THERMO CHEMICAL DEGRADATION OF MIXED

PLASTIC WASTE TO SYNTHETHIC HYDROCARBON

OIL

A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE

REQUIREMENTS FOR THE DEGREE OF
Bachelor of Chemical Engineering
By
Myo Thet Paing Tun
Under the Guidance of
Associate Prof. U San Yu Aung

Department of Chemical Engineering

West Yangon Technological University
Yangon
2019
 ACKNOWLEDGEMENT

I express sincere gratitude to my thesis supervisor U San Yu Aung, Associate

Professor, Department of Chemical Engineering, WYTU, for his kind support,
guidance and timely advice without which my thesis would not have completed.
I am also thankful to Prof. Dr. May Myat Khaing, Head of the Department, for
providing us the necessary opportunities for the completion of my thesis.
I am also thankful to Dr. Yu Yu Wah, Daw May Soe Moe and other
department’s teacher for their timely help which have helped me a lot to make
this thesis successful.

Myo Thet Paing Tun (VI-ChE-10)

Final Year,
Chemical Engineering,
W.Y.T.U
CONTENTS
LIST OF TABLE
LIST OF FIGURE
 ABSTRACT

Plastic is an indispensable part of our daily life. Its production and consumption
has been rising very rapidly due to its wide range of application. Due to its non-
biodegradable nature, it cannot be easily breakdown. So, nowadays new
technology is being used to treat the waste plastic. One of such process is
pyrolysis. This paper describes non catalytic pyrolysis and catalytic cracking of
plastic wastes into useful gasoline range hydrocarbons. Under the pyrolysis and
cracking conditions, the plastic wastes can be decomposed into three fractions:
gas, liquid and solid residue. The main objective is the recovery of liquid
products which are composed of higher boiling point hydrocarbons. The waste
plastics consisting of polyethylene terephthalate (PETE), low density
polyethylene (LDPE) and high density polyethylene (HDPE) was pyrolyzed in
this study. Pyrolysis appears to be a technique that is able to reduce a bulky,
high polluting plastic waste while producing energy or valuable chemical
compounds. The pyrolysis of plastic wastes produces a whole spectrum of
hydrocarbons including paraffin, olefins, naphthalene and aromatics. By
catalytic cracking more aromatics and naphthenic in the range of C6-C8 which
are valuable gasoline range hydrocarbons can be produced. Different catalysts
like Activated Carbon, Calcium Oxide and Potato Peels were used for catalytic
cracking. The catalysts were used in different ratios with feed to find out the
optimum range at which maximum yield occurs. The liquid product yield is
about 60% in all the cases. This process is combined with proper methods of
plastic wastes collection, classification and pretreatment at front end and
purification and testing at back end to determine the properties of the products.
 CHAPTER 1 INTRODUCTION

Plastics have become an indispensable part of our daily life and its production
and consumption have increased drastically. Plastics play a key role from
clothing to shelter, from transportation to communication and from
entertainment to health care [5]. Plastics have become an indispensable part in
today’s world due to their light-weight, durability, energy efficiency, coupled
with a faster rate of production and design flexibility.

Plastics are non-biodegradable polymers mostly containing carbon, hydrogen,

and few other elements such as chlorine, nitrogen etc. Due to its non-
biodegradable nature, the plastic waste contributes significantly to the problem
of Municipal Waste Management. The plastic production is more than 350
million tons worldwide annually [2]. The total generation of plastics waste from
a last few decades is increasing rapidly. In the table below show the total plastic
waste generation in some selected countries, measured in tons per year. This
takes account of per capita waste generation and population size. [8]

Table 1.1 Per capita Consumption of Plastics in Some Selected Countries.

Country Plastic Waste Generation, million tons/year
Myanmar 1.37
India 4.49
China 59.08
Thailand 3.53
Vietnam 3.27
Japan 7.99

According to a worldwide survey, conducted in the year 2015, only 6% of

plastics waste was recycled, 55 percent went straight to landfill or was discarded
and 8 percent was incinerated. So gradually it goes on accumulating, thereby
leading to serious disposal problems. [2]

Figure 1.1 Estimated share of global plastic waste by disposal method [2]

Plastic is derived from petrochemical resources. In fact these plastics are

essentially solidified oil. Therefore they have inherently high calorific value.
Table 1.2 [7] shows that, the calorific values of some of polyethylene is similar
to that of fuel oil.

Table 1.2 Calorific Values of plastics compare with conventional fuels.

Material Calorific Value (KJ/Kg)
Methane 53,000
Gasoline 46,000
Fuel Oil 43,000
Coal 30,000
Polypropylene 45,000
Polyethylene 43,000
Polystyrene 41,600
PETE 21,600
Waste Plastics are mostly land filled or incinerated; however, these methods are
facing environmental problems such as air pollution and soil contamination, as
well as disposal costs [3]. The land filling method is expensive, and the
incineration stimulates the growing emission of harmful gases such as NOx,
SOx and COx [6]. Accordingly, recycling has become an important issue
worldwide. This method can be classified as energy recovery, material recycling
and chemical recycling. Among them one of the prevalent alternative methods
is the production of converted fuel and chemicals by means of the thermal or
catalytic degradation of polymers [4].

