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Pyrolysis of Textile Wastes
Pyrolysis of Textile Wastes
Abstract
Thermal behavior of textile waste was studied by thermogravimetry at different heating rates and also by semi-batch pyrolysis. It was shown
that the onset temperature of mass loss is within 104–156 8C and the final reaction temperature is within 423–500 8C. The average mass loss is
89.5%. There are three DTG peaks located at the temperature ranges of 135–309, 276–394 and 374–500 8C, respectively. The first two might be
associated with either with decomposition of the hemicellulose and cellulose or with different processes of cellulose decomposition. The third peak
is possibly associated to a synthetic polymer. At a temperature of 460 8C, the expected amount of volatiles of this waste is within 85–89%. The
kinetic parameters of the individual degradation processes were determined by using a parallel model. Their dependence on the heating rate was
also established. The pyrolysis rate is considered as the sum of the three reaction rates. The pyrolysis in a batch reactor at 700 8C and nitrogen flow
of 60 ml/min produces 72 wt.% of oil, 13.5 wt.% of gas and 12.5 wt.% of char. The kinetic parameters of the first peak do not vary with heating rate,
while those of the second and the third peak increase and decrease, respectively, with an increasing heating rate, proving the existence of complex
reaction mechanisms for both cases.
# 2007 Elsevier B.V. All rights reserved.
0165-2370/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2007.03.008
490 R. Miranda et al. / J. Anal. Appl. Pyrolysis 80 (2007) 489–495
Table 1
Elemental analysis and proximate analysis (wt. %)
Sample C H N O S H/C O/C Moisture FC a Ash HVb
Textile waste 53.60 7.28 0.30 38.80 0.005 1.63 0.54 2.40 3.50 2.64 22,600
Cotton 45.50 6.60 0.30 47.50 0.10 1.74 0.78 5.00 ND 0.10 17,110
Residue of pyrolysis at 700 8C 94.82 4.86 0.32 ND ND ND ND 0.00 69.75 30.25 25,210
ND: not determined.
a
Fix carbon.
b
Net calorific value (kJ/kg).
1341). Ash residue was obtained by thermogravimetry (ASTM- 2.5. Bench scale pyrolysis
D5630 method).
The elemental analysis and proximate analysis of the The batch stainless steel reactor used for the experiments has
sample, using Avicel PH-105 and xylan as standards and an usable volume of three liters, and is externally heated by
the solid residues obtained after pyrolysis are presented in electrical elements. Pyrolysis experiments were performed with
Table 1. approximately 200 g of feedstock. The gas and vapors produced
passed through a series of four Pyrex traps, with 310 mm height
2.2. Thermogravimetric study and a 50 mm inner diameter. The traps were maintained at 4,
78, 78 and 200 8C, respectively. The first trap was used to
The thermal analysis experiments were performed on a TA collect the heavy liquid phase called ‘‘tar fraction’’ using
Q500 microprocessor-controlled TG/DTG system connected to water–ice mixture, the following second and third traps were
a Data Station. The sample mass was 6.0 0.1 mg for each used to collect the light liquid phase from condensable gases
experiment. The runs were carried out under dynamic called ‘‘light liquid fraction’’ using limonene, and the fourth
conditions with nitrogen flow (60 ml/min), at five different trap was used to trap the major gases using liquid nitrogen. The
heating rates: 1, 5, 10, 20, 40 and 60 8C/min. The sample still non-condensable gas collected into a plastic bag (5 l in
temperature is measured with a thermocouple directly at the volume) adapted with a valve for future chromatography
crucible. The tests were made in a wide temperature range analysis. Pyrolysis end temperatures were fixed at 600 and
between room temperature and 1000 8C. 700 8C. All the experiments were carried out under a nitrogen
atmosphere (100 ml/min).
2.3. Stepwise isothermal TGA
2.6. Product analysis
In order to separate the overlapping differential thermo-
gravimetric curves (DTG, %/min) the stepwise method was The liquid products collected separately from each trap were
used. In this TGA method the operator defines a maximum weighed and then analyzed and quantified by gas chromato-
heating rate and two weight loss per minute thresholds. A graphy GC. The last solid residue from the different pyrolysis
typical thermal cycle is described as follows (where % means runs was analyzed by TG and elemental analysis. Fig. 1
weight loss and %/min means DTG). illustrates the schematic flow sheet of the process, as well as the
places where the temperature and pressure were measured and
(1) Abort next segment if %/min > 5.0 recorded every 30 s, by means of a data acquisition system.
