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Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
Introduction to bioplastics
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Introduction to bioplastics

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Overview of Bioplastics and the developments in the Industry

Overview of Bioplastics and the developments in the Industry

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  • There are several existing and emerging players in the field of PHA polymers. Here in the USA the predominant player is Metabolix. Others are emerging globally. If all companies realize their expectations there will be over 70,000MT of the 3HB-4HB PHA available by end of 2009. Tianan Biologic is still the only company producing specifically PHBV. In addition Tianan is the only company who has the technology to efficiently extract the polymer for the microorganisms using low temperature water extraction. This process is patented by Tianan Biologic.
  • Transcript

    • 1. Introduction To Bioplastics Dr. Jim Lunt
    • 2. Basic Definitions for Bioplastics. Drivers for Bioplastics. Growth Projections and Market Trends. The Evolving Biobased ―Landscape.‖ Performance Issues for Today’s Bioplastics. Emerging Technologies. Conclusions. Presentation Outline
    • 3. Basic Definitions for Bioplastics Terminology Standards Measurements
    • 4. What are Biodegradable Plastics? Biodegradable or Compostable Plastics are those which meet all scientifically recognized norms for biodegradability and compostability of plastics and plastic products independent of their carbon origin. In Europe, the composting standard is EN 13432 and in the USA ASTM D6400.
    • 5. ASTM D6400 Standard Criteria For Compostability 1. Mineralization • At least 90 percent conversion to carbon dioxide, water and biomass via microbial assimilation. • Occurs at the same rate as natural materials (i.e. leaves, grass food scraps.) • Occurs within a time period of 180 days or less. 2. Disintegration • Less than 10 percent of test material remains on a 2mm sieve. 3. Safety • No impact on plants, using OECD Guide 208. • Regulated (heavy metals less than 50 percent of EPA prescribed threshold.)
    • 6. Embrittlement begins Complete Fragmentation Polymer Hydrolysis Lactic acid and Oligomers Biodegradation 0 10 20 30 40 10,000 30,000 50,000 70,000 0 20 40 60 80 100 Time (Days) Num. Avg. Mol. Wt. (Mn) % CO2 Evolved % CO2 Mn Biodegradation Mechanism For PLA (In Compost At 60oC)
    • 7. Products that are composed wholly or significantly of biological ingredients —renewable plant, animal, marine or forestry materials. Does not consider if plastics are compostable or durable. Does not refer to any standards of measurement. USDA Definition of Biobased Products
    • 8. To be classified as ―biobased,‖ the material must be organic and contain some percentage of recently fixed (new) carbon found in biological resources or crops. This definition is the basis of ASTM D6866. Uses C14 content measurement. Measurement of Biobased Content
    • 9. Measurement of Biobased Content
    • 10. Biobased Plastics Major focus is on the ―origin of life‖ or where did the carbon come from (ASTM D6866). Uses C14 content measurement. Biodegradable (Compostable) Plastics Focus is on ―end of life or disposal.‖ Independent of Carbon Source Standards EN 13432 and ASTM D6400. These two classes are, however, not mutually exclusive. Biobased & Biodegradable
    • 11. Alternative Disposal Initiatives  BIOCOR in the USA to establish an infrastructure to allow collection of PLA postconsumer and industrial waste.  Primarily, this appears to be in response to the resistance by bottle recyclers to accept PLA due to contamination concerns, but will also allow a potentially more sustainable business model.  This initiative is still in its infancy and will not materially affect PLA growth in the near term.
