. R.. J.. Van Nostrand Reinhold...Glarborg. Sci. N. Belloni. Grcar. “Analysis of Multidimensional Models of Monolith Catalysts for Hybrid Combustors.B. McGraw-Hill (1988). 2250 (1995). Peters. E.. A. S. Combustion. Adomeit.D. Implications for Reburning with Gasification Gases. Forzatti. Heck. San Diego (1996). 14. Smooke. Dam-Johansen. Groppi. ”Nitric Oxide Reduction by Non-Hydrocarbon Fuels. and R. Grcar. M..A Miller. D. B.” AIChE J. J.” Energy & Fuels. 157 (1981). ”Kinetic Model and Experimental Results for H2O and OH Production Rates on Pt. and T. Jefferson. Tronconi. SAND91-8230 (1991). Kasemo. SAND85-8240 (1985). P. ”Quenching of Laminar Iso-Octane Flames at Cold Walls. Heywood.” Society of Automotive Engineers. New York. Hasse. 828 (2000). J. 3rd Edition.J. Rosén.. M. A.. Academic Press. N. 122. and H. W. Peters. G. Fortran Chemical Kinetics Code Package" Sandia National Laboratories Report No.J. Kee. “A Fortran Program for Modeling Steady Laminar One-Dimensional Premixed Flames. Transportable. Hellsing. 851 (1987). and J.. A. Paper SAE 2000-01-1833 (2000). p. Flame. 41. Kristensen.A Dwyer. Hocks. C. A. Farrauto. Hultqvist. Bilbao. ProblemIndependent.” Combust. “The Twopnt Program for Boundary Value Problems.U..G. 189/190. Bolling. 41. Johansson. and R.. J.” Surf. and G. and T. Christensen. K.F. Flame. B. Miller. I. Catalytic Air Pollution Control – Commercial Technology.. Kee. Alzueta. "Chemkin: A General-Purpose.” Combust. 192 (1995). Wahnstrom. Millera.F. 69 . 117 (2000).” Sandia National Laboratories Report No. R. A. and B.. P. M.

" Sandia National Laboratories Report 87-8248 (1988).Warnatz. Mirsky. Dixon-Lewis. Inst. R. Combust. T.E. “An Experimental Study of the Kinetics of OH and H2O Formation on Pt in H2 + O2 Reaction. and J. Kurkov. Lindemann. A. 23. Miller. M.J. Exekoye.K. F. Farad.. R.F.A.E.M. F. A. “The Significance of Intermediate Hydrocarbons During Wall Quench of Propane Flames. Warnatz. C. J.6. Ljungstrom. R.” Trans. Moffat.. E.E. Matthews. M. A. Stewart. O.A. M. 17. Lutz.C. Meeks.. Coltrin. Sawyer. Kasemo.H. B.E. Kiehne. ”CHEMKIN-III: A Fortran Chemical Kinetics Package for the Analysis of Gas-Phase Chemical and Plasma Kinetics”.J. 441 (1990). J.. Meeks. Rosén. and H. Kee. J. "SENKIN: A Fortran Program for Predicting Homogeneous Gas Phase Chemical Kinetics with Sensitivity Analysis.R.. S.. F. Soc. Release 3. and E.. SAND86-8246 (1986). Sci. Miller. and D. Reynolds. Rupley. Kee. Kee.. Rupley. Larson.” Surf. “An Analysis of the Mechanism of Flame Extinction by a Cold Wall. Petzold. 63 (1989). Lu.Kee. 12. L.H.J.” Proc. SAND87-8215B (1990). J. H. Wahnstrom. Dixon-Lewis. A. and F. Smooke.” Proc.M. R. Wang.P. San Diego (2000).A. Combust.K.M. 21.D. Fridell. 216. CHEMKIN Collection.E. Caracotsios. T.A. E. and J.Grcar. G. Miller. G.A.. Miller. G..M Rupley. “A Fortran Computer Code Package for the Evaluation of Gas-Phase Multicomponent Transport Properties.” Sandia National Laboratories Report No. 598 (1922).E. R.. A. 615 (1969). and J. W.S. Greif. SAND96-8216 (1996).E. Moffat. Mitchell.D. F. Glarborg. R. 481 (1986). Reaction Design. “The CHEMKIN Thermodynamic Data Base. Inst. Sandia National Laboratories Report No. Coltrin. M. Lutz. and W. Inst. Evans. Inc. and O. R.. R. J. R. Kee. P. Miller. J. Adigun. ”The Radiation Theory of Chemical Action..” Proc. “Unsteady Heat Transfer during Side Wall Quenching of a Laminar Flame.J. J. W.. Wilson. Combust. 70 .” Sandia National Laboratories Report No.

