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Course Notes

FACE9 Theory of Combustion

Theory of Combustion
FACE 9
Fall 2005

Examination date: PE course


Lecturer: Chungen Yin, Ph.D.
Pon 101, room 4
chy@iet.aau.dk
Downloads: http://www.iet.aau.dk/~chy/Combustiontheory.pdf
http://www.iet.aau.dk/education/

MM1. Chemical Thermodynamics


FACE9 Theory of Combustion

MM2. Chemical Kinetics

MM3. Premixed Flames: Laminar vs. Turbulent

MM4. Diffusion Flames: Laminar vs. Turbulent

MM5. Burning of Solid Fuels

[Textbook] Stephen R. Turns. An Introduction to Combustion Concepts and


Applications. (2nd edition), McGraw-Hill, 2000 (ISBN 0-07-116910-5)

[Useful readings] Kenneth K. Kuo. Principles of Combustion (2nd edition). John Wiley & Sons,
Inc., 2005 (ISBN 0-471-04689-2)

2
MM1: Chemical Thermodynamics

Contents
FACE9 Theory of Combustion

Ideal-gas behavior
Equation of state
Reactant & product mixtures: Stoichiometry; Equivalence ratio

First law of thermodynamics energy conservation


For closed system (fixed mass)
For open system (control volume)
Enthalpy of combustion and heating values
Adiabatic flame temperature

Second law of thermodynamics equilibrium concept


Equlibrium criteria for closed system at different conditions
Chemical equilibrium principle (for given T, P and m)
Full equilibrium products of combustion

Ideal-gas behavior
Combustion: Rapid oxidation generating heat, or both light and heat; also slow
oxidation accompanied by relatively little heat and no light
Ideal gas is the system where interaction is absent (i.e., zero potential energy).
FACE9 Theory of Combustion

High temperatures associated with combustion generally result in sufficiently low


densities for the Ideal Gas Behaviour to hold.

Equation of state
P V = N Ru T P V = m RT P v = RT P = RT
Ru : universal gas constant, = 8315 J/(kmol - K)
v : specific volume, m3 / kg
R : specific gas constant, R = Ru /MW ( MW is gas molecular weight)

Calorific equations of state


The internal energy u is a function of temperature T,
du = cv dT u : specific internal energy, J / kg cv : constant volume specific heat, J /( kg K )

The enthaply h is also a function of temperature T,


d h = c p dT
h : specific enthalpy, J / kg. (h = u + P v)
c p : constant pressure specific heat, J /( kg K ). (c p = cv + R )
4
The specific heats (of gas) are generally functions of temperature: in general, the
FACE9 Theory of Combustion more complex the molecule, the greater its molar specific heats.
heats

- 3 components of internal energy:


translational, vibrational & rotational;

- Diatomic molecule:
not only translational but also
vibrational & rotational contributions.

- Monatomic molecule:
only translational kinetic energy;

Ideal-gas mixtures

Ni mi
xi = xi : mole fraction of species i Yi = Yi : mass fraction of species i
N tot mtot
FACE9 Theory of Combustion

Yi = xi MWi / MWmix xi = Yi MWmix / MWi


xi MWi = (Yi / MWi )
1
MWmix : mixture molecular weight, kg / kmol , MWmix =
i
i
Reactant & product mixtures
Stoichiometry:
Stoichiometry: The stoichiometric quantity of oxidizer is just that amount needed
to completely burn a quantity of fuel.
C x H y + a (O 2 + 3.76 N 2 ) x CO 2 + ( y / 2) H 2O + 3.76a N 2
m 4.76 a MWair
( A / F )stoic = air = a = x+ y/4
mfuel stoic 1 MWfuel

ratio commonly used to indicate quantitatively whether a fuel-


Equivalence ratio:
oxidizer mixture is rich, lean, or stoichiometric.
( A / F )stoic ( F / A) > 1 : fuel rich mixtures
= =
(A/ F) ( F / A)stoic < 1 : fuel lean mixtures

Percent excess air


(1 )
% excess air = 100%
6
First law of thermodynamics Energy conservation
For closed system (fixed mass): exchange energy but no mass with surroundings
d
Q& net in
123
+ W&shaft,net in =
14243
dEsys / dt
1424 3

dt sys
e dV
(shaft work- to produce an
FACE9 Theory of Combustion

Net rate of heat Net rate of work Time rate of change


into system effect external to system)
done on system of system energy

(total energy is property; its value


e{ = u{ + 12 V 2 + gz
{ (kJ/kg) will NOT change unless the state of
total internal
{
kinetic potential the system changes)

For open system (control volume): exchange both energy & mass with surroundings
P
e flowing = h{ + 12 V 2 + gz
{ = u + + 12 V 2 + g z (kJ/kg)
1424 3 enthalpy {
123
total kinetic potential
h

Whats important: [example] The total energy of a steady stream of N2 at 500K, 10bar
& velocity of 50 m/s in a pipe. The pipe is 10 m above zero datum.
[Solution]
h = 211 kJ/kg (from tables) ~ 99.365% e

among which
e = h + 12 V 2 + g z
12 V 2 = 1.25 kJ/kg ~ 0.589% e

g z = 0.0981 kJ/kg ~ 0.046% e

Thermal energy is the largest component. Assumption of


7 neglecting KE & PE in thermodynamics is reasonable.

Transform 1st law from closed system to open system (CV) by using Reynolds
transport theorem (RTT) + Add
dd flow work (done by pressure).

Reynolds transport theorem for fixed CV:


FACE9 Theory of Combustion

dE sys
dt
=
t cv cs
e dV + e V n dA

Flow work done by pressure:


P
W& pressure,net in = cs P (V n )dA = cs (V n )dA

1st law of thermodynamics for open system

P
Q& net in + W&shaft,net in =
t cv cs
e dV + + e (V

n )dA

P V2 P V2
Q& net in + W&shaft,net in =
t cv
e dV + m& + u + 2
+ gz


m& + u + 2
+ gz


out in
(only a number of in & out streams; uniform h at each inlet & outlet)

V 2 V12
Q& net in + W&shaft,net in = m& h2 h1 + 2 + g ( z 2 z1 ) (steady
steady flow with only 1
2 stream in & 1 stream out)
8
[Example]: the heat change during the following reaction without any dissociation:
H 2 ( g ) + 12 O 2 ( g ) H 2 O (g) -240.35 kJ at 298.15 K
(1) If the reaction occurs at a constant-V, calculate the heat released during the reaction;
FACE9 Theory of Combustion

(2) If the reaction occurs at a constant-P, calculate the heat released during the reaction.

[Solution]
(1) For the constant-volume process, the first law becomes (if assuming no shaft or
viscous work and no kinetic or potential energy change)
dU = Q&
The internal energy ( U = m u ) is a property (i.e., a point
function) of the system and independent of the path, then

dU = ( Q& ) v = 240.35 kJ

(2) If the reaction is carried out isothermally at T and a


constant pressure p, then per mole of H2O we have,

( Q& ) p = dH = U + pV = U + n Ru T
where n = ( nprod nreact ) ideal gas = 0.5

( Q& ) p = 240.35 1.237 = 241.587 kJ

Q& is the path-dependent variable. In this exmple, ( Q& ) p > ( Q& ) v because of the
decrease in the volume of the system (to keep pressure constant).
constant). The
surroundings do some work on the system.
9

Enthalpy of combustion and Heating values

Absolute enthalpy = Enthalpy of formation (associated with chemical bonds)


bonds +
Sensible enthalpy change (associated only with temperature)
temperature
FACE9 Theory of Combustion

h i (T ) = h fo,i (Tref ) + hs,i (Tref )


123 14243 14243
Absolute enthalpy Enthalpy of formation Sensible enthalpy
at temperature T at standard reference change in going from
state (Tref , P 0 ) Tref to T

Standard-state: Tref = 298.15 K Pref = P o = 1 atm

(Enthalpy: with overbar: in kJ/kmol; without overbar: in kJ/kg)

Bond energy vs. Enthalpy of formation (i.e., heat of formation)


o
The bond energy for dissociation, D ( R X ) is the strength of a chemical bond
between R and X of the molecule RX. For RX R + X , the energy required to break
the bond @ 298.15K is:
o
D298 ( R X ) = h fo, R + h fo, X h fo, RX

10
[Example] Use bond energies to estimate the enthalpy of formation of C2H6O (g)
H H

H C C O H (The molecular structure of C2H6O (g))

H H
FACE9 Theory of Combustion

[Solution]
Formation enthalpy = the difference between the energy needed to break
chemical bonds of standard state elements (e.g., H2 (g), O2 (g), N2 (g), C(s))
and the energy released in the formation of new bonds in products.
3H 2 (g) + 12 O 2 ( g ) + 2C ( s ) C 2 H 6O ( g )

(1) 3H 2 (g) 6H ( g ) + 312.60 kcal


1O
2 2 (g)
O ( g ) + 59.56 kcal
2C ( s ) 2C ( g ) + 342.58 kcal

(2) 5(C-H)+(C-C)+(C-O)+(O-H)=5*98.1+85.5+86+109=771 kcal/mol


6H ( g ) + O ( g ) + 2C ( g ) C 2 H 6 O ( g ) 771 kcal/kmol

Summing up (1) & (2) gives,


3H 2 (g) + 12 O 2 ( g ) + 2C ( s ) C 2 H 6 O ( g ) + (771 + 312.6 + 59.56 + 342.58) kcal/mol C 2 H 6 O

The estimated enthalpy of formation for C2H6O (g) is 56.26 kcal/mol. The
actual value is 56.12 kcal/mol. Difference is because the estimated value
11 is based on average bond energies.
FACE9 Theory of Combustion

Bond energies are based on data for


substances in gaseous state.

