1. © Paul Wurth 2010 RECYCLING VALUABLE METALS FROM BY-PRODUCTS RODRIGUEZ David SEAISI 2010 (Manila) – November 23 rd, 2010

2. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 2 INDUSTRIAL RESIDUES SITUATION  Industrials are facing more and more stringent environmental regulations  Dumping costs and creates environmental liabilities  Extraction of valuable metals contained in residues generates financial return  Look for an alternative to high cost of “virgin” raw material Challenge: solve both environmental and economical issues

3. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 3 OVERVIEW OF RESIDUES Type of waste Recoverable metals Remarks 1 From the stainless or high alloy steel industry Ni, Cr, Mo, Fe Small quantities Recycling economical High product value 2 From electric steel plants making carbon steel (EAF dust) Zn, (Fe) Larger quantities Economics depend on Zn price (treatment fee required) 3From integrated steel plantsFe Very large quantities Economics not always favourable 4 From petrochemical industry (Spent catalysts) Mo, Ni, Co, V Small quantities High product value 5From Copper industryCu, (Mo) Very large quantity High product value 6From Zn hydrometallurgyZn, Pb, Fe, Ag Larger quantities Economics depend on Zn, Fe prices

4. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 4 PAUL WURTH EXPERIENCE IN STEELMAKING BY-PRODUCTS  Activity began 15 years ago  Recycling technologies:  RHF technologies: RedSmelt™ / RedIron™ 60ktpy RedIron plant in Piombino (IT - 2010) Recycling of integrated steelmaking residues

5. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 5 PAUL WURTH EXPERIENCE IN STEELMAKING BY-PRODUCTS  Recycling technologies:  Primus ® technology: MHF + EAF 75 ktpy Primus ® plant in Differdange (LU - 2003) Recycling of EAF dust (60 ktpy) and oily mill sludge (15 ktpy) 100 ktpy Primus ® plant in Taichung (TW - 2009) Recycling of EAF dust and integrated steelmaking residues

6. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 6 PAUL WURTH NEW PROCESS DEVELOPMENTS  i-Meltor™ furnace  Adapted AC EAF equipped with bottom gas stirring and central charging between 3 electrodes  Combined in Primus process with MHF or used as stand-alone  PLD process  PLD: Paul Wurth Lhoist Deoiling  Recycling of oily mill sludge and scales in partnership with Lhoist R&D (Worldwide leader in CaO/MgO based products)

7. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 7 PAUL WURTH NEW PROCESS DEVELOPMENTS i-MELTOR™ Intensive Melting Reactor

8. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 8 i-MELTOR™ FURNACE Specific electric arc furnace for reducing- melting-settling-fuming of slag & residues

9. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 9 i-MELTOR™ : Main components Central charging duct Graphite electrode Process offgas outlet Slag Slag door Transfer car Bottom gas stirring Electrodes arms Water cooled cover Spray coolers Hot metal Refractory lining

10. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 10 i-MELTOR™ : Process key features  Central charging  Accept fines  High specific power 1 MW/m 2  Compact design  Controlled bottom gas stirring  Enable multi-step processes (melting, reducing, refining, settling, fuming) Combination of these 3 key features ensures high melting kinetics

11. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 11 i-MELTOR™ : References 6 t pilot EAF Ø2m int. 3 MW PRIMOREC EAF Ø3,5m int. 10 MW DSC EAF Ø6m int. 21 MW

12. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 12 i-MELTOR™ : Technological highlights  Spray coolers  Key features Increased lifetime of refractory lining in the slag zone Pressure less cooling system Operated in safe conditions in case of breakthrough With staves Without staves

13. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 13 i-MELTOR™ : Technological highlights  Offgas cleaning system  Components Water cooled elbow + jacket Post combustion chamber Quench tower Baghouse filter Filter unit PCC Quench Adapted to comply with lowest emission limits

14. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 14 i-MELTOR™ : Opportunities EAF dust Fe Zn Spent catalysts Mo Ni Co SS dust & sludge Ni Cr Zn Cu slag & residues Cu Ni Mo Zn Waelz slag Fe Zn Leaching residues Zn Ag In

15. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 15 SS dust & sludge Inert slag NiCr alloy ZnO SS dust & sludge Inert slag ZnO Application  Input: dust with 4% Zn, 4% Cr and 2% Ni  Output: NiCr alloy and ZnO  10 to 70 kty dust Application  In place of SAF  Input: 80-200kt/y pre-reduced product  Output: NiCr alloy NiCr alloy i-MELTOR™ : Applications - Recycling of stainless steel dust and sludge

16. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 16 PAUL WURTH NEW PROCESS DEVELOPMENTS PLD PROCESS Paul Wurth Lhoist Deoiling

17. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 17 hot metal Ore coking coal sinter coke Oily scale / sludge Limited (Dioxins)  Reduces PCI capacity  Requires more coke  Abrasion issue  Requires charge preparation  Disturbs process  Impacts steel quality (S)  Energy consumption High T° Pyro- processes  Cost  Liabilities dump Oily sludge & scales - Treatment  Requires hard briquettes  Reduces burden permeability  Penalizes BF performances

18. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 18 PLD PROCESS : Basic principles MIXING SELF-HEATING SOFT CONTROLLED OXIDIZING Oily by-product HC: 2-20% H 2 O: 10-30% CaO: 5-15% Offgas CO < 50 ppm VOC < 10 ppm Dry powder HC < 0,1% CaCO 3 Up to 500°C Air

19. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 19 PLD PROCESS : Driving parameters Residence Time Quantity of CaO Air injection

20. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 20 PLD PROCESS : Test performances – Continuous pilot test  Throughput: 100 kg mix/h + 0 - 5 - 10% lime  Residence time: 60 min  Test duration: 4 Days  Temperatures : 500 - 400 - 300 °C 2 Continuous test campaigns: 8 hours / 4 days Sludge: 18~20% oil; 20% H 2 O Scales: 1~2% oil; 2~10% H 2 O Mix: 2-4-8-10% oil; 9-11-20% H 2 O Main conclusions:  Auto thermal process proven  De-oiling down to 0.1% achieved  PC of offgas efficient

21. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 21 PLD PROCESS : Industrial plant flowsheet Material Handling Lime Handling Sludge Handling MHF Offgas

22. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 22 PLD PROCESS : Industrial plant layout Lime Handling Sludge Handling MHF Offgas ~ 40 m ~ 20 m

23. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 23 PLD PROCESS : Industrial plant typical design Multiple Hearth Furnace: -6 hearths -internal diameter: 3,5 / 5 m -compact furnace with insulated steel casing Annual production  25 000 / 75 000 tpy (wet - oily) Availability > 95 % Sludge rating  3~10 t/h (wet) Lime charging capacity  0,1~1,5 t/h (5-15%) Output:  “iron oxide” Residual oil content < 0,1%

24. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 24 PLD PROCESS : Industrial plant typical design Costs: -Range of total investments: 8~12 mio€ -Range of operating costs: 20~40 €/t oily sludge Credits: -Value of output: 70~85 €/t iron oxide -Dumping cost avoided: ~70 €/t oily sludge -Transport cost avoided: ~10€/t oily sludge

25. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 25 PLD PROCESS : Process profitability for 75ktpy PLD plant (EXAMPLE)

26. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 26 CONCLUSIONS  By-products recycling becomes a priority for industrials  “Zero waste” technologies will be a key point for the sustainability of metallurgical operations in the near future

27. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 27 THANK YOU FOR YOUR ATTENTION

28. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 28 i-MELTOR™ : Typical layout for treating dust and sludge Material handling area Offgas treatment area I-Meltor furnace Administrative building Electrical building

29. © Paul Wurth 2010 Recycling valuable metals from by-products SEAISI2010 29 PLD PROCESS : Oily sludge & scales - Generation Casting, Re-heating Finishing Rolling Coil Volumes Oil content 60 % 30 % 10 % < 0,1 % ~ 20 %0,2 – 15 % To sinter To de-oiling