Renewable and Sustainable Energy Reviews 50 (2015) 11671180

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Current state and future prospects of plastic waste as source of fuel:

A review
S.L. Wong a, N. Ngadi a,n, T.A.T. Abdullah b, I.M. Inuwa c
a
Department of Chemical Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia
b
Institute of Hydrogen Economy, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia
c
Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia

art ic l e i nf o a b s t r a c t

Article history: Due to the depleting fossil fuel sources such as crude oil, natural gas, and coal, the present rate of
Received 3 June 2014 economic growth is unsustainable. Therefore, many sources of renewable energy have been exploited,
Received in revised form but the potentials of some other sources such as plastics waste are yet to be fully developed as full scale
3 March 2015
economic activity. Development and modernization have brought about a huge increase in the
Accepted 24 April 2015
production of all kinds of plastic commodities, which directly or indirectly generate waste due to their
wide range of applications coupled with their versatility of types and relatively low cost. The current
Keywords: scenario of the plastic recycling technology is reviewed in this paper. The aim is to provide the reader
Pyrolysis with an in-depth analysis with respect to the pyrolysis of plastic waste as obtained in the current
Polymer recycling technology. As the caloric value of the plastics is comparable to that of hydrocarbon fuel,
Review
production of fuel from plastic waste would provide a good opportunity to utilize the waste as a better
Fuel
alternative to dumpsites. Different techniques of converting plastics waste into fuel including thermal
Plastics
and catalytic pyrolysis, microwave-assisted pyrolysis and uid catalytic cracking are discussed in detail.
The co-pyrolysis of plastics waste with biomass is also highlighted. Thus, an attempt was made to
address the problem of plastic waste disposal as a partial replacement of the depleting fossil fuel with
the hope of promoting a sustainable environment.
& 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
2. Types of reactors and process design in plastic waste pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
2.1. Batch and semi-batch reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
2.2. Fluidized bed reactor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
2.3. Conical spouted bed reactor (CSBR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
2.4. Two-stage pyrolysis system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
2.5. Microwave-assisted pyrolysis (MAP). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
2.6. Pyrolysis in supercritical water (SCW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1171
2.7. Fixed bed reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1172
2.8. Fluid catalytic cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1172
3. Production of fuels from polymer pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1174
3.1. Liquid from pyrolysis of single type of plastic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1174
3.2. Liquid from co-pyrolysis of plastics with biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1175
3.3. Liquids from pyrolysis of mixed plastics and municipal plastic waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1175

Abbreviations: LDPE, low density polyethylene; HDPE, high density polyethylene; PP, polypropylene; PVC, poly (vinyl chloride); PS, polystyrene; PET, poly (ethylene
terephthalate); MSW, municipal solid waste; MPW, municipal plastic waste; BTX, benzene, toluene and xylene; BET, Brunauer, Emmett and Teller method (for surface area
analysis); LHV, lower heating value; CV, caloric value; PAH, polycyclic aromatic hydrocarbon; TMAH, tetramethyl ammonium hydroxide; TPA, terephthalic acid; AIBN,
azoisobutylnitrile; RDF, refuse-derived fuel; HBL, hard burnt lime; PLA, poly(lactic acid); CSBR, conical spouted bed reactor; FCC, uid catalytic cracking; FTIR, Fourier-
transformed infrared; MAP, microwave assisted pyrolysis; VGO, vacuum gas oil; LCO, light cycle oil; PBD, polybutadiene; LPG, liqueed petroleum gas
n
Corresponding author. Tel.: 60 75535480; fax: 60 75581463.
E-mail address: norzita@cheme.utm.my (N. Ngadi).

http://dx.doi.org/10.1016/j.rser.2015.04.063
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
1168 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
3.3.1. Production of char from polymer pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Advances in analysis techniques in polymer pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Conclusion and recommendation for further studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
The invention of plastics is a major milestone that led to
improvement in the quality of the lives of human beings. Since
its rst synthesis in early 1900s, plastics have substituted many
types of materials such as wood, metals and ceramics in produc-
tion of consumer products, as they are light, durable, resistant to
corrosion by most chemicals, diversity of applications, ease to
processing and low cost. Other than the mentioned advantages of
plastics, studies have shown that plastic-based products are
responsible for reduction in cost of production in different elds
of human endeavor [1]. In transportation, for instance, the use of
plastic in manufacturing vehicles components and accessories
reduces the weight, hence the fuel consumption of vehicles.
Human's dependence on plastic-based materials is reected in
Table 1, which indicates the production of each type of plastic
in 2012.
In spite of the above mentioned benets derived from plastics,
environmental problems arise due to accumulation of plastic waste
from the onset of their invention. As plastic waste virtually does not
degrade, it occupies the landll space for hundreds years after their
disposal. According to World Bank [4], plastic waste accounted for
812% of total municipal solid waste (MSW) generated in different
countries all over the world. The actual percentage varies according to
the income level of the people in the country. It was also estimated
that global plastic waste generation in 2025 will increase to 913% of
total MSW, which again varies according to country. In order to reduce
the adverse effects brought by plastic waste, efforts have been made in
promoting recovery of plastic waste for recycling. In average, 50% of
the plastic waste generated in Europe is recovered, while the rest is
sent to landlls [1]. The high recovery rate is largely contributed by the
nations where partial or total ban is practiced in the landlling of high
caloric waste. However, it was also pointed out that all recycling
alternatives for plastic waste are currently more costly than landlling
and incineration (excluding energy recovery). Thus, alternatives with
more economical benets are needed to increase the involvement of
private companies in the plastic waste recycling.
The recycling processes have been categorized under four main
types, namely primary recycling (in-plant recycling), secondary
recycling (mechanical recycling), tertiary recycling (chemical recy-
cling), as well as quaternary recycling (energy recovery) [5]. How-
ever, each of these methods has its limitations and can be adopted
for different purposes to a certain extent. Among all the four
methods of recycling, only chemical recycling conforms to the
principles of sustainable development because it leads to the
formation of the raw materials from which the plastics are
originally made. Since chemical recycling process is able to recover
the energy content of the plastic in the form of liquid and gas, it is
increasingly gaining the attention of more researchers. Chemical
recycling may provide a solution towards the energy crisis. Since
industrial revolution, the world has been heavily dependent on
Table 1
Annual production of different plastics in 2012 [2,3].
Type of Plastic PE PP
Production (million tonnes) [2,3] 65.41 52.75
1177
1177
1178
1178
petroleum and natural gas resources in almost all activities,
especially power generation for industrial applications. In addition,
fossil fuels are still the main energy sources for vehicles, agriculture
and housing. However, petroleum is a non-renewable energy
source, and is expected to be depleted in a foreseeable future due
to heavy utilization for industrial activities as the only means of
large and cheap source of energy. In order to address the problem of
depleting fossil fuel, concerted efforts have been made to develop
affordable renewable energy, including solar energy, hydropower,
geothermal, wind and so forth. Such efforts are recognized by the
government of different countries and incentives were offered to
the developers in the form of feed-in tariffs [613]. Meanwhile, the
potentials of converting plastic waste to fuel is yet to be recognized,
although such potential had been discussed in a number of reviews,
as summarized in Table 2.
This review presented an articulated summary (concise review)
of the recent progress in production of fuels and chemicals from
virgin and post-consumer plastic waste, with the main focus in
pyrolysis, as well as co-pyrolysis of plastic waste with other
materials. The aim is to provide the reader with an in-depth
analysis with respect to the recycling techniques of biomass and
plastic solid waste (PSW) existing today and proposed techniques
likely to be popular in the foreseeable future. Herein, a concise
summary and comparison was made, in a tabular form, of the
different processes versus yield, parameters and rector types which
is a novel approach to review writing in the pyrolysis of
plastics waste.
2. Types of reactors and process design in plastic waste
pyrolysis
Over the past few decades scientists have discovered that in the
absence of oxygen, plastic, which consist of long chain polymer
chain, can be fragmented at high temperature to form oligomers.
The term pyrolysis was used to refer to such process, although it
normally refers to thermochemical decomposition of organic mate-
rials at high temperature in the absence of oxygen. In some context,
the term cracking is used instead of pyrolysis. Nowadays, it is a
common practice to differentiate thermal pyrolysis from catalytic
pyrolysis. The former refers to the decomposition of polymers due
to the application of heat alone, while the latter refers to the
processes where catalyst is utilized to alter the reaction mechanism
of pyrolysis, hence the products yield and composition. Some recent
studies focused on plastics waste pyrolysis using different processes
are shown in Table 3.
2.1. Batch and semi-batch reactor
In most researchers utilized batch or semi-batch reactors for
thermal and catalytic pyrolysis of virgin plastic, as well as post-
consumer plastic waste, as it is easy to control the process
parameters. Some of the important parameters that were identied
include reaction temperature, mass ratio of plastic:catalyst, and
reaction time. The temperatures used for the process ranged in
PVC PET PS EVA 300900 1C, and the reaction time 3090 min [21,29]. In case of
37.98 19.8 10.55 2.8
catalytic pyrolysis, mass ratio of reactant: catalyst varied from 30:1
to 2:1 was used to increase the product yield and selectivity [21,30].
 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180 1169

Table 2
List of reviews on plastic waste recycling.

Reference Year Major area of focus in review

[14] 2008
Successful processes for large scale pyrolysis of plastic waste
[15] 2009
[16] 2010 Kinetic modeling of thermal cracking and dynamic micro-pyrolysis of HDPE
[5] 2010 Factors that affect the performance of thermal and catalytic pyrolysis
[17] 2011 Different recycling processes of HDPE
[18] 2012 Development of catalysts used in polyolen cracking
[19] 2013 Effects on mechanical recycling on properties of recycled materials

Table 3
Designs of reactors and systems for polymer pyrolysis.

Type of reactor Type of materials References

Batch and semi-batch reactor Mixture of LDPE and PP [20,21]

PE [22-31]
PP [32,33]
MPW and MSW [34-44]

Fluidized bed reactor LDPE and PP [45]

PVC [46]
MPW and MSW [47-51]

Conical spouted bed reactor (CSBR) Virgin HDPE [52-55]

Mixture of virgin LDPE, HDPE and PP [56]

Fixed bed reactor PET [57]

PE [58]

Two stages pyrolysis system Virgin LDPE [59]

Agriculture greenhouse cover lm in Spain [60]
Refuse derived fuel from Malaysia Nuclear Agency [61]

Screw kiln reactor LDPE [62,63]

MPW [64]

Microwave assisted pyrolysis HDPE and toothpaste packaging [65]

HDPE waste, PP waste and tire [66]
PS waste from computer packing material [67]
PS waste and Makarwal coal [68]
Waste tire [69-71]

Pyrolysis in supercritical water Residual oil and LDPE [72]

Heavy oil and LDPE [73]

Fluid catalytic cracking (FCC) HDPE blended with gas vacuum oil (VGO) [74]
PB,PS, PS-polybutadiene (PBD) dissolved in light cycle oil (LCO) [75]
PS dissolved in benzene [76]
PE dissolved in toluene [77]
LDPE dissolved in commercial VGO [78,79]
Cracking of HDPE in phenol [80]