Formation enthalpy net change in


enthalpy associated with breaking
chemical bonds of the standard state
elements & forming new bonds to
create species of interest.

Convention:
Convention Enthalpies of formation
are zero for the elements in their
naturally occuring state @ reference
12 state temperature & pressure.
Enthalpy of reaction (i.e., Enthalpy of combustion)
hR qcv = ho hi = hprod hreac
H R = H prod H reac = N i hi N i hi
prod reac
FACE9 Theory of Combustion

H = N h = m h (kJ) Open system


(steady state with 1
h (in kJ/kmol) stream in & 1
stream out)
h (in kJ/kg)

Heating value (i.e., Heat of combustion)

The difference between the energy needed to break the bonds in the reactants and the
products Numerically equal to the
energy released in the formation of the bonds in the products.
enthalpy of reaction, but with opposite sign.

H c H R = H reac H prod = N i hi N i hi Standard state for reactants


& products maximum
reac prod heat released!

- Upper or Higher heating value, HHV:


HHV the water in the products is in liquid;
- Lower heating value, LHV:
LHV the water in the products is in vapor;
- Latent heat vaporization:
vaporization heat required to completely vaporize unit mass of liquid at
(T & P)
h fg (T , P ) hvapor (T , P) hliquid (T , P)
13

[Example] 1 kg liquid fuel undergoing combustion in air


- Formation enthalpy, Absolute enthalpy, Enthalpy of vaporization
- LHV and HHV of the fuel at different states.
FACE9 Theory of Combustion

Absolute
Enthalpy, h
(kJ/kg-fuel) h(v ) (T ) fuel
h(l ) (T )

HHV product
h fg , fuel
(vapor fuel)
298 K LHV
(vapor fuel)
T
h of (v )
HHV
h of (l ) (in which water in liquid)
LHV (liquid fuel)
(liquid fuel) h fg , H 2O
(per kg fuel)
(in which water in vapor)

14
Adiabatic flame temperature: No heat released into surroundings.

Constant-
Constant-pressure adiabatic flame temperature: a fuel-air mixture burns
adiabatically at a constant pressure (e.g., in furnace or gas-
gas-turbine combustor).
combustor
FACE9 Theory of Combustion

H reac (Tinit , P ) = H prod (Tad , P )


- Dissociation causes a lowering of Tad since more energy is tied up in chemical bonds
(enthalpies of formation) at the expense of the sensible enthalpy.

Constant-
Constant-volume adiabatic flame temperature (e.g., in an ideal Otto-
Otto-cycle analysis)

U reac (Tinit , Pinit ) = U prod (Tad , Pf )

H reac H prod V ( Pinit Pf ) = 0


H reac H prod Ru ( N reacTinit N prodTad ) = 0

Constant-pressure vs. Constant-volume adiabatic flame temperatures


Different even for totally same initial conditions.
Normally constant-
constant-V Tad is higher than constant-
constant-P Tad. High temperature in
combustion gives rise to a much bigger volume flowrate.
flowrate. Therefore at constant
pressure, the pressure forces do work on the surroundings; while at constant
volume, the pressure forces never do work on the surroundings!

15

Second law of thermodynamics (on thermodynamic equilibrium)


Entropy = The uselessness of the energy of the universe
2nd law of thermodynamics: The entropy of the universe (i.e., system plus its
FACE9 Theory of Combustion

surroundings) increases during any spontaneous process.

[Example]:
[Example] 10 tons steams of high (T & P) + A pool of cold water
- Spontaneous process:
process mixing up & becoming warm water;
- Usefulness of energy in the process: decrease though total amount of energy is same.
- Equilibrium status:
status when there is no change in the usefulness of the total energy.

The 2nd law in entropy


(dS )U ,V , m 0 S =" Energy dispersed" / T

The equality holds only for equilibrium state.

The 2nd law in Gibbs free energy G H TS :


(dG )T , P , m 0

Criteria for chemical equilibrium depend on the condition at which certain


thermodynamic properties (or property) are kept constant. Which to use depends
on the condition of your system.
16
General equilibrium criteria for closed systems (fixed mass)

Variables held constant Thermodynamic equilibrium criteria for closed systems

P dH T dS = dG + S dT = 0
FACE9 Theory of Combustion

V dU T dS = dA + S dT = 0
T d (U TS ) + P dV = dG V dP = dA + P dV = 0
S dU + P dV = dH V dP = 0
P, T dG = 0
V, T dA = 0
P, S dH = 0
V, S dU = 0
S , U or A, T dV = 0
A, V or G, P dT = 0
U , V or H , P dS = 0
G, T or H , S dP = 0

17 A U TS (Helmholtz free energy)

What do we particularly feel interested in combustion problems?


More frequently, one need to calculate the composition of a mixture at a given
temperature, pressure & stoichiometry dGmix = 0 .
i i i
dNi [ gio,T + RuT ln(Pi / Po )] = 0
d (ln P ) = dP / P dP = 0
dGmix = 0 i (at equilibrium)
FACE9 Theory of Combustion

Pi = xi P P : pressure of the mixture, which does not necessarily equal 1atm ( = P o )

Chemical equilibrium expression (for fixed temperature, pressure & mass)


For the reaction: a A + b B +L eE + f F +L
dN A = a dN B = b L
dN E = + e dN F = + f L

[ ] ( P / P o ) e ( PF / P o ) f etc
(e g Eo ,T + f g Fo,T + L) (a g Ao ,T + b g Bo ,T + L) = Ru T ln E
14444444442444444444 3 ( PA / P o ) a ( PB / P o ) b etc
Standardstate Gibbs function change, GTo = Prod React 14 444 4244444 3
Equilibrium constant, K p

GTo = RuT ln K p or K p = exp( GTo /( RuT ))

where GTo = (e g of ,E + f g of ,F + L) T (a g of ,A + b g of ,B + L) T (Standard-


(Standard-state Gibbs
function change)

( PE / P o ) e ( PF / P o ) f etc
Kp = (Equilibrium constant)
( PA / P o ) a ( PB / P o ) b etc
18
How to calculate full equilibrium products of combustion
Assuming no dissociation: i.e., ignore some minor species in combustion product;
Adiabatic flame temperature & Composition of combustion products can be
obtained by solving (1) first law of thermodynamics, (2) chemical equilibrium criteria
and (3) element-conservation simultaneously.
FACE9 Theory of Combustion

(major species)

(minor species)

19

MM2: Chemical Kinetics

Contents
FACE9 Theory of Combustion

Global vs. Elementary reactions

Elementary reaction rates


Bimolecular reactions
Arrhenius equation

Rates of reaction for multistep mechanisms


Compact notation of reaction and stoichiometric matrices
Net production rate of each species in a multistep mechanism
In CFD, it provides the source term for transport eqn for species j

Some chemical mechanisms

20
Global vs. Elementary reactions
Global reactions Black-box approach
1mol fuel + a mols oxidizer to form b moles combustion products
FACE9 Theory of Combustion

F + a Ox b Pr
[X i ]: the molar concentration (kmol / m 3 )
d [X F ]
& F = kG (T ) [X F ] n [X Ox ] m of the i th species in the mixture.
dt
Global reaction rate kG (T ) : generally not a constant, but a strong function of T.
order exponents n & m relate to the reaction order.
Reaction order:
- the reaction is nth order with respect to the fuel, mth order with respect to the oxidizer,
and (n+m)th order overall;
- For global reactions, n and m are not necessarily integers;
- For elementary reactions, reaction orders will always be integers
integers.

