Energy 207 (2020) 118191

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Energy
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Pyrolysis kinetics of short rotation coppice poplar biomass

Filipe Rego a, b, Ana P. Soares Dias b, *, Miguel Casquilho b, Fa

tima C. Rosa b,
b, c
Abel Rodrigues
a
Aston University, Birmingham, B4 7ET, UK (current)
b
LAETA, IDMEC, CERENA, MARETEC, Instituto Superior T

ecnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisboa, Portugal
c
INIAV, Av. República, 2780-157, Oeiras, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Woody biomass can be converted into green fuels by advanced conversion technologies such as gasifi-
Received 9 May 2020 cation and pyrolysis. Due to the complexity of woody biomass, the thermochemical decomposition
Received in revised form mechanisms are complex and the knowledge of pyrolysis kinetics is mandatory for optimization of the
17 June 2020
process and reactor design of commercial scale biorefineries. Pyrolysis kinetics of short rotation coppice
Accepted 19 June 2020
Available online 29 June 2020
(SRC) poplar biomass (nine different clones) was studied using non-isothermal thermogravimetry. By
using differential thermogravimetry data, obtained for heating rates of 10e50 K/min, the Kissinger
model-free methodology showed activation energies in the range 108e320 kJ/mol, similar to those re-
Keywords:
SRC poplar
ported in the literature for cellulose pyrolysis. Isoconversional approaches of Flynn-Wall-Ozawa (FWO)
Lignocellulosic biomass and Kissinger-Akahira-Sunose (KAS) obtained similar values of activation energy (81e301 kJ/mol and 90
Thermogravimetry e306 kJ/mol, respectively. The kinetics parameters obtained by the FWO and KAS methods were higher
Pyrolysis kinetics than data reported in the literature for other biomasses, and a correlation between activation energy and
Non-isothermal methods the lignin content of the biomass samples was found. The pyrolysis activation energy seems to have no
Fixed bed pyrolysis significant effect on the pyrolysis product yields, probably because, under the tested conditions (fixed
bed reactor, 773 K), pyrolysis was controlled by mass and/or heat transfer limitations instead of kinetics
control.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction energy demand [4].

The worldwide increase in energy demand based on fossil fuels
has led to an increase in emissions and atmospheric accumulation
of greenhouse effect gases. To mitigate this problem, governments
and organizations are making common efforts for a transition to a
green, carbon neutral, sustainable economy [1].
Since the dependence on a single energy source creates socio-
economic stresses, and as it will be hard to find another single
source capable of providing all the necessary energy, multiple en-
ergy sources will be needed in the future, and biofuels will
constitute an important part of the future energy supply [2].
Biomass has an interesting characteristic of having a short
regeneration cycle, which should give biomass a major role in the
future renewable energy mix [3]. Projections show that by 2050
biofuels could satisfy around one-third of worldwide primary
* Corresponding author.
E-mail address: apsoares@tecnico.ulisboa.pt (A.P. Soares Dias).
An option for biomass production is the woody short rotation
coppice (SRC) intensively managed cultivations of forest species,
e.g., poplar or willow, with harvesting in short periods ranging
between 2 and 5 years under productive lifecycles of around 20
years. The implementation of these cultivations is now carried out
with commercial clones of the several species, which are subjected
to genetic selection and screening for enhancing management
variables such as biomass productivity, heating values or disease
resistance [5].
Lignocellulosic biomass can be converted into biofuels (second
generation) using biochemical and thermochemical routes. The
thermochemical conversion of biomass can proceed through three
different pathways: combustion, gasification, and pyrolysis [6].
Pyrolysis is the thermal decomposition of biomass occurring in
an inert atmosphere (absence of oxygen). The products of biomass
pyrolysis include char, bio-oil and gases (e.g., methane, hydrogen,
carbon monoxide, carbon dioxide). A relevant advantage of pyrol-
ysis lies in the fact that it can be performed at a relatively low scale
and in remote locations, where biomass is available, which

https://doi.org/10.1016/j.energy.2020.118191
0360-5442/© 2020 Elsevier Ltd. All rights reserved.
2 F. Rego et al. / Energy 207 (2020) 118191

enhances the energy density of the biomass resource and reduces  

transport and handling costs [7]. Another advantage of pyrolysis Ea
kðTÞ ¼ A:exp  (3)
comparing to the other thermochemical conversion routes is that RT
ash is not one of the products. The alkali metals present in the ash,
which can be present in significant amounts in biomass, are known where Ea is the activation energy, expressed in kJ/mol, T is the ab-
to cause deposition problems such as slagging, corrosion and solute temperature (K), R is the ideal gas constant and A is the pre-
fouling in the lines and equipment used for combustion and gasi- exponential factor (s1). By combining Eq. (2) and Eq. (3), Eq. (4) is
fication [8]. obtained:
Pyrolysis proceeds via a very complex set of competitive and  
concurrent reactions and thus the exact mechanism of pyrolysis da Ea
¼ A:exp  f ðaÞ (4)
remains under debate [9]. Moreover, the variability of the ligno- dt RT
cellulosic composition of woody biomass increases the complexity For non-isothermal TGA experiments, and assuming a linear
of the pyrolysis mechanism. Some simplified mechanisms have heating rate b as dT/dt, Eq. (4) is arranged into Eq. (5):
been proposed, with the simplest one involving a single step
 
