Final Thesis

SEMESTER VII
THESIS TITLE STUDY OF PET WASTE RECYCLING
PROJECT ADVISOR
ASSOCIATE PROFESSOR ARSHAD FARUQUI
GROUP MEMBERS
QASIR NAZIR YASIR ABBAS ADIL HANIF KALWAR ISRAR AHMAD IJAZ HUSSAIN FARAZ ALI KHAN MUHAMMAD FAIZAN KHALID SALEEM SIDDIQUI
16-PE-12 16-PE-18 16-PE-20 16-PE-22 16-PE-07 16-0-PE-05 16-0-PE-12 16-0-PE-18
ACKNOWLEDGEMENT
In the name of Allah, the Most Gracious and the Most Merciful Alhamdulillah, all praises to Allah for the strength and blessing in completing this thesis. Special appreciation goes to Professor Dr. Naim Masood Hasan , Associate Professor Zaheer Ahmed Chaugtai , Associate Professor Tariq Jamal . Associate Professor Arshad Faruqui for his supervision and constant support. We also wish to acknowledge Laboratory & Technical staff for helping us. Sincere thanks to all our seniors for their support during the study. Last but not least, deepest gratitude goes to our beloved parents for their endless love, prayers and encouragement. To those who indirectly contributed in this research, your kindness means a lot to us. Thank you very much.
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TABLE OF CONTENT
ACKNOWLEDGEMENT..i INTRODUCTION...................................................................................................1 CHAPTER 1. Literature Survey.......2
Poly(ethylene terephthalate)..2 History of PET.2 Chemistry of PET..3 Formation of PET.3 Morphology of PET.5 Properties of PET....6 Process ability of PET...6 Application of PET..6
CHAPTER 2. Recycling of PET Plastics...........................................9

Introduction...9 PET Recycling..11 History of PET Recycling..11 Effect of Contaminants of PET....11
CHAPTER 3. Physical Recycling Techniques..13

Flotation or Hydrocyclone Process..13 Water Bath / Hydrocyclone Process...14
Solvent /Floatation Process..14 Physical Recycling of PET bottle to Form Fibre...15 PET bottles recycling in Pakistan.....19
CHAPTER 4. Chemical Recycling to form Unsaturated Polyester Resin ..22

Glycolysis...22 Hydrolysis..24 Methanolysis...25 Chemical Recycling Of Pet on Laboratory Scale..25 Formulation of Recycled Unsaturated Polyester ..26
CHAPTER 5. Applications of Recycled PET..27

Unsaturated Polyester Products29 a. b. c. d. GRP Pipes .29 GRP SHEETS.29 GRP Houses.30 Cultured Marble..30
CHAPTER 6. Testing...33
Fibre Testing...33 Description of Test for Fibre.33 a. b. c. d. e. f. Denier Testing...33 Cut Length...34 Friction Measurement.34 Draw Ratio...34 Thermal Shrinkage....35 Tensile Strength And Elongation at Break for Fibre........37
Comparison Test Report of Virgin Unsaturated Polyester Resin with Recycled Unsaturated Polyester Resin (8THSemester) .....38 Description of Test for Unsaturated Polyester Resin..39 a. b. c. d. e. f. Density...39 Acid Value....39 Viscosity....39 Gel Time...39 Exothermic Temperature..39 Peak Time..................................................39
CHAPTER 7. Market Survey.....40

Local Market Survey..42 International & Local Manufacturer, Supplier & World Scenario..46
CHAPTER 8. Work Plan...48

