Fuel Vol. 75 No. 3, pp.

333-343, 1996
Copyright © 1996ElsevierScienceLtd
Printed in Great Britain. All rights reserved
ELSEVIER 0016-2361(95)00180-8 0016-2361/96/$15.00+ 0.00

Low-temperature oxidation of coal

1. A single-particle reaction-diffusion model

Srinivasan Krishnaswamy, Saurabh Bhat, Robert D. Gunn and Pradeep K.

Agarwal*
Chemical & Petroleum Engineering Department, University, of Wyoming, Laramie, WY
82071, USA
(Received 6 April 1994; revised 14 February 1995)

In this paper, the first of a three-part series, a kinetic model for low-temperature oxidation is developed. The
formulation, based on a single isothermal particle, permits assessment of the relative importance of various
mass transfer resistances. Through inclusion of transport resistances, the model accounts for the dependence
of the observed reaction rates on particle size and specific external surface area over the full range of particle
sizes, with smooth transition between different reaction regimes for dry as well as wet low-rank coal. The
approach also permits development of a new model which considers the effect of bulk and surface moisture
in the coal on the rate of low-temperature oxidation. This new model is expected to apply at moisture levels
above ~0.1 kg kg-%oal. It is shown that when liquid water fills the porous matrix, in situ moisture in fresh
coal must exert a very significant retarding influence on the rate of low-temperature oxidation at constant
temperature. Further, the influence of particle size on reaction rate is pronounced even at low temperatures
and small particle sizes. For dried coal on the other hand, the influence of particle size becomes important
only at significantly higher temperatures or for considerably larger particle sizes. Results of the extension of
the model to (1) the interpretation of rate data obtained in isothermal batch and fixed-bed reactors and (2)
the modelling of spontaneous combustion in coal stockpiles are reported in parts 2 and 3 respectively.

(Keywords:coal; low-temperatureoxidation; kinetic modelling)

Spontaneous combustion of stored coals poses a serious
problem for both coal producers and users. The problem
assumes even greater significance in attempts to prepare
a product of higher calorific value through thermal
drying of low-rank coals, since removal of moisture
enhances the potential for spontaneous ignition and
combustion. Low-temperature oxidation of coal is the
primary source of heat leading to spontaneous combus-
tion; its understanding is clearly important for prevention
of fires in coal stockpiles.
Experimental observations
Once coal in a stockpile reaches temperatures above
~350 K, the possibility of fire is extremely high 1. For
modelling spontaneous ignition in coal stockpiles, rate
parameters that apply at temperatures < 3 5 0 K are
required. From a review of the literature, Table 1, it is
clear that low-temperature oxidation is strongly
dependent on temperature and that the rate of
oxygen consumption follows an Arrhenius-type law 2-2°.
However, the effect of particle size on the rate of low-
temperature oxidation remains controversial and poorly
understood. Van Krevelen 21 observed that the reaction
rate increased with increasing specific external surface
area, Sex, for particles of diameter 1 > mm. For particles
with sizes between 0.1 and 1 mm, a fourfold increase in
specific external surface area increased the rate of
oxidation by a factor of 1.5. For still finer particles, the
rate of oxidation was proportional to the volume of the
sample. These observations indicate that the rate of
oxidation varies as SePxwith 0 ~<p~< 1 depending on the
particle size; however, the role of temperature in
determining the critical particle sizes for change in p is
not clear. There is evidence that particle size influences
the reaction rate at higher temperatures, whereas at
lower temperatures ( < 425 K for certain coals) the rate
could be essentially independent of particle size9-11'14
On the other hand, the reaction rate constant for oxygen
consumption has been reported 15-18'2° to depend on SePx
with p ~ 1/3 even at lower temperatures. Sondreal and
Ellman 16 preferred however to fit the exponential
function given in Table 1 even though the oxidation
rate appeared to follow the S 1/3exrelation. This approach
was taken to ensure that the oxidation rate levelled off
below a critical particle size; otherwise extremely fine
coal would be predicted to ignite immediately in contact
with air at ambient temperature.
Modelling of low-temperature oxidation
In many earlier studies of low-temperature oxidation,
the gas consumption process was modelled using the
Elovich equation 3-5'22'~3. Harris and Evans 24 showed
that this equation also fits data generated by a computer
from the unsteady-state diffusion equation. Kam et al. 5'6

Fuel 1996 Volume 75 Number 3 333

Low-temperature oxidation of coaL"S. Krishnaswamy et al.

cY

c7

~'.=
0 .~ 8
t~3
A

~o 'n o~ ~

T~v
.o ~o 0 ~' "0
"~ 0=

K
¢} '~ ,0 "8
~ '~, ~ , - , o ~I ~o' , ~ ~ I ' "o
~ =1

..~ ..
"u~
,..~1 ~r~ =0 ~ " -'-'o .o
. 0 " 0 '9 ~,. I,_, ' ~ t'~
o,"
~.0 o.o o.o

.~o~ ~.. I

8 i.o= o=~ .=

0 0 ~ ~ ~ ~ ~ ~ 0
es o
~ 0~
• • @ • • • o0 • • ,~1 •

=.
=
t~ b b -

~ "'= "= "=A ~ ' = .'o " .,.0.,

o ° s o .,.o .,-w ~ *.o
•.~ ,.~ ,~ ,'~ ~ ~ oq=.~

'4"1
a,, ,o o r-.- ,5
-: ~" 'T "f J
'~" ¢',1 ~0 ,~ t~
"R s s
o o o ,~ o
f.

"0

i I '? ? i I I I I I
--, P. P., 2,

=.
= ~ =o ~.~.

