Vous êtes sur la page 1sur 19

Combustion and Flame 146 (2006) 553571

www.elsevier.com/locate/combustame
A model for the devolatilization of a coal particle
sufciently large to be controlled by heat transfer
Jyuung-Shiauu Chern
1
, Allan N. Hayhurst

Department of Chemical Engineering, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK
Received 12 August 2005; received in revised form 7 April 2006; accepted 11 April 2006
Available online 19 June 2006
Abstract
This study follows previous experimental work showing that the shrinking-core model applies to the pyrolysis
(i.e., heating in the absence of oxygen) of particles (diam. 14 mm) of a bituminous coal or a lignite in a uidized
bed at 700950

C. These experimental facts are in accord with the production of volatile matter being endothermic
and not thermoneutral, as often assumed. Also, the rate at which volatile matter is produced in the presence of
oxygen (i.e., devolatilization) or in its absence (pyrolysis) is demonstrated here to be controlled not at all by mass
transfer, but by heat conduction to a moving reaction front inside a coal particle, provided its diameter exceeds
3 mm. The resulting steady-state model of devolatilization indicates that six dimensionless groups are required
to describe the rate of
(I) coal char +volatile matter
for a nonfragmenting and nonswelling coal. This reaction occurs for a total time of
c
1
r
0
+c
2
r
2
0
for a coal of radius r
0
. Experimental measurements of the times for pyrolysis in a bed of hot sand uidized by
N
2
indicate this dependence on r
0
holds much better than the usually accepted one of ar
n
0
. The measurements
also indicate that the enthalpy change of reaction (I) is 9.4 4.0 MJ/(kg of volatile matter) and the thermal
conductivity of char is 1.2 0.5 Wm
1
K
1
. In addition, it was deduced that reaction (I) occurs at 500 K
and that (of the heat released by burning the volatile material, a fraction is fed back to a parent coal particle
devolatilizing in a bed uidized by, e.g., air) is less than unity. These numerical considerations enable the model
of devolatilization to be simplied; it turns out that a heated particles core of virgin coal shrinks mostly with
a constant velocity, characterized by only four dimensionless groupsi.e., two of them usually turn out to be
unimportant. The important groups include a Biot number for the char, Bi
char
, and = 1 + H
comb
/

H
v
.
Given that =0 and =1 for pyrolysis, the kinetics in that case are characterized entirely by three dimensionless
groups, including Bi
char
. The conditions for the shrinking core model to apply to devolatilization and pyrolysis
are discussed and are found not to apply, e.g., toward the end of devolatilization and for coals with low volatile
contents. The model was used to calculate when reaction (I) starts after an initial heating period for a coal particle.
*
Corresponding author. Fax: +44 1223 334796.
E-mail address: allan_hayhurst@cheng.cam.ac.uk (A.N. Hayhurst).
1
Current address: Energy Commission, Ministry of Economic Affairs, 2 Fu-Hsing North Road, Taipei 104, Taiwan.
0010-2180/$ see front matter 2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.combustame.2006.04.011
554 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
The results are compared with experimental measurements (using gas chromatography of the volatiles released)
of when various species (e.g., CO, CO
2,
NO
x
, C
2
H
4
, C
2
H
6
, HCN) rst appear from a pyrolyzing coal particle.
These measurements conrm that reaction (I) can be assumed to occur at a mean temperature of 500 K.
2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
Keywords: Fluidized beds; Coal; Pyrolysis and devolatilization
1. Introduction
A previous study [1] showed that the thermal de-
composition of a large (diam. 14 mm) particle of a
bituminous coal or a lignite in an electrically heated
uidized bed occurs [1] within a narrow reaction
zone, which behaves like a moving boundary in each
particle. No reaction is observed at a point inside
a heated coal particle before this boundary arrives,
whereas the coals volatile matter is fully removed af-
ter this front has passed [1]. Thus, this reaction zone
behaves as in the shrinking-core model [2]. An expla-
nation for this narrow reaction zone comes from con-
sidering the relative rates of reaction and heat conduc-
tion. The rate of thermal decomposition, whose exact
mechanism is not fully understood, is expected to be
proportional to exp(E/T
f
), where T
f
is the temper-
ature of the moving reaction zone. Thus, a higher T
f
will increase the rate of reaction considerably. On the
other hand, the rate of internal heat transfer to the
decomposition front only varies linearly with the tem-
perature in the reaction zone. This means that if T
f
is sufciently high, the rate of thermal decomposi-
tion will be inherently faster than heat transfer. The
result is large gradients in temperature inside a de-
volatilizing or pyrolyzing particle [3], coupled with a
moving temperature front, which causes the reaction
zone to be narrow. Thus, if a coals thermal decompo-
sition is endothermic, the rate of devolatilization can
be governed by the supply of enthalpy to sustain ther-
mal decomposition; i.e., internal heat transfer is rate-
controlling. To be explicit, for internal heat conduc-
tion to be slower than reaction (I) requires [4] that the
heating-up time for the particle be much longer than
the time constant for reaction (I); i.e., r
2
0
/ 1/k
1
or r
2
0
/Aexp(E/RT ). Substituting typical val-
ues [4] indicates that this requires r
0
> 1.5 mm for a
uidized bed at 900

C. In this paper, a model based


on previous experimental observations [1,3] of py-
rolysis in hot beds uidized by N
2
is developed for
devolatilization (i.e., when the released volatile matter
burns in air around the coal particle), whereas py-
rolysis (i.e., in the absence of O
2
) is a special case.
Various assumptions will simplify the model and pro-
vide analytical solutions.
2. The importance of mass transfer
Previous work [1,4] has shown that if a piece
of devolatilizing bituminous coal or a lignite (diam.
15 mm) is extracted froma uidized bed at 800

C
and quenched rapidly in N
2
, its external layer of char
is very porous. However, a central core of undecom-
posed virgin coal is found if the coal is withdrawn
before all the volatile matter has been liberated. Evi-
dently during devolatilization, thermal decomposition
in (I) occurs at the interface between the central un-
decomposed coal and the char around it. This section
describes measurements of the pore sizes, etc. in the
char to ascertain whether the rate of devolatilization
is controlled by mass transfer of the volatile matter
through the outer layer of char. Such a check is im-
portant, because it has been asserted [5,6] that internal
mass transfer of the released volatile species can be
the rate-controlling step for devolatilization.
The experiments and coals have been described
[1]. Briey, a coal particle (2 g) was added to an
electrically heated bed (750950

C) of sand uidized
by N
2
at U/U
mf
= 3. After 10 min, pyrolysis was
easily complete, so the remaining char was extracted
and quenched in N
2
. After the char was crushed
into smaller particles, the diameters and volumes of
the pores were measured with a mercury porosime-
ter (Micromeritics Autopore II 9220). These results
were found to be reproducible and independent of
the size of the char particles; this provides important
validation for the mercury porosimetry. In addition,
internal surface areas in pores of different diameters
were measured with a BET analyzer (Micromeritics
ASAP 2000) using N
2
as the adsorbing gas. Such a
technique inevitably has errors, e.g., underestimating
the areas within smaller micropores. These measure-
ments also provided the porosity, (the ratio of the
volume of voids to the bulk volume), which is dis-
played in Fig. 1. The chars are more porous than
the original coal, but Fig. 1 shows that their porosity,
when they are made at 750950

C, is almost constant
and as high as 0.5.
In Fig. 2a, the volume inside the pores is plotted
against the corresponding internal diameter. It will be
noticed that most of the voidage inside the char from
Baddesley coal is in pores of diameter >0.1 m, i.e.,
macropores. The internal surface area per unit mass
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 555
Nomenclature
A pre-exponential factor dened by k
1
=
Aexp(E/RT ) (s
1
)
a a constant of proportionality in Eq. (30)
Bi Biot number =r
0
h
l
/k
C
p
heat capacity (J/kg K)
c
1
c
1
=

H
v
Y

c
X/3h
l
(T

T
f
)
c
2
c
2
=

H
v
Y

c
/6k
char
(T

T
f
)
E mean activation energy for devolatiliza-
tion (kJ/mol)
Fo pseudo-Fourier number (dimensionless)
as dened in Eq. (18)
H
comb
heat of combustion per unit mass of
volatile matter (J/kg)
H
v
heat of devolatilization per unit mass of
volatile matter (J/kg)


