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Bioresource Technology 100 (2009) 39633973

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Use of autocatalytic kinetics to obtain composition of lignocellulosic materials


Agustn Garca Barneto a,*, Jos Ariza Carmona a, Jos E. Martn Alfonso a, Lus Jimnez Alcaide b
a
b

Chemical Engineering Department, Campus El Carmen, University of Huelva, 21071 Huelva, Spain
Chemical Engineering Department, Campus de Rabanales, C-3, University of Crdoba, 14004 Crdoba, Spain

a r t i c l e

i n f o

Article history:
Received 26 January 2009
Received in revised form 13 March 2009
Accepted 16 March 2009
Available online 14 April 2009
Keywords:
Biomass
Pulp
Pyrolysis
Combustion
Kinetic

a b s t r a c t
Non-isothermal thermogravimetric analysis (TGA) data of biomasses and pulps originating from nonwood and alternatives materials (i.e., Tagasaste or rice straw) have been tted with rened models, which
include autocatalytic kinetics. Data sets were obtained for different experimental conditions, such as variations of heating rate and atmosphere, i.e., inert (pyrolysis) versus oxidative atmosphere (combustion).
Besides the access to classical kinetic parameters (pre-exponential factor, activation energy, and reaction
order), the improved data analysis enabled the determination of the chemical composition of the samples
(cellulose, hemicellulose, extractives, lignin). The latter compared very well with those obtained by conventional methods (chemical analysis, HPLC). Given the reduced environmental impact and rapidness of
the method, potential applications for research related to new biomasses and industrial processes can be
foreseen.
The herein implemented method is based on the assumption that samples contain pseudo-components, which independently degrade, and that combustion is the combination of an initial volatilization
process (similar to pyrolysis) and a subsequent char oxidation process. Further, it was found that for a
reliable modeling of the volatilization stage, extractives should be considered as well, together with
the classical pseudo-components: hemicellulose, cellulose and lignin. The char oxidation stage has been
simulated as a sum of the oxidation of three char types, one for each main pseudo-component.
Importantly, tting of TGA curves under consideration of autocatalytic kinetics allows the determination of a consistent set of kinetic parameters at different heating rates and leads to signicant suppression
of the compensation effect. While autocatalysis (characterized by the nucleation order) is not very significant for pyrolysis of biomasses, it can reach high levels for combustion, especially when high heating
rates are used. In cellulosic char oxidation a nucleation order larger than one was tted. The autocatalysis
level of the char oxidation can rapidly increase with small modications of the heating rate (i.e. to pass
from 5 to 10 C/min). In this case, the classically applied nth-order kinetic is particularly insufcient to t
experimental data with the same set of the kinetic parameters.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
The increasing demand for paper raised the need for low-cost
raw materials and also to develop new processes in order to boost
production. From 1999 to 2003, production of cellulose pulp from
wood species rose only about 4%, whereas that pulp from nonwood species increased by 10% (Rodriguez et al., 2008a). The use
of non-wood biomass for pulp production has been studied intensively. It was found that fast growing plants like Tagasaste, Pawlovnia or Leucaena, residual biomass like rice straw or, even, sludge
waste (Roliadi et al., 2003) can be an alternative to the traditional
use of wood-based biomass in paper production (Jimenez et al.,
2002, 2005; Rodriguez et al., 2008a). The search for such alterna-

* Corresponding author. Tel.: +34 959 219982; fax: +34 959 219983.
E-mail address: agustin.garcia@diq.uhu.es (A.G. Barneto).
0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.03.048

tives has also dramatic social and environmental impact, e.g.,


reduction of deforestation.
Research related to new biomasses and innovative industrial
processes, based on lignocellulosic materials, required an accurate
knowledge of the composition of biomass feedstocks, mainly its
hemicellulose, cellulose, lignin and extractives contents. Conventional chemical methods for composition analysis of biomass are
not appropriate for large quantities of samples. Furthermore, their
implementation causes serious issues with regard to environmental impact, cost and time requirements. Today, beside chemical
analysis different alternatives exist, including liquid chromatography (HPLC) (Parajo et al., 1995; Garrote et al., 1999) or near infrared spectroscopy (NIRS) (Bruno-Soares et al., 1998; Kays and
Barton, 2002; Kelley et al., 2004).
On the other hand, thermogravimetric analysis has been traditionally used to obtain kinetic parameters, thereby assuring
an adequate control of pyrolysis and combustion processes

