THE PROMISE OF BIOPLASTICS

Using biobased carbon content and end-of-life options (biodegradability-compostability & recycling) for sustainable

packagingpackaging

Ramani NarayanUniversity Distinguished Professornarayan@msu.edu

• Ramani Narayan, Biobased & Biodegradable Polymer Materials: Rationale, Drivers, and Technology Exemplars; ACS (an A i Ch i l S i t bli ti ) S i S 1114 Ch t 2 13 31 2012American Chemical Society publication) Symposium Ser. 1114, Chapter 2, pg 13-31, 2012

• Ramani Narayan, Carbon footprint of bioplastics using biocarbon content analysis and life cycle assessment, MRS (Materials Research Society) Bulletin, Vol 36 Issue 09, pg. 716 – 721, 2011

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If you use any of the slides/materials, please reference authorship and affiliation (Ramani Narayan, Michigan State University) – thank you

Copyright Ramani Narayan

PACKAGING MATERIALSPackaging is also a very large consumer of materialsPackaging is also a very large consumer of materials

Metals – Aluminium

GlassGlass

Paper and paperboard

WoodWood

Plastics

Hybrid constructs:Hybrid constructs:

Plastics/polymeric materials + paper & paperboard

Pl ti / l i t i l t lPlastics/polymeric materials + metals

102 million tons (40%) of plastic resin production

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102 million tons (40%) of plastic resin production of 280 million tons used in packaging

• Carbon footprint – material carbon footprint

MAJOR ISSUES FOR CARBON BASED PLASTICS USECa bo ootp t ate a ca bo ootp t

• origin of the carbon in the product • Biological carbon feedstock vs petro/fossil carbon feedstock

• Carbon footprint – process carbon footprint • arising from the conversion of feedstock to product – process • Life Cycle Assessment (LCA) methodologyLife Cycle Assessment (LCA) methodology

• End of life—what happens to the product after use when it enters the waste stream

• Recycling • Biodegradability – composting & anaerobic digestion• Soil – agriculture/horticulture filmsg• Misleading and Deceptive biodegradability/compostability

claims – BEWARE !

• SUSTAINABILITY Closed loop biological or chemical c cling of

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• SUSTAINABILITY – Closed loop biological or chemical cycling of materials & nutrients – driving to zero waste solutions

Basics of Material and Process Carbon Footprint -- Origins of the carbon

MATERIAL CARBON FOOTPRINT PROCESS CARBON FOOTPRINTMATERIAL CARBON FOOTPRINT PROCESS CARBON FOOTPRINT

Napthaethylene/propylene Polyethylene (PE)

aromatics

Bi / bl

ethylene/propylene polypropylene (PP)

EtOH H2C CH2H2C CH

Natural gasEG

TPABio/renewable feedstock

Crops & residues

EtOH H2C CH2nPE

CH3 nPP

TPA

(e.g. Corn, soybean sugarcane)

Tree plantations

BIO monomers

sugars, C-18 & C-9 platform oils

C

O

O CH2 CH2 OC

O nBIOPET

CH C O

Tree plantations Lignocellulosics

Algal biomassPLA PHA’s

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CH3 OPLA

nPlant Oils PLA, PHA’s

Carbon footprint reduction strategy using bio contentWhat Value Proposition does Biobased Plastics offer?

Switching from the “petro/fossil” carbon in plastics to “biobased” carbon provides a zero material carbon footprint [not process carbon footprint]footprint – [not process carbon footprint]

• carbon footprint equates to heat trapping CO2 emissions which is implicated in global warming/climate changewhich is implicated in global warming/climate change problems

• Using plant/biomass feedstock as opposed to petro/fossil g p pp pfeedstock equates to energy/environmental security

• Equates to Economic development – empowering rural farm, forestry and allied manufacturing industry

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Carbon footprint reduction strategy using bio contentUnderstanding the Value Proposition based on the origins of the carbon in the product -- biobased carbon vs petro/fossil carbon

