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Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838

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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 7080% 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 3845.86 MJ/kg, a density of 0.770.84 g/cm3 , a viscosity of 1.742.5 mm2 /s, a kinematic vis-
Liquid oil cosity of 1.12.27 cSt, a pour point of (9) to (67) C, a boiling point of 68352 C, and a ash
Catalyst point of 26.148 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 ) 822838 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 modication 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 1520% 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 gasication and plasma arc gasication 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 (300900 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 worlds 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 difcult 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).
sufcient 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, hasnt been widely-published
824 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838

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 was easily carried out in comparison to HDPE, LDPE and PP
the progress and challenges of the catalytic pyrolysis of plastic pyrolysis (Uddin et al., 1997), as the PE (HDPE and LDPE) and
waste along with future perspectives in comparison to ther- PP require higher temperatures for degradation (Miskolczi
mal pyrolysis. In addition, the factors affecting the catalytic et al., 2009). Furthermore, in absence of a catalyst, PE is con-
pyrolysis process such as temperature, retention time, feed- verted into wax instead of liquid oil (Lee, 2012). The liquid oil
stock composition, and the use of catalysts, were evaluated in produced by thermal pyrolysis contains large carbon chains
detail to improve the process of catalytic pyrolysis. The effect compounds (Lopez et al., 2011c) and has low quality due to low
of different catalysts on the quantity and quality of pyrolysis octane number, presence of high solid residues (Kim and Kim,
products has been examined in detail against characteristics 2004; Seth and Sarker, 2004) and impurities such as sulphur,
of catalyst. Moreover, catalyst reforming and regeneration and nitrogen, chlorine and phosphorous (Miskolczi et al., 2009).
exploration of new cheaper catalysts were also focused upon
in order to make the catalytic pyrolysis process more econom- 2.2. Catalytic pyrolysis
ical and sustainable.
The catalytic pyrolysis is carried out using a catalyst. The pro-
2. Pyrolysis cess showed high potential for the conversion of plastic waste
into liquid oil with improved quality at lower temperatures
Pyrolysis is a tertiary recycling technique in which organic and reaction times as compared to thermal pyrolysis (Table 1).
polymers are converted into liquid oil, char and gases at These factors can reduce the process parasitic energy demand
high temperatures via thermal decomposition (Chen et al., and optimize the overall pyrolysis process (Manos et al., 2002).
2014; Ouda et al., 2016; Anjum et al., 2016). Pyrolysis studies Different catalysts such as FCC (Achilias et al., 2007), spent
were carried out at different temperatures ranging from 300 FCC (Lee, 2009), HZSM-5 (Lee, 2012), ZSM-5 (Miskolczi et al.,
to 900 C, however typical optimum temperatures for plastic 2009; Lopez et al., 2011a), Cu-Al2 O3 (Adnan et al., 2014), Co-
waste were around 500550 C (Chen et al., 2014). Kumar and Mo/Z (Sriningsih et al., 2014), Zeolite- (Ojha and Vinu, 2015),
Singh (2011) carried out pyrolysis of HDPE at different tem- natural zeolite (NZ) (Syamsiro et al., 2014), Red Mud (Lopez
peratures ranging from 400 to 550 C and concluded that with et al., 2011a), Al(OH)3 Ca(OH)2 (Sarker et al., 2011a,b) and Fe2O3
the increase of temperature, there was a decrease in retention (Sarker and Rashid, 2013) have been used to enhance the yield
time e.g. 760 min (400 C), 290 min (450 C), 68 min (500 C) and mechanism of catalytic pyrolysis. Hydrocarbons (HCs)
and 54 min (550 C). Moreover, pyrolysis of different plas- from different plastics pyrolysis such as HDPE, LDPE (Park
tic waste was carried out at different heating rates such as et al., 2002), PP (Hwang et al., 1999; Hwang et al., 2002) and
4 C/min (Velghe et al., 2011), 2025 C/min (Zhao et al., 2011) PS (Bagri et al., 2002; Kim et al., 2002) contain low carbon
and 10 C/min (Buah et al., 2007). In addition, researchers have chain compounds including, gasoline range HCs in compar-
used different retention times for pyrolysis process. For exam- ison to thermal pyrolysis (Scott et al., 1990; Park et al., 1999;
ple, Lopez et al. (2011) carried out pyrolysis of plastic waste at Aguado et al., 2000; Rehan et al., 2016a). Moreover, the cata-
retention times of 015, 30 and 120 min. Other similar studies lysts increase the gaseous fraction and reduce the liquid oil
used retention times of 4070 min (Buah et al., 2007), 120 min yield when compared to thermal pyrolysis (Park et al., 1999;
(Velghe et al., 2011), and 45 min (Zeaiter, 2014). However, there Beltrame et al., 1989). Furthermore, the conversion rate was
is a scope for further reduction of process temperature and increased at low temperature in catalytic conditions in com-
retention time to optimize the overall process. The pyrolysis parison to thermal pyrolysis (Ding et al., 1997; Park et al., 1999;
can be carried out via thermal and catalytic routes (Table 1). Lee, 2001).

