Energy Conversion and Management 148 (2017) 925–934

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Energy recovery from pyrolysis of plastic waste: Study on non-recycled

plastics (NRP) data as the real measure of plastic waste
Shafferina Dayana Anuar Sharuddin, Faisal Abnisa ⇑, Wan Mohd Ashri Wan Daud,
Mohamed Kheireddine Aroua
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

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

Article history: Oil produced from pyrolysis of plastics have been known for its higher calorific value than wood-based
Received 13 March 2017 oil, in which comparable to conventional diesel. Even though many studies have been conducted on
Received in revised form 15 June 2017 pyrolysis of plastics, the findings of those studies are not applied and reported yet according to the real
Accepted 16 June 2017
portion of plastic waste. The real amount of plastic waste available is mainly derived from non-recycled
plastics (NRP). NRP is defined as the plastic waste that remain in the recycling centers, which unable to be
processed due to the certain restrictions. The amounts of NRP vary for each country based on daily appli-
Keywords:
cations. In this study, data of NRP in Malaysia, US, UK, as well as global were used to investigate the
Plastic waste
Pyrolysis
potential production of liquid fuel based on their different composition of plastic waste. Pyrolysis was
Polystyrene conducted in a fixed bed reactor at 500 °C with nitrogen flow of 200 ml/min for 30 min reaction time.
Fuel The addition of polystyrene (PS) into the NRP composition was also studied to evaluate the improvement
Energy recovery of the liquid quality. Several important findings were discussed in this paper including some technical
problems, features of the liquid product, characteristics of the by-products and potential energy recovery
from NRP. The liquid product was analyzed by various methods such as FTIR, GCMS, elemental analysis
and water content.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction produced were less in comparison to the individual plastic pyroly-

Pyrolysis of plastic waste currently gained high attention from
the researchers in order to convert it into liquid fuel to overcome
the depletion of liquid fossil fuel. Studies have been started from
analyzing the characteristics of liquid fuel produced from different
type of plastics, up till the usage of catalysts in order to upgrade
the liquid quality. In terms of quantity, most researchers reported
high amount of liquid yield more than 80 wt% could be produced in
pyrolysis of individual plastic, which was higher than the pyrolysis
of wood-based biomass in general [1,2]. As for the quality, the
obtained liquid also had high calorific value around 40 MJ/kg [3–
6]. With the addition of catalyst, the impurities contained in plastic
waste could be removed, besides reducing the water content in liq-
uid fuel [7].
The scenario in pyrolyzing the plastic waste into liquid fuel has
also been extended to the mixing of various types of plastics. The
results from the mixture of plastic pyrolysis showed that the liquid
⇑ Corresponding author.
E-mail addresses: dayanareen@gmail.com (S.D. Anuar Sharuddin), faisal.abnisa@
gmail.com (F. Abnisa), ashri@um.edu.my (W.M.A. Wan Daud), mk_aroua@um.
edu.my (M.K. Aroua).
sis. According to Miskolczi et al. [8], only 21 wt% liquid oil was
obtained in the pyrolysis of plastic mixtures collected from the
municipal solid waste (MSW). Kaminsky et al. [9] also obtained
about 38 wt% liquid oil in the pyrolysis of plastic mixtures running
in fluidized bed reactor. Furthermore, studies on operating param-
eters also became an important objective to be investigated in this
scenario. The parameters included temperature, ratio of plastic
component, types of plastic waste, different bed material and type
of fluidizing gas [5,10–12]. According to Pinto et al. [5], besides
temperature, ratio also played an important role in determining
the liquid product characteristics produced from pyrolysis of plas-
tic mixtures.
Even though different plastic ratios have been studied, the
ratios used in the studies are not the representative of the real
plastic waste statistic. The real plastic waste statistic can be
referred to the data of non-recycled plastics (NRP) waste which
provided by the waste management authorities. NRP is defined
as plastics not redirected for recycling that remain in MSW or in
materials recovery facility residue [13]. By using the NRP data in
pyrolysis process, the actual product obtained is more convincing
to be used as reference data in order to calculate the real target

