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

5 13/09/2012

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

7 13/09/2012

Tailoring of nanocellulose structures

Printed film of nanocellulose

manufactured in pilot scale through

controlled adhesion, spreading and

drying of NFC without any

wiremarkings.

8 13/09/2012

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

9 13/09/2012

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

10 13/09/2012

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.

14 13/09/2012

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

15 13/09/2012

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

16 13/09/2012

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

17 13/09/2012

GA production by fermentation

18 13/09/2012

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

19 13/09/2012

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

20 13/09/2012

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.

21 13/09/2012

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

22 13/09/2012

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)

23 13/09/2012

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%

24 13/09/2012

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

25 13/09/2012

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

26 13/09/2012

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

27 13/09/2012

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

28 13/09/2012

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

29 13/09/2012

VTT - 70 years of

technology for business

and society