[Example] The global oxidation reaction of propane


k
C3 H 8 + 5 O2 3 CO2 + 4 H 2O
The following global mechanism is proposed for this reaction:

) [C3 H 8 ] 0.1 [O2 ]1.65


30
k = (8.6 1011 ) exp(
RuT
(where CGS units- cm, s, gmol, kcal, K, are used)

Global reaction reveals nothing about the actual chemistry involved in a


reaction and is only an empirical curvefit of experimental data.
data
21

Elementary reactions
Intermediate species: unrealistic to believe a oxidizer molecules simultaneously collide
with 1 single fuel molecule to form b product molecules, since this would require
breaking several bonds and subsequently forming many new bonds.
FACE9 Theory of Combustion

2H 2 + O 2 2H 2O (Global reaction)

H 2 + O 2 HO 2 + H (1)
H + O OH + O (2)
2
(Important elementary reaction)
OH + H 2 H 2 O + H (3)
H + O 2 + M HO 2 + M (4)

L
mechanism the collection of elementary reactions necessary to describe
Reaction mechanism:
overall reaction.

[Question] Why is the global reaction highly improbable? Why is the 1st reaction likely to
be an elementary reaction? (based on simple molecules collision)
H2 : HH O2 : O=O
H 2O : HOH HO 2 : HOO

Keep in mind: In order for a reaction to occur, molecules must (1) collide in
an appropriate orientation and (2) with sufficient energy to
initiate the rearrangement of chemical bonds (i.e., the proper
bonds must be broken and formed).
formed
22
[Answer] (1) For the global reaction to occur, two H2 molecules must simultaneously
collide with one O2 molecule in the appropriate orientation, e.g.,

H H
FACE9 Theory of Combustion

O=O
H H

1 double bond & 2 single bonds must be broken;


4 single bonds must be formed;
Based on the chance of the molecules colliding correctly and the appropriate
bonds being broken and formed, it is apparent that the global reaction is
highly improbable.

(2) For the 1st reaction to occur, one H2 molecule must collide with one O2
molecule (with fairly general orientation), e.g.,

HH O=O

In addition, only 1 single bond must be broken, 1 double bond must be


transformed to a single bond, and one single bond must be formed.

The probability of the molecules colliding correctly and the appropriate bonds
being broken and formed is relatively large, indicating this reaction could be
an elementary reaction.

23

Elementary reaction rates


Bimolecular reactions: Most elementary reactions in combustion are bimolecular
A+BC+D
d [A ]
= kbimolec [A ] [B] [A ], [B]: the molar concentration (kmol/m 3 ) of A and B, respectively
FACE9 Theory of Combustion

dt
Reaction order & rate
- All elementary bimolecular reactions are overall second order, being first order with respect
to each of the reacting species;
- The rate coefficient, k bimolec , again is a function of T, but has a theoretical basis.

Collision theory:
No. of collisions between
d [A ] all A and all B molecules
Probability that a
kmol of A
= collision leads to
dt
reaction 144424443
Unit volum e unit time No. of A molecules

144444244444
3
1 4 4 4 2 4 4 43 3rd term = Constant
2nd term
1st term
1st term depends on 3 factors:
- Number of A & B molecules, i.e., their molar concentrations. So, the first term ~ [A][B];
- Mean traveling speed of the molecules v , which is T-dependent, v ~ T 1 / 2 ;
- Diameters and mass of A and B molecules.

2nd term depends on 2 factors, it can be expressed as a product of the two factors:
- An energy factor, exp( E / RuT ) , which expresses the fraction of collisions that occur with an
energy above the threshold level necessary for reaction, E, or activation energy;
- A geometrical or steric factor, p, that takes into account the geometry of collision between
A and B. e.g., OH + H H 2O , a reaction is more likely if H atom strikes the O side of OH
24 rather than the H side, since the products bond: H-O-H.
Arrhenius equation

d [A ]
C1 T 1 / 2 [A ][B] C2 p exp( E / RuT ) 1 / N AV
dt 14 4244 3 14442444 3 123
1st term 2nd term 3rd term
FACE9 Theory of Combustion

- Arrhenius equation: The bimolecular rate coefficient kbimolec can be expressed by

d [A ]
= kbimolec [A ] [B]
dt
k (T ) = A exp( E / Ru T ) (Arrhenius form)

A : pre exponential factor (or frequency factor), a constant, including all the units for rate coefficient.
1/ 2
But from the derivation based on collision theory, A is not strictly constant but A ~ T .
- Arrhenius plots of log k ~ 1 / T for experimental data are used to get the two parameters.
- Three-parameter function form for the rate coefficient, kbimolec:

k (T ) = A T b exp( E / RuT )

Other elementary reactions (Unimolecular & Termolecular reactions)


Unimolecular reactions: a single species to form one or two product species
AB AB+C d [A ]
or = k uni [A ]
dt
Termolecular reactions: involve three reactant species. General form:
A+B+MC+M d [A ]
= k ter [A ][B][M ]
M: any molecule & frequently referred to as a third body. dt
25

[Example] Global or Elementary (unimolecular, bimolecular or termolecular) reaction?


(Elementary
Elementary: the required collision is likely; only 1 bond must be
CO + OH CO 2 + H broken and 2 formed)
(Bimolecular
Bimolecular: 2 molecules collide to form 2 molecules)
FACE9 Theory of Combustion

(Global
Global: the required collision, involving 3 molecules with specific
2CO + O 2 2CO 2 orientations, is unlikely; 1 double bond must be broken and
2 double bonds formed)
O=C O=O C=O

H 2 + O 2 H + H + O 2 (Elementary
Elementary: only require the breaking of 1 single bond; no
requirement on the collision orientation at all)
(Unimolecular
Unimolecular: it invloves the decomposition of one single species)

HOCO H + CO 2 (Elementary
Elementary: only 1 bond must be broken; no requirement on the
collision orientation at all)
(Unimolecular
Unimolecular: it invloves the decomposition of one single species)

(Global
Global: 4 single bonds & 2 double bonds must be broken; 4
CH 4 + 2O 2 CO 2 + 2H 2 O single & 2 double bonds formed; require specific
collision orientations)

OH + H + M H 2 O + M (Elementary
Elementary: only 1 bond must be formed; the required collision
is fairly likely)
(termolecular
termolecular: it invloves 3 reactants: 2 radicals (OH & H) must
collide with a third body M to transfer excess
energy to kinetic energy of M, preventing H2O from
immediately separating into OH & H radicals again)
26
Rates of reaction for multistep mechanisms
Net production rate of species A
d [A ]
kf
a A+bB cC+d D
kr
& A = k f [A ] [B] + k r [C] [D]
dt
k f , k r : elementary forward & reverse rate coefficients
FACE9 Theory of Combustion

How to express net production rate of each species in a complex system

27

Compact notation for the numerous elementary reactions

N N
ji X j ji X j for i = 1, 2, L, L
FACE9 Theory of Combustion

j =1 j =1

ji : the stoichiometric coefficients on the reactants side in i-th elementary reaction;


ji : the stoichiometric coefficients on the products side in i-th elementary reaction;
[ X j ] : the molar concenstration of species j, unit of kmol/m3;

L : the total number of reactions;


i : for reaction no.;

N : the total number of species;

j : for species no.;

It represents a reaction mechanism of totally L reactions, in which N different


species are involved.

28
[Example] How to use the compact notation for the 4-reaction & 8 species?

FACE9 Theory of Combustion

Define j (the
the species No.)
No. and i (the
the reaction No.)
No. as follows:

Using j as the column & i as the row index, we can get the following stoichiometric matrices:

O2 H2 H2O HO2 O H OH M
Reaction 1 i

reactions
Reaction 2
Reaction 3
Reaction 4
different species
29 j

Express the net production rate of each species in a multi-


multi-step mechanism

d Xj[ ] L
& j =
dt

= ( ji qi ) for j = 1, 2, L, N
Laminar flame (finite-rate model)
i =1
FACE9 Theory of Combustion

[ X j ] : the molar concenstration of species j, unit: kmol/m3;


& j : net production rate of species j in the reaction mechanism, unit: kmol/(m3-s);

ji = ( ji ji )
N N
[X j ] kr i [X j ]

qi = k f i
ji ji
(Rate
Rate--of-
of-progress variable for
the i-th elementary reaction)
j =1 j =1

It corresponds to the source term for component Xj in the species transport


equation for Xj.

[Example] Express qi=q1 for the R1 ( ) in previous slide from the


stoichiometric matrices:

In the similar way, q2, q3, q4, ... can be expressed from the stoichiometric
30 matrices, then the net production rate of each species.
The compact notation is useful in solving chemical kinetics problems
problems using
computers;
Y j
( Y j ) + ( ui Y j ) = ( j ) + & j MW j +
FACE9 Theory of Combustion

Sj

1 t
424 3 142 x i4 43 x i 4 43 xi 1 4 2 4 3 {
4 142 4 source other sources
transient convective diffusion (e.g., by particle)
by reaction
No matter how many species or reaction involved, the source term in the
transport equation of each species can be easily obtained from the
the stoichiometric
matrices;
Chemical reaction analysis needs numerical methods applicable to stiff equation
equation;
The software package named CHEMKIN is a widely used general purpose
purpose package
for solving chemical kinetics problems.

