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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.

Introduction to bioplastics Introduction to bioplastics Presentation Transcript

  • Introduction To Bioplastics Dr. Jim Lunt
  • Presentation OutlineBasic Definitions for Bioplastics.Drivers for Bioplastics.Growth Projections and Market Trends.The Evolving Biobased ―Landscape.‖Performance Issues for Today’s Bioplastics.Emerging Technologies.Conclusions.
  • Basic Definitions for Bioplastics Terminology Standards Measurements
  • What are Biodegradable Plastics?Biodegradable or Compostable Plastics arethose which meet all scientifically recognizednorms for biodegradability and compostabilityof plastics and plastic products independentof their carbon origin.In Europe, the composting standard isEN 13432 and in the USA ASTM D6400.
  • ASTM D6400 Standard Criteria For Compostability1. 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.)
  • Biodegradation Mechanism For PLA (In Compost At 60oC)Num. Avg. Mol. Wt. (Mn) % CO2 Evolved70,000 100 8050,000 Embrittlement begins 60 % CO230,000 40 Mn Complete Fragmentation 2010,000 0 0 10 20 30 40 Polymer Hydrolysis Time (Days) Lactic acid and Oligomers Biodegradation
  • USDA Definition of Biobased Products 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.
  • Measurement of Biobased ContentTo be classified as ―biobased,‖ the materialmust be organic and contain somepercentage of recently fixed (new) carbonfound in biological resources or crops.This definition is the basis of ASTM D6866. Uses C14 content measurement.
  • Measurement of Biobased Content
  • Biobased & Biodegradable 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.
  • 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.
  • Drivers for BioplasticsRenewable resource versus oil based.Reduced environmental impact.Concerns about human health.End-of-Life disposal issues – Landfill.Legislative initiatives.
  • Oil Versus Corn Price Courtesy Gevo
  • Oil Carbon V Corn Carbon Price% Carbon in oil = 84% based on isooctaneThere 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 = 65Weight of a bushel = 56#Cost of corn based carbon example $3.50/(56*0.65*0.4) =$0.240
  • Oil Versus Corn Price100.00 4.90 Cost of Carbon 90.00 Oil v Corn Sugar 4.40 80.00 $Oil/barrel $Corn/Bu 3.90 70.00 3.40 60.00 2.90 crude oil cost 50.00 2.40 corn cost 40.00 1.90 30.00 1.40 0.05 0.15 0.25 0.35 $Carbon Cost
  • Corn as A Feedstock Starch Gluten Meal (65%) (5%) •Fructose forSweeteners Dextrose for Hull & Fiber Fermentation (23%) Feedstocks Germ (7%) Number 2 Yellow Dent is used in the USA for Lactic Acid Production
  • Net Corn Pricing CalculationTypical yields from a bushel of corn (56 pounds) from the wetmill 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 acomputed price for net corn of $1.13/bu to $3.82/bu.Based on these values, the USDA reports a corn sweetener(dextrose) cost.
  • White Pollution-China
  • Increasing Litter Concerns
  • Health Concerns
  • Legislation Against Petroleum Based Plastics
  • Key Legislative Initiatives for Bioplastics 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.
  • Definition of SustainabilitySustainability 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 measurethis?
  • How Do We Really Measure Sustainability? Life Cycle Analysis - One attempt to measure sustainability.Complex and Inputs/Outputs still Debated
  • Life Cycle AnalysisISO 14040 or ASTM D7075 -LCA involves thecompilation of a comprehensive inventory (Life CycleInventory, or LCI) of relevant inputs and outputs of aproduction system.This means an organized effort to measure specificinput components contributing to the production anddelivery of the material to its end-use application.In addition, an LCA requires an evaluation andassessment of the environmental impacts associatedwith the processes.
