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**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 ﬁrst-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.

䉷 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, gasiﬁcation 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 䉷 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 difﬁcult; 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 ﬁrst-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,

. Mvo is the initial value of Mv (t). Gauss–Hermite integration to evaluate the integral in the distributed activation energy model. e. results from TGA experiments can. because such a wide variety of chemical groups exist in coal. the adjustable parameters are the mean and standard deviation of g(E). there are many possible distributions and functional dependencies of the preexponential factors. (E. In fact. Thus. For example. t) dE. nevertheless.. (2003) have reported kinetic parameters for the formation of a large number of different species. the double exponential term (denoted by (E.. In the case of an assumed Gaussian distribution. Mv (t). produced during the pyrolysis of tobacco. t) cannot be measured. or the total rates of decomposition are measured. 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. can only be inferred from the integral over all energies. (3). g(E). as the ﬁrst-order decomposition of many different chemical groups. (2003). Burnham and Braun (1999) suggest that a deviation from ﬁrst-order kinetics is often either due to the existence of a distribution of activation energies. Eq.g. Such an assumption leads to the distributed activation energy model. Mvo − Mv (t)) and g(E) is the underlying (initial) distribution of activation energies. The inverse problem. If g(E) and A(E) are known. t). t) −E = −A(E) exp m(E. with a pre-exponential factor A(E) dm(E. especially when it is used as a sub-model in combustion codes with variations in temperature from point to point. changes very rapidly from zero to unity over a narrow range of . an expression which allows the rate of mass loss to be calculated without numerical integration). V (t) is the yield of volatiles (i. The integration over all activation energies adds an extra dimension to the problem. A. it is possible to build up more complicated distributions by assuming that a product can be produced from more than one type of precursor. 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. Anthony and Howard (1976) assumed that the distribution of activation energies was Gaussian. (3)) have been proposed to give closed forms of the model. the distributed activation energy model can be difﬁcult to use. by assuming that as conversion proceeds. of volatile matter is ∞ Mv (t) = m(E. where such a distribution is assumed a priori.e. appear to follow simple nth order kinetics. which could give the same dependence of Mv on time. In their review of the kinetics of thermal decomposition. described below. Scott et al. (1) dt RT so t m(E. or to the propagation of a decomposition front through the solid. 0 Assuming that the material in the interval E to E + dE decomposes via a ﬁrst-order reaction. which circumvent the need for numerical integration. at a given time t is m(E. only the total amounts. Mv (t). for the pyrolysis of coal.e. In this paper we will restrict ourselves to the overall loss of mass. m0 (E) is the initial mass of volatile material decomposing with an activation energy in the interval E to E + dE. Braun and Burnham (1987) showed that where a distribution of activation energies exists. (2004) showed how it is possible to obtain an approximate closed form of the model (i. Pitt (1962) recognised that. (3). Several workers have presented methods of estimating the actual distribution of activation energies for devolatilisation. there is a continuous distribution of reactions. 1. A more complete discussion of the various approximations is given by Please et al.A. Even when the kinetic parameters are fully speciﬁed.1. each group being characterised uniquely by its activation energy for decomposition. Thus the total mass. (2) 0 Here.g. by assuming a constant value for the pre-exponential factor. m0 (E) dE It should also be noted that the distributed activation energy model can be applied to the formation of individual species. t) is the double exponential term in Eq. corresponding to three types of CO2 precursor. Pitt (1962) measured the rate of devolatilisation of coal at a constant temperature in a ﬂuidised bed. for the formation of CO2 . he was able to estimate the shape of the distribution of activation energies. i. For the case of a Gaussian distribution of activation energies. / Chemical Engineering Science 61 (2006) 2339 – 2348 that. One way forward has been to assume the shape of the distribution. Although each distribution is assumed to be a Gaussian distribution.t) where. e. Rostami et al. of determining g(E) and A(E) from measurements of the rate of devolatilisation is ill-posed. Wojtowicz et al. which characterises the material. t) dE.e. However. g(E) is given by g(E) = ∞ 0 m0 (E) . In practice. t) in Eq. Eq. i. the problem reverts to one of ﬁtting the model to the measurements. since the distribution. coal. (3)). t) = m0 (E) exp −A(E) exp(−E/RT ) dt . who used high order. these kinetics cannot be extrapolated reliably beyond the original experimental conditions. Wojtowicz et al. However..e. (3) 0 (E. the quantity m(E. Numerous approximations to the double integral (i. the yield of volatile material can be calculated from Eq. The distributed activation energy model (DAEM) This approach models the pyrolysis of a complex fuel. under isothermal conditions. Efﬁcient evaluation of the integral over all activation energies has been addressed by Donskoi and McElwain (2000). (2003) give three different activation energy distributions.e. the functional groups with the lowest activation energies are lost ﬁrst. (3). for a given t.2340 S..