But one still can see the potential problem in the reaction simulation:
simulation: the source
(chemical net production rate) is non-
non-linear, so there should be some problems in
obtaining the time average __Turbulence-
__Turbulence-chemistry interaction model, for new
expression of j !!
&

31

Relation between rate coefficients and equilibrium constants


Why need it?
- Difficult to measure rate coefficients of elementary reactions, with a rather large degree of
uncertainty. The more reliable rate coefficients are no better than within a factor of two;
FACE9 Theory of Combustion

- Equilibrium constants, which are based on thermodynamic measurements or calculations,


are very accurate and precise in most cases.

How get it?


- At equilibrium condition: the Net Production Rate of any species must be zero:
[C] [D] = k f
k f [A ] [B] + kr [C] [D] = 0
[A ] [B] kr
- The equilibrium constant based on partial pressures for an arbitrary equilibrium reaction:
( P / P o )c ( P / P o ) d L
Kp = C o a D o b c, d , a, b (superscripts) : the stoichiometric coefficients
( PA / P ) ( PB / P ) L

- Define an equilibrium constant based on molar concentration, Kc

[C]c [D] d L Ni P
Kc = Molar concentration X i = [ ] = i
[A]a [B] b L V RuT

K p = K c ( RuT / P o )c + d +L a b L K c = K p (for bimolecular reaction)

k f (T )
= K c (T )
32 k r (T )
Some chemical mechanisms
Methane combustion (CH4+O2 system)
CH 4 + 2O 2 CO 2 + 2H 2 O (One-step global reaction)
CH 4 + 1.5O 2 CO + 2H 2 O CO + 0.5O 2 CO 2 (Two-step global reaction)
FACE9 Theory of Combustion

actually very complex mechanism: 277 elementary reactions involving 49 species


simplifications: Low-T (left, <1500K) vs High-T (right, =2200K)

Carbon monoxide oxidation


33 Oxidation of higher paraffins

The H2-O2 system: three explosion limits


2H 2 + O 2 2H 2O (global reaction)

(1) Chain-initiation reaction:


H2 + M H + H + M (very high temperatures) (1)
FACE9 Theory of Combustion

H + O HO + H
2 2 2 (other temperatures) (2)

(2) Chain-propagating reactions involving the free radicals (O, H & OH):
H H ++ O
O22 O + OH (3)
O + H H + OH (4) Fast reaction in both forward and reverse directions
2
H + OH H O + H (5)
2 2
O + H 2 O OH + OH (6)
(3) Chain-terminating reactions involving the free radicals (O, H & OH):
H + H + M H2 + M (7)
O + O + M O 2 + M (8)
H + O + M OH + M (9) Slow reaction

H + OH + M H 2 O + M (10)

(4) Include reactions involving radical HO2 & species H2O2 to complete the mechanism:

H + O 2 + M HO 2 + M (11) - Chain terminating reaction @ low T & middle P;


- Active at high pressures.

HO 2 + H OH + OH (12)

M HO
HO2-involved chain
2 - involved chainsequence
sequence
HO 2 + H 2 H 2 O 2 + H (13)

H 2 O 2 + OH H 2 O + HO 2 (14)

H 2 O 2 + H H 2 O + OH (15) H2HO22O 2 involved
-involved chain sequence
chain sequence
34 M
3 explosion limits
(if follow a vertical line, say at 500C)
limit Mean-free path becomes
- 1st explosion limit:
short enough for O, H & OH radicals to react
with other species before destroyed at walls.
At low pressures: molecular mean-free path is
long enough for O, H, & OH radicals to reach & be
FACE9 Theory of Combustion

destroyed by walls before reacting with other


3000 species, resulting in the quenching of the chain-
propagating reactions and no explosion occurs.
As the pressure increases: molecular mean-free
path decreases and the O, H, & OH radicals begin to
react with other species. At some pressure (e.g.,
~1.5mmHg for 500C),
500C the chain-
chain-propagating
reactions prevail over wall radical destruction
& the mixture can explode.
explode
- 2nd explosion limit: HO2 radical destruction at
walls.
As pressure is increased past the 1st explosion
limit, reaction (11) begins to compete with (3)
50 atoms HO2 radical is relatively inactive and
for H atoms.
can reach walls & be destroyed. At some pressure
(e.g., ~50mmHg for 500C),
500C reaction (11) prevails
over reaction (3), which effectively quenches the H
radicals and terminates the explosion process.
- 3rd explosion limit: Mean-free path becomes
short enough for HO2 radical to react with other
species before being destroyed at alls.
At higher pressure (e.g., ~3000mmHg for 500C),
500C
the mean-free path becomes short enough for HO2
1.5 radicals to react with other species, e.g., reactions
(12)-(13), before being destructed at walls.
Reaction (13) adds a chain-branching step which
opens up the H2O2 chain sequence.
35

MM3: Premixed Flames: Laminar vs. Turbulent

Contents
FACE9 Theory of Combustion

Two types of flames


Premixed flames vs. Duffusion flames (i.e., nonpremixed flame)

Laminar premixed flames


Typical laminar flame structure
Phenomena & problems (All related to flame speed & thickness)
- Ignition & quenching; Flammability
- Flame stability: Flashback & Liftoff & Blowoff
Flame speed & thickness and influencing factors

Turbulent premixed flames


Basic concepts
- Length scales & time scales
- Turbulence Reynolds number & Damkohler number
Three turbulent-flame regimes
Turbulent flame stabilization

36
Two type of flames
Flame: A flame is a self-sustaining propagation of a localized combustion zone at
subsonic velocities.
FACE9 Theory of Combustion

(1) Premixed flame


Gaseous fuel and oxidizer are perfectly mixed before combustion;
Rapid, essentially constant-pressure, exothermic reaction;
Laminar premixed flames have a unique burning velocity for given fuel-oxidizer
mixture; Turbulence increases the burning velocity.

(2) Diffusion flame (i.e., Nonpremixed flame)


Gaseous fuel and oxidizer streams are separated;
Combust as they mix;
Dominated by the mixing of reactants, which can be either laminar or turbulent;
Reaction take place at interface between fuel and oxidizer.

37

Laminar premixed flames


Example: Typical Bunsen-buner flame of CH4 & air
FACE9 Theory of Combustion

Outer flame
(diffusion)
Outer cone

Hot region
Conical flame
(premixed)

Inner cone

Cool preheating region containing unburned fuel & O2

Premixed fuel (CH4) & oxidizer (air)

Typical Bunsen-burner flame is a dual flame:


- a fuel-rich premixed inner flame;
- a diffusion outer flame: the CO & H2 products from inner flame encounter ambient air.
38
Experimental evidences for the presence of a cool preheating region

FACE9 Theory of Combustion

A wire to reveal the presence of a cool preheating region containing unburned CH4 & O2.

A match placed in the preheating region does not ignite until it is moved into the inner cone.
39

Basic features of laminar premixed flames

Colour of the flame (luminous zone)

Fuel/air ratio Fuel-


Fuel-lean Stoichiometric Fuel-
Fuel-rich Highly fuel-
fuel-rich
FACE9 Theory of Combustion

Flame colour Deep violet Blue Green Yellow


(i.e., the due to large
colour of the concentrations
cone surface) of C2 molecules
(high-T burned
gases usually
show a reddish
glow due to
due to large radiation from
concentrations of CO2 and water due to carbon
excited CH radicals vapour) particles formed

Thickness, speed, pressure drop across the flame (ffor stoichiometric hydrocarbon
mixtures in ambient air)
air
- The flame is ~1 mm thick and moves at ~0.5 m/s;
- Pressure drop through the flame is very small: ~1 Pa;
- Temperature in reaction zone is high: 2200-2600 K;
- Density ratio of reactant to product: ~7;
- 2 sub-reaction zones: (1) Fast-chemistry (dominated by bimolecular reactions: destruction
of fuel molecules & creation of many intermediate species); (2) Slow-chemistry, dominated
by three-body radical recombination reactions & burnout of CO (via CO+OH= CO2+H).
40
Flame
height (a) Flow configuration near
the mouth of a Bunsen
Standoff burner
distance
(b) Relative locations of
FACE9 Theory of Combustion

different conical
surfaces (!!! Differences
exaggerated: total
thickness is on the order
of 1 mm)

Cool reactants Product zone


zone (little heat released) (Bulk of chemical energy released) (burned gas)

Fast- Slow-chemistry region

Temperature & heat-


release-rate profiles
in a laminar
premixed flame

41

What do we particularly feel interested or really care about?

Ignition criteria
- Criterion I Ignition will only occur if enough energy is added to the gas to heat a slab
about as thick as a steadily propagating laminar flame to the adiabatic flame temperature;
FACE9 Theory of Combustion

- Criterion II The rate of liberation of heat by chemical reactions inside the slab must
approximately balance the rate of heat loss from the slab by thermal conduction.

