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FROM WASTE TO VALUABLE PRODUCTS
Hülya Ucar Sokoli, Erik Gydesen Søgaard
Aalborg University Esbjerg, Denmark
Department of Chemistry and Bioscience
DI 19.01.2016 1
DI 19.01.2016 2
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.
DI 19.01.2016 3
Thermosets vs. Thermoplastics
• Thermoplastict  Moldable
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 every
year. This number is increase each year!
Fact: 1 MW wind turbine produce 10 ton
composite waste.
DI 19.01.2016 4
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 waste
on landfills or incineration plants – No regulations.
Germany forbids companies to landfill their waste!
 Landfilling  No attempt to recycle at all, but cheapest
disposal 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.
DI 19.01.2016 5
Genvind – Innovation Consortium
Funded by the Danish Agency for Science, Technology and Innovation
Sustaniable
recycling of
composite waste
Furniture
Building
panels
New wind
turbine
blades Paint
Fibre
reinforced
concrete
Textiles
Plastic
construc-
tions
DI 19.01.2016 6
Contec
Dyrup
Recycling Technologies
Recycling
Thermoset Polymer
Composites
Thermal
Chemical
Mechanical
Pyrolysis Fludized bed
Glycolysis HydrolysisSolvolysis
Filler
particle
Fibrous
particle
DI 19.01.2016 7
Recycling Technologies
Recycling
Thermoset Polymer
Composites
Thermal
Chemical
Mechanical
Pyrolysis Fludized bed
Glycolysis HydrolysisSolvolysis
Filler
particle
Fibrous
particle
DI 19.01.2016 8
Solvolysis
Batch Reactor
200 -325 ˚C
300 Bar
Methodology
DI 19.01.2016 9
Investigation 1, The fibers
Type of recovery process
Reference Varying Parameters
TENSILE STRENGTH
Gpa % chg.
Fluidised bed
Pickering
(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
350oC – 5 minutes 1,24 -42
350oC – 5 minutes 0,69 -67
350oC –30 minutes 0,68 -68
300oC – 30 minutes 1,04 -51
DI 19.01.2016 10
DI 19.01.2016 11
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
DI 19.01.2016 12
Virgin
fiber
3 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
Strength[Gpa] Experiment no.
Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116
Fiber Properties - SEM
DI 19.01.2016 13
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.
DI 19.01.2016 14
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 residence
time
Results:
Up to 50 ml oil from one batch.
DI 19.01.2016 15
Is it beneficial?
Costs related to one batch
Production 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 g
Price (USD): $ 3,040 / 1 g (FOB, NY, USA)
Lead time: 2 weeks
DI 19.01.2016 16
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
Recovered
Resin
Recovered
carbon/glass
fibers
Recovered
solvent
Solvent
200-325 ˚C,
40-300 bar
Monomers
Chemicals
Fuel
New
materials
DI 19.01.2016 17
Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116
Recovery of chemicals
Composite waste
Recovered
Resin
Recovered
carbon/glass
fibers
Recovered
solvent
Solvent
200-325 ˚C,
40-300 bar
Monomers
Chemicals
Fuel
New
materials
Great potential
DI 19.01.2016 18
Succes of turning other kind of waste
into 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 disposed
their waste at the biogas
plant
The biogas plant received
money from the farmers
and slaughterhouses back
then.
DI 19.01.2016 19
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 composite
types
DI 19.01.2016 20
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
DI 19.01.2016 21
Thank you
DI 19.01.2016 22
Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116
DI 19.01.2016 23
Tak for jeres opmærksomhed 
Spørgsmål?
egs@bio.aau.dk
ucar@bio.aau.dk

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From waste to valuable products

  • 1. FROM WASTE TO VALUABLE PRODUCTS Hülya Ucar Sokoli, Erik Gydesen Søgaard Aalborg University Esbjerg, Denmark Department of Chemistry and Bioscience DI 19.01.2016 1
  • 2. DI 19.01.2016 2 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.