This ratio used was based on properties exhibited by the selected
catalysts.
It is also possible to perform catalytic pyrolysis on polymer waste
at low temperature (200275 1C) [20]. The reaction was carried out
in a locally manufactured reactor, with the volume of 1 l. The reactor
was added with a pressure valve. During the pyrolysis process, the
production of condensable vapor and fuel gases exerted pressure on
the pressure valve, and the valve opened at certain pressure to
release these products into condenser and collection system. Thermal
pyrolysis of LDPE bags at 275 1C produced 48.6 wt% of oil, 40.7 wt% of
gases, and 10.1% of char. This result was comparable to some thermal
pyrolysis process in batch reactor [22] and xed-bed reactor [81] in
laboratories. Catalytic pyrolysis of the polymer waste using zeolite at
255 1C, on the other hand, was able to produce 51.19 wt% of oil,
35.88 wt% of gases, and 12.50 wt% of waxes. The oil was identied to
be a mixture of hydrocarbons in the range of kerosene and petrol,
and could be used as fuel after upgrading. Although the reason of the
superior performance was not discussed by the author, further
examination on the reaction conditions revealed that the exertion
of pressure on the reaction system by the vapor and gases can be the
possible reason that increased the products yield at such low reaction
temperature. However, there are insufcient references in literature
of polymer pyrolysis regarding the effect of pressure on such
processes, hence further studies are needed to inspect such effect.
Nevertheless, this study also revealed the possibility that families and
households can participate in the recycling activity via smaller scale
pyrolysis reactor. This will greatly increase the rate of plastic waste
recycling, as the sorting, cleaning and pyrolysis of the plastic waste
can be carried out at homes or certain location in neighborhoods,
hence the transportation of plastic waste, storage and pretreatment
of the waste prior to the pyrolysis process at recycling plants can be
eliminated.
Among the studies on catalytic pyrolysis of polymer, the one
associated with azoisobutylnitrile (AIBN) as an initiator of plastic
pyrolysis is worth mentioned[82]. The use of AIBN produced higher
conversion of HDPE, LDPE and PP when compared to thermal and
even catalytic pyrolysis [17]. AIBN was also able to increase PET
conversion compared to catalytic pyrolysis. It was deduced that
AIBN forms radicals when heated, hence initiate pyrolysis via free
radical mechanism. Due to low cost of AIBN (compared to other
1170 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180

catalysts) and less harms it brings to the environment (it dissociates When continuous thermal pyrolysis was performed on plastic
during pyrolysis, hence no problem of spent catalyst), the use of waste at moderate temperature range in CSBR, waxes with high
AIBN in pyrolysis is worth more attention in future studies. selectivity was reported [56]. The study on waxes produced from
LDPE, HDPE and PP showed that they were rich in heavy cycle oil
(HCO) fraction compared to gasoline fraction and light cycle oil
2.2. Fluidized bed reactor
(LCO) fraction. However, the percentage of the latter fraction
increased with the pyrolysis temperature. It was also revealed that
Although pyrolysis of polymer waste in batch reactor is well
waxes that were produced at higher pyrolysis temperature had
studied, there are some drawbacks in its application in recycling
lower molecular weight compared to the waxes produced at lower
industry [53]. It is more favorable to develop a continuous pyrolysis
temperature, irrespective to the type of plastic which they were
process, as it does not require frequent materials charging and
produced from. This showed the existence of secondary and tertiary
restarting the process. In addition, continuous pyrolysis process is
reactions during thermal pyrolysis, producing more hydrocarbons
also less labor-intensive. Trials were using uidized bed reactors,
with shorter chains. The range of these short-chained products was
due to several advantages they possess, including excellent mixing
also narrowed, resulted in lower polydipersity index. This observa-
properties, as well as improved heat transfer from reactor to
tion demonstrated the ability of CSBR to produce wax with high
polymer, compared to batch reactors [46]. As polymer waste can
selectivity at high temperature. On the other hand, the waxes
be fed into reactor at constant temperature, it is possible to produce
produced at lower temperature were rich in parafns, but the
a narrower and more uniform spectrum of products by manipulat-
olens content increased with temperature. The wax is suitable to
ing the residence time of polymer waste in the reactor [45]. It is also
undergo upgrading process in FCC units to produce gasoline,
possible to periodically replace used catalyst with regenerated
naphtha and other commercial hydrocarbon fractions.
catalyst without halting the process [83]. However, care has to be
be taken to avoid bed deuidization, as this can easily when melted
2.4. Two-stage pyrolysis system
plastic stick on the uidized bed.
Following the development of catalysts, thermal pyrolysis became
Despite of the advantages mentioned in the CSBR pyrolysis, the
less attractive in plastic waste recycling. Nonetheless, Marcilla and
process tends to produce more wax rather than liquid and gaseous
Garca [79] thermally cracked the LDPEVGO blend in uidized bed
products. In order to improve the pyrolysis performance associated
reactor to study its effect towards the products distribution. The
with CSBR, a second reactor had been added to the existing reactor by
sample, consisted of 2 g of LDPEVGO blend and 10 g of sand, was
Artetxe et. al. for further cracking of waxes from CSBR. This was able to
pyrolyzed in 460 g of sand at 500 1C. The proportion of LDPE and
produce gases and liquids with reported yields similar to other
VGO were varied in the blend. From the result, the increase of LDPE
systems [84,85].
percentage in the blend increased the yields of dry gas and liqueed
Another two-stage pyrolysis system was designed by Aguado
petroleum gas (LPG). The main components in the product gas were
and Serrano [59], as shown in Fig. 2. In such design, the plastic
ethane and propene. Compared to the result given by Ng [74],
waste was rstly melted and thermally cracked in the reactor at the
thermal pyrolysis of polymer on a uidized bed could produce
bottom, and the vapor formed was then own upwards and reacted
higher degree of cracking (indicated by the ratio of dry gas/LPG)
with the catalyst on the xed bed reactor. Such design avoided the
compared to catalytic pyrolysis in a xed bed reactor. It is important
direct contact of the catalysts with melted plastic, which causes
to realize that the temperature prole difference produced distinct
several problems: difculty in catalyst recovery after pyrolysis
effect on the products distribution, especially those from the pyr-
process, and rapid deactivation of catalyst when contacted with
olysis of VGO oil. A decrease of the outlet temperature (denoted as T2
melted plastic, as well as impurities that are present. In such
in original paper) has signicantly lowered the yield of heavy
system, conversion of the polymer depended only on the tempera-
hydrocarbons. However, the effect became less signicant with the
ture of the thermal reactor. Complete conversion of LDPE in such
increase of LDPE in the blend. Synergetic effect was not observed in
system was achieved in 475 1C, together with high liquid yield, with
this study, most probably due to the absence of catalyst which
16% of the product being grouped in light species, while 41% in
altered the reaction route. Thus, the experimental gas yield agreed
gasoline fraction, and 40% in diesel fraction. The use of HZSM-5
with the theoretical yield, which was the addition of individual yield
zeolites in the reactor was able to increase the cracking of gasoline
from LDPE and VGO respectively. The condensable products, on the
to form more light species, due to the strong acidic sites that caused
other hand, showed a gradual decrease in yield with the increase of
high rate of cracking. Similar result was also obtained by the work
LDPE percentage in the blend. It is worth mentioned that without the
of San et al. [60], which investigated on the sequential pyrolysis and
use of catalyst, the pyrolysis of LDPEVGO mixture could have the
catalytic hydroreforming of waste agricultural lms, as well as work
products yield comparable to the catalytic pyrolysis [77,78]. When
by Miskolczi and Buyong [61], who studied on the thermal-catalytic
considering the reduction of costs in catalyst replacement and
pyrolysis system for refuse-derived-fuel (RDF). These studies
regeneration, this process might be feasible in term of economy.
demonstrated the feasibility of the two-stage thermo-catalytic
However, consideration from other aspects has to be taken into
reactors for the purpose of polymer pyrolysis to produce liquid
account.
products with the desired quality.