Flashback & liftoff (balance between flame speed & unburned mixture velocity)
- Flashback: flame enters & propagates in burner tube without quenching. Dangerous!!!
- Liftoff: flame is not attached to burner tube, rather than, stabilized at some distance from
the tube. Further increase in velocity will cause blowoff, then flame extinguishing.

Flame speed is one of the most important issues we particularly feel interested!
interested!
- If knowing flame speed, we can stabilize the flame (combustion) in burners/boilers, and can
avoid the dangerous flashback by adjusting unburned mixture velocity;
- In fire-fighting, we can extinguish a fire by making use of blowoff (with higher velocity).

Other ways to extinguish a fire


- Addition of diluents; flammability only flammable in the range of the
diluents (knowledge on mixture flammability:
leanest mixture and the richest mixture)
- Cooling the fire,
fire e.g., water spray; (knowledge on ignition criterion:
criterion if remove sufficient heat
from flame, then chemical reaction heat can not balance the heat loss flame quenching)
- Passing flame through narrow passageways; thickness if the diameter
passageways (knowledge on flame thickness:
of a circular tube is small comparing with flame thickness, then a flame extinguishes.

42
Flame speed

Flame speed (burning velocity), SL


Ignition point (moving toward unburned fuel) A thin layer of gasoline (stationary)
FACE9 Theory of Combustion

et
she
e
m
F la
Flame speed, SL
(burning velocity)

S L = vu sin (for the flame to remain stationary: the flame speed must equal the
speed of the normal component of unburned gas at each location)

43

(1) Flashback
The least tolerance to flashback @
slightly rich stoichiometries where
maximum laminar flame speed occur.
FACE9 Theory of Combustion

(effect
effect of stoichiometry on flame speed)
speed
Flashback stability of natural gas (CH4)
is much greater than manufactured gas,
as a result of high flame speed for H2.
(effect of species on laminar flame speed)
Due to soot formation in rich flame
(2) Liftoff
Natural gas (CH4) At low flow velocity: flame edge is close
to burner lip attached;
attached
At increased velocity: cone angle of
flame decrease (=arcsin(SL/vu)), the edge
of flame displaced a small distance
downstream;
Further increase in velocity: flame edge
jumps to a downstream position far from
burner lip lifted;
lifted then blowoff.
blowoff
Decreased heat & radical loss to burner
tube vs. Increased dilution with ambient
fluid.
Greater liftoff stability of manufactured
gas flame than natural gas flame due
to high flame speed for H2.

44 Manufactured gas (containing H2)


How to obtain flame speed & thickness? A simplified analysis
Major assumptions:
- 1D, constant-area, steady flow;
- Kinetic & potential energies, viscous shear work, and thermal radiation are all neglected;
FACE9 Theory of Combustion

- Small pressure difference across the flame is neglected: thus the pressure is constant;
- Diffusion of heat and mass are governed by Fouriers and Ficks laws, respectively;
k
- Lewis number, thermal/mass diffusivity, is 1 to simplify energy equation, Le = =1 ;
D cpD
- Individual species specific heats are all equal and constant;
- Fuel and oxidizer form products in a single-step exothermic reaction;
- Fuel is completely consumed at the flame;
- Reaction is confined to the second half of the flame thickness,
thickness /2< x <.
1 kg Fuel + kg Oxidizer ( + 1) kg Products

45

Energy conservation equation

m& c p
dT
dx
+
d
dx
( D c p )
dT
dx 14243 (
= h of ,i m& i = h of ,F m& F + h of ,Ox ( m& F ) h of ,Pr ( + 1) m& F )
1424 3 144424443 by chemical reaction
by convection /volume by diffusion / volume

( )
FACE9 Theory of Combustion

= m& F h of ,F + h of ,Ox ( + 1) h of ,Pr m& F hc


m& F : the reaction rate (per unit volum e), = & F MWF , kg /( s m 3 ), (dependent on tempera ture)
hc : heat of combustion of the fuel m& : the mass burning rate dm& i
m& i =
dx
dT 1 d dT m& h
m& k = F c (a) Species conservation
dx c p dx dx cp
(1) Integrate the energy conservation equation (a) over < x < +
dT / dx = 0
T =T k dT hc
m& T T =Tb
u c p dx dT / dx = 0
=
cp m& F dx

Tb
hc linear between dx & dT hc hc
m& (Tb Tu ) =
cp m& F dx =
cp m& F
Tb Tu
dT =
c p Tb Tu m& F dT
0 0 Tu

hc
m& (Tb Tu ) = m& F (1) & , )
1st equation between ( m
cp
& F = & F MWF k (T ) [X F ] n [X Ox ] m MWF
! Attention in calculating the reaction rate, m

Since assuming reaction takes place in 2nd half flame thickness, use mean temperature
in / 2 < x < to evaluate the rate coefficient, k (T ) , in
in Arrhenius equation.
equation
46
(2) Integrate the energy conservation equation over < x / 2 for the 2nd equation.
dT / dx = (T Tu ) / /2
T = (T +T ) / 2 k dT b
hc
m& T T =T u b
u

c p dx dT / dx = 0
=
cp
m& F dx = 0

14442444 3
FACE9 Theory of Combustion

reaction occurs in 2nd half

m& / 2 k / c p = 0 (2) & , )


2nd equation between ( m

! Attention in calculating all the properties: Since conduction occurs over entire flame
thickness while not only in 2nd half where reaction is confined, both conductivity &
specific heat should be based on the mean temperature over the entire
entire flame thickness.
thickness

From the two equations on (m& , ) , the mass burning rate and the flame thickness
can be solved (from Energy Conservation equation)

Mass conservation equation

m& = v x = u S L = constant (b)

Since the mass burning rate m& is solved, then S L can be obtained from Equation (b).
1/ 2
m&
S L = 2 ( + 1) F (Laminar premixed flame speed)
u
u (density of unburned gas)
= 2 / S L (flame thickness)
m& F = & F MWF k (T ) [X F ] n [X Ox ] m MWF

47
k /( u c p ) (thermal diffusivity) (mass oxidizer-to-fuel ratio, kg/kg, in reaction)

Influence of different factors on flame speed & thickness

Influence of different factors on flame speed & thickness


FACE9 Theory of Combustion

1 1 k (T ) 0.75
~Tu P ; ~T
k (T ) u
TuT 0.75 P 1
c p (T )
where T 0.5(Tu + Tb )
u c p (T )

k (T ) ~ exp( E / R T ); [ X ]= P /( R Tb )
m& F u (Tu P 1 ) k (T )[X ] n ub u (Tu P 1 ) exp( E / RuTb ) P n / Tbn
1424 3 1424 3 n : overall reaction order
1/ u &

m& F u TuTb n P n 1 exp( E / RuTb )

S L T 0.375TuTb n / 2 exp( E / 2 RuTb ) P ( n 2) / 2

T 0.375Tbn / 2 exp( + E / 2 RuTb ) P n / 2

- Strong temperature dependence of laminar flame speed;


- Pressure dependence of laminar flame speed: depend on the reaction
reaction order n;
- Equivalence-
Equivalence-ratio dependence of laminar flame speed;
- Fuel type;
-
48
Effect of temperature on flame speed

FACE9 Theory of Combustion Effect of pressure on flame speed

Theory indicates a dependency on reaction order

Experimental measurements generally show a


negative dependence of pressure

49

Effect of equivalence ratio


FACE9 Theory of Combustion

Except for very rich mixtures, the primary


effect of equivalence ratio on flame speed
for similar fuels is a result of how this
parameter affects flame temperature.

one would expect flame speeds to be a


maximum at a slightly rich mixture and
fall off on either side.

Flame thickness shows the inverse


trend, having a minimum near
stoichiometric.
50
Effect of fuel type
FACE9 Theory of Combustion

- Roughly speaking, the flame velocities of


C3-C6 hydrocarbons all follow the same
trend as a function flame temperature.
- C2H4 and C2H2 have flame velocities
greater than the C3-C6 group, while CH4
lies somewhat below.
- H2s maximum flame speed is many times
greater than that of C3H8, because (1) the
thermal diffusivity of pure H2 is many
times greater than the hydrocarbon fuels;
(2) the mass diffusivity of hydrogen is
much greater than for the hydrocarbons;
(3) the reaction kinetics for H2 are very
rapid since the relatively slow step
CO CO 2 that is a major factor in
hydrocarbon combustion is absent.

51

Turbulent premixed flame


Basic concepts
Turbulent flow increases the flame propagation, but no evidence that turbulence
substantially alters the chemistry.
FACE9 Theory of Combustion

No practical universal method to predict turbulent flame behavior.


3 kinds of turbulent-flame regimes:
- Wrinkled laminar-flame regime;
- Distributed-reaction regime;
- Flamelets-in-eddies regime.

