Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

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

Review

Catalytic pyrolysis of plastic waste: A review

R. Miandad a,b , M.A. Barakat a,b , Asad S. Aburiazaiza a,b , M. Rehan b ,

A.S. Nizami b,∗
a Department of Environmental Sciences, Faculty of Meteorology, Environment and Arid Land Agriculture, King
Abdulaziz University, Jeddah, Saudi Arabia
b Centre of Excellence in Environmental Studies (CEES), King Abdulaziz University, Jeddah, Saudi Arabia

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

Article history: This paper reviews the progress and challenges of the catalytic pyrolysis of plastic waste
Received 6 December 2015 along with future perspectives in comparison to thermal pyrolysis. The factors affecting the
Received in revised form 30 May catalytic pyrolysis process such as the temperature, retention time, feedstock composition
2016 and the use of catalyst were evaluated in detail to improve the process of catalytic pyroly-
Accepted 13 June 2016 sis. Pyrolysis can be carried out via thermal or catalytic routes. Thermal pyrolysis produces
Available online 23 June 2016 low quality liquid oil and requires both a high temperature and retention time. In order
to overcome these issues, catalytic pyrolysis of plastic waste has emerged with the use of
Keywords: a catalyst. It has the potential to convert 70–80% of plastic waste into liquid oil that has
Plastic waste similar characteristics to conventional diesel fuel; such as the high heating value (HHV) of
Pyrolysis 38–45.86 MJ/kg, a density of 0.77–0.84 g/cm3 , a viscosity of 1.74–2.5 mm2 /s, a kinematic vis-
Liquid oil cosity of 1.1–2.27 cSt, a pour point of (−9) to (−67) ◦ C, a boiling point of 68–352 ◦ C, and a flash
Catalyst point of 26.1–48 ◦ C. Thus the liquid oil from catalytic pyrolysis is of higher quality and can be
Value-added products used in several energy-related applications such as electricity generation, transport fuel and
Fuel production heating source. Moreover, process by-products such as char has the potential to be used as
an adsorbent material for the removal of heavy metals, pollutants and odor from wastewater
and polluted air, while the produced gases have the potential to be used as energy carri-
ers. Despite all the potential advantages of the catalytic pyrolysis, some limitations such as
high parasitic energy demand, catalyst costs and less reuse of catalyst are still remaining.
The recommended solutions for these challenges include exploration of cheaper catalysts,
catalyst regeneration and overall process optimization.
© 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823
2. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
2.1. Thermal pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
2.2. Catalytic pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
2.3. Suitable plastic types for pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
2.4. Factors affecting pyrolysis process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
2.4.1. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825

Corresponding author.
∗

E-mail addresses: nizami pk@yahoo.com, anizami@kau.edu.sa (A.S. Nizami).

http://dx.doi.org/10.1016/j.psep.2016.06.022
0957-5820/© 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838 823

2.4.2. Retention time and feedstock composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825

2.4.3. Use of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
2.5. Products of pyrolysis process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
2.5.1. Liquid oil and its potential applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
2.5.2. Char and its potential applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827
2.5.3. Gases and its potential applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .827
3. Catalyst and pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827
3.1. Advantages of catalyst use in pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 828
3.1.1. Effect of catalyst on quality of liquid oil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .828
3.1.2. Effect of catalyst on retention time and temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 828
3.1.3. Effect of catalyst on liquid oil compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 828
3.1.4. Effect of catalyst on physical properties of liquid oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 831
3.1.5. Effect of catalyst on gases produced . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 832
3.1.6. Effect of catalyst on char produced . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 832
4. Types of catalysts and their characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 832
4.1. Catalyst types. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .832
4.2. Catalyst characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 832
5. Catalyst modification and future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 834
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835

1. Introduction Conventional recycling methods such as sorting and grind-

ing can recycle only 15–20% of total plastic waste (Khan and
The municipal solid waste (MSW) is one of the chronic envi- Kaneesamkandi, 2013; Siddiqui and Redhwi, 2009). The energy
ronmental, health and economic problems in most developing recovery technologies such as thermal and catalytic pyrolysis,
countries (Nizami et al., 2016). The high generation rate of gasification and plasma arc gasification are receiving more
MSW (up to 1.3 billion tons per year) in developing world is attention as alternative methods of plastic waste recycling
the result of both rapid increase in population and urbaniza- (Nizami et al., 2015a; Ouda et al., 2016; Miandad et al., 2016b).
tion along with raised living standards (Nizami et al., 2015a; Pyrolysis process converts plastic waste into liquid oil, solid
Martinot et al., 2002). In last few decades, millions of peo- residue (char) and gases at high temperatures (300–900 ◦ C)
ple have shifted from rural to urban areas in many parts of via thermal decomposition. However, there are certain lim-
the world (Nizami et al., 2015b). Currently half of the world’s itations with the conventional thermal pyrolysis, where the
population lies within urban areas (Tacoli, 2012). Moreover, whole process is temperature-dependent (Sadaf et al., 2015;
according to a United Nation (UN) report, the 3.9 billion current Tahir et al., 2015). The liquid oil from thermal pyrolysis may
urban population will increase to 6.3 billion by 2050, with a 90% contain impurities and residues (Borsodi et al., 2011). More-
increase only in urban areas of Africa and Asia (UN, 2014). over, the thermal pyrolysis of PE type plastics such as HDPE
MSW can be a valuable source of biomass, recycled mate- and LDPE along with PP are difficult to conduct due to their
rials, energy and revenue if properly and wisely managed crossed chain hydrocarbon structures (Achilias et al., 2007).
(Nizami et al., 2015a; Miandad et al., 2016a). However, many Therefore, catalytic pyrolysis is being developed to overcome
of the municipalities within the developing world do not have the problems of thermal pyrolysis (Lopez et al., 2011a).
sufficient technical and economical capasities to treat and A range of catalysts have been utilized, including Red Mud
dispose MSW in an eco-friendly manner (Tacoli, 2012). The (Lopez et al., 2011a), FCC (Lee, 2009), ZSM-5 (Lopez et al.,
Kingdom of Saudi Arabia (KSA) is facing the same problem 2011a), HZSM-5 (Hernandez et al., 2007), Y-zeolite (Lee, 2012),
with MSW management, like other developing nations (Ouda Fe2 O3 (Sarker and Rashid, 2013), Al2 O3 , Ca(OH)2 (Sarker et al.,
et al., 2016). MSW is generated at an alarming rate of around 2011a,b) and natural zeolite (Syamsiro et al., 2014), in catalytic
15 million tons per year and is estimated to double (30 million pyrolysis to improve the quality of liquid oil (Wang and Wang,
tons) by 2033. Plastic waste is the second largest waste stream 2011). The catalysts increase the lighter fractions in the liquid
(up to 17.4%) of MSW in KSA (Nizami et al., 2015a, 2016). oil such as gasoline (Lerici et al., 2015), and decrease the overall
Plastic waste has become an indelible component of MSW, process energy-inputs (Lopez et al., 2011a). For instance, the
as being used in a wide range of products due to its durability, use of ZSM-5 catalyst decreased the impurities such as solid
light weight and low cost (Serrano et al., 2002; Aguado et al., residue, sulphur, nitrogen, and phosphorous in the produced
2007). In 2011, the total world plastic waste production was liquid oil (Miskolczi et al., 2009). It is also reported that the
around 280 million tons that was estimated to further increase use of catalysts with a high BET surface area allows more con-
with a rate of 4% by 2016 (Sriningsih et al., 2014). Plastic tact between reactants and the catalyst surface, resulting in
waste is the mixture of different plastic products that are pre- an increased rate of cracking reaction to produce more gases
dominantly made from low density polyethylene (LDPE), high than liquid oil (Syamsiro et al., 2014).
density polyethylene (HDPE), polypropylene (PP), polystyrene Although substantial research is underway to explore dif-
(PS), polyvinyl chloride (PVC) and polyethylene-terephthalate ferent types of catalysts and their dynamic role in the pyrolysis
(PET). PE and PS plastics are the main components of munici- process and its products, but a comprehensive review on
pal plastic waste (Onwudili et al., 2009). what has been achieved in the catalytic pyrolysis of plas-
The plastics are mostly non-biodegradable and remain in tic waste, the challenges and limitations of this process, and
the environment for hundreds of years (Ashworth et al., 2014). what the future directions are, hasn’t been widely-published
824 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838

Table 1 – Thermal versus catalytic pyrolysis.