2.3. Conical spouted bed reactor (CSBR) 2.5. Microwave-assisted pyrolysis (MAP)

In order to avoid deuidization caused by melted plastic in
uidized bed reactor, the use of CSBR was proposed, as the vigorous
contact between different phases and collision between particles
reduced the chance of particle agglomeration in the bed materials.
The extremely short residence time of polymer materials in CSBR
(20 m s-1) is also important to avoid secondary reactions which lead
to formation of coke precursor [53]. Another advantage of CSBR
over other uidized bed reactor is lower pressure drop. The
schematic diagram of a CSBR is showed in Fig. 1.
Recently, microwave-assisted pyrolysis is receiving increasing
attention from researchers, due to several advantages it has over
the traditional pyrolysis, including faster heating rate and cost
effectiveness. One distinctive feature in MAP is the application of
microwave power on polymer materials, which is converted into heat
at a fast rate. It is possible to raise the reaction temperature up to
1000 1C in a short period of time in MAP using microwave absorber,
usually carbon material or metal [67]. The study on MAP started as
early as 2001, when Ludlow-Palafox and Chase [65] pyrolyzed the
 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
Fig. 1. Dimension of the conical spouted bed reactor (CSBR). Adapted with
permission from [47].
Fig. 2. Two-stage reactor system. Adapted with permission from [51].
HDPE and toothpaste packaging, which was a combination of
aluminum and PVC. It was found that the increase in reaction
temperature shortened the reaction time, but did not have much
effect on the products distribution. However, it is more important to
know that MAP was successfully applied to the Al/PVC mixture. PVC
1171
was pyrolyzed to form products with distribution similar to that of
HDPE [65], while aluminum was left in the reactor, which could be
separated easily from the carbon, the absorbent in the process.
Almost 100% aluminum recovery was reported in the study. Further
examination on the process revealed that higher microwave power
caused more efcient degradation of polymer [66]. The study showed
the possibility of MAP to convert commingled polymer waste that
cannot be separated from the impurities using manual sorting, which
is another advantage of MAP over traditional pyrolysis.
The shape of the absorbers plays important part in MAP, as it affects
the amount of heat generated from the microwave. Hussain and Khan
[67] studied the effect of shape difference for the aluminum metal in
the MAP of polystyrene. It was observed that when aluminum cane
was used in the pyrolysis, the microwave was reected instead of
absorbed, hence no pyrolysis occurred. However, when aluminum cane
was broken into pieces, pyrolysis occurred, indicated the change of
microwave to heat. When aluminum coil was used, the large surface
area of the coil and the repeated reections of the microwave inside
the coil greatly facilitated the pyrolysis process. The increase of coil
gauge size was also observed to increase the reaction temperature,
hence reduced the time needed for the pyrolysis process. The process
was able to yield 88% of liquid, 910% of gaseous product, and 23% of
coke, depending on the shape of coil. During the MAP process, a layer
of oxide was produced on the surface of aluminum coil, due to the
oxygen present in the reactor. This aluminum oxide was believed to act
as solid acid catalyst, and produced substituted aromatic compounds in
the liquid product. On the other hand, the gas collected contained
acetylene and some other alkene gases.
Microwave-assisted co-pyrolysis of waste PS with coal was also
reported to produce aromatic liquid products in narrow range, together
with acetylene and H2S as gaseous products [68]. Other than polymer
waste, MAP can also be used to produce fuels from agricultural waste
[86] and tire waste [6971]. Although there are several reviews on MAP
[87,88], more studies are needed to fully understand the performance
of MAP on different types of plastic waste, as well as the effect of
catalysts in MAP. The effect of interaction of different types of plastic
waste on the products distribution in MAP is also an important feature
to be explored.
2.6. Pyrolysis in supercritical water (SCW)
The use of sub-critical water (CW) system and supercritical
water system (SCW), which are usually used in cracking of heavy
oil [89], was also attempted in plastic recycling, as supercritical
water behaves as solvent and catalyst simultaneously in the
process [72,90]. The small hydrocarbons molecules formed during
polymer pyrolysis can easily disperse in SCW, hence the chance of
subsequent condensation and coke formation is reduced [73,91].
Excellent property of debromination was also discovered during
pyrolysis of brominated polymer waste [92,93]. The use of SCW in
polymer waste pyrolysis also produce negligible amount of NOx,
SOx and particulate emission [94].
On the other hand, the possibility of using CW and SCW system
in polymer pyrolysis was also studied by Bai, Zhu [72]. During
pyrolysis, the phase structure of residual oil/LDPE alternated
between liquid/liquid/solid three-phase structure and liquid/solid
two-phase structure. In former structure, partially miscible oil
phase and water phase were in dynamic equilibrium, and LDPE
was mostly suspended in the oil phase. In latter structure, oil
containing saturates, aromatics and resins formed a continuous
medium with CW or SCW, while asphaltene molecules were highly
dispersed. At high water densities (liquid/solid phase structure),
pyrolysis products from LDPE caused dealkylation of aromatic
radicals that were produced from asphaltenes, hence the coke-
inducing components were suppressed.
1172 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
Another study on similar process and system [73] revealed that
extension of reaction time resulted in improved liquid product
quality, but coke formation also increased. It was proposed that
coke was formed from condensed asphaltenes, which existed in
heavy oil itself, or formed from condensation of light oil fractions.
Further data comparison revealed that coke formation seemed to
be retarded at later reaction stage. Increased LDPE loading in co-
pyrolysis also caused reduction in coke formation and increased
aromatics formation. This is an evidence of LDPE as source of H in
co-pyrolysis. Due to donation of H from LDPE to pyrolysis inter-
mediates from heavy oil, condensation of the intermediates (that
caused coke formation) can be suppressed. It was also found that
release of LDPE oligomers was independent of heavy oil pyrolysis.
However, the H-donating effect from LDPE can only occur with
sufcient distribution of products from LDPE pyrolysis.
2.7. Fixed bed reactor
Although the use of xed bed reactor is more common in
pyrolysis of biomass waste [9597], there were few studies on
polymer pyrolysis using xed bed reactor alone. However, there
are several reports regarding combination of xed bed reactor
after thermal pyrolysis of polymer feed. It is also used extensively
in uid catalytic cracking, which is discussed in the next section.
2.8. Fluid catalytic cracking
Following the development of pyrolysis technology, there is a
need to develop continuous process for polymer pyrolysis before it
can be applied in scalable production in the industries. However,
one of the challenges faced is the continuous feeding of plastic
waste in solid form into the reactor. In order to solve this problem,
some researchers look into the possibility of dissolving plastic feed
in suitable solvent, followed by pyrolysis of the solution. Ng
[74,98] performed catalytic pyrolysis on HDPE resin pellets dis-
solved in the vacuum gas oil (VGO). The conversion of HDPE was
up to 77.4% (for 5 wt% HDPE concentration) and 52.4% (for 10 wt%
HDPE concentration) respectively. It was also discovered that
when the ratio of catalyst to oil (expressed as cat/oil afterwards)
increased, generally there was an increase in conversion and yield
of products (dry gas, liqueed petroleum gas, gasoline, light cycle
oil, heavy cycle oil and coke), although not in linear form. A
synergistic effect was also observed in the pyrolysis of HDPEVGO
(which is termed as HDPE-RZ in original paper), causing different
conversion of VGO under the presence of HDPE, compared to the
conversion of VGO alone under the same conditions.
The rationale of investigating the plastic dissolution in solvent
is to incorporate the tertiary recycling process in the uid catalytic
cracking (FCC) process in petroleum renery. In order to study the
viability of this idea, Arandes and Abajo [75] dissolved PP, PS, and
PS-PBD in the light cycle oil (LCO) which is used in a commercial
FCC unit. Almost complete conversion in thermal pyrolysis of the
plastics was observed at 550 1C, where gases, gasoline and cokes
were formed. PP tended to produce olens and isoparafns during
the thermal pyrolysis, while thermal pyrolysis of PS produced
mainly styrene, together with small amount of ethylbenzene,
toluene and benzene. The same observation was obtained for
thermal pyrolysis of PS-PBD. On the other hand, catalytic pyrolysis
using commercial catalyst produced almost the same products
yield for PS and PS-PBD, with only minor difference with respect
to certain products. Similar result was obtained when HZSM-5 [99]
and HY zeolites [100] were used as the catalysts in the reaction. It
was also discovered that the use of fresh catalyst did not produce
higher conversion compared to used catalyst, and higher acidity in
fresh catalyst caused higher coke formation.
The possible effect of solvents used to dissolve plastic was
studied by several researchers. It was shown that benzene did not
react with polymer or decompose to form hydrocarbon molecules
at temperature up to 550 1C [76]. On the other hand, when toluene
was used as solvent, it disproportionated to form benzene and
xylene, but did not react with polymer or its pyrolysis products
[77]. Another study using phenol as solvent indicated that the
polymer degradation was increased in the presence of phenol, as
phenoxy radicals formed during pyrolysis enhanced the pyrolysis
rate via free radical mechanism [80].
A more detailed study was carried out on the process mentioned
above, but with different solvent [78]. LDPE dissolved in vacuum gas
oil (VGO) at 2% and 6% was catalytically cracked using two equili-
brium catalysts, namely E-cat-M and E-cat-R. It was found that LDPE
conversion increased with temperature, and did not change much
with the LDPE concentration. However, difference in pyrolysis
behavior over different temperature suggested that the LDPE has
higher activation energy compared to VGO. Analysis on different
categories of products showed the increase of dry gas, LPG and
gasoline yield at 1012%. The coke formation also showed the same
trend, however, it was limited to 7.7% for E-cat-R, and thus it should
not affect the heat balance in the FCC unit. The study showed the
feasibility of the process to be adopted in FCC unit, but a detailed
study is required before it can be applied in a scalable production in
the industry.
The advantages of using uid catalytic cracking in polymer
pyrolysis include [101]:
a. Dissolution of plastic waste in the solvent increases its bulk
density, hence reduce the volume of the plastic waste prior to
the process.
b. The contaminants (labeling, dyes etc.) can be removed during
the dissolution stage, hence the negative effect by these
contaminants towards pyrolysis performance can be reduced.
c. Separation of mixed plastic to different components is believed
to be vital, as it is often reported that pyrolysis of single type of
plastic is higher than that for mixed plastic. It is possible to
separate mixed plastic waste to their components by using
selective dissolution as introduced by Papaspyrides and Poula-
kis [101]. This is possible as different plastic can only dissolve in
certain solvent at specied temperature range. This provides an
alternative over manual sorting of plastic waste that require
extra effort to separate by mechanical means (for example,
certain HDPE bottles that have caps or plastic labels which are
made of LDPE).
d. Value added activities for petroleum rening companies that
engaged in this type of plastics recycling.
However, some limitations are observed where large scale
application of this method is considered:
a. Pretreatment is needed to clear the contaminants in the
municipal plastic waste. To ensure the efciency of the process,
the presence of the contaminants has to be minimized during
the solvent recovery at the expense of other useful products
that can be extracted from the solution.
b. Since most solvents are volatile, dissolution process has to be
done with extra safety measures.
c. Since investigation of this method is somewhat novel with
limited research reports, the reaction data and the kinetic
models are not available yet, and this may cause considerable
difculties in reactor design.
d. Since the use of solvent was observed to affect the pyrolysis
mechanism, suitable solvent has to be selected to
ensure positive inuence towards the products yield and
distribution.
 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180 1173

Table 4
Product yields for pyrolysis different pyrolysis systems.

Type of reactor/ Type of materials Ref. Parameters Yield of gas (G), liquid (L), aqueous
system (A), wax (W) and solid(S)

Batch and semi- Mixture of LDPE and PP [21] H2, 400 1C, Ni/h-ZSM-5, 90 min 54% L
batch reactor
PE [29] 460 1C, H-ZSM5, 30 min 40% G, 55% L, 5% S
Cleaned PP waste [32] 360 1C, H-ZSM5, reaction proceed until no products evolved 2%G, 92% L, 6% S
PP [33] 430 1C, 60 min 4.3% G, 80.7% L, 6.1% S
PVC containing waste [50] 1dm3 N2/min, dechlorination at 300 1C using CaCO3 as 36.6% G, 62.4% L, 1% S
dechlorination agent, then heating to 500 1C
MSW [34] 500 1C, H-ZSM5, 5772 min 20% G, 19% L, 17% W, 44% S
MPW 35% G, 45% L, 21% S
MPW [38] 500 1C, no catalyst, 30 min 41.5%G, 53% L, 5.5% S
MSW rich in lm 65.7% L, 26.5% G, 7.8% S
MSW rich in paper 26% G, 35.1% L, 12.4% A, 26.6% S
MSW rich in glass 25.6% G, 40.9% L, 33.5% S
MSW rich in lm [39] 440 1C, ZSM-5, 30 min 49.9% G, 41.5% L, 8.6% S
MSW rich in paper 29.4% G, 25.5% L, 17.1% A, 28.1% S
MSW rich in glass 13.8% G, 39.2% L, 3.3% A, 43.7% S

Fluidized bed LDPE and PP [45] 680 1C, quartz sand as uidizing bed, product gas as uidizing 42.8% G, 56.7% L, 0.5% S
reactor gas
MPW [47] 360 1C, MCM-41 as catalyst bed, 570 ml N2/min 87.3% G, 5.6% L, 7.1% S
MPW [49] 677 1C, 6.7 g N2/min, quartz sand as uidized bed, no 35.3% G, 57.8% L, 6.9% S
dechlorination agent
Mixed polymer [102] 600 1C, hard burnt lime as uidizing bed, 5 L steam/min 43% G,49% L, 8% S

CSBR HDPE [53] 12 L N2/min, 500 1C, HY zeolite as catalyst bed, 1 g plastic/min 24.44% G, 72.56% L, 3% S
[52] N2, 650 1C, sand as uidizing bed, 1 g plastic/min 18% G, 46% L, 36% W
Mixture of virgin LDPE, HDPE and PP [56] 11 L N2/min, 450600 1C, sand as uidizing bed, 1 g plastic/ 100% W
min

Two stages HDPE (CSBR thermal cracking) [84] CSBR: 5 L N2/min, 500 1C, sand as uidized bed, 1 g plastic/ CSBR:1.5% G, 31.5% L, 67% W
pyrolysis min
system Cracking reactor: 900 1C After thermal cracking: 87% G, 13% L

[85] CSBR: 5 L N2/min, sand as uidized bed, 500 1C, 1 g plastic/ CSBR:1.5% G, 31.5% L, 67% W
min
Cracking reactor: H-ZSM5, 500 1C After catalytic cracking: 41% G, 59% L

MPW (Batch pyrolysis catalytic
cracking)
MSW (pyrolysis in tubular
reactor batch catalytic cracking)
[60] Reactor 1: 450 1C, 120 min After pyrolysis: not given
Reactor 2: N2, 450 1C, no catalyst After cracking: 18% G, 74% L, 8% S
[61] Reactor 1: 550 1C After pyrolysis: 10.2% G, 67.3% L, 4.1%
W, 18.4% S
Reactor 2: 450 1C, 45 min, FCC catalyst After cracking: 9.7% G, 74.6% L, 0.5% W,
15.2% S

Microwave HDPE and toothpaste packaging [65] 500 1C, reaction proceed till completion 19% G, 81% L, 100% recovery of metal
assisted
pyrolysis
HDPE waste [66] 40 min, 500 1C 34.4% G, 56.5% L, 9.1% S
PS waste [67] Temperature not specied,10 min 10% G, 88% L, 2% G
Pyrolysis in Residual oil and PE [72] 420 1C, 20 min 90% L, 10% S
supercritical
water
Heavy oil and LDPE [73] 420 1C, 30 min 85% L, 15% S
Fluid catalytic PS-polybutadiene (PBD) dissolved in [99] 450 1C, 3 s, H-ZSM5 4.2% G,54.6% L, 1.5% S
cracking (FCC) light cycle oil (LCO)
PS dissolved in benzene [76] 6.5 wt% polymer in benzene, FCC catalyst, 550 1C, retention 5.97% G, 94.03% L
time:9 s
PE dissolved in toluene [77] 2 wt% polymer in toluene, FCC catalys,500 C, retention 10.2% G, 84% L, 4.8% S
time:3 s
Cracking of HDPE blended with [80] 400 1C, 5 h 52.5% G, 43.5% L, 4% S
phenol

