biomass to biopolymers
TRANSCRIPT
Biomassto
biopolymers Andrej Kržan
National Institute of Chemistry Ljubljana
Laboratory for Polymer Chemistry and Technology
Outline• Introduction
• Examples
• Trends
• Experiences
• Conclusions
Biopolymers?Biopolymer = natural polymer, biomacromolecule (strickt)
= biobased polymer, etc. (not well defined)
Bioplastics = biobased and/or biodegradable plastics (ind.)
polymer vs. plastics
Biodegradable = compostable, soil, water, marine, in vivo
Biocomposite = (at least) partially part biobased
Know (understand) - be consistent
BioBiodegradable ON/OFF(regardless of selected conditions,
also compostable)
Biobased plastics: 0 - 100 %- biobased content
- non-fossil (new) carbon content,
C14 (standard/certificate)
= biomass = renewable resource (plant/animal/microbial)Oil?
Biobased ≠ Biodegradable
In the beginning…First polymers/plastics were biobased
• No other sources available (and understood)
proteins, cellulose, oils, phenol, formaldehyde
Polymers started with sustainability in mind
• Substituting and supplementing natural materials
o overcoming scarcity – limited sources
o easier processability
o meeting demand
Nitrocellulose• First plastic (Hyatt 1869)
• Substituting and supplementing natural materials
Popularity of pool >>
balls made from ivory >>
not enough elephants
• Plastics in function of saving valuable natural resources (biodiversity)
Plastics –unparalleled success
• Synthetic polymers unknown in 1850
- first practical discoveries 1860s (nitrocellulose)
• Development in 1930s and commercial boom after WW2
- annual global production approaching 300 million tons
BioplasticsDiscovered in Europe
- EU funding schemes analysis (Braunegg 2009)
equal distribution PLA / PHB / TPS equally 1/3 each
PLAPolylactic acid = polylactide
Production
Organic fermentation substrate Bio
Fermentation to Lactic acid Fermentation
Lactic acid to lactide (cyclic dimer) Chemical
Polymerization to PLA Chemical
PLAProperties
Similar to PS
Various stereoisomers – different properties D/L
1st gen PDLA/ PLLA not stable above 55 °C
Recently: stereocomplex sc-PLA stable to 120 °C
Compostable
Commercial: Natureworks,
Corbion-Purac…
C
C
O
C
C
O
O
O
H
H
CH3
CH3
C
C
O
C
C
O
O
O
H
H
CH3
CH3
C
C
O
C
C
O
O
O
H
H
CH3
CH3
LL-Laktid
(mp 97 C)
LD-Laktid
(mp 52 C)
DD-Laktid
(mp 97C)
PHAPolyhydroxyalkanoates (group of materials)
poly-3-hydroxybutyrate = PHB
polyhydroxybutyratevalerate = PHBV
polyhydroxyhexanoate = PHH
Production
• Organic fermentation substrate Bio
• Fermentation to polymer Fermentation
• Extraction/postprocessing
PHAProperties
Similar to PP, PHB slow crystallization � brittle
Copolymers or blends needed
Compostable, soil, marine degradable
Commercial /rel. low production
Efficient/viable production not trivial
Years of ups and downs
Metabolix: PHA as plasticizer for PVC
TPSThermoplastic Starch based materials
Production
• Granular starch plasticized Bio
• Blending with other polymers
(biodegradable fossil or biobased)
Compostable
Commercial: Novamont…
Not for engineering uses
OthersPartialy biobased
Aliphatic polyesters (as PLA, PHA)PBS polybutylene succinatePBSA polybutylene succinate adipatePCL polycaprolactone
Aliphatic aromatic polyestersModifications of PETPBAT polybutylene adipate terephthalatePBMAT
(Ecoflex BASF, Eastar bio)Watersoluble polymers
PVOH polyvinylalcoholEVOH ethylenevinyl alcohol (O2 $$)
But also cellulose based: e.g cellophane (biobased & compostable)
PEPolyethylene
Production
Biobased organic substrate Bio
Fermentation to ethanol Fermentation
Dehydration to ethylene Chemical
Polymerization Chemical
Indistinguishable from fossil-based PE (except C14 ratio)
Biobased not biodegradable
Commercial / rel. large scale
PET
• Bio PET / Coca Cola, Heinz: in late stage of R&D
• 30% (soon 100 % bio C)
• Partner for TA: Virent
• BTX also for:
• PS, PA, PC, PU,
• Phenolics
• PEF?
