from waste to valuable products

FROM WASTE TO VALUABLE PRODUCTS

Hülya Ucar Sokoli, Erik Gydesen SøgaardAalborg University Esbjerg, Denmark

Department of Chemistry and Bioscience

DI 19.01.2016 1

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Polymer Composites

• What is a composite?

A composite is the combination of two or more materials that when combined together creates a superior and unique material. Ex. Glass- or carbon fibers held together with a polymer matrix.

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Thermosets vs. Thermoplastics

• ThermoplastictMoldable when heated.

• Thermoset plastic Crosslinked by covalent bonds. NOT moldable when heated

Why recycle composites?

400.000 ton composite waste is deposited on landfills in Europe everyyear. This number is increase each year!

Fact: 1 MW wind turbine produce 10 ton composite waste.

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Reference: Miljøstyrelsen & DTU

www2.mst.dkReference: Miljøstyrelsen

www2.mst.dk

Compositewaste.eu

What do we do in Denmark?

Problems in the field of recycling composite waste in Denmark

1. Companies in Denmark can dispose their composite wasteon landfills or incineration plants – No regulations. Germany forbids companies to landfill their waste!

Landfilling No attempt to recycle at all, but cheapestdisposal route

Incineration Not always possible. (Where limits are imposed on the energy content of the waste). The plants are not suitable for large parts and glass fibre residue can cause process stoppages.

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Genvind – Innovation ConsortiumFunded by the Danish Agency for Science, Technology and Innovation

Sustaniablerecycling of

composite waste

Furniture

Buildingpanels

New windturbine blades Paint

Fibre reinforced concrete

Textiles

Plasticconstruc-

tions

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Contec

Dyrup

Recycling Technologies

RecyclingThermoset Polymer

Composites

Thermal

Chemical

Mechanical

Pyrolysis Fludized bed

Glycolysis HydrolysisSolvolysis

Fillerparticle

Fibrousparticle

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Recycling Technologies

RecyclingThermoset Polymer

Composites

Thermal

Chemical

Mechanical

Pyrolysis Fludized bed

Glycolysis HydrolysisSolvolysis

Fillerparticle

Fibrousparticle

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Solvolysis

Batch Reactor

200 -325 ˚C300 Bar

Methodology

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Investigation 1, The fibers

Type of recovery processReference Varying Parameters

TENSILE STRENGTH

Gpa % chg.

Fluidised bedPickering

(2000)

Standard fiber 2,80 -

450 oC 1,45 -48

550 oC 0,50 -82

650 oC 0,18 -93

Pyrolysis

Cunliffe and Williams

(2003)

Standard fiber 2,02 -

400 oC and oxidized 1,06 -48

450 oC and oxidized 0,71 -65

500 oC and oxidized 1,06 -47

650 oC and oxidized 0,99 -51

800 oC and oxidized 0,36 -82

Knudsen et al.,

(2005)

Standard fiber 3,50 -

450 oC 0,96 -72

600 oC 0,50 -86

Subcritical water Kao et al., (2012)

Standard fiber 2,14 -

350 oC – 5 minutes 0,75 -65

350 oC – 5 minutes 1,24 -42

350 oC – 5 minutes 0,69 -67

350 oC –30 minutes 0,68 -68

300 oC – 30 minutes 1,04 -51

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Initial experiments

11

Run Solvent Temperature

[°C]

Pressure

[bar]

Reaction

time

[min]

Composite

covered with

solvent inside

reactor

(%)

Quantity of

solvent

[mL]

# 1 Water 280 300 0 100 250

# 2 Water 280 300 0 100 250

# 3 Water 280 300 30 100 250

# 4 Water 280 300 60 100 250

# 5 Water 300 300 0 100 250

# 6 Water 300 300 0 100 250

# 7 Water 300 300 30 100 250

# 8 Water 300 300 60 100 250

Results

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Virgin

fiber3 4 5 6 7 8

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4

2.6

Str

ength

[G

pa]

Experiment no.

Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116

Fiber Properties - SEM

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Investigation 2, Oil recovery

Initial thoughts

There needs to be a higher value (more gain) in the process of recovering fibers using this technology Particularly for glass fiber reinforced composite waste, since more than 95 % of all fiber reinforced waste originates from glass fibers.

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Oil Recovery

Experiments:

50/50 vol. % acetone /water

and a catalyst. Approximately 80 g

composite waste was degraded in one batch and 250 ml was applied

Process conditions:

300 °C, < 150 bar, 30 min residencetime

Results:

Up to 50 ml oil from one batch.

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Is it beneficial?

Costs related to one batchProduction of 50 ml oil costs:

Beneficial because:1. It is possible to produce oil

simultaneously with the elimination of a problematic waste product

2. The oil has properties close to petroleum fuel oil and can potentially be used as a fuel oil

3. The long range of chemicals produced through acetone aldol reactions are valuable petrochemical feedstock.

4. In fact, up to 20 g/L was found through quantification of one of the high value chemicals.

Assay: 98%Quantity: 1 gPrice (USD): $ 3,040 / 1 g (FOB, NY, USA)Lead time: 2 weeks

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0

0.5

1

1.5

2

2.5

Kr.

2,5

0,1

Acetone Catalyst Energy Consumption

0,50

Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116

Recovery of chemicals

Composite waste

RecoveredResin

Recoveredcarbon/glass

fibers

Recoveredsolvent

Solvent

200-325 ˚C, 40-300 bar

Monomers

Chemicals

Fuel

Newmaterials

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Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116

Recovery of chemicals

Composite waste

RecoveredResin

Recoveredcarbon/glass

fibers

Recoveredsolvent

Solvent

200-325 ˚C, 40-300 bar

Monomers

Chemicals

Fuel

Newmaterials

Great potential

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Succes of turning other kind of wasteinto valuable products

RIBE BIOGAS A/S startet in 1990. Biggest biogas plant in the world in the beginning.Farmers disposed their

manure waste at the biogas plant

Slaughterhouses disposedtheir waste at the biogas plant

The biogas plant receivedmoney from the farmers and slaughterhouses back then.

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More work done so far

• Up scaling from 250 mL to 1 L

• Microwave assisted degradation

• Investigations of different solvents activity in solvolysis

• Chemical analysis of chemicals from the elimination of resins from several compositetypes

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More work to be done

• Reuse of resins for the production of new composites (in collaboration with DTU)

• Reaction kinetical investigations of the elimination process in up-scaled reactor in collaboration with Force Technology

• Use of inorganic binder (Aalbinder) in the reuse of partly purified fibres

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Thank you

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Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116

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Tak for jeres opmærksomhed

Spørgsmål?egs@bio.aau.dk

ucar@bio.aau.dk