Catalyst used Amount of Feedstock used Temp (◦ C) Thermal pyrolysis Catalytic pyrolysis References
catalyst
Liquid Gases Char Liquid Gases Char

ZSM-5 10% PE, PP, PS, PET, PVC 450 79.3 17.7 3.0 56.9 40.4 3.2 Lopez et al. (2012)
ZSM-5 10% PE, PP, PS, PET, PVC 440 79.3 17.7 3.0 56.9 40.4 3.2 Lopez et al. (2011c)
Red Mud 10% PE, PP, PS, PET, PVC 440 79.3 17.7 3.0 76.2 21.6 2.2 Lopez et al. (2011c)
ZSM-5 10% PE, PP, PS, PET, PVC 500 65.2 34.0 0.8 39.8 58.4 1.8 Lopez et al. (2011c)
Red Mud 10% PE, PP, PS, PET, PVC 500 65.2 34.0 0.8 57.0 41.3 1.7 Lopez et al. (2011c)
Y-zeolite 50% Municipal plastic waste 450 58 28 14 52 36 12 Syamsiro et al. (2014)
Natural Zeolite 50% Municipal plastic waste 450 58 28 14 50 34 16 Syamsiro et al. (2014)

(Nizami et al., 2015a,b,c, 2016). Therefore, this paper reviews
the progress and challenges of the catalytic pyrolysis of plastic
waste along with future perspectives in comparison to ther-
mal pyrolysis. In addition, the factors affecting the catalytic
pyrolysis process such as temperature, retention time, feed-
stock composition, and the use of catalysts, were evaluated in
detail to improve the process of catalytic pyrolysis. The effect
of different catalysts on the quantity and quality of pyrolysis
products has been examined in detail against characteristics
of catalyst. Moreover, catalyst reforming and regeneration and
exploration of new cheaper catalysts were also focused upon
in order to make the catalytic pyrolysis process more econom-
ical and sustainable.
2. Pyrolysis
Pyrolysis is a tertiary recycling technique in which organic
polymers are converted into liquid oil, char and gases at
high temperatures via thermal decomposition (Chen et al.,
2014; Ouda et al., 2016; Anjum et al., 2016). Pyrolysis studies
were carried out at different temperatures ranging from 300
to 900 ◦ C, however typical optimum temperatures for plastic
waste were around 500–550 ◦ C (Chen et al., 2014). Kumar and
Singh (2011) carried out pyrolysis of HDPE at different tem-
peratures ranging from 400 to 550 ◦ C and concluded that with
the increase of temperature, there was a decrease in retention
time e.g. 760 min (400 ◦ C), 290 min (450 ◦ C), 68 min (500 ◦ C)
and 54 min (550 ◦ C). Moreover, pyrolysis of different plas-
tic waste was carried out at different heating rates such as
4 ◦ C/min (Velghe et al., 2011), 20–25 ◦ C/min (Zhao et al., 2011)
and 10 ◦ C/min (Buah et al., 2007). In addition, researchers have
used different retention times for pyrolysis process. For exam-
ple, Lopez et al. (2011) carried out pyrolysis of plastic waste at
retention times of 0–15, 30 and 120 min. Other similar studies
used retention times of 40–70 min (Buah et al., 2007), 120 min
(Velghe et al., 2011), and 45 min (Zeaiter, 2014). However, there
is a scope for further reduction of process temperature and
retention time to optimize the overall process. The pyrolysis
can be carried out via thermal and catalytic routes (Table 1).
was easily carried out in comparison to HDPE, LDPE and PP
pyrolysis (Uddin et al., 1997), as the PE (HDPE and LDPE) and
PP require higher temperatures for degradation (Miskolczi
et al., 2009). Furthermore, in absence of a catalyst, PE is con-
verted into wax instead of liquid oil (Lee, 2012). The liquid oil
produced by thermal pyrolysis contains large carbon chains
compounds (Lopez et al., 2011c) and has low quality due to low
octane number, presence of high solid residues (Kim and Kim,
2004; Seth and Sarker, 2004) and impurities such as sulphur,
nitrogen, chlorine and phosphorous (Miskolczi et al., 2009).
2.2. Catalytic pyrolysis
The catalytic pyrolysis is carried out using a catalyst. The pro-
cess showed high potential for the conversion of plastic waste
into liquid oil with improved quality at lower temperatures
and reaction times as compared to thermal pyrolysis (Table 1).
These factors can reduce the process parasitic energy demand
and optimize the overall pyrolysis process (Manos et al., 2002).
Different catalysts such as FCC (Achilias et al., 2007), spent
FCC (Lee, 2009), HZSM-5 (Lee, 2012), ZSM-5 (Miskolczi et al.,
2009; Lopez et al., 2011a), Cu-Al2 O3 (Adnan et al., 2014), Co-
Mo/Z (Sriningsih et al., 2014), Zeolite-ß (Ojha and Vinu, 2015),
natural zeolite (NZ) (Syamsiro et al., 2014), Red Mud (Lopez
et al., 2011a), Al(OH)3 Ca(OH)2 (Sarker et al., 2011a,b) and Fe2O3
(Sarker and Rashid, 2013) have been used to enhance the yield
and mechanism of catalytic pyrolysis. Hydrocarbons (HCs)
from different plastics pyrolysis such as HDPE, LDPE (Park
et al., 2002), PP (Hwang et al., 1999; Hwang et al., 2002) and
PS (Bagri et al., 2002; Kim et al., 2002) contain low carbon
chain compounds including, gasoline range HCs in compar-
ison to thermal pyrolysis (Scott et al., 1990; Park et al., 1999;
Aguado et al., 2000; Rehan et al., 2016a). Moreover, the cata-
lysts increase the gaseous fraction and reduce the liquid oil
yield when compared to thermal pyrolysis (Park et al., 1999;
Beltrame et al., 1989). Furthermore, the conversion rate was
increased at low temperature in catalytic conditions in com-
parison to thermal pyrolysis (Ding et al., 1997; Park et al., 1999;
Lee, 2001).

2.1. Thermal pyrolysis 2.3. Suitable plastic types for pyrolysis

The non-catalytic or thermal pyrolysis is an endothermic pro-
cess that does not employ any catalyst. The thermal pyrolysis
of different types of plastic has been carried out extensively
in the past, including PE (Murata et al., 2004; Cha et al., 2002),
PP (Dolezal et al., 2001; Kim and Kim, 2004) and PS plastics
(Faravelli et al., 2001; Cha et al., 2002), as grouped in Table 2.
Moreover, only few studies have focused on PVC, PET, poly-
methyl methacrylate and polyurethane pyrolysis (Kaminsky
et al., 2004a; Miskolczi et al., 2004). Thermal pyrolysis of PS
Thermal and catalytic pyrolysis of all plastic types such as
PS, PE (HDPE, LDPE), PP, PVC and PET as single substrate has
been carried out in the last few years (Table 2). Lee (2009) and
Miskolczi et al. (2009) carried out pyrolysis of mixed munic-
ipal plastic waste that was comprised of almost all types of
plastics. In addition, a few studies were carried out on pyrol-
ysis of polymethyl methacrylate (Kaminsky et al., 2004b) and
polyurethane (Miskolczi et al., 2004). Sakata et al. (1996) and
Lopez et al. (2012) studied the pyrolysis of PVC that produced
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838 825

Table 2 – Suitability of plastic.

Resin Suitability for pyrolysis Remarks References

Polystyrene (PS) Very good and gives (1) Low temperature required as compare Lee and Shin (2007)
excellent fuel properties to PP and PE. Siddiqui and Redhwi (2009)
(2) Produce Less viscous oil as compared
to PE and PP.

Polyethylene (PE)
Very good for pyrolysis. (1) Required temperature is high >500 ◦ C Miskolczi et al. (2009)
due to its branched chain structure Lee (2012)
(2) In thermal pyrolysis it converts into
wax instead of liquid oil
(3) In catalytic pyrolysis wax formation is
occurred on external site of catalyst while
further cracking of wax into gases and
liquid occurred in internal site of catalyst.

Polypropylene (PP)
Polyvinyl chloride (PVC)
Polyethylen-tetraethate (PET)
Very good (1) Required high temperature. Miskolczi et al. (2009)
(2) After PE it is difficult to degrade
thermal pyrolysis of PP.
(3) In catalytic pyrolysis produces liquid
yield with high aromatic compounds.
Not suitable. (1) Produce hazardous Chlorine gas Lopez et al. (2011a)
Only few studies was (2) Dechlorination via low temperature Lopez et al. (2012)
carried out by different (250–320 ◦ C) or physical or chemical
scientists adsorption.
(3) In catalytic pyrolysis presence of
chlorine and deposition of coke affect the
catalytic activity of catalyst.
Not suitable (1) It contains Heteroatom’s Thorat et al. (2013)

hazardous chlorine gas. Therefore, the dechlorination step at
a low temperature was recommended to stop the hazardous
chlorine as a process product in the form of HCl (Lopez et al.,
2011a, 2012).
2.4. Factors affecting pyrolysis process
The pyrolysis of plastic waste is affected by a number of pro-
cess parameters such as temperature (Yoshioka et al., 2004; Ji
et al., 2006), retention time (Lopez et al., 2011c; Lee and Shin,
2007), feedstock composition (Tröger et al., 2013; Acomb et al.,
2015), use of catalyst (Lerici et al., 2015; Miskolczi et al., 2013;
Chen et al., 2014), moisture content (Chen et al., 2014), heat-
ing rate (Sharma et al., 2014) and particle size (Luo et al., 2010).
The most important parameters are discussed below.
2.4.1. Temperature
Temperature is considered to be one of the most important
factors affecting both the quality and quantity of pyrolysis
products (Lopez et al., 2011c), as it affects the cracking reac-
tions that alter the yield of gases and liquid oil. However, there
is little effect on the amount of produced char (Yoshioka et al.,
2004; Ji et al., 2006; Lopez et al., 2011c). At a low temperature
long chain hydrocarbons are produced, while an increase in
temperature results in short carbon chain compounds due
to the cracking of C–C bonds. Hernandez et al. (2007), Lopez
et al. (2011) and Li et al. (2005) have reported that aromatic
compounds were produced at higher temperatures due to
triggering of secondary process reactions.
2.4.2. Retention time and feedstock composition
Retention time has shown little effect on the quality of pyrol-
ysis products. Lopez et al. (2011) have stated that the same
yield of liquid oil was observed at 30 min and 120 min retention
times. Similarly, the aromatic compounds present in liquid
oil were similar at different retention times against the same
temperature (Lee and Shin, 2007). The feedstock composition
also affects the yield of pyrolysis products, although this has
yet to be explored in more detail (Tröger et al., 2013). According
to Miskolczi et al. (2009), PE and PP types plastic require higher
temperatures for their complete degradation as compared to
PS plastic, due to their complex structures.
2.4.3. Use of catalyst
Catalysts play an important role in improving the quality of
pyrolysis products as well as reducing the process temper-
ature and retention time. Fe2 O3 (Sarker and Rashid, 2013),
Ca(OH)2 (Sarker et al., 2011a,b), FCC (Lee, 2009), natural zeo-
lite (Syamsiro et al., 2014) and synthetic zeolite (Lopez et al.,
2011) are different catalysts used in the process of catalytic
pyrolysis. The use of catalysts increase the rate of the crack-
ing reactions that lead to an increase in the yield of gases with
a reduction in liquid oil yield (Syamsiro et al., 2014). However,
the quality of liquid oil is improved, as some of the larger car-
bon chain compounds are either adsorbed in the catalyst or
further broken down into smaller carbon chain compounds.
Catalyst characteristics such as BET surface area, pore size,
pore volume, and acidity are the main factors that affect the
catalytic activity of any catalyst in the pyrolysis process.
826 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838

2.5. Products of pyrolysis process
2.5.1. Liquid oil and its potential applications
Liquid oil from plastic pyrolysis has the potential to be used
as an alternative source of energy (Rehan et al., 2016b) . Lopez
et al. (2011) and Williams (2006) reported that the pyrolysis
process can convert 78–84% plastic by weight into liquid oil.
Moreover, the theoretical energy required to convert 1 kg of PE
into liquid oil and other value-added products is 1.047 MJ/kg;
whilst the liquid oil has similar properties in comparison with
conventional diesel (Table 3). Various studies have been car-
ried out for the application of pyrolysis liquid oil as a transport
fuel (Mukherjee and Thamotharan, 2014; Nileshkumar et al.,
2015; Lee et al., 2015). The liquid oil has been blended with
diesel with the ratio of 10%, 20%, 30%, and 40% and used in
different types of diesel engines in various studies (Frigo et al.,
2014; Mukherjee and Thamotharan, 2014; Nileshkumar et al.,
2015; Lee et al., 2015; Gardy et al., 2014). The aims of these
studies were to examine the effect of pyrolysis liquid oil blend-
ing with conventional diesel on the performance of engine and
exhaust emissions. Lee et al. (2015) reported that at 20/80%
(pyrolytic oil/conventional diesel), the engine performance
was decreased by 13% at 2450 rpm, while it reached up to
17% at 3500 rpm. Moreover, the engine running was achieved
only for few min with 37%, and at 56% there was a decrease
in engine performance under intermediate load. Nileshkumar
et al. (2015) reported that engine performance did not change
up to the blending ratio of 20%/80%. The fuel consumption
decreases as the ratio of pyrolytic liquid oil increases. How-
ever, Cleetus et al. (2013), reported that fuel consumption was
increased due to the low calorific value of pyrolysis liquid oil
in comparison to conventional diesel.
Conventional diesel shows better thermal brake effi-
ciency in comparison to blended diesel (Mukherjee and
Thamotharan, 2014). Nileshkumar et al. (2015) examined the
load effect on Brake Mean Effective Pressure (BMEP) and

Table 3 – Physical properties of liquid oil produced from different types of plastic waste.
Parameters Units Liquid oil vs. Value References
conventional diesel

Liquid oil from;

HDPE 0.790 Kumar et al. (2010)
Density g/cm3 LDPE 0.7787 Panda et al. (2010)
PE Bag 0.8544 Syamsiro et al. (2014)
Waste plastic 0.8355 Mani et al. (2010)
Conventional diesel 0.815–0.870 Syamsiro et al. (2014)

Liquid oil from;

HDPE 2.1 Kumar et al. (2010)
Viscosity mm2 /s PE Bag 1.739 Syamsiro et al. (2014)
LDPE 1.89 Panda et al. (2010)
Waste plastic 2.52 Mani et al. (2010)
Conventional diesel 2.0–5.0 Syamsiro et al. (2014)

Liquid oil from;

PP 2.27 Panda and Singh (2013)
Kinematic viscosity cSt
HDPE 1.63 Kumar and Singh (2011)
PS 1.10 Murata et al. (2002)
Conventional diesel 2.0–5.0 Syamsiro et al. (2014)

Liquid oil from;