Turbulent flame speed


m& m& : reactant flow rate; u : unburned gas density; A : time averaged flame area
St =
A u

Turbulent fluctuation velocity = (u ) 2 + (v ) 2 + ( w) 2


v rms

Turbulent length scales Integral scale & Kolmogorov scale


l0 integral scale, i.e., the largest eddy scale 0.25
3l0
lk Kolmogorov microscale, i.e., the smallest eddy scale, =
( v ) 3
rms
v l
Turbulence Reynolds number Re l0 = rms 0

Damkohler number: a characteristic flow (mixing) time / a characteristc chemical time

" eddy turnover time" for the largest eddies l 0 / v rms
Da =
chemical reaction time L / SL
52
Three turbulent-flame regimes
L lK Wrinkled laminar-flame regime

The reaction zone thickness is much thinner than the


smallest scale of turbulence: the turbulent motion can only
wrinkle or distort the thin laminar flame zone.
FACE9 Theory of Combustion

l0 > L > l K Flamelets-in-eddies regime

parcels of
unburned gas

Kolmogorov microscale l K
= (100, 1, 0.01)
Laminar flame thickness L
Largest eddy scale l l0 < L Distributed-reaction regime
= 0 (1, 10000)
Laminar flame thickness L All turbulent motion scales smaller than reaction zone
Turbulent intensity vrms thickness, then transport in reaction zone is governed by
= (0.01, 1, 100, 10000)
53 Laminar flame speed S L both molecular processes and turbulence.

Wrinkled laminar-flame regime


- Chemical reactions occur in thin sheets (thinner than Kolmogorov scale);
- Damkohler number always greater than 1 Fast chemistry (comparing with fluid
mixing);
- Flame becomes wrinkled flame area larger than laminar flame;
FACE9 Theory of Combustion

- Flame speed less dependent on laminar burning velocity & thus less on fuel/air
or fuel type; 3~5 times laminar burning velocity.

Distributed-reaction regime
- Difficult to achieve in a practical device: require simultaneously small integral
length scale (l0) & large turbulent intensity very high velocity in small passages
(huge pressure loss & less sustainable flame)
- Damkohler number always less than 1 Slow chemistry (comparing with mixing);
- Many pollution formation reactions are slow & occur in distributed regions;
- Difficult to handle: transport in reaction zone governed by both molecules &
turbulence.

Flamelets-in-eddies regime
- Characterized by moderate Damkohler number & high turbulence ( v rms / S L >> 1 );
- Of particular interest:
interest some practical combustion devices operate in this regime;
- Follow the ideas that support eddy-
eddy-breakup model (1) burning zone consists of
parcels of unburned gas & almost fully burned gas; (2) combustion rate determined
by the rate at which parcels of unburned gas are broken down into smaller ones
(create sufficient interfacial area between unburned mixture & hot gases to enable
reaction); (3) thus chemical reaction rates play no role in determining burning rate
while turbulent mixing rates controlled.
54
Methods to turbulent flame stabilization
Low-velocity bypass ports;
Refractory burner tiles;
Bluff-body flame-holders;
Swirl or jet-induced recirculating flows;
FACE9 Theory of Combustion

Rapid increase in flow area creating recirculating separated flow;

Creation of a strong recirculation zone of hot products close to the burner throat
(1) ignites unburned gases; (2) provides a zone where local turbulent flame speed match local
flow velocity

55

MM4: Diffusion Flames: Laminar vs. Turbulent

Contents
FACE9 Theory of Combustion

Laminar diffusion flames


Laminar constant-density jets
Laminar jet flame
- Flame contour: Temperature, species mass fractions & velocity field
- A few important features: Flame surface, soot, length vs. initial condition
Theoretical analysis for flame length
- Conserved scalars: Mixture fraction
- Flame length and its dependence on flowrate & stoichiometry

Turbulent diffusion flames


Flame shape and size flame length
Flame holding and stability Liftoff & blowout

56
Laminar diffusion flame
FACE9 Theory of Combustion Laminar constant-density jet (nonreacting)

Still air

Fuel jet
e , ve
Y F ,e 1

Potential core the effects of viscous shear & diffusion have not yet to be felt;
both the velocity and nozzle-fluid mass fraction remain unchanged from their
nozzle-exit values and are uniform in this core.
The initial jet momentum is conserved: The jet velocity decreases, while larger
and larger amount of air is entrained into the jet as it proceeds downstream.
The mass of fuel issuing from the nozzle is conserved.
? Detailed velocity and fuel mass-fraction field in the jet.
57

Assumptions

- Uniform fluid density throughout the flow field;


( r , x ) = e = constant
- Species molecular transport is by simple binary diffusion governed by Ficks law;
FACE9 Theory of Combustion

- Momentum & species diffusivities are constant & equal, i.e., Schmidt number=1
Sc / D = 1
- Only radial diffusion of momentum & species is important; ignore axial diffusion. (it
implies that the solution only applies some distance downstream of the nozzle exit).

Governing equations
- Mass conservation
vx 1 (vr r )
+ =0
x r r

- Axial momentum conservation

vx v 1 vx
vx + vr x = r
x r r r r
- Species conservation

YF Y 1 YF
vx + vr F = D r YOx = 1 YF
x r r r r
58
Boundary conditions

- Along the jet centerline:


centerline (1) no source/sink of fluid; (2) Symmetry condition;
v r (0, x ) = 0; v x (0, x ) / r = 0; Y F (0, x ) / r = 0
- At large radius:
radius (1) stagnant fluid; (2) no fuel present;
FACE9 Theory of Combustion

v x (, x ) = 0; YF (, x ) = 0
- At jet exit:
exit uniform axial velocity & fuel mass fraction at nozzle mouth; 0 elsewhere.
v x (r R, 0) = ve ; YF (r R, 0) = YF , e = 1; v x (r > R, 0) = 0; YF (r > R, 0) = 0

Solution

v x / ve = 0.375 Re j ( x / R) 1 (1 + 2 / 4) 2 valid for ( x / R ) 0.375 Re j


3
1 4
0.5
3J e
vr =
16 e x (1 + 2 ) 2
4

YF = 0.375 Re j ( x / R ) 1 (1 + 2 / 4) 2
1
3 e J e 2 1 r
Re j : Jet Reynolds number, Re j eve R / =
16 x
J e : initial momentum flow , J e = e ve2 R 2
59

Diffusion becomes more important comparing


Dimensionless centerline fuel mass fraction, YF,0/1

with initial jet convection @ decreased Rej


FACE9 Theory of Combustion

Relative importance of
(1) Radial diffusion vs
(2) Initial jet axial
convection.

- Spread rate:
rate the ratio of the jet
half width (the radial location
where the jet velocity equals
1/2 of centerline value) to the
axial distance: high-Rej jets are
narrow.
r1 / 2 2.97 r1 / 2 - Spread angle:
angle the angle whose
= tan 1 ( ) tangent is the spread rate;
60 x Re j x
Laminar jet flame
FACE9 Theory of Combustion

(r = 0, x = L f ) = 1

Oxidizer diffuses inward

Fuel diffuses outward

Flame surface: Locus of points where the equivalence ratio equals unity.
unity
High-T zone occurs in an angular region until flame tip is reached.
Two offsetting effects in upper regions of a vertical flame:
flame (1) Buoyancy accelerates
flow & narrows flame; (2) Narrowing flow increases fuel concentration gradient,
enhancing diffusion. Ignore in predicting flame length for circular-/square-pot nozzle.
conditions L f ~ QF / YF , stoic
Relationship between flame length & initial conditions:
61

Simplified theoretical analysis of laminar jet flame


Why need conserved scalars?
- For a three-
three-species system 1 kg Fuel + kg Oxidizer ( + 1) kg Products
species system:
In flame analysis, the assumption is always made: Inside flame zone, only fuel
and products exist; beyond the flame, only oxidizer and products exist;
FACE9 Theory of Combustion

- Closed problem:
problem 5 equations for 5 unknowns;
5 Equations: 1 Mass conservation;
1 Axial momentum conservation;
2 Species conservation (1 for fuel, YF , & 1 for oxidizer, YOx):
Y
(r v x Yi ) + (r v r Yi ) (r D i ) = 0
x r r r
1 Energy conservation (based on mixture temperature):
c p dT

( ) (
r v x c p dT +

)
r vr c p dT r =0

x r r r

5 Unknowns: vr (r , x), v x (r , x), T (r , x), YF (r , x), YOx (r , x) YPr ( r , x ) = 1 YF ( r , x ) YOx ( r , x )

- Major difficulties
Some BCs necessary to solve fuel & oxidizer species & energy equations must be
specified at the flame, whose location is not yet known before solving the problem.
Yi C1 when r r f ( x) (inside flame sheet)
= due to discontinuity at flame sheet
r C2 when r > r f ( x) (outside flame sheet)
- Solution:
Solution: Use of conserved scalars to rewrite the governing equations
Use of conserved scalars can eliminate the BC dilemma, which require BCs only
62 (1) along flame axis,
axis (2) far from flame & (3) at nozzle exit plane.
plane
What is a conserved scalar?
- It is any scalar property that is conserved through the flow field

