WOLLO UNIVERSITY

KOMBOLCHA INSTITUTE OF TECHNOLOGY

SCHOOL OF MECHANICAL AND CHEMICALENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING
Environmental Engineering Stream

B.Sc. Thesis Submitted to Wollo University Kombolcha Institute of Technology,

Department of Chemical Engineering as Partial Fulfillment of the Requirement for
the Bachelor of Science Degree in
Chemical Engineering
(Stream of Environmental Engineering)

PRODUCTION AND CHARACTERIZATION OF CRUDE OIL FROM PLASTIC

WASTES USING PYROLYSIS

By:
1. FIRAOL SINTAYEHU
2. FIREHIWOT TSEGU
3. ZEBADER ANDEBET
Advisor:
FASIL ALEMAYEHU (ASST.PROF)

KOMBOLCHA, ETHIOPIA

1
 SEPTEMBER,2022

CHARACTERIZATION AND PRODUCTION OF CRUDE OIL FROM PLASTIC

WASTES USING PYROLYSIS

By
NAME ID NO
1. FIRAOL SINTAYEHU WOUR/1244/10
2. FIREHIWOT TSEGU WOUR/1247/10
3. ZEBADER ANDEBET WOUR/2329/10

A Thesis Submitted to the School of Chemical and Mechanical Engineering of Kombolcha

Institute of Technology, Wollo University in Partial Fulfillment of the Requirements for the
Degree of Bachelor of Science in Chemical Engineering in the Department of Chemical
Engineering

Advisor Signature Date

Asst. Prof Fasil Alemayehu

KOMBOLCHA, ETHIOPIA
SEPTEMBER,2022

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 DECLARATION
We declare that this thesis is our own original work carried out under the supervisions of
Asst.prof Fasil Alemayehu. It is being submitted to the Department of Chemical Engineering for
the Degree Bachelor of Science in Chemical Engineering. It has not been submitted before for
any degree or evaluation to other University. Permission is herewith granted to Kombolcha
Institute of Technology to circulate and to have copied for noncommercial purpose while the
author reserves other publication rights. Besides, neither the thesis nor extensive extracts from it
may be printed or otherwise reproduced without the author’s written permission.

Members Sign
1. FIRAOL SINTAYEHU ______________
2. FIREHIWOT TSEGU ______________
3. ZEBADER ANDEBET ______________

Date of submission: _________________

Place: Kombolcha

This thesis has been submitted for examination with my approval as a university advisor.
Advisor Name: Asst.prof Fasil Alemayehu
Advisor’s Signature: _________________

Department Head
Name Sign Date
Mr. Lukas Gelibo (MSc) _______________ _________________

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 ACKNOWLEDGEMENTS
First and for all we would like to thank our almighty GOD for helping us to make this proposal.
Next to GOD we would like to express our deepest appreciation and gratitude to our advisor
Asst.prof Fasil Alemayehu for his valuable guidance, constructive criticism and encouragement
during every stage of this research proposal. And also, we would like to thank the laboratory
assistants and technicians Mr. Getahun, Mrs. Wubalem and Mr. Wasihun for their help during
our experiments in the laboratory.

Lastly, we would honestly like to thank all who support us directly or indirectly during our
preparation of the proposal.

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Table Contents
Declaration.......................................................................................................................................I

Acknowledgements.........................................................................................................................Ii

Abstract..........................................................................................................................................Iii

List Of Tables................................................................................................................................Vi

List Of Figures..............................................................................................................................Vii

Acronyms....................................................................................................................................Viii

List Of Symbols..............................................................................................................................Ix

Chapter One.....................................................................................................................................1

Introduction......................................................................................................................................1

1.1. Background...........................................................................................................................1

1.2. Statement Of The Problem...................................................................................................2

1.3. Objectives.............................................................................................................................3

1.3.1. General Objective..........................................................................................................3

1.3.2. Specific Objectives........................................................................................................3

1.4. Scope Of The Study..............................................................................................................3

1.5. Significance Of The Study....................................................................................................4

Chapter Two..............................................................................................................5

Literature Review......................................................................................................5
2.1. Plastic Recycling..................................................................................................................5

2.2. Classification Of Plastic.......................................................................................................5

2.3 Different Methods Of Waste Plastic Management................................................................6

2.4. Land Fill................................................................................................................................6

2.5. Incineration Or Open Burning..............................................................................................6

2.6. Mechanical Recycling........................................................................................................7

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 2.6.1. Down-Cycling Of Plastic Waste..................................................................................8

2.6.2. Up-Cycling Of Plastic Waste........................................................................................8

2.7. Pyrolysis............................................................................................................................9

2.7.1 Classification Of Pyrolysis Based On Heating Rates.....................................................10

2.7.2. Other Classification Of Pyrolysis..............................................................................10

2.8. Factors Affecting Plastic Pyrolysis.....................................................................................12

2.8.1. Temperature And Heating Rate...................................................................................12

2.8.2. Time.............................................................................................................................12

2.8.3. Catalyst........................................................................................................................13

2.9. Characterization Of Liquid Fuel Oil...................................................................................13

Chapter Three..........................................................................................................15

Materials And Methods...........................................................................................15

3.1. Materials And Equipment’s................................................................................................15

3.2. Chemicals Used..................................................................................................................15

3.2.1. Mixed Plastic Waste....................................................................................................15

3.2.2.Catalysts And Equipment.............................................................................................15

3.3. Experimental Method.........................................................................................................16

3.3.2 Raw Material Preparation.............................................................................................17

3.3.3. Overall Production Process..............................................................................................18

3.3.4. Characterization Of The Fuel Oil................................................................................18

Chapter Four............................................................................................................20

Result And Discussion............................................................................................20

4.1. Effect Of Temperature........................................................................................................20

4.2.Effect Of Time.....................................................................................................................20

4.3. Effect of Catalyst Amount..................................................................................................21

