Accepted Manuscript

Title: Catalytic Pyrolysis of Plastic Waste: A Review

Author: R. Miandad M.A. Barakat Asad S. Aburiazaiza M.

Rehan A.S. Nizami

PII: S0957-5820(16)30108-2
DOI: http://dx.doi.org/doi:10.1016/j.psep.2016.06.022
Reference: PSEP 810

To appear in: Process Safety and Environment Protection

Received date: 6-12-2015

Revised date: 30-5-2016
Accepted date: 13-6-2016

Please cite this article as: Miandad, R., Barakat, M.A., Aburiazaiza, A.S., Rehan,
M., Nizami, A.S.,Catalytic Pyrolysis of Plastic Waste: A Review, Process Safety and
Environment Protection (2016), http://dx.doi.org/10.1016/j.psep.2016.06.022

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 1

1 Catalytic Pyrolysis of Plastic Waste: A Review

2 R Miandad1,2, MA Barakat1,2, Asad S. Aburiazaiza1,2, M Rehan2, AS Nizami2*

1
3 Department of Environmental Sciences, Faculty of Meteorology, Environment and Arid Land
4 Agriculture, King Abdulaziz University, Jeddah, Saudi Arabia
2
5

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Centre of Excellence in Environmental Studies (CEES), King Abdulaziz University, Jeddah, Saudi
6

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Arabia
7

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8 Abstract
9 This paper reviews the progress and challenges of the catalytic pyrolysis of plastic waste and its

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10 future perspectives in comparison to thermal pyrolysis. The factors affecting the catalytic pyrolysis
11 process such as the temperature, retention time, feedstock composition and the use of catalyst were
12 identified. Pyrolysis can be carried out via thermal or catalytic routes. Thermal pyrolysis produces
13
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low quality liquid oil and requires both a high temperature and retention time. In order to overcome
14 these issues, catalytic pyrolysis of plastic waste has emerged with the use of a catalyst. It has the
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15 potential to convert 70-80% of plastic waste into liquid oil that has similar characteristics to
16 conventional diesel fuel; such as the high heating value (HHV) of 38-45.86 MJ/kg, a density of
17 0.77-0.84 g/cm3, a viscosity of 1.74-2.5 mm2/s, a kinematic viscosity of 1.1-2.27 cSt, a pour point of
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18 (-9)-(-67)°C, a boiling point of 68-352°C, and a flash point of 26.1-48°C. Thus the produced liquid
19 oil is of higher quality and can be used in several energy-related applications such as electricity
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20 generation, transport fuel and heating source. Moreover, process by-products such as char has the
21 potential to be used as an adsorbent material for the removal of heavy metals, pollutants and odor
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22 from wastewater and polluted air, while the produced gases have the potential to be used as energy
23 carriers. Despite all the potential advantages of the catalytic pyrolysis, some challenges such as high
24 process energy input, catalyst costs and catalyst low reuse still remain. The possible solutions for
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25 these challenges include exploration of cheaper catalysts, catalyst regeneration and overall process
26 optimization.

27 Keywords: Plastic waste; Pyrolysis; Liquid oil; Catalyst; Value-added products; Fuel production

28
29 * Corresponding author:
30 Email: nizami_pk@yahoo.com
31

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1 LIST OF ACRONYMS AND ABBREVIATIONS

BET: Brunauer, Emmett and Teller
HDPE: High Density polyethylene
2
HHV: Higher Heating Value
3 KSA: Kingdom of Saudi Arabia
LDPE: Low Density Polyethylene
4 MSW: Municipal Solid Waste

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NZ: Natural Zeolite

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5 PET: Polyethylene-Terephthalate
PP: Polypropylene
6 PS: Polystyrene

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PVC: Polyvinyl Chloride
7 RDF: Refuse Derived Fuel

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8

9 1. Introduction
10
11
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The municipal solid waste (MSW) is one of the chronic environmental, health and economic
12 problems in most developing countries (Nizami et al., 2016). The high generation rate of MSW (up
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13 to 1.3 billion tons per year) in developing world is the result of both rapid increase in population
14 and urbanization, and raised living standards (Nizami et al., 2015a; Martinot et al., 2002). In last
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15 few decades, millions of people have shifted from rural to urban areas in many parts of the world
16 (Nizami et al., 2015b). Currently half of the world’s population lies within urban areas (Tacoli,
17 2012). Moreover, according to a United Nation (UN) report, the 3.9 billion current urban population
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18 will increase to 6.3 billion by 2050, with a 90% increase only in urban areas of Africa and Asia
19 (UN, 2014).
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20
21 MSW can be a valuable source of biomass, recycled materials, energy and revenue if properly and
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22 wisely managed (Nizami et al., 2015a). However, many of the municipalities within the developing
23 world do not have sufficient technical and economical capabilities to treat and dispose MSW in an
24 eco-friendly manner (Tacoli, 2012). The Kingdom of Saudi Arabia (KSA) is facing the same
25 problems with MSW management, like other developing nations (Ouda et al., 2016). MSW is
26 generated at an alarming rate of around 15 million tons per year in KSA and is estimated to double
27 (30 million tons) by 2033. In KSA, plastic waste is the second largest waste stream (up to 17.4%) of
28 MSW after organic waste (Nizami et al., 2015a; Nizami et al., 2016).
29

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1 Plastic waste has become one of the indelible component of MSW, as used in a wide range of
2 products due to its durability, light weight and low cost (Serrano et al., 2002; Aguado et al., 2007).
3 In 2011, the total world plastic waste production was 280 million tons. This was estimated to further
4 increase with a rate of 4% by 2016 (Sriningsih et al., 2014). Plastic waste is the mixture of different
5 plastic products that are predominantly made from low density polyethylene (LDPE), high density

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6 polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and
7 polyethylene-terephthalate (PET). PE and PS plastics are the main components of municipal plastic

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8 waste (Onwudili et al., 2009).
9

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10 The plastics are mostly non-biodegradable and remain in the environment for hundreds of years
11 (Ashworth et al., 2014). Conventional recycling methods such as sorting and grinding can recycle
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only 15-20% of total plastic waste (Khan and Kaneesamkandi, 2013; Siddiqui and Redhwi, 2009).
The energy recovery technologies such as thermal and catalytic pyrolysis, gasification and plasma
14 arc gasification are receiving more attention nowadays as alternative methods of plastic waste
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15 recycling (Nizami et al., 2015a; Ouda et al., 2016). Pyrolysis process converts plastic waste into
16 liquid oil, solid residue (char) and gases at high temperatures (300-900°C) via thermal
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17 decomposition. However, there are certain limitations in the conventional thermal pyrolysis, where
18 the whole process is temperature-dependent (Sadaf et al., 2015; Tahir et al., 2015). The liquid oil
19 produced from thermal pyrolysis may contain impurities like residues, chlorine, and sulphur
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20 (Borsodi et al., 2011). Moreover, the thermal pyrolysis of PE type plastics such as HDPE and LDPE
21 along with PP are difficult to conduct due to their crossed chain hydrocarbon structures (Achilias et
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22 al., 2007). Therefore, catalytic pyrolysis is being developed to overcome the problems of thermal
23 pyrolysis (Lopez et al., 2011a).
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24
25 A range of catalysts have been utilized, including Red Mud (Lopez et al., 2011a), FCC (Lee, 2009),
26 ZSM-5 (Lopez et al., 2011a), HZSM-5 (Hernandez et al., 2007), Y-Zeolite (Lee, 2012), Fe2O3
27 (Sarker et al., 2013), Al2O3, Ca(OH)2 (Sarker et al., 2011a) and natural zeolite (Syamsiro et al.,
28 2014), in catalytic pyrolysis to improve the quality of liquid oil (Wang and Wang, 2011). The
29 catalyst increases the lighter fractions in the liquid oil produced, such as gasoline (Lerici et al.,
30 2015), and decreases the overall process energy-inputs (Lopez et al., 2011a). Moreover, the use of
31 the ZSM-5 catalyst decreases impurities like sulphur, nitrogen, and phosphorous in the produced

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1 liquid oil (Miskolczi et al., 2009). It is also reported that the use of catalysts with a high BET
2 surface area allows more contact between reactants and the catalyst surface, resulting in an
3 increased rate of cracking reaction to produce more gases (Syamsiro et al., 2014).
4
5 Although substantial research is underway to explore different types of catalysts and their dynamic

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6 role in the pyrolysis process and its products, but a comprehensive review on what has been
7 achieved in the catalytic pyrolysis of plastic waste, the challenges and limitations of this process,

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8 and what the future directions are, hasn’t been widely-published (Nizami et al., 2015a, b; Nizami et
9 al., 2016). Therefore, this paper reviews the progress and challenges of the catalytic pyrolysis of

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10 plastic waste and its future perspectives in comparison to thermal pyrolysis. In addition, the factors
11 affecting the catalytic pyrolysis process, such as temperature, retention time, feedstock composition,
12
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and the use of catalysts, were evaluated. The effect of different catalysts on the quantity and quality
of pyrolysis products has been examined in detail against characteristics of catalyst. Moreover,
14 catalyst reforming and the regeneration and exploration of new cheaper catalysts were also focused
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15 upon in order to make the catalytic pyrolysis process more economical and sustainable.
16
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17 2. Pyrolysis
18
19 Pyrolysis is a tertiary recycling technique in which organic polymers are converted into liquid oil,
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20 char and gases at high temperatures via thermal decomposition (Chen et al., 2014; Ouda et al.,
21 2015; Anjum et al., 2016). Pyrolysis studies were carried out at different temperatures ranging from
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22 300-900°C, however typical optimum temperatures for plastic waste were around 500-550°C (Chen
23 et al., 2014). Moreover, pyrolysis of different plastic waste was carried out at different heating rates
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24 such as 4°C/min (Velghe et al., 2011), 20-25°C/min (Zhao et al., 2011) and 10°C/min (Buah et al.,
25 2007). In addition, different researchers used different retention times for pyrolysis process. Lopez
26 et al. (2011) carried out pyrolysis of plastic waste at retention times of 0-15, 15-30 and 120 min.
27 Other studies were carried out at different retention times of 40-70 min (Buah et al., 2007), 120 min
28 (Velghe et al., 2011), and 45 min (Zeaiter, 2014). Kumar and Singh (2011) carried out pyrolysis of
29 HDPE at different temperatures ranging from 400-550°C. The study concluded that with the
30 increase of temperature, there was decrease in retention time e.g. 760 min (400°C), 290 min
31 (450°C), 68 min (500°C) and 54 min (550°C). However, there is scope for further reduction of

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1 process temperature and retention time to optimize the overall process. The pyrolysis can be carried
2 out via thermal and catalytic routes (Table 1).
3
4 2.1 Thermal Pyrolysis
5

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6 The non-catalytic or thermal pyrolysis of plastic waste is an endothermic process that doesn’t
7 employ any catalyst. The thermal pyrolysis of different types of plastic has been carried out

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8 extensively in the past, including PE (Murata et al., 2004; Cha et al., 2002), PP (Dolezal et al.,
9 2001; Kim and Kim, 2004) and PS plastics (Faravelli et al., 2001; Cha et al., 2002), as grouped in

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10 Table 2. Moreover, few studies have been carried out on PVC, PET, polymethyl methacrylate and
11 polyurethane (Kaminsky et al., 2004; Miskolczi et al., 2004). Thermal degradation of PS was easily
12
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carried out in comparison to thermal degradation of HDPE, LDPE and PP (Uddin et al., 1997)
because the PE (HDPE and LDPE) and PP require high temperatures for degradation, as compared
14 to PS plastic (Miskolczi et al., 2009). Furthermore, in the absence of a catalyst, PE is converted into
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15 wax instead of liquid oil (Lee, 2012). The liquid oil produced by thermal degradation contains
16 heavy oil compounds with large carbon chains as the major compounds (Lopez et al., 2011c).
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17 Moreover, liquid oil is of low quality due to its low octane number and presence of high solid
18 residues (Kim and Kim, 2004; Seth and Sarker, 2004) and impurities such as sulphur, nitrogen, and
19 phosphorous (Miskolczi et al., 2009).
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20 2.2. Catalytic Pyrolysis

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21
22 The catalytic pyrolysis is carried out with the utilization of a catalyst. The catalytic process shows
23 high potential for the conversion of plastic waste into liquid oil, with better product quality at lower
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24 temperatures and reaction times when compared to thermal pyrolysis (Table 1). These factors can
25 reduce the process parasitic energy demand and thus optimize the overall pyrolysis process (Manos
26 et al., 2002). In this regard, different catalysts such as FCC (Achilias et al., 2007), spent FCC (Lee,
27 2009), HZSM-5 (Lee, 2012), ZSM-5 (Miskolczi et al., 2009; Lopez et al., 2011a), Cu-Al2O3 (Adnan
28 et al., 2014), Co-Mo/Z (Sriningsih et al., 2014), Zeolite-ß (Ojha and Vinu, 2015), natural zeolite
29 (NZ) (Syamsiro et al., 2014), Red Mud (Lopez et al., 2011a), Al(OH)3 Ca(OH)2 (Sarker et al.,
30 2011a) and Fe2O3 (Sarker et al., 2013) have been used to enhance the yield and mechanism of
31 catalytic pyrolysis. Hydrocarbon (HCs) produced from different plastics such as HDPE, LDPE

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1 (Park et al., 2002), PP (Hwang et al., 1999; Hwang et al., 2002) and PS (Bagri et al., 2002; Kim et
2 al., 2002) contains low carbon chain compounds (gasoline range (HCs)) in comparison to thermal
3 pyrolysis (Scott et al., 1990; Park et al., 1999; Aguado et al., 2000). Moreover, the catalyst increases
4 the gaseous products and reduces the liquid yield when compared to thermal pyrolysis (Park et al.,
5 1999: Beltrame et al., 1989). Nonetheless, the conversion rate was increased at low temperature

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6 under the catalytic conditions in comparison to thermal pyrolysis (Ding et al., 1997: Park et al.,
7 1999, Lee et al., 2001).

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8
9 2.3. Suitable Plastic Types for Pyrolysis

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10
11 Thermal and catalytic pyrolysis of all plastic types such as PS, PE (HDPE, LDPE), PP, PVC and
12
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PET as single substrate has been carried out in the last few decades (Table 2). Lee (2009) and
Miskolczi et al. (2009) carried out pyrolysis of mixed plastic wastes, real MSW and municipal
14 plastic waste that was comprised of almost all kinds of plastics. In addition, a few studies were
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15 carried out on polymethyl methacrylate (Kaminsky et al., 2004) and polyurethane (Miskolczi et al.,
16 2004). Sakata et al. (1996) and Lopez et al. (2012) studied the pyrolysis of PVC that produces
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17 hazardous chlorine gas. To overcome the problem of chlorine gas production, the dechlorination
18 step at a low temperature is recommended to remove the hazardous chlorine in the form of HCl
19 (Lopez et al., 2011a; Lopez et al., 2012).
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20
21 2.4. Factors Affecting Pyrolysis Process
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22
23 The pyrolysis of plastic waste is affected by a number of process parameters such as temperature
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24 (Yoshioka et al., 2004; Ji et al., 2006), retention time (Lopez et al., 2011c; Lee and Shin, 2007),
25 feedstock composition (Troger et al., 2013; Acomb et al., 2015), use of catalyst (Lerici et al., 2015;
26 Miskolczi et al., 2013; Chen et al., 2014), moisture content (Chen et al., 2014), heating rate (Sharma
27 et al., 2014) and particle size (Luo et al., 2010).
28
29 2.4.1. Temperature
30 Temperature is considered as to be one of the most important factors affecting both the quality and
31 quantity of pyrolysis products (Lopez et al., 2011c). The temperature affects the cracking reactions

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1 that alter the amount of gases and liquid produced. However there is little effect upon the amount of
2 char produced (Yoshioka et al., 2004; Ji et al., 2006; Lopez et al., 2011c). At a low temperature long
3 chain hydrocarbons are produced but an increase in temperature results in the production of short
4 carbon chain compounds due to the cracking of C-C bonds. Hernández et al. (2007), Lopez et al.
5 (2011) and Li et al. (2005) have reported that aromatic compounds are produced at higher

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6 temperatures due to the triggering of secondary reactions.
7

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8 2.4.2. Retention Time and Feedstock Composition
9 Retention time has shown no significant effect upon the yield of the pyrolysis process. Lopez et al.