decomposition of solid biomass into solid and gaseous (condens- da A Ea
able and non-condensable) products [10], where k(T) is the tem- ¼ exp  f ðaÞ (5)
dT b RT
perature dependent kinetic constant:
According to Zsako
[19] the analytical form of the function f(a)
depends on the thermal decomposition mechanism. Several
kðTÞ
biomassðsolidÞ










!volatilesðgases þ tarÞ mathematical expressions of f(a) have been developed, based on
the assumption of a certain reaction order and a reaction model,
þ charðsolid residueÞ such as nucleation, Mampel power law, diffusional autocatalytic
and contracting geometry [20]. Some of the published models are
Understanding the reaction mechanism of biomass pyrolysis
summarized in Table 1 [21e23].
will facilitate the process optimization and reactor design of com-
Kinetics data from thermogravimetry can be analyzed by the
mercial scale biorefineries [11,12].
integration of Eq. (5). Such integration can be accomplished using
Thermogravimetric analysis (TGA) under inert gas flow is
thermal decomposition reaction models, or model-free/
commonly used to study biomass pyrolysis kinetics, and a sub-
isoconversional methods [21,24]. Recently, Osman et al. [16]
stantial number of published papers on the subject can be found in
stated that model free isoconversional kinetics analysis methods
the literature [13e15]. Recently, Osman et al. [16] underlined the
are simpler than model fitting methods and that those methods
relevance of kinetics studies in biomass for energy conversion
minimize the errors associated with the incorrect choice of a kinetic
processes, using thermal analysis techniques such as differential
model. An incorrect choice of kinetic model can lead to an erro-
scanning calorimetry (DSC) and differential thermal analysis (DTA).
neous estimation of kinetic parameters [25].
Silva et al. [17] studied the energy potential of agricultural waste
The Kissinger, model-free method is the most widely used
biomasses using thermogravimetric pyrolysis kinetics data.
method to compute kinetics parameters from non-isothermal
The thermal decomposition by TGA in small biomass particles is
thermogravimetric kinetics data. The method was deduced for
controlled mainly by chemical kinetics without significant influ-
monomolecular solids [26], method allows to obtain the activation
ence of heat and mass transfer processes. The chemical reactions in
energy from a series of experiments at different heating rates ac-
the thermal degradation of biomass are heterogeneous and must be
cording to Eq. (6) [27]:
characterized through conversion a [18]. Normalized conversion
(Eq. (1)) can be calculated for each point of thermogravimetric !  
analysis: b AR Ea
Ln 2
¼ Ln  (6)
Tm Ea RTm

mo  m
a¼ (1) where Tm is the temperature corresponding to the maximum rate of
mo  mf thermal degradation. Although biomass is not a monomolecular
material, the Kissinger method is widely used for the determina-
The variable m0 corresponds to the initial weight of the sample,
tion of pyrolysis kinetics. Since the temperature corresponding to
m corresponds to each point of analysis and mf is the final weight of
the maximum rate of thermal decomposition is used, the activation
the sample.
energy estimated by this method can give an estimation of the
The reaction progress with time can be followed using a con-
version function, f(a), which characterizes the reaction mechanism.
Generally, the kinetic methods used in thermal analysis consider Table 1
the rate of conversion as a function of the variables temperature Mathematical expressions for f(a) (adapted from Ref. [21e23]).
and conversion. For the quantitative analysis of TGA data, the Model f ðaÞ
conversion rate constant of reaction k(T) for biomass from solid
Mampel power law (n ¼ 1/4; 1/3; 1/2; 3/2) 1 n
state to char and volatiles, considered as the sum of gases and tars, a
n
under a one-step model, can be defined as in Eq. (2): Random nucleation with one nucleus per particle ð1  aÞ
two nuclei per particle ð1  aÞ2
three nuclei per particle ð1  aÞ3
da Diffusional, one dimension 1 1
¼ kðTÞf ðaÞ (2) 2
a
dt
Diffusional, two dimensions ðLnð1  aÞÞ1
In Eq. (2), k(T) and f(a) reflect the dependence of the process rate Diffusional, three dimensions 3
ð1  aÞ2=3 ½1  ð1  aÞ1=3 1
on temperature and extent of conversion, respectively. The tem- 2
perature dependent function k(T) is usually expressed by the
Contracting sphere 3ð1  aÞ2=3

Arrhenius equation (Eq. (3)):

