DISSERTATION REPORT

ON
WASTE PLASTIC TO FUELS

(5th January to 5th may)

SUBMITTED BY

JAYANT BALI

UNDER THE GUIDANCE of

DR AJAY KUMAR DR DWARIKA PRASAD MAITHANI

Principle scientist HOD of chemistry, SGRR UNIVERSITY

HOA, waste plastic conversion - Dehradun

Process technology

Department of basic and applied science (CHEMISTRY)

SGRRU DEHRADUN
 DECLARATION

I hereby declare that the dissertation entitled “Waste Plastics To Fuels’’

submitted to Shri Guru Ram Rai University , Dehradun is a faithful record
of bonafide research work carried out by me under the kind and the expert
guidance as well as direct supervision of Dr. Dwarika Prasad Mithani
Head of Department of chemistry, School of Basic & Applied Sciences,
SGRR University, Dehradun and Co supervision of Dr Ajay kumar .The
assistance and help received during the dissertation work and the source of
literature have been daily anknowledged. No part of the dissertation should
be extracted for any publication material without the permission of the
author and/or the supervisor.
Date:
Sign.
JAYANT BALI
 ACKNOWLEDGEMENTS

It gives me immense pleasure to take this opportunity to thank and express my sincere gratitude to
my teacher for guiding me and provided me the opportunity to do this work. I would also like to
thank Dr. Anjan Ray, Director CSIR-IIP for giving me this wonderful opportunity to work with this
esteem organization and chance to improve my skills and enhance my knowledge in my field of
Chemistry.

I am deeply gratified to Dr. Ajay Kumar (Principal Scientist Head of waste plastic to fuels), under
whose guidance I am able to make my stay truly valuable and explore more new facts. This could
have not been possible without his dynamic leadership and support.

I would like to thank to all my university professors Dr. Dwarika Prasad Maithani and Dr.
Sheetal Dasgupta and all others in the Department of Chemistry for teaching and providing me
such a deep knowledge of industrial and research operations, without which it was impossible for
me to complete my whole training semester successfully.

Date: Jayant Bali

Place: MSc Chemistry (IV Semester)

TABLE OF CONTENTS
CONTENT PAGE NO
CHAPTER 1 –INTRODUCTION OF IIP & PLASTICS 5-8

1.1 General
1.2 Plastics
1.3 Selection of waste plastics

CHAPTER 2 – LITERATURE REVIEW 9-19

2.1 plastics, types, properties and their uses

2.1.1 Definition of plastics

2.1.2 Statistics of consumption of plastics and generation of plastics waste

2.1.3 Source and properties of plastic waste
2.1.4 Different methods of plastic waste management

CHAPTER3- METHODOLOGY 20-28

3.1 Material

3.2 Properties of molten HDPE

3.3 Experimental work on HDPE

3.4 Modification of catalyst by using wet IMPREGENATION METHOD

3.5 Physical characterization of catalyst

CHAPTER4- RESULT AND DISCUSSION 29-30

4.1 ASTM method use for LIQUID PRODUCTS (D86)

6.2 SVM viscometer for measuring density and viscosity

4.3 flash point

CHAPTER 5- CONCLUSION 31-32

CHAPTER 6- REFERENCES 33-34

CHAPTER 1
1.1 BRIEF PROFILE OF IIP
Indian institute of petroleum is ISO 9001 accredited organization, is a national
laboratory under council of scientific and industrial research (CSIR) New Delhi. It
was established in the September 1960 in technical collaboration with the institute
france petroleum(IFP),France under UNESCO programme and started functioning at
Dehradun from April 1963. The major organization structure chart is shown below:

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IIP AND TRAINING ACTIVITIES :

The institute is equipped with state-of-the-art equipments, bench/pilot

scale facilities and other infra-structural support for research in petroleum
refining, petrochemicals and application of petroleum products. It also conducts market demand
surveys and techno-economic feasibility studies of petroleum products. It has more than 1800
publication in national and international journals. IIP has been granted 135 patents several processes
& products and bagged several prestigious national Awards. The institute has so far licensed 32
major technologies to Indian refineries and petrochemicals plants with cumulative licensed capacity
of all the plants around 32 MMTPA. The institute has bagged 10 CSIR Technology awards in the
last 12 years. In addition to carrying out research in the frontier areas of petroleum , IIP ( as one of
its mandate) also plays a leading role in organizing specialized training programmes, for engineers,
and chemistin the petroleum refining, petrochemicals and transport sector. IIP, offers a variety of
courses to scientific, technical and management trainee employed in petroleum refininig & user
industry, government and academic institutions. These are moderately priced courses designed to
impart the necessary knowledge and skills and are conducted by talented and highly competence and
experienced scientists. Participants is provided ample opportunities to have hands on experience.

1.3 NEED FOR TRAINING :

Training is an important process through which a person enhances and maintain his efficiency,
capability and effectiveness at work by improving and updating his knowledge, understanding &
skills relevant to the job. Training prepares the brain of an individual how troubleshoot certain
problems at work by giving hands on experience to the smaller problems.

1.4 OBJECTIVE OF TRAINING

Generally training is the responsibility of the training institution, the participating organization and
the participants. Generally , training is intended to:

 Help the Trainees in acquiring knowledge of the subject

Matter
 Bring about the change in the attitudes, understanding and
behavior among the trainees towards the particular
programme and problem.
 Help in putting the theory into practice and bringing
generalization from the various hypotheses.
 Help in evaluating the abilities, potential & competence of
the trainees for the particular assingnment /job skill.
 Motivate the trainees for self –learning and development.
 Enhance the problem solving and decision making
capabilities of the trainees.
 Help in narrowing down the gap between expected level of
performance among the trainees.
1.5 SIGNIFICANCE OF TRAINING ACTIVITIES AT IIP

IIP attaches chief significance to these programmes in view of the following:

 IIP acts as a window to the latest information on the subject

for the participants in these programmes.
 Participants in the programme have the physical feel of IIP’s
research and development facilities and appreciation of its
strength and the services it can provide to industry.
 It acts as R&D for various petroleum refineries so training
at IIP gives a good exposure of the whole process in short
which is carried out at large refineries.

INTRODUCTION OF PLASTICS
1. 1GENERAL
Plastic waste is regarded as a potentially cheap source of chemicals and energy. Lots of us
have encountered a variety of products that use plastics materials today. As a results of the
increasing levels of private consumptions of these plastics materials huge amount of wastes are
discharged to the environment.

Plastic materials are a type of materials that cannot be decomposed easily in a short
period of time. Substantial quantities of plastics have accumulated in the natural environment
and in landfills. Those wastes can be classified according to their origins.

They are

 Industrial Waste
 Municipal Waste

These groups have different qualities and properties and are subjected to different management
strategies. Huge amounts of plastics wastes arise as a by-product or defective products in industry
and agriculture.

The main components of municipal solid waste (MSW) are food wastes, wood, paper, cardboard etc.
On the other words, more than half of the municipal solid waste components are organic species
mainly thermoplastics, which can be used as energy sources.
 The traditional MSW disposal method is landfill. Because of the longevity of plastic, disposal to
landfill may simply be storing problems for the future. For example, plasticizers and other additives
chemicals have been shown to leach from landfill. The extent of varies accordingly, particularly pH
and organic contents.

1.2 PLASTICS
As a brief introduction to plastics, it can be said that plastics are synthetic organic
materials produced by polymerization. They are typically of high molecular mass, and
may contain other substances besides polymers to improves performance and/or reduce
costs.

These polymers are made of a series of repeating units known as monomers. Therefore
polymers can be molded or extruded into desired shapes. There are main two types of
plastics: thermosetting and thermoplastics polymers.

 Thermosetting plastics can melts and take shape only once. They are not
suitable for repeated heat treatment; therefore after they have solidified, they stay
solid.
Examples are phenol formaldehyde and urea formaldehyde.

 Thermoplastics can repeatedly soften and melt if enough heat is applied and
hardened on Cooling, so that they can be made into new plastics products.
Examples are polyethylene, polystyrene and PVC

Plastic is one of the most commonly used materials in daily life which can be
classified in many ways such as based on its chemical structure, synthesis process,
density, and other properties. In order to assist recycling of waste plastic, Society of
plastics industry (SPI) defined a resin identification code system that divides
plastics into the following seven groups based on the chemical structure and
application:

1. PET(Polyethylene Terephthalate )
2. HDPE(High Density Polyethylene)
3. PVC(Polyvinyl Chloride)
4. LDPE(Low Density Polyethylene)
5. PP(Polypropylene)
6. PS(Polystyrene)
7. Others
1.3 SELECTION OF WASTE PLASTICS

Waste plastics are one of the most promising resources for fuel production because of its
high heat of combustion and due to the increasing availability in local communities.
Unlike paper and wood, plastics do not absorb much moisture and the water content of
plastics is far lower than the water content of biomass such as crops and kitchen wastes.
The conversion methods of waste plastics into fuel depend on the types of plastics to be
targeted and the properties of other wastes that might be used in the process. Additionally
the effective conversion requires technologies to be selected according to local economic,
environmental, social and technical characteristics.

In general, the conversion of waste plastic into fuel requires feeds stock which are non-
hazardous and combustible. In particular each type of waste plastic conversion method
has its own suitable feedstock. The composition of the plastics used as feedstock may be
very different and sonic plastic articles might contain undesirable substances (e.g.
additives such as flame-retardants containing bromine and antimony compounds or
plastics containing nitrogen, halogens, sulfur or any other hazardous substances) which
pose potential risks to humans and to the environment. The types of plastics and their
composition will condition the conversion process and will determine the pretreatment
requirements, the combustion temperature for the conversion and therefore the energy
consumption required, the fuel quality output, the flue gas composition (e.g. formation of
hazardous flue gases such as NOx and HO), the fly ash and bottom ash composition, and
the potential of chemical corrosion of the equipment. Major factors to be considered
while selection are -

• Smooth feeding for equipment

• Effective conversion

• Well-controlled melting

PE, and PP thermoplastics are preferable as feedstock in the production of liquid

hydrocarbons. The addition of thermosetting plastics, wood, and paper lo the feedstock
leads to the formation of carbonous substances and lowers the rate and yield of liquid
products.

The municipal plastic waste comprises of 80% thermoplastics and 20% thermosetting
plastic. Since thermoplastics are can be further processed, basic types of thermoplastics
can be used. Simple and common thermoplastics are polyethylene and polypropylene.
Table 1.1 Products types of some plastics pyrolysis
Main products Type of plastics Feedstock of liquid fuel

Polyethylene (PE) Allowed.

Liquid Polypropylene (PP) Allowed.

hydrocarbons
Polystyrene (PS) Allowed.

Polymethyl metacrylate
Allowed.
(PMMA)
Acrylonitrile-Butadiene-
Allowed. But not suitable.
Styrene
Liquid
Nitrogen-containing fuel is
hydrocarbons
copolymer (ABS) obtained. Special attention
required to cyanide in oil-
Not suitable, formation of
No hydrocarbons Polyvinyl alcohol (PVA)
water and alcohol.
suitable for
Not suitable. Formation of
fuel Polyoxymethylene (POM)
formaldehyde.
Not suitable. Formation of
Polyethylene terephthalate
Solid products terephthalic acid and
(PET)
benzoic acid.

Polyurethane (PUR) Not suitable.