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973

(Varhegyi et al., 1996; Conesa et al., 2001). Using small sample


quantities and sufciently low heating rates, the mass loss curve
of biomass can be interpreted as the sum of partial mass losses
associated to the main components (hemicellulose, cellulose and
lignin). The three-component (or better three-pseudo-component) model is widely used to explain biomass pyrolysis (Orfao
et al., 1999; Gronli et al., 2002). In this case, simulations based
on nth-order kinetics show that hemicellulose and cellulose
decomposes consecutively, being responsible for the main mass
loss between 175 and 375 C. Lignin decomposes in a broad temperature range (between 175 and 700 C), which superposes the
hemicellulose and cellulose mass loss peaks (Varhegyi et al.,
1996; Caballero et al., 1997). The tting procedure yields a set
of kinetic parameters (pre-exponential factor, activation energy,
reaction order and stoichiometric coefcients). However, this
method is subject to inaccuracy, basically caused by the compensation effect (Agrawall, 1985) which, according Conesa
et al. (2001), can be avoided using the same set of kinetic
parameters for several runs performed at different heating rates.
In order to obtain a realistic model about biomass volatilization
it is necessary to take extractives and inorganic components into
account. For this reason, volatilization should be simulated by
means of four (including extractives) or more pseudo-components (Muller-Hagedorn et al., 2003). According to Meszaros
et al. (2007b) thermal decomposition of extractives (fatty acids,
hydrocarbons, phytosterols, carbohydrates and phenol derivatives) occurs in two main ranges between 130 and 550 C. The
rst decomposition peak of the extractable materials is seen as
a shoulder in the DTG curve (130250 C), and the second peak
(250500 C) is superimposed to polymeric constituents of the
biomass. In some biomasses (i.e. Hesperaloe) an inorganic fraction degrades, approximately, between 600 and 700 C. This
mass loss is associated with decomposition of carbonates (Hartman et al., 1996; Samtani et al., 2002).
Thermogravimetric analysis has been occasionally employed
as analytical method. Orfao and Figueiredo (2001) carried out isothermal thermogravimetric experiments (high, medium and low
temperature) in order to obtain kinetic parameters for each pseudo-component. On the basis of a kinetic scheme consisting of the
decomposition of three pseudo-components, this method was
successfully applied to data simulation for three different lignocellulosic materials (pinewood, eucalyptus wood and pine bark).
Muller-Hagedorn et al. (2003) and Muller-Hagedorn and Bockhorn (2007) proposed a transferable kinetic model for biomass
pyrolysis based on the independent pyrolysis of its main components (four components: two hemicelluloses, lignin and cellulose,
or ve components: two hemicelluloses, lignin and two celluloses). Both, Ghetti et al. (1996) and Serapiglia et al. (2008), used
thermogravimetric analysis in oxygen atmosphere to determine
hemicellulose, cellulose and lignin content. In both cases, the
DTG curve was divided in three zones (245290 C; 290350 C;
and 350525 C), supposing that only one pseudo-component degrades in each one of the temperature intervals: hemicellulose at
low temperature, cellulose at medium temperature and lignin at
high temperature.
In the present study pyrolysis and combustion of different biomasses (non-wood and alternative biomasses) and pulps has been
modelled. In order to improve the tting of experimental data obtained from thermogravimetric analysis, autocatalytic kinetics has
been used to simulate thermal degradation of the main components of samples, including extractives and inorganic components. As consequence of the tting process a set of kinetic
parameters, including weight percentage of each component, is
obtained. The results were found to be comparable to those to obtained using traditional chemical methods and high pressure liquid chromatography.

2. Methods
In this study two types of lignocellulosic materials have been
used: biomasses and pulps. This selection has been made for two
reasons: (a) it allows to verify the applicability of the herein used
method with commonly used materials in paper industry, and
(b) it enables to test the validity of the kinetic models in systems
with very different cellulose and lignin contents.
Non-wood biomasses used in this work are considered energetic crops useful in soil restoration. Leucaena (Leucaena Leucocephala) is a leguminous tree that grows quickly in arid spaces
being used as rewood or cattle feed. Tagasaste (Chamaecytisus
Palmensis) is a small spreading evergreen shrub used as fodder in
arid regions. Table 1 shows the typical biochemical composition
of these raw materials. Alternative biomasses used in this work
have been rice straw and empty fruit bunches (EFB). The rice straw
used was the O. sativa variety Senia from the Arroz de Valencia
denomination of origin. The empty fruit bunches (EFB) consist of
the lignocellulosic material accompanying oil palm fruits. The oil
palm used in this paper is known as African palm (Elaeis guineensis), because it originated in West Africa. It has been provided by
the company Straw Pulping Engineering, S.L. (Zaragoza, Spain).
Samples were milled to pass through an 8 mm screen, then
were air-dried to constant moisture, homogenized in a single batch
to avoid differences in composition among aliquots, and then
stored.
2.1. Pulping
The biomass was cooked in a 15 l batch reactor that was heated
by an outer jacket containing electrical wires. The biomass was
placed in the reactor and pulped by using soda (15%) and anthraquinone (1%), during a cooking time of 90 min at a temperature
of 180 C. Following pulping, the cooked material was washed to
remove residual cooking liquor and berized in a disintegrator at
1200 rpm for 30 min, after which the pulp was beaten in a
Sprout-Bauer rener. The berized material was passed through
a screen of 0.16 mm mesh size in order to remove uncooked particles. Finally, the pulp was drained in a centrifuge and allowed to
dry at room temperature.
2.2. Thermogravimetric analysis
The TG runs was carried out with a Setaram 92-12.18 Model
TGA on samples of around 5 mg. Pyrolysis runs were carried out
in nitrogen atmosphere and combustion runs in synthetic air
(N2:O2 4:1). Three heating rates (5, 10 and 20 C/min) have been
used from 25 to 900 C.
2.3. Hemicellulose and cellulose determination using HPLC
Samples were homogenized in a single lot to avoid differences
in composition among aliquots. Aliquots from the homogenized
feedstocks were subjected to quantitative acid hydrolysis with
5 ml of 72% sulphuric acid for one hour and quantitative posthydrolysis with 4% sulphuric acid (adding water until 148.67 g)

Table 1
Chemical properties of various biomasses.