H
v
apparent heat of devolatilization per
unit mass of volatile matter (J/kg); see
Eq. (1)
H
w
heat of vaporization per unit mass of
moisture (J/kg)
h convective heat transfer coefcient be-
tween a uidized bed and a devolatiliz-
ing coal
h
l
heat transfer coefcient (W/m
2
K), de-
ned in Eq. (3)
Kn Knudsen number
k thermal conductivity (W/mK)
k
1
rst-order rate constant for thermal de-
composition in (I) (s
1
)
L characteristic distance for a transport
process (m)
Le pseudo-Lewis number
M
A
relative molecular mass of species A
(kg/kmol)
n an exponent in Eq. (30) (dimensionless)
n
p
number of pores per unit external surface
area of char (m
2
)
Q rate of exchange of enthalpy (W)
R universal gas constant = 8.31441
(J/Kmol)
r radial position inside a particle of
coal/char (m)
r
f
the radial position where thermal decom-
position occurs (m)
r
p
radius of a pore (m)
r
0
radius of a coal particle (m)
S
g
internal surface area per unit mass of
char (m
2
/kg)
T temperature (K)
T
f
mean temperature of the devolatilization
front
t time (s)
U supercial velocity of the gas uidizing
a bed of sand (m/s)
U
mf
minimum value of U for incipient u-
idization (m/s)
V
g
volume of the voids in a unit mass of
char (m
3
/kg)
W

mass of water content per unit mass of


moisture-free original coal (kg/kg)
Y

mass of volatile material released from


unit mass of moisture-free original coal
(kg/kg)
thermal diffusivity (m
2
/s)

m
mth eigenvalue of Eq. (51) (dimension-
less)

rad
emissivity at the surface of a coal parti-
cle
the fraction of the enthalpy from com-
bustion reaching the particle


H
v
/C
p,v
(T

T
f
)
=Bi
c
1, as dened in Eq. (52)
Y


H
v
/
char
C
p,char
(T


T
f
)(1 Y

)
mean free path
voidage or porosity of a char
density (kg/m
3
)
r
f
/r
0
, dimensionless radius

rad
StefanBoltzmann constant = 5.67
10
8
(W/m
2
K
4
)
tortuosity of the pores in a char
X dened by Eq. (33)
1 +H
comb
/

H
v
Superscript
dimensionless quantity
Subscript
c of or pertaining to coal
char of or pertaining to char
devo of or pertaining to devolatilization
l of or pertaining to the surrounding gases
pyro of or pertaining to pyrolysis
s of or pertaining to the external surface of
a particle
v of or pertaining to volatile material
w of or pertaining to water
0 initial value
nal value
556 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
Fig. 1. The porosity of the char from Baddesley coal pyrolyzed at different temperatures for 10 min at 850

C.
Fig. 2. For the pores of different diameters in char from
Baddesley coal after pyrolysis at 850

C for 10 min: (a) the


volumes, (b) the internal surface areas.
is plotted in Fig. 2b against the internal diameter of
the pores. Most of the internal surface area is located
in narrow pores of diameter <0.1 m, i.e., meso- and
micropores; for macropores (>0.1 m), no signicant
contribution to the internal surface area is found. In
Fig. 2 different roles for the macropores and micro-
pores are revealed: porosity is mainly contributed by
macropores, whereas the micropores possess most of
the internal surface area. This agrees with the litera-
ture [7,8]. Knowing the sizes of all the pores is useful,
but inconvenient, so an average pore radius will be de-
vised for further discussion. Using the parallel-pore
model [9], the average pore radius is dened as r
p
=
2V
g
/S
g
. Here, V
g
is the void volume, and S
g
is the
internal surface area, both per unit mass of char. Such
average pore radii are shown in Fig. 3a, where it will
be noticed that r
p
is larger for chars made in a hot-
ter bed. The original coal has about the same average
pore radius as the chars. In the following discussion,
the average radius for the macropores will be arbitrar-
ily designated as r
macro
= 10r
p
, and for the average
radius in the micropores, r
micro
= r
p
/10. Using the
parallel-pore model [9], if all the pores are distributed
homogeneously inside the char, the area of the pores
per unit outer surface area will equal the porosity [10].
If the pores meet the outer surface of the particle at
an average angle of 45

, the number of pores per


unit outer surface area is [10]: n
p
= /

2r
p
2
. The
resulting values of n
p
are shown in Fig. 3b, which in-
dicates that a lower temperature in the uidized bed
produces more, but smaller pores (see Fig. 3a) in a
char. However, the macropores do not appear to be
inuenced by temperature, because the porosity (see
Fig. 1) is fairly constant after pyrolysis at different
temperatures.
During pyrolysis or devolatilization, the volatiles
generated in the reaction zone must transfer through
the outer layer of char to the surroundings. To forecast
the rate of mass transfer of various chemical species
inside the char, their effective diffusivities are now
estimated. The binary diffusion coefcients of CH
4
,
HCN, H
2
S, N
2
O, and COS in nitrogen were chosen
as examples; these chemical species are commonly
found in the volatiles [11]. The rst thing to be es-
tablished is what type of diffusion dominates inside
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 557
Fig. 3. For the chars from Baddesley coal pyrolyzed at dif-
ferent temperatures for 10 min: (a) the average pore radii,
(b) the number of pores per unit external surface area.
a char particle: is it Knudsen or bulk (i.e., molec-
ular) diffusion? This question can be answered by
examining the magnitude of the mean free path, ,
of the volatiles inside the pores. For CH
4
at a pres-
sure of 1 atm and 0

C, 0.2 m. The Knudsen


number Kn = /2r
p
lies in the range 1 to 20 for the
above gases. Now when Kn 10, Knudsen diffusion
dominates; i.e., the diffusion of a molecule is con-
trolled more by collisions with the pores walls than
with other gaseous molecules, whereas molecular dif-
fusion prevails for Kn 0.1 [10], when the pores
are relatively wide. It must be concluded that for the
chars in this study, diffusion inside the pores of ra-
dius r
p
, i.e., the average, is either Knudsen or in the
transitional region between molecular and Knudsen
diffusion. Hence, Knudsen diffusion should prevail
in the micropores, whereas bulk diffusion dominates
in the macropores. The diffusivities of the volatiles
for bulk and also Knudsen diffusion are now esti-
mated.
First, a binary bulk diffusion coefcient was pre-
dicted using the ChapmanEnskog equation [12].
Then, the effective diffusivity for bulk diffusion in
the macropores is [13] D
macro
=D
AB
/ for the two
gases A and B, i.e., for N
2
and another gas. Here, the
tortuosity was assumed to be 1.5 (for most circum-
stances, lies between 1 and 2) to account for the
irregular shapes of the pores. For the micropores, the
Knudsen diffusion coefcient was calculated [10] for
a species A from D
micro
= 9700r
micro
(T/M
A
)
1/2
.
The diffusivities for the macropores are about 100
times bigger than those for the micropores. A higher
temperature results in both D
macro
and D
micro
being
increased. With the above estimates of D
macro
and
D
micro
, the relative rates of mass transfer and thermal
conduction inside a char particle can be investigated.
The characteristic times for mass transfer and thermal
conduction are L
2
/D and L
2
/ [13], where L is the
characteristic distance. For a particle of coal during
pyrolysis or devolatilization, the radius of the particle
is the characteristic distance for both bulk diffusion
and thermal conduction, because the volatiles must
diffuse to the surroundings; also, thermal conduction
occurs inside all the particle. However, the gas in a
micropore needs only to diffuse to the nearest macro-
pore; hence, the characteristic distance for Knudsen
diffusion, L
micro
, is roughly half the thickness of
the solid skeleton between macropores. Because the
porosity of chars is 0.5 (see Fig. 1), the thickness
of the solid part between the pores is expected (if a
regular hexagonal array of holes is assumed) to be
roughly the mean diameter of the macropores; i.e.,
L
micro
= 10r
p
. The ratio of the characteristic times
for mass transfer and thermal conduction is a pseudo-
Lewis number:
Le =
L
2
mass
/D
L
2
cond
/
.
When Le 1, mass transfer is much slower than ther-
mal conduction, whereas Le 1 corresponds to the
opposite situation. The thermal diffusivity,
char
, of
the char was taken as 10
7
m
2
/s, a typical value for
a char [14]. The resulting pseudo-Lewis numbers for
the various gases mentioned above in either macro- or
micropores are plotted against temperature in Fig. 4
for a particle of radius 5 mm. All the values are
10
3
or less, i.e., very much smaller than 1; this
means that mass transfer inside such a char particle
is always very much faster than internal heat conduc-
tion. Such a conclusion still holds if the above argu-
ment is adjusted for errors in V
g
, S
g
, and L
micro
. In
the real situation of a devolatilizing or pyrolyzing coal
particle, there are forced ows of the volatiles (often
giving jets [15]), because of pressure differences, so
that mass transfer will be even quicker than the above
estimate. Thus, it is clear that devolatilization and py-
rolysis are denitely not controlled by mass transfer
of gaseous volatiles within the pores of a coal particle.
On the contrary, it is likely that internal heat transfer
is rate-controlling.
558 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
Fig. 4. The pseudo-Lewis numbers for various gases diffusing inside macro- and micropores of Baddesley chars prepared at
different temperatures.
3. An approximate model of devolatilization
A shrinking-core model [1] is rened below to
describe devolatilization under heat transfer control,
with the volatiles burning. However, this model is not
universally valid for all coals undergoing devolatiliza-
tion. One requirement is a sharp, spatial change of
the volatile content in a coal particle during its de-
volatilization. To have a sharp temperature change in
space, the particle of coal must be big enough to be
nonisothermal. This requires that the Biot number of,
e.g., a near-spherical coal particle, Bi
c
r
0
h
l
/k
c
, has
to be larger than 1/2 [16]. Here, h
l
and k
c
are, re-
spectively, the external heat transfer coefcient [1]
and the thermal conductivity of coal; r
0
is the radius
of the coal particle. However, if the thermal conduc-
tivity, k
char
, of the char produced is much smaller than
k
c
, the particle can also be nonisothermal, even when
Bi
c
< 1/2 during devolatilization or pyrolysis. Thus,
it is also possible to use Bi
char
(r
0
h
l
/k
char
) > 1/2
as the requirement for nonisothermality. Whether it is
better to use Bi
c
or Bi
char
will be examined below, but
at this stage it can be noted that Bi
char
>0.5 requires
r
0
> 1.4 mm, using values of h
l
and k
char
deduced
below. The situations for which this model is valid
are discussed in Section 5.3. The physical properties
of the coals considered below have been given previ-
ously [1].
3.1. The assumptions of the model
A spherical coal particle is considered for sim-
plicity. During devolatilization the reaction zone is
located at r
f
, as illustrated in Fig. 5. For r < r
f
, the
coal remains unreacted. The reacted coal, i.e., char,
lies between r
f
and r
0
. The temperature in the reaction
Fig. 5. The radial prole of temperature in a devolatilizing
coal particle. The temperature in the uidized bed is T

