Recupero di biomasse di scarto per la produzione di ......Source: 2008-09-12 YU L. et al. 2006 •...
Transcript of Recupero di biomasse di scarto per la produzione di ......Source: 2008-09-12 YU L. et al. 2006 •...
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Combattere lo spreco alimentare
Edoardo Puglisi Istituto di Microbiologia, Facoltà di Scienze Agrarie, Alimentari ed Ambientali, Università Cattolica del Sacro Cuore , Piacenza
Recupero di biomasse di scarto per la produzione di bioplastiche microbiche
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CHEMISTRY OF ORGANIC COMPOUNDS
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New materials?
• Before 1940 approx. 80 % of commercially available biodegradable plastic and its monomers were discovered and described
• 1938 Polyethylen • In the 70s:
– Oil crises (1973) – Set point for further development
• In the 80s: – Oil crises (1980) – pilot plants for bioplastics – Oxodegrable products – inhibited the further
development?
Source: NARAYAN R. et al. 1994 www.n24.de 2010-02-17
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Definition of Bioplastic
§ Up to now not fixed (CEN/TC 249/WG 17 planed release 2010)
§ According to European BioplasEcs: Plas&c based on renewable resources Biodegradable polymers which meet all criteria of scien&fically recognized norms for biodegradability and compostability of plas&cs and plas&c products (EU: EN 13432 / EN 14995, US: ASTM D-‐6400, ISO 17088).
§ NOT oxodegradable!
Source: www.european-‐bioplasEcs.org 2010-‐02-‐17
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BACKGROUND
– Degradable polymers that are naturally degraded by the acEon of microorganisms such as bacteria, fungi and algae
n What are Bioplastics?
n Benefits Include: n 100 % biodegradable n Produced from natural, renewable resources n Able to be recycled, composted or burned without
producing toxic byproducts
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From ANIMPOL project, FP7
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CARBON CYCLE OF BIOPLASTICS
CO2 H2O
Biodegradation
Carbohydrates Plastic Products
Plants
Fermentation PHA Polymer
Photosynthesis
Recycle
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Definition of Bioplastic
Biodegradable material based on renewable resources
Biodegradable material based
on petrochemical resources
Non degradable material based on renewable resources
Non degradable material based
on petrochemical resources (OXODEG.)
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IMPORTANCE
• 2003-‐ North America – 107 billion pounds of syntheEc plasEcs produced from petroleum
– Take >50 years to degrade
– Improper disposal and failure to recycle à overflowing landfills
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Development of the market
§ Capacity 2009 400.000 t worldwide § Small market, but high growth rates up to 10 %
Source: www.european-‐bioplasEcs.org 2010-‐02-‐17
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Research > Development > Pilot Plant > Commercialization > World-scale Plant > Industrial production
State of development
Source: bioplastics Magazine 03/2007
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Biodegradable materials
§ In general 4 materials commercially available
• Starch-based polymers
• Polylactic acid
• Polyhydroxyalkanoates • Cellulose derivates
§ Polymer blends and composites
Source: www.basf.com 2008-09-12 YU L. et al. 2006
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• Maize and/or potatoe starch in blend with polycaprolactones and other biodegradable esters
• Europeas most common bioplastic
Starch-based polymers Mater-Bi®
Source: www.novamont.com 2009-12-01
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§ Plantic® Starch from maize and hydroxypropyl, Plantic Technologies (AUS)
§ Solanyl® Starch from potatoes, Rodenburg Biopolymers (NL)
§ Bioplast® Starch blend, Biotec (DE)
§ Biopar® Starch from potatoes and blends, Biop AG (D)
Similar to PE (converting)
Limited applications!
Starch-based polymers Others
Source: www.plantic.com.au 2009-04-01
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Polylactic acid
§ Main producer: NatureWorks (US) § Other Producers: Hycail (FI), Toyota (J) and Uhde Inventa (D)
§ Glucose from maize or lactose from whey
Source: LIM L.-T. et al. 2008
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Polylactic acid
• PolylacEc acid (PLA) is not a new polymer, it has been known since 1932.
• Producing low molecular weight PLA is a simple process, however, making high molecular weight PLA is a more complicated affair.
• Cargill-‐Dow has developed a novel p r o c e s s i n v o l v i n g s e l e c E v e depolymerisaEon of low molecular weight PLA to a cyclic intermediate ( lacEde) , which i s pur ified by disEllaEon.
