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Department of Chemical Engineering and Technology, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden
Department of Fiber and Polymer Technology, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden
h i g h l i g h t s
We derive a model-free rate expression using isoconversional principles.
Thermal and kinetic analysis revealed inuence of initial sample mass.
Derived kinetics, based on dynamic data, can model isothermal cellulose pyrolysis.
a r t i c l e
i n f o
Article history:
Received 22 September 2014
Received in revised form 21 November 2014
Accepted 24 November 2014
Available online 4 December 2014
Keywords:
Model-free
Isoconversional
Kinetics
Thermogravimetric analysis
Pyrolysis
Cellulose
a b s t r a c t
We explore the possibility to derive a completely model-free rate expression using isoconversional
methods. The Friedman differential method (Friedman, 1964) and the incremental integral method by
Vyazovkin (2001) were both extended to allow for an estimation of not only the apparent activation
energy but also the effective kinetic prefactor, dened as the product of the pre-exponential factor and
the conversion function. Analyzing experimental thermogravimetric data for the pyrolytic decomposition
of microcrystalline cellulose, measured at six different heating rates and three different initial sample
masses (1.510 mg), revealed the presence of secondary char forming reactions and thermal lag, both
increasing with increased sample mass. Conditioning of the temperature function enables extraction of
more reliable prefactors and we found that the derived kinetic parameters show weak dependence on
initial sample mass. Finally, by successful modeling of quasi-isothermal experimental curves, we show
that the discrete rate expression estimated from linear heating rate experiments enables modeling of
the thermal decomposition rate without any assumptions regarding the chemical process present. These
ndings can facilitate the design and optimization of industrial isothermal biomass fed reactors.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
The threat of global warming and decreasing fossil fuel supplies
have paved the way for increased utilization of biomass as a feedstock for chemical production and thermochemical conversion
processes. For environmental and economic reasons, such processes need to be energy efcient and selective, something that
can be achieved partly through modeling of the reaction kinetics.
As cellulose is one of the main components in agricultural and
forestry biomass its pyrolysis kinetics has been systematically
studied for more than half a century [1]. In a majority of these
studies, the kinetic triplet, i.e. the activation energy, the preexponential factor and the conversion function (also called kinetic
model) has been completed through so-called model-tting
Corresponding author. Tel.: +46 70 759 54 34.
E-mail address: rosana@kth.se (R. Moriana).
http://dx.doi.org/10.1016/j.fuel.2014.11.079
0016-2361/ 2014 Elsevier Ltd. All rights reserved.
439
at
m1 mt
;
m1 m2
440
3. Isoconversional analysis
3.1. Isoconversional methods
Isoconversional methods are based on the isoconversional principle stating that, at a certain extent of conversion, the rate of
decomposition is uniquely determined by the current sample
temperature.
The single-step approximation is the simplest model following
this principle:
da
kTtf a
dt
Ea
;
kT A exp
RT
c0a Af a
Da c0a Ji Ea ;
where
J i Ea
r i;a c0a exp
Ea
;
RT i;a t
Fig. 1. Schematic of the evolution of conversion at two heating rates b1 and b2 , and
the quantities used in the isoconversional methods (see text for details).
t i;a
t i;aDa
Ea
dt;
exp
RT i t
UEa
n X
n
X
J Ea
i
i1 ji
Jj Ea
where n is the number of experiments. Having found Ea from minimizing Eq. (8), we can recompute the J i s, which allows for extracting the prefactor c0a using:
E a i;
c0a Da=hJ i b
where hJi b
E a i is the average of Ji b
E a evaluated at the optimized
activation energy b
E a . Details on the implementation of both methods are given below.
3.2. Error estimation and conditioning
Estimation of pyrolysis kinetics is typically based on a large set
of experimental data where the extracted parameters represent
the best t of the underlying model to the data. To get an idea
of the quality of this best t and the adequacy of the proposed
model, next to visual inspection of the tted data, analysis of the
uncertainty of the estimated parameters is crucial. In this section,
we rst discuss how to estimate the uncertainty in the integral
method of Vyazovkin and thereafter we show how to condition
the problem in order to reduce the uncertainty. The latter strategy
is also applicable to the differential method, discussed at the end of
this section.
