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Structure & Calculation of A Gas Flame: Y.V. Kryzhanovsky V.N. Kryzhanovsky
Structure & Calculation of A Gas Flame: Y.V. Kryzhanovsky V.N. Kryzhanovsky
Kryzhanovsky
539.91.01
Kyiv
2012
2
539.91.01
24.54
K 85
Kryzhanovsky Y.V.
Structure and calculation of a gas flame: monography/ Y.V. Kryzhanovsky, V. N. Kryzhanovsky. –
Kyiv, Ukraine, 2012.
ISBN 978-966-188-200-2
The basic concepts and constants of gas burning have been defined. The mathematical
apparatus for calculation of the characteristics of a gas flame to organize combustion process have
been presented. The structure of a gas flame and the structure of a flame front were considered.
Independence of structure of a flame front from turbulence was proved. The experimental results
which were laid down in the base of phenomenological combustion theory of gases were presented.
The book is intended for the researchers and the engineers working on combustion, and can be
used as the education guidance.
Yuri Kryzhanovsky
01135, Kyiv, Peremogy ave., 16-34
+380 44 243 04 50
+380 67 465 27 92
ju.kryzhanovskiy@gmail.com
3
TABLE OF CONTENTS
Preface …………………………………………………………………….. 3
Legend …………………………………………………………………….. 4
1. Definition of a subject of inquiry and its phenomenological properties ….. 5
2. Laminar flame …………………………………………………………… 7
3. Turbulent flame ………………………………………………………….. 8
4. Demonstration of the independence of chemical kinetics and combustion
constants on turbulent characteristics at homogenous mixture burning…... 9
5. Calculation of the thickness of a laminar flame front …………………… 18
6. Calculation of λn and Un for different initial parameters ………………….. 21
6.1. Comparison of the calculated thickness of a flame front with the space
characteristics of a flame …………………………………………………. 23
6.2. Physical interpretation of a Peclet number for a flame …………………… 28
7. Calculation of the peak heat density of combustion ……………………… 28
8. Calculation of length of a turbulent flame and combustion chamber ……. 30
9. Structure of the laminar flame front ……………………………………… 32
9.1. Temperature measurements on the flame front thickness ………………. 33
9.2. Measurements of LPR concentrations on the flame front thickness ……… 39
9.3. Chemical interpretation of the structure of a laminar front ……………… 43
9.4. The general combustion mechanism of hydrocarbons ……………………. 47
10. Formation of nitrogen oxides in a flame front …………………………… 49
10.1. Formation of nitrogen oxides at a stage burning of gas ………………….. 51
10.2. Definition of the minimum theoretical NОх concentration ……………….. 57
11. Stabilization of a flame and the flame-out characteristic ………………… 59
12. The microdiffusion mechanism of burning ……………………………….. 60
12.1. Structure of a microdiffusion flame ………………………………………. 60
12.2. Calculation of a microdiffusion flame ……………………………………. 65
References ………………………………………………………………… 67
4
PREFACE
The example of the combustion theory development described in this work is significant from
the point of view of the methodological optimization of cognitive processes and the precise carrying
over of these methods for the solutions of various applied problems.
In this work on the instance of combustion theory the basic technology and algorithm of
scientific researches is shown.
The interconnection of all fundamental characteristics of combustion process presented by
this theory and its practical efficiency is not only above than in existing directions, but also it gives
physically adequate picture of the nature of phenomenon and establishes laws, constants and
universal interconnections unknown earlier.
The mathematical apparatus of the new combustion theory presented here can serve as the
manual for making a database for advanced developments with the subsequent comparative
analysis.
Inconsistency of traditional directions of the theory of physical process and phenomenon is
the sufficient reason for carrying out phenomenological controversial theory. Necessity of the
development of such theory can be considered as the element of new scientific culture and ethics.
In 1964 Kryzhanovsky Vladimir Nikolayevich has initiated the investigations related to the
maximization of burning rate in the combustion chambers of gas-turbine engines. Misfit of design
techniques and computational methods to test data pointed to the necessity of carrying out
additional experiments and revising of basic positions of combustion theory of that time.
I express huge gratitude to my father, Kryzhanovsky Vladimir Nikolayevich, for the
possibility presented to me to work freely and to think freely about everything that interests me,
being assured that my interests have social and spiritual worth.
Yuri Kryzhanovsky
5
LEGEND
2. Process Parameters:
U – flame front propagation rate, m/s;
λ – a flame front thickness, m;
ω - volume intensity of combustion (specific), s-1;
V0 - a gas mixture volume flow, m3/with;
v0 - Velocity of a gas mixture, km/s;
v, - velocity of turbulent pulsations, m3/with;
δ - gauge of crushing of moles, m;
lт - turbulence gauge.
Geometrical sizes:
d0 - diameter of a burner, m;
β - flame (or jet) expansion angle;
DCC - diameter of combustion chamber;
V – volume, m3;
L – length, m;
Subscripts:
n - normal;
0 - standard conditions;
L - the laminar torch;
t - a turbulent torch;
f – concerns to a torch;
cc - «a cold cone» (flame zone);
fr - flame front;
cz - combustion zone;
LP - limiting combustion product;
oz - a outlet zone of combustion chamber;
rz - a recirculation zone;
c - at combustion;
in - internal;
ex – external;
p - polytropic process.
6
The object of combustion theory of gases is a gas flame. The flame front is a
flame part only. It follows from this that the stabile flame front takes place only in a
case when the following conditions are met: the presence of certain concentration
pattern of fuel and oxidizer, the presence of stabilization zone of a flame and the
exhaust of combustion products.
In the beginning we will consider a kinetic flame which diffusion processes of
oxidizer and fuel do not influence. It will allow to eliminate the factors not significant
from a point of view of chemical and physical kinetics of combustion. In the final
chapter a comparison of the optimal diffusion flame from technological point of view
termed a microdiffusion flame, with a kinetic flame will be made.
So, a kinetic flame (further a flame) has physical fields of different structure
located only in certain sequence and existing in unison.
A flame consists of three characteristic zones:
- flame front;
- «a cold cone»;
- a stabilization zone or a zone of reverse currents.
The stabilization zone or the zone of reverse currents is a flame part in which
formation of flame front in the concentration pattern of a gas mixture begins due to
combustion products diffusion in this zone.
The volume of a stabilization zone is a part of the first two ones simultaneously,
therefore for simplification of the further reasoning we will consider flame volume
equal to the sum of volumes of "a cold cone» and flame front.
To the phenomenological characteristics of stabilization zone we will return after
the examination of flame front structure.
The flame can be laminar or turbulent. The models of a laminar and a turbulent
flame are shown in Fig. 1.1.
7
a) b)
Fig. 1.1. The phenomenological models of laminar (a) and turbulent (b) flames.
1– «a cold cone», 2 – flame front, 3 – a stabilization zone.
The kinetic flame forms under the influence of the next factors.
The shape of mouth of a burner determines the form of a stabilization zone in
which flame front begins a steady forming. Flame front moves itself orthogonally to
the vector of velocity of combustible mixture in direction from a stabilization zone
with flame front propagation velocity, U. The flame front has thickness, λ.
Flame front spreading in an immobile gas mixture is termed normal front. It
can be characterized by normal propagation velocity, Un and by the thickness of
normal flame front, λn. Value λn represents the size of a flat reaction wave (on a
normal line to it) within which all the physical and chemical transformations of an
initial gas mixture begin and finish.