  • 5 Ingeo PET 4.5 kg CO2 eq. / kg Ingeo 4 3.49 3.49 3.5 3 2.52 2.5 2.02 2 1.5 1 0.75 0.5 0.27 0 2005 2006 2009 ACC Plastics Gabi With REC Technology Europe PEA Source Data: Ingeo - NatureWorks LLC ; Improvements PET: M. Binder, Technical Director, PE Americas;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
  • Cradle-to-Pellet Primary Non-renewable Energy Use 90 Ingeo PET 85.6 77.8 80 69.6 70 MJ/kg Ingeo 60 50.2 50 40 35.2 27.2 30 20 10 0 2005 2006 2009 ACC Plastics Gabi With REC Technology Europe PEASource Data: Ingeo - NatureWorks LLC ; Improvements PET: M. Binder, Technical Director, PE Americas; Compared to any of the PET data sets, all of the Ingeo profiles have a lower non-renewable energy use PLA: Vink E.T.H. et all
  • But There Are Other IssuesThe Food versus Fuel Debate:• Food Crops V Biomass• The ―Ripple Effect ―Use of GMOsEnd-of-Life disposal options:• Compostability• Recyclability
  • Projected Biomaterials Trends
  • Projected Biomaterials Trends Global Demandfor bioplastics will increase more than fourfold to 900,000tonnes in 2013. (Freedonia)
  • Projected Biomaterials Trends Global Production Global of bioplastics Demand will increase for bioplastics will sixfold toincrease more than fourfold to 1.5 900,000 million tonnes in tonnes 2013. by 2011. up from 262,000 (Freedonia) tonnes in 2007. (European Bioplastics)
  • Projected Biomaterials Trends Production Capacity Global of bio-based Production plastics is Global of bioplastics projected Demand will increase six to increase fromfor bioplastics fold to 360,000 tons will increase in 2007 to aboutmore than four fold to 1.5 million 2.3 900,000 tons million tons tons in by 2011. by 2013. 2013. up from 262,000 (European Bioplastics) tonnes in 2007. (Freedonia) (European Bioplastics)
  • Projected Biomaterials Trends Bioplastics will still only be 1% of the approximate 230 million tons of plastics in use today.
  • The Evolving Biobased Plastics Landscape
  • Biobased Polymer Capacities For Major PlayersProduct Company Location Capacity/mt Price/#PLA Natureworks USA 140,000 0.85-1.20PLA Hisun China 5,000 1.25PHA’s Metabolix USA 300/50,000 2.50-2.75 (2010)PHBH Meridian/Kaneka USA 150,000? n/aPHBV Tianan China 2,000 2.40-2.50Materbi Novamont EU 75,000 2.0-3.0Cereplast Cereplast USA 25,000 1.50-2.50HDPE/LDPE Braskem SA 200,000 0.80-1.00 /PP (2010)
  • The Biobased Leaders TodayWHO? WHAT?………………………………………………………………………………………………………………NatureWorks, Hisun PLANovamont Mater-Bi, Origo BiCereplast CereplastDupont BIOMAX (PTT, Plantic)Tianjin Bio Green /DSM PHATianan Biologic PHBVMetabolix PHA………………………………………………………………………………………………………………Braskem Green Polyethylene
  • Key Compostable Bioplastics …………………….……………………………………………………………Starch/PLA/ECOFLEX Polylactic Acid (PLA) O O HO HO OH OH H H3C CH3 H L-Lactic Acid D-Lactic Acid (0.5%) CompoundedBiobased Compostable 100% Renewable & Compostable
  • Compostable Bioplastics Second GenerationPoly Hydroxy Alkanoates (PHA’s
  • 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.
  • Plastic Films Market SizeUS plastic bag market is estimated by Omni Tech*to be 68 million tons in 2007.Growth rate of 15% per year through 2011 to119 million tons. *http://soynewuses.org/downloads/reports/DisposalblePlasticsMOS.PDF
  • Major Markets for Biobased FilmsClear wrapping films (blown and cast) for food- and non-foodwrap.Clear biaxially-orientated film for tamper proof seals and shrinkwrap.Translucent cast and blown film for: Trash bags Yard & Garden Industrial refuse Kitchen and other Newspaper and magazine wrap Diaper back sheets Agricultural mulch filmsAlmost all biobased film applications today are single-usedisposables where compostability is a perceived benefit alongwith biobased content.
  • Bioplastic Manufacturers for Film ApplicationsTransparent 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)
  • 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.
  • Comparative Gas Transmission Properties 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
  • Biaxially Orientated PLA
  • Cellulose Acetate
  • Compounded PLA/Starch Blends
  • Tomorrow’s Biobased Leaders WHO? WHAT?……………………………………………………………………………………………………………………… Braskem HDPE, LLDPE, PP Dow/Crystalsev HDPE DuPont PTT; PBT; Nylon 6,12 Arkema Nylon 11,PebaxDurable BASF Nylon 6,10 Rohm & Haas Acrylics Dow, Cargill Soy based urethanes NatureWorks LLC PLA Blends……………………………………………………………………………………………………………………… Novamont Origo BioDegradable NatureWorks PLA Metabolix PHA’s DSM PHA’S
  • Why The Change?Continuing lack of infrastructure for use and disposal of compostable plastics.Many biobased plastics players too focused oncompostability as the key differentiating asset.Increasing demand for biobased, semi-durableand durable products for household goods,electronics and automotive applications.Increasing interest and developments in existingand new monomers from renewable resources.
