Process Safety and Environmental Protection 127 (2019) 171–179

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Process Safety and Environmental Protection

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

Thermal pyrolysis of high density polyethylene (HDPE) in a novel

fixed bed reactor system for the production of high value gasoline
range hydrocarbons (HC)
S.M. Al-Salem ∗
Enviornment & Life Sciences Research Centre, Kuwait Institute for Scientific Research, P.O. Box: 24885, Safat, 13109, Kuwait

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

Article history: Pyrolysis is a promising thermolysis technique to recover valuable oils and light hydrocarbons (HC) with
Received 24 February 2019 high yields from plastic solid waste (PSW). In this work, thermal pyrolysis of high density polyethylene
Received in revised form 14 April 2019 (HDPE) with the aim of producing gasoline range hydrocarbon oils, has been carried out in a novel fixed
Accepted 6 May 2019
bed (batch) reactor. The pyrolysis of HDPE has been conducted between 500 to 800 ◦ C in the presence
Available online 11 May 2019
of nitrogen as an inert carrier gas media to produce liquid fuel oil, gaseous products and solid char. The
optimum temperature of obtaining maximum oil product yield (70%) was 550◦ C. A comprehensive gas
Keywords:
chromatography (GC) analysis of the liquid and gaseous products was conducted to quantify high molec-
Pyrolysis
Plastic waste
ular weight individual HC components. Moreover, light molecular weight HC constituting the gaseous
Aromatics fraction were identified. A chemical kinetic analysis of the cracking reactions, was performed to investi-
Hydrocarbons gate the reaction mechanism of yielding the maximum oil product. The oil product recovered had a high
Naphthenic compounds proportion of aliphatic HC especially in the range of C8 to C12 , whilst aromatic HC were of lower propor-
Reclaimed waste tion. The carbon number of the pyrolysis oil was noted to increase proportionally with the increasing
operating temperature. The gaseous product had a high percentage (> 70%) of C2 to C4 HC, which was
attributed to the high activity of carbon/carbon (C-C) chain scission reaction.
© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
The dependency on synthetic plastics is increasing on an annual
basis due to the high consumer demand on day to day commodi-
ties. In fact, plastics are noted to be durable, chemically stable and
versatile; making them ideal for household appliances, automotive
and building applications, medical equipment manufacturing and
horticultural use. This results in an estimated global production rate
of 355 million tonnes per annum (tpa), with the European Union
Abbreviations: din , nner diameter (mm); do , outer diameter (mm); EU, Euro-
pean Union; FBR, fluidised bed reactors; GC, gas chromatography; GCC, gulf council
countries; GDP, gross domestic product; GNI, gross national income; HC, hydrocar-
bons; HDPE, high density polyethylene; HHV, higher heating value (MJ kg−1 ); MS,
mass spectrometry; PE, polyethylene; PP, polypropylene; PSW, plastic solid waste;
SCADA, supervisory control and data acquisition; SWM, solid waste management;
Tm , melting point (o C); Top , operating temperature (o C); tpa, tonnes per annum; tpd,
tonnes per day; A, polymer charge to reactor; I, intermediate product; G, gas fraction
(Product); L, liquid Fraction Product; S, solid (Coke) char.
∗ Correspondence to: Waste Management Research Unit (WMRU), Environment
and Life Sciences Research Centre (ELSRC), Kuwait Institute for Scientific Research
(KISR), Main Building (No. 44), Suite# 2208. P.O. Box: 24885, Safat, 13109, Kuwait.
E-mail address: ssalem@kisr.edu.kw
(EU) and mainland Asia occupying a share of 19% and 50% of the
market, respectively (Plastics Europe, 2017). These estimates will
only result in an ever increasing rate of plastic solid waste (PSW)
accumulation, where in the EU alone over 25 million tpa is gener-
ated (Ratnasari et al., 2017). Arabian Gulf Council Countries (GCC),
where readily available and cheap petrochemical feedstock is avail-
able, have a higher rate of PSW production rate (Al-Salem et al.,
2009). This is due to consumers behaviour, high income and gross
domestic product (GDP) economic index and a lack of appropri-
ate infrastructure for solid waste management (SWM) (Al-Salem,
2019a). The main source of PSW is related to the municipal sec-
tor resulting from various household waste fractions. A selection of
world developed and developing countries PSW generation rates
with a projection of waste generation till the year 2025, their cur-
rent income level and main SWM route is presented in Table S1 of
the Supplementary Material File.
PSW is typically recycled via mechanical or thermal means,
where low to medium value range products are recovered (Grigore,
2017). On the other hand, renewed attention in thermolysis of
plastics is noted as of late especially with respect to both pyrol-
ysis and gasification techniques (Lopes et al., 2018; Tang et al.,
2018; Ye et al., 2018). Pyrolysis involves the treatment of the plastic

https://doi.org/10.1016/j.psep.2019.05.008
0957-5820/© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
172 S.M. Al-Salem / Process Safety and Environmental Protection 127 (2019) 171–179
feedstock material in moderate temperatures (≈500◦ C) and inert
atmospheres to produce short molecular chain products. Pyroly-
sis products result in oils that can be used as a liquid fuel with
minimal pre-treatment (Kumar et al., 2011). Plastics posses high
hydrocarbon (HC) content with higher heating values (HHV) com-
parable to those of conventional fuels ranging between 42.1 –
49.4 MJ kg−1 for common synthetic polymers (Kunwar et al., 2016).
The oil produced from the pyrolysis process is the condensate of
the evolved volatiles resulting from the feedstock’s degradation.
It typically contains complex mixtures of organic chemicals such
as aromatic, alicyclic and aliphatic HC (Rathsack et al., 2015). Trace
amount of oxygen, sulphuric compounds and nitrogen based chem-
icals are also reported depending on the treated waste material and
its origin (Al-Salem et al., 2017; Quek and Balasubramanian, 2013;
Ignatyev et al., 2014). Pyrolysis, namely in vacuum operation, has
also shown an increase and renewed attention as of late. Ruan et al.
(2018a) has effectively studied the vacuum pyrolysis of epoxy par-
ticles collected from waste printed circuit boards and have also
reported its heat transfer process. The heat transfer model proposed
can immensely support future modifications of vacuum pyrolysis
operation. Thermo-chemical conversion using vacuum gasification
(coupled with condensation of products) has also shown promise
for managing SW namely micro plastics and nano pollutant toner
(Ruan et al., 2018b). Pyrolysis is also noted to produce bio-char (e.g.
solid fraction of biomass treatment). Yuan et al. (2018) have also
shown that bio-leaching for metal recovery of waste printed boards,
which can be enhanced with bio-char addition. The concoction of
pyrolysis oil will also show various branched and cyclic HC com-
pounds as previously reported in recent work (Al-Dhafeeri et al.,
2017). Light HC are also recovered in the gaseous fraction of PSW
pyrolysis yield. These gases typically comprise 6 – 55% by weight
of the total product yield depending on the experimental setup,
feedstock material, presence of catalyst and operating conditions
(Al-Salem et al., 2017; Alston et al., 2011; Sharma et al., 2014).
Pyrolysis can be achieved by thermal or catalytic means. Both
heterogeneous and homogenous catalysts have been reported to
be used in the pyrolysis of plastics, in order to, reduce operating
temperatures (e.g. 390◦ C to 425◦ C) and the residence time in the
reactor (Czajczyńska et al., 2017; Al-Salem et al., 2017; Hafeez et al.,
2018). On the other hand, thermal pyrolysis is considered to be an
economical option for treating PSW with a relatively more easy
operation (Butler et al., 2011; Chen et al., 2014; Miandad et al.,
2016). The operating conditions can also be optimized for a con-
tinuous process in a more manageable manner. This is due to the
elimination of the catalysts (and associated properties/influencing
factors) in the framework of an industrial setup. Thermal pyrolysis
is also known to produce clean distillates from PSW with minimal
required pre-treatment. Past studies conducted in the UK also indi-
cate that thermal pyrolysis presents a very economical option for
PSW at scales exceeding 100 ktpa (Al-Salem et al., 2014). There-
fore, it can be considered as a more lucrative option for oil based
economy countries such the GCC, where petroleum derivative feed-
stock is more abundant and cheaper. The most common pyrolysis
reactor setups used are fixed bed reactors, fluidised bed reactors
(FBR) and rotary kilns (Rathsack et al., 2015). The type of the reactor
unit influences the products yield recovery to a great extent, due to
the influence on the materials interaction, degradation behaviour,
residence time and heat/mass transfer. The reviews by Al-Salem
et al. (2009, 2017) and Kunwar et al. (2016) showcase the advan-
tages of pyrolysis and the various reactor setups typically used.
Furthermore, fixed bed reactors have been noted to be one of the
most advantageous reactor setups due to ease in operation and
design. Table S2 reviews major studies conducted in the past on
plastics pyrolysis using fixed bed reactor setups indicating varia-
tion of product yields with respect to feedstock type and operating
conditions.
Nowadays, it is well documented that the majority of fossil
fuel based processes for energy production are environmentally
harmful. As a consequence, more stringent regulations have been
deployed on the use and processing of fuels. The most common
commodity fuel used nowadays is gasoline, where pyrolysis has
been noted to produce in various setups with a number of feed-
stock materials. Gasoline is typically classified based on its volatility
and octane number (Ratnasari et al., 2017). It is essential for gaso-
line fuel to have smooth operation in spark ignition engines with
a HC range of C5 – C8 (Buekens and Huang, 1998). Higher HC (i.e.
> C9 ) may be added depending on the quality and climatic condi-
tions. On the other hand, majority of the PSW that constitute MSW
are polyolefin (PO) in origin, of which polyethylene (PE) comprise
its majority. PE of various types makes up 98% of Kuwait’s plas-
tic film waste (Al-Salem et al., 2015). It also constitutes more than
29% of the European demand on plastic resin where over 23% of it
ends up in landfill sites (Plastics Europe, 2017). This paper reports
the thermal pyrolysis of one of the most commonly used plastic
types (e.g. high density polyethylene, HDPE) in a novel fixed bed
reactor presented for a patent claim for a proof of concept in the
United States Patent Office (USPO). The reactor system presents a
number of advantages over conventional ones, and the influence of
operating conditions is studied and reported for the product yields
recovered. Analysis of the gaseous and oil products is also presented
along with the proof of concept of the reactor system. The reac-
tor system presented in this work resolves commonly encountered
operational problems faced when performing pyrolysis, as it will be
discussed in the next section. A kinetic study of the pyrolytic disso-
ciation mechanism, which is essential for the determination of the
influential parameters for obtaining maximum pyrolysis oil, has
been modelled and presented in this work. The kinetic study pre-
sented in this work can also be used for the design and simulation
of commercial reactor units.
2. Materials and methods
2.1. Materials
Film extrusion grade of virgin HDPE supplied from EQUATE
Petrochemical Company (DOW Chemicals) was used as received in
pellet form (3 mm) with a reported particle density of ( =0.952 g
cm−3 ), MFI 10 g/10 min and a melting point (Tm ) of 131◦ C. The
amount of 100 g was used as a charge in the reactor setup for each
experimental run. Thermal stability, micro kinetics analysis and
other properties of the material can be found elsewhere (Al-Salem
et al., 2018a).
2.2. Experimental reactor setup
The thermal pyrolysis of HDPE is carried out in a novel fixed bed
(batch) reactor. The reactor system and configuration is of a novel
design under patent claim file (USPTO, 2017). The pyrolysis sys-
tem for the conversion and analysis of plastics discussed herein is
a dual gas-liquid separation assembly, allowing for the conversion
of organic solids as well as the analysis of the conversion prod-
ucts. The reactor’s vessel is of a cylindrical shape (internal inconel
tube 800 alloy) with an outer part made of SS 316 stainless steel
(do =120 mm) whereas its inner part is ceramic (din = 240.4 mm,
l =600 mm). The system’s specifications and details are provided
in the Supplementary Material File. The samples is placed in the
fixed bed within the middle section of the furnace casing during the
whole experimental run. There exists a 0.23 mm air gap between
the ceramic insulation and stainless steel casing and 120 mm is
outer radius of Ceramic and 60 mm is inner radius. The outer fur-
nace casing has three different temperature zones (thermal heating
 S.M. Al-Salem / Process Safety and Environmental Protection 127 (2019) 171–179 173

Fig. 1. Left: Schematic flow diagram of the pyrolysis reactor system used in this work, Right: Pyrolytic system showing (1) furnace/reactor body, (2) GLS units, (3) chiller and
(4) collection outlet (vessel).
Source Al-Salem (2019b) published with permission from Elsevier.

elements) allowing for three different outer and inner temperature of two duplicate runs were conducted on the HDPE in the range
controlled segments (5 in apart) within the reactor’s bed. A ther- between 500◦ C–800◦ C, with a nitrogen gas flow rate of 20 ml min-1
mal lag (T) of some 50–100◦ C exists and the temperature profile throughout the whole experimental run. Readers are referred to Al-
of a experimental runs is shown in a tabulated form in the Sup- Dhafeeri et al. (2017) for further details. Energy flux calculations are
plementary Material File. The temperature across the respective also appended in this communication (see Supplementary Material
zones is indicated by the three thermocouples which are inserted File).
inside the reactor tube and the readings are depicted in the Supervi-
sory Control and Data Acquisition (SCADA) system. The novelty of
2.3. Sample preparation and gas chromatography coupled with
the design is the configuration of the batch reactor system with
mass spectrometry (GC/MS) analysis
two gas/liquid separators (GLS), where the first is applicable to
be used for a gas chromatograph (GC) immediately after cooling
Solid phase extraction (SPE) was used in the pyrolysis oil anal-
with the chiller shell operated in this work at a cooling tempera-
ysis. SPE was performed in cartridges packed with various packing
ture of 20◦ C. The second GLS is for the separation and collection
materials ranging from polar to non-polar ones, similar to the
of the gas and liquid products. Two lines for the second GLS exist,
phases as used in liquid chromatography. The stationary phase is
the first is for the gas fraction collection where gaseous products
conditioned prior to loading of the sample. Conditioning was per-
are trapped and collected using a 5 l Tedlar bag. Both the oil and
formed by using different solvents to remove any impurities and to
gas samples were collected post condensation (< 3 h of pyrolysis
wetten the stationary phase. After conditioning the silica cartridge
time) and slow pyrolysis conditions were applied throughout the
(1.0 g/6 ml) with hexane the sample (0.2 ml in one ml hexane) was
experiment, maintaining a heating rate of 5◦ C min−1 . The initial
loaded. Subsequently, the analytes of interest are eluted by a 6.0 ml
furnace and bed temperatures were recorded and kept at laboratory
dichloromethane with a polarity similar to target compounds. Sol-
conditions (≈ 21◦ C) with a furnace and reactor bed temperatures
vent was evaporated under nitrogen for GC/MS injection. In order
reaching an average of 566◦ C and 400◦ C after 120 min of experi-
to improve the flow of the sample and solvents, vacuum conditions
mental time, respectively. A gradual increase in the temperatures
were used. The main fuel compounds were targeted in the analy-
was also recorded until the final desired temperatures are reached
sis via GC/MS including naphtha, gasoline, diesel, heavy oil profile,
(Supplementary Material File). After the completion of the experi-
in addition to, olefins, light hydrocarbons, BTX, PAH, styrene, oil
mental run including cooling time period (≈ 5 ½ hours), the system
derived products, heptane (C5 ), C5 + products. The fragment pat-
was flushed with toluene and air, after which the nitrogen carrier
terns were searched against the NIST 2012 and Wiley 10th edition
was used to purge and stabilise the system. The second line is for
databases of spectra (900,000 spectra). An ALS injector was used
the condensable product (liquid) collection which can sustain an
to inject the amount of 1 ␮m sample at 280 ◦ C and ten solvent
80 samples of 3 ml minimum volume capacity. At the bottom of
flushes before and after injection using methylene chloride was con-
the reactor, a newly designed nut and bolt collection hopper is
ducted. A method run time of 74 min was used in the instrument
also introduced for ash/char product collection. Fig. 1 shows the
(Agilent 7820A GC, Agilent 5977E MS Single quadropole - Column
schematic flow diagram of the system used in this work and a
HP5MS and a length of 30 m). A high purity hydrogen carrier gas was
pictorial depiction of the reactor unit (Al-Salem, 2019b). In this
used (1.2 ml min−1 ) and the peaks were identified using the peak
study, offline gas chromatography analysis was conducted for the
integrator analysis routines in Masshunter software. The injector
pyrolysis products as discussed in the next section. A minimum
temperature was maintained at 280 ◦ C and the method utilised an
174 S.M. Al-Salem / Process Safety and Environmental Protection 127 (2019) 171–179
Fig. 2. Product yield and mass balance for the pyrolysis of HDPE in the reactor
system.
oven temperature of 35◦ C for 1 min with an increase to 85◦ C at a
rate of 5◦ C min−1 . The dwell at 85◦ C was kept for 2 mintues with
a ramping rate to a final 290◦ C of 5◦ C min−1 . Baseline subtraction
was carried out just prior to the peak to remove the effect of column
bleed on the mass spectra. The gas products in the gas sample bag
were analysed immediately after each experiment using An Agilent
6890 series II GC instrument (Agilent, Midland, Canada) equipped
with mass spectrometric detector (Agilent 5973, Palo Alto, CA)
coupled with a molecular sieve column and thermal conductivity
detection and HC gases from C1 to C4 were analysed using a flame
ionisation detector (Al-Salem et al., 2018b; Al-Dhafeeri et al., 2017;
Al-Salem, 2019b).
3. Results and discussion
3.1. Pyrolysis product Yield/Mass balance
Fig. 2 shows the products yield obtained from the fixed bed
pyrolysis of HDPE between 500◦ C to 800◦ C. There was a negligi-
ble yield of solid char where the HDPE was thermally cracking to
result in a majority of HC gases and condensate using the aforemen-
tioned experimental conditions (Fig.S2). The reactor system also
allowed for the collection of wax product when the chiller tem-
perature was reduced. Precipitating chemical waxes were flushed
out during the cleaning procedure of the reactor system. On the
other hand, the primary focus of this communication was to study
the pyrolysis oil yield; hence wax product intensification and anal-
ysis falls out of scope. Polyolefin (PO) plastics pyrolysis has been
previously described via a three reaction steps mechanism where
secondary reactions will lead to the liquid and wax evolution from
the alkanes and alkenes produced (Westerhout et al., 1998). FBR
and fixed bed pyrolysis have also been associated with large yields
of chemical waxes in past research (Williams and Williams, 1999a,
1999b; Mastral et al., 2002; Al-Salem et al., 2017).
The major product obtained in this work was a low-medium
viscosity oil, which was yellowish in colour (Fig.S2). The maximum
oil conversion was obtained at 550◦ C (70 wt.%), which has a higher
yield than the typical pyrolysis oil product in past work excluding
chemical waxes collected using a fixed bed reactor. The wax prod-
uct in this work was considered as part of the total tars yield which
was considered as the total fluid (liquid) phase of the products
obtained. This makes the reactor system and experimental condi-
tions used in this work more lucrative for oil production in a more
direct manner. This was attributed to the design of the reactor and
the thermal heating mechanism of the feedstock material where
three dedicated heating zones exist that provide uniform heating
across the reactor bed. This allows for more distribution of thermal
conductivity along the profile of the reactor, which allows for the
Fig. 3. Gases produced from the HDPE pyrolysis with respect to reactor bed tem-
perature (◦ C).
release of volatiles in a more uniform manner resulting in higher
condensates (see Supplementary Materials File for the energy flux
determination along the reactor’s body). A clear increasing trend
in the gas product was also observed (Fig. 2). This was also corre-
sponding to a lesser oil product yield as the temperature increased.
This could be attributed to the rapid release of volatile materials at
fast pyrolysis conditions coupled with secondary cracking reactions
of PO (Conesa et al., 1994a; Conesa and Font, 1999). This will also
account for the losses in the material balance of the system stud-
ied in this work. It is also well established that by increasing the
operating temperature, the cracking reactions rate will reduce due
to the reduction of residence time in the pyrolysis reactor which
leads to the conversion of high molecular chain compounds and
aromatics in the oil/wax product (Adrados et al., 2012). Past work
on polyethylene (PE) pyrolysis has shown large yields of gaseous
products using 100 g and above samples with oil residues at around
45 wt.% (Muhammad et al., 2015; Wong et al., 2015).
3.2. Gas composition
Fig. 3 shows the concentration of the product gases produced
from the HDPE pyrolysis with respect to the reactor bed tempera-
ture. The detailed gas composition is shown in Table S6. The main
product gases are alkenes and alkanes (C2 – C4 ). There was a noted
proportional relationship between the bed temperature and indi-
vidual gas concentration. This reflects the total gas yields previously
shown in Fig. 2. Williams and Williams (1999b) have previously
analysed gaseous product composition from PE pyrolysis between
500◦ C to 700◦ C in an FBR. Low molecular weight gases in this work
are shown to be higher by almost double the concentration to the
aforementioned FBR pyrolysis. The experimental setup was also
evident in hindering solid char (coke) deposition. High molecu-
lar weight gases (C5 +) were noticed to reduce with the increase in
temperature. This indicates that the operating temperature used in
this work doesn’t permit evolution of higher weight compounds,
consequently chemical wax condensates. An optimum gas yield
was measured at 750◦ C (36 wt.%) which could be reduced if cat-
alytic pyrolysis is to be applied due to catalyst surface interaction,
increase in selective cracking reaction rate and hydrogen produc-
tion (Westerhout et al., 1998; Nishino et al., 2008; Al-Salem et al.,
2017).
The gas products concentration, mainly alkenes, can also be
increased with increasing residence time as indicated previously by
Lopez et al. (2017). Scott et al. (1990) has also shown that alkenes
are the dominant species in PE pyrolysis gas composition. HDPE
thermal degradation in this reactor promoted the production of
gas oil over other products namely benzene as indicated in Fig.S3.
Product analysis showed that the gaseous fraction obtained was
 S.M. Al-Salem / Process Safety and Environmental Protection 127 (2019) 171–179 175