http://dx.doi.org/10.1016/j.enconman.2017.06.046
0196-8904/Ó 2017 Elsevier Ltd. All rights reserved.
926 S.D. Anuar Sharuddin et al. / Energy Conversion and Management 148 (2017) 925–934
production of liquid fuel and determine the quality standard.
Besides, if the calorific value of NRP pyrolysis has been known,
then the total of energy recovery can be easily and accurately pre-
dicted for a particular location. The use of NRP data is considered
important if this strategy is to be further advanced and
commercialized.
The accumulation of NRP is mainly due to different physical
properties of plastics during recycling. A major challenge in recy-
cling plastics is most plastics are not compatible with each other
to be processed together during recycling. For instance, a slight
amount of polyvinyl chloride (PVC) contaminant present in poly-
ethylene terephthalate (PET) recycle stream will degrade the
whole PET resin by becoming yellowish and brittle that requires
reprocessing [14]. Hence, proper sorting process is required before
recycling to avoid any contaminants from entering the recycling
stream since plastics are made of different resin compound, trans-
parency and colours. As for physical properties, normally pig-
mented or dyed plastics have lower market value. Clearly
transparent plastics are often desirable by the manufacturers since
they can be dyed to transform into new products, thus have greater
flexibility [15]. Plastic bags, for instance, are not accepted by most
recycling centre since they may clog the machineries during recy-
cling. Polystyrene (PS) is also not accepted in recycling program
due to its lightness that easily blown away and creates litter during
collection. Besides, its bulky characteristic is also one of the rea-
sons PS is not preferred since it requires high transportation cost.
PS is also hazardous to be in contact with any food since there
are some researches have shown that PS can create health prob-
lem. Hence, it is often not profitable to recycle PS.
The worldwide plastic consumption has reached about 322 mil-
lion tons in 2015, representing a 4% increase over 2014 [16]. Con-
sequently, the increase in plastic consumption will definitely result
in the accumulation of plastic waste. This means that the amount
of NRP is also growing each year. In developed countries particu-
larly US, the amount of plastic waste has reached to 39.3 million
tons in 2014, indicating a 13% increase over 2011 [17,18]. As in
UK, the plastic waste has risen over 60% from 2005 to 2015 [19].
The same trend is also observed in developing country such as
Malaysia which experiencing a growth in plastic waste by 18% in
5 years [2]. These phenomena show that different countries tend
to produce different amount of NRP, indicating the production of
liquid fuel by pyrolysis of NRP will be varied in terms of quantity
and quality.
In this study, the NRP data were used as feedstock ratio in
pyrolysis process to observe the production of liquid yield as well
as the by-products. The NRP data of global and three different
countries which were Malaysia, US and UK were selected to be
studied. Besides, the effect of PS addition into the feedstock ratio
was also studied to investigate the product improvement. The
obtained products were tested for viscosity, pH, density, elemental
analysis, water content, Fourier transform infrared (FTIR) and gas
chromatography-mass spectrometry (GCMS). In addition, the
energy recovery from liquid as the main product, while gas and
tar as the by-products were also calculated.
2. Materials and experimental procedures
2.1. Materials
Plastic samples of PET, PVC, high-density polyethylene (HDPE),
low-density polyethylene (LDPE), polypropylene (PP) and PS were
obtained from the post-consumer polymer waste stream in Malay-
sia. The collected plastics were washed and dried using oven at
105 °C for 24 h. Dry plastic waste was cut into small pieces and
fed into the reactor as feedstock. The plastic mixture ratio was
determined according to the NRP data obtained from Malaysia,
US, UK and global. However, PVC and PET were excluded in this
study due to their undesired properties. Pyrolysis of PVC mainly
released HCl which tend to be corrosive and toxic when heated
moderately that caused damage to the process equipment [1].
Besides, PVC waste accumulated in MSW was very minimal, about
3% in plastic waste category which the source was very limited. As
for the PET, the discussion was provided in Section 3.2. Table 1
shows the global composition of NRP waste consisted in MSW
within several years.
2.2. Experimental setup and procedures
The pyrolysis experiments were performed using an updraft
stainless steel fixed bed reactor under atmospheric pressure with
an internal diameter of 0.05 m and total length of 1.27 m. The
updraft fixed bed reactor was chosen due to its simple design,
more robust since it was less sensitive to variation in particle sizes
and quality of feedstock, low gas exit temperature, high burnout
and thermal efficiency [23]. The reactor was equipped with a K-
type thermocouple inside to monitor the temperature when
heated by an external furnace. A condenser that sustained the fur-
nace temperature at the desired level of ±0.5 °C was connected in
order to obtain the liquid oil through the gas condensation. The
experimental setup was illustrated in Fig. 1.
This study was divided into two scenarios. The first scenario
was arranged to obtain an overview of the potential liquid yield
produced based on different compositions of NRP in Malaysia,
US, UK and also global. A total of 400 g was used as a basic weight
for calculation for each NRP based on the percentage shown in
Table 1, where the PET and PVC were excluded. The pyrolysis pro-
cess was performed at 500 °C with a heating rate of 20 °C/min by
using the electrical furnace. Each experiment was performed at
30 min reaction time. Nitrogen was used as carrier gas with flow
rate of 200 ml/min to remove the products from the reaction site
and minimize the secondary reaction of vapors that would reduce
the yield of liquid oil. The second scenario was aimed to improve
the liquid quality by adding PS into the NRP composition. Malay-
sia’s NRP was selected as a model for this study. The ratios of PS
were varied in the range of 25, 50, 75 and 100 wt%. The ratios of
PS were calculated based on the basic weight of total NRP after
excluded PET and PVC. The process parameters were similar with
scenario 1. Each experiment was repeated three times to take the
average of the results. The product yield of the liquid oil, non-
condensable gas and tar were calculated using Eq. (1). Tar is
defined as the black viscous organic liquid produced in the product
stream that is condensable and generally assumed to be largely
aromatic [24].
Desired product ðgÞ
Yield of product ðwt%Þ ¼  100% ð1Þ
Total feed ðgÞ
2.3. Characterizations
2.3.1. Characterization of raw materials
Proximate analysis can be defined as a technique to measure
the chemical properties of the plastic compound based on four par-
ticular elements which are moisture content, fixed carbon, volatile
matter and ash content. Volatile matter and ash content are the
major factors that influence the liquid oil yield in pyrolysis process.
High volatile matter favors the liquid oil production while high ash
content decreases the amount of liquid oil, consequently increases
the gaseous yield and char formation [25]. In this study, the prox-
imate analysis was conducted according to the ASTM standards
prescribed in literature [26].
 S.D. Anuar Sharuddin et al. / Energy Conversion and Management 148 (2017) 925–934 927

Table 1
Global composition of NRP waste consisted in MSW.

