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CHEMICAL PROCESS AND SUSTAINABILITY (BNQ20603) ASSIGNMENT 1: EXAMPLES OF GREEN CHEMISTRY TITTLE: BIODEGRADABLE PET & PEF FROM RENEWABLE RESOURCES CHANG WEN XI AN120195 KHAIRUL ANWAR BIN ROSLI AN120228 NOR HAZLIZA BINTI MAT SIRIP AN120015 FACULTY OF ENGINEERING TECHNOLOGY 1.0 INTRODUCTION Polymers are a large class of materials which consist of many small molecules called monomers that are linked together to form long chains, thus they are known as macromolecules. A typical polymer may include tens of thousands of monomers. Because of their large size, polymers are classified as macromolecules. Humans have taken advantage of the various usages of polymers for many years in the form of oils, tars, resins, and gums. In the diversity of their properties, polymers such as cotton, wool, rubber, Teflon(tm), and all plastics are used in almost every industry. Natural and synthetic polymers can be produced with a wide range of stiffness, heat resistance, strength, density, and even price. With continued research into the science and applications of polymers, they play as ever increasing role in society. 1.1 Biodegradable Polymers Biodegradable Plastics are polymers which derived from natural materials, such as cellulose, starch and hydroxycarboxylic acids are more easily decomposed when exposed to oxygen, water, soil organisms and sunlight compared to the most petroleum based polymers. The glycoside linkages in polysaccharides and the ester groups in polyesters represent points of attack by the enzymes released from microorganisms that facilitate their decomposition. Such biodegradable materials can be composted, broken down and returned to the earth as useful nutrients. Such materials are placed in a landfill resulting in a slower anaerobic decomposition, which will produce a greenhouse gas i.e. methane. Derivatives of cellulose, such as cellulose acetate, have long served for the manufacture of films and fibers. The other major polysaccharide, starch, is less robust than cellulose, but in pelletized form it is now replacing polystyrene as a packing material. 1.2 Classes of Polymers Elastomers or rubbery materials have a loose cross-linked structure. This type of chain structure causes elastomers to possess memory. Typically, it consists of about 1 in 100 molecules that are cross-linked on average. When the average number of cross-links rises to about 1 in 30 the material becomes more rigid and brittle. Natural and synthetic rubbers are both common examples of elastomers. Plastics, which under appropriate conditions of temperature and pressure can be molded or shaped. In contrast to elastomers, plastics have a greater stiffness and lack reversible elasticity. All plastics are polymers but not all polymers are plastics. Cellulose is a kind of a polymeric material which must be substantially modified before processing with the usual methods used for plastics. Some plastics, such as nylon and cellulose acetate, are formed into fibers, they are regarded as a separate class of polymers in spite of a considerable overlap with plastics. Some of the main chain polymer liquid crystals also are the constituents of important fibers. 1.3 Polyethylene Terephthalate, PET Polyethylene terephthalate (PET or PETE) is a strong, stiff synthetic fibre and resin, and a member of the polyester family of polymers. PET can be spun into fibres for permanent-press fabrics, blow-molded into disposable beverage bottles, and extruded into photographic film and magnetic recording tape. PET is produced by the polymerization of ethylene glycol and terephthalic acid. When heated together under the presence of chemical catalysts, ethylene glycol and terephthalic acid produce PET in the form of a molten, viscous mass that can be spun directly to fibres or solidified for later processing as a plastic. In chemical terms, ethylene glycol is a diol, and terephthalic acid is a dicarboxylic aromatic acid. Under the influence of heat and catalysts, the hydroxyl and carboxyl groups react to form ester (CO-O) groups, which serve as the chemical links joining multiple PET units together into long-chain polymers. The resulting spaghetti-like strands of PET are extruded, quickly cooled, and cut into small pellets. The resin pellets are then heated to a molten liquid that can be easily extruded or molded into items of practically any shape. 