Journal of Environmental Management 239 (2019) 395–406

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Journal of Environmental Management

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

Research article

Thermal degradation of waste plastics under non-sweeping atmosphere: Part T

1: Effect of temperature, product optimization, and degradation mechanism
R.K. Singha, Biswajit Rujb,∗, A.K. Sadhukhana, P. Guptaa
a
Department of Chemical Engineering, National Institute of Technology, Durgapur-713209, West Bengal, India
b
Environmental Engineering Group, CSIR-Central Mechanical Engineering Research Institute, Durgapur-713209, West Bengal, India

ARTICLE INFO ABSTRACT

Keywords: Continuous generation of plastic waste has prompted substantial research efforts in its utilization as a feedstock
Plastic waste for energy generation. Pyrolysis has emerged as one of the best waste management technique for energy ex-
Pyrolysis traction from the plastic waste. The objective of this work is to investigate the effect of operating temperature on
Degradation the liquid product yields in the pyrolysis process by non-isothermal heating. Non-catalytic thermal pyrolysis of
Fuel recovery
waste polyethylene (PE) [high density polyethylene (HDPE)], waste polypropene (PP), waste polystyrene (PS),
TGA
waste polyethylene terephthalate (PET) and mixed plastic waste (MPW) was carried out in a non-sweeping
atmosphere in a semi-batch reactor at four different temperatures 450, 500, 550, and 600 °C. The minimum
degradation temperature of the mixed and individual plastics was obtained using a thermogravimetric apparatus
(TGA) at a heating rate of 20 °C/min. The TGA results show that all plastics degrade in a single step and the
degradation temperatures of PS > PET > PP > HDPE, while mixed plastic degradation indicates two distinct
degradation steps. Further, a waste polymer shows a lower degradation temperature than the virgin polymer.
The degradation of HDPE is found to produce the maximum oil yield with minimum solid residue. The de-
gradation of PET results in the highest amount of solid and benzoic acid as crystals and gas with no oil.
Degradation of mixed plastic causes oil yield in the intermediate range of pyrolysis of individual plastic wastes.
Overall, 500 °C is observed to be an optimum temperature for the recovery of low-density pyrolytic oil with the
highest liquid yield. The degradation of PE and PP is found to be caused by random chain scission followed by
inter and intramolecular hydrogen transfer. The degradation of PS occurs by side elimination or end chain
scission followed by β-scission mechanism. The degradation of mix plastics results from random chain scission
followed by β-scission mechanism. The effect of temperature on oil and gas recovery as well as recovery time
was also assessed.

1. Introduction
Over the last few decades, the plastic industry has witnessed an
explosive growth with a large proportion of thermoplastics such as PE,
PP, PS, PET, and polyvinyl chloride (PVC) (Lettieri and Al-Salem, 2011;
Buekens and Huang, 1998; Singh and Ruj, 2015). US-EPA (2015) re-
ported a generation of approximately 262 million tonne of municipal
solid waste (MSW) in 2015 of which 34.50 million tonne (13.1%) was
waste plastics. Approximately 15% of the waste plastic generated was
used for energy generation via incineration while 75.4% of the waste
was sent to dumpsites. In Europe, the plastic production in the year
2015 was reported to be 322 million with 28.5 million tonne being
generated as waste (Elliot and Elliot, 2018). A more recent study in UK
(EUNOMIA, 2018) reported that in the year 2015 approximately 2.26
million tonne of household plastic packaging waste was produced from
out of a total 11.5 million tonne of waste packaging plastics produced
from different sources. Europe produced about 58 million tonne of
plastics in 2015 of which 4.9 million tonne was generated in the UK
(EUNOMIA, 2018), 15,342 tonne of plastic waste is estimated to be
produced in India per day (CPCB, 2018) with 10.5% annual growth in
the plastics production. With the increase in production and a lack of
organized disposal technique of the waste plastic, waste management
has become a serious concern.
It has been estimated that about 10.6 ± 0.5 wt% of plastic waste
comprising of PE, PP, PS, PET, and PVC contributes towards the mu-
nicipal waste. About 60% of the total polymer production is used in
packaging industries (Achilias et al., 2007). 70% of the total packaging
plastic is contributed by PP, PS, and PE, PE being dominant (63%)

∗
Corresponding author. ;
E-mail addresses: bruj@cmeri.res.in, biswajitruj@yahoo.co.in (B. Ruj).

