Applied Thermal Engineering 113 (2017) 1410–1418

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Research Paper

Kinetic modelling of torrefaction of olive tree pruning

M.A. Martín-Lara ⇑, G. Blázquez, M.C. Zamora, M. Calero
Department of Chemical Engineering, University of Granada, 18071 Granada, Spain

h i g h l i g h t s

Thermogravimetric analysis of material under torrefaction conditions was studied.

Mass loses during torrefaction was modeled by a pseudo-mechanistic model.

The model included moisture, hemicellulose, cellulose and lignin content.

The model can predict the mass yield under different operating conditions.

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

Article history: The objective of this study is the proposal of a pyrolysis kinetic model that describes the thermal decom-
Received 15 August 2016 position of olive tree pruning in different torrefaction conditions via thermogravimetrical measurements
Revised 3 November 2016 in nitrogen atmosphere. First, the determination of activation energies was performed by isoconversional
Accepted 20 November 2016
methods of Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose and Friedman. Three stages were distin-
Available online 21 November 2016
guished in which the activation energy keeps approximately constant and were related to the thermal
degradation of the different constituents of the material (cellulose, hemicellulose and lignin). Then,
Keywords:
Coast-Redfern method was applied to determine the kinetic function. The kinetic function that seems
Kinetic
Modelling
to determine the mechanism of thermal degradation of main components of olive tree pruning was
Non-isothermal thermogravimetry nth order reaction. Finally, a detailed pseudo-mechanistic model (using least squares fitting in a parallel
Olive tree pruning reaction scheme) was analyzed. This model was appropriate to predict the pyrolysis behavior of the olive
Torrefaction tree pruning in all torrefaction conditions studied.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction researchers compared different methods for predicting kinetic

Torrefaction is a thermochemical treatment of biomass pro-
duced at temperatures between 200 and 300 °C in the absence of
oxygen to produce beneficial changes in the composition of bio-
mass: increases calorific value, improves grindability and resis-
tance to degradation, among other properties [45]. Torrefaction
can be applied to a wide range of organic materials and can
increase the use of biomass for power generation in conventional
power plants and for producing a combustible gas in gasifiers [42].
Kinetic modeling is a crucial tool to predict the performance of
biomass during torrefaction [39,40] and the most usual way of per-
forming a kinetic analysis is through thermogravimetric analysis
(TGA). In most of recent works [10,32,33,38,43,48], an overall
kinetic model has been developed to describe the mass loss or
thermal degradation of lignocellulosic biomass. In general, most
⇑ Corresponding author.
E-mail addresses: marianml@ugr.es (M.A. Martín-Lara), gblazque@ugr.es
(G. Blázquez), mczm@correo.ugr.es (M.C. Zamora), mcaleroh@ugr.es (M. Calero).
parameters (for example, Kisssinger model, Kissinger-Akahira-
Sunose (KAS), Flynn-Wall-Ozawa (FWO) and Friedmann (FR) meth-
ods). However, other researchers have successfully applied the dis-
tributed activation energy model (DAEM) to describe biomass
decomposition in an inert environment. This model assumes that
several irreversible first order parallel reactions having unique
kinetic parameters take place simultaneously [13,44]. In addition,
a great number of studied have proposed diverse reaction schemes
consisting of multiple reactions that assume the decomposition of
lignocellulosic materials as the sum of the decomposition of its
major constituents, hemicellulose, cellulose and lignin. Most of
these studies indicated that the different chemical steps can be
characterized using a nth-order reaction kinetic model [4,16,28].
In mature olive trees, pruning is mainly required to renew the
fruiting surface of the tree and achieve high yields, maintain vege-
tative growth of fruiting shoots, maintain the skeleton structure,
favor air circulation and light penetration through the foliage to
prevent bacterial and fungal diseases which grow more easily in
humid, stagnant air. Also, it helps to decrease the alternation of

http://dx.doi.org/10.1016/j.applthermaleng.2016.11.147
1359-4311/Ó 2016 Elsevier Ltd. All rights reserved.
 M.A. Martín-Lara et al. / Applied Thermal Engineering 113 (2017) 1410–1418 1411

w0  w
production which naturally affect the olive and, finally, to elimi- a¼ ð2Þ
nate dead wood and manage the size of the plant to engage the w0  w1
harvest in safe conditions.
where w0, w and w1 correspond to the initial sample mass, the
The objective of this study has been the proposal of a compre-
sample mass at any time and the final residual mass obtained at
hensive pyrolysis kinetic model that describes the thermal decom-
the end of the decomposition process, respectively.
position process of olive tree pruning in different torrefaction
Moreover, the dependence of kinetic constant with temperature
conditions via thermogravimetrical measurements in nitrogen
is described by Arrhenius equation:
atmosphere. First, the determination of activation energies of the


kinetics of biomass torrefaction was carried out by isoconversional E
methods, then, Coast-Redfern method was applied to determine
kðTÞ ¼ k0  exp ð3Þ
RT
kinetic function and, finally, a detailed pseudo-mechanistic model
based in a parallel reaction scheme was analyzed. where k0 is the pre-exponential factor or frequency factor, E is the
apparent activation energy and R is the gas constant.
2. Material and methods Also, as it is operated in dynamic regime (non-isothermal con-
ditions) and the temperature increases linearly with time, a linear
2.1. Biomass sample heating rate can be defined as:

