Biomaterials in packaging
Swedish Brewmasters Association
THE 26TH NORDIC MEETING ON BREWING TECHNOLOGY
12 – 14 September 2012, Stockholm
Ali Harlin, Jouni Lattu, Thomas Gädda
2 13/09/2012
Reduce
Renew
Recycle BIO
ECONOMY
OIL
ECONOMY
3 13/09/2012
Energy and materials joint development
Wood: H/C = 0,1
Coal: H/C = 1
Oil: H/C = 2
Methane: H/C = 4
H/(H+C)
0,09
0,50
0,67
0,80
0,90
1800
2100
1900
2000
Source: IIASA, Nakicenovic
Hydrogen economy
Methane economy
Oil
pe
ak
Co
alp
ea
k
Bio
pe
ak
Sustainchem
Petrochemicals
Coal conversion - Wood
- Bioplastics
- Synthetic plastics
Copy right Ali Harlin, VTT 2012
4 13/09/2012
Why biopolymers?
Drivers
Limited resources for petroleum based raw materials
Shale gas causing instability on aromatic market – risk on PET
Current activities on biomass derived products: biorefinery approaches within
forest and agro-based industries i.e. bio fuels
Environment and customer driven needs towards sustainability and recyclability
Availability
Polysaccharides: vast amounts as industrial by-products and waste
Possible source for sugars through hydrolysis
Hydroxyacids; industrial by-products and waste with low calorimetric value
No serious competitive end-uses today; non-food
Properties and processing
Good properties achievable for packaging applications
Biochemical and/or enzymatic methods possible
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Well performing materials
General purpose plastics
High performance compared to price
Easy to produce and convert
Wide spectrum of applications
Hard to replace
Bioreplacement alternatives
Biobased feedstock for GPP’s
Totally new & high performance
Reduction and recycling
Existing
market
Emerging
market
Introduction
Bio feed stock
Novel products
High performance
Resource
efficency
Copy right Ali Harlin, VTT 2012
6 13/09/2012
100% bio based packaging
Recyclable fiber based and biopolymer materials.
Efficiently processable biopolymer solutions for packaging applications.
Flexible working models to interact and co-operate with the industry and
packaging value chain.
Mouldable
Lightweight
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Tailoring of nanocellulose structures
Printed film of nanocellulose
manufactured in pilot scale through
controlled adhesion, spreading and
drying of NFC without any
wiremarkings.
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Barrier properties of typical coatings (normalized to 100μm thickness)
Source: SustainPack and Pira International Ltd
Grafted
Hemicel.
PO
+C
ell
ble
nd
Nanocel.
PGA
Plasma
ALD
Pectin
hybride
TOFA
Cellulose
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Development of bio-based polymers
Requirements on:
Biomimicry (models, systems,
processes, and elements to
emulate in order to solve human
problems)
Biodegradability
100% bio-based
Bio-based processes
Performance issues
Recycling
Carbon foot print
Raw material sourcing
Opens door for development PRO-BIP 2009, Final report, June 2009, Li Shen, Juliane Haufe, Martin K.Patel
Copy right Ali Harlin, VTT 2012
- 2nd generation b-PET
- PEF
Bioplymers
PLA Replacements
Bio PET
PEF
Fossil
PET
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Sugar - biomass
Competition with food - available agricultural land area
Competition with bio fuel
Production efficiency – tropical areas
GMO
Alternative sources – lignocellulosic
Agricultural left overs
Recycled fibre
Non-food based
Efficiency?
Tro
pic
al
Ta
iga
Gra
ssla
nd
Tundra
Bio
pro
duction
EU Biomass (TWh):
France 107
Germany 106
Sweden 98
Finland 83
Poland 53
Spain 49
Copy right Ali Harlin, VTT 2012
11 13/09/2012
Hydrolyzed cellulose sugar
Sugar platform is very broad and developing fast
Focus is moving from biofuels towards added chemicals
Lignocellulosic sugar would solve problems on the availabilty
Technologies covering the whole value chain requested
VTT has piloted ethanol from recycled paper
Fibre containing waste & fiber sludge as feed
Hydrolysis & fermentation of feed
glucose 40-55 %
total hexoses 43-58 %
Fermentation and absolutation
Fibre EtOH
Copy right Ali Harlin, VTT 2012
12 13/09/2012
Economics of different bio PE
Different process alternatives were calculated for Northern European raw materials.
Methanol to olefin (based on gasification of lignin)
Costs 400-450 €/ton when energy from gasification is recovered.
Out of this olefin 40-60% can be converted to to ethylene.
Disadvantage: large scale required
Ethanol to ethylene
Costs 1300 €/ton and if produced of hydrolyzed fibers 1900 €/ton.
