AU2013203996A1 - Bio-based polyethylene terephthalate packaging and method of making thereof - Google Patents

Abstract

This invention relates to a method of making a bio-based PET packaging and particularly to a method of producing a bio-based PET from at least one bio-based material 5 comprising: a) forming at least one PET component from at least one bio-based material, wherein the at least one PET component is selected from a monoethylene glycol ("MEG"), a terephthalic acid ("TA"), and combinations thereof; (b) processing said bio-based PET component into a bio-based PET.

Description

1 BIO-BASED POLYETHYLENE TEREPHTHALATE PACKAGING AND METHOD OF MAKING THEREOF The present application is a divisional application from Australian patent application 5 number 2010221723, the entire disclosure of which is incorporated herein by reference. RELATED APPLCA ION DATA {M001] The. praeent aplicaton is at cntinuatiounnpar of UA. non-rovxisioal applicaion Ser, No. I2110,2018, enitld "Bio-based Polyethylene TerehthaLate and Anicles Madc fromf Rio-based PAyethylenme Te' phthahe"and filed on Sepember 14-, 2008, which daims priority r 3 USC. 1 j S,(c119) to US P, vision Application Number 6 U(44349 of thes tite, filed on March 28, 2008. The ,forcmenod diselosures are herebv incorporad by reference in their entirety for all purposes, TECHNICAL FIELD OF THE INVENTION 00 his invention relates to a method of mnakinxgct biO-based PET packain anid paticulady to a method of making and reycing bio-based PET BACKGROU ND OF THE INVENTION 0001] Ase hAr,,in\ thtrm 'PT Irefers t pol ywetlne tcrphlak1t, it copolyesters, and Comiain hro in 1ny for -M inclu~dig PE1-T flakes, pellevts and rccvded PET 'Thet term "P F products" rpfes to p IIuct mad fromn P, incuding but not i t t priors, ad i PET packagIn. The verm "fT packaging" as used bA shall refer to all PET packaging ncltding but not imitdQ to PT packaging ued for xlpacgng fto.d producso oft drinks, acoholic beverages, dtergents cometcs phamcutalproducth and edIhie Oils such as' PET nir (whIch encomnpasse botites) and P1T secondary packaging which is usual used for organizing and secIring for anspot, display, and storage ofPET cIntainers wel, a-for advertising We contained withinl. [0002 The term. "bio-hased." as used herein, indicates the inclusion of some component .ha partially or totally derives from it last ne bio-based atxil, As an WO 2010/101698 2 PCT/US2010/023457 example, a "bio-based PET" would be a PET that comprises at least one component that partially or totally derives from at least one bio-based material. The term "bio-based materials" and "renewable materials" both refer to organic materials in which the carbon 30 comes from non-fossil biological sources. 100031 PET is a widely used raw composition for making packaging articles in part due to their excellent combination of clarity, mechanical, and gas barrier properties. Today, most commercial methods produce PET with petrochemically derived raw materials (hereinafter referred to as "petroleum-based PET"). Therefore, the cost of 35 production is closely tied to the price of petroleum. Petroleum-based PET contributes to greenhouse emissions due to its high petroleum derived carbon content. Furthermore, petrochemicals take hundreds of thousands of years to form naturally, making petrochemically-derived products non-renewable, which means they cannot be re-made, re-grown, or regenerated at a rate comparable to its consumption. 40 [00031 As regulations become more rigorous with regard to the environmental impact of industrial activities and as petroleum resources become increasingly scarce, there exists a growing need for a bio-based PET that may serve as an alternative to petroleum-based PET. It would be further desirable if the bio-based PET has similar chemical and/or physical properties and/or chemical structures as petroleum-based PET so that technology 45 and facilities currently designed for petroleum-based PET can be readily applied to bio based PET. For example, in some applications, it would be desirable if bio-based PET products may be processed through existing petroleum-based PET product manufacturing facilities and/or readily recycled through the systems designed for recycling petroleum based PET products. 