2.1. Thermal pyrolysis 2.3. Suitable plastic types for pyrolysis

The non-catalytic or thermal pyrolysis is an endothermic pro- Thermal and catalytic pyrolysis of all plastic types such as
cess that does not employ any catalyst. The thermal pyrolysis PS, PE (HDPE, LDPE), PP, PVC and PET as single substrate has
of different types of plastic has been carried out extensively been carried out in the last few years (Table 2). Lee (2009) and
in the past, including PE (Murata et al., 2004; Cha et al., 2002), Miskolczi et al. (2009) carried out pyrolysis of mixed munic-
PP (Dolezal et al., 2001; Kim and Kim, 2004) and PS plastics ipal plastic waste that was comprised of almost all types of
(Faravelli et al., 2001; Cha et al., 2002), as grouped in Table 2. plastics. In addition, a few studies were carried out on pyrol-
Moreover, only few studies have focused on PVC, PET, poly- ysis of polymethyl methacrylate (Kaminsky et al., 2004b) and
methyl methacrylate and polyurethane pyrolysis (Kaminsky polyurethane (Miskolczi et al., 2004). Sakata et al. (1996) and
et al., 2004a; Miskolczi et al., 2004). Thermal pyrolysis of PS Lopez et al. (2012) studied the pyrolysis of PVC that produced
Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838 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) Very good (1) Required high temperature. Miskolczi et al. (2009)
(2) After PE it is difcult to degrade
thermal pyrolysis of PP.
(3) In catalytic pyrolysis produces liquid
yield with high aromatic compounds.
Polyvinyl chloride (PVC) 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 (250320 C) or physical or chemical
scientists adsorption.
(3) In catalytic pyrolysis presence of
chlorine and deposition of coke affect the
catalytic activity of catalyst.
Polyethylen-tetraethate (PET) Not suitable (1) It contains Heteroatoms Thorat et al. (2013)

hazardous chlorine gas. Therefore, the dechlorination step at 2.4.2. Retention time and feedstock composition
a low temperature was recommended to stop the hazardous Retention time has shown little effect on the quality of pyrol-
chlorine as a process product in the form of HCl (Lopez et al., ysis products. Lopez et al. (2011) have stated that the same
2011a, 2012). yield of liquid oil was observed at 30 min and 120 min retention
times. Similarly, the aromatic compounds present in liquid
2.4. Factors affecting pyrolysis process oil were similar at different retention times against the same
temperature (Lee and Shin, 2007). The feedstock composition
The pyrolysis of plastic waste is affected by a number of pro- also affects the yield of pyrolysis products, although this has
cess parameters such as temperature (Yoshioka et al., 2004; Ji yet to be explored in more detail (Trger et al., 2013). According
et al., 2006), retention time (Lopez et al., 2011c; Lee and Shin, to Miskolczi et al. (2009), PE and PP types plastic require higher
2007), feedstock composition (Trger et al., 2013; Acomb et al., temperatures for their complete degradation as compared to
2015), use of catalyst (Lerici et al., 2015; Miskolczi et al., 2013; PS plastic, due to their complex structures.
Chen et al., 2014), moisture content (Chen et al., 2014), heat-
ing rate (Sharma et al., 2014) and particle size (Luo et al., 2010).
2.4.3. Use of catalyst
The most important parameters are discussed below.
Catalysts play an important role in improving the quality of
pyrolysis products as well as reducing the process temper-
2.4.1. Temperature ature and retention time. Fe2 O3 (Sarker and Rashid, 2013),
Temperature is considered to be one of the most important Ca(OH)2 (Sarker et al., 2011a,b), FCC (Lee, 2009), natural zeo-
factors affecting both the quality and quantity of pyrolysis lite (Syamsiro et al., 2014) and synthetic zeolite (Lopez et al.,
products (Lopez et al., 2011c), as it affects the cracking reac- 2011) are different catalysts used in the process of catalytic
tions that alter the yield of gases and liquid oil. However, there pyrolysis. The use of catalysts increase the rate of the crack-
is little effect on the amount of produced char (Yoshioka et al., ing reactions that lead to an increase in the yield of gases with
2004; Ji et al., 2006; Lopez et al., 2011c). At a low temperature a reduction in liquid oil yield (Syamsiro et al., 2014). However,
long chain hydrocarbons are produced, while an increase in the quality of liquid oil is improved, as some of the larger car-
temperature results in short carbon chain compounds due bon chain compounds are either adsorbed in the catalyst or
to the cracking of CC bonds. Hernandez et al. (2007), Lopez further broken down into smaller carbon chain compounds.
et al. (2011) and Li et al. (2005) have reported that aromatic Catalyst characteristics such as BET surface area, pore size,
compounds were produced at higher temperatures due to pore volume, and acidity are the main factors that affect the
triggering of secondary process reactions. catalytic activity of any catalyst in the pyrolysis process.
826 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838