mainly a mixture of paraffin and olefin hydrocarbons in the molec-

ular range of C2 – C4 . It gradually increased with the increase in
temperature from 500◦ C – 800◦ C. The yields of C2 to C4 HC with
an increment of 50 ◦ C were 70.63%, 76.96%, 78.83%, 75.12%, 78.83%,
70.47%, and 79.59% respectively. HC in the range of C5 – C10 showed
a decrease with the increase in temperature reflecting decomposi-
tion to low molecular weight compounds. Aromatics fractions were
obtained at very low percentage. Total light gas concentration in
this work has also shown a great compensation effect with both
liquid and char produced. This makes it easier to consider in produc-
ing more pyrolysis oil or activated carbon (as solid char product) by
selecting the appropriate temperature for plastic-waste pyrolysis.
Pyrolysis has been previously perceived to promote aromatisation
reactions at elevated temperatures along with dehydrogenation
ones. This results in the detection of aromatic compounds in pyrol-
ysis yields in both thermal and catalytic processes (Das and Tiwari, Fig. 4. Influence of reactor bed temperature on the gasoline range product obtained
2018; Akubo et al., 2019; Park et al., 2019). The aromatics content in the pyrolysis oil.

can also be increased with the application of zeolite and clay based
catalysts (Auxilio et al., 2017). In this work, the detection of ben-
zene and toluene at elevated bed temperatures can be attributed to
the slow pyrolysis process which induces aromatisation of the long
chain HC feedstock. The accumulation of aromatics in the gas line
of the experimental assembly increases with elevated bed temper-
atures. This is also in-line with overall gas yields obtained in this
work, which increases gradually with the operating temperature
(Fig. 2).
Papuga et al. (2016) have previously presented fuel production
from a PSW mixture using a fixed bed reactor. The fractions of
gaseous and liquid fuel were 65.75% and 32.8% at 500 ◦ C, while at
higher temperature gaseous product fraction increased to 69.98%
at the expense of liquid/oil fraction, which reduced to about 29%
at 525◦ C. Conesa et al. (1994b) have also investigated pyrolysis
of PE in a fluidized bed reactor where the gaseous products had
the highest fraction of ethene followed by methane and benzene
and then propene. The effects of residence time and temperature
have been reported showing maximum yield of gaseous products
at 700◦ C. The gaseous fraction in the products increased at elevated
temperatures in accordance to the previously reported results. In
the present work, higher thermal degradation temperatures have
resulted into an elevated yield of gaseous product fraction at the
cost of liquid/oil product fraction. The primary pyrolytic reactions
occurred in the liquid phase as HDPE initially degraded (i.e. depoly-
merised) and free-radical transformations occurred resulting into
low gaseous product yield of mainly ethene coupled with high
yields of liquid/waxes. The high yields of ethene (monomer) at
elevated temperatures was acquired from the secondary pyroly-
sis cracking reaction of intermediate compounds attributed to the
propagation reaction of HDPE. The propene yield from the pyrolysis
of waxes can be related to (a) the propagation reaction where the
last radical formed had three carbon atoms, and (b) stable radical
formation due to the ramifications that had favoured a hydrogen
transfer before the propagation step.
3.3. Pyrolysis oil analysis
Pyrolysis oil derived from the experiments conducted was eval-
uated for quality in terms of gasoline range HC as depicted in Fig. 4.
There was a noticed variation with the oil yield with respect to
the bed temperature. It can be seen than at elevated temperature
the gasoline profile of the products analysed increased to a maxi-
mum at 800◦ C. In addition, majority of liquid product consisted of
gasoline range HC (Table S7). This shows that the work conducted
using this particular reactor system favours fuel production, regard-
less of the fact that it operates under thermal pyrolysis conditions
rather than catalytic. This could be attributed to the long operating
time previously mentioned in the materials and methods section,
Fig. 5. Distribution of aliphatic and aromatic hydrocarbons with respect to operat-
ing temperature.
which promotes condensation of liquid fuel after prolonged exper-
imental time. It could also be attributed to the fact that the reactor
body operates under three different heating zones which gradually
promotes the cracking of the HC compounds and allows higher col-
lection yield in the vessel. The work conducted in this study is also
in agreement with past analytical reports conducted using catalytic
pyrolysis on HDPE (Manos et al., 2000; Aguado et al., 1997). HDPE
is known to be of long linear HC chains with low branching. It is
also well understood that pyrolysis will cause the breakdown of the
HDPE backbone chains to form HC radicals, which lead to the forma-
tion of free radicals (Williams and Williams, 1999b; Al-Salem and
Lettieri, 2010; Al-Salem et al., 2010). This will lead to the increase
in the formation of aromatic HC with increase in temperature as it
promotes rapid radical release. This was clearly witnessed in this
work after analysing the pyrolysis oil product obtained (Fig. 5).
The oil produced was mostly aliphatic in nature and its percent-
age decreased with the increase in temperature. At 500 ◦ C, 98.38%
aliphatic oil range HC was obtained. Aromatic HC were produced in
small percentage and the highest yield was obtained at 600◦ C. The
manipulation of temperature can also change the aromatic content
which is needed to comply with international gasoline standards
used in fuel products (Sharma et al., 2014). This also conforms with
the past findings of Das and Tiwari (2018) where slow pyrolysis
with a final hold up time of eight hours (reaching 400◦ C) was
utilised on virgin and waste PE material (including HDPE). The con-
version of pyrolysis oil was observed to increase with time and the
aromatics content was also noted to increase with the use of var-
ious types of catalysts in Gaurh and Pramanik (2018). Wong et al.
(2016) have also used a fixed bed reactor to study the cracking of
176 S.M. Al-Salem / Process Safety and Environmental Protection 127 (2019) 171–179
low density polyethylene (LDPE) post benzene dissolution. Zeolite
and nickel impregnated catalysts were used to reach a short reten-
tion time with high yields of C1 –C4 gas products and gasoline range
HCs coupled with 98% LDPE conversion.
Thermal degradations of HDPE was presumed to be conducted
over two stages, a primary one that results in gaseous products;
and an intermediate that further decomposed to provide gaseous,
liquid product fractions and char. The readers are referred to the
next section where a mechanism is proposed for the degradation
kinetics. Conesa et al (1994b) showed that for the pyrolysis of HDPE
an average molecular weight of 300 (C20 range) was obtained. The
formation of vinyl radical with inherited double bonds is low in the
start of the degradation reaction but increased with the increase in
reaction temperature. Therefore, transfer reaction was prevalent
for PE, consequently generating very few monomers but various
sizes of oligomers due to chain cleavage. Williams and Williams
(1999c) have summarized their results with regards to the analysis
of oil/wax product fractions of thermally degraded mixed plastics.
Their results had exclusively confirmed aliphatic products, com-
prising of alkane, alkene and alkadienes. The eluted compounds
were identified as diene. The oil product in the experimental work
of Papuga et al. (2016) comprised of 11.49% aromatic, 82.11% paraf-
fins and 6.4% naphthens. On a global premise, the energy demand
is increasing on an annual basis tied closely with a proportional
effect with the ever increasing world population. Fossil fuels are
still considered to be the main feed substance used to drive the
energy market where gasoline is one of its main commodities used
for automobile fuel and other purposes. According to the recent
report published by Global Petrol Prices (GB, 2019), the average
gasoline price around the world is 1.13 $ litre−1 . The pyrolysis pro-
cess presented in this work can potentially provide gasoline fuel
from a relatively cheap feedstock material (PSW). Based on the
heat flux, energy input and thermal conductivity estimations for
the whole temperature range used in the reactor’s operation, the
energy requirement of the unit is estimated to be 7.05 $ per kW−1 .
This is considering the new increased tariff introduced in the State
of Kuwait which represent some 500% increase to the previous one
recently declared to be 0.016 $ kW−1 (KT, 2019). In a European
context, Germany and Denmark are considered to be among the
highest countries with energy tariffs declared by Eurostat (2019)
to be 30.5 Euros per kWh (≈ 1.13 $ per kWh). Therefore, the unit in
this work is estimated to have an economic demand of about 500
$ per kW−1 considering its surface area and energy input. It should
also be noted that a life cycle costing (LCC) analysis can ultimately
off-set these estimations based on the availability of the feed-
stock material (PSW) and other levy or subsidization schemes for
waste management (out of scope of this research). Past research has
also confirmed high economic internal rate of return for pyrolytic
units in a European context which can also take into account the
high environmental burdens off-setting such units provide for local
environments (Al-Salem et al., 2014). Therefore, these estimations
are anticipated to decrease when applied to industrial scale scenar-
ios. Readers are referred to the Supplementary Material File for the
energy and heat flux calculations.
3.4. Degradation kinetics approach and analysis
A kinetic study of the degradation (cracking) of HDPE was also
conducted, in order to, identify the possible reaction routes using
experimental data obtained. Different pyrolysis reaction pathways
were presumed, e.g. primary, secondary and tertiary, yielding dif-
ferent products (Panda et al., 2010; Al-Salem et al., 2010). The
intermediate products obtained from the primary degradation step
further cracks into condensable and non-condensable lighter HC in
the secondary reaction step. Tertiary reactions result into the for-
mation of the solid char (coke) and contribute to the production of
aromatics and cyclic compounds from alkanes and alkenes at ele-
vated temperatures. It is assumed that the conversion of HDPE into
various products such as gas, liquid and solid is favoured through
independent parallel first order reactions. The kinetic parameters of
the conversion of HDPE into different products based on the pyrol-
ysis results are evaluated. In order to validate the reaction pathway,
the experimental results are compared with those obtained by the
kinetic model to assess the true mechanism of thermal degradation
of HDPE. Kinetic data obtained by earlier studies confirmed that
polymers having different molecular structures lead to different
mechanisms of decomposition and corresponding reaction rates
(Al-Salem et al., 2010; Ceamanos et al., 2002; Costa et al., 2007).
Depending on the nature of polymer, the pyrolysis involves three
different reaction pathways. These are: i) successive enchained ˇ-
scission reactions, which yield monomer from the polymer chain;
ii) specific intramolecular proton transfer reactions followed by
mid-chain ˇ-scission to yield a series of specific low molecular
weight products (LMWPs); iii) intermolecular proton transfer fol-
lowed by mid-chain ˇ-scission to yield a diverse set of LMWP.
Depending on the nature of polymeric materials, there is a domi-
nancy of one or two degradation modes among the three proposed
steps. PE is especially susceptible to both of the last two afore-
mentioned pathways. The loss of proton from every mid chain of
polythene generates second degree carbon radical from which the
decomposition of the chain normally initiates. The role of these
free radicals is very important for governing the reaction products
upon which the kinetic scheme depends. The pyrolytic reaction is
assumed to take place over two stages as depicted in Eq.(1):
(1)
In the first step, gaseous HC (G) are obtained along with an
intermediate molten polymeric product (I) from the original reac-
tor charge (A). Furthermore, the second stage further decomposes
the I fraction into lighter non-condensable gaseous HC (G), liquid
hydrocarbons (L) and solid char (S). The decomposition reactions
are expressed by the set of equations in the following mathematical
breakdown:
dA
= −k1 Am − k1S An
dt
dI  
= k1s An − k2 I m + k2L I o + k2S I p
dt
dG (2)
= k1 Am + k2 I m
dt
dL
= k2L I o
dt
dS
= k2S I p
dt
Where k’s are velocity (reaction rate) constants for each cracking
reaction shown in the mechanism above and m, n, o and p are the
corresponding order of the reactions. In case of HDPE, all orders
of reactions are presumed to be unity. This set of kinetics equa-
tions expressing pyrolytic reactions in the fixed bed was solved
using numerical Runga-Kutta fourth order method for numerically
evaluating the series of non-linear ordinary first order differen-
tial equations (Al-Salem and Lettieri, 2010). The experimentally
collected amounts of gas, liquid/wax and solid char fractional prod-
ucts were optimized with the theoretically calculated amount of
products after the specified reaction time, implementing build-in
excel function of Microsoft office 2010 using the following objective
 S.M. Al-Salem / Process Safety and Environmental Protection 127 (2019) 171–179 177

Table 1 reflecting internal energy and molecular motion resulting into

Arrhenius Coefficients For Set Of Chemical Reactions Reflecting Pyrolysis Mecha-
rapid decomposition. This phenomenon indicates an increase in
nism of HDPE.
product concentrations with an increase in temperature. Since the
Type ko (min−1 ) Energy of Activation (Ea, kJ mole−1 ) apparent activation energy (Ea ) of production of liquid range HC is
k1 6.653 × 10 9
165.12 less in magnitude, larger amount of liquid is obtained compared to
k1S 3.76 × 1010 149.28 other product fractions. Conesa et al (1994a) have previously pos-
k2 2.70 × 105 115.15 tulated different kinetic models to describe pyrolysis reaction of PE.
k2L 1.03 × 105 76.95
A three reaction scheme coupled with a zero-order reactions were
k2S 4.17 × 107 98.05
tried and the best fit values were reported for the pyrolysis of HDPE.
The values of Ea obtained in the secondary reaction were 196.3 and
232.2 kJ mol−1 . There isn’t much variation in the computed val-
ues of Arrhenius coefficients based on experimental data of HDPE
pyrolysis. The numerical model based on the present study of HDPE
pyrolysis in fixed bed presented reflected the true mechanism indi-
cating, which reaction was favoured at certain given conditions.
Secondary stage reaction had lower values of Ea thus generating
larger fraction of gaseous product and liquid and solid product
fraction. Conesa and Font (1999) have introduced the kinetic sever-
ity function (KSF) which was related to n-pentane conversion. The
application of this analysis was applied for the data that showed
logical slope of ln(n-pentane yield) plot versus KSF for the decom-
position kinetic law of n-pentane. The work presented in this study
takes into account the analysis of the whole products range and
is not restricted on certain evolved products obtained with time.
Fig. 6. Experimental and Theoretical Yield (Logarithmic Scale) of Products (Gas, Liq- In a follow-up study, Conesa et al. (2001) have solved numeri-
uid and Solid) of Pyrolytic Reaction of HDPE at Different Temperatures. cal problems related to kinetic analysis using different modelling
approach based on (nth) order and more complex models using
a number of reactions. Recently, Wang et al. (2019) have studied
the pyrolytic reaction kinetic parameters in a thermogravimetric
setup and reported ones similar to those found in this study. These
findings can be indicative to the kinetic parameters range of PE
materials in various experimental set-up complementing the work
previously reported in Al-Salem et al. (2018a). Ballice (2001) has
also explained the pyrolitic reaction mechanism for the evalua-
tion of kinetic parameters for dynamic thermal degradation of PE
using heating rate 20 ◦ C min-1 in a fixed bed reactor. Iso-kinetics
models for the evaluation of Arrhenius coefficients for the thermal
degradation of LDPE and HDPE, were used. In the case of this work,
comparative assessment can initially be used with micro and macro
kinetics obtained for the feedstock at hand (Al-Salem et al., 2018a).
Comparison to other research work can also help in understanding
the behaviour of mono feedstock treatment, which can also lead
Fig. 7. Arrhenius Plots For All Evaluated Velocity Constants For Pyrolytic Reaction to the understanding of how to mange the operation in future for
Of HDPE At Different Temperatures. co-pyrolytic treatment. The scale-up opportunities can be consid-
ered after taking into account the environmental factors for pilot
operation and the change of product yields with larger amount
function (OF).
of feedstock. This will ultimately show the industrial application
    
