ADAMA SCIENCE AND TECHNOLOGY UNIVERSIT

SCHOOL OF MECHANICAL, CHEMICAL AND MATERIAL

ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING

A FINAL YEAR PROJECT SUBMITTED TO THE DEPARTMENT OF CHEMICAL

ENGINERING IN PARTIAL FULFILMENT OF REQUIREMENTS FOR THE DEGREE
OF BACHELOR OF SCINCE IN CHEMICAL ENGINEERING

RECYCLING OF PLASTICS USING SOLVENT

NAME ID.NO

1. KEYRU SERBARA R/1043/04

2. BESHIR REDWAN R/0315/04
3. AMDET EBRAHIM R/0179/04

ADVISOR PROF.HONG KU KANG

JUNE, 2016
ADAMA, ETHIOPIA
 ADAMA SCIENCE AND TECHNOLOGY UNIVERSIT
SCHOOL OF MECHANICAL, CHEMICAL AND MATERIAL
ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING

A FINAL YEAR PROJECT SUBMITTED TO THE DEPARTMENT OF CHEMICAL

ENGINERING IN PARTIAL FULFILMENT OF REQUIREMENTS FOR THE DEGREE OF
BACHELOR OF SCINCE IN CHEMICAL ENGINEERING

PLASTIC RFECYCLING USING SOLVENT

Prof.Hong Ku Kang
Adviser Signature date

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 Acknowledgement

First of all, we would like to express our profound gratitude and sincerest appreciation to our advisor,
prof.hong ku kang for his encouragement, invaluable constructive ideas and suggestions on our thesis
work. And valuable advice throughout the study period. Our gratitude are extended to lab assistants
Mr seid, Mr Mengistu Tadese, and others whose name are not listed here for their valuable advice
and kindly serving us in any aspect. Last but not the least, we would like to express our gratitude to
all respondents of our final year project thesis, whom they share us their valuable time and
knowledge. Finally, we would like to thank our families who helped us in different ways related with
our thesis project.

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 Abstract

The project was mainly concerned to recycling of plastics using solvent. This method works on the
principle of solubility, as a function of temperature, to dissolve only certain polymers at certain
temperatures. The process involves four basic steps .First plastics are dissolved in solvent next anti
solvent is added to precipitate dissolved bulk then each of the polymers present can be dissolved and
then crystallized separately for further processing and finally solvent-anti solvent mixture separated
and recycled. Two experiments were performed by using 600 ml of xylene, 1800 ml of n-hexane as
solvents and 500 gram of high density polyethylene as in put for dissolution and different bulk
densities with similar ratio of solvents/non-solvents ratios. The major criteria for determining rate of
dissolution basically considered were, bulk density, retention time, and temperature. Observed
dissolution time for two polymer to solvents(S+AS) ratio, 1:4, and 1:5.3 are 24 and 30 minutes for
each experiments respectively

This project predicted the establishment of a plant for the recycling of plastics using solvent with a
capacity of 17100 pieces of conduit per annum with Total production cost of 1148266 birr and Net
profit of 333553 birr. The project is financially viable with rate of return 33.2% and payback period
three.

Key words: bulk, conduit, density, n-hexane, plastics, polyethylene, Recycle, solvent, xylene

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 Table of contents

Chapter Title Page

Title page i
Acknowledgements ii
Abstract iii
Table of Contents iv
List of Tables vii
List of Figures viii
List of Acronyms and Abbreviations ix
List of Appendices x
CHAPTER ONE 1
1. INTRODUCTION 1
1.1. Background 1
1.2. Statement of the problem 2
1.3. Objectives 2
1.3.1. General objectives 2
1.3.2. Specific objectives 2
1.4. Scope of project 2
CHAPER TWO 3
2. LITERATURE REVIEW 3
2.1. Fundamentals of plastics 3
2.2. Classification of plastics 3
2.3. Application of plastics 7
2.4. Advantages and disadvantages of plastics 8
2.5. Sources of plastic wastes 8
2.6. Methods of reusing and disposing plastic wastes 9
2.6.1. Hydrolysis 9
2.6.2. Alcholysis 9
2.6.3. Hydrogenation 9
2.6.4. Combustion 9
2.6.5. Dumping and degradation 9
2.6.6. Pyrolysis 10

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 2.6.7. Recycling 10
2.7. Approach for plastics recycling 11
2.8. Plastics recycling using solvent 12
2.8.1. History of plastics recycling using solvent 13
2.8.2. Solvent selection 21
2.8.3. Important Factors in Polymeric Solubility 22
2.8.4. Factors affecting rate of dissolution 27
2.8.5. Measurements used to characterize final product 28
2.8.6. Drawback of solvent recycling 28
2.8.7. Process description 29
CHAPTER THREE 33
3. MATERIALS AND METHODS 33
3.1. Study area description 33
3.2. Sampling Techniques 33
3.3. Physical and chemical properties measured 33
3.4. Materials used 33
3.5. Laboratory procedure 34
3.5.1. Equipments used 34
3.5.2. Raw materials Used 34
3.5.3. The procedures for recycling 35
3.6. Recycling of the solvents 35
CHAPTER FOUR 36
4. RESULTS AND DISCUSSION 36
4.1. Recycling of plastics by the dissolution/reprecipitation 36
technique
CHAPTER FIVE 37
5. TECHNO-ECONOMIC AND FEASIBILITY STUDY 37
5.1. Material and energy balance 37
5.1.1. Material balance 37
5.1.2. Energy balance 40
5.2. Equipment layout of the plant 41
5.3. Economic evaluation of the plant 42
5.3.1. Purchased Equipment Cost 42

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 5.3.2. Total capital investment 43
5.3.3. Raw Material Cost 45
5.3.4. Operating Labor 46
5.3.5. Unit cost 47
5.3.6. Profit analysis 47
5.3.7. Rate of return and payback period 48
5.4. Plant location and environmental pollution 49
5.4.1. Plant location 49
5.4.2. Environmental pollution 49
CHAPTER SIX 50
6. CONCLUSIONS AND RECOMMENDATION 50
6.1. Conclusions 51
6.2. Recommendation 51
References 52
Appendices 54

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 List of Tables

Table No. Title Page

2.1. Classification of plastics based on their application 4
2.2. Types of plastics and common uses 5
2.3. Dissolution temperatures and recovery weight percentage of 17
different polymers in pure and blend solvent at various ratios by
dissolution technique.
2.4. Experimental Extraction Efficiencies Using Xylene as a 21
Solvent Selective Dissolution.
2.5. Physical properties of C8 aromatic compounds 24
3.1. Materials Used for the experiment 34
4.1. Laboratory results 36
5.1. Purchased equipment cost 42
5.2. Total capital investment 43
5.3. Operating labor cost 46

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 List of Figures
Figure No. Title Page
2.1. Classification of plastics based on their hardening Process 3
2.2. FTIR Spectra for LDPE: a) virgin; b) waste; c) recycled. 18
2.3. FTIR Spectra for HDPE: a) virgin; b) waste; c) recycled. 19
2.4. FTIR Spectra for PP: a) virgin; b) waste; c) recycled. 19
2.5. Single Solvent Dissolution process description 20
2.6. Effect of dissolution temperature on the recovery of polymer 27
from waste polyolefins using xylene
2.7. Block flow diagram for Polymer dissolution as sorting and 30
pelletizaton
2.8. Simplified scheme of plastic molding 32
5.1 Process flow diagram 41
5.2 Break even analysis graph 48

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 List of Acronyms and Abbreviations