Plastics pyrolysis provides an alternative means for disposal of plastic wastes

with recovery of valuable liquid hydrocarbons. In pyrolysis or thermal cracking,
the polymeric materials are heated to high temperatures, so their
macromolecular structures are broken down into smaller molecules and a wide
spectrum of hydrocarbons are formed. These pyrolysis products can be divided
into a gas fraction, a liquid fraction consisting of paraffin, olefins, naphthenic
and aromatics, and solid residues. Fluid cracking catalysts (FCC) or reforming
catalysts were used to improve the productivity and economic of pyrolysis
process to produce more aromatics and naphthenic [5]. Cracking can be both
batch and continuous systems. The experimental results obtained by batch
system are useable to the continuous reactor planning. The goal of these
experiments was for the developing of a zero waste green technology [6].

The objective of this study was to investigate the effect of plastic type
(especially PETE, LDPE and HDPE), reaction temperature and pressure, and
waste plastic to catalyst weight ratio in a batch reactor based on the quality of
yields and yield distributions of liquid product. And also to study the product
yields and their distribution with different types of catalysts (Activated Carbon,
Calcium oxide and Biocatalyst) with respect to time and temperature. Moreover,
to analyze gaseous, liquid and solid products from the thermal and catalytic
degradation of waste plastic and to compare physical properties of the liquid
products and to suggest the best reactor design with the economic factors. Along
with this, the main objective was to find out the best catalyst for the catalytic
cracking process under vacuum.
 CHAPTER 2 LITERATURE REVIEW

2.1 Plastics

Plastics are macromolecules, formed by polymerization and have the ability to

be shaped by heat and pressure or some other form of force [10].

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

molecules (“mers”) combine together by chemical reactions to form large or
macromolecules (“polymers”) in the form of long chain structures, having
altogether different properties than those of starting molecules (“mers”).
Depending upon their nature and properties, the polymers are classified as
Plastics, Rubbers or Elastomers and Fibers.

There are mainly two types of plastics: Thermoplastics and Thermosetting

plastics. Thermoplastics can be shaped or softened by the heat and can be
reshaped repeatedly, till it loses its property. Example: Polyethylene Buckets,
Polystyrene Cups, Nylon Ropes, Polycarbonate Bottles, etc. Thermosetting
Plastics cannot be softened by heat. Excess heat will become charring of the
materials. Example: Phenol Formaldehyde Bakelite electrical switches, Urea
Formaldehyde desk lamps casing, Melamine Formaldehyde cutlery,
Thermosetting Polyester fabric, etc.

2.1.1 Physical Properties of Plastics [9]

Plastics have physical characteristics, which need to be considered when

processing any product. The following table contains physical data for several
commercially available plastics.
Table 2.1 Physical properties of several commercial plastics.
Plastic Thermal Strength Density
Properties
Tm Tg Td Tensile Compressive g/cc
°C °C °C psi Psi
Polycaprolactam, 210- 185- 7400 13000-16000 1.12-
Nylon6 220 190 1.14
Polycarbonate, PC 150 138 9500 12500 1.2
Polyethylene 245- 73- 21- 7000- 11000-15000 1.29-
terephthalate, PET 265 80 38 10500 1.40
Low density 98- -25 40- 1200- 0.917-
polyethylene, LDPE 115 44 4550 0.932
Linear low density 122- 1900- 0 0.918-
polyethylene, LLDPE 124 4000 0.940
High density 130- 79- 3200- 2700-3600 0.952-
polyethylene, HDPE 137 91 4500 0.965
Polypropylene, PP 168- -20 107- 4500- 5500-8000 0.900-
175 121 6000 0.910
Polystyrene, PS 74- 68- 5200- 12000-13000 1.04-
105 96 7500 1.05
Polyvinylchloride, PVC 75- 57- 5900- 8000-13000 1.30-
105 82 7500 1.58

Here, Tm - crystalline melting temperature (some plastics have no crystallinity

and are said to be amorphous). Tg - glass transition temperature (the plastic
becomes brittle below this temperature). Td - heat distortion temperature under
a 66 psi load. Tensile Strength is the load necessary to pull a sample of the
plastic apart. Compressive Strength is the load necessary to crush a sample of
the plastic. Density or specific gravity is the mass of plastic per unit volume.

2.1.2 Types of Waste Plastics & Their Recyclability

The following table shows different types waste plastics and their recyclability
with standard mark for recycling to identify easily with many examples.

Table 2.2 Types of waste plastics and their recyclables: [13]

Mark Type Recycle Name Example
Type-1 YES Polyethylene Beverages bottle
Terephthalate

Type-2 YES High Density Milk container, detergent & oil

Polyethylene bottles, toys, plastic bags

Type-3 YES Polyvinyl Food wrap, vegetable oil bottles,

Chloride automotive parts

Type-4 YES Low Density plastic bags, shrink-wraps,

Polyethylene containers

Type-5 YES Poly Refrigerated containers, bags,

Propylene bottle tops, carpets, and food
wrap
Type-6 YES Polystyrenes utensils, meatpacking, protective
packing

Type-7 Some OTHER mixed plastic sheets

For recycling of waste plastic, Contamination can cause reduction of the quality
of recycling.

