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SYNTHESIS OF FUEL FROM WASTE PLASTIC A PROJECT REPORT

Thesis · April 2016

DOI: 10.13140/RG.2.2.21630.64329

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 SYNTHESIS OF FUEL FROM

WASTE PLASTIC

A PROJECT REPORT

Submitted by

A. AADHIK (710712114001)

V. ATHMANATHAN (710712114020)

N. HARI (710712114032)

in partial fulfillment for the award of the degree

of

BACHELOR OF ENGINEERING

in
MECHANICAL ENGINEERING

Dr. N. G. P. INSTITUTE OF TECHNOLOGY

COIMBATORE – 641048

ANNA UNIVERSITY: CHENNAI 600 025

APRIL 2016
 ANNA UNIVERSITY: CHENNAI 600 025

BONAFIDE CERTIFICATE

Certified that this project report “SYNTHESIS OF FUEL FROM

WASTE PLASTIC” is the Bonafide work of “A.AADHIK, V.
ATHMANATHAN, N. HARI” who carried out the project work under my
supervision.

SIGNATURE SIGNATURE

Dr. V. S SREEBALAJI Mr. V. M. MANIVASAGAM

HEAD OF THE DEPARTMENT SUPERVISOR
Professor Associate Professor
Mechanical Engineering Mechanical Engineering
Dr. N. G. P Institute of Dr. N. G. P Institute of
Technology Technology
Coimbatore – 641048 Coimbatore - 641048

Submitted for the University Examination held on

----------------------------------------------------------

INTERNAL EXAMINER EXTERNAL EXAMINER

 ACKNOWLEDGEMENT

We express our deepest gratitude to our Dr.NALLA.G.PALANISWAMI,

Chairman, KMCH and Dr.N.G.P Institutions for providing us with an
environment to complete our project successfully.

We are greatly indebted to our honorable madam secretary Dr. THAVAMANI.

D. PALANISWAMI, for our motivation and support.

We are very grateful to Dr.K.PORKUMARAN, Principal, for his valuable

guidance and blessings.

We would also like to thank Dr.V.S.SREEBALAJI, Professor and Head,

Department of Mechanical Engineering for his unwavering support during the
entire course of the project work who modeled us both technically and morally
for achieving greater success in this project work.

We thank our Project coordinator Dr.K.RAVIKUMAR, Associate Professor,

Department of Mechanical Engineering for his help and innovative ideas in
making this project a successful one.

We express our sincere thanks to our Supervisor Mr.V.M.MANIVASAGAM,

Associate Professor, Department of Mechanical Engineering for his constant
encouragement and support throughout our course, especially for the useful
suggestions given during the course of the project period and being instrumental
in the completion of our project with his complete guidance.

We also thank our Faculties and Lab Technicians, Department of Mechanical

Engineering for their assistance in completing the fabrication work.

Finally, we take this opportunity to extend our deep appreciation to our family
and friends, for all that they meant to us during the crucial times of the completion
of our project.
 ABSTRACT

The increased demand and high price for energy sources are driving efforts to
convert organic compounds into useful hydrocarbon fuels. Although much of this
work has focused on biomass, there are strong benefits to deriving fuels from
waste plastic material. Waste plastic is abundant and its disposal creates large
problems for the environment. Plastic does not break down in landfills, it is not
easily recycled and degrades in quality during the recycling process, and it can
produce waste ash, heavy metals, and potentially harmful gas emissions if
incinerated at high temperatures. However, thermal processes can be used to
convert plastics into hydrocarbon fuels such as gasoline, diesel, aviation / jet fuel,
which have unlimited applications in airline industries, helicopter, heavy
transportation, and electricity generation. The method and principal of the
production / process will be discussed.
 TABLE OF CONTENT

CHAPTER NO TITLE PAGE NO

ABSTRACT iv

LIST OF TABLES viii

LIST OF FIGURES ix

1 INTRODUCTION 1

1.1 General 1

1.2 Plastics 2

1.3 Selection of Waste Plastic 3

2 LITERATURE REVIEW ON PLASTIC 7

PYROLYSIS

2.1 Factors Affecting Plastic Pyrolysis 7

2.1.1Chemical Composition of Feedstock 7

2.1.2 Cracking Temperature and Heating Rate 9

2.1.3 Types of Reactor 12

2.1.3.1 Batch, Semi-Batch and Continuous 12

Reactors

2.1.3.2 Fixed Bed, Fluidized Bed and 12

Screw Kiln Reactors

2.1.4 Residence Time 14

 2.1.5 Use of Catalyst 15

2.1.5.1 Advantages of Using Catalyst 15

2.1.5.2 Catalyst Classification 16

2.1.6 Pressure 17

2.1.7 Other Influencing Factors 19

2.1.8 Multi-Factor Effect on Pyrolysis Process 19

2.2 Quality Comparison of Pyrolysis Products and

Petroleum Fuels 21

2.2.1 Review of Pyrolysis Monitoring and 21

Product Analysis

2.2.1.1 Pyrolysis Process Monitoring 21

2.2.1.2 Product Analysis Method 22

2.2.2 Comparison of Diesel with Plastic 23

Derived Fuels

2.3 Existing Commercial Plastic Pyrolysis 25

Technologies and Processes

2.3.1 Feedstock Effects 25

2.3.2 Technology 26

2.3.2.1 Feeding System 26

2.3.2.2 Pyrolysis 27

2.3.2.3 Product Separation and Collection 27

3 FUEL SYNTHESIS 28

3.1 Process 28

3.1.1 Raw Material 29

3.1.2 Pre-Treatment 38

3.1.2.1 Solid Fuel Production 38

3.1.2.2 Production Method 40

3.1.2.3 Industrial Pretreatment 40

3.1.3 Pyrolysis Process 43

3.1.3.1 Scope of Liquid Fuel 43

3.1.3.2 Production Method 44

3.1.4 Filtration & Purification 46

3.1.5 Fuel Testing and Analysis 47

4. RESULT INTERPRETATION 48

5. CONCLUSION & FUTURE SCOPE 51

5.1 Conclusion 51

5.2 Future Scope 51

REFERENCE 52
 LIST OF TABLES

TABLE NO TITLE PAGE NO

1.1 Product types of some plastic Pyrolysis 5

1.2 Comparison of Carbon footprint 6

2.1 Types of Chain Structures 9

2.2 Pyrolysis processed and target products 14

4.1 Polypropylene Oil and Diesel comparison 48

4.2 FTIR Test Results 49

4.3 GC/MS Test Results 49

4.4 Hydrocarbon range in commercial fuels 50

 LIST OF FIGURES

FIGURE NO TITLE PAGE NO

1.1 SPI Code 3

2.1 Influence of Temperature on product distribution 11

2.2 GC analysis results of plastic pyrolysis liquid 11

2.3 Influence of residence time on production of 15

Gaseous product

2.4 Effect of pressure on the distribution of PE 18

Pyrolysis products

2.5 Effect of pressure on the yield of Gas at different 18

Temperature

3.1 Example of RPF 38

3.2 Schematic diagram of pretreatment process 41

3.3 Example of Pretreatment process 41

3.4 Schematic diagram of pelletizing process 42

3.5 Typical pelletizing process facility 42

3.6 Polypropylene 44

3.7 Schematic diagram of a production plant of 45

Plastics derived fuel

4.1 Comparison of Polypropylene oil vs diesel 48

 CHAPTER 1

INTRODUCTION

1.1 GENERAL

Plastic waste is regarded as a potentially cheap source of chemicals

and energy. Lots of us have encountered a variety of products that use plastic
materials today. As a result of the increasing level of private consumption of these
plastic materials huge amount of wastes are discharged to the environment.

Plastic materials are a type of material that cannot be decomposed easily

in a short period of time. Substantial quantities of plastic have accumulated in the
natural environment and in landfills. Those wastes can be classified according to
their origins. They are

• Industrial

• Municipal

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

The main components of municipal solid waste (MSW) are food waste,
wood, paper, cardboard, plastics, rubbers, fabrics, and metals. 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 plastics, disposal to landfill may simply be storing problems for the future. For
example, plasticizers and other additive chemicals have been shown to leach from
landfills. The extent of varies accordingly, particularly pH and organic content.