• CatalyEc ring opening of the lacEde results in conEnuous controlled weight PLA preparaEon.
OHCH3H
OHO
H2O OO
OCH3
CH3
O*
O*
H CH3
O
n
Lactic acid Lactide poly(3,6-dimethyl-1,4-dioxan-2,5-dione)
J. Lunt, Polymer DegradaEon and Stability, 59, (1998), 145-‐152 hbp://www.cargilldow.com/home.asp
Lac$c acid
Low MW PLA
Lac$de
High MW PLA
PolymerisaEon
DepolymerisaEon
CatalyEc polymerisaEon
SeparaEon by conEnuous disEllaEon
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Properties and uses of Polylactic acid (PLA)
• The PLA materials have mechanical properEes that lie somewhere in between that of polystyrene and PET.
• Packaging – Films – Packaging foam – Containers (biodegradable) – CoaEngs for papers and boards
• Fibres – Clothing – Carpet Eles (Interface Inc.) – Nappies
• Bobles – Biodegradable bobles
h2p://www.cargilldow.com
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• Ecovio®
45 % PLA + Ecoflex®, BASF (D)
• Ecovio® L-Foam 75 % PLA + Ecoflex®, BASF (D)
• Bio-Flex® PLA + Copolyester, FKuR (D)
Similar to PET and/or PS (converting)
Sensitive to temperature!
Polylactic acid blends
Source: www.basf.com 2008-09-12 YU L. et al. 2006
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NatureFlex™ Innovia (UK)
Cellulose derivates
Source: www.innoviafilms.com 2008-09-12
Barrier coatings!
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• Mirel™ Metabolix (US) • Biomer™ Biomer (D)
Fermentation of starch, rape, plant residues, etc. Only Injection Moulding!
PHB, PHV, PHBV, ...
Polyhydroxyalkanoates
Source: www.metabolix.com 2008-09-12
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Thermal properties: Melting temperature Biopolymers comparable with conventional plastics
Source: WEBER C. J. 2000
Comparision
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Oxygen transmission rate Biopolymers in the midfield
Source: WEBER C. J. 2000
Comparision
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Water vapour transmission rate Biopolymers in the midfield
Source: WEBER C. J. 2000
Comparision
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Transmission of UV-light
Comparision
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End of life Composting?
Source: WEBER C. J. 2000
End of life
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End of life Compsoting?
Source: ENDRES H.-J. 2009
End of life
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From ANIMPOL project, FP7
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From ANIMPOL project, FP7
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From ANIMPOL project, FP7
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CHEMISTRY OF ORGANIC COMPOUNDS
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RECOVERY OF PHAs
• PHA producing microorganisms stained with Sudan black or Nile blue
• Cells separated out by centrifugaEon or filtraEon
• PHA is recovered using solvents (chloroform) to break cell wall & extract polymer
• PurificaEon of polymer
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Polyhydroxybutyrate (PHB)
• Example of short-chain-length PHA
• Produced in activated sludge • Found in Alcaligenes eutrophus • Accumulated intracellularly as
granules (>80% cell dry weight)
Lee et al., 1996
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PHA Biosynthesis
Ojumu et al., 2004
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POLYHYDROXYALKANOATES
• Polyesters accumulated inside microbial cells as carbon & energy source storage
Ojumu et al., 2004
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POLYHYDROXYALKANOATES
• Produced under condiEons of: – Low limiEng nutrients (P, S, N, O) – Excess carbon
n 2 different types: n Short-chain-length 3-5 Carbons n Medium-chain-length 6-14 Carbons
n ~250 different bacteria have been found to produce some form of PHAs
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From ANIMPOL project, FP7
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CHEMISTRY OF ORGANIC COMPOUNDS
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CHEMISTRY OF ORGANIC COMPOUNDS
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APPLICATIONS
• Industry – Products, films, paper laminates & sheets, bags and containers
– Automobiles
n Medical n Sutures, ligament replacements, controlled
drug release mechanisms, arterial grafts…
n Household n Disposable razors, utensils, diapers, feminine
hygiene products, containers…
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CHEMISTRY OF ORGANIC COMPOUNDS
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CHEMISTRY OF ORGANIC COMPOUNDS