NATISS. Nature for Innovative and Sustainable Solutions. White Biotechnology

Transcription

1 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

2 History End of 2002 Creation of the 1 st R&D center in Walloon Region dedicated to the non-food valorization of bio-based resources for replacement of oil-based products. Universities : ULB (Brussels), UMH (Mons) Companies : Warcoing SA, Vandeputte Oleochemichals, Galactic End of 2003 Launch of the 1 st R&D activities of the center May 2007 team of 18 persons : 10 researchers and 5 technical assistants technological platform : 3,5 M

3 NATISS : Agro-industrial R&D center CO 2, H 2 O White Biotechnology Oil, gas Agrocompanies Crossroads between agrocompanies & chemical companies Chemical companies Biodegradation Bioplastics

4 Positioning with the wire of time bioplastics : - starch - gluten - cellulose blends, additivation Acquisition of competences bioplastics : - PLA BIOWALL reactive extrusion, macromolecular engineering, synthesis (ROP) - white biotechnology : - PHA fermentation, biocatalysis Notorious control bioplastics : - PLA - PHA - PBS polycondensation - white biotechnology : - chiral molecules - aromas, colour agents biocatalysis High specialization

5 Life cycle of products BIOTECHNOLOGY BIOMASS CHEMICAL SYNTHESIS SYNTHONS BIODEGRADATION BIOPLASTICS BIOCOMPOSITES MOLECULES WITH BIOMATERIALS HIGH ADDED VALUE

6 WHITE BIOTECHNOLOGY Use of biological systems for the production of chemical substances Biological catalysis (enzymes) Fermentation technology Biocatalysis Less - solvents -energy -CO 2 emission -waste Metabolic engineering White Biotechnology Fermentation Processing

7 BIOPLASTICS Synthesis of bioplastics ring opening polymerization polycondensation continuous (reactive extrusion) batch Formulation of bioplastics additivation mixtures biocomposites lab-scale or semi-pilot PLA : laboratory to the end-user

8 BIODEGRADATION & ENVIRONNEMENTAL IMPACT Standardized Tests (ISO, EN, ASTM, ) biodegradation (compost, ground, liquid) fragmentation ecotoxicity (fauna and flora) ageing Validation of chemical products / polymers before introduction on the market (for example Reach) Biodegradation and ecotoxicity tests available from NATISS

9 Plastics from renewable resources? Plastics = 4-6 % of worldwide oil cosumption Bioplastics production won t affect oil consumption will enable plastics producers and transformers less dependent from oil prices Biobased plastics life cycle BIOPLASTIcS Biodegradable bioplastics (CO 2 saving) Non biodegradable bioplastics (CO 2 well)

10 Plastics versus Bioplastics Plastics world newcomers (Cargill-Dow, Galactic, Novamont, P&G,..) Most of cellulose derivatives (eg : cellophane) Thermosets PA (eg Rilsan) RFS based Starch PLA PHA Chitin, chitosan, gluten, lignin, Industrial scale Lab-scale NON - BIODEGRADABLE BIODEGRADABLE New product Most of plastics (PE, PP, PS, PVC, PET, PMMA, ) RFS : renewable feedstock FR (or FFS) : fossil resources FR based PCL, PBT, PBS, PBA, PEA, YES NO NO Historical leading groups (Solvay, Dupont, Eastman, Bayer, ) YES New process

11 Bioplastics Market : figures EU bioplastics market (kt) Part of bioplastics in EU plastics market (%) without P&M with P&M high growth ,5 4 3,5 3 2,5 2 1,5 1 0,5 0.1 without P&M with P&M high growth 0,9 1,7 2,2 1,1 3 1,25 4,7 2, VERSUS PP kt kt kt EU plastics market kt Sales (kt) BP BP : bioplastics PP : petroplastics Time

12 Worldwide production

13 20% PEs 80% starch 50% PEs 50% starch 20% starch 80% PEs % Agriculture 25 % 20 % + others Packaging 75 % 70 % Fibers Transport Others 50 % 50 % 55 % 25 % 30 % 25 % 20 % 20 % Starch PLA Starch PLA (Cargill Dow) PLA (Hycail) Starch = thermoplastic starch and blends with plastics PEs = PLA + others aliphatic polyesters

14 Prospects for the European market 2010 EU market : 0,5 1,0 Mt bioplastics bio-based > 80 % Products : films (50 %), foams (20%), fibers and rigid packaging Segments : packaging, textile / non-non-woven, automotive, agriculture / horticulture, electronics, 2020 EU market : 2 5 Mt bioplastics Technical substitution potential might amount 33 % RFS-based prices < FFS-based prices ********************** 3 leverageswillcontrolthe growthof the market ECONOMIC LEVERAGE R&D / TECHNOLOGICAL LEVERAGE REGULATORY LEVERAGE - Price balance - Production capacity -Technical performance - Products conception -Production processes -Taxes - Recycling -Approvement