=,
p,

334 Fuel 1996 Volume 75 Number 3

 Low-temperature oxidationof coak S, Krishnaswamy et al.
proposed the following reaction scheme:
coal + 02 ~ CO2, CO, H20 (1)
coal + 02 ~ complex ~ CO2, CO, H20 (2)
The overall burnoff reaction, (1), was assumed to consist
of two individual reactions which were zero- and first-
order with respect to oxygen concentration. The overall
chemisorption reaction, (2), involved individual reactions
for active site creation, deactivation and oxygenated
product formation. On the assumption that diffusion of
oxygen within the coal was negligible (that is, the coal for
the purposes of low-temperature oxidation could be
treated as a non-porous solid), the overall rate based on
the external surface area was expressed in terms of
external mass transfer and reaction resistances. Agree-
ment between model and experiment for different
particle sizes requiredoxthes
j~ asymptotic reaction rate to
be proportional to . Subsequently, Karsner and
Perlmutter 10,11proposed a reaction scheme consisting of
three paths:
coal + 02 ~ CO2, CO (3)
coal + 0 2 ~ physisorbedO2 -~
chemisorbed O2 ~ CO2, CO (4)
coal + O2 -~ H20 (5)
There are several significant differences between the
proposals of Kam et al. 5'6 and Karsner and
Perlmutter 1°'11. In terms of the reaction scheme, the
latter isolated water production from the burnoff and
sorption reactions and recognized the possibility of 02
being physically adsorbed on the coal surface. In
addition, Karsner and Perlmutter l°'ll considered the
burnoff reaction rate to depend on the concentration of
active sites on the coal surface. They also argued that the
sorption reaction did not lead to formation of oxyge-
nated products; reaction (4) then contributes to the rate
of oxygen consumption but not the rates of production
of carbon oxides. Recognizing that oxygen can penetrate
within the coal, these authors developed a model in
which effectiveness factors were invoked to account for
intraparticle diffusion. However, these effectiveness
factors were adjustable parameters; the relation between
reaction kinetics, transport processes and effectiveness
factors was not explored.
Itay et a l Y recently suggested that the direct burnoff
reaction did not occur at low temperatures. They
proposed the reaction scheme
coal + 02 ~ physisorbed 0 2 --+
oxycoal -~ CO2, CO, H20 (6)
This is somewhat similar to reaction (4); however, unlike
the proposal of Karsner and Perlmutter 10,11, oxygenated
products--carbon oxides and water--are generated
entirely by this reaction. This model does not appear to
have been used for the determination of kinetic rate
parameters from experimental data.
The present series of three papers presents the results
of an investigation covering both theoretical and
modelling aspects of low-temperature oxidation and
spontaneous combustion of stockpiled coat. Part 1
develops a kinetic model for low-temperature oxidation.
The formulation, based on a single isothermal particle,
permits assessment of the relative importance of various
mass transfer resistances and defines the effect of particle
size and temperature on the rate of oxidation of dried
and fresh coat at low temperatures. In Part 2, the single-
particle model is used to interpret experimental measure-
ments of the rates of 02 consumption and CO2
formation. Data were taken from the literature and
additional measurements were obtained for Wyoming
subbituminous coal as part of this investigation. In Part
3, the kinetic model for low-temperature oxidation is
incorporated into a mathematical model of spontaneous
combustion in a coal stockpile.
MODEL DEVELOPMENT
Chemical kinetics
Experiments to be described in detail in Part 226
showed that CO2 is the major product of the low-
temperature (300-330K) oxidation of fresh Wyoming
subbituminous coal; only negligible amounts of CO were
formed. Similar results have been reported in the
literature for subbituminous coal 8 and lignite 16. In this
work, the consumption of 02 and the formation of CO2
are assumed to be consequences of the reactions
coal + 02 ~ CO 2 (7)
coal + 02 ~ coal--O2 --~ CO2 (8)
Reactions (7) and (8) represent respectively the direct
burn off and sorption reactions. In contrast, reactions (4)
and (6) are based on reversible adsorption of oxygen on
the coal surface, where the physisorbed oxygen under-
goes irreversible molecular rearrangement to form a
chemisorbed complex which in turn decomposes to
oxygenated products. Reaction (8) avoids the distinction
between physisorbed and chemisorbed oxygen forming
the coal-O2 intermediate complex. This assumption,
justified by the low rates of desorption of physisorbed
oxygen 1°'11, presents two other advantages:
(1) The number of adjustable rate parameters is
minimized. Since rates of oxygen consumption
and CO2 production are the only independent
measurements, unequivocal extraction of rate con-
stants for reaction schemes such as (6) will be a
formidable task.
(2) The rate of oxygen consumption (and CO2 produc-
tion) is first-order in oxygen concentration. This
permits direct use of the results reported for
effectiveness factors and particle size dependence
in the literature on reaction and diffusion in catalyst
pellets. The effectiveness factors can thus be
calculated and need not be left as adjustable
parameters.
The chemistry of low-temperature oxidation of coal is
complex. Recently it has been shown 27 that the aliphatic
structure undergoes selective transformation, with the
aromatic structure remaining unaffected. Further, the
aliphatic groups have different susceptibilities to
Fuel 1996 Volume 75 Number 3 335
Low-temperature oxidation of coal." S. Krishnaswamy et al.