1
 Recently, the conception of energy recovery from MSW has been a very
hot topic. It is also undesirable to dispose of waste plastics by landfill due to poor
biodegradability.

An alternative strategy is that of chemical recycling, known as feedstock

recycling or tertiary recycling, which has attracted much interest recently with
the aim of converting waste plastics into basic petrochemicals to be used as
chemical feedstock or fuels for a variety of downstream processes.

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 improve
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 two main types of plastics: thermoplastics and thermosetting polymers.

• 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

• Thermosets or thermosetting plastics can melt and take shape only

once. They are not suitable for repeated heat treatments; therefore
after they have solidified, they stay solid.
Examples are phenol formaldehyde and urea formaldehyde.

2
 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 the waste
plastic, Society of Plastic Industry (SPI) defined a resin identification code
system that divides plastics into the following seven groups based on the chemical
structure and applications:

1. PET (Polyethylene Terephthalate)

2. HDPE (High Density Polyethylene)

3. PVC (Polyvinyl Chloride)

4. LDPE (Low Density Polyethylene)

5. PP (Polypropylene)

6. PS (Polystyrene) Figure 1.1 SPI code

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.

3
 In general, the conversion of waste plastic into fuel requires feedstock
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 combustion

As shown in Table 1.1, PE, PP and PS 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.

4
 Table 1.1 Product 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.

Hydrogen chloride Polyvinyl chloride (PVC) Not allowed.

and
Polyvinylidene chloride
carbonous products Not allowed.
(PVDC)

5
 For our experiment, we took Polypropylene as the raw material for
the following reasons and factors.

• One of major factor to consider PP over PE is the carbon footprint

as shown in the table 1.2.

Table 1.2 Comparison of Carbon footprint

Total
Kg of C0 2 Material
Forming Transport Disposal Carbon
eq/Tonne production
Footprint

PP 1975 1250 38 193 3456

PET 2985 1250 38 250 4523

HDPE 1935 1250 38 157 3380

PVC 1915 1250 38 250 3453

PS 3415 1250 38 158 4861

PC 7776 1250 38 193 9257

• PP is abundantly used in Plastic bags, plastic bottles so raw material

is easy to get.
• The crystallinity of PP is less than PE.
• PP fuel has more calorific value than all fuels.

As a result we preferred Polypropylene over Polyethylene and other

polymers.

6
 CHAPTER 2

LITERATURE REVIEW ON PLASTIC PYROLYSIS

This literature review was taken from a thesis work done by Feng Gao,
University of Canterbury, 2010

2.1 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.

These factors are summarized in this section as follows.

2.1.1 CHEMICAL COMPOSITION OF FEEDSTOCK

The pyrolysis products are directly related to the chemical composition and
chemical structure of the plastics to be pyrolyzed.

In addition, the chemical composition of the feedstock also affects the

pyrolysis processes. In reality, waste plastics are possibly contaminated before
recycling which could also have effects on the pyrolysis process and products.

PE, PP and PS are most commonly used polymeric hydrocarbons and were
selected as the investigated materials in this study. Polyethylene is formed from
ethylene through chain polymerization which is shown in Formula

7
 Plastics can be classified, according to structural shape of polymer
molecules, as linear, branched, or cross-linked in Figure. The units in linear
polymer are linked only to two others, one to each ends. The polymer is termed
branched when branches extend beyond the main polymer chain randomly.
Regularly repeating of side groups are considered to be part of the unit but
not considered as branches.

Based on the above description, polystyrene is called linear polymer

although it contains functional groups as part of the monomer structure. In
branched polymers, at least one of the monomers is connected to more than two
functional groups due to the branching points produced from the
polymerization process. The functional side group and the branch structure
have significant effects on the pyrolysis product. For example, the dominant
component in PS pyrolysis products is styrene that is the side group come off
from PS carbon backbone.

There is a significant relationship between the density and the branching

intensity of polymers. The PE with more branches has relatively lower density.
The branched polyethylene is also called low density polyethylene (LDPE),
which is different from linear polyethylene that is called high density
polyethylene (HDPE).

In pyrolysis process, cross linked polymer will crack rather than melt or
evaporate. This is different from the reactions of linear or branched polymers
in pyrolysis process.

A cross linked polymer can be described as an interconnected branched

polymer with all polymer chains are linked to form a large molecule. Thus, the
cross linked polymer constitutes large molecule. Theoretically, the molecular
weight of a cross linked polymer can be infinite. In reality, the molecular weight
of a cross linked polymer will be limited due to breaking down of the molecular

8
inter-connections during the processing or the weight of the polymer sample. The
cross linked polymer cannot be dissolved in solvents or be melted by heat because
of their network structure. The table 2.1 shows the various chain structures.

Table 2.1 Types of Chain Structures

Chain Structure Type of Chain

Linear

Branched

Cross Linked

For example, PEX, a common abbreviate of cross-linked polyethylene, is

widely used in oil and water piping. In pyrolysis process, cross linked polymer
will crack rather than melt or evaporate. This is different from the reactions of
linear or branched polymers in pyrolysis process.

2.1.2 CRACKING TEMPERATURE AND HEATING RATE

Temperature is one of the most important operating variable, since the

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

9
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.

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.

According to the provided schemes, the most likely reason is the

difference in the temperature measurement location where the temperature
sensors were located. There was significant temperature gradient along the
apparatus in which the melted plastic at the bottom of a fix-bed batch reactor
had much lower temperature than that on the top surface of the reactor. It was
also found that the space temperature in the pyrolyzer was strongly influenced
by the product vapor. Different locations of the temperature sensors in different
studies are believed to be one of the most important factors on the different
cracking temperature reported.

Figure 2.1 shows the Influence of temperature on product distribution and

figure 2.2 shows the gas chromatography (GC) analysis results of the liquid
products with the temperature on the curves indicating the cracking temperature.
It is seen that the liquids produced at higher cracking temperatures have lower
flash-off percentage at the same GC temperature during the analysis. This
shows higher proportion of heavy molecular weight components in the liquid.
Similar conclusion was also found in other research using virgin plastics and
fluidized-bed, semi-batch reactor.

10
 Figure 2.1 Influence of temperature on product distribution

Figure 2.2 GC analysis results of plastic pyrolysis liquid

However, the overall gas proportion of gas product increased with

increasing cracking temperature up to 730°C while the liquid product proportion
decreased with the cracking temperature in the full range of temperature used.

11
2.1.3 TYPE OF REACTOR

The reactor type for the plastic pyrolysis significantly influences on the
heat transfer rate, mixing of plastics with pyrolysis products, residence time and
the reflux level of the primary products. Reactors can be classified into batch,
semi-batch and continuous or classified based on types of reactor bed.

2.1.3.1 BATCH, SEMI-BATCH AND CONTINUOUS REACTORS

According to the feeding and product removal processes, the pyrolysis

reactor is categorized into batch, semi-batch and continuous reactors. In the
batch reactor, the materials are fed into the reactor in batches for pyrolysis either
at the start of the process or after all of the fed materials are processed. In
the continuous reactor, the feed materials are input from one part and the
products are led out from the other part of the reactor. A semi-batch reactor
removes the pyrolysis products continuously once they are generated but the feed
materials are added initially before the pyrolysis process starts. Some semi-batch
process uses inert carrier gas to help remove the pyrolysis products. Batch and
semi-batch reactors are mainly applied on research, and continuous reactor is
mainly for industrial production. Particular reactions and phenomenon such as
secondary pyrolysis may occur in semi-batch reactors and does not occur in
batch reactors.

