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Bioresource Technology 178 (2015) 126–131

Contents lists available at ScienceDirect

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

Kinetic study of solid waste pyrolysis using distributed activation energy


model
Anjireddy Bhavanam ⇑, R.C. Sastry
Department of Chemical Engineering, National Institute of Technology, Warangal 506004, AP, India

h i g h l i g h t s

 The proposed DAE model explained the solid waste pyrolysis process successfully.
 The activation energy of MSW significantly decreased with addition of agri-residues.
 The reactivity (RM) of groundnut shell was higher compared to the other solid wastes.
 The pyrolysis process of MSW and MSW + agri-residues occurred in three stages.
 The maximum degradation was observed in the second stage, with all the solid wastes.

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

Article history: The pyrolysis characteristics of municipal solid waste, agricultural residues such as ground nut shell, cot-
Received 31 July 2014 ton husk and their blends are investigated using non-isothermal thermogravimetric analysis (TGA) with
Received in revised form 5 October 2014 in a temperature range of 30–900 °C at different heating rates of 10 °C, 30 °C and 50 °C/min in inert atmo-
Accepted 7 October 2014
sphere. From the thermograms obtained from TGA, it is observed that the maximum rate of degradation
Available online 14 October 2014
occurred in the second stage of the pyrolysis process for all the solid wastes. The distributed activation
energy model (DAEM) is used to study the pyrolysis kinetics of the solid wastes. The kinetic parameters
Keywords:
E (activation energy), k0 (frequency factor) are calculated from this model. It is found that the range of
Municipal solid waste
Agricultural residues
activation energies for agricultural residues are lower than the municipal solid waste. The activation
Thermogravimetric analysis energies for the municipal solid waste pyrolysis process drastically decreased with addition of agricul-
Distributed activation energy model tural residues. The proposed DAEM is successfully validated with TGA experimental data.
Pyrolysis kinetics Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction cation. A better understanding of the pyrolysis will be of immense


help in designing the gasifiers with better efficiency. The pyrolysis
Rapid urbanization and increased population add large amount process can be understood thoroughly by knowing the kinetic
of municipal solid waste to our planet. Currently, world cities gen- parameters. Thermogravimetric analysis (TGA) is one of the most
erate about 1.3 billion tonnes of solid waste per year and expected widely used techniques for studying the degradation mechanism
to increase to 2.2 billion tonnes by 2025 (Hoornweg and Bhada- and for the determination of the kinetics parameters of pyrolysis
Tata, 2012). This has significant impact on disposal area, economics and other thermochemical conversion processes. By using the
of waste management and the environmental consequences. So, TGA data, researchers have developed different models such as sin-
there is a growing interest in developing efficient biomass thermal gle step model, two parallel reaction model, three-pseudo compo-
modification technologies worldwide to combat climate change nent model and distributed activation energy model (Li et al.,
and to provide solutions for the current energy crisis. In recent 2009) for establishing the kinetic mechanism of pyrolysis process.
years many investigations have been done for the possible use of Distributed activation energy model (DAEM) has been widely used
solid waste biomass, such as combustion, pyrolysis and gasifica- for analyzing the complex reactions of coal and biomass pyrolysis.
tion. In all the thermochemical systems, pyrolysis is the first step Cai et al. (2013) studied the pyrolysis behavior of lingo-cellulosic
taking place with consequent occurring of combustion and gasifi- biomass samples by considering the three parallel reactions associ-
ated with the primary pyrolysis of hemicellulose, cellulose and lig-
⇑ Corresponding author. Tel.: +91 870 2462603; fax: +91 870 2459547. nin present in the lingo-cellulosic biomass. Kinetic study from
E-mail address: anjireddy.bhavanam@gmail.com (A. Bhavanam).
DAEM revealed that the activation energy distribution for lignin

http://dx.doi.org/10.1016/j.biortech.2014.10.028
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
A. Bhavanam, R.C. Sastry / Bioresource Technology 178 (2015) 126–131 127

is wide compared to cellulose, which has the narrowest distribu- Table 1


tion. From the DAEM, it was observed that the activation energy Proximate and ultimate analysis of selected solid waste biomass.