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Chapter Five Conclusion And Recommendations.................................................23
5.1. Conclusion..........................................................................................................................23

5.2. Recommendations...............................................................................................................24

References...............................................................................................................25

Appendices..............................................................................................................27

LIST OF TABLES
v
Table 4. 1: Effect of temperature on the amount of liquid oil produced.......................................20

Table 4. 2: effect of time on the yield of liquid fuel......................................................................21

Table 4.3. Liquid fuel produced and its appearance......................................................................21

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 LIST OF FIGURES
Figure 2.1: Consumption of oil and petroleum based fuel..............................................................5

Figure 3. 1 : Schematic diagram of Production assembly for fuel from mixed plastic waste.......15
Figure 3. 2 : mixed waste plastic to crude oil production process.................................................17

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 ACRONYMS
MSW Municipal Solid Waste

PE Polyethylene

PP Polypropylene

PS Polystyrene

CO Carbon monoxide

VOCs Volatile organic compounds

PAH's Polycyclic aromatic hydrocarbons

PCDF's Polychlorinated dibenzofurans

TCT Thermochemical treatment

LDPE Low-Density Polyethylene

HDPE High-Density Polyethylene

PETE Polyethylene terephthalate

viii
 LIST OF SYMBOLS
°C Degree Celsius

h Hour

g Gram

T Temperature

mL Milli Liter

C-C Carbon-Carbon bond

C Carbon

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 ABSTRACT
Over 100 million tons of plastics are produced annually worldwide, and the used products have
become a common feature at over flowing bins and landfills. The engagement of this study was
to investigate the Production and characterization of crude oil from waste plastic using
pyrolysis process. The process of converting waste plastic into value added fuels is explained as
a viable solution for recycling of plastics. Pyrolysis runs without oxygen and in high
temperature of about 300°C which is why a reactor was fabricated to provide the required
temperature for the reaction. Converting waste plastics into fuel hold great promise for both the
environmental and economic scenarios. The oil produced can be used as a fuel for domestic
purposes and also in vehicles and industries when further refined. additionally, it minimizes the
pollution caused waste plastics. The new environmentally friendly method for removal of plastic
wastes is pyrolysis. Pyrolysis is a principal way to convert plastic wastes to fuel oil. it studies the
production and characterization of liquid fuel from mixed plastic wastes was carried out the
applicability and usefulness of catalytic pyrolysis with an aim of reduction of plastic waste in an
environmentally friendly way and produce alternative fuel. It was done with silica-alumina
synthesized catalysts and use of sodium carbonate to reduce the emission of dioxins in the
environment. The production was done by batch system containing 200 grams of plastic wastes,
10% silica-alumina as catalyst and 10% sodium carbonate as a scavenger. The plastic wastes
were collected around Kombolcha city. These included; LDPE and some HDPE, commonly used
in carriers or packages. The main variables during production process were contact time and
temperature. The characterization involved physical and chemical analysis of different
parameters. The production yielded a yellowish liquid which was characterized based on a list
of parameters. Plastics have woven their way into our daily lives and now pose a tremendous
threat to the environment.
Key words: Contact-time, Package, Plastic, Pyrolysis, Temperature

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 CHAPTER ONE
INTRODUCTION
1.1. Background
Plastics production has increased to a global value of 311 million tons (MT) since the 1930s,
with a growth rate of about 4%. However, plastic usage is necessary for everyday living, and
without it, modern markets and shopping can become much intricate. Plastics are used daily in
packaging wide assorted goods, drinks, food for easier transportation, footwear, clothing,
telecommunications, transport, among other things. The large-scale production and proliferation
of plastics have become a global concern due to their polluting effects. They are primarily un-
recycled and end up either in the natural environment or landfill and also, the burning of plastics
in landfills and various homes unabatedly has increased global anthropogenic carbon footprint. It
is further estimated that the importation of plastics to the continent would likely double in the
next five years, contributing to the rise in world’s temperature significantly (Andrewu et
al,2020). World’s temperature is also projected to increase from 1.5 to 3 °C with a corresponding
impact on food insecurity, water supply, inequality, and poverty. Although plastic waste has
been a ban on the environment, humans, aquatic animals, and increasing climatic conditions, its
benefits cannot be overlooked. It is essential to argue that the material is highly resistant,
lightweight, versatile, and cheap. Thus, it gives a valuable position in providing several
environmental benefits critical in reducing food waste and maintaining food safety and quality.
The trade-offs between plastics and a complete ban on plastic could be intricate and lead to a
negative knock-on effect on the environment. It is against this backdrop that this paper explores
two eco-friendly techniques to transform plastic waste into valuable products in a sustainable
environment(Amankwa et al., 2021)

Extant literature has explored eco-friendly techniques to transform plastic waste into valuable
products in a sustainable environment; however, there is limited literature in the African context.
First, ASCE, Elsevier, Google Scholar, and Web of Science were some databases that were
employed to search for peer-reviewed publications, and the researchers selected publications
written in English. Some of the keywords used were ‘production’, eco-friendly techniques’,
‘plastic’, and ‘plastic waste Plastic is an outcome of petroleum industry. Most of the plastics are
recyclable but some are not due to their chemical structure and physical parameters. Since early

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 1950s, the production of plastics has grown from 200 million tons to 400 million tons per
year(Ado,2021).
In the world a total of over 400 million tons of plastic is manufactured to meet global plastic
demand. This much production and consumption of plastic is a threat to environment as it takes
several years to decompose naturally. There are many ways of degradation and conversion of
this waste plastics into different useful chemical products such as crude oil. Among those the
tertiary or chemical recycling degradation is one of the categories. From this method of chemical
degradation, liquid fuels and high value-added chemicals are produced by waste plastic
fragments. One of tertiary recycling method is pyrolysis(Okunola,2019).
1.2. Statement of the problem
Production and consumption of plastics material has been increased due to its diversified
application. Plastics have become an indispensable part in today’s world. Due to their light-
weight, durability, energy efficiency, coupled with a faster rate of production and design
flexibility, these plastics are employed in entire range of industrial and domestic areas. Even
though theses plastics have wide range of applications majority of them cannot be degraded
which in turn creates environmental pollution(Andrady & Neal, 2009)