https://doi.org/10.1016/j.jenvman.2019.03.067
Received 24 December 2018; Received in revised form 21 February 2019; Accepted 14 March 2019
Available online 28 March 2019
0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
R.K. Singh, et al.
(Singh and Ruj, 2015; Scott et al., 1990). The use of plastics in in-
dustries such as packaging significantly affects as the sustainability as
their lifespan is below one month (Achilias et al., 2007). Being het-
erogeneous and contaminated, recycling of MPW is more difficult than
other industrial wastes (Singh and Ruj, 2015). With the convenience
that plastic provides, increased consumption has caused disposal issues
due to their non-degradable nature as well as potential health risk to
aquatic and other animals and impacted the environment severely
(Kunwar et al., 2016).
Plastic wastes, made of different hydrocarbons, possess a large
amount of chemical energy which can be recovered to meet the energy
crisis (Singh and Ruj, 2016). It was estimated that the recycling of all
global plastic wastes could replace the energy obtained from 3.5 billion
barrels of oil per year (Bhattacharya et al., 2018). Several techniques
have been proposed for minimizing the waste as well as recovery of
energy. Energy generation by incineration of plastic waste contributes
about 400 million tonne of CO2 in the atmosphere. Pyrolysis has
emerged as a promising option where plastic both waste management
and energy demand can be addressed simultaneously (Al-Salem et al.,
2009, 2010; Aguado et al., 2008). It involves heating the waste in an
inert atmosphere when the polymer degrades into small chain hydro-
carbons as well as monomers. This generates (i) liquid products called
pyrolytic oil; (ii) some gases and; (iii) a very small amount of solid
carbonaceous residue called char (Singh and Ruj, 2016). Pyrolysis
process is suitable for the mixed plastic wastes for production of fuel
and chemicals as polymers such as PE, PP, PS, and PET are composed of
similar chain compounds (hydrocarbons), and the same valorization
process maybe applicable to all (Aguado et al., 2008; Wong et al.,
2015). Development of a suitable reactor for pyrolysis faces a great
challenge as the low softening and melting temperatures cause severe
problems in a continuous feeding process which needs special care.
Fixed bed reactor is preferred because of its simple design and opera-
tion (Grieken et al., 2001; Kaminsky et al., 2004; Elordi et al., 2011;
Guddeti et al., 2000; Williams and Williams, 1997). In a fluidized or
continuous flow reactor, the sweeping fluidizing gas decreases the ca-
lorific value of the obtained gaseous products. Also, the formation of
clumps enhances the chance of reactor blockage with high heat loss and
high energy consumption.
Experiments in TGA, micro-reactors and batch reactors provide a
preliminary insight into pyrolysis and results showed more than 96%
recovery of high-quality oil (Wong et al., 2015). Utilization of real
waste as well as mixed plastic waste on a large-scale has been less re-
ported (Williams and Slaney, 2007; Ates et al., 2013; Adrados et al.,
2012; Muhammad et al., 2015). Sharma et al. (2014) pyrolyzed 500 g of
waste HDPE at 440 °C, producing 74% of wax and oil, while Miskolezi
et al. (2006) obtained 54% oil at 430 °C with a sample size of 600 g.
Miskolezi et al. (2004) and Seo et al. (2003) obtained 74.5% and 79.2%
oil respectively at 450 °C. Miandad et al. (2016a,b) used a batch size of
1 kg of PP at 450 °C, and Ciliz et al. (2004) pyrolyzed at a temperature
of 600 °C. A continuous screw kiln reactor was used by Kodera et al.
(2006) at 500–700 °C, producing a high amount of gases at higher
temperatures. Papuga et al. (2016) used a mixture of PP, HDPE and
LDPE (500 g sample) in a fixed batch reactor, producing up to 28.8%
liquid and 70% gaseous component at a temperature of 525 °C. Waste
PP was pyrolyzed by Yan et al. (2015) in a batch reactor producing a
liquid product at 460 °C, and virgin plastics were used to analyze the
effect temperature on pyrolysis. Miandad et al. (2016a,b) obtained 42%
oil at a temperature of 450 °C and reported that virgin plastics always
produced a higher liquid fraction (> 85%). Pyrolysis of waste PS was
also investigated for the recovery of fuel oil, styrene or other chemical
compounds ((William and Slaney, 2007; Siddhiqui and Redhwi, 2009;
Hussain et al., 2012; Panda et al., 2012; Kunwar et al., 2016a). Williams