dT
Olive tree pruning is a waste from olive pruning, characteristi- b¼ ð4Þ
dt
cally required for maintenance and reshaping of olive trees. The
OTP used for this study was obtained from olive plantation located So, an expression of the rate law for non-isothermal conditions
in Vilches, province of Jaen (Spain). The solid was reduced to par- can be obtained combining equations (1), (3) and (4):


ticles lower than 1.00 mm by powdering in an analytical mill da A E
(IKA MF-10) and was stored for later use in all tests. A complete ¼  exp  fðaÞ ð5Þ
dT b RT
physic-chemical characterization of this material has been previ-
ously published in [8]. Setting in order and integrating both sides of Eq. (5), can be
obtained:
2.2. Experimental method Z a Z

da A T
E A
gðaÞ ¼ ¼ exp dT ¼  pðxÞ ð6Þ
A total of seven experiments were conducted under nitrogen 0 fðaÞ b T0 RT b
atmosphere in a thermobalance Perkin Elmer, model STA 6000.
where p(x) in Eq. (6) is known as the temperature integral. The tem-
Five experiments were carried out in dynamic conditions at five
perature integral does not have an exact analytical solution but it
different heating rates (5, 10, 15, 20 and 25 °C/min), while two
can be approximated by different empirical interpolation equations
other tests were performed in dynamic + isothermal conditions,
as term proposed by Doyle, Agrawal, Gorbatchev, etc.
i.e. with a first stage at a constant heating rate of 15 °C/min and
a second isothermal stage keeping constant the final temperature
for a time of 60 min; specifically, an experiment to 200 °C and 2.3.1. Determination of the activation energies by isoconversional
the other one to 300 °C. All experiments were performed by dupli- methods of Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose
cate with an initial mass of sample about 25 mg (±3 mg) and a (KAS) and Friedman (FR)
nitrogen flow rate of 20 mL/min. In Table 1 the set of experimental The isoconversional methods (also called ‘‘model-free” meth-
conditions for each experiment are detailed. ods) are based on an isoconversional basis. They assume that the
reaction rate at constant degree of conversion is only a function
of the reaction temperature, allowing the determination of the val-
2.3. Kinetic analysis
ues of the activation energy for the same degree of conversion, Ea,
without assuming any particular model. Hence, isoconversional
In most developed kinetic formulations of thermal decomposi-
tion of biomass, the calculation of the kinetic parameters is based methods do not require previous knowledge of the reaction mech-
anism for biomass thermal degradation. But, although it is not nec-
on the assumption that the decomposition rate (da/dt) is a function
of two variables, temperature (T) and degree of conversion or essary to identify a particular model, it is assumed that the
dependence of the conversion due to a differential model f(a) [46].
extend of reaction (a) related to the kinetic constant k(T) and the
reaction model f(a), respectively, and described as a single reaction: In this work, activation energy for each degree of conversion is
calculated by the integral isoconversional methods of Flynn-
da
¼ kðTÞfðaÞ ð1Þ Ozawa-Wall (FOW) and Kissinger-Akahira-Sunose (KAS) and the
dt differential isoconversional method of Friedman (FR) as they are
The function f(a) depends on the controlling mechanism and some of the most common model-free methods for the determina-
the extent of reaction or conversion can be calculated by the tion of kinetic parameters in a thermal decomposition. The main
following equation: reason is easiness in treatment of the experimental data to obtain

Table 1
Set of experimental conditions for each thermal decomposition test in thermobalance.

Atmosphere Flow rate, Initial temperature, Final temperature, Dynamic stage: Heating Isothermal stage: Time at
mL/min °C °C rate, °C/min final temperature, min
Nitrogen 20 30 800 5 0
Nitrogen 20 30 800 10 0
Nitrogen 20 30 800 15 0
Nitrogen 20 30 800 20 0
Nitrogen 20 30 800 25 0
Nitrogen 20 30 200 15 60
Nitrogen 20 30 300 15 60
1412 M.A. Martín-Lara et al. / Applied Thermal Engineering 113 (2017) 1410–1418

the values of the activation energy by simple linear mechanism which governs the decomposition process, in the dif-
representations. ferent range of conversion tested, one with which the energy val-
ues are closest to the values obtained using the methods of FWO,

Flynn-Wall-Ozawa (FWO) method KAS and FR.
Some of the more important rate equations used to describe the
The equation used in the methodology developed by Flynn- kinetic behavior of solid state reactions and applied in this work on
Wall-Ozawa [20,22,35–37] uses the approximation of Doyle [19]. Coast & Redfern method are listed in Table 2.