Benefit is that ethanol is converted over 80% to ethylene.
Bio oil cracking
Cost 1000-2300 €/ton depending on bio-oil source.
Total conversion to olefins is 67% and to ethylene 34% (recycle mode)
Use of FT wax may reduce the price further, when produced in integrated plant
Copy right Ali Harlin, VTT 2012
13 13/09/2012
Polymer
Tensile
strength
[MPa]
Modulus
[GPa]
Elonga
tion
[%]
Tg
[C]
Tm
[C]
Degr.
time
[month]
Density
[g/cm3]
OTR
100m
[cm3/m2
bar]
PLA 60 3.5 6 60 162 18 1.24 ~200
PLLA 150 4.1 10 65 200 >24 1.26 ---
PDLLA 50 3.5 10 60 NA 12 1.26 ---
PGA 100 7 20 45 233 12 1.61 <<0.1
Comparision of PLA and PGA
PLA is used for beverage bottles
Main limitations in barrier properties
Polyglycolic acid is barrier polymer that is compatible with PLA
GA monomer can be copolymerized also with LA monomer, results intermediate properties
GA can also be copolymerized with e.g. caprolactone to receive improved processability.
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What makes glycolic acid an attractive monomer?
Bio-based source by fermentation or in black liquor.
Also available from chemical sources.
Reactive in polymerization, also copolymerization with
other lactones (or hydroxy acids).
No need to stereo-purity.
Unique properties of glycolic acid polymers
High Tm and crystallinity => good mechanical
properties and temperature resistance,
Relatively good biodegradation, controlled release
Very high O2 barrier.
Good chemical resistance
Potential for PLA substitution and versatile
modifications through copolymers:
Enhanced biodegradabilty
Heat resistance and mechanical properties
glycolic acid glycolide
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Poly(glycolic acid) material properties
Tm 230 C
Tg ~40 C
Tdeg ~300 C
Not soluble to most
solvents
HDT 168 C
Tensile str 117 MPa
Flex mod. 7.6 GPA
Izod impact notc 2.9 MPa
melt processable polymers
High HDT
Very stiff Superior barrier properties
PEF
PGA
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VTT process for glycolic acid
VTT has proprietary
technology in microbiological
production of monomer
• Glycolic acid can be produced of hydrolysed sugars (VTT patent pending)
• Not stereoselective – easier to produce
• Alternate route = fractionation from pulping black liquor
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GA production by fermentation
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New catalytic polymerisation process
for glycolide (co)polymers
Patent application pending
by VTT.
Industrially feasible particle
forming polymerization
process.
Free flowing polymer powder
can be recovered from the
”conventional slurry
polymerization process”.
Polymerisation can be
conducted even at room
temperature.
organic
solvent
dissolved
reagentsglycolide
(monomer)
-caprolactone
(comonomer)
(D/L 50/50)-lactide
(comonomer)
stabilizer
alcohol
(initiator)
organic
catalyst
added
polymer
precipitates
2-6 µm particles
The process concept offers interesting
possibilities for new applications
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Particle forming polymerizations
Solvent
Monomers and other reagents soluble
Polymer insoluble
Suitable solvents: e.g. DMF, acetonitrile, acetone, DMSO
Catalyst
Organic bases, active at room temperature (VTT patent pending)
Sample Solvent Solid content in
reaction (%) Yield (%)
Particle size
(µm)
1 CH2Cl2 3,5 97 17
2 DMF 25 98 3,3
3 DMF 37 97 3,6
4 DMF 25 96 6,2
Examples of precipitation polymerization results:
Solvent S.c. Reaction
time
Yield
[%]
Mn
[g/mol]
Mw
[g/mol]
1 Acetonitrile 25% 10s 69 51,200 144,400
2 Acetonitrile 25% 20s 84 58,700 154,800
3 Acetonitrile 25% 30s 97 62,200 155,500
4 Acetonitrile 25% 2h 99 73,800 174,300
5 Acetone 60% 2h 56 48,500 148,800
Before
catalyst
addition
After
catalyst
addition
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Run for bio-PET
The Coca-Cola Company launched PlantBottle 2009 with Dasani
The PlantBottles in the Great Britain: up to 22.5% plant-based
material and up to 25% recycled PET.
Avantium and TCCC sign 2011 partnership agreement to develop
next generation 100% plant based plastic: PEF (furan polymer)
Gevo Inc. with TCCC 2011: Sugar based isobutanol converted into
para-xylene using chemical processes.
Co-operation with Heinz
PepsiCo will pilot production of the new bottle in 2012
Announced renewable sources including switch
grass, pine bark, and corn husks
To extend raw materials to orange peels, potato
peels, oat hulls, and other agricultural
byproducts from its foods business.