oxidation. Mathematical treatment of such reactions
could require inclusion of a distribution function to
represent the reactivity of different sites, with an
attendant increase in the number of adjustable
parameters. At this stage it appears more useful to
keep the formulation simple. In this model, it is
assumed that (1) highly active sites, forming a fraction
fa of the total accessible surface, are involved in
reaction (8) and deactivate subsequent reaction with
oxygen, and (2) the burnoff reaction occurs at the
remaining sites, forming a fraction ( 1 - f a ) of the
accessible surface.
The rate of oxygen consumption per unit particle
volume in the burnoff reaction--assuming a first order
dependence on oxygen concentration--is
R1 = -kl(1 -fa)Co2 (9)
Note that k 1 is a volumetric reaction rate constant and is
fundamentally the product of the intrinsic surface
reaction rate (in m s -1) and the specific internal surface
area (in m 2 m- 3). However, it is not clear whether Sin
based on N 2 or CO2 adsorption measurements should be
used, as discussed in the Appendix. It appears more
convenient to leave kl in the form used in Equation (9).
The rate of decay of the active sites as a consequence of
sorption of oxygen is assumed to be given by
0fa
Ra -- Ot -- "kafaC°2 (10a)
The rate of oxygen consumption by the sorption
reaction, R2, must be proportional to the rate of decay
of active sites. Thus
The effectiveness factor permits the rate of oxygen
consumption to be written in terms of the oxygen
concentration at the external surface of the particle
rather than the local concentration of oxygen, which will
vary with depth within the particle. For the first-order
reaction, it can be shown theoretically 28 that
3( 1 1) (12b)
=~ tanla(hs) hs
where the Thiele modulus, hs, is the ratio of the tendency
for reaction relative to that for intraparticle mass
transfer and is defined as
/ Kr
hs = r0 VDeff (12c)
The effective diffusivity of oxygen in the coal is calculated
as Deft = Do2¢s/7-, where es is the porosity of the coal, 7-
is the tortuosity factor and Doz is the diffusivity of
oxygen.
External resistances to transfer of oxygen relate the
concentration of oxygen at the surface to that in the bulk
phase. At this stage it is important to distinguish between
dry and fresh low-rank coal. Fresh low-rank coal
contains in situ moisture. Moisture can exist in coal in
several forms--chemisorbed, physisorbed, bulk, and
surface--and the effect of moisture on the rate of low-
temperature oxidation is not understood. The present
approach permits consideration of the effect of bulk and
surface moisture in the coal; the new model developed
here is expected to apply at moisture levels above

R 2 cx R a o r R 2 = C R a (10b)
I
where ¢, the proportionality constant, is the oxygen .,..°'°'i ..... "-..
equivalent of active sites per unit volume. Clearly ¢ must
depend on the pore surface area available for the
sorption reaction; an estimation procedure is discussed
in the Appendix.
The total rate of consumption of oxygen per unit
particle volume, combining Equations (9) and (10b), is

Ro2=Ra¢+R1 =
-[kaCfa + k](1 -fa)]Co2 = -KrCo2 (11)
The overall first-order rate constant, Kr, in the above
equation depends on the time-dependent value of the
fraction of active sites.

Transport processes
To model the transport processes that will influence
the movement of oxygen from the bulk phase to the
reaction sites within the coal, consider a single coal
particle within a stockpile or within a laboratory fixed-
bed reactor. The influence of the diffusional resistance to
ICoal ~ Gas Bulk
mass transfer within the pores of the particle on the Particle / film gas
observed rate of oxygen consumption can be accounted
for by incorporation of an effectiveness factor, q,
according to Gas-Liquid interface
Figure 1 Resistances to mass transfer of oxygen from the bulk phase
R o 2 ~-~ ~ K r C o 2 , s (12a) for fresh wet coal

336 Fuel 1996 Volume 75 Number 3

 Low-temperature oxidationof coaL"S. Krishnaswamy et al.

,,~0.1 kgkg -1 coal. In the presence of bulk and surface it can be shown that
moisture inherent in fresh coal, the oxygen in the bulk
gas phase has to dissolve in the moisture within the 1 1 h~
pores before it can diffuse to the reactive sites on the ~/( Rr ) +
pore surfaces. This imposes a resistance, in the form r/G t 18Hw) 3kg rO/Deff
of a gas-liquid interface, to mass transfer of oxygen, 1 roKr
Figure 1. It is assumed that the bulk gas-phase oxygen rff nr ~ + - ~ - g for fresh wet coal (16b)
is in equilibrium with the oxygen dissolved in the \ 18Hw ]
water, and Henry's law is used to relate the
concentrations of oxygen in the two phases. Under
In this case, where oxygen has to diffuse through the
steady-state conditions,
moisture, the calculation of the effective diffusivity and
requires the use of Do2 as the diffusivity of oxygen in
.o2 =, ( Sp) coab- o2s liquid water, with a value of ~ 2.5 x 10-9mZs-rin the
temperature region of interest.