* The term solid include solid residue, char and coke that remained after pyrolysis.
* The term aqueous include water and hydrocarbons dissolved in it.
* All processes proceed in nitrogen atmosphere unless stated otherwise.

produced similar liquid yield within short retention time of

Table 4 compares the products yield of polymer pyrolysis in
different systems under different conditions.
It is clear that catalytic pyrolysis of PE in batch reactor produces
nearly 50% of liquid product, depending on the reaction para-
meters used. This value is comparable to the result obtained in
microwave pyrolysis. Thermal pyrolysis of PE in uidized bed
polymer in the reactor, most probably due to faster heat transfer
from uidized medium to polymer. However, performance of such
process is heavily dependent on process parameters, as indicated
by high uctuation in liquid products (4676%). Same observation
can be made regarding the use of the two-stage pyrolysis system,
where CBSR was used. The liquid yield can be improved up to 90%
1174 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
by pyrolysing PE in supercritical water, using suitable H-donor.
Another option to increase liquid yield in PE pyrolysis is to
perform uid catalytic cracking, which can produce liquid yield
of 94%.
Compared to PE, pyrolysis of MPW and MSW in batch reactors
resulted in lower liquid yield, and its actual value depends heavily
on the presence of other components in the waste. Similar trend
can be seen in the pyrolysis of MPW and MSW using different
systems. This effect can be minimized by two-stage pyrolysis that
retains undesired materials in the rst reactor. Although the liquid
yield for polymer pyrolysis can possibly be increased by using
other systems as listed in Table 2, more research is required to
verify the feasibility of the system operationally.
3. Production of fuels from polymer pyrolysis
3.1. Liquid from pyrolysis of single type of plastic
Although there are variations from different studies, it is generally
shown that pyrolysis of PE and PP produced mainly n-parafns and 1-
olens in liquid products via free radical mechanism (for thermal
pyrolysis) [103] or carbonium mechanism (for catalytic pyrolysis)
[104]. However, the carbon number of hydrocarbons in liquid product
depends heavily on reaction parameters, as well as the type of reactor
used. The presence of olens is generally undesirable, as they can
easily recombine with each other to form larger molecules, hence
causing difculty in industrial usage. This problem can be solved by
running pyrolysis in hydrogen atmosphere to convert olens to n-
parafns [21,105]. In hydrogen atmosphere, LDPE pyrolysis produces
more parafn instead of olens, with the help of suitable catalyst [21].
The double bonds in the products become saturated by the hydrogen
present, resulting in high yield of parafn. In addition, the hydrogen
atmosphere also prevents cyclo-parafn in the liquid product to form
aromatics. It is also reported that extending reaction time results in
higher volume of straight chain hydrocarbons. In order to enhance
the hydroreforming reaction, where hydrogen gas is used as carrier
gas in pyrolysis reactor, suitable catalysts are needed to provide
reaction sites for the unsaturated hydrocarbons. The liquid product
formed from polymer pyrolysis is suitable to be used as fuel in most
tropical climate regions, however, freezing problem might be encoun-
tered in colder regions [106]. After suitable upgrading, pyrolysis liquid
can be blended with commercial gasoline or diesel and used in
combustion engines [31].
Other than parafn production, the formation of aromatic com-
pounds was reported in pyrolysis of waste polymers that were
produced from straight chain monomers. Jung and Cho [45] studied
on pyrolysis of PE and PS, and the obtained liquid products contained
53% (for PP fraction) and 32% (for PE fractions) BTX compounds. The
aromatic compounds are also formed when polymers from aromatic
monomers are pyrolyzed. Cho and Jung [49] studied the thermal
pyrolysis of mixed plastic waste, and showed that the production of
Fig. 3. Pyrolysis of PET under acidic and basic conditions [1].
benzene, toluene and xylene (BTX) increased with reaction tempera-
ture. The highest yield of BTX compounds was recorded at 719 1C,
which was 18%. It was also found that the use of suitable catalyst
greatly enhanced the production of BTX compounds at lower
temperature compared to thermal pyrolysis. Aromatic compounds
are formed as a result of secondary reactions, as well as the shape
selectivity of the catalysts used in pyrolysis.
Recycling of post-consumer PET by mechanical means is well
developed in most countries [107]. However, Dimitrov et al. [57]
showed that it is possible to pyrolyze PET together with other type of
polymers. When pyrolyzed individually, PET can be converted to
different products, depending on the medium. When acidic con-
taminants present together with the waste PET, CO2/acetaldehyde,
benzoic acid and vinyloxycarbonyl benzoic acid are formed. On the
other hand, in the presence of tetramethyl ammonium hydroxide
(TMAH), which is a base, dimethyl terephthalate is formed, together
with trimethylamine and short chain alcohol, which are resulted
from the dissociation of TMAH. Different mechanisms involved in
PET pyrolysis are shown in Fig. 3. During pyrolysis in basic condition,
TMAH assisted in the bond cleavage and in the transesterication
process. The hydroxide anion attacked the carboxyl group in basic
conditions to produce hydroxyl and carboxyl end groups. However,
the base concentration in the PET sample also induced different
mechanism and degradation velocity. Hence, more in-depth studies
are needed to fully understand the underlying mechanisms involved.
On the other hand, studies by Kumagai and Grause [108,109]
indicated that terephthalic acid (TPA) can be formed from pyrolysis of
PET, and it can be converted to benzene in the presence of calcium
oxide (CaO) under suitable conditions. However, without careful
control of reaction condition, secondary reactions cause char forma-
tion. Hence, it is important to determine the desired reaction condi-
tion. Attempt was also made to recover benzene-rich oil and metals
(-Fe2O3, silver, anatase or TiO2, as well as Al) simultaneously, while
studying the possible effects of existing metals and polymer additives
in pyrolysis of PET-based waste (X-ray lm, magnetic tape, and prepaid
card) in the waste [110]. In steam atmosphere, the polymer compo-
nent in PET-metal composite underwent hydrolysis to form terephtha-
lic acid (TPA), and metals remained. Further decarboxylation of TPA by
calcium oxide resulted in formation of benzene and CaCO3. On the
other hand, gelatin in X-ray lm and dioctyl phthalate (DOP) as
plasticizer in PET waste were degraded to form acid, alcohol, aromatics
and parafn under reaction condition, hence their effect on the
reaction were negligible. Effect of silver (Ag) and maghemite
(-Fe2O3) in the reaction was also negligible. Addition of calcium
oxide into the pyrolysis system of PET-metal composite increased the
formation of benzene and CO2, due to the decomposition of TPA.
However, the comparatively low decomposition of TPA (79%) indicated
the need to improve the hydrolysis efciency. -Fe2O3 showed mild
catalytic effect, while silver and anatase were not able to catalyze the
formation of benzene. This study showed a plausible method to
recover useful materials from commingled plastic waste, which can
be tested on more similar waste.
 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180 1175

3.2. Liquid from co-pyrolysis of plastics with biomass
Other than plastic waste, it was also found that organic waste can
be converted to useful chemicals when pyrolyzed. Studies showed that
biomass can be a great source of renewable energy [911]. In addition,
biomass pyrolysis is also highly feasible [12]. The products from
biomass pyrolysis include hydrocarbons, carbon monoxide and hydro-
gen gas, which can be used to generate energy. However, there are
several drawbacks related to biomass pyrolysis, including production
of liquid with low caloric value compared to polymer pyrolysis. In
addition, the liquids are richer in oxygenated compounds, while
having lower hydrocarbon content [111]. Therefore, attempts had been
made to combine polymer and certain biomass in co-pyrolysis, with
the objective to improve the quality of the products formed. Numerous
studies, as listed in Table 5, pointed out the occurrence of positive
synergistic effects during co-pyrolysis. For instance, Liu and Hu [58]
discovered that presence of pubescens in LDPE pyrolysis increases the
gas yield at the expense of the oil yield, and the effect is enhanced by
addition of HZSM-5 catalyst into the mixture. This effect was more
pronounced when the zeolites was used in vapor phase contact mode.
The difference was possibly due to the difference in sequence of
catalytic reaction and interaction between biomass and plastic. The
intermediates' interaction also affected the oil quality in term of the
alkane, alkene and cyclo-parafn content.
In petroleum renery, the renery process produces different
types of fuels, depending on their boiling points. The process often
produces long-chained residues that are difcult to crack, and
having low commercial values. In order to determine the alter-
native uses of such products, pyrolysis was applied on the mixture
of PP, coals and petroleum residues [33]. High amount of liquid
products with boiling point range in 100480 1C was obtained. On
the other hand, pyrolysis of PP waste with Brazilian heavy oil [112]
produced liquid products similar to diesel and heavy vacuum gas
oil fractions in petroleum renery unit. Even coffee waste [95]
produced similar result. Pyrolysis of PE/PS/PP in petroleum residue
was also found to be effective in production of hexane soluble
materials [113]. All these studies showed that pyrolysis on mixture
of plastic waste and materials with low commercial values are able
to produce liquid fuels which have high commercial values.
One of the latest studies on co-pyrolysis of HDPE waste with
biomass waste and polylactic acid (PLA, well known biopolymer that
is derived from lactic acid) was done by Miskolczi [114]. It was found
that biomass waste and PLA waste, when pyrolyzed alone, produced
a lot of CO and CO2, which decreased the heating value of the product
gas. Even when the HDPE waste was pyrolyzed together with
biomass and PLA, the resulting vapor has far too low heating value
compared to that when it was pyrolyzed alone. However, increasing
reaction temperature was found to decrease CO2 level and increased
CO level, due to secondary cracking of product gas. On the other
hand, pyrolytic oil with 526 carbon atoms was obtained from the
pyrolysis. Although pyrolytic oil of PLA and biomass contained high
amount of oxygenated compounds, including phenol, the liquid
quality could be improved by the addition of HDPE and the increase
in reaction temperature. Aromatic compounds that presented in the
pyrolytic oil can be increased with temperature as well. By combining
HDPE together with LPA and organic waste in pyrolysis, the pyrolysis
temperature can be decreased.
Synergistic effect was observed in co-pyrolysis of different
biomasspolymer combination. Such effect can be veried when
the experimental yield or conversion of co-pyrolysis is higher than
the corresponding theoretical value, which is the summation of
yield or conversions for pyrolysis of individual component
[116,118,119,121]. It is hypothesized that one of the compounds
in the combination, either polymer or biomass [115], degraded at
lower temperature, hence produced radicals that initiated degra-
dation of another. In certain studies, synergistic effect was
observed in thermal co-pyrolysis of the mixture. However, catalyst
is needed to induce the effect in other cases [117]. It is also pointed
out that the synergistic effect can only be observed in pyrolysis of
certain biomasspolymer mixture [120].
The interaction of plastic waste and organic waste during
pyrolysis is an interesting issue, as it may increase the efciency
of plastic recycling process, if manipulated correctly, while adding
values to organic waste that otherwise has to be sent to landll.
However, as different types of organic waste interact with plastic
waste in different way, detailed studies have to be done to
determine the suitable biomass-polymer mixture that increases
the process performance and yield of desired products.
3.3. Liquids from pyrolysis of mixed plastics and municipal plastic
waste
Although there are many studies that indicate potential of pyrolysis
to be applied in single type of plastic, there are needs to understand
the performance of the process on mixture of different types of
plastics. Such understanding is important in plastic waste recycling,
where the plastic waste is processed as a whole to save the hassle of
plastic separation according to types. According to literature [32], the
products of PP and PVC pyrolysis are similar to that of PE. The
polymers depolymerize to form monomers and oligomers, which
then repolymerize to form larger aliphatic compounds. Another study
on pyrolysis of polymer mixture containing PP, PVC and PS reported
high aromatic content (470%) and unsaturated compounds (420%)
in liquid products, most probably caused by long reaction time and
high temperature used, as well as interaction between plastics [43].
The aromatic content consisted of styrene, toluene and ethylbenzene.