1.4 Polyethylene Furanoate, PEF Polyethylene furanoate (PEF) is an analogue of polyethylene-terephthalate (PET). PEF is a generation of 100% bio-based and recyclable polyester. It has better mechanical and barrier properties than the current biggest selling polyester polyethylene terephthalate (PET). PEF could replace PET in typical applications like films, fibers and in particular bottles for the packaging of soft drinks, water, alcoholic beverages, fruit juices food and non-food products. A company, ALPLA will develop PEF bottles for personal and home care applications, such as cosmetics, detergents and food applications i.e. sauces, dressings, baby foods and edible oils. ALPLA and Avantium will also work on the development of bottles for beer and other alcoholic beverages. 2.0 CONVENTIONAL PROCESS OF POLYETHYLENE TEREPHTHALATE Background on Polyethylene Terephthalate (PET) The first fiber–forming polyesters were prepared by Carothers and Hill in 1932 using the melt condensation of dicarboxylic acids and aliphatic diols. Because of their low melting points and ready dissolution in organic solvents, these polymers were not considered to be significant advance. The development of polyester fibers having high melting points and more chemical resistance was possible through the use of terephthalic acid. The technical development of PET fibers began after DuPont and ICI purchased the rights to the technology of Darcon and Terylene, respectively. Polyethylene terephthalate (PET) is a polycondensation polymer. It is most commonly produced from a reaction of ethylene glycol (EG) with either purified terephthalic acid (TPA) or dimethyl terephthalate (DMT), using a continuous melt-phase polymerization process. However, water is produced as a polycondensation by-product with no important economical values. In many cases, melt phase polymerization is followed by solid-state polymerization FIRST STEP (TRANSESTERIFICATION) This polymer is the most common thermoplastic polyester. It is often called “polyester”, which often causes confusion. PET is a hard, stiff, strong, dimensionally stable material that absorbs very little water. It has good gas barrier properties and good chemical resistance except to alkalis (which hydrolyze it). Its crystallinity varies from amorphous to fairly high crystalline. It can be highly transparent and colorless but thicker sections are usually opaque and off-white (Salaeh A. Jabarin, 1996). PET is widely known in the form of thermally stabilized films used for capacitors, graphics, film base and recording tapes etc. It is also used for fibres for a very wide range of textile and industrial uses. Other applications include bottles and electrical components. 2.2 Basic Principles of Polyethylene Terephthalate (PET) Formation Polyethylene Terephthalate, (PET) is generally produced via two different routes; Trans-esterification of dimethyl terephthalate (DMT) with ethylene glycol (EG) and direct esterification of purified terephthalic acid (TPA) with EG. The first stage of the two routes, known respectively as trans-esterification (ester interchange) and direct esterification, both produce a mixture of ethylene glycol ester of terephthalic acid. This mixture of linear oligomers (mainly bis-hydroxyethyl terephthalate BHET) is subjected to a further stage known as polycondensation that produces polyethylene terephthalate of fiber-forming molecular weight. Solid-state polymerization is required only for the production of bottles. Figure 1.0 Monomer of polyethylene terephthalate. Figure 1.1 Chemical structure of Polyethylene Terephthalate. The first stage in the polymer synthesis is esterification, which results from the reaction of carboxylic group with an alcoholic group. Since these groups occur at the ends of bi-functional compounds, PET with a linear structure is produced. However, it is necessary during esterification for the compound that is eliminated (water or methanol) to be rapidly removed from the reaction mixture so that the equilibrium shifts preferentially in favour of the polycondensation product. The second stage in the polymer synthesis is similar