EG
Bio
+ =
⌃⌃⌃⌃ ⌃⌃⌃⌃
Bio
TA PET
• New polymers? Roquette
Polyethylene isosorbide terephthalate
PU
Isosorbide polycarbonate
Polyisosorbide succinate 100% biobased
And it continues…• 1,3 propanediol (DuPont, 45.000 t/a, Sorona)• 1,4 butanediol• succinic acid• levulinic ketals (chemical route)• soy oil based polyols
• Olefinic methathesis: plant oils → waxes, functional oils, lubricants•Etc etc
• A question of costs
CO2 as feedstockBiobased, renewable?
BASF polyols
Algal oils (CO2 from fossil fuel combustion?) Biobased?
Overall• Where is this going?
• PET: 452 kT >> 4.628 kT• BP: 1.161 kT >> 5.778 kT Almost no incentives! Large ind.
Trend• Bioplastics growing
• Transition of focus: Biodegradable >> Biobased
• Reinventing known polymers as biobased (0-100 % !)
• Biosourced plug-in chemicals
� Biorefineries
This project is implemented through the CENTRAL EUROPE programme co-financed by the ERDF
www.plastice.org
Innovative value chain development for sustainable
plastics in Central Europe
Plastics use growing >> environmental pressures
Solution: more sustainable use and materials (bioplastics)
CE: science good but little use
PLASTiCE in brief• 13 partners, 4 countries, 36 month, 2,5 MEuro
• Not a research project
• Supporting conditions for a wider use of bioplastics
(biodegradable + biobased)
o Informing / dissemination (publications events…)
o Case studies (with companies)
o Establishment of certification portals (DIN Certco)
o Information point network (17 countries)
• UV dye printing
• Ecovio, Prismabio
• printing should be no more than
48 hours after extrusion
• film slip was issue
• commercial marker
• Ready implementation and detection
MarkersTesting of markers for easy identification of biodegradable plastics in the waste stream
- injection molding- number of materials tested- flexibility / postcrystallization
PE applicator PHA applicator Water soluble app.
Use of bioedegradable plastics in hygiene, sanitary and auxiliary medical products
Tampon Applicator
Injection molding / Sterilization
- Water-steam sterilization
- Problems:
- loss of elasticity - fragile
- reduction of size
- torsion, closing of tweezers
Surgical Tweezers
Straws
Food contact disposable products
Food contact testing
OVERALL MIGRATION
• PLA overall migrations from all samples into all simulants after first
and third cycle are below level of detection
• PHA overall migrations above limits (BUT: used grades not intended
for FC use)
• Thermoplastic starch:o Laminated cup: 1 cycle pass
o Bags: pass, although they are not intended for FC
o Foil: first cycle exceeds limits, third cycle pass prewashed – lower
overall migration, still exceeds the limit
3 types of carrier bags:
• LDPE plastic bag : produced in Slovenia (Plasta d.o.o, …)• PP plastic bag : produced in Vietnam, supplied by Vicbag
S.A.S.• Biodegradable Mater-Bi bag : produced in Slovenia (Plasta
d.o.o.)
LCA of carrier bags
Results: Mass equality - 20 g
Equality / Competitiveness of Mater-BI bag!
Opportunity
• Implementation of agricultural composting � credits!
• 34 % of overall burden (GWP) comes from industrial composting
Full scale industrial composting
• Collection of 100t (200 m3) of bio – waste
• Removal of unsuitable waste –conventional plastics etc. (15+%)
• Inserting the samples – Biodegradable shopping bags 380 kg
CompostingWeek 3: Temp 76 °C, material damaged ,visible
Week 5: material found
only where several layers
Together
Week 7: no more found, Week 11: stopped, sieving
WM company surprised!! Certified materials. Potential to avoid up
to 25 wt % loss…
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Value Chain
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ConclusionsLimited availability of materials and additives
- Covered applications – easy adoption
- New/difficult/specific applications – quickly run out of
options
- Information a limitation
Key for growth
- Framework conditions (standards, certifications,
demands for cert. in laws, procurement…)
- Demand ?
Options for CEE?Polymer production
- must be large scale for viability.
on what substrate? � bio-refineries?
local availability?
Material formulation
- high knowledge content
- which ingredients (bio, local)? Fillers, fibers etc.
option to supply raw materials?
Product production
- large capacity exists in region
need: (some) R&D support, demand creation
Potential for local component insertion
TasksDemand creation
Cost. Why?
reduction of environmental burdens
sustianable products development
Collateral result: business opportunities, solutions leadership
(in niches)
Example: biodegradable carrier bags in Italy (Novamont?)
Production of biocomponents
- alternative (value added) use of waste (sawdust, straw..)
Supply into a value chain (domestic or foreign)
- Full fledged biorefineries
Future?
