bioplastics

NATISS
Nature for Innovative and Sustainable Solutions
White
Biotechnology
Bioplastics
Biodegradation
GCI 2007
A Greener Chemistry for Industry
Villeneuve d’Ascq 2-5 octobre 2007
History …
•
st
End of 2002 ¾ Creation of the 1 R&D center in Walloon Region
dedicated to the non-food valorization of bio-based
resources for replacement of oil-based products.
¾ Universities : ULB (Brussels), UMH (Mons)
Companies : Warcoing SA, Vandeputte Oleochemichals,
Galactic…
•
End of 2003 ¾ Launch of the 1st R&D activities of the center
•
May 2007
¾ team of 18 persons : 10 researchers and 5 technical
assistants
¾ technological platform : € 3,5 M
NATISS : Agro-industrial R&D center
CO2, H2O
Agrocompanies
Oil, gas
White
Biotechnology
Crossroads between agrocompanies & chemical
companies
Biodegradation
Bioplastics
Chemical
companies
Positioning with the wire of time…
2004
- bioplastics :
- starch
- gluten
- cellulose
blends, additivation
2005
- bioplastics :
Acquisition
of
competences
- PLA Æ BIOWALL
reactive extrusion, macromolecular engineering, synthesis (ROP)
- white biotechnology :
- PHA
fermentation, biocatalysis
2007
- bioplastics :
- PLA
Notorious control
- PHA
- PBS
polycondensation
- white biotechnology :
- chiral molecules
- aromas, colour agents
biocatalysis
High
specialization
Life cycle of products
BIOMASS
BIOTECHNOLOGY
CHEMICAL
SYNTHESIS
BIODEGRADATION
SYNTHONS
BIOPLASTICS
BIOCOMPOSITES
MOLECULES WITH BIOMATERIALS
HIGH ADDED VALUE
WHITE BIOTECHNOLOGY
Use of biological systems
for the production of
chemical substances
-
¾ Biological catalysis (enzymes)
¾ Fermentation technology
Less
solvents
energy
CO2 emission
waste
White
Biotechnology
Processing
Fermentation
Metabolic
engineering
Biocatalysis
BIOPLASTICS …
9 Synthesis of bioplastics
9 ring opening polymerization
9 polycondensation
9 Formulation of bioplastics
9 additivation
9 mixtures
9 biocomposites
lab-scale or semi-pilot
PLA : laboratory to the end-user
continuous (reactive extrusion)
batch
BIODEGRADATION & ENVIRONNEMENTAL IMPACT …
9 Standardized Tests (ISO, EN, ASTM, …)
9 biodegradation (compost, ground, liquid)
9 fragmentation
9 ecotoxicity (fauna and flora)
9 ageing
9 Validation of chemical products / polymers before introduction on
the market (for example Reach)
Biodegradation and ecotoxicity tests available from NATISS
Plastics from renewable resources ?
ƒ Plastics = 4-6 % of worldwide oil cosumption
ƒ Bioplastics production
ƒ won’t affect oil consumption
ƒ will enable plastics producers and transformers less dependent from oil prices
Biobased plastics life cycle Æ BIOPLASTIcS
Biodegradable
bioplastics
(CO2 saving)
½
Non biodegradable
bioplastics
(CO2 well)
Most of
cellulose
derivatives
(eg : cellophane)
Thermosets
PA (eg Rilsan)
RFS based
Plastics versus Bioplastics
Starch
PLA
PHA
Plastics world newcomers
(Cargill-Dow, Galactic,
Novamont, P&G, ..)