for both the ester interchange and direct esterification routes. A further catalyst is added to the mixture of linear oligomers, free glycol is distilled out by using very low pressure until the required molecular weight is attained. The most popular catalyst for this stage is antimony trioxide, although antimony pentoxide and germanium dioxide have also been used. With the rising worldwide demand for polyethylene terephthalate, prospective PET producers are faced with a lot of decision; whether to use purified terephthalic acid or dimethyl terephthalate as the raw material, batch or continuous process, and whether to use the conventional process or to add some modifications to reduce the costs and increase the productivity. 2.3 Raw materials During 1970 DMT production exceeded that for TPA by more than three to one. In 1980s TPA production was about 53 percent of the total. The shift from DMT to TPA as the dominant raw material for PET production occurred for several reasons, the most important of which are quality, price, and overall PET production costs. Terephthalic acid gives a higher yield (15% over DMT) of polyester and therefore results in obvious savings in material cost. The capital to construct a PET facility based on TPA is reported to be at least 20 percent less than one based on DMT. This saving is attributed to many factors. In the direct esterification of TPA, the by-product is less costly to recover besides being less bothersome from a disposal standpoint as compared to methanol by-product from DMT process. Furthermore, a TPA process is capable of requiring less EG during the initial stages of the reaction. Currently PET producers operate in the range of 1.1-1.3 moles of EG per mole of TPA with a 1 to1 mole ratio perhaps becoming possible by introducing the pervaporation technology to the process in contrast to that at least 1.8 moles of EG per mole DMT. Hence there is less EG to be recovered when processing TPA, resulting in a lower investment for a glycol recovery and recycle system. Furthermore, the importance of using less glycol is that less diethylene glycol (DEG) is formed. However, it is worthy to mention certain disadvantages of TPA as a raw material, TPA has a very low solubility in boiling EG at atmospheric pressure, so, it is necessary to raise the reaction temperature and pressure in order to obtain an adequate reaction rate. In addition, trace impurities can be responsible for undesirable discoloration of the polymer. And finally, not all TPA’s are capable of processing at the lower glycol-to-acid ratios. A TPA with specially “engineered” particle size is required. Ethylene glycol is derived from ethylene by catalytic oxidation with air to ethylene oxide followed by acid hydrolysis. The EG must be pure and free from color-forming impurities and traces of strong acids or bases. 2.3.1 Terephthalic acid Figure 1.4 Chemical structure of Terephthalic Polyethylene terephthalate is increasingly produced from very pure terephthalic acid. As mentioned, the terephthalic acid has some advantages over dimethyl terephthalate for the production of PET. • Lower price • Does not need catalyst like transesterification • Higher polycondensation speed • No recovery of methanol necessary Because of these benefits, the world production of terephthalic acid has been increasing; the world capacity for 1994 is 10.8 million tons compared to 5.3 million tons for dimethyl terephthalate. Terephthalic acid is produced mainly by the Amoco process, and then the raw terephthalic acid, containing 4-carboxybenzaldehyde as the main contaminant, is purified by hydrogenation and crystallization. The final terephthalic acid has a purity of 99.99 wt%. 2.3.2 Ethylene glycol Figure 1.5 Chemical structure of Ethylene Glycol Ethylene glycol is produced industrially by the reaction of ethylene oxide with excess water. The typical product distribution between the products of this reaction, which are ethylene glycol, diethylene glycol, and triethylene glycol, is a mass relation of 30:4:1 respectively. The glycols are separated by purification under vacuum in distillation columns connected in series. 