Contracting cylinder 2ð1  aÞ1=2
 F. Rego et al. / Energy 207 (2020) 118191 3

activation energy of the thermal degradation of cellulose [28]. Table 2

Two integral isoconversional non-isothermal methods Lignocellulosic composition of the poplar genotypes (assessed by thermogravimetry
[28]).
commonly used are the Flynn-Wall-Ozawa (FWO) and Kissinger-
Akahira-Sunose (KAS) [25]. The isoconversional principle states Genotype Sample acronym Hemicellulose Cellulose Lignin
that, for the same extension of conversion, the reaction rate is a (wt.%, dry basis)
function of temperature, allowing thereby that the evaluation of
AF2 AF2 26 50 23
the activation energy to be carried out without assuming or AF8 AF8 23 48 28
determining any particular form of reaction model. Isoconversional Bakan Bak 19 52 28
model-free methods can, therefore, be used for the analysis of Brandaris Bra 23 47 29
Ellert Ell 24 48 26
complex processes, where chemical reactions are occurring
Grimminge Gri 24 48 27
simultaneously. Under isoconversional methodologies, it is possible Hees Hee 23 50 26
to obtain kinetic parameters along a thermal degradation process. Skado Ska 20 49 30
Thus, estimates of Ea and A are carried out at a given ai, obtaining Wolterson Wol 24 48 27
thereby a profile of variation of these kinetic parameters with
conversion. For the FWO method, the representative equation is
(Eq. (7)): 30e70 mg of ground sample (<750 mm) were placed in a 200 mL
    alumina crucible. The effect of the sample mass on the TG results
  Ea;ai Aai Ea;ai was investigated using lower sample weights (<10 mg) in order to
Ln bj ¼  1:052 þ Ln  5:331 (7)
RTai RgðaiÞ discard heat and mass transfer limitations during thermal degra-
dation tests. No significant differences were found between ther-
The Kissinger-Akahira-Sunose (KAS) method for calculation of
mograms obtained from using different sample weights. During the
kinetic variables reflects a linear relationship between ln(bi/T2ai)
TG tests, the thermobalance oven was flushed with N2 (18 L/h) thus
and 1/Tai, as expressed by the following equation (Eq. (8)):
creating an inert atmosphere in the sample’s surroundings. TG data
! !
were collected from 303 K to 1373 K. The data acquisition of weight
bi Ea;ai Aai R
Ln ¼ þ Ln (8) loss of biomass samples was carried out at every 2.5 K, and the
T2ai RTai gðaiÞEa;ai
individual thermal runs lasted between approximately 20 and
The kinetic parameters obtained from isoconversional methods 110 min. The reproducibility of the thermogravimetry tests was
are adequate as initial guess values for complex multi-step parallel evaluated using five replicas of a biomass sample and one heating
reaction model (PRM) calculations for evaluation of the individual rate (30 K/min), as described in previous work [28].
pyrolytic process constants. TGA can also be used, for expeditious The kinetics parameters Ea (activation energy) and A (pre-
assessment of percent amounts of pseudo-components of bio- exponential factor) were computed through the Kissinger, Flynn-
masses, which can be for example input data for distributed acti- Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods.
vation energy models (DAEM) considered as an accurate and For the FWO and KAS methods, the considered values of conversion
reliable pseudo-mechanistic approach for biomass pyrolysis. ai ranged from 0.1 to 0.8, with intervals of 0.1. A first order reaction
Furthermore, results from model-free methods can be used in was used, with the conversion function f(a) being assumed as (1-a).
computational fluid dynamics for simulation of mass loss and en- For these methods, only linear correlations with R2 above 0.70 were
ergy balances in thermal devolatilization describing changes in the considered. In the thermal decomposition of the biomass, when the
structure of biomass. conversion values did not reach 0.8 (or even 0.7 in some cases), the
Within this entire context, it is beneficial to relate calculated corresponding points were not included in the FWO and KAS
kinetics parameters to the proportions of lignocellulosic com- methods.
pounds in the biomass, and also to the thermal decomposition of Pyrolysis experiments at 773 K were carried out in a fixed bed
those compounds through lab-scale pyrolysis experiments. The tubular pyrex reactor under N2 flow, as described elsewhere [29]
following sections report the analysis of pyrolysis kinetics of woody and with a scheme in Fig. 1. The reactor had an internal diameter of
biomass from short rotation coppice poplar. Nine different poplar 16 mm and a length of 150 mm. Each pyrolysis test was accom-
clones, harvested in Portugal and Belgium, were used for the plished using 10 g of ground biomass for each poplar genotype
evaluation of the effect of their lignocellulosic composition on the (granulometry < 750 mm). The reactor was filled with inert carbo-
pyrolysis kinetics. Kinetics parameters were estimated through rundum (particle size 0.5 mm) and heated using a circular electric
model-free, non-isothermal methods. The obtained parameters furnace equipped with a PID temperature controller.
were related to the lignocellulosic composition of the biomass and
to the pyrolysis product distribution (bio-oil, char and pyrogas)
3. Results and discussion
obtained in a fixed bed pyrolysis reactor.