AE E
logb ¼ log  2; 315  0; 4567 ð7Þ
RgðaÞ RT 2.3.3. A pseudo-mechanistic model based on a parallel reaction scheme
Finally, in this work, a devolatilization scheme has been pro-
The activation energy can be obtained from the plot of log (b) posed based on four parallel reactions considering the olive tree
versus 1/T for different heating rates for each degree of conversion. pruning a heterogeneous mixture formed by four independent
fractions (moisture, hemicellulose, cellulose and lignin) that

Kissinger-Akahira-Sinose (KAS) method decompose at different temperatures following an independent
The approximation of the integral of Doyle may introduce some reaction,
errors in the estimation of Ea, especially if it varies with the degree
s1 Moisture ) s1 Volatiles1
of conversion. Another widely used empirical approach is proposed
by Murray and White [34] that produces equation known as s2 Hemicellulose ) m2 Volatiles2 þ c2 Char2
Kissinger-Akahira-Sinose [2,31]. s3 Cellulose ) m3 Volatiles3 þ c3 Char3

 s4 Lignin ) m4 Volatiles4 þ c4 Char4
b AR E
ln 2 ¼ ln  ð8Þ
T Egða Þ RT As an important part of this model, moisture evaporation has
Activation energy can be determined from the slope of the been included into the model. Actually, most of published works
straight line obtained by plotting ln (b/T2) versus 1/T for a fixed about thermal degradation of lignocellulosic materials don’t
degree of conversion. include this fraction as an independent reaction on their reaction
schemes. However, it is important to highlight that some old works

Friedman (FR) method already included the moisture release in the chemical reaction
model [11].
Friedman method [24] is also an isoconversional method in Volatiles1, Volatiles2, Volatiles3 and Volatiles4 are the gases and
which the values of E for a given conversión value, are obtained condensable volatiles evolved in the decomposition reactions of
plotting ln(da/dT) versus 1/T, according to the following equation, moisture, hemicellulose, cellulose and lignin, respectively, and

 
da E Char2, Char3 and Char4 refer to char formed in the decomposition
ln b ¼ ln½Aa fðaÞ  ð9Þ reactions of hemicellulose, cellulose and lignin, respectively. Also,
dT a RT
in the reaction scheme proposed, si is the initial contribution of
the fraction or component ‘i’ to the total weight of the material
2.3.2. Determination of reaction model by Coats & Redfern (CR) and they have been experimentally obtained (7.7% moisture,
method 28.9% hemicellulose, 38.4% cellulose and 25.0% lignin); ʋi repre-
Once the variation of the activation energy for the degradation sents the maximum amount of volatile obtained by reaction ‘i’ at
process is evaluated, the next step is to determine what reaction infinite time, that is, the yield coefficient of volatile that represents
mechanisms control the process obtaining the form of the function the maximum amount of volatiles that can be evolved during cor-
f(a). For this study, the method of Coats & Redfern, CR, applied at responding reaction when the substrate reacts completely and,
conversion ranges in which the activation energy can be consid- likewise, ci refers to the maximum amount of carbonaceous resi-
ered approximately constant, is used. due obtained by reaction ‘‘i” (c = 1  ʋ). For the moisture ʋ1 = s1
The method approximates p(x) using a Taylor series expansion as any char is obtained from this fraction and total conversion of
to yield the following simplified expression [14,15]: moisture in volatiles are supposed.


 In this paper, according to results of Coast-Redfern method
gðaÞ AR E
ln ¼ ln  ð10Þ (Section 3.3), an nth reaction model has been assumed. Therefore,
T2 bE RT
given the mass balance of the products and reactants and the
By plotting ln[g(a)/T2] versus 1/T, the value of the activation degree of conversion (a), the kinetic equations associated with
energy is obtained. From the results, it can be set as a reaction independent reactions can be expressed as follows:

Table 2
Common mechanisms of degradation of a solid state material.

Degradation model f(a) = (1/k)(da/dt) g(a) = kt

Nucleation Avrami-Erofeev A2 2(1  a)[ln(1  a)]1/2 [ln(1  a)]1/2
Nucleation Avrami-Erofeev A3 3(1  a)[ln(1  a)]2/3 [ln(1  a)]1/3
Nucleation Avrami-Erofeev A4 4(1  a)[ln(1  a)]3/4 [ln(1  a)]1/4
Contraction area R2 2(1  a)1/2 1(1  a)1/2
Contraction volume R3 3(1  a)2/3 1(1  a)1/3
Undimensional diffusion D1 1
2a
a2
Bidimensional diffusion D2 1
½ lnð1aÞ
(1  a)ln(1  a)+a
Three-dimensional diffusion (Jander) D3 3ð1aÞ2=3 [1(1  a)1/3]2
2½1ð1aÞ1=3 
Three-dimensional diffusion (Ginstling-Brounshtein) D4 3 1–2/3a(1  a)2/3
2½ð1aÞ1=3 1
First order reaction F1 (1  a) ln(1  a)
Nth order reaction Fn (1  a)n 1ð1aÞ1n
1n
 M.A. Martín-Lara et al. / Applied Thermal Engineering 113 (2017) 1410–1418 1413

da1 1.0
¼ k1  ð1  a1 Þn1 ð11Þ (a)
dt
da2
¼ k2  ð1  a2 Þn2 ð12Þ 0.8
5 ºC/min
dt 10 ºC/min
da3 15 ºC/min
¼ k3  ð1  a3 Þn3 ð13Þ 20 ºC/min
dt 25 ºC/min

w = m/m0
0.6
da4
¼ k4  ð1  a4 Þn4 ð14Þ
dt
0.4
In these equations ni is the order reaction, ki is the rate constant
of the corresponding reaction ‘‘i”. These kinetic constants follow
the Arrhenius law: 0.2