and Slaney (2007) pyrolyzed virgin PS at 440 °C producing a high
percentage of residue (27%). Most of the large-scale studies reported a
much lower product yield from individual waste plastic than that in
mini or micro reactors while the yield reduced further for MPW.
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Journal of Environmental Management 239 (2019) 395–406
Williams and Slaney (2007) used DSD waste and Fost plus waste while
Ates et al. (2013) pyrolyzed waste obtained from a Hungarian waste
plastic facility at three different temperatures. About 80% liquid yield
with 10% gases in the product stream was obtained by Muhammad
et al. (2015) from foster waste. Lopez et al. (2011) pyrolyzed a simu-
lated waste obtained from virgin plastics producing 72% of oil at 460 °C
with a small amount of residue (1.1%). Adrados et al. (2012) pyrolyze a
real waste sample obtained from the packaging sector and obtained
40.9% liquid and 25.6% gas yields at 500 °C.
Nowadays, there are other pyrolysis processes available for the
conversion of waste to energy like fluidized bed pyrolysis, microwave
pyrolysis and plasma pyrolysis (Backstrom et al., 2017; Grieken et al.,
2001; Kaminsky et al., 2004; Puncochar et al., 2012; Pragnesh and
Asim, 2010). All these methods have their advantages and dis-
advantages over the batch process. Conversion is higher in case of
fluidized bed and plasma whereas the main product (Pyrolytic/Syn gas)
was diluted with the use of fluidizing agent (such as Nitrogen, Argon
etc.). Further high energy consumption was reported for the conversion
of waste to fuel gas via plasma pyrolysis (Pragnesh and Asim, 2010;
Puncochar et al., 2012). In case of microwave pyrolysis an absorbent is
required which further increases the cost of the processing (Backstrom
et al., 2017). Further at higher temperature during fluidization a high
amount of wax was observed while in case of plasma pyrolysis only gas
and solid phase products were recovered (Williams and Williams,
1997).
Most of the studies dealing with pyrolysis of plastics wastes showed
a high fraction of wax in the liquid product and high residual yield. The
pyrolysis temperature ranged between 400 and 700 °C with different
researchers obtaining different yields of liquid fractions. The present
study assessed the suitability of slow pyrolysis process for the de-
gradation of different kind of waste plastics individually as well as in
the mixed ones (excluding PVC) obtained from waste disposal sites. The
effect of temperature on the formation of pyrolytic products such as oil
and gases and the selection of the optimum pyrolysis temperature for
maximum recovery of oil products has been investigated.
The effect of heating rate on the minimum degradation temperature
of different type of waste and virgin polymers and their mixture was
explored by TGA. Further, the effect of heating rate and the mass of
sample at different temperatures in semi-batch pyrolysis was in-
vestigated for the recovery of pyrolytic products and compared with the
published results. The product yields at optimum temperature were
compared between the degradation of virgin and waste polymers. The
degradation mechanism of individual and mixed plastic wastes was
explored.
2. Material and methods
2.1. Raw material
Plastic wastes (excluding PVC waste) were collected from MSW at
different location in Durgapur (West Bengal, India). The wastes com-
prised of PP, PET, PS, PE (HDPE and LDPE), Polyamide (PA),
Polycarbonate (PC) (CD's), labeling paper and inert which were sepa-
rated/sorted/characterized on the basis of the resin identification
codes. PVC was removed from the plastic waste as the chlorine present
in the PVC forms HCl during the process and corrodes the reactor
(Singh and Ruj, 2016). The thermoset plastics were also removed from
the waste mixture. The MPW was separated into component fractions:
58.6% PE (HDPE and LDPE), 26.7% PP, 8.7% PS, 5.6% PET and 0.4%
others (thermoset). Individual waste and virgin plastics and their mix
were pyrolyzed to study their degradation behaviour. Individual and
mixed waste plastics were cut into small chips (2.54 cm) by a shredder,
dried and sieved for the removal of sand. A simulated waste was pre-
pared from the virgin plastics containing 40% of HDPE, 40% of PP, 15%
of PS and 5% of PET. 500 g of sample was used in a semi-batch pyr-
olyzer similar to a pilot plant scale analysis. For TGA experiments,
R.K. Singh, et al. Journal of Environmental Management 239 (2019) 395–406