In order to analyze the poplar biomass pyrolysis kinetics, the

2. Experimental
The pyrolysis kinetics analysis was performed on poplar
biomass from SRC energy crops grown in Portugal and Belgium. The
thermogravimetry tests were performed using ground samples of
nine poplar genotypes with similar lignocellulosic compositions,
determined in previous work [28] (Table 2). The lignocellulosic
compounds add up to 100 wt% with the ashes fraction, of around
1 wt%.
The thermograms were acquired on a Netzsch STA 490 PC
thermobalance with Proteus software (oven layout in Fig. 1) using
as heating rates from 10, 20, 30, 40, and 50 K/min. For each test,
thermograms were acquired for heating rates of 10e50 K/min. The
thermal degradation profiles were similar between the biomasses
from different poplar genotypes, which is a consequence of their
analogous lignocellulosic compositions (Table 2). The obtained
thermograms were similar to those reported in the literature for
poplar [27,30] and other lignocellulosic biomasses [10]. Fig. 2 shows
the thermogram for the Ellert genotype, and the corresponding
DTG curve, with the DTG temperature scale enlarged for improved
visualization of the differences in the weight loss rate peak for
different heating rates. All the thermograms were composed of a
first mass loss process, in the temperature range 300e450 K, which
is ascribed to the sample drying (moisture and adsorbed water).
4 F. Rego et al. / Energy 207 (2020) 118191
Fig. 1. Experimental layout of the thermobalance oven and fixed bed reactor used in the pyrolysis tests.
The second process, more pronounced than the first one, occurred
in the temperature range 450e650 K and corresponded to active
pyrolysis [31]. A third process, from 650 K to 800 K corresponded to
passive pyrolysis [32]. In the active pyrolysis zone, two processes,
around 580 K and 630 K, indicated the devolatilization of hemi-
celluloses and cellulose, respectively [28]. The degradation of lignin
occurs in a wider temperature range, which can be from 433 to
1073 K [33], and is included in both active and passive pyrolysis
zones. For increasing heating rates, the start and end of the
decomposition steps are shifted to higher temperatures, as well as
the maximum degradation rate. This effect is due to a higher degree
of heat transfer limitations with increasing heating rate, as seen by
other authors for poplar and other biomasses [12,27,31].
The thermobalance software was used to determine the
maximum pyrolysis rates and the correspondent temperature, in
order to compute the kinetics parameters according to the Kis-
singer method. The parameters of pyrolysis kinetics (activation
energy and pre-exponential factor) obtained by the Kissinger
method for all the poplar genotypes are displayed in Table 3, along
with the respective correlation coefficients (R2).
The activation energy obtained with Kissinger method averaged
for the nine genotypes was 207 kJ/mol, and the average pre-
exponential factor averaged 5.6  1025 s1. The lowest value of
activation energy was obtained for the genotype AF2, with also one
of the highest deviations from the average, for which the low cor-
relation coefficient (R2 ¼ 0.77) probably contributed to.
Overall, Ea values are in agreement with activation energy
values reported in the literature (195e286 kJ/mol) for cellulose
decomposition [34], which is the main component of the analyzed
biomass (Table 2). Also, the maximum decomposition rates in the
thermograms are mainly due to cellulose decomposition [28], and
the temperature corresponding to the maximum decomposition
rate is the parameter used for the Kissinger method, as aforemen-
tioned. The Kissinger method is, however, an oversimplification of
the pyrolysis process, and more detailed methods are required,
such as FWO and KAS [35].
Fig. 3 shows the Kissinger activation energy of biomass of each
SRC poplar clone, plotted against the respective lignin contents,
where a linear variation between the two properties was observed.
To the best of our knowledge, this is the first time that such a
relationship is established for biomasses of SRC poplar clones.
Regarding the cellulose and hemicellulose contents, no trend was
found between them and the activation energy determined by the
Kissinger method. Indeed, a trend of Ea with cellulose content
should be expected since this is the lignocellulosic component
mainly responsible for the DTG peaks. The observed correlation
between the Kissinger activation energies and the lignin contents
thus seems to indicate a synergistic effect between the lignocellu-
losic components of the poplar biomass during pyrolysis. In the
region corresponding to the DTG peak (maximum weight loss rate),
and thus to the temperature used for the Kissinger method, both
cellulose and lignin are decomposing (588e673 K) [33]. The liter-
ature indicates that individually, both cellulose and lignin present
relatively high values of activation energy, with the values
depending on the employed methods and the origin of the samples
[11,36,37]. Nevertheless, kinetics studies of the pyrolytic degrada-
tion of whole biomass from pine, SRC poplar, and others, using
DAEM methods, have determined higher activation energy values
for the Gaussian functions characterizing lignin degradation than
the ones corresponding to cellulose degradation [38e40]. Hence,
the effect of having more lignin decomposing at the same time as
cellulose causes an increase in the activation energy from the Kis-
singer method, since biomass pyrolysis can be described as the
lumped degradation of three pseudo-components: cellulose,
hemicellulose, and lignin [11,41]. Considering the woody biomass
morphology with lignin fibers reinforcing the cohesion of cellulose
and hemicellulose fibers [42], it seems reasonable that an increase
of the lignin content will improve the resistance of wood to thermal
degradation, thus increasing the pyrolysis activation energy.
However, more research in this field must be done to prove this
theory.
The biomasses from clones Ellert, Grimminge and, to a lesser
extent, Wolterson, showed deviances to the observed tendency,
insofar that their activation energies varied along a relatively large
 F. Rego et al. / Energy 207 (2020) 118191 5