= Co2.s (13a)
RESULTS AND DISCUSSION
If the mass transfer coefficient is sufficiently high,
where [RT/(18Hw)]Co2,s is the concentration of oxygen Equations (16a) and (16b) reduce to forms which
in water. Equation (13a) can be rearranged, through would lead to the rate of oxidation being independent
elimination of the surface concentration Co2,s, to express of particle size for small particles and inversely propor-
the rate of oxidation in terms of the bulk-phase oxygen tional to particle size for large particles in accordance
concentration, with the limits observed experimentally21. In this section,
calculations are presented to illustrate the combined
K [" R T "~k (Sp~ influence of particle size, ambient temperature and coal
reactivity on the oxidation rate of coal at low tempera-
RO2 = -~--~ --~KTK 7---R-~,,x Co2,b (13b) tures. Although parametric analyses could have been
presented with arbitrary chemical reaction rate para-
kgt ,) +' ' t77-DTw) meters, it is preferred to use values derived from
experimental data, as described in Part 226, for Wyoming
subbituminous coal: k~ = 2.643 × 10Sexp(-6420/T)
Similarly, for dry coal--without the gas-liquid inter- m3(kmol O2) -l s -l, kl = 8.828 x 106exp(-6950/T) s -1,
face--it can be shown that and initial fraction of active sites f'a = 2.5 x 10-2. The
partial pressure of oxygen in the atmosphere has been
R02 = kg(Sp/Vp)(Co2,b - C02,s ) --- r/KrCo2,s (14a) fixed at 0.21 atm (21.3 kPa) in all these calculations. The
porosity of the coal particle is taken as es = 0.2 and r has
been assumed to be 3. Henry's law constant was taken
and from Perry and Green 3°. The external gas-phase mass
transfer coefficient, for a bed porosity Eb---~0.35, was
,Kr g(Sp/G) (14b) estimated using the semi-theoretical relation 31'32
RO2 = kg( Sp/ Vp) + •K r C°2'B
Sh - 2kgr° - 0.522[(1 + ReSc) U3 -l]
The global effectiveness factor, BG, is defined29 such that Do2
the rate of oxygen consumption can be related to the x (44.44 + 4Re U2 + 0.4Re)1/3 (17)
oxygen concentration in the bulk gas phase according
to
The superficial gas velocity in all these calculations was
Ro2 = r/o Kr C02,b (15) fixed at 1.29 x 10-3m s -1. The results of the calculations
are most conveniently presented in terms of the variation
of r/G for the various conditions.
Using Equations (14b) and (15) with (Sp/Vp) = 3/r o it It was noted earlier that the overall first-order rate
can be shown that for dry coal, constant, Kr, and consequently the effectiveness factors,
r/and r/o vary with time. In Figure 2 the variation of r/c
1 1 hZs 1 roKr with time is shown for three particle sizes of dry and fresh
--=-+r/G - = - + ~ ' / f f / 1 3Kg f o r d r y c o a l
7/ 3kgro'De (16a) coal. For these calculations, Equation (10a) was inte-
grated, assuming constant Co2,b leading to fa =
f'aexp(kaCo2,bt). Substitution of the time-dependent
Note that for dry coal, the calculation of the effective fraction of active sites in Equation (11) then permits
diffusivity and ~/ from Equation (12) requires the use calculation ofr/G(t). Since the active sites react faster, the
of Do2 as the diffusivity of oxygen in air, with a value initial rate of oxygen consumption is high. As the active
of ~ 2 x lO-SmZs -1 in the temperature region of sites decay, the rate approaches a steady value. In
interest. keeping with this picture, r/G is lower initially and then
Similarly, for wet coal, using Equations (14a) and (15), increases to a steady value for both dry and fresh coal.

Fuel 1996 Volume 75 Number 3 337

Low-temperature oxidation of coal: S. Krishnaswamy et al.

0.1 1
(a) (a) x.
\
\
\
\
\
\
\
001- 01'
"qG "qG

/
/
/
I J

0.001 i i i i iiii I i i iiillj 001 J i iiiiil] i t iiiiii I i i i lllll I i

100 1000 10000 0001 001 01 1

ro X 102 (m)
"nine(see)
1

(b)
\

"qG
~qG /
/

01 ~ ' ~ ~ ~ J~'] ~
0.1 i i ii11,11 i i iiiiii I i i ii11,= I , i
01 1
10 100 1000 10000
ro x l o 2 (m)
lqrne (sec)
Figure 2 V a r i a t i o n o f g l o b a l effectiveness factor r/o w i t h time for Figure 3 Variation of global effectivenessfactor ~ with particle
particle sizes r o (mm): - - , 0.1; . . . . , l; - - - , 10. a, F r e s h wet coal at radius r0 for dry coal. a, Effectof temperature:- - , 300;. . . . ,350;
300 K; b, dry coal a t 400 K - - -, 400. b, effect of coal reactivity: . . . . ; 0.1Kr; - - , Kr;
- - - 10Kr
,

The retarding influence of the /n situ moisture on the simulated by calculations with multiples of the reaction
overall rate of oxidation appears in two forms in Figure constant Kr for the Wyoming subbituminous coal, is
2: (1) for dry coal, the rate of approach to the steady shown in Figure 3b. It is clear that the effect of particle
value is significantly higher, since the diffusivity of size is significantly less pronounced for less reactive
oxygen in air is higher and the oxygen required to react coals.
and cause deactivation of the active sites is more readily These observations, consequences of the interplay
available within the particle; (2) the global effectiveness between particle size, temperature and coal reactivity,
factor for dry coal even at a higher temperature is higher can be examined qualitatively through Equation (16a).
than that for fresh coal for particle radii 1 and 0.1 mm as For sufficiently small particle sizes and low temperatures,
a consequence of the low solubility of oxygen in water, as the Thiele modulus hs calculated from Equation (12c) is
explained later. small and the effectiveness factor 7? in Equation (12b)
It is noted from Figure 2 that the change in the approaches unity. If the mass transfer coefficient kg is
effectiveness factor with time is not large. For sufficiently high in Equation (16a), then ~1o ~ 1. Physi-
illustration of the effect of ambient temperature, cally, this limit implies that diffusion rates within the
particle size and coal type on ~o, it has been preferred particle are much higher than the reaction rates and the
to present results applicable at long times, that is, oxygen concentration profile within the coal particle is
times greater than those required for the deactivation uniform. The reaction occurs on the entire internal
of the active sites. surface area offered by the pore system. Note that the
Consider dry coal first. The influence of the ambient pore surface area per unit volume is independent of
temperature on the rate of oxygen consumption is shown particle size and is significantly larger than the external
in Figure 3a, where 77Gis plotted as a function of particle surface area, which does depend on the particle size.
radius for three different temperatures. At temperatures Consequently, in this limit the rate of oxidation is
300 K, the effect of particle size is evident only for independent of particle size. For Wyoming subbitumi-
large radii (> 10mm) At an ambient temperature of nous coal, as shown in Figure 3a, this limit is r 0 ~ 10 mm
400 K, the size effect is observed even for particles of at an ambient temperature of 300 K. Since Sex c< ro ], the
1 mm radius. The effect of coal type and reactivity, oxidation rate is independent of the specific external