Specific volume intensity of combustion in the field of reaction wave can
be presented as:
ωn = Un / λn, [s-1]. (1.1)
Flame is characterized by the volume, Vf, and the volume intensity of
combustion, ωf, i.e. by substance quantity (the volume of combustible mixture) which
burns down in flame volume per unit time:
ωf = W / Vf = S v0 / Vf , [s-1] (1.2)
2. Laminar flame
8
At laminar current the flow speed, vо, and the geometrical form of a burner does
not influence flame front propagation rate, what explains the shape of laminar front
quantitatively. The special researches show that flame front thickness in the basic part
of length of laminar flame is constant. In the limits of accuracies of measuring,
thickness of front does not depend on laminar flow velocity, sizes and the shape of
elements of a burner. Thus the following takes place:
Un = UL = const , λn = λL = const. (2.1)
Let us consider phenomenological model of a laminar flame (Fig. 1.1а). Let
velocity vо is constant on cross-section of a jet. Then for the flame volume of a
circular burner that includes the volumes of “a cold cone” and flame front, it is
possible to write down:
VfL = VCCL + VfrL, (2.2)
where for a circular burner with diameter, d0, VCCL = f LCC / 3. The length of “a
cold cone” is defined by the converging of flame front that moves with speed Un to
the centre of a burner, passing path d0/2. For the same time, flow with velocity v0
will translocate front on distance,
LCC = d0 v0 / (2Un).
The volume of front, VfrL = FfrL ∙ λn, where flame front square is defined by the
standing what through all volume of a gas mixture per unit time the flame front goes
with velocity Un, i.e. FfrL = W / Un.
As a result for a circular burner it is received:
Thus, for the given burner the volume characteristics of intensity of process are
function only of chemical-physical properties of mixture.
9
Analogously, assuming for a fantail (rectangular) burner VCCL = f LCC/2, it can
be obtained: ωfL=4 Un / (d0 + 4λn).
For the burner of any shape the relation (2.2) will be written as:
Tab. 1. The specific volume combustion rate for burners of different shapes and
with different conditions of stabilization
ωf = 6 Un / (d0 + 6λn) Circular burner with peripherical ignition
3. Turbulent flame
The volumetrical combustion rate in laminar and turbulent flames ωf, being most
a general characteristic of the kinetic combustion, does not depend on the flow rate, a
flow regime and the turbulence characteristics.
The quantity ωf for the given burner is defined by fundamental velocity Un and by
characteristic of normal front with the dimensionality of length, λn, the same for
burners of any shape and sizes. It will be shown this characteristic is the thickness of a
normal flame front is the fundamental characteristic of flame front and the chemical-
physical constant of a combustible mixture, as well as velocity Un.
Quantities Un and λn are related among themselves univalently through the
phenomenological characteristics of combustion process: 1) the diffusion coefficient of
a limiting product of reaction; 2) an adiabatic combustion temperature; 3) the initial
parameters of a mixture. That fact that quantity ωft is completely spotted by chemical-
physical constants Un and λn and by the geometrical parameters of a burner l and Π
11
and depends on them absolutely in the same way as ωfL, and has allowed to define
chemical-physical constants on characteristics of a turbulent flame.
From the equations (2.5) that have been written down for flames of two burners of
various diameters, we receive relations directly linking Un and λn with ωf:
The single conclusion here can be made: turbulent characteristics do not influence
not only chemical-physical constants, but also details of chemical kinetics.
It is naturally, that other integrated characteristics of the kinetic combustion
should not depend on turbulence characteristics.
In the light of this, that fact that flame radiation as the integral characteristic of
combustion zone, does not depend on turbulence is absolutely natural.
A flame radiates electromagnetic waves of various length and intensity, including
visible ones, depending on composition and parameters of molecules and corpuscles in
a reaction zone.
12
In [1, p. 419] the data on comparison of the light intensity radiated by the
laminar and turbulent propane-air flame at equal flow velocities and ratio of mixture
is cited. For receiving various flow regimes the diameter of a burner has been
changing. By means of a photoelectric cell the light intensity, transiting through a
yellow light filter (mainly radiation of С atoms) and blue filter (mainly radiation of
СН) was measured.
It is revealed that at equal fuel flow rates the radiant intensities of the laminar and
turbulent flame coincide.
The relation of the light intensity, transiting through a blue or yellow light filter is
identical for the laminar and turbulent flame.
Thus, in the laminar and turbulent kinetic flames a equal concentrations of
molecules and radicals are formed and have the same thermal and radiation
characteristics. This fact rather convincingly says that both of flame types at a different
macrostructure have equal microcomposition and that the chemical kinetics in both
cases is identical.
Independence of a Reynolds criterion from an ionic conductivity or strength of
current transiting through the flame which has been put in an electric field [2 - 4] is
so natural. Here the strength of current, irrespective of a flow regime, is proportional
to the flow rate of a mixture of the given composition. In [3] stoichiometrical
methane-oxygen mixtures with the different content of nitrogen, for example, were
used. As a anode the burner was used, and the cathode represented a water-cooled
spiral which had been put round a flame.
The experimental results have strictly confirmed proportionality of the strength
of current to the mixture flow rate. It means that in unit volume of a flame, irrespective
of a flow regime, the same quantity of charged particles occur.
Importance of this fact as the demonstration that a flow regime does not
influence process kinetics increases because communication between velocities of
chemical ionization and combustion is complex and does not represent linear relation
from initial conditions, including from α [5].
13
Therefore changing of kinetics under the influence of turbulence if it would
occur, including the local changes α as it is supposed in [6], would detect at once
change of a current of ionization.
So, we again confirm that the demonstration of correctness of phenomenological
equation (2.5) is at the same time and the most general demonstration of
independence of chemical kinetics of combustion of homogeneous mixture from
aerodynamic and turbulent characteristics of a flow. The effects viewed above are only
special cases of the many possible acknowledgments of this standing.
The some examples confirming relation ωft = ωfL = ωf = const.
In [7] the photos of flames received on the burner with diameter dо = of 2,54 cm (Fig. 4.1) are
given. An average flow rate is same - v0 = 2,14 m/s. A gas mixture: the Cambridge urban gas - air
with Un = 41,8 cm/s. The calculated value of thickness of the laminar front λn = 1,9 mm (a
substantiation of λn on an independent base will be given in the next chapter). Difference in the
form of flames is caused by artificial turbulization of the flow the intensity of which has been
changing by means of turbulators (the perforated plates) in limits, ε = 2,2-7,12 %.
According to equation (2.5) volume intensity of the represented flames: ωft=68,15 s-1, whence
it is possible to receive calculated volume of a flame: Vft = 15, 9 cm3 that is close to the average one
measured on a photo Vtf (meas.) = 16,2 sm3; the discrepancy makes 1,85 %.
Fig.4.1. Photos of circular turbulent flames by [7]: dо =2,54 cm; Vо=2,14 m/s; turbulent scale
l =1,63 1,87 mm; turbulence level: 1 – ε = 2,2%; 2 – 3,02; 3 – 3,8; 4 – 5,15; 5 – 6,05; 6 – 6,35; 7
– 7,12.
On fig. 4.2 the photos of the laminar and turbulent flames are presented at equal flow rates,
ratios of mixture and the same diameters of the burners [1]. The measurings show that flame
volumes are close one to another and equal in arbitrary units approximately 180.
14
Fig. 4.2. A photo of the laminar (a) and turbulent (b) flames¸ taking place at equal flow rates,
ratios of mixture and the same diameters of the burners.
Let's consider now the data available in the literature about a so-called flat flame.
Photos of a flat flame give the square of its cross-section which keeps a constant value on a
normal line to a photo. Thus the flame volume is spotted by equation: Vft = Ff (meas) S, where Ff (meas)
- the square of a longitudinal section of the flame, being measured on a photo.
In Fig. 4.3 the photos of flat flames [8] are presented. Here the square of cross-section of a
burner 40 х 40 mm was used. The two lateral walls of the burner had the continuation optical quartz
bars with 150 mm altitude; on upper and low wall the auxiliary stabilizing burners have been
placed. Apart 55 mm before a burner section were positioned turbulators of a different construction.
Experiment was carried out on a gasoil-air mixture at velocity v0 = 33 m/s, Tmix = 440 - 470 K
at changing only one parameter - turbulence level in limits ε = 1,7 - 15,0 %.
Quantity Un for hydrocarbon-air mixtures with excess-air coefficient near 1,0 can be spotted
by relation:
Un = Un (0) (Tmix/T0) 1,95. (4.3)
This relation extrapolate the data well. For Un(0) = 30 cm/s and Tmix = 455К is received Un = 71
cm/s. It corresponds, by the way, to average value of the data on Un in [8 and 9].
Fig. 4.3. Photos of turbulent flames in burner 40х40 mm for the same flow rates and various
turbulence levels [8].
Calculated value λn =1,9 mm. Then, according to (2.5), assuming Π = 6; l = 4 cm, we receive
ωf = 82 s-1, and flame volume: Vtf (meas) = F0V0 / ωf = 42 3300/82 = 643 cm3.
15
The average measured volume was, Vtf(calc.) = 636m3. The peak diversion Vtf (calc.) from the
average value is 5 %, and Vtf (meas.) from Vtf (calc.) - hardly is more 1 %. As we see, coincidence is
almost absolute.
Let's view the data received on the fantail burner 50,8 х152,4 mm, with unclosed sides [10].
Both cases differ only by the turbulence level which is 7,0 % and 1,55 %. Quantity V0 =9,15 m/s;
Un = 40 cm/s. Sectional areas of flames are 165 cm2 and 167 cm2 accordingly, and the same
quantity in 1 sm3 the flame volume have on 1 sm of length of the slot. The mixture flow rate on 1
sm of length is equal 915 х 5,08 = 4648 cm3/s, then ωf = 27,8 s-1.
The calculated value ωf in this case is defined by equation (2.5) when П = 4, practically
coincides with the measured value: ωf = 4 40 / (5,08+4 0,19) = 27, 4 s-1.
In the theory of the "superficial" combustion for small-scale turbulence the empirical formulas
are received:
Ut = β1 (l / λ)0,5 v’Un, λt = β2 (lλv '/Un) 0,5. (4.4)
Integrating, for example, on a surface of “a cold cone”, we receive:
ωfrt = F-1 ∫∫ Ut / λt dF = (β1 / β 2) Un /λn. (4.5)
Using (1.2) and assuming that intensity in flame front does not depend on the turbulence
characteristics, it is possible to write down:
ωf = 1/(1 / ωcc + 1 / ωn). (4.6)
Using an average integral Ut and λt and on the base (3.1 and 3.2) we obtain:
l / Π Un + 1 / ωn = l / Π Ut+1 / ωfrt . (4.7)
Introducing ωtfr = β ωn we will receive:
β = ΠUtUn / (Π UtUn + lωn (Ut - Un)). (4.8)
Calculations show that for the hydrocarbon fuels with Un = 0,3 - 1,2 m/ s and dо = 0,04 - 0,4 m
and vо = 30 m/s β = 0,3 - 0,04, i.e. the quantity ωtfr approximately 10 times less ωn, it is proved by
numerous experimental data.
In the Longvell reactor [11, 12, 13] at investigations of fuel-air mixtures at standard initial
parameters at flow rate equals sound velocity, at completeness of combustion in the reactor η = 1,0
is received Qv = 330∙106 kcal/m3bar∙hour [14]. At increasing of the flow rate to a flame-out the
quantity ηсг quickly falls (combustion products contains carbon, CO and even Н2) [15]. Thus, as it
is considered, a limiting heat density of combustion for a stoichiometric mixture at atmospheric
pressure and Tmix = 400 K is 2,67∙109 kcal/m3bar∙hour. In the viewed investigation as a fuel 2,2,4-
three-methyl-pentane and heptanes were used.
Let's compare the result received above at η = 1 with calculation by our equations. For an
explored gas mixture it is possible to take over Un = 0,32 m/s, λn = 0,002m, Н = 3300 kJ/m3. For
do=0,00175 m; Π =6 and accordingly with (2.5) and (4.8) is received Qv (meas.) = 4,5∙105 kW/m3. If
the factor of usage of reactor volume - 0,9 (as it quantity is appreciated in the literature), for
example [16], we have Qv (meas.) = 4,0∙105 kW/m3 or 344∙106 kcal/m3bar∙hour that is close to
received in [14].
At use of the jet conical and cylindrical front devices as a model of highly forced combustion
chambers [17] with diameter of holes in lateral walls do=4mm at forcing of a cross-section of
combustion chamber 120∙106 kcal/m2 the heat density of combustion zone is 3,72∙105 kW/m3
(320∙106 kcal/m3), and calculation for a single jet gives quantity of 3,77∙105 kW/m3 (324∙106
kcal/m3).
16
For given burner at a constant flow rate of combustible mixture the value Vf
remains constant, while at transition from laminar flow regime to turbulent one the
volume ratio Vcc to Vcz is changing. Thus, as it was shown, microcomposition of a
flame did not change, but the macrostructure was changing.
For the laminar flame of the circular burner in uniform field of velocities a value of
each of two parts of total amount of a torch is proportional to velocity v0, and the
ratio between them is a constant,
VccL/VczL= d0/6λn . (4.10)
Write down relation for ωf in view,
Thus, in a laminar flame the combustion zone volume is a flame front volume.
Equation (4.12) we can rewrite in view
Accordingly (2.5) for a turbulent flame the common equation (4.12) and Eq.
(4.15) are valid.
Let’s rewrite Eq. (4.12) in view
Introducing that
Let's view a case of the strong turbulence; here according to [11] velocity of
turbulent front is close to velocity of turbulent conduction, i.e. Uт ~ v’. Then on the
basis of (2.5), (4.15) and (4.18) we receive
According to the data [21] where reaction rate was appreciated by strength of current of
ionization, combustion rate in a turbulent flame was 10 times less, than in the laminar front.
18
In this work the investigations were fulfilled on the burner with diameter d0=0,3m; a gasoil-air
mixture was applied; initial temperature Tmix = 240 0С. If Un = 1,0 m/s, λn = 0,0018m then ωn =555s-1.
A flow rate was 30 m/s. For a case of natural tubal turbulence ε = 0,05, v ’ = 1,5 m/s. Introducing all
data in (4.20), we receive the result matching [21]: β = 0,097.
So, we will consider flame front as the area that exists between two surfaces on
which the chemical reactions and increasing of temperature from initial value Т0 to the
peak adiabatic combustion temperature ТC begin (the forward boundary) and finish
(the back boundary of front) accordingly.
The thickness of normal flame front is more than free length of molecules and
radicals, Λ, in combustion zone in some orders; the collision number of one corpuscle
for residence time in a front can attain 106 - 107. Whatever a way of the chemical
reactions (number of its links is only tens at burning of organic fuel) it is necessary to
expect that distributing of reaction products in space, and, hence, the thickness and
velocity of a flame front will be essentially spotted by the molecular diffusion laws.
Such a method allows to avoid necessity of considering of chemical kinetics of
a given mixture connected with intermediate reaction products, length and branching
of chains.
As Λ << λn, then without an appreciable lapse for an estimate λn, it is possible to
take over that the beginning of formation of finished combustion products coincides
with forward boundary of flame front, i.e. with the beginning of reaction and with
increasing of temperature in an mixture. It follows also from a statement that the
kinetic mechanism outruns the thermal conductivity mechanism in a gas mixture; it
had been stated still in [23, 24] . At the basis of it the following reasoning lies.
A sense of the Arrhenius equation for reaction rate and temperature consists that
reaction rate is spotted by the quantity of the active molecules fallen into the "tail"
maksvell-boltsman allocation, i.e. ones having the greatest forward speed and energy.
20
All molecules of finished combustion products formed again belong to these active
ones (in view of high formation heat). There are no reasons to consider that at first
these molecules will lose the energy in the course of collisions, and only after this the
molecules arisen as a result of Maksvell-Boltsman allocations with high energy will
take a part in chemical reaction extending. With the greatest probability a
participation in reaction extending will be taken over by non-equilibrium products of
combustion. Such picture matches also to the phenomenon of an energy branching of
chains in chemical reactions [25].
When in the course of reaction the single finished combustion product is formed
the value λn can be spotted on two points: the beginning of its formation and
achievement of the peak concentration. At formation of several substances the
representative product, limiting process should be chosen. At burning of hydrocarbons
in an mixture with air (oxygen) the finished combustion products are Н2О and СО2.
