European Tyre Recycling Association Université Libre de Bruxelles Recovered Carbon Black from tyre pyrolysis Dr. C. Gisèle JUNG Senior Researcher , Université Libre de Bruxelles, Applied Sciences Faculty – 4MAT Vice-President , ETRA Ir. Jean-Paul Bouysset Phenix-Technologies Partner ASTM Member Vice President, ETRA DEPOTEC Life project– Thurles – IRELAND – November 2015
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European Tyre Recycling AssociationUniversité Libre de Bruxelles
Recovered Carbon Black fromtyre pyrolysisDr. C. Gisèle JUNG
Ir. Jean-Paul BouyssetPhenix-Technologies PartnerASTM Member Vice President, ETRA
DEPOTEC Life project– Thurles – IRELAND – November 2015
European Tyre Recycling AssociationUniversité Libre de Bruxelles
Outline1. Introduction2. Pyrolysis - process and technology3. From tyre to pyrolysis end-products4. Pyrolysis plants and projects5. recovered-Carbon Black (r-CB) properties
and performances - tests / ASTM standards6. CB and r-CB markets/economics, future
challenges and conclusion.
2DEPOTEC Life Project – ThurlesNovember 2015 - Bouysset & Jung
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1. Introduction
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Approximately 3,400,000 tonnes of post-consumer tyres are permanently removed each year from cars, utility vehicles and trucks in the 27 EU States and Norway - and defined as waste.
Estimates are that an additional ± 70,000 - +100,000 tonnes are permanently removed each year from agricultural and other off-road vehicles - but not defined as waste
Tyre materials are a valuable resource
Another ±30% may be available from non-EU producers
End of life Tyres (ELT)
April 2013 DEPOTEC Life Project – ThurlesNovember 2015 - Bouysset & Jung
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European Tyre Recycling AssociationUniversité Libre de Bruxelles
80
60
40
20
0
Temperature (°C)300 400 500 600 700
Yiel
ds (%
)
Oil
Pyrolysis char
Gas
Source: Prof. J.B. Donnet (2008)
Tyre pyrolysis under vacuum pressure
Dr. C.Gisèle Jung 12DEPOTEC Life Project – ThurlesNovember 2015 - Bouysset & Jung
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3. PRODUITS DE LA PYROLYSE DES CAOUTCHOUCS Process yields vs plant capacity
Process ConditionsLaboratory Reactor,
G-821Pilot Plant,
H-70Demonstration
Plant, JT-1Temperature [°C] 500 450 530
Pressure [kPa] 0.4-0.8 20 15-20
Input [kg/h] 0.9a 20 540
Pyrolysis Yields
Pyrolytic oil 57.0 41.5 < 50.7b
Pyrolytic CB 35.1 38.4 >30.0b
Gas 7.9 20.1 19.3a Batch experiment: The tire crumb was heated at a rate of 10°C/min to a final temperature of 500°C; the temperature was held constant for 3 h.b The mass balance closure was not entirely satisfactory. The yield of CBp is probably higher than 30%. The oil yield is probably overestimated.
Source: « Conversion of Used Tires to Carbon Black and Oils » Roy, C. et al. , pp. 429-467, Rubber Recycling, CRC Press, 2005.
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3. From tyre to pyrolysis end-products
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Carbon black grade
N110 N234N326 N330 N347 N375
N539 N550N650 N660 N774
N330 N375 N339
N330 N339
N660 N772 N774
N330 N347 N339
N330 N347
N550 N650
serie
modified by J-P Bouysset –ETRA
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Carbon Black grades in tyresCOMPONENT CARBON BLACK
European Tyre Recycling AssociationUniversité Libre de Bruxelles
Pyrolysis plants in operation in EuropePlants in Operation COUNTRY TECHNOLOGY Batch /
continuousCAPACITY
(announced 10/2015)
CARBON CLEAN TECHPYROLYX (MERGER)
GERMANY‘’
multiple traysscrews
BatchContinuous
4500 t (?)
BLACK BEAR CARBON NETHERLANDS rotary kiln Continuous 5000 t (2016?)
SCANDINAVIAN ENVIRO SYSTEMS
SWEDEN fixed bed Bacth 3000 t
ALPHA-RECYCLAGE FRANCE rotary kiln Continuous 5000 t
ETIA-BIOGREEN FRANCE moving screw Continuous 1000 t
ECO-CAPITAL POLAND rotary kiln Continuous 1500 t
ECOMATION FINLAND rotary kiln Continuous 1000 t
MODUL BULGARIA/GREECE moving screw Continuous 3000 t
PILOT PLANTS
DAFNE ITALY rotary kiln Continuous Non Applic.
CURTI ITALY fixed bedmoving bed (?)
BatchContinuous
Non Applic.
ALFYMA FRANCE moving bed Continuous Non Applic.
European Tyre Recycling AssociationUniversité Libre de Bruxelles
5. r-CB properties and performances -Tests / ASTM standards
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Surface coating of r-CB
Carbon
hydrocarbon and mineraldeposits
less reinforcement
Estimated 82% carbon black, 18% residues
Source: Elastomer Research Testing B.V.
