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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 Products…………………………………………………………………………………………29 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). capability of being oriented and reasonable cost. The main objective of this study is to obtain fibre and unsaturated polyester resin from recycling of PET. PET is being recycled [1]. Hydrolysis. PET containers are lightweight and shatter-resistance. such as physical recycling and chemical recycling. Each year millions of tons of PET remain as scrap after being used in several areas. Methanoylsis etc. They provide an acceptable barrier and they are considered as the most recyclable plastics in world. The great acceptance of PET as a packaging material is due to its toughness. Because of the governmental and environmental regulations. there are different methods in chemical recycling such as. 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]. in industry glycolysis method is used for chemical recycling. clarity. However. Compared to glass. PET is a condensation polymer derived from terephthalic acid (TPA) or dimethyl terephthalate (DMT) and ethylene glycol (EG). PLASTICS TECHNOLOGY CENTRE Page 1 . PET is an important engineering thermoplastic which is widely used all around the world. Glycolysis. In physical recycling the PET bottle were crushed washed and extruded to get fibre but In Chemical recycling PET bottle flakes were used. bottle grade and fibre grade Polyester was recycled by two different methods. The basic sources of raw materials for PET resin production are crude oil and natural gas. In this study.

The structure of PET is as follows [3].1. this research was based on textiles such as DuPont's Dacron™ and ICI's Terylene™. In the 1950s. sheet.1. The following milestones mark the development from polyester fibres in the early 1940ies to modern PET bottles. the consumption of the resin has grown rapidly.STUDY OF PET WASTE RECYCLING 2012 CHAPTER 1 LITERATURE SURVEY 1. Since then due to the new improvements in mechanical and barrier properties.although oriented PET film was available in the 1950s. including boil-in-bags for frozen vegetables. In 1977. and bottles . a small English company. 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. PET. developed the first laboratory samples of poly (ethylene terephthalate) in fiber form in 1941. Chemical structure of PET 1. PET was used as food packaging film. primarily for carbonated beverage bottles. Calico Printers Association [4]. In 1962. the first polyester tire cord was manufactured by Goodyear [4]. Polyester research began in the United States after World War II.  1941: production of first polyester Fibres. Poly(ethylene terephthalate) Poly (ethylene terephthalate). Nathaniel C. Prior to this surge in use. “Dralon”) PLASTICS TECHNOLOGY CENTRE Page 2 . Figure. Wyeth is a inventor of PET bottle.1. and most commonly for the production of fiber for clothing and other applications. coatings. HISTORY OF PET PET has been well known under the name of polyester for more than 60 years. PET was produced commercially for packaging applications such as film.  1950s: production of textile fibres (brand names: “Trevira”. is one of the most commercially used thermoplastic.

CHEMISTRY OF PET PET is made industrially by two methods.2. ethylene oxide is produced by oxidation of ethylene.STUDY OF PET WASTE RECYCLING 2012  1950-60s: extended use in textile industry  1970s: first production of packaging containers  End of 1980s: first refillable beverage containers 1. However. DMT was made by esterification of terephthalic acid. 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 2.3.3 PET formations via ester interchange PLASTICS TECHNOLOGY CENTRE Page 3 . polymer technology was not developed to produce TPA with sufficient purity. a different process involving two oxidation and esterification stages is now used to produce most DMT. 1. The intermediate product.1. pure TPA was produced directly from p-xylene with bromide-controlled oxidation. 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 1960s. Then ethylene glycol is obtained by reaction of ethylene oxide with water. In the early stages.1.

PLASTICS TECHNOLOGY CENTRE Page 4 . SSP is proved to be an efficient recycling technique [29. The molecular weights of the PET are adjusted to the intended application area”[5]. technical Bottles Films 0. 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).59 – 0.65 0. respectively [26–28].00 0. textile Filaments. if the system is heated with antimony catalyst. thus permitting processing without severe recycled material deterioration. which are produced commercially to reduce the crystallinity of PET.00 0. which is then transesterified to form a high molecular weight reactor grade resin. an equilibrium is established which can be shifted at high temperatures by controlling the amounts of the reactants and products.72-0.e. To the same perspective. low-molecular-weight polymers derived from conventional polymerization techniques). condensation is also performed in solid phase in a vacuum or under nitrogen. which were given in Table 2. through which the molar mass of the post consumer material is increased.1 Application areas and molecular weights of PET PET Application Fibers Fibers.69 IVDCA (dl/g) MW Range 38500 . “Copolyesters.39 – 0.68 0. The former process is usually referred as direct SSP. To achieve very high molecular weights (I. meanwhile. The polycondensation rate is heavily dependent on the type and concentration of the catalyst.84) and thus avoid thermal degradation in the melt. low pilling Filaments. a reversible reaction takes place between two polyfunctional molecules to produce one larger polyfunctional molecule. The reaction continues until almost all of one of the reagents is used up..V.: 0. with the possible elimination of a small molecule such as water or methanol. in the latter case.30].65 – 0.70 – 1.65 – 1.46000 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. post-SSP (SSP finishing) is used to further increase the molecular weight and to improve processability and endproduct properties.STUDY OF PET WASTE RECYCLING 2012 In condensation polymerization.51 0.57 – 0.