The methodological approaches such as waste management of non-degradable materials, through

protection and conservation technology in the field of logistics (Yadav et al., 2021; Sarkar et al.,
2021). Closed loop supply chain management for remanufacturing was introduced by Ullah et al.
(2021) to reduce the deleterious ecological impact of disposals. In other areas of transportation, a
lack of proper supply chain network will result in more undesirable being emitted into the
environment as a national concern. Sarkar et al. (2021) created a supply chain network model to
address the transportation issue in the biofuel and bioenergy production areas. The developed
concept of multi setup multi delivery reduces both time lead and transportation carbon emissions.
Sarkar et al. (2021) is taking steps to reduce energy consumption and carbon emissions by
introducing a multi-fuel manufacturing system with an initiative to produce sheer biofuel with
lower carbon emissions via a smart suspension manufacturing frame network.

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The current problem in the management of plastic waste with expected increase in the
consumption of the plastic items, the problem will certainly grow correspondingly. In addition to
this the depletion of non-renewable energy sources and the emission of pollutant during and after
production of fossil fuel will also continue. So liquid fuel from waste plastics is useful to
eliminate greater problem of plastics waste management and is a good alternative method for
obtaining new energy resource. Efficient conversion of waste plastics into advanced materials is
conspicuous environmental, social and economic benefits( Philipp et al,2020)
The rampant use of plastics is creating havoc. The endless toxicity and long-term disadvantage
of plastics to our nature and environment has concerned us. The extensive use of plastics must be
given a second thought. The problems due to plastics should be mitigated before it is too late. So,
one of the better options could be pyrolysis of plastics using catalyst like zeolite
(Rhiannon,2021).
1.3. Objectives
1.3.1. General Objective
 The general objective of this thesis is Production and characterization of crude oil from
waste plastic using pyrolysis process.
1.3.2. Specific objectives
 To examine the effect of different factors (catalyst, temperature, time).
 To investigate the yield of fuel produced by batch reactor.
 To characterize the properties of crude oil.
1.4. Scope of the study
The study was the production and characterization of crude oil from plastic wastes with the use
of catalytic pyrolysis with silica-alumina synthesized catalysts. The study also involved the
control of toxic gas emission. The production was by batch system containing 500 grams of
plastic wastes, 10% silica-alumina as catalyst and 10% sodium carbonate as a scavenger. The
vapors from the batch were condensed down into liquid fuel. Apart from producing crude oil
from waste plastic the study was also used to control the emission of gases into the environment.

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1.5. Significance of the study
Countless amount of waste plastics is generated all over the world every day. While the
traditional methods of landfill or incineration costs a lot resources and did not solve the
environmental problem in a proper way. Pyrolysis technology offers a practical solution to
recycling of waste plastics by converting it to liquid fuel oil as main product with high
marketing values. It creates environmental benefits and economic benefits at the same time.

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 CHAPTER TWO
LITERATURE REVIEW
2.1. Plastic recycling
As the rate of consumption of plastic materials in the world is greatly expanded, more waste
plastics are generated. The disposal of plastic waste is mostly done by conventional ways such as
landfill or incineration. However, these methods have a problem of a social resistance due to the
air pollution, soil contamination, and the economical resistance caused by an increase of a space
and a disposal cost. Thus, the recycling of plastic wastes as a cheap source of raw materials has
become a predominant subject in most countries(Kehinde et al., 2020).

The development of technologies acceptable from the environmental and economic fields is one
of the most important key factors. Generally, the recycling methods are classified as the material
recycling and chemical recycling. The former is one of the most conventional methods but is
limited by difficulties in maintaining the high quality and adequate price of final products, in
particular, for the mixture of plastic wastes. Thus, application of other methods such as chemical
recycling and energy recovery is required (Al-Salem et al., 2009).

2.2. Classification of plastic

Plastics can be categorized by various criteria including chemical composition, chemical
structure, stiffness, the type of application, and processing method. From these, the most
common categories are chemical composition and structure. Chemical composition classifies
plastics by the type of monomer and polymerization (e.g., polyolefin, polyesters, poly-carbonates
etc.). Chemical structure meanwhile is associated with bonding linearity, branching, and cross-
linking. Plastics are further divided into two categories thermoplastics and thermosets.
Thermoplastics, make up 80% of the plastics which are most commodity plastics like HDPE or
PET, soften when heated since there is little bonding within the molecular chains.

Thermosets meanwhile make up of remaining 20% of plastics produced today, which plastics are
found in circuit boards and epoxy resins, thermally decompose while heating .as previous studies

5
 shows that oil as well as petroleum-based fuel consumption had increased year to year.

Figure 2.1: consumption of oil and petroleum-based fuel

2.3 Different methods of waste plastic management

The suitable treatment of plastic is the most important factor in waste plastic management. This
is quite important from the energetic, environmental, and economic point of view even though
the recycling rate for postconsumer plastics has increased in the recent years, this increase has
been only meager coming to only around 1.5%. This increase in the recycling is due to the strict
legal regulations and growing awareness. Different techniques for the waste plastic management
are being followed today(Hopewell et al., 2009)
2.4. Land fill
Landfilling is the most common conventional approach for waste management in many
countries, however, due to increasing human population and consequential urbanization has led
to scarcity of space for landfills. Plastic waste landfilling is the least favored waste management
option today because of growing environmental and public health concern. The types and
quantities of toxic chemicals and their potential for leaching at landfill sites into groundwater is a
huge public health issue (Vaverková, 2019).

