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Fuel Processing Technology 77 78 (2002) 159 166

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Thermogravimetric studies of the behavior of


lignitebiomass blends during devolatilization
E. Kastanaki a, D. Vamvuka a, P. Grammelis b,c, E. Kakaras b,c,*
a

Department of Mineral Resources Engineering, Technical University of Crete, Greece


b
Laboratory of Steam Boilers and Thermal Plants, Thermal Engineering Section,
Mechanical Engineering Department, National Technical University of Athens,
9 Heroon Polytechniou Ave., 15780 Zografou, Greece
c
Centre for Solid Fuels Technology and Applications, Ptolemais, Greece

Received 11 February 2002; received in revised form 19 March 2002; accepted 20 March 2002

Abstract
The behaviour of Greek pre-dried lignite, four biomass materials and their blends in the
devolatilization stage was investigated by thermogravimetry. Biomass was added in the percentages
of 5, 10 and 20% wt. in the fuel blend. All the tests were carried out in nitrogen atmosphere under
dynamic conditions at a heating rate of 10 jC/min. The kinetic parameters for the thermal conversion
of the pure fuels were determined through the independent parallel, first-order, reaction model. No
significant interaction was detected in the solid phase between the components of the coal biomass
blends, under the same experimental conditions. D 2002 Elsevier Science B.V. All rights reserved.
Keywords: Lignite; Biomass; Kinetics; Pyrolysis

1. Introduction
The development of systems for the conversion of coal biomass blends to energy by
thermochemical processes requires a fundamental understanding of the thermal properties
and reaction kinetics. Recognizing that solid fuel devolatilization is always a fundamental
step, this study focuses on the investigation of the devolatilization behavior and the
kinetics of Greek lignite and four biomass materials, which are characteristic for the
Mediterranean region. In the literature, kinetic modeling of lignite biomass blends [1] has
*
Corresponding author. Laboratory of Steam Boilers and Thermal Plants, Thermal Engineering Section,
Mechanical Engineering Department, National Technical University of Athens, 9 Heroon Polytechniou Ave.,
15780 Zografou, Greece. Tel.: +30-1-7723662; fax: +30-1-7723663.
E-mail address: ekak@central.ntua.gr (E. Kakaras).

0378-3820/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 2 0 ( 0 2 ) 0 0 0 4 9 - 8

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E. Kastanaki et al. / Fuel Processing Technology 77 78 (2002) 159166

Table 1
Proximate (wt.%), ultimate (wt.%) analysis and calorific values of pure samples on a dry basis
Sample

VM

FC

Ash

HHV
(MJ/kg)

Dry lignite
Olive kernel A
Olive kernel B
Forest residue
Cotton residue

47.71
72.64
73.62
79.80
72.80

39.28
24.78
24.25
20.0
20.59

13.01
2.58
2.13
0.20
6.61

55.02
51.19
52.44
53.16
47.03

5.30
6.06
6.17
6.25
5.96

1.92
0.76
1.32
0.30
1.79

24.10
39.32
37.85
40.0
38.42

0.65
0.09
0.09
0.09
0.19

20.8
20.4
21.4
21.7
18.25

VM: volatile matter, FC: fixed carbon, HHV: high heating value.

been reported by a single first-order reaction model. More detailed models have been
applied to describe the pyrolysis of mixtures of municipal solid wastes [2] or sugarcane
bagasse with petroleum residue [3], but not for lignite with biomass. The aim of this work
is to investigate the thermal decomposition behavior of lignite biomass blends, in a
thermogravimetric analyser (TGA) and to examine the possibility of kinetic modeling,
considering the kinetics of the isolated compounds of the blend.

2. Experimental
Greek pre-dried lignite from the Ptolemais basin and four biomass materials, that is,
two samples of olive kernel, forest residue and cotton residue were used in this study. The
results of proximate and elemental analyses of biomass and lignite materials, as well as
their calorific values, are presented in Table 1. All samples were milled to  250 Am.
Blends of lignite with each one of the abovementioned biomass materials were also
prepared, in three different biomass percentages, that is, 5, 10, 20% wt.
All experiments were performed in a Perkin Elmer TGA-6 thermobalance. To avoid
heat and mass transfer limitations, sample masses between 20 and 25 mg were used, a
nitrogen flow of 45 ml/min and a low heating rate of 10 jC/min. The samples were heated
from room temperature up to 850 jC, where they remained for 10 min. Mass loss and rate
were continuously recorded under these conditions.