Table 5
Recent on co-pyrolysis of polymer and biomass.

Reference Year Combination of polymer and biomass

[58] 2010 LDPE/pubescens

[33] 2011 Coal/petroleum residue/PP
[112] 2011 PP/Brazilian oil
[95] 2013 PP/coffee waste
[113] 2009 PE/PS/PP/petroleum residue
[114] 2013 HDPE/organic waste/polylactic acid (PLA)
[115] 2014 HDPE/almond shell (AS)
[116] 2012 HDPE/oil shale from Tarfaya deposit in South Morocco
[72,73] 2013 LDPE/residual oil in supercritical water (CW) and sub-supercritical water (SCW)
[117] 2013 LDPE/cellulose
[118] 2014 PP and PE/Chi-Feng lignite (CF)
[119] 2014 PP/alder wood and soft wood
[120] 2013 Different combination of biomass (switchgrass, cellulose, xylan, lignin) and plastic (PET,PP, HDPE, LDPE, PS)
[121] 2014 Combination of pine sawdust and different plastics (PE, PP, PS)
1176 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
At higher temperature (600 1C), PAH formation was observed, which
caused the increase of aromatic content in products. Reaction time of
1530 min was sufcient to achieve desired conversion, with liquid
and gases products that are suitable to be used as fuel.
One potential problem identied in pyrolysis of PVC-containing
polymer waste is the production of chlorine compounds, espe-
cially hydrochloric acid. This causes corrosion to the pyrolysis
equipment, as well as lowering the viability of the liquid product
to be used as fuel [50,64]. Thus, it is important to eliminate any
possible chlorine content in the products through dechlorination.
There are several possible dechlorination methods [50]:
(1) Catalytic pyrolysis, where catalysts inhibits HCl formation in
pyrolysis. The use of ZSM-5 is sufcient for the purpose, but
the liquid product from pyrolysis using this method is heavier
in carbon number. This happened due to the reduced catalyst
activity caused by pore blockage.
(2) Use of HCl absorbents such as carbonates to prevent its
presence in pyrolysis products. The absorbent also exhibited
mere catalytic effect towards the pyrolysis.
(3) Stepwise pyrolysis, where the polymer waste is dechlorinated at
300 1C prior to pyrolysis. The release of HCl gas during dechlor-
ination can be captured and neutralized in the scrubbing tower.
The chance of catalyst deactivation can be reduced as it is not
involved in dechlorination step. When higher temperature and
longer reaction time was used for dechlorination, the liquid
products obtained were heavier in term of carbon number.
It was found that method (3) produced higher chlorine removal
compared to the others options [50]. This is supported by the
studies on dechlorination kinetics, which showed that 99.5 wt% of
HCl could be released at 300 1C when heated for 96 s, before the
degradation of main hydrocarbon chain started [46,51]. Another
dechlorination method is displayed by an operating plastic waste
recycling plant in Japan, where ammonia spray is used for cooling
of product gas while absorbing HCl gas [122]. Total elimination of
chlorine is reported in such case.
The ultimate goal of plastic waste pyrolysis is to present a
practical method in obtaining the useful chemicals or fuels from
plastic waste. However, there are many uncertainties involved when
pyrolysis is extended to municipal plastic waste, for example, the
possible interactions between different types of plastic among
themselves, or with the catalyst used in the process. The impurities
that present in the municipal waste, including dirt and sand, water,
metals, as well as glasses, can affect the pyrolysis process and its
products. These factors reduce the actual products yield, hence the
economic viability of plastic recycling through pyrolysis. In order to
gain further understandings on pyrolysis of municipal plastic waste,
various studies had been carried out as listed in Table 6.
Ate and Miskolczi [34] performed the pyrolysis on municipal
solid waste (MSW), as well as the municipal plastic waste (MPW)
Table 6
Recent studies in pyrolysis of MPW and MSW.
Reference Year Type of plastic used
[34] 2013 MSW and MPW from a Hungarian waste recycling plant
[37] 2012 MSW from a material recovery facility in Biskaia, Spain
[36] 2013 MSW from a material recovery facility in Biskaia, Spain
[35] 2013 MPW and MSW from a landll
[123] 2012 Mixture of PE, wood, paper
[124] 2009 Waste plastic from agricultural and packaging plant
[125] 2011 MSW from a waste treatment plant
[126] 2009 Mixture of different plastics (PET,HDPE, LDPE and PP) with PS
[127] 2014 Mixture of PE,PVC, PS
that is separated from the MSW. Seven catalysts that are normally
used in plastic pyrolysis were tested, which was performed at 500
600 1C in the nitrogen environment. When compared to MSW, the
full pyrolysis of MPW took less time at the same temperature and
using the same catalyst. This is due to the decrease in catalysts
ability by the impurities present in the MSW, mainly water. The
reported result is different from other work [128], which stated that
the water presence enhanced catalytic activity in biomass or MSW
pyrolysis. In terms of products distribution, MSW pyrolysis pro-
duces compounds that are normally resulted from the pyrolysis of
biomass, in addition to that from MPW. For example, the pyrolysis
gas from MSW contains high percentage of CO and CO2 (20.43% and
41.52% respectively at 500 1C), which are not present in pyrolysis
gas from MPW. This was mostly due to cellulose-containing
materials in MSW, including paper. These cellulosic materials also
increased the CO2 yield in the product gas, besides causing forma-
tion of water layer in addition to oil layer. Other researchers also
reported the same result [36,37]. On the other hand, the pyrolysis
liquid from the MPW consisted of mainly alkanes and alkenes,
while that from MSW also contained the same compounds, added
with oxygenated products (aldehydes, ketones, acids, phenols,
furfural etc.) that were derived from biomass. In term of char
formation, the MSW pyrolysis produced more char, again caused by
the paper and biomass (vegetable) in MSW. The same observation
was made in other studies [35,123].
There is less literature regarding the role of PS during pyrolysis.
Siddiqui and Redhwi [126] showed that PS has higher degree of
degradation among different types of plastics. It has been shown
to degrade almost completely under pyrolysis conditions used
(430440 1C, 5.56 MPa, reaction time 60 min, 1 wt% catalyst),
while PP and PET produced medium to high conversion. In
comparison, LDPE and HDPE produced low conversion. Thus,
pyrolysis of PS combined with other plastic were attempted to
increase the conversion. Plastics mixture ratio of 1:1 was able to
give highest conversion when compared to other ratios. The same
observation on effect of PS towards pyrolysis rate was also made in
another work [127]. In term of composition, the liquid product
consisted mainly benzene, styrene and their oligomers from PS, as
well as aliphatic compounds from LDPE, HDPE and PP. However,
how PS affect the pyrolysis mechanism is still a mystery, and more
studies are needed to gure it out.
The effect of metals present in MSW on plastic waste pyrolysis
was also studied [38]. Thermal pyrolysis was done on municipal
plastic waste, which contained different polymers and impurities,
in order to study the inuence of raw material composition on the
products distribution. The process was carried out at 500 1C in
nitrogen atmosphere. Their study showed that the presence of
metal in the plastic waste pyrolysis causes formation of more
aromatics, due to its catalytic property. This was supported by the
work of Gorghiu and Jipa [129]. When ZSM-5 was used in the
pyrolysis of the same feed, the catalyst activity was largely
suppressed by the presence of the impurities and waste produced
from the reaction. In order to solve this problem, a stepwise
pyrolysis was proposed, where the real municipal plastic waste is
heated at 300 1C for 60 min before entering the pyrolysis reactor.
This step was able to greatly reduce the water and chlorine
content of the nal pyrolysis product. The liquid that was pro-
duced the heating process had similar composition to the bio-oils
that were normally produced by biomass pyrolysis, and suitable
application could be developed for the liquid based on existing
technologies [39].
Studies were also conducted to produce fuels from unsorted MSW
through pyrolysis, as it requires less labor in waste segregation. For
instance, Velghe and Carleer [125] performed fast pyrolysis and slow
pyrolysis on waste collected from a waste treatment plant in Belgium.
The waste, consisted of disposed carpet, cartons residues, paper waste
 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
and synthesis materials, was dried before pyrolysis. Slow pyrolysis was
done for 2 h at heating rate of 4 1C/min to 550 1C, while fast pyrolysis
was done in few seconds at temperature of 450550 1C. For slow
pyrolysis, production of solids was reported, together with the
pyrolysis liquid, which was then separated into oily product and water
rich phase. On the other hand, fast pyrolysis produced oily product
and waxy compound due to short reaction time. As there was
insufcient energy to break all the bonds, the wax contained mostly
long chain hydrocarbons. It was shown that hydrocarbon gas can be
produced in the pyrolysis, with lower heating value (LHV) up to 45 MJ/
Nm3. However, the metals presented in the waste appeared in the oils
formed, thus further treatment for removal is required in order to
increase its viability to be used as fuel. The study showed that when
segregation step was skipped before the pyrolysis, the products could
be polluted by unwanted compounds, especially metals. However,
segregation step usually requires a lot of manpower (for manual
sorting) or energy (for automatic sorting system), thus a balance has to
be achieve between cost saving and products quality.
It is revealed from the mentioned reports that impurities affect
the outcome of plastic waste pyrolysis to a certain degree. As it is
difcult to obtain totally cleaned plastic waste from waste genera-
tion sources, a carefully planned collection method can effectively
reduce the content of impurities, hence the effects they bring to
pyrolysis. It was shown that with selective collection and proper
washing, the plastic waste can be catalytically pyrolyzed to produce
considerable amount of light oil and gasoline [124]. As the polymer
waste used was collected from agricultural source, there were some
elements that presented in fertilizers, including calcium, sulfur,
nitrogen, phosphorus, that remained on the polymer when entering
the pyrolysis unit, and these elements constituted the contaminants
in the products, especially in light and heavy oil fractions. Although
the catalyst used in this study, namely ZSM-5, was able to reduce
the amount of the contaminants in the products, the deterioration
of the products' quality by these elements was still signicant. The
nding again showed the possibility of contaminants to affect the
quality of the polymer pyrolysis products, thus more efcient
pretreatment methods are required to clean the contaminants of
the polymer products prior to pyrolysis. Collection of the waste