Plastic material Malaysia plastic wastea (%) US plastic wasteb (%) UK plastic wastec (%) Global plastic wasted (%)
PET 16.2 12.4 15.3 15.43
HDPE 26.2 17.8 13.5 16.97
PVC 3.9 5.5 3.5 3.08
LDPE 31.1 19.6 25 33.95
PP 8.2 13.9 22.2 15.43
PS 13 8.7 4 12.35
a
Data taken in 2012 [20].
b
Data taken in 2014 [18].
c
Data taken in 2008 [21].
d
Data taken in 2011 [22].

Legend:
F: Furnace, R: Reactor, S: Sample, TC: Temperature controller, FC: Flow controller, V: Valve, C1:
Condenser, C2: Chiller, ST: Storage tank, FU: Filter unit, GA: Gas analyzer

Fig. 1. Schematic diagram of experimental setup for pyrolysis of plastic mixtures.

On the other hand, the ultimate analysis determines the mass m ðkgÞ
q ðkg=m3 Þ ¼ ð2Þ
fractions of carbon, hydrogen, nitrogen and heteroatoms of a sam- V ðm3 Þ
ple. This elemental composition of plastics was determined accord-
where q is density of liquid, m is the mass of liquid and V represents
ing to ASTM D-5291 using a Model 2400 Perkin-Elmer Series II
the volume of the pycnometer. The measurement of acidity or
CHNS/O Analyzer and the oxygen content was calculated by
basicity of the pyrolysis oil is also crucial to avoid corrosion when
difference.
using as fuel. The pH was determined at 25 °C using a Mettler
Toledo pH meter series 320. Besides, the water content in the pyrol-
2.3.2. Characterization of pyrolysis oil
ysis oil was also analyzed using a Karl Fischer 737 KF Coulometer
In order to evaluate the quality of pyrolysis oil, several impor-
from Metrohm. For this analysis, about 2–6 mg of sample was used
tant properties such as the viscosity, pH, density, water content,
to measure the water content.
elemental analysis, FTIR and GCMS were determined. Viscosity is
Elemental analysis was also done on the pyrolysis oil to measure
defined as a measurement of the fluid resistance to flow. Viscosity
the mass fractions of carbon, hydrogen, nitrogen and heteroatoms in
is very crucial in petroleum industry since it determines how easy
the composition. This analysis was useful in identifying any
the oil can flow from the reservoir to the well during extraction
unknown compounds, besides determining the purity of the syn-
process and also plays a crucial role in fuel injection process
thesized compound. The elemental analysis was done using a Model
[3,27]. In this study, the viscosity was measured using a rotational
2400 Perkin-Elmer Series II CHNS/O Analyzer in which elements
viscometer equipped with an SC4-18 spindle (Brookfield Viscome-
such as C, H, N and S were determined while oxygen content was
ter model DVII+ Pro EXTRA). About 7 ml of sample at 50 °C was
obtained by the difference. The high heating value (HHV) was calcu-
taken for the viscosity measurement.
lated based on Eq. (3) as below since the oxygen compound was less
Besides that, density is another important physical characteris-
than 15%, where the units for C, H and O elements should be in wt%.
tic for fuel generally expressed in kg/m3 in SI unit or also equiva-
lent to g/ml. As for this study, a 25 mL pycnometer was used to MJ
 