(at
r =), at the particles exterior (r =r
0
) it is T
s
, and in the
reaction zone (r =r
f
) it is T
f
.
front at r
f
is T
f
, which in this model will be assumed
to be a constant during devolatilization. For simplic-
ity, fragmentation, swelling and any change of shape
are assumed not to happen. Although the concept of
one single primary reaction is questionable [17], the
phenomenological statement
(I) coal
(s)
volatiles
(g)
+char
(s)
will be assumed to describe thermal decomposition.
Thus, although several parallel paths for reaction (I)
are likely [17], it is assumed that all of them are suf-
ciently rapid for the rate of (I) to be controlled by
heat transfer. Consequently, the idea of thermal de-
composition via many parallel reactions is preserved,
but only one step is needed in this model, because the
kinetics of each step contributing to (I) is fast enough
not to be rate-controlling. For the same reason, only
one heat of devolatilization is dened and employed
for reaction (I), whose overall rate is determined by
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 559
heat conduction through the char. The rate of de-
volatilization will be expressed by the advancement of
only one reaction front (i.e., dr
f
/dt , as indicated by
microscopic examination of sectioned particles [1]),
in spite of some volatile matter being more tightly
bound than the remainder. Any secondary reactions of
the volatile material (e.g., with the char to yield soot)
will be ignored.
Evaporation of water in a coal occurs at 100

C
and complicates this model. When a thin thermocou-
ple (see below) was cemented into a coal particle to
measure the temperature midway between its exterior
and center, the temperature was found to be 100

C
for 25 s during its pyrolysis or devolatilization. Of
course, drying and the evolution of volatile matter
will occur simultaneously, but at different places. It
was noticed [3] that water in the particle delays the
subsequent increase of temperature and eventually
lengthens the time of devolatilization (or pyrolysis).
Such effects have been reported before [1820]. To
incorporate drying into this model, two approaches
seem possible. First, a narrow moving zone for evap-
oration at 100

C can be considered, so that, during


devolatilization, there are two reaction fronts. Each
reaction front has its own specic temperature and
requires a distinctive amount of enthalpy to effect a
change of phase. The second approach is to treat water
as the least tightly bound volatile species and assume
it is included in reaction (I). Hence, the latent heat of
vaporization of water is part of the apparent heat of
devolatilization,

H
v
, per unit mass of (true) volatile
matter, and only one reaction front is required, in view
of the steep temperature gradients at r =r
f
in Fig. 5.
Furthermore, the sensible heat, from T
0
to T
f
, of the
unreacted coal at r
f
is incorporated into

H
v
for sim-
plicity. This inclusion of sensible heat will contradict
the treatment in Section 5.1 for predicting the heat-
ing time before drying; however, the error is expected
to be small. The apparent heat of devolatilization (per
unit mass of true volatile matter) is thus dened as


H
v
=H
v
+
_
H
w
+C
p,w
(T
f
373)
_
W

/Y

(1) +C
p,c
(T
f
T
0
)/Y

.
Here, W

and Y

are the masses of water and


volatile material, respectively, per unit mass of mois-
ture-free original coal. In addition, H
w
is the latent
heat of vaporization per unit mass of water at 373 K,
and H
v
is the overall enthalpy of devolatilization
per unit mass of the volatiles for reaction (I) at tem-
perature T
f
. In Eq. (1), T
0
was taken to be the initial
temperature. Although the rst method seems more
realistic, various attempts at using the rst one failed
to give a simple, analytical solution for the time of
devolatilization. Furthermore, the inadequacy of de-
scribing drying as a reaction front will be demon-
strated in Sections 5.2 and 5.3. Thus here the second
method is adopted.
The rate at which enthalpy is transferred from the
surroundings to the particles exterior is
(2) Q
r
0
=4r
2
0
h
l
(T

T
s
).
Here the overall heat transfer coefcient includes con-
vective and radiative contributions and so is
(3) h
l
=h +
rad

rad
_
T
3

+T
2

T
s
+T

T
2
s
+T
3
s
_
.
The temperature of the volatile matter is assumed to
be T
f
at r
f
, but T

outside the particle. Hence, the


transpirational enthalpy per unit time is assumed to
be
(4) Q
t
=4r
2
f
C
p,v
Y

c
(T

T
f
)
dr
f
dt
.
Here, C
p,v
is the mean heat capacity of the volatile
material (including water) between T

and T
f
. Be-
cause water is treated as part of the volatile matter, the
value of C
p,v
will depend on the water content. Inside
the particle, a quasi-steady state is assumed between
r
0
and r
f
, i.e., across the char. The change of sensible
heat and the enthalpy ow across the char layer are
treated separately. Without considering any change of
sensible heat in the char, the resulting enthalpy ow
by conduction [21] is
(5) Q
r
0
r
f
=4k
char
(T
s
T
f
)r
0
r
f
/(r
0
r
f
).
The change in the sensible heat of the char layer (pre-
viously neglected [1]) is
(6) Q
sen
=4
char
C
p,char
d
dt
r
0
_
r
f
T r
2
dr.
However, it is difcult to derive an analytical solution
if Eq. (6) is used. Consequently, a perfectly good ap-
proximation, found using the temperature distribution
(shown in Fig. 13) in a particle, after considering non-
steady conduction of heat, was employed:
(7) Q
sen
=
4
3

char
C
p,char
(T

T
f
)r
2
0
dr
f
dt
.
The rate of enthalpy consumption in the endothermic
reaction (I) is
(8) Q
chem
=4r
2
f


H
v
Y

c
dr
f
dt
.
The enthalpy to heat up the unreacted central part,
i.e., a change of sensible heat of the raw coal (again
neglected previously [1]), has already been incorpo-
rated into Eq. (1) as part of the apparent enthalpy of
devolatilization.
If there is enough oxygen in the uidizing gas,
e.g., the bed is uidized by air, and if the temperature
560 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
of the bed is high enough (>850

C [22]) to ignite
the volatile matter, these vapors start to burn. Such
combustion around a coal particle liberates heat and
provides enthalpy for devolatilization. The rate of lib-
eration of enthalpy, Q
comb
, from burning the volatiles
is
(9) Q
comb
=4r
2
f

c
H
comb
Y

dr
f
dt
.
Although the volatile matter burns, probably fairly
rapidly, the vigorous ow of uidizing gas might
carry much of the liberated enthalpy away from the
particle; hence not all the liberated heat of combus-
tion will be used in heating the coal particle. Here it
is assumed that Q
comb
is the enthalpy of combus-
tion that reaches the particle and thus contributes to
its heating, with 0 1. This was of course ig-
nored in the previous [1] treatment of pyrolysis. If the
bed is cooler than 850

C, the volatile matter cannot


self-ignite [22], so =0 even for devolatilization. If
equals 0, this model can also be used for the pyrolysis
of coal; no other modication is needed. Hence, the
steady-state relationship between the above enthalpy
ow rates is
(10)
Q
r
0
+Q
comb
=Q
r
0
r
f
+Q
sen
+Q
t
(at r =r
0
)
and
(11) Q
r
0
r
f
=Q
chem
(at r =r
f
),
where every quantity is positive for simplicity.
In summary, the assumptions of this steady-state
model include the following:
(a) The primary reaction, (I), with one dominant
path, occurs irreversibly in a moving front at r
f
.
(b) The temperature at the reaction front, T
f
, is con-
stant during devolatilization.
(c) Mass transfer of the volatile material across the
layer of char is not rate-controlling.
(d) Bi
char
or Bi
c
>1/2 to ensure that the distribution
of temperature inside the particle is not uniform.
(e) The changes of the sensible heat of both the unre-
acted coal and the layer of char are approximated
as in Eqs. (1) and (7).
(f) Fragmentation, swelling, and change of shape of
the particle do not occur.
(g) The latent heat of evaporation of water is viewed
as part of the apparent heat of devolatilization;
i.e., drying and the primary reaction (I) in effect
occur simultaneously.
(h) From burning the released volatile material, the
fraction of its heat of combustion that is used for
further heating of the particle is . This parameter
is estimated below, but for the pyrolysis of a coal,
is zero.
(i) The particle is large enough for r
2
0
/
Aexp(E/RT ), as discussed above. As an
aside, this could mean that if reaction (I) were
really several reactions in parallel, any steps with
a very large activation energy, E, could be ki-
netically controlled. Such a possibility is ignored
below.
3.2. Derivation of the model
Equation (10) gives
4r
2
0
h
l
(T