50 [00041 Bio-based materials would also satisfy consumers' increasing demand of products that are environmentally friendly. It would be more desirable if the bio-based materials do not compete with foods or food-grade materials that may potentially increase the costs of necessity items for consumers. For example, the bio-based materials may be obtain frm a foxd or agricuhural wa stream. Thus there is a need to produce PEis derived from bio-based materials that do not compete with foods or food:-grade aerial, [0005] Other aspects, features, and advantages of this invention will be apparent from the following detailed description, drawings, and claims. [0005A] The discussion of documents, acts, materials, devices, articles and the like is 5 included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application. [0005B] Where the terms "comprise", "comprises", "comprised" or "comprising" are 10 used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not precluding the presence of one or more other features, integers, steps or components, or group thereof. BRIEF DESCRIPTION OF THE FIGURES 0006 F. I is a flowhat It rationf an embkdimntA of making a bi(-based PEI cotaier from sugarcane 00071 F1G, 2 is a flowchan llutmaion of n embodiment of making a bi-ad PE'T 00 0 8 F . 3 i.- a flowchar t iiu.Itftraotot of an mbadimnt of recycIn(g a 4iv-based 0009 The dtaed descrtion explains the embodiments of the invention, togeber w dv d .features by way of example with krerce to the drawing, DETAILED DESCRIPTION OF THE INVEN TION 100101 Embodimnts of the presetinenion enc a bio-based PET comprising at least orn bio-based mterial Aetively, the bi-based PET imay be procssed ino a c(onposioni sexleted from a PET resin, a PEf fiber, a PET package an d co io hectt i n particular embodiments, dhe bio-based material mayv C. e6ecWd frmn sugars starches, coma, n tibers, uaens beets,,, Citrus finuibs, woody phuanscluki liguocelluosics. hemicelose, potoes, plant oils, yood feedstockother poyt hardes \uch as pecti, cinp levin, pulluan, and combinations theQref Mure paruarly, 0e bio-basod material may be elected from wood chips, ci pcdsfoestry wat, agrhuewaste, crop hus,& and bio-hase-d mnaterial, with411 greater th~an 3%x in cOntent of closed, hemicelluloseS, ligni,ancobainstee Teeetonf WO 2010/101698 4 PCT/US2010/023457 bio-based materials may depend on factors including, but not limited to, supply availability, cost, type of technology used, and environmental impact. 80 [00111 Steps of method in the embodiments recited herein need not be performed in the order of steps described. One skilled in the art would know which steps may be performed simultaneously or chronologically and at the same or different locations. 100121 Embodiments of the present invention also encompass methods of producing a bio-based PET from at least one bio-based material comprising the following steps: a) 85 forming at least one PET component from at least one bio-based material, wherein the at least one PET component is selected from a monoethylene glycol ("MEG"), a terephthalic acid ("TA"), and combinations thereof; and b) processing said bio-based PET component into a bio-based PET. More particularly, the PET component may be a MEG and melt polymerized with a TA to produce a PET. Alternatively, the PET component may be a 90 TA and melt polymerized with a MEG to produce a PET. Yet more alternatively, the PET component may be combinations of MEG and TA, which may be melt polymerized to produce a PET. More particularly, the melt polymerization step further comprises mixing the MEG and the TA in a catalyst solution, promoting esterification between the MEG and TA at atmospheric pressure to form a bio-based PET, optionally separating the impurities 95 from the bio-based PET, and polycondensing the bio-based PET. Alternatively, the method further comprises processing the bio-based PET to form a fiber or a filament. In yet another alternative embodiment, the method further comprises solid state polymerizing the bio-based PET to form a PET resin. More particularly, the PET resin may be further processed into a PET perform, a PET packaging, and combinations thereof. 100 [00131 More particularly, the MEG and the TA may be produced from the bio-based material using methods including but not limited to fast pyrolysis, acid hydrolysis, enzymatic hydrolysis, microbial degradation, mycological degradation, and hydrogenolysis. Alternatively, the PET packaging may be partially or totally derived from at least one bio-based material.