who normally dries the recycled PET before using it.STUDY OF PET WASTE RECYCLING 2012 1. the molecules are highly organized and form crystallites. PLASTICS TECHNOLOGY CENTRE Page 5 . MORPHOLOGY OF PET PET is a linear molecule that exists either in an amorphous or in a crystalline state. A recycler of PET who produces pellets by extrusion will normally produce crystalline polymer.1. PET produced by solid stating comes from the reactor in crystalline form. because strain induced orientation usually imparts some crystallinity. The maximum crystallinity level that can be achieved is probably no more than 55 %. orientation greatly increases the strength of PET. However. 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. which are crystalline regions that extend no more than a few hundred angstrom units. forming clumps and adhering to the walls of the drying unit. prefers pellets of crystalline PET. clarity can be achieved in spite of the crystallinity of the polymer. In either case. slow cooling of the molten resin will produce a crystalline polymer. Polymers in either amorphous or crystalline form can be uniaxially or biaxiallly oriented.4. if the size of the crystallite is small enough to minimize light scattering. On the other hand. the amorphous PET is produced deliberately. The crystallinity in the PET soft drink bottle is normally about 25 % [4]. In the crystalline state. Amorphous resin tends to soften and stick at elevated temperatures of drying. It is shipped to the fabricator in this form. As the crystalline state is the normal state for PET. It is important to do so because the processor. The crystallization rate of PET is very important in processing. Crystallinity has a great effect on the product clarity and process ability.

5. APPLICATTION OF PET The fact that the mechanical properties of PET. especially its impact resistance. flat-film extrusion.1.38 Crystalline Melting Point 250 – 255 Vicat Softening Point 261 Moisture absorption (in water) 24 h at 23°C 0.02 2 h at 100°C 0. leaving virtually no residue. welded. PROCESSABILITY OF PET PET can be processed by different methods such as melt spinning. adhesive bonded.37 – 1.9 Flexural Strength 110. thermoforming. it can be recycled or incinerated to form carbon dioxide and water.  very good chemical resistance Some properties are given in the Table [6]. injection-molded articles. injection molding. Property Value Specific Gravity 1.1. films. stretch blow molding.5 (at break) 52. improved by biaxial drawing have contributed to the success that PET has PLASTICS TECHNOLOGY CENTRE Page 6 .  has good impact strength.1 Tensile Strength (at yield) 71. 1. etc.  permits continuous service temperatures of around 180 °C (partially crystalline) and 60 °C (amorphous). The resulting products (e. painted and laser marked.  can be made transparent or opaque as required. fibers.  is environment-friendly.3 Flexural Modulus 2758 Izod Impact Strength 29 – 38 Elongation 70 Units --°C °C % % MPa MPa MPa MPa J/m % 1.STUDY OF PET WASTE RECYCLING 2012 1. and sheets) can be colored.7. bottles.g. PROPERTIES OF PET The rapid growth of PET is due to the following properties:  can be used as an amorphous or crystalline material.  Offers an excellent price/performance ratio.1.6.

Nonfood packaging items include those for cosmetics. has developed foam of crystalline PET. Shatter-resistance up to drop height of 2. Disposable PET containers are now being used in hospitals for wound drainage systems [9]. known as Cell-PET. New developments have led to use of PET in manufacturing of beer and other hot fill applications [8]. and household products. Shock-resistant and tough. toiletries. Approved for food contact (FDA/ BGA). Very good mechanical properties. This trend is continuing and PET is also expected to expand its future market share. PET has also gained favor in other food packaging applications other than carbonated beverage containers. oils. Readily recyclable. radiation sterilized. It can be used in appliances such as PLASTICS TECHNOLOGY CENTRE Page 7 . Glass fiber reinforced PET can also be used in electrical and electronic goods [11]. and mustard can now be found in PET bottles.5 m. Sekisui Kaseihin Kogyo Company.STUDY OF PET WASTE RECYCLING 2012 experienced throughout the packaging sector. PET film is used for photographic film and magnetic tapes [7]. and they exert and maintain a constant starting vacuum of 600 mmHg to provide optimum suction for wound drainage. Japan [10].  High barrier properties. Polyester bottles have gained wide acceptance as soft drink containers for the following reasons:  93 % weight saving compared to glass. Very good chemical resistance. Syrups. especially for oxygen (O2) and carbon dioxide (CO2)        Excellent transparency and gloss. The bottles are extrusion blow molded. This foam has high thermal resistance and has good potential to be used in packaging of foodstuffs.