References......49
STUDY OF PET WASTE RECYCLING 2012

INTRODUCTION
Poly (ethylene terephthalate), PET is an important engineering thermoplastic which is widely used all around the world. The basic sources of raw materials for PET resin production are crude oil and natural gas. PET is a condensation polymer derived from terephthalic acid (TPA) or dimethyl terephthalate (DMT) and ethylene glycol (EG). The great acceptance of PET as a packaging material is due to its toughness, clarity, capability of being oriented and reasonable cost. Compared to glass, PET containers are lightweight and shatter-resistance. They provide an acceptable barrier and they are considered as the most recyclable plastics in world. Each year millions of tons of PET remain as scrap after being used in several areas. Because of the governmental and environmental regulations, PET is being recycled [1]. In this study, bottle grade and fibre grade Polyester was recycled by two different methods, such as physical recycling and chemical recycling. In physical recycling the PET bottle were crushed washed and extruded to get fibre but In Chemical recycling PET bottle flakes were used, there are different methods in chemical recycling such as, Glycolysis, Hydrolysis, Methanoylsis etc. However, in industry glycolysis method is used for chemical recycling. The main objective of this study is to obtain fibre and unsaturated polyester resin from recycling of PET. In addition to this main objective is to reduce the manufacturing cost of fibre and to manufacture unsaturated polyester resin from bottle grade PET to reduce the manufacturing cost of UP resin and improve the physical and chemical properties of UP resin[2].
PLASTICS TECHNOLOGY CENTRE
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CHAPTER 1
LITERATURE SURVEY
1.1.
Poly(ethylene terephthalate)
Poly (ethylene terephthalate), PET, is one of the most commercially used thermoplastic. PET is a linear condensation polymer that has been used in applications that have seen rapid growth especially as packaging material for carbonated beverages since it was introduced as a container resin. Prior to this surge in use, PET was used as food packaging film, including boil-in-bags for frozen vegetables, and most commonly for the production of fiber for clothing and other applications. The structure of PET is as follows [3].
Figure. Chemical structure of PET
1.1.1.
HISTORY OF PET
PET has been well known under the name of polyester for more than 60 years. The following milestones mark the development from polyester fibres in the early 1940ies to modern PET bottles. Calico Printers Association [4], a small English company, developed the first laboratory samples of poly (ethylene terephthalate) in fiber form in 1941. Polyester research began in the United States after World War II. Nathaniel C. Wyeth is a inventor of PET bottle. In the 1950s, this research was based on textiles such as DuPont's Dacron and ICI's Terylene. In 1962, the first polyester tire cord was manufactured by Goodyear [4]. In 1977, PET was produced commercially for packaging applications such as film, sheet, coatings, and bottles - although oriented PET film was available in the 1950s. Since then due to the new improvements in mechanical and barrier properties, the consumption of the resin has grown rapidly, primarily for carbonated beverage bottles. 1941: production of first polyester Fibres. 1950s: production of textile fibres (brand names: Trevira, Dralon)
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1950-60s: extended use in textile industry 1970s: first production of packaging containers End of 1980s: first refillable beverage containers
1.1.2.
CHEMISTRY OF PET
PET is made industrially by two methods, the first step in each of which involves conversion of the TPA and DMT feed stock with ethylene glycol (EG) into bis (hydroxyethyl) terephthalate (BHET). In the early stages, polymer technology was not developed to produce TPA with sufficient purity. In the early 1960s, pure TPA was produced directly from p-xylene with bromide-controlled oxidation. DMT was made by esterification of terephthalic acid. However, a different process involving two oxidation and esterification stages is now used to produce most DMT. The intermediate product, ethylene oxide is produced by oxidation of ethylene. Then ethylene glycol is obtained by reaction of ethylene oxide with water.
1.1.3.
FORMATION OF PET
PET is a step-growth (condensation) polymer derived from terephthalic acid (TPA) or dimethyl terephthalate (DMT) and ethylene glycol (EG) according to the following chemical reactions
Figure 2.2 PET formation via acid route
Figure 2.3 PET formations via ester interchange
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In condensation polymerization, if the system is heated with antimony catalyst, a reversible reaction takes place between two polyfunctional molecules to produce one larger polyfunctional molecule, with the possible elimination of a small molecule such as water or methanol. The polycondensation rate is heavily dependent on the type and concentration of the catalyst. The reaction continues until almost all of one of the reagents is used up; an equilibrium is established which can be shifted at high temperatures by controlling the amounts of the reactants and products. Copolyesters, which are produced commercially to reduce the crystallinity of PET, are made by replacing the TPA or EG portion with another dibasic acid or glycol or both. The step growth polymerization occurs in two steps: First, a low molecular weight precursor is formed (BHET), which is then transesterified to form a high molecular weight reactor grade resin. To achieve very high molecular weights (I.V.: 0.72-0.84) and thus avoid thermal degradation in the melt, condensation is also performed in solid phase in a vacuum or under nitrogen. The molecular weights of the PET are adjusted to the intended application area[5], which were given in
Table 2.1 Application areas and molecular weights of PET
PET Application Fibers Fibers, low pilling Filaments, textile Filaments, technical Bottles Films
0.57 0.65 0.39 0.51 0.65 0.68 0.65 1.00 0.70 1.00 0.59 0.69
IVDCA (dl/g)
MW Range 38500 - 46000 23000 32000 46000 49000 46000 84000 51000 84000 41000 51000
Solid State Polymerization: Dry monomers can be submitted to solid state polymerization as well as solid prepolymers (i.e., low-molecular-weight polymers derived from conventional polymerization techniques). The former process is usually referred as direct SSP; meanwhile, in the latter case, post-SSP (SSP finishing) is used to further increase the molecular weight and to improve processability and endproduct properties, respectively [2628]. To the same perspective, SSP is proved to be an efficient recycling technique [29,30], through which the molar mass of the post consumer material is increased, thus permitting processing without severe recycled material deterioration.
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1.1.4.
MORPHOLOGY OF PET
PET is a linear molecule that exists either in an amorphous or in a crystalline state. In the crystalline state, the molecules are highly organized and form crystallites, which are crystalline regions that extend no more than a few hundred angstrom units. The maximum crystallinity level that can be achieved is probably no more than 55 %. The crystallinity in the PET soft drink bottle is normally about 25 % [4]. PET produced by solid stating comes from the reactor in crystalline form. It is shipped to the fabricator in this form. Polymers in either amorphous or crystalline form can be uniaxially or biaxiallly oriented. In either case, orientation greatly increases the strength of PET; because strain induced orientation usually imparts some crystallinity. As the crystalline state is the normal state for PET, the amorphous PET is produced deliberately. Amorphous PET is prepared by rapidly cooling the molten resin from a melt temperature of 260 C to temperature below the glass transition of 73 C. On the other hand, slow cooling of the molten resin will produce a crystalline polymer. A recycler of PET who produces pellets by extrusion will normally produce crystalline polymer. It is important to do so because the processor, who normally dries the recycled PET before using it, prefers pellets of crystalline PET. Amorphous resin tends to soften and stick at elevated temperatures of drying, forming clumps and adhering to the walls of the drying unit. The crystallization rate of PET is very important in processing. Crystallinity has a great effect on the product clarity and process ability. However, if the size of the crystallite is small enough to minimize light scattering, clarity can be achieved in spite of the crystallinity of the polymer.
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1.1.5.
PROPERTIES OF PET
The rapid growth of PET is due to the following properties: can be used as an amorphous or crystalline material, has good impact strength, can be made transparent or opaque as required, permits continuous service temperatures of around 180 C (partially crystalline) and 60 C (amorphous), is environment-friendly; it can be recycled or incinerated to form carbon dioxide and water, leaving virtually no residue, Offers an excellent price/performance ratio. very good chemical resistance Some properties are given in the Table [6]. Property Value Specific Gravity 1.37 1.38 Crystalline Melting Point 250 255 Vicat Softening Point 261 Moisture absorption (in water) 24 h at 23C 0.02 2 h at 100C 0.1 Tensile Strength (at yield) 71.5 (at break) 52.9 Flexural Strength 110.3 Flexural Modulus 2758 Izod Impact Strength 29 38 Elongation 70 Units --C C % % MPa MPa MPa MPa J/m %
1.1.6.
PROCESSABILITY OF PET
PET can be processed by different methods such as melt spinning, injection molding, stretch blow molding, flat-film extrusion, thermoforming, etc. The resulting products (e.g. fibers, films, injection-molded articles, bottles, and sheets) can be colored, adhesive bonded, welded, painted and laser marked.
1.1.7.
APPLICATTION OF PET
The fact that the mechanical properties of PET, especially its impact resistance, improved by biaxial drawing have contributed to the success that PET has
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experienced throughout the packaging sector. This trend is continuing and PET is also expected to expand its future market share. Polyester bottles have gained wide acceptance as soft drink containers for the following reasons:
93 % weight saving compared to glass, High barrier properties, especially for oxygen (O2) and carbon dioxide (CO2) Excellent transparency and gloss, Very good mechanical properties, Shatter-resistance up to drop height of 2.5 m, Shock-resistant and tough, Very good chemical resistance, Approved for food contact (FDA/ BGA), Readily recyclable.
PET has also gained favor in other food packaging applications other than carbonated beverage containers. Syrups, oils, and mustard can now be found in PET bottles. Nonfood packaging items include those for cosmetics, toiletries, and household products. PET film is used for photographic film and magnetic tapes [7]. New developments have led to use of PET in manufacturing of beer and other hot fill applications [8]. Disposable PET containers are now being used in hospitals for wound drainage systems [9]. The bottles are extrusion blow molded, radiation sterilized, and they exert and maintain a constant starting vacuum of 600 mmHg to provide optimum suction for wound drainage. Sekisui Kaseihin Kogyo Company, Japan [10], has developed foam of crystalline PET, known as Cell-PET. This foam has high thermal resistance and has good potential to be used in packaging of foodstuffs. Glass fiber reinforced PET can also be used in electrical and electronic goods [11]. It can be used in appliances such as
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sandwich toasters, tabletop ovens, cooker components and electric irons. PET can also be used in electrical components such as power switches, light bulb bases, and sensor housings, as well as in specialized applications such as housings for measuring instruments.
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CHAPTER 2
RECYCLING OF PET PLASTICS
2.
INTRODUCTION
Although the percentage of refillable PET beverage containers increases in Europe and North America, the majority of PET bottles worldwide are one-way bottles which are discarded after use. PET-bottles contribute increasingly to the generation of waste and litter especially in developing countries [12]. One-way discarded PET-bottles have a negative impact on the environments because they: waste resources pollute soil, rivers, coastal areas pollute the air when burned consume a lot of landfill site space get scattered and make the environment look untidy.
Recycling of PET-bottles saves 65% of the energy for primary PET-production Offers jobs and income for low-income groups. Depending on the type of raw material, three types of recycling are possible: Recycling of PET material by re-melting Recycling of feedstock material Energy recycling
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FIGURE: - 1
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2.1.
PET RECYCLING
Plastics are a small but significant component of the waste stream. Plastics have become an integral part of our lives. The amount of plastics consumed annually has been grown steadily. Its low density, strength, user-friendly design and fabrication capabilities and low cost, are the drivers to such growth [13]. Besides its wide use in packaging, automotive and industrial applications, they are extensively used in medical delivery systems, artificial implants and other healthcare applications, etc. The main problem during material recycling is the segregation of polymers. A polymer after segregation is typically not completely pure. The presence of contaminants generates some problems such as cleavage of chains, an increase in carboxylic end groups, a reduction in molecular weight, a decrease in intrinsic viscosity (I.V.) leading to a decrease in mechanical properties of the material. The main problem in recycling of PET is the elimination of all impurities that may catalyze hydrolysis [14].
2.2.
HISTORY OF PET RECYCLING