(2) Ramp 5 8C/min to 1000 8C/min
(3) Abort next segment if %/min < 0.5
(4) Isothermal for 1000 mins
(5) Repeat from segment 1 until 1000 8C
3. Results and discussion cellulose were performed at 10 8C/min under nitrogen atmo-
sphere (Fig. 3). TGA curves of textile reveal that the pyrolysis
3.1. Thermogravimetric analysis includes three steps. The initial stage occurs at a temperature
range below 300 8C, the second and the most important weight
Fig. 2 shows the TG and DTG curves of the textile waste loss change occurs in the temperature range of 300–380 8C.
decomposition recorded at different heating rates under These two stages could be associated either with decomposition
nitrogen atmosphere. A three stage weight loss is observed, of the hemicellulose and cellulose or with different processes of
with the three stages overlapping. For example, the TG curve cellulose decomposition [24]. The third one, with a lower
measured at 10 8C/min, shows that the first stage, located weight loss change, appears at a temperature above 430 8C,
between 115 and 284 8C, represents a 22.6 wt.% weight loss. corresponding to pyrolytic char formation. The maximum
The second stage, located around 284–390 8C, represents a
55.3 wt.% weight loss. The third stage, ranging from 395 to
474 8C, represents a 10.7 wt.% weight loss with 11.4 wt.% for
the weight of the final solid residue and 2.2 wt.% of moisture.
Corresponding to the three-stage weight loss on the TG curves,
three peaks are observed on the DTG curves. For example, on
the DTG curve at 10 8C/min, the first peak is observed at
264 8C. The second peak is observed at 374 8C and the third
peak is observed at 433 8C. These results are presented in
Table 2.
In order to relate the temperature of maximum decomposi-
tion rate (Tp) of the textile waste, with its pseudocomponents,
TG/DTG curves of xylan as hemicellulose, textile waste and
Fig. 2. (a) TG and (b) DTG curves of textile thermal decomposition under Fig. 3. TG and DTG curves for (a) textile waste, (b) xylan as hemicellulose and
nitrogen obtained at 1, 5, 10, 20, 40 and 60 8C/min. The heating rate increases (c) cellulose and thermal decomposition in nitrogen atmosphere obtained at
from left to right for TG and from down to up for DTG. 10 8C/min.
R. Miranda et al. / J. Anal. Appl. Pyrolysis 80 (2007) 489–495 493
Table 2
TG results for textile waste decomposition at different heating rates
Heating rate T0 Tf TP1 TP2 TP3 Humidity Total volatiles R to Tf RT 1000 8C
(8C/min) (wt.%) (wt.%) (wt.%) (wt.%)
1 105 433 199 318 377 2.68 85.32 12.00 4.0
5 107 470 229 346 408 2.68 85.45 11.50 4.0
10 115 474 245 354 424 3.06 86.40 10.54 4.0
20 116 487 264 374 433 2.73 86.95 10.32 5.2
40 118 511 284 388 447 2.78 87.56 9.66 7.5
60 119 520 291 392 449 20.09 88.85 9.66 7.4
T0 = initial temperature (8C) corresponding to 0.1 wt.% of weight loss.
Tf = final degradation temperature (8C).
TPi = peak temperature (8C) corresponding to a maximum weight loss rate.
R = final residue (wt.%).
decomposition rate of cellulose pyrolysis occurs at 356 8C, In this work, three stages of weight loss observed during TG
which corresponds to the second peak of textile waste DTG study of textile waste pyrolysis agree with the results of Antal
curve. Similar results were reported by Zhu et al. [5]. [26] and Zhu et al. [5]. When the parallel kinetic model is
In the attempt to identify the zones associated with the applied, it is reasonable to consider each stage of weight loss to
devolatilization of the textile components, different heating be a result of one of the three parallel apparent reactions. In the
programs have been employed. Fig. 4 presents the TG and DTG first stage of the pyrolysis of cellulose fiber [5] the most
of textile waste by stepwise method. Gomez et al. [25] used important changes of the sample were some physical properties
stepwise method to study the kinetics of woody residues an and a little weight loss. Here, according with the authors [5], the
herbaceous biomass. The results showed those four stages have damage of the cellulose occurs mostly in amorphous region of
been clearly separated. The first stage had 2.2 wt.% of weight the polymer. The main pyrolysis stage occurs in the temperature
lfoss corresponding to moisture evolution, the second one with range of 300–380 8C. In this stage, the weight loss is very fast
22 wt.%, the third and the four stage had 56 and 10.2 wt.%, and significant. Most of the pyrolysis products are produced in
respectively. The final residue was 9.6 wt.%. These results are this stage. Pyrolysis takes place in crystalline regions of
quite similar of those reported above under dynamic conditions. cellulose fibers in this stage. Char pyrolysis occurs at a
temperature above 430 8C. During this stage, dehydration and
3.2. Kinetic study of textile waste thermal decomposition decarboxylation, releasing water and carbon dioxide and
producing double bond, carboxyl and carbonyl products are the
This work’s main interest was to improve knowledge on the main products.
kinetics of textile waste thermal decomposition in pyrolysis Based on the parallel model of Moltó et al. [6], Antal [26]
reactors. The purpose of the kinetics study is to characterize and the results of Zhu et al. [5] a three apparent reaction parallel
each possible apparent reaction. A simple first order parallel kinetic model is proposed in this work, which considers the
kinetic model was tested and adapted to describe the different three stages of weight loss during textile waste pyrolysis as
apparent reactions and to obtain the kinetic parameters. The resulting from two parallel and one sequential reactions. Where
evaluation of the activation energy (Ea), reaction order (n), rate the first and second reaction correspond to cellulose decom-
constant (k), and pre-exponential factor (A) is based on the position and the third one correspond to char formation. The
utilization of classical laws of chemical kinetics. corresponding kinetic equations are described by Eqs. (1)–(3).