2.1.3.2 FIXED BED, FLUIDIZED BED AND SCREW KILN REACTORS

Based on the heat transfer methods and flow patterns of the feedstock and
products, the pyrolysis reactors can be classified into fixed bed reactor, fluidized
bed reactor and screw kiln reactor. In the fixed bed reactor, the pyrolysis occurs
on a stationary bed which is easy to design and operate. However, the irregular
sizes and shape of the feedstock plastics may cause feeding problems in
continuous process and the low thermal conductivity of the plastics results in

12
large temperature gradient in batch process devices. In some systems, the fixed
bed reactors are only used as the secondary pyrolysis reactor because the products
from the primary pyrolysis are mainly in liquid and gaseous phase which can be
easily fed into the fixed bed.

The fluidized bed reactor has been used in most commercial plants in
which gaseous products or inert gas flow through an expanded bed of feedstock
and other bed materials, forming bubbles or eddies.

The advantages of fluidized bed reactor are the homogeneity of both

temperature and composition. Heat and mass transfer rates are much higher than
the fixed bed thus the low thermal conductivity in fluidized bed reactors is no
longer a problem. In the fluidized bed reactor, the dimensions and the material of
the bed material are the key parameters affecting the pyrolysis and products. Bed
materials loss and separation from the gases are other issues which need
consideration.

In recent years, a new reaction system named screw kiln reactor has been
widely applied for plastic processing. In this type of reactor, here is an extruder
to screw the feedstock from a feeder in an oxygen free environment. The extruder
is heated by external heat sources. Solid residues and pyrolysis products are
separated and collected from the other end of the extruder.

The high viscosity of plastics is not a problem for the flow in screw kiln
reactor because the flow is driven by the external motor. Melted plastic or even
plastic solid particles can be fed into this reactor.

The small diameter of the extruder and good mixing of the materials make
the radial temperature gradient negligible. The process is relatively stable and
does not use bed material as in the fluidized bed reactor. The feeding rate can be
controlled by adjusting the rotation speed of the extruder, which also determines
the residence time of plastics.

13
2.1.4 RESIDENCE TIME

The definition of residence time differs in various studies. The table 2.2
shows the various target products. 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.

Table 2.2 Pyrolysis processes and target products

Residence Temperature Target

Process Heating rate
time (°C) Products

Slow
Very low Days 450-600 Charcoal
carbonization

10- Gas, oil,

Slow pyrolysis 10-60 min 450-600
100K/min char

Up to Gas, oil,
Fast pyrolysis 0.5-5 s 550-650
1000K/s (char)

Up to Gas, oil,
Flash pyrolysis <1 s 450-900
10000K/s (char)

Except for the batch pyrolysis reactor in a closed system, residence time is
difficult to be controlled directly but can be adjusted by altering other operation
parameters such as feeding rate, carrier gas flow rate and product discharge rate.
Residence time was, then, calculated for these controllable operation parameters.
14
 Secondary pyrolysis cracking occurs when residence time is long enough,
which enhances the yield of gaseous product. Higher value of V/m represents
longer residence time in Figure 2.3 .The Y axis is the conversion of HDPE to
gaseous product. There is a significant effect on the conversion when the
residence time varies in a certain range during the non-catalyst thermal reaction.

Figure 2.3 Influence of residence time on the production of

gaseous product (from HDPE thermal and catalytic cracking)

2.1.5 USE OF CATALYST

2.1.5.1 ADVANTAGES OF USING 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 PE 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

15
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 PE pyrolysis because the primary product from other plastics, such as
PP and PS, are mainly light hydrocarbons, with similar carbon chain length to the
range of commercial fuels. The products from non-catalytic PE pyrolysis
contain high proportion of 1-alkenes and dialkenes.

Some catalysts are applied specifically to reduce the unsaturated

hydrocarbons and promote the yield of aromatics and naphthenes. This can
significantly increase the stability and cetane number of the oil products.
Moreover, it is reported that activation energies (Ea) measured in the PE
pyrolysis with catalysts (such as HZSM-5, HY, and MCM-41) were much lower
than those when no catalyst was added.

2.1.5.2 CATALYST CLASSIFICATION

The catalyst are classified into two. They are

• Homogeneous

• Heterogeneous

Homogeneous catalysts used for polyolefin pyrolysis have mostly been

classical Lewis acids such as AlCl 3 . Generally, heterogeneous catalysts are
preferred due to their easy separation and recovery from the reacting medium.
Heterogeneous catalysts can be summarized as nanocrystalline zeolites,
aluminium pillared clays, conventional acid solids, mesostructured catalysts,
superacid solids, gallosilicates, metals supported on carbon, and basic oxides.
Among the mentioned catalysts, nanocrystalline zeolites have been extensively
studied for polyolefin pyrolysis and this type of catalysts will be discussed in
more details as follows.

16
 A zeolite is a crystalline aluminosilicate with a three-dimensional
framework structure that forms uniform pores of molecular dimensions. Zeolites
act as sieves on a molecular scale and exclude molecules that are too large to pass
through the pores.

The three-dimensional frame structure significantly increases the area of

the sieves and absorbs molecules that have similar sizes as the pores. According
to the structure of zeolites, 176 zeolite framework types have been confirmed.

A three-letter code, such as MFI, is assigned to framework types by the

Structure Commission of the International Zeolite Association. The codes are
derived from the name of the zeolite, for example, MFI from ZSM-5.The pore
openings and sizes are key parameters for the catalytic effect in the plastic
pyrolysis, which are determined by the size of single ring and the structure
features

2.1.6 PRESSURE

Operating pressure has significantly effect on both the pyrolysis

process and the products. The boiling points of the pyrolysis products are
increased under higher pressure, therefore, under pressurized environment heavy
hydrocarbons are further pyrolyzed instead of vaporized at given operation
temperature. Figure 2.4 shows Effect of pressure on the distribution of PE
pyrolysis products

In effect, under pressurized pyrolysis, more energy is required for further

hydrocarbon cracking. It was also found that high pressure increases the yield of
non-condensable gases and decreases the yield of liquid products. (Figure 2.5)

The average molecular weight of gas product also decreases with the
increase of pressure. The influence of pressure on the concentration of double
bond, C=C, of the liquid product was not significant.

17
 In summary, pressure has major effects on the pyrolysis reaction and the
distribution of PE pyrolysis products, but has minor effect on the double bond
components.

Figure 2.4 Effect of pressure on the distribution of PE pyrolysis

products

Figure 2.5 Effect of pressure on the yield of gas at different

temperature.

18
2.1.7 OTHER INFLUENCING FACTORS

There are a number of other factors which also affect pyrolysis process to
a certain extent. For example, reactive additives such as air, oxygen, or hydrogen
are sometimes present in the reaction for different purposes, which will interfere
with the reactions and affect the quality of the products.

Further pyrolysis of the primary product occurs in most processes.

Secondary cracking reactions were found in many reports which are enhanced by
high pressure, long residence time, and low heating rate and high refluxes.

Although many researchers observed the impact of secondary cracking,

few have investigated the influence of secondary cracking process on the yield
and the quality of the products. Most secondary cracking occurred during the
pyrolysis of PE and very limited cracking was found in PS pyrolysis. This is
possibly due to the difference in their primary products.

The primary products produced from PE pyrolysis contain large proportion

of heavy hydrocarbons with carbon chain number up to 80. The average
molecular weight of the primary products from PE is much higher than that of
other plastics, PS, PP, PVC and PET.

The secondary cracking is mainly effective for heavy hydrocarbons, hence,

has less effect on the pyrolysis of PS, PVC, PET and other plastics. The
importance of secondary cracking on PE pyrolysis has intensively been studied
in this research.

2.1.8 MULTI-FACTOR EFFECT ON PYROLYSIS PROCESS

It is difficult to directly compare the product yields obtained for a specific

plastic in different researches as the operating conditions and reactors can be very
different. In general pyrolysis processes, thermal degradation occurs in the initial
stages of the pyrolysis with absence of oxygen.

19
 The pyrolytic products immediately after the pyrolysis consist of solid
residue, oil vapor and non-condensable gases among which the oil vapour will
become liquid after cooling down.