The peak concentration Н2О is attained already in the front area (as the examinations
show). Thus, here СО2 acts in the role of the limiting product.
According to offered model of the process, СО2 molecules, forming and diffusing
from back to the forward boundary of front with high energy , as well as other active
particles, will cause origin of reactions. The new СО2 molecules formed in a front will
pitch "relay race" in a new mixture with the greatest probability as a result of the first
collisions after the moment of the formation when their temperature (energy) is close
to peak or the adiabatic combustion temperature Тc. It is necessary to notice that the
idea of "relay race" process with the maximum diffusion rate is considered in [14,
with. 93], but here it concerns to narrow zone near to outlet temperature. In the present
reasonings this standing is concerning all thickness of a flame front and all corpuscles
which initiate reaction.
But at the phenomenological description the question is restricted by a
considering of behavior of molecules СО2.
As pressure in flame front is almost equal initial pressure Р0, for СО2 on all
thickness of flame front it is possible to consider a self-diffusion coefficient as a
constant value,
21
DCO2c = ΛСО2c vCO2c /3, (5.1)
where ΛСО2c and vCO2c are free length and an average velocity of СО2 molecules at
parameters Р0 and Тc.
Here is not only ρCO2 is relatively small at ρN/ρ ≈ 1, but ΛNc vNc <<ΛСО2c vCO2c.
Therefore it can be obtained:
This assuming makes the task considerably simpler. Hence the diffusive model of
flame front propagation has been reduced to one-dimension scheme, in which diffusion
coefficient does not depend on X.
Accordingly to the Fick’s second low, we write down:
δnCO2/δx = DCO2c (δ2 nCO2/ δx2), (5.4)
where nCO2 denotes СО2 concentration.
For initial (I) and final (II) cross-sections of a flame front we have nCO2(I) = 0 and
nCO2(II) = nCO2max accordingly. For the steady-state diffusion processes the left part of
Eq. (5.4) equal zero, then
This quantity must be the same on any area of flame front because the process is
steady-state. The quantity of flow we can define also by average flow velocity of
substance,
In this case substance velocity is identical to propagation rate of normal flame front:
WCO2 ≡ Un. Taking into account it on the basis of (5.7) and (5.8) it is obtained
λn = DCO2c / Un . (5.9)
Z ~ v n2. (6.1)
Here v and n denote average velocity and a number of particles in unit volume.
At constant pressure for ideal gas v ~ T0,5; n ~ T-1 then
Z ~ T-1,5 . (6.2)
Thus, for the laminar flame front thickness of hydrocarbon-air mixture at standard
pressure it is obtains:
λn = (DLP(0)/Un(0))(Tc/T0)1,9(T/T0)1,5(Р/Р0)-0,7 . (6.6)
λn = (DLP(0)/Un)(Tc/T0)1,9(Р0/Р)-0,27. (6.8)
A number of the space characteristics of the laminar flame front (widely explored
experimentally) is closely tied to the thickness of a laminar flame front and practically
coincides with it on quantity. So, at ignition of a mixture by means of an electrical
spark the characteristic quantities are – the quenching electrode spacing having flanges
on the ends, lqs, and almost equal to it the minimal electrode spacing at the minimal
25
ignition energy, lminМIE. The comparisons have shown that values lqs and lminМIE are
almost equal to the value λn received by us for the given mixture. The critical
(quenching) spacing, lcr(s), defined by flame passage through a slot, is close to the
flame front thickness also.
In Fig. 6.1 the photos illustrating a measurement procedure of critical diameter
of flame flash-back in tube, dcr, are given. Internal tube is changeable. For every
diameter of this tube, dt, the certain value α exists at which ceasing or deceleration of
mixture flow rate causes flame quenching, but not extending it in a tube.
For this α a given value dt was accepted as dcr. Conformity λn to the empirical
values (2/π)dcr is quite satisfactory.
Fig. 6.1. Illustration to definition dcr by means of flame-out on a tube inlet of small diameter. In the
instance in a photo dt > dcr for a gas mixture with given α.
For definition lcr (s) other procedure was applied. In a tube of big diameter (d = 36
mm) the shutter with the adjusting slot was installed. Interior volume was filling by a
mixture of the same composition and was igniting on the one side of tube. After each
ignition the slot was incremented by 0,1 mm.
If the flame flash-back occurred at a given slot thickness then previous value lcr(s)
(i.e. 0,1 mm less) is accepted as the critical one. Data lcr(s) depends on experimental
conditions a little, however, being received in the same conditions, they are correlated
with data λn well.
In Tab. 6.2 values λn, calculated by Eq. (6.3) and experimental data lcr(s) [29, Tab.
58] for a stoichiometric mixtures of various hydrocarbons with air are given at
standard initial parameters. Conformity is in limits of measurement accuracy.
26
Tab. 6.2. – Comparison of lcr(s) ([29], tab. 58) with calculated values λn, received
by Eq. (6.6), for hydrocarbon-air mixtures; initial parameters – normal; DСО20 = 0,11
sm2/s; n = 1,95; α = 1,0.
Chemical Un Тc λn lcr(s)
Hydrocarbon
formula cm/s К mm mm
Methane series
Methane СН4 31.0 2236 2.00 2.03
Ethane С2Н6 35.5 2245 1.84 1.78
Propane С3Н8 34.5 2250 1.70 1.78
Butane С4Н10 33.5 2255 1.78 1.78
Pentane С5Н12 34.0 2250 1.74 1.78
Hexane С6Н14 34.0 2239 1.73 1.78
Heptane С7Н16 34.0 2214 1.67 1.78
Ethylene series
Ethylene С2Н4 62.0 2375 1.19 1.27
Propene С3Н6 38.6 2339 1.64 2.03
Acetylene series
Acetylene С2Н2 125.0 2600 0.71 0.76
Propine С3Н4 62.5 2470 1.29 1.27
Cyclopropane С3Н6 42.0 2328 1.49 1.78
Cyclohexane С6Н12 34.0 2250 1.74 1.78
Benzol С6Н6 35.8 2305 1.72 1.78
The data of lqs and lminMIE at various pressures Р0 are available in literature and
allow to check legitimacy of Eq. (6.3).
Accordingly to Fig. 6.2 the calculated values λn, obtained by equation (6.3) for
different hydrocarbon-air mixtures, coincide with empirical data of the space
characteristics of the laminar flame front in these mixtures: lqs, lcr(s), lminМIE. This fact
is rather important, as it allows making the validation of obtained relations for λn by
means of references data.
min
Fig. 6.2. Flame front straight-line characteristics dependence of pressure; Т = 293К. 1 – l МIE СН4
– air [14]; 2 – lqs [30]; 3 – lcr(s) [31], С3Н8 – air; 4 – lqs, С2Н6 – air [14]; – λn – calculation by (6.3)
and (6.6).
27
Computational model, as we have seen, does not demand considering of the
complex chemical kinetics. This statement is principal. Its validation is comparison of
calculated values with empirical results for mixtures with different physical and
chemical properties. Certainly, using equations (6.3) and (6.6) for every mixture it is
necessary to choose a matching reactant product limiting the process. Furthermore, it
is necessary to consider that combustion temperature Тc can be significantly less than
a calculated temperature especially at low pressures [5]. For calculations λn the real
adiabatic temperature of process, which is taking into account dissociation, should be
used.
The results of calculation λn by Eq. (5.9) and empirical data of values lcr(s) for
ammonia gas mixtures [32] at choosing nitrogen N2, as a limiting reaction product,
which forms as a result of recombination of atoms N at a finish stage of process,
provides almost full conformity of calculation and experiment.
In Tab. 6.3 a comparison of values λn calculated by equations (6.3 and 6.6) with
references data of typical dimensions of flame front for various gas mixtures, with
very different intensity and type of chemical reactions proceeding in them is yielded.
Tab. 6.3. Comparison of calculated values λn with the typical dimensions of a normal
flame front of gas mixtures with various compositions and initial parameters.