Table 2.3: Common contaminants in recycled polymers [9]

Polymer Recycle source Contamination
PET Beverage bottles PVC, green PET, Al, water, glue, oligomers
Photographic film Silver halides, gelatin, caustic residues
HDPE Milk/water bottles PP, milk residue, pigments, paper, EPS, cork
Detergent bottles Paper, glue, surfactants, bleach, white spirit
PVC Beverage bottles PET, PE, paper, Al foil, PP
LDPE Greenhouse films Insecticides, soil, Ni, oxidation products
Shopping bags Paper receipts, printing ink, food scraps
Multi-layer film Ethylene vinyl alcohol, polyamide, ionomer
Mulch film Soil (up to 30%), iron (up to 3% in soil)
PP Battery cases Pb, Cu, acid, grease, dirt
ABS Appliance housings Polybrominated flame retardants
SBR Automobile tires Steel wire, fiber, oil extender
Phenolic Circuit boards Cu, tetrabromobisphenol A

The simple and widely used process for separation is by using differences in
density, e.g. HDPE Cups and PET bottles. Chemical method such as selective
dissolution reaction can give better results for separation and purification.

2.1.3 Sources of Waste Plastics [13]

Plastic wastes can be classified as industrial and municipal plastic wastes

according to their origins. Industrial plastic wastes are from the plastics
manufacturing and processing industry. Usually they are homogeneous or
heterogeneous plastic resins, relatively less contamination and available large
quantities. Repelletizing and remolding seem to be a simple and effective means
of recycling for industrial plastic wastes. But if this plastic wastes are
heterogeneous, thermal cracking or chemical recycling into hydrocarbons may
provide a suitable means of recycling.

Municipal plastic wastes are part of municipal solid wastes and collected as
household wastes. Plastics usually account for about 7% of the total MSW by
weight and much more by volume. In order to recycle municipal plastic wastes,
separation of plastics from other household wastes is required. Although MSW
separation technologies have been studied extensively, it is still not possible to
classify MSW mechanically and obtain marketable fractions. So for recycling of
municipal plastic wastes, waste separation is required at the household. For this
reason the household wastes are separately disposed into three parts:
 Combustibles such as paper, kitchen waste, textiles, and wood,
 Incombustibles such as metals, glass, ceramics, and
 Plastics, then the collected plastics will be mixed plastic wastes with major
components of PE, PP, PS, PVC, etc.

2.2. Recycling techniques of waste plastics [9]

Basically there are 4 different ways of recycling of plastics:

 Primary Recycling - Conversion of waste plastics into products having
performance level comparable to that of original products. These methods
are undergone in to material recycling methods.
 Secondary Recycling - Conversion of waste plastics into products having
less performance level than the original material. These are also a part of
material recycling methods.
 Tertiary Recycling - The producing chemical or fuels or similar products
from waste plastics. These methods are known as chemical recycling or
feedstock recycling methods.
 Quaternary Recycling - The process of energy recovering from waste
plastics by incineration.

Plastics recycling will cover a wide range of different methods. The main areas
are given below.
 Material recycling
 Energy recycling
 Chemical Recycling

Combinations of these are also used to some extent. In all these methods is
common that the yield of organic material is no more than the input of plastic
waste material.

2.2.1. Material recycling of waste Plastics [5]

Once the plastic has been collected, it will have to be cleaned and sorted. The
techniques will depend on the scale of the operation and the type of waste.
Sorting of plastics can be by polymer type (thermo set or thermoplastic), by
product (bottles, plastic sheeting, etc.), by color, etc.

Size reduction is required for several reasons; to reduce larger plastic waste to a
size manageable for small machines, to make the material denser for storage,
transportation, and processing. There are several techniques commonly used for
size reduction of plastics. Cutting is usually carried out with scissors, shears,
saw, etc., for initial size reduction of large objects. Shredding machine has a
series of rotating blades driven by an electric motor, grid for size grading, a
collection bin and a hopper. The product of shredding is small irregularly
shaped plastic flakes. Agglomeration is the process of pre-palletizing soft plastic
by heating, rapid cooling to solidify and cutting into small pieces. This is
usually carried out in a single machine. The product is coarse, irregular grain,
often called crumbs.

Further processing techniques are as follow:

Extrusion is employed to homogenize the reclaimed polymer and produce a
material that it subsequently easy to work. The reclaimed polymer pieces are fed
into the extruder, are heated to induce plastic behavior and then forced through
a die to form plastic spaghetti, which is then cooled in a water bath before being
palletized. The extrusion product is usually in the form of a continuous ‘tube’ of
plastic such as piping.

Injection molding process is identical to that of extrusion, but the plastic

polymer emerges through a nozzle into a split mold. This type of production
technique is used to produce molded products such as plates, bowls, buckets,
etc.

Blow molding technique is used for manufacturing closed vessels such as

bottles and other containers by spiral screw forces the plasticized polymer
through a die.

Film blowing is a process used to manufacture such as garbage bags. It is a

technically more complex process than the others and requires high quality raw
material input. The process involves blowing compressed air into a thin tube of
polymer to expand it to the point where it becomes a thin film tube. One end can
then be sealed and the bag or sack is formed.
2.2.2. Energy Recycling

The alternatives for treating municipal and industrial polymer wastes is energy
recycling, where wastes are incinerated with some energy recovery. The
incineration of polymer waste meets with strong societal opposition.