338:2C þ 1442:8 H O


8
determine the density of the pyrolysis oil which was tested at HHV ¼ ð3Þ
kg 1000
24 °C. The density was calculated based on Eq. (2):
928 S.D. Anuar Sharuddin et al. / Energy Conversion and Management 148 (2017) 925–934
FTIR analysis was also done to identify various characteristic
functional groups present in the oil in which a Perkin Elmer FTIR
spectrometer (Spectrum 400) was used in this study. The samples
were scanned in the range of 400–4000 cm 1 with a resolution of
4 cm 1. Besides that, the component of the liquid product was also
analyzed using gas chromatography/mass spectroscopy (GCMS).
An Agilent Technologies 7890A gas chromatograph equipped with
an Agilent 5975C mass-selective detector (mass spectrometer) was
utilized for the component analysis. The Agilent HP-5 50 m column
with an inner diameter of 0.32 mm and a film thickness of 0.25 mm
was used in the GCMS. High purity helium was used as carrier gas
at constant flow rate of 1.0 mL/min. The analysis was started by
heating the column at 50 °C and kept isothermal for 1 min, then
increased to 270 °C with a rate of 7 °C/min. This condition was held
for 10 min. The volume of sample injected was about 1 mL.
3. Result and discussion
3.1. Characterization of plastic materials
The proximate and ultimate analyses of different plastic materi-
als are shown in Table 2. Based on the proximate analysis results,
the moisture content of all plastics were very low except for PET
which was slightly high compared to others. No fixed carbon was
found in all plastics except PET and PVC. The amount of volatiles
compound was found high in all type of plastics except PET and
PVC which somewhat lower. Besides that, PET and PVC also had sub-
stantial amount of ash. The lower amount of volatiles compound
and high ash content in PET and PVC signified the potential of pro-
ducing very less liquid oil in pyrolysis [25]. For the ultimate analysis,
the oxygen content of PET was determined to be very high around
31.49 wt% whereas high chlorine content was found in PVC around
57.61 wt%. The high oxygen content indicated that PET had lower
calorific values while the high chlorine content made the liquid pro-
duced from pyrolysis of PVC not suitable to be used as fuel [28].
The TGA thermographs of different type of plastics at heating
rate of 20 °C/min are illustrated in Fig. 2. TGA analysis was useful
to define the starting degradation temperature for each sample.
The results showed that all plastics started to degrade at 300 °C
and completed the degradation at 500 °C except PVC. Unlike other
plastics, the degradation of PVC occurred in two steps. The first
degradation step occurred within 200–350 °C where a complete
dehydrochlorination happened. The process followed by the
decomposition of polyene chain that happened during the second
step within 400–500 °C [30]. From Fig. 2, it can be concluded that
500 °C was selected as the most effective temperature for pyrolysis
since all type of plastics have completed their decompositions
when reaching this temperature.
3.2. Pyrolysis yield
In a preliminary study, pyrolysis of PET alone was conducted to
observe the potential product being produced from it. A transpar-
Table 2
Proximate and ultimate analyses of different plastic materials.
Type of plastics Proximate analysis (wt%)
Moisture Fixed carbon Volatiles
PET 0.22 6.2 86.75
HDPE 0.01 0 99.77
PVC 0 5.12 85.77
LDPE 0.03 0 99.85
PP 0 0 99.64
PS 0 0 99.78
*
Calculated by difference [29].
ent condenser made by acrylic was used for an easy observation in
the same experimental setup. It was discovered that yellowish liq-
uid was produced in the condenser as shown in Fig. 3. After several
minutes, the yellowish liquid turned into solid and adhered to the
wall of condenser. The yellowish substance had clogged piping
from reactor to condenser which caused problems in product col-
lection and sterilization of system. According to Cepeliogullar
and Putun [31], the yellowish substance was benzoic acid that
could clog piping and heat exchanger, thus might need serious
attention if running at industrial scale. This signifies that the pyrol-
ysis of PET was inefficient in terms of time and cost since it
required regular maintenance [32,33]. Hence, PET was excluded
in this experiment. Besides PET, PVC was also excluded since the
pyrolysis of PVC produced hydrogen chloride (HCl) which tends
to be corrosive and toxic when heated moderately that could cause
damage to process equipment [28,34].
Table 3 shows the product yields from pyrolysis of NRP at var-
ious ratios for selected countries and globally based on the NRP
ratio consisted in MSW. Based on Table 3, it can be seen that the
pyrolysis of NRP from US produced the lowest liquid yield which
was only 26.33 wt%. From the plastic composition, it can be
observed that the amount of LDPE in the NRP composition of US
was the lowest among other countries, besides having low content
of PS. According to Sharuddin et al. [1], the sequence of the pyrol-
ysis oil yield of the four thermoplastics in an ascending order
would be HDPE, PP, LDPE and PS. Since LDPE and PS produced high
amount of pyrolysis oil, this briefly explained the reason of the
higher liquid yield obtained from Malaysia’s NRP (29 wt%) com-
pared to the US. Even though Malaysia had the highest amount
of HDPE in its waste stream, the high composition of LDPE and
PS helped to boost the liquid product obtained from pyrolysis,
which in returns produced higher liquid yield than US. This
denotes that the studied polymers did not react independently
and there was an interaction occurred between the plastic sam-
ples. The waste of LDPE basically contributed by trash bags, wrap-
ping foils for packaging and plastic bags, while the PS waste mostly
contributed by toys, medical stuff, electronics, food packaging and
construction stuff.
In order to further enhance the liquid production from pyrolysis
of NRP mixture, the effect of PS to the pyrolysis performance was
further explored. In this study, Malaysia was selected as a repre-
sentative of the countries. PS was added at various ratios of 25,
50, 75 and 100 wt% into the feed of Malaysia’s NRP composition
that was fixed throughout the study. The product yield of pyrolysis
oil, tar and non-condensable gases were summarized in Table 4.
From the table, it was observed that the pyrolysis oil kept increas-
ing with the increase of PS. The same trends during pyrolysis of
individual plastics with PS were also observed by Lee et al. [35]
and Onwudili et al. [36]. The maximum oil yield obtained from this
study was 72.08 wt% at 100 wt% PS addition. Besides, the tar for-
mation and non-condensable gases also reduced as the ratio of
PS was increased. According to Onwudili et al. [36], there was a
synergy existed between plastic such as LDPE when mixed with
Ultimate analysis (wt%)
Ash C H N S O* Cl*
6.83 63.94 4.52 0.01 0.04 31.49 0
0.22 86.99 12.12 0.27 0.07 0.56 0
9.11 37.24 4.99 0.08 0.08 0 57.61
0.12 85.6 13.4 0.26 0 0.74 0
0.36 86.88 12.5 0.28 0.03 0.32 0
0.22 91.57 7.8 0.15 0.04 0.45 0
 S.D. Anuar Sharuddin et al. / Energy Conversion and Management 148 (2017) 925–934 929

100 HDPE
LDPE
80

Weight loss (%)

PP
PS
60
PET
40 PVC

20

0
0 100 200 300 400 500 600 700 800 900
Temperature (ºC)

Fig. 2. TGA thermographs of different type of plastics.