According to the residence time or the heating rate during the pyrolysis
process, the pyrolysis can be classified into slow carbonization, slow pyrolysis,
fast pyrolysis, and flash pyrolysis. With slow heating rate (less than 10K/min),
the carbonization occurs and the process proceeds from the outer surface to the
core of the plastic particles with the local carbonization temperature of
above 300 ºC.

The carbonization process is determined by the heat transfer rate to the

material surface and the heat transfer rate within the material. At given
temperature and heating rate, the residence time is also the most important
variable to achieve the desired carbonization. The residence time required is also
related to the dimensions of the material. If the size of material is too large which
needs much longer residence time, incomplete carbonization may occur at the
centre of the plastic particles.

On the other extreme situation, if the operation temperature is very high,

for example 800 to 1000 ºC, gasification process occurs and in this case, the
plastics are directly converted to short chain gases and the yield of non-
condensable gases in the product is maximized. High heating rate is required to
minimize the proportion of solid char production and rapid quenching favors the
liquid production before further cracking into gaseous products.

The above mentioned processes are applied to all of the plastic types to be
examined including HDPE, LDPE, PP, and PS all of which have similar cracking
temperature from 320 to 500 ºC. However, in the pyrolysis of PVC the cracking
temperature (250ºC) is much lower than that of other common plastics mentioned
above.

20
 In most practical pyrolysis processes, particularly those applied in
industries, preheating and melting the plastic feedstock between 200 and 300 ºC
are applied in order to reduce the volume of the feedstock and to eliminate the
oxygen from the feeding system. The melting temperature is also high enough for
PVC to crack and form hazardous gases and acid.

2.2 QUALITY COMPARISON OF PYROLYSIS PRODUCTS AND

PETROLEUM FUELS

2.2.1 REVIEW OF PYROLYSIS MONITORING AND PRODUCT

ANALYSIS

2.2.1.1 PYROLYSIS PROCESS MONITORING

In the plastic pyrolysis, plastic type and operation conditions applied in the
researches and the industries varied largely. Consequently, the variation of the
yield and the quality of the pyrolysis products are significant in the literature.

However, when the same plastic is used and same operation conditions are
applied, there are similarities in the product yield and production distribution. In
most of the research work, the pyrolysis rate of feedstock plastics is measured by
using thermo gravimetric analysis (TGA) in fix-bed batch pyrolysis reactor.

The percentage of gaseous products is measured simultaneously with the

occurrence of the reactions. In fluidized bed reactor or continuous reactor, feeding
rate is controlled and monitored to determine the reaction rate.

Operation temperature is normally monitored by using thermocouples

along the process line, which is used for estimating thermal reactions including
heating-up, decomposition, cracking, and condensation. Some studies used high
pressure pyrolysis in which pressure gauge is applied to control and monitor the
operation pressure.

21
 With these monitoring devices, the processes can be controlled by
adjusting the operating factors such as heating power, feeding rate, pressure and
carrier gas flow rate when needed. .

2.2.1.2 PRODUCT ANALYSIS METHOD

The pyrolysis products of plastics are mainly hydrocarbons presenting in

gaseous, liquids and solid wax phases under standard conditions of temperature
of 25 ºC and pressure of 100 kPa. Minor amounts of char and hydrogen gas may
be found in the products.

The char product can be analyzed by elemental analyzer or electron-

microscope dispersive X-ray analyzer. In research, the hydrocarbon products can
be firstly separated though gas chromatography (GC) and then identified by either
comparing with hydrocarbon standards or passing through mass spectrometry
(MS).

Hydrocarbon products from industrial pyrolysis of waste plastics are used

as a substitute for commercial fuels. Instead of investigation on individual
components, the commercial fuel regulation requirements focus on the physical
and chemical properties of fuels relate to engine performance.

The New Zealand regulation requirements on the properties of petroleum

fuels such as LPG, petrol and diesel adapted standard test methods from the
American Society for Testing and Materials (ASTM) and institute of petroleum
(IP) testing methods.

The properties of plastic pyrolysis fuels are analyzed in some studies. It

was found that the pyrolysis products from PE, PP, and PS are mainly
hydrocarbons with molecular weights similar to the petrol and diesel range. A
certain amount of non-condensable gases and insignificant amount of heavy wax
were also found in the pyrolysis products.

22
 Heavy hydrocarbon wax can be processed into gases or light liquid by
further high temperature treatments or catalytic cracking so that the yields of non-
condensable gases and wax vary largely in different studies. The plastic derived
fuels were also found to have higher unsaturated hydrocarbon content and lower
stability than those of commercial fuels.

2.2.2 COMPARISON OF DIESEL WITH PLASTIC DERIVED FUELS

The New Zealand diesel regulations have 18 requirements those can be

characterized into four groups: thermodynamic properties, flowing properties,
component distribution, and performance properties. In the regulation for
commercial diesels, one of the most important thermodynamic properties is
cetane number or cetane index that can be a substitute as cetane number, which
indicates the auto-ignition conditions of the fuel. Cetane index is calculated from
fuel density and distillation range which is also listed in the regulation
requirements. Therefore, cetane number, density, and distillation range are all
important properties to diesel fuel.

The next important properties are the fuel flow properties which include
viscosity, cloud point, pour point, cold filter plugging point and flash point. The
importance of these properties will depend on the extent of known information of
fundamental properties mentioned above, e.g., density and distillation range. If
all of the fundamental properties are well known, the flow properties are less
critical.

Miscellaneous properties reflects the effects of the minorities in diesel

fuels, including carbon residues, sulphur content, water content, ash content and
polycyclic aromatic hydrocarbon content. The carbon residue is fine solid
particles in the fuel that may form combustion chamber deposits. The sulphur
content in the fuel above a certain level causes high engine wear and poisons
catalysts. The water content can contribute to corrosion in tanks and fuel injection

23
equipment whereas the ash content is the solid residue when fuel is burnt off. The
polycyclic aromatic hydrocarbon content is used to increase the cetane number
due to their low boiling point and high density.

The properties of fuel performance consist of colour, particulate, filter

blocking tendency, lubricity, oxidation stability and copper corrosion. These
properties result from one or more effects of the fundamental and the
miscellaneous properties. For example, the copper corrosion is an indicator
mainly due to sulphur content in the diesel.

Based on the diesel regulation, the fundamental properties of plastic

derived fuels are examined in most studies because the diesel fuel is produced
from synthetic hydrocarbon polymers that do not contain any other elements
except for carbon and hydrogen.

Therefore, some of the miscellaneous properties are not important for the
diesel from plastic pyrolysis, such as sulphur content and water content. The
quality of the liquid fuels from pyrolysis of plastics will vary with pyrolysis
operation conditions, pyrolysis reactor type and types of plastic feedstock.

The quality of plastic derived fuels varies largely based on the process and
the feedstock. The diesel range products in the LDPE derived fuels contain the
same linear chain alkanes as those in the fresh diesel. The content of alkene in
LDPE derived products is much higher than that in diesel, which decreases the
storage stability of fuel.

Compared to naphtha, aromatic compounds, and branched hydrocarbons,

linear alkanes have relative higher cloud point with the same carbon number or
density. Therefore, many catalysts and processes were used to reduce linear
hydrocarbons and increase the proportion of others.

It was found that plastic derived diesel contains high proportion of linear
alkane that has low solubility in diesel. This can significantly increase the cloud
24
point that is the temperature at which the first crystals appear in diesel.

De-waxing, hydrogenation, isomerization and cyclization are normally

used in the pyrolysis processes to change the chemical composition in the
products. Other properties of plastic derived fuels are controlled in the producing
processes such as distillation range and carbon residue in the fuel.

2.3 EXISTING COMMERCIAL PLASTIC PYROLYSIS

TECHNOLOGIES AND PROCESSES

The waste plastic pyrolysis plants were developed and built in many
countries. The selection of the process and the plant is determined mainly on the
feedstock composition and the target products.

2.3.1 FEEDSTOCK EFFECTS

According to a summary of existing processes and technologies reported

by Arena and Mastellone, the most important property of plastic feedstock is
whether it contains PVC.