from specic sources could be one of the solutions, as it narrows the
type of impurities present on the waste, and enables specic
pretreatment steps to be applied accordingly.
Pyrolysis of plastic mixture on the hard burnt lime (HBL) and
silica bed in the presence of steam was carried out [102] to study
the possible catalytic effect by HBL. When SiO2 (as reference
material) was used as catalyst bed, products included 36 wt%
wax, 45 wt% oil, 19 wt% gas, at 600 1C. Styrene from PS was the
compound with highest percentage despite of various tempera-
ture and uidizing media used. Use of steam and increase in
temperature both increased the gases yield. When HBL was used
as catalyst bed, pyrolysis of the plastic mixture at 600 1C under
steam ow produced less wax (10%) compared to the process on
SiO2 bed. Furthermore, calcium oxide modied the oil composi-
tion, due to its ability to catalyze degradation of PET. However, its
limited catalytic ability has to be compensated by the use of high
reaction temperature.
In short, pyrolysis of single type of plastic is considerably well
understood by researchers based on the previous studies. However,
when the process was extended to plastic mixtures, it was found
that the products yield often deviate from expectation, due to the
interaction among different types of plastics. When impurities
(glass, biomass, waster etc.) are present in the plastic waste, the
oxygen atoms contained in them can lead to production of aqueous
phase and oxygenated compounds in the products. Thus, separation
of impurities, especially paper waste and metal, from the plastic
waste, is required to increase the efciency of the process.
1177
3.3.1. Production of char from polymer pyrolysis
As most polymer pyrolysis produce char, the possibility of using
it as another energy source can be considered. In a recent study
conducted by Jamradloedluk and Lertsatitthanakorn [130] to
characterize the char formed from the fast pyrolysis of HDPE
waste, they reported that the char consisted mainly C and H, with
caloric value 4500 cal/g, which is lower than the caloric value of
most plastics, as well as char from gasication. When activated in
air at 900 1C for 3 h, porous structure was observed in char,
evidenced by 55% and 44% increase in BET surface area and
specic pore volume respectively. Undesirable combustion beha-
vior was observed when the char was used as burning fuel.
However, the potential application of char as activated carbon
has to be further studied. In order to modify the combustion
behavior of the char, co-pyrolysis of HDPE waste with organic
material is suggested. It is presumed that the mixing of organic
matter with plastic char can have a stabilizing effect on the char
morphology and prevent its melting during combustion. Char
formed from fast pyrolysis of other types of plastics can be studied
and compared.
4. Advances in analysis techniques in polymer pyrolysis
On the studies of polymer pyrolysis, various techniques are
required to characterize the pyrolysis products. Some of the widely
used techniques include gas chromatography coupled with different
types of detector (MSD, TCD, or FID), thermogravimetric analysis
(TGA) and Fourier-transform infrared (FTIR) etc. Recently, the use of
coupling technique is getting popular in product identication and
analysis of pyrolysis kinetics. For example, Singh and Wu [131]
identied and characterized the volatile species produced from
different materials using TGAFTIR and TGAMS technique. The
samples tested included RDF sample from Malaysian Nuclear Agency,
waste tire rubber (WTR), pine wood waste (PW), as well as municipal
plastic waste (MSW). Good repeatability and agreement between the
results of TGAMS and TGAFTIR was observed. Thermograms of
TGAFTIR and TGAMS provided information on products formation,
major thermal events, as well as reaction kinetics of the process.
However, there were certain limitations on data provided by both
techniques, as they could be easily affected by interference. Careful
interpretation is needed in order to make the technique more useful.
In characterizing pyrolysis, methods or techniques to identify and
correct the possible errors and peaks masking in the thermogram
have to be developed. The possibility of developing TGAFTIRMS
has to be studied to facilitate simpler method in characterizing
pyrolysis.
Another interesting approach in characterizing pyrolysis process
is presented by Wang and Chen [132]. In their work, morphological
changes during pyrolysis of PE/PP waste was observed using Infrared
(IR) camera in order to study the effect of impurities on the pyrolysis
behavior. It was observed that polymer pyrolysis undergoes several
steps: melting, bubbling, and ash deposition. Two parameters that
were used to relate the captured images to the pyrolysis behaviors
are pixel area (PA) and bubble ratio (BR). In melting stage, PA
increased while BR decreased. During bubbling, the bubble ratio
started to increase, corresponding to increase rate of bubbling inside
the melted polymer. BR decreased at the same time. As the polymer
was converted to gaseous products, BR started to decrease, while PA
increased. During ash deposition stage, BR started to increase again,
corresponding to ash formation stage. At the end of ash deposition,
BR decreased to zero, as all the volatile compounds had evaporated.
On the other hand, PA increased during ash deposition stage until a
constant value, corresponding to the area of the ash. Impurities
seemed to have less effect on the morphological changes during
1178 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
pyrolysis; however deuidization on the impurities may cause it to
mix with the gaseous products during collection, hence increase
difculty in products purication. Such technique is suitable to
monitor instantaneous changes of pyrolysis process, but its applica-
tion on pyrolysis of mixed plastic waste or municipal solid wastes can
be difcult, as the presence of multiple items hinder clear observa-
tion of the process. Therefore, modication is needed for its applica-
tion under different circumstances.
5. Conclusion and recommendation for further studies
The advances in research on polymer waste pyrolysis are
leading to the commercialization of the technology. There are a
number of companies in many countries, including India, Taiwan,
Malaysia [133], Japan [134], and Thailand [135], that is currently
adopting, or considering the adoption of pyrolysis technology in
waste management plan. In addition, there are private companies
that are providing expert services on pyrolysis technology to their
customers in different countries [136138]. There is a high prob-
ability that polymer pyrolysis programs will be incorporated into
the national waste management plans for many countries in the
coming future due to the obvious advantages. In this paper,
different methods of converting plastic waste to fuel with high
caloric value have been reviewed with a view to solving the
problem of conventional fossil fuel shortage and the environmen-
tal degradation effect of plastic waste. Since pyrolysis of plastic
waste is able to produce liquid products that can be used as fuel,
there is a high potential for the process to be adopted in recycling
industry. However, there are still many underlying issues to be
resolved and the main issue lies in the quality of the liquid fuel,
which is mainly inuenced by the choice of catalyst. In order to
obtain liquid products that are suitable to replace fossil fuel,
especially in the range of gasoline and diesel, there is a need to
search for catalysts that possess lower acidity, yet producing high
conversion.
There are also many factors, including condition of plastic waste,
presence of impurities in the plastic waste, and types of reactors,
which inuence the mechanism of the catalytic pyrolysis, and
subsequently the products yield and distribution, as highlighted in
this paper. Thus, the effects of all these factors must be known and
controlled precisely to ensure the viability of the process. Another
challenge is to develop the standards for the processes and products
for post-consumer recycled plastics and to adopt the more
advanced pyrolysis technologies as highlighted in this article.
Furthermore, while it is possible to produce satisfactory product
yield and composition in laboratory scale, it will be a challenge for
the industrial developers to maintain the desired result when
scaling up the polymer pyrolysis. If these challenges are resolved,
cheap partial replacement of the depleting fossil fuel, together with
the reduction of plastic waste that is currently the main issue in
environmental pollution and reduction of crude fuel import will be
achieved.
Although microwave-assisted pyrolysis is another possible
solution to the problem, especially in the treatment of com-
mingled plastic waste, this relatively new concept require more
studies on its feasibility to be applied in recycling of commingled
plastic waste. On the other hand, dissolution of plastic waste in
compatible solvent prior to catalytic pyrolysis might serve as
solution to current existing problems in this eld, thus more
research is required to study the process in depth. Further analysis
would help reduce the capital investment and also the operating
cost and thus would enhance the economic viability of the process.
Further studies are required to improve the quality of the liquid
products obtained from pyrolysis process, before it can be used as
a substitution of conventional fuel.
This review is limited to the performance of pyrolysis applied to
different polymers in different types of reactors. However, there are
other issues that must be considered in studying polymer pyrolysis.
One of such issues includes the effects of the catalysts, especially
metal-impregnated catalysts, on the process performance. In addi-
tion, the study of the kinetics of plastic pyrolysis is also important
for process design purposes. In this context further studies are
required for a thorough understanding of the polymer pyrolysis.
References
[1] Sartorius I. Materials case study 4: plastics. OECD Global Forum on Environ-
ment. Mechelen, Belgium: OECD Environment Directorate, OECD; 2010.
[2] Sagel E. Polyethylene global overview; 2012.
[3] Anonymous. Research and markets: China's ethylene vinyl acetate (EVA)
Industry, 20132017. Business Wire; 2013.
[4] Hoornweg D, Bhada-Tata P. What a wastea global review of solid waste
management. The World Bank; 2012.
[5] Panda AK, Singh RK, Mishra DK. Thermolysis of waste plastics to liquid fuel: a
suitable method for plastic waste management and manufacture of value added
productsa world prospective. Renew Sustain Energy Rev 2010;14:23348.
[6] Wong SL, Ngadi N, Abdullah TAT, Inuwa IM. Recent advances of feed-in tariff
in Malaysia. Renew Sustain Energy Rev 2015;41:4252.
[7] Chua SC, Oh TH, Goh WW. Feed-in tariff outlook in Malaysia. Renew Sustain
Energy Rev 2011;15:70512.
[8] Tongsopit S, Greacen C. An assessment of Thailand's feed-in tariff program.
Renew Energy 2013;60:43945.
[9] Ming Z, Ximei L, Na L, Song X. Overall review of renewable energy tariff