for pyrolysis of Pine pellets was low (in the range of 160–270 kJ/ Biomass Cotton husk Groundnut shell Municipal solid waste
mol) compared to the activation energy of Sewage sludge samples, Proximate analysis (wt.%)
which was in the range of 170–400 kJ/mol (Soria-Verdugo et al., Moisture content 7.9 4.9 6
2013). It also was observed that the activation energy distribution Volatile matter 66.0 70.2 29
of bituminous, lean coals and biomass such as corn-stalk skins fol- Fixed carbon 20.1 19.0 10
Ash 6.0 5.9 55
low the approximate Gaussian distribution (Li et al., 2009). The
complex reactions of typical medical waste pyrolysis and the evo- Ultimate analysis (wt.%)
Carbon 46.88 48.2 16.14
lution of various volatile species were successfully explained by Hydrogen 4.83 5.7 1.79
DAEM model (Yan et al., 2009). This model was also used for study- Nitrogen 0.93 0.80 1.36
ing the pyrolysis kinetics of fresh water algae, fungal pre-treated Sulfur 0.36 0.33 0.26
a
corn stover (Kirtania and Bhattacharya, 2012; Ma et al., 2013). Oxygen 41 39.07 25.45
HHV (MJ/kg) 17.34 17.58 6.46
DAEM model was also used to check the accuracy of other integral
iso-conversional methods in estimating the activation energy of a
By difference.
the pyrolysis process of various materials such as wood, algae, corn
stalk skin, kerogen, cellulose, lignin and coal (Wu et al., 2013). It
was known from this model that, the catalytic effects of alkali moisture content and volatile matter respectively. The fixed carbon
and alkali earth metals present in the biomass play a key role in is calculated as a difference. The ultimate analysis is done using
the variation of activation energy during the pyrolysis process CHNS analyzer (Elementar Vario EL III, Elementar Analysensysteme
(Sonobe and Worasuwannarak, 2008). This model was used for GmbH, Germany). The higher heating values (HHV) are calculated
knowing the combustion characteristic of wood and from the by using the correlation proposed by Parikh et al. (2005), based on
results it was observed that the DAEM was not suitable for know- the proximate analysis, considering the entire spectrum of solid
ing the combustion behavior (Shen et al., 2011). Till date, there is carbonaceous materials like coals, lignite and all types of biomass
no reported work on pyrolysis of municipal solid waste, groundnut material.
shell and cotton husk using DAEM. The present study is focused on
understanding the pyrolysis characteristics of municipal solid HHV ¼ 0:3536FC þ 0:1559VM  0:0078ASH ðMJ=kgÞ:
waste, agricultural residues and their blends and provides the nec-
essary information in filling the present knowledge gap on solid
waste pyrolysis.
2.4. Methods