and sensor housings. cooker components and electric irons. PLASTICS TECHNOLOGY CENTRE Page 8 . PET can also be used in electrical components such as power switches. as well as in specialized applications such as housings for measuring instruments. tabletop ovens.STUDY OF PET WASTE RECYCLING 2012 sandwich toasters. light bulb bases.

STUDY OF PET WASTE RECYCLING 2012 CHAPTER 2 RECYCLING OF PET PLASTICS 2. coastal areas pollute the air when burned consume a lot of landfill site space get scattered and make the environment look untidy. the majority of PET bottles worldwide are one-way bottles which are discarded after use. Recycling of PET-bottles  saves 65% of the energy for primary PET-production  Offers jobs and income for low-income groups. One-way discarded PET-bottles have a negative impact on the environments because they:      waste resources pollute soil. PET-bottles contribute increasingly to the generation of waste and litter especially in developing countries [12]. rivers. Depending on the type of raw material. INTRODUCTION Although the percentage of refillable PET beverage containers increases in Europe and North America. three types of recycling are possible:  Recycling of PET material by re-melting  Recycling of feedstock material  Energy recycling PLASTICS TECHNOLOGY CENTRE Page 9 .

STUDY OF PET WASTE RECYCLING 2012 FIGURE: .1 PLASTICS TECHNOLOGY CENTRE Page 10 .

PET RECYCLING Plastics are a small but significant component of the waste stream.STUDY OF PET WASTE RECYCLING 2012 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. Also. EFFECT OF CONTAMINANTS OF PET “A major concern during reprocessing of PET is to remove all contaminants that can catalyze the hydrolysis of PET. 2. etc. an increase in carboxylic end groups. By 1989. new technology has minimized this problem and has allowed the recycling industry to produce a very pure recycled PET [4]. the reprocess or must avoid adding such cleaning agents as caustic soda in the wash step. Today. a decrease in intrinsic viscosity (I. a reduction in molecular weight. ASG (Analytical Sciences Group) determined that 2.. user-friendly design and fabrication capabilities and low cost. Its low density.S.3. are expected to lead this continued strong growth in 1998. According to a survey carried by NAPCOR the PET bottle.S.V. the recycling rate had increased to 23 % up from only 10 % in 1982. artificial implants and other healthcare applications. which represents an almost 16 % increase from 1996. industry continued its strong growth in 1997. The amount of plastics consumed annually has been grown steadily. 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.) 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]. However. alternative systems have been developed. most commercial recycling systems depend on some flotation system to separate PET from the high-density polyethylene (HDPE) base-cup resin. Plastics have become an integral part of our lives. strength. they are extensively used in medical delivery systems. These compounds are PLASTICS TECHNOLOGY CENTRE Page 11 . particularly in the area of hot filled bottles and jars. automotive and industrial applications. The main problem during material recycling is the segregation of polymers. Besides its wide use in packaging. One of the serious contaminants in PET recycling is the adhesive used to attach the base cup and the label to the PET bottle. In U.. The additional new applications.2.551 billion pounds of PET bottles and jars were available for recycling in 1997 in the U. 2. The presence of contaminants generates some problems such as cleavage of chains. A polymer after segregation is typically not completely pure.1. are the drivers to such growth [13].

adhesive residues are trapped in the PET granules and remain there after washing. PLASTICS TECHNOLOGY CENTRE Page 12 . ionic or non-ionic surfactants are used to prevent the re-sticking of the PVA adhesive on to the flakes. Since these adhesives darken when treated at PET extrusion temperatures. Often. In addition.STUDY OF PET WASTE RECYCLING 2012 sometimes used to help removal of labels. During removal of labels. the recycled PET becomes discolored and hazy. residual contaminants in recycled PET could be a risk to the public health. If not cleaned properly. PVC content exceeding 50 ppm in the scrap PET makes it worthless for advanced applications such as film forming. especially when intended to use for direct food contact applications”.