338 Fuel 1996 Volume 75 Number 3

 Low- temperature oxidationof coal. S. Krishnaswamy et a l.
surface area for smaller particles. As the ambient
temperature increases, the rate of reaction increases. To
counterbalance this effect, the limiting particle size must
be smaller, as shown by the calculations in Figure 3a. The
effect of coal reactivity is also clear from this discussion:
lower reactivities and reaction rates imply that the
critical particle size becomes larger, as Figure 3b
indicates. Note that different values of Kr could arise
from differences in the intrinsic reactivity or from
variations in the internal surface area available for
oxidation. In fact, from the extensive literature on
reaction and diffusion inside catalyst particles, the
criterion for absence of particle size effects--following
Weisz and Prater 33 and the deduction 34 that external
transport limitations cannot exist unless internal limita-
tions are also present--can be written as
Ro2(ro/3) 2
<< 1 (18)
DeffCo2,b
At the other extreme, for sufficiently large particle sizes
and high temperatures, the rate of reaction is much
higher than the rate of diffusion and hs in Equation (12c)
becomes large. In this limit, 7/~ 3/hs. Consequently,
Equation (16a) reduces to
1
--~--
hs( 14 hs ) (19a)
riG 3 kgr~-Deff
For sufficiently large hs,
1 h~ roKr
,.~ - (19b)
~IG 3kgro/ Deff 3kg
The dependence of kg on Reynolds number and particle
size is complex, as seen in Equation (17). For larger
particle sizes, kg is expected to become virtually
independent of particle size. The rate of oxidation from
Equation (19b) is then inversely proportional to particle
size. Since Sex oc ro I the consumption rate of oxygen
becomes proportional to the specific external surface
area. This limit, too, is readily explained in physical
terms. In the region of strong intraparticle diffusion, the
oxygen cannot penetrate into the particle and reaction is
confined to a thin outer rind. Consequently the reaction
rate is proportional to the external surface area per unit
volume, which is how the specific external surface area is
defined. In the region between the limits discussed,
depending on particle size and temperature, the rate of
oxygen consumption is proportional to SePx with
0 ~<p ~<l. The calculations shown in Figure 3 are clearly
in accordance with this discussion.
Now consider a comparison between the oxidation
rates of dry and fresh coal. Through calculations of qG
shown in Figure 4 the differences in the overall oxidation
rate arising from physical considerations can be exam-
ined on the assumption that the chemical reaction rate
parameters are the same. It is likely that the chemical
reaction rates are influenced by the moisture content 16. A
detailed investigation to examine the influence of
moisture on the chemical reaction rate has been
commenced and results will be reported in due course.
Figure 4 clearly shows that the presence of in situ
moisture in the coal leads to (1) lowering of the global
effectiveness factor and consequently to lower rates of
oxidation, and (2) the influence of particle size becoming
significant for particles an order of magnitude smaller.
For dry coal, the simulations in Figure 3b show that the
influence of particle size on the oxidation rate is evident
for smaller particles with more reactive coal. The results
in Figure 4 then appear anomalous in that although the
effectiveness factor--and hence the effective reactiv-
i t y - i s lower, the rate of oxidation is influenced by
comparatively smaller particle sizes. An explanation for
these apparently contradictory results can be obtained
through consideration of Equation (16b). Calculations
revealed that the resistance imposed by the dissolution of
oxygen in water is large enough for external gas-phase
resistance to be negligible. Thus Equation (16b) reduces
to
RT
r/o ~ r/18Hw (20a)
The solubility of oxygen in water imposes a strong
resistance to transfer of oxygen and leads, under
otherwise identical conditions, to effectiveness factors
significantly lower than that for dry coal. Hence the
moisture exerts a strong retarding influence on the rate of
oxidation. However, since Deff in Equation (17) for wet
coal is significantly lower than for dry coal, the critical
particle size at which the overall reaction rate begins to
be influenced by particle size is significantly lower for wet
coal.
The influence of the ambient temperature on the rate
of oxygen consumption is shown in Figure 5a, where ~6
is plotted as a function of particle radius at four different
temperatures. The effect of particle size is evident even
for smaller particles at temperatures ~ 300K, in
accordance with the previous discussion. From the
calculations shown in Figure 5b it is clear that the effect
of particle size is significantly smaller for less reactive
coals. These results, similar to those for dry coal, can be
01-
~G O.Ol-
1E-3-
1E4
' ' '''"'I ' ' '''"'I ' ' '''"'f
0 001 O01 0.1 1
ro X 102 (rnl
Figure 4 Variation of global effectiveness factor ~/6 with particle
radius r0: comparison of oxidation rates for d r y ( - - ) and fresh
wet (. . . . ) coal at 300 K
Fuel 1996 V o l u m e 75 N u m b e r 3 339
Low-temperature oxidation of coal." S. Krishnaswamy et al.