Mixed plastic 44.40 Kim et al. (2010)
HDPE 45.86 Sharma et al. (2014)
HHV MJ/kg Tires 43.22 Wongkhorsub and Chindaprasert (2013)
LDPE 38–39 Panda et al. (2010)
Mix Plastic 40–40.5 Mani et al. (2011)
PE bags 41.45 Syamsiro et al. (2014)
Conventional diesel 46.67 Syamsiro et al. (2014)
Liquid oil from;
PP <−45 Panda and Singh (2013
Pour point ◦
C HDPE −15 Kumar and Singh (2011)
PP −9 Ahmad et al. (2015)
PS −67 Pinto et al. (1998)
Conventional diesel 6 Ahmad et al. (2015)

Liquid oil from;

PVC 40 Pinto et al. (1998
HDPE 48 Ahmad et al. (2015)
Flash point ◦
C
LDPE 41 Desai et al. (2015)
PP 30 Ahmad et al. (2015)
PS 26.1 Blazso (2006)
Conventional diesel 52 Ahmad et al. (2015)

Liquid oil from; 82–352 Kumar and Singh (2011)

Boiling point range ◦
C HDPE
PP 68–346 Panda and Singh (2013)
Conventional diesel 150–390 Boundy et al. (2011)
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838
Indicated Mean Effective Pressure (IMEP) of engine, when run-
ning with different blending ratios. The results concluded that
at low load, there is no significant difference on BMEP. How-
ever, at higher loads there was an increase in peak pressure
with the increase in the blending ratios. Moreover, there was
a decrease in IMEP with the increase in blended ratio of pyrol-
ysis oil that may be due to the high consumption of fuel.
The emissions of NOx, CO and CO2 have been analyzed at
different blending ratios by various researchers (Frigo et al.,
2014; Mukherjee and Thamotharan, 2014; Nileshkumar et al.,
2015; Lee et al., 2015). The results concluded that increase
in blending ratios increased the exhaust emissions that were
exceeding from 30% blended ratio and reached to maximum
at 50% blended ratio (Nileshkumar et al., 2015). Mukherjee and
Thamotharan. (2014) reported exhaust emissions of 0.26 g/km
and 0.40 g/km, and 0.52 g/km and 0.69 g/km for NOx for low
and full load respectively at 20% blended ratio. Moreover, for
conventional diesel at low and full loads, NOx emissions were
found to be 0.26 - 0.41 g/km and 0.51 - 0.71 g/km respectively.
However, few CO emissions were increased with the blended
oil due to incomplete combustion (Frigo et al., 2014).
2.5.2. Char and its potential applications
Char is a by-product of the pyrolysis process. It is basically
the unburnt plastic left over in the reactor. Production of char
is very low in quantity (1–1.3 g from 1 kg plastic) in compar-
ison to other process products such as liquid oil and gases
(Lopez et al., 2009; Williams, 2006). The char has the potential
to be used in various environmental and energy applications.
Jindaporn and Lertsatitthanakorn (2014), reported that char
from HDPE pyrolysis has fixed carbon (46.03%), volatile mat-
ter (51.40%), moisture content (2.41%), and a small amount of
ash. The char from PS and HDPE pyrolysis has HHV of 36.29 and
23.04 MJ/kg respectively (Syamsiro et al., 2014). Jindaporn and
Lertsatitthanakorn (2014) prepared a briquette after crushing
the HDPE char into powder. The produced briquette (1 kg) was
used to heat 1 liter of water (from room temperature to boiling
temperature) within 13 min. Moreover, char has the poten-
tial to be used in various environmental applications such
as heavy metal adsorption from the municipal and industrial
wastewater and toxic gases (Heras et al., 2014). Lopez et al.
(2009), thermally activated the waste tire char at 900 ◦ C for
3 h. It increased the char BET pore volume and surface area to
44 and 55% respectively, with decreased pore size by 5%. The
steam activation of char from waste tires pyrolysis decreased
the sulphur contents of char, thus making it more environ-
ment friendly product. Bernando (2011) upgraded the char
from co-pyrolysis of PE, PS and PP waste with biomass and
waste tires. The activated char was used for the adsorption
of methylene blue dye that showed a significant adsorption of
dye (3.59–22.2 mg/g). Moreover, char can be used as a feedstock
for activated carbon or source of energy for boilers (Fernandez
et al., 2011).
2.5.3. Gases and its potential applications
The main components of produced gases from pyrolysis of
different types of plastic are methane, hydrogen, propane,
propene, ethane, ethene and butane (Williams and Williams,
1998). Only the pyrolysis of PVC produces hazardous chlo-
rine gas (Chen et al., 2014). Increase in process temperature
increases the production of gases (Lopez et al., 2011). It
is reported that 1 kg of plastic feedstock produces around
13–26.9% gases by weight (Chen et al., 2014). The use of a cat-
alyst increases the cracking process that also increases the
827
production of gases. The produced gases from plastic waste
have high calorific values. Miskolczi et al. (2009) reported
that gases produced from pyrolysis of agriculture plastic
waste have 45.9 and 46.6 MJ/kg HHV. In addition, gases pro-
duced from PP and PE pyrolysis have HHV of 50 and 42 MJ/kg
respectively (Jung et al., 2010). Moreover, similar results for
HHV of waste tires pyrolysis (45 MJ/kg) were also reported by
Frigo et al. (2014). Therefore, the produced gases can be used
in boiler for heating or in gas turbine for the generation of
electricity without any flue gas treatment (Fernandez et al.,
2011). Moreover on the basis of their composition, 1-butene
and isoprene can be recovered through condensation and can
be used in tires production (Frigo et al., 2014). While, after sep-
aration from other gases, propene and ethane can be used as
chemical feedstocks to produce polyolefins (Sharuddin et al.,
2016).
3. Catalyst and pyrolysis
Plastic waste may contain different kinds of pollutants such
as nitrogen, sulphur, and chlorine due to surface contamina-
tion, additives, and heteroatoms containing plastic such as
PVC (Miskolczi et al., 2013). Therefore, the quality of liquid oil is
compromised by the presence of these pollutants. The thermal
pyrolysis of plastic requires high temperatures (350–500 ◦ C) for
degradation (Murata et al., 2004; Faravelli et al., 2001). However,
a few studies have reported that temperature demand may
increase up to 700 or 900 ◦ C to achieve high quality products
(Demirbas, 2004; Mastral et al., 2002). The gases produced from
thermal pyrolysis are also not suitable as a fuel source, and
they need refining prior to use (Joo and Guin, 1998). The low
thermal conductivity with endothermic cracking makes the
thermal pyrolysis a high energy-intensive process (Achilias
et al., 2007). To overcome these challenges, especially the feed-
stock contamination, ‘in situ’ methods are adopted with the
use of different catalysts in the pyrolysis process (Mitan et al.,
2007).
In the initial stage of catalytic pyrolysis, the thermal crack-
ing occurs on the external surface of the catalyst. The internal
porous structure of the catalyst then acts as channels for
selective movement and breakdown of larger compounds into
smaller ones (Lee, 2009). Due to small pore size the gases
are mainly produced inside the pores, whilst wax production
occurs due to external cracking on the external site of the cat-
alyst (Lin, 2000; Mastral et al., 2006). This phenomenon shows
that the degradation of high olefin molecules occurs in the
outer surface of the catalyst, but further degradation and prod-
ucts selectivity takes place in the internal pores of the catalyst
(You et al., 2000).
The solid catalyst can be applied either directly with feed-
stock in the reactor or on organic vapors produced in a
separate catalyst chamber. Either a liquid phase or direct
contact with feedstock will improve the cracking process by
reducing the reaction temperature and retention time (Lopez
et al., 2011a; Chen et al., 2014). However, the catalyst recovery is
difficult in direct contact, since the catalyst pores are blocked
due to the sticky nature of the plastic feedstock (Syamsiro
et al., 2014). Only a few studies have reported catalyst regen-
eration (Lopez et al., 2011b; Serrano et al., 2007). Additionally,
direct contact affects the catalytic activity with the deposi-
tion of impurities such as chlorine, sulphur and nitrogen on
the surface of the catalyst during the thermal cracking reac-
tion (Aguado et al., 2007). Vapor phase contact was carried out
828 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838
by using different catalysts such as Y-zeolite for PE (Bagri and
Williams, 2002a,b), ZSM-5 for PS (Williams and Bagri, 2004) and
ZSM-5 for industrial packaging waste pyrolysis (Lopez et al.,
2011a).
There are three main types of catalysts that are used in
pyrolysis of plastic waste. These catalysts includes; FCC, zeo-
lites and silica–alumina catalysts. FCC catalysts are known
as silica–alumina with the binder made up of non-zeolites
matrix and zeolites crystal (Degnan, 2000; Magee and Mitchell,
1993). These catalysts are extensively used in the petroleum
refineries for cracking of heavy oil into gasoline and liquid
oil petroleum. The FCC catalysts used in the pyrolysis pro-
cess are known as spent FCC catalysts, as they come from
refining industries. Moreover, these catalysts are successfully
used in pyrolysis process even though they contain some
impurities. Abbas-Abadi et al. (2014) reported that 20 wt%
catalyst/polymer ratio was optimum ratio for the maximum
conversion of HDPE plastics wastes into liquid oil. However,
increase in catalyst/polymer ratio increases the gases and
char production. Kyong et al. (2002) carried out the pyrol-
ysis of different types of plastic waste such as PS, LDPE,
HDPE, and PP by using the FCC catalyst and reported 80–90%
of liquid oil production. Overall in comparison to other cat-
alysts, FCC catalyst increases the liquid oil yield (Degnan,
2000).
Silica-alumina catalysts are amorphous catalysts having
Lewis acid sites as electron acceptors and Bronsted acid sites
with ionizable hydrogen atoms. The acidity of these catalysts
was determined by using mole ratio of SiO2 /Al2 O3 . Acidity of
these catalysts affects the production of liquid oil from pyrol-
ysis of plastics wastes. The higher the acidity, the lower will
be the production of liquid oil. Sakata et al. (1996) carried out
the pyrolysis of HDPE by using three different types of silica-
alumina catalysts such as SA-1, SA-2, and ZSM-5. The obtained
results indicated that SA-2 catalyst with lower acidity pro-
duced maximum quantity of liquid oil (74.3 wt%), while ZSM-5
with higher acidity produced lower quantity of liquid oil (49.8
wt%). However, during vapor phase contact, gases production
was increased due to further decomposition of hydrocarbons.
In addition, temperature affects the performance of these cat-
alysts. Luo et al. (2000) carried out the pyrolysis of PP and HDPE
at higher temperature (500 ◦ C) that increased the production
of liquid oil to 90 and 85 wt% respectively. Hence, the liquid oil
production can be increased by using silica-alumina catalysts
with low acidity and high process temperature.
Zeolites catalysts are the crystalline alumino-silicates
sieves having three-dimensional framework with cavities
and channels, where cations may reside. The ion exchange
capabilities and open pores are the main characteristics
of these catalysts. Zeolites catalysts have different ratio of
SiO2 /Al2 O3 that determine their reactivity and also affect
the end products of pyrolysis process. Zeolites catalysts
having high acidity are more active in cracking process, hence
increase the production of light olefins and decrease the
heavy fractions (Artetxe et al., 2013). Moreover, the use of
these catalysts increase the gases production and decrease
the liquid oil yields. Catalytic pyrolysis of HDPE with HZSM-5
at 450 ◦ C produced 35 wt% liquid oil with 65 wt% gases (Seo
et al., 2003), while using same catalyst and feedstock at
500 ◦ C, liquid oil was decreased to 4.4 wt% with 86.1 wt%
gases production (Hernandez et al., 2007). Overall zeolites
catalysts increase the volatile hydrocarbon production. More-
over HZSM-5 has very low rate of deactivation, thus more
suitable for catalyst reuse. All the above mentioned catalysts
have different characteristics and affect the products of
pyrolysis process (Table 4). However, among these catalysts,
FCC and silica–alumina catalysts increase the liquid oil yields
and decrease the gases fraction in comparison to zeolites
catalysts. Furthermore, the use of spent catalysts instead of
fresh make them more economical (Sharuddin et al., 2016).
3.1. Advantages of catalyst use in pyrolysis
A catalyst is used to improve the product quality and overall
performance of the pyrolysis process. As mentioned earlier
that different researchers used different types of catalysts
such as ZSM-5, HZSM-5, FCC, natural zeolite, activated alu-
mina, and red mud (Miskolczi et al., 2009; Hernandez et al.,
2007; Achilias et al., 2007; Sriningsih et al., 2014). Catalysts
have different impacts on the pyrolysis process and its prod-
ucts (Table 4).
3.1.1. Effect of catalyst on quality of liquid oil
According to Miskolczi et al. (2006), and Lopez et al. (2012),
use of a catalyst increases the quality of liquid oil. Miskolczi
et al. (2013) further explained that a catalyst affects the pyrol-
ysis mechanism and converts the heteroatoms into a gaseous
phase. Moreover, according to Bhaskar et al. (2002), the use
of a catalyst can decrease the concentration of halogens in
the pyrolysis liquid oil. The use of a silica-alumina cata-
lyst decreased the bromine contents in pyrolysis liquid oil
(Blazsó et al., 2002). The use of a ZSM-5 catalyst decreased
the nitrogen, phosphorous and sulphur contents in the pyrol-
ysis liquid oil, especially in the gasoline, as according to
Miskolczi et al. (2009), the degradation process of pollutants
occurs at greater scale in small internal pores of ZSM-5.
During the catalytic conversion of refuse derived fuel (RDF),
the use of a catalyst reduced the formation of less corro-
sive carboxylic acid (Whyte et al., 2015). Moreover, catalysts
involve the removal of oxygenated species that lead to an
increase in the HHV of liquid oil (Pattiya et al., 2008). Metal
containing catalysts showed a high efficiency of impuri-
ties removal from the pyrolysis liquid oil (Miskolczi et al.,
2013).
3.1.2. Effect of catalyst on retention time and temperature
Catalytic cracking of plastic was promoted in the pyrolysis
to make the overall process economically feasible by reduc-
ing the retention time and temperature (Chen et al., 2014;
Achilias et al., 2007). Different researchers have reported that
the use of a catalyst gives similar product yields at a lower
temperature and retention time in comparison to thermal
pyrolysis (Lopez et al., 2011; Ohkita et al., 1993). Increase
in the cracking rate at lower temperatures was observed
under catalytic conditions (Lee, 2001). The zeolite catalyst
showed a high rate of C–C cracking reaction due to its high
pore surface area that leads to acceleration in the thermal
degradation of plastic (Bridgewater, 2012; Miskolczi et al.,
2009).
3.1.3. Effect of catalyst on liquid oil compounds
As stated earlier, catalyst use in pyrolysis process increases
the quality of pyrolysis liquid oil (Panda et al., 2010) with aro-
matic compounds (Lee, 2012). Moreover, the use of a catalyst
improves the control production of hydrocarbons from HDPE,
LDPE, PP, and PS plastic types. Thermal pyrolysis of plastic
produces high carbon chain compounds ranging from C5 to
C28 , whilst the use of a catalyst decreases the heavy oil and
Table 4 – Effect of catalyst on pyrolysis process.
Catalyst used Quantity of Feedstock Effect on yield Catalyst effect References
catalyst used
Liquid Gases Char

HZSM-5 20% HDPE NR NR NR • Increases the yield of volatile compounds Hernandez

• Increases the cracking process and in the result increase the overall yield of pyrolysis et al. (2007)
FCC 50% LDPE, HDPE, 72.1, 44.2, 19.4, 52.5, 8.5, 3.3, 15.3. • Thermal cracking of HDPE is more difficult and followed by LDPE and PP. Achilias et al.
PP 64.7 20.0 • Thermal cracking of PE produce wax. (2007)

Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838

Thermal cracking increases the demand of energy however uses of catalyst increase
the cracking process. Hence reduces the demand of energy.
Na2 CO3 2, 5 and 10% Tires NR NR NR • Decrease the reaction temperature. Demirbas
• Increase the conversion with increase in liquid yield. et al. (2015)
ZSM-5 5% HDPE, PP NR NR NR • Increase the process of cracking. Miskolczi
• Increase the overall yield of each fraction i.e. gases, gasoline and light oil. et al. (2009)
• Yield of lighter fraction (gasoline) increased.
Promoted the production of i-butane in gases.
HZSM-5, Zeolite 30% PE wax 47.18, 66.98, 51.04, 28.95, 1.78, 4.08, 2.3. • Overall increase the aromatic compounds in the oil. Lee (2012)
Y and 82.59 15.11. • Catalyst dimension plays a vital role in the conversion of wax into light hydrocarbon.
Mordenite Catalyst with more than one dimension (HZSM-5 and zeolite Y) shows high
conversion of wax into light hydrocarbon than one dimension (mordenite) catalyst.
ZSM-5 10% Industrial 41.5 8.6 49.9 • Decrease the temperature of pyrolysis process from 500 ◦ C to 440 ◦ C. Lopez et al.
Packing • Liquid oil produce from catalytic pyrolysis contain high fraction of aromatic, while (2011)
waste gases contains high fraction of C3-C4 contents.
ZSM-5 10% PE, PP, PS, 56.9 40.4 3.2 • For the removal of chlorine, dechlorination step was carried out at low temperature Lopez et al.
PET, PVC that reduces the chlorination but also negatively affect the catalyst performance. (2012)
• Increases the yield of gases that the decrease in liquid yield. Moreover a very slight
increase in solid fraction.
• 80% of the liquid yield contains C5-C9 compounds due to presence of catalyst.
However dechlorination step in with catalyst decreases the C5-C9 fraction that means
it effect the catalytic activity of ZSM-5.
• Decholrination step increases the yield of C13 compounds in liquid yield.
Catalytic pyrolysis produces liquid with 95% aromatic compounds.
Natural Zeolite 5% LDPE 23.88, 12.20, 75.18, 86.30, 0.94, 1.51, • Natural zeolite (NZ) modification was carried out by metal (Ni, Ni-Mo, Co and Sriningsih
(Ni/Z, NiMo/Z, 23.92, 14.91. 76.00, 83.71. 0.92, 1.39. Co-Mo) impregnation on NZ to increase the catalyst activity and its selectivity for et al. (2014)
Co/Z, CoMo/Z) hydrocracking process.
• Impregnation of catalyst didn’t affect the crystallinity of the NZ.
• Ni/Z composite produces high liquid yield. However maximum gasoline (71.49%) is
produced from Co-Mo/Z at 350 ◦ C due to its high acidic nature.
• Produced liquid oil contains compounds with atom chain C6 until C19 that shows
that it contains paraffins, napthenes and olefins.
H-Y Zeolite 50% PE, PP, PS 42, 44, 71 46, 52, 24 8, 10, 5. • Polyolefin (PE and PP) shows high yield of gaseous hydrocarbon while PS shows high Lerici et al.
yield of liquid hydrocarbon due to its stable benzene ring structure. (2015)
• Polyolefin produces wax while PS didn’t produce any wax.
• Liquid oil produces from PS mainly consist of styrene (81%).

829
 830
FCC, ZSM-5, 2% HDPE, PS • FCC and NZ (Clinoptillolite) have less microporous while ZSM-5 has high porous Miskolczi
natural zeolite area. et al. (2006)
(Clinoptillolit) • Less porous area catalyst produce high liquid yield; however high porous catalyst
(ZSM-5) produces more gaseous products.
• Increase in temperature increases the volatile yield in liquid product. Moreover C2
and C4 increase and methane decrease in gaseous product with the increase in

Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838

temperature.
• Use of catalyst lead to the formation of branched hydrocarbon in liquid due to the
carbon-chain isomerization.
• Higher micro and macroporous surface area increase the carbon-chain
isomerization phenomena that effect decreases with the increase of temperature as
well.
• Use of catalyst decrease the concentration of heavy aliphatic compounds (C20+ ) and
increase the concentration of lighter hydrocarbons i.e. (C13− ).
ZSM-5, Red Mud 10% PE, PP, PS, 56.9, 76.2 40.4, 58.4 3.2, 2.2 • Increase in temperature in the presence of catalyst increases the gaseous yield due Lopez et al.
PET, PVC to increase in the cracking ability of catalyst. (2011c)
• ZSM-5 zeolite was more porous and acidic then Red Mud, hence ZSM-5 catalyst
produced more gases then Red Mud.
• High temperature in the presence of catalyst produces more aromatic compounds.
• ZSM-5 produces 95.2 and 98.4% aromatic compounds at the temperature of 440 and
500 ◦ C respectively. However without using catalyst only 67.7 and 73.9% aromatic are
produced respectively under same temperature conditions. This is due to the
presences of high number of Bronsted acid site present in the internal structure of
ZSM-5 catalyst.
• Red Mud catalytic activity increase with the increase of temperature. It was found
that Red Mud effect was limited at 440 ◦ C then 500 ◦ C.
• Red Mud produces high aromatic compound then thermal pyrolysis but less than
ZSM-5 catalyst.
• Presence of Na2 O may affect the catalytic activity of Red Mud.
• ZSM-5 and Red Mud increase the concentration of H2 in gaseous product. Moreover
produce gases have same HHV (48–53 MJ/kg) as natural gas. Hence it can be used as
alternative of natural gas.
Y-zeolite and 50% Municipal 52, 50 36, 34 12, 16 • Y-zeolite decreases the liquid yield as compare to natural zeolite due to high BET Syamsiro
Natural zeolite plastic surface area. et al. (2014)
waste • Use of catalyst decreases the pour point of liquid oil.
• Use of catalyst decreases the heavy oil fraction and increases the gasoline fraction.
• Presence of impurities effect the catalytic activity of catalyst. Hence it was found
that with the passage of time catalyst activity was decreased
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838
increases the gasoline fraction (C5 –C12 ) in the pyrolysis liquid
oil (Syamsiro et al., 2014).
Manos et al. (2000) reported that catalytic degradation
of PE with Y-zeolite produced more gasoline range com-
pounds, mainly the isoparaffins with high octane numbers.
Catalytic degradation of HDPE and LDPE with the FCC cata-
lyst produced gasoline range hydrocarbons (C7 –C12 ) with the
main components of iso-alkenes or iso-alkanes. For HDPE,
few higher compounds with normal alkanes were found
in the liquid oil (Achilias et al., 2007). According to Panda
et al. (2010) and Grieken et al. (2001), use of a ZSM-5 cat-
alyst in the batch reactor for the degradation of PE plastic
type increased the cracking, aromatization and isomerization
process.
Thermal degradation of PP on clinoptiloite zeolite
increased the gasoline range compounds and decreased
the char (Kima et al., 2002). Moreover, ZSM-5 resulted in the
formation of branched hydrocarbons with aromatics in liquid
oil. It has high catalytic activity for the degradation of heavy
hydrocarbons into lower gaseous hydrocarbons (Seo et al.,
2003; Mastral et al., 2006). Miskolczi et al. (2009) reported that
catalytic degradation of agricultural and packaging waste
using ZSM-5 catalyst increased the yield of gases, gasoline and
light oil to 12.2, 34.5 and 24.1% respectively. In non-catalytic
pyrolysis, the concentration was 5.1, 18.2 and 17.9% respec-
tively. Liquid oil produced from catalytic degradation of PS
plastic with HY-zeolite was affected by the reforming temper-
ature. At 450 ◦ C, the liquid oil was 80% composed of C6 –C8 and
C14 –C16 compounds. The temperature increase from 400 to
450 ◦ C increased the benzene and toluene, and decreased the
styrene, ethylbeneze, styrene dimmer and PAH concentration.
This is due to the increase in catalytic activity of HY-zeolite
that resulted in the degradation of higher molecular weight
Fig. 1 – Flow chart of pyrolysis process.
831
hydrocarbons into smaller molecular hydrocarbons (Onwudili
et al., 2009).
PVC plastic is widely used in construction, electronic and
automotive applications. Pyrolysis of PVC produces hazardous
chlorine gas (Lopez et al., 2012). A catalytic pyrolysis of PVC
plastic with other plastics was carried out with the main
focus of adsorbing the HCl produced during pyrolysis. In
addition, a few studies were also carried out to inhibit the
formation of HCl during the pyrolysis (Lopez et al., 2012).
However, the dual effect of a catalyst, dechlorination and
catalytic pyrolysis on the mixture of plastic including PVC
plastic (Zhou et al., 2008; Yanik et al., 2001) was rarely reported
by scientists. Lopez et al. (2011) stated that 50% removal
of chlorine from liquid oil was achieved by following step-
wise pyrolysis of PVC plastic that included dechlorination and
pyrolysis steps. The dechlorination step was carried out at a
low temperature to remove the chlorine, and then later on
the pyrolysis process was carried out for the conversion of
PVC into liquid oil. The experiment was carried out with and
without catalysts at the dechlorination step. The obtained
results showed that the dechlorination step with a catalyst
decreased the catalyst efficiency by blocking its active sites
(Fig. 1).
3.1.4. Effect of catalyst on physical properties of liquid oil
The use of a catalyst affects the physical properties of pyrol-
ysis liquid oil (Whyte et al., 2015), such as viscosity that is
one of the important parameters for any petroleum product.
Abdullah et al. (2010) reported that the suitable viscosity for
fuel oil at 25 ◦ C is ≤1000. High viscous oil affects the engine per-
formance as it is hard to pump the oil into the engine during
its operation. Therefore a pump is required to inject the fuel
into atomizer, hence making the process costly (Kim et al.,
832 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838
2009; Mohan et al., 2006). Feedstock composition is another
factor that affects the viscosity of liquid oil. Liquid oil from
PE and PP pyrolysis had viscosities of 2.32 and 2.18 mm2 /s
respectively (Syamsiro et al., 2014; Panda and Singh, 2013).
However, liquid oil produced from PS is less viscous (Siddiqui
and Redhwi, 2009). The differences in viscosity results are
due to the composition and structure of different feedstocks
(Ates et al., 2013). Any factor in the pyrolysis process that
cracks the liquid oil to a lower molecular weight leads to low-
ers the viscosity (Diebold, 2000) and it is achieved by using
a catalyst (Miskolczi et al., 2013). Ates et al. (2013) reported
that all the catalysts show a high conversion of long chain
aliphatic compounds into aromatic compounds. In addition,
reduction of oxygenated lignin species can result in less vis-
cous oil (He et al., 2009). Miskolczi et al. (2013) reported that
the use of a catalyst decreased the moisture content and
cetane index of liquid oil. In addition, use of Y-zeolite and
natural zeolite (NZ) decreased the pour point of liquid oil
from municipal plastic waste pyrolysis (Syamsiro et al., 2014).
Moreover, the use of a catalyst decreases the density, flash
point, boiling range and HHV of liquid oil (Miskolczi et al.,
2009).
3.1.5. Effect of catalyst on gases produced
The use of a catalyst increases the production of gases and
decreases the liquid oil yield but improves its quality. Gases
produced from pyrolysis process consist of CO, CO2 , H2 and
CH4 (Whyte et al., 2015). However, pyrolysis of PVC produce
chlroine gas (Lopez et al., 2011b). The use of catalyst favors
the decarboxylation route, and hence increases the CO2 pro-
duction and decreases the concentration of CO (Whyte et al.,
2015; Ates et al., 2013). However, the most important effect of
a catalyst on the produced gases is the increase of hydrogen
concentration and carbon frame isomerization that resulted
in an increase of i-butane concentration (Ates et al., 2013).
Miskolczi et al. (2009) reported that the use of ZSM-5 catalyst
produced gases that contain mainly C3 hydrocarbons from PP,
while C2 and C4 hydrocarbons were produced from packaging
waste. The difference between the compositions of produced
gases is due to the structure of used feedstock. In addition, the
HHV of produced gases was 45.9–46.6 MJ/kg from agriculture
and packaging waste respectively (Miskolczi et al., 2009) and
17.1–21.9 MJ/m3 from RDF (Whyte et al., 2015).
3.1.6. Effect of catalyst on char produced
Char (solid residue) formation in the pyrolysis occurred
through the process of condensation (Miskolczi et al., 2013).
The use of a microporous catalyst decreases the char produc-
tion (Lee, 2012). Catalyst separation from the char is difficult
(Lopez et al., 2011). The catalyst does not affect the ele-
mental characteristics of char (Whyte et al., 2015). However,
it increases the ash contents in char (Lopez et al., 2011).
Char produced from the catalytic pyrolysis of RDF contained
53–54% of ash that decreased its caloric value and caused
problems during its combustion (Whyte et al., 2015). In addi-
tion, the use of a catalyst increased the H/C ratio in the char
(Lopez et al., 2011). Moreover, char deposition on the catalyst
during the pyrolysis process decreases the active sites, and
hence negatively affects the catalytic activity (Miskolczi et al.,
2013).
4. Types of catalysts and their
characteristics
4.1. Catalyst types
In catalytic pyrolysis, different types of catalysts such as
homogenous catalyst (Kaminsky and Nunez, 2007), acid meso-
porous materials (Aguado et al., 2007), non-acid mesoporous
solid (Chaianansutcharit et al., 2007), FCC catalyst (Olazar
et al., 2009), zeolite (Aguado et al., 2009), and metallic oxide
(Siddiqui and Redhwi, 2009) have been examined (Table 5).
However, the most commonly used catalysts are zeolite, silica-
alumina, MCM-41 and FCC (Lin and Yang, 2007; Miskolczi
et al., 2006). Zeolite catalyst has been extensively studied by
different scientists and found to be better in the degrada-
tion of polyolefin (Lopez et al., 2011). The key features of the
zeolite catalyst are acid strength, pore size and pore distri-
bution (Panda et al., 2010). In advanced catalytic pyrolysis,
bi-functional (reforming) catalysts that have both acidic and
metal sites are characterized (Panda et al., 2010). Different
kinds of metals such as Ni, Co, and Mo are doped over the
acidic sites provided by alumina-silicate (Sriningsih et al.,
2014). Hydrogenation and dehydrogenation reactions are car-
ried out by the metallic sites, while the acidic sites accelerate
the process of isomerization (Buekens and Huang, 1998; Panda
et al., 2010).
An increase in the yield of gases in catalytic pyrolysis is due
to high inter-crystalline structure of the catalyst that acceler-
ates the cracking, isomerization and aromatization reactions
(Panda et al., 2010). Furthermore, it increases the production
of aromatics in the liquid oil (Lopez et al., 2011). HZSM-5
increases the volatile compounds in the liquid oil (Hernandez
et al., 2007). In addition, it increases the branched carbon
ratio and reduces the formation of straight chain paraffins and
olefins (Panda et al., 2010). Moreover, nanocrystalline HZSM-5
increases the production of gases during the catalytic pyrolysis
(Mastral et al., 2006). FCC catalyst has Si/Al ratio of 1.5 (Chung
et al., 2003). These catalysts have smaller microporous and BET
surface areas, and hence produce more liquid oil as compared
to other catalysts such as ZSM-5 that has high microporous
area (Seo et al., 2003). Mordenite and Clinoptillolite are the NZ
with a microporous area that favors the liquid oil yield in com-
parison to gases (Lee, 2012; Miskolczi et al., 2006). Reforming
catalyst such as doping via wet impregnation of Ni, Co and
Mo with NZ was examined. The results showed that doping
did not affect the overall crystallinity of the catalyst. However,
Co–Mo/Z showed a high efficiency in the conversion of plastic
into gasoline range liquid oil due to its high acidity (Sriningsih
et al., 2014).
4.2. Catalyst characteristics
Catalytic cracking on acid catalysts takes place with the for-
mation of carbocations that require strong acid sites (Achilias
et al., 2007). Acid strength and textural properties such as
BET surface area, acidity, pore size, pore volume, Si/Al ratio,
thermal stability, and dimension are the main characteris-
tics of acid catalysts (Fig. 2). Acidity of the catalyst plays a
vital role in the catalytic pyrolysis. Bronsted and Lewis acid
sites are considered during the acidity measurement of cata-
lysts. The majority of acid sites are present inside the catalysts
that enhance the cracking process (Venuto and Landis, 1968;
Panda et al., 2010). Sriningsih et al. (2014) reported that treating
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838
Fig. 2 – Flow chart showing the characteristics of catalysts.
catalysts with HCl increased the catalyst acidity. Acidic cata-
lyst increases the gasoline range hydrocarbon production in
liquid oil (Lopez et al., 2011). Porosity in another catalyst fea-
ture that affects the catalytic activity by selective adsorption
mechanism (Miskolczi et al., 2006).
A microporous catalyst with a high internal crystalline
structure increases the catalytic process, produces more
gases, and decreases the liquid oil yield but improves its qual-
ity (Lopez et al., 2011). While a catalyst with macropore volume
has little effect on the liquid oil quantity, as it produces large
carbon chain compounds (Miskolczi et al., 2006). The ther-
mal stability of a catalyst is very important for the pyrolysis
process. Nizami et al. (2015b) reported that NZ present in
KSA showed thermal stability at high temperatures (up to
900 ◦ C) that shows its potential to be used as a catalyst in
the pyrolysis process. Different studies showed that catalyst
activity improves with the increase in process temperature
(Syamsiro et al., 2014). However, with the passage of time,
catalyst activity decreases due to the deposition of coke or
impurities present in the feedstock that reduces the strength
of the acidic sites (Syamsiro et al., 2014; Lopez et al., 2012).
In addition, a catalyst with more than one dimension allows
more cracking than a mono dimensions catalyst because it
provides more surface area for cracking (Lee, 2012).
5. Catalyst modification and future
perspective
The selection of a catalyst for the degradation of plastic waste
is a critical step in pyrolysis. The catalyst modification has
been under consideration for the last decade to improve the
pyrolysis process’s efficiency. Modification in catalysts can be
carried out in different ways, such as acid leaching, thermal,
833
and wet impregnation. Syamsiro et al. (2014) stated that by
heating the NZ at a temperature of 500 ◦ C for 3 h removed
the volatile impurities of the catalyst, thus lead to an increase
in its catalytic activity. Moreover, the acid leaching with HCl
removes the impurities from the NZ catalyst and increases its
acidity (Sriningsih et al., 2014). Similarly, the wet impregna-
tion method is an important technique that is widely used to
generate heterogeneous catalysts (Adnan et al., 2014).
Reformed catalysts show a bi-functional effect. Metallic
sites accelerate the hydrogenation and dehydrogenation reac-
tions, whilst acidic sites accelerate the isomerization reactions
(Panda et al., 2010). Making the composite of zeolite with zinc
increases the adsorption capacity of the zeolite catalyst. It nar-
rows the pores of zeolites that improve the effective sieving
effect. It allows only small molecules to pass through their
pores. Modified zeolites have an average particle size of a few
microns. The internal surface area can represent more than
99% of the total surface area. Almost all the active sites are
located inside the pores that increase its adsorption capac-
ity, thereby enhancing its purification capacity (Ciobanu et al.,
2008). Adnan et al. (2014) reported that doping of Cu on Al2 O3
increased the BET surface area, pore volume and pore size.
Moreover, the use of these reformed catalysts will increase the
overall catalytic pyrolysis efficiency and improve the products
quality. However, some challenges and scope for improve-
ment still remain in the catalytic pyrolysis of plastic waste.
After a detailed review of all aspects of the catalytic pyroly-
sis process, the recommended areas for further research and
development including detailed life cycle assessment (LCA)
for pyrolysis sustainability as an alternative energy genera-
tion technology (Chan et al., 2016; Demirbas et al., 2016a and
b; Shahzad et al., 2015; Rathore et al., 2016) are grouped in
Box 1.
834 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838