Carbonous
products
Phenol resin (PF) Not suitable.
Chapter 2
LITREATURE REVIEW
2.1 plastics, types, properties and their uses

2.1.1 Definition of plastics

Plastics are ‘‘one of the greatest innovations of the millennium’’ and have certainly proved their
reputation to be true. There are a numerous ways that plastic is and will be used in the years to
come. The fact that plastic is lightweight, does not rust or rot, low cost, reusable and conserves
natural resources is the reason for which plastic has gained this much popularity. Again, Plastics
save energy and CO2 emissions during their use phase. If we were to substitute all plastics in all
applications with the prevailing mix of alternative materials, and look from a life cycle perspective,
then 22.4 million additional tons of crude oil per year would be required[1]

Plastic covers a range of synthetic or semi synthetic polymerization products which can be moulded
into any desired shape when subjected to heat and pressure. They composed of organic condensation
or addition polymers and may contain other substances to improve performance or economics. A
finished high-polymer article not only consists solely of high polymeric material (polymer or resin)
but is mixed with 4 to 6 ingredients, such as lubricant, filler, plasticizer, stabilizer, catalysts, and
colouring material, each of which either discharges a useful function during moulding or imparts
some useful property to the finished artefact.

Polymerization is the process by which individual units of similar or different molecules

("mers/monomers") combine together by chemical reactions to form large or macromolecules in the
form of long chain structures, having altogether different properties than those of starting molecules.
Several hundreds and even thousands of "mers" combine together to form the macromolecules,
polymers.[3]

2. 1.2 Physical properties of Plastics

Table 2.1 Important physical properties of Plastics

Plastic Plastic Thermal Strength Properties Density

No. Properties Kg/m3
Tm Tg Tensile Compressive
ºC ºC (Pa) (Pa)
1 PET (polyethylene 245 73 48263301 75842330.2 1290
terephthalate 265 80 72394951.5 103421359.3 1400
2 HDPE (high density 130 22063223.3 18615844.6 952
polyethylene) 137 31026407.8 24821126.2 965
3 PVC (polyvinyl 75 40679068 55158058.3 1300
chloride) 105 51710679.6 89631844.8 1580
4 LDPE (low density 98 -25 8273708.7 9652660.2 917
polyethylene) 115 31371145.6 932
5 PP (polypropylene) 168 -20 31026407.8 37921165.1 900
175 41368543.7 55158058.3 910
6 PS (polystyrene) 74 35852737.9 82737087.5 1040
105 51710679.6 89631844.8 1050

Types of Waste Plastics and Their Recyclability

There are mainly two types of Plastics: Thermoplastics and Thermosetting Plastics

Thermoplastics are those, which once shaped or formed, can be softened by the
application of heat and can be reshaped repeatedly, till it loses its property. Example:
Polyethylene, Polypropylene, Nylon, Polycarbonate etc. Applications are: Polyethylene
Buckets, Polystyrene cups, Nylon ropes etc[5]

Thermosetting Plastics are those, which once shaped or formed, cannot be softened by
the application of heat. Excess heat will char the material. Example: Phenol
formaldehyde, Urea Formaldehyde, Melamine Formaldehyde, Thermosetting Polyester
 Mark Type Recyclable Abbreviation Description & Common uses
Type Yes PET Polyethylene Terephthalate
1 Beverages.

High-Density Polyethylene
Type Milk, detergent & oil bottles, toys,
Yes HDPE
2 containers used outside, parts and
plastic bags.
Type Yes, Vinyl/Polyvinyl Chloride
3 But PVC Food wrap, vegetable oil bottles,
not common blister packages or automotive parts.
Type Low Density Polyethylene, Many
4 Yes LDPE plastic bags, shrink-wraps, garment
bags or containers.
Poly Propylene.
Type Refrigerated containers, some bags,
Yes PP
5 most bottle tops, some carpets, and
some food wrap.
Type Yes, but not Polystyrenes.
6 common PS Through away utensils, meatpacking,
protective packing.
Type Some ------------ Other. Usually layered or mixed
7 plastic.

e
tc. Applications are: Bakelite Electrical switches, Formica / sermica table tops,
melamine Cutlery etc.

The following Table 2.2 shows different types thermoplastics plastics and their
recyclability with standard identification mark to identify easily
2.1.5 Statistics of consumption of plastics and generation of plastics waste

Constant developments in polymer technology, processing machineries, know-how and cost

effective production is fast replacing conventional materials in every segment with plastics.
Continuous innovation explains that, plastics production has increased by an average of almost 10%
every year on a global basis since 1950[7]. The total global production of plastics has grown from
around 1.3 million tonnes (MT) in 1950 to 368 million metri tons in worldwide. Only 9 percent of
the total plastic waste in the world is recycled. A Central Pollution Control Board (CPCB) report
(2018-2019) puts the total annual plastic waste generation in India at a humungous 3.3 million
metric tonnes per year. In 2011, the amount of plastic waste generated across the country was close to
seven million metric tons per year and is estimated to be over 50 million metric tons per year in the
year 2041.

This statistic illustrates the amount of plastic waste generated across India from 2001 to 2011, with
estimates up to 2041. In 2011, the amount of plastic waste generated across the country was close to
seven million metric tons per year and is estimated to be over 50 million metric tons per year in the
year 2041.