2.5. Products of pyrolysis process studies were to examine the effect of pyrolysis liquid oil blend-
ing with conventional diesel on the performance of engine and
2.5.1. Liquid oil and its potential applications exhaust emissions. Lee et al. (2015) reported that at 20/80%
Liquid oil from plastic pyrolysis has the potential to be used (pyrolytic oil/conventional diesel), the engine performance
as an alternative source of energy (Rehan et al., 2016b) . Lopez was decreased by 13% at 2450 rpm, while it reached up to
et al. (2011) and Williams (2006) reported that the pyrolysis 17% at 3500 rpm. Moreover, the engine running was achieved
process can convert 7884% plastic by weight into liquid oil. only for few min with 37%, and at 56% there was a decrease
Moreover, the theoretical energy required to convert 1 kg of PE in engine performance under intermediate load. Nileshkumar
into liquid oil and other value-added products is 1.047 MJ/kg; et al. (2015) reported that engine performance did not change
whilst the liquid oil has similar properties in comparison with up to the blending ratio of 20%/80%. The fuel consumption
conventional diesel (Table 3). Various studies have been car- decreases as the ratio of pyrolytic liquid oil increases. How-
ried out for the application of pyrolysis liquid oil as a transport ever, Cleetus et al. (2013), reported that fuel consumption was
fuel (Mukherjee and Thamotharan, 2014; Nileshkumar et al., increased due to the low caloric value of pyrolysis liquid oil
2015; Lee et al., 2015). The liquid oil has been blended with in comparison to conventional diesel.
diesel with the ratio of 10%, 20%, 30%, and 40% and used in Conventional diesel shows better thermal brake ef-
different types of diesel engines in various studies (Frigo et al., ciency in comparison to blended diesel (Mukherjee and
2014; Mukherjee and Thamotharan, 2014; Nileshkumar et al., Thamotharan, 2014). Nileshkumar et al. (2015) examined the
2015; Lee et al., 2015; Gardy et al., 2014). The aims of these 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 0.8150.870 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 2.05.0 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 2.05.0 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 3839 Panda et al. (2010)
Mix Plastic 4040.5 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 HDPE 15 Kumar and Singh (2011)
C
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; 82352 Kumar and Singh (2011)


Boiling point range HDPE
C
PP 68346 Panda and Singh (2013)
Conventional diesel 150390 Boundy et al. (2011)
Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838 827

Indicated Mean Effective Pressure (IMEP) of engine, when run- production of gases. The produced gases from plastic waste
ning with different blending ratios. The results concluded that have high caloric values. Miskolczi et al. (2009) reported
at low load, there is no signicant difference on BMEP. How- that gases produced from pyrolysis of agriculture plastic
ever, at higher loads there was an increase in peak pressure waste have 45.9 and 46.6 MJ/kg HHV. In addition, gases pro-
with the increase in the blending ratios. Moreover, there was duced from PP and PE pyrolysis have HHV of 50 and 42 MJ/kg
a decrease in IMEP with the increase in blended ratio of pyrol- respectively (Jung et al., 2010). Moreover, similar results for
ysis oil that may be due to the high consumption of fuel. HHV of waste tires pyrolysis (45 MJ/kg) were also reported by
The emissions of NOx, CO and CO2 have been analyzed at Frigo et al. (2014). Therefore, the produced gases can be used
different blending ratios by various researchers (Frigo et al., in boiler for heating or in gas turbine for the generation of
2014; Mukherjee and Thamotharan, 2014; Nileshkumar et al., electricity without any ue gas treatment (Fernandez et al.,
2015; Lee et al., 2015). The results concluded that increase 2011). Moreover on the basis of their composition, 1-butene
in blending ratios increased the exhaust emissions that were and isoprene can be recovered through condensation and can
exceeding from 30% blended ratio and reached to maximum be used in tires production (Frigo et al., 2014). While, after sep-
at 50% blended ratio (Nileshkumar et al., 2015). Mukherjee and aration from other gases, propene and ethane can be used as
Thamotharan. (2014) reported exhaust emissions of 0.26 g/km chemical feedstocks to produce polyolens (Sharuddin et al.,
and 0.40 g/km, and 0.52 g/km and 0.69 g/km for NOx for low 2016).
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. 3. Catalyst and pyrolysis
However, few CO emissions were increased with the blended
oil due to incomplete combustion (Frigo et al., 2014). Plastic waste may contain different kinds of pollutants such
as nitrogen, sulphur, and chlorine due to surface contamina-
2.5.2. Char and its potential applications tion, additives, and heteroatoms containing plastic such as
Char is a by-product of the pyrolysis process. It is basically PVC (Miskolczi et al., 2013). Therefore, the quality of liquid oil is
the unburnt plastic left over in the reactor. Production of char compromised by the presence of these pollutants. The thermal
is very low in quantity (11.3 g from 1 kg plastic) in compar- pyrolysis of plastic requires high temperatures (350500 C) for
ison to other process products such as liquid oil and gases degradation (Murata et al., 2004; Faravelli et al., 2001). However,
(Lopez et al., 2009; Williams, 2006). The char has the potential a few studies have reported that temperature demand may
to be used in various environmental and energy applications. increase up to 700 or 900 C to achieve high quality products
Jindaporn and Lertsatitthanakorn (2014), reported that char (Demirbas, 2004; Mastral et al., 2002). The gases produced from
from HDPE pyrolysis has xed carbon (46.03%), volatile mat- thermal pyrolysis are also not suitable as a fuel source, and
ter (51.40%), moisture content (2.41%), and a small amount of they need rening prior to use (Joo and Guin, 1998). The low
ash. The char from PS and HDPE pyrolysis has HHV of 36.29 and thermal conductivity with endothermic cracking makes the
23.04 MJ/kg respectively (Syamsiro et al., 2014). Jindaporn and thermal pyrolysis a high energy-intensive process (Achilias
Lertsatitthanakorn (2014) prepared a briquette after crushing et al., 2007). To overcome these challenges, especially the feed-
the HDPE char into powder. The produced briquette (1 kg) was stock contamination, in situ methods are adopted with the
used to heat 1 liter of water (from room temperature to boiling use of different catalysts in the pyrolysis process (Mitan et al.,
temperature) within 13 min. Moreover, char has the poten- 2007).
tial to be used in various environmental applications such In the initial stage of catalytic pyrolysis, the thermal crack-
as heavy metal adsorption from the municipal and industrial ing occurs on the external surface of the catalyst. The internal
wastewater and toxic gases (Heras et al., 2014). Lopez et al. porous structure of the catalyst then acts as channels for
(2009), thermally activated the waste tire char at 900 C for selective movement and breakdown of larger compounds into
3 h. It increased the char BET pore volume and surface area to smaller ones (Lee, 2009). Due to small pore size the gases
44 and 55% respectively, with decreased pore size by 5%. The are mainly produced inside the pores, whilst wax production
steam activation of char from waste tires pyrolysis decreased occurs due to external cracking on the external site of the cat-
the sulphur contents of char, thus making it more environ- alyst (Lin, 2000; Mastral et al., 2006). This phenomenon shows
ment friendly product. Bernando (2011) upgraded the char that the degradation of high olen molecules occurs in the
from co-pyrolysis of PE, PS and PP waste with biomass and outer surface of the catalyst, but further degradation and prod-
waste tires. The activated char was used for the adsorption ucts selectivity takes place in the internal pores of the catalyst
of methylene blue dye that showed a signicant adsorption of (You et al., 2000).
dye (3.5922.2 mg/g). Moreover, char can be used as a feedstock The solid catalyst can be applied either directly with feed-
for activated carbon or source of energy for boilers (Fernandez stock in the reactor or on organic vapors produced in a
et al., 2011). separate catalyst chamber. Either a liquid phase or direct
contact with feedstock will improve the cracking process by
2.5.3. Gases and its potential applications reducing the reaction temperature and retention time (Lopez
The main components of produced gases from pyrolysis of et al., 2011a; Chen et al., 2014). However, the catalyst recovery is
different types of plastic are methane, hydrogen, propane, difcult in direct contact, since the catalyst pores are blocked
propene, ethane, ethene and butane (Williams and Williams, due to the sticky nature of the plastic feedstock (Syamsiro
1998). Only the pyrolysis of PVC produces hazardous chlo- et al., 2014). Only a few studies have reported catalyst regen-
rine gas (Chen et al., 2014). Increase in process temperature eration (Lopez et al., 2011b; Serrano et al., 2007). Additionally,
increases the production of gases (Lopez et al., 2011). It direct contact affects the catalytic activity with the deposi-
is reported that 1 kg of plastic feedstock produces around tion of impurities such as chlorine, sulphur and nitrogen on
1326.9% gases by weight (Chen et al., 2014). The use of a cat- the surface of the catalyst during the thermal cracking reac-
alyst increases the cracking process that also increases the tion (Aguado et al., 2007). Vapor phase contact was carried out
828 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838

by using different catalysts such as Y-zeolite for PE (Bagri and have different characteristics and affect the products of
Williams, 2002a,b), ZSM-5 for PS (Williams and Bagri, 2004) and pyrolysis process (Table 4). However, among these catalysts,
ZSM-5 for industrial packaging waste pyrolysis (Lopez et al., FCC and silicaalumina catalysts increase the liquid oil yields
2011a). and decrease the gases fraction in comparison to zeolites
There are three main types of catalysts that are used in catalysts. Furthermore, the use of spent catalysts instead of
pyrolysis of plastic waste. These catalysts includes; FCC, zeo- fresh make them more economical (Sharuddin et al., 2016).
lites and silicaalumina catalysts. FCC catalysts are known
as silicaalumina with the binder made up of non-zeolites 3.1. Advantages of catalyst use in pyrolysis
matrix and zeolites crystal (Degnan, 2000; Magee and Mitchell,
1993). These catalysts are extensively used in the petroleum A catalyst is used to improve the product quality and overall
reneries for cracking of heavy oil into gasoline and liquid performance of the pyrolysis process. As mentioned earlier
oil petroleum. The FCC catalysts used in the pyrolysis pro- that different researchers used different types of catalysts
cess are known as spent FCC catalysts, as they come from such as ZSM-5, HZSM-5, FCC, natural zeolite, activated alu-
rening industries. Moreover, these catalysts are successfully mina, and red mud (Miskolczi et al., 2009; Hernandez et al.,
used in pyrolysis process even though they contain some 2007; Achilias et al., 2007; Sriningsih et al., 2014). Catalysts
impurities. Abbas-Abadi et al. (2014) reported that 20 wt% have different impacts on the pyrolysis process and its prod-
catalyst/polymer ratio was optimum ratio for the maximum ucts (Table 4).
conversion of HDPE plastics wastes into liquid oil. However,
increase in catalyst/polymer ratio increases the gases and 3.1.1. Effect of catalyst on quality of liquid oil
char production. Kyong et al. (2002) carried out the pyrol- According to Miskolczi et al. (2006), and Lopez et al. (2012),
ysis of different types of plastic waste such as PS, LDPE, use of a catalyst increases the quality of liquid oil. Miskolczi
HDPE, and PP by using the FCC catalyst and reported 8090% et al. (2013) further explained that a catalyst affects the pyrol-
of liquid oil production. Overall in comparison to other cat- ysis mechanism and converts the heteroatoms into a gaseous
alysts, FCC catalyst increases the liquid oil yield (Degnan, phase. Moreover, according to Bhaskar et al. (2002), the use
2000). of a catalyst can decrease the concentration of halogens in
Silica-alumina catalysts are amorphous catalysts having the pyrolysis liquid oil. The use of a silica-alumina cata-
Lewis acid sites as electron acceptors and Bronsted acid sites lyst decreased the bromine contents in pyrolysis liquid oil
with ionizable hydrogen atoms. The acidity of these catalysts (Blazs et al., 2002). The use of a ZSM-5 catalyst decreased
was determined by using mole ratio of SiO2 /Al2 O3 . Acidity of the nitrogen, phosphorous and sulphur contents in the pyrol-
these catalysts affects the production of liquid oil from pyrol- ysis liquid oil, especially in the gasoline, as according to
ysis of plastics wastes. The higher the acidity, the lower will Miskolczi et al. (2009), the degradation process of pollutants
be the production of liquid oil. Sakata et al. (1996) carried out occurs at greater scale in small internal pores of ZSM-5.
the pyrolysis of HDPE by using three different types of silica- During the catalytic conversion of refuse derived fuel (RDF),
alumina catalysts such as SA-1, SA-2, and ZSM-5. The obtained the use of a catalyst reduced the formation of less corro-
results indicated that SA-2 catalyst with lower acidity pro- sive carboxylic acid (Whyte et al., 2015). Moreover, catalysts
duced maximum quantity of liquid oil (74.3 wt%), while ZSM-5 involve the removal of oxygenated species that lead to an
with higher acidity produced lower quantity of liquid oil (49.8 increase in the HHV of liquid oil (Pattiya et al., 2008). Metal
wt%). However, during vapor phase contact, gases production containing catalysts showed a high efciency of impuri-
was increased due to further decomposition of hydrocarbons. ties removal from the pyrolysis liquid oil (Miskolczi et al.,
In addition, temperature affects the performance of these cat- 2013).
alysts. Luo et al. (2000) carried out the pyrolysis of PP and HDPE
at higher temperature (500 C) that increased the production 3.1.2. Effect of catalyst on retention time and temperature
of liquid oil to 90 and 85 wt% respectively. Hence, the liquid oil Catalytic cracking of plastic was promoted in the pyrolysis
production can be increased by using silica-alumina catalysts to make the overall process economically feasible by reduc-
with low acidity and high process temperature. ing the retention time and temperature (Chen et al., 2014;
Zeolites catalysts are the crystalline alumino-silicates Achilias et al., 2007). Different researchers have reported that
sieves having three-dimensional framework with cavities the use of a catalyst gives similar product yields at a lower
and channels, where cations may reside. The ion exchange temperature and retention time in comparison to thermal
capabilities and open pores are the main characteristics pyrolysis (Lopez et al., 2011; Ohkita et al., 1993). Increase
of these catalysts. Zeolites catalysts have different ratio of in the cracking rate at lower temperatures was observed
SiO2 /Al2 O3 that determine their reactivity and also affect under catalytic conditions (Lee, 2001). The zeolite catalyst
the end products of pyrolysis process. Zeolites catalysts showed a high rate of CC cracking reaction due to its high
having high acidity are more active in cracking process, hence pore surface area that leads to acceleration in the thermal
increase the production of light olens and decrease the degradation of plastic (Bridgewater, 2012; Miskolczi et al.,
heavy fractions (Artetxe et al., 2013). Moreover, the use of 2009).
these catalysts increase the gases production and decrease
the liquid oil yields. Catalytic pyrolysis of HDPE with HZSM-5 3.1.3. Effect of catalyst on liquid oil compounds
at 450 C produced 35 wt% liquid oil with 65 wt% gases (Seo As stated earlier, catalyst use in pyrolysis process increases
et al., 2003), while using same catalyst and feedstock at the quality of pyrolysis liquid oil (Panda et al., 2010) with aro-
500 C, liquid oil was decreased to 4.4 wt% with 86.1 wt% matic compounds (Lee, 2012). Moreover, the use of a catalyst
gases production (Hernandez et al., 2007). Overall zeolites improves the control production of hydrocarbons from HDPE,
catalysts increase the volatile hydrocarbon production. More- LDPE, PP, and PS plastic types. Thermal pyrolysis of plastic
over HZSM-5 has very low rate of deactivation, thus more produces high carbon chain compounds ranging from C5 to
suitable for catalyst reuse. All the above mentioned catalysts 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 difcult 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 ) 822838


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) modication 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 didnt 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 parafns, napthenes and olens.
H-Y Zeolite 50% PE, PP, PS 42, 44, 71 46, 52, 24 8, 10, 5. Polyolen (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)
Polyolen produces wax while PS didnt produce any wax.
Liquid oil produces from PS mainly consist of styrene (81%).

829
830
Table 4 (Continued)
Catalyst used Quantity of Feedstock Effect on yield Catalyst effect References
catalyst used
Liquid Gases Char

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.

Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838


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
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 (4853 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 ) 822838 831

increases the gasoline fraction (C5 C12 ) in the pyrolysis liquid hydrocarbons into smaller molecular hydrocarbons (Onwudili
oil (Syamsiro et al., 2014). et al., 2009).
Manos et al. (2000) reported that catalytic degradation PVC plastic is widely used in construction, electronic and
of PE with Y-zeolite produced more gasoline range com- automotive applications. Pyrolysis of PVC produces hazardous
pounds, mainly the isoparafns with high octane numbers. chlorine gas (Lopez et al., 2012). A catalytic pyrolysis of PVC
Catalytic degradation of HDPE and LDPE with the FCC cata- plastic with other plastics was carried out with the main
lyst produced gasoline range hydrocarbons (C7 C12 ) with the focus of adsorbing the HCl produced during pyrolysis. In
main components of iso-alkenes or iso-alkanes. For HDPE, addition, a few studies were also carried out to inhibit the
few higher compounds with normal alkanes were found formation of HCl during the pyrolysis (Lopez et al., 2012).
in the liquid oil (Achilias et al., 2007). According to Panda However, the dual effect of a catalyst, dechlorination and
et al. (2010) and Grieken et al. (2001), use of a ZSM-5 cat- catalytic pyrolysis on the mixture of plastic including PVC
alyst in the batch reactor for the degradation of PE plastic plastic (Zhou et al., 2008; Yanik et al., 2001) was rarely reported
type increased the cracking, aromatization and isomerization by scientists. Lopez et al. (2011) stated that 50% removal
process. of chlorine from liquid oil was achieved by following step-
Thermal degradation of PP on clinoptiloite zeolite wise pyrolysis of PVC plastic that included dechlorination and
increased the gasoline range compounds and decreased pyrolysis steps. The dechlorination step was carried out at a
the char (Kima et al., 2002). Moreover, ZSM-5 resulted in the low temperature to remove the chlorine, and then later on
formation of branched hydrocarbons with aromatics in liquid the pyrolysis process was carried out for the conversion of
oil. It has high catalytic activity for the degradation of heavy PVC into liquid oil. The experiment was carried out with and
hydrocarbons into lower gaseous hydrocarbons (Seo et al., without catalysts at the dechlorination step. The obtained
2003; Mastral et al., 2006). Miskolczi et al. (2009) reported that results showed that the dechlorination step with a catalyst
catalytic degradation of agricultural and packaging waste decreased the catalyst efciency by blocking its active sites
using ZSM-5 catalyst increased the yield of gases, gasoline and (Fig. 1).
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- 3.1.4. Effect of catalyst on physical properties of liquid oil
tively. Liquid oil produced from catalytic degradation of PS The use of a catalyst affects the physical properties of pyrol-
plastic with HY-zeolite was affected by the reforming temper- ysis liquid oil (Whyte et al., 2015), such as viscosity that is
ature. At 450 C, the liquid oil was 80% composed of C6 C8 and one of the important parameters for any petroleum product.
C14 C16 compounds. The temperature increase from 400 to Abdullah et al. (2010) reported that the suitable viscosity for
450 C increased the benzene and toluene, and decreased the fuel oil at 25 C is 1000. High viscous oil affects the engine per-
styrene, ethylbeneze, styrene dimmer and PAH concentration. formance as it is hard to pump the oil into the engine during
This is due to the increase in catalytic activity of HY-zeolite its operation. Therefore a pump is required to inject the fuel
that resulted in the degradation of higher molecular weight into atomizer, hence making the process costly (Kim et al.,

Fig. 1 Flow chart of pyrolysis process.