0,1
(a) independent of particle size for r0~0.5mm. For
r0 ~>2mm, the oxidation rate is inversely proportional
to particle size, as established earlier. In the intermediate
\ "\'"\ A
range, a line marked A with slope ( - 1/3) has been plotted.
0.01 - \
.
. .\ For 0.5 < r0 < 2ram this line is in remarkable agreement
with detailed calculations; in this size range then, the
1/3
oxidation rate has an approximately Sex -dependence.
•

\ ",, \ \
"qG \ ",, \\ Although the 1/3-power dependence is convenient, it
\ "
\ '
\ does not have any apparent physical significance, and
\ , different values of temperature and coal reactivity shift
\ ', its range of applicability to different particle sizes.
\
x Further, Figure 5a clearly shows that extrapolation of
1/3
the Sex -dependence to smaller as well as larger particle
0.0(]01 i i i ,1111[ i 111111[ i i Ill,,,[ I IIIII I sizes results in serious overestimation of the oxidation rate.
0001 0.01 0.1 1 10

0,1
0.01 -
"qG
0.001 I
0.0001 i i illlll I .
0.001 0.01
F i g u r e 5 V a r i a t i o n o f g l o b a l effectiveness f a c t o r r/G w i t h p a r t i c l e
r a d i u s r0 f o r f r e s h w e t coal. a, Effect o f t e m p e r a t u r e (K):
- 325; 350; A , line w i t h slope o f ( - l / 3 ) r e p r e s e n t i n g r/c ~ ql13
Effect o f c o a l reactivity: . . . . , 0 . 1 K r ;
readily explained using the qualitative arguments presented
earlier.
Now consider the dependence of the oxidation rate of
wet coal on the specific external surface area. For small
particle sizes and low temperatures, for reasons discussed
earlier, r/~ 1. In this limit, ~/~ ~ RT/(18Hw). At any
given temperature, Hw is constant. Hence the rate of
oxidation, though significantly lower than that of dry
coal, is independent of particle size and the external
specific surface area. When the pore diffusion resistance
is strong, ~ ~ 3/hs. Consequently,
3 RT
r/G ~ hs 18Hw
Since hs oc r0 and Sex ~ %1, the rate of oxygen con-
sumption is directly proportional to Sex.
These qualitative and quantitative results show that
for dry as well as fresh coal, the oxidation rate depends
on SPx with 0 ~<p ~<1; the exponent p varies with particle
size, temperature and coal reactivity. The origin of the
1/~-dependence of the oxidation rate reported in several
Sex
previous investigations is now examined. Considering
the plot corresponding to an ambient temperature of
300K in Figure 5a, r/G and the oxidation rate are
ro X 102 (m)
In the model developed here, it has been assumed that
the burnoff and sorption reactions are first-order with
respect to oxygen concentration. Kelemen and Freund 13,
(b) in a detailed investigation of the influence of oxygen
partial pressure, concluded that the reaction order
shifted from 1 at lower partial pressures to zero at
\ "-, higher partial pressures. A comparison of model
calculations with data 3'4 on the rate of oxygen consump-
\ "',
tion for dried PSOC 190 coal in an isothermal fixed-bed
reactor showed excellent agreement, as revealed in Part
226, with these data for oxygen partial pressures in the
\
range 0.161-0.353 atm (16.3-35.8 kPa) at 433 K. The
\ effectiveness approach can be extended, with some
increase in algebraic and computational difficulty, to
nth-order reaction rates (as shown in the Appendix) or to
a shifting reaction order in oxygen concentration;
i i illllll i i illll= I however, since a coal stockpile is unlikely to experience
O.1 1
oxygen partial pressures >0.21atm (21.3kPa), the
ro X 102 (m)
additional complexity cannot be justified.
300; - - -
~ex . r,~, CONCLUSIONS
, Kr; - - - , 10Kr
A kinetic model for low-temperature oxidation of coal
has been developed, based on a single isothermal
particle, which permits assessment of the relative
importance of various mass transfer resistances.
Through inclusion of transport resistances, the model
accounts for the dependence of the reaction rates on
particle size over the full range of particle sizes, with
smooth transition between different reaction regimes•
The approach also permits development of a new model
which considers the effect of bulk and surface moisture in
the coal on the rate of low-temperature oxidation. This
new model is expected to apply at moisture levels above
0.1kgkg -1 coal. The model developed explains the
reported variation in reaction rate with SePx, where
0 ~<p ~<1, for dry and fresh wet coal.
Calculations also show the following:
(20b)
(1) If liquid water fills the porous matrix, then in situ
moisture in must exert a very significant retarding
influence on low-temperature oxidation at constant
temperature. Oxygen in the bulk phase has to dissolve
in the moisture before it can react with reactive sites
on the coal surface, and the solubility of oxygen in
water is low.
(2) The effects of particle size on low-temperature
oxidation can be explained through incorporation
of effectiveness factors in the model. For fresh coal,
the influence of particle size on reaction rate is
pronounced even at low temperatures and small

340 Fuel 1996 Volume 75 Number 3

 Low-temperature oxidationof coaL S. Krishnaswamy et al.