In terms of the physical appearance, the liquid obtained from

the pure NRP pyrolysis without any addition of PS was mainly in
wax form. This created technical problem especially during product
collection when the condensed wax accumulated in the condenser
led to a serious blockage. The same problem was experienced by
Kiran et al. [37] during pyrolysis of polyethylene (PE) when plug-
ging of the product lines and condenser tube by the wax formed
was considered as the most serious operating problem. In order
to solve the blockage problem, the temperature of the condenser
was increased up to 50 °C to heat up the wax inside so that it would
melt to liquid and made the product collection process became
easier. According to Williams and Williams [38], the wax was
mostly produced by the HDPE, LDPE and PP plastics. The increase
in PS addition in this study managed to reduce the waxy appear-
ance of the liquid product. At 25 wt% PS addition, a mixture of
wax and liquid was collected from the condenser. A very minor
wax was observed during product collection when 50 wt% PS was
added. As for 75 wt% and 100 wt% PS addition, the collected prod-
ucts were mainly in liquid form with no wax appearance. This indi-
cates that a reactant containing high PS content was easily cracked
to light liquid product [35]. Besides plastics, other biomass such as
Fig. 3. Yellowish substance formed in the condenser from preliminary study of palm shell and cellulose also showed remarkable results when the
pyrolysis of PET. liquid product increased after the addition of PS [2,39,40].

3.3. Characterization of pyrolysis product

PS, which they reacted to produce more oil, lesser by-products
than the pyrolysis of LDPE and PS alone. This synergy effect also 3.3.1. Pyrolysis oil
seemed to exist in the pyrolysis of NRP and PS when similar trend The oil properties obtained from pyrolysis of pure NRP based on
of product yield was observed. Malaysia’s data, as well as after the addition of PS are summarized

Table 3
Distribution of products for three countries as well as global from pyrolysis of NRP waste at different ratios.

Countries Plastic composition Yield

Liquid Gas Tar
Malaysia HDPE (26.2 wt%) 29.00 20.89 50.11
LDPE (31.1 wt%)
PP (8.2 wt%)
PS (13.0 wt%)
US HDPE (17.8 wt%) 26.33 19.17 54.50
LDPE (19.6 wt%)
PP (13.9 wt%)
PS (8.7 wt%)
UK HDPE (13.5 wt%) 44.62 39.00 16.38
LDPE (25.0 wt%)
PP (22.2 wt%)
PS (4 wt%)
Global HDPE (17.0 wt%) 43.20 9.28 47.52
LDPE (34.0 wt%)
PP (15.4 wt%)
PS (12.4 wt%)
930 S.D. Anuar Sharuddin et al. / Energy Conversion and Management 148 (2017) 925–934

Table 4
Products distribution from pyrolysis of Malaysia’s NRP at different ratio of added PS.

Malaysia NRP fixed feed ratio Products PS mixed ratio (wt%)

0a 25 50 75 100
HDPE (26.2 wt%) Pyrolysis oil (wt%) 29 59.29 66.95 68.41 72.08
LDPE (31.1 wt%) Tar (wt%) 50.11 32.54 19.59 17.91 16.31
PP (8.2 wt%) Non-condensable gases (wt%)* 20.89 8.17 13.46 13.69 11.61
PS (13.0 wt%)
*
Calculated by difference.
a
Pure NRP.

in Table 5. For the comparison purpose, conventional diesel stan-
dard was also included in the table. It can be observed from Table 5
that the water content of oil obtained from pure NRP was 0.92%
which was higher than the conventional diesel. However, the mea-
sured water content decreased when the ratio of PS was increased.
The low water content indicates that the pyrolysis oil has good fuel
property since high water content is often undesirable as it can be
damaging to the ignition performance and causes rust to build up
in the engines.
The measurement of the viscosity shown in Table 5 was
dynamic viscosity. No significant change observed from the viscos-
ity properties for pyrolysis of pure NRP or after the addition of PS.
The viscosity of oil from pure NRP as well as after the addition of PS
was even lower than the diesel. This signified that the pyrolysis oil
produced was less viscous and therefore, easier to pump and suit-
able to be used in fuel injection process [1]. Besides, same trend
was observed for density which was no significant change and
the density of the pyrolysis oil was similar with the conventional
diesel.
The pH value for the liquid from pure NRP was 7.03 and the
addition of PS reduced the pH slightly from 6.76 to 6.51. This
shows that the pyrolysis oil obtained from NRP had non-
corrosive property. The non-corrosive property makes the pyroly-
sis oil suitable to be used in engines, boilers, refinery equipment
and can even be stored in any storage containers without causing
corrosion problem.
The ultimate analyses to determine the elemental composition
of the pyrolysis oil are also shown in Table 5. Referring to Table 5, it
can be seen that the elemental composition of oxygen in liquid
from pyrolysis of pure NRP was found high at 3.83 wt%. High oxy-
gen content resulted in low calorific value, corrosion problems and
instability [42]. However, the increase of PS able to reduce the oxy-
gen content to 0 wt%, which was similar with the diesel standard.
The major element contributed to high HHV value was hydrogen.
As the trend shown in Table 5, the hydrogen element of liquid from
pure NRP was 7.18 wt% which was the lowest. With the addition of
PS, the hydrogen increased from 7.98 to 9.12 wt% and this shows
that the higher portion of PS being added could improve the
HHV of the pyrolysis oil. The HHV of the oil from pure NRP was
39.70 MJ/kg. The calorific value of the oil improved from 41.96 to
43.94 MJ/kg and almost approaching the HHV for diesel which
was 44.94 MJ/kg. In addition to that, the sulfur content of the
pyrolysis oil was also much lower than the standard diesel. Lower
sulfur content was a key to reduce the vehicle emission of sulfur
oxides (SOx) [43,44]. Hence, the addition of PS into NRP in pyroly-
sis managed to improve the physical and chemical properties of
the pyrolysis oil to be comparable to conventional diesel. From
the results, the energy density of the oil produced from the
100 wt% PS addition was very close to the standard diesel and in
terms of the environment aspect, the oil was found superior than
the diesel due to its lower sulfur content (by 50% difference).
FTIR is a very important analysis technique that can be used to
detect various functional groups in oil. The FTIR spectra obtained
for the pyrolysis oil from different ratio of added PS to the Malay-
sia’s NRP are shown in Fig. 4. The peaks of the spectra were similar
for all the ratios due to their similar structures. The preceded peaks
in the range of 2923 and 2852 cm 1 indicated the presence of
alkane with the CAH stretching vibration. The small peaks
between 1494 and 1448 cm 1 implied the presence of aromatic
group that represented the C@C stretching vibration. Many peaks
appeared in the range of 989–694 cm 1 with 694 cm 1 to be the
strongest peak which reinforced the identification of alkene @CAH
bending vibration. This illustrates that the pyrolysis oil had highly
aliphatic nature.
GCMS analysis was also conducted to identify the substances in
the pyrolysis oil. The detected substances were identified by
searching the MS library database. Priority was given to the peaks
with high degree of probability (70%) and also with area of 0.1%
and greater since more than 100 peaks were detected. The results
were summarized in Tables 6and 7 for the two extreme composi-