ABS Acrylonitrile-butadiene-styrene
AS Anti-solvent
CO2 Carbon dioxide

CRM Raw material cost

TPC Total production cost
FCI Fixed capital cost
COL Labor cost
DSC Differential scanning calorimetry
FTIR Fourier transform infrared
HDPE High density polyethylene
LCPS Liquid crystalline polymers
LDPE Low density polyethylene
MIF Malt flow index
MJ Mega joule
MSW Municipal solid waste
NMP n-methyl-2-pyrrolidinone
NOX Nitrogen oxides
PEEK Polyether ether Kenton
PET Polyethylene terephthalate
PP Poly propylene
PS polystyrene
PVC Polyvinyl chloride
RI Refractive index
RIP Renesselaer polytechnic institute
S Solvent
SAN Styrene-acrylonitrile
SDP Selective dissolution/precipitation
SO2 Sulphur dioxide
STP Standard temperature and pressure
THF Tetrahydrofuran
TLCP Thermotropic liquid crystalline polymer
UTM Universal testing machine

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 List of appendix
Appendix No Title Page
I. photos 54

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RECYCLE OF PLASTICS USING SOLVENT

CHAPTER ONE

1. INTRODUCTION

1.1. Background

Plastics are made up of individual molecules called monomers, which are linked together to form
long chains called polymers. Various types of polymers can be made from hydrocarbons derived
from coal, natural gas, oil and organic oils which are transformed into materials with desirable
properties. Each polymer has unique chemical properties, physical properties, and functions [4].
During last decades, the great population increase worldwide together with the need of people to
adopt improved conditions of living led to dramatically increase of the consumption of polymers
plastics. Plastics find application in almost all aspects of modern society but their waste and
environmental management remains a challenge. Plastics is extensively used by the people and are
referred to as one of the greatest advancement of the millennium. The prominence of plastic
pollution is correlated with plastics being inexpensive and durable, which lends to high levels of
plastics used by humans.
Plastics have become an important environmental issue even though they do not generally possess
a direct hazard to the environment. Rapid industrialization and population explosion in the world
has generate thousands tons of municipal solid waste daily, which is one of the important
contributors for environmental degradation at national level. Improper management of municipal
solid waste (MSW) causes hazards to inhabitant.

Plastic pollution has the potential to poison animals, which can then adversely affect human
food supplies. Plastics are non-biodegradable; they cannot be easily returned to the natural carbon
cycle; hence the life cycle of plastic materials ends at waste disposal facilities. The growing
number of plastic wastes connected with growth of population and socio economic change of
countries becoming a serious global issue. To overcome these environmental effects treatment and
recycling of waste plastics gained the utmost importance. In developing countries the scope for
recycling of plastics is growing as the amount of plastic being consumed increases. Collecting,
sorting and recycling plastic waste becomes a viable activity

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Polymer can be separated and recycled using different techniques. For this purpose different
solvents/non-solvents were examined at different weight percent amounts and temperatures using
either model polymers as raw material or commercial products (packaging film, bags, pipes, and
food retail products). Two solvents with different properties were chosen for the recycling process,
based on the fact that plastics can be dissolved in solvents with similar values of the solubility
parameter.

1.2. Statement of the problem

Products made of plastics degrade slowly in landfills and take approximately 20-30 years to get
completely decomposed. This poses a severe effect on our environment mainly because of
additives used in plastic products as these additives contain many toxins such as lead and cadmium.
Studies suggest that cadmium contained in plastic products has the potential to percolate other
systems and can have extremely harmful consequences for a number of bio-systems. Recycling is
the best available option in our hand to handle this situation in an eco-friendly and cost effective
way. It is also an alternative way of producing different products from an already used waste
plastics that could substitute or used along with polymer based raw materials with high efficiency,
economically feasible and environmental friendly processes.

1.3 Objective

1.3.1 General Objective

 The objective of this project is recycle of waste plastics using effective solvent
1.3.2 Specific Objectives
 Reduction of environmental pollution due to plastic wastes.
 Increase supply of plastic materials which decrease dependency on products from polymer
based raw materials.
 Evaluate techno economical visibility of recycling plastics by using solvent.
1.4 Scope of project
This paper is intended to provide an insight on the recycling of plastic wastes by using solvents in
efficient and economical way by investigating different raw materials, equipment’s, and
operational parameters.
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CHAPTER TWO

2. LITERATURE REVIEW

2.1 Fundamentals of Plastics

Plastics are made up of long chain molecules called polymers. Early plastic resembled as natural
resins. These natural resins are organic solids that break with a conchoidalfracture in contrast to
the planar surfaces created upon the fracture of crystalline materials or the drawn-out zones formed
up on the breaking of gums and waxes. Natural resins refer mainly to oleoresins from tree sap but
is also used for shellac, insect exudations, and mineral hydrocarbons.

2.2 Classifications of plastics

Plastics are classified under thermosetting and thermoplastic based on their hardening process.

Plastics

Thermoplastics Thermosets

Fig.2.1 Classification of plastics based on their hardening Process.

Thermoplastics are formed by simple cooling of polymer melt, and soften again if heated. They
are normally composed of fairly high molar mass molecules because many physical properties
effectively become molar mass independent only above certain molar mass, for instance melting
temperature and the moduli of elasticity. Thermosets are usually generated from fairly low molar
mass polymer called oligomers (science) or prepolymers (industry).

Plastics are usually divided into four groups based on their application. These are Commodity
plastics (standard plastics), Engineering plastics (technical plastics), High performance plastics
and functional plastics. Functional plastic only serve specific task. Commodity plastics are
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manufactured in great amounts and hence the terms bulk plastics or standard plastics. Engineering
plastics possess improved mechanical properties compared to commodity plastics. Such improved
properties may be higher module of elasticity, smaller cold flows, higher impact strengths etc.
Engineering plastics are also often defined as those thermoplastics that maintain dimensional
stability and most mechanical properties above 1000C or below 0oC.

Table 2.1classification of plastics based on their application

Commodity Plastics Poly vinyl chloride

Polyethylene (High and low density)

Isotactic polypropylene

Standard polystyrene

Engineering plastics Polyethylene teraphatalate

Poly butylenesterephatalte

Poly amides

Poly Carbonates

Polyoxymethylenes

Poly methyl methacrylate

Styrene-acrylonitrile (SAN)

Acrylonitrile-butadiene-styrene(ABS)

High performance Liquid crystalline polymers(LCPs)

Polyetherether ketone(PEEK), Poly sulfonene

Plastics are classified in to different groups based on their common uses. The six most common
types of plastic can easily be recycled. The plastics industry has voluntarily devised a coding

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system which makes recycling plastics easier. The following table shows these six types of plastics
with their identification code, general properties and common uses. (5)

Table 2.2 Types of plastics and common uses

Type of Identifi General properties Common uses

plastic cation
code

Polyethylene Clear Mineral water bottles

terephthalate Hard
(PET/PETE)
Tough Cooking oil bottles

Barrier to gas and water Powder detergent jars

Resistance to heat Fiber for clothing

Resistance to grease/oil for carpets

Strapping

Peanut butter jars

High density Barrier to water Jerry cans

polyethylene Chemical resistance “Crinkly” shopping
(HDPE) bags
Hard to semi-flexible
Film
Strong
Milk packaging
Soft waxy surface
Toys
Low cost
Buckets
Permeable to gas
Rigid pipes
Natural milky white colour

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Crates

Bottle caps

Polyvinyl Transparent Pipes and fittings

chloride Hard, rigid (flexible when Carpet backing
(PVC) plasticised) Window frames Water,
Good chemical resistance shampoo and vegetable
oil bottles
Long term stability
Credit cards
Electrical insulation
Wire and cable
Low gas permeability
sheathing

Floor coverings

Shoe soles and uppers

Low density Tough Agricultural films

polyethylene Flexible Refuse sacks
(LDPE) Waxy surface Packaging films

Soft - scratches easily Foams

Good transparency Bubble wrap

Low melting point Flexible bottles

Stable electrical properties Wire and cable

applications
Moisture barrier

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Poly Excellent chemical resistance Yoghurt containers

propylene (PP) High melting point Potato crisp bags

hard, but flexible Drinking straws

Medicine bottles crates,
Waxy surface
plant pots
Translucent

Strong

Car battery cases

Polystyrene • Clear to opaque Packaging pellets

(PS) Glassy surface Yoghurt containers
Fast food trays
Rigid
disposable cutlery
Hard
Coat hangers
Brittle

High clarity

Affected by fats and solvents

Other plastics Mostly not available in

sufficient quantities for
recycling

2.3 Application of plastics

Plastics are being implemented in all branches of industry and everyday life and represent useful
modern technical materials with versatile and to some extent, irreplaceable applications. It seems
difficult today to imagine our world without plastic devices. In fact, since the end of the Second
World War (1945), almost all the industrial sectors such as, agriculture, building construction,
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communication, packaging, medicine, transport, defense etc. use at least one plastic material in
some way. Plastics have high resistance to physical and chemical attack; light weight is also
characteristics of plastics. General applications of plastics include clothing, packaging, in
manufacture of machinery, motor vehicle, in agriculture, electronics and communication
technology. Now a day’s high composite materials are used in Air space travel, construction, sports
and recreation.