Gas mixture Т Р LPR Un D0 n Тc λn, lcr(s), λn,by Т-
calculat. lqs profile
2
- К Pa - cm/s cm /s - К mm mm mm
СН4 - 2O2 293 105 CO2 330 0,11 1,95 3100 0,24 0,28
СН4-О2 -Air 298 4.2*103 CO2 81 0,11 1,95 1850 13,40 - 14,0
30%Н2 – air 293 105 H2O 170 0,23 1,80 2260 0,62 0,62 0,64
20%Н2 – air 293 105 H2O 100 0,23 1,80 1910 0,69 0,70
10%Н2 – air 293 105 H2O 28 0,23 1,80 1440 1,48 1,50
7%Н2 – air 293 105 H2O 8 0,23 1,80 1000 2,67 2,80
Н2 - O2 - N2 336 105 H2O 9 0,23 1,80 1076 3,42 - 3,5
2Н2 - O2 293 1,5∙105 H2O 900 0,23 1,80 3020 0,12 - 0,127
2Н2 - O2 293 4,5∙105 H2O 1300 0,23 1,80 3020 0,038 - 0,037
21,85 % NH3- air 293 105 N2 6 0,17 1,90 1750 7,80 7,80
19,0 % NH3- air 293 105 N2 4 0,17 1,90 1460 8,50 8,60
17,0 % NH3- air 293 105 N2 3 0,17 1,90 1260 9,88 10,00
4NH3 – 3 O2 293 105 N2 125 0,17 1,90 2700 0,92 0,92
NH3 – O2 293 105 N2 150 0,17 1,90 2400 0,62 0,65
Decomposition
reactions
28
O3 O2 293 105 O2 54 0,18 1,80 1260 0,55 - 0,55
N2H4 NH3 ; H2 ; N2 293 105 N2 155 0,17 1,90 1850 0,35 - 0,25
Remarks. The values lcr(s) and lqs are taken from the following references: for СН4 – 2O2, СН4 – О2 –
Ar and Н2 – air – [14]; for NH3 – air – [33]; for NH3 – O2 – [34]. Value λn, defined by Т-profile, is
taken from the following references: СН4-О2 – Ar [35]; Н2 – air – [1]; Н2 – O2 – N2 – [36]; 2Н2 –
O2 –[25]; O3 O2 – [37].
Calculation of basic flame characteristics has a great practical interest for the
creation of highly forced devices, for instance, of aircraft engines as it allows to find
the maximum volumetric intensity of combustion for various "fuel-oxidizer" mixtures
at various initial parameters.
Let’s write down a formula for ωn using a general relation ωn = Un / λn and Eq.
(6.6),
wherе H = cv∙Qlw denotes the lower working combustion heat of a mixture, kJ/m3; cv denotes the
dimensionless volume fraction of a combustible gas in a mixture; Qlw denotes the lower working
combustion heat of gas, kJ/m3
Example. For a stoichiometrical methane-air mixture at normal initial parameters, using values
Un and λn from Tab. 6.3 and other data from [39], we receive
Qvmax =0,0947 ∙ 35875 (0,31/0,002) = 5,27 105 kW/m3.
Let's notice here that almost same value QVmax for a natural gas mixture (СН4 98 %) with air
has been received in [24] on the basis of investigations of turbulent combustion. For a stoichiometric
propane-air mixture in normal conditions it is received
Qvmax =0,0402 ∙ 91350 (0,345/0,0017) = 7,44 105 kW/m3.
For the mixture СО(29%) – air Тc = 2370 К; Un = 26,5 cm/s [14]. Then accordingly to (6.3)
we obtain:
λn = (0,11/26,5) ∙ (2370/293)1,95 = 0,245 cm,
Qvmax = 0,29 ∙ 12645 (0,265/0,00245) = 3,97 105 kW/m3.
The greatest values of a volumetric heat density of combustion are attained in mixtures С2Н2
and Н2. For a stoichiometrical acetylene-air mixture at normal initial parameters it is received
Qvmax = 0,077 ∙ 56092 (1,25/0,00071) = 7,6 106 kW/m3.
For the mixture hydrogen (30 %) – air
Qvmax = 0,03 ∙ 10806 (1,7/0,00062) = 8,9 106 kW/m3.
30
The volumetric heat density of burning is increasing sharply at replacement of air by oxygen.
So, for a mixture 2Н2 - О2 at normal initial parameters and values Un = 900 cm/s and λn = 0,018 cm it
is received: Qvmax = 3,6 108 kW/m3.
The increasing of initial mixture temperature yields considerable possibilities of combustion
intensification. So, for example, for a stoichiometric methane-air mixture at standard pressure and Т0
= 693 K the value Qvmax = 1,5 106 kW/m3 that 2,85 times more than at Т0 = 293 K.
Un = m/(Π∙p), λn = a / Π. (8.2)
In such conditions the flame length, Ltf ≈ Vf / FCC. On the basis (1.2) it is
possible to write down,
Vf = m∙FCC∙v0/ωf . (8.3)
31
Then for the circular burner on the basis (2.4) we have
The formula (8.4) can be used and for burners of other type at m ≈ 0,5. Over the
range of velocities (υо = 20 50 m/s) the result is underrated on 5 10 % accordingly.
At the further increasing υо and m the lapse is decreasing.
For more exact calculation of sizes of combustion chamber it is necessary to
consider a flame filling factor as its volume (besides combustion zone) includes two
more zones. One of them is a recirculation zone with volume VRZ, second one is exit
zone of chamber - VEZ which spots concentration and temperature outlet patterns.
Volume VZR (at a flame tangency of combustion chamber walls) is spotted by its
sizes and an disclosing angle of a burning jet, β. The angle β for a flat burning jet is
equal 14 180, and for round jet - 21 230. For the circular burner and combustion
chamber it is received,
The value VEZ as well as VRZ is spotted by cross-section of a jet, by a free area
coefficient, m and for a developed turbulent flow does not depend from υо
practically. Therefore the total volume of specified zones of combustion chamber can
be written down as,
For example, for a slot-hole combustion chamber, taking into account empirical
equation for k, (8.6) and (8.7) it can be received,
Tab. 8.1. Comparison of experimental data ([14], p. 303) and the values of
length of an open turbulent flame in an air cocurrent flow calculated by (8.8).
№ d0 v0 Df Lf(exp) Lf(c) Lf(exp) /Lf(c)
experiment calculation
- cm cm/s cm cm cm -
Natural gas - air; Un =40 cm/s; λn = 2,0 mm; β = 180 .
1 3,16 1220 4,00 23,14 24,0 0,97
2 2450 4,11 34,23 36,5 0,94
3 3680 4,10 43,08 49,0 0,88
4 4900 4,71 58,82 49,0 1,20
5 5,08 2320 6,05 38,40 52,5 0,73
6 3085 7,10 53,08 49,5 1,07
7 4940 6,78 60,00 80,0 0,75
Acetylene – air; Un =175 cm/s; λn= 0,63 mm; β = 240 .
8 2,06 2540 2,30 9,38 11,0 0,85
9 3630 2,36 12,30 12,5 0,98
10 5450 2,57 14,43 13,5 1,08
11 7250 2,52 16,22 16,5 0,98
33
The T-profile general view in a flame front can be received on the basis of
following reasoning. Admitting that a thermal conductivity Λ on a flame front
thickness is constant at the given value of density ρ0 and heat capacity сp we will
write down: ΔT ~ ρ0 cp / Λ. Each of the specified quantities is temperature function
(and, hence, is co-ordinate X function), and the complex which they form, is an
34
inverse quantity to a thermal diffusivity a. As it is known, for real gases a is function
of temperature of a view a = а0 Тn (here the exponent n is close to 2,0). Taking into
account the told above, equation for dT/dx becomes,
If integrate this equation with n = 1,9 - 1,95 the result will reflect the real
character of dependence. The basic part of a real T-profile on the considerable length
from forward boundary of flame front represents almost straight line.