T
s
) +4r
2
f

c
Y

C
p,v
(T

T
f
)
dr
f
dt
+
4
3

char
C
p,char
(T

T
f
)r
2
0
dr
f
dt
+4r
2
f

c
H
comb
Y

dr
f
dt
(12) =4k
char
(T
s
T
f
)r
0
r
f
/(r
0
r
f
).
Rearranging the above equation gives the temperature
at the outer surface of the particle as
(13)
T
s
=
_
_
_
r
2
0
h
l
T

+T
f
k
char
r
0
r
f
/(r
0
r
f
)
+r
2
f

c
Y

[H
comb
+C
p,v
(T

T
f
)]
dr
f
dt
+r
2
0

char
C
p,char
(1 Y

)(T

T
f
)
dr
f
dt
/3
_

_
r
2
0
h
l
+k
char
r
0
r
f
/(r
0
r
f
)
.
Also, Eq. (11) gives
4k
char
(T

T
s
)r
0
r
f
/(r
0
r
f
)
(14) =4r
2
f


H
v
Y

c
dr
f
dt
.
Furthermore, T
s
can be eliminated from Eqs. (13)
and (14) to give
(15)
dr
f
dt
=
(T

T
f
)r
2
0
h
l
_

_
r
2
f
Y

c
[

H
v


H
v
r
0
h
l
/k
char
+H
comb
+C
p,v
(T

T
f
)]
+r
f
(

H
v
Y

c
r
2
0
h
l
/k
char
)
+r
2
0

char
C
p,char
(T

T
f
)(1 Y

)/3
_

_
.
After integration, Eq. (15) becomes
t =r
3
f

c
Y

3r
2
0
h
l
(T

T
f
)
_


H
v
_
1
r
0
h
l
k
char
_
+H
comb
+C
p,v
(T

T
f
)
_
r
2
f

c
Y

2r
0
h
l
(T

T
f
)


H
v
r
0
h
l
k
char
r
f

char
C
p,char
(1 Y

)
3h
l
+
r
0

c
Y

3h
l
(T

T
f
)
_


H
v
_
1 +
r
0
h
l
2k
char
_
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 561
+H
comb
+C
p,v
(T

T
f
)
(16) +C
p,char
(T

T
f
)
(1 Y

)
char
Y

c
_
.
Two boundary conditions were employed for Eq. (16),
viz., r
f
= r
0
at zero time, and r
f
= r
f
at time t . The
time t = 0 is chosen as the moment volatile material
starts to evolve. The time interval between inserting
a coal particle into a uidized bed and when volatiles
start to evolve is designated as the time of heating; it
will be dealt with in Sections 5.1 and 5.2.
Six dimensionless parameters are employed to
simplify Eq. (16); they are
(17) Bi
char
r
0
h
l
/k
char
,
(18) Fo k
char
t /
c
C
p,v
r
2
0
h
l
t /Bi
char

c
C
p,v
r
0
,
(19)

H
v
/C
p,v
(T

T
f
),
(20)
Y


H
v
/
char
C
p,char
(T

T
f
)(1 Y

),
(21) 1 +H
comb
/

H
v
,
(22) r
f
/r
0
.
The pseudo-Fourier number, Fo, is an arbitrary mea-
sure of time. It differs from its conventional den-
ition [21], because here Fo uses physical properties
from different materials, namely, the heat capacity of
the volatile matter, the thermal conductivity of the
char, and the density of the original coal. The ratio
of the apparent heat of devolatilization to the change
of the sensible heat of the volatile material is des-
ignated as . The relative importance of the heat
of devolatilization and the sensible heat of the char
is . Furthermore, indicates the contribution to the
heat of devolatilization fromburning the volatiles. Be-
cause combustion is exothermic and the pyrolysis of
coal is probably endothermic, 1. The dimension-
less position of the reaction front, , varies from 1 to
zero. Using these dimensionless groups, Eq. (16) be-
comes
Fo
Y

=

3
3
_
1

Bi
char

1
Bi
char


2
2


3Bi
char

(23)
+
1
3
_
1
2
+

Bi
char
+
1
Bi
char

+
1
Bi
char

_
.
The signicance of the cubic Eq. (23) is that the rela-
tionship between Fo and , i.e., the movement of the
reaction front, is characterized by only ve dimen-
sionless groups, namely, Y

, Bi
char
, , , and .
For the pyrolysis of coal, both Eq. (16) and its dimen-
sionless version, Eq. (23), are applicable, provided
equals zero, i.e., = 1. Hence, in this model, only
four parameters, i.e., Y

, Bi
char
, , and , govern
the relationship between Fo and for the pyrolysis of
any solid fuel.
4. The time of devolatilization
The time of devolatilization is the interval of time
from the beginning to the end of volatile material be-
ing released in (I), when oxygen is present in the sur-
roundings, i.e., the time for the reaction front to move
from = 1 to 0. From Eq. (23), the dimensionless
time of devolatilization is
Fo
devo
=Y

/6 +Y

/3Bi
char
(24) +Y

/3Bi
char
+Y

/3Bi
char
.
Similarly, the time of pyrolysis is given when =1
in Eq. (24); hence,
Fo
pyro
=Y

/6 +Y

/3Bi
char
(25) +Y

/3Bi
char
+Y

/3Bi
char
.
The difference between the above two times is
Fo Fo
devo
Fo
pyro
(26) =( 1)Y

/3Bi
char
.
Equations (24)(26) can be revamped into the dimen-
sional expressions
(27)
t
devo
=
Y


H
v

c
3(T

T
f
)
_
r
2
0
2k
char
+
_
1 +
H
comb


H
v
+
C
p,v
(T

T
f
)


H
v
+
C
p,char

char
(T

T
f
)(1 Y

)
Y


H
v
_
r
0
h
l
_
,
(28)
t
pyro
=
Y


H
v

c
3(T

T
f
)
_
r
2
0
2k
char
+
_
1 +
C
p,v
(T

T
f
)


H
v
+
C
p,char

char
(T

T
f
)(1 Y

)
Y


H
v
_
r
0
h
l
_
,
(29)
t t
devo
t
pyro
=Y

H
comb

c
r
0
/3h
l
(T

T
f
).
The time required to heat up the particle, before the
volatiles appear, is explored below. It is worth not-
ing that Eqs. (27) and (28) both contain terms in r
0
and r
2
0
. In fact, if either t
devo
or t
pyro
is proportional
562 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
to r
2
0
, heat conduction through the outer layer of char
is totally rate-controlling. Also, Eqs. (27) and (28)
conrm that t
devo
and t
pyro
are both characterized by
k
char
, not k
c
.
4.1. Comparison with the conventional expression
for the time of devolatilization
A comparison of Eq. (27) with the conventional
empirical expression,
(30) t
devo
=ar
n
0
(with r
0
in mm and t
devo
in s),
for the time of devolatilization is made here. The
value of n can be deduced from
(31) n = lnt
devo
/ lnr
0
.
Hence, using Eq. (27) for t
devo
, the value of n is
n =

lnr
0
_
ln
_
r
2
0
2k
char
+
_
1 +
H
comb


H
v
+
1

+
1

_
r
0
h
l
_
_
=r
0

r
0
_
ln
_
r
2
0
2k
char
+X
r
0
h
l
__
(32) =
X r
0
/h
l
+r
2
0
/k
char
X r
0
/h
l
+r
2
0
/2k
char
,
where a new quantity
X1 +
H
comb


H
v
+
C
p,v
(T

T
f
)
Y


H
v
(33) +
C
p,char

char
(T

T
f
)(1 Y

)
Y

char


H
v
has been used in Eq. (32) for simplicity. It should be
noticed that using the Biot number for char, Eq. (32)
can be simplied to
(34) n =(X+Bi
char
)/(X+Bi
char
/2).
After rearrangement, Eq. (34) gives
(35) Bi
char
=X(n 1)/(1 0.5n).
Hence, using Eq. (35), the value of n can indicate
Bi
char
, which reveals whether external or internal heat
transfer is rate-controlling. Therefore, the common
practice of using n to identify the rate-controlling
process, in spite of Eq. (30) being empirical, has some
theoretical basis. A small Bi
char
(i.e., Bi
char
X)
gives n 1, which seems to jeopardize the idea of
an uneven temperature distribution inside the parti-
cle (because it will be found later that X 1.3),
and hence invalidate this model. However, it will be
demonstrated in Section 4.3 that Bi
c
, the Biot number
for coal, is more relevant for establishing a sharp re-
action front. Hence, a small Bi
char
, or n 1, will not
alter the validity of this model, provided Bi
c
>1/2.
4.2. Estimates of the values of the governing
parameters
Equation (27) can be simplied to t
devo
=c
1
r
0
+
c
2
r
2
0
, with two parameters, c
1
and c
2
, to be deter-
mined. Here, c
1
=