3. Kinetic modeling
Kinetic evaluation of biomass devolatilization was accomplished by the independent
parallel, first-order, reaction model. This is considered the most recent and realistic
approach, which has been applied for several biomass species [3 6]. According to this
model, the decomposition of biomass material is described by three independent parallel
reactions, each one corresponding to the decomposition of the constituent components of
hemicellulose, cellulose and lignin. The equations that describe the overall rate of
conversion and the thermal decomposition of the individual components are:
N
X
dm=dt
ci dai =dt,
i 1, 2, 3, . . . N
1
1

E. Kastanaki et al. / Fuel Processing Technology 77 78 (2002) 159166

dai =dt Ai expEi =RT 1  ai

161

where: dm/dt = mass loss rate; Ai = pre-exponential factor; i = component; Ei = activation


energy; ai = conversion rate; R = gas constant; ci = contribution of the partial process to the
overall mass loss, m0  mchar; T = temperature.
The model equations and the variation coefficient are reported in detail by Grnli [5],
Grnli et al. [7] and Srum et al. [2].
In the same way, kinetics for lignite devolatilization was estimated assuming five
pseudo-reactions. The mathematical description is given through the same equations,
considering five first-order independent parallel reactions and taking into account the DTG
curves course. Similar models, considering that coal components are evolved through noncompetitive independent reactions, can be found in the literature [9,10].

4. Results and discussion


4.1. Thermal decomposition and modeling of biomass materials
The TG and DTG curves of pure biomass materials are shown in Fig. 1. As can be seen,
the initial decomposition temperaturecalculated as the temperature where 1% of the
material has been decomposed, on dry basiswas around 200 jC for all samples. The
highest pyrolysis rate was obtained for the forest residue, while the temperature
corresponding to the maximum pyrolysis rate was lower for olive kernel A, indicating
its higher reactivity among the samples. Furthermore, the forest residue produced the
smallest amount of char (17.1% wt., dry basis), whereas olive A the highest (26.7% wt.,
dry basis).
Studying the DTG curves, two overlapping peaks and a flat tailing section are observed.
The overlapping peaks produce a single DTG peak with a shoulder located on the left. It has
been debated [5,11 13] that the lower temperature shoulder represents the decomposition of
hemicellulose present in the biomass material and the higher temperature peak the
decomposition of cellulose. Lignin is known to decompose slowly over a broad temperature
range, providing thus the flat tailing section of the DTG curve. Based on the above
observations, the DTG curve of cotton residue exhibits a less pronounced shoulder,
indicating that it contains less hemicellulose than the other samples. On the contrary, forest
residue seems to contain the largest amount of hemicellulose, due to its well-pronounced
shoulder. Finally, olive kernel B seems to be the sample with the highest amount of lignin, as
its tailing section is quite profound. The kinetic evaluation of one of the samples is illustrated
in Fig. 2, while the kinetic parameters are summarized in Table 2. In all cases, a good fit was
obtained and the results agree reasonably well with those of similar studies [4,5,14].
4.2. Thermal decomposition and modeling of lignite
The TG and DTG curves of pre-dried lignite are shown in Fig. 3. Decomposition of
lignite starts at about 174 jC, which is slightly lower than the corresponding initial
temperature values of biomass pyrolysis and it extends to temperatures above 850 jC.

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Fig. 1. TG and DTG curves of biomass materials.

However, mass loss above 850 jC is inconsiderable. The maximum devolatilization rate is
1.37  10  2 min  1, which is five to seven times lower than the rate corresponding to
biomass devolatilization. In addition, the highest volatile release takes place at a higher
temperature up to 414 jC, indicating that lignite is less reactive compared to biomass

Fig. 2. Kinetic evaluation of olive kernel B.

E. Kastanaki et al. / Fuel Processing Technology 77 78 (2002) 159166

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Table 2
Calculated kinetic parameters for the pyrolysis of biomass materials
Biomass
components

Kinetic
Sample
parameters Olive kernel A Olive kernel B Forest residue Forest residue Cotton residue

Hemicellulose A (1/min)
E (kJ/mol)
c (%)
Cellulose
A (1/min)
E (kJ/mol)
c (%)
Lignin
A (1/min)
E (kJ/mol)
c (%)
Dev (%)a
a

2.45  108
92.9
18.2
1.40  1018
210.6
27.5
2.76  101
30.6
28.5
1.54

1.42  108
92.8
19.1
5.99  1016
201.7
24.1
1.37  102
39.5
33.3
1.67

1.56  107
89.5
35.7
9.43  1022
284.6
24.5
2.85  101
30.9
24.5
1.12

1.99  1010
108.2
4.5
7.23  1018
233.8
35.7
4.72  101
34.5
20.3
0.84

4.19  108
95.1
13.0
1.66  1012
145.1
35.8
2.47  101
30.8
25.2
1.41

Dev is the deviation between experimental and calculated DTG values at the optimal set of parameters.