Industrial scale
½
Chitin, chitosan,
gluten, lignin, …
Lab-scale
BIODEGRADABLE
NON - BIODEGRADABLE
Most of plastics
(PE, PP, PS, PVC,
PET, PMMA, …)
FR based
New product
PCL, PBT, PBS,
PBA, PEA, …
YES
NO
NO
YES
Historical leading groups
(Solvay, Dupont, Eastman, Bayer, …)
RFS : renewable feedstock
FR (or FFS) : fossil resources
New
process
Bioplastics Market : figures
EU bioplastics market (kt)
3000
2000
without P&M
1500
500
500
0
2000
3,5
1750
1400
1000
1000
1
2015
2020
0
57000
kt
65000
kt
EU plastics market
1,25
1,1
0,9
0.1
2002
2010
VERSUS
45000
kt
2,5
1,7
1,5
750
0,5
2010
2,2
2
875
4,7
3
3
2,5
30
2002
without P&M
with P&M
high growth
4,5
4
with P&M
high growth
5
2015
2020
PP
80000
kt
Sales (kt)
2500
3000
Part of bioplastics in EU plastics market (%)
BP
BP : bioplastics
PP : petroplastics
Time
Worldwide production
20%
PEs
20%
starch
50% 50%
PEs starch
80%
starch
2003
80%
PEs
2020
2010
10 %
25 %
Agriculture
Packaging
Fibers
Transport
Others
75 %
Starch
+ others
70 %
50 %
25 %
20 %
30 %
25 %
PLA
Starch
Starch = thermoplastic starch and blends with plastics
PEs = PLA + others aliphatic polyesters
50 %
55 %
20 %
20 %
PLA
PLA
(Cargill Dow) (Hycail)
Prospects for the European market …
2010
ƒ EU market : 0,5 – 1,0 Mt bioplastics
ƒ bio-based > 80 %
ƒ Products : films (50 %), foams (20%), fibers and rigid packaging
ƒ Segments : packaging, textile / non-non-woven, automotive, agriculture /
horticulture, electronics, …
2020
ƒ EU market : 2 – 5 Mt bioplastics
ƒ Technical substitution potential might amount 33 %
ƒ RFS-based prices < FFS-based prices
**********************
3 leverages will control the growth of the market
ECONOMIC LEVERAGE
- Price balance
- Production capacity
R&D / TECHNOLOGICAL LEVERAGE
-Technical performance
- Products conception
-Production processes
REGULATORY LEVERAGE
- Taxes
- Recycling
- Approvement
Keys for market development
ƒ
ƒ
ƒ
ƒ
ƒ
ƒ
ƒ
ƒ
Technical properties of new bioplastics
Fossil resources dependence reduction
Waste management
New outlets for agriculture (CAP)
Innovations from chemistry industry
Contribution to sustainable development
Ultimate consumers demand
Legislation, incentives
-Belgium: (june 2007) packaging tax exemption for biodegradable plastics (EN 13432)
-Germany : Grüne Punkt for biodegradable plastics
-France : t-shirt bags banned in 2010
-Scotland and Scandinavia : t-shirt bags tax exemption for biodegradable bags
-USA : Green Public Procurement law
-Japan : discussion about various incentives
-China : promotion of bioplastics for Olympic Games Beijing 2008
What will bioplastics be used for ?
Packaging materials in EU
Plastics uses in EU
3%
5%
7%
7%
38 %
18 %
22 %
8%
Packaging
Home
Building
Automotive
Industry
Agriculture
Others
Packaging plastics uses in EU
Paper, cardboard
11 %
Glass
Plastics
Metal
Others
40 %
17 %
24 %
Figures in w% !
50 % of goods are
packed in plastics
Packaging plastics consumption in EU
1.6 %
10 %
10 %
65 %
15 %
Weight %, EU data
Agrobusiness
Cleaning
Health, hygiene
Industrial products
transportation
L(L)DPE
11 %
7.5 %
5%
33.5 %
19 %
22.4 %
HDPE
PP
PET
PS
PVC
EPS
Bioplastics positioning
Starch
Properties
• Chemical and physical properties
–
–
–
–
Partially crystaline
Density > polyolefins
Good transparency when blended
Poor water, oil and solvents resistance
may be enhanced in blends
• Mechanical and thermal properties
– Inferior to traditional FR-based plastics
– Easily degrades with temperature and humidity
– Water sensibility may de improved by blending with long repeating
unit polyesters
• Gas permeation properties
– Highly permeable to water vapor
– Medium to good permeability to O2 and CO2
•
Antistatic
Substitution potential and applications
•
Targets
HDPE, LDPE, PP, EPS
•
Applications
– Packaging (75%)
– Agriculture (25%)
Producers and production costs
Com pany
Product
Novamont (It)
Mater-Bi®
starpol®
bioplast®
Stanelco
BIOP Biopolymer Technologies (D) BIOpar®
Rodenburg Biopolymers (NL)
Japan Corn Starch (Jp)
Solanyl®
Prod.
kT/yr 2006
20
12
10 (17-2007)
40
from 1,50 €/kg (foams) to 4,50 €/kg
(specialty films)
usually 2,50 to 3 €/kg
Solanyl® 1€/kg
Nihon Shokuhin Kako (Jp)
Potatopak (UK)
Cost essentially due to starch
transformation processes.