  Gexp − Gtheo   Lexp − Ltheo   Sexp − Stheo  pathway of the system studied in this work and how the utilisation
OF =  + + 
 Gexp   Lexp   Sexp  × 100 of various product collection and sampling points can result in a
(3) more collective product yield. The operation will also have to take
into account the continuous nature of the pilot scale process, in the
where G, L and S represent gas, liquid and solid product fractions, case where it is deemed necessary to do so in the light of ineffec-
respectively; and exp and theo denote experimental and theoretical tive batch process with the studied configuration. The degradation
values, respectively. The model fitted very well and the overall OF kinetics will provide the in-depth understanding with future com-
values were less than 0.01% and the average absolute error between parative studies between micro, macro (current bench scale) and
practical and theoretical product fractions has been less than 5%. pilot operation.
The temperature dependence of the rate constants of all the reac- The thermal degradation process has been considered as a free
tions is analysed by the Arrhenius equation. The corresponding radical chain reaction starting with initiation (chain scission), fol-
values of pre-exponential factor and energy of activations are eval- lowed by propagation (formation of free radical), and hydrogen
uated (Table 1). The comparison of the theoretical and experimental atom intermolecules and intramolecular transfer and then termi-
results is shown in Fig. 6. An excellent agreement between numeri- nation as final step with activation energies values ranging between
cal results and experimental data was observed and the mechanism 190–250 kJ mol−1 . Coats-Redfern and Chen-Nuttall methods were
is considered to be validated under all the experimental conditions. applied to the pyrolysis data for the evaluation of 1-olefin and
The plot of Arrhenius equation for all rate constants is pre- n-parrafins formation. Aboulkas et al. (2010) have also used iso-
sented in Fig. 7. It represents that with an increasing temperature, kinetics models reported in the literature to determine the kinetic
the velocity rate constants of degradation reactions are increased parameters. They have determined the contracting sphere model
178 S.M. Al-Salem / Process Safety and Environmental Protection 127 (2019) 171–179
√   √ 
(i.e.f (˛) = 2. 1 − ˛ andg(˛) = 1 − 1 − ˛ ) using Criado mas-
ter plots that fitted the experimental data explaining the true
mechanism and had provided realistic kinetic parameters. Random
and end chain scission were previously attributed to produce C6
– C20 compounds in pyrolysis oil (Das and Tiwari, 2018). Accord-
ing to their research work, ␣-scission is less thermodynamically
favourable with lower temperatures around 300◦ C. It should be
dully noted at this stage that ␣-scission refers to the breaking
of the carbon bond of C H with an overlap of 120◦ angle. Fur-
thermore, olefin compounds formation were also associated with
radical recombination which are followed by inter or intramolec-
ular transfer of hydrogen (Bockhorn et al., 1999). Therefore, the
heavy oil fraction (> C20 ) detected in the pyrolysis oil examined in
this work can be attributed to the to the ␣-scission part of the HDPE
degradation mechanism (Table S7).
4. Conclusion
The energy demand is directly proportional to the increase
in the world’s population and their standards of living. There-
fore, vast challenges are presented to cover their energy and fuel
demand in an environmentally and green manner. In this work,
HDPE was thermally degraded in a novel pyrolysis batch reac-
tor yielding high percentage of tars including pyrolysis oil (70%
at 550 ◦ C) and gas (36% at 750 ◦ C) fractions. The compositional
analysis using gas chromatography showed gasoline range liquid
hydrocarbons (HC) evolution at high proportions. The work has also
showed that the major portion (> 96%) of oil obtained was aliphatic
(either normal or branched chain) within the range of C8 –C12 . C13
and higher range HC were obtained in the smaller proportions. In
the oil product analysis, the production of aromatic HC was much
lower compared to aliphatic hydrocarbons. Among the gaseous
hydrocarbons, C2 to C4 were obtained as major product (>70%).
The experimental measurements have also been modelled using
chemical reaction kinetics of the degradation of HDPE, express-
ing the true reaction mechanism comprising of two stages. The
kinetic parameters of reaction mechanism for the primary stage
decomposition showed high energy of activation while in the sec-
ond stage of decomposition of the intermediate product evolution
to gas, liquid and solid fractions, it showed lower values reflect-
ing propagation, intermolecular and intramolecular hydrogen shift
followed by termination step. The model developed in this work
has major applications in the design of commercial plastic waste
handling facilities utilizing thermal techniques aimed at generating
fuel and energy.
Acknowledgments
The author would like to thank the Kuwait Institute for Scientific
Research (KISR) and the Supreme Council for Planning (Govern-
ment of The State of Kuwait) for supporting research project
P-KISR-06-11. The management team of ELSRC (KISR) are also
acknowledged for their kind support to this research work. The
author is also grateful to the three blind reviewers to this arti-
cle for their constructive comments. Dr. Gobinda Karmarkar (West
Bengal University), Dr. B.K. Sharma (University of Illinois - Urbana
Champaign) and Prof. Animesh Dutta (University of Guelph) are
gratefully acknowledged for their feedback and support.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.psep.2019.05.
008.
References
Adrados, A., De Marco, I., Caballero, B., Lopez, A., Laresgoiti, M., Torres, A., 2012. Pyrol-
ysis of plastic packaging waste: a comparison of plastic residuals from material
recovery facilities with simulated plastic waste. Waste Mange 32, 826–832.