The recycling of poly (ethylene terephthalate) soft drink bottles began after their introduction in 1977 because some states had laws requiring a deposit on all beverage containers. By 1989, the recycling rate had increased to 23 % up from only 10 % in 1982. In U.S., more than 90 % of the bottles were collected from deposit sites in 1989. Over the past decade, the technology for recycling PET soft drink bottles has been advancing rapidly. However, most commercial recycling systems depend on some flotation system to separate PET from the high-density polyethylene (HDPE) base-cup resin, alternative systems have been developed. One of the serious contaminants in PET recycling is the adhesive used to attach the base cup and the label to the PET bottle. Today, new technology has minimized this problem and has allowed the recycling industry to produce a very pure recycled PET [4]. According to a survey carried by NAPCOR the PET bottle, industry continued its strong growth in 1997. ASG (Analytical Sciences Group) determined that 2.551 billion pounds of PET bottles and jars were available for recycling in 1997 in the U.S., which represents an almost 16 % increase from 1996. The additional new applications, particularly in the area of hot filled bottles and jars, are expected to lead this continued strong growth in 1998.
2.3.
EFFECT OF CONTAMINANTS OF PET

A major concern during reprocessing of PET is to remove all contaminants that can catalyze the hydrolysis of PET. Also, the reprocess or must avoid adding such cleaning agents as caustic soda in the wash step. These compounds are
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sometimes used to help removal of labels. Often, adhesive residues are trapped in the PET granules and remain there after washing. Since these adhesives darken when treated at PET extrusion temperatures, the recycled PET becomes discolored and hazy. During removal of labels, ionic or non-ionic surfactants are used to prevent the re-sticking of the PVA adhesive on to the flakes. If not cleaned properly, residual contaminants in recycled PET could be a risk to the public health, especially when intended to use for direct food contact applications. In addition, PVC content exceeding 50 ppm in the scrap PET makes it worthless for advanced applications such as film forming.
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CHAPTER 3
PET RECYCLIGN TECHNIQUES
3.1.
FLOTATION OR HYDROCYCLONE PROCESS

