Hydrometallurgical processes for the recovery of precious and critical metals from spent lamps and cathode ray tubes

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1 Hydrometallurgical processes for the recovery of precious and critical metals from spent lamps and cathode V. Innocenzi, I. De Michelis, M. Centofanti, F. Vegliò University of L Aquila (L Aquila - Italy) EcoRecycling Srl (Civita Castellana Italy) Contents 1 Treatment of spent fluorescent lamps and cathode Valentina.innocenzi1@univaq.it 2 Importance of rare earths 3 4 Discussion:further implementations of the processes 5 Conclusions

2 1 Treatment of spent fluorescent lamps andcathode WASTE FROM... Cathode Fluorescent lamps CLASSIFIED AS WASTE FROM ELECTRONIC AND ELECTRIC EQUIPMENT CER code: * , Main legislations: Directive 2002/95 / EC, Directive 2002/96 / EC, Directive 2003/108 / EC, Directive 2008/34 / EC, Directive 2012/19/Ec Decree no. 151 (2005), Decree n. 65 (2010) 1 Treatment of spent fluorescent lamps andcathode Main goal of the legislation Encourage recycling of urban waste and WEEE With beneficts for... Reduction of consumption of natural sources (for the production) Reduction of enviromental impact Economical and social advantages for europeean company

physical pretreatment to remove glass, plastics, metalic elements,.

3 1 Treatment of spent fluorescent lamps andcathode WHY THE OUR ACTIVITIES ARE FOCUSED ON THE DEVELOPMENT OF TREATMENT FOR SPENT LAMPS AND CRTS? These devices contains several types of base metals and critical metals Ca Eu Y RE Gd Tb Si Ce Zn Eu RE Y Si RE are contained in the fluorescent powders and could be obtained after physical pretreatment to remove glass, plastics, metalic elements,.. 1 Treatment of spent fluorescent lamps andcathode Literature Analysis Clean glass used for production of new lamps, or to make new glass products Metallic parts can be sent to metal recycling facilities Fluorescent powders that contain RE Plastics can be burn for energy production In our activities fluorescent powders were treated

4 1 Literature Analysis: HOW IT IS POSSIBLE TO RECOVER RARE EARTHS? Authors Materials Principal aspects of the process Toouru et al., 2011 Fluorescent lamps Sulfuric acid leaching, Precipitation by oxalic acid Shimizu et al., 2009 Fluorescent lamps Supercritical solven extraction Otsuki et al., 2007 Fluorescent lamps Heterocoagulation in organic solvent Rabah, 2008 Fluorescent lamps Nitric/sulfuric acid leaching, solvent extraction, stripping and thermal reduction Porob et al., 2011 Fluorescent materials Leaching, solvent extraction, cristallization Otto and Wojtalrwicz-kaspraz, 2012 Fluorescent lamps Leaching with HCl/H2SO4, NaOH Yang et al Fluorescent lamps Acid leaching, solvent extraction with ionic liquids De Michelis et al., 2012 Fluorescent lamps Leaching with HCl/HNO3/H2SO4, precipitation Innocenzi et al, 2013 a,b Fluorescent lamps Sulfuric leaching, purification, precipitation bu oxalic acid Tedjar et al., 2007, 2010 CRT Sulfuric leaching, precipitation by NaOH, KOH Lee et al., 2009 CRT Acid leaching, vibrating with ultrasonic, precipitation Pan et al., 2013 CRT Roasting, dissolution, purification, precipitation with oxalic acid Innocenzi et al., 2013 CRT Sulfuric leaching, purification, precipitation by oxalic acid For more informations: V.Innocenzi, I.De Michelis, B. Kopacek, F.Vegliò, Yttrium recovery from primary and secondary sources: a review of main hydrometallurgical processes. Waste Management 33, Importance of rare aerths WHY THE NEW RESEARCHES ARE CONCENTRATED ON THE RECOVERY OF RARE EARTHS? ESSENTIALS FOR THE PRODUCTIONS OF ELECTRONIC/ELECTRIC DEVICES These elements are not easily replaced by OTHERS And not only...

CRT in the HYDROWEEE project HYDROWEEE demo projects PARTNERS OF THE PROJECTS: University of L Aquila, Italy SAT, Austria University of Ancona, Italy University of Rome,

5 2 Importance of rare aerths Furhermore... Furhermore... Risk supply for the europeean countries High economical values metal-pages.com All these make rare earths as materials critical 3 From 2008 the our activities are concentrated in the recoveries of rare earths from fluorescent powders of lamps and CRT in the HYDROWEEE project HYDROWEEE demo projects PARTNERS OF THE PROJECTS: University of L Aquila, