Fuel 81 (2002) 391±396

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Extinction of burning particles due to unstable combustion modes q

Bernhard Peters*
AVL List GmbH, Abt: CT, Hans-List-Platz 1, A-8020 Graz, Austria
Received 12 July 2001; accepted 5 October 2001; available online 13 November 2001

Abstract
The objective of this paper is to derive analytically the conditions under which burning particles extinguish. Experiments indicate that the
extinction may occur with a rapid drop in particle temperature, thus causing an insuf®cient burn-out. Both qualitative and quantitative
description of this phenomenon is presented in this study. Based on Semenov's theory of thermal explosion, global heat release and loss
balance determines the critical particle size, at which a rapid change of particle temperature occurs while the particle is burning. Under more
general conditions, particles experience a temperature and oxidizer distribution, which is described by the conservation equations of mass
and energy. By applying a linear stability analysis to these equations, regions are identi®ed, for which the combustion mode becomes
unstable, e.g. for which the hot solution changes rapidly to the cold solution and, thus leads to the extinction of the particle. The analysis
shows that the regions of stable and unstable combustion are separated by critical heat and mass transfer conditions. These results enable
engineers to assess the size of particles due to incomplete combustion, to apply appropriate ®lters or to change conditions favourable to
further burn-out. q 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Solid fuel; Combustion; Extinction; Instability

1. Introduction numerical model based on an unsteady mass and energy

Insuf®cient burn-out, e.g. extinction, of particles is a
commonly encountered phenomenon in solid fuel combus-
tion, such as pulverised fuel ¯ames. In the past, the incom-
plete burn-out was not considered to be signi®cant as it
caused only marginal losses in the overall thermal
ef®ciency. However, recently the problem of insuf®cient
burn-out was brought up again, because the products of
incomplete combustion (PIC) are considered precursors of
unacceptable pollution formation [1] and lead to inferior ash
quality. In the past the phenomenon of insuf®cient burn-out
often was attributed to thermal annealing [2], sintering, and
the effect of ash layers [3].
Other investigations based on numerical models suggest
that a change in the combustion mode of the particles is
likely to cause incomplete burn-out. Ubhayakar [4] used a
one-dimensional model to describe the quasi-steady-state
burning of a spherical particle and to determine the extinc-
tion limits in quiescent oxidising gas. His analysis yielded
burning and extinction regimes dependent on the ambient
temperature, the concentration of oxidiser, radiation and
reaction conditions. Srinivas and Amundson [5] used a
* Tel.: 149-7247-823491; fax: 149-7247-824837.
E-mail addresses: bernard.peters@avl.com (B. Peters).
q
Published ®rst on the web via Fuel®rst.comÐhttp://www.fuel®rst.com
0016-2361/02/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0016-236 1(01)00183-1
balance in conjunction with a probabilistic relation to
predict the evolution of the internal surface area for a porous
spherical particle and found that a critical particle size,
ambient temperature, ambient oxygen concentration, and
boundary layer thickness exist, above which a particle
ignites. Recently, Hurt et al. [6] observed an immediate
drop of particle temperature during the combustion of a
fuel particle exposed to a hot environment of 1600 K.
They injected spherical particles of sizes between R ˆ
0:55 and 0.60 mm into a heated ¯ow reactor. Due to conver-
sion, the particle shrank and after having reached a critical
size a rapid temperature drop occurred.
As already pointed out by Wicke et al. [7] and Essenhigh
et al. [8], a particle experiences different regimes of
combustion, depending on the ratio of internal mass trans-
port to reaction time scale which is referred to as the Thiele
modulus. A rapid change of temperatures accompanies the
shift from zone 2 (reacting core) to zone 1 (shrinking core)
behaviour. This behaviour was con®rmed by investigations
of Essenhigh et al. [9,10]. This temperature predictions
obtained from an unsteady mass and energy balance for a
spherical particle were in good agreement with the experi-
ments of Hurt et al. [6].
Due to the non-linear behaviour of the reaction rate
expression, several steady states for the combustion of a
particle are possible, among which are the so-called hot
392 B. Peters / Fuel 81 (2002) 391±396