Rice straw
Leucaena
Tagasaste

Hemicellulose
g/100 g

Cellulose
g/l00 g

Lignin
g/l00 g

19.520.1
31.537.8
31.534.5

41.244.0
40.144.4
43.647.7

18.021.9
19.121.4
14.115.7

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973

at 121 C during 60 min. Before HPLC analysis, the solid residue


from the post-hydrolysis process was recovered by ltration and
considered as Klason lignin. The monosaccharides (glucose, xylose
and arabinose) and acetic acid contained in hydrolysates were
determined by HPLC. Chromatographic separation was performed
using
an
ion-exchange
resin
Metacarb
87H
column
(300  7.8 mm, Varian, USA) under the following conditions: mobile phase 0.05 mol l1 sulphuric acid, ow rate 0.5 ml/min, and
column temperature 30 C (Parajo et al., 1995; Garrote et al., 1999).
2.4. Chemical characterization of pulps and biomasses
The components of raw materials were determined in accordance with respective Tappi standard procedures: T-222 for lignin,
T-203 0S-61 for a-cellulose, T-204 for ethanolbenzene extractives
and T-211 for ash. Holocellulose was quantied using the method
described by Wise et al. (1946).

Fig. 2. Experimental TG and DTG under N2 at different heating rates for pulp from
rice straw.

3. Results and discussion


Usually biomass is a term for all organic material that stems
from plants (McKendry, 2002). Main components of biomass are
cellulose, hemicellulose, lignin and extractives. Its respective proportions changes according to the type of biomass. For example,
wood plants (hardwoods and softwoods) contain 2030% hemicellulose, 3550% cellulose, 2030% lignin, and 510% extractives.
Herbaceous plants and grasses contain less lignin, but more hemicellulose than wood plants (McKendry, 2002; Theander, 1985).
Composition ranges, as reported in the literature (Deng et al.,
2007; Sangnark and Noomhorm, 2004; Rodriguez et al., 2008b),
are compiled in Table 1.
3.1. Raw materials. Thermogravimetric analysis
Figs. 1 and 2 show the variation of experimental mass loss (TG)
and mass loss rate (DTG) with temperature under nitrogen atmosphere at different heating rates for a biomass (Tagasaste) and a
pulp (obtained from rice straw), respectively.
Table 2 shows characteristic parameters of these curves at the
same heating rate (10 C/min) (MLmax is the higher mass loss; vmax
is the highest mass loss rate, and Tmax the temperature at highest
mass loss rate) for two different biomasses and pulps.
Based on these data it is evident that pyrolysis of pulp produces
less char (higher MLmax) and shows a higher mass loss rate than
biomass. This general behavior can be explained considering that
pulp has a much lower lignin content, a substance that is difcult
to volatilize and produces a high amount of char. The temperature

Fig. 1. Experimental TG and DTG under N2 at different heating rates for Tagasaste.

Table 2
Characteristic pyrolysis parameters for biomass or pulp.

Biomass
Pulp

Tagasaste
Leucaena
Rice straw
EFB

MLmax (g/100 g)

Tmax (C)

vmax (min1)

77.2
77.9
86.1
94.0

347
341
358
356

8.3
8.5
17.1
20.0

at the highest mass loss rate is similar for both pulps, and higher
than obtained for biomasses.
As expected, an increase in the heating rate produces a shift of
the curves to higher temperatures without signicant change in
their shapes. The characteristic shape of the TG curve of biomass
pyrolysis is explained with the independent volatilization of its
components (hemicellulose, cellulose and lignin). It is generally accepted that the main peak in the DTG curve is produced by cellulose volatilization (close 350 C). The hemicellulose degradation
is found as a characteristic shoulder in cellulose-related peak at
temperatures lower than 300 C. The volatilization of these two
components is overlapped with lignin volatilization, that starts at
low temperatures (like hemicellulose) and completes at temperatures greater than 700 C (Orfao et al., 1999).
In sharp contrast are TG-DTG curves obtained for pulp pyrolysis.
Fig. 2 shows a narrow peak, almost symmetric, without hemicellulosic shoulder at low temperature and almost without lignin tail at
higher temperature (Soares et al., 1995). Both changes, as compared to biomass, are a consequence of the pulping process.
Figs. 3 and 4 show TG and DTG curves in air atmosphere for biomass (Tagasaste) and pulp (from rice straw) samples.
For both materials two different steps (peaks) are observed. The
rst step (between 250 and 400 C) is associated with a thermal
volatilization (similar to pyrolysis) (Mamleev et al., 2007) of the
main component of the samples, producing volatiles and char. In
biomass, this peak could have a hemicellulosic shoulder like for
pyrolysis. Pulp volatilization (at higher temperature than biomass)
produces a sharper peak than for biomass. The second step (at temperatures higher than 400 C for both samples) is associated with
char oxidation, resulting in new volatiles and nally solid residues
(Evans and Milne, 1987; Conesa et al., 1998; Meszaros et al.,
2007a). The shape of this second peak is more complex and,
according to our data, is subjected to variations depending on the
type of sample and heating rate. Usually, using low heating rates
this peak is broader. However, when the heating rate is increased,
the peak becomes narrower, and in certain conditions can appear
very sharp, which is related to rapid char combustion.