WO 2010/101698 5 PCT/US2010/023457 105 [00141 Alternatively, the bio-based material is used to produce a PET packaging, wherein the PET packaging comprises an edible product. More particularly, the edible product further comprises the bio-based material. In another embodiment, the bio-based material may be used to produce an ingredient and the edible product further comprises the ingredient. In yet another embodiment, the ingredient may be selected from sugar, 110 ethanol, carbon dioxide, and combinations thereof. Method of Producing Bio-Based PET: Sugarcane [00151 Today, a typical shortcoming of sugarcane refining is that after the sugarcane has been refined into sugar and molasses, the leftover cane husks (or sometimes called bagasse) are often discarded in landfills or burned for fuel or used for animal feed. 115 Bagasse is rich in cellulose, hemicelluloses, and lignin but has practically no food value. Finding alternative ways to use the leftover bagasse to produce a bio-based PET would reduce waste. In the following methods, sugar beets may also be used in place of sugarcane. [00161 Referring to Figure 1, a particular embodiment of the present invention 120 encompasses a method of producing a bio-based PET from sugar comprising the following steps: a) refining a sugarcane 102 into a molasses 104 and a sugar 106; b) fermenting the molasses 104 to produce an ethanol 108; c) refining the ethanol into an ethylene 110; refining the ethylene 110 into a MEG 112; and melt polymerizing the MEG 112 with a TA 128 to form a bio-based PET 120. In a more particular embodiment, the TA 128 may be a 125 bio-based TA. In another embodiment, the method further comprises solid state polymerizing the bio-based PET to form a PET resin 122. Alternatively, the method further comprises a non solid-state polymerization step such as melt-to-resin technologies to produce the PET resin 122. [00171 Alternatively, the PET resin 122 may be molded into a PET container 124 by 130 various methods including but not limited to making preforms, blowing vessels, thermoforming, extrusion molding, compression molding, injection molding, extrusion WO 2010/101698 6 PCT/US2010/023457 blow molding and other methods. A skilled artisan would be able to determine which method is more suitable for each application considering factors including but not limited to time, cost, availability, location, design of the vessel, and function of the vessel. The 135 PET container 124 may be used but is not limited to packaging food products, soft drinks, alcoholic beverages, detergents, cosmetics, pharmaceutical products, edible oils, and combinations thereof. [00181 In a particular embodiment, the sugarcane 102 may be refined into the molasses 104 and the sugar 106 by crystallization and purification to produce pure sugar 140 and residual molasses. One typical process of refining sugarcane 102 to sugar 106 and molasses 104 is by milling the sugarcane 102, mixing the sugarcane 102 with water to produce a sugarjuice, heating the sugar juice to about 65'C to 70'C, mixing the sugar juice with lime and with gaseous sulfur dioxide, further heating the sugar juice to about 100'C to 105'C, precipitating the impurities, evaporating the sugar juice to create a syrup, 145 cooling the syrup so that the sugar 106 may crystallize, and separating the sugar 106 to produce the molasses 104 (residual liquid syrup). Other refining processes may use calcium phosphate in place of lime and/or treatment activated carbon in place of sulfur dioxide for decolonization. [00191 Alternatively, the molasses 104 may be fermented to ethanol 108 using yeast or 150 other suitable fermentation organisms held at nutrient and temperature conditions familiar to those skilled in the art. Optionally, the method further comprises fermenting the molasses 104 to produce a carbon dioxide 114. More particularly, the carbon dioxide 114 may be captured and used to carbonate beverages stored in the PET container 124. [00201 In one embodiment, the ethanol 108 may be refined into the ethylene 110 by 155 dehydration with mineral acids, strong organic acids, suitable catalysts and combinations thereof. In another embodiment., the ethylene 110 may be converted to ethylene oxide by use of a catalyst and oxygen. The ethylene oxide may further be converted to MEG 112 by a reaction with water or by a reaction with acetic acid and/or carbon dioxide to produce an intermediate compound that may be hydrolyzed to MEG 112.

