DEPOTEC Life+ End Of Project Workshop Pyrolysis ys s of tyre rubber for solids and fuels November 2015 Guillermo San Miguel Professor and Senior Research Fellow Email: g.sanmiguel@upm.es www.eabiolab.industriales.upm.es www.grupodeagroenergetica.com g g
INDEX 1. INTRODUCTION 2. DIRECT COMBUSTION (TDF) 3. TYRE PYROLYSIS TECHNOLOGIES AND PLANTS 4. TYRE PYROLYSIS PRODUCTS - Tyre pyrolysis solids - Tyre pyrolysis oil 5. CONCLUSSIONS Fichas docentes Biomasa energética 2
INTRODUCTION The tyre problem still unsolved. A residue or a resource? Waste Framework Directive 2008/98/EC i) Reuse: retreading-remoulding ii) Recycled rubber: surfaces, soil amendment, civil eng., rubber reclaim, pyrolysis. iv) Recovery: direct combustion/ co- combustion/gasification. v) Disposal: safe manner. http://www.theguardian.com/world/2015/oct/16/s hredder-sought-five-million-tyres-dumped-spainmadrid 3
Tyre composition Ingredients Car tyre (wt%) Lorry tyre (wt%) Thermal stability Elastomer (BR, SBR, PIR...) 45-5050 43-4747 Low Fillers (carbon black/silica/clay) 20-23 21-24 Very high Steel (cord and wire) 15-18 23-27 Very high Textile (nylon, PEster) 5-7 - Low ZnO 1.0-1.5 1.5-2.5 Very high S 10-1 1.0-1.5 10-1 1.0-1.5 Low Additives (wax, pigment, oils...) 7-8 4-6 Low 4
DIRECT COMBUSTION (TDF) - Cement kilns - Power plants - Paper mills - Iron foundries - 7 cement plants and 2 waste-to-energy licensed in Spain for TDF - Tyre pre-treatment: whole tyres, shredded (20-30 cm), ground (5-10 cm) - Plant: máx. 5-20 % TDF not to affect emissions or cement quality. - Sulphur and PAH emissions. 5
(* all costs aprox. excluding taxes, or incentives) Rough economics of TDF Seseña scrap yard 90.000 tonne tyres 3.15 * 10 9 MJ POTENTIAL INCOME Fuel type replacement Cost energy unit* ( /t) Cost energy unit* ( /GJ) M replacing fuels Powdered coke 60 200 2.00 630 6.30 Low range coal 50 1.67 5.25 Wood pellets 80 4.10 12.92 Residential heating oil 375 9.44 29.74 POTENTIAL COSTS ( /t) M Shredding (2.5 cm) 50 4.50 Shredding (10 cm) 20 180 1.80 Transport 0.6 /(km*t) 200 km 1.08 BENEFITS M Coke replaced by ground tyre (2.5 cm) 0.72 Coal replaced by shredded tyre (10 cm) 2.37 Residential heating scenario (2.5 cm) 24.16 Additional requirements: adapt cement kiln. Added benefits: waste management (paid activity, depending on demand) 6
TYRE PYROLYSIS TECHNOLOGIES AND PLANTS - Fixed bed/autoclave reactors - Rotary kilns - Screw conveyors (auger type) - Fluidized bed (bubbling, spouted ) - Other (plasma, vacuum, ablative, etc) Metso (Finland); Depotec (EU) Pirorec-B&G (Spain) 7
Tyre pyrolysis in Spain: PRENASA (2015) Alloza (Teruel), Spain Capacity: 9.100 t/year GUASCOR Enviroil (2008) As Somozas (La Coruña), Spain Capacity: 12.000 t/yr Pirorec-Black & Green (2010) Guadassequies (Valencia) Capacity: 16.500 t/yr http://www.grupotec.es/proyectos/plant a-termolisis-tratamiento-neumaticos.html Tyre pyrolysis in Europe: Metso (Finland) BTG, EnergyPY (Netherlands) GB Energy (Czech Republic), etc. - Limited operation. - For demonstration and research. - Non marketable products. -adapted for tyres, plastics, biomass... 8
Other tyre pyrolysis technologies: China, India... http://www.huayinenergy.com/ http://www.doinggroup.com http://www.bestongroup.net/ 9
TYRE PYROLYSIS PRODUCTS Waste tyre Shredding Transport Pyrolysis Carbon solids Pyro-oil oil Steel wire Gases 20-30 wt% 30-40 wt% 12-18 wt% 10-20 wt% - PAC - Tyre fuel oil - Recycled steel - Onsite use - Carbon black - Chemicals 10
TYRE PYROLYSIS SOLIDS: carbon black for rubber filling Carbon black: spherical particles in linear aggregates due to partial combustion of natural gas or fuel oil. Superstructures of CB spheres bound by tar-like material. BET S.A.: 80-100 m 2 /g Ash: 5-10 wt% S: 1.9 wt% Zn: 3.1 wt% 11
Tyre pyrolysis solids: carbon black Grade N 220 N 330 N 550 N 660 ASTM test Iodine adsorp. No, g/kg 121±5 82±5 43±5 36±5 D 1510 CTABabsorp absorp. m2/kg 111±5 82±5 42±5 36±5 D 3765 Heating loss at 125 C (max %) 1,0 1,0 1,0 1,0 D 1509 Ash content (max %) 1,0 1,0 1,0 1,0 D 1506 Sieve residue 0.045 mesh 0,001 max 0,001 max 0,001 max 0,001 max Sieve residue 0.500 mesh 0,10 max 0,10 max 0,10 max 0,10 max D 1514 Fine Content (max %) 7 7 7 7 D 1508 pour density kg/m3 345±30 375±30 360±30 425±30 D 1513 Sulphur content (max %) 1,1 1,1 1,1 1,1 D 1619 Colour strength % 115±5 103±5 D 3265 ph value 7 10 7 10 7 10 7 10 D 1508 Pellet hardness g 15 100 15 100 15 100 15 100 D 3303 Some parameters our of standards and some not properly assessed. Carbon processing: solvent/ash washing, milling, desulphurization. Use in low grade alternative applications (outside standard). Tentative market price: uncertain (500-2000 /tonne if standardized) 12