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973

(b) Peak deformation. A symmetrical sharp peak, usually present for char oxidation, can not be simulated using a reaction
order close to zero in a nth-order kinetic equation.
Both problems can be approached using autocatalytic models.
According to autocatalytic models the reaction rate depends on
both, reacted and not reacted fractions. According Burnham et al.
(1996), they are based on the concept that the reaction starts at
various nuclei that react at an accelerating rate as their reaction
interface grows until the reaction spheres coalesce as the reaction
nears completion. ProutTompkims (PT) equation (an autocatalytic
model) is an empirical law Eq. (3) useful in reactions that show an
acceleratory period, inconsistent with any nth-order reaction model (Prout and Tompkins, 1944, 1946; Burnham, 2000).

dx
n
kx 1  qxm
dt
Fig. 3. TG and DTG curves of biomass (Tagasaste) at different heating rates.

In this equation x is the reacted fraction (1a), n the reaction order and m the nucleation order, exponent that affects to reacted
fraction and measures the autocatalysis level. If m = 0 then the
PT equation simplies into a nth-order equation. The PT equation
and other a versus time sigmoid functions like the Avrami-Erofeev
equation, can be derived from the Sestak-Berggren equation (Sestak and Bergreen, 1971; Sestak, 1990) Eq. (4).

dx
n
kx 1  qxm  lnxp
dt

Fig. 4. TG and DTG curves of pulp (obtained from rice straw) at different heating
rates.

3.2. Autocatalytic thermal degradation of lignocellulosic materials


Thermal volatilization of biomass pseudo-components, in both
inert and oxidative atmosphere, is usually tted using nth-order
kinetics Eq. (1).

da
k1  an
dt

Where a is the conversion, n the reaction order and k the kinetic


constant which is usually expressed according to the Arrhenius
law (k0 is the pre-exponential factor and E the activation energy)
Eq. (2).
E

k k0 eRT

Using inert atmosphere (pyrolysis) and moderate heating rates,


nth-order kinetic is suitable to simulate the thermal degradation of
a biomass. Under these conditions the mass loss rates curves (DTG)
do not show narrow peaks, and the calculated curves adequately t
experimental data. Nevertheless, the use of nth-order kinetic model for other lignocellulosic materials (for example pulps) and distinct experimental conditions (for example, oxidative atmosphere
and higher heating rates), is limited, at least, for two reasons:
(a) Compensation effect. A change in activation which is compensated with another change in pre-exponential factor. In
this case, optimization methods provide k0E values unusually high when the tting of narrow peaks is forced (Varhegyi et al., 1994; Aggarwal et al., 1997).

According to Burnham et al. (1996, 2000), the ProutTompkins


(PT) model yields activation energies which are lower (and more
realistic) than obtained from simple nth-order kinetic ts. In a similar way, Benoit et al. (1985) have shown that excessively high activation energy values can be avoided using a PT model.
According to the obtained data (see below), autocatalysis relevance changes with sample type and decomposition conditions.
Thermal degradation of extractives and lignin pseudo-components
does not involve autocatalytic processes under any conditions
(nitrogen or air atmosphere) studied herein. Thermal volatilization
of hemicellulose and cellulose shows autocatalytic behaviour only
under air atmosphere. However, char oxidation (under air atmosphere) is a clear autocatalytic process, except for lignin char. As
a general observation, autocatalysis is promoted by oxygen presence and higher heating rates.
3.3. Pyrolysis model
Pyrolysis of lignocellulosic materials is usually explained as the
sum of the thermal degradation of its main components: hemicellulose (H), cellulose (C) and lignin (L) (Meszaros et al., 2004; Antal
and Varhegyi, 1995; Szabo et al., 1996; Caballero et al., 1996; Gronli et al., 2002; Varhegyi et al., 2004). In this work, if necessary, two
other components were included in the tting of the experimental
data: organic extractives (E) and inorganic (I). In the proposed
pyrolysis model, thermal volatilization of hemicellulose, cellulose
and lignin results in volatiles and char, however, extractives only
produce volatiles, and inorganics (basically carbonates) yield volatiles and ash. It is assumed that under inert atmosphere both char
and ash do not undergo any transformation. This approach does
not imply that the content of each fraction was a pure substance,
although the real content of these types of fractions are only related to its parent materials. Scheme 1 shows the detailed pyrolysis
model including all components: Si represents the initial solids
fractions in the samples, Ri the solids residues, Vi the volatiles
and A the ash produced. This model must be adapted to the concrete lignocellulosic material studied. For example extractives are
present in biomass but not in pulp, and inorganic fraction must
be considered only in certain biomasses (and pulps) like Hesperaloe or compost.

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973

The variables mexp and mcal are the experimental and calculated
mass, respectively, for the n points in each experiment.
The model validity was tested by calculating the variation coefcient (VC)

VC%

Scheme 1.

Usually, in the pyrolysis model for biomass we considered four


fractions: hemicellulose, cellulose, lignin and extractives. However,
pulp pyrolysis is adequately simulated using just three fractions
(without extractives). The respective thermal degradations have
been simulated combining autocatalytic (hemicellulose and cellulose) and nth-order kinetics (lignin and extractives). Noteworthy,
in principle, pyrolysis of the components of the lignocellulosic
materials can be satisfactorily described by nth-order kinetics.
However, in order to compare the tted parameters with the ones
obtained for combustion (see below), the simulation also includes
autocatalytic kinetics.
For lignin and extractives it is necessary to resolve Eq. (5).

