Chemical Engineering Science 61 (2006) 2339 2348

www.elsevier.com/locate/ces

An algorithm for determining the kinetics of devolatilisation of complex solid

fuels from thermogravimetric experiments
S.A. Scott , J.S. Dennis, J.F. Davidson, A.N. Hayhurst
Department of Chemical Engineering, University of Cambridge, Pembroke Street, CB2 3RA, UK
Received 4 May 2005; received in revised form 23 September 2005; accepted 1 November 2005
Available online 15 December 2005

Abstract
An algorithm is introduced for determining the kinetics of devolatilisation of complex fuels, e.g. coal or biomass, when heated in an inert
atmosphere. The algorithm uses information from thermogravimetric experiments, at several different, but constant, rates of heating, to identify
and characterise the underlying distribution of reactions governing devolatilisation. The algorithm also provides an approximate way of inverting
the distributed activation energy model (DAEM), commonly used to model the pyrolysis of coal. Such techniques provide the activation energy,
E, and pre-exponential factor, A, for each parallel step participating in the thermal decomposition of a solid fuel. In addition, the amount of
material associated with each pair of A and E can be derived.
The method is tested on (i) imaginary data from simulated TGA experiments with one or more rst-order reactions and (ii) real data from
thermogravimetric experiments on the pyrolysis of sewage sludge. In every case the algorithm gave excellent predictions for heating rates other
than those at which the pair of E and A were derived. Thus, the algorithm is a useful method of analysing and summarising measurements to
provide kinetic data and facilitate predictions.
2005 Elsevier Ltd. All rights reserved.
Keywords: Solid fuels; Pyrolysis; Kinetics; Thermal decomposition; Thermogravimetric analysis

1. Introduction
The physical processes occurring during the loss of volatile
matter, when a solid fuel, such as coal, biomass etc., is heated,
are common to pyrolysis, gasication and combustion; in each,
the solid fuel decomposes and emits gases and vapours, whilst
heat is transferred to it. For example, during combustion, the
devolatilisation is likely to be driven by the transmission of heat
from the combustion of the volatile material at the periphery
of the particle, as well as heat transfer from the surrounding
medium to the particle of fuel (Chern and Hayhurst, 2004).
The motivation for this work is to understand more about the
kinetics of pyrolysis of those fuels with a large volatile content, in particular, fuels derived from biomass or waste. Many
complex models for devolatilisation have been proposed and
usually involve several competing reactions, all of them producing volatile material and char. These models allow the yield
Corresponding author. Tel.: +44 0 1223 334788; fax: +44 0 1223 334796.

E-mail address: sas37@hermes.cam.ac.uk (S.A. Scott).

0009-2509/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2005.11.002

of volatile matter to depend on the rate of heating of the fuel.

However, it has been demonstrated (Antal and Varhegyi, 1995;
Howard, 1981) that effects attributed to heating rate can often
be explained by other experimental factors, such as temperature gradients within the fuel particles and secondary reactions,
in which the released volatile matter cracks to form char. Measuring the kinetics of devolatilisation is difcult; likewise, correctly accounting for heat transfer and secondary reactions of
the volatile matter is not trivial.
Experiments in a thermogravimetric analyser (TGA) are considered here. The pyrolysis of a solid fuel is studied by continuously weighing a small sample of fuel, whilst subjecting it to a
constant rise in temperature. Further details are given by Scott et
al. (2005). The approach used here is to assume that a complex
fuel is a mixture of components, each of which decomposes following a rst-order reaction. This strategy has been used previously (Pitt, 1962) to model the devolatilisation of coal. Coal is
a mixture of organic and inorganic materials and the kinetics of
its pyrolysis are complex. To cope with this complexity, many
(e.g. Pitt, 1962; Howard, 1981) have assumed, additionally,

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S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

that, because such a wide variety of chemical groups exist in

coal, there is a continuous distribution of reactions. Such an assumption leads to the distributed activation energy model, described below. Braun and Burnham (1987) showed that where
a distribution of activation energies exists, results from TGA
experiments can, nevertheless, appear to follow simple nth order kinetics. However, these kinetics cannot be extrapolated
reliably beyond the original experimental conditions. In their
review of the kinetics of thermal decomposition, Burnham and
Braun (1999) suggest that a deviation from rst-order kinetics
is often either due to the existence of a distribution of activation energies, or to the propagation of a decomposition front
through the solid.
1.1. The distributed activation energy model (DAEM)
This approach models the pyrolysis of a complex fuel, e.g.
coal, as the rst-order decomposition of many different chemical groups, each group being characterised uniquely by its activation energy for decomposition. The complexity of a coal is
such that a continuous distribution of activation energies is assumed where the mass of volatile material with activation energies between E and E + dE, at a given time t is m(E, t) dE.
Thus the total mass, Mv (t), of volatile matter is


Mv (t) =
m(E, t) dE.
0

Assuming that the material in the interval E to E + dE decomposes via a rst-order reaction, with a pre-exponential factor
A(E)


dm(E, t)
E
= A(E) exp
m(E, t),
(1)
dt
RT
so

m(E, t) = m0 (E) exp A(E)


exp(E/RT ) dt .