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10 (2011) have stated that the same yield of oil is observed at 30 min and 120 min retention times.
11 Similarly, the aromatic compounds present in liquid oil were the same at different retention times
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using the same temperature (Lee and Shin, 2007). Nevertheless, feedstock composition also affects
the yield of the pyrolysis process, although this has yet to be explored in detail (Troger et al., 2013).
14 According to Miskolczi et al. (2009), the PE and PP require higher temperatures for their
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15 degradation as compared to PS plastic, due to different and more complex structures.
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17 2.4.3. Use of Catalyst

18 The catalysts play an important role in improving the quality of products as well as reducing the
19 process temperature and retention time for overall process optimization. Fe2O3 (Sarker et al., 2013),
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20 Ca(OH)2 (Sarker et al., 2011a), FCC (Lee, 2009), natural zeolite (Syamsiro et al., 2014) and
21 synthetic zeolite (Lopez et al., 2011) are different catalysts that are mostly used by different
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22 scientists in the catalytic pyrolysis process. The use of catalysts increases the rate of the cracking
23 reactions that lead to an increase in the production of gases with the reduction in liquid oil yield
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24 (Syamsiro et al., 2014). However, the quality of the liquid oil produced is improved because some
25 of the larger carbon chain compounds are either adsorbed in the catalyst or further broken down into
26 smaller carbon chain compounds. Catalyst characteristics such as BET surface area, pore size, pore
27 volume, and acidity are the main factors that affect the catalytic activity of any catalyst.
28

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1 2.5. Products of Pyrolysis Process

2
3 2.5.1. Liquid Oil and Its Potential Applications
4 Liquid oil produced from the plastic pyrolysis has the potential to be used as an alternative source of
5 energy. Lopez et al. (2011) and William (2006) reported that the pyrolysis process can convert 78-

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6 84% by weight plastic into liquid oil. Moreover, the theoretical energy required to convert 1 kg of
7 PE into liquid oil and other value-added products is 1.047 MJ/kg; whilst the liquid oil produced has

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8 similar properties in comparison with conventional diesel (Table 3). The pyrolytic liquid oil of
9 different plastic types can be used for different heating and energy purposes. Various studies have

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10 been carried out for the application of pyrolytic liquid oil as transport fuel (Mukherjee and
11 Thamotharan, 2014; Nileshkumar et al., 2015; Lee et al., 2015). The liquid oil was further blended
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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;
14 Lee et al., 2015; Gardy et al., 2014). The aims of these studies were to examine the effect of
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15 pyrolytic liquid oil blended with conventional diesel on the performance of engine and exhaust
16 emissions. Lee et al. (2015) reported that at 20/80% (pyrolytic fuel/ conventional diesel), the engine
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17 performance decreased by13% at 2450 rpm, while it reached up to 17% at 3500 rpm. However, at
18 40-60%, the engine running was achieved only for few min with 37 and 56% decrease in engine
19 performance under intermediate load. Nileshkumar et al. (2015) reported that engine performance
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20 didn’t change up to blending ratio of 20%/80%. In addition, fuel consumption decreases as the ratio
21 of pyrolytic liquid oil increases. However, Cleetus et al. (2013), reported that fuel consumption
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22 increases due to the low calorific value of pyrolytic liquid oil in comparison to conventional diesel.
23
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24 Conventional diesel shows better thermal brake efficiency in comparison to blended diesel
25 (Mukherjee and Thamotharan, 2014). Nileshkumar et al. (2015) examined the load effect on Brake
26 Mean Effective Pressure (BMEP) and Indicated Mean Effective Pressure (IMEP) of engine, when
27 running with different blending ratios. The results concluded that at low load, there is no significant
28 difference on BMEP. However, at higher loads there was an increase in peak pressure with the
29 increase in the blending ratios. Moreover, there was a decrease in IMEP with the increase in
30 blended ratio of pyrolytic fuel that may be due to the high consumption of fuel. The emissions of
31 NOx, CO and CO2 have been analyzed at different blending ratios by various researchers (Frigo et

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1 al., 2014; Mukherjee and Thamotharan, 2014; Nileshkumar et al., 2015; Lee et al., 2015). The
2 results concluded that increase in blending ratios increase the exhaust emissions that start exceeding
3 from 30% blended ratio and reach to maximum at 50% blended ratio (Nileshkumar et al., 2015).
4 Mukherjee and Thamotharan. (2014) reported exhaust emissions of 0.26 g/km and 0.40 g/km and
5 0.52 g/km and 0.69 g/km for NOx for low and full load respectively at 20% blended ratio.

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6 Moreover, for conventional diesel at low and full loads, NOx emissions were found to be 0.26, 0.41
7 g/km and 0.51, 0.71 g/km respectively. However, few CO emissions increased with the blended oil

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8 due to the incomplete combustion (Frigo et al., 2014). Nevertheless, increase in the blended oil
9 ratios overall increase the exhaust emissions.

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11 2.5.2. Char and Its Potential Applications
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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 comparison to other
14 process products such as liquid oil and gases (Lopez et al., 2009; William, 2006). The produced
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15 char has the potential to be used for various environmental and energy applications. Jamradloedluk
16 and Lertsatitthanakorn (2014), reported that char produced from HDPE has fixed carbon (46.03%),
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17 volatile matter (51.40%), moisture content (2.41%), and a small amount of ash. Produced char from
18 PS and HDPE has HHV of 36.29 and 23.04 MJ/kg respectively (Syamsiro et al., 2013).
19 Jamradloedluk and Lertsatitthanakorn, (2014) prepared a briquettes after crushing the HDPE char
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20 into powder. The produced briquette (1kg) was used to heat 1 liter of water (from room temperature
21 to boiling temperature) within around 13 minutes. Moreover, produced char has the potential to be
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22 used in various environmental applications such as heavy metal adsorption from the municipal and
23 industrial wastewater and toxic gases (Heras et al., 2014). Lopez et al. (2009), thermally activated
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24 the waste tire char at 900oC for 3 hours. It increased the char BET pore volume and surface area to
25 44% and 55% respectively, with decreased pore size by 5%. The steam activation of char produced
26 from waste tires decreased the sulphur contents of char, thus making it more environmental friendly
27 product. Bernando. (2011) upgraded the char produced from co-pyrolysis of PE, PS and PP waste
28 with biomass and waste tires. The activated char was used for the adsorption of methylene blue dye
29 that shows a significant adsorption of dye (3.59-22.2 mg/g). Moreover, char can be used as a
30 feedstock for the activated carbon or source of energy for boilers (Fernandez et al., 2011).
31

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1 2.5.3. Gases and Its Potential Applications

2 The main components of produced gases from pyrolysis of different types of plastic are methane,
3 hydrogen, propane, propene, ethane, ethene, butane and butane (Williams and Williams, 1998).
4 Only the pyrolysis of PVC produces hazardous chlorine gas (Chen et al., 2014). Increase in process
5 temperature increases the production of gases (Lopez et al., 2011). It is reported that 1 kg of plastic

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6 feedstock produces around 13 to 26.9% gases by weight (Chen et al., 2014). The use of a catalyst
7 increases the cracking process that further increases the production of gases. The produced gases

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8 from plastic waste have high calorific values. Miskolczi et al. (2009) reported that gases produced
9 from agriculture plastic waste have 45.9 and 46.6 MJ/kg HHV. In addition, gases produced from PP

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10 and PE have HHV of 50 and 42 MJ/kg respectively (Jung et al., 2010). Moreover, similar results for
11 HHV of waste tires (45 MJ/kg) were also reported (Frigo et al., 2014). The produced gases have
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high HHV and hence showing potential to be used for energy generation. Additionally, the
produced gases can be used in boiler for heating or in gas turbine for the generation of electricity
14 without any flue gas treatment (Fernandez et al., 2011). Moreover on the basis of their composition,
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15 1-butene and isoprene can be recovered through condensation and can be used in tires production
16 (Frigo et al., 2014). While, after separation from other gases, propene and ethane can be used as
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17 chemical feedstocks to produce polyolefins (Sharuddin et al., 2016).

