Plastics and Ecology. Reuse, Reduce, Replace. Reuse - multiple use; i.e. refill containers.

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1 Plastics and Ecology Reuse, Reduce, Replace Reuse - multiple use; i.e. refill containers. Originally used for glass; collect and wash. Washing uses detergent discarded into sewage stream. Today, even glass mainly disposed of. For plastic containers not economical except for very large containers. Reduce - possible through reduction in packaging. Replace with stronger plastic and make thinner. Better design can reduce size; usually marginal. Packaging essential - shipping, handling, display.

2 Reuse, Reduce, Replace Replace - with other conventional materials; glass, metal, paper. Historically, plastic has replaced conventional materials because of superior properties. Lower weight. Moisture resistant. Processability. Chemically inert. Safety. Cost.

3 Illustrative example of replacement problems. Replace expanded polystyrene cups (EPS) with uncoated paper products. Weight of paper cup is 6x that of plastic cup. Paper uses:- 2x cooling water 12x steam 36x electricity 580x volume of waste water x amount of water contaminants True, air emissions are higher per ton for EPS vs. paper (53 kg/ton Vs 23 kg/ton) but have to multiply the paper figure by six to be on a per cup basis.

4 Illustrative example of replacement problems. Compare PE grocery bags to Kraft paper bags. PE uses: % less energy to create % less solid waste generated % less atmospheric emissions. Energy cost for manufacture of containers. Container Wt. (oz) E KWH E Kcals 2 quart glass milk bottle quart plastic PE pouch

5 Recovery and recycling Various modes of recycling Primary recycle. Secondary recycle. Tertiary recycle via chemical treatment. Energy recovery. Convert plastic waste to self degrade.

6 Primary - reuse of scrap or off-grade directly by the converter. Thermoplastics only, which encompasses 80% of all polymers used. During processing there is always some scrap (as much as 20-30%). Runners and sprues -Injection molding Trimmings -Blow molding/extrusion Off shapes/pieces that didn't pass quality control. Material is only slightly (if at all) contaminated. Has seen thermal history, is often added as regrind (10-25%) to virgin material. Regrind may not be allowed; medical applications. Sell to other converters or reprocessors. Primary recycling of homogeneous well defined plastics is the easiest solution - if possible.

7 Secondary - implies that used products are collected, often separated, cleaned, often ground and finally reused. Provided one polymer type is dominant this option of secondary recovery is promising (though not necessarily economically feasible). If the source is municipal solid waste (MSW) need to separate :- * plastics from other materials in solid waste; * further separation into individual resins (HDPE, Styrenics, LDPE, PET etc.)

8 Typical domestic waste in the US ( 1990) Percentage of Material Total Waste. Paper 37 Yard waste 18 Metals 10 Glass 9 Food waste 8 Plastics 7 Other 9

9 Economic considerations Total municipal waste (MSW) 180 million tons. Recovered (Recycled) 13% Used for Energy 14% Landfill 73% Domestic waste treatment cost $150/ton Generally, the recycle industry (all materials) is subsidized by local authorities for solid waste disposal, to decrease the bulk of waste in landfills.

10 Plastics recycler/reprocessor confronted with several problem:- Purity and consistency of available sources. Price differential with virgin material. Even small amounts of contaminant polymer leads to drastic reduction in properties. Most polymer pairs are incompatible. Avoid separation; find homogeneous source. Material reprocessors want to deal directly with:- large resin manufacturers for excess production, large resin processors for 'purge', large component manufacturers for reject parts.

11 Packaging a major source of waste - a major outlet for plastic use. Plastics Usage (US) % of Total Resin % of Total. Packaging 30 HDPE 34 Construction 24 LLDPE 19 Household 6 LDPE 18 Transport 5 PP 11 Electronics 5 PET 11 Furniture 2 PS 6 Toys 2 PVC 2 Medicine 2

12 Packaging, potentially a good source of single type polymer materials. Problem - most of the polymers used in packaging are low cost commodity resins even as virgin materials. It's tough to make a $ when cost differential is small. PET is the lone exception in packaging materials, considerable interest in secondary recycle; all soft drink bottles are PET so it's easy to identify a single material source.

13 Prices (cents/lb) Virgin Regrind or Flake Recycle Wide Spec. or Excess Resin HDPE - gp Pipe grade Natural Mixed color PS - crystal EPS cups

14 Prices (cents/lb) Resin Virgin Regrind or Flake Recycle Wide Spec. or Excess ABS - gp Hi - impact ABS - Eng PC-ABS Mixed color PET -bottle CPET Clear Green PC - gp Optical Clear ind Mixed color

15 Price range of virgin resin in cents/lb (1998). Specialty 'engineering' resins.. ECTFE PEEK 3300 PTFE PEI PVDF PPS LCP PSulphone PAI PArylate

16 Regrind, recycle, wide-spec. and excess resin usually bought and sold in trailer lots (20,000lb.) A load of PC would cost you $10,000. A load of LCP would be $200,000 A medium to large reprocessor 40 loads/month. Cash flow $500,000 to $8 million/month. Resin producer pricing/politics. * In general, any material from a large resin manufacturer has to be sold under the reprocessors name and repackaged. * Require any excess or regrind be sold offshore; want to minimize competition in the US. * Use a single large (or very few) reprocessor(s) and limit countries where materials can be sold; resin manufacturers don't want to be in direct competition with there own foreign subsidiaries. * Send excess to landfill rather than sell cheaper to keep the price up for virgin polymer.