Here V, A, Hm, Ea, Rg, a , e , s , T, Tw and T1 denote the

Nomenclature volume and surface of a particle, the reaction enthalpy,
A surface activation energy, gas constant, heat transfer coef®cient,
cp speci®c heat capacity emissivity, Boltzmann constant, particle, wall and ambient
cr reactive species temperature, respectively. The kinetics of the process is
D diffusion coef®cient described by a global, unsteady energy balance of the
Ea activation energy following form:
Hm reaction enthalpy dT
k pre-exponential factor rc p V ˆ Qrel 2 Qloss …3†
dt
Qloss heat loss
Qrel heat release with r and cp being the density and the speci®c heat of the
r independent variable particle. For a qualitative description of the process the
R radius burn-up of initial material and its effect on the reaction
Rg gas constant rate will be neglected. The condition of stationarity requires
t time equality of heat loss and release Qrel ˆ Qloss and determines
T temperature the values of the steady-state temperatures of the particle.
T1 ambient temperature For a slab …n ˆ 1†; a cylinder …n ˆ 2† and a sphere …n ˆ 3†;
Tw wall temperature the equality yields the following equation:
V volume an an  4 
Greek symbols Hm k e2Ea =Rg T ˆ …T 2 T1 † 1 es T 2 Tw4 …4†
R R
a heat transfer coef®cient
b mass transfer coef®cient where R denotes a representative dimension of the
r density geometry.
l conductivity Fig. 1 shows a qualitative plot of a heat release curve and
s Boltzmann constant different heat losses as a function of temperature.
Dimensionless numbers Depending on the heat transfer conditions, several values
Nu Nusselt number for the steady-state temperature are possible. While the
Sh Sherwood number curves for the heat loss rise steadily with the temperature,
Th Thiele modulus the curve for heat generation displays the common S-shape
of the Arrhenius law with the point of in¯ection at the
temperature TI ˆ Ea =2Rg : For an ambient temperature Ta .
and cold solutions. In the course of combustion, a steady TI ; only one steady-state temperature exists at the point of
state may be rendered unstable which is followed by a intersection of the heat release and the heat loss (#1) curves.
change of the combustion behaviour. This paper provides If the slope of the heat loss curve increases, e.g. due to a
complementary explanations based on a linear stability shrinking particle size, the point intersection moves down-
analysis of this phenomenon. A global balance between ward on the hear release curve until the temperature Ta is
heat release and loss of a particle already reveals the possi- reached.
ble steady states, whereas in a more rigid approach addi- However, in the case of Ta , TI ; several modes of
tional temperature and concentration distributions inside the combustion are possible. For a very steep heat loss line
particles are taken into account. (#4), one intersection point D with the heat release curve
occurs, indicating an equilibrium between loss and genera-
1.1. Theory of thermal extinction tion. Thus, a stable steady-state temperature prevails at low
reaction rates.
Although Semenov [11±14] developed his theory for the For certain gradients of the heat loss curve (#3), three
thermal explosion of gases in vessels, its basics are also points …D; E; F† of intersection with the heat release curve
applicable to the burning and extinction of particles. If a exist. The intersection point E at the temperature TE corre-
combustible particle is introduced into a hot oxidising envir- sponds to an unstable regime. For an initial particle
onment, the rate of heat release, assuming a zero-order temperature below TE the particle cools down to tempera-
Arrhenius reaction without any mass transfer limitations ture TD, while for an initial temperature above TE the particle
similar to a well-stirred reactor, is described as follows: burns at a high reaction rate with the temperature TF. Similar
Qrel ˆ VHm k e2Ea =Rg T …1† conditions apply to the intersection point B, where the heat
loss line (#2) is a tangent to the heat release curve. During
and the rate of heat loss due to heat transfer to the gaseous the combustion of a particle, the slope of the heat loss line
phase and radiation to walls is (#2) increases due to a shrinking size, so that the intersection
  point B represents the condition of an unstable regime.
Qloss ˆ aA…T 2 T1 † 1 esA T 4 2 Tw4 …2† Therefore, the tangent to the heat release curve determines
 B. Peters / Fuel 81 (2002) 391±396 393