18
19 3. Catalyst and Pyrolysis
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20
21 Plastic waste may contains different kinds of pollutants such as nitrogen, sulphur, and chlorine that
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22 can arise due to surface contamination, additives, and heteroatoms containing plastic such as PVC
23 (Miskolczi et al., 2013). Therefore, the quality of liquid oil produced is compromised by the
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24 presence of these pollutants. The thermal pyrolysis of plastic requires high temperatures (350-
25 500°C) for degradation (Murata et al., 2004; Faravelli et al., 2001). However, a few studies have
26 reported that temperature demand may increase up to 700 or 900°C to achieve high quality products
27 (Demirbas, 2004; Mastral et al., 2002). The gases produced from thermal pyrolysis are also not
28 suitable as a fuel source, and they need intensive refining prior to use (Joo and Guin, 1998). The
29 low thermal conductivity with endothermic cracking makes the thermal pyrolysis a high energy-
30 intensive process (Achilias et al., 2007). To overcome these problems, especially for feedstock

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1 contamination, ‘in situ’ methods are adopted that involve the use of different catalysts in the
2 pyrolysis process (Mitan et al., 2007).
3
4 In the initial stage of the catalytic pyrolysis, the thermal cracking occurs on the external surface of
5 the catalyst. The internal porous structure of the catalyst then acts as channels for selective

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6 movement and breakdown of larger compounds into smaller ones (Lee, 2009). Due to small pore
7 size the gases are mainly produced inside the pores, whilst wax production occurs due to external

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8 cracking on the external site of the catalyst (Lin, 2000; Mastral et al., 2006). This phenomenon
9 shows that the degradation of high olefin molecules occurs in the outer surface of the catalyst, but

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10 further degradation and products selectivity takes place in the internal pores of the catalyst (You et
11 al., 2000).
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The solid catalyst can be applied when either directly mixed with feedstock in the reactor or on
14 organic vapors produced in a separate catalyst chamber. Either a liquid phase or direct contact with
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15 feedstock will improve the cracking process by reducing the reaction temperature and retention time
16 (Lopez et al., 2011a; Chen et al., 2014). However, the catalyst recovery is difficult in direct contact,
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17 since the catalyst pores are blocked due to the sticky nature of the plastic feedstock (Syamsiro et al.,
18 2014). Only a few studies have reported catalyst regeneration (Lopez et al., 2011b; Serrano et al.,
19 2007). Additionally, direct contact affects the catalytic activity with the deposition of impurities
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20 such as chlorine, sulphur and nitrogen on the surface of the catalyst during the thermal cracking
21 reaction (Aguado et al., 2007). Vapor phase contact was carried out by using different catalysts such
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22 as Y-zeolite for PE (Bagri and William, 2002), ZSM-5 for PS (William and Bagri, 2004) and ZSM-
23 5 for industrial packaging waste (Lopez et al., 2011a).
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24
25 There are three main types of catalysts that are mainly used in pyrolysis of plastic waste. These
26 catalysts includes; FCC, zeolites and silica–alumina catalysts. FCC catalysts are known as silica–
27 alumina with the binder made up of non- zeolites matrix and zeolites crystal (Degnan, 2000; Magee
28 and Mitchell, 1993). These FCC catalysts are extensively used in the petroleum refineries for
29 cracking of heavy oil into gasoline and liquid oil petroleum. The FCC catalysts used in the pyrolysis
30 process are known as spent FCC catalysts, as they come from refining industries. Moreover, these
31 catalysts are successfully used in pyrolysis process even though they contain some impurities.

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1 Abbas-Abadi et al. (2014) reported that 20 wt% catalyst/polymer ratio was optimum ratio for the
2 maximum conversion of HDPE plastics wastes into liquid oil. However, increase in
3 catalyst/polymer ratio increases the gases and char production. Kyong et al. (2002) carried out the
4 pyrolysis of different types of plastic waste such as PS, LDPE, HDPE, and PP by using the FCC
5 catalyst and reported 80-90% of liquid oil production. Overall in comparison to other catalysts, FCC

t
ip
6 catalyst increases the liquid yield (Degnan, 2000).
7

cr
8 Silica-alumina catalysts are amorphous catalysts having Lewis acid site as an electron acceptor and
9 Bronsted acid site with an ionizable hydrogen atom. The acidity of these catalysts was determined

us
10 by using mole ratio of SiO2/Al2O3. Acidity of these catalyst effect the production of liquid oil from
11 pyrolysis of plastics wastes. The higher the acidity, the lower will be the production of liquid oil.
12
13
an
Sakata et al. (1997) 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
14 with lower acidity produced maximum quantity of liquid oil (74.3 wt%), while ZSM-5 with higher
M
15 acidity produced lower quantity of liquid oil (49.8 wt%). However, during vapor phase contact,
16 gases production was increased due to further decomposition of hydrocarbons. In addition,
ed

17 temperature also affects the performance of these catalysts. Luo et al. (2000) carried out the
18 pyrolysis of PP and HDPE at higher temperature (500oC) that increased the production of liquid oil
19 to 90 wt% and 85 wt% respectively. Hence, the liquid oil production can be increased by using
pt

20 silica-alumina catalysts with low acidity and high process temperature.

21
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22 Zeolites catalysts are the crystalline alumino-silicates sieves having three-dimensional framework
23 with cavities and channels, where cations may reside. The ion exchange capabilities and open pores
Ac

24 are the main characteristics of these catalysts. Zeolites catalysts have different ratio of SiO2/Al2O3
25 that determines its reactivity and also affect the end product of pyrolysis process. Zeolites catalysts
26 having high acidity are more active in cracking process, hence increase the production of light
27 olefins and decrease the heavy fractions (Artetxe et al., 2013). Moreover, the use of these catalysts
28 increase the gases production and decrease the liquid yields. Catalytic pyrolysis of HDPE with
29 HZSM-5 at 450oC produced 35 wt% liquid yield with 65 wt% gases (Seo et al., 2003), while using
30 same catalyst and feedstock at 500oC, liquid oil decreased to 4.4 wt% with 86.1 wt% gases
31 production (Hernández et al., 2007). Overall zeolites catalysts increase the volatile hydrocarbon

Page 12 of 44
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1 production. Moreover, HZSM-5 has very low rate of deactivation thus it is more suitable for reuse.
2 Nevertheless, all the above mentioned catalysts have different characteristics and affect the products
3 of pyrolysis process (Table 4). However, among these catalysts, FCC and silica–alumina catalysts
4 increase the liquid yields and decrease the gases in comparison to zeolites catalysts. Furthermore,
5 the use of spent catalyst instead of fresh, makes it more economical in comparison to other catalysts

t
ip
6 (Sharuddin et al., 2016).
7

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8 3.1 Advantages of Catalyst Use in Pyrolysis
9