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2.5. Incineration or open burning
Open burning of plastics fraction in municipal solid waste (MSW) is an old practice that is still
prevalent in most communities around the world especially in underdeveloped and developing
countries. Incineration of plastic waste in open fields is a major source of air pollution. About 12
percent of most municipal solid waste is made up of plastics of different kind, and 40 percent of
the world's garbage is burned.(Vaverková, 2019)

The burning of plastics releases toxic gases like dioxins, furans, mercury and polychlorinated
biphenyls (better known as BCPs) into the atmosphere, and poses a threat to vegetation, and
human and animal health. Disposal of waste into landfills implies an irreversible loss of valuable
raw materials and energy. The incomplete combustion of Polyethylene (PE), Polypropylene (PP)
and Polystyrene (PS) during open burning can cause high concentrations of carbon monoxide
(CO) and noxious emissions, while PVC generates dioxins, carbon black and aromatics like
pyrene and chrysene(Verma et al., 2016)

Furthermore, the by-products of plastic combustion are airborne particulate emission (soot) and
solid residue ash (black carbonaceous color). Many studies have reported that soot and solid
residue ash possess a high potential of causing health and environmental concerns, especially
Volatile organic compounds (VOCs), semi-VOCs, smoke (particulate matter), particulate bound
heavy metals, polycyclic aromatic hydrocarbons (PAH's), polychlorinated dibenzofurans
(PCDF's) and dioxins(Verma et al., 2016)

Currently, landfills and dumpsites pose threat in most cities around the world as plastic fraction
in MSW is burnt along with other wastes, a concerted and deliberate effort is needed to
communicate information about danger of this practice, its health and environmental
consequences in the long and short time(Verma et al., 2016)

2.6. Mechanical recycling

Mechanical recycling of plastics refers to the processing of plastics waste into secondary raw
material or products without significantly changing the chemical structure of the material. In
principle, all types of thermoplastics can be mechanically recycled with little quality impairment
which depends on the number of time the article is recycled. Additions of additive and blending
with virgin plastic could help improve the quality of the new article. It is currently the almost, if

7
not, the sole form of recycling in most countries, representing more than 99% of the recycled
quantities(Schyns & Shaver, 2021)

The burden from collection, sorting, transport and recycling operations tends to render the
process cost ineffective; as such most plastic processing companies tends to prefer the use of
virgin material to the detriment of the environment.

Mechanical recycling of plastic wastes can be classified into: down-cycling and up-cycling.

2.6.1. Down-cycling of plastic waste

Down-cycling, is the recycling of plastic waste where the recycled material is of lower quality
and functionality than the original material. However, unlike other materials like glass and metal,
recycled plastics are not able to continually serve the same purpose after recycling. This is
usually so because plastics tend to lose certain qualities like, mechanical integrity, optical clarity
and other inherent properties, as such renders it unfits for its initial application. For example, a
plastic water bottle may be down-cycled to become artificial turf or plastic furniture. Generally,
mechanical recycling of plastics by heating and remolding operations leads to down-cycling in
the long run; this is because the material overtime is no longer suitable for articles with stringent
engineering requirements(Maris et al., 2018)

2.6.2. Up-cycling of plastic waste

Up-cycling, also known as creative reuse, is the process of transforming waste plastic materials
into new materials or products perceived to be of greater quality, such as artistic value or
environmental value. For example, Plastic bottles can be up-cycled into flower pots, bird feeders,
garden sprinklers, green parking canopy, chandeliers, Christmas trees, kid's toys, and more.
However, if heating and remolding is involved in the repurposing process of waste plastics
articles is not able to serve in most stringent engineering application over time, hence are down-
cycled. Up-cycling of waste single and mixed plastics have been achieved through thermo-
chemical processes. Pyrolysis is one of such thermo-chemical processes techniques that is
gaining much attention today(Maris et al., 2018).

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2.7. Pyrolysis
Pyrolysis is the thermal degradation of plastic waste at different temperatures (300–900℃), in
the absence of oxygen, to produced liquid and gaseous fuel. In pyrolysis, feedstock such as waste
plastic is heated in the absence of oxygen or low-oxygen environment and, instead of burning,
breaks down into mixture of simpler hydrocarbons. This process is simply thermal
depolymerisation, plastics are made from small building blocks (monomers) through a process
known as polymerization. Pyrolysis is a process that revert used, discarded plastics into valuable
resource in the form of monomers, fuel and other useful resources(Demirbas & Arin, 2002)

Pyrolysis presents a several advantages over other conventional waste plastic management
approaches. For instance, most waste plastics during recycling are down cycled; plastics are used
in producing articles of lower quality and application. This is because the plastic tends to lose
properties such as clarity, strength and flexibility as they are recycled again and again(Demirbas
& Arin, 2002)

Secondly, the cost associated with sorting, washing and blending before waste plastics are
recycled mechanically is completely non-existing in pyrolysis technique.

Furthermore, mechanical recycling involves melting and remolding of used or discarded plastics
into new articles. This implies that only wastes from thermoplastic articles are suitable for this
technique, therefore thermoset fraction will persist in the dumpsites since they cannot be
remolded. On the other hand, in pyrolysis techniques, both thermoset and thermoplastic can be
used as feedstock. Pyrolysis technique can also be used to treat waste of many novel materials,
such as composites, especially in the emerging technology were polymer composites are
replacing traditional materials in most engineered application(Schyns & Shaver, 2021).

Finally, depending on the feedstock composition, process condition (temperature, heating rate,
reaction gas) and presence of catalyst (catalytic pyrolysis) or absence of catalyst (thermal
pyrolysis), the product and yield composition can be varied(Maris et al., 2018).