CO2 + H2O (CH2O)X + O2

sunlight energy

Biomass, Ag & Forestry crops & residues2 2 ( 2 )X 2

photosynthesisresidues

NEW CARBON1-10 years

> 106 YEARSUSE – for materials, chemicals and fuels

1-10 years

Fossil Resources (Oil, Coal, Natural gas) -- OLD CARBON

Rate and time scales of CO2 utilization is in balance using biobased/plant feedstocks(1 10 years) as opposed to using fossil feedstocks

MATERIAL CARBON FOOTPRINT

(1-10 years) as opposed to using fossil feedstocksShort (in balance) sustainable carbon cycle using bio based carbon feedstock

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Ramani Narayan, Carbon footprint of bioplastics using biocarbon content analysis and life cycle assessment, MRS (Materials Research Society) Bulletin, Vol 36 Issue 09, pg. 716 – 721, 2011

Carbon emissions – the problem

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Carbon footprint reduction strategy using bio contentMaterial Carbon Footprint

What is the impact of the products material carbon footprint on the environment ?

I t f th b ’ i i i th d t?Impact of the carbon’s origins in the product?

Impact of manufacturing 100 Kg of PE and bio-PE or bio-PLA in terms of Kg of CO2 released from the origins of the carbonterms of Kg of CO2 released from the origins of the carbon

H2C CH22 2nPE

PET

CHC

CO

O

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CH3 OPLA

n

Material Carbon Footprint

300

350 Kg of CO2 per 100 Kg resin

314 kg of CO2 emissions reduction for every 100 kg of PE resin in which the petro carbon is replaced with bio carbon

250

300314 kg of CO2 emissions reduction for every 100 kg of PE resin in which the petro carbon is replaced with bio carbon

Experimentally determine

150

200

p yusing ASTM D6866 based on the principle of C-14 analysis

100

150

0

50ZERO CARBON

FOOTPRINT

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0PE/PP PET Bio-PE/PET/PLA

Carbon footprint reduction strategy using bio contentMeasurement of bio (carbon) content – an important and critical Standard for the bio industry

Biomass14CO2 – Solar radiation

(12CH2O)x (14CH2O)x

C-14 signature forms the basis of Standard test method to quantify

12CO2

> 106 years

( 2 )x ( 2 )x

NEW CARBON

Standard test method to quantify biobased content (ASTM D6866)

Fossil Resources

> 106 years

Cosmic Fossil Resources(petroleum, natural gas, coal)

(12CH2)n (12CHO)x

14N 14C 14CO2

Cosmicradiation

OLD CARBON

Narayan, ACS (an American Chemical Society publication) Symposium Ser.939, Chapter 18, pg 282, 2006; Narayan MRS (Materials Research Society) Bulletin Vol 36 Issue 09 pg 716 721 2011

12CO2

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2006; Narayan, MRS (Materials Research Society) Bulletin, Vol 36 Issue 09, pg. 716 – 721, 2011

Process Carbon Footprint – the LCA trap

Kg of CO2 released per 100 kg resin

Process carbon footprint Material carbon footprint

zero

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CARBON FOOTPRINT – Kg of CO2 per Kg of g p gpolymer – cradle to factory gate

Source: www plasticseurope org

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Source: www.plasticseurope.org

NarayanCourtsey: Braskem

For bottles:37.5 MM tons PET used17.2 MM tons CO2 savings40 million barrels of oil/yrsavings

Courtesy Ford Motor Company

+

Biobased & compostable PLA products

Carbon footprint reduction strategy using bio contentBiodegradability – A misused and abused term

• Can microorganisms present in the disposal environment (soil,

QUESTION

g p p ( ,composting) utilize/assimilate the plastic carbon substrate – the biotic process

Wh t t t d i h t ti f ?• What extent and in what time frame?

• Need complete microbial assimilation and removal from the environmental compartment in a short time period otherwise may haveenvironmental compartment in a short time period otherwise may have environmental and health consequences

• Degradable, partial biodegradable not acceptable – serious h lth d i t lhealth and environmental consequences

• Phil. Trans. Royal. Soc. (Biology) July 27, 2009; 364

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Misleading and Deceptive biodegradability/compostabilityclaims – BEWARE!