{ + kg Oxidizer
1 kg Fuel 1424 3 ( + 1) kg Products
1424 3
Cm H n O2 + N 2 CO2 + H 2 O
FACE9 Theory of Combustion

e.g., the element mass fraction of (C+H) is a conserved scalar,


scalar, since elements
(C+H) are neither created nor destroyed by chemical reaction (just
(just change in form)
form)

The mixture (absolute) enthalpy, h, is also a conserved scalar in a flow field without
sources (or sinks) of thermal energy (e.g., radiation; viscous dissipation)
T
h Yi hof ,i + T ref
c p dT

- Mixture fraction, f

Mass of elements originating from Fuel stream


f
Mass of mixture
For the above three-species reaction: all (C+H) originates from the fuel stream.

f = ({
1)
{ { {
( )
YF + 1+1 YPr + ({ 0) YOx
{
kg (C+ H) kg Fuel kg products kg (C+ H) kg oxidizer
kg (C+ H)
kg Fuel kg mixture kg mixture kg oxidizer kg mixture
kg products

1 at fuel stream
1
f = YF + YPr f =0 far from the flame (all are oxidizer)
+ 1 (0, 1) inside & beyond the flame
Particularly useful For diffusion flames;
Premixed flames: uniform f everywhere assuming same diffusivity for all species.
63

How to eliminate the BC dilemma by using mixture fraction?


- 4 Equations for 4 unknowns (instead of 5 equations for 5 unknowns)
4 Equations: 1 Mass conservation; (same as before)
1 Axial momentum conservation; (same as before)
1 Mixture-fraction equation (instead of 2 species conservation!):
FACE9 Theory of Combustion

f
(r v x f ) + (r vr f ) (r D ) = 0
x r r r
1 Energy equation (based on absolute enthalpy!):
h
(r v x h) + (r vr h) (r ) = 0
x r r r
4 Unknowns: v r ( r , x ), v x ( r , x ), h( r , x ), f ( r , x )
- Boundary conditions:
conditions No need to use BC at flame sheet for both Mixture-fraction &
Energy equations thanks to no discontinuities in f & h at the flame sheet.
f (0, x) / r = 0 (symmetry)

BCs for mixture fraction = f (, x) = 0 (no fuel in oxidizer)
f (r R, 0) = 1; f (r > R, 0) = 0 (top hat exit profile)
h(0, x) / r = 0

BCs for absolute enthalpy = h(, x) = hOx,
h ( r R , 0) = h ; h ( r > R , 0) = h
F ,e Ox ,
h hOx ,
Under assumption = D, if we use a dimensionless mixture enthalpy h* =
hF , e hOx ,
then h* = f : thanks to totally same equation & boundary condition for them.
3 equations for 3 unknowns in fact!!
- Once f(r,x) is solved, the flame sheet is easily located by f = f stoic
1
+1.
64 - Remaining problems: Find state relations to get species (Y
(Yi, T) from f.
How to get state relationships?
- Take inside-the-flame as an example

{ + kg Oxidizer
(1 + a) kg Fuel 1424 3 ( + 1) kg Products
1424 3 + a kg Fuel
{
Cm H n O2 + N 2 CO2 + H 2O Cm H n
1 (1 + ) 1+
FACE9 Theory of Combustion

f = 1 + =
(1 + ) + 1 + (1 + ) + (1 + ) +

YF =
(1 + ) +

f 1+1 f stoic = 1 f f stoic


+1
YF = =
1 +1
1 1 f stoic

- State relationships
YF = ( f f stoic ) /(1 f stoic )

Inside the flame ( f stoic < f 1) YOx = 0
YPr = (1 f ) /(1 f stoic )

YF = 0

At the flame ( f = f stoic ) YOx = 0
YPr = 1

YF = 0

Outside the flame (0 f < f stoic ) YOx = 1 f / f stoic
YPr = f / f stoic

The mixture temperature can also be determined from mixture fraction. See Eqns
65 (9.51a)~(9.51c) (P327) for Inside flame, At flame & Outside flame, respectively.

- The simple and closed-form state relationships are based on the use of only 3
species (fuel, oxidizer & products) and greatly simplified thermodynamics;
FACE9 Theory of Combustion

Simplified-state relationships for species mass fraction

Simplified-state relationships for mixture temperature

- For complex mixtures, state relationships are frequently based on equilibrium, partial
equilibrium methods, or experiments the idea behind the use of mixture fraction is
same.

66
Correlations for laminar jet flame length

(1) based on the simplified theoretical analysis:


analysis once mixture fraction, f(r,x), is
solved, then the flame length will be obtained.

1 QF D: mass diffusivity
FACE9 Theory of Combustion

Lf
D YF ,stoic QF : volume flowrate of fuel stream

(2) Roper
Ropers correlations (e.g., for Circular port)

0.67
Q (T / TF ) 1 T TF : fuel stream temperature
L f ,thy = F
4D ln(1 + S1 ) Tflame
T : oxidizer stream temperature
Q (T / TF ) D : diffusion coefficient for oxidizer at T
L f ,expt = 1330 F
ln(1 + S1 )
S : molar stoichiometric oxidizer-fuel ratio

(3) from phenomenological analysis (practical conclusion verified in many ways)

volumetric flowrate QF
Lf
mass diffusivity D

(4) Other correlations......

67

Effects of different factors on laminar jet flame length

(1) Effects of flowrate & geometry L f (QF ) n ( n > 0)


FACE9 Theory of Combustion

In all these conditions: Buoyancy-controlled flame

Linear dependence of flame length


on flowrate for circular port

Somehow greater-than-linear
dependence for the slot burners.

At same flowrate: The more narrow


the slot burner ports (h/d
increasing), the significantly shorter
the flame becomes.

Short flame frequently desired in


design.

Increased surface area of jet, thus radial diffusion


becomes more important (shorten flames)

Predicted flame lengths for circular & slot burners having equal port areas

68
(2) Factors affecting stoichiometry
Pure fuel from nozzle

Lf Sn
(C4H10)
(n > 0)
(C3H8) moles ambient fluid
S : molar stoichiometric ratio, =
moles nozzle fluid stoic
FACE9 Theory of Combustion

(C2H6)
[Example]: Pure fuel from nozzle, ambient fluid is air
(CH4) C x H y + a (O 2 + 3.76 N 2 ) x CO 2 + ( y / 2) H 2 O + 3.76a N 2
( x + y / 4) y
xO2 x+ y
S= = 1 4 = 4.76( x + 4 )
1
1+ 3.76

Fuel + air (0% ~ 80%)


from nozzle

Decreased S Increased xO2, thus decreased S

69

Turbulent diffusion flame


- visually have brushy edges
- width of the flame zone increases
with downstream distance
FACE9 Theory of Combustion

- Laminar flame:
flame height independent
of jet diameter; only on flowrate

- Transition:
Transition turbulence plays roles

- Fully turbulent flame :


(1) shorter than laminar flame;
(2) further increase in flowrate,
flame height keeps constant, or
increase slowly (increased axial
convection & radial diffusion);
diffusion
(3) Significant dependence of flame
length on jet diameter.

Turbulent flame length based on


Phenomenological analysis (practical
practical
conclusion, verified in many ways)
ways
L f ,T port size = r j
(proportional to the port radius only!)

70
Turbulent flame length based on simplified analysis
- Same as laminar flame analysis: 4 eqns for 4 unknowns by using Mixture Fraction;
- Difference lies on:
(1) time-averaged variables (v r , v x , f , h ) replace instantaneous ones (v r , v x , h, f ) ;
(2) turbulent transport properties ( t , Dt , t ) replace the molecular counterparts;
FACE9 Theory of Combustion

- By assuming turbulent viscosity, mass diffusivity and thermal diffusivity are all same,
then one turbulent model is required to obtain the turbulent viscosity.
- Calculated results:
(1) Predicted flame length is about 45 nozzle diameters;
(2) Flame aspect ratio (flame length/width) is about 11:1, which is somehow greater
than experimental values of ~7:1 for hydrocarbon jet flames (neglecting density
fluctuations is probably the most serious oversimplification).

f /2
Calculated mixture-fraction distribution
hf using Prandtls mixing-length model (for
turbulent viscosity) applied to a jet flame

71

Factors affecting flame length


- For vertical flames by a fuel jet issuing into a still environment, 4 primary factors:
forces, Fr f ;
(1) Relative importance of initial jet momentum flux vs. buoyant forces
(2) Stoichiometry, f s ;
(3) Ratio of nozzle fluid to ambient gas density, e / ;
FACE9 Theory of Combustion

diameter d j .
(4) Initial jet diameter,

ve f s1.5
Fr f : Flame Froude number, T f T f : characteristic temperature rise

( e )0.25 ( T g d j )0.5
resulting from combustion

- Increased mixing, produced from buoyancy-induced motion, results in relatively


shorter flames in comparison with the non-buoyant case.

