Dr. Adrian Merrington Senior Associate Scientist and Assistant Professor Michigan Molecular Institute Midland, MI 48640-

1. e-Live® Presentation December 18, 2009 Plastics Recycling: Processes, Opportunities and Issues Dr. Adrian Merrington Senior Associate Scientist and Assistant Professor Michigan Molecular Institute Midland, MI 48640-2696 (989) 832-5555 ext. 638 merrington@mmi.org www.mmi.org

2. Welcome • SPE e-Live® on-line audience • SPE mid-Michigan Section • MMI monthly technical meeting attendees

3. Background - MMI • MMI is an independent, not-for-profit research and educational organization, conducting both basic and applied research in polymer science and technology. • Collaborators in Plastics Recycling • American Commodities • Chrysler • Dow • DuPont • Eastman Chemical • Midland Compounding and Consulting • Recycling Projects International • Resource Recovery Corporation • Strategic Materials • University of Florida • Vehicle Recycling Partnership • Visteon

4. “Recycle” Icons Source: http://www.resourcefulschools.org, 2008

5. Not “Recycle” Icons • “The only information in the symbol is the number inside the arrows, which indicates the general class of resin used to make the container.” • “The arrows are meaningless”. • The attorneys general of 11 states objected to “false and misleading claims about plastic recyclability.” • “The recent settlement that they reached with the American Plastics Council paves the way for a first-ever definition of what claims can or cannot be made about plastic recycling and recyclability.” Source: http://www.ecologycenter.org, 2008

6. Real Recycle Icons

7. Real Recycle Icons Recyclable (USA) Green DOT (Germany) Recycle Now (UK) Recyclable (EU) Contains Recycled Materials (USA) Compostable (UK)

8. 35 30 25 20 15 10 5 0 Production Million Tons Recovery 1960 1965 1970 1975 1980 1985 1990 1995 20002005 2010 Plastics Production and Recovery Source: Municipal Solid Waste in the United States, 2007 Facts and Figures, US Environmental Protection Agency, Office of Solid Waste

9. State Recycling Rates Source: BioCycle, 2004

10. Recycling Rate Calculation • US EPA • Presenting a recycling measurement tool that does all of the following: • Ensures fair comparisons of recycling rates among states and local governments. • Produces useful information for planning and decision-making. • Provides accurate, up-to-date numbers for market development. • Allows for easy data collection from the private sector. • Saves you time and effort. • 164 Page Document • Australia • Australia Debates True Plastics Recycling Rates Source: http://www.epa.gov/osw/conserve/tools/recmeas/index.htm Source: Plastics News, November 17, 2008

11. Quotes from GPEC 2007 • SPE’s annual “Global Plastic’s Environmental Conference” • Recycling, Bio-based and Biodegradable • Dr. Seetha Coleman-Kammula , NextLife, LLC • For every 100 lbs of product manufactured, we create about 3,200 lbs of waste. • 6% of the materials we extract from the earth are turned into durable products. The other 94% is waste within 6 months. • 87% of the plastics produced are landfilled within 8 weeks.

12. Why Not Recycle Plastics? • The properties of recycled glass, steel or aluminum are essentially equivalent to those of virgin but this is not true with plastics • Properties are diminished by: • Heat histories • Chain scission • Action of additives • Mixed plastics - incompatible blends • Economics • Virgin plastics production is still relatively cheap • Collection, cleaning, separation, melt processing, etc. to recycle plastics is costly

13. What is a Plastic? PLASTIC (ASTM D883-54T) A material that contains as an essential ingredient an organic substance of large molecular weight, is solid in its finished state and, at some stage in its manufacture or in its processing into finished articles, can be shaped by flow.

14. Additives or Compounding Constituents • Common additives • Antiblocking agent • Antifogging agent • Antioxidant • Antistatic agent • Blowing agent • Colorant • Coupling agent • Cross-linking agent • Curing agent • Filler • Flame retardant • Heat stabilizer • Hydrolytic stabilizer • Impact modifier • Lubricant • Pigment • Plasticizer • Preservative • Release agent • Thermal stabilizer • UV stabilizer • Viscosity depressant • etc., etc., etc.

15. Cotton Wood flour Wood pulp Shell flour Keratin Rayon Nylon Coal Asbestos Mica Quartz Glass Clay Calcium silicate Calcium carbonate Alumina trihydrate Aluminum powder Aramid Bronze powder Talc Carbon black Carbon fiber Additives or Compounding Constituents • Common additives • Antiblocking agent • Antifogging agent • Antioxidant • Antistatic agent • Blowing agent • Colorant • Coupling agent • Cross-linking agent • Curing agent • Filler • Flame retardant • Heat stabilizer • Hydrolytic stabilizer • Impact modifier • Lubricant • Pigment • Plasticizer • Preservative • Release agent • Thermal stabilizer • UV stabilizer • Viscosity depressant • etc., etc., etc.