PVC pyrolysis has different the thermal cracking process and different
products from those of other common waste plastics including PE, PP and PS. In
the PVC pyrolysis, the products containing HCl are particularly hazardous for
fuels. If the feedstock contains PVC, the plants must have re-treatment system to
remove and a solvent scrubber to remove HCl from the pyrolysis products.

The other important property for some current processes is the size
of feedstock. The requirement for the feedstock size is to avoid the feeding
blockage and to enhance the heat transfer between the heating medium and the
plastics particles.

25
 It was found that in most cases, the feedstock is a mixture of various waste
plastic in municipal solid wastes or industrial residues. In pyrolysis of the mixed
plastics, interactive effects among the different plastic types may occur due to the
difference in cracking temperatures and different products. . However, no report
has been found where the pyrolysis technology is designed for a specific type of
the waste plastic.

2.3.2. TECHNOLOGY

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.

2.3.2.1 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
feeding system. In addition, the pre-treatment may be required for cracking the
PVC 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 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 overheating

in the feeding system should be avoided. Free-fall feeding system is widely
applied in fixed bed and fluidized bed reactors.

26
2.3.2.2 PYROLYSIS

The description and classification of pyrolysis reactors are given in Section

2.1 of this thesis and the 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 atmospheric pressure. 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.

2.3.2.3 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 gases are
sent to an incinerator flaring off with the air.

27
 CHAPTER 3

FUEL SYNTHESIS

3.1 PROCESS

Raw material

Pre-Treatment

Pyrolysis process

Filtration &
Purification

Fuel Testing &

Analysis

28
3.1.1 RAW MATERIAL

The Raw material used for extracting oil by the process of Pyrolysis
is Polypropylene (PP).

The Material Safety Data Sheet taken from Indian Oil Corporation
gives detailed information about various safety aspects of the material
used.

SECTION 1 - CHEMICAL PRODUCT AND COMPANY

Chemical Name & Synonyms : Polypropylene (PP) Homopolymer

Chemical Family : Polyolefin

C.A.S. No. : 9003-07-0

Manufacturer's Name : Indian Oil Corporation Limited

Address : Product Application and Development

Centre (PADC), Panipat Petrochemical
Marketing Complex (PPMC), Panipat
Refinery, Baholi, Panipat – 132 140

Telephone No : +91 180-2578091

Fax No. : +91 180-2578098

29
SECTION 2 - COMPOSITION / INFORMATION ON INGREDIENTS
EXPOSURE LIMITS IN AIR
CHEMICAL CONTENT CAS ACGIH
NAME (Normal)* NUMBER ACGIH
TLV- IDLH
TLV-TWA
STEL
10 mg/m3
Polypropylene 99.25 wt% 9003-07-0 (inhalable NA NA
fraction)
Proprietary
<=0.75 wt% Mixture
additives
* For different grades of PP ; minor changes may be there.

SECTION 3 - HAZARDS IDENTIFICATION

Information Pertaining To Particular Dangers for Man and

Environment. Negligible hazard at ambient temperature (-18°C to +50°C)

Classification System

Product is not considered to be hazardous under normal processing

conditions.

SECTION 4 - FIRST AID MEASURES

GENERAL INFORMATION

• At room temperature the product is neither an irritant nor gives off

hazardous vapors.
• The measures listed below apply to critical situations (Fire, incorrect
process conditions).

Skin Contact

If molten material contacts the skin, immediately flush with large

amounts of water to cool the affected tissues and polymer. Do not attempt to
peel the polymer from skin. Obtain immediately emergency medical attention if
burn is deep or extensive.

30
Eye Contact

Flush eyes thoroughly with water for several minutes and seek medical
attention if discomfort persists.

Inhalation

If symptoms are experienced, move victim to fresh air. Obtain medical

attention if breathing difficulty persists.

Ingestion

Adverse health effects due to ingestion are not anticipated.

SECTION 5 - FIRE FIGHTING MEASURES

Flash Ignition Temperature : 335°C

Auto Ignition Temperature : 350°C

Flammable Limits : NA

Suitable Extinguishing Media: Water, Foam, Carbon Dioxide, Dry

Chemical Powder

For Safety reasons, unsuitable extinguishing media: None

Protective Equipment: Respiratory & Eye protection for firefighting personnel

Special hazards caused by the material, its products of combustion or

resulting gases: In case of fire it can release: Carbon dioxide (C0 2 ), and when
lacking oxygen (0 2 ), carbon monoxide (CO), Ketones & Aldehydes. The
products of the burning are dangerous. The formation of hydrocarbons and
aldehydes are possible in the initial stages of a fire (especially in between 400°C
and 700°C).

Additional information: Heat value: 8000 -11000 kcal/kg

31
SECTION 6 - ACCIDENTAL RELEASE MEASURES

Spill and Leak procedure: Sweep up spilled material for use or disposal.
Good housekeeping must be maintained to avoid potential slipping problem.

Caution: Keep walking surface free of spilled material to avoid slipping hazard.

SECTION 7 - HANDLING AND STORAGE

HANDLING

Information for safe handling:

No special requirements necessary, if handled at room temperature-Avoid

spilling the product, as this might cause falls.

STORAGE

Requirements to be met by storerooms and containers:

This product may react with strong oxidizing agents & should not be
stored near such materials. Store the bags in areas protected with automatic
sprinklers.

• Storage temperature should be below 60°C.

• Do not smoke.

• Take precautionary measures to prevent the formation of static electricity.

• Electric safety equipment.

• Open flames prohibited.

• Store the product in bags, car silos, container, or large cartons.

Information about storage in one common storage facility: Not required.

32
Further information about storage conditions:

• Protect from heat and direct sunlight.

• Store container in a well-ventilated position.
• Store under dry conditions.
• Specific applications for safe stacking follow the storage
recommendations specific for this product.

SECTION 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION

ENGINEERING CONTROLS:

Use in a well-ventilated area. If handling results in dust generation,

special ventilation may be needed to minimize dust exposure. If heated material
generates vapor or fumes, use process enclosures, local exhaust ventilation, or
other engineering controls to control exposure.

PERSONAL PROTECTIVE EQUIPMENT:

Respiratory system

Product processing, heat sealing of film or operations involving the use of

wires or blades heated above 300°C may produce dust, vapor or fumes . To
minimize risk of over exposure to dust, vapor or fumes it is recommended that a
local exhaust system is placed above the equipment, and that the working area is
properly ventilated. If ventilation is inadequate, use certified respirator that will
protect against dust/mist.

Skin and body

Hot material: Wear heat-resistant protective gloves, clothing and face

shield able to withstand the temperature of the molten product. Cold material:
None required; however, use of gloves is good industrial practice.

33
Hand

Hot material: Wear heat-resistant protective gloves able to withstand the

temperature of the molten product. Cold material: None required; however, use
of gloves is good industrial practice.

The correct choice of protective gloves depends upon the chemicals being
handled, the conditions of work and use, and the condition of the gloves (even
the best chemically resistant glove will break down after repeated chemical
exposures). Most gloves provide only short time of protection before they must
be discarded and replaced. Because specific work environments and material
handling practices very, safety procedures should be developed for each
intended application. Gloves should therefore be chosen in consultation with the
supplier/manufacturer and with a full assessment of the working conditions.

Eyes

Safety glasses with side shields. Use dust goggles if high dust
concentration is generated.

SECTION 9 - PHYSICAL AND CHEMICAL PROPERTIES

General Information
Form ; Solid Granules
Colour : Translucent to White
Odor : Slight Waxy Odor
Melting point/Melting range :130-167°C
Flash point : > 329°C
Ignition temperature : > 400°C
Decomposition temperature : > 300°C
Danger of explosion : Product is not explosive.
Density : 0.89-0.94 q/cm3

34
Solubility in / Miscibility with
: Insoluble
Water
: Soluble in boiling, aromatic chlorinated
Additional information
solvents
SECTION 10 - STABILITY AND REACTIVITY

Chemical stability

This product is stable under normal use conditions for shock, vibration,
pressure or Temperature.