    • 12. Renewable resource versus oil based. Reduced environmental impact. Concerns about human health. End-of-Life disposal issues – Landfill. Legislative initiatives. Drivers for Bioplastics
    • 13. Oil Versus Corn Price Courtesy Gevo
    • 14. Oil Carbon V Corn Carbon Price % Carbon in oil = 84% based on isooctane There are several grades of crude oil, Assuming 35.6° API, is 847 kg / m3 and a barrel is 0.159 m3 it would be 134 kg or 295.4 lbs A US barrel of oil is 42 gal. Cost of oil based carbon example $60/(0.84*295.4) = $0.242 % carbon in Dextrose = 40 % dextrose from corn = 65 Weight of a bushel = 56# Cost of corn based carbon example $3.50/(56*0.65*0.4) =$0.240
    • 15. Oil Versus Corn Price 1.40 1.90 2.40 2.90 3.40 3.90 4.40 4.90 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.00 0.05 0.15 0.25 0.35 crude oil cost corn cost $Oil/barrel $Carbon Cost $Corn/Bu Cost of Carbon Oil v Corn Sugar
    • 16. Hull & Fiber (23%) • Starch (65%) Germ (7%) Gluten Meal (5%) Fructose for Sweeteners Dextrose for Fermentation Feedstocks Number 2Yellow Dent is used in the USA for Lactic Acid Production Corn as A Feedstock
    • 17. Typical yields from a bushel of corn (56 pounds) from the wet mill include:  31.50 lbs starch (33.3 lbs sweetener, due to hydrolysis weight gain.)  1.55 lbs of corn oil.  13.50 lbs of corn gluten feed.  2.60 lbs of corn gluten meal. The value of these by products ranged from $1.35/bu to $2.95/bu during the period of 2007-2008. Corn ranged from $3.03/bu to $6.55/bu, resulting in a computed price for net corn of $1.13/bu to $3.82/bu. Based on these values, the USDA reports a corn sweetener (dextrose) cost. Net Corn Pricing Calculation
    • 18. White Pollution-China
    • 19. Increasing Litter Concerns
    • 20. Health Concerns
    • 21. Legislation Against Petroleum Based Plastics
    • 22. Japan Government has set a goal that 20% of all plastics consumed in Japan will be renewably sourced by 2020. Germany Ban on land filling solid waste with over 5% organic content. Biodegradable plastics exempt from the recycling directive until 2012. Savings of 1.3 €/kg in favor of compostable bioplastics. Netherlands Implementing a 40 euro cents/kg tax on PET vs. tax on PLA of 8 euro cents/kg. USA Federal Farm Bill - Energy Title 9 Each Federal agency must design a plan to purchase as many biobased plastics as practically possible. Federal procurement plan will be based on biobased content, price and performance. Key Legislative Initiatives for Bioplastics
    • 23. Definition of Sustainability Sustainability is simply stated as: “meeting the needs of the present without compromising the ability of future generations to meet their own needs." BUT….. How do we achieve and measure this?
    • 24. How Do We Really Measure Sustainability? Life Cycle Analysis - One attempt to measure sustainability. Complex and Inputs/Outputs still Debated
    • 25. Life Cycle Analysis ISO 14040 or ASTM D7075 -LCA involves the compilation of a comprehensive inventory (Life Cycle Inventory, or LCI) of relevant inputs and outputs of a production system. This means an organized effort to measure specific input components contributing to the production and delivery of the material to its end-use application. In addition, an LCA requires an evaluation and assessment of the environmental impacts associated with the processes.
    • 26. 2.02 0.27 0.75 2.52 3.49 3.49 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 2005 2006 2009 ACC Plastics Europe Gabi PEA kgCO2eq./kgIngeo Source Data: Ingeo - NatureWorks LLC ; PET: M. Binder, Technical Director, PE Americas; Ingeo PET With REC Technology Improvements Compared to any of the PET data sets, all of the Ingeo profiles have a lower contribution to climate change PLA: Vink E.T.H. et all
    • 27. 50.2 27.2 35.2 69.6 77.8 85.6 0 10 20 30 40 50 60 70 80 90 2005 2006 2009 ACC Plastics Europe Gabi PEA MJ/kgIngeo Source Data: Ingeo - NatureWorks LLC ; PET: M. Binder, Technical Director, PE Americas; Ingeo PET With REC Technology Improvements Compared to any of the PET data sets, all of the Ingeo profiles have a lower non-renewable energy use Cradle-to-Pellet Primary Non-renewable Energy Use PLA: Vink E.T.H. et all