Table 1 was removed after the experiment ends. This process is easy to operate
Component analysis of mix and individual plastic wastes (Proximate and ulti- and handle with the production of refined products in separated phases.
mate). In this process liquid fraction is the main product. Also there are very
Samples few losses as compared to other processes like fluidization process
producing dilute gas phase products, plasma pyrolysis requires high
Ultimate Analysis (%) HDPE PP PS PET Mixed Plastic energy consumption, as both have gaseous phase as their main pro-
Carbon 83.4 83.28 89.2 62.48 79.77
ducts.
Hydrogen 12.71 13.81 8.78 4.80 15.47
Nitrogen 1.08 1.01 0.01 0.32 2.76
Sulphur 0.002 0.001 0.00 0.00 0.00 2.3. Analytical instrument
Oxygen 2.8 1.90 2.01 32.4 2.00
Proximate analysis (%)
Moisture 0.32 0.44 0.28 0.46 0.6 A TG/DTA (make: SHIMADZU; model: DTG-60/60H) was used for
Ash 3.9 3.68 0.84 1.84 13.3 the determination of degradation temperature range. A heating rate of
Volatiles 91.88 93.84 94.33 83.92 85.7 20 °C min−1 was used in an inert nitrogen atmosphere with a flow rate
Fixed Carbons 3.9 2.04 4.55 13.78 0.4
of 200 ml/min based on the previous results of the author (Singh and
Gross Calorific value (MJ/kg) 46.48 44.43 40.34 23.97 39.46
Ruj, 2016). Experiments were repeated thrice with a reproducibility
error of ± 1.18%.
individual waste plastic samples were washed, dried, pulverized into
102–104μm particles and then quenched in liquid nitrogen and pow- 3. Result and discussion
dered for analysis. The mixed plastic waste samples were homogenized.
The proximate and ultimate analyses of the individual and the mixed 3.1. Thermal degradation of plastics in TGA
plastics are presented in Table 1.
Samples were pyrolyzed in TGA at a heating rate of 20 °C/min to
2.2. Experimental setup and procedure determine an optimum degradation temperature range for scale-up.
Fig. 2(a-e) represents the comparative degradation of virgin and waste
An electrically heated, single step, semi-batch pyrolysis reactor with plastics at a heating rate of 20 °C/min. The presence of additives,
a capacity of 800 g, equipped with two K-type thermocouples for the plasticizers, etc. is found to cause an early mass loss and reduction in
determination of reactor wall and centre temperatures, was used for the the degradation temperature of waste plastics. Multiple recycling ad-
experiment (Fig. 1). The pyrolyzer was equipped with oil and gas col- versely affects the physical properties leading to a lower degradation
lection units for the recovery of oil and gas during the pyrolysis reac- temperature. A single reaction peak is observed in both virgin and
tion. The reactor was made of SS with a diameter of 5.08 cm inserted in waste HDPE, PP, PS and PET (Fig. 2a–d). Degradation of mixed virgin
an electrically-heated furnace capable to withstand 2 atm pressure in- plastics (simulated) shows two sharp and distinct peaks while mixed
side the reactor. The sample was placed in the reactor with an inert waste plastics exhibit a combination of peak due to different degrada-
atmosphere of nitrogen gas flowing at 200 ml/min for 10–20 min fol- tion range (Fig. 2e). MPW consisting of several polymeric components
lowing which the purging was stopped. Then the system was closed and with degradation ranges between 380 and 520 °C causes a wide de-
the reactor was heated in a non-sweeping atmosphere at ∼20 °C/min up gradation temperature span. Individual plastics have a short degrada-
to the desired temperature range based on the previous work of the tion temperature range, and a single peak represents single phase de-
authors (Singh and Ruj, 2016; Singh et al., 2019). At the desired tem- gradation in each polymer while in MPW two different degradation
perature, the sample decomposed into volatiles which were collected as peaks are observed (Fig. 2e). The first peak is a combination of de-
condensable volatiles as pyrolytic oil while the non-condensable gases gradation of PS and PET while the second peak represents the dis-
were cooled in a chiller and collected in a gas collection tank. To avoid sociation of HDPE and PP.
the formation of high pressure inside the reactor, the gases were re- A comparative analysis of degradation between individual waste
leased from the system at the defined interval and were periodically plastic and mixed plastic waste is carried out at a heating rate of 20 °C/
analyzed. The gas pressure was monitored at regular time intervals. The min (Fig. 3(a&b)). It is observed that the mixed waste plastic starts
char formed during the process settled at the base of the reactor and degrading earlier than the individual plastics, causing a synergistic