2. Methods
2.4.1. Thermogravimetry
Thermogravimetric analysis (TGA) is carried out for studying
2.1. Materials
the thermal degradation behavior of municipal solid waste, agri-
culture residues and their blends using Perkin Elmer, Diamond
The solid waste biomasses of different origin such as Municipal
TG/DTA analyser. Non-isothermal TGA analysis is conducted at dif-
solid waste (MSW), Agricultural Residues (AR) are chosen in the
ferent heating rates of 10, 30 and 50 °C/min in inert (Nitrogen)
present study. The municipal solid waste is collected from the
atmosphere from 30 to 850 °C. The purge flowrate of nitrgen is
dump sites of Warangal city. The agricultural residue, particularly
maintained constantly at 100 ml/min. For analysis, 5–10 mg of bio-
cotton husk (CH) is collected from the cotton fields and groundnut
mass sample is taken in the pan of TGA microbalance. The residual
shell (GS) is collected from oil processing mills. The collected
weights and derivative weights are recorded with respect to time
municipal solid waste contains combustible organic materials
and temperature.
(paper waste, food waste, used plastic, cloth waste, yard waste
etc.) along with soil, mud, sand and other inert materials that are
not separated manually. The recyclable materials like glass, metals
2.4.2. Distributed activation energy model
and most of the plastic are separated from the collected MSW.
The distributed activation energy model (DAEM), originally
developed by Vand (1943), has been extensively used for analyzing
2.2. Sample preparation the complex reactions occurring during the pyrolysis of fossil fuels.
Later this model is successfully applied to different biomass fuels
About 2 kg of material is taken from the collected municipal for understanding the reaction kinetics of pyrolysis process
solid waste and agricultural residues. These collected samples of (Sonobe and Worasuwannarak, 2008; Wang et al., 2008; Shen
MSW, CH, and GS are grounded thoroughly using lab scale grinding et al., 2011; Navarro et al., 2009). This model assumes that number
mill and sieve analysis is carried out using sieves with ASTM mesh of parallel irreversible first order reactions that have different
numbers of 30, 40, 50, 60 and 70 to obtain uniform particle size of kinetic parameters occur simultaneously. The change in total vola-
250 lm for the preparation of samples. In total, four samples are tiles at time t, is given by
prepared using MSW, CH, GS and MSW + AR. The MSW + AR sam-
ple is prepared by mixing 70% of MSW, 15% of CH and 15% of GS. Z 1  Z t 
Finally the samples are stored in air-tight plastic containers for fur- 1  V=V  ¼ exp k0 eE=RT dt f ðEÞdE ð1Þ
ther analysis. 0 0

where V⁄ is the effective volatile content, V is the volatile con-


2.3. Material characterization tent at temperature T, f(E) is the distribution curve of activation
energy that represents the difference in the activation energies of
The proximate and ultimate analysis of MSW, CH and GS sam- all the reactions and k0 is the frequency factor corresponding to E
ples are presented in Table 1. The proximate analysis is done value. In this study, the integral method proposed by Miura and
according to ASTM standards of D 1102, E871 and E872 for ash, Maki (1998) is used for estimating the kinetic parameters.
128 A. Bhavanam, R.C. Sastry / Bioresource Technology 178 (2015) 126–131

2.5. Theory Eq. (13) is the integral form of the basic equation and by substi-
tuting 1  DV/DV⁄ with 0.58, which is an approximation
The temperature of the biomass or coal at any time t is given by (1  DV=DV  ¼ UðE; TÞ  0:58), the equation is further simplified as
(Miura, 1995)    
a k0 R E
T ¼ T o þ at ð2Þ ln ¼ ln þ 0:6075  ð14Þ
T2 E RT
where To is the lowest temperature at which the reaction cannot Finally, using the Eq. (14), the activation energy and frequency
occur and a is the heating rate. The Eq. (1) can be rewritten as factor are determined from the slope and intercept of Arrhenius
Z 1 plot of ln (a/T2) vs. 1/T at selected values of V/V⁄ at different heating
1  V=V  ¼ UðE; TÞf ðEÞdE ð3Þ rates. The activation energy distribution function f(E) can be
0
obtained by differentiating the plot of V/V⁄ vs E. The term 0.6075
 Z  in the Eq. (14) is set to zero for simplicity, which corresponds to
k0 T E=RT
where; UðE; TÞ ¼ exp e dT ð4Þ the assumption that 1  DV/DV⁄ = U(E, T) = e1 in Eq. (14) and is
a 0 equivalent to replacing 0.545 by 1 in Eq. (10).
Z  Z  Following procedure is adopted to estimate f(E) and k0.
1
k0 T E=RT
1  V=V  ¼ exp e dT f ðEÞdE ð5Þ
0 a 0  At three different heating rates of 10°, 30° and 50 °C/min, the V/
By taking the variable x = E/RT, the Eq. (4) can be written as V⁄ values with respect to the temperatures (T) are calculated
from the TGA experimental data.
  Z 1 x 
k0 E ex e  From the data obtained from V/V⁄ vs. T relationships at different
UðE; TÞ ¼ exp  dx ð6Þ
aR x 0 x heating rates, the values of a/T2 at selected V/V⁄ values (0–0.9)
are calculated.
 