At measuring of T-profile in flame front by means of a thermoelectric couple it
is necessary to consider some specific moments. At measuring of temperature
difference with accuracy 0,5 degrees in the T-profile beginning, the area with rather
slow increase of temperature occurs 2-5 K/mm. It is less on 2-3 orders than it is
received at calculation by means of a thermal conductivity or the diffusion of high-
temperature reaction products.
The carried out investigations allow to explain the T-profile shape on an initial
sector of the front by influence of a radiant flux from a flame on thermoelectric
couple indications. This effect practically does not affect the basic part of a profile
when the thermoelectric couple is in flame front, but is rather essential at approach to
front when a thermocouple junction which is still in the field of an intermixture with
initial temperature and receives heat only at the expense of radiation. It is the reason
of appearance of an additional ("transitive") area of a T-profile in its beginning.
Let's build profiles of a relative temperature in co-ordinates (T-T0) / (Tc-T0) and
x / λn for different values of an excess-air coefficient and for the same other
conditions (Fig. 9.1).
Extrapolation to the field of initial temperature Т0 allows to receive a beginning
point of the real T-profile, Xa (Fig. 9.2). Distance change between a point of Xa and a
point of Xa(meas.) in which the beginning of temperature increase takes place will be
caused by radiation from a flame mainly.
35
Fig. 9.1. Influence of a flame radiation on initial area of a Т-profile at different values α.1 -
extrapolation of the basic area of the T-profile to initial temperature; the measured segment of the
T-profile; 2 - α = 1,13; 3 - α =1,29; 4 - α = 1,56.
Fig. 9.2. Effect of various factors on the measured T-profile: 1 - an initial arbitrary profile; 2 -
effect of the diameter of a thermocouple junction, dj = Δl; 3 - effect of oscillations of a front with
amplitude los; 4 - radiation effect.
The segment length on which Т-х profile distorts from each side is equal: 0,5 (dj
+ los). Value los during our measuring makes about 0,1 mm. The same estimate is
made for flame front of a propane-air mixture in [40].
At finding of a point of Xa by extrapolation of the basic segment of the T-profile
in area of initial temperature its contortion on an initial segment on account of a
thermocouple junction finite value are automatically cut.
Thus, the breadth of normal front at a probe motion on a normal line to it is
spotted by equation
Value Хb* is spotted as co-ordinate of the first point where the peak value of a
flame front temperature is attained.
The catalytic effect cannot exert appreciable agency on the T-profile and,
anyway, on a position of points of Xa and Xb* where process only begins or has been
already finished.
The arrangement in one horizontal plane and attachment on a co-ordinate
support of a thermoelectric couple and a probe simultaneously (Fig. 9.3) allows at
certain spacing between them to receive satisfactory combination of profiles of
temperature and concentration for front of a V-shaped flame.
37
Fig. 9.4. Temperature profiles of the laminar flames: a - a versed cone; υ = 1,50 m/s; α = 1,37;
b - a right cone, υ = 1,70; α =1,13; c - a versed flat flame, d = 0,75 mm, υ = 2,0, α = 1,29; 1, 2, 3, 4,
5 - fields of temperatures in cross-sections 1, 2, 3, 4, 5accordingly.
Fig. 9.5. Input data as in Fig. 9.4. V - shaped flame, α =1,29; β = 260; 1 - h = 3,0 mm; 2 - 5,0;
3 - 8,0; 4 - 12,0; 5 - 15,0; 6 - α =1,48; β = 250; h = 12,0.
Fig. 9.6. The same input data; a versed conical flame, db = 21,5 mm; 1 – dfh = 13,0 mm; β =
0
40 ; h = 10 mm; 2 - 4,0; 50; 10; 3 - 2,0; 40; 12; 4 - 4,0; 30; 15.
39
Fig. 9.7. T-profile at Tmix = 4200С. 1 - α =1,8; β = 550; 2 - 2,05; 50; 3 - 2,16; 26; 4 - 2,3; 45;
5 - 2,6; 18.
In Fig. 9.8 the graphs λn - α for a natural gas-air mixture at different values of Tmix
are given. The values λn, received by direct measurement (by T- and СО2- profiles),
and also the values λn, calculated by the formulas given above for characteristics of a
turbulent flame are superimposed. Values λn, received by two independent expedients,
practically coincide.
Fig. 9.8. Relation of λn - α for a natural gas-air mixture at various initial temperatures of a
mixture.
1, 2, 3 - measurements on the laminar flame front; 4, 5, 6 - calculation by characteristics of a
turbulent flame.
40
For hydrocarbon-air mixtures the limiting product of reaction is СО2. The results
of investigations of temperature and CO2 concentration profiles at different initial
temperatures of a mixture are presented below. The thickness of profiles of
temperature and CO2 concentration are equal for the same mixture. Thus, each of them
can be used for definition of λn.
Measuring of volume concentrations СО2 on the laminar flame front thickness of
a methane-air mixture at different initial temperatures of a mixture and an excess-air
coefficients reveal the complex ordered structure of a normal flame front [41, 42].
In Fig. 9.9 and in Fig. 9.10 the observed data of temperatures and volume
concentrations СО2 on the normal flame front thickness for initial temperatures of a
mixture 20 and 275 oС are presented at the different excess-air coefficients.
Tab. 9.1. Sizes of the typical zones of flame front and temperature in points A, B and C.
Т0= 20 оС
α λOA λAB λBC λn TA TB TC=Тc
1,08 0,34 0,2 1,41 1,95 540 725 2150
1,23 0,58 0,22 1,38 2,18 725 970 1625
1,45 1,0 0,2 1,39 2,59 920 1080 1440
1,70 2,2 0,2 1,32 3,72 1090 1080 1250
Т0= 275 оС
α λOA λAB λBC λn TA TB TC=Тc
1,12 0,2 0,47 1,18 1,85 590 1150 2150
1,30 0,35 0,48 1,35 2,18 680 1180 1900
1,80 0,8 0,52 1,53 2,85 835 1150 1410
2,2 1,7 0,50 1,32 3,52 1000 1150 1260
Note. Sizes ОА, АВ and ВС are given in mm, temperatures – in oC.
43
Табл. 9.2. Dependence of temperature of a front from LPR concentration at the same point
Т0 = 20 оС Т0 = 275 оС
α СО2, Тfr, СО2, Тfr, СО2, Тfr, α СО2, Тfr, СО2, Тfr, СО2, Тfr,
о о о о о о
%vol. С %vol. С %vol. С %vol. С %vol. С %vol. С
1,08 2 550 4 650 6 750 1,12 2 800 3 900 4 1000
1,23 2 680 4 950 6 1150 1,30 2 850 3 1020 4 1030
1,45 2 690 4 1080 6 1200 1,80 2 900 3 1080 4 1180
1,70 2 680 4 1080 6 1200 2,20 2 900 3 1080 4 1180
For an intermixture of natural gas with air at α close to 1,0 and at normal initial parametres it is
received: λn1 = Xa - Х0 = 0,25mm.
At a flame-out regime in Longvell reactor with d0 = 1,0mm the heat density of volume spotted
by the rate of flux of an intermixture at ηсг = 0,83 has made at Р =1bar the value QV = 26,7 108
kcal/m3∙h [15].
On the reactor with d0=1,75 at mixture complete combustion it has been received QV = 33,0 107
kcal/m3h. Recomputation by (2.5) for d0 =1,0mm yields QV = 37,0 107 kcal/m3h.
Let's assume λn = 2mm. Then the average thickness of combustion zone attained in the reactor volume
on a flame-out regime can be spotted as the proportional quantity to the residence time of an intermixture in
the reactor or as inversely proportional to its rate of flux and correlates to λn1: λn (flame-out) = λn (37,0 107/26,7
108) (0,83/1,0) =0,23 mm.
Let's view, how the molecular weight and molecular composition of hydrocarbon
fuels influence chemical-physical constants. We already could be convinced that the
relations between chemical-physical constants have physical character. At the same
time constants are integrated characteristics of chemical kinetics. The description of
their by means of the dependences based on simplified mechanisms considering to
some extent «the basic features» of chemical process is possible with adequate
accuracy. But this accuracy is attained at the expense of empirical coefficients, suitable
only for a separated case. The formal character of these dependences detects itself
when the similar fuels (by the chemical nature), for example - hydrocarbons, cannot be
aggregated description Un on a general basis. Thus, the empirical coefficients entering
into these equations reflect properties of only narrow kind of hydrocarbon compounds.