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CB and r-CB surface activity
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Particle size distribution of r-CB
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Source: ETRA
Sequence of structure development
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r-CB structure modification
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Source: DIK/project PYROL-X
N 660 vs blends r-CB: dispersion
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r-CB: mainly a molding product
• r-CB have medium or low structure :– r-CB difficult to be used in single extrusion .– r-CB must be used in mixture with high structure
carbon black such as N550 or N765
• Conclusion– r-CB is rather a molding product then an extrusion
product
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CB/r-CB : structure vs extrusion properties
High structureCB grades: N121/347/550/683OAN: 120 to 135 m3/kg
Medium structureCB grades: N220/N330/N660OAN: 90 to 102 m3/kg
Low structureCB grades: N326/N772/N990OAN: 35 to 75 m3/kg
r-CB
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r-CB performances vs characterisitics
RecoveredCarbon Black
Characteristics
Recovered Carbon Black Performance
(Mechanical and Dynamic)
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r-CB : unexpected tests resultsr-CB give similar results as N660 or N772 if used in a standard rubber compound.Properties of r-CB :• surface area of r-CB is higher than N660 :
60-70m2/g (r-CB and N330 )> 35m2/g (N660) ⇒ reinforcing properties of r-CB are lower than those of N330, more in the range of N 660 .• rubber tests : r-CB show lower values than N330 for
– tensile strength– modulus at higher strain– tear strength
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Tensile strength
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r-CB compared to N330/N660/N772• r-CB contains 10 to 15% of mineral fillers (inert fillers)
which were included in the tyre compounds • Surface area of r-CB (70 m2/g) is a statistical average
(mix of all the grades originally included in the tyre, from10m2/g to 150m2/g) i.e: large PSD
• Dispersion of r-CB in the rubber compound is bad due principally to the physical presentation of the r-CB (hard parts)
• Surface activity & Chemistry of Carbon Blacks are modified during the pyrolysis process ⇒ impact on the reinforcing properties (lack of rubber-CB bonding)
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Tyre pyrolysis – present situation• Several commercial pyrolysis companies are active
in the field of rubber. These technologies produceoil, gas and a pyrolytic solid called r-CB (ASTM ) .
• Methods of characterization of r -CB* must be improved to facilitate their integration as a substitution material in the market for various applications.
* Using ASTM standards for carbon black andactivated carbon .
European Tyre Recycling AssociationUniversité Libre de Bruxelles
ASTM D24-67 SUB-COMMITEErecovered -Carbon Black (r-CB )
r-CB is a semi-reinforcing filler having a large particle sizedistribution and a surface chemistry altered during pyrolysis.• For colloidal properties (specific surface area), under ASTM
standard methodology, r-CB belongs to N300 to N500 CB series• For performances in reinforcing properties in rubber
compounds, r-CB belongs to N600 to N700 CB series.CONCLUSION
New or revised protocols are necessaryACTION
Revised CB Standards and adapt them to the evaluation of r-CB colloidal characteristics and in-rubber properties
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CB and r-CB technical testing centers• LRCCP (BIOPROOF Program)- www.irccp.com- France
Dr. M. Herblot [email protected]• ARTIS(Cross-Check Program)- www.artis.com - UK
European Tyre Recycling AssociationUniversité Libre de Bruxelles
ELT’s pyrolysis : future challenges• CHARACTERISATION of r-CB:
Surface area and structure measured with CB testing methods are not a correct indicator for in-rubber performances
new or revised protocols are needed (i.e.ASTM sub-committeeD24-67)
• PROCESS OPTIMISATION:Surface treatment, activation and refining, beading processes are needed to offer improvement for in-rubber performances (dispersion)
Pyrolysis and post-treatments processes have to be optimized
Source : ASTM/ARTIS
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Sustainability – carbon footprint(*Estimation: depends on technology)
VirginCarbon Black
RecoveredCarbon Black
INPUT 1.8 t to 2.0 tOil feedstock
2.2 to 2.5 tELT granulate
OUPUT 1.0 tVirgin Carbon Black
1.0 tRecoveredCarbon Black
ENVIRONMENTALIMPACT *
2.2 to 2.8 tCO2 EMISSIONS
0.5 to 0.8 tCO2 EMISSIONS
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CONCLUSION on r-CB market acceptanceInitial market acceptance Important issues
• Technical considerationsTesting (by rubber companies) and qualification by potentialusers
• Financial considerationsPrice level acceptance
• Industrial considerationsProduction at the level of future demand.
Sustainability /Circular economy for
potential users
• Volume considerations :
– Pyrolysis plants of 40kt of ELTsproduce only 10 kt of r-CB
– Carbon Black plant ~ 100-300kt/y.
Difficulties for large companies to accept dealing with small compagnies.
• Future implantations :10% of the CB market in Europe (200kt) would need more than 20 pyrolysis plants using each 40 kt of ELTs
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Tyre Pyrolysis
recovered-Carbon Black
ProductCharacteristics Market and
development
Productspecifications
Customer
Applications
The role of market and development
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ASTM D24-67 for r-CB : to be discussedat the next ASTM meeting
COLLOIDAL PROPERTIESD 1510 Iodine N AD 6556 STSA A CD 2414 OAN A RD 3493 COAN A RD 6086 Void Vol.WithdrawnD 7854 Void Vol. A CD 1512 p H AD 1618 Tol extract AD 1619 Sulfur A
PHYSICAL CHARACTERISTICSD 1509 Ash % and composition (mineral fillers ,chemicals) ACD 1514 Sieve Residue ACD 1508 /D1511/D5230/D1937D 4324 Pellets tests AD 2663 Dispersion A
Legend : A : Applicable - NA: Non ApplicableAC: Applicable with commentsAR: Applicable with reserves
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