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A publication of

CHEMICAL ENGINEERINGTRANSACTIONS
VOL. 56, 2017 The Italian Association
of Chemical Engineering
Online at www.aidic.it/cet
Guest Editors: Jiří Jaromír Klemeš, Peng Yen Liew, Wai Shin Ho, Jeng Shiun Lim
Copyright © 2017, AIDIC Servizi S.r.l.,
I SBN978-88-95608-47-1; I SSN 2283-9216 DOI: 10.3303/CET1756033

Kinetic Study on the Pyrolysis and Gasification of Plastic

Waste
Vergel Castañeda Bungay
Chemical Engineering Department, De La Salle University, 2401 Taft Avenue, Manila, Philippines
[email protected]

With the large volume of consumer plastic waste generated worldwide, one common problem in the
Philippines involves the disposal and treatment of solid wastes. Current processes in the disposal of post-
consumer plastic wastes such as incineration or landfill are not fully acceptable based on international
standards. As such, there is an urgent need for a practical, safe and efficient disposal method which can also
convert waste into useful energy. Pyrolysis and gasification are very well-known thermal degradation
processes that convert carbonaceous materials into useful gaseous products that still contain significant
amount of energy. The parameters obtained from the kinetic study of these processes are very essential in the
design of useful conversion technologies such as reactors and gasifiers. In this study, the pyrolysis and
gasification of plastic waste samples were investigated in a thermogravimetric analyser (TGA).
The kinetic parameters for the pyrolysis of the samples were obtained at heating rates ranging from 10 - 30
K/min. The mean activation energies for the pyrolysis reaction were found to be 124.1 kJ/mol and 107.3
kJ/mol, for samples X and Y. In terms of the temperature at which maximum degradation occurs, the
differential thermogravimetric (DTG) curve of the plastic waste sample resembles that of a ternary mixture
containing polypropylene (PP), polyethylene (PE) and polyethylene terephthalate (PET). For the gasification of
the plastic waste samples with CO2, a temperature higher than 600 °C is required to attain significant
conversion. The activation energies for the gasification of the waste plastic samples were found to be 144.7
and 147.8 kJ/mol for samples X and Y.

1. Introduction
Current technologies that involve disposal of post-consumer plastic wastes such as incineration or landfill are
known to have many disadvantages with respect to international standards which focus on recovery of energy
and raw material (Encinar and Gonzalez, 2008). The packaging industry is considered as one of the major
plastic consumers with about 52 % of the total consumption (Hujuri et al, 2008). A significant increase in the
consumption of plastics resulted to increased generation of plastic wastes. Plastic wastes consist primarily of
mixture of polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET), low-density
polyethylene (LDPE), polyvinyl chloride (PVC), and polystyrene (PS). These wastes are known to be non-
biodegradable and add to the problems of solid waste management in many areas.
Most studies are focused on the conversion of these plastic wastes to valuable chemical products using
various thermal degradation processes such as pyrolysis and gasification. Pyrolysis is a thermal degradation
of a material in the absence of oxygen and involves the removal of volatile components such as hydrocarbon
gases, tars and phenols. Gasification, on the other hand, involves reaction of a carbonaceous material with
either steam or CO2 producing carbon monoxide, hydrogen and light hydrocarbons. The most common device
to carry out these reactions is the thermogravimetric analyser (TGA) due to its simplicity and the valuable
information obtained from it is enough to derive kinetic information from the reactions.
In this study, two plastic waste samples obtained from different sources underwent pyrolysis and gasification
in a TGA. Kinetic information obtained from this reaction includes activation energies and reaction rate
constants.

Please cite this article as: Bungay V.C., 2017, Kinetic study on the pyrolysis and gasification of plastic wastes, Chemical Engineering
Transactions, 56, 193-198 DOI:10.3303/CET1756033
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2. Methodology
2.1 Samples and Materials
Two types of plastic wastes were obtained from two different damp sites and labelled as Sample X and
Sample Y. Only the plastic components of the wastes were isolated, crushed and grinded to yield particle
sizes ranging from 1 - 2 mm. The proximate and ultimate analyses of the plastic samples are shown in Table
1. Gasification and pyrolysis of the plastic samples were done using ultra-high purity N2 and CO2 gas along
with air to oxidise the remaining char and combustibles in the sample.