2.4 Atomic economy One of the fundamental and most important principles of Green Chemistry is that of atom economy. This essentially is a measure of how many atoms of reactants end up in the final product and how many end up in by-products or waste. The percent atom economy was calculated as below (refer Figure 1.6 and Figure 1.8). Comparison between the atomic economy of two different routes producing polyethylene terephthalate: 2.4.1 Dimethyl Terephthalate (DMT) Process General process: (2) (1) (3) Figure 1.5 Chemical reaction of Dimethyl terephthalate process Formula weights: 194 (2) 62 (3) 193 % Atom Economy = 100 X 193/ (194+62) = 75.4% Figure 1.6 Atom economy calculation for Dimethyl terephthalate process 2.4.2 Terephthalic acid (TPA) process (3) (1) (2) Figure 1.7 Chemical reaction of Terephthalic acid process. Formula weights: 166 (2) 62 (3) 193 % Atom Economy = 100 X 193/ (166+62) = 84.6% Figure 1.8 Atom economy calculations for Terephthalic acid process. As a result, dimethyl terephthalate (DMT) process yields 75.4% of atom economy while the reaction process of terephthalic acid (TPA) yields 84.6% atom economy to produce polyethylene terephthalate (PET). These two different routes proved that producing PET by the reaction of TPA with EG is preferable compared to the reaction of DMT with EG by referring to their percent of atom economy. As discussed before, TPA has some advantages over dimethyl terephthalate for the production of PET.  2.3 Designs for Degradations PET is subjected to various types of degradations during processing. The main degradations that can occur are hydrolytic, thermal and, probably most important, thermal oxidation. When PET degrades, several things happen: discoloration, chain scissions resulting in reduced molecular weight, formation of acetaldehyde, and cross-links ("gel" or "fish-eye" formation). Discoloration is due to the formation of various chromophoric systems following prolonged thermal treatment at elevated temperatures. This becomes a problem when the optical requirements of the polymer are very high, such as in packaging applications. The thermal and thermooxidative degradation results in poor processibility characteristics and performance of the material. One way to alleviate this is to use a copolymer. Comonomers such as CHDM or isophthalic acid lower the melting temperature and reduce the degree of crystallinity of PET (especially important when the material is used for bottle manufacturing). Thus, the resin can be plastically formed at lower temperatures and/or with lower force. This helps to prevent degradation, reducing the acetaldehyde content of the finished product to an acceptable (that is, unnoticeable) level. Another way to improve the stability of the polymer is to use stabilizers, mainly antioxidants such as phosphites. Recently, molecular level stabilization of the material using nanostructured chemicals has also been considered.  3.0 GREEN ROUTE PRODUCTION FOR BIO-PLASTIC Over the last decades, research has led to the rapid development of materials from biomass, for non-food and polymer applications. These materials are bio-based and biodegradable which capable of undergoing decomposition into carbon dioxide, methane, water, inorganic compounds, and biomass. Biofuels and bio-based also have better greenhouse gas emissions compared to fossil fuels and petrochemicals because the carbon from biomass can be directly traced to atmospheric CO2 via photosynthesis. The predominant mechanism is the enzymatic action of micro-organisms such as fermentation and catalytic process. Currently, bio-plastics (plastics from renewable source – from biomass) represent enormous potential due to a growing demand for more friendly and environmental materials. These materials can be either for short term applications such as packaging and also for durable and long terms applications such as building and automotive. For example, Coca Cola Company investing and funding research project to develop bio-based plastics for beverage containers. The first phase of this massive project has resulted in the PlantBottleTM which is made using bio-PET where the ethylene glycol starting monomer is made from renewable sources. The PlantBottleTM contains approximately 30% bio-based carbon. Coca Cola also continued to establish three other Research and Development(R&D) partners (Virent, Gevo, and Avantium) to