WO 2010/101698 7 PCT/US2010/023457 160 [00211 Alternatively, the method comprises refining the ethylene 110 into at least one polyethylene 116, wherein the polyethylene may be selected from a low-density polyethylene ("LDPE"), a high-density polyethylene ("IDPE"), a linear low density polyethylene ("!LLDPE"), ultra-high molecular weight polyethylene ("UHM WPE") and combinations thereof. In a particular embodiment, the method further comprises 165 polymerizing the ethylene 110 with a suitable catalyst under high monomer pressure and elevated temperature to produce the at least one polyethylene 116. More particularly, the at least one polyethylene 116 may be processed to form a PET packaging. 100221 Alternatively, the method further comprises using the at least one polyethylene 116 to manufacture a closure 120 for a PET container 124. Particularly, the closure 118 170 may be a cap, a lid, and or other similar or suitable PET container 124 closures to be attached and or used to seal the product into the PET container 124. Alternatively, the closure 118 may be a screw type closure, snap type closure, and or other type of closure that can be used to seal and reseal the PET container 124. In another embodiment, the method further comprises using the at least one polyethylene 116 to produce a packaging 175 label. In a more particular embodiment, the packaging label may be manufactured by extrusion of the at least one polyethylene 116 into a film of appropriate thickness and desired properties, fol lowed by pretreatment and printing depending on applications. 100231 Alternatively, at least one PET additive 126 may be added to the PET resin 122 and/or the PET closure 120. The PET additives 126 may be selected from colorants, 180 ultraviolet protection additives, thermal stabilizers, reheat additives, barrier protection enhancers to improve reduction in transmission of oxygen, carbon dioxide, and or other gasses, liquids, light, or other materials through the vessel surface, and combinations thereof. 100241 According to a particular embodiment, the PET container 124 may contain a 185 product that comprises at least one of the sugar 106, the ethanol 108, the carbon dioxide 114, and combinations thereof produced by the methods recited above. The sugar 106, the ethanol 108, the carbon dioxide 114, and combinations thereof may be added to the WO 2010/101698 8 PCT/US2010/023457 product using any known industrial method such as blending, dosing, or the use of a CarboCooler