H
v
Y

c
X/3h
l
(T

T
f
) and
c
2
=

H
v
Y

c
/6k
char
(T

T
f
). The values of c
1
and c
2
can be obtained from the slope and intercept
at r
0
= 0 on a plot of measured values of t
devo
/r
0
against r
0
. The ratio of these two parameters,
(36) c
2
/c
1
=h
l
/2Xk
char
,
can be employed to give the Biot number for the char,
i.e.,
(37) Bi
char
=2Xr
0
c
2
/c
1
.
The major unknown quantities are T
f
and

H
v
, which
cannot be obtained directly from c
1
and c
2
.
It was noticed that, if a coal particle was pyrolyzed
in a hot bed of silica sand uidized by N
2
, ames
were seen on top of the quartz tube housing the bed.
These ames were of the released volatile material
burning in the laboratory air. The duration of one of
these ames was taken as a crude measure of the
time for pyrolysis; in fact it will probably be an un-
derestimate. These t
pyro
measured for three bitumi-
nous coals in a uidized bed at 950

C are plotted
in Fig. 6 as t
pyro
/r
0
against r
0
. Given that results
for coal are expected to be scattered, it is notewor-
thy that a fairly good straight line can be tted to
Fig. 6 for all three coals, which appear to be simi-
lar in Fig. 6. Linear regression gives the intercept as
c
1
=4200 s/m and the slope as c
2
=6.410
5
s/m
2
.
If X is taken as 1.3 (from an estimate of

H
v
made
after trial and error below in this section) for pyrol-
ysis and h
l
= 460 W/m
2
K [1], these values of the
slope and intercept give the thermal conductivity of
the char as 1.2 0.5 W/mK over the temperature in-
terval between T
f
and T
s
, using Eq. (36). For a coal
particle of radius 7 mm, Bi
char
equals 2.8. Hence,
for applying this model, the assumption (d) in Sec-
tion 3.1 is not violated for these coals. The slope
of Fig. 6 is c
2
, whose value gives

H
v
/(T

T
f
).
However, continuous measurements [3] with a ther-
mocouple cemented in a pyrolyzing particle of Daw
Mill indicated that the temperature in the reaction
front was 230

C. If T
f
is accordingly taken as
500 K, the value of c
2
from Fig. 6 gives

H
v
=
7.7 4.2 MJ/(kg of volatile matter). In conclusion,
because of its theoretical background and the con-
sistency of its dimensions, the expression t
devo
=
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 563
Fig. 6. The ratio of the duration of the ame of burning volatile material to the initial radius of the coal particle plotted against
the initial radius. The bed was uidized with N
2
at 950

C.
c
1
r
0
+c
2
r
2
0
is more meaningful than the conventional
empirical expression t
devo
= ar
n
0
for correlating ex-
perimental results for large particles of coal.
For a typical coal particle devolatilizing in a u-
idized bed, the governing parameters Bi
char
, , ,
and can now be estimated using the following val-
ues: the initial radius of the coal particle, r
0
=7 mm;
h
l
= 460 W/m
2
K [1]; the thermal conductivity of
char, k
char
= 1.2 W/mK (from above and compara-
ble to a previous estimate [1] of 1.7 0.9 W/mK);
the heat of combustion, H
comb
= 33 MJ/kg; the
temperature of the surroundings, T

= 1123 K; and
the heat capacity of the gaseous volatile matter,
C
p,v
= 1390 J/kgK. These values are for Daw Mill,
whose initial volatile content, Y

, is 0.36. The esti-


mate of C
p,v
was made from the assumptions that,
rst, the average molecular weight of the volatile
matter is 30 g/mol (bearing in mind that H
2
and
hydrocarbons from CH
4
up to tars are present), and
second, the heat capacity per mole of volatile mat-
ter is 5R [23]; here, R is the universal gas constant.
However, the heat of devolatilization

H
v
and T
f
are,
strictly speaking, unknown. Hence, and cannot
be estimated accurately. The values of , and hence
, are uncertain, but are estimated as follows using
previous experimental observations [1].
For pyrolysis, Eq. (23) gives
(38) =Fo/Y

f
1
() f
2
()/f
1
()Bi
char
,
where
(39)
f
1
() =
_
1 +2
3
3
2
+2(1
3
)/Bi
char
+2(1 )/Bi
char

__
6,
(40) f
2
() =(1
3
)/3.
The ratio of the two items on the right-hand side of
Eq. (38),
_
Fo/Y

f
1
()
___
f
2
()/f
1
()Bi
char
_
(41) =h
l
t /
_
r
0

c
C
p,v
Y

f
2
()
_
,
is 22, i.e., much larger than unity, when = 0.75
at t 30 s. Therefore, is mainly determined by
Fo/Y

f
1
(), so that f
2
()/f
1
()Bi
char
can be ig-
nored. In this case, after transformation into dimen-
sional form, Eq. (38) becomes
(42)


H
v
T

T
f
=
k
char
t
f
1
()Y

c
r
2
0
.
Let t
A
and t
B
be the times for the reaction front in
two identical particles to reach a specic dimension-
less radius
x
, for bed temperatures T
,A
and T
,B
,
respectively. Inserting these values into Eq. (42), the
values of T
f
and

H
v
can be estimated because
(43) T
f
=(t
B
T
,B
t
A
T
,A
)/(t
B
t
A
)
and
(44)

H
v
=k
char
t
A
(T
,A
T
f
)
__
f
1
(
x
)Y

c
r
2
0
_
.
When a particle of Daw Mill was pyrolyzed at 750
and 950

C [1], the times measured for the reac-


tion front to reach = 0.75 were 42.8 and 26.3 s,
respectively. However, these two times are subject
to two errors. First, the initial heating times were
not deducted. Second, the quenching of the parti-
cle by nitrogen is not perfect; hence, the time re-
quired to reach a specic radius is underestimated,
so it seemed reasonable to add 3 and 7 s to the
above times to compensate for the extra heating
time due to improper quenching at 750 and 950

C,
respectively. Taking
c
= 1200 kg/m
3
and r
0
=
564 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
7 mm, after deduction of the initial heating times
(see Section 5.1), Eqs. (43) and (44) give

H
v
=
10.5 MJ/(kg of the volatiles) (after trial and error,
since

H
v
changes f
1
(
x
)) and T
f
= 500 K. This
value of

H
v
is higher, but more accurate than the
estimate of 7.7 4.2 MJ/(kg of volatile matter) from
Fig. 6. However, the estimate of T
f
agrees perfectly
with the value (see above) indicated by thermocou-
ples inserted into a coal particle. With the denition
of

H
v
in Eq. (1), the true heat of devolatilization
is H
v
=9.4 4 MJ/(kg of volatiles), assuming the
following values: W

=0.065, H
w
=2257 kJ/kg,
C
p,w
= 2000 J/kgK, C
p,c
= 890 J/kgK. It must
be noted that the values of

H
v
and T
f
are very
sensitive to the values used above for t
A
and t
B
;
without deducting the errors mentioned above, the
times 42.8 and 26.3 s give

H
v
= 5000 kJ/kg
and T
f
= 700 K. Furthermore, because the thick-
ness of the char layer obtained [1] has great vari-
ation due to inhomogeneities of a coals composi-
tion, T
f
and

H
v
derived using Eqs. (43) and (44)
have resulting uncertainties. However, the values


H
v
=10.5 4 MJ/(kg of volatile matter) and T
f
=
500 K will be adopted as the most accurate esti-
mates for all three coals in Fig. 6. These values com-
pare with previous estimates [1] of

H
v
= 9.2
3.5 MJ/(kg of volatile matter) and the signicantly
higher T
f
= 550 100

C for Daw Mill coal. The


value of T
f
is discussed again below.
The temperature measurements in a particle of
Daw Mill coal of radius 7 mm [3] revealed that the
time for the reaction front to reach 0.5 during
devolatilization is 40 s shorter than during pyrol-
ysis at the same bed temperature of 850

C. Using
Eq. (23) or (29) with the typical physical properties
listed above, the value of is 0.85 for this case.
However, the difference of only 10 s between the
times of devolatilization and pyrolysis for the differ-
ent coal Reitspruit indicates that 0.21. Such a
low value of suggests that the volatiles mainly burn
away from such a coal particle in a uidized bed. The
difference in for these two coals might be caused by
the different chemical compositions of their volatiles,
especially their concentrations of H
2
.
With the above physical properties for Daw Mill,
typical values of Bi
char
2.8 (r
0
=7 mm), 0.7
( = 0.20.9), 22, and 12 for devolatiliza-
tion are obtained.
4.3. Inuence of each governing parameter in this
model
The inuence of the dimensionless groups Bi
char
,
, and will now be examined. For simplicity, the
following values are adopted for discussion: =10,
= 20, = 1 (i.e., pyrolysis), Bi
char
= 5 (r
0
=
12.5 mm). Another governing parameter, Y

, inu-
ences both and ; however, for simplicity, these
three parameters will be treated as if they were uncor-
related. The inuence of (the ratio of the apparent
heat of devolatilization to the increase in sensible heat
of the volatile material: see Eq. (19)) on the motion of
the reaction front is demonstrated in Fig. 7. This is
a plot of against Fo/Y