  • 3. DI 19.01.2016 3 Thermosets vs. Thermoplastics • Thermoplastict  Moldable when heated. • Thermoset plastic  Crosslinked by covalent bonds. NOT moldable when heated
  • 4. Why recycle composites? 400.000 ton composite waste is deposited on landfills in Europe every year. This number is increase each year! Fact: 1 MW wind turbine produce 10 ton composite waste. DI 19.01.2016 4 Reference: Miljøstyrelsen & DTU www2.mst.dkReference: Miljøstyrelsen www2.mst.dk Compositewaste.eu
  • 5. What do we do in Denmark? Problems in the field of recycling composite waste in Denmark 1. Companies in Denmark can dispose their composite waste on landfills or incineration plants – No regulations. Germany forbids companies to landfill their waste!  Landfilling  No attempt to recycle at all, but cheapest disposal 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. DI 19.01.2016 5
  • 6. Genvind – Innovation Consortium Funded by the Danish Agency for Science, Technology and Innovation Sustaniable recycling of composite waste Furniture Building panels New wind turbine blades Paint Fibre reinforced concrete Textiles Plastic construc- tions DI 19.01.2016 6 Contec Dyrup
  • 7. Recycling Technologies Recycling Thermoset Polymer Composites Thermal Chemical Mechanical Pyrolysis Fludized bed Glycolysis HydrolysisSolvolysis Filler particle Fibrous particle DI 19.01.2016 7
  • 8. Recycling Technologies Recycling Thermoset Polymer Composites Thermal Chemical Mechanical Pyrolysis Fludized bed Glycolysis HydrolysisSolvolysis Filler particle Fibrous particle DI 19.01.2016 8
  • 9. Solvolysis Batch Reactor 200 -325 ˚C 300 Bar Methodology DI 19.01.2016 9
  • 10. Investigation 1, The fibers Type of recovery process Reference Varying Parameters TENSILE STRENGTH Gpa % chg. Fluidised bed Pickering (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 350oC – 5 minutes 1,24 -42 350oC – 5 minutes 0,69 -67 350oC –30 minutes 0,68 -68 300oC – 30 minutes 1,04 -51 DI 19.01.2016 10
  • 11. DI 19.01.2016 11 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
  • 12. Results DI 19.01.2016 12 Virgin fiber 3 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 Strength[Gpa] Experiment no.
  • 13. Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116 Fiber Properties - SEM DI 19.01.2016 13
  • 14. 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. DI 19.01.2016 14
  • 15. 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 residence time Results: Up to 50 ml oil from one batch. DI 19.01.2016 15
  • 16. Is it beneficial? Costs related to one batch Production 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 g Price (USD): $ 3,040 / 1 g (FOB, NY, USA) Lead time: 2 weeks DI 19.01.2016 16 0 0.5 1 1.5 2 2.5 Kr. 2,5 0,1 Acetone Catalyst Energy Consumption 0,50
  • 17. Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116 Recovery of chemicals Composite waste Recovered Resin Recovered carbon/glass fibers Recovered solvent Solvent 200-325 ˚C, 40-300 bar Monomers Chemicals Fuel New materials DI 19.01.2016 17
  • 18. Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116 Recovery of chemicals Composite waste Recovered Resin Recovered carbon/glass fibers Recovered solvent Solvent 200-325 ˚C, 40-300 bar Monomers Chemicals Fuel New materials Great potential DI 19.01.2016 18
  • 19. Succes of turning other kind of waste into 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 disposed their waste at the biogas plant The biogas plant received money from the farmers and slaughterhouses back then. DI 19.01.2016 19
  • 20. 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 composite types DI 19.01.2016 20
  • 21. 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 DI 19.01.2016 21
  • 22. Thank you DI 19.01.2016 22 Hülya Ucar Sokoli. Mail: ucar@bio.aau.dk No.: + 45 42443116
  • 23. DI 19.01.2016 23 Tak for jeres opmærksomhed  Spørgsmål? egs@bio.aau.dk ucar@bio.aau.dk