Even the hydrocarbons entering into one homologous series, for example: 1-butin
and 2-butin, having an equal molecular weight and almost equal peak combustion
temperature (2413К and 2401К accordingly) considerably differ by value of the peak
velocity: Un =58,1 cm/s and 51,5 cm/s accordingly. Difference in structure which for
1-butina appears like C≡C-C-C, and for 2-butina C-C≡C-C and essentially changes
process kinetics that leads to individual character of the empirical coefficients entering
into relations for Un, for equations created on any base. Rather characteristic from the
point of view of blanket legitimacies of burning of hydrocarbons is the fact that (as it
was already noticed) the hydrogen which is a part of molecules of hydrocarbons, burns
out much earlier, than carbon.
46
Now there is very few data on Н2О profiles on a flame front of hydrocarbon-air,
including methane-air mixtures.
The temperature profiles, received in flame front of the same mixture at pressures,
different twice - 104 Pa and 5∙103 Pa - practically coincide, if the linear co-ordinate of
the last one to reduce twice; it has been shown in [43]. Moreover in a certain gamut of
Pmix change the analogous to the T-profile property the property of all concentration
profiles spotted by combustion kinetics follows. And, first of all, the property of СО2
profile by which, as well as by the T-profile λn is spotted. This property allows on the
basis of available data on Н2О profile to draw some pre-award deductions.
Let's view a binding energy Δh* for an atom of hydrogen in molecules and
radicals [44, 45] (Tab. 9.3):
Tab. 9.3. The binding energy, Δh*, for an atom of hydrogen in molecules and radicals
Compound Δh* [kcal/mole] Compound Δh* [kcal/mole]
Н–Н 103,3 iso – С3Н7 – Н 94
СН3 – Н 103 n – С4Н9 – Н 94
С2Н5 – Н 98 С–Н 81
n- С3Н7 – Н 95 (СН2=СН2) – Н 104
For given case Тc = 1850 K [49]. Substituting all values in (9.7), we receive
λn (Н20) = 0,33 cm. This result is in good conformity with experimental data yielded in
[48].
Let's view one more instance. In [35] profiles of concentrations of an intermixture
9,6%СН4 - 21,3%О2 - 69,1%Ar were explored at initial parameters of Tmix = 293 K
and Pmix = 4∙10-2МPa, Тc = 1850К, Un = 85 cm/s. In transfer on Н2 according to [50],
taking into account the value Pmix is found Uн(Н2О) = 180 cm/s. It is received by (5.22):
λn(Н20) = 0,45 cm. In [35] an observed Н2О profile has thickness λn (Н2О) ≈ 0,5 cm.
So, really, it is possible to consider that hydrogen burns-out in hydrocarbons thus
as if it is in the free molecular state.
48
It has been above told that not only λn, but also some building blocks of the
laminar front reflect its phenomenological properties. But at the same time, apparently,
they reflect also some common features of chemical transfomations of hydrocarbons in
flame front. This process, as we see, is in many respects spotted by general physical
characteristics. In this sense the fact of "burning-out" of hydrogen under the schema
which is not dependent on a view of hydrocarbon fuel is rather important. At the same
time and features of combustion of various fuels can be explained on general chemical-
physical basis.
A tensile energy of hydrogen atom from СН2-group in molecules of paraffin
hydrocarbons has such values (kcal/mole) [45].
93,6 88,8 86,9 86,1 85,8 85,7 85,7 85,8 86,1 86,9 88,8 93,6
C- C- C- C- C- C- C- C- C- C- C- C- (9.8)
This energy does not change practically, since the fifth carbon atom from the
chain end. Tensile energy of C-C bond is less than of С-Н bond. Tensile energy СН3-
СН2 - bond is more than dissociation energy СН2-СН2 (Tab. 9.4).
kcal/mole kcal/mole
Just the relations of tensile energies that are given in (9.8) and Tab. 9.4 are
spotting a sequence of destruction of long chained molecules of hydrocarbons in flame
front.
It is possible to draw a conclusion that the intermediate substances are formed not
as a result of a consecutive chain reaction, but arise, as it has been shown, at
49
independent "burning-out" of hydrogen, and the sequence of bond breaking is spotted
by their energy correspondingly, for example, Tab. 9.4.
This standing proves to be true also that for hexane-air mixtures a value λn is less
than for methane-air mixtures.
The beginning of burning of methane is investigated well enough [51]: СН4 + M
→СН3 + Н + M where a role of a particle M can carry out Н, OH, O, etc. It is natural
that hydrogen from chains middle comes off under the same schema, and, according to
(5.23), with more probability, than at the ends.
For methane the chain leading to СО2 looks like [51]:
С2 Н 2 НН С С О СН 2 СО (9.10)
But also in this case, Н2О formation in comparison with СО2 formation is leading
(see [53, p.169]).
The chemical-physical combustion mechanism of different hydrocarbons has
blanket character, and those features of kinetics which are caused by character of
bonds of atoms of carbon, have no principal value.
Fig. 10.1. Comparison of CO2, H2O and NO-profiles on a thickness of the laminar flame front for
different α
(Т0 = 293К, P = 1bar): 1 α = 1,08; 2 - 1,23; 3 - 1,45.
At combustion of partially aerated mixture the flame has two adjoined fronts.
Inner front in which there is an oxidizing agent lack and external front in which
products of poor combustion burn down in an atmospheric flame.
Irrespective of excess of air of preaeration α1 and a value T0 NOx the profile in
such "complex" flame front has three characteristic extremums: a maximum on an
external surface of internal front with volume concentration NOx of 0,006 %, then a
minimum of 0,001 % on internal boundary of external front and again a maximum
53
0,010 - 0,011 % on external boundary of external flame front nearby to area of the
peak temperature (Fig. 10.2).
Measuring of NOx concentration longwise combustion chambers has shown that
irrespective of Т0 and temperatures of walls of combustion chamber, ТСС, formation of
oxides of nitrogen is completely finished on external boundary of flame front. On all
other part of chamber length the increment of NOx had not been observed.
Temperature effect of walls of combustion chamber on NOx emission is revealed only
on the length of chamber matching the length of a flame which at the kinetic burning
in experimental conditions made about 25 mm.
Fig. 10.2. NOx – and Tf – profiles at burning for different aeration degree:
1 - α1 = 0,1; 2 – 0,3; 3 – 0,6. — Тf; - - - - NOx.
Fig. 10.3. The block-diagram of the process of two-stage burning with incomplete
intermediate combustion
Fig. 10.4. Dependence of the critical values α1 (for NOx emission) on a mixture initial temperature
Variant 3. Two-stage burning of a "poor" aerated mixture (α1 = 2,5 - 2,6) with
afterburning in the second stage with feeding of methane into a diffusion flame
with an intermediate heat removal.
Fig. 10.5. The block-diagram of process of two-stage burning with the complete
intermediate combustion
The methane-air mixture burns in the laminar flame with α1 = 2,5-2,6 at standard
conditions. Further the combustion products are chilled approximately to 400 oC to
avoid spontaneous ignition in the second stage in which methane immixes into them.
Further the intermixture burns down in a diffusion atmospheric flame with different
values of the total coefficient αΣ. Observed data of the peak concentrations of nitrogen
oxides are presented in Tab. 2.
58
Tab. 10.2. The measuring of concentrations of nitrogen oxides at two-stage burning with a
complete intermediate combustion
Regime Т0 α1 ТC1 CNOx(1) T2 TC2 CNOx(2) CNOx(Σ) αΣ
0 0
С - С mg/nm3 0
С mg/nm3 -
1 360 2,6 1240 8 400 1360 26 34 1,14
2 350 2,5 1260 10 400 1380 32 42 1,09
3 350 2,5 1260 10 410 1400 48 57 1,06
Apparently from Tab. 10.1 the minimum NОх concentration is attained at the
upper concentration limit at α1 ≈ 0,6 and makes about 40 mg/m3 [64, 65]. This
concentration does not depend from Т0 and from temperatures before the second stage
of combustion. At the schema with α1>> 1 according to Tab. 10.2, NОх concentration
is close to 40 mg/m3 also.