Fig. 1. Schematic of non-isothermal pyrolysis setup with product recovery units.

397
R.K. Singh, et al.
Fig. 2. Comparative analysis of residual mass fraction and reaction rate vs. temperature forwaste and virgin plastic during degradation at 20 °C/min; a) HDPE; b) PP;
c) PS; d) PET; and e) MPW.
effect (Miskolczi et al., 2006; Singh and Ruj, 2016). The presence of
foreign materials in the waste leads to an increased residue. The results
were different from that obtained by other researchers as the waste
composition varies from place to place. Different plastics are found to
show adjacent degradation ranges as reported by other researchers
(Singh and Ruj, 2016; Muhammad et al., 2015). PS degrades at the
lowest temperature among above four plastics followed by PET and PS
while HDPE degrades at the highest temperature range. A large amount
of residue is obtained for PET while other plastics such as PP, PS, and
HDPE produce almost no residue (Muhammad et al., 2015). Higher
heating rate increased the residue for waste plastic as the dissociation
rate was enhanced due to lower dissociation time as observed earlier
(Singh and Ruj, 2016; Singh et al., 2019). Overall degradation range of
mixed plastic waste is far comprehensive as compared to the individual
plastics (Muhammad et al., 2015; Ranzi et al., 1997; Williams and
Slaney, 2007). The degradation rate of PP is the largest while MPW
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Journal of Environmental Management 239 (2019) 395–406
degrades with smallest rate in a wide temperature range (Fig. 3b).
3.2. Temporal temperature profile in a semi-batch reactor
Distribution of heat in the reactor during pyrolysis with and without
MPW sample was investigated by temporal temperature profiles with
up to 500 °C which was the optimal temperature for maximum oil re-
covery (section 3.3) (Fig. 4). The rise in wall temperature is line with
programmed temperature with a considerable lag at the centre tem-
perature due to slow heat absorption inside the reactor. An optimised
heating rate of 20 °C/min was used as it takes less time for degradation
than 5oC/min but allows higher residence time for volatiles inside the
reactor for cracking than 40 °C/min (Singh and Ruj, 2016). The pre-
sence of the sample in the reactor ensures faster heat transfer to reach
the desired temperature due to higher absorption of heat by the sample
inside the reactor than the gas. At the outset, the wall gets heated up
R.K. Singh, et al.
Fig. 3. (a) Comparative analysis of residual mass fraction vs. temperature curve at 20 °C/min for individual and mixed plastic waste; (b) Comparative analysis of
reaction rate vs. temperature curve at 20 °C/min for individual and mixed plastic waste.
Fig. 4. Temperature distribution in a reactor with and without the sample at
500 °C with a heating rate of 20 °C/min.
fast and reaches the target temperature. Meanwhile, the centre tem-
perature rises slowly as heat is absorbed for melting and pyrolysis and
ensuring uniform temperature inside the reactor during 20–35 min, the
rise in temperature is rapid during 40–50 min as the heat transfer rate is
higher in liquid sample than solid. Without the sample, the temperature
lag sustained longer (Fig. 4). A similar trend was also observed at dif-
ferent temperatures for other samples though not shown here.
3.3. Effect of temperature on the product yields in a semi-batch reactor
Based on the TGA results the pyrolysis temperatures of plastic waste
was selected in the range 450–600 °C in the step of 50 °C in the semi-
batch reactor. The sample was heated from the room temperature to the
target temperature at the heating rate of ∼20 °C/min, and isothermal
conditions were maintained thereafter. The analyses of products yield
for different individual plastics are presented in Fig. 5. The products
obtained are solid (mostly contain carbon or char), liquid or oil (aro-
matic and aliphatic hydrocarbons ranging C6eC30), and gases (H2, CO,
CO2 and light hydrocarbons (LHC's)) (Singh &Ruj, 2016; Muhammad
et al., 2015; Miskolczi et al., 2006). The dominant product in pyrolysis
of all individual plastic wastes except PET is oil (Sogancioglu et al.,
2017). Benzoic acid crystals were formed in in the upper section of the
reactor which is supported by literature (Cepeliogullar& Putan, 2013).
A few researchers reported the formation of small amounts of oil during
pyrolysis (Muhammad et al., 2015; Fakhrhoseini and Dastanian, 2013).
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Journal of Environmental Management 239 (2019) 395–406
During pyrolysis of individual plastic wastes, the yield (mass frac-
tion) as well as the volume of liquid (Table 2) increase with an increase
in the operating temperature, reaches a peak and then decrease. The
char yield decreases and gas fraction increases with the formation of
lighter hydrocarbon gases (Singh et al., 2019). Though HDPE pyrolysis
shows a marginal effect of temperature on the product yields the
maximum liquid volume fraction is obtained at 500 °C while maximum
mass yield (89.5%) is observed at 550 °C (Fig. 5). Syamsiroa et al.
(2014) obtained a yield of 60% with a density of 0.799 kg/m3 with 10%
residual char. Kumar and Singh (2011a,b) and Marcilla et al. (2009)
obtained liquid yields of 79.08 and 84.7% which were closer to our
results. Sharma et al. (2014), Kodera et al. (2006) and Kunwar et al.
(2016a) obtained a lower liquid yields. The present work produced a
higher yield of wax-free liquid product. It is evident that increasing
process temperature has a positive impact on wax formation which is in
line with the findings of Kumar and Singh (2011a,b). It is also found
that waste HDPE does not produce much residue which is in line with
the observations of Williams and Slaney (2007), Miskolczi et al. (2006),
and Marcilla et al. (2009) though some other researchers reported
otherwise (Buekens and Huang, 1998; Singh &Ruj, 2015).
In case of PP, the process temperature impacts significantly the li-
quid yields; 82.5% at 450 °C and a maximum yield of 86.5% at 500 °C
(Fig. 5), An increase in the process temperature results in a lower oil
volume (Table 2) and the residue, a higher oil density and increased gas
fraction. Yan et al. (2015) obtained 65.44% liquid yield at 460 °C from
the pyrolysis of waste PP, while virgin PP produced 95% liquid yield at
500 °C. Very low liquid yields of 42% and 48.8% were observed by
Demirbas (2004) at temperatures of 450 °C and 740 °C in a batch pro-
cess and Miandad et al. (2016a,b). Sogancioglu et al. (2017) obtained
78.61 and 78.58% at 500 °C from waste PP, washed and unwashed
respectively, with the maximum yields of 81.47 and 79.62% at 300 °C.
High conversions of 82%, 80.7% and 88% were reported by Fakhroseini
and Dastanian (2013), Ali et al. (2011) and Heydariaraghi et al. (2016)
respectively, resembling the results obtained in this work. The residue
formed is in agreement with the available literature (Williams and
Slaney, 2007; Ali et al., 2011; Miandad et al., 2016a,b).
For the degradation of PS, the maximum liquid yield is obtained at
500 °C. No presence of wax components is observed in the oil product
while the density increases with temperature up to 600 °C (Fig. 5). At a
lower temperature (450 °C), the degradation of waste PS is not com-
plete resulting in a high residue while the gaseous fraction shows a
minimum at 500 °C. William and Slaney (2007) reported 71% liquid
yield at 500 °C from virgin PS while 97% liquid yield was obtained by
Siddhiqui and Redhwi (2009). Hussain et al. (2012) used assisted mi-
crowave pyrolysis of PS obtaining as high as 88% liquid yield while
Buekens and Huang (1998) and Panda et al. (2012) also observed liquid
yields of 24.6 and 28% at 581 °C and 475 °C in a batch reactor. The
R.K. Singh, et al. Journal of Environmental Management 239 (2019) 395–406

Fig. 5. Product yield analysis of individual and mixed plastic waste at different process temperatures.