Municipal solid waste incinerators (MSWIs) are a proven, robust technology for
dealing with different mixed waste types of a caloric value between 9 and 13
MJ/kg. MSWI’s are currently a default technology for the treatment of integral
household waste in countries such as Denmark, Sweden, the Netherlands and
Germany [4]. The homogeneous plastic waste is transferred to a grid-type kiln.
The rolling grid is placed under a certain slope, so that the waste is slowly
transported to take place full incineration to form slags. The slags are treated in
order to recover the ferrous and non-ferrous fraction. The flue gases pass
through cleaning equipment such as an electro filter, an acid scrubber, a caustic
scrubber, an active carbon scrubber. In modern MSWIs, the energy is also
recovered as much as possible. The flue gas cleaning process leads to fly ash
and residue, which has to be land filled. A large fraction of the chlorine input
into the MSWI ends up in the flue gas-cleaning residue. The neutralization of
flue gases with sodium bicarbonate has developed but no significant influence
on the amount of residue generated. However, this residue can be treated at a
separate plant to recover soda and salt, which can lower amounts of hazardous
waste.

2.2.3. Chemical Recycling

Feedstock recycling also known as chemical recycling or tertiary recycling,

aims to convert waste polymers into original monomers or other valuable
chemicals. These products are useful as feedstock for industrial processes or as
transportation fuels. The different routes of chemical recycling are shown
below.

Chemical Recycling or
Feedstock Recycling

Chemical Recovery Energy Recovery

Heterogeneous Homogenerous
Process Process

Gasification
Cracking Chemolysis
(Partial Oxidation)

Thermal Hydro Catalytic

Methanolysis Glycolysis Alcoholysis
Cracking Cracking Cracking

Liquid Phase Vapor Phase

Catalytic Cracking Catalytic Cracking

Fig 2.1: Ways of chemical recycling techniques.

2.2.3.1Chemolysis/ Solvolysis [9]

In Chemolysis process, individual plastics are chemically treated and

depolymerized into monomers by using catalysts. It includes a range of
processes such as glycolysis, hydrolysis, methanolysis, achoholysis,
saponification dialysis etc. Hydrolysis leads to direct recovery of the original
raw materials by targeted reaction of water molecules at the linkage points of
the starting polymers. All hydrolysable plastics such as polyamides, polyesters,
polycarbonates, polyureas, and polyurethanes are resistant to hydrolysis under
normal conditions. Hydrolysis of polyurethane foams recovered almost 100% of
the polyether polyols and 90% of the amine. The regenerated materials can be
reused together with fresh starting material to produce polyurethane foams.
Chemical degradation polyurethanes by alcoholysis give a polyhydroxy alcohol
and small urethane fragments formed by transesterification. If a diol is used as
the alcohol, then the urethane fragments also contain terminal hydroxyl groups.
These polyhydroxy alcohols can be converted directly to polyurethane foam by
addition of isocyanates. The degradation of polymers in the presence of glycol
such as ethylene glycol or diethylene glycol is known as glycolysis. And in the
presence of methanol it is known as Methanolysis.

2.2.3.2 Gasification or Partial oxidation: [3]

The direct combustion of polymer waste can produce noxious substances such
as light hydrocarbons, NOx, sulfur oxides and dioxins. However, Partial
oxidation (using oxygen and/or steam) could generate a mixture of
hydrocarbons and synthesis gas (CO and H2). A new type of waste gasification
and smelting system using iron-making and steel-making technologies has been
described by Yamamoto et al. [22], 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 partial
oxidation using O2 is also possible.

2.2.3.3 Cracking: [5]

Cracking processes break down polymer chains into useful lower molecular
weight compounds. This can be achieved by reaction with hydrogen, known as
hydrocracking or by reaction in an inert atmosphere (pyrolysis methods), which
can be either thermal or catalytic cracking.
2.2.3.3.1 Hydro cracking [5]

Hydro cracking of polymer waste typically involves reaction with hydrogen

over a catalyst in a stirred batch autoclave at moderate temperatures and
pressures. The process mainly focuses on obtaining a high quality gasoline from
polyolefins, PET, PS, PVC, scrap tires and mixed polymers from municipal
solid waste. And co-mixing of polymers with coal, and vacuum gas oil has been
studied. To aid mixing and reaction, solvents such as 1-methyl naphthalene,
tetralin and decalin have been used with some success. Several catalysts such as
transition metals (e.g., Pt, Ni, Mo, Fe) supported on acid solids (such as
alumina, amorphous silica-alumina, zeolites and sulphated zirconia) have been
evaluated. These catalysts incorporate both cracking and hydrogenation
activities.