materials. The char residue is 52.3% wt., dry basis, and the produced quantity is twofold to
threefold as much as the biomass char.
Taking into account the shape of the DTG curves, modeling of the lignite pyrolysis was
accomplished by lumping the numerous reactions into five pseudo-reactions Fig. 4. The
kinetic analysis was carried out in the temperature range 250 850 jC, since the main part
of the volatile matter is evolved in this region. The obtained kinetic parameters are given in
Table 3. However, due to the great complexity of the reactions taking place during lignite
pyrolysis, it is not possible, without further analysis, to determine from the obtained
kinetic data, which compounds are produced in each reaction.
4.3. Thermal decomposition and modeling of lignite biomass blends
Blends of lignite and biomass materials were studied under the same devolatilization
conditions. The DTG curves for the mixture of lignite olive kernel B, in three blending

Fig. 3. TG and DTG curves of dry lignite.

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E. Kastanaki et al. / Fuel Processing Technology 77 78 (2002) 159166

Fig. 4. Kinetic evaluation of dry lignite (five reactions).

ratios of biomass to lignite (5:95, 10:90, 20:80), are shown in Fig. 5. It is observed from
the DTG curves that the height of the peaks gradually increases when enhancing the
amount of biomass in the blends, leading to a substantial increase of the volatile quantities
released.
Furthermore, the position of the maximum DTG peak is shifted to lower temperatures
as the percentage of biomass in the mixture is raised. This reveals that the biomass
presence in the blends increases their reactivity.
To investigate whether interactions existed between the components of a fuel blend, a
theoretical DTG curve was calculated. This curve represented the sum of the individual
components behavior in the mixture:
dm=dtsum x1 dm=dtlignite x2 dm=dtbiomass
where (dm/dt)lignite, (dm/dt)biomass are the normalized rates of mass loss, as found from the
individual experiments and x1, x2 are the mass fractions of lignite and biomass in the
mixture, respectively. The calculated and experimental curves for olive kernel B are
illustrated in Fig. 5. Comparing the DTG curves, it is concluded that no significant
interactions occur in the solid phase during devolatilization. The shape of the curve and the
position of the peaks remain basically unaltered, in Fig. 5. However, possible synergistic
effects in the gaseous, or gas solid phase may occur.

Table 3
Calculated kinetic parameters for the pyrolysis of dry lignite

A (1/min)
E (kJ/mol)
c (%)

Reaction 1

Reaction 2

Reaction 3

Reaction 4

Reaction 5

Dev (%)

1.21  103
46.8
14.2

3.61  106
98.6
7.5

2.83  1023
65.2
10.1

4.99  1023
439.6
1.1

7.78  102
75.2
11.1

1.54

E. Kastanaki et al. / Fuel Processing Technology 77 78 (2002) 159166

165

Fig. 5. Comparison between experimental (exp) and calculated (calc) DTG values for the three blends of dry
lignite olive kernel B.

The fact that the devolatilization of the mixture is sufficiently predicted by a simple
summation of the individual behavior of its components has very significant implications. It
can permit a satisfactory prediction of the mixtures behavior based on the experimental data
for each fuel. Moreover, it is possible to simulate the kinetics of the blends using the kinetic
parameters obtained for the isolated compounds and the corresponding coefficients, taking
also into account the percentages of the fuels in the mixture. Thus, a cumulative model is
proposed, involving eight independent parallel reactions, the first three representing the
decomposition of the biomass material and the following five the decomposition of the
lignite. In all cases, the fit was quite good (Dev < 2%) to affirm that the decomposition of
separate fractions in each material can be predicted using the same kinetic constants.

5. Conclusions
Thermogravimetric studies show that the biomass materials have higher thermochemical reactivity than lignite and shorter devolatilization times that can ensure their complete
conversion within operating lignite-fired boilers. During the thermal conversion of
lignite biomass blends in the pyrolysis stage, no substantial interactions were observed
in the solid phase. However, possible gas solid interactions or interactions in the gas
phase cannot be excluded. Satisfactory prediction of a mixtures devolatilization behavior
can be acquired based only on experimental data of the individual fuels. Kinetic modeling
of the blends can be successfully performed using the kinetic parameters obtained for the
separate blends components, that is, lignite and biomass.

Acknowledgements
The financial support by the European Union in the Combustion Behaviour of Clean
Fuels in Power Generation project (Contract no.: ENK5-1999-00004) is gratefully
acknowledged.

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E. Kastanaki et al. / Fuel Processing Technology 77 78 (2002) 159166

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