17 Even small quantities of contaminant polymer a problem. Reprocessor often has to visit warehouse and bid on polymer lots. How do you know if the lot is contaminated or not?? Recycle is always inferior to virgin material. Need strong economic or legislative reasons to use secondary recycle materials.

18 Tertiary - chemical treatment of scrap plastics to produce useful products; monomers, oligomers, chemicals or fuels. Controlled depolymerization, (pyrolysis and/or hydrolysis) gives good yield in selective cases; PMMA, PET, Nylon, PolyUrethanes. When feasible, tertiary offers the possibility of producing pure monomers that can be converted back to high grade resins. New technology permits depolymerization of mixed polymers at high temperatures. Monomers easily separated using existing technology.

19 Energy recovery - incinerate plastics to utilize the high caloric value of theses materials. Not unanimously accepted; environmental hazards generated during combustion:- Toxic gases Heavy metal contamination Dioxins and other polychlorinated hydrocarbons. PVC is the usual culprit (or scapegoat).

20 Caloric value of plastics and other materials Material BTU/lb PE 19,900 PP 19,800 PS 17,800 Rubber 10,900 Newspaper 8,000 Leather 7,200 Corrugated Paper 7,000 Textiles 6,900 Wood 6,700 MSW 4,700 Yard waste 3,000 Food waste 2,600 Fuel oil 20,900 Coal 9,600

21 When used plastics not separated from MSW; lower caloric value and more ash produced. Japan leads in incineration of MSW ( 50%) Europe (30%); US ( 15%). Little spare land for landfill in Japan!! Need modern incinerator designs and efficient scrubbing and treatment of toxic gases. Use of PVC in packaging being phased out.

22 Bio- and Photodegradation often proposed as a logical and ecological solution. Most plastics are considered nondegradable by microorganisms. This is an advantage in most uses but a disadvantage in elimination of solid waste. Possible solution for restricted cases; mulch film for agricultural uses or for litter bags. Danger of self degrading plastics:- Premature failure of the container. Diminished properties in recycled materials.

23 Two basic approaches to make stable materials degradable:- Polyblend with a degradable material (PE+starch). Starch degrades and reduces mechanical properties of blend. PE residue has little strength and crumbles, but doesn't degrade. Even this simple system has problems. Although materials are sold as PE/starch blends there is only 15% starch + 50 % PE. Remainder is (expensive) compatibilizer (Poly CaproLactone). PCL necessary to produce acceptable film; overcome inherent incompatibility of PE (hydrocarbon) and Starch (polar).

24 Copolymerize with a light (UV) sensitive group. Carbonyl on exposure to UV and oxygen breaks down via photo-oxidation produces lower molecular weight chains. Shorter chains may eventually break down by microorganisms. Add UV sensitizers to the polymer. Systems rely on exposure of thin films to sufficient UV. Not always possible. Thicker containers degrade very slowly. (Even paper and food products don't degrade quickly in landfills). Water soluble polymers offer a third option for limited applications; marine debris, controlled release of fertilizer, biomedical, diapers, etc.

25 Technology of Recycling Secondary recycling currently appears to be the best general solution for scrap plastics. Economics. Legislation is the trigger for source separation for recycle; ('green revolution'). Economics starting to be favorable because of the increased cost to landfill. Integrated approach necessary to handle most MSW components:- Glass, aluminum, paper, food, plastics.

26 Separation sequence for MSW:- Collection (source separate if possible) Compaction, Grinding and shredding, Separating (air, water, magnetic, electrostatic) Wash and dry. Light weight stream (after paper separation by water slurry) is plastic. PE, PS, PP, PVC and PET. Separation of plastics based on density; float/sink. Products made from materials produced by this method are always inferior to products from virgin polymers.

27 Total resin production US 62.8 billion lbs Packaging resins 14.4 billion lbs Recycled from packaging 650 million lbs (4.5%) Of the recycle 70 % from bottles Of the bottles 50% from PET PET is an exception as a successful component. Other commodities resins are not as fortunate, Even with PE you have to separate HDPE, LDPE, LLDPE, ULDPE, mixes have poor mechanical properties. Separate collection from specialized industries can work:- LDPE collected from agricultural business, drycleaning and supermarket bags. PC or PC/ABS from CDs and computer housings.

28 Multilayer/multicomponent packages are much more difficult to use. There's drive away from blends/multicomponent to single polymers. Automotive tires; hot caustic, separate, grind and shred to produce crumb. Rubber crumb used in mats; rubber modified sports tracks; road beds, playgrounds.

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