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2.7.1 Classification of pyrolysis based on heating rates
2.7.1.1. Slow pyrolysis (non-isothermal)
Slow pyrolysis is the slow heating of the feedstock in absence of oxygen. Instead of combusting,
the volatiles from the organic material evaporate partly, and a product (char) remains, consisting
for a large part (normally 80%) of carbon. Slow pyrolysis is also called carbonization, and
emphasizes the solid char as main product, instead of fast pyrolysis which emphasizes the liquid
product. Heating rates is kept at 10℃/s(Williams & Besler, 1996)

2.7.1.2. Fast pyrolysis (Isothermal)

Fast pyrolysis involves rapidly heating the feedstock to moderate temperatures (400–600℃) at
short residence time (few seconds) to yield high amount of pyrolysis liquid fuel. Fast pyrolysis
provides a condition to maximize the production of the liquid, the reactor is considered to
operate isothermally. It is the most common of the methods, both in research and in practical use
in pyrolysis of plastics. Heating rates is kept at 100℃/s(Bridgwater et al., 1999)

2.7.1.3. Ultra-fast/flash pyrolysis

Ultra-fast, or flash pyrolysis is an extremely rapid thermal decomposition pyrolysis, with a high
heating rate, the main products are gases and bio-oil. Heating rates can vary from 100–
10,000℃/s and residence times are short in duration(Bridgwater et al., 1999)

2.7.2. Other classification of pyrolysis

2.7.2.1. Thermal pyrolysis technique
Thermal cracking or pyrolysis involves the depolymerisation or cracking of the plastics materials
by heating them to a very high temperature in the absence or low oxygen environment. The
temperature ranges between 350 and 900℃. The products formed include; gaseous, liquid and
carbonized char (solid residues). The liquid fuel is usually recovered from the condensable
fraction of the volatile product, while the remaining is a non-condensable high calorific value
gas(Al-Salem et al., 2017)

Thermal pyrolysis is a thermochemical treatment (TCT) its liquid product is a mixture of

paraffin’s, isoparaffins, olefins, naphthenes, and aromatics. Because of chain scission, breaking
of bonds, the intermolecular and intramolecular forces, elevated temperatures of up to 900℃ are
required. reported in their work that at temperatures lower than 700℃ the major part of the

10
product yielded was solid, whereas at higher temperatures the main product was a gas. The
physical properties of the liquid fuel obtained by this process largely vary with the plastic
type(Al-Salem et al., 2017)

2.7.2.2. Microwave-assisted pyrolysis technique

Microwave pyrolysis (also known as microwave-assisted pyrolysis) is pyrolysis that involves
microwave dielectric heating. Microwaves interact in three ways with different materials; it is
reflected by conductors, transmitted by perfect insulators, or absorbed and decayed on the way
inside materials depending on their dielectric properties. The heat is generated in dielectric
materials due to agitation of molecules by the alternating electromagnetic fields. The mechanism
of plastic microwave pyrolysis is based on absorbing the microwave energy via absorbent and
subsequently transferring thermal heat to the plastic via conduction. The physical properties and
the volume ratio of the absorbent affect the uniformity of heating distribution. Furthermore,
different microwave power gives completely different product distribution.

It has been established that microwave induced pyrolysis can be used to get value added
chemicals and fuels through its numerous noted advantages in contrast to thermal and catalytic
pyrolysis. The process has the potential for fast, volumetric and selective heating of plastics for
the recovery of energy. However, plastics cannot absorb microwave energy, as it has a very low
dielectric loss factor. Therefore, an absorbent must be mixed with the plastic to aid in heating the
plastic in pyrolysis. Materials with high dielectric loss factor are good candidates as absorbents
for plastic pyrolysis e.g. tire shredded and silicon carbide, carbon, iron mesh(Ludlow-Palafox &
Chase, 2001)

2.7.2.3. Catalytic pyrolysis technique

Catalytic pyrolysis involves the degradation of the polymeric materials by heating them in the
absence of oxygen and in the presence of a catalyst. Catalysts are employed in plastic pyrolysis
primarily to lower the energy requirement, influence the composition of the product through
cracking and reduce the process time. The most commonly used catalysts reported in the
literature for plastic waste pyrolysis includes silica alumina, zeolites, fluid catalytic cracking
(FCC) and Mobil classification of materials. Higher conversion is usually achieved with zeolite-
based catalysts due to their high acid strength compared to nonzeolitic catalysts, as such tends to
give more gaseous product(Al-Salem et al., 2017).

11
2.8. Factors affecting plastic pyrolysis
The major factors influencing the plastic pyrolysis process and pyrolysis product molecular
distribution include chemical composition of the feedstock, cracking temperature and heating
rate, operation pressure, reactor type, residence time and application of catalyst.

Among those major factors, we are interested to review: -

 Temperature
 Time
 Catalyst

2.8.1. Temperature and heating rate

Temperature is one of the most important operating variables, since, temperature dominates the
cracking reaction of the polymer materials. Not all of the polymer materials can be cracked by
increasing the temperature. Van der Waals force is the force between the molecules, which
attracts molecules together and prevents the collapse of molecules. When the vibration of
molecules is great enough, the molecules will evaporate from the surface of the object. However,
the carbon chain will be broken if energy induced by van der Waals force along the polymer
chains is greater than the enthalpy of the C-C bond in the chain(Demirbas, 2007)

This is the reason why high molecular weight polymer is decomposed rather than is boiled when
it is heated. In theory, the temperature of thermal breaking the C-C bonds should be constant for
a given type of plastic (polymer). However, this temperature has been found to differ in different
studies(Demirbas, 2007)

2.8.2. Time
The definition of residence time differs in various studies. In fast pyrolysis or continuous
pyrolysis process, it refers to the contact time of the plastic on the hot surface throughout the
reactor. However, in slow pyrolysis and batch process, the residence time means the duration
from the time when feedstock plastic start to be heated to the time when the products are
removed. Longer residence time favors a further conversion of the primary products thus
yielding more thermal stable products such as light molecular weight hydrocarbons, non-
condensable petroleum gases. In a slow pyrolysis, long residence time encourages the
carbonization process and produces more tar and char in the products. Secondary pyrolysis

12
 cracking occurs when residence time is long enough, which enhances the yield of gaseous
product (Mastral et al., 2002).