Fig. 3. Activation energy (Ea) from the Kissinger method versus lignin content for each
poplar clone.

into a rubbery-to-liquid state which facilitates thermochemical

conversion [43,44]. Secondly, the observed deviations can also be
due to significant changes in the lignin-cellulose-hemicellulose
matrix in woody biomasses, pointed out by Murillo et al., related
with micro-spatial variability of the hydrogen bond network of
cellulose-hemicelluloses and the covalent bonds between hemi-
celluloses and lignin [45]. Furthermore, the pyrolysis of lignin is a
very complex process, insofar that, for example, a study from Jiang
et al. proposed a set of 11 reactional mechanisms, for five specific b-
O-4-type lignin dimers, consisting of nine concerted reactions and
two hemolytic reactions with energy potential barriers with values
ranging from as low as 51 kJ/mol up to higher than 500 kJ/mol [46].
Lastly, variability of the susceptibility of woody biomass to ther-
mochemical conversion can also arise from interactions between
atomic and molecular levels [41]. Indeed, atomic-level quantum
chemistry can provide activation energies, heat of adsorption or
heat capacities, with a wide range of variability, and these processes
Fig. 2. Thermal degradation profile e sample weight (top, in wt.%) and weight loss rate are input to molecular-level highly complex phenomena related
(bottom, in wt.%/min; temperature scale is enlarged) e of Ellert genotype at different
with chemical reactions and surface processes. This reactional
heating rates with maximum degradation rates and correspondent temperatures
(evaluated using the Proteus software). variability is extended to the wood anatomy domain, with, for
example, the migration of liquid intermediates from lignin into the
middle lamella in cell walls, or with the distinct accessibility of cell
Table 3 walls to pyrolytic radical chain reactions, pointed out by Samaniego
Kinetics parameters obtained with Kissinger method for biomass of each poplar et al. and by Kawamoto [44,47].
genotype.
Activation energy values with FWO isoconversional method
Genotype Ea (kJ/mol) A (s1) R2 were calculated from the slope of the linear correlation in Eq. (7),
AF2 108 1  109
0.77 and pre-exponential factor values were calculated from the inter-
AF8 203 5  1016 0.98 cept. The linear correlation obtained with the FWO method with
Bakan 233 2  1019 0.98 genotype Skado for each conversion can be seen in Fig. 4, as an
Brandaris 250 6  1020 0.92
example.
Ellert 204 1  1017 0.82
Grimminge 175 3  1014 0.94 The results of the FWO method for each genotype are shown in
Hees 190 6  1015 0.97 Table 4. The missing points are due to either a poor correlation
Skado 320 5  1026 0.86 coefficient or a conversion higher than 0.7. The average values of
Wolterson 182 8  1014 0.96 the kinetics parameters calculated with the FWO method for all
genotypes and for each conversion ranged between 80 and 301 kJ/
mol and 3  1010e5  1036 s1, for activation energies and pre-
range (175e204 kJ/mol), although the lignin proportions had low exponential factors, respectively.
variation (26e27 wt%). This could be due to operative and struc- The variation of activation energies with conversion, computed
tural factors inherent to biomass, which can act alone or by joint with the FWO method for each genotype, is presented in Fig. 5. This
interactions. Firstly, structural factors at a molecular scale related variation is representative of the evolution of the complex process
with a softening and plasticization of lignin, turning this polymer of biomass pyrolysis, with competitive and interdependent
6 F. Rego et al. / Energy 207 (2020) 118191

Fig. 4. Graphical application of FWO method for the poplar genotype Skado.