increases as A decreases. Pitt (1962). using Eq. but constant. parallel ﬁrst-order reactions. an algorithm has been developed to determine the kinetics of devolatilisation from thermogravimetric experiments. (2005) attributed this compensation effect to changes in the entropy of activation for pyrolysis.g. (6): Ln((E ∗ )) = −A(E ∗ )RT 2 −E ∗ /RT e . (5) RT Pitt (1962) assumed that A(E) was constant and was then able to solve Eq. 2005). In conjunction with Eq. BE ∗ (7) which is valid when E ∗ /R → ∞ (Burnham and Braun. Dong et al. asymptotic to = 1. but are in a standard form. A. Maki et al. we replace the ‘S’ shaped curve. because the value of 0. (8) where M(t) is the mass of the sample. is large. The pre-exponential factor. A step function has also been used to approximate (E. (3) with E = E∗ −E ∗ ∗ ∗ Ln((E )) = −A(E ) exp t. the pre-exponential factor increased monotonically with the activation energy. / Chemical Engineering Science 61 (2006) 2339 – 2348 E. With this approximation Eq. Under these conditions with dT /dt = B = (T − T0 )/t t −E ∗ ∗ ∗ (E ) = exp −A(E ) exp dt . The value of g(E) for each of the discrete ﬁrst-order reactions was then calculated by ﬁtting the model to the experimental results using linear least squares minimisation.S. where E ∗ is deﬁned as the energy at which (E. t) in Eq. R E/RT u (6) 2341 Miura and Maki (1998) assumed a value of (E ∗ ) = 0. by noting that the preexponential factor can be linked to the entropy of activation. (3) can be written as ∞ ∞ Mvo − V (t) = g(E)(E. Miura and Maki (1998) used the following asymptotic approximation to Eq. RT (t) 0 Taking natural logarithms. although in reality parallel. t). 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 . was assumed to be constant and was determined by ﬁtting the predicted mass loss proﬁles to those measured in a thermogravimetric experiment with a constant rate of heating. Thus. They used Eq. 2. t) dE ≈ g(E) dE Mvo 0 E∗ = 1 − F (E ∗ ). Miura’s method has been applied successfully to the pyrolysis of coals (Arenillas et al. This essentially assumes that the reactions. this actually gave a Gaussian distribution of activation energies for the pyrolysis of a coal. t) reaches a speciﬁed value. (5) for the activation energy at each yield of volatile material. using the deﬁnition of (E. (4). so that the reactions were spaced over a range of activation energies with equal intervals of activation energies. (4) where F (E ∗ ) is the cumulative distribution of activation energies. t) changes from zero to unity. Scott et al. because the range of E. rates of heating. constant. Miura. for example Miura and Maki (1998) deﬁned E ∗ such that (E ∗ ) = 0.. 1995).A.0 exp −Ai exp M0 0 All Reactions. both E ∗ and A(E ∗ ) for each value of the volatile yield (or conversion). over which (E. (6) cannot be evaluated analytically. Burnham et al. Such an approximation implicitly relies on the fact that the various components are pyrolysed in order of increasing activation energy (which. 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. but they are all based upon the approximation used by e. 2001). The activation energies of these reactions were ﬁxed a priori. which contains a fraction w of inert material. 1998. irrespective of how that conversion was reached. More recent methods do not require A(E) to be a constant (Miura and Maki.58.. This amounts to ﬁnding the values of A(E ∗ ) and E ∗ from the assumed value of (E ∗ ). which is tabulated or available in mathematical packages. depending on the pre-exponential factor. (E. by comparing the same volatile yield in two or more experiments. The algorithm is intended to solve the problem of determining the kinetics of reactions for a material decomposing subject to many. To simplify the computation. A. rates of heating in a thermogravimetric balance. M0 is the initial value of M. performed at different rates of heating. t) can be approximated by a unit step function occurring at an energy E ∗ . 2001) and petroleum asphaltenes (Dong et al. when.58 and showed that it was possible to calculate. The problem remains of ﬁnding the values of A(E ∗ ) and E ∗ for the ‘reaction’ occurring at a given conversion. (6). given by (E.0 is the . 1995).. The integral terms in Eq.i × (−Ei /RT (t)) dt . replacing a continuous distribution of reactions with a ﬁnite set of discrete ﬁrst-order reactions.58 was found to minimise the errors in A for the cases they considered. Hence. Miura and Maki (1998) performed experiments in which coal was devolatilised at various. Pitt (1962) undertook experiments at constant temperature. fi. with a step function which changes from 0 to 1 at E ∗ . single reaction dominates. performed at several different. need not be the case). (4) and chose E ∗ such that (E ∗ ) = 0. For a material decomposing via several such ﬁrst-order reactions t M(t) =w+ fi. In both these cases. An algorithm for determining the kinetics of devolatilisation In this work. 1997. occur sequentially in order of increasing activation energy and do not overlap signiﬁcantly.58. t). The step function approximation is valid only when the pre-exponential factor. so that at a given conversion the same. (1987) discretised the distribution of activation energies. when the fuel is heated at a constant rate (Miura.. 1999).