(a dimensionless time)
for different values of with Bi
char
= 5, = 20,
and =1 (i.e., pyrolysis). Little difference exists be-
tween = 10 and 100, whereas the velocity is very
sensitive to when < 1. Because a typical value
of is actually larger than 10, the value of will not
inuence the relationship between Fo/Y

and .
The inuence of Bi
char
is illustrated in Fig. 8,
where again is plotted against Fo/Y

, for =
Fig. 7. Results of the shrinking-core model plotted as (dimensionless radial position of the reaction front) against dimensionless
time for the parameters =0.1, 1, 10, and 100, Bi
char
=1, 5, 10, and 100, =20, =1.
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 565
Fig. 8. Results of the shrinking-core model, again plotted as versus Fo/Y

, for the parameters =10, Bi


char
=1, 5, 10,
and 100, =20, =1.
Fig. 9. Results of the shrinking-core model for the parameters =10, Bi
char
=5, =20, =1, 0.5, and 0.
10, = 20, and = 1. The velocity of the reac-
tion front for pyrolysis is more sensitive to Bi
char
for Bi
char
< 5 than when Bi
char
> 10, e.g., for r
0
>
25 mm. A larger Bi
char
gives a smaller Fo
pyro
/Y

,
i.e., the dimensionless time of pyrolysis; however, it is
misleading, from Fig. 8, to deduce that a larger Bi
char
results in a shorter time of pyrolysis. The reason is
that when Bi
char
is changed, Fo/Y

is also altered.
The position of the reaction front, , is again plot-
ted in Fig. 9 against Fo/Y

for different values of


(a measure of ) to investigate any effect of burn-
ing the volatiles. According to Eq. (21), = 1 for
pyrolysis, whereas any heating of a coal particle from
the combustion of the volatiles gives a smaller . In
Fig. 9, for the reaction front to reach the same ,
a smaller results in a smaller Fo/Y

; i.e., the
burning of the volatile matter shortens the time of de-
volatilization.
The inuence of on the motion of the reaction
front is demonstrated in Fig. 10, which is a plot of
against Fo/Y

for different values of (a modi-


cation of the ratio of the enthalpy of devolatilization
and the sensible heat of the char) with Bi
char
= 5,
=10, and =1 (i.e., pyrolysis). Little difference
exists between =10 and 100, whereas the velocity
is very sensitive to when <1. Because a typical
value of is actually larger than 10, the value of
will not inuence the relationship between Fo/Y

and , for these selected r


0
, etc.
It will be noticed in Figs. 79 that, for some com-
binations of parameters, an almost linear relationship
exists between and Fo/Y

for most of the in-


terval between equal to unity and zero. For exam-
ple, the dimensionless velocity of the reaction front is
d/d(Fo/Y

) and is plotted (as a negative quan-


tity) against in Fig. 11 for = 1, 0.5, or 0. There
566 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
Fig. 10. Results of the shrinking-core model for the parameters =10, Bi
char
=5, =0.1, 1, 10, and 100, =1.
Fig. 11. Calculated velocity (dimensionless) of the reaction front plotted against for the parameters = 10, Bi
char
= 5,
=20, =1, 0.5, and 0.
are two regions of , one near the exterior and the
other close to the center, where according to Fig. 11,
the reaction front moves much quicker than else-
where. For pyrolysis, the reaction front moves at a
nearly constant rate for between 0.15 and 0.95. This
demonstrates that the velocity of the reaction front is
nearly constant, and explains why the char layer is
found [1] to increase in thickness at a nearly constant
rate. If the volatiles burn, the reaction front moves
quicker than during pyrolysis for > 0.7; however,
any effect of the volatiles burning is insignicant for
<0.7, i.e., near the end of devolatilization.
The rate at which volatile matter is released at
a particular time is
2
d/d(Fo/Y

) in dimen-
sionless form. Values of
2
d/d(Fo/Y

), with
= 10, = 20, and Bi
char
= 5, are plotted in
Fig. 12 against Fo/Y

for = 1, 0.5, or 0. At
an early stage, the rate of devolatilization or pyrolysis
is high, but decreases while time progresses; in fact,
for Fo/Y

>0.03, a long period with a low rate of


evolution is found. This long and low rate of evolu-
tion explains the uncertainty of determining the end
of devolatilization. A smaller value of , i.e., with
combustion of the volatiles, results in a quicker ini-
tial, but slower nal, stage of evolution. The plots in
Fig. 12 are very similar in shape to the measured rates
of evolution [3].
With the estimates of =10, =20, =1, and
Bi
char
=5, i.e., for r
0
=12.5 mm, the above analysis
shows that and exert little inuence on the re-
lationship between Fo/Y

and . In other words,


four dimensionless parameters (, Bi
char
, Fo/Y

,
) and one equation, i.e., Eq. (23), determine the
behavior of devolatilization. Consequently, there are
three degrees of freedom and the parameter =r
f
/r
0
is characterized by three other parameters, together
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 567
Fig. 12. The dimensionless rate of the release of volatile matter as dened by Eq. (52). The parameters used were = 10,
=20, Bi
char
=5, =1, 0.5, or 0.
with Eq. (23). Hence, for characterizing devolatiliza-
tion, three independent dimensionless groups are rel-
evant; they can be chosen to be
Fo/Y

k
char
t (T

T
f
)/Y


H
v
r
2
0
,
Bi
char
=r
0
h
l
/k
char
, 1 +H
comb
/

H
v
.
For pyrolysis, only Bi
char
and Fo/Y

are relevant.
Here is the demonstration that Bi
char
and not Bi
c
is
important for characterizing devolatilization times.
4.4. The inuence of moisture content
The amount of water in a particle of coal can be al-
tered before its insertion into a uidized bed. Hence,
water content is a variable and therefore controllable.
According to Eq. (1), different water contents of a
coal particle alter the value of the apparent heat of
devolatilization, and eventually change the time of
devolatilization. This inuence can be seen by using
Eq. (27) to give
(45)
t
devo
W

=

c
3(T

T
f
)
_
r
2
0
2k
char
+
r
0
h
l
_
.
Because all the items on the right-hand side of
Eq. (45) are positive, t
devo
/W

> 0; i.e., larger


water content increases the time for devolatilization.
The literature [46] conrms this prediction.
5. The temperature on the exterior of a particle
When a particle of coal is inserted into a hot (700
950

C) uidized bed, the length of time between


the insertion and when volatile matter starts to be
evolved can be deduced with the above model. The
primary reaction (I) is assumed to proceed (like a
change of phase) at a temperature T
f
; therefore, the
start of pyrolysis, i.e., the time when the temperature
of the outer surface of the particle reaches T
f
, can be
obtained by solving the corresponding heat conduc-
tion problem. However, it is found experimentally [3]
that different chemical species in the volatile matter
evolve after different residence times, so that choos-
ing the starting time of one species is somewhat ar-
bitrary and will result in uncertainties. Furthermore,
the removal of moisture from a coal particle makes
an estimate of when volatiles emerge complicated.
Because drying occurs at a lower temperature than
T
f
, and so requires a latent heat of vaporization, the
presence of moisture in a coal particle lengthens the
time of heating. Temperature measurements [3] with
a thin thermocouple (diam. 0.2 mm) cemented in a
coal particle revealed that the evaporation of water
lasts a fairly long time (25 s) at a radial position
r/r
0
=0.5. Hence, the initial heating can be roughly
separated into two stages according to the temper-
ature at the particles exterior; when this is below
100

C is the rst stage; afterward, from 100

C to
T
f
, is the second stage. It must be noticed that dry-
ing in the interior and thermal decomposition on the
exterior of the particle may occur simultaneously. Be-
cause this initial heating time concerns phenomena
before the evolution of any volatile matter, the dis-
cussion in this section should be applicable for both
pyrolysis and devolatilization. The assumption, used
in the above shrinking-core model, of regarding wa-
ter as part of the volatile matter will not be employed
in Sections 5.1 and 5.2.
5.1. The heating of the particle before drying
For the rst stage, the equation for heat transfer
inside a spherical particle of coal is
568 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
(46)
T
t
=
c
_

2
T
r
2
+
2
r
T
r
_
and the corresponding boundary conditions are
T
r

r=r
0
=
h
l
k
c
(T

T ) +

rad

rad
k
c
_
T
4

T
4
_
(47) =
h
l
k
c
(T

T )
and
(48)
T
r

r=0
=0,
where the thermal diffusivity of coal,
c
k
c
/
c
C
p,c
,
is used, and h
l
is dened in Eq. (3). The initial condi-
tion is that throughout the coal
(49) T =T
0
.
Equations (46)(49) can be transformed with the fol-
lowing three dimensionless parameters: T

=(T

T )/(T

T
0
), r

=r/r
0
, t

=
c
t /r
2
0
. The resulting
dimensionless forms are
(46a)
T

=

2
T

r
2
+
2
r

,
(47a)
T

+Bi
c
T

=0 for r

=1,
(48a)
T

=0 for r

=0,
(49a) T

=1 for t =0.
The Biot number for coal, Bi
c
r
0
h
l
/k
c
, is used in
Eq. (47a). The solution of Eqs. (46a)(49a) is [13]
T