Expected plastic produced in 2041 in metric

tons
NAME

2001 2011 2021 2031 2041

3.1 6.8 17.5 31.5 55

1 2 3 4 5

2.1.3 Sources and properties of plastic wastes

Plastic wastes can be classified as industrial and municipal plastic wastes according to
their origins these groups have different qualities and properties and are subjected to
different management strategies. Plastic wastes represent a considerable part of municipal
 wastes; furthermore huge amounts of plastic waste arise as a by-product or faulty product
in industry and agriculture. Of the total plastic waste, over 78wt% of this total
corresponds to thermoplastics and the remaining to thermosets. Thermoplastics are
composed of polyolefins such as polyethylene, polypropylene, polystyrene and polyvinyl
chloride and can be recycled. On the other hand thermosets mainly include epoxy resins
and polyurethanes and cannot be recycled[11]

Municipal plastic wastes

Municipal plastic wastes (MSW) normally remain a part of municipal solid wastes as they are
discarded and collected as household wastes. The various sources of MSW plastics includes
domestic items (food containers, packaging foam, disposable cups, plates, cutlery, CD and cassette
boxes. fridge liners, vending cups, electronic equipment cases, drainage pipe, carbonated drinks
bottles, plumbing pipes and guttering, flooring. cushioning foams, thermal insulation foams, surface
coatings, etc.), agricultural (mulch films, feed bags, fertilizer bags, and in temporary tarpaulin-like
uses such as covers for hay, silage, etc.), wire and cable, automobile wrecking, etc. Thus, the MSW
collected plastics waste is mixed one with major components of polyethylene, polypropylene,
polystyrene, polyvinyl chloride, polyethylene terephthalate, etc. The percentage of plastics in MSW
has increased significantly[13]

Industrial plastic wastes

Industrial plastic wastes (so-called primary Waste) are those arising from the large plastics
manufacturing, processing and packaging industry. The industrial waste plastic mainly constitute
plastics from construction and demolition companies (e.g. polyvinyl chloride pipes and fittings, tiles
and sheets) electrical and electronics industries (e.g. switch boxes, cable sheaths, cassette boxes, TV
screens, etc.) and the automotive industries spare-parts for cars, such as fan blades, seat coverings,
battery containers and front grills). Most of the industrial plastic waste have relatively good physical
characteristics i.e. they are sufficiently clean and free of contamination and are available in fairly
large quantities. It has been exposed to high temperatures during the manufacturing process which
may have decreased its characteristics, but it has not been used in any product applications[16]

2.1.4 Different methods of plastic waste management

Due to population increase, the demand for plastic products has steadily increased over the last 40
years. Since plastics are non-biodegradable, they cannot be easily returned to the natural carbon
cycle; hence the life cycle of plastic materials ends at waste disposal facilities. There are several
methods for disposal of municipal and industrial plastic waste, i.e. landfill, incineration (energy
recovery), true material recycling (similar recycled product or monomer recovery), and chemical
recovery. The suitable treatment of plastic wastes is one of the key questions of the waste
management and is important from energetic, environmental, economical and political aspects. In
most developed societies domestic organic waste, including plastics packaging, is disposed of in
sanitary land filled or by incineration. During early 2000, the largest amount of plastic wastes is
disposed of by land filling (65–70%), and incineration (20–25%). Recycling is only about 10%. In
2020 about 79% of plastic is disposed of by landfill, dump or the natural environment and nearly
about 12% in incineration and only 9% of plastic is recyled. This figure varies from country to
country, however they are approximately nearer to it with some. In India only 9% of plastic waste is
recyled and only 10% of plastic in incineration and about 81% is disposed by landfill.[14]

The Figure represents the different routes for plastic waste management being followed

Land filling
Landfilling is one of the major municipal solid waste (MSW) disposal methods practiced worldwide.
Though it is considered most cost-effective means of waste disposal, but poor management practices
specially in developing countries like India are the major causes of environmental pollution.
Recently several studies have been carried out to understand the effects of landfill pollution on
human health as well on the environment. Toxic gas emissions from landfills pose a serious threat to
the environment as well as on human health. Some studies have shown that toxic gases released
from landfill sites are even responsible for lung and health diseases in humans. Landfills also
generate a toxic soup known as leachate, formed when waste is subjected to biological and
physiochemical transformation. Leachate is highly toxic and cause land and groundwater pollution.
This chapter aims to address the problems, both environmental and toxicological, associated with the
landfill, the challenges faced in the current scenario, and the possible measure that can be taken to
deal with the problem of municipal solid waste management successfull.[12].

Mechanical recycling

Mechanical recycling of plastics refers to the processing of plastics waste into secondary raw
materials 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
recyled with little or no impairment.

Before recycling, most plastics are sorted according to their resin type. In the past, plastic reclaimers
used the resin identification code (RIC), a method of categorization of polymer types, which was
developed by the Society of the Plastics Industry in 1988. Although at first sight, mechanical
recycling of plastic wastes appears to be a ‘green’ operation, the re- processing operation is not cost
effective as it needs high energy for cleaning, sorting, transportation and processing in addition to
the additives used to provide a serviceable product. Again, materials recycling of household waste
plastics is particularly difficult when they are contaminated with biological residues or, as is usually
the case, when they are a mixture of different kinds of plastics. Technology is being introduced to
sort plastics automatically, using various techniques such as X-ray fluorescence, infrared and near
infrared spectroscopy, electrostatics and flotation. However the economic viability and practicability
of such process in industrial application is not apparent[10]

Biological recycling

Both natural and synthetic cis-poly (isoprene) becomes highly resistant to bio- degradation
when made into industrial products (e.g. tyres) which is a direct consequence of the presence of
highly effective antioxidants added during their manufacture. This has led to intensive
research both in industry and in universities to develop polymeric materials that conform to
user requirements but are also returned to the biological cycle after use. This resulted in
development of biodegradable polymers which can be converted back to the biomass in a
realistic time period [28–30]. Biodegradable plastics are already being used successfully in
different countries. Mostly they are introduced in food/catering industry which photo-degrades
in six weeks. There is also potential to use such plastics in non-packaging applications such as
computer or car components. However, there are a number of concerns over the use of
degradable plastics. First, these plastics will only degrade if disposed of in appropriate
conditions. For example, a photodegradable plastic product will not degrade if it is buried in a
landfill site where there is no light. Second, they may cause an increase in emissions of the
greenhouse gas methane, as methane is released when materials biodegrade anaerobically.
Third, the mixture of degradable and non-degradable plastics may complicate plastics sorting
systems. Last but not least, the use of these materials may lead to an increase in plastics waste
and litter if people believe that discarded plastics will simply. Due to all these problem all
the application area of synthetic plastic[6]
Thermal recycling/Incineration