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10 A catalyst is used to improve the overall performance of the pyrolysis process. Different researchers
11 used different types of catalysts such as ZSM-5, HZSM-5, FCC, natural zeolite, activated alumina,
12
13
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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 products (Table 4).
14
M
15 3.1.1 Effect of Catalyst on Quality of Liquid Oil
16 According to Miskolczi et al. (2006), Lopez et al. (2012), use of a catalyst increases the quality of
ed

17 liquid oil produced from the impurities. Miskolczi et al. (2013) further explained that a catalyst
18 affects the pyrolysis mechanism and converts the heteroatoms into a gaseous phase. Moreover,
19 according to Bhaskar et al. (2002), the use of a catalyst can decrease the concentration of halogens
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20 in the liquid oil produced. The use of a silica-alumina catalyst decreased the bromine contents in
21 produced liquid oil (Blazso et al., 2002). The use of a ZSM-5 catalyst decreased the nitrogen,
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22 phosphorous and sulphur impurities from the produced liquid oil, especially from the gasoline as,
23 according to Miskolczi et al. (2009), the degradation process of pollutants occurs at greater scale in
Ac

24 small internal pores of ZSM-5. During the catalytic conversion of RDF, the use of a catalyst reduces
25 the formation of less corrosive carboxylic acid (Whyte et al., 2015). Moreover, it involves the
26 removal of oxygenated species that leads to an increase in the HHV of liquid oil produced (Pattiya
27 et al., 2008). Metal containing catalysts showed a high efficiency of impurities removal from the
28 liquid oil produced (Miskolczi, 2013).

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1
2 3.1.2. Effect of Catalyst on Retention Time and Temperature
3 Catalytic cracking of plastic was promoted in the pyrolysis to make the overall process
4 economically feasible by reducing the retention time and temperature (Chen et al., 2014; Achilias et
5 al., 2007). However, different researchers reported that the use of a catalyst gave the same results at

t
ip
6 a lower temperature and retention time in comparison to thermal pyrolysis (Lopez et al., 2011;
7 Ohkita et al., 1993). Increase in the cracking rate at lower temperatures was observed under

cr
8 catalytic conditions (Lee, 2001). The zeolite catalyst showed a high rate of C-C cracking reaction
9 due to its high pore surface area that leads to acceleration in the thermal degradation of plastic

us
10 (Bridgewater et al., 2012; Miskolczi et al., 2011).
11
12
13
3.1.3. Effect of Catalyst on Liquid Oil Compounds an
As stated earlier, catalyst addition in pyrolysis process increases the quality of produced liquid oil
14 (Panda et al., 2010) with aromatic compounds in liquid oil (Lee, 2012). Moreover, the use of a
M
15 catalyst improves the control production of hydrocarbons from HDPE, LDPE, PP, and PS. Thermal
16 pyrolysis of plastic produces high carbon chain compounds ranging from C5 to C28, whilst the use of
ed

17 a catalyst decreases the heavy oil and increases the gasoline fraction (C5 - C12) in the liquid oil
18 produced (Syamsiro et al., 2014).
19
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20 Manos et al. (2000) reported that catalytic degradation of PE with Y-zeolite produced more gasoline
21 range compounds, mainly the isoparaffins with high octane numbers, hence the increase in the fuel
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22 quality. Catalytic degradation of HDPE and LDPE with the FCC catalyst produced gasoline range
23 hydrocarbons (C7 - C12) with the main components of iso-alkenes or iso-alkanes. For HDPE, few
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24 higher compounds with normal alkanes were found in the liquid oil produced (Achilias et al., 2007).
25 According to Panda et al. (2010) and Grieken et al. (2001), use of a ZSM-5 catalyst in the batch
26 reactor for the degradation of PE increased the cracking, aromatization and isomerization process.
27
28 Thermal degradation of PP on clinoptiloite zeolite increased the gasoline range compounds and
29 decreased the char (Kima et al., 2002). Moreover, ZSM-5 resulted in the formation of branched
30 hydrocarbons with aromatics in liquid oil. It has high catalytic activity for the degradation of heavy
31 hydrocarbons into lower gaseous hydrocarbons (Seo et al., 2003; Mastral et al., 2006). Miskolczi et

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1 al. (2009) reported that catalytic degradation of agricultural and packaging waste using ZSM-5
2 catalyst increased the concentration of gases, gasoline and light oil to 12.2, 34.5 and 24.1%
3 respectively. In non-catalytic pyrolysis, the concentration was 5.1, 18.2 and 17.9% respectively.
4 Liquid oil produced from catalytic degradation of PS plastic over HY-zeolite was affected by the
5 reforming temperature. At 450°C, the liquid oil was 80% composed of C6-C8 and C14-C16

t
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6 compounds. The temperature increase from 400 to 450°C increased the benzene and toluene, yet
7 decreased the styrene, ethylbeneze, styrene dimmer and PAH concentration. This is due to the

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8 increase in catalytic activity of HY-zeolite that resulted in the degradation of higher molecular
9 weight hydrocarbons into smaller molecular hydrocarbons (Onwdili et al., 2009).

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10
11 PVC plastic is widely used in construction, electronic and automotive applications. Pyrolysis of
12
13
an
PVC produces hazardous Cl gas (Lopez et al., 2012). A different catalytic study of PVC plastic with
other plastics was carried out by a different researcher with the main focus of adsorbing the HCl
14 produced during pyrolysis. In addition, a few studies were also carried out to inhibit the formation
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15 of HCl during the pyrolysis (Lopez et al., 2012). However, the dual effect of a catalyst,
16 dechlorination and catalytic pyrolysis on the mixture of plastic including PVC plastic (Zhou et al.,
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17 2008; Yanik et al., 2001) was rarely reported by scientists. Lopez et al. (2011) stated that 50%
18 removal of chlorine from liquid oil was achieved by following stepwise pyrolysis of PVC plastic
19 that included dechlorination and pyrolysis steps. The dechlorination step was carried out at a low
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20 temperature to remove the chlorine, and then later on the pyrolysis process was carried out for the
21 conversion of PVC into liquid oil and value-added products. The experiment was carried out with
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22 and without catalysts at the dechlorination step. The obtained results showed that the dechlorination
23 step with a catalyst decreased the catalyst efficiency by blocking its active sites.
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24
25 3.1.4. Effect of Catalyst on Physical Properties of Liquid Oil
26 The use of a catalyst affects the physical properties of liquid oil produced (Whyte et al., 2015) such
27 as the viscosity that is one of the important parameters for any petroleum product. Abdullah et al.
28 (2010) reported that the suitable viscosity for fuel oil at 25°C is ≤ 1000. High viscous oil affects the
29 engine performance as it is hard to pump the oil into the engine during the operation. Therefore a
30 pump is required to inject the fuel into atomizer, hence making the process costly (Kim et al., 2009;
31 Mohan et al., 2006). Feedstock composition is another factor that affects the viscosity of liquid oil

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1 produced. Liquid oil produced from PE and PP had viscosities of 2.32 mm2/s and 2.18 mm2/s
2 respectively (Syamsiro et al., 2014; Panda and Singh, 2013). However, liquid oil produced from PS
3 is less viscous (Siddiqui and Redhwi, 2009). The differences in viscosity results are due to the
4 composition and structure of feedstocks used (Ates et al., 2013). Any factor in the pyrolysis process
5 that cracks the liquid oil produced to a lower molecular weight leads to a lowering in the viscosity

t
ip
6 (Diebold, 2000) and it is achieved by using a catalyst (Miskolczi et al., 2013). Ates et al. (2013)
7 reported that all the catalysts show a high conversion of long chain aliphatic compounds into

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8 aromatic. In addition, reduction of oxygenated lignin species will result in less viscous oil (Pattia et
9 al., 2008; He et al., 2009). Miskolczi et al. (2013) reported that the use of a catalyst decreased the

us
10 moisture content and cetane index of liquid oil produced. In addition, use of Y-zeolite and natural
11 zeolite (NZ) decreased the pour point of liquid oil produced from municipal plastic waste (Syamsiro
12
13 HHV of liquid oil (Miskolczi et al., 2009).
an
et al., 2014). Nevertheless, the use of a catalyst decreases the density, flash point, boiling range and