2.8.3. Catalyst
In order to optimize plastic pyrolysis reactions and modify the distribution of pyrolysis products,
catalysts are widely used in research and industrial pyrolysis processes. Petroleum fuels, such
as LPG, petrol, kerosene, and diesel, are hydrocarbons from C1 to C24. The PP pyrolysis
products are mainly straight hydrocarbons from C1 up to C80, which contain much heavier
molecular weight components. One of the main purposes of using catalysts is to shorten the
carbon chain length of the pyrolysis products and thus to decrease the boiling point of the
products. Catalysts are found to be mainly applied to Polypropylene (PP) pyrolysis because the
primary product from other plastics, such as polyethylene (PE) and polystyrene (PS), are mainly
light hydrocarbons, with similar carbon chain length to the range of commercial fuels as
compared to polypropylene pyrolysis products.

2.9. Characterization of liquid fuel oil

As different studies showed that the fuel oil produced from waste plastic can be characterized in
terms of density, flash point, pour point, viscosity, and calorific value.

Flash point

This is a key property for determining the flammability of a fuel. The flash point is the lowest
temperature at which an applied ignition source will cause the vapors of a sample to ignite. It is a
measure of the tendency of a sample to form a flammable mixture with air. The value of the flash
point is used for the classification of flammable and combustible materials needed for safety and
shipping regulations.

The flash point was determined by heating a sample of the fuel in stirred container and passing
aflame over the surface of the liquid. Temperature at which the vapor ignited was recorded as the
value for flash point.

Viscosity

viscosity (ν) is the resistance to flow of a fluid under gravity. In measuring the viscosity, the time
taken for a fixed volume of the liquid to flow under gravity through the capillary of a calibrated

13
viscometer was measured. The measurement was done under a reproducible driving head at
closely controlled temperature using a Cannon- capillary tube viscometer.

Cloud point

The fuel property that is particularly important for the low temperature operability of fuels is the
cloud point. The cloud point is the temperature at which a cloud of wax crystals first appears in a
liquid upon cooling. Therefore, it is an index of the lowest temperature of the fuel’s utility under
certain applications. Operating at temperatures below the cloud point for fuel can result in fuel
filter clogging due to the wax crystals. This therefore has implications on the use of fuels in cold
weather applications

The cloud point is the temperature at which a cloud of wax crystals first appears in a liquid upon
cooling. The sample was cooled in an ice bath at constant rate. It was continuously monitored by
visual monitoring. The temperature that corresponds to the first formation of cloud in the sample
was recorded. This was done by monitoring the sample continuously with recording of the
temperature of the sample in comparison with that of the ice bath. The temperature at which the
fuel starts to form cloud was noted and taken to be the temperature for cloud point.

14
 CHAPTER THREE
MATERIALS AND METHODS
3.1. Materials and equipment’s
Waste plastic: the main raw material used for the production of the fuel oil.
Pyrex glass: it is used to hold and heat the raw material waste plastic. These glasses are chosen
form other glasses because of they have high resistant to heat and chemical attack.
Brass tube condenser: Brass tube was used in cooling water applications due to its good
corrosion resistance to treated cooling water, resistance to microbial corrosion and good thermal
conductivity.
Metal casserole: they provide continuous heating to process samples and materials. They are
generally built from high temperature (refractory) materials so that they can maintain high
temperatures without breaking down.
Scissor: Used to cut the waste plastic.
Fractioning column: used in distillation of liquid mixtures so as to separate the mixture into its
component parts, or fractions, based on the differences in volatilities.
Condenser: used to condense the heated plastic
3.2. Chemicals used
Silica-alumina (zoolite): it is used as a catalyst for the chemical reaction
Sodium carbonate: it is used slow down the reaction when it becomes uncontrollable.
3.2.1. Mixed plastic waste
The plastic wastes (feedstock) were collected in Kombolcha campus. These included; LDPE and
some HDPE, commonly used in carriers or packages. All the mixed plastic wastes were
subjected to a wet cleaning process to remove soil, labels and inserts. Then subjected to
shredding and air cleaning, drying and cut in particle with a size of around 1 cm.

3.2.2. Catalysts and equipment

The cracking silica-alumina catalyst, synthesized in the laboratory was used to lower the
temperature in production, which was controlled in the narrow range of 250 °C – 370 °C.
Different equipment and apparatus were used to set up a production assembly (figure 3.1). This
included; a batch reactor, a fractionating column, and a condenser with a temperature logger.
Assorted chemicals and apparatus were used in different stages from cleaning to analysis.

15
Figure 3. 1 : Schematic diagram of Production assembly for fuel from mixed plastic waste

3.3. Experimental Method

Waste plastic was collected from Kombolcha campus. An investment group found in Kombolcha
sent us this type of waste plastic. It also checked wither it is possible or not to produce fuel or
crude oil. The waste plastics was mixture of tire, rubber, LDPE, HDPE, PP, PS, PVC, Other-7,
PETE, and etc. Provided plastic had too much dirty and we did not clean as much as to be
cleaned since it was during production period.
3.3.1. Plastic waste sample collection
Plastic waste sample will be collected from different sources, polyolefin wastes like
polyethylene, polypropylene, and, shredded mixed plastic wastes. Then this waste sample will be
transported to organic chemistry lab session of chemical engineering department. The dirty
plastics wastes will be washed with water and detergent solution, be dried and then will be kept
for the further processing.