. ⎢ . T1 and T2 . it is possible to solve Eq.0 i (T ). If a solid is made up of several components. ⎥ ⎦ ⎣ (9) w f i. which can be solved for the unknown Ei . when the fuel is subjected to a constant rate of heating. This is because there is a point in the conversion process where a particular reaction is dominant. not the overall conversion of the mass of fuel to volatile material. so that its values of A and E can be measured directly. (8) may be written as a matrix equation. (10) is the same as in Eqs. (11). T2 ). (9) was inverted here using the lsqnonneg algorithm in Matlab (Matlab R14. 0 (11) using the deﬁnition of in Eq. Once the reactions have been speciﬁed.e. B1 and B2 . with. when d dfi d = fi. ⎥ . is given by Eq. each with a known value of A and E. Thus. the value of the activation energy calculated from Eq. there will be a single reaction dominating. which is altered to minimise the difference between the values of M and f . etc. e.. the problem given above is well-posed and can be solved. becomes a parameter. . fi.0 . Using experimentally measured M(t). (9) using linear least squares. T1 ) and i (B2 . and noting that i (T ) is also a function of the rate of heating.). and Ei . fi. Whilst the DAEM is ill-posed. (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 . its discrete analogue f is now used to denote an actual fraction of material with a speciﬁed activation energy and pre-exponential factor. it can be generated by increasing the number of reactions to inﬁnity and imposing the constraint that the reactions are characterised uniquely by their activation energies.0 are allowed. each mass fraction. .. (13) will be exact. Since there are usually more experimental results than reactions. If the conversion in two separate experiments at different heating rates. then Eq. . is given by ⎡ ⎤ 1 (t0 ) 2 (t0 ) · · · n (t0 ) 1 ⎡ ⎤ M(t0 ) ⎢ (t ) 2 (t1 ) · · · n (t1 ) 1 ⎥ M(t1 ) ⎥ ⎢ 1 1 ⎥ 1 ⎢ ⎢ ⎥ = ⎢ 1 (t2 ) 2 (t2 ) · · · n (t2 ) 1 ⎥ ⎥ M0 ⎣ M(t2 ) ⎦ ⎢ ⎣ 1 (t3 ) 1 (t3 ) · · · n (t3 ) 1 ⎦ . then fi (B1 . decomposing in each reaction i is then a matter of solving Eq. the conversion of the individual component i. the fraction of the initial mass remaining. The distributed activation energy model (DAEM) is a special case of this general problem. .368 is used. Errors in the value of the activation energy will occur when several reactions are occurring simultaneously at the chosen conversion. . (13) RT 2 R E/RT 2 u This is a non-linear equation. M(t). However. Eq. (12) Substituting for i (B1 . subject to the constraint that only positive values of fi. the problem is to ﬁnd fi. the matrix can be calculated. it is ﬁrst assumed that. where.0 ⎥ ⎥ ⎢ ⎢ f3. at a given conversion.0 ⎥ ⎥ ×⎢ ⎢ . T2 ) from Eq.. M = f . t3 . for an experiment with a constant dT /dt = B Ai T exp(−Ei /RT (t)) dT . (3).0 . A value of i = e−1 corresponds to the conversion at which a single ﬁrst-order reaction would reach a maximum in the rate of decomposition. there might be more than one reaction with the same activation energy. assuming a ﬁrstorder reaction.g. provided that only one reaction is dominating the overall loss of mass at the conversion of interest. t2 .2342 S.0 ⎤ ⎢ f2. If the reactions were known. (9). Scott et al. For the ith component. It should be noted that to avoid confusion with the continuous fractional density function g(E). of course. the system is over-speciﬁed. / Chemical Engineering Science 61 (2006) 2339 – 2348 fraction of M0 which decomposes with an activation energy Ei and pre-exponential factor Ai .0 . T2 ) at two particular temperatures. To determine the pre-exponential factor. the mass of fuel remaining. T1 )=fi (B2 . T0 is the initial temperature of the fuel.0 exp −Ai exp(−Ei /RT ) dt = fi. A similar method was used by Burnham et al. (2) as t fi (T ) = fi. i. This is. provided the number of reactions is ﬁnite and the reactions do not completely overlap. Ai . but a different pre-exponential factor. M ⎡f 1. (3) and (6). without interference from other reactions. Thus Eq. which is linear. B = dT /dt. It should also be noted that i in Eq. i (t)=i (T )= exp − B T0 (10) Here. (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. To use Eq. for any set of times t1 .A. together with each value of E and A. a set of reactions must ﬁrst be generated.. is considered and the ith reaction is the only reaction taking place at this conversion. it is assumed that the dominating reaction is at some conversion.e. from Eq. Ai . i (B1 . Calculating the initial mass fractions. This need not be the case. here X =1−e−1 ⇒ i =e−1 ≈ 0.0 Ai exp(−Ei /RT ) dt dt dt t × exp −Ai exp(−Ei /RT ) dt = 0 0 . once Ei has been calculated from Eq. Here. (13). T1 ) = i (B2 . if the material were heated at a constant rate.. The Mathworks Inc. (1987).. (9).