k0 E  These values are plotted in form of ln (a/T2) vs 1/T plot at the
UðE; TÞ ¼ exp PðxÞ ð7Þ selected values of V/V⁄.
aR
 The E and k0 values are determined from the slope and the
By applying the p-function approximation, P(x) = ex/x2, the Eq. intercept of the Arrhenius plots at different V/V⁄ values using
(7) can be modified as the relationship in Eq. (14).
!  Finally, the V/V⁄ vs E relationship is differentiated to obtain f(E).
k0 RT 2 E=RT
UðE; TÞ ¼ exp e ð8Þ
aE The V/V⁄ values obtained for all the solid waste biomasses are
plotted against the activation energies obtained from the model.
Since the U(E, T) function changes steeply with activation
energy at a given temperature, it is approximated by a step func-
tion at E = Es. This approximation corresponds to the assumption 3. Results and discussion
that the single reaction with activation energy Es is occurring at
temperature T. Thus, the Eq. (1) can be simplified as TGA and DTG curves of MSW, CH, GS and MSW + AR samples
Z Z under inert atmosphere are presented in the Fig. 1a and b.
1 ES
V=V  ffi 1  f ðEÞdE ¼ f ðEÞdE ð9Þ
ES 0 3.1. Thermal degradation behavior in inert atmosphere
The activation energy, Es is chosen to satisfy U(Es, T) = 0.58. The
relationship of Es to a, T, and k0 is given as In this environment the total degradation process has occured
in two stages in case of AR and in three stages in case of MSW
0:545aES =k0 RT 2 ¼ eES =RT ð10Þ and MSW + AR. It is observed from TGA and DTG curves that, at
heating rate of 10 °C/min. 7.62%, 5.8%, 3.97% and 4.07% weight loss
This treatment approximates that a reaction with activation has occurred between temperatures of 35 °C and 150 °C for CH, GS,
energy Es occurs at a specified temperature T and heating rate a.
The approximation is given mathematically by
100
dV=dt ffi dðDVÞ=dt ¼ k0 eE=RT ðDV   DVÞ ð11Þ (a)
90
This equation shows that the overall rate dV/dt is approximated
80
by the rate of the specific reaction at temperature only in which
the reaction is occurring and the DV and DV⁄ are the amount of 70 MSW
volatiles and the effective volatile content for the same reaction. 60 MSW+AR
Weight (%)

By integrating the Eq. (11), and applying the U function approxi-


mation, the resultant equation can be represented as 50

 Z t  40 GS
1  DV=DV  ¼ exp k0 eE=RT dt 30 CH
0
! 20
k0 RT 2 E=RT
ffi exp e ð12Þ 10
aE
0
By applying natural logarithm twice on both sides to Eq. (12), it 0 100 200 300 400 500 600 700 800 900
is transformed as o
Temperature ( C)
      
a k0 R DV E
ln ¼ ln  ln  ln 1    ð13Þ Fig. 1. (a) TGA curves in nitrogen atmosphere at a heating rate of 30 °C/min. (b)
T2 E DV RT DTG curves in nitrogen atmosphere at a heating rate of 30 °C/min.
A. Bhavanam, R.C. Sastry / Bioresource Technology 178 (2015) 126–131 129

0.0 -8.0
(a) o
(b) -8.5 50 C/min
Derivative Weight (mg/min)