14
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15 3.1.5. Effect of Catalyst on Gases Produced
16 The use of a catalyst increases the production of gases and decreases the liquid yield. Gases
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17 produced from pyrolysis process consist of CO, CO2, H2 and CH4 (Whyte et al., 2015). However,
18 pyrolysis of PVC produced Cl gas (Lopez et al., 2011b). Catalyst use favors the decarboxylation
19 route, and hence increases the CO2 production during the process and decreases the concentration of
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20 CO (Whyte et al., 2015; Ates et al., 2013). However, the most important effect of a catalyst on the
21 produced gases is the increase of hydrogen concentration and carbon frame isomerization that
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22 resulted in an increase of i-butane concentration (Ates et al., 2013). Miskolczi et al. (2009) reported
23 that use of ZSM-5 catalyst produced gases that contain mainly C3 hydrocarbons from PP, while C2
Ac

24 and C4 hydrocarbons were produced from packaging waste. The difference between the
25 compositions of produced gases is due to the structure of used feedstock. In addition, the HHV of
26 produced gases was 45.9 - 46.6 MJ/kg from agriculture and packaging waste respectively
27 (Miskolczi et al., 2009) and 17.1 - 21.9 MJ/m3 from RDF (Whyte et al., 2015).
28
29 3.1.6. Effect of Catalyst on Char Produced
30 Char (solid residue) formation in the pyrolysis process occurred through condensation (Miskolczi et
31 al., 2013). The use of a microporous catalyst decreases the char production (Lee, 2012). Catalyst

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1 separation from the char is difficult (Lopez et al., 2011). The catalyst does not affect the elemental
2 characteristics of char (Whyte et al., 2015). However, it increases the ash contents (Lopez et al.,
3 2011). Char produced from the catalytic pyrolysis of refuse-derived fuel (RDF) contains 53.0-
4 54.0% of ash that decreases its caloric value and causes problems during its combustion (Whyte et
5 al., 2015). In addition, the use of a catalyst increases the H/C ratio in the char produced (Lopez et

t
ip
6 al., 2011). Moreover, char deposition on the catalyst during the pyrolysis process decreases the
7 active sites, and hence negatively affects the catalytic activity (Miskolczi et al., 2013).

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8
9 4. Types of Catalysts and their Characteristics

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10
11 4.1 Catalyst Types
12
13
an
In catalytic pyrolysis, different types of catalysts such as homogenous catalyst (Kaminsky et al.,
14 2007), acid mesoporous materials (Augado et al., 2007), non-acid mesoporous solid
M
15 (Chaianansutcharit et al., 2007), FCC catalyst (Olazar et al., 2009), zeolite (Aguado et al., 2009),
16 and metallic oxide (Siddiqui and Ridhwi, 2009) have been examined (Table 5). However, the most
ed

17 commonly used catalysts are zeolite, silica-alumina, MCM-41 and FCC (Lin and Yang, 2007;
18 Miskolczi et al., 2006). Zeolite catalyst has been extensively studied by different scientists and
19 found to be better in the degradation of polyolefin (Lopez et al., 2011). The key features of the
pt

20 zeolite catalyst are acid strength, pore size and pore distribution (Panda et al., 2010). In advanced
21 catalytic pyrolysis, bi-functional (reforming) catalysts that have both acidic and metal sites are
ce

22 characterized (Panda et al., 2010). Different kinds of metals such as Ni, Co, and Mo are doped over
23 the acidic site provided by alumina-silicate (Sriningsih et al., 2014). Hydrogenation and
Ac

24 dehydrogenation reactions are carried out by the metallic site, while the acidic site accelerates the
25 process of isomerization (Bukens and Huang, 1998; Panda et al., 2010).
26
27 An increase in the yield of gases is due to the high inter-crystalline structure of the catalyst that
28 accelerates the cracking, isomerization and aromatization reactions (Panda et al., 2010).
29 Furthermore, it increases the production of aromatics in the liquid oil produced (Lopez et al., 2011).
30 HZSM-5 increases the volatile compounds in the liquid oil produced (Hernandez et al., 2007). In
31 addition, it increases the branched carbon ratio and reduces the formation of straight chain paraffins

Page 17 of 44
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1 and olefins (Panda et al., 2010). Moreover, nanocrystalline HZSM-5 increases the production of
2 gases during the catalytic pyrolysis (Mastral et al., 2006). FCC catalyst has Si/Al ratio of 1.5
3 (Chung et al., 2003). These catalysts have smaller microporous and BET surface areas, and hence
4 produce more liquid yield as compared to other catalysts such as ZSM-5 that has a high
5 microporous area (Seo et al., 2003). Mordenite and Clinoptillolite are the NZ that have a

t
ip
6 microporous area that favors the liquid yield in comparison to gases (Lee, 2012; Miskolczi et al.,
7 2006). Reforming catalyst such as doping via wet impregnation of Ni, Co and Mo with NZ was

cr
8 examined. The results showed that doping didn’t affect the overall crystallinity of the catalyst.
9 However, Co-Mo/Z showed a high efficiency in the conversion of plastic into gasoline range liquid

us
10 oil due to its high acidity (Sriningsih et al., 2014).
11

12
13
4.2 Catalyst Characteristics an
14 Catalytic cracking on acid catalysts takes place with the formation of carbocations that require
M
15 strong acid sites (Achilias et al., 2007). Acid strength and textural properties such as BET surface
16 area, acidity, pore size, pore volume, Si/Al ratio, thermal stability, and dimension are the main
ed

17 characteristics of acid catalysts (Figure 2). Acidity of the catalyst plays a vital role in the catalytic
18 pyrolysis. Bronsted and Lewis acid sites are considered during the acidity measurement of catalysts
19 (Ohikta et al., 1993). The majority of acid sites are present inside the catalysts that enhance the
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20 cracking process (Venuto and Landis, 1968; Panda et al., 2010). Sriningsih et al. (2014) reported
21 that treating catalysts with HCl increased the catalyst acidity. Acidic catalyst increases the gasoline
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22 range hydrocarbon production in liquid (Lopez et al., 2011). Porosity in another catalyst feature that
23 affect the catalytic activity by selective adsorption mechanism (Miskolczi et al., 2006).
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24
25 A microporous catalyst with a high internal crystalline structure increases the catalytic process,
26 produces more gases, and decreases the liquid yield (Lopez et al., 2011). While a catalyst with
27 macropore volume will not affect the liquid yield quantity, it produces large carbon chain
28 compounds (Miskolczi et al., 2006). The thermal stability of a catalyst is very important for the
29 pyrolysis process. Nizami et al. (2015b) reported that NZ present in KSA shows thermal stability at
30 high temperatures (up to 900°C) that shows its potential to be used as a catalyst in the pyrolysis
31 process. Different studies show that catalyst activity improves with the increase in temperature

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1 (Syamsiro et al., 2014). However, with the passage of time, catalyst activity decreases due to the
2 deposition of coke or impurities present in feedstock that reduces the strength of the acidic site
3 (Syamsiro et al., 2014; Lopez et al., 2012). In addition, a catalyst with more than one dimension
4 allows more cracking than a mono dimensions catalyst because it provides more surface area for
5 cracking (Lee, 2012).

t
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6
7 5. Catalyst Modification and Future Perspective

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8
9 The selection of a catalyst for the degradation of plastic waste is a critical step in pyrolysis. The

us
10 catalyst modification has been under consideration for the last decade to improve the process’s
11 efficiency. Modification in catalysts can be carried out in different ways, such as acid leaching,
12
13
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thermal, and wet impregnation. Syamsiro et al. (2014) stated that by heating the NZ at a temperature
of 500°C for 3 hours removed the volatile impurities of the catalyst, thus leading to an increase in
14 its catalytic activity. Moreover, the acid leaching with HCl removes the impurities from the NZ
M
15 catalyst and increases its acidity; improving the overall catalytic performance (Sriningsih et al.
16 2014). Similarly, the wet impregnation method is an important technique that is widely used to
ed

17 generate heterogeneous catalysts (Adnan et al., 2014).