  • Projected Durables GrowthIncreasing 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)
  • Durable Applications are a Reality Disposables Durables
  • Compostable Bioplastics Do Not Meet The Needs for Durables Areas of Concern…………………………………………………………………………………………………………………..…………… …………………….……………………………..…………… …………………….……………………………..……………Starch Blends PLA PHA’SHydrolytic stability Hydrolytic Stability Hydrolytic StabilityDistortion Temp Distortion Temp √ (amorphous)Vapor Transmission Vapor Transmission √Shelf Life Shelf Life Shelf Life Impact Resistance Processability Melt Strength Melt Strength Economics
  • Will Biopolymers Follow the Traditional Path to Maturity? COPOLYMERS Chemical Res., High Heat Ductility BLENDS Rigid/Flexible Low/High Temp MODIFIERS Impact modifiers, Rheology modifiers, Plasticizers, Nucleating agents ADDITIVES Fillers/Fibers, Pigments Lubricants, Mold release agentsBASE POLYMER
  • Will Biopolymers Follow the Traditional Path to Maturity? COPOLYMERS Isosorbide 2,5 FDCA PTT / Nylon 11 Bio Analogs BLENDS PLA / Ecoflex PLA / PHBV, PLA / PC MODIFIERS Acrylics, Joncryl, Citroflex, EBS ADDITIVES Talc, KenafBASE POLYMER (PLA)
  • How Will Bioplastics Meet Future Durable Products Needs?
  • How Will Bioplastics Meet Future Durable Products Needs?General trends• Short Term (1-3years) – Blends of presentgeneration bioplastics & blends with petro-basedplastics (PP, acrylics, polyamides )
  • How Will Bioplastics Meet Future Durable Products Needs?General trends• Short Term (1-3years) – Blends of presentgeneration bioplastics & blends with petro basedplastics (PP, acrylics, polyamides )• Medium Term (3-5 years) – Blends of existingbioplastics with other biobased plastics(PTT, nylon 6,10, PBS)
  • How Will Bioplastics Meet Future Durables Products Needs?General trends • 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)
  • Improved temperature performance over PLA.Improved processing window over PHBV.Wider mechanical property spectrum.Almost completely renewable-resource based.Still compostable.
  • Heat Distortion Properties of PHBV/PLA Blends 100%PLA 90%PLA/10%PHBV2Minutes 80%PLA/20%PHBV•Deformed 70%PLA/30%PHBV12Minutes 60%PLA/40%PHBV•NotDeformed 50%PLA/50%PHBV • Samples Held up to 12minutes at 100 C COURTESY OF PETER HOLLAND BV
  • Heat Distortion Properties of PHBV/PLA Blends Sample Load MPa HDT oC100% 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
  • Glass Transitions of PHBV/PLA Blends1. 10% PHBV / 90% PLA 45.2OC2. 20% PHBV / 80% PLA 34.0OC3. 30% PHBV / 70% PLA 33.4OC4. 40% PHBV / 60% PLA 23.9OC5. 50% PHBV / 50% PLA 14.7OC
  • PHBV/PLA Blended Product
  • Other Chemicals and Polymers from Plant Sugars Polyurethanes Polycarbonate/PBT Blends Nylon 6 & 6,6Polycarbonates TPE’s Adipic Acid Hexanediamine PBT Aliphatic Polyesters N-Methyl Pyrolidone THF 1,4-Butanediol Solvents New monomers Crop Succinic Acid Growth Promoters Plant Sugars Salt Replacements
  • New Biobased Materials In Development HO O OH HO O OH HO O O OH L-Ketals O NH2 succinic acid 3-hydroxypropionic acid glutamic acid O O HO OH HO O HO O NH2 OH OH O O OR glycerol 4-hydroxybutyrolactone O aspartic acid HO O O O O OH OH O HO HO OH O O itaconic acid levulinic acid 2,5-furandicacboxylic acid OH OH OH OH OH O OH OH OH *R=H, alkyl HO OH OH OH OH OH OH OH OH O xylitol sorbitol glucaric acid
  • Products and Markets Plasticizers Polyols L-KetalsAdhesives Solvents Thermoplastics
  • Biobased TPA For PET Under Development Isobutanol Isobutylene PET other polymers Xylenes and terephthalic acid Isooctene other aromatics Courtesy Gevo
  • Other Durable Bioplastics Are Appearing Polyethylene from Sugar Cane Nylon 6 from Lycine Acrylics from Sugar Polyurethane Using Soy Based Alcohols Increasing Synergism with the Biofuels Initiatives
  • Next Generation of Bioplastic ―Building Blocks" 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"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)
  • The Future For Bioplastics Will Depend OnOil 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.
  • Thank You