label and other materials. if present from the cap liner. Now cleaned. adhesive contaminants in a cryogenic process become a fine powder. a preferred solids concentration in the slurry. the system is fed with crushed. All recyclers have their own detergent recipes. sorted bottles are first reduced to 32-9. The polymer flakes are thoroughly rinsed with fresh water to remove residual wash solution. If the bales consist of both green and colorless bottles. Ethylene vinyl acetate (EVA). PET and high-density polyethylene (HDPE) are separated by differences in their density. The fines are easily removed from the coarser PET flake by screening. 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.375 in. The dirty. In this process. the bottles are color sorted by hand or by photocell (sensors). and sometimes dissolves the adhesives. Then the metal impurities (if any) are removed by feeding the PET flakes into the multistage electrostatic separator.5 mm (0. stays with the HDPE. HDPE floats in water while PET sinks. The contaminated flake is then metered into an agitated washing tank along with a hot non-foaming detergent solution. FLOTATION OR HYDROCYCLONE PROCESS Hydrocyclone is a centrifuge device with a greater gravity force that simply accentuates the action of a sink-float tank. baled bottles with and without caps.STUDY OF PET WASTE RECYCLING 2012 CHAPTER 3 PET RECYCLIGN TECHNIQUES 3. and a preferred temperature and wash cycle.125-0. 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.) flake by being processed through a granulator. An interesting variation on the flotation or hydrocyclone process is the addition of a step that granulates or grinds the PET bottles cryogenically. the crude flake or chip moves into hydro-cyclone that separates the heavy PET from light HDPE in water medium. The washing step removes the last traces of label material. The effectiveness of the hydrocyclone depends on the concentration of the solids and the speed of the centrifuge. In this process. PLASTICS TECHNOLOGY CENTRE Page 13 . Because adhesive contaminants are embrittled at cryogenic temperatures. whereas PET is not. Labels and loose dirt are removed by blowing air at low pressure. disperses.1.

a division of DSM in Holland. discussed before.3. From the immersion tank. WATER BATH/ HYDROCYCLONE PROCESS This process developed by Reko. As a result. the labels and caps.5 min. the separated components are deposited on a vibrating screen that removes the detached labels. which are blow-molded by a process that orients the PET. the PET bottles. The process begins like the conventional flotation process. bottle components are substantially separated before granulation. operates either with PET bottles that have plastics caps or with cap-free bottles. separate from the PET bottles.2. At these temperatures. but it is followed by a series of PLASTICS TECHNOLOGY CENTRE Page 14 . SOLVENT / FLOTATION This system was developed by Dow Chemical. shrink. In this process.) that is at least 70 °C and close to 100 °C. Color-sorted crushed bottles from the bale move continuously through a hot water bath (1 1. the PET flake in water medium moves through a hydrocyclone that removes any residual polyethylene and adhesives.STUDY OF PET WASTE RECYCLING 2012 DIAGRAM OF HYDROCYCLONE 3. Finally. which do not shrink. After washing and rinsing. the clean and dried recycled PET passes through a metal detector to ensure the absence of any traces of metal 3.

Finally.1.4. PHYSICAL RECYCLING OF PET BOTTLE TO FORM FIBRE Recycling is processing used materials (waste) into new products to prevent waste of potentially useful materials. and lower greenhouse gas emissions as compared to virgin production. reduce energy usage. GLOBAL RECYCLED APPLICATION OF PET 1% 4% Polyester Fibers PET Bottle Resins Polyester Film 30% 65% Others PLASTICS TECHNOLOGY CENTRE Page 15 . After the water-flotation step that separates the polyethylene and some labels from the PET flakes.STUDY OF PET WASTE RECYCLING 2012 float/sink steps using chlorinated solvents. reduce air pollution (from incineration) and water pollution (from land filling) by reducing the need for "conventional" waste disposal. the ''heavies" move first through a float/sink step with 1. 3.1-trichloroethane as the solvent and then through another float/sink step using a mixture of perchlomethylene and trichlomethane. reduce the consumption of fresh raw materials. The trichloroethane dissolves the adhesives and floats any remaining label materials. the solvents are removed and recovered in a closed distillation system and the adhesive free PET is dried.

A bale-breaking machine de-compresses the bales back into single bottles. PLASTICS TECHNOLOGY CENTRE Page 16 . Step 2 Bottle Cleaning Stage The single bottles are separated from any trash and debris and washed in hot caustic water.STUDY OF PET WASTE RECYCLING 2012 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.