(2)

Here, m0 (E) is the initial mass of volatile material decomposing with an activation energy in the interval E to E + dE. In
practice, the quantity m(E, t) cannot be measured; only the
total amounts, Mv (t), or the total rates of decomposition are
measured. Hence by integrating over all energies


Mv (t) Mvo V (t)
=
=
g(E)
Mvo
Mvo
0



t
exp A(E)
exp(E/RT ) dt dE,
(3)
0




(E,t)

where, Mvo is the initial value of Mv (t),
(E, t) is the double

exponential term in Eq. (3), V (t) is the yield of volatiles (i.e.,
Mvo Mv (t)) and g(E) is the underlying (initial) distribution
of activation energies, which characterises the material; g(E)
is given by
g(E) =

0

m0 (E)
.
m0 (E) dE

It should also be noted that the distributed activation energy

model can be applied to the formation of individual species; e.g.
Wojtowicz et al. (2003) have reported kinetic parameters for
the formation of a large number of different species, produced
during the pyrolysis of tobacco. Although each distribution is
assumed to be a Gaussian distribution, it is possible to build
up more complicated distributions by assuming that a product
can be produced from more than one type of precursor. Thus,
for the formation of CO2 , Wojtowicz et al. (2003) give three
different activation energy distributions, corresponding to three
types of CO2 precursor. In this paper we will restrict ourselves
to the overall loss of mass.
If g(E) and A(E) are known, the yield of volatile material
can be calculated from Eq. (3). Even when the kinetic parameters are fully specied, the distributed activation energy model
can be difcult to use, especially when it is used as a sub-model
in combustion codes with variations in temperature from point
to point. The integration over all activation energies adds an
extra dimension to the problem. Efcient evaluation of the integral over all activation energies has been addressed by Donskoi
and McElwain (2000), who used high order, GaussHermite
integration to evaluate the integral in the distributed activation
energy model.
Numerous approximations to the double integral (i.e.,
Eq. (3)) have been proposed to give closed forms of the model,
which circumvent the need for numerical integration. For the
case of a Gaussian distribution of activation energies, Rostami
et al. (2004) showed how it is possible to obtain an approximate
closed form of the model (i.e., an expression which allows the
rate of mass loss to be calculated without numerical integration), by assuming that as conversion proceeds, the functional
groups with the lowest activation energies are lost rst. A more
complete discussion of the various approximations is given by
Please et al. (2003).
The inverse problem, i.e., of determining g(E) and A(E)
from measurements of the rate of devolatilisation is ill-posed,
since the distribution, g(E), can only be inferred from the integral over all energies, i.e., Eq. (3). In fact, there are many
possible distributions and functional dependencies of the preexponential factors, which could give the same dependence of
Mv on time. One way forward has been to assume the shape of
the distribution. For example, for the pyrolysis of coal, Anthony
and Howard (1976) assumed that the distribution of activation
energies was Gaussian. However, where such a distribution is
assumed a priori, the problem reverts to one of tting the model
to the measurements. In the case of an assumed Gaussian distribution, the adjustable parameters are the mean and standard
deviation of g(E).
Several workers have presented methods of estimating the
actual distribution of activation energies for devolatilisation.
Pitt (1962) measured the rate of devolatilisation of coal at a
constant temperature in a uidised bed; by assuming a constant value for the pre-exponential factor, A, he was able to estimate the shape of the distribution of activation energies. Pitt
(1962) recognised that, under isothermal conditions, for a given
t, the double exponential term (denoted by
(E, t) in Eq. (3)),
changes very rapidly from zero to unity over a narrow range of

S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

E. Hence,
(E, t) can be approximated by a unit step function

occurring at an energy E , where E is dened as the energy
at which
(E, t) reaches a specied value, for example Miura
and Maki (1998) dened E such that
(E ) = 0.58. Thus,
we replace the S shaped curve, asymptotic to
= 1, given
by
(E, t), with a step function which changes from 0 to 1 at
E . With this approximation Eq. (3) can be written as




Mvo V (t)
=
g(E)
(E, t) dE
g(E) dE
Mvo
0
E
= 1 F (E ),
(4)
where F (E ) is the cumulative distribution of activation energies. This essentially assumes that the reactions, although in
reality parallel, occur sequentially in order of increasing activation energy and do not overlap signicantly, so that at a given
conversion the same, single reaction dominates, irrespective of
how that conversion was reached. A step function has also been
used to approximate
(E, t), when the fuel is heated at a constant rate (Miura, 1995). The step function approximation is
valid only when the pre-exponential factor, A, is large, because
the range of E, over which
(E, t) changes from zero to unity,
increases as A decreases. More recent methods do not require
A(E) to be a constant (Miura and Maki, 1998; Maki et al.,
1997; Miura, 1995), but they are all based upon the approximation used by e.g. Pitt (1962). Such an approximation implicitly
relies on the fact that the various components are pyrolysed in
order of increasing activation energy (which, depending on the
pre-exponential factor, need not be the case).
The problem remains of nding the values of A(E ) and E
for the reaction occurring at a given conversion. This amounts
to nding the values of A(E ) and E from the assumed value
of
(E ). Pitt (1962) undertook experiments at constant temperature, when, using the denition of
(E, t) in Eq. (3) with
E = E