dai
ki 1  ai ni
dt

This equation also can be expressed as:


n
dV i
Vi i
ki V 1i 1 
dt
V 1i

Where Vi is the mass of the volatile fraction at any time and V1i is
the mass of the volatile fraction at innite time of each component.
Therefore, for both components it is necessary to determine four
parameters: pre-exponential factor, activation energy, reaction order and mass at innite time.
For hemicellulose and cellulose it is necessary to resolve Eq. (7).
This equation is a version of PT equation used by Burnham et al.
(1996). The reaction rate depends on both, not reacted fraction
1  ai n  and reacted fraction am
i , being n the reaction order
and m the nucleation order. The factor s is related with the values
of the function when conversion is close to 0 or 1. According to
Burnham et al. (1996) s can be assumed as 0.01.

dai
ki 1  ai n s am
i
dt

This equation also can be expressed as:


n 

m 
dV i
Vi i
Vi
s
ki V 1i 1 
dt
V 1i
V 1i

n
X
mexp  mcal 2
i1

10

N and P are the number of data points and parameters tted,


respectively, and mexp is the average of the experimental masses.
The obtained results (mean value and standard deviation for
three heating rates) are shown in Tables 3 and 4.
Figs. 5 and 6 compare calculated and experimental mass loss
rates and show the evolution of mass losses for each fraction.
According to the simulation of the biomass pyrolysis, the shoulders adjacent to the main peak (cellulose) are caused by extractives
(235 C) (Meszaros et al., 2007b) and hemicellulose (295 C). At
temperatures above 395 C only lignin degrades. In cellulosic pulp
pyrolysis, the main peak (cellulose) does not present any shoulder.
Thus, the relative importance of the hemicellulosic fraction has
diminished, and the lignin fraction produces only a small tail.
Extractives are not present and hemicellulosic peak is almost overlapped with cellulosic peak.
Calculated kinetic parameters are similar for biomass and pulp
and close to the ones presented by others for lignocellulosic materials (Antal et al., 1998; Capart et al., 2004; Mamleev et al., 2006).
In both cases (biomass and pulp), the cellulosic fraction presents an
activation energy close to 200 kJ/mol (195 and 207 kJ/mol respectively), a pre-exponential factor close to 1015 s1 (3.5  1014 and
1.4  1015 s1, respectively) and a reaction order close to one
(Mamleev et al., 2007; Varhegyi et al., 1988; Varhegyi et al.,
1989). The main difference is obtained for the nucleation order
(0.01 versus 0.05 for biomass and pulp, respectively). This shows
that autocatalytic processes play a more signicant role in the
pyrolysis of the cellulosic fraction of pulp than for biomass.
Xylan is a representative hemicellulose (Orfao et al., 1999; Rao
and Sharma, 1998; Yang et al., 2007). Kinetic parameters reported
for the thermal degradation of xylan (Di Blasi and Lanzetta, 1997)
are in satisfying agreement with those calculated for the hemicellulosic fraction in both samples (pulp and biomass). The activation
energy was herein obtained is close to 95 kJ/mol, the pre-exponential factor is around 106 s1, and the reaction order was determined

Table 3
Kinetic parameters for biomass pyrolysis (Tagasaste).
Pseudo-component

ln k0 (s1)
Eact (kJ mol1)
n
m
V1 (%)
VC (%)

Hemicellulose

Cellulose

Lignin

Extractives

14.8 0.5
93 2
1.2 0.1
0.04 0.01
20.8 0.4
0.29 0.12

33.5 0.6
195 3
1.13 0.06
0.01 0.01
28 2

9.0 0.1
79 3
2.7 0.2

15.1 0.2
86 2
3.10 0.09

22 1

7.2 0.1

In consequence for each component it is necessary to determine


ve parameters: pre-exponential factor, activation energy, reaction
order, nucleation order, and mass at innite time.
Integration and optimization of the kinetic equations was carried out using the RungeKutta method and GaussNewton methods, respectively. The objective function to minimize was:

OF

p
OF=N  P
 100
mexp

Table 4
Kinetic parameters for pyrolysis of pulp (obtained from rice straw).
Pseudo-component

ln k0 (s1)
Eact (kJ mol1)
n
M
V1 (%)
VC (%)

Hemicellulose

Cellulose

Lignin

14.3 0.2
95 1
1.02 0.07
0.25 0.03
12.6 0.1
0.20 0.02

34.9 0.2
207 1
1.02 0.02
0.05 0.04
66 1

8.9 03
84 2
3.11 0.06
7.3 0.2

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973

Fig. 5. Simulation of DTG curve of biomass pyrolysis at 10 C/min (Tagasaste).

Fig. 6. Simulation of DTG curve of pulp pyrolysis at 10 C/min (rice straw).

as close to one. Once more, the main difference between both


hemicellulosic fractions is the nucleation order: 0.04 and 0.25 for
biomass and pulp respectively. As concluded for the cellulosic fraction, autocatalytic behaviour is more important for pulp than for
biomass.
Kinetic parameters for the lignin component vary more than for
other components of biomass. In a study on olive solid waste (Jauhiainen et al., 2004) values of 69.4 kJ/mol and 1.2  104 s1 for the
activation energy and pre-exponential factor, respectively, were
obtained. In the different samples studied in this work, activation
energy and reaction order for the lignin fraction are quite variable.
These differences can be related to the delignication process applied, which modies amount and characteristics of the initial lignin present in biomass. In any case volatilization of this fraction
occurs with a high reaction order (2.7 and 3.11 for biomass and
pulp, respectively) (Caballero et al., 1996, 1995; Manya et al.,
2003).
The described pyrolysis model has been applied to several lignocellulosic materials obtaining accurate tting. Figs. 7 and 8 show
the simulation of the pyrolysis of two biomasses: one woody biomass (Leucaena) and an alternative biomass (rice straw).
In both cases, the tting process was optimized from parameters obtained for Tagasaste pyrolysis. In both Figs. 7 and 8, it can
be seen that the experimental data of Leucaena and rice straw
are well described by our pyrolysis model. This corroborates the
general applicability of the model and at the same time exibility
to adapt to singularities of different sample types. The following

Fig. 7. Pyrolysis simulation for a woody biomass (Leucaena) at 10 C/min.