Energy generation by incineration of plastics waste is in principle a viable use for recovered waste
polymers since hydrocarbon polymers replace fossil fuels and thus reduce the CO2 burden on the
environment the calorific value of polyethylene is similar to that of fuel oil and the thermal energy
produced by incineration of polyethylene is of the same order as that used in its manufacture.
Incineration is the preferred energy recovery option of local authorities because there is financial
gain by selling waste plastics as fuel. Co-incineration of plastic wastes with other municipal solid
wastes may be increasingly practiced, because the high caloric value of plastics can enhance the
heating value of MSW and facilitate an efficient incineration, while their energy content can also be
recovered. However, in most developed countries public distrust of incineration at present limits the
potential of waste- to-energy technologies as it produce greenhouse gases and some highly toxic
pollutants such as polychlorinated dibenzo para dioxins (PCDD) and polychlorinated dibenzo furans
(PCDF). The potential relationship between plastics fed into an incinerator and the formation of
dioxins and furans is still unclear and has been suggested that the chlorine content in PVC and other
plastics is related to the formation of dioxins and furans[4]

Calorific values of plastics compared with conventional fuels

Fuel Calorific value (MJ/kg)

 Methane 53
Gasoline 46
Fuel oil 43
Coal 30
Polyethylene 43
Mixed plastics 30-40
Municipal solid waste 10

Chemical Recycling

Current state of the art feedstock recycling, also known as chemical recycling or tertiary
recycling, aims to convert waste polymer into original monomers or other valuable
chemicals. These products are useful as feedstock for a variety of downstream industrial
processes or as transportation fuels. There are three main approaches: depolymerisation,
partial oxidation and cracking (thermal, catalytic and hydrocracking)[8]

De-polymerization
Condensation polymers which include materials such as polyamides, polyesters, nylons
and polyethylene terephthalate can be depolymerised via reversible synthesis reactions to
initial diacids and diols or diamines. Typical depolymerisation reactions such as
alcoholysis, glycolysis and hydrolysis yield high conversion to their raw monomers.
However, addition polymers which include materials such as polyolefins, typically
making up 60–70% of municipal solid waste plastics, cannot be easily depolymerised
into the original monomers by reverse synthesis reaction.[2]
Partial oxidation
The direct combustion of polymer waste, which has a good calorific value, may be
detrimental to the environment because of the production of noxious substances such as
light hydrocarbons, NOx, sulfur oxides and dioxins. Partial oxidation (using oxygen and/or
steam), however, could generate a mixture of hydrocarbons and synthesis gas (CO and
H2), the quantity and quality being dependent on the type of polymer used. A new type of
waste gasification and smelting system using iron-making and steelmaking technologies
has been described by Yamamoto et al. [32], reportedly to produce a dioxin- free and high-
calorie purified gas. Hydrogen production efficiency of 60–70% from polymer waste has
been reported for a two-stage pyrolysis and partial oxidation process. Co-gasification of
 biomass with polymer waste has also been shown to increase the amount of hydrogen
produced while the CO content reduced. The production of bulk chemicals, such as acetic
acid, from polyolefins via oxidation using NO and/or O2, is also possible.

Cracking/Pyrolysis

Cracking process break down polymer chains into useful lower molecular weight compounds. The
products of plastic pyrolysis process could be utilized as fuels or chemicals. Three different
cracking processes such as hydrocracking , thermal cracking and catalytic cracking are reported.

(A) Hydro-cracking
Hydro-cracking of polymer waste typically involves reaction with hydrogen over a
catalyst in a stirred batch autoclave at moderate temperatures and pressures
(typically423– 673 K and 3–10 MPa hydrogen). The work reported, mainly focuses on
obtaining a high quality gasoline starting from a wide range of feeds. Typical feeds
include polyethylene, polyethylene terephthalate, polystyrene, polyvinyl chloride and
mixed polymers, polymer waste from municipal solid waste and other sources, co-mixing
of polymers with coal, co-mixing of polymers with different refinery oils such as vacuum
gas–oil and scrap tyres alone or co-processed with coal. To aid mixing and reaction,
solvents such as 1-methyl naphthalene, tetralin and decalin have been used with some
success. Several catalysts, classically used in refinery hydrocracking reactions, have been
evaluated and include transition metals (e.g., Pt, Ni, Mo, Fe) supported on acid solids
(such as alumina, amorphous silica–alumina, zeolites and sulphated zirconia). These
catalysts incorporate both cracking and hydrogenation activities and although gasoline
product range streams have been obtained, little information on effect of metal and
catalyst, surface areas, Si/Al ratio or sensitivity to deactivation is quoted.
(B) Thermal cracking
Thermal cracking or Pyrolysis, involves the degradation of the polymeric materials by
heating in the absence of oxygen. The process is usually conducted at temperatures
between 350 °C and 900 °C and results in the formation of a carbonized char (solid
residues) and a volatile fraction that may be separated into condensable hydrocarbon oil
consisting of paraffins, isoparaffins, olefins, naphthenes and aromatics, and a non-

condensable high calorific value gas. The proportion of each fraction and their precise
 composition depends primarily on the nature of the plastic waste but also on process
conditions. The extent and the nature of these reactions depend both on the reaction
temperature and also on the residence of the products in the reaction zone, an aspect that
is primarily affected by the reactor design. However, the thermal degradation of polymers
to low molecular weight materials requires high temperatures and has a major drawback
in that a very broad product range is obtained. Catalytic pyrolysis provides a means to
address these problems.
(C) Catalytic Cracking
In this method a suitable catalyst is used to carry out the cracking reaction. The presence
of catalyst lowers the reaction temperature and time. In addition, catalytic degradation
yields a much narrower product distribution of carbon atom number with a peak at lighter
hydrocarbons and occurs at considerably lower temperatures. From an economic
perspective, reducing the cost even further will make this process an even more attractive
option. This option can be optimized by reuse of catalysts and the use of effective
catalysts in lesser quantities. This method seem to be the most promising to be developed into
a cost-effective commercial polymer recycling process to solve the acute environmental
problem of plastic waste disposal[1]