18
19 Reformed catalysts show a bi-functional effect. Metallic sites accelerate the hydrogenation and
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20 dehydrogenation reactions whilst acidic sites accelerate the isomerization reaction (Panda et al.,
21 2010). Making the composite of zeolite with zinc increases the adsorption capacity of the zeolite
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22 catalyst. It narrows the pores of zeolites that increase the effective sieving effect. It allows only
23 small molecules to pass through their pores. Modified zeolites have an average particle size of a few
Ac

24 microns. The internal surface area can represent more than 99 % of the total surface area. Thus,
25 almost all the active sites are located inside the pores that increases its adsorption capacity, thereby
26 enhancing its purification capacity (Ciobanu et al., 2008). Adnan et al. (2014) reported that doping
27 of Cu on Al2O3 increases the BET surface area, pore volume and pore size. Moreover, the use of
28 these reformed catalysts will increase the overall catalytic pyrolysis efficiency and improve the
29 product quality. However, some challenges and scope for improvement still remain in the catalytic
30 pyrolysis of plastic waste. After a detailed review of all aspects of the catalytic pyrolysis process,
31 the recommended areas for further research and development are grouped in Box 1.

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1
2 6. Conclusions
3
4 The produced liquid oil and gases from pyrolysis have high HHV and maintain the potential to be

t
5 used as an alternative source of energy. Char produced during pyrolysis has a high BET surface area

ip
6 and can be used in different environmental applications, such as adsorption of heavy metal and
7 other pollutants from wastewater and air. Different parameters such as temperature, retention time,

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8 feedstock composition and use of catalyst affect pyrolysis process and end product quality and
9 yield. The thermal pyrolysis process produces low quality liquid oil and demands a high

us
10 temperature and retention time. To overcome these issues, catalytic pyrolysis of plastic wastes has
11 been introduced. Use of different catalysts makes the process more efficient by improving the liquid
12
13
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oil and gases quality with a decrease in both process temperature and time. ZSM-5, HZSM-5, FCC,
Al2O3, Red Mud, and NZ are the most important and significant catalysts used by different
14 researchers. Moreover, catalyst reforming, such as doping of the metals Ni, Co, Mo, and Zn on
M
15 acidic catalyst further improve the catalytic activity. A catalyst that has a high BET surface area and
16 acidity produces more gas yield with a decrease in liquid yield and vice versa. In addition, a
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17 microporous catalyst shows the same phenomena, while macroporous increase the liquid oil and
18 char yield with less gases production. However, modifications such as thermal, acidic and doping of
19 metal via wet impregnation can increase the catalytic activity of catalyst by improving its
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20 characteristics. The use of NZ is as a catalyst in the pyrolysis process is becoming more prominent
21 due to both its easy availability and economical factors.
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22
23 Acknowledgment
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24 We are very grateful to the Ministry of Higher Education, Kingdom of Saudi Arabia (KSA) for
25 providing funds to complete this work.
26

27 References
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ip
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1 Box. 1 Future Perspective

2 Undertaking detailed material and energy balance of catalytic pyrolysis process in
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4 Further research for exploration and utilization of cheap catalysts, such as natural zeolites, to

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6 Regeneration and reuse of catalysts need further investigation to make the process more
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8 Detailed chemical characterization of produced liquid oils from different types of plastic
9 waste, to fully understand their health risks and environmental problems.

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10 Further research is needed to understand the detailed composition of produced gases and
11 their health and environmental concerns and also their potential to be used as alternative
12
13
fuel. an
Explore further applications of produced liquid oil, gases and char to make this technology
14 more economically sustainable.
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15 Comprehensive life cycle assessment (LCA) of catalytic pyrolysis including feedstock to
16 fully understand the economic, environmental and overall sustainability of this technology.
ed

17
18
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Pyrolysis Process
Demand High Thermal Catalytic Remove Impurities in
Energy Pyrolysis Liquid Fuel
Pyrolysis

t
ip
Demand High Impurities in Demand Less Demand Less
Temperature Liquid Fuel Energy Temperature

1) Produce high liquid
Liquid yield with heavy oil.
cr
Decrease the liquid Yield
Contains low chain compounds Liquid
in gasoline range with high Fuel

us
Fuel 2) Contains impurities
3) Low octane number octane number

Increases the production of

1)Produces gases in less gases.
Gases
quantity.
2)Contains CO and CO2
in high concentration
an
Gases contains C3 and C4
compounds
Gases

Char 1) High quantity of Char 1) Decreases the Char production

Char
M
is produced at low especially catalyst having high
temperature BET surface area.

Factors Affecting Pyrolysis

ed

Retention Feedstock Use of

Temperature Heating Rate Condensation
Time Composition Catalyst
pt

1
2 Figure 1. Flow chart of pyrolysis process
3
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4
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 36

BET Surface Area

1). Higher the BET surface area more will be
cracking
2). High BET surface area will produce more
gases and decreases liquid yield.
3). ZSM-5 has high BET surface area.
4).Surface area can be increase via thermal
modification and by milling.

t
ip
cracking occurred.
enters into pores of catalyst where further
surface of catalyst and then molecule
3).Primary cracking occurred at outer
macroporous favor liquid yield.
2).Microporous produces more gases while
macroporous.
kind of catalyst i.e. microporous and
1).On the basis of pore size we have two
3). Acidic catalyst removes impurities
1). Acid base catalyst shows more
cracking in pyrolysis process as

2). High acidic catalyst produces more

gases and decrease the liquid yield.

cr Pore Size
Characteristics
Acidity

compare to basic catalyst.

of

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from produce liquid fuel.

Catalyst

an
Reforming Catalyst: Metal are doped on
the acidic base of catalyst which perform dual
function and enhance the catalytic activity of
catalyst.

1).Internal Crystalline structure increase the

M
catalytic activity of catalyst.
2).Zeolite catalyst has high internal
crystalline structure which increases the
cracking process and hence increase the
gases yield with decrease in liquid yield.
ed

1
pt

2 Figure 2. Flow chart showing the characteristics of catalysts

3
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1 Table 1. Thermal versus catalytic pyrolysis

Catalyst Amount Feedstock Temp Thermal pyrolysis Catalytic pyrolysis References

used of used (°C)
catalyst
Liquid Gases Char Liquid Gases Char

t
ZSM-5 10% PE, PP, PS, 450 79.3 17.7 3.0 56.9 40.4 3.2 Lopez et

ip
PET, PVC al., 2012
ZSM-5 10% PE, PP, PS, 440 79.3 17.7 3.0 56.9 40.4 3.2 Lopez et
PET, PVC al., 2011c.

cr
Red Mud 10% PE, PP, PS, 440 79.3 17.7 3.0 76.2 21.6 2.2 Lopez et
PET, PVC al., 2011c.
ZSM-5 10% PE, PP, PS, 500 65.2 34.0 0.8 39.8 58.4 1.8 Lopez et

us
PET, PVC al., 2011c.
Red Mud 10% PE, PP, PS, 500 65.2 34.0 0.8 57.0 41.3 1.7 Lopez et
PET, PVC al., 2011c.
Y- 50% Municipal 450 58 28 14 52 36 12 Syamsiro et
Zeolite plastic
waste
an al., 2014.