TM

. Skilled artisans would be able to determine the best method of use when 190 considering factors including but not limited to, the type of product, the availability of equipment, cost, and manufacturing and delivery time. 100251 In another embodiment, the PET container 124 may contain a beverage. In a more particular embodiment, the beverage comprises at least one of the sugar 106, the ethanol 108, the carbon dioxide 114, and combinations thereof produced by the methods 195 recited above. In yet a more particular embodiment, the PET container 124 may be sealed with the PET closure 120 made from the at least one polyethylene 116. Method of Producing Bio-Based PET: Corn Starch [00261 Another embodiment of the present invention encompasses a method of producing a bio-based PET from corn starch comprising the following steps: a) 200 solubilizing the corn starch to form a starch solution or gel; b) heating the starch solution or gel in hydrogen steam catalyst to produce a mixture of glycols, wherein the mixture of glycols comprises ethylene glycol; c) purifying the mixture of glycols to form MEG; and d) melt polymerizing the MEG with the TA to form a bio-based PET. More particularly, the method further comprises solid state polymerizing the bio-based PET to form a PET 205 resin and the PET resin may be molded into a PET container. Yet more particularly, the purification may be by distillation, crystallization, membrane separation, and combinations thereof. Method of Producing Bio-Based PET: Fruits, ParticularI 'Citrus [00271 As used herein, the term "citrus" refers to any part of a plant that produces 210 citrus fruits including but not limited to oranges, lemons, limes, grapefruits, tangerines, any edible member of the Genus Citrus, and combinations thereof. Today, a typical shortcoming related to the citrus business is that after the juice and the pulp are extracted from the citrus, the peel is usually discarded. Finding alternative ways to use the leftover WO 2010/101698 9 PCT/US2010/023457 citrus peels to produce a bio-based PET would reduce waste. The same concept may be 215 applicable to non-citrus fruits. [00281 Referring to Figure 2, an embodiment of the present invention encompasses a method of producing a bio-based PET from a fruit comprising the following steps: a) extracting a peel 208 from a fruit 202 and b) extracting at least one peel component from said peel, wherein the at least one peel component is selected from limonene, sugar, a 220 starch, a cellulose, and combinations thereof; c) refining the at least one peel component 208a into at least one of a MEG 210, a TA 212, and combinations thereof; and c) melt polymerizing the MEG I208 with the TA 212 to form a bio-based PET. Particularly, the method further comprises solid state polymerizing the bio-based PET to form a PET resin. More particularly, the PET resin may be molded into a PET container 214. Alternatively, 225 the fruit is selected from oranges, lemons, limes, grapefruits, tangerines, and combinations thereof. [00291 More particularly, the MEG 3 10 and the TA 312 may be produced using methods including but not limited to fast pyrolysis, acid hydrolysis, enzymatic hydrolysis, microbial degradation, mycological degradation, and hydrogenolysis. 230 [00301 In an alternative embodiment, the method further comprises extracting a juice 204 from the fruit 202; processing the juice 204 to form a beverage; optionally adding at least one beverage additive 216 to the beverage; sterilizing the beverage; and dispensing the beverage into the PET container 214. More particularly, the juice 204 may be processed by condensing the juice 204, debittering the juice 204, filtering the juice 204, 235 and blending the juice 204 with at least one of otherjuices, flavors, colors. Yet more particularly, the juice 204 may be sterilized by pasteurization. Alternatively, the at least one beverage additive 216 may be selected from neutraceuticals, antioxidants, vitamins, minerals, and combinations thereof. 100311 In another embodiment, the method further comprises extracting a pulp 206 240 from the fruit 202 and dosing the pulp 206 into the juice 204. Particularly, the pulp 206 WO 2010/101698 10 PCT/US2010/023457 may be selectively controlled and dosed back to the juice 204. The beverage may comprise different levels of pulp ranging from little or no pulp to extra pulp. [00321 Particularly, the method further comprises dispensing the beverage into the PET container 214. The PET container 214 may be produced in the same or a different 245 location from where the beverage/juice is dispensed into the PET container 214. Those skilled in the art would be able to determine the best location for production of the PET container 214 and the beverage/juice based on factors including but not limited to cost, logistics, contamination, facility capacity, and processing time. [00331 Alternatively, at least one PET additive 218 may be added to the PET resin 250 and/or the PET container 214. The PET additives 218 may be selected from colorants, ultraviolet protection additives, thermal stabilizers, reheat additives, barrier protection enhancers to improve reduction in transmission of oxygen, carbon dioxide, and or other gases, liquids, light, or other materials through the vessel surface, and combinations thereof. 255 [00341 A particular embodiment of the present invention encompasses a beverage comprising the juice of at least one fruit, wherein the juice 204 is dispensed into a bio based PET container, wherein the bio-based PET 214 container comprises at least one of MEG 210, TA 212, and combinations thereof that derived from the peel 208 of the fruit 202. Alternatively, the juice 204 may be further processed to form a beverage. The 260 beverage may optionally comprise at least one beverage additive 216 selected from neutraceuticals, antioxidants, vitamins, minerals, and combinations thereof. 100351 Depending on the type of fruits, certain components including but not limited to fibers may be further processed by thermal cracking processes to produce sugars and chemicals such as para-xylene, which may be further processed to bio-based TA. When a 265 particular fruit is chosen, a skilled artisan would readily be able to determine which components of the fruit may be processed into different components that may be used to form a bio-based PET and/or an edible product depending on available technology.