E

Ln(
(E )) = A(E ) exp

t.
(5)
RT
Pitt (1962) assumed that A(E) was constant and was then able
to solve Eq. (5) for the activation energy at each yield of volatile
material. In conjunction with Eq. (4), this actually gave a Gaussian distribution of activation energies for the pyrolysis of a
coal.
Miura and Maki (1998) performed experiments in which
coal was devolatilised at various, constant, rates of heating
in a thermogravimetric balance. Under these conditions with
dT /dt = B = (T T0 )/t


 

t
E

(E ) = exp A(E )

exp
dt .
RT (t)
0
Taking natural logarithms,



A(E )
E

Ln(
(E )) =
T0 exp
B
RT 0



E
E
exp(u)

du T exp
R E/RT 0
u
RT


E
exp(u)
+
du .
R E/RT
u

(6)

2341

Miura and Maki (1998) assumed a value of
(E ) = 0.58

and showed that it was possible to calculate, using Eq. (6),
both E and A(E ) for each value of the volatile yield (or
conversion), by comparing the same volatile yield in two or
more experiments, performed at different rates of heating. They
used Eq. (4) and chose E such that
(E ) = 0.58, because
the value of 0.58 was found to minimise the errors in A for
the cases they considered. The integral terms in Eq. (6) cannot
be evaluated analytically, but are in a standard form, which is
tabulated or available in mathematical packages. To simplify
the computation, Miura and Maki (1998) used the following
asymptotic approximation to Eq. (6):
Ln(
(E )) =

A(E )RT 2 E /RT

e
,
BE

(7)

which is valid when E /R (Burnham and Braun, 1999).

Miuras method has been applied successfully to the pyrolysis of coals (Arenillas et al., 2001) and petroleum asphaltenes
(Dong et al., 2005). In both these cases, the pre-exponential factor increased monotonically with the activation energy. Dong
et al. (2005) attributed this compensation effect to changes in
the entropy of activation for pyrolysis, by noting that the preexponential factor can be linked to the entropy of activation.
The method has also been used to infer activation energy distributions for the formation of sulphur-containing gases during
the pyrolysis of coals (Miura et al., 2001).
Burnham et al. (1987) discretised the distribution of activation energies, replacing a continuous distribution of reactions
with a nite set of discrete rst-order reactions. The activation
energies of these reactions were xed a priori, so that the reactions were spaced over a range of activation energies with equal
intervals of activation energies. The value of g(E) for each of
the discrete rst-order reactions was then calculated by tting
the model to the experimental results using linear least squares
minimisation. The pre-exponential factor, A, was assumed to be
constant and was determined by tting the predicted mass loss
proles to those measured in a thermogravimetric experiment
with a constant rate of heating.
2. An algorithm for determining the kinetics of
devolatilisation
In this work, an algorithm has been developed to determine
the kinetics of devolatilisation from thermogravimetric experiments, performed at several different, but constant, rates of
heating. The algorithm is intended to solve the problem of determining the kinetics of reactions for a material decomposing
subject to many, parallel rst-order reactions. For a material
decomposing via several such rst-order reactions


t

M(t)
=w+
fi,0 exp Ai
exp
M0
0
All Reactions,i

(Ei /RT (t)) dt ,
(8)
where M(t) is the mass of the sample, which contains a fraction
w of inert material; M0 is the initial value of M; fi,0 is the

2342

S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

fraction of M0 which decomposes with an activation energy Ei

and pre-exponential factor Ai . Using experimentally measured
M(t), the problem is to nd fi,0 , Ai , and Ei . It should be noted
that to avoid confusion with the continuous fractional density
function g(E), its discrete analogue f is now used to denote an
actual fraction of material with a specied activation energy
and pre-exponential factor.
The distributed activation energy model (DAEM) is a special
case of this general problem; it can be generated by increasing
the number of reactions to innity and imposing the constraint
that the reactions are characterised uniquely by their activation
energies. This need not be the case, e.g. there might be more
than one reaction with the same activation energy, but a different
pre-exponential factor.
Whilst the DAEM is ill-posed, provided the number of reactions is nite and the reactions do not completely overlap, the
problem given above is well-posed and can be solved. This is
because there is a point in the conversion process where a particular reaction is dominant, so that its values of A and E can be
measured directly, without interference from other reactions.
If the reactions were known, together with each value of E
and A, then Eq. (8) would be a linear problem: the mass of
solid fuel remaining at a given time would be the sum of the
masses of each of the components remaining. Thus Eq. (8) may
be written as a matrix equation, where, for any set of times t1 ,
t2 , t3 , etc., the mass of fuel remaining, M(t), is given by

1 (t0 )
2 (t0 )
n (t0 ) 1

M(t0 )

(t )
2 (t1 )
n (t1 ) 1
M(t1 ) 1 1

=
1 (t2 )
2 (t2 )
n (t2 ) 1

M0 M(t2 )

1 (t3 )
1 (t3 )
n (t3 ) 1
..
..
..
.