16. Cotton Wood flour Wood pulp Shell flour Keratin Rayon Nylon Coal Asbestos Mica Quartz Glass Clay Calcium silicate Calcium carbonate Alumina trihydrate Aluminum powder Aramid Bronze powder Talc Carbon black Carbon fiber Flakes Fibers Spheres Additives or Compounding Constituents • Common additives • Antiblocking agent • Antifogging agent • Antioxidant • Antistatic agent • Blowing agent • Colorant • Coupling agent • Cross-linking agent • Curing agent • Filler • Flame retardant • Heat stabilizer • Hydrolytic stabilizer • Impact modifier • Lubricant • Pigment • Plasticizer • Preservative • Release agent • Thermal stabilizer • UV stabilizer • Viscosity depressant • etc., etc., etc.

17. Cotton Wood flour Wood pulp Shell flour Keratin Rayon Nylon Coal Asbestos Mica Quartz Glass Clay Calcium silicate Calcium carbonate Alumina trihydrate Aluminum powder Aramid Bronze powder Talc Carbon black Carbon fiber Flakes Fibers Spheres Size Aspect ratio Etc. Additives or Compounding Constituents • Common additives • Antiblocking agent • Antifogging agent • Antioxidant • Antistatic agent • Blowing agent • Colorant • Coupling agent • Cross-linking agent • Curing agent • Filler • Flame retardant • Heat stabilizer • Hydrolytic stabilizer • Impact modifier • Lubricant • Pigment • Plasticizer • Preservative • Release agent • Thermal stabilizer • UV stabilizer • Viscosity depressant • etc., etc., etc.

18. Cotton Wood flour Wood pulp Shell flour Keratin Rayon Nylon Coal Asbestos Mica Quartz Glass Clay Calcium silicate Calcium carbonate Alumina trihydrate Aluminum powder Aramid Bronze powder Talc Carbon black Carbon fiber Flakes Fibers Spheres Size Aspect ratio Etc. Surface Treatments Etc. Additives or Compounding Constituents • Common additives • Antiblocking agent • Antifogging agent • Antioxidant • Antistatic agent • Blowing agent • Colorant • Coupling agent • Cross-linking agent • Curing agent • Filler • Flame retardant • Heat stabilizer • Hydrolytic stabilizer • Impact modifier • Lubricant • Pigment • Plasticizer • Preservative • Release agent • Thermal stabilizer • UV stabilizer • Viscosity depressant • etc., etc., etc.

19. Pop Bottles Versus Ketchup Bottles • Multilayer • Typically 5 layers of alternating PET (Polyethylene Terephthalate) and EVOH (ethylene-vinyl alcohol) • Monolayer • PET

20. What “Plastic” am I Trying to Recycle? • Single or multi-layered • PET or PET/EVOH • May be different from producer to producer • Production method • Mass ABS • Emulsion ABS • Compounded ABS • Additives • Filler • Paint • UV stabilizers • How do I handle these? • Do I need to remove them?

21. Generation of Plastic Waste • Post-Industrial • Resin manufacturer • Fabricator • Compounder or reprocessor • Packager, assembler, distributor • Post-Consumer • Packaging • Housewares • Toys • Construction • Appliances • Novelties, disposables • Footware • Transportation • Furniture • Wire and cable

22. Production vs. Recycle USA Source: http://www.eia.doe.gov (2007)

23. How to Handle Plastic Waste • Ban the use of plastics • “Greenpeace” • Science261 (1993) 152 • Bury them in landfills • USA vs Japan • Canada to Michigan • Burn them in municipal incinerators • USA vs Japan • Pyrolyze them to industrial chemicals or fuels • Recycle them to useful products

24. Plastics Recycling • Primary Recycling • Replace virgin resins • Same or similar types of product at a reduced price • Pop bottles • Secondary Recycling • Use in applications not typical of virgin resins • Less demanding properties, lower cost • Plastic wood • Filler • Tertiary Recycling • Recovery of chemicals • Quaternary Recycling • Recovery of energy

25. Concerns for the Plastics Recycler • Politics and legislation • Public relations • Cost • Economics • Technology • Product

26. Politics • Legislation • State, federal and international law • California and Germany • Producer responsibility, take-back laws • Special interest groups • American Chemical Council: Plastics Division • http://www.americanchemistry.com/Plastics/ • Greenpeace • http://www.greenpeace.org/ • Campaign Against The Plastic Plague • http://www.earthresource.org/campaigns/capp/capp-goals.html • Is buying a used car recycling?

27. Public Relations • Coke vs. Pepsi • First to use recycled bottles • Not use of recycled plastics in 2003 • Coke Recycling plant opened in 2008 • Sponsoring recycle collection bins around the country 2008 • IBM, Hewlett Packard • Recycler of the year • Mercedes (1997) • First totally recyclable car • What does this mean? • Would you choose your $40K car based on its recyclability?