Chemical stability - Condition to Avoid

Avoid strong oxidizing agents. Avoid Processing Material over 300°C

Hazardous Polymerization

Not likely to occur

Corrosivity

Product is not corrosive

Dangerous products of decomposition: No hazardous decomposition

products known at room temperature. At elevated temperature the material will
begin to decompose producing fumes that can contain C0 2 . CO, Ketones &
Aldehydes.

SECTION 11 - TOXICOLOGICAL INFORMATION

ACUTE TOXICITY:
Primary irritant effect:
- On the skin: No irritant effect.
- On the eye: No irritant effect.
- Sensitization: No sensitizing effect known.

35
ADDITIONAL TOXICOLOGICAL INFORMATION:
When used and handled according to specifications, the product does not
have any harmful effects according to our experience and the information
provided to us.

SECTION 12 - ECOLOGICAL INFORMATION

Information about elimination (persistence and degradability):

Other information: The product is not biodegradable.

General notes:

The product is not toxic, small particles can have physical effects on
water and soil organisms.

SECTION 13 - DISPOSAL CONSIDERATIONS

Product: Recommendation

1) Recycle (Reprocess)

2) Disposal through controlled incineration or authorized waste dump in

accordance with Local, State or Federal Regulations.

Uncleaned Packaging:

Recommendation: Disposal must be done according to official regulations.

SECTION 14 - TRANSPORT INFORMATION

Transport/Additional information:

Not regulated as a dangerous goods for transportation.

36
SECTION 15 - REGULATORY INFORMATION

National regulations, other regulations, limitations and prohibitive

regulations PP manufactured by IOCL shall meet the requirement stipulated in
IS: 10910 on "Specification for Polypropylene and its copolymer for safe use in
contact with foodstuff, Pharmaceuticals & Drinking Water".

Additives incorporated in this grade conform to the positive list of

constituents as prescribed in IS: 10909.

The products additives incorporated in it also comply with FDA: CFR

Title 21.177.1520 Olefin Polymer.

SECTION 16 - OTHER INFORMATION

The information supplied has been based upon the current level of
information available, for the purpose of specifying the requirements regarding
environment, health and safety in conjunction with the product. They are not to
be interpreted as a warranty for specific product characteristics. Indian Oil
Corporation Ltd. takes no responsibility for inappropriate use, processing and
handling by purchasers and users of the product.

37
3.1.2 PRE-TREATMENT

This process idea was taken form a journal CONVERTING WASTE

PLASTICS INTO A RESOURCE, (Compendium of Technologies),
International Environmental Technology Centre Osaka/Shiga, Japan.

3.1.2.1 SOLID FUEL PRODUCTION

Solid fuel, as referred in this is prepared from both municipal and

industrial non-hazardous waste. Additionally, the solid fuel outlined here
excludes coal and coal-derived fuels as well as solid biofuels such as firewood
and dried manure but it may contain biofuels as a component.

This differentiates two types of solid fuel: refuse derived fuel (RDF), also
called solid recovered fuel (SRF) and refuse-derived paper and plastic densified
fuel (RPF). Standardization technical specification (CEN/TS 15359:2006).

Figure 3.1 Example of RDF

38
 RDF is mainly produced from municipal kitchen waste, used paper, waste
wood and waste plastics. Due to the presence of kitchen waste, prior to the
conversion to a fuel, a drying process is required to remove the moisture from
such waste to allow the solidification of the waste in suitable shapes and
densities. This process is seen as a disadvantage due to the large amount of
energy that the process requires.

Solid recovered fuel (SRF) is defined in the European Committee for

Standardization technical specification

On the other hand RPF (Figure 3.1) is prepared from used paper, waste
plastics and other dry feedstocks. Within the plastics, the thermoplastics play a
key role as a binder for the other components such as thermosetting plastics and
other combustible wastes, which cannot form pellets or briquettes without a
binding component. Approximately 15wt% of thermoplastics is the minimum
required to be used as a binder to solidify the other components; however
excessive amounts, higher than 50%, would cause a failure in the pellet
preparation.

The components of RPFs are mainly sorted from industrial wastes and are
sometimes also obtained from well-separated municipal waste. This type of
solid fuel is set to be standardized in the Japanese Industrial Standards (JIS).

In both cases, the plastic contents can be varied (within a range) to

meet the needs of fuel users. The shape of the fuel will vary according to the
production equipment (e.g. a screw extruder is often used to create cylindrical-
shaped fuel with a variable diameter and length).

In the production of solid fuel, the contamination of the targeted plastics

with other plastics containing nitrogen, halogens (Cl, Br, and F), sulfur and
other hazardous substances may cause air and soil. Other contaminants such as
hydrogen chloride might cause serious damage to the boiler by corrosion.

39
3.1.2.2 PRODUCTION METHOD

The solid fuel production process usually involves two steps,

pretreatment and pellet production:

• Pretreatment includes coarse shredding and removal of non-

combustible materials.

• Pellet production comprises secondary shredding and pelletization

(<200°C).

However, pretreatment is not required if the solid fuel producer can

collect waste with suitable properties.

Two types of commercial production systems are described as follows.

One is a large-scale model with pretreatment for the separation of undesirable
contamination such as metals and plastics containing chlorine. The other is a
small-scale model without pretreatment equipment.

3.1.2.3 INDUSTRIAL PRETREATMENT

Industrial waste plastics, which have been separated and collected in

factories, are ideal to be used for solid fuel production. A fuel production
facility consists of a waste unloading area, stockyard, pretreatment
equipment, pelletizing equipment and solid fuel storage.

The pretreatment process includes crushing and sorting for the removal
of unsuitable materials from incoming wastes. A schematic diagram of the
pretreatment process is shown in Figure 3.2. Figure 3.3 presents a photograph
of a pretreatment process. The Industrial pretreatment process got from RPF
Association, japan

40
 Figure 3.2: Schematic diagram of pretreatment process

After pretreatment, a suitable mixture of paper and plastics are further

processed in a secondary crusher and sorting process (conveyor and magnetic
separator) and the resulting mixture is pelletized to produce solid fuel. The
resulting solid fuel is cooled in an air-cooling system to prevent natural
ignition during storage and it is further stored for shipping.

Figure 3.3: Example of pretreatment process (3 ton/h capacity)

41
 The output of the process is usually solid fuel pellets of dimensions
between 6 to 60 mm in diameter and 10 to 100 mm in length. The heating
value of the pellets will change depending on the content of the plastics.

Figure 3.4: Schematic diagram of a pelletizing process

A mixture of paper and plastics of a 1:1 weight ratio gives a heating

value of approximately 7,000 kcal/kg or higher. Figure 3.4 shows a pelletizing
process and Figure 3.5 a typical pelletizing process facility with a 1 ton/h
capacity.

Figure 3.5: Typical pelletizing process facility (1 ton/h line)

42
3.1.3 PYROLYSIS PROCESS

3.1.3.1 SCOPE OF LIQUID FUEL

Liquid fuel within this compendium is defined as plastic-

derived liquid hydrocarbons at a normal temperature and pressure. Only
several types of thermoplastics undergo thermal decomposition to yield liquid
hydrocarbons used as liquid fuel. PE, PP, and PS, are preferred for the
feedstock of the production of liquid hydrocarbons. The addition of
thermosetting plastics, wood, and paper to feedstock leads to the formation of
carbonous substance. It lowers the rate and yields of liquid products.

Depending on the components of the waste plastic being used as

feedstock for fuel production, the resulting liquid fuel may contain other
contaminants such as amines, alcohols, waxy hydrocarbons and some
inorganic substances. Contamination of nitrogen, sulfur and halogens gives flu
gas pollution. Unexpected contamination and high water contents may lower
the product yields and shorten the lifetime of a reactor for pyrolysis

Liquid fuel users require petroleum substitutes such as gasoline, diesel

fuel and heavy oil. In these fuels, various additives are often mixed with the
liquid hydrocarbons to improve the burner or the engine performance. The fuel
properties such as viscosity and ash content should conform to the
specifications of the fuel user’s burners or engines.

