Closing the loop: 1

Rubber Recycling
Joint seminar
Kumi-instituutti & MOL
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Contents

- Introduction

- Present: Rubber crumb

Surface activated rubber crumb

Reclaim / devulcanizate

- Future
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Introduction
Used tires

(V.L. Shulman, 2008, ETRA)

Others 3% Retreading 12%

Landfill 20%
Export 7%
800,000,000 tires/year
2006 Increase: 2%/year

Material recycling 27 % Energy recovery

31%

EU countries:
2000: ca. 2,700,000 tons
2006: ca. 3,200,000 tons
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Introduction
Legislation

ELV: EU legislation End of life vehicles

2015: < 5 % landfill (End of life vehicles EU legislation,

Dir. 2000/53/EC)

2006: Prohibtion of landfill of shredded tires (Dir.1999/31/EC)

2006: < 15% landfill (ELV)

2003: Prohibition of landfill of whole tires

(Dir. 1999/31/EC)
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Introduction
Recycling loops

CO2 + H2O + energy

Energy recovery
CnHm
Increasing
Monomers Feedstock recovery degree
of
Polymers
valorization
Compounds
Material recycling
Vulcanized
products
Energy consumption:
New rubber: 115 J/kg
Rubber granulate: 2 J/kg
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Rubber powder

Surface
Granulate
Vulcanized activation Rubber
rubber product
Powder
Regeneration

Buffings Rubber granulate, Rubber powder, Rubber powder,

5 mesh = 4 mm 16 mesh = 1.19 mm 30 mesh = 0.595 mm

cryogenically ground ambiently ground

10 m 2 m
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Surface activated rubber powder

Surface
Granulate
Vulcanized activation Rubber
rubber product
Powder Regeneration

Biological treatment

Mechanical treatment Surface

Granulate activated
Powder Physical treatment powder

Chemical treatment
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Surface activated rubber powder

Surface
Granulate
Vulcanized activation Rubber
rubber product
Powder Regeneration

Biological treatment

Mechanical treatment Surface

Granulate activated
Powder Physical treatment powder

Chemical treatment
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Surface activated rubber powder
Chemical treatment

Coating:
+ Polymer
Latex, low-molecular liquid polymer, polymer-oil blends
+ Curing additives

Swelling:
+ Oligomer, evtl. with functional groups
+ Oil with (curing) additives

Grafting:
+ Silanes
+ Ethylacrylate
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(Surface activated) rubber powder
Influence on compound properties

System: latex + curing agents

Powder: truck treads (70%NR/30%SBR)

NR compound SBR compound

Tensile strength [MPa] Tensile strength [MPa]

30
20
20
10

10 0
Tear strength [N] Tear strength [N]
100

50
50
25

0 0
0 10 20 30 40 50 0 10 20 30 40 50
-
Concentration rubber crumb [%] Concentration rubber crumb [%]

Surface activated rubber crumb Untreated rubber crumb

Technical Information Rubber Resources

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(Surface activated) rubber powder
Influence on compound properties

NR compound SBR compound

Abrasion [mm3] Abrasion [mm]
200
200
150

100 100

50 0
Compression set (70) [%] Compression set (70C) [%]
75 100

50 50

0
25
Rebound resilience (70C), [%] Rebound resilience(70) [%]
60 50

50 40

40 30
0 10 20 30 40 50 0 10 20 30 40 50
-
Concentration rubber crumb [%] Concentration rubber crumb [%]

Surface activated rubber crumb Untreated rubber crumb

Technical Information Rubber Resources

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Reclaim

Surface
Granulate
Vulcanized activation Rubber
rubber product
Powder
Reclaiming

Definition reclaim:
Crosslink
A process in which vulcanized rubber is scission
converted into a material which can be
blended, processed, and cured again by
using mechanical, thermal or chemical
processes
Polymer

Devulcanization: scission

Selective scission of sulfur crosslinks

Polymer

Crosslinks

http://www.coe-nr.org
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Reclaim
Processes