The uncertainty estimation for the apparent activation energy
derived with the integral method was addressed in a paper by
Vyazovkin and Wight [29]. Although the method applied in this
work is different from that in [29], both methods use the same
starting criteria. This starting criteria, i.e. the isoconversional principle, states that for a given conversion interval, independent on
heating rate, the time integral J i should be equal for all experimental curves. The variation in the J i s, evaluated with the optimized
E a , can therefore be seen as the error (or
activation energy, b
dJ i J i hJ i i:
10
dJ i X i dEa ;
11
dEa
q
1
dJ 2 X T X
12
where dJ2 is the variance of the dJi s, and X is the vector containing
X i . From the error in the activation energy given in Eq. (12) we can
proceed and deduce the error in the effective prefactor. The error in
b
E a propagates to the estimation of the prefactor c0a , whose error is:
dc0a
Da
hJ i i2
dJ:
13
dc0a dEa
;
c0a
RT a
14
Ea 1 1
;
kT kT 0 exp
R T T0
15
where kT 0 is the rate constant at a reference temperature T 0 chosen within the range of interest. In the use of kinetic data, kT 0
takes on a similar role as the pre-exponential factor A while the
treatment of its uncertainty is substantially simplied. To illustrate
this, let us repeat the derivation from above by using Eq. (15)
instead of Eq. (3):
Substituting Eq. (15) into Eq. (2) and repeating some of the previous steps will lead to slightly different expressions. In particular,
instead of Eq. (6), the starting equation for the integral method
becomes:
!
b
Ea
Da ca exp
J;
RT 0 i
16
ca kT 0 f a;
17
!
b
Ea
Da
:
ca
exp
hJ i i
RT 0
18
441
where dEa is the error in the activation energy given by Eq. (12).
Eq. (19) is the actual relation hereafter used for estimating the error
in ca in the integral method. Applying the same order of magnitude
approximation that leads to Eq. (14), the above simplies to:
dca dEa 1
1
:
ca
R Ta T0
20
Ea 1
1
ri;a ca exp
;
R T i;a T 0
21
which is equivalently solved using a least-square solver, which provides estimated values for the two unknowns ca and Ea . The errors
in these two parameters are obtained from the square root of the
diagonal elements of the covariance matrix [31].
3.3. Reconstruction of at
The extracted kinetic data is validated by reconstructing the
extent of conversion from the model equations. Reconstruction of
at is readily done by integrating Eq. (2) with the constituting
functions ca and Ea taken as piecewise constant functions, as determined by kinetic analysis. The initial condition to Eq. (2) is taken as
the rst value of a for which the kinetic analysis was performed
minus the increment Da used in the integral method, and the time
at which this conversion is achieved. For reconstructing runs with
a linear heating rate b, the temperature in Eq. (2) is simply
Tt T t0 bt, while for isothermal runs Tt T iso .
3.4. Generalized master plots
Master plots are applied in this study to enable an independent
comparison of the methodology presented in this work. Generalized master plots are chosen over the traditional master plots
since, in the case of non-isothermal data, the former enable us to
select a suitable conversion function from one single experimental
curve [27].
The criterion to use the generalized master plots is the same as
for traditional master plots, i.e. we assume that one single conversion function can describe the whole process [2]. This means that
we have to select one apparent activation energy, E0 , to represent
the whole conversion process. If the derived apparent kinetic
parameters show a signicant dependence on conversion then
master plots are not applicable [2].
Two different types of normalized generalized master plots are
used in this work, i.e. the differential form and the integral form
[27]. These two plots complement each other by creating distinguishable curves in the range a < 0:5 and a > 0:5, respectively.
The experimental master plots are compared against three theoretical conversion functions: the rst order model (F1) [27], a random
nucleation and growth model (Am, m = 2) [27], as well as the random scission model (L2), published recently [15]. All the applied
equations related to master plots are found in the Supplementary
Material.
3.5. Implementation
dca
hX i i
1
;
dEa
hJ i i RT 0
ca
19
1.0
= 15 Kmin1
m(T )/m1
0.8
0.6
= 3 Kmin1
0.2
0.0
500
550
615
610
605
600
595
590
585
580
3 Kmin1
15 Kmin1
T /K
2
10
12
14
16
/Kmin1
Fig. 3. Mean peak temperatures plotted as a function of heating rate for sample
mass 1.6 mg (squares), 4.0 mg (circles) and 9.9 mg (triangles). Bars indicate
standard deviation in peak temperatures. Inset: Mass loss rate as a function of
sample temperature. Rate curves are chosen arbitrary among the repeated runs. A
SavitskyGolay lter was used to smooth the rate curves to increase visibility.
0.4
620
dm
/mgK1
dT
Tpeak /K
442
600
650
700
750
800
T /K
Fig. 2. Normalized sample mass as a function of sample temperature for two of the
used heating rates. Three different initial sample masses, m1 , (from bottom to top):
1.6 (blue), 4.0 (red) and 9.9 mg (green) are plotted. The plotted curves were chosen
arbitrary among the repeated runs. (For interpretation of the references to color in
this gure legend, the reader is referred to the web version of this article.)
rate and sample mass, apart from some variations at lower heating
rates: For a heating rate of 3 K/min, the difference in peak temperature between the highest and lowest mass is ca. 2 K, while at
15 K/min, the difference is ca. 7 K. This increase reects the thermal
lag, i.e. the delay in temperature due to nite heat capacity and
heat (and mass) transfer limitations in the sample [9]. A common
strategy to avoid such effects is to reduce the sample mass until
the peak temperature does not vary with initial sample mass.