2.4 Advantages and Disadvantages of plastics

Lower energy cost per unit volume in processing plastics, durability, corrosion resistance,
chemical resistance and low weight makes their application advantageous than other materials.
Disadvantages are those plastics that are manufactured for short term use are polluting and
occupying large areas in the landfill. Most plastics are designed to survive on most unfavorable
conditions, these made them un-degradable biologically and by Ultra Violet radiation.

In addition, the waste created by public works and building construction sectors consumes nearly
1 300 000 tons of plastics every year. The wastes are mainly films, pieces of pipes, profiles etc.
The waste plastics are known for creating a very serious environmental challenge because of their
huge quantities and the disposal problems caused by them. To avoid the impact of the plastic in
the environment, the recycling of plastics constitutes a valid alternative.(20)

2.5 Source of plastic wastes

a. Technological wastes, manufacturing wastes or processing wastes

These occur during the production phase of plastic devices and they are usually collected
immediately. Directly or after chopping or crushing they can be recycled

b. Further Processing Wastes or Confectioning Wastes

These are usually produced in the course of processing and confectioning of the semi-finished
products. They are clean, and either repurchased by the manufacturers of the semi-finished
products, or purchased by companies specialized in waste recycling. Thus the problem of their
management is solved .Wastes of plastic products after they have been used (packaging materials,

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hollow articles, used products): This category of wastes causes the most significant problem. The
main sources of plastic wastages are the industries, agriculture and household materials. (5)

2.6 Methods of reusing and disposing plastic wastes

2.6.1 Hydrolysis

Leads to direct recovery of the original raw materials by targeted reaction of water molecules
at the linkage points of the starting materials.

2.6.2 Alcholysis

Chemical degradation of poly urethanes can be achieved by alcholysis to give a polydioxy

alcohol and small urethane fragments formed by trans esterification.

2.6.3 Hydrogenation

In hydrogenation the C-C bonds of poly-olefins and polystyrene are broken by the addition of
hydrogen. Alkanes are by far the largest group of products results from this mild decomposition
process.

2.6.4 Combustion

The calorific value of plastics is very high. Almost 94% of oil products are used in heating purpose.
There would be no objective to this form of energy recycling since it allows the substitution of the
oil and reduces the volume of garbage.(7)

Major drawbacks with combustion of plastics wastes are with emissions. Halogen containing
plastics such as polyvinylchloride and polytetrafluoroethylene create problems as they release
substantial volumes of hydrogen chloride and fluoride on combustion. Furthermore, combustion
releases metals, dyes, stabilizers, pigments and plasticizers.

2.6.5 Dumping and degradation

Because of highly visible lighter problem by materials such as plastic bags, bottles and containers
and the need to reduce space demands in dumping sites, it is often demanded that plasters should
by bio- and UV-degradable.

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2.6.6 Pyrolysis

Pyrolysis is a thermal cleavage in complete or partial absence of air, accompanied by continuous

generation of pyrolysis oils and gases suitable for chemical utilization or generation.
Thermoplastics, thermosets, elastomers and composite materials can be recycled by pyrolysis.
Major advantage of pyrolysis is 5 to 20-fold reduction in the volume of product gases which reduce
gas purification. Up to 50% of the input material can be recovered in the liquid form mixture of
gasoline and bituminous coal 95%. The product gases are high energy fuel gases with a calorific
value of 50 MJ/M3 at STP. The main gaseous compounds are methane, ethane, ethylene and
propylene.

2.6.7 Recycling

Recycling plastics has many benefits, it contributes to energy savings and the reduction of
greenhouse gas emissions. It also saves non-renewable sources like oil and gas. In addition to that,
recycling provides livelihood for millions of people and families in developing countries, either in
the form of formal employment or informal economic activities. Although there is also a rapid
growth in plastics consumption in the developing world, particularly due to the increasing demand
for plastics from Asia, plastics consumption per capital in developing countries is much lower than
in the industrialized countries. However, there is a much wider scope for recycling in developing
countries due to several factors:

• Labour costs are lower.

• In many countries there is an existing culture of reuse and recycling, with the associated
System of collection, sorting, cleaning and reuse of ‘waste’ or used materials.
• There is often an ‘informal sector’ which is ideally suited to taking on small-scale recycling
activities. Such opportunities to earn a small income are rarely missed by members of the urban
poor.
• There are fewer laws to control the standards of recycled materials. (This is not to say that
standards can be low – the consumer will always demand a certain level of quality).
• Transportation costs are often lower, with hand or ox carts often being used.
• Low cost raw materials give an edge in the competitive manufacturing world.

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• Innovative use of scrap machinery often leads to low entry costs for processing or
manufacture.(10)

Recycling of plastics can have several advantages. Some of them are listed below.

1. Conservation of non-renewable fossil fuels as plastic production uses 8% of the world’s

oil production, 4% as feedstock and 4% during manufacture.
2. Reduced consumption of energy.
3. Reduced amounts of solid waste going to landfill.
4. Reduced emissions of carbon-dioxide (CO2), nitrogen oxides (NOx) and sulphurdioxide
(SO2). Reduction in toxic chemicals into water.
2.7 Approach for plastics recycling
I. Primary recycling refers to the ‘in-plant’ recycling of the scrap material of controlled
history. This process remains the most popular as it ensures simplicity and low cost, dealing
however only with the recycling of clean uncontaminated single-type waste
II. Chemical or Feedstock recycling (tertiary recycling

Has been defined as the process leading in total depolymerization of PET to the monomers, or
partial depolymerization to oligomers and other chemical substances. The monomers
depolymerized to regenerate the original polymer

III. Energy recovery

Refers to the recovery of plastic’s energy content. Incineration aiming at the recovery of energy
is currently the most effective way to reduce the volume of organic materials. Although polymers
are actually high-yielding energy sources, this method has been widely accused as ecologically
unacceptable owing to the health risk from air born toxic substances. Apart from the
aforementioned methods, direct reuse of a plastic material (e.g. PET) could be considered as a
“zero order” recycling technique.(19)

In a lot of countries it is a common practice PET-bottles to refilled and reused. However, this
should be done with a great care since plastic bottles are more likely than glass to absorb
contaminants that could be released back into food when the bottle is refilled. Moreover, refill of

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a PET-bottle with a high-alcoholic-degree drink may lead to degradation of the macromolecular

chains with unexpected results.