    • 28. The Food versus Fuel Debate: • Food Crops V Biomass • The ―Ripple Effect ― Use of GMO's End-of-Life disposal options: • Compostability • Recyclability But There Are Other Issues
    • 29. Projected Biomaterials Trends
    • 30. Global Demand for bioplastics will increase more than fourfold to 900,000 tonnes in 2013. (Freedonia) Projected Biomaterials Trends
    • 31. Global Production of bioplastics will increase sixfold to 1.5 million tonnes by 2011. up from 262,000 tonnes in 2007. (European Bioplastics) Global Demand for bioplastics will increase more than fourfold to 900,000 tonnes in 2013. (Freedonia) Projected Biomaterials Trends
    • 32. Production Capacity of bio-based plastics is projected to increase from 360,000 tons in 2007 to about 2.3 million tons by 2013. (European Bioplastics) Global Production of bioplastics will increase six fold to 1.5 million tons by 2011. up from 262,000 tonnes in 2007. (European Bioplastics) Global Demand for bioplastics will increase more than four fold to 900,000 tons in 2013. (Freedonia) Projected Biomaterials Trends
    • 33. Bioplastics will still only be 1% of the approximate 230 million tons of plastics in use today. Projected Biomaterials Trends
    • 34. The Evolving Biobased Plastics Landscape
    • 35. Biobased Polymer Capacities For Major Players Product Company Location Capacity/mt Price/# PLA PLA PHA’s PHBH PHBV Materbi Cereplast HDPE/LDPE /PP Natureworks Hisun Metabolix Meridian/Kaneka Tianan Novamont Cereplast Braskem USA China USA USA China EU USA SA 140,000 5,000 300/50,000 (2010) 150,000? 2,000 75,000 25,000 200,000 (2010) 0.85-1.20 1.25 2.50-2.75 n/a 2.40-2.50 2.0-3.0 1.50-2.50 0.80-1.00
    • 36. NatureWorks, Hisun Novamont Cereplast Dupont Tianjin Bio Green /DSM Tianan Biologic Metabolix Braskem PLA Mater-Bi, Origo Bi Cereplast BIOMAX (PTT, Plantic) PHA PHBV PHA Green Polyethylene The Biobased Leaders Today ……………………………………………………………………………………………………………… ……………………………………………………………………………………………………………… WHO? WHAT?
    • 37. Compounded Biobased Compostable O OH HO H CH3 L-Lactic Acid O OH HO H3C H D-Lactic Acid (0.5%) Polylactic Acid (PLA) 100% Renewable & Compostable Key Compostable Bioplastics Starch/PLA/ECOFLEX …………………….……………………………………………………………
    • 38. Compostable Bioplastics Second Generation Poly Hydroxy Alkanoates (PHA’s
    • 39. Major Bioplastic Packaging Markets Four Sectors showing significant growth: 1. Compostable, single-use, bags/films. 2. Thermoformed products for food applications. 3. Gift cards. 4. Plastic foams based on soy-based polyols.
    • 40. Plastic Films Market Size US plastic bag market is estimated by Omni Tech* to be 68 million tons in 2007. Growth rate of 15% per year through 2011 to 119 million tons. *http://soynewuses.org/downloads/reports/DisposalblePlasticsMOS.PDF
    • 41. Major Markets for Biobased Films Clear wrapping films (blown and cast) for food- and non-food wrap. Clear biaxially-orientated film for tamper proof seals and shrink wrap. Translucent cast and blown film for: Trash bags Yard & Garden Industrial refuse Kitchen and other Newspaper and magazine wrap Diaper back sheets Agricultural mulch films Almost all biobased film applications today are single-use disposables where compostability is a perceived benefit along with biobased content.
    • 42. Bioplastic Manufacturers for Film Applications Transparent rigid films: PLA,( NatureWorks LLC.) Cellulose acetate (Innovia) Translucent flexible films: Starch/PLA, and/or Ecoflex synthetic polyester • Materbi, (Novamont) • Bioplast, (Stanelco / Biotec) • Ecovio, PLA/ Ecoflex (BASF) • Ecobras, Starch / Ecoflex (BASF) • Cereplast Compostables, (Cereplast) Hydroxy propoxylated starch, (Plantic Technologies)
    • 43. Major Concerns with Bioplastic Films • Cost / lb. and density v polyethylene / polypropylene. • Lack of curbside collection and municipal composting infrastructure. • Poor tear propagation. • Moisture sensitivity for starch based products. • Controlled degradation times for mulch films. • Barrier (moisture transmission) for starch and PLA formulations. • Low temperature resistance of PLA unless orientated.