Fig. 8. Pyrolysis simulation for an alternative biomass (rice straw) at 5 C/min.

general conclusions for the pyrolysis of lignocellulosic materials


can be drawn:
The rst fraction that volatizes are extractives. Its degradation
follows an nth-order kinetic and causes a broad DTG peak which
can extend until 400 C.
The second fraction that volatizes is hemicellulose. Its degradation is best described by a weakly autocatalytic rst order kinetic
and extends to temperatures of about 300400 C
The third fraction that volatizes is cellulose. Its degradation follows a weakly autocatalytic rst order kinetic and nishes close
400 C.
The last fraction that volatizes is lignin. Although its volatilization begins at low temperatures, its degradation follows a third order kinetic and nishes close to 700 C. At temperatures above
400 C lignin is the only component that is degraded.
3.4. Combustion model
Scheme 2 presents a model for biomass combustion. The combustion model is based on the pyrolysis model, but some additional processes need to be included. For the hemicellulosic and
cellulosic fractions two consecutive processes are assumed. The
rst reaction is a thermal decomposition (volatilization) (Mamleev
et al., 2007) that produces volatiles and char. The second reaction
implies char oxidation in the presence of oxygen. For the lignin
fraction, best results have been obtained assuming two competitive processes: volatilization (similar to hemicellulose and cellulose volatilization) and oxidation of lignin-derived char.

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973

using nth-order kinetics. The same applies to lignin char oxidation,


which was simulated by using an nth-order kinetics. The remaining processes (volatilization of hemicellulose and cellulose fractions, oxidation of its respective chars) have been simulated
using autocatalytic kinetics. The differential equations that must
be resolved in every case are shown in Table 5.
In all cases, conversions (a and c) can be expressed as a function
of its respective mass of the volatile fraction (Vi) and the mass of
the volatile fraction at innite time (V1i).
Taking into consideration that the kinetic constants ki are expressed by the Arrhenius equation, the most complex combustion
model has thirty-six parameters. Tables 6 and 7 show the tting results obtained for a biomass (Tagasaste) and a pulp (from rice
straw).
3.4.1. Volatilization stage
The average variation coefcients (VC) of these ttings are
0.36 0.05 for biomass and 0.38 0.05 for pulp, obtained from
three runs with different heat rates. Figs. 911 show DTG curves
at 10 C/min (experimental and calculated) for a woody biomass
(Tagasaste), an alternative biomass (rice straw) and a pulp (from
rice straw), respectively.
Kinetic parameters obtained in the volatilization stage under
oxidative atmosphere are similar those obtained under inert atmosphere (pyrolysis), showing that thermal degradation is very similar in both cases. For all fractions, pre-exponential factors and
activation energies are similar and small differences in the reaction
orders are calculated. However, oxygen presence has signicantly
effect on the nucleation order, that is to say, in the autocatalysis
of the thermal degradation. Pyrolysis of hemicellulosic and cellulosic fractions shows virtually no autocatalytic behaviors; nevertheless, under oxidative atmosphere the average order of
nucleation (three heating rates) increased signicantly (from 0.04
to 0.31 for hemicellulose; from 0.01 to 0.15 for cellulose). This signicant autocatalysis level for hemicellulose and cellulose volatilization explains the difculties to use nth-order kinetic to simulate
the rst peak of DTG combustion curves and, consequently, the
determination of unusually high activation energies and pre-exponential factors (compensation effect).
For pulp combustion similar conclusions are obtained: oxygen
presence has small effects on kinetic parameters of the volatilization step, except for lignin. It is remarkable that, in order to obtain
an accurate tting for pulp combustion, it is necessary to use autocatalytic kinetic for lignin volatilization. Using nth-order kinetic,

Scheme 2.

Extractives and inorganics (carbonates) volatize in the same manner as occurs under inert atmosphere (pyrolysis). According to our
model several chars are produced. Chemical (C/H/O ratio) and
physical differences (morphology or porosity) between these chars
can explain their distinct oxidation behavior, causing changes in
respective kinetic parameters (Senneca, 2007). In our case, the production of three different chars allows to explain the complex peak
provoked by char oxidation in the DTG curves of lignocellulosic
materials.
Considering the way in which the mass loss takes place (related
with the shape of DTG peaks), the degradation of each one of the
proposed fractions has been simulated with a certain type of kinetic. In the same way as applied for pyrolysis, volatilization processes of lignin, extractives and inorganics have been simulated

Table 5
Kinetic equations used in biomass combustion simulation.
Fraction

Volatilization

Hemicellulose and cellulose

dai
dt

ki 1  ai n 0:01 am
i

Char oxidation
dci
dt

ki ai  ci n 0:01 cm
i

Lignin

dai
dt

ki 1  ai

ni

dai
dt

ki 1  ai ni

Extractives and inorganics

dai
dt

ki 1  ai

ni

Table 6
Kinetic parameters for biomass (Tagasaste) combustion.