E1
k1 ¼ k10  exp ð15Þ
RT 0.0

 200 400 600 800
E2
k2 ¼ k20  exp ð16Þ T, ºC
RT


E3 (b) 1.0
k3 ¼ k30  exp ð17Þ
RT 5 ºC/min
10 ºC/min

 15 ºC/min
E4 0.8 20 ºC/min
k4 ¼ k40  exp ð18Þ
RT 25 ºC/min
15 ºC/min + 200 ºC during 60 min
15 ºC/min + 300 ºC during 60 min
where ki0 is the pre-exponential factor, Ei the apparent activation 0.6
energy of reaction ‘‘i”. w=m/m 0
Total solid fraction, wcalc (unreacted solid and originated car-
0.4
bonaceous solid) are related to the other variables using the fol-
lowing expression:

wcalc ¼ 1  ðs1  t1  a1 þ s2  t2  a2 þ s3  t3  a3 þ s4  t4  a4 Þ 0.2

ð19Þ
0.0
Once the model was defined with its corresponding equations, 0 2000 4000 6000 8000 10000
the next step is to obtain the kinetic parameters of the reactions.
t, s
The best parameters will be those that best correlate the calculated
values with experimental thermogravimetric curves for all tests Fig. 1. Experimental thermogravimetric curves (TG) of the olive tree pruning waste.
simultaneously (experiment 1–7). (a) Representation of mass fraction (w) versus temperature (T), (b) Representation
of mass fraction (w) versus time (t).
The simultaneous solution of four differential equations system
was carried out numerically with Euler’s method in an Excel
spreadsheet using as initial condition values of conversion factors
ple, because in this case the temperature in a given time is
equal to 0. The quality of the model was evaluated using an objec-
greater. Also, in Fig. 1a, an increase in the heating rate caused a
tive function that minimizing the differences of squares between
shift of the curves at higher temperatures. This behavior usually
experimental and calculated data in the integral and differential
occurs in any thermogravimetric analysis, and it can be inter-
forms.
preted as a consequence of the mathematical form of the kinetic
!2
X
m X
n
 2 X
m X
n exp calc law process, assuming infinitely fast heat transfer and kinetic
dwmn dwmn
Obj:function: ¼ mn  wmn
wexp calc
þf   parameters constant [17,33].
dt dt
1 1 1 1 Moreover, the representations of the data of TGs curves by
ð20Þ using the thermogravimetric derived curves (DTGs) provides use-
ful information meaning that they allow to appreciate more clearly
The parameter f is a scaling factor included to compensate the
small changes hardly observable in the curves TGs. In Fig. 2, the
differences in the obtained numeric data for integral and differen-
values of dw/dT against the temperature have been shown.
tial forms. Moreover, m represents the number of heating rate
All curves present three different stages of mass loss, identified
studied and n the number of experimental data recorded in each
by peaks in the DTG curves. The first stage (first peak on DTG
test a specific heating rate.
curves) can be attributed to the moisture release [5,7]. The second
peak corresponds to the decomposition of the hemicellulose [9,33].
3. Results and discussion The third stage (third peak on DTG curves) is mainly attributed to
the degradation of cellulose [3]. Hemicellulose usually appears as a
3.1. Analysis of thermogravimetric curves shoulder to the left of the main degradation peak in the DTG curve
corresponding to cellulose. Furthermore, a fourth stage of decom-
In Fig. 1a, the experimental curves of mass loss versus temper- position is found although it doesn’t appear as marked peak in
ature of dynamics experiments at five heating rates are shown. In the thermogravimetric derived curve and it corresponds to the
Fig. 1b, the experiments in dynamics + isotherms together with thermal degradation of lignin, the fourth major component in olive
the dynamic experiments are shown. In this case, the representa- tree pruning, whose decomposition takes place slowly over a
tion of mass loss are versus time and logically, the displacement greater temperature range (around 200–800 °C) [30]. These stages
of curves with increasing the heating rate is to lower times, that in TG and DTG curves are comparable to results found by [47] in
is to say, the higher the heating rate faster decomposes the sam- their study about hemicellulose, cellulose and lignin pyrolysis.
1414 M.A. Martín-Lara et al. / Applied Thermal Engineering 113 (2017) 1410–1418

0.000 ing is very complex, as they are involved multitude of chemical

reactions and, in general, a superposition of different chemical pro-
-0.001 cesses. In addition, physical processes (for example diffusion of
5 ºC/min
10 ºC/min
decomposition products) must be also considered, which make dif-
15 ºC/min ficult to give an interpretation with a chemical/physical meaning
-0.002 20 ºC/min
to the mathematical equation describing the process.
dw/dT, ºC-1

25 ºC/min
Still, in the bibliography simple models are presented to
-0.003
describe the kinetic of thermal decomposition process which isn’t
known a priori, setting validation criteria such as the invariance
-0.004 of activation energy determined by isoconversionals methods.