Hydrocyclone is a centrifuge device with a greater gravity force that simply accentuates the action of a sink-float tank. In this process, PET and high-density polyethylene (HDPE) are separated by differences in their density. In this process, the system is fed with crushed, baled bottles with and without caps. If the bales consist of both green and colorless bottles, the bottles are color sorted by hand or by photocell (sensors). The dirty, sorted bottles are first reduced to 32-9.5 mm (0.125-0.375 in.) flake by being processed through a granulator. Labels and loose dirt are removed by blowing air at low pressure. The contaminated flake is then metered into an agitated washing tank along with a hot non-foaming detergent solution. All recyclers have their own detergent recipes, a preferred solids concentration in the slurry, and a preferred temperature and wash cycle. The use of caustic soda in the wash solution is not recommended because it facilitates the hydrolysis of PET chains that results in drop in intrinsic viscosity. The washing step removes the last traces of label material, disperses, and sometimes dissolves the adhesives. The polymer flakes are thoroughly rinsed with fresh water to remove residual wash solution, label and other materials. Now cleaned, the crude flake or chip moves into hydro-cyclone that separates the heavy PET from light HDPE in water medium. HDPE floats in water while PET sinks. Ethylene vinyl acetate (EVA), if present from the cap liner, stays with the HDPE. The effectiveness of the hydrocyclone depends on the concentration of the solids and the speed of the centrifuge. The "heavy" and "light" product streams from the tank or the hydrocyclone are typically flushed once more with fresh water and processed first through spin dryers and then through hot air dryers. Then the metal impurities (if any) are removed by feeding the PET flakes into the multistage electrostatic separator. An interesting variation on the flotation or hydrocyclone process is the addition of a step that granulates or grinds the PET bottles cryogenically. Because adhesive contaminants are embrittled at cryogenic temperatures, whereas PET is not, adhesive contaminants in a cryogenic process become a fine powder. The fines are easily removed from the coarser PET flake by screening.
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DIAGRAM OF HYDROCYCLONE
3.2.
WATER BATH/ HYDROCYCLONE PROCESS

This process developed by Reko, a division of DSM in Holland, operates either with PET bottles that have plastics caps or with cap-free bottles. In this process, bottle components are substantially separated before granulation. Color-sorted crushed bottles from the bale move continuously through a hot water bath (1 1.5 min.) that is at least 70 C and close to 100 C. At these temperatures, the PET bottles, which are blow-molded by a process that orients the PET, shrink. As a result, the labels and caps, which do not shrink, separate from the PET bottles. From the immersion tank, the separated components are deposited on a vibrating screen that removes the detached labels. After washing and rinsing, the PET flake in water medium moves through a hydrocyclone that removes any residual polyethylene and adhesives. Finally, the clean and dried recycled PET passes through a metal detector to ensure the absence of any traces of metal
3.3.
SOLVENT / FLOTATION
This system was developed by Dow Chemical. The process begins like the conventional flotation process, discussed before, but it is followed by a series of
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float/sink steps using chlorinated solvents. After the water-flotation step that separates the polyethylene and some labels from the PET flakes, the ''heavies" move first through a float/sink step with 1,1,1-trichloroethane as the solvent and then through another float/sink step using a mixture of perchlomethylene and trichlomethane. The trichloroethane dissolves the adhesives and floats any remaining label materials. Finally, the solvents are removed and recovered in a closed distillation system and the adhesive free PET is dried.
3.4.
PHYSICAL RECYCLING OF PET BOTTLE TO FORM FIBRE