Mechanical
reclaiming

Granulate
Reclaim
Powder

Thermal Chemical
reclaiming devulcanization
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Reclaim
Thermomechanical breakdown

Softeners Polymers

mechanical thermal
Viscosity decrease

Molecular weight
120C Temperature Initial MWD
MWD after thermal breakdown
MWD after mechanical breakdown
Thermal: Mechanical:
- non-selective in terms of chain length + selective for longer chains
- non-selective for polymer chains and crosslinks - non-selective for polymer chains and crosslinks
- reactive chain ends - reactive chain ends

Polymer degradation
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Reclaim
Processes

Mechanical
reclaiming

Granulate
Reclaim
Powder

Thermal Chemical
reclaiming devulcanization
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Reclaim
Chemical devulcanization aids

Radical breakdown - Disulfides

Oxidation - Oxygen (air)

Nucleophilic breakdown - Mercaptanes

- Hydroxydes
- Amines

Breakdown of C-S bonds - Raney-Nickel

- Alkali metals
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Reclaim
Processes

Mechanical
reclaiming

Granulate
Reclaim
Powder

Thermal Chemical
reclaiming devulcanization
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Reclaim
Effect of temperature, reclaiming aid and concentration

EPDM roofing sheet compound, EV cured (short crosslinks)

200C 225C
(): HDA
CH3 (CH2)15 NH2

(): DPDS
S S
250C 275C

(): BAFD

N CO
S H
S
N CO
H

Dijkhuis, K., thesis, 2008, ISBN 978-90-365-2643-2

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Reclaim
Effect of temperature, reclaiming aid and concentration

EPDM roofing sheet compound: conventionally cured (long crosslinks)

225C 250C 275C

(): HDA (): DPDS (): BAFD

CH3 (CH2)15 NH2 S S
N CO
S H
S
N CO
H

Dijkhuis, K., thesis, 2008, ISBN 978-90-365-2643-2

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Reclaim
Influence on compound properties (EPDM)
EPDM roofing sheet compound
Conventionally cured

N CO
S H
(): HDA CH3 (CH2)15 NH2 (): DPDS S S (): BAFD S
N CO
H
EV cured

Dijkhuis, K., thesis, 2008, ISBN 978-90-365-2643-2

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Reclaim
Influence on compound properties (NR/SBR)

NR/SBR truck tire tread reclaim in a similar compound

Reclaiming aid: Diphenyldisulfide

Tensile strength [MPa]

Tensile strength [MPa]
28 Tear strength [N]
Abrasion [mm]
Compression set [%]
24
Rebound resilience [%]
0 20 40 60 80 100
20 % relative to basic compound
0 10 20 30 40 50
Basic compound (NR/SBR)
NR/SBR reclaim concentration [phr]
22% NR/SBR Reclaim

Technical Information Rubber Resources

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Reclaim
(Dis)advantages

In a blend with virgin rubber:

+ Shorter mixing, milling, extrusion cycles

+ Lower processing temperature, less scorch
+ Better tack
+ Improved temperature resistance
+ Higher green strength
+ Easier escape of air from the mold
+ Improved aging resistance

- Influence on property profile

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Reclaim
More efficient devulcanization

Influencing factors for reclaiming efficiency:

- Temperature
- Time
- Shearing forces
- Devulcanization aid
- Restoration of double bonds

Shifting to devulcanization:

- Low temperatures
- Low shearing forces
- Appropriate devulcanization aid

The right choice of the devulcanization aid is crucial!

Dijkhuis, K., thesis, ISBN 978-90-365-2643-2

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Rubber Recycling
The future

50% of recycled material back into Others 3% Retreading

Landfill 0% 12%
Export 7%
(the original) rubber products
Material
recycling Energy
50% recovery
28%

Shifting the balance between thermomechanical breakdown

and chemical devulcanization to devulcanization

Emphasis on tire rubbers

- SBR (main tire rubber) is the most difficult elastomer to reclaim

- Blend of elastomers can give only a best compromise
 Closing the loop: 25

Rubber Recycling

Thank you for your attention!