Table 5
Physical and chemical properties of pyrolysis oil.

Properties PS added into plastic mixtures (wt%) Diesel*

0 PSa 25 PS 50 PS 75 PS 100 PS
Water content (%) 0.92 0.45 0.4 0.35 0.31 <0.1
Viscosity at 50 °C (cP) 1.45 1.28 1.32 1.43 1.59 1.9–4.1
Density (g/ml) 0.814 0.776 0.809 0.809 0.86 0.807
pH 7.03 6.51 6.75 6.76 6.71 n.a.
Elemental composition
C 88.82 90.61 90.82 90.81 90.85 86.30
H 7.18 7.98 8.13 8.80 9.12 12.80
N 0.17 0.27 0.20 0.29 0.30 0.00
S 0.01 0.03 0.04 0.07 0.09 0.15
O (by difference) 3.83 1.11 0.81 0.03 0.00 0.00
High heating value, HHV (MJ/kg) 39.70 41.96 42.29 43.41 43.94 44.94

n.a., not available in literatures.

*
Ref. [41].
a
Pure NRP.
 S.D. Anuar Sharuddin et al. / Energy Conversion and Management 148 (2017) 925–934 931

and after the 100 wt% PS addition. Overall, since the compound
containing hydrogen and carbon were found abundant in both oil
categories, this gives a clear indication that the pyrolysis oil has
potential to be used as combustible fuel source. Therefore, the
results from GCMS analysis was found tally with the FTIR results.

3.3.2. Gas analysis

Fig. 4. FTIR spectra of oil produced from pyrolysis of NRP at different ratio of added
PS.
tions which were the oil obtained from pure NRP and after the 100
wt% PS addition subsequently. Referring to Table 6, it was observed
that the oil obtained from the pyrolysis of pure NRP was found
abundant with aliphatic compounds (alkanes and alkenes) that
accounted for 43.79% area. As for the 100 wt% PS addition, the
GCMS result shown in Table 7 also indicates the aliphatic com-
pound to be the most dominant with total area of 64.38%. The
increase of aliphatic compound after 100 wt% PS addition showed
a great improvement of fuel property since it released extra energy
for combustion. Besides aliphatic compound, arenes or also known
as aromatic hydrocarbons were also present in both oil with per-
cent area of 27.59% for pyrolysis of pure NRP and 17.13% after
the 100 wt% PS addition. The presence of aldehyde group as an
organic compound was also identified in both oil that represented
around 28.62% and 16.78% corresponded to pyrolysis of pure NRP
The gases produced from pyrolysis of plastics basically com-
prised of hydrocarbons up to C4 such as methane, ethane, propane,
propene, butane, butene and also hydrogen gases. Among them,
methane and hydrogen were considered very crucial in determin-
ing the HHVs of gases. However, in the case of pyrolysis of NRP, the
hydrogen contribution to the gas stream was very minor whereby
in most cases, the hydrogen composition was not detected. The
main gas produced during pyrolysis of NRP was methane, in which
the HHV was considered high among the fuel gases with value
around 55.38 MJ/kg [45]. Fig. 5 illustrates the methane gas compo-
sition produced from pyrolysis of NRP at 500 °C over 30 min reac-
tion time for different ratio of added PS. It was observed that the
maximum production of methane from pyrolysis of pure NRP
was 8%. The highest methane production (14.6%) was observed in
the pyrolysis of NRP with 50 wt% added PS. Nevertheless, the high-
est level of methane for pyrolysis of pure NRP, as well as after
25 wt% and 50 wt% PS addition happened to be within the duration
of 5–10 min whereas for the PS addition of 75 wt% and 100 wt%,
the highest level of methane were obtained at the reaction time
of 0–5 min. These results clearly indicate that the addition of PS
into the overall NRP composition reduced the reaction time.
3.3.3. Tar analysis
During pyrolysis, tar was collected as residue in the reactor. At
high temperature, the physical state of the tar was in liquid form.
However, the tar was hardened and eventually turned to solid state
when exposed to the room temperature. Therefore, instead of char,
tar was more accurate terms to be used in this study corresponding
to its physical state [37,46]. Table 8 summarizes the elemental

Table 6
GCMS result for the oil obtained from pyrolysis of pure NRP.