Pyrolysis of plastic waste to liquid fuel —The Process

Pyrolysis is generally defined as the controlled heating of a material in the absence of

oxygen. In plastics pyrolysis, the macromolecular structures of polymers are broken
down into smaller molecules or oligomers and sometimes monomeric units. Further
degradation of these subsequent molecules depends on a number of different conditions
including (and not limited to) temperature, residence time, presence of catalysts and other
process conditions. The pyrolysis reaction can be carried out with or without the presence
of catalyst. Accordingly, the reaction will be thermal and catalytic pyrolysis. Since
majority of plastic used are polyolefins, so extensive research has been done on this [5]
Methodology
There are three types of units where experiment is done

1- Lab scale

Figure (A) 200gm WASTE PLASTICS

2– Bench scale

Figure (B) 300gm daily WASTE PLASTICS

3– Pilot plant

Figure(c) 1 TOONE WASTE PLASTICS

3.1 Materials

Plastic: The plastic considered in this experiment is HIGH DENSITY POLYETHYLENE AND
POLYPROPYLENE (HDPE). The waste samples are identified by determining melting temperature and
glass transition temperature from DSC curve.

HDPE: The Hdpe use in this experiment is obtained from IOCL. It has the density of 0.941to 0.95.
The heating point of HDPE is about 135 to 150. High Density Poly Ethylene (HDPE) is a
thermoplastic polymer made from petroleum. As one of the most versatile plastic materials
around, HDPE plastic is used in a wide variety of applications, including plastic bottles, milk jugs,
shampoo bottles, bleach bottles, cutting boards, and piping

HDPE (HIGH DENSITY POLYETYLENE)

Properties of molten HDPE:

 DENSITY
At 300oC 0.70291gm/cm3
At 350oC 0.6872 gm/cm3
At 450oC 0.64725gm/cm3
 Heat capacity (nearly constant in the range 50-2000C)
Value not available at higher temperatures for liquid HDPE

 Thermal conductivity (constant after melting temperature)

@300oC=0.00435 W/cm oC
@450oC=0.00435 W/cm oC

 Dynamic viscosity of HD
  PE at 350oC at different shear rates (extrapolated from literature values at temperature of 200-280oC

Shear Rates. Per second Dynamic Viscosity, in Pa.s

Temperature=350oC Temperature=300oC

100 125 195

10 190 300

5 200 315

 Experimental work on HDPE

Process = This experimental work on HDPE is done in lab scale where we take 200gm feed in the
pyrolyser tube where the thermal cracking is done. To increase the rate of reaction we use catalyst tube
where the catalyst cracking is done and the bond breaking done more usefully. The vapours formed in the
pyrolyser tube and move towards the catalyst control unit (CCU) after that vapour moves towards the
condenser where its temperature droped and the vapours convert into THREE forms.

1. LPD ( LIQUID PRODUCT)

2. GPD ( GAS PRODUCT)
3. WAX PRODUCT

PROCESS

feed Pyro Cata Con

l- l-yst d-
yser ense
(products)

LPD GPD WAX

 PROCESS
The selection of pyrolysis technology is based on the characteristics of the feedstock and the target products.
In general, each pyrolysis technology consists of three parts: feeding system, pyrolysis reactor and separation
system.

7.1. Feeding system

In most commercial processes, the raw materials are firstly heated and melted in the feeding
system before flowing into the reactor. The air, moisture and other solid materials can be
separated from the raw plastic materials in the feedingsystem. In addition, the pre-treatment
may be required for cracking thePVC at 250 ºC. In some rotary kiln reactors, solid plastic
particles with appropriate sizes can be extruded into the reactor directly. Most feeding
systems move the highly viscous melted plastics into reactors by its gravity or by an extruder.
However, a required temperature gradient should be maintained from the feeding system to
the pyrolyzer.For although this may not be an issue for the rotary kiln reactors. The required
temperature gradient is to prevent plastic cracking before entering the pyrolyzer.For example,
the cracking temperature of PS is 420 ºC thus any overheatingin the feeding system should be
avoided. Free-fall feeding system is widely applied in fixed bed and fluidized bed reactors.
PYROLYSIS

The description and classification of pyrolysis reactors are given in Section andthe existing
commercial pyrolysis plants use various types of the reactors.Continuous pyrolysis process is
applied on most commercial plants with capability to use catalysts in which the plastic
retention time is relatively short. Very few of the commercial plants use high pressure
operation condition and most of the plants operate at or slightly above atmosphericpressure.
The operating temperature in the reactors varies largely from 250 ºC(Mazda fixed-bed
catalytic process in Japan) up to 800 ºC (Compact Power fixed-bed pyrolysis in United
Kingdom) but most of the pyrolysis reactors operate between 400 ºC and 550 ºC.It must be
noted that if the operation temperature is above 800 ºC, the process becomes gasification and
the products are mainly short chain hydrocarbons which remains as gases under room
temperature and atmospheric pressure. All of the commercial plants are fast or flash
 pyrolysis. Three types of reactors including fixed-bed, fluidized-bed, and rotary
kiln can be found in the literature review.
PRODUCT SEPARATION AND COLLECTION
The products from the plastic pyrolysis are mainly combustible gases and liquids. The liquids can
be either combusted for power generation or for further refining to produce high quality fuels.
Diesel range products can then be distilled out as in an oil refinery process. The non-
condensable gases are mainly made of hydrocarbons, and a minor amount of hydrogen and
carbon monoxide. The gases can be liquefied as fuels, or used as fuels to heat the pyrolysis
reactor, or if the amount is insignificant, the non-condensable gasarare sent to an incinerator
flaring off with the air