-0.005
-0.006
200 400 600
T, ºC
Fig. 2. Experimental thermogravimetric derived curves (DTG). Representation of
dw/dT versus temperature (only dynamics tests).
Table 3 includes the information obtained from the TG and DTG
curves for each stage of decomposition where Ti is the onset tem-
perature of decomposition, Tf is the temperature at which ends the
stage of decomposition, Tmax is the temperature at which the
decomposition in each stage has place at a higher rate (peak on
the DTG curve), wvolatilized is the percentage of mass loss corre-
sponding to each stage and (dw/dT)max is the value of maximum
loss rate corresponding to each stage which has place a Tmax.
Similar temperature ranges associated with these thermal
degradations have been found by several authors who have used
different vegetable waste, such as [27] in his study of thermal
degradation by pyrolysis of poplar sawdust, Gómez et al. [25] in
their study of the pyrolysis of biomass relevant in the Mediter-
ranean basin: olive pits, almond shell, pinewood and olive tree
pruning, and Chen et al. [12] in their kinetic analysis of pyrolysis
of maize straw and wheat straw.
As it is shown in thermogravimetric curves, the degradation
process of organic materials such as residue from olive tree prun-
3.2. Determination of the activation energies by isoconversional
methods of Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose
(KAS) and Friedman (FR)
800
In Fig. 3, the results of the analysis based on isoconversionals
models of FOW, KAS and FR for the range of values of the degree
of conversion of 0.1–0.9 are shown. The fitting lines are shown only
for those cases where the correlation coefficient was greater than
0.85. In Table 4, the parameters of the linear fits with correlation
coefficients for each of the values of the degree of conversion stud-
ies are presented. Those adjustments have a correlation coefficient
lower than 0.85 are marked in cursive. For the conversion value of
0.1 the adjustment linearity is rather low. In all cases, the worst fit
is given to the extreme levels of conversion (0.1; 0.8; 0.85; 0.9)
possibly due to the inherent error associated with the humidity
difference samples (degrees of conversion low) and a more com-
plex process in finalizing degradation (high degrees of conversion).
Moreover, Table 4 shows that activation energy determined by
these conversional methods is not constant in function of conver-
sion so, thermal decomposition under nitrogen atmosphere may
not be represented by a single kinetic model, that is, the reaction
mechanism is complex and cannot be described by a single reac-
tion or a single type of degradation for the entire process of degra-
dation. However, as it is shown in Fig. 4, three stages can be
distinguished in which the activation energy remains approxi-
mately constant meaning that the processes that controlling

Table 3
Summary of the different stages on thermal decomposition of olive tree pruning under nitrogen atmosphere to different heating rates.

b, °C/min
5 10 15 20 25
First stage of decomposition (Moisture) Ti, °C 30 30 30 30 30
Tf, °C 128 133 135 140 142
Tmáx, °C 59 76 89 93 96
wvolatilized (%) 7.7 7.7 8.0 7.7 7.8
(dw/dT)máx, °C1 1.520103 1.333103 1.445103 1.287103 1.394103
Second stage of decomposition (Hemicellulose) Ti, °C 165 170 172 174 180
Tf, °C 320 325 330 333 335
Tmáx, °C – 310 312 314 317
wvolatilized (%) 32.4 31.6 30.3 31.1 30.7
(dw/dT)máx, °C1 4.203103 4.434103 4.345103 4.385103 4.214103
Third stage of decomposition (Cellulose) Ti, °C 320 325 330 333 335
Tf, °C 388 390 393 395 400
Tmáx, °C 346 352 359 360 365
wvolatilized (%) 24.1 22.2 23.6 23.1 23.6
(dw/dT)máx, °C1 5.644103 5.256103 5.133103 5.104103 5.096103
Fourth stage of decomposition (Lignin) Ti, °C 388 390 393 395 400
Tf, °C 800 800 800 800 800
Tmáx, °C – – – – –
wvolatilized (%) 14.4 17.2 17.4 19.4 18.6
(dw/dT)máx, °C1 – – – – –

Ti is the onset temperature of decomposition.

Tf is the temperature at which ends the stage of decomposition.
Tmax is the temperature at which the decomposition in each stage has place at a higher rate.
wvolatilized is the percentage of mass loss corresponding to each stage.
(dw/dT)max is the value of maximum loss rate corresponding to each stage which has place a Tmax.
 M.A. Martín-Lara et al. / Applied Thermal Engineering 113 (2017) 1410–1418 1415