(13). step 2 in Fig.g. in the second stage of the algorithm (i. to estimate the amount of each reaction occurring. (4). / 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. (14) to get the pre-exponential factor. Thus. (13) and (14). (13) to calculate the activation energy. Scott et al. Since Ei is already known from Eq.g. (8) is summarised in Fig.. form the matrix in Eq. Overview of the algorithm. If there is more than one real reaction occurring at a particular conversion. to give the amount of each reaction. assuming that at each conversion only one reaction dominates. This error is discussed more fully. with dT /dt = B. Two test curves at low rates of heating (20 and 30 K min−1 ) were produced and used for the subsequent calculation. This is an advantage over Miura and Maki’s (1998) method. At each of the chosen conversions. (9).e. Finally. This solid was taken to contain no ash or char and to decompose with speciﬁed kinetics. using Eqs. Ei. the algorithm was applied to the results of thermogravimetric 3. when the pre-exponential factor is evaluated. resulting in a very high rate of heating. m = f. Thus. the values of A and E used for the simulation. with increasing complexities. 1.e. below.e. and Eq.A. the time constant for their heating could be of the order of a few seconds. In a real combustion or gasiﬁcation system (e. 1.. Results and discussion . (14) R E/RT 2 u the value of E given by the ﬁrst stage of the algorithm (i. lead to some error in the calculated value of Ai . The exact values used for the conversion are an input to the algorithm.S. The algorithm developed here neither requires that each reaction is uniquely characterised by its activation energy nor does it use the step function approximation. a simulation of a thermogravimetric experiment. the test program was. the algorithm ﬁrst identiﬁes a set of possible reactions. The overall procedure to solve Eq. as a function of temperature STEP 2 STEP 3 STEP 4 Choose n values of conversion.e. the values of fi. 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 . f i Fig.100 points where the activation energy Ei and pre-exponential factor Ai are to be evaluated. This is because it has been assumed that the dominant reaction is at a conversion of 63. They used the approximate form of Ln(i (E ∗ )) given by Eq. 1. which uses the approximate Eq. This provides a robust test of how well the kinetics extracted by the algorithm extrapolate to different heating rates. in effect. once the activation energy at each conversion is known. Thus. A test program was written to generate theoretical plots of mass versus temperature for a hypothetical solid experiencing a ﬁxed rate of heating. (9) Matrix STEP 5 Invert Eq. 167 K s−1 ). however. (4) to generate the distribution of activation energies. they ranged from a solid decomposing with a single ﬁrst-order reaction. i. is central to the method of Miura and Maki (1998) for inverting the distributed activation energy model. A third theoretical curve was generated for a rate of heating of 10 000 K min−1 and this was compared with that predicted by the parameters recovered by the inversion algorithm at 20 and 30 K min−1 . However. would not be unreasonable. The approximations used to derive Eq. Each chosen value of the conversion will generate one candidate reaction. where the algorithm is used to recover the kinetic parameters from a simulated ﬁrstorder reaction.. (7) to derive the equivalents of Eqs. step 3 in Fig. (13) and (14) above.0 for each of these spurious reactions can be set to zero. step 3) will be incorrect.2%. The algorithm was then applied to the simulated curves in an attempt to regenerate the original parameters. (14) do. Several scenarios were tested in this way. through to one decomposing with a Gaussian distribution of activation energies.. The method of obtaining the values of A and E at various conversions. use Eq. Ai Set of n reactions with each with known A and E Using the set of n reactions. 1. when small particles of fuel are added to a ﬂuidised bed. Miura and Maki (1998) made the assumption that each reaction is uniquely characterised by an activation energy and used Eq. which relies on the ‘step function’ approximation. a ﬂuidised bed) a heating rate of 10 000 K min−1 (i. e. steps 4 and 5). However.