Natural 50% Municipal 450 58 28 14 50 34 16 Syamsiro et

Zeolite plastic al., 2014.
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waste
2

3
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1 Table 2. Suitability of plastic

Resin Suitability for Remarks References
Pyrolysis
Polystyrene (PS) 1) Very good and 1) Low temperature required as compare to PP Lee and
gives excellent and PE. Shin, 2007.
fuel properties 2) Produce Less viscous oil as compared to PE Siddique and

t
and PP. Redhwi,

ip
2009.
Polyethylene (PE) Very good for 1) Required Temperature is high > 500°C due Miskolczi et
pyrolysis. to its branched chain structure al., 2009.

cr
2) In thermal pyrolysis it converts into wax
instead of liquid oil Lee, 2012.
3) In catalytic pyrolysis wax formation is

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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 an

1). Required high temperature.
2). After PE it is difficult to degrade thermal
pyrolysis of PP.
Miskolczi et
al., 2009.

3) In catalytic pyrolysis produces liquid yield

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with high aromatic compounds.
Polyvinyl chloride 1). Not suitable 1). Produce hazardous Chlorine gas Lopez et al.,
(PVC) 2). Only few 2). Dechlorination via low temperature (250 – 2011a.
studies was 320°C) or physical or chemical adsorption. Lopez et al.,
ed

carried out by 3). In catalytic pyrolysis presence of chlorine 2012.

different scientists and deposition of coke affect the catalytic
activity of catalyst.
Polyethylen- Not suitable 1). It contains Heteroatom’s Thorat et al.,
pt

tetraethate (PET) 2013.

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2
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3
4

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39

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Table: 3. Physical properties of liquid oil produced from different types of plastic waste

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Parameters Units Liquid oil vs. Conventional Value References
Diesel
Liquid oil from;
HDPE 0.790 Kumar et al., 2010

an
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

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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

d
Waste plastic 2.52 Mani et al., 2010
Conventional Diesel 2.0-5.0 Syamsiro et al., 2014

Kinematic
Viscosity
cSt PP
HDPE te
Liquid oil from;
2.27
1.63
Panda and Singh, 2013
Kumar and Singh, 2011
ep
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
c

HDPE 45.86 Sharma et al., 2014

Tires 43.22 Wongkhorsub and
Ac

HHV MJ/kg 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
o
Pour Point C HDPE -15 Kumar and Singh, 2011
PP -9 Ahmad et al., 2014
PS -67 Pinto et al., 1998

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40

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Conventional Diesel 6 Ahmad et al., 2014
Liquid oil from;

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PVC 40 Pinto et al., 1998
o
Flash Point C HDPE 48 Ahmad et al., 2014
LDPE 41 Desai et al., 2015
PP 30 Ahmad et al., 2014

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PS 26.1 Blazso, 2006
Conventional Diesel 52 Ahmad et al., 2014
Liquid oil from; 82-352 Kumar and Singh, 2011
o
Boiling Point C HDPE

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Range PP 68-346 Panda and Singh, 2013
Conventional Diesel 150-390 Boundy et al., 2011

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Table 4. Effect of catalyst on pyrolysis process

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Catalyst Quantity of Feedstock Effect on Yield Catalyst Effect References
Used Catalyst Used
Liquid Gases Char
HZSM-5 20% HDPE NR NR NR Increases the yield of volatile compounds Hernandez et

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

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64.7 20.0 15.3. Thermal cracking increases the demand of energy however uses of catalyst
increase the cracking process. Hence reduces the demand of energy.
Na2CO3 2, 5 Tires NR NR NR Decrease the reaction temperature. Demirbas et
and Increase the conversion with increase in liquid yield. al., 2015

d
10%
ZSM-5 5% HDPE, PP NR NR NR  Increase the process of cracking. Miskolczi et
 Increase the overall yield of each fraction i.e. gases, gasoline and light oil. al., 2009.

HZSM-5, 30% PE wax

te 47.18, 51.04, 1.78,
 Yield of lighter fraction (gasoline) increased.
 Promoted the production of i-butane in gases.
 Overall increase the aromatic compounds in the oil. Lee, 2012.
ep
Zeolite Y and 66.98, 28.95, 4.08,  Catalyst dimension plays a vital role in the conversion of wax into light
Mordenite 82.59 15.11. 2.3. hydrocarbon.
 Catalyst with more than one dimension (HZSM-5 and zeolite Y) shows high
conversion of wax into light hydrocarbon than one dimension (mordenite)
c

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.,
Ac

Packing  Liquid oil produce from catalytic pyrolysis contain high fraction of aromatic, 2011.
waste while 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 Lopez et al.,
PET, PVC temperature that reduces the chlorination but also negatively affect the 2012.
catalyst performance.
 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.

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 Catalytic pyrolysis produces liquid with 95% aromatic compounds.
Natural Zeolite 5% LDPE 23.88, 75.18, 0.94, Natural zeolite (NZ) modification was carried out by metal (Ni, Ni-Mo, Co Sriningsih et

us
(Ni/Z, NiMo/Z, 12.20, 86.30, 1.51, and Co-Mo) impregnation on NZ to increase the catalyst activity and its al., 2014.
Co/Z, CoMo/Z) 23.92, 76.00, 0.92, selectivity for hydrocracking process.
14.91. 83.71. 1.39.  Impregnation of catalyst didn’t affect the crystallinity of the NZ.
Ni/Z composite produces high liquid yield. However maximum gasoline

an
(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, 46, 52, 8, 10, Polyolefin (PE and PP) shows high yield of gaseous hydrocarbon while PS Lerici et al.,
71 24 5. shows high yield of liquid hydrocarbon due to its stable benzene ring 2015.

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structure.
Polyolefin produces wax while PS didn’t produce any wax.
Liquid oil produces from PS mainly consist of styrene (81%).
FCC, ZSM-5, 2% HDPE, PS FCC and NZ (Clinoptillolite) have less microporous while ZSM-5 has high Miskolczi et

d
natural zeolite porous area. al., 2006.
(Clinoptillolit) Less porous area catalyst produce high liquid yield; however high porous

te 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
ep
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
c

temperature as well.
Use of catalyst decrease the concentration of heavy aliphatic compounds
Ac

(C20+) and increase the concentration of lighter hydrocarbons i.e. (C13-).

ZSM-5, Red 10% PE, PP, PS, 56.9, 40.4, 3.2, Increase in temperature in the presence of catalyst increases the gaseous yield Lopez et al.,
Mud PET, PVC 76.2 58.4 2.2 due 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

Page 42 of 44
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the internal structure of ZSM-5 catalyst.
Red Mud catalytic activity increase with the increase of temperature. It was

us
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 Na2O may affect the catalytic activity of Red Mud.

an
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 Syamsiro et
Natural Zeolite plastic waste BET surface area. al., 2014.

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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

d
found that with the passage of time catalyst activity was decreased

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Table 5. Characteristics of catalyst

Catalyst SiO2/A BET Particle Pore Micropore Micropore Pore Acidity References
name l2O3 surface area Size Size Volume area (m2/g) Volume (mmol)
(w/w) (m2/g) (µm) (nm) (cm3/g) (cm3/g) NH3/g)

HZSM-5 22.2 341 37-70 0.55 0.16 - 0.18 1.15, Hernandez

t
0.88 et al., 2007.

ip
ZSM-5 24.1 319.4 39.8 NR 0.23 - NR NR Miskolczi
et al., 2009.

cr
HZSM-5 30 400 NR NR NR NR NR NR Lee K H,
2012.
ZSM-5 412 NR NR 0.1 346.1 0.4 0.2 Lopez et

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al., 2011.
ZSM-5 412 NR NR 0.1 346.1 0.397 0.176 Lopez et
al., 2012.
ZSM-5 412 10-30 NR 0.1
an 346.1 0.397 0.176 Lopez et
al., 2011c.
Red Mud 27.49 NR NR 0.009 171 0.184 NR Lopez et
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al., 2011c.
Fresh 216 NR NR 0.96 120 0.2481 NR Lee, 2009
FCC
Spent 151 NR NR 0.76 75 0.2533 NR Lee, 2009
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