.
.



M
f

1,0

f2,0

f3,0

.. ,
.

(9)

w
 
f

i.e., M =
f ,
with, for an experiment with a constant dT /dt = B




Ai T
exp(Ei /RT (t)) dT .

i (t)=
i (T )= exp
B T0

(10)

Here, T0 is the initial temperature of the fuel. It should also

be noted that
i in Eq. (10) is the same as
in Eqs. (3) and (6).
Calculating the initial mass fractions, fi,0 , decomposing in
each reaction i is then a matter of solving Eq. (9), which is
linear. Since there are usually more experimental results than
reactions, the system is over-specied. However, it is possible to solve Eq. (9) using linear least squares; each mass fraction, fi,0 , becomes a parameter, which is altered to minimise
the difference between the values of M and
f , subject to
the constraint that only positive values of fi,0 are allowed.

Eq. (9) was inverted here using the lsqnonneg algorithm in Matlab (Matlab R14, The Mathworks Inc.). A similar method was
used by Burnham et al. (1987).
To use Eq. (9), a set of reactions must rst be generated,
each with a known value of A and E. Once the reactions have
been specied, the matrix
can be calculated. Here, it is rst
assumed that, at a given conversion, there will be a single reaction dominating. For the ith component, assuming a rstorder reaction, the fraction of the initial mass remaining, when
the fuel is subjected to a constant rate of heating, is given by
Eq. (2) as



t
fi (T ) = fi,0 exp Ai
exp(Ei /RT ) dt
= fi,0
i (T ),

(11)

using the denition of
in Eq. (3). If the conversion in two

separate experiments at different heating rates, B1 and B2 , is
considered and the ith reaction is the only reaction taking place
at this conversion, then fi (B1 , T1 )=fi (B2 , T2 ) at two particular
temperatures, T1 and T2 . Thus, from Eq. (11), and noting that

i (T ) is also a function of the rate of heating, B = dT /dt,

i (B1 , T1 ) =
i (B2 , T2 ).

(12)

Substituting for
i (B1 , T1 ) and
i (B2 , T2 ) from Eq. (6) and

taking logarithms on each side yields





Ei
exp(u)
Ei
1
T0 exp

du
B1
RT 0
R E/RT 0
u





Ei
Ei
exp(u)
T1 exp
+
du
RT 1
R E/RT 1
u





1
Ei
Ei
exp(u)
=
T0 exp

du
B2
RT 0
R E/RT 0
u





Ei
exp(u)
Ei
+
T2 exp
du . (13)
RT 2
R E/RT 2
u
This is a non-linear equation, which can be solved for the unknown Ei . If a solid is made up of several components, the
value of the activation energy calculated from Eq. (13) will be
exact, provided that only one reaction is dominating the overall
loss of mass at the conversion of interest. Errors in the value
of the activation energy will occur when several reactions are
occurring simultaneously at the chosen conversion.
To determine the pre-exponential factor, Ai , once Ei has
been calculated from Eq. (13), it is assumed that the dominating
reaction is at some conversion, here X =1e1
i =e1
0.368 is used. This is, of course, the conversion of the individual
component i, not the overall conversion of the mass of fuel
to volatile material. A value of
i = e1 corresponds to the
conversion at which a single rst-order reaction would reach
a maximum in the rate of decomposition, if the material were
heated at a constant rate, i.e., when



d dfi
d
=
fi,0 Ai exp(Ei /RT )
dt dt
dt



t
exp Ai
exp(Ei /RT ) dt = 0
0

S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

STEP 1

2343

Perform at least two thermogravimetric experiments at different

rates of heating
Measured values of mass M, as a function of temperature

STEP 2

STEP 3

STEP 4

Choose n values of conversion, e.g.100 points where the

activation energy Ei and pre-exponential factor Ai are to be
evaluated.