drive to a 100% bio-based PlantBottleTM. The next piece of the puzzle is to find a synthetic route to bio-based terephthalic acid (PTA). The Virent approach uses soluble carbohydrate starting materials and the Gevo approach uses fermentable sugars to produce bio-terephthalic acid (bio-PTA). The Avantium YXY approach uses C6 sugars to produce furanics, then furandicarboxylic acid, which when polymerized with bio-EG will form bio PEF, a totally new, 100% bio-based polymer. Figure SEQ Figure \* ARABIC 1.9 Research and Development of Bio-Based plastics (PET, PlantBottleTM and PEF) Source: http://cr4.globalspec.com/blogentry/18979/Open-Happiness-from-a-Renewable-Bottle Another example of green synthetic alternative routes for production of purified terepthalic acid (PTA) and p-hydroxybenzoic acid from renewable resource. Source: http://www.chemistry.msu.edu/faculty-research/faculty-details/params/group/frostj/ Synthetic routes for production of Ethylene by conventional petrochemical routes and renewable feed stocks. Source: http://www.hydrocarbonprocessing.com/Article/2966827/Bio-based-polymers-could-be-next-big-thing.html 3.1 PlantBottleTM (70% TPA and 30% bio-EG) Bio-based Polyethylene terephthalate (PET) is synthesis by the mixing of ethylene glycol (EG) derived by sugarcane and terephthalic acid (TPA) from fossil resources. Production of BioPET from 70% petrochemical TPA and 30% biomass EG Source: Emerging bio plastics in packaging, VTT Technical Research Centre of Finland (2013) Polyethylene terephthalate, is formed by reacting terephthalic acid (or dimethyl terephthalate) with ethylene glycol Source: http://www.google.com/patents/EP0217660A2?cl=en (Publication number EP0217660 A2) 3.1.1 Green Route Synthesis of Ethylene Glycol from Glucose Reactant: C6H12O6, O2, H2O Molecular weight: C = 6(12) = 72 H = 14(1) = 14 O = 14(16) = 224 Total = 310 Product: C2H6O2 Molecular weight: C = 2(12) = 72 H = 6(1) = 14 O = 2(16) = 224 Total = 62 Atom Economy: 3.1.2 Conventional Route Synthesis of Terepthalic Acid (PTA) from Petrochemical Reactant: C7H8, 2O2, CH3OH Molecular weight: C = 8(12) = 96 H = 12(1) = 12 O = 5(16) = 80 Total = 188 Product: C8H6O4 Molecular weight: C = 8(12) = 96 H = 6(1) = 6 O = 4(16) = 64 Total = 166 Atom Economy: 3.2 Polyethylene Furanoate (PEF). C6 and C5 sugars such as Glucose (C6) and Xylose (C5) can be converted chemically into commercial molecules. For example, treatment of glucose or fructose with various acid catalysts generates 5-hydroxymethylfurfural (HMF). HMF can be oxidized efficiently by YXY-process (Avantium) to produce 2, 5-furandicarboxylic acid (FDCA) a monomer component of the novel, renewable polyester, polyethylene furanoate, or PEF, that is a potential replacement for petroleum-based PET polyester. Chemical conversion of sugar accomplished by catalytic reforming in water at elevated temperature (180-220oC) and pressure (10-90 bar) followed by treatment with catalysts that favour classical Aldol-type condensation chemistry and rearrangement or aromatic ring formation (US Patents 7,977,517B2 and 8,017,818B2). Process for the production of poly (ethylene 2, 5- furandicarboxylate) from 2,5-furandicarboxylic acid and use thereof, polyester compound and blends thereof Source: http://www.google.com/patents/WO2013097013A1?cl=en (Publication number: WO2013097013 A1) 3.2.1 Green Route Synthesis of Furandicarboxylic Acid (FDCA) from Glucose Reactant: C6H12O6, O2 Molecular weight: C = 6(12) = 72 H = 12(1) = 12 O = 8(16) = 128 Total = 212 Product: C2H4O5 Molecular weight: C = 2(12) = 24 H = 4(1) = 4 O = 5(16) = 80 Total = 108 Atom Economy: 3.2.2 Green Route Synthesis of Ethylene Glycol from Glucose Reactant: C6H12O6, O2, H2O Molecular weight: C = 6(12) = 72 H = 14(1) = 14 O = 14(16) = 224 Total = 310 Product: C2H6O2 Molecular weight: C = 2(12) = 72 H = 6(1) = 14 O = 2(16) = 224 Total = 62 Atom Economy: 3.3 Polyethylene terephthalate (PET) – 100% bio-based Coca-Cola Co. continued to established partnership agreements with three biotechnology companies to accelerate development of what will be a PTE made 100% entirely of plant-based materials. Current development routes of TPA (terephthalate acid) from biomass are complicated, leading to high capital expenditure and high operational costs. The Virent approach uses soluble carbohydrate starting materials and the Gevo approach uses fermentable sugars to produce bio-terephthalic acid (bio-PTA). 