2.8 Plastics recycling using solvent

Plastic recycling are usually referred to as the processes in which plastic wastes are collected,
separated, processed and returned to useful products. Developing an efficient and cost-effective
method for recycling plastic wastes that have served their intended purpose, retrieving them from
the waste stream and getting them back into the manufacturing process requires collection, sorting
and cleaning and finally reclamation which has been discussed in the earlier sections. For
homogeneous plastic waste streams, recycling by mechanical methods is the economically
preferred recovery option.(15)

Recycling is a function of separating only mixed, heterogeneous systems of polymers that were
adhered together due to glues, resins, or melt welding. These polymers were not intimately blended
to a degree that the size of the pure polymeric phases was on the order of microns. Because this
level of blending is found in the thermotropic liquid crystalline polymer / thermoplastic
composites, these techniques cannot be utilized. However, these techniques do support the
probability that the TLCP/TP composite system can be separated if the right conditions can be
determined and met. The same principles of utilizing differences in physical properties, to effect
a separation, can be used in developing a new process of separating these well blended systems.(9)

Fortunately, there is another method of separating well mixed polymeric materials.This method is
called selective dissolution and it deals with utilizing temperature and a solvent to bring about the
desired separation. This method works on the principle of solubility, as a function of temperature,
to dissolve only certain polymers at certain temperatures. Each of the polymers present can be
dissolved and then crystallized separately.(21)

The selective dissolution technique is broken down into two main process steps. The first step
involves adding the polymeric mixture to a solvent that has been specially chosen, and which
depends on the polymers present within the blend. This solvent is able to dissolve all of the
polymers included within the mixture, but only as a function of temperature. After dissolution,
the next step in the process is called flash devolatilization and it involves evaporating the solvent
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away from the separated polymer. The separated polymer is removed and then the evaporated
solvent is condensed and returned to the dissolution chamber for further use.

The second type involves only one solvent which is used to dissolve only one polymer in the
mixture. The first category is used to dissolve all of the polymers in the mixture and then to use
different temperatures to selectively crystallize out each polymer. The main drawback to this
process is finding a solvent that will dissolve all of the polymers present in the mixture. The more
common method used, category 2, is to find a solvent that will either only dissolve the desired
polymer, or it will dissolve all of the other polymers except the desired one.(11)

Plastics mixtures are not homogeneous. They may consist of a large number of grades with
different molecular structures and properties; and each plastic component in a mixed waste has
different melting behavior, rheology, and thermal stability. Plastic mixtures are usually
incompatible to each other and form discrete phases within a continuous phase. Plastic wastes have
relatively low density compared to virgin grades. The techniques used for separation of different
kinds of plastics are based on differences in density, shape, color, physicochemical properties and
solubility. The solubility-based processes include stages of dissolving a series of incompatible
polymers in a common solvent at various temperatures or in different solvents, so that one polymer
is separated each time. These processes differ in the method employed to recover the polymer after
the dissolution stage. It can be recovered either by rapid evaporation of the solvent or by adding a
proper ‘antisolvent’ that makes the polymer precipitate, like in the selective
dissolution/precipitation (SDP) method studied here. So far, the SDP has been successfully applied
in a laboratory scale for the recycling of PP pipes.(13)

2.8.1 History of plastics recycling using solvent

The first recycling plant to use the UN PET process was built in Switzerland in 2000, and there
are now eight around the world. The FDA has granted approval for plastics recycled in this way
to be used in food and drink packaging, Selective dissolution and flash devolitization is a plastic
sorting option that is still in the research stage. The process separates mixed or commingled plastics
waste into nearly pure reusable polymers without mechanical presorting techniques. The research
performed at the Renesselaer Polytechnic Institute (RPI), xylene is used to individually dissolve

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five of the most common post-consumer plastics: PVC, PS, LDPE, HDPE, and PP. When xylene
is placed into the plastic chip system at room temperature, the PS dissolves leaving the remaining
plastics untouched. The xylene/PS solution is next drained to another tank where the solution is
heated above xylene’s boiling point. The solution is then sent to another chamber where the
pressure is lowered quickly causing the xylene to rapidly vaporize.

This leaves behind the pure polymer PS in a flash devolitization step . The xylene is recovered and
fed back into the plastic chip system where the process is repeated at different temperatures, each
plastic with its own individual dissolution temperature in xylene. The other common post-
consumer plastic, PET, needs to be removed using a separate solvent. (15)

Other research performed at Cornell University finds that a one solvent system is not enough.
Problems that the Cornell research team found with the RPI method include the following: high
pressures involved in the process lead to high energy and equipment costs, high temperatures
increase the risk of thermally degrading the polymers, and reduced purity of polymers due to a
single solvent system. The reduction in polymer purity results from partial dissolution of polymers
at lower temperatures than intended and undissolved particles adding to the mix to be dissolved at
higher temperatures. (11)

The Cornell study suggests the use of a combined technology process for sorting plastics. Their
process would begin with separation of non-olefins and polyolefins by a simple sink float system.
Then selective dissolution would be the next step with a different solvent for each plastic group.
‘This technique would combine the ease and cost-effectiveness but low purity of sink float systems
with the high purity but high cost of selective dissolution. (12)

The reduction in polymer purity results from partial dissolution of polymers at lower
temperatures than intended and undissolved particles adding to the mix to be dissolved at high T.
The suggested solvent for the dissolution of PET (formerly a problem plastic in the
original all xylene RPI process) is n-methyl-2-pyrrolidinone (NMP). This choice of
solvent was determined upon the criteria of cost, toxicity, solvent recovery, favorable
PET solution behavior, and incompatibility with polyolefins (HDPE, LDPE, and PP. (11)

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Some work has been done on using this method to separate six engineering plastics from a mixture
[14]. The six engineering plastics used were: polyvinyl chloride (PVC), polystyrene (PS), low
density polyethylene (LDPE), polypropylene (PP), high density polyethylene (HDPE), and
polyethylene terephthalate (PET). The particular solvent chosen was tetrahydrofuran (THF), which
is a four carbon, aliphatic heterocyclic ether. This polymeric mixture was shredded down and then
combined with the THF in a tubular vessel. The flow of THF across the solids was started and the
system was heated to 25 oC.

The first extraction of solvent was sent to the devolatilization chamber, where the solvent was
evaporated away from the dissolved polymer(s). The solvent was condensed and then sent back
into the selective dissolution chamber. The temperature was raised to 70 oC and then the next
extraction was sent to the flash devolatilization chamber. The same evaporation process was
performed and the dissolved polymer(s) was collected. The first extract, at 25 oC, resulted in the
separation of both the PVC and the PS from the polymeric mixture. The next extract, at 70 oC,
resulted in the separation of only the LDPE from the polymeric mixture. The subsequent extract,
at 160 oC, resulted in both the PP and the HDPE being separated from the mixture. Finally, the
190 oC extract resulted in the separation of only the PET from the six polymer mixture. All of the
extractions resulted in a greater than 99% efficiency of separation from the polymeric mixture in
the selective dissolution chamber. (6)

However, only the PET and the LDPE were successfully isolated from the six polymer mixture.
The rest of the extracts contained two polymers that were still commingled together. Overall, this
type of selective dissolution process is somewhat effective in separating polymers that are well
mixed.