Hemicellulose volatilization
Cellulose volatilization
Lignin volatilization
Extractives volatilization
Char hemicellulose oxidation
Char cellulose oxidation
Char lignin oxidation

ln k0 (s1)

Eact (kJ mol1)

V1 (%)

14.3 0.1
35.6 0.1
8.5 0.1
15.8 0.I
19.55
19.55
19.55

87 2
194 1
76 2
88 1
143 5
132 5
149 2

0.72 0.02
1.50 0.01
3.32 0.09
3.13 0.05
1 02 0.04
1.09 0.09
0.88 0.03

0.31 0.06
0.15 0.04

15.9 0.3
28.5 0.4
19 2
7.3 0.1
112 0.2
5.9 0.5
92

0.3 0.2
1.4 0.1

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973

Table 7
Kinetic parameters for pulp (from rice straw) combustion.

Hemicellulose volatilization
Cellulose volatilization
Lignin volatilization
Char hemicellulose oxidation
Char cellulose oxidation
Char lignin oxidation

ln k0 (s1)

Eact (kJ mol1)

V1 (%)

14.5 0.1
35.4 0.9
8.5 0.1
19.55
19.55
19.55

92.6 0.1
201 3
65.9 0.9
136.9 0.S
141.2 0.9
148 2

1.0 0.1
0.95 0.08
2.73 0.06
1.14 0.06
1.08 0.09
0.91 0.05

0.40 0.02
0.48 0.04
1.00 0.04
0.52 0.02
0.72 0.01

15.1 0.7
62 2
82
2.9 0.2
8.6 0.9
1.0 0.2

unusual high values for pre-exponential factor and activation energy are calculated. This behavior can be explained considering
that pulping process alters the physico-chemical properties of
the remaining lignin.

Fig. 9. Tagasate combustion. Heating rate 10 C/min.

Fig. 10. Leucaena combustion. Heating rate 10 C/min.

Fig. 11. Rice straw combustion. Heating rate 10 C/min.

3.4.2. Char oxidation stage


Under oxygen atmosphere, after volatilization stage, the obtained chars (hemicellulosic, cellulosic and lignin chars) are oxidized. In order to simplify the study of the oxidation process of
the three chars involved, the pre-exponential factor was xed. This
led to the expression of the differences between the chars in the
other kinetic parameters, mainly in the activation energy. The selected value for the pre-exponential factor (ln k0 = 19.55) was the
average value obtained from a series of previous simulations. In
this way it could be veried that char oxidation proceeds with a
reaction order close to one, and that activation energies range between 130 and 150 kJ/mol (Jauhiainen et al., 2004), depending on
the feedstock (hemicellulose, cellulose or lignin). Low activation
energies are usually related to cellulosic char; on the other hand,
lignin char oxidation is accompanied by highest activation
energies.
According to obtained results, the char oxidation stage has signicant autocatalytic contributions. Using low heating rates, char
oxidation usually produce a broad peak (sum of three broad peaks)
in the DTG curve. However, when the heating rate increases a
sharp peak can appear (sum of one or two sharp peaks and one
broad peak). This sharp peak is related with fast char combustion
which, in agreement with simulations, shows a high autocatalysis
level. We have not found fast combustions in lignin char (always
produce a broad DTG peak), however, according to our data, cellulosic char is most prone to produce a sharp peak. This behavior affects nucleation order, which can reach 1.4 in cellulosic char
oxidation and 0.3 in hemicellulosic char oxidation. The autocatalytic behavior during char oxidation (associated to sharp peaks)
prevents the use of nth-order kinetic to simulate the experimental
data obtained in biomass combustion.
In studied range, the heating rate that produces fast char oxidation depends on the considered biomass. Using Tagasaste as feedstock, cellulosic char oxidation always produces a sharp peak,
showing a high autocatalytic level (nucleation order between 1.38
and 1.29) already at low heating rate (5 C/min). On the other hand,
hemicellulosic char oxidation increases its autocatalytic behavior
(nucleation order from 0.14 to 0.36) (Table 8) but never shows a
sharp peak. Using Leucaena as feedstock both chars (cellulosic and
hemicellulosic) show broad peaks (low autocatalytic level) at
5 C/min, however, an increase of the heating rate to 10 C/min results in dramatic changes in char oxidation. From 10 C/min hemicellulosic and cellulosic char oxidations show a high autocatalytic
level, and, consequently, sharp peaks in DTG curve (nucleation order between 1.35 and 1.38). Using rice straw as feedstock, the autocatalytic behavior during cellulosic char oxidation does not change
at any heating rate investigated herein. In this case, hemicellulosic
char oxidation has no autocatalytic character.
Similar conclusions can be reached by considering a pulp as
feedstock: hemicellulosic and cellulosic char oxidation show sig-

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973


Table 8
Char oxidation: effect of the heating rate on the nucleation order.