Peak No. Compound Area% Group Formula

1 3-Methoxybut-1-ene 9.77 Aldehyde C5H10O
2 Pentane, 2,3-dimethyl- 12.08 Alkane C7H16
3 Oxirane, 2-ethyl-2-methyl- 18.85 Aldehyde C5H10O
4 Pentane, 2-cyclopropyl- 15.99 Alkane C8H16
5 Cyclohexane 0.91 Alkane C6H12
6 Toluene 1.76 Arene C7H8
7 2,4-Dimethyl-1-heptene 1.23 Alkene C9H18
8 Ethylbenzene 1.58 Arene C8H10
9 Styrene 15.76 Arene C8H8
10 .alpha.-Methylstyrene 2.91 Arene C9H10
11 Cyclopropane, 1-heptyl-2-methyl 0.8 Alkene C11H22
12 1-Dodecene 0.92 Alkene C12H24
13 1-Tridecene 0.91 Alkene C13H26
14 Cyclohexane, 1,2,4-trimethyl- 0.89 Alkane C9H18
15 Cyclohexane, 1,2-diethyl-1-methyl- 0.92 Alkane C11H22
16 2-Tetradecene, (E)- 1.11 Alkene C14H28
17 1-Pentadecene 1.12 Alkene C15H30
18 Pentadecane 0.77 Alkane C15H32
19 1-Heptadecene 0.95 Alkene C17H34
20 Hexadecane 1 Alkane C16H34
21 Benzene, 1,10 -(1,3-propanediyl) 2.27 Arene C16H18
22 3-Heptadecene, (Z)- 0.87 Alkene C17H34
23 Heptadecane 0.79 Alkane C17H36
24 4-Phenyl-1-butyne 2.54 Arene C10H10
25 Bicyclo[4.2.1]nona-2,4,7-triene 0.77 Arene C9H10
26 1-Octadecene 0.85 Alkene C18H36
27 Nonadecane 0.9 Alkane C19H40
28 3-Eicosene, (E)- 0.78 Alkene C20H40
932 S.D. Anuar Sharuddin et al. / Energy Conversion and Management 148 (2017) 925–934

Table 7
GCMS result for the oil obtained from pyrolysis of NRP with 100 wt% PS addition.

Peak No. Compound Area% Group Formula

1 Pentane, 2-methyl- 8.97 Alkane C6H14
2 Pentane, 2,3-dimethyl- 10.91 Alkane C7H16
3 Oxirane, 2-ethyl-2-methyl- 16.78 Aldehyde C5H10O
4 Pentane, 2-cyclopropyl- 16.41 Alkane C8H16
5 Cyclohexane 1.17 Alkane C6H12
6 Toluene 2.88 Arene C7H8
7 Ethylbenzene 2.36 Arene C8H10
8 1,3,5,7-Cyclooctatetraene 26.08 Alkene C8H8
9 Benzene, (1-methylethyl)- 0.47 Arene C9H12
10 .alpha.-Methylstyrene 3.96 Arene C9H10
11 2-Tetradecene, (E)- 0.41 Alkene C14H28
12 1-Pentadecene 0.43 Alkene C15H30
13 Bibenzyl 0.41 Aromatic C14H14
14 Benzene, 1,10 -(1,3-propanediyl) 4.81 Arene C15H16
15 1-Benzyl-1,2,3-triazole 6.85 Azo compound C9H9N3
16 Bicyclo[4.2.1]nona-2,4,7-triene 1.2 Arene C9H10
17 cis-4-Benzyl-2,6-diphenyltetrahydropyran 0.44 Carboxylic acid C17H16O2
18 Naphthalene, 2-phenyl- 0.62 Arene C16H12
19 Phenanthrene, 2,3,5-trimethyl- 0.83 Arene C17H16

3.4. Discussion on PS addition scenario

Referring to the findings in scenario 2, PS has played important

Fig. 5. Methane gas composition for pyrolysis of pure NRP and with different ratio
of PS addition at 500 °C.
analysis of the tar produced from pyrolysis of NRP with various
ratios of added PS, together with the HHV results. Overall, the
major element remained in the tar was carbon since the carbon
to carbon double bonds had high dissociation energy (146 kcal/-
mol), therefore the hardest to break [38]. From Table 8, it can be
observed that the HHV of the tar decreased as the ratio of added
PS increased. The drop in HHV can be explained by the degradation
of carbon and hydrogen in the tar product. Even though the HHV of
the tar decreased during pyrolysis, the exhibited value still supe-
rior than the HHV of standard coal which usually obtained in the
range of 36–41 MJ/kg [47]. Hence, the produced tar had high
potential to be used as an alternative solid fuel.
role in increasing the liquid yield and improving the qualities such
as reducing water content in the oil, lowering the oxygen content,
increasing the HHV and reducing the waxy appearance in the pro-
duction of liquid fuel derived from NRP. Considering the PS of NRP
has been totally used in the process, it is important to find other PS
source to support this scenario. The other PS waste can be found in
the recycle stream that is not included as NRP. PS categorized in
NRP usually been derived from expanded polystyrene (EPS) or
polystyrene foam, which generally used in food packaging, elec-
tronic goods cushioning and thermal insulation board in building,
while the recyclable PS often termed as rigid polystyrene (RPS)
which normally used for CD cases, toys, yoghurt tubs, office acces-
sories, coat hangers and rigid packaging [48–50]. RPS generally
constitutes about 27.1% from the total of plastic waste in MSW that
usually been sent for recycling [48]. In order to fulfill the condition
in scenario 2, some RPS from recycle stream can be taken to substi-
tute the additional PS needed. Since the RPS density is higher than
the EPS, a small amount of RPS is considered sufficient to compen-
sate the total weight required according to the ratio of additional
PS needed.
3.5. Potential energy recovery from NRP
For energy recovery calculation, the data from Malaysia was
taken as a model to be studied. The potential energy recovery
was calculated based on the data provided by Department of
National Solid Waste of Malaysia. It was reported that about
21,627 metric tons (MT) of solid wastes were generated in Malay-
sia’s MSW per day [20]. From the total of MSW generated, the frac-
tion of plastics constituted about 13.2%. However, only 19.2% of