No additives would be needed for fuel used in a boiler. A JIS technical

specification was proposed for pyrolytic oil generated from waste plastic for
use as boiler and diesel generator fuel

Skillful operators and a well-equipped facility are required due to the

formation of highly flammable liquids and gases

43
3.1.3.2 PRODUCTION METHOD

The production method for the conversion of plastics to liquid fuel is

based on the pyrolysis of the plastics and the condensation of the resulting
hydrocarbons. Pyrolysis refers to the thermal decomposition of the matter under
an inert gas like nitrogen.

Figure 3.6 Polypropylene Granules

For the production process of liquid fuel, the plastics that are suitable for
the conversion are introduced into a reactor where they will decompose at
450°C to 550 °C.

Depending on the pyrolysis conditions and the type of plastic used,

carbonous matter gradually develops as a deposit on the inner surface of the
reactor. After pyrolysis, this deposit should be removed from the reactor in
order to maintain the heat conduction efficiency of the reactor.

The resulting oil (mixture of liquid hydrocarbons) is continuously

distilled once the waste plastics inside the reactor are decomposed enough to
evaporate upon reaching the reaction temperature.

44
 The evaporated oil is further cracked with a catalyst. The boiling point of
the produced oil is controlled by the operation conditions of the reactor, the
cracker and the condenser. In some cases, distillation equipment is installed to
perform fractional distillation to meet the user’s requirements.

After the resulting hydrocarbons are distilled from the reactor, some
hydrocarbons with high boiling points such as diesel, kerosene and gasoline are
condensed in a water-cooled condenser. The liquid hydrocarbons are then
collected in a storage tank through a receiver tank.

Gaseous hydrocarbons such as methane, ethane, propylene and butanes

cannot be condensed and are therefore incinerated in a flare stack. This flare
stack is required when the volume of the exhaust gas emitted from the reactor is
expected to be large. Figure 4.1 presents a schematic diagram of a liquid fuel
production plant. ( Apparatus idea is taken from DIY Instructables webpage –
Plastic to fuel )

3.7 Schematic diagram of a production plant of Plastics derived fuel

45
 The raw material is feeded in the furnace and closed with the lid. For
sealing, aluminium foil is used and the lid is clamped. After the process has
strated the melted plastics will evaporate and flow through the furnace outlet i.e.
through the copper tube.

The copper tube is cooled by the counter flow condesor. Vapour to liquid
phase transcition takes place during the condesation process.

The remaining un condensed vapors coming from the reactor are enters
into the condenser where these vapors condenses to liquid hydrocarbon fuels. If
we want we may distill these crude oils in a fractional distillation column.

Due to the formation of carbonous matter in the reactor, which acts as a

heat insulator, in some tank reactors the stirrer is used to remove the carbonous
matter rather than for stirring.

After the liquid product of the pyrolysis is distilled, the carbonous matter
is taken out either with a vacuum cleaner or in some cases reactors are equipped
with a screw conveyor at the bottom of the tank reactor to remove the carbonous
matter.

3.1.4 FILTRATION & PURIFICATION

The fuel collected in the collecting chamber will be impure. There will be
wax, greese, and other impurities. So to remove the impurities, the following
processes were carried out.

• Gravity seperation.

• Filteration with filter paper.

46
 Gravity seperation is the basic process. In this process the impure fluid is
poured in a container in which the bottom part is like a funnel. So when the
fluid is poured, the most denser liquid will settle down below. Most probably
the water was found.

Then the waxy and greesy substance which was pale greenish yellow was
found immediately above the water. Finally, most of the polypropylene oil is
seen above in the topmost layer. So by opening the valve at the bottom, all the
unwanted substance are removed. Remaining oil is processed further.

In filteration process, the substances which are in colloidal state can be

removed. The filter paper will allow the molecules which are smaller than its
pores. So the various size of smaller pores will give more clean fuel.

Thus the collected samples are to be tested by appropriate methods. In

such a way we analyzed the products for their existence in the range of gasoline,
diesel and petroleum.

3.1.5 FUEL TESTING AND ANALYSIS

The purified fuel is to be tested to find out its characteristics . In order to

interpret the quality and properties of fuel, various tests were carried out in the
laborotary under various testing conditions. The tests performed were:

Color, Density, Viscosity, Calorific Value, Flash Point,Ash Content,

Cloud Point , Pour Point, GC/MS Test, FTIR Test

(GC/MS - Gas chromotography / Mass Spectroscopy)

(FTIR - Fourier Transform Infrared Spectroscopy)

So with these tests, the results were interpreted in the following chapter.

47
 CHAPTER 4

RESULT INTERPRETATION

Table 4.1 Polypropylene Oil and Diesel comparison

Contents Polypropylene Diesel

Colour Reddish Orange Bright Yellow

Density 711 Kg/m3 830 Kg/m3

Flash Point 23ºC 38ºC

Cloud Point -37.7ºC -40ºC

Pour Point -43.8ºC 5.6ºC

Ash Content Nil <0.01

Viscosity 6.723cm2/sec 2.4cm2/sec

Calorific Value 49163 KJ/Kg 45000 KJ/Kg

100
PP OIL
80
DIESEL
60
40
20
0
Density Flash point Cloud Pour point Viscosity Calorific
-20
point value
-40
-60
Figure 4.1 Comparison of Polypropylene oil Vs diesel

48
 Table 4.2 FTIR Test Results
Index Match Compound name Library
38 79.86 POLYPROPYLENE}, SYNDIOTACTIC Hummel Polymer Sample Library
41 78.07 POLY(PROPYLENE), ATACTIC Hummel Polymer Sample Library
1106 74.43 Polypropylene HR Hummel Polymer and Additives
489 73.52 Polypropylene, syndiotactic HR Hummel Polymer and Additives
383 72.54 Polypropylene, syndiotactic HR Hummel Polymer and Additives
499 71.60 Polypropylene:ethylene), 83 mol% C3 HR Hummel Polymer and Additives
943 71.11 Polypropylene, atactic HR Hummel Polymer and Additives
566 67.53 Polypropylene, atactic HR Hummel Polymer and Additives
942 67.22 Polypropylene, isotactic HR Hummel Polymer and Additives
1061 66.73 Polypropylene :butenone), 2:1 HR Hummel Polymer and Additives