2.2.3.3.2 Thermal cracking [8]

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 500-800 ºC and results in the formation of a carbonized
char and a volatile fraction that may be separated into condensable hydrocarbon
oil and a non-condensable high calorific gas. The proportion of each fraction
and their composition depends primarily on the nature of the plastic waste but
also on the process conditions. Thermal cracking of polyolefins such as
polyethylene or polypropylene gave a random scission mechanism that
generates a mixture of linear olefins and paraffins over a wide range of
molecular weights. In other cases, like thermal degradation of polystyrene and
polymethylmetacrylate occurs by unzipping mechanism that yields a high
proportion of their constituent monomers [1].
In pyrolysis processes, initial degradation reaction transformed raw materials
into secondary products due to the intermolecular reactions. The nature of these
reactions depends both on the temperature and also on the residence of the
products in the reaction zone that is primarily affected by the reactor design.
Reactor has to overcome problems related to the low thermal conductivity and
high viscosity of the molten polymers. Several types of reactors have been
reported in the literature, the most frequent being fluidized bed reactors [16, 17],
batch reactors [4, 18] and screw kiln reactors [1]. Pyrolysis and gasification of
plastics and other carbonaceous fuels have been studied extensively. Converting
plastic wastes into petrochemicals by means of pyrolysis in the absence of a
catalyst has been reviewed by Kaminsky [17, 18, and 19].

Four types of mechanisms of plastics pyrolysis have been proposed:

 End-chain scission or depolymerization: The polymer is broken up from the
end groups and successively yielding the corresponding monomers.
 Random-chain scission: The polymer chain is broken up randomly into
fragments of uneven length.
 Chain-stripping: Elimination of reactive substitutes or side groups on the
polymer chain, leading to the evolution of a cracking product on one hand,
and a charring polymer chain on the other.
 Cross-linking: Formation of a chain network, which often occurs for
thermosetting polymers when heated.

These different mechanisms and product distributions are related to bond

dissociation energies, the chain defects of the polymers, and the aromaticity
degrees, as well as the presence of halogen and other hetero-atoms in the
polymer chains. The pyrolysis of PS occurs by both end-chain and random
chain scission and the monomer recovery is only 45%. For PE and PP, the
pyrolysis occurs through the random-chain scission mechanism and a whole
spectrum of hydrocarbon products is obtained. The gas and oil yields from
polyolefin pyrolysis are about 40-50% of the feed at 750°C and the oil fraction
consists mainly of higher boiling point hydrocarbons (tar).

2.2.3.3.3 Catalytic cracking [8]

Many experimental studies have been carried out by various researchers to

improve liquid hydrocarbons yield from plastics pyrolysis by using suitable
catalysts. Common plastics such as PE and PP have been studied extensively;
the catalysts are mainly those used in the petrochemical refinery industry. The
laboratory experimental set-up is a mostly flow reactor.

It may be useful to distinguish between two modes of catalyst usage: ‘liquid

phase contact’ and ‘vapor phase contact’. In ‘liquid phase contact’, the catalyst
is contacted with melted plastics and acts mainly on the partially degraded
oligomers from the polymer chains. In ‘vapor phase contact’, the polymer is
thermally degraded into hydrocarbon vapors which are then contacted with the
catalyst. The current work is production of liquid hydrocarbon fuel by the
application of liquid phase contact catalytic cracking.

FCC catalysts have been employed in the petroleum refining industry for the
cracking of heavy oil into lighter gasoline and liquefied petroleum gas (LPG)
fractions. The products fall under four major classes of HCs: Paraffin, Olefins,
Naphthalene and Aromatics (PONA). Gasoline range fuels consist of paraffin
and olefins in the C5-C12 range [11]. Reviews on the FCC process can be found
in literature [12, 13, 14, and 15]. Major commercial FCC catalysts are given in
table 2.4 along with their composition.
Table 2.4 Major FCC Catalysts and their composition
Catalyst Major cations Composition (wt. %)
exchange SiO2 Al2O3 Na Ca Re
Silica-alumina - 74-88 12-26 - - -
Zeolite A Ca2+ 42.5 37.4 7.85 13.0 -
Zeolite X and Y Ca2+ 47.8 31.5 7.7 12.3 -
RE, NH4+ 40.0 33.0 0.22 - 26.5
Zeolite ZK5 H+ 26.8 23.1 0.47 - -
Mordenite H+ 80.1 13.4 0.3 1.54 -

The main effects of catalyst addition in plastics pyrolysis are as follows.

 The pyrolysis temperature for achieving a certain conversion is reduced
drastically and as the catalyst/plastics ratio is increased, the pyrolysis
temperature can be further lowered. [16]
 More iso-alkanes and aromatics in the C5-C10 range can be produced which
are highly desirable gasoline range hydrocarbons.
 The reaction rate is increased significantly; e.g. the initial rate of degradation
of polypropylene was reported to be approximately four times faster than
that of non-catalytic thermal degradation [16]

2.3 Gasoline-range hydrocarbons

The pyrolysis of plastic wastes produces a whole spectrum of hydrocarbons

including paraffin, olefins and aromatics. But all these hydrocarbons are not
suitable for gasoline usage. Gasoline qualities are usually measured in terms of
volatility and octane number of the hydrocarbons. For gasoline production,
aromatics, naphthenic and iso-alkanes are highly desirable, whereas olefins and
n-paraffin are least desirable [3].
Adequate volatility is required for smooth operation of petrol engines. Light
hydrocarbons have higher volatilities than heavy hydrocarbons. They may cause
vapor lock when the engine is hot. However, low volatilities heavy
hydrocarbons may not be volatile enough to start the engine when the engine is
cold. Suitable hydrocarbons are in the C5-C8 range. Some C9 and above may be
added according to climate and season.