policy in China: evolution, implementation, problems and countermeasures.
Renew Sustain Energy Rev 2013;25:26071.
[10] Cherrington R, Goodship V, Longeld A, Kirwan K. The feed-in tariff in the
UK: a case study focus on domestic photovoltaic systems. Renew Energy
2013;50:4216.
[11] Wang KM, Cheng YJ. The evolution of feed-in tariff policy in Taiwan. Energy
Strategy Rev 2012;1:1303.
[12] Mabee WE, Mannion J, Carpenter T. Comparing the feed-in tariff incentives
for renewable electricity in Ontario and Germany. Energy Policy 2012;40:
4809.
[13] Rigter J, Vidican G. Cost and optimal feed-in tariff for small scale photovoltaic
systems in China. Energy Policy. 2010;38:69897000.
[14] Aguado J, Serrano DP, Escola JM. Fuels from waste plastics by thermal and
catalytic processes: a review. Ind Eng Chem Res 2008;47:798292.
[15] Al-Salem SM, Lettieri P, Baeyens J. Recycling and recovery routes of plastic
solid waste (PSW): a review. Waste Manag (Oxford) 2009;29:262543.
[16] Al-Salem SM, Lettieri P, Baeyens J. The valorization of plastic solid waste
(PSW) by primary to quaternary routes: from re-use to energy and chemi-
cals. Prog Energy Combust Sci 2010;36:10329.
[17] Kumar S, Panda AK, Singh RK. A review on tertiary recycling of high-density
polyethylene to fuel. Resour, Conserv Recycl 2011;55:893910.
[18] Serrano DP, Aguado J, Escola JM. Developing advanced catalysts for the
conversion of polyolenic waste plastics into fuels and chemicals. ACS Catal
2012;2:192441.
[19] Hamad K, Kaseem M, Deri F. Recycling of waste from polymer materials: an
overview of the recent works. Polym Degrad Stab 2013;98:280112.
[20] Shah SH, Khan ZM, Raja IA, Mahmood Q, Bhatti ZA, Khan J, et al. Low
temperature conversion of plastic waste into light hydrocarbons. J Hazard
Mater 2010;179:1520.
[21] Escola JM, Aguado J, Serrano DP, Garca A, Peral A, Briones L, et al. Catalytic
hydroreforming of the polyethylene thermal cracking oil over Ni supported
hierarchical zeolites and mesostructured aluminosilicates. Appl Catal B:
Environ 2011;106:40515.
[22] Marcilla A, Beltrn MI, Navarro R. Evolution of products during the
degradation of polyethylene in a batch reactor. J Anal Appl Pyrolysis
2009;86:1421.
[23] Miskolczi N. Co-pyrolysis of petroleum based waste HDPE, poly-lactic-acid
biopolymer and organic waste. J Ind Eng Chem 2013;19:154959.
[24] Covarrubias C, Gracia F, Palza H. Catalytic degradation of polyethylene using
nanosized ZSM-2 zeolite. Appl Catal A: Gen 2010;384:18691.
[25] Lee JY, Park SM, Saha SK, Cho SJ, Seo G. Liquid-phase degradation of
polyethylene (PE) over MFI zeolites with mesopores: effects of the structure
of PE and the characteristics of mesopores. Appl Catal B: Environ 2011;108
109:6171.
[26] Jan MR, Shah J, Gulab H. Catalytic degradation of waste high-density
polyethylene into fuel products using BaCO3 as a catalyst. Fuel Process
Technol 2010;91:142837.
[27] Rasul Jan M, Shah J, Gulab H. Degradation of waste high-density polyethy-
lene into fuel oil using basic catalyst. Fuel 2010;89:47480.
[28] Shah J, Jan MR, Mabood F, Jabeen F. Catalytic pyrolysis of LDPE leads to
valuable resource recovery and reduction of waste problems. Energy Convers
Manag 2010;51:2791801.
 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
[29] de Marco I, Caballero BM, Lpez A, Laresgoiti MF, Torres A, Chomn MJ.
Pyrolysis of the rejects of a waste packaging separation and classication
plant. J Anal Appl Pyrolysis 2009;85:38491.
[30] Renzini MS, Lerici LC, Sedran U, Pierella LB. Stability of ZSM-11 and BETA
zeolites during the catalytic cracking of low-density polyethylene. J Anal
Appl Pyrolysis 2011;92:4505.
[31] Sharma BK, Moser BR, Vermillion KE, Doll KM, Rajagopalan N. Production,
characterization and fuel properties of alternative diesel fuel from pyrolysis
of waste plastic grocery bags. Fuel Process Technol 2014;122:7990.
[32] Sarker M, Rashid MM, Molla M. Waste polypropylene plastic conversion into
liquid hydrocarbon fuel for producing electricity and energies. Environ
Technol 2012;33:270921.
[33] Ali MF, Ahmed S, Qureshi MS. Catalytic coprocessing of coal and petroleum
residues with waste plastics to produce transportation fuels. Fuel Process
Technol 2011;92:110920.
[34] Ate F, Miskolczi N, Borsodi N. Comparision of real waste (MSW and MPW)
pyrolysis in batch reactor over different catalysts. Part I: Product yields, gas
and pyrolysis oil properties. Bioresour Technol 2013;133:44354.
[35] Miskolczi N, Ate F, Borsodi N. Comparison of real waste (MSW and MPW)
pyrolysis in batch reactor over different catalysts. Part II: Contaminants, char
and pyrolysis oil properties. Bioresour Technol 2013;144:3709.
[36] Adrados A, De Marco I, Lopez-Urionabarrenechea A, Caballero BM, Laresgoiti
MF. Pyrolysis behavior of different type of materials contained in the rejects
of packaging waste sorting plants. Waste Manag (Oxford) 2013;33:529.
[37] Adrados A, de Marco I, Caballero BM, Lpez A, Laresgoiti MF, Torres A.
Pyrolysis of plastic packaging waste: a comparison of plastic residuals from
material recovery facilities with simulated plastic waste. Waste Manag
(Oxford) 2012;32:82632.
[38] Lpez A, de Marco I, Caballero BM, Laresgoiti MF, Adrados A. Pyrolysis of
municipal plastic wastes: inuence of raw material composition. Waste
Manag (Oxford) 2010;30:6207.
[39] Lpez A, de Marco I, Caballero BM, Laresgoiti MF, Adrados A, Torres A.
Pyrolysis of municipal plastic wastes II: inuence of raw material composi-
tion under catalytic conditions. Waste Manag (Oxford) 2011;31:197383.
[40] Miskolczi N, Borsodi N, Buyong F, Angyal A, Williams PT. Production of
pyrolytic oils by catalytic pyrolysis of Malaysian refuse-derived fuels in
continuously stirred batch reactor. Fuel Process Technol 2011;92:92532.
[41] Lpez A, de Marco I, Caballero BM, Adrados A, Laresgoiti MF. Deactivation
and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes.
Waste Manag (Oxford) 2011;31:18528.
[42] Lpez A, de Marco I, Caballero BM, Laresgoiti MF, Adrados A, Aranzabal A.
Catalytic pyrolysis of plastic wastes with two different types of catalysts:
ZSM-5 zeolite and red mud. Appl Catal B: Environ 2011;104:2119.
[43] Lpez A, de Marco I, Caballero BM, Laresgoiti MF, Adrados A. Inuence of
time and temperature on pyrolysis of plastic wastes in a semi-batch reactor.
Chem Eng J 2011;173:6271.
[44] Lopez-Urionabarrenechea A, de Marco I, Caballero BM, Laresgoiti MF,
Adrados A. Catalytic stepwise pyrolysis of packaging plastic waste. J Anal
Appl Pyrolysis 2012;96:5462.
[45] Jung S-H, Cho M-H, Kang B-S, Kim J-S. Pyrolysis of a fraction of waste
polypropylene and polyethylene for the recovery of BTX aromatics using a
uidized bed reactor. Fuel Process Technol 2010;91:27784.
[46] Yuan G, Chen D, Yin L, Wang Z, Zhao L, Wang JY. High efciency chlorine
removal from polyvinyl chloride (PVC) pyrolysis with a gasliquid uidized
bed reactor. Waste Manag (Oxford) 2014;34:104550.
[47] Huang W-C, Huang M-S, Huang C-F, Chen C-C, Ou K-L. Thermochemical
conversion of polymer wastes into hydrocarbon fuels over various uidizing
cracking catalysts. Fuel 2010;89:230516.
[48] Donaj PJ, Kaminsky W, Buzeto F, Yang W. Pyrolysis of polyolens for
increasing the yield of monomers' recovery. Waste Manag (Oxford)
2012;32:8406.
[49] Cho M-H, Jung S-H, Kim J-S. Pyrolysis of mixed plastic wastes for the
recovery of benzene, toluene, and xylene (BTX) aromatics in a uidized bed
and chlorine removal by applying various additives. Energy Fuels
2009;24:138995.
[50] Lpez A, de Marco I, Caballero BM, Laresgoiti MF, Adrados A. Dechlorination
of fuels in pyrolysis of PVC containing plastic wastes. Fuel Process Technol
2011;92:25360.
[51] Yuana.G, Chena.D, Yina L, Wang Z, Zhaob L, Wang JY. High efciency of hcl
removal from waste plastics pyrolysis with a gas-uidized reactor. The 1st
IWWG-ARB Symposium. Hokkaido University Japan; 2013.
[52] Elordi G, Olazar M, Lopez G, Artetxe M, Bilbao J. Product yields and
compositions in the continuous pyrolysis of high-density polyethylene in a
conical spouted bed reactor. Ind Eng Chem Res 2011;50:66509.
[53] Elordi G, Olazar M, Lopez G, Amutio M, Artetxe M, Aguado R, et al. Catalytic
pyrolysis of HDPE in continuous mode over zeolite catalysts in a conical
spouted bed reactor. J Anal Appl Pyrolysis 2009;85:34551.
[54] Castao P, Elordi G, Olazar M, Aguayo AT, Pawelec B, Bilbao J. Insights into
the coke deposited on HZSM-5, H and HY zeolites during the cracking of
polyethylene. Appl Catal B: Environ 2011;104:91100.
[55] Elordi G, Olazar M, Aguado R, Lopez G, Arabiourrutia M, Bilbao J. Catalytic
pyrolysis of high density polyethylene in a conical spouted bed reactor. J
Anal Appl Pyrolysis 2007;79:4505.
[56] Arabiourrutia M, Elordi G, Lopez G, Borsella E, Bilbao J, Olazar M. Character-
ization of the waxes obtained by the pyrolysis of polyolen plastics in a
conical spouted bed reactor. J Anal Appl Pyrolysis 2012;94:2307.
1179
[57] Dimitrov N, Kratol Krehula L, Ptiek Siroi A, Hrnjak-Murgi Z. Analysis of
recycled PET bottles products by pyrolysis-gas chromatography. Polym
Degrad Stab 2013;98:9729.
[58] Liu W, Hu C, Yang Y, Tong D, Li G, Zhu L. Inuence of ZSM-5 zeolite on the
pyrolytic intermediates from the co-pyrolysis of pubescens and LDPE. Energy
Convers Manag 2010;51:102532.
[59] Aguado J, Serrano DP, San Miguel G, Castro MC, Madrid S. Feedstock
recycling of polyethylene in a two-step thermo-catalytic reaction system. J
Anal Appl Pyrolysis 2007;79:41523.
[60] San Miguel G, Serrano DP, Aguado J. Valorization of waste agricultural
polyethylene lm by sequential pyrolysis and catalytic reforming. Ind Eng
Chem Res 2009;48:8697703.
[61] Miskolczi N, Buyong F, Angyal A, Williams PT, Bartha L. Two stages catalytic
pyrolysis of refuse derived fuel: production of biofuel via syncrude. Bioresour
Technol 2010;101:888190.
[62] Serrano DP, Aguado J, Escola JM, Garagorri E. Conversion of low density
polyethylene into petrochemical feedstocks using a continuous screw kiln
reactor. J Anal Appl Pyrolysis 2001;5859:789801.
[63] Aguado J, Serrano DP, Escola JM, Garagorri E. Catalytic conversion of low-
density polyethylene using a continuous screw kiln reactor. Catal Today
2002;75:25762.
[64] Fukushima M, Wu B, Ibe H, Wakai K, Sugiyama E, Abe H, et al. Study on
dechlorination technology for municipal waste plastics containing polyvinyl
chloride and polyethylene terephthalate. J Mater Cycles Waste Manag
2010;12:10822.
[65] Ludlow-Palafox C, Chase HA. Microwave-induced pyrolysis of plastic wastes.
Ind Eng Chem Res 2001;40:474956.
[66] Undri A, Rosi L, Frediani M, Frediani P. Efcient disposal of waste polyolens
through microwave assisted pyrolysis. Fuel 2014:116.
[67] Hussain Z, Khan KM, Perveen S, Hussain K, Voelter W. The conversion of
waste polystyrene into useful hydrocarbons by microwavemetal interaction
pyrolysis. Fuel Process Technol 2012;94:14550.
[68] Hussain Z, Khan KM, Basheer N, Hussain K. Co-liquefaction of Makarwal coal
and waste polystyrene by microwavemetal interaction pyrolysis in copper
coil reactor. J Anal Appl Pyrolysis 2011;90:535.
[69] Undri A, Rosi L, Frediani M, Frediani P. Upgraded fuel from microwave
assisted pyrolysis of waste tire. Fuel 2014;115:6008.
[70] Undri A, Meini S, Rosi L, Frediani M, Frediani P. Microwave pyrolysis of