In recent years, there has been a dramatic increase in investigating ways in which mixed plastics
can be recycled or reclaimed for reprocessing. Population growth in large urban centers, social and
technological developments and changes in consumers’ habits have led to greatly increasing
amounts of solid wastes. Thus, nowadays, waste management is one of the most significant issues
that modern society deals with. It is estimated that in Greece the increase of waste produced in
urban regions has exceeded 20% from 1987 to 1994. Today more than 3,600,000 t/year of waste

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are produced in Greece, 1,500,000 t/year of which in the region of Athens. The typical composition
of this waste is 19.5% paper, 4% metal, 2.5% glass, 7% plastics, 59%food waste and 8% various
materials .(21)

Despite the fact that polymers contribute only 7.0% to the total weight of the solid waste, they are
sometimes responsible for more than 30% of its volume, causing significant problems in the
landfill sites. In addition, polymers are non-biodegradable materials and, thus, they retain their
initial form for a very longtime. The suitability of polymers for a large number of applications and
uses is a consequent result of their numerous advantages: polymers are lightweight, flexible and
versatile, offering many practical benefits to various uses. They match optimum design with
functional solutions, they are economic to produce in custom-made forms and are extremely
durable.(5)

At Malaysia Sdn Bhd Xylene and the three grades of petroleum ether were tested as solvents using
different compositions as shown in Table 2.2 n-Hexane, and petroleum ether in the three grades
were used as non-solvents. In order to recognize the polymer class from which the used plastic
material was made of, its FTIR spectra was recorded and compared to the corresponding virgin
polyolefins polymer. Figures 2.2–2.4 represent the FTIR graphs of polyolefin classification, which
correspond to LDPE, HDPE and PP, respectively. The distinction between each polymer was made
clearly, even though the differences between the characteristic bands are not large. (15)

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Table 2.3 Dissolution temperatures and recovery weight percentage of different polymers in pure
and blend solvent at various ratios by dissolution technique

Composition of the blend Dissolution temperature, °C Recovery percentage

solvents as a volume ratio
LDPE HDPE PP LDPE HDPE PP

Xylene 75 100 118 99.4 98 98

Xylene/petroleum
ether (A)

25:75 68 68 68 49 Zero Zero

50:50 89 89 89 97 40 Zero

75:25 100 100 100 99 92 50

90:10 100 100 108 99 97 85

Xylene/petroleum
ether (B)

25:75 80 80 80 90 Zero Zero

50:50 67 95 98 99 89 90

75:25 75 100 105 99 93 91

90:10 75 100 105 99 97 97

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Xylene/petroleum
ether (C)

25:75 80 100 100 99 89 45

50:50 70 100 108 98 97 94

75:25 70 100 108 98 96.4 94.9

90:10 75 100 118 99 98 98

Figure 2.2 FTIR Spectra for LDPE: a) virgin; b) waste; c) recycled.

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Fig 2.3 FTIR Spectra for HDPE: a) virgin; b) waste; c) recycled.

Fig 2.4 FTIR Spectra for PP: a) virgin; b) waste; c) recycled.

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Figure 2.5 Single Solvent Dissolution block Flow diagram.

As mentioned above Polyolefins (LDPE, HDPE and PP) are prominently used thermoplastics for
items such as bags, toys, containers, pipes, industrial wrappings, film, house ware, gas pipes
(HDPE), battery cases, automotive parts and electric components. In line with the high recent
growth in logical polymer synthesis [7], this paper examines the recycling of polymers from waste
plastic (LDPE, HDPE and PP) using the dissolution method. According to Pappa et al. [8], who
have investigated this technique using a pilot plan, the cost of the recycled polymer from this
method has the same cost of the virgin polymer. The purpose of repeating this investigation is to
examine the new solvents and non-solvent with new anti-solvent ratios to reduce the cost of the
polymer recycling. Heterogeneous plastic waste streams, however, are more efficiently treated or
handled by chemical and thermal processes, for recovery of basic chemicals and /or energy.(12)

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By taking advantage of the physical and chemical properties of polymers, new processes that
eliminate the sorting step can be implemented. This process is known as plastic recycle by solvent.
In general this process starts with comingled plastics being shredded, washed, and dried, then
placed in a dissolver where a solvent is added. At a certain temperature polymer dissolves and
drains through a filter from the dissolver to be placed in a holding tank. Next, more solvent is
added and the temperature is increased to dissolve the next polymer resin. The process is repeated
until only undissolved are left in the mix. (9)

2.8.2 Solvent selection

When looking at using solvents to dissolve a polymer, some very important issues arise that are
applicable to developing a process that is industrially and environmentally suitable. The area of
toxicity, volatility, and cost are the main issues that must be addressed when dealing with using
solvents to generate a new, recycling process. Another important area in using solvents is that, due
to the large molecular structures of polymeric materials, the thermodynamics begin to play a very
important role in solubility. The best solvent for dissolution of polyethylene is Xylene because it
is simply available, low cost, low contamination, and low toxic.(16)

Table 2.4 Experimental Extraction Efficiencies Using Xylene as a Solvent Selective Dissolution.

material Extraction Temperature(0C) Efficiency (%)

PVC First 25 >99

PS First 25 >99

LDPE Second 70 >99

DDPE Second 100 >99

PP Third 160 >99

HDPE Third 160 >99

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2.8.3 Important Factors in Polymeric Solubility

The area of polymeric solubility has been widely studied over the years and much work has been
done to get at a good fundamental understanding of what influences solubility in the area of
polymers (13). And although much is known in the area of small molecular solubility, less is
known about polymeric solubility. What is understood is that there are three main factors which
control the thermodynamics of polymeric solubility within a solvent. All of these factors are a
function of the thermodynamics behind the mixing of two species. The first factor is the
combinatorial entropy of mixing. This term comes from the entropic effect of mixing the two
species together and relates to the fact that the amount of disorder in the system must increase
when going from a solid polymer to a dissolved polymer. (12)

The next important factor in polymeric solubility is the enthalpic effect arising from the mixing of
the two species. This change can be either positive (the components prefer to be with themselves)
or it can be a negative (the polymer likes the solvent more than itself). And lastly, the other
important factor is the free volume effects between the polymer and the solvent. This factor deals
with the solvent’s ability to surround and contain the polymeric molecule in solution. The
combination of the first two factors is the basis for an important thermodynamic relationship.

In order for a polymeric material to be dissolved, or any other solute, then the Gibb’s free energy
of mixing must be zero or negative [29]. As can be seen in equation(2.1), in order for the total
Gibb’s free energy of mixing (∆Gmix) to be negative, then the enthalpy of mixing (∆Hmix) needs
to be negative or weakly positive and the entropy of mixing (∆Smix) needs to be positive (12)

∆G mix = ∆H mix - T ∆S mix (2.1)

However, because one of the terms will always be positive, the entropy of mixing (∆S mix) , then
the only terms that influence the solubility are the absolute temperature (T) and the enthalpy of
mixing (∆H mix). But, in order for this to be true, then the entropic contribution needs to be
substantially large and positive. It has been seen that for polymeric solutions, the entropy of mixing
is not substantially large in comparison to equivalent masses or volume. This is due to the nature
of polymeric materials and their ability to move and get into different configurations. Small

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molecules can pack tightly together and can rotate around, whereas polymeric chains are confined
to a lower number of conformations.(11)

Based on the principle that polymers, generally, can be dissolved in solvents with similar values
of the solubility parameter, δ, two solvents were selected for the recycling process. These solvents
were xylene [δ=8.8 (cal/cm3)1/2] and n-hexane [δ=8.9 (cal/cm3)1/2]. Polyolefins present a value of
solubility parameter near to 8.0 (cal/cm3)1/2. It is obvious that at all different experimental
conditions and for all commercial samples examined the polymer recovery was always high.
Xylene was found to be a very good solvent for all polyolefins examined. An increase in
dissolution temperature leads to increased polymer recovery values. (18)

Properties of xylene

a) Physical properties of xylene

Because of their similar structure, the three xylenes and the isomeric ethyl benzene exhibit
similar properties. The distillation characteristics of the C8 aromatic compounds are of
considerable importance.