Table 2
Effect of operating temperature on the density of pyrolytic oil obtained from individual and mixed plastic wastes.
Plastic Type Properties Temperature (°C)

450 500 550 600

HDPE Waste Mass (%) 87.5 89 89.5 88

Volume (ml)a 115 117 117 115
Density (g/cm3) 0.76087 0.760684 0.764957 0.765217
PP Waste Mass (%) 82.5 86.5 83.5 82.5
Volume (ml)a 113 117 111 109
Density (g/cm3) 0.730088 0.739316 0.752252 0.756881
PS Waste Mass (%) 70 84 82.5 80.5
Volume (ml)a 81 98 94 91
Density (g/cm3) 0.864286 0.875 0.883838 0.887755
Mix Waste Mass (%) 75.5 80.5 82 84
Volume (ml)a 106 111 108 106
Density (g/cm3) 0.712264 0.725225 0.759259 0.792453

a
The volume calculation is based on per 100 g plastic.

400
R.K. Singh, et al.
Fig. 6. Comparative analysis of waste and virgin polymers/plastics product
yields at an optimum temperature of 500 °C.
maximum of 84% liquid yield, obtained here, is similar to the results
reported by Demirbas (2004), Achilias et al. (2007a) though lower than
that obtained by other a few other researchers (Buekens and Huang,
1998; Kunwar et al., 2016a).
It is observed that as reported by Sogancioglu et al. (2017), the
degradation of PET produces no oil with the formation of benzoic acid
and the residue char decreasing and the gas increasing with the rise in
temperature (Fig. 5). The increase in temperature causes rapid de-
gradation causing more gaseous form product at all the temperatures
(Muhammad et al., 2015; Cepeliogullar and Putun, 2013; Fakhrhoseini
and Dastanian, 2013). The higher gaseous product results from high
oxygen content in the feed producing oxygenated gases such as CO and
CO2.
Fig. 7. Effect of time and temperature on liquid product recovery for individual and mixed plastic waste at a heating rate of ∼20 °C/min.
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Journal of Environmental Management 239 (2019) 395–406
The liquid yield increases with the increase in the operating tem-
perature for pyrolysis of MPW. However, above 500 °C, the temperature
has no effect on the liquid volume though the mass fraction continues to
increases due to the formation of wax with long-chain hydrocarbons,
increasing the density of the oil. A very light oil (0.712 kg/m3) is pro-
duced at a lower temperature (450 °C) while at a higher temperature
(600 °C) the oil is denser (0.792 kg/m3). The liquid obtained at 450 °C is
pale yellow and at 500 °C it turns brown. A further increase in process
temperature does not impact the colour though the formation of wax is
observed. Different mixed plastic wastes were investigated by the re-
searchers (Singh and Ruj, 2016). William and Slaney (2007) pyrolyzed
two different plastic mix obtaining 48.2 and 70.6% liquid yield while
Ates et al. (2013) pyrolyzed waste from a Hungarian recycling plant at
600 °C to obtain a maximum yield of 49.9% liquid yield. Muhammad
et al. (2015) obtained a liquid yield of approx. 80% at 500 °C while a
simulated waste of a mixture of virgin plastics was pyrolyzed at
460–600 °C obtaining a liquid yield of 72–42.9%. Adrados et al. (2012)
has obtained 40.9% liquid yield from a waste similar to packaging
waste.
The present work has shown larger liquid yield (Table 2) perhaps
due to the different nature of the waste and reactor design and process
selected. Individual as well as mixed plastic waste produces a higher
residue compared to the virgin plastic (Singh &Ruj, 2016; Muhammad
et al., 2015). The process temperature plays a vital role in the formation
of products in plastic pyrolysis. A lower than optimum temperature
enhances the solid yield while a higher temperature increases gaseous
fraction. A process temperature of 500 °C was found to be optimum for
pyrolysis based on the liquid volume, density, wax percentage and re-
covery time.
PS waste produces the highest density pyrolytic oil with no wax
even at higher operating temperatures due to the formation of styrene,
while PP waste forms the lightest oil with wax component at all
R.K. Singh, et al.
temperatures (Table 2). Density of oil obtained from HDPE waste does
not change much with the increase in temperature till 500 °C above
which there is a slight increase due to the formation of wax. Unlike
individual plastic wastes, oil produced from the mixed plastic waste
shows a significant increase in density from 0.712 g/cm3 at 450 °C to
0.792 g/cm3 at 600 °C (Table 2).
Fig. 6 shows a comparison of product yields of different wastes and
virgin polymers at an optimum temperature of 500 °C. The presence of
foreign materials in the waste causes greater yields of char and gaseous
fractions, while the oil yield is larger in for virgin polymers
(Muhammad et al., 2015). The char yields are identical for both waste
and virgin in case of HDPE and PP while for PS and MPW decrease in
the percentage is reported when compared to virgin polymers (Ates
et al., 2013; Muhammad et al., 2015; Siddiqui and Redhwi, 2009).
Pyrolysis of virgin polymer degrades long chain hydrocarbons to more
average length hydrocarbons producing more liquid products.
3.4. Effect of time and temperature on oil recovery in a semi-batch reactor
The study shows that an increase in the operating temperature de-
creases the oil recovery time (Fig. 7). A reduction in the residence time