Fig. 5. Pyrolysis activation energy versus conversion computed using the FWO
method.
reactions.
The results for activation energy and pre-exponential factor
with the application of KAS method (Eq. (8)) for the 9 poplar clones
SRC biomass of Slopiecka et al.: activation energies of
are shown in Table 5. The linear correlations obtained for Skado
107.9e209.5 kJ/mol and 105.0e209.9 kJ/mol calculated with the
genotype as an example for the application of KAS method can be
FWO and KAS methods, respectively [27]. That study employed
visualized in Fig. 6. With the KAS method, the range of average
lower heating rates of 2, 5, 10, and 15 K/min, which shows the
values of activation energy and pre-exponential factor were,
flexibility of isoconversional methods for the estimation of pyrol-
respectively: 90e306 kJ/mol and 8  1010e2  1037 s1. The vari-
ysis kinetics parameters. With the clone Skado, activation energies
ation of activation energies (obtained with KAS method) with
averaged 306 kJ/mol and ranged between 135 and 448 kJ/mol. As a
biomass conversion is shown in Fig. 7 with a graphical represen-
comparison with these values, e.g., Maryandyshev et al. [48] re-
tation for all the poplar genotypes.
ported ranges of Ea of 156e207 kJ/mol, 205e267 kJ/mol and
Overall, comparing the results of the KAS method (Table 4) with
202e239 kJ/mol for pine, spruce and birch, respectively.
the ones from the FWO method (Table 5), they were found to be
For the FWO and KAS model-free methods, the observed vari-
similar, and varying with conversion. The changing activation en-
ation of activation energies with biomass conversion during py-
ergy with conversion indicates the complex multi-reaction thermal
rolysis (Figs. 5 and 7) reflects a maximum for conversion values of
degradation of the biomass under inert atmosphere [12,31].
40e60%, for all the biomasses of SRC poplar clones. This is due to
Activation energy values obtained with all the poplar clones
the simultaneous thermal decomposition of cellulose and lignin,
(except the clone Skado) are comparable with the results for poplar
which have the highest values of activation energy [11,36,37], and

Table 4
Kinetics parameters obtained with the Kissinger-Akahira-Sunose (KAS) method for each poplar genotype.

a AF2 AF8 Bakan

Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2

13 10
0.1 e e e 141.8 1.4  10 0.99 111.2 2.1  10 0.98
0.2 69.1 4.8  105 0.88 163.4 1.9  1014 0.81 243.8 7.5  1021 0.82
0.3 98.5 2.1  108 0.90 195.9 5.1  1016 0.85 248.5 2.7  1021 0.90
0.4 176.2 1.5  1015 0.84 230.8 1.7  1019 0.89 267.8 3.9  1022 0.94
0.5 189.7 1.3  1016 0.97 240.6 6.4  1019 0.85 243.1 1.5  1020 0.96
0.6 160.6 2.7  1013 0.92 220.9 8.6  1017 0.84 228.1 5.1  1018 0.94
0.7 e e e 50.1 1.6  101 0.90 252.4 5.0  1019 0.99

a Brandaris Ellert Grimminge

Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2

0.1 16.5 1.6  100 0.83 16.8 1.9  100 0.76 53.0 1.3  104 0.93
0.2 198.1 5.8  1017 0.89 163.6 2.8  1014 0.98 130.0 1.5  1011 0.80
0.3 221.1 1.5  1019 0.82 188.9 1.8  1016 0.97 164.7 8.3  1013 0.99
0.4 245.3 5.1  1020 0.90 221.6 4.8  1018 0.99 178.3 6.7  1014 0.80
0.5 234.1 2.7  1019 0.92 245.8 3.4  1020 0.79 211.5 2.8  1017 0.87
0.6 214.3 3.9  1017 0.80 257.5 1.8  1021 0.86 209.3 1.2  1017 0.80
0.7 141.2 9.9  1010 0.99 e e e e e e

a Hees Skado Wolterson

Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2
18
0.1 e e e 183.3 2.5  10 0.87 e e e
0.2 37.1 3.3  102 0.82 295.9 8.0  1026 0.85 188.5 3.7  1016 0.96
0.3 70.1 3.0  105 0.80 390.1 1.8  1034 0.85 428.0 2.1  1037 0.87
0.4 97.5 7.1  107 0.85 448.1 1.9  1038 0.89 395.8 2.8  1033 0.96
0.5 132.5 7.8  1010 0.91 355.0 6.0  1029 0.89 238.8 4.9  1019 0.84
0.6 142.5 4.3  1011 0.92 312.0 7.3  1025 0.94 247.5 1.4  1020 0.86
0.7 57.7 1.2  104 0.89 328.9 4.2  1026 0.96 e e e
0.8 e e e 134.7 2.2  107 0.98 e e e
 F. Rego et al. / Energy 207 (2020) 118191 7

Table 5
Kinetics parameters obtained with Flynn-Wall-Ozawa (FWO) method for each poplar genotype.