16
 3.3.2 Raw material preparation
3.3.2.1. Palletization Technique
This is a process of forming plastic pellets from the light to bulky plastic materials. This will be
helped to reduce their surface area and makes them easy to be transported and packed inside the
during this process the cleaned plastics will be cut in to small pieces and will be placed on the
hot Plate heating machine covered by aluminum foil will be, and heated to a temperature. The
pellets will be then cooled and stored for the pyrolysis experiment.
3.3.2.2. Preparation of catalyst
Catalyst material that will be used for this experiment are zeolites, Aluminum chlorides
supported by activated carbon both will be obtained from the local market.
3.3.2.3. Laboratory Preparation of Inert Gas
Since the pyrolysis experiment is mostly carried out under an inert atmosphere, unfortunately the
only limitation for this experiment will be absence of nitrogen source. This limitation will be
overcome by preparing the inert gas in the laboratory by removing all the reactive gases like
oxygen, carbon dioxides, water vapor from the atmospheric air using simple laboratory
technique.
3.3.2.4. Hydrocarbon fuel production
A mixture of HDPE and LDPE plastic resins will be fed into the reactor flask and a catalyst will
be added. The electrode of the thermocouple thermometer will be inserted in the reactor flask
and the tip will be immersed in the fed stoke catalyst mixture from the vertical opening and be
sealed completely. The inert gas generated will be fed into the reactor flask and the reactor flask
will be placed on sand in a steel basin which will be heated electrically. The system will be
isolated from the surrounding in terms of air movement, and the power will be switched on, and
the time and temperature taken for the fed stoke to melt will be recorded.

Starting temperature was use 25 ºC and temperature was increased slowly up to 400 ºC. At the
end time temperature was increased 420 ºC for finished the whole process. During production
process liquid fuel or crude oil was condensed by condensing unit and this experiment cooling
water was not use for condensing purpose.

3.3.3. Overall production process

17
First the raw material waste plastic was collected from Kombolcha campus. After the raw
material has been collected the plastic was prepared by cutting into pieces by using scissor.
After it was cut into pieces the assembly for the production of the fuel was prepared in the
laboratory. Then 500g of waste plastic pieces was measured using measuring balance. Then the
measured waste plastic was inserted into metal casserole. Then sodium carbonate and silica
alumina were added to the waste plastic in the metal casserole. Then we canned the metal
casserole to prevent the air from flowing into the metal casserole and from the metal casserole
into the surrounding. The confessor was connected directly with fractioning column. The aim of
the condenser was converting the gas into the liquid fuel. Then finally the liquid fuel was
collected using measuring cylinder. Here the condenser didn’t fully convert the gas into liquid,
some part of the gas wasn’t converted into liquid. This gas called light gas is further cleaned and
collected using light gas storage.

Figure 3. 2 : mixed waste plastic to crude oil production process

18
3.3.4. Characterization of the fuel oil.
Flash point
Flash point” is the minimum temperature at which a liquid gives off vapor within a test vessel in
sufficient concentration to form an ignitable mixture with the air near the surface of the liquid.
The lower the flash point, the easier it is to ignite a liquid solvent. It is also used to characterize
the fire hazards of fuels. Fuels which have a flash point less than 37.8 °C are called flammable
whereas fuels having a flash point above that temperature are called combustible.
Flash points are determined experimentally by heating the liquid in a container and then
introducing a small flame just above the liquid surface. The temperature at which there is a
flash/ignition is recorded as the flash point.
Fire point: It the minimum liquid temperature for which sustained burning of the liquid occurs
after ignition of vapors. (Fire point is slightly higher than flash point.
Viscosity: the internal friction of a fuel causing its resistance to change of form and is an
essential physical property by which a fluid differs from an elastic solid viscometer is used to
measure the viscosity of fuel oil at the fuel injection system of the engine. It consists of a
capillary tube inside of which a gear pump is fitted which rotates at very slow rpm.
Density fuel: of fuel is “the mass of fuel per unit volume”. In some cases, the density is
expressed as a specific gravity or relative density, in which case it is expressed in multiples of
the density of some other standard material, usually water or air.
Calorific Value: the amount of heat energy present in fuel and which is determined by the
complete combustion of specified quantity at constant pressure and in normal conditions.
Hydrocarbon and carbon monoxide emission: the emitted values must be less than the
standard values to meet environmental restrictions.
3.3.4.1. The characteristics of a good fuel are as follows:
 It should have a high calorific value.
 It should be environment-friendly and burn completely without leaving any solid or
gaseous residue.
 It should be cheap and readily available.
 It should be easy to store, transport and handle.

19
 CHAPTER FOUR
RESULT AND DISCUSSION
4.1. Effect of temperature
We had worked an experiment using 500 grams of mixed plastic waste were used for one run
with temperature variations in the heating process, namely 250°C, 300°C, and 350°C. we
concluded that as the cracking temperature increases the yield of fuel production also increased.
But, as his results showed that the process that is going to be determined is still going on,
because, the maximum temperature that gives a better yield could not be determined.
Table 4. 1: Effect of temperature on the amount of liquid oil produced
Plastic waste Operation Liquid produced
No Time(minute)
mass(gram) temperature(°C) Volume(ml) colour
1 500 250 60 45 yellow
2 Deep
500 300 60 55
brown
2 500 350 60 70 black

We had also worked an experiment on the conversion of waste plastics to fuel oil and checked
yield as shown in the table below. our result showed that a maximum yield of liquid fuel which
was 22.5gm obtained at temperature of 350℃ and a time of 60 minutes. From the results it is
easy to conclude that a further increase in temperature leads to a formation of gaseous fuel than
liquid.

4.2. Effect of time

We had worked an experiment to see the effect of time during the conversion of waste plastics to
fuel oil. We used 250 gm at a time of one hour (1hr) and two hour (2hr) through 320 ℃ and
application of zeolite catalyst. Finally, our results are shown below. From the results shown
below, it easy to conclude that as the reaction time prolongs, the conversion yield of the liquid
fuel also increased.