Table 1: Analysis of the plastic samples

Proximate analysis (wt% wet basis) Ultimate analysis (wt% dry, ash-
free)
Sample
Moisture Volatile Fixed Carbon Ash C H O N
Matter
X 0.6 90.5 3.7 5.2 65.3 13.9 20.7 0.3
Y 0.9 92.1 3.1 3.9 73.1 22.4 4.4 0.1

2.2 Pyrolysis and gasification experiments

Plastic wastes were crushed to yield particle sizes ranging from 1 - 2 mm. Plastic samples weighing 15 ± 1
mg was used in the thermogravimetric analyser (TA Q50) and heated under N2 environment to 600 °C at a
heating rate ranging from 10 - 30 °C/min. Nitrogen gas used in the TGA flowed at a flow rate of approximately
80 mL/min. Mass, time and temperature data were recorded every 2 s to yield weight loss (TG) and differential
weight loss (DTG) curves.
Gasification with CO2 was performed in the same TGA using 15 ± 1 mg of plastic sample. Gasification of the
sample initially involved heating of the sample at 110 °C to remove the moisture under N2 environment. The
-1
temperature of the sample was then elevated at a rate of 90 °C min to the desired gasification temperature,
which was varied from 600 to 900 °C. At this point, the volatile matter was removed. When the mass of the
sample became constant, CO2 was introduced to the reactor to gasify the resulting char. After a definite period
of gasification, the gas mixture was then switched to an air/N2 mixture for the combustion of the remaining
char.
2.3 Modelling of the pyrolysis reaction
In this study, the single reaction model was used. The extent of conversion (X) or the fraction of the pyrolysed
material is calculated as Eq(1):
mi - m
X= (1)
mi - m f

where mi = initial mass of the sample after removal of moisture (mg), m = mass of the sample at any time, t
(min) and mf = mass at the end of the pyrolysis process (mg). The reactivity or the reaction rate of pyrolysis is
given by Eq(2):
dX
= k(T)f (X) (2)
dt

where k(T) = rate constant (min-1) and f(X) = kinetic model-dependent function. The temperature dependence
of the rate constant is further defined as Eq(3):
 E 
k (T ) = A exp  −  (3)
 RT 
-1 -1
where A, E, R and T are the frequency factor (min ), the activation energy (kJ mol ), the universal gas
-1 -1
constant (kJ mol K ) and the gas temperature (K). With f(X) = 1 – X and defining β = dT/dt, the Coats and
Redfern (1964) method was used to calculate the pre-exponential factor and the activation energy. The
resulting equation after ignoring the higher order terms will give Eq(4):

 ln(1 − X ) E  AR  2RT 
ln− =− + ln 1 −  (4)
 T 2  RT  βE  E 
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In the plot of the left-hand side of the equation versus 1/T, the slope will be -E/R and the y-intercept can
readily evaluate the frequency factor at the given heating rate β. The activation energy of the pyrolysis
reaction is then reported as the average of the activation energies obtained from each runs with a specific
heating rate.
2.4 Modelling of the gasification reaction
For the gasification reaction, the char conversion (x) was calculated as Eq(5):
W0 - W
x= (5)
W0 - Wash

where W0 = sample mass at the start of the gasification (mg), W = sample mass (mg) at gasification time, t
(min) and Wash = mass of the ash that remained after complete combustion with air/N2 mixture (mg). The
modified volumetric model proposed by Kasaoka et al (1985) is given by the Eq(6):

x = 1 - exp(- αt β ) (6)

where α and β are empirical constants obtained from the conversion data by the least-square method.
Differentiation of this equation leads to the determination of a specific reaction rate constant as follows
1
β -1
1 dx β (7)
k(x ) = = α β[- ln(1 - x )] β
1 - X dt

For consistency, all models were evaluated at char conversion range of 0 to 0.5 to unify all gasification curves.
Previous investigation also used x = 0.50 to evaluate the rate constant for gasification reactions of various
carbonaceous materials at gasification temperatures ranging from 700 °C to 900 °C (Kim et al., 2014). The
capability of the model to represent the experimental data was assessed using the squared value of
2
correlation index, R .

(a) (b)

Figure 1: Thermograms of (a) sample X and (b) sample Y at different heating rates during pyrolysis

3. Results and discussion

This sections discusses variation of activation energies and frequency factors at different heating (pyrolysis)
rates of plastic samples, and the impact of CO2 gasification on the plastic wastes samples.
3.1 Pyrolysis of plastic samples
Figure 1 shows the TGA curves of the waste plastic samples at various heating rates. It can be seen from
these plots that the mass of Samples X and Y started to decrease at about 240 °C. Sample Y appears to have
greater initial pyrolysis rate than Sample X which can be explained from the lower activation energy of the
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pyrolysis reaction of Sample Y. The faster pyrolysis rate of Sample Y can also be attributed to its slightly
higher volatile component compared to Sample X. The presence of higher amounts of volatile matter of
Sample Y will influence faster pyrolysis reaction rate. For both plastic samples, the mass became nearly
constant at about 5 % of the initial mass at approximately 500 °C.
The activation energies (EA) of the reaction were obtained using Eq(4) and tabulated in Table 2. The variation
of the activation energies with the heating rate can be explained by the heat transfer limitation within the
sample. The values of the activation energies obtained were found to be similar to that of PS and PP (Encinar
and Gonzalez, 2008) at heating rates between 10 - 30 K/min.
To compare the rate of pyrolysis of both plastic samples, Figure 2 shows the variation of pyrolysis rate with the
heating rate. From this plot, Sample Y shows higher pyrolysis rate compared to Sample X as determined from
the lower activation energy of pyrolysis of Sample Y compared to that of Sample X. Sample X shows an
approximate linear relationship between the heating rate and maximum pyrolysis rate compared to sample Y
which may indicate that Sample X has more uniform composition than Sample Y.