O-xylene is more readily separated from m-xylene because of a 5°C difference in boiling point.
The difference in freezing point between the p-xylene and other C8 aromatic compounds is utilized
for p-xylene separation. The critical compression ratios are 14.2, 13.6, and 9.6 for p-xylene, m-
xylene and o-xylene respectively. The research octane values are 113, 116.4, 117.5 and 107.4 for
Ethyl benzene, p-xylene, m-xylene and o-xylene respectively. The physical properties of these for
compounds are summarized as follows:

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Table 2.5 physical properties of C8 aromatic compounds

Property p-xylene m-xylene o-xylene Ethyl benzene

Molecular 106.167 106.167 106.167 106.167

weight

Density @ 0.8610 0.8642 0.8802 0.8671

25°C, g/ cm3

Boiling point 138.37 139.12 144.41 136.19

°C

Freezing point 13.263 -47.872 -25.182 -94.975

°C

Refractive 1.4958 1.4971 1.5054 1.4959

index @25°C

Surface 28.27 31.23 32.5 31.50

tension mN/m

Dielectric 2.27 2.367 2.568 2.412

constant

@25°C

Dipole 0.0 0.30 0.51 0.36

moment of
liquid, C-m

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Critical Properties

Critical 2.64 2.66 2.71 2.67

density,

mmol/cm3

Critical vol 379.0 376.0 369.0 374.0

cm3/ mol

Critical 3.511 3.535 3.730 3.701

pressure Mpa

Critical 343.05 343.90 357.15 343.05

temperature

°C

Thermodynamic Properties

Cs @25°C, J/ 181.66 183.44 180.7 185.96

(mol. K)

Ss @25°C, J/ 247.36 253.25 246.61 255.19

(mol. K)

(H-H o) @ 44.641 40.616 42.382 40.219

25°C

J/ (mol. K)

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(GS-Ho/ T) @ 97.633 117.03 104.46 120.29

25 °C J/ (mol.

K)

Heat of transition

Vaporization 42.036 42.036 43.413 42.226

@ 25°C

Fusion 17.112 11.569 13.598 9.164

Formation @ -24.43 -25.418 -24.439 -12.456

25°C

Entropy of 247.4 252.2 246.5 255.2

formation

Vapor Pressure, Antoine Equation

A 6.1155 6.1349 6.1239 6.0821

B 1453.4 1462.266 1474.679 1424.255

b) Chemical properties

Reactions involving the position of the alkyl substituents

These reactions include isomerization, disproportionation and dealkylation. Acids catalyze the
interconversion of the three-xylene isomers. Xylenes isomerize to near equilibrium levels in a
hydrogen fluoride–boron trifluoride system with low boron trifluoride concentrations.

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Isomerization at lower temperatures produces more p-xylene and o-xylene .All category of xylene
are good solvent for all thermoplastic plastics

2.8.4 Factors affecting rate of dissolution

1. Bulk size

We know that when the size decrease surface area will be increased. We should have to cut waste
plastics in to small size of less than 2 cm to achieve uniform mixing and it also increase contact
surface area bulk polymer with solvent. This also encourage heat transfer rate.
2. Temperature

The following Figures illustrate the effect of the dissolution temperature and the initial
concentration of the polymer on the wt.% recovery of the three waste polyolefins (LDPE, HDPE
and PP). The polymer recovery remained high at all experimental conditions. High polymer
recovery corresponds to high dissolution temperature and low initial polymer concentrations. The
recovery of LDPE was higher than HDPE and PP even at low dissolution temperature.

Figure 2.6 Effect of dissolution temperature on the recovery of polymer from waste polyolefins
using xylene

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3. Time

Dissolving Time is one of the most influencing factor for dissolution of plastics. Each plastics
have specific time to completely dissolve in specific solvent.

2.8.5 Measurements used to characterize final product

Fourier transform infrared (FTIR). FTIR was used to determine the functional group
of the product, based on the peak value. The chemical structure of the standard polymers and waste
sample plastics, before and after the restoration process was confirmed by recording their IR
spectra. The instrument used was a Nicolet (Magna-IR560) FT-IR spectrophotometer with a
resolution of 4 cm–1. The recorded wavenumber range will be from 400 to 4000 cm–1.

Differential scanning calorimetry (DSC). Thermal properties such as melting

temperature (Tm) and heat of fusion of the polymer produced after recycling, the waste samples
and the model polymers was measured using a DSC Q1000 (V9.6, Build 290) from TA
Instruments. 10 mg samples were prefaced onto the instrument and the heat emitted was recorded
at a temperature interval of 20–300 °C and a scan rate of 10 °C/min, in N2 atmosphere.

Universal testing machine (UTM) .A Shimadzu AG-X universal testing machine is used to
measure the mechanical properties of the virgin and waste polymers before and after recycling.
Stress at maximum load, strain at break, stress at yield and elasticity must be noted. There are five
specimens to be examined for each sample and the average values is reported. The testing was
performed according to the standard method (ASTM D638-03).

2.8.6 Drawback of solvent recycling

The main disadvantages of this process are that it may only separate certain polymers from the
mixture, the chosen solvent must be able to dissolve all or at least one of the polymers present, and
it utilizes solvents that are hazardous and / or toxic to use. The most important point of this process
is that it can successfully separate well mixed systems, but it may run into difficulties in dissolving
intimately blended polymers. The starting materials used in this study were not well blended, but
were just a mixture of pure components

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2.8.7 Process description

Shredder-fragmentation

After the cleaning and sorting of plastic wastages, it has to be cut into smaller pieces before
recycling. This shredder-fragmentation operation aims to reduce the size of the waste which in
turn facilitates not only in the separation of different polymers, but also to recover the micronized
powders that used to feed processing machines. The end products of shredding can be irregularly
shaped pieces of plastics that can then be sold to reprocessing industries and workshops. In this
method depending on the quality and type of raw material and the desired quality of the end
product, different types of plastic wastes may be mixed to a certain extent.(5)

Agglomeration

Clean film sheet is processed in an agglomerator. The agglomerator consists of a vertical Crum
with a set of fast moving blades in the bottom. The agglomerator chops the sheets into thin film
flakes. Due to the cutting and friction energy of the process, the flakes are heated until they start
to melt and form crumbs or agglomerate. This will increase the bulk density of the material which
is now fit to be feed directly into the extruder.(8)

Pelletizing
For many purposes it is recommended to convert plastic flakes or agglomerate (crumbs) into
pellets before processing. The plastic pieces are fed into the extruder, are heated and then
forced through a die to form a plastic spaghetti which can then be cooled in a water bath
before being chopped into pellets.

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Fig: 2.7 Block flow diagram for Polymer dissolution as sorting and pelletizaton

Further process after pelletization

Extrusion. The extrusion process used for manufacturing new products is similar to that
outlined above for the process preceding palletization, except that the product is usually in the
form of a continuous ‘tube’ of plastic such as piping or hose.

Injection moulding. The first stage of this manufacturing process is identical to that of
extrusion, but then the plastic polymer emerges through a nozzle into a split would. The quantity
of polymer being forced out is carefully controlled, usually by moving the screw forward in the
heated barrel. A series of moulds would be used to allow continual production while cooling takes
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place. This type of production technique is used to produce products such as plates, bowls, buckets,
etc.

Blow moulding. Again the spiral screw forces the plasticized polymer through a die. A short
piece of tube, or ‘parison’ is then enclosed between a split die -which is the final shape of the
product - and compressed air is used to expand the parison until it fills the mould and achieves its
required shape. This manufacturing technique is used for manufacturing closed vessels such as
bottles and other containers.

Film blowing. Film blowing is a process used to manufacture such items as garbage bags. It is
a technically more complex process than the others described in this brief 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. Sheet plastic can also be manufactured using a variation of the process described.

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Fig. 2.8 Simplified scheme of plastic molding

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CHAPTER THREE

3. MATERIALS AND METHOD

3.1 Study area description

The study is conducted in the laboratory with set up of different equipment

3.2 Sampling Techniques

Sample is taken from high density poly ethylene plastics with size distribution (thickness) lower
than 2cm.

3.3 Physical and chemical properties measured

 Physical properties measured are mass and Volume raw materials
 Dissolution temperature and time required to complete dissolution
 Size distribution of input plastics

3.4 Materials used

Model plastic obtained from Adama science and technology university waste plastic storage. It
is category of commercial products made from high density poly ethylene. The solvent used are
xylene for reagent grade (solvent) and n-hexane as non-solvent (precipitating agent).