at least in principle.. Fig. say. the hypothetical fuel was assumed to decompose by seven reactions. 175. the inversion of Eq. the values of A in Fig. Hypothetical fuel which decomposes by a single ﬁrst-order reaction having E = 200 kJ mol−1 and A = 1015 s−1 .368)/Ln(actual ) = 13 (c) Fraction 0. apart from those values on the right: these In this test.4 0.8 Fraction of mass remaining 1 Fig. and. In this example. Eq. Test 1—single ﬁrst-order reaction In the case of a single ﬁrst-order reaction.e. the recovered activation energy was correct at all conversions.368. as a function of the fraction of mass remaining at which the reaction was evaluated. The ﬁgure shows the results from the algorithm: (a) and (b) give the value of E and A (in units of s−1 ) for the 50 candidate reactions. 2(c) are the amounts allocated to each reaction by the matrix inversion. 275 kJ mol−1 . Aalgorithm . Test 2—seven ﬁrst-order reactions 3. be a considerable error in the value of the pre-exponential factor. is given by (a) 200 190 17 (b) Log10 (A) 16 15 14 Ln( = 0. which generates the amounts of each reaction. 2. Scott et al. 3.2344 S.6 0. (9). derived from the algorithm parameters. the actual value of = actual could be anywhere from zero to unity. is almost identical to the theoretical curve for a single ﬁrst-order reaction.2 0.368. (15) shows that there can. with many reactions.0 ).. its rate of reaction must be high. 3. Therefore.368. will tend to set the amounts of these spurious reactions . mass is only allocated to the reactions with the correct value of A.368 abscissa. The error from this simpliﬁcation can be estimated from Eq. 2(a) and (b). if there are. The values of E and A calculated at each value of the fraction of mass remaining are shown in Fig. occur simultaneously). Aactual (15) because the algorithm assumes that A is derived from the point where i (=fi /fi. 4(a) and (b). the algorithm should be able to produce a nearly exact answer.e. in reality. the amounts of these spurious reactions will be set to zero by the matrix inversion..99.1. here the method has two advantages over the method of Miura and Maki (1998). because they were derived using a conversion of 1 − 0. 225. Whereas for a single reaction.e. many of them have an incorrect pre-exponential factor. the values of E were 150.368.01–0. each with A = 1015 s−1 . A fuller discussion of both the experiment and its results are given elsewhere (Scott et al. An equal mass fraction was allocated to each reaction. 2(a) are exact. 250. when several reactions are occurring. i. 2(b) are only correct when the mass remaining is 0. However. The plot for a rate of heating of 10 000 K min−1 . as in this case. when the reactions overlap (i. 200. However.2. i. experiments performed on dried sewage sludge. The results of two trials are given below.A. corresponding to an unreacted fraction in the range 0. 2(c) shows that the amounts allocated to each reaction by the matrix inversion are zero for all except the two straddling the 0. in the more general case. whereas.368. it is not always possible to say what the conversion is for the dominating reaction.4 0. 2005). which is zero for all but the two straddling the point where the fraction of mass remaining = 0. 190.2 0 0 0. the others are somewhat incorrect. Since the value of E is determined correctly. (7). it would be possible to evaluate the value of A at each conversion correctly. (c) gives the mass fraction allocated to each of the 50 possible reactions. for the simple case of a hypothetical fuel decomposing by a single ﬁrst-order reaction. The values of E in Fig. Plots of mass against temperature are shown in Fig. Secondly. In these tests the inversion algorithm evaluated E and A at 50 equally spaced intervals of the conversion. This can clearly be seen in Fig. the recovered activation energy is incorrect. in Fig. For the imaginary fuel. However. the ratio of the actual value of A to that determined by the algorithm. 2. / Chemical Engineering Science 61 (2006) 2339 – 2348 E (kJ mol-1) 210 slightly low values arise from numerics. the value of Aalgorithm /Aactual . where the error in the estimated value of A is low. the values of A and E were E = 200 kJ mol−1 and A = 1015 s−1 . to determine the kinetics of devolatilisation. because there is only one reaction.. 200 kJ mol−1 . The complete set of possible reactions generated by the ﬁrst stage of the algorithm is shown in Fig. However. the approximate form for i (=fi /fi.0 )=0.6 0. Firstly. the algorithm produces the correct answer. Also shown. thus. The reactions with E = 190 and 200 kJ mol−1 were chosen because they overlap signiﬁcantly and so should be more difﬁcult for the algorithm to identify separately. for a reaction to be dominating. an individual reaction is more likely to be important at a conversion near actual = 0. 50 candidate reactions generated by the ﬁrst part of the algorithm.