Step 4 Washing Stage The clear and green streams of bottles are ground into cornflake-like flakes. green PET and non-PET. This system of de-contamination is recognized by the FDA as PLASTICS TECHNOLOGY CENTRE Page 17 . The non-PET stream is re-baled and sold to others for subsequent processing into various plastic products.STUDY OF PET WASTE RECYCLING 2012 Step 3 Bottle Sorting Stage Automatic sorting equipment segregates the bottles into three streams: clear PET. Step 5 Solid State De-contamination Stage The dried clean flakes are heated under vacuum to remove any contaminates that may exist. These flakes are intensively washed. rinsed and dried.

Step 6 Final Packaging Stage The food-grade pellets are transported to bottle manufacturers and other customers in bulk hopper road trucks or railcars. home furnishings such as carpets ad drapes. 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." The polymers of synthetic fibers do not occur in nature. unlike those man-made fibers derived from such natural substances as cellulose or protein.STUDY OF PET WASTE RECYCLING 2012 acceptable for subsequent use in direct food packaging." Of these polymers is polyethylene terephthalate/polyester. they are produced from scratch in chemical plants or laboratories. Gel Coats. The purified flakes are melted and extruded into pellets. from garments such as shirts and scarves. "usually from by-products of petroleum and natural gas. films. Coating applications and different other applications. Synthetic fibers are "spun and woven into huge consumer and industrial products". This is our finished product and it is similar in consistency to rice. 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. to industrial parts such as flameproof linings and drive belts. instead. Stages in the Melt Spinning of polyester fibers PLASTICS TECHNOLOGY CENTRE Page 18 .

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 Page 19 .STUDY OF PET WASTE RECYCLING 2012 3.5.

STUDY OF PET WASTE RECYCLING 2012 Crusher front view Washing line used for cleaning up the pet flakes PLASTICS TECHNOLOGY CENTRE Page 20 .

STUDY OF PET WASTE RECYCLING 2012 PET flakes are drying in SUN Final Recycled PET flakes (Final Product) PLASTICS TECHNOLOGY CENTRE Page 21 .

the resulting polyol has a number average molecular weight of 480 and a hydroxyl number of 480. and mixed EG/PG terephthalate diesters. Typical catalysts are zinc. If a higher molecular PLASTICS TECHNOLOGY CENTRE Page 22 .STUDY OF PET WASTE RECYCLING 2012 CHAPTER 4 CHEMICAL RECYCLING OF PET TO FORM UNSATURATED POLYESTER RESIN Chemical recycling is also an established method for the recovery of process waste. 4. a transesterification reaction takes place. bis-bydroxypropyl terephthalate. Typically this glycolysis reaction takes place over an 8 hour period at 200 °C with a PG/PET and major products are bishydroxyethyl terephthalate. equipment costs are high and require large turnovers to be economically viable. 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. Under these reaction conditions. 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. or cobalt acetic acid.1. plus some free EG and PG. The reaction is carried out under continuous nitrogen purge to inhibit degradation of the resulting polyols. manganese. However.

STUDY OF PET WASTE RECYCLING 2012 weight polyol were desired. less PG is used per mole of PET. the PG/PET ratio is lowered. [17] PLASTICS TECHNOLOGY CENTRE Page 23 . or with diethylene or dipropylene glycol (DEG). Glycolysis reaction can also be done using glycerol.e. i. which produces a polyol with higher hydroxyl number.

Alternatively. [17] PLASTICS TECHNOLOGY CENTRE Page 24 . An acid catalyst will promote the hydrolysis in 10-30 minutes at 60-95 °C. A typical PET/methanol ratio is 1:4. to produce dimethyl terephthalate (DMT) and EG.2.STUDY OF PET WASTE RECYCLING 2012 PIOLET PLANT 4. 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]. PET can be treated with an excess of methanol.

methanol and ionic liquids were added in an autoclave with a stirrer and a thermometer. iv. Such as PET flakes are converted to BHET (Bis Hydroxyethyl Terephthalate). METHANOLYSIS Weighed amounts of PET (w1). CHEMICAL RECYCLING OF PET ON LABORATORY SCALE It is a process in which polymer chain breakdown into oligomer. the residue that is mainly composed of ionic liquid and catalyst was reused directly as solvent and catalyst. PLASTICS TECHNOLOGY CENTRE Page 25 . The mixture was heated up to the given temperature for certain time.STUDY OF PET WASTE RECYCLING 2012 4.After this it is cooled down to 100oC at room temperature.Nitrogen gas is supplied throughout the reaction. iii. The reaction mixture was filtered to remove the unreacted PET (w2). And this reaction takes place in three neck round bottle flask.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. v. As transesterifaction decrease the molecular weight of the polymeric chain. So this process consists of following Steps.First PET bottle Cut into Flakes of size 10mm ii. The obtained filtrate was distilled under vacuum to remove water and ethanediol.3. The filter cake which is mainly composed of dimethyl terephthalate(DMT) was dried to obtain DMT product .4.And then Zinc Acetate is added which is used as a catalyst and temperature is 210oC for 5 hour. The obtained filtrate was diluted with an equal volume of water and a precipitate was obtained and filtered. i. [17] 4.