Table 4
1.4 0,1 Activation energy values (Ea) and correlation coefficients (r2) determined by FOW,
0,2
0,3
KAS and FR methods for thermal degradation of olive tree pruning under nitrogen
0,4 atmosphere.
0,5
1.2 0,6 Conversion Method
0,7
logβ, K/min

degree
0,8 FWO KAS FR
0,9
1.0
Ea, kJ/mol r2 Ea, kJ/mol r2 Ea, kJ/mol r2
0.05 64.03 0.980 61.56 0.997 64.03 0.980
0.8 0.10 41.52 0.399 36.68 0.319 37.49 0.370
0.15 126.96 0.921 125.04 0.911 126.96 0.921
0.20 144.57 0.947 143.14 0.941 160.07 0.976
0.6 0.25 160.85 0.967 160.02 0.963 160.85 0.967
0.30 173.18 0.985 172.79 0.984 185.03 0.994
0.35 185.34 0.994 185.40 0.993 185.34 0.994
0.0010 0.0015 0.0020 0.0025 0.0030
0.40 195.32 0.998 195.73 0.997 209.60 1.000
1/T, K -1 0.45 202.53 1.000 203.15 1.000 202.53 1.000
a) FOW 0.50 208.75 0.999 209.53 0.999 215.89 0.998
0.55 211.88 0.999 212.66 0.999 211.88 0.999
0.60 214.52 0.999 215.29 0.999 217.83 0.999
-12
0.65 213.78 0.999 214.39 0.999 213.78 0.999
0,1
0,2 0.70 205.58 0.999 205.64 0.999 180.30 0.988
0,3 0.75 172.35 0.987 170.51 0.985 172.35 0.987
0,4 0.80 108.83 0.955 103.27 0.945 82.13 0.899
-11 0,5
0.85 94.40 0.935 87.35 0.918 94.40 0.935
lnβ/Τ , 1/K·min

0,6
0,7 0.90 90.74 0.936 82.48 0.916 82.73 0.892
0,8
0,9
2

-10

250

-9
200

0.0010 0.0015 0.0020 0.0025 0.0030

-1
Eα, kJ/mol

1/T, K 150
b) KAS
100
-7
0,1
0,2
-6 0,3 50 FOW
0,4 KAS
0,5
FR
-5 0,6
ln[β(dα/dT)]

0,7
0,8 0
0,9 0.0 0.2 0.4 0.6 0.8 1.0
-4
α
-3 Fig. 4. Dependence of activation energy (Ea), obtained with isoconversionals
methods of FOW, KAS and FR for analysis of thermal degradation under nitrogen
-2 atmosphere of olive tree pruning waste, on conversion degree (a).

-1
0.0010 0.0015 0.0020 0.0025 0.0030 nents, and the third stage, with lower activation energy values
1/T, K -1 correspond to degrees of conversion between 0.8 and 0.9. This
c) FR decrease in activation energy in the last stage indicates that the
degradation process takes place more easily and this behavior
Fig. 3. Representation of isoconversional methods of FOW (a), KAS (b) and FR (c) for can be attributed to final lignin degradation.
the analysis of thermal degradation of olive tree pruning waste under inert
atmosphere (b is heating rate, a is conversion degree).
3.3. Determination of reaction model by Coats & Redfern (CR) method

Once the variation of activation energy for the degradation is

weight loss not vary significantly throughout the intervals [21] and
also, coincide with the intervals at which marked peaks appear in
the DTG curve, that is, are related to the different degradation of
the various constituents of the material. The first stage corresponds
to the degree of conversion between 0.35 and 0.45 and is due to the
thermal decomposition of hemicellulose. The second stage affects
to conversion degrees between 0.5 and 0.7 with higher activation
energies and may be associated mainly to degradation of cellulose,
as is well known that cellulose has apparent activation energies
greater the hemicellulose because the crystallinity of its compo-
known, the next step is to determine what reaction mechanisms
direct the process, that is to say, the form of the function f(a).
For this study, the method Coats & Redfern (CR) has been applied
at intervals of conversion in which the activation energy can be
considered approximately constant.
In general, in the studies of thermal degradation of biomass is
admitted a model of first or nth order [6,10,18,43]. However, poly-
meric materials, as in the case of lignocellulosic residues studied in
this work, can also present a mechanism of degradation of sig-
moidal or diminishing type different from the reaction of first or
1416 M.A. Martín-Lara et al. / Applied Thermal Engineering 113 (2017) 1410–1418

nth order so, the assumption of first or nth order is not recom-

0.997
0.998
0.998
0.982
0.986
0.949
0.557
0.985
0.449
0.955
0.988
0.987
0.987
0.988
mended without verification because, perhaps, another kinetic

r2
model could be more convenient to describe the degradation pro-
cess in a given interval conversion [29]. In Table 2, the possible
mechanisms that have been considered in this study are shown.

115.66
Lignin

9.71
5.43

5.41
1.38
6.09
8.50

7.00

22.87
51.99
83.55

97.99

86.42
91.03
1.14
6.20
1.00
The first conversion interval to be analyzed, from the point of

E
view of the reaction mechanism, includes the degradation temper-
ature of hemicellulose which, as discussed above, has associated

0.996
0.993
0.975
0.999
0.999

0.999
0.999
0.998
0.994
0.991

0.988
0.990
1.000
1.000
the second peak obtained in the thermogravimetric derived curve.

r2
The second interval includes the temperature to the rate of thermal
degradation is maximum and occurs most volatile emissions, that

Cellulose

145.49
189.34
105.24

211.50
207.94
210.90
is, includes the largest peak obtained for the thermogravimetric

15.89

27.73
53.85
65.25
79.63

42.26
31.05

70.32
70.00
Numerical results obtained for the activation energy (in kJ/mol) using the method of CR for the heating rates of 5, 15 and 25 °C/min compared with the values obtained by FOW, KAS and FR.