Environmental impact
Polylactic acid
•
Obtained polyesters
– Lactic acid polycondensation (MITSUI)
– Ring opening polymerization (ROP) (CARGILL)
•
Number average molecular weight 60 000-100 000 (DP: 800-1400)
•
Chiral molecule : stereochemistry
PLA synthesis … (Basics)
A. Route ‘Mitsui Toatsu’ – 1995
ƒ Azeotropic distillation process with
high boiling point solvent for water
elimination
B
A
ƒ Molecular mass limitation due to the
equilibrated esterification reaction
B. Route ‘Cargill Dow’ – 1992 -1996
ƒ Use of Sn(oct)2 (II) (100 – 1000 ppm)
(soluble in melt LA fondu, high catalytic activity, low racemization < 1%)
ƒ 180 – 210 °C
ƒ 2 – 5 h for 95 % conversion
ƒ Mn modulated and ROP accelerated by 1-octanol addition
PLA vs. other polymers : intrisic properties
ƒ Properties of PLA still too low to enter large market applications
Tm (°C)
Tg (°C)
Modulus
(GPa)
Tensile
strength
(MPa)
Elongation
(%)
PE
115 -135
< - 50
0,2
10 - 30
450 - 650
PP
155 - 165
- 10
1,3 - 1,7
27 - 35
350 - 450
PS
-
74 - 110
2,0 – 2,5
25 - 45
1,5 – 52
PET
255 - 265
73 - 78
2,8 – 3,5
50 - 60
30 – 70
PLA homo
160 – 170
50 - 55
3,5
50 - 55
3
PCL
60
- 60
0,2
45 - 50
800 – 1100
P(HB-coHV) 10
mol%
160
6
2
35 - 40
50 – 55
MaterBi Z
-
-
0,18 – 0,19
28 - 30
750 – 900
Gas permeation properties
Comparison between some polymers (indicial values)
1
1,4
2,8
14,3
30
33
PP
PET
PVC
HIPS
PLA
1
1-2
2-7
13
50
100 - 130
Nylon 6
PET
PVC
PLA
PP
HIPS
1-2
1,4 – 3,3
12
MVTR
Nylon 6
O2
CO2
PO
PET
PVC
PLA
Substitution potential
and applications
•
Targets
PET, PS
•
Applications
– Packaging (70%), Fibers and houseware (28%),
Agriculture (1%),
Electric appliances and electronics (1%)
Producers and costs
Com pany
Product
Prod. kt/y
CARGILL
Nature Works®
MiTSUI Chemicals
LACEA®
from 1,80 €/kg to 3,00 €/kg
toyota eco-plastic® 50 (2004)
Cost essentially due to lactic acid
production (40-50 %)
Present production insufficient to
match the demand
140
UNITIKA
SHIMADZU Corporation
TOYOTA
HYCAIL
Prospects (End 2007)
1
Building of pilot plant (1.5 kt/y) near Tournai by Futerro (JV TOTAL-Galactic)
Environmental impact
Polyhydroxyalkanoates
•
Bacterial polyesters
•
Obtained by carbon source fermentation
•
Number average molecular weight 600 000 - 700 000
•
Influence of moities length :
– Glucose, fructose, methanol, glycerol, hexane and higher
alkanes…
– Hydrophoby, Tg, Tm, crystallinity
PHB
- Degradation T close to processing T
- Resistant to hydrolysis
- Highly crystalline (brittle)
- Chemical resistance : good to solvents, medium to oils, poor to acids and
bases
O2 permeability lower than PET (X2) or PE (X40)
- Low water vapor permeability, still higher than PP or PE
PHBV and PHBH (Nodax)
- Processability and mechanical properties enhanced
Brittle (comonomer < 5%)
Flexible (5% < comonomer < 15%)
Elastic (comonomer > 15%)
Substitution potential
Targets
PVC, LDPE, HDPE, PP
Producers and costs
Com pany
Product
Prod. kt/y
2006
METABOLIX
Biopol®
50
PROCTER&GAMBEL
Nodax®
BIOMER
biomer®
PHB industrial
MITSUBISHI GAS CHEM.
0,5
10*
biogreen
BIOMATERA inc.
* blends et composites
Cost
10 €/kg (Biopol : 2.5€-2008)
50% = carbon source and 50% = fermentation and down stream processing
Environmental impact
Other polyesters
Conclusions
• High growth trend expected
– Maximum substitution potential of biobased polymers ~ 33%
– In 2010, market share of bioplastics (with P&M) ~ 1-2 % (2020 : 4% 3.000 kt)
• How to improve the competitiveness of bioplastics
– Undertake R&D efforts
• More efficient technologies
– Cost reducing (monomer production-polymerization process)
• Improve the bioplastics properties (mechanical, thermal, control of
biodegradation…)
• Broaden the variety of bioplastics
– Large scale production
– Policies and measures
Research & Development
www.natiss.be
Analytical services
Contacts :
R&D manager :
Administrative manager :
Valorization of the
technological platform
Laurent Paternostre ([email protected])
Marylise Ledouble ([email protected])