3.3.1 Green Route Synthesis of Ethylene Glycol from Glucose Reactant: C6H12O6, O2, H2O Molecular weight: C = 6(12) = 72 H = 14(1) = 14 O = 14(16) = 224 Total = 310 Product: C2H6O2 Molecular weight: C = 2(12) = 72 H = 6(1) = 14 O = 2(16) = 224 Total = 62 Atom Economy: 3.3.2 Synthesis of Terepthalic Acid (PTA) from Glucose (Givo Approach) Reactant: C6H12O6, H2, C2H4, O2 Molecular weight: C = 8(12) = 96 H = 18(1) = 18 O = 8(16) = 128 Total = 242 Product: C8H6O4 Molecular weight: C = 8(12) = 96 H = 6(1) = 6 O = 4(16) = 64 Total = 166 Atom Economy:  ROLE OF GREEN CHEMISTRY IN POLYMER PRODUCTION. Bio-based rigid bio-PTE and bio-PEF is design to fulfill the expectations to have of modern plastics. These plastics meet the performance requirements for packing and are competitive with conventional packaging. Building upon renewable feedstock, bio-based plastics offers an opportunity to achieving a low carbon economy. Businesses can tap the advantages of bio-based rigid packaging to decouple their growth from the consumption of fossil resources and greenhouse gas emissions. The slow or resistance to degradation of traditional plastics is the significant factor in landfill capacity. In the landfills, the plastics undergo reaction that contributes to leachate production. The leachate when flow to the water resources can cause pollution. The design of Bio-Plastics such as PET and PEF from the use of renewable feedstock such as Glucose from plant can reduce the landfill capacity as the plastics is biodegradable which capable of undergoing decomposition into carbon dioxide, methane, water, inorganic compounds, and biomass naturally. Since the Biofuels and bio-based also have better greenhouse gas emissions compared to fossil fuels and petrochemicals because the carbon from biomass can be directly traced to atmospheric CO2 via photosynthesis. This is a very important goal considering the energy savings and the climatic change which has become a global environmental problem. Because of its resistance to degradation, enhancing the degradation process such as using incineration technic offered as a solution. However, plastics contained heavy metal-based additives, colourants, stabilizers and others chemical which when burnt it emits toxic fumes. Traditional plastics also increase the cost to build the incinerators and for the treatment and clean up waste formed by the traditional plastics. Bio-Plastics also undergo less hazardous chemical synthesis; most of the Bio-Plastics raw material is synthesis by fermentation of C6 and C5 sugars. In recent years there are many more alternative or “greener” reaction techniques improving substantially the product yield, saving energy and minimize waste. Photochemical reactions, microwave and ultrasound assisted organic synthetic techniques, reactions using water as solvent, catalytic reaction and others are some of the new techniques in synthesizing chemicals. Atom Economy Conventional Plastics Synthesis route of PET from: Atom Economy Dimethyl Terephthalate (DMT) Process 75% Terephthalic Acid (PTA) Process 84.6% Bio-Plastics Bio-Plastics Atom Economy Synthesis of Bio-PET TPA:Bio-EG (70:30) Petrochemical TPA Bio-EG 20% 88.3% Synthesis of PEF FDCA from Glucose Bio-EG 51% 20% Synthesis of 100% Bio-PET Bio-TPA Bio-EG 68.6% 20% BioPET consists of 70% TPA and 30% EG Process for Bio-EG (bio-ethyleneglycol) exists Current development routes of TPA (tereftalic acid) from biomass are complicated, leading to high capex and high operational costs Production process of TPA can be simplified and made more resource efficient: • Gevo devolepment route (CocaCola) has 4 steps • VTT develops a 2 step process BioPEF Avantium is developing bioPEF with superior barrierand mechanical properties compared to PET Production route is complicated, and the yellowishcolor still prevents its use in most packagingapplications Production from furans. Possibly from hemisugars inthe future.Wood based bio-TPA for cheap bio-PET bottles. Comparison of PET and PEF Superior functional properties: Avantium’s research has proven that PEF bottles outperform PET bottles in