this large pre-exponential factor results in less overlap between reactions.7 30 K min-1 0. the theoretical curves of mass against time were generated using a continuous. (d) the rate of mass loss when the fuel is heated at a rate of 10 000 K s−1 . when A was reduced to 108 (and the activation energies reduced by a factor 0. Fraction of mass remaining when a hypothetical fuel.3 0. 275 kJ mol−1 and A = 1015 s−1 .2 0 150 200 250 E (kJ mol-1) 300 0.2 0. 250. is heated at rates of 20. Hypothetical fuel with seven components.4 0. the mass fraction of each component was 17 . 175. 200.4 0.A. However.1 0 0 200 400 600 Temperature (˚C) 800 Fig. Scott et al.15 (b) 2345 (c) 0. 4(d).6 0. the algorithm is able to recover the original distribution of activation energies.9%.8 0. A good measure of the performance of the algorithm is how well the determined kinetics extrapolate to higher rates of heating.5 0. / Chemical Engineering Science 61 (2006) 2339 – 2348 1 10000 K min-1 0. 4(d). . Test 3—a Gaussian distribution of activation energies In this trial.4 0.2 0.75) the performance of the algorithm was the same. the third peak from the left is. (b) the mass fraction allocated to each of the 50 reactions. between 1% and 99. 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. whilst the dashed lines were produced using the parameters recovered by the algorithm at 20 and 30 K min−1 . each of which decomposes by a ﬁrst-order reaction: the values of E were 150. with a mean value of E of 225 kJ mol−1 and a standard deviation of 25 kJ mol−1 . 4(c). The algorithm was made to generate a set of 100 reactions by evaluating the activation energy at 100 discrete values of conversion. 30 and 10 000 K min−1 (solid lines). as in Fig. again A was constant at 1015 s−1 . the solid line was generated using the original set of reactions. These reactions were chosen to be relatively sharp. Despite the overlap of the reactions.9 Fraction of mass remaining 0. The overlap between the reactions with E = 190 and 200 kJ mol−1 can be seen in Fig.7 (d) 0.3. actually. Gaussian distribution of activation energies. 2. The thick dashed lines show the curves generated using the parameters recovered by the algorithm.6 0.1 0 300 400 500 600 700 Temperature (°C) 800 900 Fig. 225.05 0 0 0. 3. Thus. The agreement between the pseudoexperiment and the extrapolated kinetics is excellent. The distribution of activation energies recovered by the algorithm is compared with the assumed distribution in Fig.4 0. to zero.2 0.6 20 K min-1 0. In (c) and (d).5 0.3 0.6 0. with A=1015 s−1 .S.8 0. The predicted rate of mass loss at a heating rate of 10 000 K min−1 is shown in Fig. 4.1 0. E (kJ mol-1) 250 200 Cumulative fraction of mass 1 (a) 150 Fraction 0. the dashed lines show the results from the algorithm and the solid lines are for the original (seven) ﬁrst-order reactions. a composite of the peaks produced by these two reactions. which decomposes according to a single ﬁrst-order reaction having E = 200 kJ mol−1 and A = 1015 s−1 . 190. 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. (c) the cumulative mass fraction having activation energy less a given abscissa.8 Mass Remaining 1 Normalised rate of mass loss (s-1) 0. 3.

In fact.e. (2005). 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. Miura et al. The solid lines in Fig. for both the original Gaussian distribution and the distribution determined by the algorithm.003 1 0.2 0 200 The recovered distribution of activation energies is compared with the original Gaussian distribution in Fig. The thick dashed lines show the predicted results using the parameters from the ∼ 50 reactions recovered by the algorithm. 2001. 3.8 0. which should be allocated to several neighbouring reactions. It is also worth noting that the ﬁnal set of reactions recovered by the algorithm contained less than 100 reactions. 7 show the experimental rates of loss of mass as a function of temperature. in part. 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. 2001). however. This tendency has been reported in numerous other systems (e. Arenillas et al. Thus. when small samples of sewage sludge were heated in an inert atmosphere using three different rates of heating. 6.4. the algorithm is also able to recover suitable kinetic parameters when there is 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. The ﬁrst part of the algorithm generates the set of 100 reactions. 20 K min-1 400 600 Temperature (°C) 800 Fig. 5). in which the rate of loss of mass is plotted as a function of temperature. 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. whilst the value of the pre-exponential factor obtained for each reaction is plotted (as a function of the activation energy) in Fig. 30 K min−1 only. It is also worth noting that the algorithm determined the kinetic parameters from the pseudoexperiments at rates of heating of 20.2 0 100 30 K min-1 0. but at . The cumulative distribution of activation energies produced by the algorithm is given in Fig. The heating rates were (a) 20 and 30 K min−1 (used by the algorithm to determine the kinetic parameters) and (b) 10 000 K min−1 . 5.A. Fig.4 0.6 0. The results from these experiments are discussed further by Scott et al. Scott et al.6 0. 2005. results from the algorithm having been forced to approximate a continuous distribution with a discrete number (i. the rate of mass loss at 10 000 K min−1 was calculated by assuming that these parameters will be valid at this heating rate.g. 7 show the excellent ﬁt given by the kinetic information deduced by the algorithm. It is also worth noting that there is a tendency for the pre-exponential factor to increase with activation energy. because the amounts of many of the reactions were equated to zero by the matrix inversion.. 5. The circles in Fig. 8(a). Normalised rate of mass loss (s-1) Cumulative Mass Fraction (-) (a) 0 (b) 10000 K min-1 0. it is possible to lump all the mass. 8(b). / Chemical Engineering Science 61 (2006) 2339 – 2348 0. The recovered distribution contains bigger steps than the original distribution. 8 shows that the majority of the devolatilisation was governed by approximately eight.. Dong et al. some of these 100 reactions are very close in behaviour..001 0. 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).002 150 200 250 300 350 E (kJ mol-1) Fig. primary reactions.2346 S.. into one reaction. Thus. 100) of reactions.4 0. 7. which. 6.