of volatiles in the reactor results in carbon chain rupture with high
molecular weight components which increases the density of the pro-
duced pyrolytic oil. Oil recovery in PS waste is the fastest followed by
HDPE and PP. In mixed waste, the interaction of different components
lags the oil recovery times which are 140 min at 450 °C and 23 min at
600 °C (Fig. 7). In all cases, the production of oil starts when the reactor
core temperature reaches above 400 °C with a slow recovery in the
initial phase and accelerating as the reactor temperature crosses 480 °C.
At higher operating temperature the recovery is very rapid (Fig. 7). At a
lower temperature, the degradation of PP and PE is followed by random
scission and then hydrogen abstraction. PS degradation is caused by
end chain scission followed by β-scission resulting in greater production
of gases such as H2, and CH4in the initial phase. An increase in the
process temperature in both cases results in the degradation followed
by β-scission producing greater quantities of long chain hydrocarbons
which results in higher liquid yield.
A study on the temporal profile of the yield of oil and gas pressure
(Fig. 8) shows that the liquid product starts being evolved at 55 min.
The reaction rate is initially small due to low temperature, producing
less volatiles which provide high residence time to the volatiles for
further cracking inside the reactor thereby producing more gaseous
components. With time the temperatures is found to increase leading to
higher reaction rate and volatile generation and lower volatiles re-
sidence time which produces more long chain hydrocarbons in the
products (Singh et al., 2019).
Low temperature and low reaction rate during 55–67 minis followed
by a rate increases to a maximum in 67–90 min resulting in rapid re-
covery of products which further reduces as the plastic gets converted
(Fig. 8). The gas pressure is initially high due to the greater formation of
the gaseous components, CO and CO2. As the reaction proceeds, the
reaction rate becomes stable within 65–85 min producing near constant
gaseous product inthe range of 35–45 mbar pressure. Towards the end,
the conversion of the sample causes a decrease in gaseous product and
the pressure (Fig. 8). After 150 min there is no further formation of any
gaseous components as well as liquid product indicating the completion
of the reaction. The trend of the degradation profile remain identical for
other plastics such as HDPE, PP, and PS.
402
Journal of Environmental Management 239 (2019) 395–406
Fig. 8. Temporal generation of oil and gas at 500 °C for MPW.
3.5. Degradation mechanism
Polymeric chain scission, side group reaction, and recombination
constitute the primary degradation mechanism of plastic polymers.
Heat degrades the polymers bonds mostly by a chain or random chain
scission at weaker bonds (sp3 bonds), producing free radicals.
Plastic polymer cracking is generally initiated by free-radical for-
mation. The presence of anomalous weak links in the polymer causes
instability of the macromolecules on heating. The degradation reaction
consists of 1) Initiation; 2) Formation of secondary radicals which in-
clude (i) depolymerization and formation of monomers; (ii) in-
tramolecular (favorable and unfavourable) hydrogen transfer; (iii) in-
termolecular hydrogen transfer (paraffin and dienes formation); (iv)
Isomerization via vinyl groups; and 3) termination by recombination or
cyclization, aromatization or polycondensation.
The scission reaction generally acts at the beta position of polymer
chain creating small chain hydrocarbons which releases a higher
amount of H+ as ion free radical. At low-temperature pyrolysis, the
degradation is typically followed by end-chain beta scission compared
to the random chain as it requires a lot less energy to breakdown,
producing more non-condensable gases or gaseous hydrocarbons. The
liquid fraction in pyrolytic oil (C6eC34) is formed due to both random
and end chain beta scission reaction. Radical recombination (de-poly-
merization) followed by intramolecular hydrogen shift results in the
formation of olefins. However, at a higher temperature, the degradation
of polymers is caused by the side chain elimination followed by alpha
scission mechanism producing heavier hydrocarbon fractions in the
pyrolytic oil which can be confirmed by the presence of wax compo-
nents at higher temperatures. The breaking of the sigma bond (sp2
bond) generally occurs due to alpha scission which utilizes a high
amount of dissociation energy compared to beta scission.
In the case of PE, degradation occurs via random chain scission
mechanism forming free-radical fragments. Followed by hydrogen
chain transfer reaction, these free radical fragments are converted to
saturated and unsaturated straight molecules such as alkanes and al-
kenes. Sakata et al. (1996) and Vasile et al. (2001) showed that the
same PE samples produced long-chain hydrocarbons, independent of
reaction geometry. The yield of condensate or non-condensable is
highly dependent on reactor geometry (Aguado and Serrano, 1999).
(a) Beta-scission
R.K. Singh, et al. Journal of Environmental Management 239 (2019) 395–406