    • 44. Resin OTR WVTR CO2 PLA 38-42 18-22 201 PET (OPET) 3-6.1 1-2.8 15-25 HDPE 130-185 0.3-0.4 400-700 PP 150-800 0.5-0.7 150-650 Nylon 6 2-2.6 16-22 10-12 EVOH 0.01-0.16 1.4-6.5 PVC 4-30 0.9-5.1 4-50 Comparative Gas Transmission Properties
    • 45. Biaxially Orientated PLA
    • 46. Cellulose Acetate
    • 47. Compounded PLA/Starch Blends
    • 48. Braskem Dow/Crystalsev DuPont Arkema BASF Rohm & Haas Dow, Cargill NatureWorks LLC HDPE, LLDPE, PP HDPE PTT; PBT; Nylon 6,12 Nylon 11,Pebax Nylon 6,10 Acrylics Soy based urethanes PLA Blends Degradable Tomorrow’s Biobased Leaders Durable Novamont NatureWorks Metabolix DSM Origo Bio PLA PHA’s PHA’S ……………………………………………………………………………………………………………………… ……………………………………………………………………………………………………………………… WHO? WHAT?
    • 49. Continuing lack of infrastructure for use and disposal of compostable plastics. Many biobased plastics players too focused on compostability as the key differentiating asset. Increasing demand for biobased, semi-durable and durable products for household goods, electronics and automotive applications. Increasing interest and developments in existing and new monomers from renewable resources. Why The Change?
    • 50. Increasing demand for biobased, durable products in electronics and automotive applications. By 2011 durables are expected to account for almost 40% of bioplastics – compared with 12% today. (European Bioplastics) Projected Durables Growth
    • 51. Durable Applications are a Reality Disposables Durables
    • 52. Starch Blends Hydrolytic stability Distortion Temp Vapor Transmission Shelf Life Areas of Concern PLA Hydrolytic Stability Distortion Temp (amorphous) Vapor Transmission Shelf Life Impact Resistance Melt Strength PHA’S Hydrolytic Stability √ √ Shelf Life Processability Melt Strength Economics Compostable Bioplastics Do Not Meet The Needs for Durables …………………….……………………………..…………… …………………….……………………………..…………… …………………………………………………………………………………………………………………..……………
    • 53. Will Biopolymers Follow the Traditional Path to Maturity? BASE POLYMER ADDITIVES Fillers/Fibers, Pigments Lubricants, Mold release agents MODIFIERS Impact modifiers, Rheology modifiers, Plasticizers, Nucleating agents BLENDS Rigid/Flexible Low/High Temp COPOLYMERS Chemical Res., High Heat Ductility
    • 54. Will Biopolymers Follow the Traditional Path to Maturity? BASE POLYMER (PLA) ADDITIVES Talc, Kenaf MODIFIERS Acrylics, Joncryl, Citroflex, EBS BLENDS PLA / Ecoflex PLA / PHBV, PLA / PC COPOLYMERS Isosorbide 2,5 FDCA PTT / Nylon 11 Bio Analogs
    • 55. How Will Bioplastics Meet Future Durable Products Needs?
    • 56. General trends How Will Bioplastics Meet Future Durable Products Needs? • Short Term (1-3years) – Blends of present generation bioplastics & blends with petro-based plastics (PP, acrylics, polyamides )
    • 57. General trends How Will Bioplastics Meet Future Durable Products Needs? • Short Term (1-3years) – Blends of present generation bioplastics & blends with petro based plastics (PP, acrylics, polyamides ) • Medium Term (3-5 years) – Blends of existing bioplastics with other biobased plastics (PTT, nylon 6,10, PBS)
    • 58. General trends How Will Bioplastics Meet Future Durables Products Needs? • Short Term (1-3years) – Blends of present generation bioplastics & blends with petro based plastics (PP, acrylics, polyamides) • Medium Term (3-5 years) – Blends of existing bioplastics with other biobased plastics (PTT, nylon 6,10, PBS) • Longer term (5-10 years) – Biobased plastics & bioderived conventional plastics?(PET,PE,PP, nylon 6)
    • 59. Improved temperature performance over PLA. Improved processing window over PHBV. Wider mechanical property spectrum. Almost completely renewable-resource based. Still compostable.
