Recovered Carbon Black from tyre pyrolysis

European Tyre Recycling AssociationUniversité Libre de Bruxelles

Recovered Carbon Black fromtyre pyrolysisDr. C. Gisèle JUNG

Senior Researcher , Université Libre de Bruxelles,Applied Sciences Faculty – 4MATVice-President , ETRA

Ir. Jean-Paul BouyssetPhenix-Technologies PartnerASTM Member Vice President, ETRA

DEPOTEC Life project– Thurles – IRELAND – November 2015


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


1. Introduction



4

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


Introduction : ELT valorisation paths• Product valorisation : Reuse and retreading

• Material valorisation– Rubber recovery – In situ pyrolysis in electric furnaces– Using the pyrolytic char

• as reductant in blast furnaces (carbon feed for steel making)• to produce Active Carbon• as “fillers” and named recovered Carbon Black (r-CB)

– New assembling of technologies and mixed feed to produce high added value material

• Energy valorisation– Tyres Derived Fuels (TDF)– in Cement kilns



Indirect heating

SYNGAS

ASHESFEED

AIR

PYROLYSIS

GASIFICATION

Air default

GASOILSSOLID

FEED

No air

Direct heating

by fuel, flue gas or electricity• Production: rich gas and char

By partial combustion of pyrolytic gas and/or char• Production : poor gas

Flue gasASHES

FEEDAIR

INCINERATIONAir excessDirect heating

By direct combustion• Production:energy

01

Air

stoe

chio

met

ry

Thermal conversion ways

+ energy



About pyrolysis – indirect heating

• Decomposition of the organic matter with• easy separation of steel

• Pre-treatment by heating in absence of air between 450°C and 650°C.

(atmospheric pressure or under vacuum)

with production of• hot gases (high NCV)• carboneous solid

7November 2015 - Bouysset & Jung DEPOTEC Life Project – Thurles


2. Pyrolysis and process technologies



Pyrolysis - technologies • Types of indirect heated reactors:

– Rotary kiln with external heating jacket– Heated screw feeder– Hearth furnace– Microwave reactor

Fixed or moving bedBatch or continuous process



• Temperature• Pressure• Residence time• Use of catalysts• Heating rate• Heat transfert

• input size (depending on it’s nature)• bed hight• internal motion (i.e: rotating speed…)⇒Importance of furnace technology

Important parameters in pyrolysis

⇒ extrapolation from lab > pilot > industrial scale



Oil

Pyrolysis char

Gas

Temperature (°C)300 400 500 600 700

60

40

20

0

Yiel

ds (%

)

Source: Prof. J.B. Donnet (2008)

Tyre pyrolysis at atmospheric pressure

11Dr. C.Gisèle Jung 11DEPOTEC Life Project – ThurlesNovember 2015 - Bouysset & Jung


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


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.



3. From tyre to pyrolysis end-products



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



Carbon Black grades in tyresCOMPONENT CARBON BLACK

SERIECARBON BLACK GRADE EXAMPLES

PROPERITIESREQUIRED

TREAD N100 N200 N300 N100/220/N234N326/N330/N347/N375 …..

Low abrasion, lowrolling resistance, wet skid, high modulus.

SIDEWALL N500 N600 N700 N539/N550N650/N660/N765/N774

Good fatigue and cut resistance

BELTS N 300 N330/N375/N339 Adhesion, fatigue high modulus

PLIES N300 N600 N330/N347/N339 Adhesion, fatigue

INNER LINER N600 N700 N660/N772/N774 Air retention fatigue

CHAFER N 300 N330/N347/N339 Hardness, stiffness,abrasion

BEAD APEX N300 N330/N347 Hardness, stiffness

TREAD BASE N700 N765/N774 Low hysteresis, high modulus



ELT pyrolysis : primary products

~50% rubber~25% C Black

~ 5% Textile~2,0% ZnO~1,5% S~15% steel76% C, 7% HNCV=34GJ/t

H2, CO, CO2,light CxHy~ 1% S

GAS : NCV ~35 GJ/t

10-25 %PYROLYSIS

30-50%Aromaticsheavy CxHy~ 0.3 - 1% S

OIL

NCV ~40 GJ/t

Steel8-15 %

~15% Ash30-90 m2/g

~ 3 - 5% S

SOLIDNCV ~28 GJ/t25-40 %

25-40%



Tyre pyrolysis : primary products• Mass balance for 1ton tyres:

– char (~ 300kg), oil (~ 440kg), gas (~ 110 kg), steel (~ 150 kg)Yield depending on parameters

• Products:1. Solid called recovered Carbon Black (r-CB ): particle size,

particle size distribution, structure, physical form, surface activity, ash content, impurity contentNCV ~ 28 GJ/t

2. Oil : composition (heavy aromatics), impurities (S), NCV ~ 35 - 40 GJ/t

3. Gas: composition(H2/CO/CO2), impurities (S),NCV ~ 35 GJ/t



What is r-CB from tyre pyrolysis?• The solid called recovered - Carbon Black (r-CB) is a

mixture of Carbon Blacks initially present in tyre with pyrolytic Carbon issued from rubber cracking (usually less than 5%) and containing

• 8 - 15% ashes• 3 - 5 % sulphur• 5 % zincNCV= 28 MJ/kg



4. Pyrolysis plants and projects



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.


5. r-CB properties and performances -Tests / ASTM standards



Surface coating of r-CB

Carbon

hydrocarbon and mineraldeposits

less reinforcement

Estimated 82% carbon black, 18% residues

Source: Elastomer Research Testing B.V.



CB and r-CB surface activity



Particle size distribution of r-CB

Source : DIK and Prof Donnet25DEPOTEC Life Project – ThurlesNovember 2015 - Bouysset & Jung


Source: ETRA

Sequence of structure development



r-CB structure modification



Source: DIK/project PYROL-X

N 660 vs blends r-CB: dispersion



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



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



r-CB performances vs characterisitics

RecoveredCarbon Black

Characteristics

Recovered Carbon Black Performance

(Mechanical and Dynamic)



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

WHY?32DEPOTEC Life Project – ThurlesNovember 2015 - Bouysset & Jung


Tensile strength



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)



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 .

35 35DEPOTEC Life Project – ThurlesNovember 2015 - Bouysset & Jung


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



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

Dr. M. Bennett [email protected]. C. Norris [email protected]

• D.I.K. - www.dikautschuck.de - Germany Dr. H. Geisler [email protected]

• ERT Bv - www.ertbv.com - NederlandsIr. J. Van Kranenburg [email protected]


mailto:[email protected]






ASTM committee D24 – Carbon BlackSub-committee D24-67 - SustainabilityFor recovered- Carbon Black (r-CB)- Joe KOURY , staff Manager, [email protected] Ricky MAGEE, technical Manager, [email protected]

For more information, contact :- Jean-Paul BOUYSSET- AFICEP - ETRA - PHENIX TECHNOLOGIES,[email protected]






