Beruflich Dokumente
Kultur Dokumente
Theory of Combustion
FACE 9
Fall 2005
[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
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
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)
- 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
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
Transform 1st law from closed system to open system (CV) by using Reynolds
transport theorem (RTT) + Add
dd flow work (done by pressure).
dE sys
dt
=
t cv cs
e dV + e V n dA
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
( Q& ) p = dH = U + pV = U + n Ru T
where n = ( nprod nreact ) ideal gas = 0.5
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
10
[Example] Use bond energies to estimate the enthalpy of formation of C2H6O (g)
H H
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 )
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
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
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.
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
Constant-
Constant-volume adiabatic flame temperature (e.g., in an ideal Otto-
Otto-cycle analysis)
15
[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.
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
[ ] ( 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
( 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
Contents
FACE9 Theory of Combustion
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.
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
(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
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
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
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 )
(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
27
N N
ji X j ji X j for i = 1, 2, L, L
FACE9 Theory of Combustion
j =1 j =1
28
[Example] How to use the compact notation for the 4-reaction & 8 species?
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
d Xj[ ] L
& j =
dt
= ( ji qi ) for j = 1, 2, L, N
Laminar flame (finite-rate model)
i =1
FACE9 Theory of Combustion
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
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
[C]c [D] d L Ni P
Kc = Molar concentration X i = [ ] = i
[A]a [B] b L V RuT
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
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:
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
Contents
FACE9 Theory of Combustion
36
Two type of flames
Flame: A flame is a self-sustaining propagation of a localized combustion zone at
subsonic velocities.
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37
Outer flame
(diffusion)
Outer cone
Hot region
Conical flame
(premixed)
Inner cone
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
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
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different conical
surfaces (!!! Differences
exaggerated: total
thickness is on the order
of 1 mm)
41
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).
42
Flame speed
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.
- 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
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
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
! 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)
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)
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 &
49
51
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.
- 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
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
Contents
FACE9 Theory of Combustion
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
- 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
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
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
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
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
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
- 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
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
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
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 + ) +
- 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
- 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 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
volumetric flowrate QF
Lf
mass diffusivity D
67
Somehow greater-than-linear
dependence for the slot burners.
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
69
- Laminar flame:
flame height independent
of jet diameter; only on flowrate
- Transition:
Transition turbulence plays roles
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
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
72
FACE9 Theory of Combustion
(C3H8)
(CH4)
73
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
= 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
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
C+O2=CO2
79
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?
= 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.
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
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
[
, s = & C MWC = kc (T ) O2,s MWC
m& C ] (kg/s m 2 )
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
=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
(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.
A C H O N S MI Ma
(1) As the wet coal particle heats up, water is driven off
87
FACE9 Theory of Combustion
88