linear stability analysis in conjunction with the collocation

method [15].
The one-dimensional unsteady energy equation for the
temperature distribution T of a spherical particle in dimen-
sionless coordinates, taking conduction and a ®rst order
Arrhenius reaction into account, is written as follows:
 
rcp R2 2T 1 2 2 2T kHm cr R2 2Ea =Rg T
ˆ 2 r 1 e …6†
l 2t r 2r 2r l
where r , cp, l and R denote density, heat capacity, heat
conductivity and the particle radius, respectively. The
reactive source term contains k, Hm, cr, Ea and Rg as the
pre-exponential factor, reaction enthalpy, concentration of
a reactive specie, activation energy and the gas constant,
respectively. The thermal boundary conditions representing
Fig. 1. Heat release and loss curves. convective and radiative heat transfer are employed in a
dimensionless form as follows:
the radius of the particle at which instability occurs. The gas 2T
temperature of Tg ˆ 1600 K in the experiments of Hurt et rˆ0: ˆ0 …7†
2r
al. [6] is below the temperature of the point of in¯ection
TI ˆ 10 820 K; so that instability may occur. At a tempera- 2T esR  4 
ture of T ˆ 1712 K the heat loss curve is a tangent onto the rˆ1: 2 ˆ Nu…T 2 T1 † 1 T 2 Tw4 …8†
2r l
heat release curve, so that this condition suf®ces to deter-
mine the particle radius for which the combustion becomes where e , s , l , Tw, T1 and Nu are the emissivity, the
unstable. In conjunction with the equality between heat loss Boltzmann constant, the conductivity, the wall temperature,
and release the critical particle radius is estimated as the ambient gas temperature and the Nusselt number Nu ˆ
follows: aR=l:
In the present analysis the orthogonal collocation method
  [15] is employed to discretise the conservation equation.
3a…T 2 T1 † 1 3es T 4 2 Tw4
Rcrit ˆ …5† The orthogonal collocation method has the advantage of
Hm k e2Ea =Rg T distributing discontinuous masses along the domain of
discretisation as compared to the ®nite volume and ®nite
Eq. 5 yields a value of R ˆ 47 mm, at which instability element method. This results in a functional evaluation at
occurs and the burn-out time extends signi®cantly due to a discrete points whereas the other methods require the
temperature drop. Essenhigh et al. [8] predicted the evaluation of integrals. With respect to the non-linear reac-
temperature and conversion rate of a particle under the tion term, the collocation method, therefore, signi®cantly
same conditions and obtained a critical radius of facilitates the mathematical analysis. In order to discretise
R < 44 mm, which agrees well with the present value. the radiative boundary condition, the temperature depen-
dence is linearised around T0 in the following form:
   
T 4 2 Tw4 ˆ T03 1 T02 Tw 1 T0 Tw2 1 Tw3 …T 2 Tw †
2. Extinction under a non-uniform temperature
distribution
ˆ gR …T 2 Tw † …9†
Within the previous analysis, uniform temperature and so that the boundary condition at r ˆ 1 writes as follows:
concentration pro®les were assumed for a particle, which
lead to a global energy balance. However, a gradient of the 2T
2 ˆ Nu…T 2 T1 † 1 Nu 0 …T 2 Tw † …10†
temperature always exists in order to allow for a heat trans- 2r
fer, which holds also for small particles. This applies Due to a similar appearance between the convective and the
certainly to larger particles, for which the inertia effects of radiation boundary condition, the term
heat transport enhance a non-uniformity of the temperature
esR  3 
distribution. The conservation equation of energy describes T 0 1 T02 Tw 1 T0 Tw2 1 Tw3
the evolution of temperature in space and time for a particle, l
whereas the pro®le of reactive species is assumed to be is labeled Nu 0 :
uniform e.g. no mass transfer limitations. This assumption In the present context the collocation method of ®rst order
will be neglected in the analysis in Section 3. For the iden- for spherical geometries is applied, which leads to analytical
ti®cation of instabilities the energy equation is subject to a expressions and represents the behaviour suf®ciently
394 B. Peters / Fuel 81 (2002) 391±396