Recycling is processing used materials (waste) into new products to prevent waste of potentially useful materials, reduce the consumption of fresh raw materials, reduce energy usage, reduce air pollution (from incineration) and water pollution (from land filling) by reducing the need for "conventional" waste disposal, and lower greenhouse gas emissions as compared to virgin production.
GLOBAL RECYCLED APPLICATION OF PET
1% 4%
Polyester Fibers PET Bottle Resins Polyester Film
30% 65%
Others
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FOLLOWING STEPS INVOLVE IN PHYSICAL RECYCLING OF PET BOTTLE TO FORM FIBR
Step 1 Bale Breaking Stage
Used plastic bottles are collected from municipal curbside systems and deposit centers and are compressed into half-ton bales for delivery to the Carbon LITE process facility in Riverside CA. A bale-breaking machine de-compresses the bales back into single bottles.
Step 2 Bottle Cleaning Stage
The single bottles are separated from any trash and debris and washed in hot caustic water.
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Step 3 Bottle Sorting Stage
Automatic sorting equipment segregates the bottles into three streams: clear PET, green PET and non-PET. The non-PET stream is re-baled and sold to others for subsequent processing into various plastic products.
Step 4 Washing Stage
The clear and green streams of bottles are ground into cornflake-like flakes. These flakes are intensively washed, rinsed and dried. Step 5 Solid State De-contamination Stage
The dried clean flakes are heated under vacuum to remove any contaminates that may exist. This system of de-contamination is recognized by the FDA as
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acceptable for subsequent use in direct food packaging. The purified flakes are melted and extruded into pellets. This is our finished product and it is similar in consistency to rice.
Step 6 Final Packaging Stage
The food-grade pellets are transported to bottle manufacturers and other customers in bulk hopper road trucks or railcars. Some customers prefer the pellets to be packaged in one-ton plastic bags on pallets. And then these bags of flakes goes to different industries to achieve final production just like these flakes can be use in the production of Synthetic fiber, films, Gel Coats, Coating applications and different other applications. The example of Polyester Synthetic fiber with processing is given bellow:
Synthetic Fibers
Synthetic fibers are "man-made textile fibers produced entirely from chemical substances, unlike those man-made fibers derived from such natural substances as cellulose or protein." The polymers of synthetic fibers do not occur in nature, instead, they are produced from scratch in chemical plants or laboratories, "usually from by-products of petroleum and natural gas." Of these polymers is polyethylene terephthalate/polyester. Synthetic fibers are "spun and woven into huge consumer and industrial products", from garments such as shirts and scarves, home furnishings such as carpets ad drapes, to industrial parts such as flameproof linings and drive belts.
Stages in the Melt Spinning of polyester fibers
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3.5.
PET BOTTLES RECYCLING IN PAKISTAN
Bales of used bottles (Post Consumer Bottles for Recycling)
Crusher used for cutting the used bottles into flakes
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Crusher front view
Washing line used for cleaning up the pet flakes
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PET flakes are drying in SUN
Final Recycled PET flakes (Final Product)
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CHAPTER 4
CHEMICAL RECYCLING OF PET TO FORM UNSATURATED POLYESTER RESIN
Chemical recycling is also an established method for the recovery of process waste. However, equipment costs are high and require large turnovers to be economically viable.
4.1.
GLYCOLYSIS
Glycolysis is a chemical process of PET waste recycling which required heat for processing so it is an endothermic reaction. If recycled PET is treated with excess glycol, a transesterification reaction takes place. The reduction of high molecular weight PET to short-chain fragments is achieved by heating the PET with a glycol such as propylene glycol (PG) in the presence of a catalyst. Typical catalysts are zinc, manganese, or cobalt acetic acid. Typically this glycolysis reaction takes place over an 8 hour period at 200 C with a PG/PET and major products are bishydroxyethyl terephthalate, bis-bydroxypropyl terephthalate, and mixed EG/PG terephthalate diesters, plus some free EG and PG. The reaction is carried out under continuous nitrogen purge to inhibit degradation of the resulting polyols. Under these reaction conditions, the resulting polyol has a number average molecular weight of 480 and a hydroxyl number of 480. If a higher molecular
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weight polyol were desired, the PG/PET ratio is lowered; i.e. less PG is used per mole of PET. Glycolysis reaction can also be done using glycerol, which produces a polyol with higher hydroxyl number, or with diethylene or dipropylene glycol (DEG). [17]
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PIOLET PLANT
4.2.
HYDROLYSIS
Treating PET with water in excess at an elevated temperature of 150-250 C in the presence of sodium acetate as catalyst produces terephthalic acid (TPA) and ethylene glycol (EG) in four hours. Catalysts for hydrolysis are either acids (such as sulfuric) or bases (such as ammonium hydroxide) [16]. An acid catalyst will promote the hydrolysis in 10-30 minutes at 60-95 C. Alternatively, PET can be treated with an excess of methanol, to produce dimethyl terephthalate (DMT) and EG. A typical PET/methanol ratio is 1:4. [17]
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4.3.
METHANOLYSIS
Weighed amounts of PET (w1), methanol and ionic liquids were added in an autoclave with a stirrer and a thermometer. The mixture was heated up to the given temperature for certain time. The reaction mixture was filtered to remove the unreacted PET (w2). The obtained filtrate was diluted with an equal volume of water and a precipitate was obtained and filtered. The obtained filtrate was distilled under vacuum to remove water and ethanediol, the residue that is mainly composed of ionic liquid and catalyst was reused directly as solvent and catalyst. The filter cake which is mainly composed of dimethyl terephthalate(DMT) was dried to obtain DMT product . [17]
4.4.
CHEMICAL RECYCLING OF PET ON LABORATORY SCALE
It is a process in which polymer chain breakdown into oligomer. Such as PET flakes are converted to BHET (Bis Hydroxyethyl Terephthalate). So this process consists of following Steps. i- First PET bottle Cut into Flakes of size 10mm ii- We take three neck Flask in which we put PET flakes and Diethylene Glycol (DEG) as we know that glycolysis consist of transesterifaction of PET. As transesterifaction decrease the molecular weight of the polymeric chain. iii- And then Zinc Acetate is added which is used as a catalyst and temperature is 210oC for 5 hour. And this reaction takes place in three neck round bottle flask. iv- Nitrogen gas is supplied throughout the reaction. v- After this it is cooled down to 100oC at room temperature.
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vi- Now After this the solution is filtered and again pour it in to the flask vii- Then nitrogen supply is started to the flask to avoid oxygen to react with the solution. viii- After this heating is started and phthalic anhydride, hydroquinone and maleic anhydride is added to the flash. Due to which unsaturated polyester resin is formed ix- After this styrene, monomer is added to the flask because it can start cross linking and stop the pre maturing. x- And our unsaturated polyester resin is ready to use.
FORMULATION OF RECYCLED UNSATURATED POLYESTER

The Below formulation is approximate by weight.
S.No
1 2 3 4 5 6 7 8 9
MATERIALS
PET Flakes DEG MA Styrene THQ HQ WAX Zn. Act St. Acid
PERCENTAGE %
24 27 18 28 0.01 0.001 0.05 0.007 0.05
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CHAPTER 5
APPLICATION OF RECYCLED PET
Regrind PET can be used for reprocessing into cheap fiberfill for pillows and sleeping bags or used directly in filled and reinforced PET molding compounds. Another outlet for used PET is as a fuel source. According to Eastman, PET burns cleanly to produce carbon, oxygen, and water, and one pound of PET has the same heating value as one pound of soft coal. There are different uses of waste PET it will be converted in to UP resin which is thermosetting material and it can be uses for variety of purposes and PET waste can also be converted to polyols for use in rigid or flexible urethane foams. Urethane foams made from recycled PET are relatively cheaper than those made from normal virgin polyols. A variety of clothing, including uniforms, working wear, T-shirts, polo shirts, sweatshirts and using filament yarn, sweatshirts (jersey), windbreakers (woven), bags (woven), tents (woven) and umbrellas (woven), are being manufactured from recycled PET bottles. Recycled PET is also used as the plastics clamshells for bakery and deli products.
This clamshell is produced by thermoforming a 3-layer sheet in which the middle layer contains the recycled PET. Previously recycled PET cannot be used for food packaging due to the restriction of Food and Drug Association (FDA). Now after the development of new, advanced and sophisticated recycling processes, the FDA has started giving approval to recycled PET up to a certain level. This has opened new doors for the use of recycled PET. As one of the major users of plastic containers for food use, and as a leader in the beverage industry, The Coca-Cola Company has been involved in PET recycling from the start and was one of the first companies to receive a "no-objection" letter from U.S. FDA,
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allowing the use of recycled PET for food-contact application. Since then many different companies have taken an interest in developing some process for recycling PET so that it can be used in direct food contact packaging and have gained success [18]. The market of recycled PET for beer bottles is also igniting interest of various manufacturers [19].Development in the field of reinforced recycled PET is also catching up. Glass/mineral filled PET is now being used as automotive grille opening retainers by Ford Motor Company, Mitsubishi Motors and Toyoda Gosei Co. Ltd. jointly are now molding car engine covers entirely from recycled PET soft drink bottles. [20]
RECYCLED PET T SHIRT & Lamp made with recycled PET straps
Extensive research investigated the use of resin based on recycled poly (ethylene terephthalate) plastics waste for the production of a high performance composite material, namely polyester concrete, for the construction industry. Resins using recycled PET offered the lower source cost of materials for forming good quality polyester concrete. Other applications include polyester resin for sail boats, shower units, and floor tiles, lumber, floor coverings, corrugated roofing, home insulation, industrial strapping, rope, non-food containers, light weight auto body parts, and machine housings.
Athletic shoes made from recycled PET Recycled bottles & Recycled PET Grocery Bag
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UNSATURATED POLYESTER PRODUCTS
GRP PIPE GRP Pipes are manufactured using filament winding process on computer controlled machines. By adjusting the relative speed of mandrel rotation and glass distribution head movement, helical reinforced layers with different angles can be wound. In order to increase the pipe stiffness, especially on large diameter pipes, silica sand can be added to parallel layers of wall. Pipes manufactured using this process are used for aboveground and underground installations, with gravity flow, medium and high internal pressure.
GRP SHEET
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GRP HOUSE
CULTURED MARBLE
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Building (panels, corrugated/flat sheets, profiles, infrastructure, bridges, sanitary ware, swimming pools, subsea construction etc.) Tanks, Containers, Pipes (incl. relining of pipes) Electrical (wind turbines, appliance) Marine (pleasure boats, utility vessels) Automotive (cars, trucks, trains, container panels) Castings (artificial stone, marble etc.) Shirt Buttons Synthetic marble castings Formulated products (gel coats, adhesives, putties) Air conditional Panels Air craft Components Archery Bows Arrow Shafts Hoods Trunk Lids Floor Pans Airscoopes Bathroom Products Building Panels Cable Trays Dish Washer Parts Furniture Helmets Solar Energy Panels
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Unsaturated Polyester Button
Front Panel of Train
Cultured marble
CAR Putty
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CHAPTER 6
TESTING
6.1. 6.1.1.
FIBRE TESTING DESCRIPTION OF TEST FOR FIBRE
a. DENIER TESTING TESTING STANDARD: - ASTM D 1059 Scope: To determine the Denier and filament count of all types of yarns.