Reducing the sample mass is meaningful only as long as the noise
in the recorded signal is low enough to allow the reduced sample
mass to be measured accurately. In this study, a balance noise of
2 lg hindered us from decreasing the initial sample mass below
1.6 mg. For this initial sample mass the nal mass was 1664 lg
(14% in Fig. 4a), resulting in a maximum noise in the signal of
10%. This must be considered an upper limit of what we can
accept.
The presence of thermal lag was investigated through a series of
additional tests at 15 K/min, including a fourth sample mass of
2.7 mg, see Fig. S2 in the Supplementary Material. These tests support the trend seen in Fig. 3, namely the peak temperatures
increase with increased initial sample mass for all investigated
masses. This indicates that thermal lag cannot be ruled out completely for the lowest sample mass. Note also that, due to the
low temperature accuracy of the instrument, the small differences
in thermal lag resulting from similar masses are difcult to measure accurately.
Returning our attention to Fig. 2, we notice that the nal masses
increase with increased initial sample mass. This behavior, also
reported in earlier studies [9,12,13,33], may hint to a secondary
solidvapor reaction, resulting in increased char yield [4,12].
Secondary solidvapor reactions are favored by increased sample
thickness, which increases the residence time of the vapors in
the solid matrix, giving molecules increased possibility to react.
Fig. 4 shows the char yields in each of our experiments, plotted
versus the initial sample mass, and versus heating rate. A clear correlation between end mass and sample mass is revealed, Fig. 4a,
while the data shows no consistent trend between end mass and
heating rate among the whole dataset, Fig. 4b: the discrepancy in
char yield for a given heating rate is in some cases larger than
the difference observed between different heating rates. These
observations are in agreement with the results of Vrhegyi et al.
[34], justifying the use of isoconversional analysis at these process
conditions, since kinetics is not a function of the temperature
m2 /m1 100
6
5
4
2 K/min
3 K/min
5 K/min
7 K/min
10 K/min
15 K/min
3
2
1
0
10
m1 /mg
(a)
8
7
m2 /m1 100
6
5
4
3
2
1
0
10
12
443
14
16
/Kmin1
(b)
Fig. 4. Char yield, as a function of initial dry mass m1 (a) and heating rate b (b). In
(a) different heating rates are indicated by different markers. In (b) initial sample
mass 1.6 mg (squares), 4.0 mg (circles) and 9.9 mg (triangles).
program [35]. From Fig. 4a, we also notice that the experiments
with the lowest sample mass are subject to stronger variations in
char yield compared to the experiments performed with higher
masses. This behavior may be a result of the balance resolution
or inhomogeneities in the cellulose sample, both of probable relevance at such low sample masses.
Table 1 compares the peak temperatures shown in Fig. 3 with
peak temperatures reported in the literature, including also cellulose type, char yields m2 =m1 , and some relevant experimental
conditions (initial sample mass m1 , heating rate b, end temperature
T 2 and volumetric ow rate m_ ). References included in Table 1 were
selected based on two criteria: (i) similarity to our study and (ii)
availability of data. The peak temperature reported by Grnli
et al. [6] is very similar to those found in this study. In the four
other studies the peak temperatures are signicantly higher,
despite the similar sample mass and heating rates. This discrepancy could be due to thermal gradients (internal or external) or
more thermally stable samples due to e.g. larger particle size
(which would decrease the reactivity in a nucleation type process
[14]), higher crystallinity or higher degree of polymerization [37].
Note also that the peak temperature and char yield, reported by
Grnli et al. [6], are mean values derived from a round-robin study
including eight laboratories.
444
Table 1
Mean peak temperatures and char yields, both with standard deviations, for pyrolysis of microcrystalline cellulose. Values in parenthesis correspond to heating rates in
parenthesis.
Ref.
