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REVIEW ON GREEN TECHNOLOGY PYROLYSIS FOR PLASTIC WASTES

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 7th Postgraduate Seminar on Natural Fibre reinforced Polymer Composites 2020

REVIEW ON GREEN TECHNOLOGY PYROLYSIS FOR PLASTIC WASTES

M.M. Harussani1, S.M. Sapuan1,2*, A. Khalina2, R.A. Ilyas1,2, M.D. Hazrol1

1Advanced Engineering Materials and Composites Research Centre (AEMC), Department of Mechanical and Manufacturing
Engineering, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.
2Laboratory of Biocomposite Technology, Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia,

43400 UPM Serdang, Selangor, Malaysia

*Corresponding author’s e-mail: sapuan@upm.edu.my; Tel: +603-97696318

ABSTRACT

Plastic wastes normally take up almost 1000 years to decompose in landfills. Recently, incineration of plastic waste is the common
option in waste management, better than recycling method. However, burning plastic releasing toxic gases such as dioxins, mercury and
polychlorinated biphenyls into the environment. Thus, the needs in sustainable green technology to treat the plastic wastes to produce
valuable oil, char and gas products, are paramount. This paper review will be focused on a comprehensive literature review of thermal
decomposition pyrolysis system for plastic wastes, especially PP wastes. Slow, fast and flash pyrolysis are three famous pyrolysis type.
Slow pyrolysis with lower process temperature is the best in char production, while, fast and flash pyrolysis lead to produce high quality
bio-oil and gas. The most frequent reactors used are fixed-bed (batch), vacuum, screw kiln, rotary kiln and fluidised-bed. The key
parameters that affect the composition of the end-products are the process temperature, residence time, presence of catalysts, particle
size and physical structure of the wastes. The development of green technology leads interest of companies to commercialise the end-
products from plastic waste treatment.

Keywords: green technology, pyrolysis, polypropylene, char, environment

INTRODUCTION

Natural decomposition of plastic can last from 400-1000 years and few types of plastics are non-degradable as well [1]–[8]. Thus,
biodegradable plastics such as polylactic acid (PLA) [9], [10], starch [11]–[18], polyhydroxybutyrate (PHB) [19], polycaprolactone
(PCL), and poly(vinyl alcohol) (PVA) [20], [21] were introduced to catter this problems. According to Geyer et al. [22], the global
production of plastics in the year 2015 was estimated as 381 million metric tons (MT), increased by 75% since the year 2000. Moreover,
approximately 1 million plastic wastes produce in every minute. Polypropylene wastes (PP) degrade in approximately 20 to 30 years in
landfills [23]. These plastics contain additive materials as colourants, plasticizers and stabilizers [24]. Waste plastics can account for
about 28% of the total cadmium in municipal solid wastes. Plastic waste management is a crucial part to ensure the environment health.
Recently, the most effective ways to dispose the infectious plastic wastes is using incineration method. However, the use of incineration
to manage plastic waste can release important atmospheric pollutants [25]. Due to these bad impacts, environmental friendly methods
should be developed for the disposal of plastic wastes, pyrolysis method.

There are huge differences between current practice incinerator and suggested process pyrolysis. Thermal treatments such as combustion
or incineration will permanently eliminate the plastic waste, but these methods create harmful environmental pollution. Recycling
(mechanical/chemical) is a possible path for disposing of plastic waste. Most recycling processes, though, are expensive, energy-
intensive and end up producing low-grade products. Pyrolysis is a very viable and efficient waste management method in the treatment
of municipal solid waste containing carbonaceous materials including biomass and plastics [26]. The end products of incineration are
mainly carbon dioxide and water, while the end products of waste pyrolysis plant are mainly combustible low molecular weight
compounds. Gaseous substances are hydrogen, methane, carbon monoxide; liquid substances are methanol, acetone, acetic acid,
acetaldehyde and other organic matter as well as tar, solvent oil, etc; solid substances are mainly coke and carbon black.

Some studies on pyrolysis process are summarized in Table 1. In literature studies, PP pyrolysis char was usually evaluated as adsorbent
for water treatment. There is no scientific study that solid product (char) obtained from pyrolysis of PP wastes is used as briquette char.
Table 2 shows the elemental composition and filler content of waste raw PP [27]. This review presents the previous study for pyrolysis
of PP waste and other plastic wastes, as well as their valuable end-products.

Table 1. Evaluation area of char from previous studies

Plastic Waste Pyrolysis Process Evaluation area of char References
PET Laboratory-scale reactor As composite additive [28], [29]
PE, PP, PS Stirred batch autoclave As adsorbent [27], [28]
HDPE Fast pyrolysis As adsorbent [29]
PET, PVC, PP Tubular reactor As adsorbent [30]
PS Small-scale pilot reactor As adsorbent [31]

Table 2. Elemental composition and filler content of waste raw PP

Element Amount (wt.%)
Carbon 54.38
Hydrogen 34.00
Sodium 4.52
Aluminium 4.69
Silicon 0.57

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 7th Postgraduate Seminar on Natural Fibre reinforced Polymer Composites 2020

Sulphur 0.46
Magnesium 1.38
Ash 3.80

PRINCIPLES AND TYPE OF PYROLYSIS

Pyrolysis is a thermochemical decomposition process of materials like plastic wastes at elevated temperatures in the absence of oxygen
[32]. In this decomposition, the complex molecules of plastic wastes degrade into organic substances with lower molecular weight, short
chain and less complex molecules due to heat and/or pressure applied. Generally, the products will include a solid product and a range
of volatile oil and gas products, which are condensable and non-condensable. The yields of products depend essentially on both the
physical and chemical characteristics of the waste, as well as some pyrolysis conditions, which include pyrolysis temperature, media
pressure, heating rate [33]. Pyrolysis produces little pollution. In this process, various useful products are produced. It would be an ideal
application for plastic wastes to be converted to useful products [34]. The converting of plastic wastes to hydrocarbon mixtures via
pyrolysis have attracted much attention, because this process might allow the reduction of the amount of waste, the recovery of chemicals
and the replacement of other fuels [35].

Generally, there are two main types of pyrolysis, depending on the heating rate: (1) slow pyrolysis and (2) fast pyrolysis, respectively.
In slow pyrolysis process, the time of heating the biomass substrate to pyrolysis temperature is longer than the time of retention of the
substrate at characteristic pyrolysis reaction temperature. However, in fast pyrolysis, the initial heating time of the precursors is smaller
than the final retention time at pyrolysis peak temperature. Based on medium, two types of pyrolysis namely: (1) hydrous pyrolysis and
(2) hydro‐pyrolysis. Slow and fast pyrolysis is usually carried out in inert atmosphere whereas hydrous pyrolysis is carried out in presence
of water and hydro‐pyrolysis is carried out in presence of hydrogen. The residence time of vapour in the pyrolysis medium is longer for
slow pyrolysis process. This process is mainly used to produce char production. It can be further classified as: (1) Carbonization and (2)
Conventional. On the contrary, the vapour residence time is only for seconds or milliseconds. This type of pyrolysis, used primarily for
the production of bio‐oil and gas, is of two main types: (1) flash and (2) ultra‐rapid [36]. Table 3 summarises the main types of pyrolysis.

Table 3. Classification of pyrolysis methods with difference in residence time, rate of heating, temperature and major products
Pyrolysis methods Residence time Heating rate Final temperature (ºC) Major products
Fast <2 s High ~100 ºC/s 650 Bio-oil
Flash <1 s Very high >500 ºC/s >650 Bio-oil, gas, chemicals
Ultra-rapid <0.5 s Very high 1000 Gas, chemicals
Hydro-pyrolysis <10 s High <500 Bio-oil
Vacuum 2-30 s Medium 400 Bio-oil
Carbonization Days Very low 400 Charcoal
Conventional/slow 5-30 min Low ~10 ºC/s 500 Char, bio-oil, gas

Most plastics pyrolysis plants utilize high temperature (700 ºC) to moderate temperature (~500 ºC) in the presence of a suitable catalyst
[28], [37]. In the study of Miandad et al. [38], a pilot-scale pyrolysis reactor was used for pyrolysis of polystyrene (PS), polyethylene
(PE), polyethylene terephthalate (PET) and PP wastes at 450 °C. Fifty-four percent and 50% oil product yields were obtained from
natural and synthetic zeolite catalysts, respectively [38]. Das and Tiwari studied the slow pyrolysis oil quality of high and low-density
polyethylene (HDPE and LDPE) and PP wastes under low temperature conditions (300 to 400 °C) in a semi-batch reactor. They observed
that the pyrolysis oil product of waste PP has a high octane number value (∼ 92) and low viscosity Das2018. In pyrolysis of PP, main
gaseous components are C3 and C4 hydrocarbons [39]. Pyrolysis char of PP wastes has been determined to have a moisture content
ranging between 0.15 and 0.18%, and fixed carbon content ranging between 0.16 and 0.22% [38]. In many studies, char obtained from
plastic pyrolysis was used as adsorbent material for water and wastewater treatment [31].

OPERATING PARAMETERS

Reaction conditions are very important in the pyrolysis. Oil, chemicals, char and gaseous production through pyrolysis is affected by the
operating parameters: reaction time, particle size, heating rate, temperature, catalysts etc. At the effective process parameters, the
production of the desired major products can be maximized, as shown in Table 3.

Effect of residence time

The time of how long the material will be in the pyrolysis chamber influences the degree of thermal conversion of the solid products as
well as affect the composition of the vapours. Longer residence time increases the conversion primary product, thus more thermal stable
product is yield such as light molecular weight hydrocarbons and noncondensable gas [40].

Effect of temperature

Temperature controls the cracking reaction of the polymer chain. When temperature in the system increases, the vibration molecules
inside the system will be greater and molecules tend to evaporate away from the surface of the object. This happens when the energy
induced by force along the polymer chains is greater than the enthalpy of the C–C bond in the chain, resulted in the broken of carbon
chain [41].

Effect of catalysts

Catalysts are widely used in industries and researches to optimize product distribution and increase the product selectivity. When catalyst
used, the energy of the process is lowered, thus speeds up the rate of reaction. Therefore, catalyst reduces the temperature that required
in the process and this is very crucial since the pyrolysis process requires high energy that hinders its commercial application [40].

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 7th Postgraduate Seminar on Natural Fibre reinforced Polymer Composites 2020

CONCLUSIONS

A review of the literature related to the pyrolysis of plastic wastes has shown that, instead of incinerations and recycling, there is one
efficient method to decompose the infectious wastes into commercializable products such as bio-oil, gas, chemicals and char. Here, the
pyrolysis principles and the process parameters had been discussed. Plastic wastes, especially PP wastes, has also been investigated
using many types of pyrolysis and reactors. Slow pyrolysis with final temperature of 400-500 ºC is the suitable method to manage PP
wastes into char.

ACKNOWLEDGMENTS

The author gratefully acknowledges Universiti Putra Malaysia and Ministry of Education, Malaysia for funding this project via
COVID19 Special Research Grant (2020) Ministry of Higher Education.

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