The two parallel reactions: 0 < T < 380 8C
k1
C1 !a1 V1 þ g 1 R1 (1)
k2
C2 !a2 V2 þ g 2 R2 (2)
The one sequential reaction: 380 < T < 520 8C
k3
a3 SR!a4 V3 þ g 3 R3 (3)
where SR = R1 + R2, a 3 = g1 + g2, a1 + a2 + a3 = 1,
[C1]0+[C2]0 = 1.
Three kinetic equations corresponding to the three apparent
reactions are described by Eqs. (4)–(6).
dX X N
dX i
Fig. 4. TG and DTG curves of textile waste thermal decomposition in a ¼ ai (4)
stepwise temperature program and nitrogen atmosphere.
dt i¼1
dt
494 R. Miranda et al. / J. Anal. Appl. Pyrolysis 80 (2007) 489–495
X
N Table 3
1¼ ai (5) Kinetic parameters obtained for the three stages of textile decomposition under
i¼1 nitrogen atmosphere.
Heating rate Stage E (kJ/mol) A (min1) Yield
dX dX 1 dX 2 dX 3
¼ a1 þ a2 þ a3 (6) (8C/min) coefficient
dt dt dt dt
1 1 40 1 10 3 a1 = 0.23
where Xi is the conversion degree, the ratio between the weight 2 190 4 10 15 a2 = 0.52
loss at the time ‘‘t’’ of the reaction and the weight loss (WL) at 3 186 5 10 14 a3 = 0.25
the end of each stage. 5 1 40 1.5 10 3 a1 = 0.25
Then the thermal decomposition of textile waste for the 2 190 4 10 15 a2 = 0.52
entire range of conversion can be expressed by the weight sum 3 186 9 10 13 a3 = 0.23
(dW/dt) of individual reaction rates as follows: 10 1 38 1.5 10 3 a1 = 0.23
2 190 5 10 15 a2 = 0.52
dTextile dC1 dC2 d SR 3 186 5.5 10 13 a3 = 0.25
¼ a1 þ a2 þ a3 (7)
dt dt dt dt 20 1 39.6 2.7 10 3 a1 = 0.24
dTextile 2 203 5 10 16 a2 = 0.52
¼ a1 ðA1 eEa1 =RT Cn11 Þ þ a2 ðA2 eEa2 =RT Cn21 Þ 3 180 1.2 10 13 a3 = 0.24
dt
40 1 41 5 10 3 a1 = 0.24
þ a3 ðA3 eEa3 =RT SRn3 Þ (8) 2 204 5 10 16 a2 = 0.52
3 180 1 10 13 a3 = 0.24
To obtain the kinetic parameters (A1, A2, A3, Ea1, Ea2, Ea3, n1,
n2 and n3) and the yield factors (a1, a2, a3), the above equations 1, 5, 10, 20 1 40 1.5 10 3 a1 = 0.24
2 200 5 10 15 a2 = 0.52
have been applied to simulate the DTG curves of textile
3 186 5.5 10 13 a3 = 0.24
pyrolysis. The same groups of kinetic parameters were used
to fit all the experimental data obtained at five different heating
rates. The system of differential equations from the model was The primary decomposition of the textile waste exhibited an
solved using a fourth order Runge–Kutta algorithm. A simplex activation energy of about 40 kJ/mol, with a fraction of 0.24.
algorithm of optimization was used to minimize the least square Concerning the kinetics parameters of the main fraction in the
criteria defined in the following equation: pyrolysis decomposition, activation energy of 200 kJ/mol is
X obtained. These are similar to the values proposed by Antal
error ¼ ðW Lexperimental W Lsimulated Þ2 (9)
et al. [13]. The activation energy for the third step is 186 kJ/mol
The obtained kinetic parameters and the conversion factor of with a fraction of 0.24. Fisher et al. [27] reported, an activation
each apparent reaction are presented in Table 3. Fig. 5 shows energy for cellulose of 151 kJ/mol corresponding to the
the simulation of every DTG peak at 10 8C/min. It shows a good secondary reactions in the char. This discrepancy is primarily
agreement of TGA and DTG curves from experimental due to the complexity of the reactions taking place with the char
measurement and from simulation by the proposed kinetic matrix as the char is heated. The kinetic parameters of the first
model. peak do not vary with heating rate, while those of the second
Fig. 5. Comparison between experimental and simulated data with a heating rate of 10 8C/min under nitrogen atmosphere.
R. Miranda et al. / J. Anal. Appl. Pyrolysis 80 (2007) 489–495 495