Due to which unsaturated polyester resin is formed ix. hydroquinone and maleic anhydride is added to the flash.No 1 2 3 4 5 6 7 8 9 MATERIALS PET Flakes DEG MA Styrene THQ HQ WAX Zn. Acid PERCENTAGE % 24 27 18 28 0. S.05 PLASTICS TECHNOLOGY CENTRE Page 26 . monomer is added to the flask because it can start cross linking and stop the pre maturing.01 0.Then nitrogen supply is started to the flask to avoid oxygen to react with the solution. FORMULATION OF RECYCLED UNSATURATED POLYESTER The Below formulation is approximate by weight.After this heating is started and phthalic anhydride. Act St.Now After this the solution is filtered and again pour it in to the flask vii.001 0.05 0. viii. x.And our unsaturated polyester resin is ready to use.007 0.STUDY OF PET WASTE RECYCLING 2012 vi.After this styrene.

STUDY OF PET WASTE RECYCLING 2012 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. As one of the major users of plastic containers for food use. This has opened new doors for the use of recycled PET. Now after the development of new. working wear. including uniforms. sweatshirts (jersey). 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. According to Eastman. windbreakers (woven). the FDA has started giving approval to recycled PET up to a certain level. oxygen. This clamshell is produced by thermoforming a 3-layer sheet in which the middle layer contains the recycled PET. advanced and sophisticated recycling processes. are being manufactured from recycled PET bottles. A variety of clothing. sweatshirts and using filament yarn. T-shirts.S. Previously recycled PET cannot be used for food packaging due to the restriction of Food and Drug Association (FDA). and one pound of PET has the same heating value as one pound of soft coal. Recycled PET is also used as the plastics clamshells for bakery and deli products. Another outlet for used PET is as a fuel source. Urethane foams made from recycled PET are relatively cheaper than those made from normal virgin polyols. PLASTICS TECHNOLOGY CENTRE Page 27 . polo shirts. FDA. tents (woven) and umbrellas (woven). PET burns cleanly to produce carbon. bags (woven). 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. and water. and as a leader in the beverage industry.

Other applications include polyester resin for sail boats. Ltd. and machine housings. floor coverings.STUDY OF PET WASTE RECYCLING 2012 allowing the use of recycled PET for food-contact application. corrugated roofing. for the construction industry. shower units. namely polyester concrete. jointly are now molding car engine covers entirely from recycled PET soft drink bottles. and floor tiles. industrial strapping. home insulation. [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.Development in the field of reinforced recycled PET is also catching up. Resins using recycled PET offered the lower source cost of materials for forming good quality polyester concrete. non-food containers. lumber. Mitsubishi Motors and Toyoda Gosei Co. 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]. Athletic shoes made from recycled PET Recycled bottles & Recycled PET Grocery Bag PLASTICS TECHNOLOGY CENTRE Page 28 . light weight auto body parts. The market of recycled PET for beer bottles is also igniting interest of various manufacturers [19]. rope. Glass/mineral filled PET is now being used as automotive grille opening retainers by Ford Motor Company.

silica sand can be added to parallel layers of wall. medium and high internal pressure. GRP SHEET PLASTICS TECHNOLOGY CENTRE Page 29 . In order to increase the pipe stiffness.STUDY OF PET WASTE RECYCLING 2012 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. with gravity flow. especially on large diameter pipes. Pipes manufactured using this process are used for aboveground and underground installations.

STUDY OF PET WASTE RECYCLING 2012 GRP HOUSE CULTURED MARBLE PLASTICS TECHNOLOGY CENTRE Page 30 .

subsea construction etc. infrastructure. 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 PLASTICS TECHNOLOGY CENTRE Page 31 . corrugated/flat sheets. marble etc.) Shirt Buttons Synthetic marble castings Formulated products (gel coats. trains. trucks. relining of pipes) Electrical (wind turbines. appliance) Marine (pleasure boats. Containers. sanitary ware. utility vessels) Automotive (cars. swimming pools.STUDY OF PET WASTE RECYCLING 2012                         Building (panels. container panels) Castings (artificial stone. Pipes (incl. profiles. bridges.) Tanks.