Octane number is the measurement of the gasoline quality for prevention of

early ignition which leads to cylinder knock. Higher octane numbers are
preferred for internal combustion engines. The octane numbers of selected
hydrocarbons are listed in Table 2.4. Accordingly, it is desirable that the
pyrolysis conversion of plastic wastes produces more aromatics, naphthenic and
iso-alkanes with carbon number in the range C5-C8.

Table 2.4 Octane numbers and boiling point of some hydrocarbons.

Compounds Octane Number BP, °C
(blending, Research method)
Paraffin
n-Butane 113 0
n-Pentane 62 36
n-Hexane 19 69
n-Haptane 0 98
Isooctane 100
2-Methylhexane 41 90
2, 2-Dimethylpentane 89
2, 2, 3-Trimethylbutane 113
Naphthenic
Cyclopentane 141 49
 Methylcyclopentane 107 72
Cyclohexane 110 81
Olefins
2-Methyl-1-hexene 91 91
3-Methyl-2-pentene 97 68
Aromatics
Benzene 99 80
Toluene 124 111
m-Xylene 145
1, 3-Dimethylbenzene 145 139
1, 3, 5-Trimethylbenzene 171
Isopropylbenzene 132
 CHAPTER 3 MATERIALS AND METHOD

3.1 Raw Materials Collection

The waste plastics for the process consisted mainly of PETE, HDPE and LDPE
products in the form of used plastic disposable bottles and packaging. We
collected the waste plastic materials that were used by students and staff in our
university. The picture below shows the material, which we collected.

Fig 3.1: The waste plastic materials collected for process

Chemical catalysts (activated carbon, calcium hydroxide) used in this study

were obtained from commercial sources. Biocatalyst (potato peels) were collect
from food court and reduced to a fine size after drying.

Fig 3.2 Activate Carbon, Calcium Oxide and Potato Peels

Other chemicals such as concentrated sulfuric acid, potassium dichromate,
sodium hydroxide were also used in this experiment.

3.2 Methods

3.2.1 Preparation of PETE, HDPE & LDPE scraps

The collected waste plastics were subjected to cutting by using scissors

manually. This was done to increase the surface area of contact of the material
during cracking process. The plastic scraps were severely washed with tab water
to clean contaminants. After1hr sun drying, the sample were directly taken for
the cracking process.

3.2.2 Equipment Setup

The cracking process was performed under laboratory fume hood in a

borosilicate round bottom flask of 500ml capacity as a reactor. The weight of
the reactor was 339 g. Reactor was sealed off to create adequate inside pressure.
Domestic hot plate with thermostat was used as a heat source. The reactor was
put on the hot plate and temperature around 150°C was maintained for melting
and subsequent cracking. Total time taken for single batch of reaction was
around 40-160 minutes. A lab scale borosilicate reflux condenser was suitable
for the experiment, whereas the coolant used is tap water. The collector is
simple borosilicate flasks of 250 ml capacity. To ensure minimum loss of
product obtained, collector was sealed with cork. Rotary vane vacuum pump of
0.5 hp capacity was used to create vacuum in the reactor. Use of vacuum create
inert atmosphere and reduces the temperature of the pyrolysis reaction to take
place inside the reactor. The experiments were conducted in a batch mode. As
shown in figure 3.3, the un-condensable gases coming from the process are
directed into the NaOH solution for scrubbing. Here the gases are completely
absorbed. According to literature the gases coming from the process are in the
range of LPG and HCl gases [1].

Fig 3.3 Batch pyrolysis process setup

3.2.2 Pyrolysis

Pyrolysis or cracking processes break down polymer chains into useful lower
molecular weight compounds. This can be achieved by the application of heat at
atmospheric pressure in the absence of oxygen, which can be either thermal or
catalytic cracking.

A particular quantity of sample and catalyst were charged into the reactor. The
reactor was completely packed with the materials and perfectly sealed to
prevent the leakage of vapors. The reactor was place inside the sand bath and
put on the hot plate with the support of a stand. The reactor was placed inside
the sand bath to prevent direct contact of hot surface and to uniform heating.

The experiment was carried out in five different batches. The first batch was run
in the absence of vacuum and catalyst. The remaining batches were conducted
under vacuum conditions. The temperature is monitored by temperature
controller. The rate of increase of temperature is 5 °C/min. The catalyst/feed
ratios are 0.05, 0.10 and 0.15 in this study. The following catalysts were used
for the pyrolysis process:
 Calcium Oxide
 Activated Carbon
 Potato Peels

Pyrolysis reaction is allowed to take place for a specific duration. The vapors
coming from the reactor were passed through a glass condenser where
condensation of the vapors takes place. Proper arrangement was made for the
condensation by putting wet jute over the pipelines to support further
condensation. Then the condensed liquid oil was collected in a receiver. The
major part of the vapor condensed is collected as fuel oil. The vapors which do
not condense are allowed to pass through NaOH solution. The liquid fuel
products obtained by thermal and catalytic pyrolysis were examined by gas
chromatography (GC). The yield was calculated as follows [23]:
weight of liquid produce
% liquid yield = × 100
weight of waste plastic

Fig 3.4 The vapors of cracked plastic moving into the glass condenser for
condensation.
The temperature maintained during catalytic cracking is much lower than that
maintained during thermal cracking.