    • 60. Heat Distortion Properties of PHBV/PLA Blends COURTESY OF PETER HOLLAND BV • Samples Held up to 12minutes at 100 C 100%PLA 90%PLA/10%PHBV 80%PLA/20%PHBV 70%PLA/30%PHBV 60%PLA/40%PHBV 50%PLA/50%PHBV 2Minutes •Deformed 12Minutes •Not Deformed
    • 61. Sample Load MPa HDT oC 100% PLA 0.45 52.0 90/10 0.45 53.4 80/20 0.45 54.5 70/30 0.45 54.6 60/40 0.45 63.0 50/50 0.45 66.3 Heat Distortion Properties of PHBV/PLA Blends
    • 62. 1. 10% PHBV / 90% PLA 45.2OC 2. 20% PHBV / 80% PLA 34.0OC 3. 30% PHBV / 70% PLA 33.4OC 4. 40% PHBV / 60% PLA 23.9OC 5. 50% PHBV / 50% PLA 14.7OC Glass Transitions of PHBV/PLA Blends
    • 63. PHBV/PLA Blended Product
    • 64. Succinic Acid THF 1,4-Butanediol Polyurethanes Aliphatic Polyesters Polycarbonates PBT Polycarbonate/PBT Blends Solvents New monomers TPE’s Salt Replacements Crop Growth Promoters N-Methyl Pyrolidone Adipic Acid Hexanediamine Nylon 6 & 6,6 Other Chemicals and Polymers from Plant Sugars Plant Sugars
    • 65. L-KetalsHO OH O O succinic acid HO OH O 3-hydroxypropionic acid OH O NH2 HO O glutamic acid aspartic acid OH HO O O NH2 HO OH OH glycerol O OHO 4-hydroxybutyrolactone itaconic acid HO OH O O O O OH levulinic acid O O OH O HO 2,5-furandicacboxylic acid OH OHOH OH OH xylitol OH OHOH OH OH OH sorbitol HO OH OH OH OH OH O O glucaric acid O O HO O OR *R=H, alkyl New Biobased Materials In Development
    • 66. Thermoplastics Products and Markets L-Ketals Plasticizers Polyols Adhesives Solvents
    • 67. IsobutyleneIsobutanol Xylenes and other aromatics terephthalic acid PET other polymers Isooctene Courtesy Gevo Biobased TPA For PET Under Development
    • 68. Polyethylene from Sugar Cane Nylon 6 from Lycine Acrylics from Sugar Polyurethane Using Soy Based Alcohols Increasing Synergism with the Biofuels Initiatives Other Durable Bioplastics Are Appearing
    • 69. Monomers from Sugar / Cellulosic Biomass Succinic acid (DSM, Bioamber, Roquette, Mitsubishi Chemical Myriant) 3-hydroxy propionic acid (Cargill, Codexis) Acrylic acid (Ceres, Rohm & Haas) Aspartic acid (China) Levulinic acid (China) Sorbitol (Cargill, ADM, Roquette) Ethylene/ethylene glycol (Braskem, India Glycols) Propylene/propane 1,3 diol (Braskem, DuPont / Tate & Lyle) Butylene/butane diol (Genomatica) Lysine/caprolactam (Draths) Terephthalic acid (Gevo) Adipic acid Isoprene (Goodyear, Genenco) FDCA- Avantium Next Generation of Bioplastic ―Building Blocks" …………………………..……………………………………………………………………………………………….
    • 70. Monomers / Intermediates from Vegetable Oils Glycerol Acrylic acid (Arkema) Propane, 1,2 diol (ADM) Soy based polyols (Dow, Cargill) Castor oil / 12 hydroxy stearic acid (India) Amino undecanoic acid (Atofina) Next Generation of Bioplastic ―Building Blocks" ……………...………………..……………………………………………………………………………………………….
    • 71. The Future For Bioplastics Will Depend On Oil pricing continuing to increase. Expanding from Single-Use Compostable to Durable Applications. Transitioning from Oil-Based to Renewable Feedstocks. Addressing Issues: – Sociological, Environmental & Political. Composting/Recycling Infrastructure Developments.
    • 72. Thank You

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