Tagasaste
Leucaena
Rice straw
Pulp (from rice straw)

Hemicellulosic
Cellulosic char
Hemicellulosic
Cellulosic char
Hemicellulosic
Cellulosic char
Hemicellulosic
Cellulosic char

char
char
char
char

Heating rate 5 C/min

Heating rate 10 C/min

Heating rate 20 C/min

0.14
1.38
0.05
0.44
0.01
0.62
0.52
0.71

0.29
1.31
1.38
1.37
0.02
0.59
0.54
0.73

0.36
1.29
1.37
1.35
0.05
0.59
0.50
0.72

nicant autocatalytic behavior. In this case, using pulp obtained


from rice straw, the nucleation order reaches high values, which,
however, do not vary with the heating range. As observed for biomass, the nucleation order for hemicellulosic char oxidation is lower than for cellulosic char oxidation (Table 8).
3.5. Thermogravimetric analysis as analytical method
The use of autocatalytic kinetic to simulate the combustion of
lignocellulosic materials has advantages over data treatment solely
based on to nth-order kinetic, allowing the characterization of the
biochemical composition of the analyzed samples. The consideration of the nucleation order in the kinetic equations avoids the
compensation effect, allowing the extraction of a set of kinetic
parameters characteristic of each biomass fraction. Accurate tting
of the experimental data are obtained although sharp peaks appear
in DTG curves. Kinetic parameters (pre-exponential factor, activation energy and reaction order) are independent of the applied
heating rate and, moreover, the calculated weight percentages
for each fraction agree with those obtained by other analytical
methods (traditional chemical analysis and HPLC).
In order to obtain the weight percentage of each component in
analyzed samples (biomasses and pulps) mass losses produced
during initial volatilization and posterior char oxidation need to
be taken into account. The sum of both masses is the percentage
of that component in the initial sample (Figs. 12 and 13). For example, according to Tables 6 and 7, Tagasaste biomass composition is:
hemicellulose 27.1% (15.9 + 11.2), cellulose 34.4% (28.5 + 5.9), lignin 28% (19 + 9) and extractives 7.3%. The pulp composition is:
hemicellulose 18.0% (15.1 + 2.9), cellulose 70.6% (62 + 8.6) and lignin 9.0% (8 + 1.0). Tables 9 and 10 compare the biochemical compositions of the samples obtained from three analytical methods,
included TGA.
The compositions determined with each method are comparable, although some differences are unavoidable, for example for

Fig. 13. Biochemical composition of a pulp (rice straw).

Table 9
Biochemical composition of a biomass (Tagasaste) from several analytical methods.

Hemicellulose
Cellulose
Lignin
Extractives

TGA

HPLC

TAPPI

27.1
34.4
28
7.3

26.4
31.2

23.7
35.5
20.8
5.6

Table 10
Biochemical composition of a pulp (rice straw) from several analytical methods.

Hemicellulose
Cellulose
Lignin

TGA

HPLC

TAPPI

18.0
70.6
9.0

20.3
75.3

16.4
77.9
2.3

the lignin content. With classical chemical analysis, according to


TAPPI rules, lignin is only determined as acid-insoluble lignin (Klason lignin). However, with thermogravimetric analysis, both soluble and insoluble lignin is measured.
4. Conclusions

Fig. 12. Biochemical composition of a biomass (Tagasaste).

In this study the applicability of the thermogravimetric analysis


for the determination of the contents of the main components
(hemicellulose, cellulose, lignin and extractives) of biomass and
pulp has been veried. The substitution of nth-order kinetic by
autocatalytic kinetic has allowed us to obtain accurate tting of
the experimental data under inert as well as under oxidative atmosphere. Hence, the presence of narrow peaks in the curves DTG,
caused by the well-known compensation effect, no longer affects
the calculation of the kinetic parameters. Reliable sets of kinetic

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A.G. Barneto et al. / Bioresource Technology 100 (2009) 39633973

parameters for each of the components of the lignocellulosic materials were thus obtained.
The nucleation order can be used to measure the autocatalytic
level reached in the thermal degradation processes. Usually, this
parameter increases when oxygen atmosphere and/or high heating
rates are used. For the heating rate ranges used (5, 10 and 20 C/
min) it has been observed that the pyrolysis of hemicellulosic
and cellulosic fractions of biomasses and pulps show very low
autocatalysis (nucleation order close to 0.01). In this case, contrary
to what occurs for combustion, experimental data can be tted
using nth-order kinetic.
Combustion of lignocellulosic materials shows two stages: volatilization and char oxidation. The former process, volatilization, is
similar to pyrolysis, showing comparable kinetic parameters like
obtained under inert atmosphere. Nevertheless, its autocatalytic
level is considerably higher (for example for the hemicellulosic
fraction of woody biomass the nucleation order change from 0.04
to 0.31). The mass loss associated to char oxidation has been explained supposing that the three main components of the samples
(hemicellulose, cellulose and lignin) produce its respective chars,
which oxidize independently. Supposing for all of them the same
pre-exponential factor, it has been veried that chars show similar
reaction orders (close to one), but differences for the activation energy (from 130 to 150 kJ/mol) and nucleation order. The oxidation
of cellulosic char presents the lowest activation energy and the
highest autocatalysis level (close 1.4). On the contrary, lignin char
presents the highest activation energy and the slowest combustion
rate. These different behaviors explain that a part of the total char
can give rise to a sharp peak while another part results in a broad
DTG peak. It has been veried that the nucleation order might rapidly increase with small increases of the heating rate. In this case
narrower peaks appear in DTG curves, mainly in the zone of char
oxidation. These changes cannot be adequately simulated using
nth-order kinetic.
The improved tting of the thermogravimetric data enables the
reliable determination of biomass sample composition. The optimization of the kinetic equations allows the calculation of the mass
of each component that is affected by volatilization or oxidation
processes. By adding both amounts, the weight percentage of each
component in the original sample can be determined. The calculated results are similar to those obtained by other analytical techniques (traditional chemical analysis and HPLC).
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