polymeric materials: waste tires treatment and characterization of the value-
added products. J Anal Appl Pyrolysis 2013;103:14958.
[71] Undri A, Sacchi B, Cantisani E, Toccafondi N, Rosi L, Frediani M, et al. Carbon
from microwave assisted pyrolysis of waste tires. J Anal Appl Pyrolysis
2013:104.
[72] Bai F, Zhu C-C, Liu Y, Yuan P-Q, Cheng Z-M, Yuan W-K. Co-pyrolysis of
residual oil and polyethylene in sub- and supercritical water. Fuel Process
Technol 2013;106:26774.
[73] Tan X-C, Zhu C-C, Liu Q-K, Ma T-Y, Yuan P-Q, Cheng Z-M, et al. Co-pyrolysis of
heavy oil and low density polyethylene in the presence of supercritical water:
the suppression of coke formation. Fuel Process Technol 2014;118:4954.
[74] Ng SH. Conversion of polyethylene blended with vgo to transportation fuels
by catalytic cracking. Energy Fuels 1995;9:21624.
[75] Arandes JM, Abajo I, Lpez-Valerio D, Fernndez I, Azkoiti MJ, Olazar M, et al.
Transformation of several plastic wastes into fuels by catalytic cracking. Ind
Eng Chem Res 1997;36:45239.
[76] de la Puente G, Arandes JM, Sedran UA. Recycled plastics in FCC feedstocks:
specic contributions. Ind Eng Chem Res 1997;36:45304.
[77] de la Puente G, Klocker C, Sedran U. Conversion of waste plastics into fuels:
recycling polyethylene in FCC. Appl Catal B: Environ 2002;36:27985.
[78] Passamonti FJ, Sedran U. Recycling of waste plastics into fuels. LDPE
conversion in FCC. Appl Catal B: Environ 2012;125:499506.
[79] Marcilla A, Garca N, del Remedio Hernndez M. Thermal degradation of
LDPEvacuum gas oil mixtures for plastic wastes valorization. Energy Fuels
2007;21:87080.
[80] Vicente G, Aguado J, Serrano DP, Snchez N. HDPE chemical recycling
promoted by phenol solvent. J Anal Appl Pyrolysis 2009;85:36671.
[81] Achilias DS, Roupakias C, Megalokonomos P, Lappas AA, Antonakou V.
Chemical recycling of plastic wastes made from polyethylene (LDPE and
HDPE) and polypropylene (PP). J Hazard Mater 2007;149:53642.
[82] Siddiqui MN. Conversion of hazardous plastic wastes into useful chemical
products. J Hazard Mater 2009;167:72835.
[83] Iliopoulou EF, Stefanidis S, Kalogiannis K, Psarras AC, Delimitis A, Trianta-
fyllidis KS, et al. Pilot-scale validation of Co-ZSM-5 catalyst performance in
the catalytic upgrading of biomass pyrolysis vapours. Green Chem
2014;16:66274.
[84] Artetxe M, Lopez G, Elordi G, Amutio M, Bilbao J, Olazar M. Production of
light olens from polyethylene in a two-step process: pyrolysis in a conical
spouted bed and downstream high-temperature thermal cracking. Ind Eng
Chem Res 2012;51:1391523.
[85] Artetxe M, Lopez G, Amutio M, Elordi G, Bilbao J, Olazar M. Cracking of high
density polyethylene pyrolysis waxes on HZSM-5 catalysts of different
acidity. Ind Eng Chem Res 2013;52:1063745.
[86] Abdul Aziz SM, Wahi R, Ngaini Z, Hamdan S. Bio-oils from microwave
pyrolysis of agricultural wastes. Fuel Process Technol 2013;106:74450.
[87] Motasemi F, Afzal MT. A review on the microwave-assisted pyrolysis
technique. Renew. Sustain. Energy Rev. 2003;28:31730.
1180 S.L. Wong et al. / Renewable and Sustainable Energy Reviews 50 (2015) 11671180
[88] Lam SS, Chase HA. A review on waste to energy processes using microwave
pyrolysis. Energies 2012;5:420932.
[89] Yuan X, Cao H, Li H, Zeng G, Tong J, Wang L. Quantitative and qualitative
analysis of products formed during co-liquefaction of biomass and synthetic
polymer mixtures in sub-and supercritical water. Fuel Process Technol
2009;90:42834.
[90] Goto M. Chemical recycling of plastics using sub-and supercritical uids. J
Supercrit Fluids 2009;47:5007.
[91] Su X, Zhao Y, Zhang R, Bi J. Investigation on degradation of polyethylene to
oils in supercritical water. Fuel Process Technol 2004;85:124958.
[92] Wang Y, Zhang F-S. Degradation of brominated ame retardant in computer
housing plastic by supercritical uids. J Hazard Mater 2012;205:15663.
[93] Onwudili JA, Williams PT. Degradation of brominated ame-retarded plastics
(Br-ABS and Br-HIPS) in supercritical water. J Supercrit Fluids 2009;49:35668.
[94] Lilac WD, Lee S. Kinetics and mechanisms of styrene monomer recovery
from waste polystyrene by supercritical water partial oxidation. Adv Environ
Res 2001;6:916.
[95] Zanella E, Della Zassa M, Navarini L, Canu P. Low-temperature co-pyrolysis of
polypropylene and coffee wastes to fuels. Energy Fuels 2013;27:135764.
[96] Fu P, Hu S, Xiang J, Li P, Huang D, Jiang L, et al. FTIR study of pyrolysis
products evolving from typical agricultural residues. J Anal Appl Pyrolysis
2010;88:11723.
[97] He M, Xiao B, Liu S, Guo X, Luo S, Xu Z, et al. Hydrogen-rich gas from
catalytic steam gasication of municipal solid waste (MSW): inuence of
steam to MSW ratios and weight hourly space velocity on gas production
and composition. Int J Hydrog Energy 2009;34:217483.
[98] Ng SH, Seoud H, Stanciulescu M, Sugimoto Y. Conversion of polyethylene to
transportation fuels through pyrolysis and catalytic cracking. Energy Fuels
1995;9:73542.
[99] Arandes JM, Erea J, Bilbao J, Lpez-Valerio D, de la Puente G. Valorization of
the blends polystyrene/light cycle oil and polystyrene  butadiene/light cycle
oil over HZSM-5 zeolites. Ind Eng Chem Res 2003;42:370010.
[100] Arandes JM, Erea J, Bilbao J, Lpez-Valerio D, De la Puente G. Valorization of
polyolens dissolved in light cycle oil over hy zeolites under uid catalytic
cracking unit conditions. Ind Eng Chem Res 2003;42:395261.
[101] Papaspyrides CD, Poulakis JG, Varelides PC. A model recycling process for low
density polyethylene. Resour, Conserv Recycl 1994;12:17784.
[102] Grause G, Matsumoto S, Kameda T, Yoshioka T. Pyrolysis of mixed plastics in
a uidized bed of hard burnt lime. Ind Eng Chem Res 2011;50:545966.
[103] Rice FO. The thermal decomposition of organic compounds from the
standpoint of free radicals. I. Saturated hydrocarbons. J Am Chem Soc
1931;53:195972.
[104] Greensfelder BS, Voge HH, Good GM. Catalytic and thermal cracking of pure
hydrocarbons: mechanisms of reaction. Ind Eng Chem 1949;41:257384.
[105] Aguado J, Serrano DP, Escola JM, Briones L. Deactivation and regeneration of a
Ni supported hierarchical beta zeolite catalyst used in the hydroreforming of
the oil produced by LDPE thermal cracking. Fuel 2013;109:67986.
[106] Kumar S, Prakash R, Murugan S, Singh RK. Performance and emission
analysis of blends of waste plastic oil obtained by catalytic pyrolysis of waste
HDPE with diesel in a CI engine. Energy Convers Manag 2013;74:32331.
[107] Welle F. Twenty years of PET bottle to bottle recyclingan overview. Resour,
Conserv Recycl 2011;55:86575.
[108] Kumagai S, Grause G, Kameda T, Takano T, Horiuchi H, Yoshioka T. Decom-
position of gaseous terephthalic acid in the presence of CaO. Ind Eng Chem
Res 2011;50:18316.
[109] Kumagai S, Grause G, Kameda T, Takano T, Horiuchi H, Yoshioka T. Improve-
ment of the benzene yield during pyrolysis of terephthalic acid using a CaO
xed-bed reactor. Ind Eng Chem Res 2011;50:6594600.
[110] Gui B, Qiao Y, Wan D, Liu S, Han Z, Yao H, et al. Nascent tar formation during
polyvinylchloride (PVC) pyrolysis. Proceedings of the Combustion Institute,
vol. 34; 2013. p. 23212329.
[111] Hossain AK, Davies PA. Pyrolysis liquids and gases as alternative fuels in
internal combustion enginesa review. Renew Sustain Energy Rev 2013;21:
16589.
[112] Assumpo LCFN, Carbonell MM, Marques MRC. Co-pyrolysis of polypropy-
lene waste with Brazilian heavy oil. J Environ Sci Health, Part A 2011;46:
4614.
[113] Siddiqui MN, Redhwi HH. Catalytic coprocessing of waste plastics and
petroleum residue into liquid fuel oils. J Anal Appl Pyrolysis 2009;86:1417.
[114] Miskolczi N. Co-pyrolysis of petroleum based waste HDPE, poly-lactic-acid
biopolymer and organic waste. J Ind Eng Chem 2013;19:154959.
[115] nal E, Uzun BB, Ptn AE. Bio-oil production via co-pyrolysis of almond
shell as biomass and high density polyethylene. Energy Convers Manag
2014;78:70410.
[116] Aboulkas A, Makayssi T, Bilali L, El har K, Nadiyine M, Benchanaa M. Co-
pyrolysis of oil shale and high density polyethylene: structural characteriza-
tion of the oil. Fuel Process Technol 2012;96:2038.
[117] Li X, Zhang H, Li J, Su L, Zuo J, Komarneni S, et al. Improving the aromatic
production in catalytic fast pyrolysis of cellulose by co-feeding low-density
polyethylene. Appl Catal A: Gen 2013;455:11421.
[118] Qian C, Zhou M, Wei J, Ye P, Yang X. Pyrolysis and co-pyrolysis of lignite and
plastic. Int J Min Sci Technol 2014;24:13741.
[119] Sajdak M, Muzyka R. Use of plastic waste as a fuel in the co-pyrolysis of
biomass. Part I: The effect of the addition of plastic waste on the process and
products. J Anal Appl Pyrolysis 2014.
[120] Dorado C, Mullen CA, Boateng AA. H-ZSM5 catalyzed co-pyrolysis of biomass
and plastics. ACS Sustain Chem Eng 2013;2:30111.
[121] Zhang H, Nie J, Xiao R, Jin B, Dong C, Xiao G. Catalytic co-pyrolysis of biomass
and different plastics (polyethylene, polypropylene, and polystyrene) to
improve hydrocarbon yield in a uidized-bed reactor. Energy Fuels
2014;28:19407.
[122] Nomura S. Use of waste plastics in coke oven: a review. J Sustain Metall
2015:19.
[123] Grieco EM, Baldi G. Pyrolysis of polyethylene mixed with paper and wood:
interaction effects on tar, char and gas yields. Waste Manag (Oxford)
2012;32:8339.
[124] Miskolczi N, Angyal A, Bartha L, Valkai I. Fuels by pyrolysis of waste plastics
from agricultural and packaging sectors in a pilot scale reactor. Fuel Process
Technol 2009;90:103240.
[125] Velghe I, Carleer R, Yperman J, Schreurs S. Study of the pyrolysis of municipal
solid waste for the production of valuable products. J Anal Appl Pyrolysis
2011;92:36675.
[126] Siddiqui MN, Redhwi HH. Pyrolysis of mixed plastics for the recovery of
useful products. Fuel Process Technol 2009;90:54552.
[127] Wu J, Chen T, Luo X, Han D, Wang Z, Wu J. TG/FTIR analysis on co-pyrolysis
behavior of PE, PVC and PS. Waste Manag (Oxford) 2014;34:67682.
[128] Karagz S, Karayildirim T, Uar S, Yuksel M, Yanik J. Liquefaction of municipal
waste plastics in VGO over acidic and non-acidic catalysts. Fuel 2003;82:41523.
[129] Gorghiu LM, Jipa S, Zaharescu T, Setnescu R, Mihalcea I. The effect of metals
on thermal degradation of polyethylenes. Polym Degrad Stab 2004;84:711.
[130] Jamradloedluk J, Lertsatitthanakorn C. Characterization and utilization of
char derived from fast pyrolysis of plastic wastes. Procedia Eng 2014;69:
143742.
[131] Singh S, Wu C, Williams PT. Pyrolysis of waste materials using TGAMS and
TGAFTIR as complementary characterisation techniques. J Anal Appl Pyr-
olysis 2012;94:99107.
[132] Wang H, Chen D, Yuan G, Ma X, Dai X. Morphological characteristics of waste
polyethylene/polypropylene plastics during pyrolysis and representative
morphological signal characterizing pyrolysis stages. Waste Manag (Oxford)
2013;33:32739.
[133] Group C. Notice of contract with malaysian corporation to supply waste
plasic-to-oil plant; 2014.
[134] PPP. Dow plans north american plastic waste recovery facilities; 2014.
[135] Kaewprom N. The rst polymer energy project of Thailand and Southeast
Asia; 2010.
[136] Envoland. Waste plastic to fuel conversion plant; 2014.
[137] Nanopure. Plastic pyrolysis plant; 2014.
[138] RESEM. About RESEM; 2014.