832 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838

2009; Mohan et al., 2006). Feedstock composition is another 4. Types of catalysts and their
factor that affects the viscosity of liquid oil. Liquid oil from characteristics
PE and PP pyrolysis had viscosities of 2.32 and 2.18 mm2 /s
respectively (Syamsiro et al., 2014; Panda and Singh, 2013). 4.1. Catalyst types
However, liquid oil produced from PS is less viscous (Siddiqui
and Redhwi, 2009). The differences in viscosity results are In catalytic pyrolysis, different types of catalysts such as
due to the composition and structure of different feedstocks homogenous catalyst (Kaminsky and Nunez, 2007), acid meso-
(Ates et al., 2013). Any factor in the pyrolysis process that porous materials (Aguado et al., 2007), non-acid mesoporous
cracks the liquid oil to a lower molecular weight leads to low- solid (Chaianansutcharit et al., 2007), FCC catalyst (Olazar
ers the viscosity (Diebold, 2000) and it is achieved by using et al., 2009), zeolite (Aguado et al., 2009), and metallic oxide
a catalyst (Miskolczi et al., 2013). Ates et al. (2013) reported (Siddiqui and Redhwi, 2009) have been examined (Table 5).
that all the catalysts show a high conversion of long chain However, the most commonly used catalysts are zeolite, silica-
aliphatic compounds into aromatic compounds. In addition, alumina, MCM-41 and FCC (Lin and Yang, 2007; Miskolczi
reduction of oxygenated lignin species can result in less vis- et al., 2006). Zeolite catalyst has been extensively studied by
cous oil (He et al., 2009). Miskolczi et al. (2013) reported that different scientists and found to be better in the degrada-
the use of a catalyst decreased the moisture content and tion of polyolen (Lopez et al., 2011). The key features of the
cetane index of liquid oil. In addition, use of Y-zeolite and zeolite catalyst are acid strength, pore size and pore distri-
natural zeolite (NZ) decreased the pour point of liquid oil bution (Panda et al., 2010). In advanced catalytic pyrolysis,
from municipal plastic waste pyrolysis (Syamsiro et al., 2014). bi-functional (reforming) catalysts that have both acidic and
Moreover, the use of a catalyst decreases the density, ash metal sites are characterized (Panda et al., 2010). Different
point, boiling range and HHV of liquid oil (Miskolczi et al., kinds of metals such as Ni, Co, and Mo are doped over the
2009). 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
3.1.5. Effect of catalyst on gases produced et al., 2010).
The use of a catalyst increases the production of gases and An increase in the yield of gases in catalytic pyrolysis is due
decreases the liquid oil yield but improves its quality. Gases to high inter-crystalline structure of the catalyst that acceler-
produced from pyrolysis process consist of CO, CO2 , H2 and ates the cracking, isomerization and aromatization reactions
CH4 (Whyte et al., 2015). However, pyrolysis of PVC produce (Panda et al., 2010). Furthermore, it increases the production
chlroine gas (Lopez et al., 2011b). The use of catalyst favors of aromatics in the liquid oil (Lopez et al., 2011). HZSM-5
the decarboxylation route, and hence increases the CO2 pro- increases the volatile compounds in the liquid oil (Hernandez
duction and decreases the concentration of CO (Whyte et al., et al., 2007). In addition, it increases the branched carbon
2015; Ates et al., 2013). However, the most important effect of ratio and reduces the formation of straight chain parafns and
a catalyst on the produced gases is the increase of hydrogen olens (Panda et al., 2010). Moreover, nanocrystalline HZSM-5
concentration and carbon frame isomerization that resulted increases the production of gases during the catalytic pyrolysis
in an increase of i-butane concentration (Ates et al., 2013). (Mastral et al., 2006). FCC catalyst has Si/Al ratio of 1.5 (Chung
Miskolczi et al. (2009) reported that the use of ZSM-5 catalyst et al., 2003). These catalysts have smaller microporous and BET
produced gases that contain mainly C3 hydrocarbons from PP, surface areas, and hence produce more liquid oil as compared
while C2 and C4 hydrocarbons were produced from packaging to other catalysts such as ZSM-5 that has high microporous
waste. The difference between the compositions of produced area (Seo et al., 2003). Mordenite and Clinoptillolite are the NZ
gases is due to the structure of used feedstock. In addition, the with a microporous area that favors the liquid oil yield in com-
HHV of produced gases was 45.946.6 MJ/kg from agriculture parison to gases (Lee, 2012; Miskolczi et al., 2006). Reforming
and packaging waste respectively (Miskolczi et al., 2009) and catalyst such as doping via wet impregnation of Ni, Co and
17.121.9 MJ/m3 from RDF (Whyte et al., 2015). Mo with NZ was examined. The results showed that doping
did not affect the overall crystallinity of the catalyst. However,
CoMo/Z showed a high efciency in the conversion of plastic
into gasoline range liquid oil due to its high acidity (Sriningsih
3.1.6. Effect of catalyst on char produced et al., 2014).
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- 4.2. Catalyst characteristics
tion (Lee, 2012). Catalyst separation from the char is difcult
(Lopez et al., 2011). The catalyst does not affect the ele- Catalytic cracking on acid catalysts takes place with the for-
mental characteristics of char (Whyte et al., 2015). However, mation of carbocations that require strong acid sites (Achilias
it increases the ash contents in char (Lopez et al., 2011). et al., 2007). Acid strength and textural properties such as
Char produced from the catalytic pyrolysis of RDF contained BET surface area, acidity, pore size, pore volume, Si/Al ratio,
5354% of ash that decreased its caloric value and caused thermal stability, and dimension are the main characteris-
problems during its combustion (Whyte et al., 2015). In addi- tics of acid catalysts (Fig. 2). Acidity of the catalyst plays a
tion, the use of a catalyst increased the H/C ratio in the char vital role in the catalytic pyrolysis. Bronsted and Lewis acid
(Lopez et al., 2011). Moreover, char deposition on the catalyst sites are considered during the acidity measurement of cata-
during the pyrolysis process decreases the active sites, and lysts. The majority of acid sites are present inside the catalysts
hence negatively affects the catalytic activity (Miskolczi et al., that enhance the cracking process (Venuto and Landis, 1968;
2013). Panda et al., 2010). Sriningsih et al. (2014) reported that treating
Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838 833