Carbon footprint reduction strategy using bio contentBasics of microbial utilization -- biodegradability

Microorganisms utilize carbon substrates as “food” to extract chemical energy for their life processes.

They do so by transporting to the C-substrate inside their cells and:They do so by transporting to the C substrate inside their cells and:

Under aerobic conditions, the carbon is biologically oxidized to CO2releasing energy that is harnessed by the microorganisms for its life processes Under anaerobic conditions CO +CH are producedprocesses. Under anaerobic conditions, CO2+CH4 are produced.

Thus, a measure of the rate and amount of CO2 or CO2+CH4 evolved as a function of total carbon input to the process is a direct measure of the amount of carbon substrate being utilized by the microorganism (percent biodegradation)

0’Glucose/C-bioplastic + 6 O2 6 CO2 + 6 H2O; ΔG0’ = -686 kcal/mol

Glucose/C-bioplastic 2 lactate; ΔG0’ = -47 kcal/mol

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CO2 + CH4

Carbon footprint reduction strategy using bio contentMeasuring biodegradability

80

90

100

dati

on) biodegradation degree

level of biodegradation needed to claim

60

70

(% b

iode

grad

plateau phaseO2

CO2level of biodegradation needed to claim safe and efficacious removal of the plastic carbon from the environmental compartment

40

50

ion

to C

O2

(

biodegradation phase

10

20

30

% C

con

vers

lagphase

Compost & Test

Materials

0

10

0 20 40 60 80 100 120 140 160 180 200

Time (days)

% p

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( y )

ASTM D5338; ISO 14855; EN 13432

Carbon footprint reduction strategy using bio contentBiodegradability under composting conditions

• Specification Standards ASTM D6400, D6868 (coatings)Specification Standards ASTM D6400, D6868 (coatings)• Specification Standards EN 13432 (European Norm)• Specification Standards ISO 17088 (International Standard)

Biodegradability under marine environment• Specification Standard D 7021

Biodegradability under soil environmentg y• ASTM – under development – 90% carbon assimilation by

microorganism as measured by evolved CO2 in 2 years or less

New set of ISO standard from ISO TC 122 SC4 “Packaging & the Environment”

The standards address optimization of the packaging system, reuse, material recycling, energy recovery and composting, as well as the way these aspects of each package are related to each other before and after its use

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ISO 18606 “Packaging & the environment – Organic Recycling”

Carbon footprint reduction strategy using bio contentBiodegradability Test MethodsASTM

S il D5988• Soil D5988• Anaerobic digestors D 5511, ISO 15985• Biogas energy plant• Accelerated landfill D 5526• Guide to testing plastics ASTM D 6954

ISOISOISO 14852, Determination of the ultimate aerobic biodegradability of plastic materials in an aqueous medium – Method by analysis of evolved carbon dioxideISO 14853, Determination of the ultimate anaerobic biodegradability in an aqueous system – Method by measurement of biogas productionISO 14855; Determination of the ultimate aerobic biodegradability of plastic materials

Must provide results from the test methods could be zero or 50 or 100 percent

under controlled composting conditions – Part 1: Method by analysis of evolved carbon dioxide and Part 2: Gravimetric measurement of carbon dioxide evolved in a laboratory-scale test

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Must provide results from the test methods – could be zero or 50 or 100 percent ---generally not provided but claim of complete biodegradability made

Consequences of degradable plastics – White Pollution – CHINA

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Colonized Plastic Particle becomes food for marine species and birds and transports absorbed toxins up the food chain

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Captain Charles MooreAlgalita Marine Research Foundation

Carbon footprint reduction strategy using bio contentSerious human health and environmental consequences of degradable and partially degradable plastics

PCBs, DDE, and nonylphenols (NP) were detected in high concentrations in degraded polypropylene (PP) resin pelletsconcentrations in degraded polypropylene (PP) resin pellets collected from four Japanese coasts.