The revealed ambiguity of dependence on Т0 of peak NOx concentration in a
flame front is proved also by the fact described in [66]. At combustion temperature
1600K NOx concentration does not depend on Т0 and an excess-air coefficient. If
combustion temperature is increasing above 1600K then NOx concentration is
increasing, however, if TC is decreasing below 1600К then NOx concentration is
decreasing also.
Characteristicly that straight lines NOxmax = f (Т0) at TC = const are intercrossed
in point T0 ≈ 0K (a Fig. 10.6). Graphs 4 and 5 on fig. 10.5 are received from [67] for
combustion chambers of gas-turbine plants with air preheating in revivifiers and
constant temperature in the turbine inlet 650 and 500 0С accordingly. These graphs are
a special case of transiting of operating temperature in combustion chamber across
1600K.
59
Various character of dependence NOx - Т0 at various combustion temperatures
represents as theoretical interest for definition of kinetics of formation NOx at burning
and has practical importance.
The phenomenology of NO formation at combustion demonstrates that they are
formed only within flame front and mechanisms of their formation should be
considered together with LPR formation. The explanation of the results received here
cannot be carried out on the basis of the thermal theory applied at present.
Fig. 10.6. Dependence of NOx - Tmix at Тc = const. 1 - Тc = 18750C; 2 - 1480; 3 - 1250. The
data given in [66], temperature in combustion chamber outlet, t2 = const: 4 - t2 = 650 0С; 5 - 500.
Flame stabilization in a gas mixture flow is a base of all processes of burning. The
stabilizing zone of reverse currents (RCZ) represents the same reactor, as well as a
flame front. Numerous observations of flames allow to guess that if the relation of an
average temperature and size of RCZ less than certain value the flame is not stabilized
in a flow and occurs flame-out.
Velocity at which there is a flame-out is directly proportional to a size of RCZ.
We already know that a flame front comprises of three typical zones. And the
temperature in a point A of a front is close to self-ignition point of an intermixture.
Thus, it is possible to guess that for flame stabilization a necessary size RCZ should be
sufficient for formation of the OA segment of thickness of a flame front. Thus in RCZ
the self-ignition temperature will be attained. In other words, RCZ should have such
60
size that transiting time across it of a flow of an intermixture with velocity v0 would
not less a formation time of a OA segment of a front, moving with velocity Un.
I.e. a requirement of stabilization of a flame:
Fig. 11.1. Association between flow rate at flame-out and a stabilizer typical dimension.
(Methane-air; Рmix = 0,1 МPa; Тmix = 300 K; α = 1.)
61
Fig. 12.1. Flame-out characteristics of a circular (a) and a flat (b) stabilizer. 1 - Dн = 8мм; 2 - 14; 3 - 22;
4 - 32; 1 - аст = 7,5 mm; 2 - 12; 3 - 18.
For achievement of the peak stability of a flame it is necessary to use the flat
stabilizers providing optimum concentration of an intermixture in RCZ i.e. optimized
by an initial allocation of gas and arranging a microdiffusion flame (Fig. 12.2).
62
The arranging of burning of gas in a diffusion flame when a fuel and an air are
approaching to a flame front on the one hand and combustion products do not separate
gas and air or their areas with various concentration is termed as the microdiffusion
combustion mechanism. Formally such schema is analogous to the schema of turbulent
burning of homogeneous mixture, but in this case the corpuscles of fuel shattered by a
pulsation and air form a cellular structure where the gas or air mole is surrounded by
the second component. Here gauge of crushing of moles of gas and air of the same
order, as turbulence gauge, i.e. δ ~ lt.
The turbulent flame front moves on a surface of meshes according to the go-ahead
mechanism of transfer of a flame. Extending of process inside of moles occurs with the
help of the microdiffusion mechanism. For the first time the analogous schema
theoretically has been approximately viewed in [10]. The field of steady burning of a
microdiffusion flame is shown in Fig. 12.3.
From the received data it is visible that the microdiffusion flame on a small
interval from the peak flame-out velocity has wide "platform" of steady burning over
the gamut of α changes; this gamut almost 10 times more, than for the kinetic burning.
Fig. 12.4. Dependence of completeness of combustion on a relative step for a slot channel; fuel
- natural gas (СН498 %) and air at normal initial parameters: b = 20mm, l = 14mm; water-cooled
combustion chamber 100 х 100 mm, LCC = 600 mm, υair = 15 m/s: 1 - d =1,2 mm; 2 - 2,0; 3 - 3,0; -. -
boundary of a steady burning.
64
The stated above design philosophies and the design procedure of stabilizers are
necessary at making advanced combustion chambers.
The combustion chamber with the frontal device made of three ring
microdiffusion stabilizers have been developed [68]. The middle stabilizer has double-
row gas feeding system with two gaseous feeds. Three combinations of the turning on
of these stabilizers allow to provide the maximal optimized performances of
combustion chamber in all gamut of regimes. Feature of combustion chamber is that
opposite walls of collecting channels are extended and are simultaneously walls of the
module and its flame tube (Fig. 12.5).
65
The maximal analogy to the optimum organization of a gas flame for oil burning
can be provided at the expense of application of air spraying of liquid fuel and its
feeding, as well as gas by a great quantity of jets (in this case two-phase ones) [69].
Gauge of crushing of moles of gas and air in the microdiffusion mechanism of the
same order, as turbulence gauge, i.e. δ ≈ lt. The time of mixing is approximately equal
to the burning time,
τphys = δ2 / Dт = δ / (lt v ’ + D). (12.5)
It means that for a strong turbulence the propagation rate of a flame front is close
to the pulsation component of a velocity stream,
Ut = ((lt v ’ + D) / τphys) 0,5 ≈ v’. (12.6)
The thickness of flame front is spotted at the guess that through the mole of gas a
flame front with velocity Uт transits, then,
λMD = Ut τphys = ((lt v ’ + D) / δ) (δ2 / (lt v ’ + D) = δ. (12.7)
Intensity of combustion process, characterized by quantity of the intermixture
which is burning down in a unit volume of combustion zone, at a flat flame front for
this schema makes,
ωMD = Ut / λMD ≈ v ’ / δ. (12.8)
Let's find out the range of application of dependence (12.8). For this purpose a
viewed case with homogeneous mixture burning is comparable, assuming that a
kinetic burning has peak intensity. According to the model of surface burn of
homogeneous mixture in a turbulent flow the rate of propagation of flame front,
66
Ut ≈ Un (1 + v ’/Un). (12.9)
For a large turbulence when v ’>> Uн, neglecting the value of a normal flame
front velocity Un, as well as above, we receive Ut ≈ v ’. For the time of burning of a
mole, lt / Ut, the thickness of a turbulent flame front will make (with accuracy up to λn
which at the real conditions less lt on 1-2 order):
λt ~ lt v’/ Ut (12.10)
Thus, in the process of growth of the velocity of a flame the thickness of its front
grows also. Intensity in the flat turbulent flame front of homogeneous mixture,
ωk = Ut / λt ≈ Un / lt. (12.11)
Hence, at the given gauge of turbulence of a flow the combustion rate is spotted
by the macrokinetic characteristic of a hot intermixture Un and remains a stationary
value. However, for lt → 0 we will have again ωk → ∞.
The gauge of crushing decreases the combustion rate grows and in this case is
maximally approaching to combustion rate in a turbulent homogeneous flame. In a
case when δ ≈ lt, the gas particle is not intercrossed by a pulsation and concerning
velocity of its burning out we need to draw an analogy with burning of a mole of
homogeneous mixture from its surface. In this case for the thickness of a front of a
microdiffusion flame using (12.10) we can to write down,
References