15 Keys for market development 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 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

16 What will bioplastics be used for? Plastics uses in EU Packaging materials in EU 38 % 22 % 3 % 5 % 7 % 7 % 18 % Packaging Home Building Automotive Industry Agriculture Others 40 % 8 % 11 % 17 % 24 % Paper, cardboard Glass Plastics Metal Others Figures in w%! 50 % of goods are packed in plastics Packaging plastics uses in EU Packaging plastics consumption in EU 1.6 % 10 % 10 % 65 % 15 % Agrobusiness Cleaning Health, hygiene Industrial products transportation 11 % 7.5 % 33.5 % 5 % 19 % 22.4 % L(L)DPE HDPE PP PET PS PVC EPS Weight %, EU data

17 Bioplastics positioning

18 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 O 2 and CO 2 Antistatic

19 Substitution potential and applications Targets HDPE, LDPE, PP, EPS Applications Packaging (75%) Agriculture (25%) Producers and production costs Company Product Prod. kt/yr 2006 Novamont (It) Mater-Bi 20 Stanelco starpol bioplast 12 BIOP Biopolymer Technologies (D) BIOpar 10 ( ) Rodenburg Biopolymers (NL) Solanyl 40 Japan Corn Starch (Jp) Nihon Shokuhin Kako (Jp) Potatopak (UK) from 1,50 /kg (foams) to 4,50 /kg (specialty films) usually 2,50 to 3 /kg Solanyl 1 /kg Cost essentially due to starch transformation processes.

20 Environmental impact

21 Polylactic acid Obtained polyesters Lactic acid polycondensation (MITSUI) Ring opening polymerization (ROP) (CARGILL) Number average molecular weight (DP: ) Chiral molecule : stereochemistry

22 PLA synthesis (Basics) A. Route Mitsui Toatsu 1995 B A Azeotropic distillation process with high boiling point solvent for water elimination Molecular mass limitation due to the equilibrated esterification reaction B. Route Cargill Dow Use of Sn(oct) 2 (II) ( ppm) (soluble in melt LA fondu, high catalytic activity, low racemization < 1%) C 2 5 h for 95 % conversion Mn modulated and ROP accelerated by 1-octanol addition

23 PLA vs. other polymers : intrisic properties Properties of PLA still too low to enter large market applications Tm ( C) Tg ( C) Modulus (GPa) Tensile strength (MPa) Elongation (%) PE < , PP ,3-1, PS ,0 2, ,5 52 PET ,8 3, PLA homo , PCL , P(HB-co- HV) 10 mol% MaterBi Z - - 0,18 0,

24 Gas permeation properties Comparison between some polymers (indicial values) MVTR 1 1,4 2,8 14, PP PET PVC HIPS PLA Nylon O 2 Nylon 6 PET PVC PLA PP HIPS 1-2 1,4 3,3 12 CO 2 PET PVC PLA PO

25 Targets Substitution potential and applications PET, PS Applications Packaging (70%), Fibers and houseware (28%), Agriculture (1%), Electric appliances and electronics (1%) Producers and costs Company Product Prod. kt/y CARGILL Nature Works 140 MiTSUI Chemicals LACEA UNITIKA SHIMADZU Corporation TOYOTA toyota eco-plastic 50 (2004) HYCAIL 1 from 1,80 /kg to 3,00 /kg Cost essentially due to lactic acid production (40-50 %) Present production insufficient to match the demand Prospects (End 2007) Building of pilot plant (1.5 kt/y) near Tournai by Futerro (JV TOTAL-Galactic)

26 Environmental impact

27 Polyhydroxyalkanoates Bacterial polyesters Obtained by carbon source fermentation Glucose, fructose, methanol, glycerol, hexane and higher alkanes Number average molecular weight Influence of moities length : Hydrophoby, T g, T m, crystallinity

28 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 O 2 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%)

29 Substitution potential Targets PVC, LDPE, HDPE, PP Producers and costs Company Product Prod. kt/y 2006 METABOLIX Biopol 50 PROCTER&GAMBEL Nodax BIOMER biomer 0,5 PHB industrial 10* MITSUBISHI GAS CHEM. biogreen BIOMATERA inc. * blends et composites Cost 10 /kg (Biopol : ) 50% = carbon source and 50% = fermentation and down stream processing

30 Environmental impact

31 Other polyesters

32 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% 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

33 Research & Development Analytical services Valorization of the technological platform Contacts : R&D manager : Administrative manager : Laurent Paternostre (paternostre.l@natiss.be) Marylise Ledouble (ledouble.m@natiss.be)