biomass to biopolymers

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…

34

Value Chain

35

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?

Keep the future coming!

Andrej Kržanandrej.krzan@ki.si

www.plastice.org