accurately. For higher accuracy, a high-order collocation 1700 K; where the heat loss curve is a tangent to the heat
formula may be applied. Hence, the energy equation is release curve and assuming Tw ˆ 1500 K; the above-
discretised in space in the following form: mentioned analysis yields a value of R ˆ 36:4 mm, which
is in fair agreement with the analysis of Section 1.
rcp R2 2T1 kHm cr R2 2Ea =Rg T1
ˆ 210:5…T1 2 T2 † 1 e …11†
l 2t l
Application of the collocation method to the boundary 3. Extinction under non-uniform temperature and
conditions eliminates the unknown temperature T2 and concentration distributions
yields the following equation:
For heterogeneous combustion, in general a distribution
rcp R2 2T 10:5…Nu 1 Nu 0 † 10:5…NuT1 1 Nu 0 Tw † for one or several reactive species has to be considered
ˆ2 0 T1
l 2t Nu 1 Nu 1 3:5 Nu 1 Nu 0 1 3:5 additionally to the temperature pro®le. The conservation
of energy is therefore accompanied by the conservation of
kHm cr R2 2Ea =Rg T
1 e (12) mass including a reaction source term. This results in a
l coupled set of differential equations, to which the same
For the stability analysis the reaction source term may be procedure to analyse stability is applied. Assuming a ®rst
linearised around the steady state solution T0 to obtain: order reaction for the combustion of a porous and spherical
particle, the energy equation for the solid material neglect-
rcp R2 2T 10:5…Nu 1 Nu 0 † 10:5…NuT1 1 Nu 0 Tw † ing the contribution of the gaseous pore space and the mass
ˆ2 T 1 conservation equation for the gaseous phase of the pores are
l 2t Nu 1 Nu 0 1 3:5 Nu 1 Nu 0 1 3:5
! written as follows:
kHm cr R2 2Ea =Rg T0 e2Ea =Rg T0 Ea …T 2 T0 †
1 e 1 Energy:
l Rg T02
 
…13† rcp R2 2T 1 2 2 2T kHm cr R2 2Ea =Rg T
ˆ 2 r 1 e …16†
A linear perturbation equation for the temperature T ˆ T0 1 l 2t r 2r 2r l
eu with u ˆ A eSt is chosen for insertion into Eq. (13). It
Mass:
yields a condition for S , under which a stable and unstable
region is identi®ed depending on the radius R of the particle.  
R2 2cr 1 2 2 2cr kc R2
Under the condition of S ˆ 0 the thermal instability occurs ˆ 2 r 2 r e2Ea =Rg T …17†
D 2t r 2r 2r D
and it is deduced from the following equation:
  where cr and D denote the concentration of a reactive
e Rs  3
10:5 aR=l 1 T 0 1 T02 Tw 1 T0 Tw2 1 Tw3 species and the diffusion coef®cient, respectively.
l
Sˆ2
The following boundary conditions are applied for heat
esR 3
aR=l 1 T 0 1 T02 Tw 1 T0 Tw2 1 Tw3 1 3:5 and mass transfer:
l
Heat transfer:
kHm cr R2 e2Ea =Rg T0 Ea
1 ˆ0 (14) 2T
l Rg T02 rˆ0: ˆ0 …18†
2r
Eq. (14) represents a third-order polynomial in R and has
three roots, of which only one is positive and is expressed as 2T esR  4 
rˆ1: 2 ˆ Nu…T 2 T1 † 1 T 2 Tw4 …19†
follows: 2r l
27l Mass transfer:
Rcrit ˆ
4…a 1 seg R †
q 2cr
rˆ0: ˆ0 …20†
49c2r Ea2 Hm2 k2 l2 r2 1 168cr e2Ea =Rg T0 Ea Hm kRg T02 lr…a 1 seg R †2 2r
1
4cr Ea Hm kr…a 1 seg R †
…15† 2cr
rˆ1: 2 ˆ Sh…cr 2 cr;1 † …21†
2r
For values of R , Rcrit S becomes negative, which indicates
a stable solution at low reactions rates, e.g. extinction. This where cr,1 and Sh are the ambient concentration and the
result agrees well with the ®ndings of Essenhigh et al. [9], Sherwood number Sh ˆ bR=D:
according to which, after the size of the particle is reduced By applying the orthogonal collocation method to
to a critical radius, the temperature distribution changes Eqs. (16) and (17) in conjunction with the boundary condi-
from the hot branch to the cold branch and, thus signi®- tions and linearising the reaction source term around the
cantly extends the time for burn-out. By setting T 0 ˆ steady state solution T0 and cr,0 leads to the following system
 B. Peters / Fuel 81 (2002) 391±396 395