-0.5 -9.0 30 C/min


o
MSW

ln (a/(T+273) )
-9.5

2
o
10 C/min
-1.0 MSW+AR -10.0

-10.5 v/v*=0.1

-1.5 -11.0
0.9
CH
-11.5
GS

-2.0 -12.0
0 100 200 300 400 500 600 700 800 900 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
2 3
o
Temperature ( C) 1/(T+273) x 10

Fig. 1 (continued) Fig. 2. (a) Arrhenius plot of ln (a/T2) vs. 1/T at selected V/V⁄ values for groundnut
shell. (b) Arrhenius plot of ln (a/T2) vs. 1/T at selected V/V⁄ values for cotton husk. (c)
Arrhenius plot of ln (a/T2) vs. 1/T at selected V/V⁄ values for MSW. (d) Arrhenius plot
of ln (a/T2) vs. 1/T at selected V/V⁄ values for MSW + AR.
MSW and MSW + AR, respectively. The initial weight loss is mainly
due to dehydration. In the second stage, weight loss of 46.95%,
55.28%, 14.78% and 29.56% is due to devolatilization of CH, GS,
MSW and MSW + AR in the temperature range of 180–550 °C.
-8.0
The third stage of degradation occurs only in MSW and MSW + AR.
(b)
Such variations in the degradation of biomasses have been attrib- -8.5 50 C/min
o

uted to the elemental and chemical compositions of the solid


wastes (Mansaray and Ghaly, 1999a,b). Comparing the degradation -9.0 30 C/min
o

of all the biomasses from TGA and DTG curves, it is observed that
ln(a/(T+273) )

-9.5
2

with blending of MSW with AR, the degradation has taken place up o
10 C/min
to 54% (MSW + AR) from 75% (MSW) at heating rate of 10 °C/min,
-10.0
64% from 67% at heating rate of 30 °C/min and 56% from 65% at
heating rate of 50 °C/min respectively. From the DTG curves, it is -10.5 v/v*=0.1
known that the rate of degradation has increased with increasing
in the heating rate for all the selected solid wastes and the maxi- -11.0
0.9
mum degradation has occured in second stage, which corresponds
to the pyrolysis (devolatization) reactions. The peak temperature, -11.5
maximum rate of degradation and the residual weight after
-12.0
800 °C for all the biomasses at different heating rates are presented 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
in Table 2. The mean reactivity (RM) is calculated based on the 2 3
1/(T+273) x 10
method developed by Ghetti et al. (1996) and later used by many
researchers (Munir et al., 2009). The order of reactivity of solid Fig. 2 (continued)
wastes in pyrolysis process is found to be GS > CH > MSW +
AR > MSW.
selected solid wastes. This temperature range is selected for the
3.2. Estimation of kinetic parameters using DAEM kinetic study of the pyrolysis process. The Arrhenius plots for var-
ious solid wastes of different origin are plotted by the procedure
From the thermograms, the effective change in the volatile con- explained earlier. These plots are drawn at conversions from 0.1
tent is observed in the temperature range of 180–550 °C for all the to 0.9. The Arrhenius plots are linear and parallel up to a conver-

Table 2
Thermal degradation of solid wastes during the pyrolysis process at different heating rates.

Biomass Heating rates Maximum rate of degradation -DTG Tpeak RM  103 Residual weight (%) after 800 °C
(°C min1) (mg min1) (°C) (mg min1 °C1)
Cotton husk 10 0.182 312 0.583 15.54
30 1.511 326 4.274 27.23
50 2.570 337 6.230 27.11
Groundnut 10 0.222 329 0.674 17.17
shell 30 1.594 339 4.889 34.15
50 4.239 354 12.50 35.50
MSW 10 0.072 331 0.285 71.65
30 0.521 342 1.793 64.22
50 1.159 343 3.387 65.06
MSW + AR 10 0.150 324 0.510 54.17
30 0.901 337 2.915 67.24
50 1.227 356 3.96 56.85
130 A. Bhavanam, R.C. Sastry / Bioresource Technology 178 (2015) 126–131