Material
m1 /mg
m2
m1
T peak /K
100
T 2 /K
m_ /mL min1
b/K min1
2 (2.1)
3 (4)
7 (8)
10
15 (16)
This
Sigmacell
1.6 5 %
4.0 3 %
9.9 2 %
585 0.4
586 0.9
591 0.3
590 0.1
593 0.6
597 0.1
598 0.2
601 0.4
601 0.1
603 0.3
606 0.0
607 0.5
610 0.9
611 0.3
612 0.1
616 0.7
619 0.5
2.6 0.8
4.2 0.6
6.8 0.3
1023
1023
1023
70
[19]
[6]
[36]
[13]
[7]
Avicel PH 105
Avicel PH 105
Quimsul cellulose
Whatman CC31
Acros cellulose
23
4.1 1.3
5
5.84
69
(600)
(603 0.3)
607 0.9
600 5
622
(617 0.2)
621 0.2
(629 0.2)
624
3.024.05
7.2 2.4
11.8
14.21
5.1
873
873
973
1073
20
100
1500
100
280
260
E /kJmol1
240
220
200
180
160
140
120
100
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
m1 /mg
1.6 5%
223 12a
216 0.25a
4.0 3%
178 3.0
183 0.12
9.9 2%
172.5 1.8
178.4 0.12
445
0.5
2.5
0.4
2.0
f ()/f (0.5)
c /min1
0.3
0.2
0.1
0.0
1.5
1.0
0.5
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.0
0.9
0.2
0.8
(a)
g()/g(0.5)
0.6
sample mass. This plateau is more pronounced for the intermediate sample mass than for the highest mass, where the trend is
smoother.
0.4
0
0.0
0.2
0.4
0.6
0.8
1.0
(b)
Fig. 7. Normalized experimental and theoretical master plots based on (a) the
differential form of the generalized kinetic equation and (b) the integral form of the
generalized kinetic equation. Solid lines: experimental curves at 3 K/min and
1.6 mg (blue), 4.0 mg (red) and 9.9 mg (green). Theoretical curves are F1 (dashed),
L2 (dotted) and A2 (dash-dotted). E0 : 219 kJ/mol (1.6 mg), 180 kJ/mol (4.0 mg) and
175 kJ/mol (9.9 mg). (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of this article.)
conversion function (or functions) as the kinetic information it carries is contained within the effective prefactor, obtained in discrete
form. This is illustrated in the next section.
4.3. Reconstructed and modeled conversion under dynamic and quasiisothermal conditions
To validate the derived kinetic parameters, the evolution of at
under both dynamic and isothermal conditions was reconstructed
and compared to experimental data. Fig. 8 shows reconstructed
dynamic experiments for three heating rates. The reconstructed
curves are based on kinetic data obtained from the intermediate
sample mass and compared to experiments with the same initial
sample mass. The agreement is generally good and both of the
kinetic methods applied in this work lead to satisfactory results.
Similar results were found when reconstructing data for the low
and high sample masses; the low mass gave slightly worse t
while the agreement was somewhat better for the highest sample
mass (data not shown).
Fig. 9 shows the quasi-isothermal extent of conversion (lines)
together with the modeled conversion (symbols) using the kinetic
446
data obtained from dynamic experiments. The experimental conversion is obtained by using the nal mass from the mass loss
curves shown in the inset of Fig. 9. From this inset, it is visible that
the end mass for the high temperature isotherm levels out at 9%. For
the low temperature isotherm the sample mass exhibits a relatively
slow decay, not reaching a plateau within the duration of the experiment. This leaves us with some uncertainty regarding the end mass
that would be achieved for the given isotherm and sufciently long
time. By visual inspection we estimate the end mass for the low isotherm to be 15%. Additionally, the well-known issue with isothermal experiments arose, i.e. non-negligible conversion occurred
during the dynamic segment preceding the isothermal stage. For
the 553-K isotherm, a conversion of 5% was achieved before the isotherm was reached, while for the 573-K isotherm 18% conversion
was reached. In the modeling this non-isothermal step was ignored.
Despite this, in general, the t is satisfactory.
For both of the isotherms, the modeled curves based on intermediate (circles) and the high (triangles) sample mass data, show
a clearly better t compared to kinetic data obtained from the
1.0
0.8
0.6
0.4
0.2
0.0
520
540
560
580
600
620
640
660
680
T /K
Fig. 8. Reconstructed conversion for dynamic experiments at heating rates (from
left to right): 3, 7 and 15 K/min. Solid lines: experimental 4.0 mg sample mass;
symbols: reconstructed data, differential (closed symbols) and integral method
(open symbols). Experimental curves were chosen arbitrary among the repeated
runs.
573 K
553 K
1.0
0.8
1.0
m(t)/m1
0.6
0.4
0.2
0.8
0.6
553 K
0.4
573 K
0.2
0.0
50
0.0
0
100
200
300
400
500
t/min
Fig. 9. Conversion for quasi-isothermal curves as a function of time. Solid thick
lines: experiments. Symbols: modeled data with kinetic parameters derived from
sample mass 1.6 mg (squares), 4.0 mg (circles) and 9.9 mg (triangles). Closed
symbols: differential method, open symbols: integral method. Inset: experimental
mass loss curves for the two isotherms. In both panels, time zero is at 10%
conversion.
Acknowledgements
This work was carried out within the Swedish Gasication
Centre consortium. Funding from the Swedish Energy Agency and
the academic and industrial partners is gratefully acknowledged.
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