7.11
2.71
derived curve (the third peak) and is the interval of the

E
temperature-conversion which is associated with the degradation
of cellulose. Finally, with the third interval will be evaluated the

0.999
0.998
0.992
0.999
0.999
0.999
0.999

0.999
1.000

1.000
1.000
1.000
1.000
1.000
reaction mechanism, which would correspond to lignin because

r2
Hemicellulose
high conversion values where practically only this component is

25 °C/min
degraded.

155.85
104.33
156.60

161.80
14.49

32.89

64.79
71.69
79.46
74.27
38.83
52.29
67.81
85.23
31.02
The numerical results obtained for the activation energy, in

6.37
2.32
kJ/mol, applying the method of CR are shown in Table 5. Only

E
results obtained for three of the five heating rates studied in this
work have been reported in order to simplify and improve the

0.995
0.997
0.998
0.975
0.983
0.939
0.464
0.974

0.993
0.991
0.991
0.991
0.408
0.905
clearness of Table 5, however, similar results were found for the

r2
other two heating rates.
Based on the results presented in Table 5 and the main research

114.59
Lignin

8.28
9.47
5.26
6.81
5.25
1.28
5.90

22.76
51.59
82.82

97.99

86.42
91.03
strategy of choosing one model that provides a good fit to the

6.21

1.24
1.07
experimental data and provides an activation energy close to that
estimated by the isoconversionals methods of FWO, KAS and FR, E
the kinetic function f(a) that seems to determine the kinetic model 0995
0991
0971
0999
0999

0999
0999
0997
0994
0991
0989
0987
1000
1000
r2

of the mechanism of thermal degradation for cellulose and lignin

components is the reaction of nth order, being the most common
Cellulose

reaction order the fourth or fifth order. The activation energy val-

145.43
105.46

189.02

211.50
207.94
210.90
16.27

31.68
28.36
54.96
66.39

71.13
42.87
80.74

70.79
2.97
7.40

ues of the other models are significantly different to the values

E

obtained by isoconversional methods. Moreover, the function cap-

able of reproducing the first stage considered in this method
0.999
0.998
0.994
0.999
0.999
0.999
0.999

0.999
1.000

1.000
1.000
1.000
1.000
1.000
(a = 0.35–0.45) which correspond to part of the thermal degrada-
Hemicellulose
r2

tion of hemicellulose, seem to be nth reaction model but with

15 °C/min

order of reaction higher to 5, but, also is important to remake that

155.85
156.60

161.80
108.60
activation energy in this stage is not constant, it increases slightly
15.33

34.25
32.31

74.16
82.24
76.85

54.42

88.71
67.02

40.42

70.57
6.97
2.79

with increasing conversion degree.

E
0.969
0.989
0.993
0.941
0.966
0.919
0.566
0.726

0.989
0.996
0.997
0.998
0.026
0.027

3.4. Proposal of a pseudo-mechanistic model based on a parallel

r2

reaction scheme
108.65
Lignin

6.15

9.37
5.81
7.24
6.11
2.56
8.30

0.39

In the thermal degradation of organic materials, even the sim-

48.63
78.43

97.99

86.42
20.96

91.03
4.40

0.29

plest, are involved multitudes of chemical reactions. One way to

E

study the kinetics of the thermal decomposition is to propose

pseudo-mechanistic models. In them, the products of decomposi-
0.992
0.985
0.959
0.997
0.998
0.999
0.999
0.997
0.998
0.995
0.991
0.988
0.986
0.985

tion in an inert atmosphere are divided in solids (non-volatile resi-

r2

due with a high carbon content), tars (mixtures of a large number

Cellulose

of compounds of high molecular weight which are volatile at the

153.85
110.97

211.50
207.94
200.51
210.90
16.94

32.18
28.69
54.84
66.77
81.91
71.76

73.78
44.01

temperature of pyrolysis or torrefaction but condense at ambient

7.92
3.41

temperature) and gases (volatile products with low molecular

E

weight at ambient temperature). Because in a thermobalance is

not possible to distinguish between the fractions corresponding
0.999
0.993

0.999
0.999

0.999
1.000

1.000

1.000
1.000
1.000
1.000
1.000
1.000
1.000
Hemicellulose

gases and tars, these fraction are grouped into a single fraction,
r2

and in the proposed models is considered only solids and volatiles

5 °C/min

155.85
156.60

161.80

as products. Moreover, the reactions include a set of several simple

12.99

29.98
28.25
59.43

68.19
35.47
47.93
62.29
78.42
65.80

96.09
73.00
1.75
5.50

reactions, and kinetic parameters that have been obtained are rep-
E

resentative of each global reaction.