Measure length of sample Weigh in grams Calculate count Count filaments
DENIER TESING MACHINE
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b. CUT LENGTH TESTING STANDARD: - ASTM D 5319
c. FRICTION MEASUREMENT TESTING STANDARD: - ASTM D 3412 METHOD:The test yarn is pulled over a friction body at a certain speed and a certain angle. The tensile force is measured before and behind this friction body. The friction coefficient is calculated
- METER
d. DRAW RATIO TESTING STANDARD: - ASTM D1708 METHOD:During the course of a cycle, machine continuously measures the tension produced in a sample yarn, which is heated to a certain temperature and drawn to a certain percentage.
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DRAW TENSION TESTING INSTRUMENT
e. THERMAL SHRINKAGE TESTING STANDARD: - ASTM D 4974 METHOD:Up to 10 samples are heated to a certain temperature for a specified period of time or they are exposed to a temperature ramp. Either the sampleschanges in length and/or the forces built up in the samples are monitored via the connected computer. Since the instrument is computer controlled, all test parameters are easily set and stored corresponding to different tested materials. Therefore, once the test configuration is set, the operator just needs to prepare the samples onto the measuring sensors and the whole test takes place automatically.
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THERMAL SHRINAGE TESTING INSTRUMENT
f. TESNILE STRENGTH AND ELONGATION AT BREAK FOR FIBRE TESTING STANDARD: - ASTM D 2343
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UNIVERSAL TESTING MACHINE
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6.2.
COMPARISON TEST REPORT OF VIRGIN UNSATURATED POLYESTER RESIN WITH RECYCLED UNSATURATED POLYESTER RESIN. (8TH SEMESTER)
S.NO 1 2 3 4 5 6 7
PROPERTIES
VIRGIN UP RESIN VALUE

clear
UP RESIN FROM PET VALUE -
Appearance Viscosity 25oC (DIN CUP) Density (25oC) Acid Value (mgkoh/g) Gel time 30oC Exothermic Temperature Peak Time
90-110sec
1.15
35-40
(7-10)min
(155-170)0C
(14-25)min
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6.2.1.
DESCRIPTION OF TEST FOR UNSATURATED POLYESTER RESIN
A. B. C. D. E. F.
DENSITY TEST ACID VALUE TEST VISCOSITY TEST GEL TIME TEST EXOTHERMIC TEMPERATURE TEST PEAK TIME TEST
ASTM D4052 ASTM D3643 DIN 53211 ASTM D3532 ASTM D2471 ASTM D2499
The above mentioned tests will be performed in semester 8th.
Page 39
CHAPTER 7
MARKET SURVEY
7.1.
LOCAL MARKET SURVEY PET FLAKES DEALERS
NHN PETRO INDUSTRIES Contact Person:- Mr. Shareef Siddiqui (PLANT INCHARGE) Phone No:- 0213-512-1136 Cell No:- 0300-272-7911 / 0313-209-2092 Address:- Plot No:-44, Sector No:-24, Korangi Industrial Area Karachi Pakistan. PRICE White Flakes Blue Flakes Green Flakes Rs. 96/Kg Rs. 94/Kg Rs. 90/kg
QUALITY TRADER Contact Person:- Yunus Lodhi Phone No:- 0213-825-0533 Cell No:- 0334-303-0140 Address:- Plot No:- 120-A, Sector No:- 27, Korangi Industrial Area Karachi Pakistan. PRICE White Flakes Blue Flakes Green Flakes Rs. 98/Kg Rs. 97/Kg Rs. 89/kg
Page 40
SHER SHAH KARACHI Contact Person:- Mr. Bilal Cell No:- 0345-256-9235 Address:- Phanka hotel Street near Caltex Petrol Pump Karachi Pakistan.
PRICE White Flakes Blue Flakes Green Flakes Rs. 73-75/Kg Rs. 73-74/Kg Rs. 73-74/kg
IMPORTANT INFORMATION
A. PRICE FLUCATION: In summer price per kg 50-55 In winter price per kg 72-75 B. CRUSH SELLING COST: In summer Crush = Rs 60/kg In Winter Crush = Rs (80-85)/kg C. WASH PRICES: Hot wash (SODA CASTIC)= Rs. 10/kg Cold Wash =Rs. 5/kg D. OTHER COST: Crush (LABOUR COST)= 3/kg Separation Labor Cost = 2-3/kg
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LOCAL CHEMICAL MARKET SURVEY
AHMED CHEMICAL CO.