STUDY OF PET WASTE RECYCLING 2012 Unsaturated Polyester Button Front Panel of Train Cultured marble CAR Putty PLASTICS TECHNOLOGY CENTRE Page 32 .

DENIER TESTING TESTING STANDARD: . FIBRE TESTING DESCRIPTION OF TEST FOR FIBRE a.STUDY OF PET WASTE RECYCLING 2012 CHAPTER 6 TESTING 6. 6.     Measure length of sample Weigh in grams Calculate count Count filaments DENIER TESING MACHINE PLASTICS TECHNOLOGY CENTRE Page 33 .1.ASTM D 1059 Scope: To determine the Denier and filament count of all types of yarns.1.1.

which is heated to a certain temperature and drawn to a certain percentage. DRAW RATIO TESTING STANDARD: .METER d.ASTM D 5319 c.STUDY OF PET WASTE RECYCLING 2012 b. PLASTICS TECHNOLOGY CENTRE Page 34 . FRICTION MEASUREMENT TESTING STANDARD: . The friction coefficient is calculated µ . The tensile force is measured before and behind this friction body. CUT LENGTH TESTING STANDARD: .ASTM D 3412 METHOD:The test yarn is pulled over a friction body at a certain speed and a certain angle. machine continuously measures the tension produced in a sample yarn.ASTM D1708 METHOD:During the course of a cycle.

STUDY OF PET WASTE RECYCLING 2012 DRAW TENSION TESTING INSTRUMENT e. PLASTICS TECHNOLOGY CENTRE Page 35 . once the test configuration is set. all test parameters are easily set and stored corresponding to different tested materials. Therefore. Either the samples‘changes in length and/or the forces built up in the samples are monitored via the connected computer. THERMAL SHRINKAGE TESTING STANDARD: . the operator just needs to prepare the samples onto the measuring sensors and the whole test takes place automatically. Since the instrument is computer controlled.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.

STUDY OF PET WASTE RECYCLING 2012 THERMAL SHRINAGE TESTING INSTRUMENT f.ASTM D 2343 PLASTICS TECHNOLOGY CENTRE Page 36 . TESNILE STRENGTH AND ELONGATION AT BREAK FOR FIBRE TESTING STANDARD: .

STUDY OF PET WASTE RECYCLING 2012 UNIVERSAL TESTING MACHINE PLASTICS TECHNOLOGY CENTRE Page 37 .

COMPARISON TEST REPORT OF VIRGIN UNSATURATED POLYESTER RESIN WITH RECYCLED UNSATURATED POLYESTER RESIN.2.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 PLASTICS TECHNOLOGY CENTRE Page 38 .STUDY OF PET WASTE RECYCLING 2012 6. (8TH SEMESTER) S.

1.2. DESCRIPTION OF TEST FOR UNSATURATED POLYESTER RESIN A. F. PLASTICS TECHNOLOGY CENTRE Page 39 . C. B. 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. E. D.STUDY OF PET WASTE RECYCLING 2012 6.

Shareef Siddiqui (PLANT INCHARGE) Phone No:. Sector No:-24. Sector No:.Mr.Plot No:.Plot No:-44.120-A.0334-303-0140 Address:. 89/kg PLASTICS TECHNOLOGY CENTRE Page 40 .27. Korangi Industrial Area Karachi Pakistan. 98/Kg Rs.1. 94/Kg Rs.0300-272-7911 / 0313-209-2092 Address:.Yunus Lodhi Phone No:. LOCAL MARKET SURVEY PET FLAKES DEALERS NHN PETRO INDUSTRIES Contact Person:.0213-825-0533 Cell No:. Korangi Industrial Area Karachi Pakistan. 90/kg QUALITY TRADER Contact Person:. PRICE White Flakes Blue Flakes Green Flakes Rs.0213-512-1136 Cell No:.STUDY OF PET WASTE RECYCLING 2012 CHAPTER 7 MARKET SURVEY 7. 96/Kg Rs. 97/Kg Rs. PRICE White Flakes Blue Flakes Green Flakes Rs.