28. Cost • Purchase • Collection • Storage, warehousing • Consolidation • Transportation • Sorting • Separation • Washing • Drying • Compounding • Melting • Pelletizing

29. Diamonds Gold Catalytic Metals Copper Aluminum PC Dollars per unit Engineering Plastics Recovery Cost Steel PET Glass HDPE Market Value Paper PS PVC PP Retained Performance Value Economics: Which Resins to Pursue? D. Nutter, G.E. Plastics, Pittsfield MA reproduced in J. Schiers, Polymer Recycling, Wiley, Victoria, Australia, 1998

30. 1.25 1.00 0.75 0.5 Virgin 40¢ Price per pound / $ 25¢ Recycle March April May June Date / Months Economics • Cost to recycle 15-40 cents / lb • Would you pay more for a product using recycle? Source: What goes up … now coming down hard, Plastics News, November 24, 2008

31. Technology • Is the technology really available? • Is it economic to use with a given resin? • Solvolysis • Pyrolysis • Stabilization • Compatibilization • Blending • Hydrogenation • Melt reprocessing • Chemical modification • Thermoset recycling Source: sankojapan.co.jp, 2008

32. Recycling Industry Sectors • Bottle • Automotive • Electronics • Packaging • White Goods • Construction

33. Bottle Recycling by Type Source: R.W. Beck, Inc., 2004

34. 100% 50% 0% 1995 2000 2005 2010 Bottle Recycling Rates • Milk Bottles HDPE • Pop Bottles PET 100% 50% 0% 1995 2000 2005 2010 Source: Container Recycling Institute, 2006 PET recycling rate improves The PET bottle recycling rate rose for the fourth straight year to 24.6 (2007) Source: Plastics News, December 4, 2008

35. Pop Bottle Recycling in Rates By State 100% 50% 0% Michigan California New York USA 1985 1990 1995 2000 2005 Source: bottlebill.org, 2008

36. Bottle Bill States • www.bottlebill.org • 10¢ states • Michigan • 5¢ states • California (10¢ over 24 oz) • Connecticut • Delaware • Hawaii • Iowa • Maine (15¢ wine and liquor) • Massachusetts • New York • Oregon (2¢ refillable) • Vermont (15¢ liquor) • Artificially subsidizes bottle recycling in bottle bill states Source: bottlebill.org, 2008

37. PET – Problems (Chain Scission) Source: J. Leider, 1981

38. Contaminant Effect on Recycled HDPE PP Unfused lumps, weld-lines, weakness, delamination PET Unfused lumps, plugs melt delivery channels Metal fragments Plugs injection nozzle, catalyzes polymer oxidation Paper fibers “Blow outs” in blow-molded bottles Soil, dirt Gels, inclusions and stress concentrations Pigments Undesirable color variations Milk Rancid odor due to butyric acid lipolysis products Plasticization of polymer lowering its impact strength Motor oil Residual odor problems Hydroperoxides Initiation of thermal and photo-oxidative reactions HDPE - Problems

39. Use of Plastics Recovered from Bottles

40. Use of Plastics Recovered from Bottles , 2004

41. PET Bottle Recycling 20 15 10 5 0 Beverage Bottles Per Unit Source: Container Recycling Institute, 2006 Not Recycled Containers per person per year Recycled 1990 1995 2000 2005 By Weight in 2004 Source: American Plastics Council, 2004

42. Automotive Recycling • Automotive recycling is a mature industry • But not because of plastics recycling • Steel, glass, etc. • Recycle-content mandates • Cherry pick • Shred • Separate • Use mixed

43. Recycling a Selectively ChosenPlastic • Look for big parts • Easily identifiable • Easily recovered • Example: Car bumpers

44. Year Cost From What Material is a Car Bumper Made? • Steel • Polyurethane • Xenoy (PC/PBT) • TPO

45. TPO? Really? • Post-Industrial • Paint • How do you remove it? • How many layers of paint? • Do I have to remove it? • Additives • Filler • Manufacturing process • Post-Consumer • And… • Mixed resins • Different TPOs, etc. • Aftermarket • PP replacements, etc. • Bondo • Bumper stickers • Dead animal parts • etc., etc.

46. ABS 71.5% PP 26.5% PE 0.5% PET 0.2% PVC 0.2% PUR 0.1% Unknown 1.0% Density Separation r<1 PP(A) 21.2% PE 0.6% Unknown 0.4% Subtotal 22.2% PP/PE/Unknown (96/3/1) 1<r<1.2 ABS 71.4% PP(B) 5.3% Unknown 0.3% Subtotal 77.0% ABS/PP/Unknown (96/3/1) r>1.2 PET 0.2% PVC 0.2% PUR 0.1% Unknown 0.3% Subtotal 0.8% Can be compatibilized with SIS Can be compatibilized with SIS Landfill Recycling a Part – Minivan Door Source: Vehicle Recycling Partnership, 2002

47. Automotive Shredder Residue • Shred the car • Remove steel by magnets • ASR is the rest • Thermoplastics • Thermosets • Fluids • Heavy metals • What do you do with ASR? • Separate? • Use in asphalt, cement? • Landfill?

48. Pop Bottle Beetle

49. Alternative “Green” Options to Traditional Recycling • Designing for recycling • Part re-use • Material re-use, sustainability • Material reduction • Biodegradable polymers

50. Designing for Recycle • Use compatible plastics or similar plastics • For example • Original car door • ABS panel • PU foam in arm-rest • Rigid PU window handle • PVC coverings • Nylon cogs and gears • New car door • PP panel • PP arm-rest • Filled PP window handle or electronic window control with PP buttons • Nylon cogs and gears