Preparation of used poly ethylene product sample

The waste plastic containers were first rinsed with tap water and then cut with a scissor into
random pieces of 2–4 cm in size. The pieces were then cleaned with distilled water and placed in
simple vacuumed oven for 3 h at 50 °C.

Dissolution/re precipitation technique in a first approach, model HDPE was used together with
different commercial products containing HDPE. Xylene was used as solvents, while n-hexane as
non-solvent. Some other parameters include concentration of the polymers: 20% w/v, solvent/non-
solvent volume ratio: 1/3 and different dissolution temperature below the boiling point for each
solvent. The solvent and pieces of waste polymer were added to a flask. A mercury thermometer
was to measure temperature, and a stirrer to achieve uniform mixing. An electric stove was used
for heating purpose and a high speed stirrer doing the mixing. The system was heated for 24-30
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min and brought to the desired temperature. Once the polymer pieces had dissolved completely,
the flask was removed from the electric stove and left to cool for 15–30 min, after which the
solution was carefully poured into a non-solvent. The precipitate was then washed, filtrated and
dried at 70 °C in a vacuumed oven for 10 h. The resulting polymer or the pellet was in granular
(powder) form.

3.5 Laboratory procedure

3.5.1 Equipments used

Table 3.1 Materials Used for the experiment

Equipments Capacity

Glass connecting Tube with three Outlets -

Electrical Stove 400w

Digital Balance -

Glass fiber insulating material -

Measuring Beaker -

Erlenmeyer flask -

Laboratory cutting mill -

Glass tube condenser -

3.5.2 Raw materials Used

High Density density Polyethylene

n-hexane

Xylene, Distilled water

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3.5.3 The procedures for recycling

Step 1: Cutting the waste into smaller pieces and washing with water.

Step 2: Preliminary separation of the initial mixture to two or more mixtures by floatation
in water or another liquid.

Step 3: Addition of a solvent (S) that selectively dissolves only one of the polymers at
certain conditions.

Step 4: Heating of polymer at a certain temperature which varies based on target type of
plastics to dissolve

Filtration to remove the non-dissolved polymers.

Step 5: Addition of an anti-solvent (AS) to precipitate the dissolved polymer.

Step 6: Separation of the S/AS mixture by distillation for reuse.

Step 7: Drying and Filtration of the precipitated polymer.

Step 8: Production of pellets

3.6 Recycling of the solvents

The solvent mixture was separated using a simple distillation process. The total amount of the
solvent and non-solvent used in the experiment was 2400 ml (600 ml xylene and 1800 ml n-
hexane). Approximately 1750 ml of the mixture was received from filtration while the remaining
650 ml was evaporated by drying since oven is not suited for solvent recycling. The solvents,
especially n-hexane, have high vapor pressure and some amount was lost during handling. Only
1200 ml of n-hexane was separated from mixture.

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CHAPER FOUR

4. RESULTS AND DISCUSSION

4.1 Recycling of plastics by the dissolution/reprecipitation technique

One solvent/non -solvent systems, three dissolution temperatures and four initial polymer
concentrations were investigated. The effect of these parameters on the time of complete
dissolution of model HDPE and several commercial products based on these polymers was
investigated.

Polymer recovery was favoured by an increase in dissolution temperature and lower

concentrations of polymer in solvent. The type of polymer used did not affect much the recovery
values, while it was observed that HDPE can be recovered in high values even at low dissolution
temperatures. In contrast, lower amounts of polymer were recovered in first experiments.

Table 4.1. Laboratory results

Experimen Solven Weight of Solvent(ml Kg Time recover

t no t ratio sample(LDPE ) plastic/ elapsed for y
S/AS ) L of complete
(S+AS) dissolutio
n

1 1:3 200 g 0.8 1:4 30 min 190 g

2 1:3 300 g 1.6 1:5.3 24 min 292 g

It is obvious that at all different experimental conditions and for all commercial samples examined
the polymer recovery was always high. An increase in dissolution temperature leads to increased
polymer recovery values. This experiment indicates that increase in bulk density have negative
effect on dissolution.

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CHAPTER FIVE

5. TECHNO-ECONOMIC AND FEASIBILITY STUDY

5.1 Material and energy balance

5.1.1 Material balance

Polymer solutions with concentration higher than 20% w/v are quite viscous and, thus, difficult
to handle. In the procedure described below, the concentration of the resulting solutions is chosen
to be equal to 10% w/v. Lower concentrations would result in higher volumes of solvents to treat.
The AS/S ratio used will be 3:1, which is sufficient for complete precipitation of the dissolved
polymers.

Since most of plastic types that exist and cause a great effect are low and high density poly
ethylene. So that we select these as input raw materials. Our design for material balance is the
volume of dissolution vessel. Our design is to process 60 kg feed with 5% impurities at one batch.
A mixture of 30 kg LDPE and 30 kg HDPE fed to the first vessel and 300 liter xylene was added.
The mixture was stirred for 30 min at 70° C to ensure that all the quantity of LDPE has been
dissolved. It was then moved to the second vessel through the preheated (at 70° C) filter to remove
the non-dissolved HDPE pellets. In the second vessel, LDPE was precipitated by adding 900 L n-
hexane. The mixture was filtered back to the first vessel and 177 kg wet LDPE was received on
the filter. The wet LDPE was dried under vacuum at 70° C for 10 h.

Mass Balance

We use the law of conservation of mass which states that Mass input to process is equal to mass
output(use densities of each solvent to calculate mass of each)

Mass input=mass output

Mass of xylene in=mass of xylene out

Mass of n-hexane in=mass of n-hexane out

Mass of plastics in=mass of plastics out

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300 l (xylene) =258 kg+900 L n-hexane (588 kg)

60 kg
Dissolving
173 kg solution

6 kg impurities

27 kg HDPE 993 L(S+AS)

The non-dissolved HDPE recovered from the first filtration will be dissolved in 300 L xylene at
100° C and then precipitated and dried as described above. For both polymers the recovery will be
larger than 99 %.

1200(S+AS)

27 kg HDPE
Dissolving
177 kg solution

1000 L (S+AS)

The total amount of S and AS required for the procedure will be 2400L. approximately 2000
L of the mixture will be received from filtrations while the remaining 400 L is obtained from the
drying stage.

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Drying
376 kg solution 54 kg pellets

407L (S+AS)

This mixture is separated by batch differential distillation. The purity of the recovered solvents is
determined through refractive index (RI) measurements. From the 2400 L of mixture used in the
process, approximately 2360 L of products (1960 L n-hexane 90% vol. and 400 L xylene 97%
vol.) will be finally recovered (recovery98%) while a small amount of the solvent is received as
residue in the boiler of the distillation column along with traces of polymers. Although the purity
of the distilled solvents is not very high, they were successfully reused in similar experiments.(15)

The quality of the recycled polymers was tested with melt flow index (MFI) measurements and
found to be comparable to that of the virgin polymers used as feed. An increase at most equal to
10% was found for both polymers that may be attributed to some degradation occurring during the
MFI measurements because of the lack of additives (antioxidants, etc.) in the recycled polymers.
No further quality tests were conducted for the pilot unit products since according to the laboratory
experiments and the literature data the process itself only slightly affects the properties of the
treated polymers. More specifically, differential scanning calorimeter (DSC) analysis data
indicated a small increase in crystallinity as a result of the mild cooling conditions. The melting
points remain practically unchanged but the melting range is narrower due to the increase of
crystallinity. In addition, no substantial variation in the mechanical properties (elongation, tensile
strength, etc.).