many areas, particularly barrier properties (the ability of the polymer to withstand gas permeability through the bottle). PEF’s ability to seal out oxygen, for example, results in longer-lasting carbonated drinks and extended shelf life. Moreover, PEF makes certain packaging coatings redundant, like the coatings used on bottles to keep beer fresh. In terms of thermal properties, PEF is widely considered more attractive than PET due to its superior ability to withstand heat (expressed in the glass transition temperature or Tg) and process-ability at lower temperatures (expressed in the melting temperature or Tm). Superior barrier properties: PEF oxygen barrier is 10 times better than PET PEF carbon dioxide barrier is 4 times better than PET PEF water barrier is 2 times better than PET More attractive thermal properties: The Tg of PEF is 86°C compared to the Tg of PET of 74°C The Tm of PEF is 235°C compared to the Tm of PET of 265°C 5.0 CONCLUSION Bio-based rigid packaging products fulfilled the expectations users have of modern plastics. They meet the performance requirements for packing and are competitive with conventional packaging. This applies to the invention of PEF which provide a green route on polymer industry. Building upon renewable feedstock, bio-based rigid packaging offers an opportunity to achieving a low carbon economy. The production and use of bioplastics is generally regarded as a more sustainable activity when compared with plastic production from petroleum (petroplastic), because it relies less on fossil fuel as a carbon source and also introduces fewer greenhouse emissions if it biodegrades. They significantly reduce hazardous waste caused by oil-derived plastics, which remain solid for centuries on the earth. With increasing shares of bio-based content in the packaging products and foreseeable improvements in the waste management, bioplastics in rigid packaging applications can contribute to mitigating or lowering significant and potentially irreversible changes to the climate. However, manufacturing of bioplastic materials is often still relying upon petroleum as an energy and materials source. This comes in the form of energy required to power farm machinery and irrigate growing crops, to produce fertilisers and pesticides, to transport crops and crop products to processing plants, to process raw materials, and ultimately to produce the bioplastic, although renewable energy can be used to obtain petroleum independence. 6.0 REFERENCES Acid catalysed alcoholysis of lignocellulose; towards second generation furan-derivatives,” by Ruud J.H. Grisel (ECN), Jan Kees van der Waal (Avantium), Ed de Jong (Avantium) and Wouter J.J. Huijgen (ECN); presented at COST Action CM0903 (UBIOCHEM), 3rd workshop, Thessaloniki (Greece), November 1-3, 2012. M. Doble, A.K Kruthiventi Green Chemistry & Engineering. Academic press is an imprint of Elseviere Inc. UK, 2007 R.M. Kriegel, X.Huang, M. Schultheis, B.H Kolls. Bio-based polyethylene terephthalate packaging and method of making thereof. Publication number EP2403894 A2 (text from WO2010101698A2) (2009). Source from: https://www.google.com/patents/EP2403894A2?cl=en (accessed on 6th March 2014) C. Berti, E. Binassi, M. Colonna, M. Fiorini, G. Kannan, S. Karanam, M. Mazzacurati, I. Odeh, M. Vannini, Bio-based terephthalate polyesters. Publication number WO2010078328 A2 (2008) Source from: https://www.google.com/patents/WO2010078328A2?cl=en&dq=Gevo+Bio+Terephthalic+acid&hl=en&sa=X&ei=ptsZU_XmN82Arge-zYCYAw&ved=0CEIQ6AEwAg (accessed on 5th March 2014) Method for producing a bio-pet polymer by Societe Anonyme Des Eaux Minerales D'evian Et En Abrege "S.A.E.M.E". Publication number WO2013034743 A1. (2011) Source from: https://www.google.com/patents/WO2013034743A1?cl=en (accessed on 7th March 2014) Product Application Avantium Company Source from: http://avantium.com/yxy/products-applications/fdca/PEF-bottles.html (accessed on 6th March 2014) Polyethylene Furanoate 100% Bio-Based Polymer Source from: http://polymerinnovationblog.com/polyethylene-furanoate-pef-100-biobased-polymer-to-compete-with-pet/ (accessed on 5th March 2014) Why PEF is Better than PET Source from: http://www.biobased-society.eu/2012/07/why-pef-is-better-than-pet/ (accesed on 6th March 2014)