The kinetic reaction schemes proposed for torrefaction can be
Mechanism

very different (reactions in parallel, series, competitive, etc.), and

there are proposed in function of the shape of the thermogravimet-
FOW
Table 5

KAS
D1
D2
D3
D4

ric curves, the nature of the material (homogeneous or heteroge-

A2
A3
A4
R2
R3

FR
F1
F2
F3
F4
F5

neous sample) and information provided by the analysis of the

 M.A. Martín-Lara et al. / Applied Thermal Engineering 113 (2017) 1410–1418 1417

Table 6
Kinetic parameters obtained for the pyrolitic thermal decomposition of olive tree pruning according to the pseudo-mechanistic model proposed.

Parameter Moisture Hemicellulose Cellulose Lignin

1 9 12 15
ki0 (s ) 4.6410 3.5310 8.9810 3.781014
Ei (kJ/mol) 74.55 151.65 209.25 76.56
ni 6.99 3.90 4.83 4.51
ʋi 1.00 1.00 0.99 0.57

generated products (by TG coupled with mass spectrometry

(TG-MS) or infrared spectrophotometry (TG-FTIR), for example). (a) 1.0

The kinetic parameters obtained for the fit of the experimental Experimental
Calculated
data are shown in Table 6. The kinetic parameters obtained are 0.8 Hemicellulose
similar to those found by other authors in previous works. For Celullose
Lignin
example, Sharma et al. [41] found apparent activation energies
Moisture
between 53 and 68 kJ/mol for reaction of moisture release. Grønly 0.6
et al. [26] studied the kinetics of devolatilization of wood and

w
obtained apparent activation energies of 100 kJ/mol for the ther- 0.4
mal decomposition of hemicellulose, 236 kJ/mol for the decompo-
sition of cellulose and 46 kJ/mol for the decomposition of lignin.
Also, [1] presented values of 88.36, 171.96 and 54.05 kJ/mol for 0.2
hemicellulose, cellulose and lignin, respectively. With respect to
the reaction order, authors as Ceylan and Topçu [10], working with
0.0
hazelnut shell, found that thermal degradation of this residue in an 0 1000 2000 3000 4000 5000
inert atmosphere of nitrogen is adequately described with a model Time, s
reaction of twelve order. Moreover, the reaction orders obtained
through the pseudo-mechanistic model and presented in Table 6, (b) 0.0000
are consistent with the results obtained by applying the method
of CR (see Table 5).
-0.0002

Experimental
Calculated
(a) 1.0 -0.0004
dw/dt, s-1

Hemicellulose
Celullose
Lignin
0.8 -0.0006 Moisture
Experimental
Calculated
Hemicellulose
0.6 Cellulose -0.0008
Lignin
w

Moisture

0.4 -0.0010
0 1000 2000 3000 4000 5000
Time, s
0.2
Fig. 6. Simulation of TG (a) and DTG (b) curves of torrefaction of olive tree pruning
at 300 °C at a heating rate of 15 °C/min and a holding time of 60 min at 300 °C.
0.0
0 1000 2000 3000 4000 5000
Time, s Regarding the values of yield coefficients to volatiles (ʋ), these
are in conformity with the results presented by other authors
(b) 0.0000 who have analyzed the thermal decomposition in an inert atmo-
sphere of similar lignocellulose residues. For example, [4] had
yields of char (1  ʋ) for hemicellulose and cellulose fractions com-
-0.0001 Experimental parable to those found in this work. Also, [30] obtained a char yield
Calculated of 36.9 wt.% of the initial weights for lignin. Similarly, [23] studied
Hemicellulose
the pyrolytic decomposition of pine leaf and pinecone shell and
dw/dt, s-1

Cellulose

-0.0002
Lignin found values of yield coefficient to volatiles very similar to those
Moisture
shown in Table 6, for each pseudocomponent.
Finally, Figs. 5 and 6 present experimental and calculated TG
and DTG curves. These figures show the evolution of experimental
-0.0003
and calculated solid fractions for the torrefaction process at 200 °C
and 300 °C to simulate the lower and higher temperatures of tor-
refaction. Also, pyrolytic decomposition of each pseudocomponent
-0.0004 is presented. At 200 °C only the moisture of the sample is lost and
0 1000 2000 3000 4000 5000
is very slightly begins to degrade part of lignin and hemicellulose,
Time, s
however cellulose is unaffected. Moreover, in curves of the tor-
Fig. 5. Simulation of TG (a) and DTG (b) curves of torrefaction of olive tree pruning refaction performed at 300 °C is observed as cellulose and hemicel-
at 200 °C at a heating rate of 15 °C/min and a holding time of 60 min at 200 °C. lulose have an evident degradation.
1418 M.A. Martín-Lara et al. / Applied Thermal Engineering 113 (2017) 1410–1418
4. Conclusions
In this work, kinetic of torrefaction of olive tree pruning was
evaluated based on thermogravimetric data in nitrogen atmo-
sphere. Torrefaction of olive tree pruning could not be modeled
by isoconversional kinetics for one-step global reaction. The tor-
refaction activation energies ranged from 61.56–217.83 kJ/mol. A
pseudo-mechanistic model based on four independent parallel
reactions was proposed to modeling torrefaction kinetics of olive
tree pruning. This pseudo-mechanistic model provided a good
agreement with the experimental data; therefore, the kinetic
parameters obtained could be used to predict olive tree pruning
torrefaction.
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