Hernandez et al. (2007)

Miskolczi et al. (2009)
Box 1: Future perspective

Lopez et al. (2011c)

Lopez et al. (2011c)
Lopez et al. (2011)
Lopez et al. (2012)
• Undertaking detailed material and energy balance of
References catalytic pyrolysis process in continuous operational

Lee (2012)

Lee (2009)
Lee (2009)
mode at commercial scale.
• Further research for exploration and utilization of
cheap catalysts, such as natural zeolites, to further
reduce the process cost, improve product quality and
overall process optimization.
Acidity (mmol)

• Regeneration and reuse of catalysts need further

investigation to make the process more efficient both
1.15, 0.88
NH3 /g)

economically and environmentally.

0.176
0.176
NR
NR

NR
NR
NR
0.2

• Detailed chemical characterization of produced liquid

oils from different types of plastic waste, to fully under-
stand their health risks and environmental problems.
• Further research is needed to understand the detailed
Pore Volume

composition of produced gases and their health and

environmental concerns and also their potential to be
(cm3 /g)

0.2481
0.2533
0.397
0.397
0.184

used as alternative fuel.

0.18
NR
NR
0.4

• Explore further applications of produced liquid oil,

gases and char to make this technology more econom-
ically sustainable.
Micropore area

• Comprehensive life cycle assessment (LCA) of catalytic

pyrolysis including feedstock to fully understand the
economic, environmental and overall sustainability of
(m2 /g)

346.1
346.1
346.1

this technology.
171
120
NR

75
–
–
Volume (cm3 /g)
Micropore

0.009
0.16
0.23

0.96
0.76
NR
0.1
0.1
0.1

6. Conclusions

The liquid oil and gases from pyrolysis have high HHV and
maintain the potential to be used as an alternative source of
Pore Size

energy. Char produced during pyrolysis has a high BET surface

(nm)

0.55
NR
NR
NR
NR
NR
NR
NR
NR

area and can be used in different environmental applications,

such as adsorption of heavy metal and other pollutants from
wastewater and polluted air. Different parameters such as
Size (␮m)

temperature, retention time, feedstock composition and use

Particle

37–70

10–30

of catalyst in pyrolysis process and end products quality and

39.8
NR
NR
NR

NR
NR
NR

yield were evaluated in detail. The thermal pyrolysis process

produces low quality liquid oil with impurities and demands a
high temperature and retention time. To overcome these chal-
BET surface area

lenges, catalytic pyrolysis of plastic wastes has been evolved.

Use of different catalysts makes the process more efficient by
improving the liquid oil and gases quality with a decrease in
both process temperature and retention time. ZSM-5, HZSM-5,
27.49
(m2 /g)

319.4
341

400
412
412
412

216
151

FCC, Al2 O3 , Red Mud, and NZ are the most widely used and sig-
Table 5 – Characteristics of catalyst.

nificant catalysts. The catalyst reforming, including doping of

the metals such as Ni, Co, Mo, and Zn on acidic catalyst further
SiO2 /Al2 O3 (w/w)

improves the catalytic activity. A catalyst that has a high BET

surface area and acidity produces more gases yield and low
liquid oil yield. In addition, a microporous catalyst shows the
same phenomena, while macroporous catalyst increases the
22.2
24.1
30

liquid oil and char yield with less gases production. However,
modifications such as thermal, acidic and doping of metal
Catalyst name

via wet impregnation can increase the catalytic activity of

Spent FCC

catalyst by improving its characteristics. The use of NZ as a

Fresh FCC
Red Mud
HZSM-5

HZSM-5

catalyst in the pyrolysis process is becoming more prominent

ZSM-5

ZSM-5
ZSM-5
ZSM-5

due to both its easy availability and economical factors in the

KSA.
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822–838 835

Acknowledgment Feedstock recycling and pyrolysis of waste plastics: converting

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