a AF2 AF8 Bakan

Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2

2 13 10
0.1 19.5 1.0  10 0.79 143.1 2.0  10 0.99 113.8 4.5  10 0.98
0.2 74.5 3.0  106 0.90 164.5 2.5  1014 0.83 240.8 4.4  1021 0.83
0.3 102.8 7.5  108 0.92 195.7 5.0  1016 0.87 245.6 1.7  1021 0.91
0.4 177.0 1.8  1015 0.86 229.3 1.3  1019 0.90 264.3 2.2  1022 0.94
0.5 190.2 1.4  1016 0.98 238.8 4.8  1019 0.86 241.1 1.1  1020 0.96
0.6 162.6 4.3  1013 0.93 220.2 7.9  1017 0.85 227.0 4.3  1018 0.94
0.7 e e e 66.9 7.7  102 0.94 250.6 3.8  1019 0.99
0.8 e e e e e e 24.0 3.4  101 0.69

a Brandaris Ellert Grimminge

Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2

0.1 23.0 9.3  101 0.91 18.4 2.7  101 0.89 58.4 1.2  105 0.95
0.2 197.3 5.1  1017 0.89 164.5 3.6  1014 0.98 132.6 3.0  1011 0.82
0.3 219.5 1.2  1019 0.84 188.9 1.8  1016 0.97 166.1 1.2  1014 0.99
0.4 242.9 3.4  1020 0.91 220.3 3.9  1018 0.99 210.9 4.6  1017 0.82
0.5 232.4 2.0  1019 0.92 243.5 2.4  1020 0.81 199.3 2.9  1016 0.80
0.6 213.9 3.6  1017 0.81 254.8 1.2  1021 0.87 209.1 1.2  1017 0.82
0.7 144.7 2.3  1011 0.99 e e e e e e
0.8 49.2 4.6  102 0.69 e e e e e e

a Hees Skado Wolterson

Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2 Ea.a (kJ/mol) Aa (s1) R2
1 18
0.1 13.7 1.6  10 0.99 182.1 2.0  10 0.88 e e e
0.2 39.5 2.3  103 0.82 290.3 3.2  1026 0.86 188.3 3.7  1016 0.96
0.3 75.9 2.0  106 0.83 380.2 4.5  1033 0.86 221.4 9.8  1018 0.84
0.4 102.3 2.8  108 0.87 435.6 3.8  1037 0.89 225.0 6.2  1018 0.88
0.5 129.2 4.5  1010 0.80 347.3 2.0  1029 0.90 237.1 3.7  1019 0.85
0.6 137.5 1.7  1011 0.80 306.7 3.3  1025 0.94 245.5 1.0  1020 0.87
0.7 65.5 1.5  105 0.92 323.1 1.8  1026 0.96 e e e
0.8 e e e 143.0 1.1  108 0.98 e e e