. to appear (2002).G. Deutschmann. P. Petzold. and H.” Sandia National Laboratories Report No. Smooke. 1349 (2000). Section 29. L.” Proc. McGraw-Hill. Gesammelte Abhandlungen. Gas Turbines. “Diffusion and Heterogeneous Reaction. 1893 (1960). Perry's Chemical Engineers' Handbook. Deutschmann. and B. Today. L. 28. and M. SAND82-8637 (1982). 312 (1997). Motz. 111. Phys. 32. 2.” Proc. A. Kasemo. Inst. Princeton. Boundary-Layer. and M. 327 (1997).. Warnatz. “Heterogeneous/Homogeneous Reaction and Transport Coupling During Flame-Wall Interaction. Vol IV. O. Combust. F..R.Mantzaras.. and Plug-Flow Models of the Flow and Chemistry in a Catalytic-Combustion Monolith. Schmidt. Princeton University Press. 59. Popp.” Combust. Papavassiliou. 29. Raja.. and P.” J.. 108.” Proc. III. Baum. Combust. Rinnemo.. J. Flame. Reaction Mechanisms and Unburnt Hydrocarbons during the Head-On Quenching of a Laminar Methane Flame. P. F.B..K. C. Behrendt. “A Description of DASSL. Atom Recombination at a Catalytic Boundary. 575. L. New York. Springer-Verlag.L. ”A Critical Evaluation of Navier-Stokes. Appel. NJ (1964). P. ”Surface Reaction Mechanism Development for Platinum Catalyzed Oxidation of Methane. V. ”Experimental and Numerical Investigation of the Catalytic Ignition of Hydrogen and Oxygen on Platinum. M. Combust.. Theory of Laminar Flows. H. pp. 29-40 (1999). Prandtl. “Analysis of Wall Heat Fluxes. Flame. R.. Inst. Inst. J. Baum. M. 71 . Chem. 47 (2000).J. Kee.D. Wise.. and L. p. Moore. High Speed Aerodynamics and Jet Propulsion. Benz.” Catal... Berlin (1961).D. Aghalayam.” Combust. and D. 2693 (1996). Mhadeshwar. O. “Catalytic Combustion of Methane/Air Mixtures over Platinum: Homogeneous Ignition Distances in Channel Flow Configurations. 26. Popp. Vlachos.

J. 1663 (2000). Schmidt..D. and C.” Proc..G. Westbrook. E. R. Vlachos. “Resolution of Gas-Phase and Surface Combustion Chemistry Into Elementary Reactions. Inst. Combust.. 28. Yang. Davis.. Warnatz. Warnatz. D. Flame. Allendorf. K..D. 2429 (1996). M. 40(6). “Unsteady Heat Transfer During Laminar Flame Quenching. Sci. Jr. R. Kee. S..” Combust. Westbrook. Inst.G. U. “Computational Studies of End-Wall Flame Quenching at Low Pressure: The Effects of Heterogeneous Radical Recombination and Crevices.. Aris. 4. “Thermal Theory of a Laminar Flame Front Near a Cold Wall.C. Schmidt. Flame. and R. “Ignition and Extinction of Flames Near Surfaces: Combustion of CH4 in Air. Millàn.. Von Kàrmàn. Aris. L. Eng. T. A. 40. J. Warnatz.Y. Combust.. Lavoie..G. Schmidt. 20. S. 40(6).. Vosen. 81 (1981).. Heidelberg. 1018 (1994b). Experiments. W. D. Germany (1996). “Combustion Chemistry of Propane: A Case Study of Detailed Reaction Mechanism Optimization.. 24. and R....Qin. Proc. 95. Z. “A Numerical Study of Laminar Flame Wall Quenching. Inst. 393 (1994). 313 (1993). and M. 72 . and G. R. “Homogeneous-Heterogeneous Oxidation Reactions over Platinum and Inert Surfaces. Springer Verlag. H. “Products in Methane Combustion Near Surfaces. Schoene. 51..G. D. and R. Modeling and Simulation. Flame.” Combust. J. Greif.” Combust.W. and R.” AIChE J. Gardiner. Dibble.. G.M..” Proc. A. Maas. J. 553 (1992).. Vlachos. 109 (1983). Inst. Flame. L.D. 96. Sloane. and A. Vlachos. Coltrin. K.” Chem. 75 (1984).” Invited Lecture. Wang. Combustion-Physical and Chemical Fundamentals. Vlachos.” AIChE J. “Ignition and Extinction of Flames Near Surfaces: Combustion of H2 in Air. Pollutant Formation. Combust.” Proc. “A Model of Elementary Chemistry and Fluid Mechanics in the Combustion of Hydrogen on Platinum Surfaces. Aris.G. Combust. and H. T. 49. 1005 (1994a). L. C. V. D. D. Adamczyk.” Combust. 173 (1953). A. Lissianski.

S. Marks. C. Bruneaux. 103. Flame. and L. 5922 (1992).. W.” Combust.Wichman. 73 . Schmidt... Chem. and G. Phys. 296 (1995).” J. Williams. “Steps in the Reaction H2 + O2 = H2O on Pt – OH Desorption at High Temperatures. “Head-On Quenching of a Premixed Flame by a Cold Wall. M. I. 96. R. D.