3.3 Liquid oil characterization

The quality of liquid fuel obtained by catalytic and thermal cracking was
verified using certain chemical and physical tests [24]. According to the
literature, the liquid fuel products obtained contains mostly paraffin, olefins,
naphthenic and aromatics (PONA). The chemical composition of liquid oil
product was analyzed by GC. But due to economic reasons we were not able to
find their composition. So, we selected to measure the physical properties like
specific gravity, pour point, flash point etc.

The density and the specific gravity of the sample are evaluated by simple
laboratory method using specific gravity bottle [25]. The specific gravity was
found out by using a 10 ml specific gravity bottle. 10 ml of the sample was
taken in a pipette and the pre-weighted bottle was filled with the fuel sample to
its brim. The final weight of the bottle was taken. This gave the weight of the
sample which when divided by 10 to give the specific gravity and hence the
density of the sample.

Viscosity was determined using viscometer. Kinematic viscosity was

determined in accordance with ASTM method.

Pour point of liquid product was determined using pour point manual method
(ASTM D97) [23]. For finding the pour point, the sample was taken in a test
tube and kept in the cooling bath/refrigerator. After every 5°C drop in
temperature, the sample was taken out and its fluidity was checked. At a
particular temperature the liquid ceases to flow, this temperature was taken as
the pour point of the fluid.

For flash point determination, Cleveland open-cup method was employed [23].
First, About 30 ml of the sample was taken in the cup of the apparatus and it
was cooled by using a water bath. Continuous stirring was done during the
process. Then, the temperature of sample is increased at constant rate. The
increase in temperature will cause the chemical to begin to produce flammable
vapor. The lowest temperature point at which flame passing over the surface of
the liquid causes the vapor to ignite is known as flash point.
 Chapter 4 Results and Discussing

4.1. Comparison between thermal and catalytic cracking

In the present study, catalytic cracking was performed using activated carbon,
calcium oxide and biocatalyst and compared with that of thermal cracking. The
experiments on pyrolysis were conducted by using PETE, LDPE and HDPE as
the raw material. Table 1 shows the quantity of liquid product obtained for
thermal and catalytic cracking. Batch 1 was run in the absence of vacuum where
no conversion was achieved. Batches 2-5 were performed by maintaining
vacuum condition in the reactor.

Table 4.1 Experimental results of thermal and catalytic pyrolysis oil.

Batch Feed Catalyst Product
1 200 g - -
(No Vacuum)
2 200 g - 105 ml of fuel + waxy end
(Vacuum) product
3 200 g Activated Carbon = 148 ml of fuel + Waxy end
(Vacuum) 30 g product
4 200 g CaO = 30 g 133 ml of fuel + Waxy end
(Vacuum) product
5 200 g Bio Catalyst = 30 g 113 ml of fuel + Waxy end
(Vacuum) product

It was observed that thermal cracking (batch 2) resulted in the formation of 105
ml of liquid fuel product with coke formation. Catalytic cracking (batches 3-5)
resulted in a significant increase in the liquid fuel product with lower quantity of
coke formation with respect to thermal cracking. For batch 3-5 the ratio of
catalyst to feed maintained was same. The maximum quantity of liquid product
was obtained for potato peels as a catalyst. With CaO as a catalyst, 133 ml of
liquid fuel product was obtained. Catalytic cracking resulted in less wax
formation with respect to thermal cracking. Thus, catalytic cracking proved to
be a promising technique which enhances the product yield as compared with
thermal cracking under the same operating conditions.

4.2 Activated Carbon cracking

Activated carbon is black granular catalyst. It constitutes of carbon that contains

some amount of pores which are filled up after use. Thus, if activated carbon is
reused again then it cannot yield good product.

Table 4.2 Product composition for different catalyst ratio of activated carbon
Catalyst Ratio %Solid %Liquid %Gas
Activated Carbon 1:0.20 3 72.7 24.3
Activated Carbon 1:0.15 3.2 74 22.8
Activated Carbon 1:0.10 3.2 74 22.8
Activated Carbon 1:0.05 3.2 64 32.8

Table 4.3 The feed to catalyst ratio, time required for conversion, temperature
needed and the percentage yield of liquid products.
Feed, g Catalyst, g F:C T, °C Time, Liquid, %Yield
min ml
200 10 1:0.05 235 150 128 64
200 20 1:0.10 245 80 148 74
200 30 1:0.15 255 60 148 74
200 40 1:0.2 265 40 145.4 72.7
 Catalyst Vs Yield
100
%Yield 80
60
40
%Yield
20
0
0 10 20 30 40 50
Catalyst

Fig 4.1 Relation of yield of product with catalyst ratio for activated carbon

4.3 Calcium Oxide Cracking

Calcium oxide (CaO), commonly known as quicklime is a white, caustic,
alkaline, crystalline solid at room temperature. Calcium oxide (CaO) is usually
used as catalyst in biodiesel production.