importer distributor & supplier of chemicals
Phone No:- 0213-243-0561 / 0213-243-7345 E-mail:- ahmedchm@cyber.net.pk Address:- Daryalall Street, Jodia Bazar, Karachi Pakistan S.No 1 2 3 4 5 6 7 CHEMICALS Monoethylene Glycol Diethylene Glycol Propylene Glycol Malic Anhydride Phthalic Anhydride Zinc Acetate
Hydroquinone
PRICES 140/Kg 135/Kg 250/Kg 220/kg N/A N/A 7800/Kg
Page 42
COC [CENTER OF CHEMICALS] dealer & importer of chemical Phone No:- 0213-400-6934 / 0213-243-3522 E-mail:- tariq.ikhlas@gmail.com Address:- Shop # 6, Maryam Manzil, Katchi Gali # 1, Jodia Bazar Karachi-Pakistan. S.No 1 2 3 4 5 6 7 CHEMICALS Monoethylene Glycol Diethylene Glycol Propylene Glycol Malice Anhydride Phthalic Anhydride Zinc Acetate
Hydroquinone
PRICES 140/Kg N/A N/A 220/kg 340/Kg N/A 7380/Kg
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ILYAS SONS CORPORATIN HOUSE OF SPECIALTY CHEMICALS

(IMPORTER & MANUFACTURES REPRESENTATIVE)
Phone No:- 0213-400-6934 / 0213-243-3522 E-mail:- tariq.ikhlas@gmail.com Address:- 156/3-A, Kutchi Gali No. 1, Jodia Bazar, Karachi-74000 S.No 1 2 3 4 5 6 7 CHEMICALS Monoethylene Glycol Diethylene Glycol Propylene Glycol Malice Anhydride Phthalic Anhydride Zinc Acetate
Hydroquinone
PRICES 140/Kg 300/Kg 250/Kg 220/kg N/A N/A N/A
Page 44
Karachi Scientific Traders (Stockiest & suppliers) of Laboratory Chemicals, Glassware, Scientific Instruments, P.H. & TDS Meters.
Phone No:- 02132513527 / 02132526057 E-mail:- mohsinadeel@yahoo.com Address:- Shop #. G-13 Union Chamber, North Napier Road, Karachi. S.No 1 2 3 4 5 6 7 CHEMICALS Monoethylene Glycol Diethylene Glycol Propylene Glycol Malice Anhydride Phthalic Anhydride Zinc Acetate
Hydroquinone
PRICES 140/Kg N/A 250/Kg 220/kg N/A N/A 8500/kg
Page 45

International Chemical Market Survey
CHEMICALS
COMPANY Nangong Xihua Felt Co., Ltd. China
PRICE US $1200-2000 / Metric Ton US $1200-1600 / Ton
DEG
Adinath Chemicals India YOUNG'S CORPORATION South Korea
US $1.2-1.5 / Kilogram
Shanghai Homore Industrial Co., Ltd China Adinath Chemicals India
US $700-1000 / Ton
MEG
US $1000-1500 / Ton
Hana International Trade Co. Iran(Islamic Republic of) Qingdao Baijie International Trade Co., Ltd. China PG BeoChems Industrial US Fancying Industrial LTD South korea Zhengzhou Qiangjin Science And Technology Trading Co., Ltd. China Shijiazhuang Baicheng Chemical Co., Ltd. China Tianjin Flourish Chemical Co.,
US $1020 / Metric Ton
US $1500-1800 / Ton US $3-9 / kg
US $1500-1540 / Metric Ton US $1610-1750 / Metric Ton
MALEIC ANHYDRIDE
PHTHALIC ANHYDRIDE ZINC ACETATE
US $1535-1800 / Ton
US $1846-2153 /
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Ltd. China Shijiazhuang Haosheng Chemical Co., Ltd China Beijing Sanyoujinbiao Chemical Co., Ltd. China Xi'an Aladdin Biological Technology Co., Ltd China Ton
US $1650-1950 / Metric Ton
US $30-200 / Kilogram
HYDROQUINONE
N.A.K.P. Foto Inc Canada
CA $11.50-12.00 / Kilogram
Protech Science Corp. US
US $9850.0010835.00 / Ton
AK-TAS DIS TICARET A. S. Turkey STYRENE MONOMER Shandong Hao Na Import & Export Co., Ltd. China
US $1250-1550 / Ton
Page 47
WORK PLAN
The Strategy for this Project,
PET WASTE RECYCLING

Consist of two sections on which our work is based. The content to be covered in two sections is summarized below according to the semester.
SEMESTER-7
In this semester our strategy consist of theoretical detail about, Bottle Grade & Fiber Grade Recycling Physical Recycling Process Chemical Recycling Process Market Survey Testing Techniques Application of Unsaturated Polyester Resin
SEMESTER-8
Semester 8th will include brief detail about, the structural analysis of material on which the PET recycling is based. Practical work will include physical and chemical recycling to form fiber and unsaturated polyester (UP) resin respectively. Testing results and data from recycling process will be obtained and discussed in detail.
Page 48