At each of the chosen conversions, use Eq. (13) to calculate the

activation energy, Ei, and Eq. (14) to get the pre-exponential
factor, Ai
Set of n reactions with each with known A and E
Using the set of n reactions, form the matrix
in Eq. (9)
Matrix

STEP 5

Invert Eq. (9), m =
f, to give the amount of each reaction, f i

Fig. 1. Overview of the algorithm.

with dT /dt = B. Since Ei is already known from Eq. (13), this

allows Ai to be calculated from



Ai
Ei
Ln(
i ) = 1 =
T0 exp
B
RT 0



1
Ei
exp(u)
Ei

du T2 exp
R E/RT 0
u
RT 2



Ei
exp(u)
+
du .
(14)
R E/RT 2
u

the value of E given by the rst stage of the algorithm (i.e.,

step 3) will be incorrect. However, in the second stage of the
algorithm (i.e., steps 4 and 5), the values of fi,0 for each of these
spurious reactions can be set to zero. This is an advantage over
Miura and Makis (1998) method, which uses the approximate
Eq. (4) to generate the distribution of activation energies, once
the activation energy at each conversion is known.

The approximations used to derive Eq. (14) do, however, lead

to some error in the calculated value of Ai . This is because it
has been assumed that the dominant reaction is at a conversion
of 63.2%, when the pre-exponential factor is evaluated. This
error is discussed more fully, below, where the algorithm is
used to recover the kinetic parameters from a simulated rstorder reaction.
The method of obtaining the values of A and E at various
conversions, using Eqs. (13) and (14) above, is central to the
method of Miura and Maki (1998) for inverting the distributed
activation energy model. They used the approximate form
of Ln(
i (E )) given by Eq. (7) to derive the equivalents of
Eqs. (13) and (14). However, Miura and Maki (1998) made the
assumption that each reaction is uniquely characterised by an
activation energy and used Eq. (4), which relies on the step
function approximation, to estimate the amount of each reaction occurring. The algorithm developed here neither requires
that each reaction is uniquely characterised by its activation
energy nor does it use the step function approximation. The
overall procedure to solve Eq. (8) is summarised in Fig. 1.
Thus, the algorithm rst identies a set of possible reactions,
assuming that at each conversion only one reaction dominates.
The exact values used for the conversion are an input to the
algorithm, step 2 in Fig. 1. Each chosen value of the conversion
will generate one candidate reaction, step 3 in Fig. 1. If there is
more than one real reaction occurring at a particular conversion,

A test program was written to generate theoretical plots of

mass versus temperature for a hypothetical solid experiencing
a xed rate of heating. This solid was taken to contain no ash
or char and to decompose with specied kinetics. Thus, the test
program was, in effect, a simulation of a thermogravimetric
experiment. The algorithm was then applied to the simulated
curves in an attempt to regenerate the original parameters, i.e.,
the values of A and E used for the simulation. Two test curves
at low rates of heating (20 and 30 K min1 ) were produced
and used for the subsequent calculation. A third theoretical
curve was generated for a rate of heating of 10 000 K min1
and this was compared with that predicted by the parameters
recovered by the inversion algorithm at 20 and 30 K min1 .
This provides a robust test of how well the kinetics extracted
by the algorithm extrapolate to different heating rates. In a
real combustion or gasication system (e.g. a uidised bed) a
heating rate of 10 000 K min1 (i.e., 167 K s1 ), would not be
unreasonable. Thus, when small particles of fuel are added to
a uidised bed, the time constant for their heating could be
of the order of a few seconds, resulting in a very high rate
of heating.
Several scenarios were tested in this way, with increasing
complexities; they ranged from a solid decomposing with a
single rst-order reaction, through to one decomposing with
a Gaussian distribution of activation energies. Finally, the
algorithm was applied to the results of thermogravimetric

3. Results and discussion

2344

S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

E (kJ mol-1)

210

slightly low values arise from numerics. However, the values

of A in Fig. 2(b) are only correct when the mass remaining is
0.368; the others are somewhat incorrect, because they were
derived using a conversion of 1 0.368. In this example, it
would be possible to evaluate the value of A at each conversion
correctly, because there is only one reaction. However, in the
more general case, with many reactions, it is not always possible to say what the conversion is for the dominating reaction.
The error from this simplication can be estimated from Eq.
(7), the approximate form for
i (=fi /fi,0 ). Since the value of
E is determined correctly, the value of Aalgorithm /Aactual , i.e.,
the ratio of the actual value of A to that determined by the algorithm, is given by

(a)

200

190

17 (b)
Log10 (A)

16
15
14

Ln(
= 0.368)/Ln(
actual ) =

13

(c)

Fraction

0.6
0.4
0.2
0
0

0.2

0.4
0.6
0.8
Fraction of mass remaining

Fig. 2. Hypothetical fuel which decomposes by a single rst-order reaction

having E = 200 kJ mol1 and A = 1015 s1 . The gure shows the results
from the algorithm: (a) and (b) give the value of E and A (in units of s1 )
for the 50 candidate reactions; (c) gives the mass fraction allocated to each
of the 50 possible reactions, which is zero for all but the two straddling the
point where the fraction of mass remaining = 0.368.

experiments performed on dried sewage sludge, to determine

the kinetics of devolatilisation. A fuller discussion of both the
experiment and its results are given elsewhere (Scott et al.,
2005).