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5.1.2 Energy balance

The stove power is 400w in which an experiment lasted an average of 30 minute

E =P*t

Where E= Energy

P= Power

T=time

Energy utilized for one experiment

=0.4KW * 0.5 hr

=0.2 kWh to produce 200 g pellets

Energy utilized for experiment two

0.6 kW*0.5 hr

=0.3 kwh

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5.2 Equipment lay out

Fig 5.1 process flow diagram

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5.3 Economic evaluation of plant

5. 3.1 Purchased Equipment Cost

The Purchased equipment cost can be calculated as follows

Table: 5.1 Purchased equipment cost

equipment type Equipmen price ($)

single shaft plastic shredder 1200

1 Dissolving tank 1500

2 Dryer 2500

3 mechanical sieve 1000

4 bucket elevator 1520

5 belt conveyor 1700

6 plastic extruder and heater 6000

7 screw conveyor 1500

Purchased equipment cost 16420

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5.3.2 Total capital investment

Total capital investment calculated based on the purchased equipment cost.

Table 5.2 total capital investment

Direct cost Cost

Purchased equipment cost 16420

Equipment erection 6240

Purchased equipment installation 164

Instrumentation and controls 2464

Piping 2120

Electrical 1642

Buildings 2670

Yard improvements 1670

Service facilities 1010

Land 2136

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Total Direct Plant Cost

=$36534

Indirect Cost

Engineering and supervision & Construction

expenses 4060

Contingency 1200

Contractors fee 821

Total Indirect Plant Cost $6081

Fixed capital investment(FCI) $ 42615

Working Capital 4262

Total Capital Investment $46877=937540 birr

Total physical plant cost (PPC) =cost of equipment installation + cost of erection
+……..+cost of land)

=$36534
PCE= Physical Cost of Equipment
Fixed capital = 36534+6081=$42615=852300 birr

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5.3.3 Raw Material Cost

Waste Plastic

Labor cost for plastic collection is about 15 birr/kg which encourage enterprouner to start a
business (information from salesan compound P.L.C)

Assuming this factory process eight batches with each batch 60 kg of plastic.

Then the amount of plastic waste processed per day is

8*60=420 kg per day

For 420 kg/day the money invested will be = 420*15 = 6300 birr/day

Assume it works for 300 days per year.

6300 birr/day*300 day/year

Annual raw material cost =189000 birr /year=$94500

Solvent and anti-solvent

Amount of money invested on solvent (xylene) and anti-solvent (n-hexane) will be calculated
per a week since they are recyclable.

400 liter/week consumption*20 birr/liter and 1000 liter/week*30 birr/liter respectively

=8000 birr/week solvent and 30000 birr/week anti-solvent

=10000+30000=38000 birr/week

Total annual cost= 43 working weeks*38000 birr/week

=1634000 birr/year=$ 81700

Raw material cost annually = 1720000+189000=1909000 birr/year=$95450

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5.3.4 Operating Labor

The factory works 18 hours a day and 3 shift per day

Table 5.3 operating labor cost

Unit wage
Personnel Per Personnel wage birr/mont
Process requirement shift birr /month h

Washing 6 2 800 4800

Shredder 3 1 1000 3000

Sieving 3 1 600 2400

Dissolving 3 1 1200 3600

Extrusion 3 1 1000 3000

Material handling 6 2 700 4200

Total
wage/month 21000

Total wage per month = 21000 birr/month=$1050

Total operation labor cost annually= 21000birr/month*12 months/year

Total labor cost = 252000birr/year=$126000

Total production cost without depreciation

TPC = 1.24(CRM) + 2.74COL + 0.233*FCI + 1.24CUT

Taking CUT = 0.15 TPC=0

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Rearranging and calculating f for TPC

TPC = 1.24(CRM) + 2.74COL + 0.233FCI + 1.24*0.15 TPC

TPC = (1.24/0.814)CRM + (2.74/0.814) COL + (0.233/0.814)FCI

= (1.523*189000 birr /year) + (3.366*252000birr/year) + (0.286*42615)

Total Production cost = $22965320=1148266 birr/annum

5.3.5 Unit cost

We want to produce water conduit with a unit size of 1 kg weight, 3 inch diameter and 3 meter
in length.

Conduit production per annum = 57 pieces/day * 300days = 17100

Unit cost = Total Production cost/ annual production capacity

Unit cost = 1148266 /17100= 67 birr Taking a profit margin of 20% the selling price = 80 birr/
unit conduit

5.3.6 Profit analysis

Gross profit

Annual Sales = Total rate of production * Unit selling cost

= 17100*80 birr/unit conduit= 1368000 birr

Gross profit = sales – TPC = 1368000- 1148266

Gross Profit = 219734

Depreciation =FCI / 10 years

=42615/10

Depreciation = 4261.5 =85230 birr

Assuming income tax = 30%

Income tax = Tax rate * (Gross profit- Depreciation)

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Income tax = 0.3(561734–85230) = 142951.2 birr

Net profit = gross profit – income tax – depreciation

=561734-142951-85230

=333553 birr

Net profit = 333553 birr/year

5.3.7 Rate of Return and Pay Back Period

Rate of return=333553/937540*100

=33.2%

Payback period= 100/ROR=3

Chart Title
3000000

2500000

2000000

1500000

1000000

500000

0
0 2 4 6 8 10 12 14
-500000

-1000000

-1500000

Fig: 5.2 payback period

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5.4 Plant location and environmental pollution

5.4.1 Plant location

The geographical location of the production site has an influence on the profitability of a project,
the visibility of the project and the final product of the production.

The main factors considered during site selection are as follows.

1, the site should far away from the residential area. That is because the factory may produce
massive smoke during the operation process.

2, the site had better have plenty of water to use in case that the factory may catch fire when the
machine is working.

3, the site should be close to the place we get our raw material. This can reduce the cost that paid
to transport the material.

By using the above three main factors our production site is sebeta Around Addis Ababa city.

In addition to the above criteria’s those are the reasons that helps to select the city are:

 Availability of raw material

 Availability of infrastructure
 Since the city is near to Addis Ababa it is easy to distribute the products
 Supply of utility. Eg (electricity, water…)
 Easy to gate maintenance for equipment’s
 Labor and land supply with relatively minimum cost.
 High transport facilities.

5.4.2 Environmental pollution

The industry have waste on the process of pretreatment of waste plastics which is used as
fertilizers. In distillation of solvent there are additives of plastics which remain in a column.it
should be cleaned properly on time. But other operations have no significant environmental
pollution.

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CHAPTER SIX

6. CONCLUSIONS AND RECOMMENDATION

6.1 Conclusions

In this study, the selective dissolution/precipitation method for polymer mixture separation and
recycling is presented. The main advantage of this method over the ones applied today is that it
separates mixtures of polymers without any significant decrease in the value of the polymer and it
can be applied in treating non-homogeneous plastic waste, such as municipal waste.

The technique was successfully applied in a pilot unit for the separation/recycling of LDPE/PP
mixtures. Excellent recoveries were achieved and with good quality of the recycled polymers

The feasibility study of the method for a high capacity unit, based on the scale up of the pilot
one, showed that the cost of the recycled polymer is comparable to the commercial price of the
virgin one.

 Pure solvents such as xylene as well as mixtures in different fractions of anti-solvent were
used and good recovery was seen for the solvents.
 Since other mechanical recycling techniques need high amount of investment for sorting.
But this technique is quite effective for the recovery of waste polymer since no need of sorting.
 This study shows that plastics recycling is a good business with low pay back period
 Since plastics are non-bio degradable materials recycling is a must to protect our
environment in addition to supply of plastic materials from those wastes

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6.2 Recommendations
 Waste plastics cause pollution to our environment. Plastics recycling is green engineering since it
is integrated activity of production with environmental protection.so that governmental and non-
governmental organizations should initiate entrepreneur on plastics recycling area.
 Creating awareness on the society to store the plastic wastes separately because it is very difficult
to collect them.
 There is high potential of waste plastic resources to the recycling .since plastics are available, so
that it is cost effective to recycle a west plastics.

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Appendix

I. Photos

Plastics selection for laboratory study cutting of plastics by scissor

Measurement of chemicals and raw material dissolution

Dissolution (experiment 2) product from dissolution

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