6. CB and r-CB markets/economics -future challenges and conclusion



EU Carbon Black market per sector of activityIn 2014 : 2,000.000 t

MARKET SECTOR TOTAL t/y %

RUBBER -TYRE-RUBBER GOODS

1,760.0001,360.000

400.000

88%68%20%

PLASTICS 100.000 5%

PRINTING INKS 80.000 4%

COATINGS /PAINTS 20.000 1%

OTHERS-ACTIVE CARBON-CONCRETE/BRICKS-PAPERS/TONERS-ROAD FILLERS

40.000 2%



EU Carbon Black market per sector of activity

RUBBER TYRERUBBER GOODSPLASTICSPRINTING INKSCOATINGS PAINTSOTHERS

RUBBER TYRE 68%

RUBBER GOODS20%

PLASTICS 5%

INKS 4%

PAINTS1% OTHERS 2%

Year 2014 : 2,000.000 t



EU Carbon Black market per gradeCB SERIE MARKET

t/ySHARE

%N 100 60.000 3

N 200 320.000 16

N 300 800.000 40

N 500 340.000 17

N 600 200.000 10

N 700 240.000 12

N 900 40.000 2

Year2014: 2,000.000 t



EU Carbon Black market per grade

N 100N 200N 300N 500N 600N 700N 900

N 300 40%

N 500 17%

N 200 16%

N 600 10%

N 700 12% N 100 3%N 900 2%



r-CB potential markets

SECTOR OFACTIVITY

POTENTIAL MARKETSCOMMENTS

RUBBER TYRE SUBJECT TO LONG APPROVAL PROCEDURESPOSSIBLE USE IN DIFFERENT PARTS OF THE TYRE IN REPLACEMENT OF MEDIUM AND LOW SURFACE AREA GRADES

RUBBER GOODS POSSIBLE USE IN MOULDED GOODS IN REPLACEMENT OF N600/N700 SERIES OR IN BLEND WITH N500 OR EVENTUALLY N 300 SERIES

PLASTICS POSSIBLE USE IN NON TECHNICAL PLASTICS (e.i.:UV protection , agricultural bags)

PRINTING INKS POSSIBLE USE IN SOME SECTORS: NEWS-INKS, PACKAGING for instance

for Sectors representing 97 % of the Carbon-Black Market



Rubber goods CB marketGlobal by industry

AUTOMOTIVEINDUSTRIALCONSTRUCTIONOTHERS

48%

26%

20%

2%

Europe (2014) : 400.000 t

Source: M.ROWLINSON TECHNOLOGY45November 2015 - Bouysset & Jung DEPOTEC Life Project – Thurles


Rubber goods CB market

N 200N 300N 500N 600N 700N 900

25%

30%

15%

25%

2% 3%

Europe (2014): 400.000 tPer grade



Rubber goods CB - automotive marketper sub-categories

EXTRUDED SEALSHOSESMOULDINGSEALSANTI VIBRATIONBELTSWIPERS

27%

23%21%

13%

10%5% 1%

Europe (2014) : 200.000 t

Source: M.ROWLINSON TECHNOLOGY



Rubber goods CB market per sectorCATEGORY APPLICATIONS COMMENTS r-CB

AUTOMOTIVE Anti-vibration/Vbelts/Extruded profiles/wipers/Hoses/Moulding/seals,Brake cups .

Moulded parts /Belts/moulded seals and gaskets .

INDUSTRIAL Conveyor belts/Hoses for oil,gaz,water/sealing/gaskets

Conveyor belts,mouldedpath and gaskets,

CONSTRUCTION Seals/profiles/constructionpaths

Anti UV applications.Thickmoulded parts

OTHERS Footwear/electrical goods/Hoses .

Anti-static applications

CUSTOM COMPOUNDSMASTERBACHES *

To be used in all above* mentioned applications.

Principally in blending withvirgin CARBON BLACK



r-CB potential markets subject to furtherdevelopments

SECTOR OF ACTIVITY

POTENTIAL MARKETSCOMMENTS

ACTIVE CARBON POSSIBLE USE FOR AIR/WATER PURIFICATION IN REPLACEMENT OF CB OF VEGETAL ORIGIN

CONCRETE BRICKS POSSIBLE USE USE IN REPLACEMENT OF METALLIC OXIDES (manganese etc )

PAPERS TONERS POSSIBLE USE IN THE PACKAGING SECTOR

ROAD FILLERS POSSIBLE USE AS ASPHALT MODIFIER (improvement of rutting and wear resistance )



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



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



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



Tyre Pyrolysis

recovered-Carbon Black

ProductCharacteristics Market and

development

Productspecifications

Customer

Applications

The role of market and development



DEPOTEC Life Project – ThurlesNovember 2015 - Bouysset & Jung 54


Thank you for your attention!

Dr.C.Gisele Jung - [email protected]

Ir. J-P. Bouysset - [email protected]





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


Recovered Carbon Black from tyre pyrolysis

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