of differential equations: Taking uncertainties of the measurement into account,

the predicted values of the radii deviate by less than 15%.
rcp R2 2T 10:5…Nu 1 Nu 0 † 10:5…NuT1 1 Nu 0 Tw † A simple energy balance with a uniform representative
ˆ2 0 T1
l 2t Nu 1 Nu 1 3:5 Nu 1 Nu 0 1 3:5 temperature of the particle yields already good estimation.
The two remaining approaches predict values, which differ
kHm R2  
1 cr;0 e2Ea =Rg T0 1 gT …T 2 T0 † 1 gc …cr 2 cr;0 † to a small extent only, so that in the present case the simpler
l
method considering only a temperature distribution suf®ces.
…22†
However, the principal applicability of the above-
R2 2cr 10:5Sh 10:5cr;1 Sh mentioned methods to predict extinction of spherical
ˆ2 c 1 particles is shown in the present contribution.
D 2t Sh 1 3:5 r Sh 1 3:5
For engineering applications the previous results as a
kR2   relationship between a critical particle radius and heat/
2 cr;0 e2Ea =Rg T0 1 gT …T 2 T0 † 1 gc …cr 2 cr;0 † (23) mass transfer conditions can be arranged in a graph to deter-
D
mine critical conditions for a particle. This relationship with
Here gT and gc are the partial derivatives of temperature the mass transfer coef®cient as a parameter is shown for the
and concentration of the source term due to linearisation. Illinois coal as a representative example in Fig. 2.
The perturbed temperature and concentration equations In Fig. 2 the parameter of a constant mass transfer coef®-
T ˆ T0 1 eA eSt and c ˆ c0 1 eB eSt inserted into the cient distinguishes into a region of extinction above the
system yield a system of linear equations for the unknown curve and a region of combustion below the curve. Thus,
variables A and B: for given Nusselt and Sherwood numbers the behaviour,
0 1
r c R2 10:5…Nu 1 Nu 0 † kH m R2 gT kH R2 gc
B p S1 2 2 m C A! 0
!
B l 0
Nu 1 Nu 1 3:5 l D C
B C ˆ (24)
B C
@ 2
kR gT R 2
10:5Sh kR gc A B
2 0
S1 1
D D Sh 1 3:5 D

The system has a non-trivial solution for a vanishing deter- whether extinction or combustion takes place, is easily
minant, which leads to the following equation for S : determinable.
gT Hm k 10:5DSh
S 2 1 gc k 2
cp R2 …Sh 1 3:5†
! 4. Summary
10:5l…Nu 1 Nu 0 †
1 S The stability of the combustion mode for spherical parti-
rcp R2 …Nu 1 Nu 0 1 3:5†
cles in particular was investigated. Based on the classical
110:25DlSh…Nu 1 Nu 0 † theory of thermal explosion by Semenov the conditions for a
1
rc p R4 …Sh 1 3:5†…Nu 1 Nu 0 1 3:5† shift from the hot to the cold solution of a reacting particle were
derived both qualitatively and quantitatively. Under burning
10:5lkgc …Nu 1 Nu 0 † 10:5DgT Hm kSh
1 2 0
2 ˆ 0 (25) conditions, a particle experiences temperature and concen-
rcp R …Nu 1 Nu 1 3:5† cp R2 …Sh 1 3:5† tration pro®les which are determined by the combustion
Eq. (25) yields two values S 1,2 to determine the region of
instability by setting S 1;2 ˆ 0: One of the two solutions does
not have real roots and, therefore, is excluded for further
analysis. The second solution furnishes a value of
R ˆ 38:6 mm which agrees satisfactory with the results
obtained from the previous analysis.
For a better comparison the critical radii obtained by the
different approaches are listed in the following table:

Method Critical radius

(mm)

Experimental 44
Energy balance 47
Non-uniform temperature distribution 36.4
Non-uniform temperature/species distribution 38.6 Fig. 2. Combustion and extinction regimes.
396 B. Peters / Fuel 81 (2002) 391±396
of the particle and its heat/mass transfer rates. A system of
conservation equations is applied to describe the evolution
of temperature and concentration in time and space for a
spherical particle assuming a ®rst-order reaction. A linear
stability analysis in conjunction with the collocation method
yields conditions dependent on the particle size, the heat and
mass transfer conditions to determine regions of unstable
combustion modes. In particular, for particle sizes smaller
than a critical value, the combustion mode changes to slow
reaction rates causing extinction of the particle. These
conditions are usually encountered for particles, as the
size shrinks during the combustion and eventually reaches
a critical value, at which extinction occurs. This result
enables engineers either to assess the size of particulate
emissions due to sooting combustion or to design combus-
tion chambers with suf®ciently high temperatures and
residence times to allow for a suf®cient burn-out.
References
[1] Stieglitz L, Vogg H. Formation and decomposition of polychlorodi-
benzodioxins and- furans in municipal waste incineration. KfK
1988;4379:1±16.
[2] Essenhigh RH. Fundamentals of coal combustion. Chemistry of coal
utilization: second supplementary volume. New York: Wiley, 1981.
p. 1153±312.
[3] Hurt RH, Sun JK, Lunden M. A kinetic model of carbon burnout in
pulverized coal combustion. Combust Flame 1998;113:181±97.
[4] Ubhayakar SK. Burning characteristics of a spherical particle reacting
with ambient oxidizing gas at its surface. Combust Flame
1976;26:23±34.
[5] Srinivas B, Amundson NR. Intraparticle effects in char combustion III
transient studies. Can J Chem Engng 1981;59:728±38.
[6] Hurt RH, Davis KA. 25th Symposium (International) on Combustion,
1994.
[7] Wicke E, Rossberg M. Z Elektrochem 1953;57:641±5.
[8] Essenhigh RH, Klimesh HE, FoÈrtsch D. Combustion characteristics of
carbon: dependence of the zone I±zone II transition temperature (Tc)
on particle radius. Energy Fuels 1999;13:826±31.
[9] FoÈrtsch D, Essenhigh RH, Klimesh HE, Schnell U, Hein KRG.
Modeling of time-dependent behavior of particle temperature and
burnout during combustion of pulverized char particles. Joint Meeting
of the US Sections of The Combustion Institute, 1999. p. 1±4.
[10] Essenhigh RH, Klimesh HE, FoÈrtsch D. Combustion characteristics of
carbon: in¯uence of the zone I±zone II transition on burn-out in
pulverized coal ¯ames. Energy Fuels 1999.
[11] Zel'dovich B, Semenov N. J Exp Theor Phys USSR 1940;10:1116.
[12] Semenov NN. Z Physik 1928;48:571.
[13] Kuo KK. Principles of combustion. New York: Wiley, 1986.
[14] Zeldovich YaB, Barenblatt GI, Librovich VB, Makhviladze GM. The
mathematical theory of combustion and explosions. Acad Sci USSR
1985.
[15] Finalyson BA. The method of weighted residuals and variational
principles. New York: Academic Press, 1972.