72
FACE9 Theory of Combustion

(C3H8)
(CH4)

- The smaller the stoichiometric mixture fractions ( f s


1
+1 ), the longer the flames.
because the larger amount of air to be entrained per kg fuel.
- Increasing the density of the nozzle fluid produces the same effect as increasing the
nozzle diameter.

73

Liftoff and blowout


- At sufficiently low flowrates: attached flame flame quite close to burner tube outlet;
- At increased flowrates: liffoff no continuous flame close to the burner port. Should be
avoided so that stable flame keeps close to the burner, allowing for positive ignition by
FACE9 Theory of Combustion

a spark/pilot flame at burner and assuring a controlled flame position;


- Further increase in flowrates: blowout flame blows out. Should be avoided.

Universal blowout stability curve

- For a fixed fuel, blowout velocities increase with jet diameter


That is why it is hard to blow out oil-well fires.

74
MM5: Burning of Solid Fuels
FACE9 Theory of Combustion

Contents

Heterogeneous reactions
Homogeneous reaction: as a result of colliding gas-phase molecules (MM3-4)
Heterogeneous reaction: reaction involving species in different physical states

Burning of carbon
Overview
One-film model: three important regimes (diffusion-, kinetics-, competing)
Two-film model

Burning of coal/biomass

75

Heterogeneous reactions
Overall process of gas-solid reactions
1. Transport of reactant molecule to solid surface by convection and/or diffusion;
2. Adsorption of the reactant molecule on the surface;
FACE9 Theory of Combustion

3. Elementary reaction steps (complex physical chemistry). Instead, three rate


laws could be used, as a result of how strongly the reactant and/or product
molecules are adsorbed on the surface:
If the reactant molecules A is weakly adsorbed, then reaction rate is proportional to
the gas-phase concentration of A adjacent to the surface,
= k (T ) [ A ]
If A is strongly adsorbed, then reaction rate is independent of the gas-phase
concentration of A,
= k (T )
If the reactant molecules A is weakly adsorbed, while the product molecules B is
strongly absorbed, then reaction rate is proportional to the concentration ratio of A
immediately adjacent to the surface,

= k (T )
[A]
[B ]
4. Desorption of product molecules from the surface;
5. Transport of product molecules away from the surface by convection / diffusion.
76
Burning of carbon
FACE9 Theory of Combustion Overview

77

Carbon attacked by either O2, CO2 or H2O, undergoing 4 global reactions at


its surface;
FACE9 Theory of Combustion

The principal product at carbon surface is CO;


CO

CO diffuses away from the surface and reacts with inward-diffusing O2 by


global homogeneous reaction: CO+1/2O2 = CO2;

In principle, carbon oxidation problem could be solved by species, energy


and mass conservation equations (defining all of the elementary reactions),
together with appropriate boundary conditions;

Difficulties:
Difficulties Carbon surface is porous & the surface property changes as the
reaction proceeds Intraparticle diffusion plays a major role sometimes.

Simplified models rely on the global reactions & usually assume the surface
is impervious to diffusion One-
One-film, two-
two-film or continuous film models.

78
One-film model

: temperature peak
FACE9 Theory of Combustion

No flame (reaction) in gas phase!

C+O2=CO2

79

At particle surface: Carbon reacts kinetically with O2 to produce CO2. In general,


this reaction choice is not particularly good since CO is the preferred product at
combustion temperatures. This assumption eliminates the problem of how and
where CO oxidizes into CO2.
FACE9 Theory of Combustion

How to evaluate (1) mass burning rate of carbon m & C ; (2) carbon surface
temperature Ts ; (3) mass fractions of O2 and CO2 at carbon surface?

(No gas-phase reactions at all)

Gas phase consists of


O2, CO2 and inert gas.

= m& CO
m& net
m& O O2 diffuses inward,
= m& CO
m& C m& O
kg/(s m 2 ) 2 2
reacting with surface to
2 2
form CO2, which then
(mass flux) kg/(s m 2 ) diffuses outward.

The inert gas forms a


stagnant layer.
80
Burning rate of char: from mass transfer (diffusion to particle surface)

1 kg C + I kg O2 ( I + 1) kg CO 2
m& O2 = I m& C kg/s (mass flowrate)
I =
MWO 2
= 12
32 = 2.664
FACE9 Theory of Combustion

MWC
m& CO2 = ( I + 1) m& C kg/s (mass flowrate)

m& ( r ) = 4 r 2 m& (r )
Substituting the above expressions into the diffusion law:
dYO2

m& O + m& CO
= YO2 (m& O ) D kg/(s m 2 ) (Ficks law of diffusion)
{2 144 42 444 3 142dr
2 2

mass flux
43
mass flux of O 2 mass flux of O 2 by
of O 2 by bulk flow molecular diffusion

YO2 = YO2 , s at particle surface (r = rs )


Together with 2 boundary conditions:
YO2 = YO2 , at infinitely faraway (r )

1 + YO2 , / I Y Y
m& C = 4 rs D ln = 4 r D ln1 + O2 , O2 ,s
1 + YO , s / I s
2 I + YO2 ,s
if B is small, then ln(1 + B) B

YO2 , YO2 ,s YO2 , YO2 ,s Y


m& C = 4 rs D =
I + YO2 ,s I +YO2 ,s Rdiff
4 r D
81 s

Burning rate of char: derived from chemical kinetics @ particle surface

Assume the reaction C + O 2 CO 2 is the first-order with respect to O2.


FACE9 Theory of Combustion

[
, s = & C MWC = kc (T ) O2,s MWC
m& C ] (kg/s m 2 )

where kc = A exp( E A / RuTs )

YO , s
[O2,s ] = P RMWT mix MW 2
(kmol/m3 )
u s O2
(O2 weakly adsorbed at carbon surface)

m
&C
C + O=
2ACO
sm , s
&2C
P MWmix YO2 , s
= 4 rs2 A exp( E A / RuTs ) MWC
RuTs MWO 2 (kg/s)

YO2 ,s 0 Y
=
Rkin Rkin
I RuTs
where Rkin =
(4 rs ) A exp( E A / RuTs ) P MWmix
2

82
Net burning rate of char: circuit analog & different regimes
FACE9 Theory of Combustion

Particle surface

I + YO2 , s
YO2 , Rdiff
(4 rs ) D
m& C = (kg/s)
Rdiff + Rkin I RuTs
Rkin
(4 rs ) A exp( E A / RuTs ) P MWmix
2

Rkin 1 1 I Ru D
= Ts exp( E A / RuTs )
Rdiff rs P A MWmix ( I + YO2 , s )

83

How to calculate particle surface temperature? Energy conservation


FACE9 Theory of Combustion

=0 (steady state)

dT
m& C hC + m& O2 hO2 m& CO2 hCO2 = Q& s i + Q& s f + Q& rad = k g As + s As (Ts4 Tsurr
4
)
144444244444 3 { dr r
= m& C hC =0 s

84 Ts
Two-film model: more realistical than one-film model

: temperature peak & only products


FACE9 Theory of Combustion

(No CO or O2!)
(CO & CO2)
(CO2 & O2)

C+CO2=2CO

CO+0.5O2=CO2

The mass burning rate of carbon is solved in the similar way as one-film model.

Continuous- model a flame zone is distributed within the boundary layer,


Continuous-film model:
85 rather than in a sheet.

Burning of coal (biomass or other solid fuels)


Different basis: AR (as received), DAF (Dry and Ash Free)

As Received (AR) basis


Dry basis
FACE9 Theory of Combustion

Dry and Ash Free (DAF) basis

A C H O N S MI Ma

Ash Fixed Carbon Volatile Matters Moisture

Proximate analysis vs. Ultimate analysis of the fuel

Proximate analysis (AR) Ultimate analysis (DAF)

Moisture (M), %wt C, %wt


Volatile matters (VM), %wt H, %wt
Fixed carbon (FC), %wt O, %wt
Ash (A), %wt N, %wt There are still some other minor or
LHV, kJ/kg (as received) S, %wt trace elements, such as Cl, Hg, ...

sum up to 100%wt sum up to 100%wt

Ash analysis (mineral matter)


e.g., contents (SiO2, K2O, Na2O, Al2O3, ...) and Softening & Deforming temperature;...
86
May burn in the different ways due to the heterogeneous nature & the wide
variation in composition. But generally described by:
FACE9 Theory of Combustion

(1) As the wet coal particle heats up, water is driven off

(2) Drying continues and devolatilization begins

(3) Drying & devolatilization continue; volatiles ignite

(4) Drying complete, devolatilization continues; and volatiles


combustion continues

(5) Devolatilization & volatiles combustion complete; and


residual char combusts

87
FACE9 Theory of Combustion

Experts will further this topic in 2nd period:


(1) Combustion modelling
(2) Practical combustion technology

88

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