(r

, t

) =
2
r

m=1
exp
_

2
m
t

_

2
m
+
2
(
2
m
+
2
) +
(50) sin(
m
r

)
r

_
0
r
#
sin(
m
r
#
) dr
#
.
Here,
m
is the mth eigenvalue of the eigenfunction
(51)
m
cot
m
+ =0
and
(52) =Bi
c
1 =r
0
h
l
/k
c
1.
Because of the presence of exp(
2
m
t

) in Eq. (50),
only the rst eigenvalue
1
[13] is important. Further-
more, the initial condition Eq. (49a), i.e.,
T

(r

=1, t

=0) =1

=
2
r

2
1
+
2
(
2
1
+
2
) +
(53) sin(
1
r

)
r

_
0
r
#
sin(
1
r
#
) dr
#
,
must be fullled. Thus, inserting Eq. (53) into
Eq. (50), the simplied solution
(54)
T

T
s
T

T
0
exp
_

2
1
t
r
2
0
_
is obtained for the surface temperature. The heating
time in the rst stage is accordingly
(55) t
1
=
_
r
2
0
/
c

2
1
_
ln
_
(T

T
0
)/(T

373)
_
from letting T
s
= 373 K. The value of
1
can be
found [13] for different values of ; in fact, for Bi
c
(= + 1) > 10,
1
3; for Bi
c
= 1,
1
1.6.
The following values are adopted to estimate t
1
:
T
0
= 298 K; T

= 1123 K (850

C); r
0
= 7 mm;

c
= 1200 kg/m
3
for Baddesley coal. The thermal
conductivity of coal at (298 + 373)/2 = 336 K can
be estimated from Merricks correlation [24] to be
0.30 W/mK (based on the ultimate analysis of Bad-
desley [1]). Likewise, the heat capacity of Baddesley
coal at 336 K is estimated [24] to be 890 J/kg K.
Therefore,
c
= 2.8 10
7
m
2
/s and Bi
c
= 11;
hence
1
= 3.07 [13]. With the above values, t
1
=
1.8 s for Baddesley of radius 7 mm. Furthermore, if
the particle is moisture-free, Eq. (55) can be used up
to T
f
, when reaction (I) starts on the surface of the
particle; this occurs after a further time of t
2
=3.4 s,
i.e., after a total of 5.2 s.
5.2. The heating during and after drying
After the surface temperature of a coal particle
reaches 100

C, water starts to evaporate. If evapo-


ration inside the particle occurs in a moving reac-
tion front at 100

C, drying proceeds according to the


shrinking-core model. Hence, that model can be used
with only slight modications. The validity of this
treatment of drying using a shrinking-core model will
be examined later. The primary reaction (I) begins
after a further heating time, t
2
, when the particles
exterior reaches T
f
. Let the vaporization front be at
radius r
w
and temperature T
w
(=100

C). Of course,
there is no contribution from any combustion of the
volatiles. The governing equation, derived in the same
way as above, is
Fo
w
W

w
=

3
w
3
_
1
1
Bi
c

1
Bi
c

w
_


2
w
2


w
3Bi
c

w
(56)
+
1
3
_
1
2
+
1
Bi
c
+
1
Bi
c

w
+
1
Bi
c

w
_
,
where
(57) Fo
w
k
c
t /
c
C
p,w
r
2
0
=h
l
t /Bi
c

c
C
p,w
r
0
,
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 569
(58)
w


H
w
/C
p,w
(T

T
w
),
(59)
w
r
w
/r
0
,
(60)
w


H
w
W

/C
p,c
(T

T
w
)(1 W

).
The temperature at the external surface of the particle
is
T
s
=
T

+T
w

w
/Bi
c
(1
w
)
1 +
w
/Bi
c
(1
w
)
(61)
+
(
2
w
+
w
/3
w
)W

(T

T
w
)/Bi
c
d
w
dFo
w
1 +
w
/Bi
c
(1
w
)
fromrearranging terms in Eq. (13). Hence, the heating
time in the second stage, t
2
, is given when T
s
= T
f
.
This time was computed as follows: rst, values of

w
were tabulated from 1 to 0 at intervals of, say,
0.01; second, using Eq. (56), the values of Fo
w
for
each
w
were derived. Then the derivative d
w
/dFo
w
was obtained numerically. The value of T
s
is given
by Eq. (61). Finally, choosing the value of Fo
w
, for
which T
s
= T
f
, the heating time t
2
was obtained us-
ing Eq. (57).
The following parameters for the pyrolysis of
a Baddesley coal particle were adopted for these
computations: T

= 1123 K, T
f
= 500 K, T
w
=
373 K, r
0
=7 mm, W

=0.065, h
l
=460 W/m
2
K,
C
p,w
= 2000 J/kgK, H
w
= 2257 kJ/kg (hence


H
w
= 3380 kJ/kg), and
c
= 1200 kg/m
3
. The
thermal conductivity for Baddesley at a temperature
(T
w
+T
f
)/2 is 0.37 W/mK. The value of Bi
c
is 8.7,

w
= 0.32, and
w
= 2.3. Using the above values,
t
2
2.2 s, which is smaller than t
2
=3.4 s, from us-
ing Eq. (55) for a moisture-free particle. Because the
time estimated using Eq. (55) did not consider the de-
lay of drying, it should give a shorter time than that
using Eqs. (56) and (61). Therefore, a re-examination
of the shrinking-core model is now in order.
5.3. Discussion: validity of the shrinking-core model
The region of validity of the shrinking-core model
has not been explored fully. The unreasonable pre-
diction of t
2
in Section 5.2 gives a good example
of blindly and wrongly applying the shrinking-core
model. The reason that drying cannot be described
using this model is probably that assumption (e) in
Section 3.1 is being violated. Continuous measure-
ments of the temperature inside a pyrolyzing coal par-
ticle [3] using inserted thermocouples revealed that
drying probably occurs over a wide region, rather than
at a sharp front. As a result, assumption (e) underesti-
mates the enthalpy required for drying. Another way
of violating assumption (e) is for the neglect of sensi-
ble heat from Eq. (7) to be serious and problematic.
Because the changes of sensible heat are approxi-
mated using Eqs. (1) and (7), errors from using these
two approximate expressions will be signicant when
the volatile content is low ( < 1). Hence, for high
rank coals, this model might well be inadequate. For
the same reason, when 1, i.e., near the end of
devolatilization, this model may be inadequate. Sim-
ilarly, for coals of low water content, this model is
potentially wrong.
Another assumption that is probably wrong is (a),
i.e., that one primary reaction occurs at a sharp front.
It is clear [17,25,26] that several reactions of ther-
mal decomposition occur at different temperatures
and hence at different spatial locations. However, the
high thermal conductivity in the outer layer of char
(1.2 W/mK; see Section 4.1) and a relatively low one
(0.30 W/mK, from Merricks correlation [24]) for
the inner core of virgin coal help to maintain a sharp
temperature front, i.e., a quick temperature change
before reaction occurs. It is very likely that this tem-
perature front leads to the appearance of a shrinking
core. Hence, for the bituminous coals in this study,
this model is still correct, in spite of assumption (a) in
Section 3.1 probably being violated.
5.4. The temperature within a moisture-free particle
of coal in a hot uidized bed
If a coal particle contains water, as yet no sat-
isfactory way of calculating the temperature, T
s
, at
its outer surface has been presented. However, for
a moisture-free particle of coal, the relationship be-
tween time and T
s
is described by Eq. (54), before
T
f
is reached at the particles exterior. Afterward, the
temperature at the surface of a pyrolyzing particle is
T
s
=
T

+T
f
/Bi
char
(1 )
1 +/Bi
char
(1 )
(62)
+
(
2
+/3)Y

(T

T
f
)/Bi
char
d
dFo
1 +/Bi
char
(1 )
.
The solution of Eq. (62) was explained in Sec-
tion 5.2 for the case of drying, when Eq. (61) was
used. The following physical properties for dry Bad-
desley can be used: T

= 1123 K, T
f
= 500 K,
T
w
= 373 K, T
0
= 298 K, r
0
= 7 mm, Y

= 0.402,
h
l
= 460 W/m
2
K, C
p,v
= 1390 J/kgK, H
v
=
9.4 MJ/kg, and
c
= 1200 kg/m
3
. Again, the ther-
mal conductivity for Baddesley coal at a tempera-
ture (T
w
+ T
0
)/2 = 336 K is 0.30 W/mK; but it is
1.2 W/mK for its char at (T
f
+T

)/2 =812 K (see


Section 5.1). The value of T
s
(i.e., at r = r
0
) is plot-
ted against residence time in Fig. 13. Furthermore, the
temperatures throughout the particle are also plotted
in Fig. 13. The temperature T at r/r
0
, with r > r
f
,
570 J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571
Fig. 13. The temperature of the outer surface of a particle of Baddesley coal (radius 7 mm) during pyrolysis at 850

C. The
position of the reaction front is also displayed using the axis on the right.
Table 1
The temperature and the starting time the evolution of vari-
ous chemical species during the pyrolysis of Baddesley in a
uidized bed at 850

C
Chemical species CO CO
2
NO
x
C
2
H
4
C
2
H
6
HCN
Starting time of 7.5 7 9.5 20 20 50
evolution (s)
Temperature of 260 250 280 380 380 570
exterior (