73-74/Kg Rs. WASH PRICES: Hot wash (SODA CASTIC)= Rs. 73-75/Kg Rs. 10/kg  Cold Wash =Rs.Mr.STUDY OF PET WASTE RECYCLING 2012 SHER SHAH KARACHI Contact Person:. Bilal Cell No:. CRUSH SELLING COST: In summer Crush = Rs 60/kg  In Winter Crush = Rs (80-85)/kg C. 73-74/kg IMPORTANT INFORMATION A.0345-256-9235 Address:. OTHER COST: Crush (LABOUR COST)= 3/kg  Separation Labor Cost = 2-3/kg PLASTICS TECHNOLOGY CENTRE Page 41 .Phanka hotel Street near Caltex Petrol Pump Karachi Pakistan. PRICE FLUCATION: In summer price per kg 50-55  In winter price per kg 72-75 B. PRICE White Flakes Blue Flakes Green Flakes Rs. 5/kg D.

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 PLASTICS TECHNOLOGY CENTRE Page 42 . Karachi Pakistan S.net.ahmedchm@cyber.pk Address:.Daryalall Street. Jodia Bazar.0213-243-0561 / 0213-243-7345 E-mail:.STUDY OF PET WASTE RECYCLING 2012 LOCAL CHEMICAL MARKET SURVEY AHMED CHEMICAL CO. importer distributor & supplier of chemicals Phone No:.

Shop # 6.tariq. Katchi Gali # 1.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 PLASTICS TECHNOLOGY CENTRE Page 43 . Maryam Manzil. S.com Address:.0213-400-6934 / 0213-243-3522 E-mail:. Jodia Bazar Karachi-Pakistan.STUDY OF PET WASTE RECYCLING 2012 COC [CENTER OF CHEMICALS] dealer & importer of chemical Phone No:.ikhlas@gmail.

156/3-A. 1.0213-400-6934 / 0213-243-3522 E-mail:.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 PLASTICS TECHNOLOGY CENTRE Page 44 . Kutchi Gali No.ikhlas@gmail. Jodia Bazar.STUDY OF PET WASTE RECYCLING 2012 ILYAS SONS CORPORATIN HOUSE OF SPECIALTY CHEMICALS (IMPORTER & MANUFACTURES REPRESENTATIVE) Phone No:.tariq. Karachi-74000 S.com Address:.

& TDS Meters. Karachi.STUDY OF PET WASTE RECYCLING 2012 Karachi Scientific Traders (Stockiest & suppliers) of Laboratory Chemicals. Phone No:.H.mohsinadeel@yahoo.Shop #.02132513527 / 02132526057 E-mail:. P.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 PLASTICS TECHNOLOGY CENTRE Page 45 . Glassware.com Address:. S. G-13 Union Chamber. North Napier Road. Scientific Instruments.

Ltd China Adinath Chemicals India US $700-1000 / Ton MEG US $1000-1500 / Ton Hana International Trade Co. Ltd. Ltd.2-1. China PG BeoChems Industrial US Fancying Industrial LTD South korea Zhengzhou Qiangjin Science And Technology Trading Co.STUDY OF PET WASTE RECYCLING 2012 International Chemical Market Survey CHEMICALS COMPANY Nangong Xihua Felt Co. China Tianjin Flourish Chemical Co.. Iran(Islamic Republic of) Qingdao Baijie International Trade 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 / PLASTICS TECHNOLOGY CENTRE Page 46 ... China PRICE US $1200-2000 / Metric Ton US $1200-1600 / Ton DEG Adinath Chemicals India YOUNG'S CORPORATION South Korea US $1. Ltd. Ltd. China Shijiazhuang Baicheng Chemical Co..5 / Kilogram Shanghai Homore Industrial Co...

Ltd. China Xi'an Aladdin Biological Technology Co. China Shijiazhuang Haosheng Chemical Co.. S.K.P.STUDY OF PET WASTE RECYCLING 2012 Ltd.00 / Kilogram Protech Science Corp.A. Foto Inc Canada CA $11..0010835. US US $9850. Turkey STYRENE MONOMER Shandong Hao Na Import & Export Co..00 / Ton AK-TAS DIS TICARET A. China US $1200-1600 / Metric Ton US $1250-1550 / Ton PLASTICS TECHNOLOGY CENTRE Page 47 .. Ltd China Beijing Sanyoujinbiao Chemical Co. Ltd.50-12. Ltd China Ton US $1650-1950 / Metric Ton US $1035-1527 / Metric Ton US $30-200 / Kilogram HYDROQUINONE N.

PLASTICS TECHNOLOGY CENTRE Page 48 . SEMESTER-7 In this semester our strategy consist of theoretical detail about.  Practical work will include physical and chemical recycling to form fiber and unsaturated polyester (UP) resin respectively.       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.STUDY OF PET WASTE RECYCLING 2012 WORK PLAN The Strategy for this Project.  Testing results and data from recycling process will be obtained and discussed in detail. 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.

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