WO 2010/101698 11 PCT/US2010/023457 Method of Producing Bio-Based PET: Agricultural Waste Steams [00361 A particular embodiment encompasses a method of producing a bio-based PET 270 from agricultural waste comprising the following steps: a) collecting an agricultural waste stream; b) refining the agricultural waste stream into a. MEG; and c) melt polymerizing the MEG with a TA to form a PET. In a more particular embodiment, the TA may be a bio based TA. In one embodiment, the method further comprises solid state polymerizing the PET to form a PET resin. More particularly, the agricultural waste stream may be selected 275 from sugar husk, bagasse, corn stover, woodchips, other agricultural waste streams and products, and combinations thereof. Reeveline bio-based PET Packaging [00371 Once a bio-based PET packaging is filled with a product, the bio-based PET packaging may be distributed to a consumer through marketing outlets and other means. 280 After the product is removed or consumed, the used bio-based PET packaging may be collected in a recycle supply chain. The recycle supply chain may include, but is not limited, one or more of the an organized array of curb side pickup, special containers available to the public in building, at events, and in other locations, using designated collection sites, and municipal recycling programs. After entering the recycle supply 285 chain, the used bio-based PET packaging may be processed into a PET chip. The term "PET chip" as used herein refers to PET resin in the forms of chips (or sometimes referred to as pellets) and flakes that are primarily made form used PET packaging, including used bio-based PET packaging and used petroleum-based PET packaging. PET chips typically require only minimal cleaning and re-melting in order to be used in a new PET packaging. 290 [00381 The used bio-based PET packaging may also be processed to a recycled MEG or a recycled TA by chemical depolymerization methods such as hydrolysis, methanolysis, glycolysis, alcoholysis, aminolysis and combinations thereof.. The PET chip, the recycled MEG, and/or the recycled TA may be further processed to form new bio-based PET products. Under the industrial recycling operations available today, existing recycle WO 2010/101698 12 PCT/US2010/023457 295 supply chains are unlikely to recover a sufficient amount of used bio-based PET packaging to generate all the new PET products in demand. Thus, a supply of new bio-based MEG and new bio-based-TA will need to be continually produced to satisfy demands. [00391 Referring to Fig. 3, a particular embodiment of the present invention encompasses a method of recycling a used bio-based PET packaging 302a comprising the 300 steps of: a) processing a used bio-based PET 302a through a PET processing center to produce at least one recycled material 303 selected from a PET chip 306, a recycled MEG 308, a recycled TA 310, and combinations thereof. Alternatively, the method further comprises separating the at least one recycled material 303 into groups of PET chips 306, recycled MEG 308, and recycled TA 310. In one embodiment, the recycled material is a 305 PET chip 306 and the method further comprises routing the PET chip to a molding process. Alternatively, the recycled material is a recycled MEG 308 or a recycled TA 310 and the method optionally comprises combining the recycled MEG 308 with a new bio based MEG 312 to form a combination MEG and combining the recycled TA 310 with a new bio-based TA 313 to form a combination TA. More particularly, the method 310 comprises polymerizing the combination MEG and the combination TA to form a new PET. Yet more particularly, the method comprises combining the recycled MEG with the new MEG at a specific ratio. Even more particularly, the method comprises combining the recycled TA with the new TA at a specific ratio. Alternatively, the new PET may be combined with the PET chip 306 to produce a PET container 302b. 315 [00401 Thus, a sustainable bio-based packaging may be created by utilizing both new MEG and TA made from fresh bio-based materials and recycled MEG and TA made from recycled bio-based materials. [00411 The capabilities of the present invention can be implemented in software, firmware, hardware or combinations thereof. 320 100421 As one example, one or more aspects of the present invention can be included in an article of manufacture (e.g., one or more computer program products) having, for WO 2010/101698 13 PCT/US2010/023457 instance, computer usable media. The media has embodied therein, for instance, computer readable program code means for providing and facilitating the capabilities of the present invention. The article of manufacture can be included as a part of a computer system or 325 sold separately. 100431 Additionally, at least one program storage device readable by a machine, tangibly embodying at least one program of instructions executable by the machine to perform the capabilities of the present invention can be provided. [00441 The flow diagrams depicted herein are just examples. There may be many 330 variations to these diagrams or the steps (or operations) described therein without departing from the spirit of the invention. For instance, the steps may be performed in a differing order, or steps may be added, deleted or modified. All of these variations are considered a part of the claimed invention. [00451 While the preferred embodiment to the invention has been described, it will be 335 understood that those skilled in the art, both now and in the future, may make various improvements and enhancements which fall within the scope of the claims which follow.

Claims (22)

1. A method of making a bio-based polyethylene terephthalate (PET), comprising: (a) 340 forming at least one PET component from at least one bio-based material, wherein the at least one PET component is selected from a monoethylene glycol ("MEG"), a terephthalic acid ("TA"), and combinations thereof; (b) processing said bio-based PET component into a bio-based PET.

2. The method of claim 1, wherein the method further comprises solid state 345 polymerizing the bio-based PET to form a PET resin and processing the PET resin into a PET perform, a PET packaging, and combinations thereof.