Aalgorithm
,
Aactual

(15)

because the algorithm assumes that A is derived from the point

where
i (=fi /fi,0 )=0.368, whereas, in reality, the actual value
of
=
actual could be anywhere from zero to unity. Eq. (15)
shows that there can, at least in principle, be a considerable
error in the value of the pre-exponential factor. However, here
the method has two advantages over the method of Miura and
Maki (1998). Firstly, if there are, say, 50 candidate reactions
generated by the rst part of the algorithm, and, as in this
case, many of them have an incorrect pre-exponential factor,
the amounts of these spurious reactions will be set to zero by
the matrix inversion. This can clearly be seen in Fig. 2; mass
is only allocated to the reactions with the correct value of A.
Secondly, when several reactions are occurring, for a reaction
to be dominating, its rate of reaction must be high; thus, an
individual reaction is more likely to be important at a conversion
near
actual = 0.368, where the error in the estimated value of
A is low.
Plots of mass against temperature are shown in Fig. 3. The
plot for a rate of heating of 10 000 K min1 , derived from the
algorithm parameters, is almost identical to the theoretical curve
for a single rst-order reaction. Therefore, for the simple case of
a hypothetical fuel decomposing by a single rst-order reaction,
the algorithm produces the correct answer.
3.2. Test 2seven rst-order reactions

3.1. Test 1single rst-order reaction

In the case of a single rst-order reaction, the algorithm
should be able to produce a nearly exact answer. The results
of two trials are given below. In these tests the inversion algorithm evaluated E and A at 50 equally spaced intervals of
the conversion, corresponding to an unreacted fraction in the
range 0.010.99. For the imaginary fuel, the values of A and
E were E = 200 kJ mol1 and A = 1015 s1 . The values of E
and A calculated at each value of the fraction of mass remaining are shown in Fig. 2(a) and (b). Also shown, in Fig. 2(c) are
the amounts allocated to each reaction by the matrix inversion.
Fig. 2(c) shows that the amounts allocated to each reaction
by the matrix inversion are zero for all except the two straddling the 0.368 abscissa. The values of E in Fig. 2(a) are exact,
i.e., 200 kJ mol1 , apart from those values on the right: these

In this test, the hypothetical fuel was assumed to decompose by seven reactions; the values of E were 150, 175, 190,
200, 225, 250, 275 kJ mol1 , each with A = 1015 s1 . An equal
mass fraction was allocated to each reaction. The reactions with
E = 190 and 200 kJ mol1 were chosen because they overlap signicantly and so should be more difcult for the algorithm to identify separately. The complete set of possible reactions generated by the rst stage of the algorithm is shown in
Fig. 4(a) and (b), as a function of the fraction of mass remaining at which the reaction was evaluated. Whereas for a single reaction, the recovered activation energy was correct at all
conversions, when the reactions overlap (i.e., occur simultaneously), the recovered activation energy is incorrect. However,
the inversion of Eq. (9), which generates the amounts of each
reaction, will tend to set the amounts of these spurious reactions

S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

1
10000 K min-1

0.9

Fraction of mass remaining

0.8
0.7
30 K min-1

0.6
20 K min-1

0.5
0.4
0.3
0.2
0.1
0
300

400

500
600
700
Temperature (C)

800

900

Fig. 3. Fraction of mass remaining when a hypothetical fuel, which decomposes according to a single rst-order reaction having E = 200 kJ mol1 and
A = 1015 s1 , is heated at rates of 20, 30 and 10 000 K min1 (solid lines).
The thick dashed lines show the curves generated using the parameters recovered by the algorithm, as in Fig. 2.

to zero. Thus, all that is required for the algorithm to identify

correctly the activation energy of a reaction is that at some
temperature that reaction must dominate completely the rate of
loss of mass. The distribution of activation energies recovered

by the algorithm is compared with the assumed distribution

in Fig. 4(c). Despite the overlap of the reactions, the algorithm is able to recover the original distribution of activation
energies.
A good measure of the performance of the algorithm is
how well the determined kinetics extrapolate to higher rates of
heating. The predicted rate of mass loss at a heating rate of
10 000 K min1 is shown in Fig. 4(d); the solid line was generated using the original set of reactions, whilst the dashed lines
were produced using the parameters recovered by the algorithm
at 20 and 30 K min1 . The agreement between the pseudoexperiment and the extrapolated kinetics is excellent. The overlap between the reactions with E = 190 and 200 kJ mol1 can
be seen in Fig. 4(d); the third peak from the left is, actually, a
composite of the peaks produced by these two reactions. These
reactions were chosen to be relatively sharp, with A=1015 s1 ;
this large pre-exponential factor results in less overlap between
reactions. However, when A was reduced to 108 (and the activation energies reduced by a factor 0.75) the performance of
the algorithm was the same.
3.3. Test 3a Gaussian distribution of activation energies
In this trial, the theoretical curves of mass against time were
generated using a continuous, Gaussian distribution of activation energies, with a mean value of E of 225 kJ mol1 and
a standard deviation of 25 kJ mol1 ; again A was constant at
1015 s1 . The algorithm was made to generate a set of 100 reactions by evaluating the activation energy at 100 discrete values
of conversion, between 1% and 99.9%.