particle sizes. For dried coal on the other hand, the C02,s oxygen concentration at particle surface
influence of particle size becomes important only at (kmol O2 m -3)
significantly higher temperatures or for considerably C02,b oxygen concentration in the bulk gas phase
larger particles sizes. (kmol 02 m -3)
Deft effective diffusivity (m 2 s-l)
ACKNOWLEDGEMENTS Do2 diffusivity of oxygen (m2 s-1)
fa fraction of active sites at any time
The authors gratefully acknowledge the continued f ia initial fraction of active sites
financial support of ARCO and Thunder Basin Coal hs Thiele modulus, Equations (12c) and (A.2)
Company through the Western Coal Consortium at the
Hw Henry's law constant (kPa [kmol O2
University of Wyoming. The contributions of Mr B. (kmol solution)- l] 1)
Denney and Dr C-Y. Cha to the research project are also kl reaction rate constant for the burnoff reaction
acknowledged with appreciation. The assistance of (s -1)
Ashley Hull in the preparation of the manuscript is
ka reaction rate constant for decay of active sites
also acknowledged. [m3(kmol 02) - 1S- l]
kg gas phase mass transfer coefficient (m s-1)
REFERENCES Kr k~,Cfa + kl ( l - fa), overall rate constant (s -1)
1 Parr, S. W. University of Illinois, Engineering Experiment Sta- n reaction order
tion, Bulletin 97, 1917 p parameter
2 Carpenter, D. L. and Giddings, D. G. Fuel 1966, 45, 247 r0 particle radius (m)
3 Carpenter, D. L. and Giddings, D. G. Fuel 1966, 45, 429 R molar gas constant, 8.314 jK-lmo1-1
4 Carpenter, D. L. and Sergeant, G. D. Fuel 1966, 45, 311
5 Kam, A. Y., Hixson, A. N. and Perlmutter, D. D. Chem. Eng. R1 molar oxygen consumption rate per unit particle
Sci. 1976, 31, 815 volume from the burn-off reaction
6 Kam, A. Y., Hixson, A. N. and Perlmutter, D. D. Chem. Eng. ( k m o l 0 2 m-3s -1)
Sci. 1976, 31, 821 R2 molar oxygen consumption rate per unit particle
7 Kaji, R., Hishinuma, Y. and Nakamura, Y. Fuel 1985, 64, 297
8 Kaji, R., Hishinuma, Y. and Nakamura, Y. Fuel 1987, 66, 154 volume from the sorption reaction
9 Karsner, G. G and Perlmutter, D. D. AIChE J. 1981, 27, 920 (kmol 02 m-3s -t)
10 Karsner, G. G. and Perlmutter, D. D. Fuel 1982, 61, 29 Ra reaction rate for consumption of active sites (s- l)
11 Karsner, G. G. and Perlmutter, D. D. Fuel 1982, 61, 35 R02 total molar oxygen consumption rate per unit
12 Kelemen, S. R. and Freund, H. Energy Fuels 1989, 3, 498
13 Kelemen, S. R. and Freund, H. Energy Fuels 1990, 4, 165
particle volume (kmol 02 m-~s -1)
14 Polat, S. and Harris, I. J. Fuel, 1984, 63, 669 Re particle Reynolds number
15 Rahman, M., Hasan, A. R. and Baria, d. N. Chem. Eng. Sex specific external surface area (m2m -3 )
Commun. 1986, 46, 209 Sin specific internal surface area (m2m -3)
16 Sondreal, E. A. and Ellman, R. C. US Bureau of Mines, Report Sp particle surface area (m2)
of Investigations 7887, 1974
17 Schmidt, L. D., Elder, J. L., Steiner, W. A. and Davis, J. D. US Sc Schmidt number
Bureau of Mines, Technical Paper 681, 1945 Sh Sherwood number
18 Schmidt, L. D. In 'Chemistry of Coal Utilization' (Ed. H. H. t time (s)
Lowry), Vol. I, Wiley, New York, 1945, pp. 627-676 T temperature (K)
19 Smith, A. C. and Lazzara, C. P. US Bureau of Mines, Report of Vp particle volume (m 3)
Investigations 9079, 1987
20 Winmill, T. F. Trans. Inst. Min. Eng. 1914, 46, 563 es coal particle porosity
21 Van Krevelen, D. W. 'Coal', Elsevier, Amsterdam, 1961 eb bed porosity
22 Taylor, H. A. and Then, N. J. Am. Chem. Soc. 1952, 74, 4169 r/ effectiveness factor
23 Sevenster, P. G. Fuel 1960, 40, 18 ~?G overall effectiveness factor
24 Harris, J. A. and Evans, D. G. Fuel 1975, 54, 276
25 Itay, M., Hill, C. R. and Glasser, D. Fuel Process. Technol. 1989, r tortuosity factor
21, 81 ¢ conversion factor (kmol 02 m -3)
26 Krishnaswamy, S., Gunn, R. D. and Agarwal, P. K. Fuel 1995,
74, 344
27 Calemma, V., Rausa, R., Maragrit, R. and Girardi, E. Fuel APPENDIX
1988, 67, 764
28 Hill, C. G. 'Chemical Engineering Kinetics and Reactor Design', Estimation of ¢
Wiley, New York, 1977, p. 447-449 The conversion factor ¢ is expected to depend on the
29 Froment, G. F. and Bischoff, K. B. 'Chemical Reactor Analysis
and Design', 2nd Edn, Wiley, New York, p. 171 internal surface area and the surface coverage of oxygen
30 Perry, R. H. and Green, D. 'Perry's Chemical Engineers' Hand- molecules. It has been estimated that each adsorbed
book', 6th Edn, McGraw-Hill, New York, 1984, p.3-103 molecule of oxygen occupies ~ 0.166 × 10-tSm2 of the
31 Agarwal, P. K. Chem. Eng. Sci. 1988, 43, 2501 surface9. Denoting Sin as the specific internal surface
32 Agarwal, P. K., Mitchell, W. J. and la Nauze, R. D. Chem. Eng. area and assuming monolayer surface coverage by
Sci. 1988, 43, 2511
33 Weisz, P. B. and Prater, C. D. Adv. Catal. 1954, 6, 143 oxygen,
34 Petersen, E. E. Chem. Eng. Sci. 1965, 20, 587
35 Gan, H., Nandi, S. P. and Walker, P. L. Fuel 1972, 51, 272 [ kmol 02 m2
36 Ng, S. W., Fung, D. P. C. and Kim, S. D. Fuel 1988, 67, 700
37 Mehta, B. N. and Aris, R. Chem. Eng. Sci. 1971, 26, 1699
38 Mears, D. E. Ind. Eng. Chem. Process Des. Dev. 1971, 10, 541
0.166 × 10 -18( 1112 ] l026(m°leculesO2"l
NOMENCLATURE kmoleculeO2] × 6.023 × ~ kmolO2 ]

Coz oxygen concentration (kmol 02 m 3) (A.1)

Fuel 1996 Volume 75 Number 3 341

Low-temperature oxidation of coal." S. Krishnaswamy et al.