3. The method of claim 2, wherein said bio-based PET packaging comprises an edible product and said edible product comprises an ingredient which is made from said bio-based material. 350

4. The method of claim 1, wherein the at least one PET component is produced from the bio-based material using methods of fast pyrolysis, acid hydrolysis, enzymatic hydrolysis, microbial degradation, mycological degradation, or hydrogenolysis.

5. The method of claim 1, wherein the method further comprises processing the bio based PET to form a fiber or a filament. 355

6. A method of making a bio-based polyethylene terephthalate (PET), comprising (a) refining a sugarcane into a molasses and a sugar; (b) fermenting the molasses to produce an ethanol; (c) refining the ethanol into an ethylene; and (d) refining the ethylene into a MEG, at least one polyethylene, and combinations thereof.

7. The method of claim 6, further comprising melt polymerizing the MEG with a TA 360 to form a bio-based PET and processing said bio-based PET to a PET container. WO 2010/101698 15 PCT/US2010/023457

8. The method of claim 7, further comprising fermenting the molasses to produce a carbon dioxide and using said carbon dioxide and said sugar as a beverage component for a beverage stored in said PET container.

9. The method of claim 7, further comprising processing the at least one polyethylene 365 to form a closure for said PET container.

10. The method of claim 7, further comprising processing the at least one polyethylene to form a PET secondary packaging for said PET container.

11. The method of claim 6, further comprising processing the at least one polyethylene into a PET packaging, wherein the at least one polyethylene is selected from a low 370 density polyethylene ("LDPE"), a high-density polyethylene ("HDPE"), a linear low density polyethylene ("LLDPE"), ultra-high molecular weight polyethylene ("LHMWPE") and combinations thereof.

12. A method of making a bio-based polyethylene terephthalate (PET), comprising (a) solubilizing the corn starch 202 to form a starch solution; (b) heating said starch 375 solution in hydrogen steam catalyst to produce a mixture of glycols, wherein said mixture of glycols comprises ethylene glycol; (c) purifying said mixture of glycols to form a MEG; and (d) melt polymerizing said MEG with a TA to form a bio based PET.

13. A method of making a bio-based polyethylene terephithalate (PET), comprising: (a) 380 extracting a peel from a fruit; (b) extracting at least one peel component from said peel, wherein the at least one peel component is selected from limonene, sugar, a starch, a cellulose, and combinations thereof; (c) refining the at least one peel component into at least one PET component, wherein the at least one PET component is selected from a MEG, a TA, and combinations thereof; and (d) melt 385 polymerizing the at least one PET component to form a bio-based PET. WO 2010/101698 16 PCT/US2010/023457

14. The method of claim 13, wherein the fruit is selected from is selected from oranges, lemons, limes, grapefruits, tangerines, coconuts, and combinations thereof.

15. The method of claim 13, further comprising extracting a juice from said fruit, 390 processing said juice to form a beverage.

16. The method of claim 15, further comprising extracting a pulp from said fruit and dosing said pulp into said juice or beverage.

17. The method of claims 15-16, further processing said bio-based PET to form a bio based PET container and dispensing said beverage into said PET container. 395

18. A method of making a bio-based polyethylene terephthalate (PET), comprising (a) collecting an agricultural waste stream; (b) refining the agricultural waste stream into a MEG; and (c) melt polymerizing the MEG with a TA to form a bio-based PET.

19. A method of recycling a bio-based PET packaging comprising (a) processing a 400 bio-based PET through a PET processing center to produce at least one recycled material selected from a PET chip, a recycled MEG, a recycled TA, and combinations thereof; (b) separating the at least one recycled material into groups of PET chips, recycled MEG, and recycled TA.

20. The method of claim 19, wherein the at least one recycled material is a recycled 405 MEG, the method further comprising said recycled MEG with a new bio-based MEG to form a combination MEG stream.

21. The method of claims 19-20, wherein the at least one recycled material is a recycled TA, the method further comprising said recycled TA with a new bio based MEG to form a combination TA stream. WO 2010/101698 17 PCT/US2010/023457 410

22. The method of claim 21, further comprising polymerizing the combination MEG stream and the combination TA stream to form a new bio-based PET.