E (kJ mol-1)

250

200

Cumulative fraction of
mass

1
(a)

150

Fraction

0.1

0.05

0.2
0.4
0.6
0.8
Mass Remaining

Normalised rate of mass

loss (s-1)

0.15
(b)

2345

(c)

0.8
0.6
0.4
0.2
0
150

200
250
E (kJ mol-1)

300

0.7
(d)

0.6
0.5
0.4
0.3
0.2
0.1
0

200
400
600
Temperature (C)

800

Fig. 4. Hypothetical fuel with seven components, each of which decomposes by a rst-order reaction: the values of E were 150, 175, 190, 200, 225, 250,
275 kJ mol1 and A = 1015 s1 ; the mass fraction of each component was 17 . The diagram gives the results from the algorithm: (a) the values of E for each
of the 50 values of conversion (resulting in a set of 50 reactions) used in the algorithm; (b) the mass fraction allocated to each of the 50 reactions; (c) the
cumulative mass fraction having activation energy less a given abscissa; (d) the rate of mass loss when the fuel is heated at a rate of 10 000 K s1 . In (c) and
(d), the dashed lines show the results from the algorithm and the solid lines are for the original (seven) rst-order reactions.

2346

S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

0.003

0.8

0.6

0.001

0.4

0.2

0
100

30 K min-1

0.002

150

200

250

300

350

E (kJ mol-1)
Fig. 5. The cumulative distribution of activation energies determined by the
algorithm (solid line) for a hypothetical fuel with a Gaussian cumulative
distribution of activation energies (dashed line).

Normalised rate of mass loss (s-1)

Cumulative Mass Fraction (-)

(a)

(b)

10000 K min-1

0.6

0.4

0.2

0
200

The recovered distribution of activation energies is compared with the original Gaussian distribution in Fig. 5. The
recovered distribution contains bigger steps than the original
distribution, which, in part, results from the algorithm having been forced to approximate a continuous distribution with
a discrete number (i.e., 100) of reactions. It is also worth
noting that the nal set of reactions recovered by the algorithm contained less than 100 reactions, because the amounts
of many of the reactions were equated to zero by the matrix inversion. The rst part of the algorithm generates the set
of 100 reactions; however, some of these 100 reactions are
very close in behaviour. Thus, it is possible to lump all the
mass, which should be allocated to several neighbouring reactions, into one reaction. In fact, a relatively small number
of discrete reactions ( 50 in this case) are able to give a
good approximation to a continuous distribution of activation
energies.
The fact that the recovered distribution of activation energies
provides a good approximation to the behaviour of a continuous distribution can be seen from Fig. 6, in which the rate
of loss of mass is plotted as a function of temperature, for
both the original Gaussian distribution and the distribution determined by the algorithm. It is also worth noting that the algorithm determined the kinetic parameters from the pseudoexperiments at rates of heating of 20, 30 K min1 only; the
rate of mass loss at 10 000 K min1 was calculated by assuming that these parameters will be valid at this heating rate.
Thus, the algorithm is also able to recover suitable kinetic parameters when there is a continuous distribution of activation
energies.

20 K min-1

400

600
Temperature (C)

800

Fig. 6. Rates of mass loss (solid lines) for a hypothetical fuel decomposing
with a continuous distribution of activation energies (given by the dashed
line in Fig. 5). The thick dashed lines show the predicted results using the
parameters from the 50 reactions recovered by the algorithm. The heating
rates were (a) 20 and 30 K min1 (used by the algorithm to determine the
kinetic parameters) and (b) 10 000 K min1 .

3.4. Application of the algorithm to the results of

thermogravimetric experiments on the pyrolysis of dried
sewage sludge
The results of applying the algorithm to real thermogravimetric measurements of the pyrolysis of dried sewage sludge are
given in Fig. 7. The solid lines in Fig. 7 show the experimental
rates of loss of mass as a function of temperature, when small
samples of sewage sludge were heated in an inert atmosphere
using three different rates of heating. The circles in Fig. 7 show
the excellent t given by the kinetic information deduced by
the algorithm. The cumulative distribution of activation energies produced by the algorithm is given in Fig. 8(a), whilst the
value of the pre-exponential factor obtained for each reaction
is plotted (as a function of the activation energy) in Fig. 8(b).
Fig. 8 shows that the majority of the devolatilisation was governed by approximately eight, primary reactions. It is also worth
noting that there is a tendency for the pre-exponential factor
to increase with activation energy. This tendency has been reported in numerous other systems (e.g. Arenillas et al., 2001;
Dong et al., 2005; Miura et al., 2001). The results from these
experiments are discussed further by Scott et al. (2005), but at

S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

x 10-3

Cumulative fraction of mass (-)

3
20 K min-1

10 K min-1

(a)

0.9

40 K min-1
Normalised rate of mass loss (s-1)

2347

0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1

0
200

300

400
500
Temperature (C)

600

700

800

(b)
18

this stage it can be seen that the algorithm is able to handle real
results from a fairly complex fuel.