C)
was obtained from Eq. (6); the nal form is
T =
(63)
T
s
(r/r
0
)/[1 (r/r
0
)] +T
f
(r/r
0
)/[(r/r
0
) ]
(r/r
0
)/[1 (r/r
0
)] +(r/r
0
)/[(r/r
0
) ]
.
Here, < r/r
0
< 1, where r
f
/r
0
. Because dry-
ing has not been considered, these temperatures at
each residence time are slightly overestimated in
Fig. 13.
Table 1 lists the times when various chemical
species were rst detected [3] gas chromatographi-
cally in the off-gases after one particle of Baddesley
coal had been added to a bed of sand at 850

C when
uidized by N
2
. Table 1 also lists the corresponding
external temperatures calculated from Eq. (62) for the
pyrolysis of Baddesley coal at 850

C. Of course, as
already mentioned, these temperatures are overesti-
mates, because moisture in the coal delays its heating.
However, the results in Table 1 and Fig. 13 are in-
teresting. The reason for different chemical species
appearing at different times is that different parallel
steps in reaction (I) occur [17,25,26] at different tem-
peratures. Certainly, Table 1 indicates that the mean
value of T
f
is much less than 570

C. This conrms
that the previous estimate [1] of T
f
= 550 100

C
is too high. The difculty of estimating a mean value
for T
f
was noted in Section 4.2. The nal estimate
of 500 K was made above from measured tempera-
tures of devolatilization inside one of these particles,
as well as a consideration (see Section 4.2) of the
times for the devolatilization front to reach =0.75.
It is also worth noting that when small particles of
bituminous coals are heated slowly, after losing mois-
ture they start to lose mass, probably by releasing tars
at 500 K [7,27,28]. The relatively late appearance
of HCN is due to the fact that it requires a compara-
tively high temperature to generate it. If a temperature
of almost 570

C is required to generate HCN, the ni-


trogen may be bound relatively tightly, e.g., in some
aromatic structure in the coal. On the other hand, one
unknown, unidentied nitrogenous compound (possi-
bly NH
3
), which is one of the precursors of N
2
O, was
found [3] to start to evolve at a time much earlier than
HCN, but similar to those for C
2
H
4
or C
2
H
6
. Hence,
the temperature at which what is conjectured as NH
3
is generated is below 380

C, the same as for C


2
H
4
or C
2
H
6
. This suggests that the source of the nitrogen
for this NH
3
is some less tightly bound structure in
coal, bearing in mind that C
2
H
4
and C
2
H
6
are likely
to be the products of decomposition of aliphatic hy-
drocarbons of higher molecular weight.
6. Conclusions
This steady-state, shrinking-core model is a rene-
ment of a previous one [1]. It cannot be applied to the
devolatilization or pyrolysis of all coals. In particular,
for a coal of low volatile content, e.g., an anthracite,
this model might be inadequate. In any event, assump-
tion (f) is far from true in this case, because an an-
thracite rapidly fragments when added to a uidized
J.-S. Chern, A.N. Hayhurst / Combustion and Flame 146 (2006) 553571 571
bed [1,4]. Within the range of validity (e.g., with lig-
nite and bituminous coals, where such reaction fronts
have been observed visually [1]), the predictions of
this model agree qualitatively with the literature. The
time of devolatilization or pyrolysis can be predicted.
Dimensionless forms of the relevant parameters have
been found. The equation governing the devolatiliza-
tion of a largish coal particle is Eq. (23); the analyses
revealed that the following four dimensionless groups
are important:
Fo/Y

k
char
t (T

T
f
)/Y


H
v
r
2
0
,
r
f
/r
0
, Bi
char
=r
0
h
l
/k
char
,
1 +H
comb
/

H
v
.
The initial heating time can be predicted using
Eq. (55) for a moisture-free coal. To correlate exper-
imental measurements of the time of devolatilization
(or pyrolysis), the expression t
devo
= c
1
r
0
+ c
2
r
2
0
is more useful and meaningful than the commonly
used empirical expression t
devo
= ar
n
0
. Measure-
ments of c
1
and c
2
provided values of k
char
, Bi
char
,
and

H
v
/(T

T
f
).
The time of pyrolysis or devolatilization is deter-
mined by the Biot number for char, Bi
char
, not Bi
c
,
based on the coals properties. However, for the ini-
tial heating time, Bi
c
is the relevant parameter. The
heat of devolatilization turns out to be much larger
than the usually assumed negligible quantity. The
value of H
v
is 9.4 MJ/(kg of volatile matter)
for Daw Mill, whose char has a thermal conductiv-
ity of 1.2 0.5 Wm
1
K
1
. A mean temperature at
the reaction front for Daw Mill equal to T
f
= 500 K
(230

C) was estimated. The thermal diffusivities of


these bituminous coals and char are 2.8 10
8
and
8.8 10
7
m
2
/s, respectively.
The above model has the attraction that its basic
equations have analytical solutions. Detailed consid-
eration of the model indicates that in reality a de-
volatilizing or pyrolyzing particle of coal initially has
a fairly wide drying front passing from its exterior to
its middle. This is followed at progressively higher
temperatures by a succession of other fronts, so close
to one another that they were modeled above as one
front. Each front corresponds to one of the individ-
ual steps for thermal decomposition in (I) and has
its own activation energy and pre-exponential factor.
The velocities of these fonts are controlled by heat
conduction inside the particles outer layer of char.
However, of course, it could well be that, for a coal
of a given size, some steps in (I) have activation ener-
gies large enough to be kinetically controlled. These
steps release the most tightly bound volatiles and oc-
cur near the end of devolatilization without a front
moving inside a particle, whose temperature is uni-
form and close to that of the uidized bed.
Acknowledgments
Financial support from B.C.U.R.A. and from The
Ministry of Education, Republic of China (Taiwan),
is gratefully acknowledged.
References
[1] J.-S. Chern, A.N. Hayhurst, Combust. Flame 139
(2004) 208221.
[2] O. Levenspiel, Chemical Reaction Engineering, second
ed., Wiley, New York, 1972.
[3] J.-S. Chern, Ph.D. thesis, University of Cambridge,
1997.
[4] J.-S. Chern, A.N. Hayhurst, J. Energy Inst. 78 (2005)
6275.
[5] R.D. La Nauze, Fuel 61 (1982) 771774.
[6] R.H. Essenhigh, Trans. Am. Soc. Mech. Eng. J. Eng.
Power 85 (1963) 183188.
[7] D.W. van Krevelen, Coal, Elsevier, Amsterdam, 1961.
[8] W.E. White, C.H. Bartholomew, W.C. Hecker, D.M.
Smith, Adsorpt. Sci. Technol. 7 (1991) 180.
[9] A. Wheeler, in: L.K. Doraiswamy, M.M. Sharma
(Eds.), Heterogeneous Reactions: Analysis, Examples
and Reactor Design, vol. 1, Wiley, New York, 1984.
[10] L.K. Doraiswamy, M.M. Sharma (Eds.), Heteroge-
neous Reactions: Analysis, Examples and Reactor De-
sign, vol. 1, Wiley, New York, 1984.
[11] P.R. Solomon, M.A. Serio, E.M. Suuberg, Prog. Energy
Combust. Sci. 18 (1992) 133220.
[12] R.M. Fristrom, Flame Structure and Processes, Oxford
Univ. Press, Oxford, 1995, p. 240.
[13] M.N. zisik, Heat Conduction, second ed., Wiley, New
York, 1993.
[14] K. Annamalai, W. Ryan, Prog. Energy Combust.
Sci. 19 (1993) 383446.
[15] M.A. Andrei, A.F. Sarom, J.M. Ber, Combust.
Flame 61 (1985) 1727.
[16] O. Levenspiel, Engineering Flow and Heat Exchange,
Plenum, New York, 1984, p. 202.
[17] D.B. Anthony, J.B. Howard, AIChE J. 22 (1976) 625
655.
[18] J.F. Stubington, J. Inst. Energy 53 (1980) 191195.
[19] W. Prins, R. Siemons, W.P.M. van Swaaij, M. Rado-
vanovic, Combust. Flame 75 (1989) 5779.
[20] M.K. Urkan, M. Arikol, Fuel 73 (1994) 768772.
[21] M.N. zisik, Heat Transfer, Wiley, New York, 1985.
[22] J.S. Dennis, A.N. Hayhurst, I.G. Mackley, Proc. Com-
bust. Inst. 19 (1982) 12051212.
[23] R. Hill, An Introduction to Statistical Thermodynam-
ics, AddisonWesley, 1960.
[24] D. Merrick, Fuel 62 (1983) 540546.
[25] S.A. Scott, J.S. Dennis, J.F. Davidson, A.N. Hayhurst,
Chem. Eng. Sci. 61 (2006) 23392348.
[26] S.A. Scott, J.S. Dennis, J.F. Davidson, A.N. Hayhurst,
Fuel 85 (2006) 12481253.
[27] S. Niksa, G.-S. Liu, R.H. Hurt, Prog. Energy Combust.
Sci. 29 (2003) 425477.
[28] A. Arenillas, F. Rubiera, J.J. Pis, J. Anal. Appl. Py-
rol. 50 (1999) 3146.