THIS ALL EQUIPMENT ARE DESIGNED BY IIP

(A) FEED
Here in this experiment the feed is HDPE (HIGH DENSITY POLYETHYLENE) or
polyethylene high-density (PEHD) is a thermoplastics polymer produced from the monomer
ethylene. It is sometimes called alkathene or polythene when used for HDPE pipes. With a
high strength-to-density ratio, HDPE is used in the production of plastics bottles, corrosion
resisting piping, geomembranes and plastics lumber. HDPE is commonly recycled, and has
the number “2’’ as its resin identification code.

Figure A

(B) PYROLYSER
Pyrolyser is a tube where the pyrolysis process is done. Pyrolysis is the thermal
decomposition of materials at elevated temperatures in an inert atmosphere. It involves a
change of chemical composition. Here pyrolysis played an important because pyrolsis is
most commonly used in treatment of organic materials and here all the thermal cracing is
done in pyrolyser.
 Figure B

(C) CATALYST REACTOR

A slurry reactor contains the catalyst in a powdered or granular form. This reactor is typically
used when one reactant is a gas and the other a liquid while the catalyst is a solid. In catalyst
reactor the catalyst is filled to increase the rate of reaction with the help of catalyst bed.
Multiple catalyst bed reactors control the reaction temperature by separating the catalyst mass
into several section with cooling device placed between the section. Bed sizes are generally
designed to allow the reaction to reach equillibrum.

Figure C
(D) CONDENSOR
In system involving heat transfer, a condenser is a heat exchanger used to condense a gaseous
substance into a liquid state .

Figure D

(E) WATER BATH

A water bath is laboratory equipment made from a container filled with heated water. It is
used to incubate samples in water at a constant temperature over a period of time.

Figure E

(F) GAS FLOW METER

A gas meter is a specialized flow meter, used to measure the volume of fuel gases such as
natural gas and liquefied petroleum gas. Gases are more difficult to measure than liquid,
because measured volumes are highly affected by temperature and pressure.
 Figure F

MODIFICTION OF CATALYST BY USING WET IMPREGENATION METHOD

For 100gm catalyst by calcination process

1. Take 100 gm of catalyst and pre heat for 2hr

2. After 2hr we notice that the weight of catalyst is reduced to 88.88gm
3. Add water to the catalyst in the top and left for the overnight.
4. Then filter it with the filter paper.
5. Now we notice that the weight of catalyst Is increased upto 122.39gm
6. The difference between initial and final weight of the catalyst is 33.33 gm
7. It means that we need to add only 33.33gm of water to modified the catalyst.

At last doped the metal into the catalyst to increase its yield, quality and selectivity.

PHYSICAL CHARACTERIZATION OF CATALYST

 The zeolites have been characterized by different techniques. The crystallographic structure of
these catalysts were determined using X-ray powder diffraction (XRD) performed on a Bruker D8
advance differactometer with Cu Kα radiation, λ = 1.54 Å at 40 kV and 40 mA. Diffraction patterns in
the 2°–80° region were recorded at a rate of 0.5 degrees (2θ) per minute. Total acidity and type of
acid sites have been determined by ammonia temperature programmed desorption (TPD) carried
out on the catalysts using a Micromeritics Auto Chemistry II 2920 instrument connected with a
thermal conductivity detector (TCD).
The specific surface areas was measured by nitrogen adsorption-desorption isotherm at 77 K
using an Autosorb 1C setup (Quanta chrome) adsorption analyzer. Prior to the measurements,
the samples were degassed under vacuum (1 × 10−5 Torr) for 2 h at 200 °C. The BET
specific surface areas were determined from the adsorption data in the relative pressure
(P/P0) range from 0.06 to 0.2. The total pore volume was determined from adsorption data at
P/P0=0.95. Micropore volume and external surface area of the catalysts were determined
using t-plot method. The mesopore size distribution was derived from adsorption branch by
using the Barrett–Joyner–Halenda (BJH) method.  

RESULT AND DISCUSSION

 
ASTM METHOD USED FOR LIQUID PRODUCT (d86)

Distillation limits are included in petroleum product specifications in all aspects of the supply
chain from the refinery to product specification and regulatory compliance.  ASTM D86 is
the basic test method of determining the boiling range of a petroleum product by performing
a simple batch distillation and has been in use for as long as the petroleum industry has
existed. It is one of the oldest test methods under the jurisdiction of ASTM Committee D02.
However, it does have some significant drawbacks for use in modern petroleum laboratories
including:

• ASTM D86 requires at least a 100ml sample which may not always be available and in
addition many laboratories are actively trying to reduce the quantity of highly flammable
samples they process,     analyse and store in the laboratory.
• ASTM D86 is labour intensive requiring constant operator monitoring and control of the
distillation rate throughout to comply with the method.
• It has a relatively long cycle time, a full distillation cycle according to ASTM D86
requirements takes 29 to 39 minutes, but many laboratories and processes require faster
response times.
• The manual handling, transfer and physical distillation of highly flammable samples in an
open laboratory poses a significant safety risk.
As a result, many laboratories and suppliers have looked at faster and safer alternative routes
to obtain comparable data to ASTM D86. Simulated Distillation (SIMDIS) of Petroleum
products by gas chromatography has been widely accepted by the industry, but SIMDIS is
not suited for light end hydrocarbon samples such as gasoline and naphtha.
 Figure A (ASTM DISTILLATION MACHINE)