16

Log10 (A)

Fig. 7. Devolatilisation of small samples of dried sewage sludge in a thermogravimetric experiment at three heating rates, as shown. Experimental results
(Scott et al., 2005) are continuous lines; circles show the predictions from the
algorithm, using kinetic parameters deduced from the experimental results at
heating rates of 20 and 40 K min1 .

12
10
8

4. Conclusions
A new algorithm has been presented for characterising the
kinetics of thermal decomposition of a solid fuel, from the
results of thermogravimetric measurements of the mass lost
during its pyrolysis. The algorithm inverts the distributed activation energy (DAE) problem to derive the distribution of activation energies of the reactions undergone by the sample. This
differs from previous attempts to invert the DAE problem in
that there is assumed to be only a nite number of reactions
occurring, though this number may be large enough to approximate a continuous distribution of activation energies. This approach has been attempted before (e.g. Burnham et al., 1987)
The method presented here makes use of this approach, but
differs in that there is an initial stage, which rst calculates a
set of plausible reactions, followed by a linear t to assign the
contributions from each reaction. The method has been tested
on results from both real and simulated thermogravimetric experiments. The simulated experiments used a hypothetical fuel
whose decomposition was governed by

14

100

150
200
250
300
Activation energy, E (kJ mol-1)

350

Fig. 8. (a) The cumulative distribution of activation energies produced by the

algorithm for the pyrolysis of dried sewage sludge; (b) shows the value of the
logarithm of pre-exponential factor, in units of s1 , log10 (A) as a function
of the activation energy. The area of each data point in (b) is proportional to
the mass allocated to the reaction.

Notation
A
Ai
B
B1 , B2

(1) a single rst-order reaction,

(2) seven rst-order reactions, each with given E and A,
(3) a continuous, Gaussian distribution of activation energies.

Ei
E
E

In addition, the algorithm was applied to experimental results

for the thermogravimetric analysis of the pyrolysis of dried
sewage sludge.
In all these cases, the algorithm gave values of E and A, from
which the results of thermogravimetric experiments, imaginary
or real, at a variety of heating rates were accurately predicted.

f
fi
fi,0
f

pre-exponential factor, s1
pre-exponential factor for reaction i, s1
rate of heating (dT /dt), K s1
rate of heating (dT /dt) is experiments 1
and 2, K s1
activation energy for reaction i, kJ mol1
activation energy, kJ mol1
activation energy at which
(E) = 0.58,
kJ mol1
mass fraction of material, dimensionless
mass fraction of material associated with
reaction i, dimensionless
initial value of fi , dimensionless
a vector containing the values of fi,0 for
all reactions, dimensionless

2348

F (E)
g(E)

i
m(E)

m0 (E)
M
M0
M
Mv
Mv0
R
t
t0 , t1 , t2 , t3 , . . .
T
T0
T1 , T2
u
w
V

S.A. Scott et al. / Chemical Engineering Science 61 (2006) 2339 2348

E
= 0 g(E) dE, dimensionless
cumulative fraction of material with activation energy less than E
fractional density function such that
g(E) dE= fraction of material with activation energy between E and E + dE,
mol kJ1
reaction number, dimensionless
mass density function such that
m(E) dE= mass of material with activation energy between E and E + dE,
kg mol kJ1
initial value of m(E), kg mol kJ1
mass of fuel, kg
initial mass of fuel, kg
a vector which contains the mass of fuel
remaining at different points in time, kg
mass of volatiles, kg
initial mass of volatile matter, kg
ideal gas constant, kJ mol1 K 1
time, s
times at which the mass of fuel is measured, s
temperature, K
initial temperature, K
temperatures (for experiments and at a
constant rates of heating, B1 and B2 ) at
which a specied conversion is reached, K
dummy variable for integration in Eq. (6),
kJ mol1
mass fraction of sample which is inert, dimensionless
yield of volatiles, kg

Greek letters





i



 

t
E
= exp A(E) 0 exp RT
di(t) dt ,
mensionless
a matrix whose elements i, j are given by

i (tj ),dimensionless
the value of
i (t)
 
 for reaction
i (a function

t
Ei
of time) = exp Ai 0 exp RT
(t) dt ,
dimensionless

Acknowledgements
The authors are grateful for the support of the Engineering
and Physical Sciences Research Council (GR/R21547) in the

United Kingdom, Anglian Water Plc and EMC Environmental

Engineering LTD. We would also like to acknowledge the assistance of Mr Robert Cornell at the Department of Materials
Science and Metallurgy, University of Cambridge.
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