20
 Table 4. 2: effect of time on the yield of liquid fuel
Trials Time(hr.) Temperature ( Catalyst Liquid Cake(residue) gas
℃¿ used produced
1 1 320 Zoolite 51 37 12
2 1 320 Zoolite 52 34 14
3 1 320 Zoolite 55 30 15
1 2 320 Zoolite 72 12 16
2 2 320 Zoolite 77 12 15
3 2 320 Zoolite 68.9 13 16.1

4.3. Effect of catalyst amount

Effect of catalyst amount the higher the catalyst amount gave, the higher the yield of liquid
product and solid residues mass for catalytic pyrolysis of plastic waste at lower and higher
temperature respectively. The lower amount of the catalyst was given lower and higher liquid
product at lower and higher temperature respectively this increased with increasing amount of
catalyst. The lower amount of catalyst gives a higher mass of gaseous fraction. The effect of
catalyst amount in the product mass was highly significant and similar trends was shown also in
statistical analysis data. The advantages include the fact that toxic components and pathogens are
degraded by the use of high temperatures. There is also a reduction in water volume due to the
high operating temperature. By using the produced gases as fuel, one is able to limit the supply
of external fuel.
4.4. Production and quantification of the fuel
In production the key focus was on the resident/contact time of heating and temperature
of the plastic waste in a batch reactor. The reaction temperature for one hour (K/5) and two
hours (M/5) was observed in the range of 250 to 370 oC. The production was done and the
fuel samples were characterized as shown in table 4.3 below.

21
Table 4.3. Liquid fuel produced and its appearance
Batch no. Contact/heating time Labeling Appearance
1 One hour K/5 Yellowish liquid
2 73
Two hours M/5 Yellowish liquid

80 58
70
60 Percentage yield
34
50
40
18
30 Liquid oil
20 cake(solid)
10
0
One hour (K/5) Two hours (M/5)
Contact/heating Time
Figure 4. 1: Appearance of liquid fuel
The quantitative results of the plastic waste decomposition are shown in figure 4.1, where it can
be seen that the yields of valuable products (liquid oil and gas) increased with an increase in
contact/ heating time. It also showed a decrease in cake ( solid) formation with the increase in
contact/heating time. According to the data the batch that was subjected to one hour of heating
time, converted plastic waste into fractions with yields of 58% liquid oil, 34% cake (solid)
and 8% was estimated to be the gas. However, the finding of Lee (2012) show a high yield
of liquid oil (66.98%), gas (28.95%) and cake (4.08%) for the same contact time of one
hour. The low yields in the study were due to low temperature range (250 – 370 oC) used
that affected the degradation of plastic into fuel compared to 450 oC used by Lee (2012). For
the two hours heating contact time, the yield of the liquid oil showed an increase of 15% with a

22
 decrease in cake (solid) formation of 16%. The gas conversion also showed an increase of one
percent due to the prolonged contact time which farther decomposed the plastic waste into
gaseous products. Therefore, the results show considerable increase in yield of the liquid oil
which was attributed by increase in contact time.

CHAPTER FIVE
CONCLUSION AND RECOMMENDATIONS
5.1. Conclusion
Both the land-filling and incineration processes of plastic waste management system are
identified as sources of pollutant gas emitters. Reprocessing also uneconomical in comparison to
the virgin plastic products in terms of commercial values due to polymeric contamination. On the
other hand, the world currently consumes large quantities of non-renewable hydrocarbons at an
ever-increasing rate. The reserves of fossil fuels are limited, and there are many other problems
associated with their consumption. The study and analysis of this paper showed that
polypropylene, polystyrene and PETE waste can be used as a fuel.

Results show that the temperature of process production was in the range of 250 to 370 oC. In
the process, silica-alumina was used as catalyst to lower the temperature and sodium carbonate
was used as a scavenger to control the emission of the gases. The temperature of 350 oC was
found to be the best optimum temperature which was giving maximum heating noted by the
volume yield collected.

The fuel was characterized by carrying out analysis for the physical parameters using
standard methods. Using the standard parameters of regular diesel as the reference, the fuel was
conforming to the standards with their applicability.

The results obtained are in agreement when compared with the distillation characteristics and
the carbon number distribution. This means that sample fuels if produced at large production,
they can both be used in position of regular diesel. Also, with the test runs carried out of the
fuel and its comparison with diesel, we can conclusively say that the fuel can be used as
diesel fuel in most of the systems which use diesel to power the system.

23
5.2. Recommendations
On the basis of study and the conclusion from study finding the researchers forwarded the
following important recommendations
 The conversion of plastic waste into liquid oil and other valuable products using catalytic
pyrolysis process is getting significant attention both as waste management and an
alternative energy generation technology. Catalytic pyrolysis of polypropylene,
polystyrene and PETE plastic waste using synthesized catalyst (Silica-Alumina) needs
further works.
 Mechanical trials have to be performed first to be certain with some sophisticated
engines if it is to be used as fuel. There is need for future studies on the side mechanical
performance and trials of spark ignition must be studied further from the flash point.
Simulation of the laboratory analytical work should be adopted to create a wide data
range due to some circumstances in the laboratories which inhibit the production of
wide range data.
 Due to leakages or lack of proper sealing, condensable and non-condensable gaseous
fraction move out from the system. The release of those gaseous product has an effect on
the environment. The gaseous fraction had high calorific value so collection of gas
product must be available. Future work will require for collection and characterization of
gaseous product.
 Future researches that would Synthesis and Characterization of Liquid Fuel from PP, PS
and PETE waste via Catalytic Pyrolysis Be complementary to the present study aiming at
investigation of the process are, therefore, strongly recommended to put due focus on the
following points.

24
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 APPENDICES

Figure 1: waste plastic PS, PP and PETE

28
Figure 2: Assembly of metal casserole

29
Figure 3: Assembly of casserole and product holder

30
Figure 4: First Trial assembly

31
Figure 5: 100-degree Celsius Hot plate, and casserole in lab

32
Figure 6: 450 Degree Celsius hot plate and casserole with waste plastic

33