4 0. each with given E and A. Devolatilisation of small samples of dried sewage sludge in a thermogravimetric experiment at three heating rates.8 0. (2) seven ﬁrst-order reactions. from the results of thermogravimetric measurements of the mass lost during its pyrolysis.3 0.A. This approach has been attempted before (e. imaginary or real. In all these cases. (a) The cumulative distribution of activation energies produced by the algorithm for the pyrolysis of dried sewage sludge. dimensionless . / Chemical Engineering Science 61 (2006) 2339 – 2348 5 1 x 10-3 Cumulative fraction of mass (-) 4 3 20 K min-1 2 10 K min-1 1 (a) 0. The method has been tested on results from both real and simulated thermogravimetric experiments. at a variety of heating rates were accurately predicted. (3) a continuous. using kinetic parameters deduced from the experimental results at heating rates of 20 and 40 K min−1 .1 0 200 300 400 500 Temperature (°C) 600 700 0 800 (b) 18 this stage it can be seen that the algorithm is able to handle real results from a fairly complex fuel. Conclusions A new algorithm has been presented for characterising the kinetics of thermal decomposition of a solid fuel. Burnham et al. The algorithm inverts the distributed activation energy (DAE) problem to derive the distribution of activation energies of the reactions undergone by the sample. K s−1 rate of heating (dT /dt) is experiments 1 and 2. dimensionless initial value of fi . kJ mol−1 activation energy.. log10 (A) as a function of the activation energy. 2005) are continuous lines. K s−1 activation energy for reaction i.5 0. from which the results of thermogravimetric experiments.. f fi fi. The area of each data point in (b) is proportional to the mass allocated to the reaction. 7. kJ mol−1 mass fraction of material. The simulated experiments used a hypothetical fuel whose decomposition was governed by 14 100 150 200 250 300 Activation energy.S.g. which ﬁrst calculates a set of plausible reactions. kJ mol−1 activation energy at which (E) = 0.0 f pre-exponential factor. 1987) The method presented here makes use of this approach. This differs from previous attempts to invert the DAE problem in that there is assumed to be only a ﬁnite number of reactions occurring.58.0 for all reactions. dimensionless a vector containing the values of fi. Scott et al. the algorithm gave values of E and A. Gaussian distribution of activation energies. (b) shows the value of the logarithm of pre-exponential factor. B2 (1) a single ﬁrst-order reaction. 8. 16 Log10 (A) Fig. Ei E E∗ In addition. Experimental results (Scott et al. but differs in that there is an initial stage.2 0. 12 10 8 4.6 0.9 40 K min-1 Normalised rate of mass loss (s-1) 2347 0. in units of s−1 . followed by a linear ﬁt to assign the contributions from each reaction. the algorithm was applied to experimental results for the thermogravimetric analysis of the pyrolysis of dried sewage sludge. dimensionless mass fraction of material associated with reaction i. s−1 pre-exponential factor for reaction i. though this number may be large enough to approximate a continuous distribution of activation energies.7 0. s−1 rate of heating (dT /dt). circles show the predictions from the algorithm. E (kJ mol-1) 350 Fig. as shown. Notation A Ai B B1 .