overlap in the region of cellulose decomposition [33], as already

Fig. 6. Graphical application of KAS method for the poplar genotype Skado.
Fig. 7. Pyrolysis activation energy versus conversion computed using the KAS method.
mentioned. Due to its aromatic composition and structure, lignin is
harder to decompose, and the decomposition above 773 K is
endothermic in nature [33]. The thermal decomposition of lignin
occurs slower (e.g. has a lower weight loss rate), over a wider
temperature range, and leaves a higher final char residue (z40 wt
%) than the other lignocellulosic components [12,33]. After a con-
version degree of approximately 50e70%, depending on the poplar
genotype sample, the pyrolysis process proceeds at a slower rate,
causing the weight loss rate to approach zero, and activation energy
to decrease drastically.
Xiao et al. [12] in their kinetics study using DAEM, detected that
activation energies reached a maximum around 0.60e0.65 con-
version, for pine sawdust and leaves of Phoenix Tree. The maximum
activation energies achieved in that study were between approxi-
mately 300 and 350 kJ/mol, with the relatively high values being
attributed to the relatively high lignin contents in the biomass
(27e30 wt% for the leaves). Since comparable lignin contents are
present in the poplar biomass (23e30 wt%, Table 2), this can be the
cause of the relatively high activation energy values obtained,
particularly for the genotype Skado. In fact, genotype Skado had the
highest lignin content, and was also the genotype which obtained
the highest values of activation energy and pre-exponential factor,
for the three methods employed. Furthermore, the clone AF2 is the
genotype with the lowest proportion of lignin, and obtained the
lowest value of activation energy with the Kissinger method, and
also relatively low values with the FWO and KAS methods. In the
study of Xiao et al., rice straw, with relatively lower lignin contents
(5e20 wt%) also obtained the lowest values of activation energy
[12]. Overall, this tendency was also observed, for the other clones,
although no significant linear trend was verified: the clones Skado,
Bakan and Brandaris are the ones with the highest values of acti-
vation energy from FWO and KAS methods, and are also the clones
8 F. Rego et al. / Energy 207 (2020) 118191
with the highest lignin contents (30, 28 and 29 wt%, respectively),
while the clones Hees and AF2 obtained overall the lowest activa-
tion energies, and have the lowest lignin proportions (26 and 23 wt
%, respectively). The lack of a clear linear trend of activation en-
ergies from FWO and KAS methods with lignin contents is related
to the fact that these methods rely on different and specific con-
version values, unlike the Kissinger method which uses the tem-
perature at which the peak weight loss rate occurs. Furthermore,
the methods of FWO and KAS are known to be sensitive to noise
and this can be another factor leading to a lack of linear correlation
[37]. Noticeably, the clone Wolterson has the most visible deviation
from the overall tendency for the KAS method (Fig. 7), and was one
of the clones that had a deviation from the trend observed with the
Kissinger method. Nevertheless, the observed connections be-
tween the Ea obtained with the FWO and KAS methods and the
lignin contents in some of the SRC poplar samples, consolidated the
previous conclusion that the activation energies, determined with
the Kissinger method, increased with increasing lignin proportions
in the feedstock.
An analysis of the evolved gases during TGA, although not
available for the equipment used, could be used to confirm the
degradation of the lignocellulosic components and the different
reactions taking place with increasing conversion.
Overall, the pre-exponential factor increased with conversion,
following the variation patterns of activation energy. Globally, the
pre-exponential factor values were higher than those reported in
the literature, e.g. a range in order of magnitude of 107e1014 for
poplar wood [27], and 1013e1020 and 109e1013 for larch and white
oak, respectively [49]. Moreover, taking into account that a model-
free kinetics approach is used, there is a mathematical dependence
between the pre-exponential factor and the activation energy. As
the activation energy varies with the extent of pyrolysis, the pre-
exponential factor varies in the same way.
Fixed bed reactor pyrolysis was performed at 773 K for all the
poplar genotypes. Data in Fig. 8 shows similar pyrolysis products
distribution for all the tested poplar clones, which is in agreement
with their similar lignocellulosic compositions, as above discussed.
The observed average bio-oil yield, slightly above 50 wt%, is com-
parable to reported data for woody biomass pyrolysis [50]. The char
was the pyrolysis product with the lowest variation in yield be-
tween the different poplar clones, with an average of approxi-
mately 21 wt%. The different pyrolysis activation energies obtained
for the 9 poplar genotypes seemed to have no significant effect on
the pyrolysis product yields, probably because, under the tested
conditions, pyrolysis was controlled by mass and/or heat transfer
limitations instead of kinetics control [51].
Fig. 8. Pyrolysis products distributions (fixed bed reactor; 773 K) and Kissinger acti-
vation energies.
4. Conclusions
The kinetics of SRC poplar biomass pyrolysis was studied using
thermogravimetry and model-free methods. The Kissinger method
obtained activation energies in the range of 108e320 kJ/mol, which
are consistent with the values of Ea for cellulose pyrolysis. A linear
correlation was obtained between the activation energies obtained
with the Kissinger method and the lignin contents of the SRC poplar
samples, which was explained by a synergistic effect from the
simultaneous decomposition of cellulose and lignin. The iso-
conversional methods of FWO and KAS obtained Ea in the range
81e301 kJ/mol and 90e306 kJ/mol, respectively, with Ea varying
with the conversion degree. The values of activation energy peaked
at a range of conversion of 40e60%, which was related to the full
conversion of cellulose concomitantly with lignin decomposition,
which continues at a slower rate. The pyrolysis products distribu-
tion from fixed bed experiments was similar for all the poplar ge-
notypes and thus seemed to be unaffected by the different kinetics
parameters obtained, probably because pyrolysis was controlled by
mass and/or heat transfer limitations instead of kinetics control.
The kinetic study allows for an improved understanding of the
complex mechanisms of pyrolysis reactions.
CRediT authorship contribution statement
Filipe Rego: Investigation, Writing - original draft, Supervision,
Writing - review & editing. Ana P. Soares Dias: Conceptualization,
Resources, Investigation, Writing - review & editing. Miguel Cas-
quilho: Formal analysis, Data curation, Supervision, Writing - re-
view & editing. Fa
tima C. Rosa: Supervision, Writing - review &
editing. Abel Rodrigues: Resources, Data curation, Supervision,
Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The authors thank (FRego, FRosa, MCasquilho) CERENA (“Centro
de Recursos Naturais e Ambiente”, Centre for Natural Resources and
the Environment), FCT Project UID/ECI/04028/2019; and (ARo-
~o Agra

ria e
drigues) INIAV, I. P. (“Instituto Nacional de Investigaça

ria”, National Institute for Agrarian and Veterinarian
Veterina
Research), Ministry of Agriculture, Portugal, and MARETEC (“Centro
^ncia e Tecnologia do Ambiente e do Mar”, Environment and
de Cie
Marine Science and Technology Centre). The authors also thank R.
Ceulemans and S. Vanbeveren from PLECO Research Centre of
Antwerp University, who kindly provided the Belgian poplar clones
from the Lochristi Belgian SRC site. This work was also supported
through IDMEC, under LAETA, project FCT UIDB/50022/2020.
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