Fig. 2 Flow chart showing the characteristics of catalysts.

catalysts with HCl increased the catalyst acidity. Acidic cata- and wet impregnation. Syamsiro et al. (2014) stated that by
lyst increases the gasoline range hydrocarbon production in heating the NZ at a temperature of 500 C for 3 h removed
liquid oil (Lopez et al., 2011). Porosity in another catalyst fea- the volatile impurities of the catalyst, thus lead to an increase
ture that affects the catalytic activity by selective adsorption in its catalytic activity. Moreover, the acid leaching with HCl
mechanism (Miskolczi et al., 2006). removes the impurities from the NZ catalyst and increases its
A microporous catalyst with a high internal crystalline acidity (Sriningsih et al., 2014). Similarly, the wet impregna-
structure increases the catalytic process, produces more tion method is an important technique that is widely used to
gases, and decreases the liquid oil yield but improves its qual- generate heterogeneous catalysts (Adnan et al., 2014).
ity (Lopez et al., 2011). While a catalyst with macropore volume Reformed catalysts show a bi-functional effect. Metallic
has little effect on the liquid oil quantity, as it produces large sites accelerate the hydrogenation and dehydrogenation reac-
carbon chain compounds (Miskolczi et al., 2006). The ther- tions, whilst acidic sites accelerate the isomerization reactions
mal stability of a catalyst is very important for the pyrolysis (Panda et al., 2010). Making the composite of zeolite with zinc
process. Nizami et al. (2015b) reported that NZ present in increases the adsorption capacity of the zeolite catalyst. It nar-
KSA showed thermal stability at high temperatures (up to rows the pores of zeolites that improve the effective sieving
900 C) that shows its potential to be used as a catalyst in effect. It allows only small molecules to pass through their
the pyrolysis process. Different studies showed that catalyst pores. Modied zeolites have an average particle size of a few
activity improves with the increase in process temperature microns. The internal surface area can represent more than
(Syamsiro et al., 2014). However, with the passage of time, 99% of the total surface area. Almost all the active sites are
catalyst activity decreases due to the deposition of coke or located inside the pores that increase its adsorption capac-
impurities present in the feedstock that reduces the strength ity, thereby enhancing its purication capacity (Ciobanu et al.,
of the acidic sites (Syamsiro et al., 2014; Lopez et al., 2012). 2008). Adnan et al. (2014) reported that doping of Cu on Al2 O3
In addition, a catalyst with more than one dimension allows increased the BET surface area, pore volume and pore size.
more cracking than a mono dimensions catalyst because it Moreover, the use of these reformed catalysts will increase the
provides more surface area for cracking (Lee, 2012). overall catalytic pyrolysis efciency and improve the products
quality. However, some challenges and scope for improve-
5. Catalyst modication and future ment still remain in the catalytic pyrolysis of plastic waste.
perspective After a detailed review of all aspects of the catalytic pyroly-
sis process, the recommended areas for further research and
The selection of a catalyst for the degradation of plastic waste development including detailed life cycle assessment (LCA)
is a critical step in pyrolysis. The catalyst modication has for pyrolysis sustainability as an alternative energy genera-
been under consideration for the last decade to improve the tion technology (Chan et al., 2016; Demirbas et al., 2016a and
pyrolysis processs efciency. Modication in catalysts can be b; Shahzad et al., 2015; Rathore et al., 2016) are grouped in
carried out in different ways, such as acid leaching, thermal, Box 1.
834 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 822838

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 efcient both
1.15, 0.88
NH3 /g)

economically and environmentally.


0.176
0.176

Detailed chemical characterization of produced liquid


NR
NR

NR
NR
NR
0.2

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
171
120

this technology.
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

3770

1030

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 efcient 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.

nicant 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,
modications 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 ) 822838 835

Acknowledgment Feedstock recycling and pyrolysis of waste plastics: converting


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