Table 8
Elemental analysis of the tar by-product and the HHV results.

PS added into plastic mixtures (wt%) Elemental composition (wt%) HHV (MJ/kg)
*
C H N S O
0 89.16 16.16 0.04 0.49 0.00 53.47
25 85.88 16.01 0.05 0.43 0.00 52.14
50 85.49 15.79 0.06 0.39 0.00 51.69
75 83.32 14.39 0.04 0.37 1.88 48.60
100 81.59 14.29 0.07 0.32 3.73 47.54
*
Calculated by difference.
 S.D. Anuar Sharuddin et al. / Energy Conversion and Management 148 (2017) 925–934
Fig. 6. Potential energy recovered based on pyrolysis of pure NRP without PS addition.
plastics were recycled while the balance remained in the landfill
which fell into the category of NRP. From this statistic, it can be
seen that the percentage of recycled plastics was still at the lowest.
This makes the amount of NRP being disposed in the landfill to be
about 79.7% or equivalent to 2272 MT/day. Since this study sug-
gested that PET and PVC plastics to be excluded from the pyrolysis,
the new total of NRP would be 2189 MT/day or 659,920 MT/year.
Fig. 6 displays an example of calculation for potential energy con-
tained in the produced liquid from NRP through pyrolysis technol-
ogy. The calculation shows that the energy contained in the liquid
from pure NRP was 7200 billion Btu per year. This amount of
energy was equivalent to 1,257,336 barrels of oil. Considering the
high heating value of methane gas and tar, this study also recom-
mended their usage as source of fuel. Methane gas as by-product
contributed 450 billion Btu/year of energy recovery which equal
to 78,561 barrels of oil. Tar also managed to contribute 16,800 bil-
lion Btu of energy to Malaysia’s energy supply per year or equal to
2,928,270 barrels of oil. In summary, total of 24,450 billion Btu per
year or equivalent to 4,264,167 barrels of oil per year could be
recovered from the pyrolysis of pure NRP. In addition, the potential
energy of the liquid from NRP increased to 19,800 billion Btu per
year or equivalent to 3,457,675 barrels of oil when 100 wt% PS
was added. A substantial increase of energy almost triple from
the liquid produced from pure NRP signified the great advantages
of additional PS. The additional energy produced would help to
strengthen the future energy security of Malaysia in facing the glo-
bal oil crisis, as well as increasing the domestic energy reserve.
4. Conclusions
The study has proven that the pyrolysis technology could be
used in utilizing the NRP into the alternative energy sources.
Among the plastic types, PET and PVC were recommended to be
removed from the NRP before pyrolysis. All products from pyroly-
sis of NRP which were liquid, gas and tar had high energy content,
consequently having great potential to be used as fuel. From
Malaysia’s NRP, the energy content in the obtained liquid product
was 39.7 MJ/kg, the maximum methane gas production of 8% and
energy content for tar was 53.47 MJ/kg which was higher than
coal. The potential energy recovery from liquid and by-products
from pyrolysis of pure NRP was about 24,450 billion Btu per year
or equivalent to 4,264,167 barrels of oil per year. Furthermore,
the addition of PS in the pyrolysis of NRP has improved the quan-
933
tity and quality of the oil produced. The oil obtained was increased
by 85% after the addition of 100 wt% PS. The addition of PS also
reduced the tar and gas formation by increasing the oil yield.
Besides, the oil properties also improved in terms of HHV, pH val-
ues and water content. The HHV of the oil increased with the addi-
tion of PS to 44.94 MJ/kg which was almost comparable to the HHV
of diesel. Moreover, the potential energy recovered from the liquid
of NRP pyrolysis also increased to 19,800 billion Btu per year after
the 100 wt% PS addition. In addition to that, the pH values for the
oil produced from the pure NRP as well as after the addition of PS
were found very near to neutral (pH7) and these were good indi-
cator that the oil was not corrosive and very suitable for engines
and refinery equipment. Remarkably, the sulfur content in the oil
was also much lower than the diesel standard, thereby more envi-
ronmental friendly. The increase of aliphatic compound in the oil
after the addition of PS also implied the oil potential to be used
as fuel as it released extra energy for combustion. To add the PS
in the NRP pyrolysis, the source of PS can be obtained from the
RPS available in the recycle stream.
Acknowledgements
The authors would like to thank the University of Malaya for
fully funding the work described in this publication through the
PPP project number PG066-2015B. A special thanks is also
extended to the University Technology Mara (UiTM) and Ministry
of Higher Education (MOHE) for providing financial support under
the Young Lecturer’s Scheme (TPM).
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