Tyre pyrolysis solids: PAC for wastewater treatment applications: Porosity and surface area Powdered form High surface area Micro-mesoporous character 13
Aqueous phase: adsorption capacity High adsorption capacity for dyes due to mesoporous character. Medium adsorption capacity for smaller molecular weight compounds. Optimum burn off: 40-50 % 800 m 2 /g Carbon yield: 25 % original tyre Tentative market price: uncertain (500 /tonne if usable) 14
Aqueous phase: leaching of inorganic species 15
Very low mobility of inorganic species in neutral conditions (ph 7) - Sulfur = 1.0% - Zinc = 15 % Formation of insoluble metallic sulfides during the pyrolysis/activation. y 16
TYRE PYROLYSIS OIL as fuel: Biomass pyrolysis oil Tyre pyrolysis oil Heavy fuel oil (No. 5) Diesel fuel (No. 2) Application?? Marine Residential heating Moisture content (wt %) 15-30 < 0.1 < 0.1 < 0.05 ph 2.5-3.0 - - - Density (kg/m3) 1100-12501250 950 950 820-860860 C 40-50 86 85 84 87 Elemental H 6-8 10 11 15 32 analysis N 0.1-0.5 0.5 0.3 < 0.1 (wt %) O 45-5555 20 2.0 10 1.0 < 0.1 S < 0.05 1.0-1.9 1.5-2.5 < 0.001 High heating value (MJ/kg) 16-19 3 40 45 Energy density (GJ/m3) 19-22 38 38 38 Viscosity at 40ºC (cp) 20-500 50 180 2-5 Solids (char and ash) (wt %) 0.05-0.5??? 1 < 0.01 Flash point ( C) 45-100 90 60 Autoignition temp (ºC) > 500 290 260 Water solubility Aprox. 50% Negligible Negligible Negligible 17
Tyre Pyrolysis Oil desulfurization - Hydrodesulfurization (HDS), - extractive desulfurization, - oxidative desulfurization, - biodesulfurization - supercritical water Conventional: expensive Experimental Pyrolysis with alkaline desulphurizers More afordable, but generates a residue 18
Catalytic pyrolysis of tyre rubber: zeolites, mesostructured solids, For improved fuel properties p of tyre derived oil: - Increased aromaticity in zeolites, reduced molecular size. - Fuel composition of catalytic oil similar to gasolines. -Rapid catalyst a deactivation a (poisoning) due to sulphur. u 19
POTENTIAL INCOME FROM PYROLYSIS SOLIDS Yield (%) Tonnes M Powdered coke 2.0 /GJ 100 90000 6.30 PAC 500 /t 25 22500 11.25 Carbon black 1000 /t 35 31500 18.90 POTENTIAL INCOME FROM PYROLYSIS OILS /GJ Yield (%) Tonnes M Crude oil 7.36 35 31500 23,18 Bunker oil (High S) 4.94 35 31500 15,56 Diesel (No 2) 9.44 35 31500 29,74 Seseña Scrap yard 3.15 * 10 9 MJ ADDITIONAL COSTS M Shredding (2.5 cm) 50 /tonne 4.50 Shredding (10 cm) 20 /tonne 180 1.80 Transport 200 km 1.08 Pyrolysis XXXX? Carbon black processing YYYY? Pyrolysis oil desulfurization ZZZZ? 20
(* all costs aprox. excluding taxes, or incentives) Rough economics of TDF Seseña scrap yard 90.000 tonne tyres 3.15 * 10 9 MJ POTENTIAL INCOME Fuel type replacement Cost energy unit* ( /t) Cost energy unit* ( /GJ) M replacing fuels Powdered coke 60 200 2.00 630 6.30 Low range coal 50 1.67 5.25 Wood pellets 80 4.10 12.92 Residential heating oil 375 9.44 29.74 POTENTIAL COSTS ( /t) M Shredding (2.5 cm) 50 4.50 Shredding (10 cm) 20 180 1.80 Transport 0.6 /(km*t) 200 km 1.08 BENEFITS M Coke replaced by ground tyre (2.5 cm) 0.72 Coal replaced by shredded tyre (10 cm) 2.37 Residential heating scenario (2.5 cm) 24.16 Additional requirements: adapt cement kiln. Added benefits: waste management (paid activity, depending on demand) 21
CONCLUSSIONS C O S - Need for waste tyre management technologies. - Tyre pyrolysis demonstrated, but products not fulfilling quality standards no market acceptance additional processing (?) (ash removal, desulphurization, activation, particulate size reduction and fractionation, etc) - Need for complete market and economic analysis. - Environmental benefits not fully investigated. - Need to ensure real demand for pyrolysis products. 22
DEPOTEC Life+ End Of Project Workshop Pyrolysis of tyre rubber for solids and fuels November 2015 Guillermo San Miguel Professor and Senior Research Fellow Email: g.sanmiguel@upm.es www.eabiolab.industriales.upm.es www.grupodeagroenergetica.com