Aguado, J., Sotelo, J.L., Serrano, D.P., Calles, J.A., Escola, J.M., 1997. Catalytic con-
versionof polyolefins into liquid fuels over MCM-41: comparison with ZSM-5
andmmorphous SiO2-Al2O3. Energy & Fuel 11, 1225–1231.
Akubo, K., Nahil, M.A., Williams, P.T., 2019. Aromatic fuel oils produced from the
pyrolysis-catalysis of polyethylene plastic with metal-impregnated zeolite cat-
alysts. J. Energy Inst. 92, 195–202.
Al-Dhafeeri, A.T., Al-Salem, S.M., Al-Wadi, M.H., Sultan, H.H., Karam, H.J., 2017. Vari-
ation in gas chromatography (GC) analysis in setting up laboratory protocols for
waste to energy novel fixed bed reactor setups. Int. J. Energy Product. Mange. 2
(3), 294–305.
Al-Salem, S.M., 2019a. Influential parameters on natural weathering under harsh
climatic conditions of mechanically recycled plastic film specimens. J. Environ.
Mange. 230, 355–365.
Al-Salem, S.M., 2019b. Feedstock and optimal operation for plastics to fuel con-
version in pyrolysis, chapter 5. In: Plastics to Energy: Fuel, Chemicals, and
Sustainability Implications, 1st edition book. Elsevier, pp. 117–146.
Al-Salem, S.M., Lettieri, P., 2010. Kinetic study of high density polyethylene (HDPE)
pyrolysis. Chem. Eng. Res. Des. 88, 1599–1606.
Al-Salem, S.M., Lettieri, P., Baeyens, J., 2009. Recycling and recovery routes of plastic
solid waste (PSW): a review. Waste Mange. 29 (10), 2625–2643.
Al-Salem, S.M., Lettieri, P., Baeyens, J., 2010. The valorization of plastic solid waste
(PSW) by primary to quaternary routes: from re-use to energy and chemicals.
Prog. Energy Combust. Sci. 36 (1), 103–129.
Al-Salem, S.M., Papageorgiou, L.G., Lettieri, P., 2014. Techno-economic assessment
of thermo-chemical treatment (TCT) units in the Greater London area. Chem.
Eng. J. 248, 253–263.
Al-Salem, S.M., Abraham, G., Al-Qabandi, O.A., Dashti, A.M., 2015. Investigating the
effect of accelerated weathering on the mechanical and physical properties of
high content plastic solid waste (PSW) blends with virgin linear low density
polyethylene (LLDPE). Polym. Test. 46, 116–121.
Al-Salem, S.M., Antelava, A., Constantinou, A., Manos, G., Dutta, A., 2017. A review on
thermal and catalytic pyrolysis of plastic solid waste (PSW). J. Environ. Mange.
197, 177–198.
Al-Salem, S.M., Bumajdad, A., Khan, A.R., Sharma, B.K., Chandrasekaran, S.R., Al-Turki,
F.A., Jassem, F.H., Al-Dhafeeri, A.T., 2018a. Non-isothermal degradation kinetics
of virgin linear low density polyethylene (LLDPE) and biodegradable polymer
blends. J. Polym. Res. 25 (5), 111.
Al-Salem, S., Al-Nasser, A., Al-Wadi, M., Al-Foudaree, M., Al-Qassimi, M., Al-Dhafeeri,
A., Asiri, F., Sultan, H., Karam, H., 2018b. Established protocols and research
methods acquired. In: The Waste Management Research Unit (WMRU), Techni-
cal Report, KISR no.14854, Project Code: P-KISR-06-11, April.
Alston, S.M., Clark, A.D., Arnold, J.C., Stein, B.K., 2011. Environmental impact of pyrol-
ysis of mixed WEEE plastics Part1: experimental pyrolysis data. Environ. Sci.
Tech. 45 (21), 9380–9385.
Auxilio, A.R., Choo, W.L., Kohli, I., Srivatsa, S.C., Bhattacharya, S., 2017. An experi-
mental study on thermo-catalytic pyrolysis of plastic waste using a continuous
pyrolyser. Waste Manag. 67, 143–154.
Ballice, L., 2001. A kinetic approach to the temperature programmed pyrolysis of Low
and high density polyethylene in a fixed bed reactler: determination of kinetic
parameters for evoluation of n-praffins and 1-olefiens. Fuel 80, 1923–1935.
Bockhorn, H., Hornung, A., Hornung, U., Schawaller, D., 1999. Kinetic study on the
thermal degradation of polypropylene and polyethylene. J. Anal. Appl. Pyrolysis
48, 93–109.
Buekens, A.G., Huang, H., 1998. Catalytic plastics cracking for recovery of gasoline-
range hydrocarbons from municipal plastic waste. Res. Conserv. Rec. 23,
163–181.
Butler, E., Devlin, G., Meier, D., McDonnell, K., 2011. A review recent laboratory
research and commercial developments in fast pyrolysis and upgrading. Ren.
Sustain. Energy Rev. 15, 4171–4186.
Ceamanos, J., Mastral, J.F., Millera, A., Aldea, M.E., 2002. Kinetics of high density
polyethylene: comparison of isothermal and dynamic experiments. J. Anal. App.
Pyrolysis 65 (2), 93–110.
Chen, D., Yin, L., Wang, H., He, P., 2014. Pyrolysis technologies for municipal solid
waste: a review. Waste Mange. 34, 2466–2486.
Conesa, J.A., Font, R., 1999. Kinetic severity function as a test for kinetic analysis.
Application to polyethylene pyrolysis. Energy Fuel 13 (3), 678–685.
Conesa, J.A., Marcilla, A., Font, R., 1994a. Kinetic model of the pyrolysis of polyethy-
lene in a fluidized bed reactor. J. Anal. App. Pyrolysis 30 (1), 101–120.
Conesa, J.A., Font, R., Marcilla, A., Gracia, A.N., 1994b. Pyrolysis of polyethylene in a
fluidized bed reactor. Energy Fuel 8 (6), 1238–1246.
Costa, P.A., Pinto, F.J., Ramos, A.M., Gulyurtlu, I.K., Cabrita, I.A., Bernardo, M.S., 2007.
Kinetic evaluation of the pyrolysis of polyethylene waste. Energy Fuel 21 (5),
2489–2498.
Czajczyńska, D., Anguilano, L., Ghazal, H., Krzyżyńska, R., Reynolds, A.J., Spencer, N.,
Jouhara, H., 2017. Potential of pyrolysis processes in the waste management
sector. Therm. Sci. Eng. Prog. 3, 171–197.
Das, P., Tiwari, P., 2018. Valorization of packaging plastic waste by slow pyrolysis.
Resourc. Conser. Recy. 128, 69–77.
Eurostat, Accessed on 9th April 2019. Available at: 2019. Energy Prices in the
EU, 2017. https://ec.europa.eu/eurostat/news/themes-in-the-spotlight/energy-
prices-2017.
 S.M. Al-Salem / Process Safety and Environmental Protection 127 (2019) 171–179
Gaurh, P., Pramanik, H., 2018. A novel approach of solid waste management
via aromatization using multiphase catalytic pyrolysis of waste polyethylene.
Waste Mange. 71, 86–96.
GB, Available at: 2019. Gasoline prices, Gasoline prices, liter. 08 April 2019. Accessed
on 9th April 2019. https://www.globalpetrolprices.com/gasoline prices/.
Grigore, M.E., 2017. Methods of recycling, properties and applications of recycled
thermoplastic polymers. Recycling 2, 24.
Hafeez, S., Manos, G., Al-Salem, S.M., Aristodemou, E., Constantinou, A., 2018. Liquid