Table 2: Activation energies and frequency factors at various (pyrolysis) heating rates
Heating Sample X Sample Y
-1 2 -1 2
Rate, β EA (kJ/mol) A (h ) R EA (kJ/mol) A (h ) R
14 13
10 124.17 9.12 x 10 0.9897 109.34 2.27 x 10 0.9705
14 13
20 120.94 6.03 x 10 0.9893 110.04 3.10 x 10 0.9963
14 13
30 127.24 9.88 x 10 0.9880 102.78 8.68 x 10 0.9883
14 13
Mean 124.11 8.34 x 10 107.39 2.08 x 10

Figure 2: Variation of maximum pyrolysis rate with heating rate

3.2 Gasification of plastic waste samples with CO2

For Sample X, an increase from 600 °C to 700 °C resulted to about 7.5 times increase in gasification rate
while about 5 times for Sample Y. The increase in gasification temperature from 700 °C and 800 °C resulted
to almost the same increase in gasification rate for both Samples X and Y. When temperature was increased
to 900 °C, the increase in gasification rate was found to be 3 times and 7 times, for Samples X and Y. At
higher temperatures, it can be deduced that some of the inorganic constituents of the plastic waste samples
responsible for its catalysis may have been volatilised and the enhancement of the gasification rate is mainly
due to the increase in the temperature.
In a related study which involved co-gasification of rubber seed shell and high-density polyethylene mixtures,
high conversions at higher temperatures was also due to promotion of secondary cracking and other
endothermic gasification reactions such as the water gas shift reaction (Chin et al., 2014). At 600 °C, the two
samples behaved similarly in terms of the extent of char conversion as shown in Figure 3. Such low
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conversion can be attributed to the complex nature of the polymeric materials present in the waste plastic
samples which requires higher temperature for its thermal degradation. Using the modified volumetric model,
the Arrhenius parameters can be obtained and showed in Table 3.

Table 3: Activation energies and frequency factors of gasification of plastic samples with CO2
Sample EA (kJ/mol) A (h-1) R2
X 144.77 9.12 x 1014 0.9897
Y 147.78 6.03 x 1014 0.9893

From these constants, lower activation energy for Sample X is a clear manifestation of the catalytic effect from
the inorganic components present in its ash. This trend in the rate is a complete reverse of what was observed
from the rate of the pyrolysis reaction. It is therefore evident that the ash component in the plastic samples
possesses catalytic activity and enhances the rate of gasification. Numerous investigations support this result
since ash contains inorganic species that catalyses gasification reactions. In pyrolysis, the volatile matter in
the samples is being removed until char is produced. The rate of pyrolysis can therefore be influenced by the
volatile components of the samples.
Unlike gasification, the char produced was practically free from volatile matter and reacts directly to CO2 with
the inorganic species present in the ash acting as a catalytic agent. Although this study did not quantify the
component of the ash, it is believed that the enhancement of the gasification reactions at lower temperatures
is greatly influenced by these components. The modified volumetric model was found to best correlate the
gasification of the plastic waste samples.

(a) (b)

Figure 3: Time-conversion plots for the CO2 gasification of plastic waste samples, (a) sample X, (b) sample Y

4. Conclusions
In this study, the kinetics of pyrolysis and gasification of plastic waste samples was investigated in terms of
kinetic parameters such as activation energy and relative reaction rates. Initial decomposition of both plastic
wastes was observed at 240 °C and terminated at 500 °C. Nearly 5 % of the samples remained at 500 °C and
the activation energies of both samples was similar to a mixture of polystyrene and polypropylene. Sample Y
was observed to react faster compared to Sample X during pyrolysis which may be due to a slightly higher
amount of volatile matter in Sample Y. Sample X was found to be more reactive to gasification compared to
Sample Y. This is due to the relatively higher amount of ash in Sample X compared to Sample Y. Highly
reactive ash components may account for the high reactivity towards gasification of plastic samples. Increase
in the gasification rate was found to range from 5 - 7 times at lower temperatures and negligible effect at
higher temperatures. Both the single-reaction and modified volumetric models were sufficient to correlate
pyrolysis and gasification reactions of plastic waste samples.
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