Copy right Ali Harlin, VTT 2012
• VTT is developing own route to TPA precursor.
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Furan dicarboxylic acid FDCA
Sleeping giant - Studied over 100 years
Extremely hard to make biobased in an economic manner
Biotechnical route
Catalytic oxidation of sugars
Drop in - enabling 100% biobased replacement for terephthalic acid TPA
Enables several polymers:
polyesters,
polyamides and
polyurethanes
Less hazardous chemical than TPA (non-aromatic)
Carbohydrates RMF FDCA
Polyesters
Polyamides
Polyuretanes
Dehydration Oxidation
Polymerization
Possible alternative
Hydroxymethylfuranacid
HDFA homopolymer
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Biobased PEF
Can be used for various PET applications
Blown molding
Spun fibre
Extruded film
Excellent properties (based on Avantium):
O2 barrier 6 times better than PET
CO2 barrier 2 times better than PET
H2O barrier 2 times better than PET
Tg is 11C higher than PET
Tm is 40C lower than PET
Special: Golden color (not a problem with
beer)
Enabling sustainability
100% biosourced when used green EG
100% recyclable (up to 5% can be mixed
with PET)
Significant reduction in NREU and GHG
(Utrecht University; Patel & Faaij)
NREU reduction 60% (62 and 26GJ/ton
for PET+ and PEF respectively)
GHG reduction 50% (3,8 and 1,9 ton CO2
eq. / ton for PET+ and PEF)
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Bales of crushed PET bottles
RPET and biobased alternatives
• Worldwide, approximately 5.8 million tons of PET were collected in 2009.
• This gave 4.7 million tons of flake:
• 3.4 million tons were used to produce fibre – demand increasing
• 500,000 tons to produce bottles – demand increasing rapidly
• 500,000 tons to produce APET sheet for thermoforming,
• 200,000 tons to produce strapping tape and
• 100,000 tons for miscellaneous applications.
(Source: PCI, www.pcipetpackaging.co.uk )
PEF can be recycled (based on Avantium) to
Blown molding
Spun fibre
Extruded film
Can be mixed with PET up to 5%
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PEF business status
Agreement with The Coca-Cola Company
First milestones include the start-up of an Avantium PEF pilot
plant in 2012
The Coca-Cola Company is key to secure a smooth
transition into the mass production phase of PEF bottles
Joint Development Agreement for the development of PEF bottles
for Danone in bottled water business.
PEF has a 50-60% lower carbon footprint than oil-based PET
The process economics suitable for PET alternative
Targeted PEF production volumes:
2015 demo plant 40ktons (commercial delivery from pilot)
2018 full scale production unit 300ktons
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Polymerization of sugar acid based monomers
VTT has studied route to utilize sugar acids produced by biochemical methods in
polyesters.
Two routes have been chosen in the scientific work:
Modification of sugar diacids to hydroxyl functional polymerisable monomers,
and their use in polyester modification
Use of biotechnically produced diacids as such together with aromatic
diols to make aromatic polyesters
Procedure (ref. Biradar et al. Applied Catalysis A: General 285 (2005) 190-195)
Diethyl oxalate and hydroquinone were mixed in glass reactor and reacted
at 180 oC for 5 h under nitrogen flow. 1% SiO2/MoO3 catalyst was prepared
and used 15 w-% of monomer
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Properties of polyesters from interfacial polycondensation
Figure: DSC heating sequence (10 0C/min) Figure: DSC cooling sequence (10 0C/min)
Polymers were prepared,
• with interesting properties,
• but Mw was too low
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Conclusions
Contemporary plastic materials, e.g. PET are technically acceptable and
economically efficient materials for beverage packaging
Seek for new bio based alternatives is based on three drivers:
Need to reduce oil-dependency – cost of fossil plastics
Risks in PTA availability - shale gas effect on aromates
Consumers preferences – sustainability and GHG emissions
Biodegradable alternative PLA has been developed, but has limitations in its
performance. Further developments are needed:
Novel PLA grades
New barrier materials – promising PGA
Drop in replacement of PET
bioPET enetering market place – competition of bio-TPA
PEF seems promising, but still in early stage
New materials are improving performance and reduces threshold to plastic beer
bottle
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INDICATORS AND SENSORS FOR PRODUCT
QUALITY AND SAFETY
28
Development of visual product quality
indicators for food packages
Various types of indicators:
indicating humidity, leakage (oxygen),
food freshness, ethylene
Indicators applicable directly on packaging using
inkjet printing technique
Indicator ink formulation
Several patents/pat.pending technologies*
Humidity
Humidity
Leakage
Enzymatic humidity
indicator colour change
Leakage
*US2007059837A, WO2009/153405, WO2007/017555, WO09153406
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VTT - 70 years of
technology for business
and society