fuel synthesis in microreactors: a review. React. Eng. Chemst. 3, 414–432.
Ignatyev, I.A., Thielemans, W., Beke, B.V., 2014. Recycling of polymers: a review.
ChemSusChem 7 (6), 1579–1593.
KT, Accessed on 9th April 2019. Available at: 2019. Kuwait Times, Kuwait Water,
Electricity Prices up by 500 Per Cent. https://www.khaleejtimes.com/region/
kuwait/kuwait-water-electricity-prices-up-by-500-per-cent.
Kumar, S., Panda, A.K., Singh, R.K., 2011. A review on tertiary recycling of high-
density polyethylene to fuel. Res. Conserv. Rec. 55 (11), 893–910.
Kunwar, B., Cheng, H.N., Chandrashekaran, S.R., Sharma, B.K., 2016. Plastics to fuel:
a review. Ren. Sustain. Energy Rev 54, 421–428.
Lopes, E.J., Queiroz, N., Yamamoto, C.I., Neto, P.R., 2018. Evaluating the emissions
from the gasification processing of municipal solid waste followed by combus-
tion. Waste Mange. 73, 504–510.
Lopez, G., Artetxe, M., Amutio, M., Bilbao, J., Olazar, M., 2017. Thermochemical routes
for the valorization of waste polyolefinic plastics to produce fuels and chemicals.
A review. Ren. Sustain. Energy Rev. 73, 346–368.
Manos, G., Garforth, A.A., Dwyer, J., 2000. Catalytic degradation of high-
densitypolyethylene over different zeolitic structures. Indust. Eng. Chemst. Res.
39, 1198–1202.
Mastral, F.J., Esperanza, E., García, P., Juste, M., 2002. Pyrolysis of high-density
polyethylene in a fluidised bed reactor: influence of the temperature and resi-
dence time. J. Anal. App. Pyrolysis 63 (1), 1–15.
Miandad, R., Barakat, M.A., Aburiazaiza, A.S., Rehan, M., Nizami, A.S., 2016. Catalytic
pyrolysis of plastics: a review. Process Saf. Environ. Prot. 102, 822–838.
Muhammad, C., Onwudili, J.A., Williams, P.T., 2015. Catalytic pyrolysis of waste
plastic from electrical and electronic equipment. J. Anal. App. Pyrolysis 113,
332–339.
Nishino, J., Itoh, M., Fujiyoshi, H., Uemichi, Y., 2008. Catalytic degradation of plastic
waste to petrochemicals using Ga-ZSM-5. Fuel 87, 3681–3686.
Panda, A.K., Singh, R.K., Mishra, D.K., 2010. Thermolysis of waste plastics to liquid
fuel: a suitable method for plastic waste management and manufacture of value
added products-A world prospective. Ren. Sustain. Energy Rev. 14, 233–248.
Papuga, S.V., Gvero, P.M., Vukić, L.M., 2016. Temperature and time influence on the
waste plastics pyrolysis in the fixed bed reactor. Therm. Sci. 20 (2), 731–741.
Park, K., Jeong, Y., Guzelciftci, B., Kim, J., 2019. Characteristics of a new type contin-
uous two-stage pyrolysis of waste polyethylene. Energy 166, 343–351.
Plastics Europe, 2017. Plastics the Facts, Plastics Europe. Association of Plastics Man-
ufacturers, Brussels (Belgium).
Quek, A., Balasubramanian, R., 2013. Liquefaction of waste tires by pyrolysis for oil
and chemicals - A review. J. Anal. App. Pyrolysis 101, 1–16.
179
Rathsack, P., Riedewald, F., Sousa-Gallagher, M., 2015. Analysis of pyrolysis liq-
uid obtained from whole tyre pyrolysis with molten zinc as the heat transfer
media using comprehensive gas chromatography mass spectrometry. J. Anal.
App. Pyrolysis 116, 49–57.
Ratnasari, D.K., Nahil, M.A., Williams, P.T., 2017. Catalytic pyrolysis of waste plastics
using staged catalysis forproduction of gasoline range hydrocarbon oils. J. Anal.
App. Pyrolysis 124, 631–637.
Ruan, J., Huang, J., Qin, B., Dong, L., 2018a. Heat transfer in vacuum pyrolysis
of decomposing hazardous plastic wastes. ACS Sustainable Chem. Eng. 6 (4),
5424–5430.
Ruan, J., Qin, B., Huang, J., 2018b. Controlling measures of micro-plastic and nano
pollutants: a short review of disposing waste toners. Environ. Int. 118, 92–96.
Scott, D.S., Czernik, S.R., Piskorz, J., Radlein, D.S.A.G., 1990. Fast pyrolysis of plastic
wastes. Energy Fuels 4, 407.
Sharma, B.K., Moser, B.R., Vermillion, K.E., Doll, K.M., Rajagopalan, N., 2014. Produc-
tion, characterization and fuel properties of alternative diesel fuel from pyrolysis
of waste plastic grocery bags. Fuel. Process. Tech. 122, 79–90.
Tang, X., Xie, Q., Qiu, R., Yang, Y., 2018. Development of a relationship between kinetic
triplets and heating rates to improve pyrolysis kinetic modeling of polymer.
Polym. Degrad. Stab. 154, 10–26.
USPTO, 2017. United States Patent & Trademark OFFICE, Pyrolysis reactor system for
the conversion and analysis of organic solid waste, Application No. 15/487,351.
Wang, Z., Shen, D., Wu, C., Gu, S., (Accepted) 2019. Co-pyrolysis of lignin and
polyethylene with the addition of transition metals - Part I: thermal behav-
ior and kinetics analysis. J.Energy Inst., http://dx.doi.org/10.1016/j.joei.2019.03.
003.
Westerhout, R.W.J., Kuipers, J.A.M., van Swaaij, W.P.M., 1998. Experimental deter-
mination of the yield of pyrolysis products of polyethylene and polypropylene.
Influence of reaction conditions. Indust. Eng. Chemst. Res. 37, 841–847.
Williams, P.T., Williams, E.A., 1999a. Product composition from the fast pyrolysis of
polystyrene. Environmt. Tech. 20, 1109–1118.
Williams, P.T., Williams, E.A., 1999b. Fluidised bed pyrolysis of low density polyethy-
lene to produce petrochemical feedstock. J. Anal. App. Pyrolysis 51, 107–126.
Williams, P.T., Williams, E.A., 1999c. Interaction of plastic in mixed plastic pyrolysis.
Energy Fuel 13, 188–196.
Wong, S.L., Ngadi, N., Abdullah, T.A.T., Inuwa, I.M., 2015. Current state and future
prospects of plastic waste as source of fuel: a review. Ren. Sustain. Energy Rev.
50, 1167–1180.
Wong, S., Ngadi, N., Abdullah, T.A.T., Inuwa, I.M., 2016. Catalytic cracking of LDPE
dissolved in benzene using nickel-impregnated zeolites. Ind. Eng. Chem. Prod.
Res. Dev. 55 (9), 2543–2555.
Ye, Z., Yang, F., Lin, W., Li, S., Sun, S., 2018. Improvement of pyrolysis oil obtained
from co-pyrolysis of WPCBs and compound additive during two stage pyrolysis.
J. Anal. App. Pyrolysis 135, 415–421.
Yuan, Z., Ruan, J., Li, Y., Qiu, R., 2018. A new model for simulating microbial cyanide
production and optimizing the medium parameters for recovering precious
metals from waste printed circuit boards. J. Hazard. Mater. 353, 135.