(b) Isomerization of the carbon framework

Image 3
Isomerization of the double bond

Image 4

(c) Hydrogen transfer reactions

Image 5

Intermolecular hydrogen transfer reactions

Intramolecular hydrogen transfer reactions

Image 6

Cyclization and aromatization

Image 7

PP also undergoes random scission degradation creating free radi-
cals which undergo beta scission to produce monomers stabilized by
intramolecular or intermolecular hydrogen transfer. Also, the formation
of olefins and dienesis promoted by secondary reaction during beta
scission while inter and intramolecular hydrogen leads tothe formation
of paraffin.
In the case of PS, the degradation is generally initiated by side
elimination (end chain scission) followed by beta scission as it degrades
at a lower temperature compared to PE. Side elimination results in a
higher concentration of styrene monomer in the pyrolytic products
(Lopez et al., 2010).
The initiation step for PS can be described by two mechanisms such
as chain end scission and random scission (Faravelli et al., 2001).
End chain scission mechanism

403
R.K. Singh, et al. Journal of Environmental Management 239 (2019) 395–406

Image 8

Random chain scission mechanism

Image 9

Random chain dissociates the main chain into a primary (Rp) and a
secondary benzyl radical (Rsb) while the end chain mechanism forms a
secondary benzyl radical (Rsb) and resonantly stabilized allyl benzene
radical (Ra). Interaction of the propagation beta scission reaction results
in the formation of low molecular weight and unsaturated species
which more relates to the end chain scission mechanism. The propa-
gation step is followed by hydrogen abstraction (intermolecular and
intramolecular)and beta decomposition.
Intermolecular abstraction

Image 10

Intramolecular abstraction

Image 11

The intermolecular abstraction forms a tertiary carbon (Rt) while

intramolecular abstraction forms numbered rings from Rsb and Rp
which also called as backbiting reactions.

Image 12

404
R.K. Singh, et al.
Further, Rt undergoes scission at the beta position to form un-
saturated end.
Image 13
The unzipping reactions are beta decomposition held with the for-
mation of Rsb and a monomer.
The termination step uses the disproportionation reaction which
produces unsaturated ends.
Image 14
Mixed plastic waste degradation is nearly similar to chain scission
followed by beta scission producing low-molecular weight hydro-
carbons in higher amount and the presence of paraffin and olefins
confirms the reaction statement. The presence of low molecular weight
hydrocarbons confirms the end chain beta scission mechanism during
the degradation of the polymeric waste.
4. Conclusion
I. TGA experiments show that plastic degradation ranges between 400
and 550 °C for complete degradation though the degradation of
mixed waste starts early. Individual plastic waste degrades in a
single step while mixed plastic waste degrades in two steps.
II. The liquid yield obtained at a temperature of 500 °C from plastic
wastes is 80–90% having a density of 0.73–0.86 gm/cm3 with no
wax component. For HDPE the maximum oil yield is obtained at
550 °C while maximum low-density oil volume is recovered at
500 °C with no wax component in it. PP pyrolysis also produces
maximum oil yield at 500 °C with maximum oil volume. A similar
trend is followed by PS producing oil having density 0.875 gm/cm3
at the optimum temperature of 500 °C.
III. The oil yields obtained due to the degradation of HDPE and PP is
much higher as compared to PS which does not produce any wax
component at higher temperature while other two plastics do. PET
does not produce any liquid and produces benzoic acid during
pyrolysis002E
IV. In case of mixed plastic waste, interaction of different plastic re-
duces the density of pyrolytic oil at a lower temperature of 450 °C.
An increase in operating temperature increases oil mass yield and
density. At 500 °C, mixed waste produces a maximum volume of oil
with low-density and no wax. The recovery of oil at a high oper-
ating temperature is low while a highly viscous liquid is obtained
with a low recovery time.
V. The degradation mechanism plays a vital role in the pyrolysis of
plastic waste into high volume of low-density oil. PE and PP follow
the random chain scission mechanism followed by beta scission and
hydrogen chain transfer reaction while PS is degraded via side
chain elimination mechanism which results in the high amount of
405
Journal of Environmental Management 239 (2019) 395–406
monomer such as styrene.
The degradation of the plastic waste for energy generation in the
form of fuel oil via pyrolysis is an efficient process as well as it helps in
the disposal of the waste. The process cost could be further reduced by
utilizing the obtained gases for heating purpose or by synthesizing high-
value product such as CNT's.
Acknowledgement
Authors are thankful to Director, CSIR-CMERI, Durgapur and
Director-NIT, Durgapur for their support to carry out this research
work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jenvman.2019.03.067.
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