-8.0 1.0
(c) Calculated
-8.5 o 0.9 Experimental
50 C/min
0.8
-9.0 o
30 C/min 0.7

Conversion (V/V*)
-9.5
ln (a/(T+273) )

0.6
2

o
10 C/min
-10.0 0.5
o
0.4 10 C/min
-10.5 v/v*=0.1 o
30 C/min
0.3 o
-11.0 50 C/min
0.9 0.2
-11.5 0.1
-12.0 0.0
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 100 200 300 400 500 600 700
o
2
1/(T+273) x 10
3 Temperature ( C)

Fig. 3. Experimental and calculated TG curves at selected heating rates.


Fig. 2 (continued)

-8.0 1000
(d) 900
-8.5 o
50 C/min Activation Energy,E (kJ/Mol)
800 MSW+AR
-9.0 o
30 C/min MSW
700
Groundnut Shell
ln(a/(T+273) )

-9.5
2

600 Cottonhusk
o
10 C/min
-10.0 500
400
-10.5 v/v*=0.1
300
-11.0 200
0.9
-11.5 100
0
-12.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
2 3
Conversion (v/v*)
1/(T+273) x 10
Fig. 4. Activation energy E vs. conversion rate V/V⁄ estimated from the Arrhenius
Fig. 2 (continued) plot for selected solid waste biomasses.

sion of 0.7, and above these conversions the plots are non linear shell, cotton husk, municipal solid waste and blend of municipal
and follows different behavior. This may be due to the different solid waste and agricultural residues respectively.
chemical reactions occurring. The coefficient of correlation (R2) From these results, it can be concluded that for all the agricul-
for all the lines drawn at various conversions (0.1–0.7) is greater tural residues (GS and CH) the range of activation energies are
than 0.90, which indicates the best fit, whereas the coefficient of medium (ranging from 150 to 270 kJ/mol). The range of activation
correlation for the conversions of 0.8–0.9 is very low, indicating a energies of municipal solid waste is higher than all other selected
poor fit. Here, in all the cases, conversions between 0.1 and 0.7 solid wastes (up to 824 kJ/mol). But surprisingly, with the blend of
are only considered for describing the application of DAEM. municipal solid waste and agricultural residues the activation
The Arrhenius plots of Groundnut shell, Cotton husk, Municipal energy is drastically decreased (in the range of 73–110 kJ/mol).
Solid Waste (MSW) and Blend of Municipal Solid Waste-Agricul- This may be due to the synergistic effect of both the solid wastes
tural Residue (MSW + AR) are shown in Fig. 2a–d. The activation (agricultural residues to the municipal solid waste).
energies of the pyrolysis process are distributed in between 168 Using the kinetic parameters obtained from the DAEM, the cal-
and 218, 187–269, 150–824, 73–110 kJ/mol for groundnut shell, culated TG curves are obtained and compared with the experimen-
cotton husk, municipal solid waste and blend of municipal solid tal values obtained from the TGA experiments as shown in the
waste and agricultural residues respectively at conversion values Fig. 3 and observed that the model results are in good agreement
(V/V⁄) ranging from 0.1 to 0.7. This infers that each reaction step with the experimental results. The distribution of activation ener-
of conversion has corresponding activation energy throughout gies of selected solid waste biomasses at various conversions from
the pyrolysis process. 0.1 to 0.9 are shown in Fig. 4.
The highest activation energies are observed at 218, 269, 824
and 110 kJ/mol for groundnut shell, cotton husk, municipal solid
waste and blend of municipal solid waste and agricultural residues 4. Conclusion
respectively at various conversions. The frequency factors for the
corresponding activation energies are observed to be in the order In the present investigation, it is observed that the thermal deg-
of 1013–1015, 1015–1024, 1012–1052, 102–107 s1 for groundnut radation of GS and CH occurred in two stages, where as with MSW
A. Bhavanam, R.C. Sastry / Bioresource Technology 178 (2015) 126–131 131

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