D. Global kinetic analysis of complex materials. B1 and B2 ) at which a speciﬁed conversion is reached. J. 235–261.K. Fuel. Yu. 452–458. T. 1987. K initial temperature. kg a vector which contains the mass of fuel remaining at different points in time.1016/j.. Energy and fuels 15. 1976.. Wrenn. 1519–1525.. University of Cambridge. R. M.dimensionless the value of i (t) for reaction i (a function t −Ei of time) = exp −Ai 0 exp RT (t) dt . Hayhurst..2005. Hayhurst. G..A. M.. 2001. Bassilakis. 359–367.L. T. H.S. 2005. kg ideal gas constant..I. j are given by i (tj )..E. Coal devolatilisation and hydrogasiﬁcation. Journal 22. Industrial Engineering and Chemical Research 34.fuel. 703–717. kg mol kJ−1 initial value of m(E). Maki. s temperature. A. A comparison of different methods for predicting coal devolatilisation kinetics. . Smith. Q.. doi: 10. Burnham. Energy and Fuels 1. McElwain. Davidson. Dennis. Comparison of methods for measuring kerogen pyrolysis rates and ﬁtting kinetic parameters.. A biomass pyrolysis submodel for CFD applications. dimensionless Acknowledgements The authors are grateful for the support of the Engineering and Physical Sciences Research Council (GR/R21547) in the United Kingdom. Thermogravimetric analysis of petroleum asphaltenes along with estimation of average chemical structure by nuclear magnetic resonance spectroscopy. Journal of Analytical Application in Pyrolysis 66. K dummy variable for integration in Eq. McGuinness.. Rostami. A. in press. Burnham. A simple method for estimating f (E) and k(E) in the distributed activation energy model. Braun. X.. J. 2003. H. (6).S. J. Thermogravimetric measurements of the kinetics of pyrolysis of dried sewage sludge. 685–701.. Energy and Fuels 12. / Chemical Engineering Science 61 (2006) 2339 – 2348 E = 0 g(E) dE.. 208–221. T T0 T1 . 2004.). A.. 2003. Donskoi..A.2348 F (E) g(E) i m(E) m0 (E) M M0 M Mv Mv0 R t t0 . S. Rubiera. Journal of Analytical and Applied Pyrolysis 58–59. Gregg.L. Does a large coal particle in a hot ﬂuidised bed lose its volatile matter according to the shrinking core model? Combustion and Flame 139... Chen.. Dong. Wiley. t2 . Thermochemica Acta 427. M. Shimada. kg initial mass of fuel.. kg Greek letters i t −E = exp −A(E) 0 exp RT di(t) dt . F. kg mol kJ−1 mass of fuel. 864–869...R. Miura. D. Miura. Hajalgol. Energy and Fuels 9. Fuel 41. E.S. Chemistry of Coal Utilisation. 665–785 (second supplementary volume). 1995.J.J. Please. Analysis of pyrolysis reactions of various coals including Argonne premium coals using a new distributed activation energy model. Pis.N. 629–636. K.11. (Ed. Arenillas. kJ mol−1 mass fraction of sample which is inert. 1995. Anthony. 1981.A. 625–655. Energy and Fuels 13 (1). W. 1998. 302–307. A. Combustion and Flame 122. Approximations to the distributed activation energy model for the pyrolysis of coal. K temperatures (for experiments and at a constant rates of heating.E.L. 107–117.. D. Chern.. J. Modeling the evolution of volatile species during tobacco pyrolysis.. 264–274. Minami. dimensionless mass density function such that m(E) dE= mass of material with activation energy between E and E + dE. Fundamentals of coal pyrolysis and hydrogasiﬁcation.L...L. dimensionless yield of volatiles. K. A. Braun. 972–977. pp. t1 . R. T2 u w V S.003.. W. Analysis of chemical reaction kinetics using a distribution of activation energies and simpler models. K. Scott. Burnham.P. Fuel 83. Scott et al. 2001. Mae. Wojtowicz. 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 kJ−1 reaction number. 1999. References Antal..K. Takatsun. K. J.. 2000. Miura.. New York.B..A.F.M. M.. A. 2005.N.. M. K. J. Varhegyi.K.R.. Miura..M. A. R. C. R. Q.. 2004.. . A.. In: Elliot. Lei. 1997... 1962. kJ mol−1 K −1 time.W. Pitt.. Fang. A.. Maki. A.B. Cellulose pyrolysis kinetics revisited.S. kg initial mass of volatile matter. Optimisation of coal pyrolysis models. S. Pevida. Y. 153–161. Braun. Combustion and Flame 133.A.. 2–22... Howard.B. We would also like to acknowledge the assistance of Mr Robert Cornell at the Department of Materials Science and Metallurgy. 149–153. .. Analysis of formation rates of sulfur containing gases during the pyrolysis of various coals. Howard.J. A new and simple method to estimate f (E) and k0 (E) in the distributed activation energy model from three sets of experimental data.. Samoun. Anglian Water Plc and EMC Environmental Engineering LTD... mensionless a matrix whose elements i. . McElwain.J. s times at which the mass of fuel is measured. R. G. t3 . The Kinetics of the evolution of volatile products from coal. Carangelo. Energy and Fuels 1. Energy and Fuels 11. 1987. M. kg mass of volatiles. C.Ch.

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