SVM VISCOMETER FOR MEASURE DENSITY AND VISCOSITY OF

LIQUID
The highly precise SVM viscometers are based on a modified Coquette measuring

MEASURING PRINCIPLE
principle and consist of a density cell and a viscosity cell. The small viscosity measuring
cell contains a tube which rotates at a constant speed and is filled with sample fluid, while
a measuring rotor with a built-in magnet floats freely in the sample. The sample’s shear
forces drive the rotor while magnetic forces delay its rotation. Shortly after the
measurement begins, the rotor reaches equilibrium speed, which translates into the fluid’s
viscosity. The kinematic viscosity is automatically calculated from the dynamic viscosity
and density of the sample. This viscometer helps to find the dynamic and kinetic viscosity
of the liquid and it is easily to use

Figure B (SVM VISCOMETER) RESULT OF DIESEL

(DENSITY=0.766)

(DYN. VISC=0.572)

FLASH POINT
Flash point is the lowest temperature at which a chemical can vaporize to form an ignitable
mixture in air. A lower flash point indicates higher flammability. Measuring a flash point
required an ignition source. The flash point of diesel is 520C or 1500F.
CONCLUSION
Plastic wastes form a complex and heterogeneous stream that is currently poorly exploited. In
2014, around 26 million tonnes of post-consumer plastic waste was generated in Europe, of
which less than one third was collected for recycling (Plastics Europe 2015). This is due to
the fact that plastics recycling is almost entirely focused on mechanical recycling that is
suitable only for homogenous and contaminant-free plastic waste, which most of the plastic
wastes are not. For example, ELVs, C&D wastes, and WEEE all contain large share of
plastics that cannot be recycled via mechanical routes. Also plastic packaging wastes often
contain composite materials and laminate structures whose mechanical recycling is
challenging.

Applying thermal conversion to boost material recycling of plastic-containing wastes could

be an answer to the dilemma of under-utilised plastic wastes. In addition, a development of
novel, efficient pre-treatment and conversion method(s) for heterogenous waste streams
could reduce emission of greenhouse gases, and importantly provide a boost to local
economy by generating jobs on regional level and in different branches of society.

Apart from the production of end products directly from waste plastics with thermal
conversion, one can use these processes to convert waste fractions in a manner which enables
their co-utilisation for example as a cracker feed in oil refining or petrochemical industry.
This is considered both technically and economically an optimal route. These products have
been and also can be employed for the production of energy.

However, we don't know yet how well these products from waste-derived feedstock fit
current market needs and feeds to petrochemical industry and refineries. This needs to be
analysed and set up productisations systems to match current and future standards and
regulations. At least the following general boundary conditions for waste-derived feedstock
for thermal conversion production can be set 1) sufficient hydrocarbon content 2) volume and
availability 3) price and 4) location, but we also need to understand the needs of the potential
markets and customers and identify the possible barriers related to the new products/services.

The principal reason for proposing co-refining of waste-derived liquids in existing

petrochemical processes is economic. In pyrolysis, the aim is to remove much of the
impurities on waste plastic fractions (chlorine, bromides, water, nitrogen, etc.). Once solid
wastes are converted to liquid products, their storage and transportation becomes easier. It is
believed that this makes it possible to increase international trade of these liquids. Co-feeding
waste-derived liquids to an existing process requires much less specific capital investment
than refining wastes to final products as such. It is also believed that pyrolysis is fairly well
suited to a reasonable small plant size thus enabling transportation of product liquids to a
centralized refinery. Commercialization of thermal conversion processes has been pushed
forward for long. In order to proceed with the commercialization it is of great importance to
form a consortium covering the whole value chain from plastic waste producers to liquid end-
users. A comprehensive risk management plan should be carried out and the business and
operation environment should be clarified. The research topics which should still be covered
include
· Development of cheap and efficient pre-treatment equipment for heterogenous waste
streams

· Further research for exploration and utilisation of cheap catalysts, such as natural zeolites,
to further reduce the process cost, improve product quality and overall process optimization

· Regeneration and reuse of catalyst

· Detailed chemical characterization of end products ·

Exploration of further applications of produced liquid oil, gases and char to make this
technology more economically sustainable

Comprehensive life cycle assessment (LCA).

In order to commercialize plastic conversion systems it is clear that the availability and
quality of feedstock and legislation are the most important challenges to be solved. There are
numerous EU and national regulations for the waste management, disposal and utilisation
starting from waste classification (hazardous/non-hazardous waste) with legal procedures and
traceability requirements throughout the whole waste handling chain from storage and
shipment to ban on the mixing of hazardous waste. The use of waste feedstocks requires that
the operations and practices are in line with this waste related legislative framework and the
legal obligations concerning waste handling and utilisation are taken care of. In the utilisation
of waste environmental permission is generally required, if not otherwise stated. In addition,
there are a number of substances that already are specially regulated, e.g. organic persistent
pollutants (POP), or as more scientific evidence on potential impacts on health and the
environment emerges – may be regulated in the future, i.e. nanoparticles, fine particles,
odorous compounds, soluble compounds, to name a few, from which waste handlers should
also be aware of. Furthermore, the interpretation of the European legislation related to the use
of waste-derived products, like pyrolysis liquids, requires clarification.Current recycling
processes focus on separating single pure plastic fractions for further material use. The
efficient recycling of plastics and other economically important compounds from multi-
material wastes is also hampered by the fragmentation of recycling industry, where several
players across the value chain are optimizing their own part. This leads to losses of valuables
and weak profitability. It is therefore essential also to improve the recyclability of
plasticscontaining wastes by improving the economic viability of the whole recycling process
chain and added-value products.
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