Table 4.4 Product composition for different catalyst ratio of calcium oxide
Catalyst Ratio %Solid %Liquid %Gas
Calcium Oxide 1:0.20 3 51.5 45.5
Calcium Oxide 1:0.15 3 66.5 30.5
Calcium Oxide 1:0.10 3 78.5 18.5
Calcium Oxide 1:0.05 3 54.5 42.5

Table 4.5 The feed to catalyst ratio, time required for conversion, temperature
needed and the percentage yield of liquid products
Feed, g Catalyst, g F:C T, °C Time, Liquid, %Yield
min ml
200 10 1:0.05 250 140 109 54.5
 200 20 1:0.10 260 120 135 67.5
200 30 1:0.15 275 100 133 66.5
200 40 1:0.2 285 80 103 51.5

Catalyst Vs Yield
80

60
%Yield

40
%Yield
20

0
0 10 20 30 40 50
Catalyst

Fig 4.2 Relation of yield of product catalyst ratio for CaO

4.4 Biocatalyst cracking

Potato peels is a zero value waste produced by household and food processing
plant. It contains sufficient quantities of starch, cellulose, hemicellulose, lignin
and fermentable sugars.

Table 4.6 Composition for different catalyst ratio of biocatalyst

Catalyst Ratio %Solid %Liquid %Gas
Potato peels 1:0.20 3.2 76 20.8
Potato peels 1:0.15 3.2 56.67 40.163
Potato peels 1:0.10 3.2 60 36.8
Potato peels 1:0.05 3.2 80 16.8
Table 4.7 The feed to catalyst ratio, time required for conversion, temperature
needed and the percentage yield of liquid products.
Feed, g Catalyst, g F:C T, °C Time, Liquid, %Yield
min ml
200 10 1:0.05 230 140 160 80
200 20 1:0.10 240 120 120 60
200 30 1:0.15 250 80 113 56.5
200 40 1:0.2 260 60 88 44

Catalyst Vs Yield
100
80
%Yield

60
40
%Yield
20
0
0 20 40 60
Catalyst

Fig 4.3 Relation of yield of product with catalyst ratio for potato peels

Fig 4.4 Calcium Oxide, Potato Peels and Activated Carbon catalysts before and
after of cracking
4.5 Analyzing of liquid oil products

Different composition of liquid product was obtained for different catalyst and
its different ratio with plastic feed. The liquid obtained was highest for a
particular ratio at a particular temperature. This was the optimum range for the
particular catalyst. It was seen that biocatalyst gave the maximum liquid product
and thermal cracking give minimum products. The quality of product obtained
was also better in case of catalytic cracking. In every process about 2% of
carbon was obtained as final residue.

Fig 4.5: Different liquid products samples obtained during cracking

Fig 4.6 Solid carbon residue obtained after cracking

The samples collected were tested for the physical properties like specific
gravity, pour point and flash point. The table below shows the different
measured physical properties of the samples.

Table 4.8: The different measured physical properties of the samples collected.
Catalyst Ratio Spgr Pour Point Flash Point
AC 1 0.8506 -80 31
AC 2 0.8476 -80 31
AC 3 0.8432 -82 31
AC 4 - - -
CaO 1 0.7781 -60 31.5
CaO 2 0.7638 -60 31.5
CaO 3 0.7787 -60 31.5
CaO 4 0.7850 -60 31.5
Biocatalyst 1 0.7625 -80 32
Biocatalyst 2 0.7540 -80 32
Biocatalyst 3 0.7754 -80 32
Biocatalyst 4 0.7432 -80 32

From the literature [20] it was found out that the specific gravity of gasoline
varies from 0.72-0.75 and that of diesel oil is 0.82. The specific gravity of the
samples prepared by us varies in that range. Thus it can be inferred to be of
gasoline range fuel. The flash point of gasoline is 7°C and that of diesel oil lies
between 60°C-80°C. The flash point the sample prepared lie in the range of 30-
32. Thus the fuel may lie in between the range of gasoline and diesel oil.
 CHAPTER 5 CONCLUSION

The plastic waste was subjected to various conditions of reactions starting from
thermal cracking to catalytic cracking by using different ratio of feed to catalyst.
Cracking temperature, time required for complete cracking, product yield and
physical properties are different in each case. In thermal cracking under
vacuum, the process yielded fair amount of product. When the plastic was
catalytically cracked by using potato peels as the catalyst, it gave quite good
quantity and quality of liquid fuel.

The highest yield was obtained when the feed to catalyst ratio was 20:1. At this
condition, it required a temperature of about 260°C and 40 minutes time. The
liquid product obtained had a specific gravity of 0.7787 which is quite good and
falls in the range of gasoline fuel. It can be observed that as the feed to catalyst
ratio increases, the time of reaction decreases but the temperature required is
increase.

In case of using CaO as the catalyst, the maximum yield of liquid product was
obtained when the feed to catalyst ratio was 10:1. In this case, we can conclude
too much catalyst may cause negative catalysis reaction. The specific gravity of
the liquid product obtained was in the range of gasoline.

If activated carbon was used, then maximum product yield was obtained when
the ratio of feed to catalyst was 10:1 and 10:1.5. The specific gravity of this
product was higher than that of gasoline.

Thus from all the experiments we have performed, it can be inferred that the
maximum yield of liquid fuel product was obtained when biocatalyst was used
in the ratio of 20: 1 with the feed.
The liquid product was combustible and its specific gravity varied in the range
of gasoline and diesel oil. Thus it can be inferred to be of gasoline range fuel.
The flash point of gasoline is 7°C and that of diesel oil lies between 60°C-80°C.
The flash point the sample prepared lie in the range of 30-32. Thus the fuel may
lie in between the range of gasoline and diesel oil.

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