REFERENCES
*1+ Lubin G., Handbook of Fiberglass and Advanced Plastics Composites, Van Nostrand Reinhold Company, New York, (1969) *2+ Chaudhari K. P., Kale D. D., Impact Modification of Waste PET by Polyolefinic Elastomer, Polymer International, Vol. 52, p. 291-298 (2003) *3+ Deanin R. D., The Relationship Between Structures, Properties, and Applications in Polymer Structure, Properties and Application, Cahners Publishing Company Inc., York, Pennsylvania, (1972) *4+ Ehrig R. J., Plastics Recycling, Products & Processes, Hanser Publishers, New York, (1992) [5] Brandrup J., Bittner M., Michaeli W., Menges G., "Recycling and Recovery of Plastics", Carl Hanser Verlag, New York, (1996) *6+ Brydson I. A., Plastics Materials, 4th Ed., Buterworth Scientific Press, London, (1982) *7+ Nitschke C., Modern Plastics Encyclopedia, McGraw Hill, New York, (1985) [8] KOSA, "Innovative PET Resin for Beer and Hot-Fill Markets", Plastics News International, (2000) *9+ Eastman Chemical Products Inc., PET Bottles Move Into Medical Care Application, Modern Plastics International, Vol. 15, p.46 (1985) [10] Sekisui Kaseihin Kogyo Co., Japan, "New Polymer Applications'', Plastics Industry News (Japan), Vol. 39, p. 20-21 (1993) [11] Ticona GmbH, Hoechst GmbH, "Inform Issue 5. Electrical/ Electronics Industry - Celanex - Impet - Vmdar", Frankfurt am Main, p. 28-30 (1997) *12+ Mantia F., Handbook of Plastics Recycling, Rapra Technology Limited, Shawbury, (2002) [13] Paci M., La Mantia F., "Influence of Small Amounts of Poly Vinyl Chloride on the Recycling of Polyethylene Terephthalate", Polymer Degradation and Stability, Vol. 63, p. 1114 (1999) [14] Torres N., Robin J. J., Boutevin B., "Chemical Modification of Virgin and Recycled Poly(ethylene terephthalate) by Adding of Chain Extenders During Processing", Journal of Applied Polymer Science, Vol. 79, p. 1816-1824 (2001) *15+ Pawlak A., Pluta M., Morawiec j., Galeski A., Pracella M., Characterization of Scrap Poly(ethylene terephtahlate), European Polymer Journal, Vol. 36, p. 1875-1884 (2000)
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*16+ Lamparter R. A., Barna B. A., and Jonsrud D. R., Process for Recovering Terephthalic Acid from Waste Polyethylene Terephthalate, U.S. Patent 4,542,239, (1985) *17+ Gruschke H., et al. Process of Depolymerization of Polyethylene Terephthalate to Terephthalic Acid and Dimethyl Ester, U.S. Patent 3,403,115, (1968) [18] Doba J., "FDA Gives Go-Ahead for Recycled PET Use", Plastics News,Vol. 11, p. 4 (2000) [19] Defosse M., "Promising Beer Bottle Market is Igniting Interest in Recycled PET", Modern Plastics International, Vol. 29, p. 38 (1999) [20] Moore S., "Auto Engine Cover is Made from PET Bottles", Modern Plastics International, Vol. 30, p. 32-36 (2000) *21+ Jang B. Z., Advanced Polymer Composites: Principles and Applications, ASM International, Materials Park (1994) [22] http:// www.accessscience.com McGraw-Hill Encyclopedia of Science & Technology Online *23+ Simon G. P., Polymer Characterization Techniques and Their Applications to Blends, Oxford University Press, (2003) *24+ Strong A. B., Plastics, Materials & Processing, Prentice Hall, New York, (2000) *25+ Ylmazer U., Cansever M., Effects of Processing Conditions on the Fiber Length Distribution and Mechanical Properties of Glass Fiber Reinforced Nylon-6, Polymer Composites, Vol. 23, p. 61-71 (2001) [26]. Dujari R, Cramer G, Marks D. Method for solid phase polymerization (E.I. du Pont de Nemours & Company). WIPO Patent WO 98/23666, 1998. [27]. Flory P. Polymerization process (E.I. du Pont de Nemours & Company). U.S. Patent 2,172,374, 1939. [28]. Monroe G. Solid phase polymerization of polyamides (E.I. du Pont de Nemours & Company). U.S. Patent 3,031,433, 1962. [29]. Cruz S, Zanin M. PET recycling: evaluation of the solid state polymerization process. J. Appl. Polymer. Sci. 2006; 99:21172123. [30]. Karayannidis G, Kokkalas D, Bikiaris D. Solid-state polycondensation of poly(ethylene terephthalate) recycled from postconsumer soft-drink bottles: I. J. Appl. Polym. Sci. 1993;50(12):21352142.
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SEMESTER VII

THESIS TITLE STUDY OF PET WASTE RECYCLING

16-PE-12 16-PE-18 16-PE-20 16-PE-22 16-PE-07 16-0-PE-05 16-0-PE-12 16-0-PE-18

CHAPTER 2. Recycling of PET Plastics...........................................9

CHAPTER 3. Physical Recycling Techniques..13

CHAPTER 4. Chemical Recycling to form Unsaturated Polyester Resin ..22

CHAPTER 5. Applications of Recycled PET..27

CHAPTER 7. Market Survey.....40

CHAPTER 8. Work Plan...48

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

Figure. Chemical structure of PET

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

Figure 2.2 PET formation via acid route

Figure 2.3 PET formations via ester interchange

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

HISTORY OF PET RECYCLING

EFFECT OF CONTAMINANTS OF PET

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

FLOTATION OR HYDROCYCLONE PROCESS

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

WATER BATH/ HYDROCYCLONE PROCESS

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PHYSICAL RECYCLING OF PET BOTTLE TO FORM FIBRE

GLOBAL RECYCLED APPLICATION OF PET

Polyester Fibers PET Bottle Resins Polyester Film

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

Step 2 Bottle Cleaning Stage

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

Step 4 Washing Stage

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

Step 6 Final Packaging Stage

Stages in the Melt Spinning of polyester fibers

PLASTICS TECHNOLOGY CENTRE

STUDY OF PET WASTE RECYCLING 2012

PET BOTTLES RECYCLING IN PAKISTAN

Bales of used bottles (Post Consumer Bottles for Recycling)

Crusher used for cutting the used bottles into flakes

PLASTICS TECHNOLOGY CENTRE