Plastic residues function as a transport medium for toxic chemicals in the marine environmentin the marine environment.

• Takada et al Environ. Sci. Technol. 2001, 35, 318-324

• Blight, L.K. & A.E. Burger. 1997. Occurrence ofBlight, L.K. & A.E. Burger. 1997. Occurrence of plastic particles in seabirds from the Eastern North Pacific. Mar. Poll. Bull. 34:323-325

• Phil Trans Royal Soc (Biology) July 27 2009; 364Phil. Trans. Royal. Soc. (Biology) July 27, 2009; 364

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Sorting through facts hypes and misleading Sorting through facts, hypes, and misleading claims

GREEN WASHING

Additives (oxo or organic) added to polyethylene (PE) or polypropylene (PP) or polyethylene terephthalate (PET) or any polyolefin polymer will “degrade” the ( ) y p y p y gpolymer to small fragments which will eventually biodegrade or biodegrade in 9 months to 5 years in soil, landfilllandfill

Ramani Narayan, Michigan State University

Green Washing Claims -- Additive Technology

• “Plastic products with our additives at 1% levels will fully biodegrade in 9 months to 5 years wherever they are disposed like composting, or landfills under both aerobic and anaerobic conditions”

The 50% Bio Batch film did not degrade as completely or as quickly as the celluloseThe 50% Bio-Batch film did not degrade as completely or as quickly as the cellulose. At the end of the test, 19% of the film had degraded.The results of the aerobic degradation tests indicate that, in time, plastics produced using Bio-Batch pellets will biodegrade in aerobic conditions.

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DATA DOES NOT SUPPORT THE CONCLUSIONS!

MISLEADING BIODEGRADABILITY CLAIMS

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BIODEGRADABILITY CLAIMS• Chem. Commun., 2002, (23), 2884 - 2885 , , ( ),

– A hypothesis was developed, and successfully tested, to greatly increase the rates of biodegradation of polyolefins, by anchoring minute quantities of glucose, sucrose or lactose, onto functionalized polystyrene (polystyrene-co-maleic anhydride copolymer) and measuring

f f ftheir rates of biodegradation, which were found to be significantly improved

• PRESS• Sugar turns plastics biodegradable. Bacteria make a meal of sweetened polythene g g y

and polystyrene.

weight loss of only 2-12%,

Only sugar is being assimilated, PE chain intact – Is this a genuine example of biodegradable plastic?

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For Biodegradability-compostability

This forms the basis for all the ASTM, ISO and EN standards for i bi d d bilitmeasuring biodegradability.

Claims of degradable, partially biodegradable, or eventually biodegradable are not acceptable, because it has been shown that these degraded fragments become toxin carriers and move up the food web.

So verifiable scientifically valid evidence from approved third partSo, verifiable scientifically valid evidence from approved third part laboratory is needed to document complete biodegradability in a defined disposal system like composting or anaerobic digestion in a short time period using specified International Standards.p g p

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U.S. Farm Security and Rural Investment Act of 2002 U.S. Farm Security and Rural Investment Act of 2002 (P. L. 107(P. L. 107--171), Title IX Energy, Section 9002 171), Title IX Energy, Section 9002

FARM BILLFARM BILL

Federal Procurement of Federal Procurement of BiobasedBiobased Products Products –– the “the “biopreferredbiopreferred program” program” (www.biopreferred.gov)(www.biopreferred.gov)•• develop guidelines for designating develop guidelines for designating biobasedbiobased products for federal products for federal

procurementprocurement•• ““USDA Certified USDA Certified BiobasedBiobased Product” labeling programProduct” labeling programg p gg p g

•• Includes:Includes:•• Definition, content verification, ASTM D6866Definition, content verification, ASTM D6866•• Biodegradability using ASTM D6400 and D6868 (paper coatings) D7021 (marine)Biodegradability using ASTM D6400 and D6868 (paper coatings) D7021 (marine)•• performance requirements; andperformance requirements; and

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•• performance requirements; andperformance requirements; and•• assurance that products are available assurance that products are available

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