It is not clear whether Sin in Equation (A.1) should be
based on surface areas measured using the N2 adsorption
or CO2 adsorption techniques. The difference in Sin
measured by these two techniques is well known 35. Karsner
and Perlmutter 9 showed that the oxygen deposition
during low-temperature oxidation, assuming monolayer
surface coverage, surpasses the N2 surface areas and in
some cases the CO2 surface areas. For the coal under
consideration, N2 surface areas have been measured (H.
Wang, personal communication 1994) as 20m2g -z. Ng
et a136 have correlated the N2 and CO2 surface areas for
various chars. Assuming that their correlation applies to
Wyoming subbituminous coal, the CO2 surface area is
estimated as ,-~ 200m2g -1. For the calculations at hand,
Sin has been estimated based on the CO2 surface area;
this leads to ~ = 1.6kmolO2 m-3. The influence of the
value of Sin chosen by comparison between model and
experiment is discussed in greater detail in Part 226.
Effect of reaction order
It has been assumed that the burnoff and sorption
reactions are first-order with respect to oxygen concen-
tration. The effectiveness factor approach can be
extended, without very significant problems, to nth-
order kinetic forms. However, lumping of the burnoff
and sorption reactions does require that both reactions
have the same dependence on oxygen concentration. For
nth-order dependence of kinetic reaction rates on oxygen
concentration, the Thiele modulus is defined as
~/(n + n- 1
1)KrCo2's forn > - 1
hs = r0 2Deff
with the effectiveness factor for characterizing internal
resistance still given by Equation (12b) as
,( 1 ,)
r/=~ tanh(hs) h~
regarding the dependence of the reaction rate on particle
size are now considered. For small particle sizes and at
low temperatures, once again the reaction rate is
independent of particle size. The criterion for the absence
of particle size effects can be written as 29'38
Ro2(ro/3) 2 2
<< - - (A.5)
OeffCoz,b n+ 1
The ratio of the critical radius determined for n = 1 to
that for any other reaction order in the range 0 ~<n ~<1 for
the same observed reaction rate, according to Equation
(A.5), is x/n + 1/2. The error in estimation of the critical
radius is at worst ,,~30% . At the other extreme, for larger
particles and at higher temperatures, r/~ 3/hs. Conse-
quently, for sufficiently large hs and kg,
r..,-(n+ l )/2 (.,(n-1)(n+ l )/2
--~/G1 fr0]k3) [ ( _....~_._
) n + l (1-n)/2(~rk, ~ g•O2,beft. )]
(A.6)
Although the dependence of other parameters depends
on the reaction order, the rate of oxidation remains
inversely proportional to the particle size, regardless of
reaction order. These results suggest that the qualitative
particle size dependence and the critical conditions for
reaction regimes do not depend very strongly on the
assumed reaction order.
(A.2)
The rate constants determined by experiment do of
course depend on the assumed reaction order. A
comparison between the reaction rate constants for
different orders is best accomplished assuming that
observed reaction rate is the same. Under conditions
where external mass transfer limitations are negligible,
R02 --- T]G,n=1Kr,n=1Co2,b ----TlG,nKr,nC~32, b (A.7a)

Considering a dry particle and using Recognizing that under reaction-controlled conditions,

RO2 = r/KrC~32,s =
7/GKtC~)2,b = kg(3/ro)(Co2,b -- Co2,s ) (A.3)

it can be shown that

[ 2 n
1 rll l_l_(n_~)k3kgro/Deffy j
~IG
for dry coal
~1 G

(A.4)

Note that Equations (A.2)-(A.4) reduce to the forms

used in the main text for n = 1. The presence of C02,s in 01 i i iiiiii I i i iiiiii I i I IIIIII I I i iiiii

the definition of Thiele modulus in Equation (A.2) for 1E-3 0.01 01 1 "~0

n ¢ 1 does somewhat complicate the calculation proce- r0 X 10 2 (rn)

dure. Calculations of 7/as a function of hs for several

values of n are available in the literature 29'37. Figure A.I Variation of global effectivenessfactor r/6 with particle
radius r0: comparison of oxidation rates at 350 K, for half- (. . . . ) and
The effect of reaction order on the critical conditions first ( ) order burnoff reaction rates, assuming the same observed
for different reaction regimes and the conclusions reaction rate.

342 Fuel 1996 Volume 75 Number 3

 Low-temperature oxidationof coak S. Krishnaswamyet al.

r~G ~ 1 and that under internal diffusion control, An example of detailed calculations, with kg calculated
rlG ~ 3/hs (for a dry particle with negligible external using Equation (17), is shown in Figure A.1, where ~G is
mass transfer limitations), it can be shown that plotted as a function of particle radius with the burnoff
reaction rate (simulating conditions at times beyond that
1--?/ required for deactivation of active sites) assumed as first-
Kr,n= 1Co2,b 2
1 ~< Krn, ~< n q - l ' O<~n<~1 (A.7b) and then as half-order in oxygen concentration.

Fuel 1996 Volume 75 Number 3 343