Table 4.3 GC/MS Test Results

S.No SI RSI Compound Name Probability M. Formula M. Wt Area %
1 536 782 2-(l-Methylkeptyl)[l,3>2]dioxaaborane 22.59 C10H21BO2 184 1.02
2 693 770 ETHYL-2 METHYL-3 PENTENE-1 12.1 C8H16 112 5.69
3 726 783 (2,4,6-TrimetliYlcvclohex\4) methanol 11.75 C10H20O 156 1.91
4 639 695 (4E)-7-METHYL-4-UNDECENE # 5.66 C12H24 168 1.84
5 850 857 2-Isopropvl-5-methyl-l-heptanol 11.47 C11H24O 172 18.88
6 769 771 Cyclododecanemethanol 8.79 C13H26O 198 3.49
7 810 826 DECANE, 2,3,5,8-TETRAMETHYL- 7.24 C14H30 198 0.93
8 414 723 Methyl l-methoxypyrrole-2-carboxYlate 10.23 C7H9NO3 155 5.51
9 814 845 2-Hexyl-1 -octanol 6.04 C14H30O 214 2.41
10 744 818 (2,4,6-TnmethyieyclohexYl) methanol 6.96 C10H20O 156 3.82
11 479 769 (R)-3-Beiizyloxv-2-plienYlpropan-2-ol 24.39 C16H18O2 242 5.1
12 591 878 (3 -Cyano- 5-fluorophenoxy)amine 6.85 C7H5FN20 152 4.21
13 781 782 1-Dodecanol, 2-hexyl- 3.77 C18H38O 270 1.42
14 758 772 hydroxymethylcyclododecane 10.45 C13H26O 198 4
15 778 796 Trichloroacetic acid, hexadecyl ester 4.34 C13H33C13O2 386 3.41
16 785 801 Trichloroacetic acid, hexadecyl ester 4.97 C13H33C13O2 386 1.54
17 688 699 11.13-Dimetliyl-12-tetradeeen-l-ol acetate 10.93 C18H34O2 282 4.42
18 731 741 Neophytadiene 6.39 C20H38 278 0.95
19 681 687 1-Heptadecene (CAS) 3.23 C17H34 238 2.9
20 773 785 Trichloroacetic acid, hexadecyl ester 3.33 C18H33C13O2 386 1.77
21 676 691 11.13-Dimethyl-12-tetradecen-l-ol acetate 21.94 C18H34O2 282 4.53
22 757 961 #A 92.59 C23H22N2O4 390 0.98
23 556 798 l-Methoxy-2-methylsulfinylbenzene 14.46 C8H10O2S 170 2.08
24 751 762 Dodecane, l-cyclopentyl-4-(3-cyclopentylpropyl)-(CAS) 5.78 C25H48 348 3.85
25 803 803 1-Dodecanol, 2-octyl- 5.94 C20H42O 29S 2.7
26 920 921 #B 44.94 C29H25N5O2 475 3.82
27 769 779 1-Dodecanol, 2-octyl- 4.22 C20H42O 29S 1.47
28 572 691 PERDEUTERIOBENZYLIDENE-(N-BUTYL)AMINE 5.23 C11H9D6N 161 2.51
29 762 773 Octacosyl trifluoroacetate 3.71 C30H57F3O2 506 1.14
30 749 781 1-Hentetracontanol (CAS) 5.49 C41H84O 592 1.7
#A = 4,4-Dimetliyl-2-(4-nitrophenyl)-l-(4-methoxypheny l)-4,5 6,7-tetrahydro-
lH- indolone
#B = 5-(p-Methoxyphenyl)-2-[(a-phenyUiydrazino)benzyl idene]-1,3,4-triazole
From that above results from tables and graph it is interpreted that:
49
• The colour of the Polypropylene oil is reddish orange and its density is
711 Kg/m3 which is lesser than both Diesel and Gasoline.

• The fuel is flammable and combustible at room temperature which

according to test was 23ºC. The high combustibility of the fuel means it
is capable of having a much lower flash point that actually found.
However the flash point of gasoline is much lower.

• The cloud point and pour point are low as -37.7ºC and -43.8ºC
respectively, as a result this fuel can be used in extreme cold conditions
with ease.

• The above fuel has no ash content as compared to diesel which as an ash
content of <0.01.

• The Calorific value of the fuel is as high as 49163 KJ/Kg which is better
than both Diesel and Petrol and hence can be used for heavy duty Diesel
engines.

• From the above GC/MS test, the fuel has a major Hydrocarbon range
from C7-C30 which is similar to the Hydrocarbon range of Diesel. So this
fuel has the characteristics more or less of that of Diesel.

• The FTIR test result shows the presence of Polypropylene on a large scale
as a result Secondary and Tertiary Pyrolysis can be carried out and more
commercial Gasoline like products can be obtained.

Table 4.4 Hydrocarbon Range in Commercial Fuels

Heavy Fuel
Fuels LPG Petrol Kerosene Diesel*
oil
Hydrocarbon
C 3 to C 4 C 4 to C I2 C 12 to C I5 C 12 to C 24 C 12 to C 70
s

50
 CHAPTER 5

CONCLUSION & FUTURE SCOPE

5.1 CONCLUSION

Pyrolysis of hydrocarbon polymers is a very complex process, which

consists of hundreds of reactions and products. Several factors have significant
effects on the reactions and the products.

Based on previous research, this chapter investigated the fundamental

plastic processes and reactions. With temperature increasing, plastic will go
through glassy state, rubbery state, liquid state, and decomposition.
Decomposition of plastic in an inert environment into liquid is called pyrolysis.
There are four stages of reactions during the plastic pyrolysis process: initiation,
propagation, hydrogen transfer, and termination reactions.

It was found that heavy molecular weight hydrocarbons produced from

primary cracking can be further cracked into light molecular weight products
through a secondary cracking process. This secondary cracking process has
significantly influence on the distribution of the product. This process converts
heavy hydrocarbons into gas or light liquid product.

5.2 FUTURE SCOPE

The project shows some light on the possibility of manufacturing liquid

fuels which could be used as feed stock refinery for further modification or
commercial use. By using this technology we could solve the waste plastic
problem and also significantly reduce the landfills-which are the cause of
infertility of Agriculture land. Waste plastics can also become a very good
source of energy and an alternative to fossil fuel which have caused an
environment imbalance.

51
 REFERENCE

1. Yuan, X., Converting Waste Plastics into Liquid Fuel by Pyrolysis:

Developments in China, in Feedstock Recycling and Pyrolysis of Waste
Plastics, J. Scheirs and W. Kaminsky, Editors. 2006, John Wiley & Sons,
Ltd: Changsha, P.R. China.

2. Material Safety Data Sheet Polypropylene (PP) Indian Oil Corporation

Ltd.

3. Ciliz, N.K., E. Ekinci, and C.E. Snape, Pyrolysis of virgin and waste
polypropylene and its mixtures with waste polyethylene and polystyrene.
Waste Management, 2004.

4. Aguado, J., D.P. Serrano, and J.M. Escola, Catalytic Upgrading of Plastic
Wastes, in Feedstock Recycling and Pyrolysis of Waste Plastics, J.
Scheirs and W. Kaminsky, Editors. 2006, John Wiley & Sons, Ltd:
Mostoles, Spain.

5. Williams, P.T., J. Scheirs and W. Kaminsky, Editors. 2006, John Wiley &
Sons, Ltd: Leeds. Yield and composition of gases and oils/waxes from
the feedstock recycling of waste plastic, in Feedstock Recycling and
pyrolysis of waste plastics,

6. Moinuddin Sarker, Mohammad Mamunor Rashid and Muhammad

Sadikur Rahman. International Journal of Modern Engineering Research
(IJMER), Vol.2, Issue.4, July-Aug. 2012 pp-2168-2173, ISSN: 2249-
6645. Natural State Research, Inc. Department of Research and
Development USA.

7. British Plastics Federation website: http://www.bpf.co.uk/Recycling and

Sustainability.

52
 8. Preliminary study on the conversion of different waste plastics
into fuel oil, Munich, GRIN Verlag, http://www.grin.com/en/e-
book/206451/preliminary-study-on-the-conversion-of-differcnt-wastc-
plastics-into-ruel.

9. European Association of Plastics Recycling website:http://

www.eproplasticsrecycling.org

10. CONVERTING WASTE PLASTICS INTO A RESOURCE

(Compendium of Technologies) United Nations Environmental
Programme Division of Technology, Industry and Economics
International Environmental Technology Centre Osaka/Shiga, Japan.

11. Oluwafunmilayo A. Aworanti, Samuel E. Agarry, Ayobami O. Ajani.

Advances in Chemical Engineering and Science, 2012
http://dx.doi.org/10.4236/aces.2012.24054 Published Online October
2012 (http://www.SciRP.org/journal/aces)

12. A. C. Pinto, L. N. G. Lilian, J. C. R. Michelle, M. R. Nu-bia, A. T.

Ednildo, A. L. Wilson, A. de P. P. Pedro and B. de A. Jailson, “Biodiesel:
An Overview,” Journal of the Brazilian Chemical Society, Vol. 16, No.
6b, 2005.

13. K. Barnwal and M. P. Sharma, “Prospects of Biodiesel Production from

Vegetable Oils in India,” Renewable and Sustainable Energy Reviews,
Vol. 9, No. 4, 2005.

14. RECOUP, Recycling of Used Plastics webpage: http://www.recoup.org/

15. Plastics Europe, Plastics the Facts 2013 - An analysis of European latest
plastics production, demand and waste data, October 2013.

16. Plastics Recyclers Europe, How to boost plastics recycling and increase
resource efficiency – Strategy Paper, 2012.

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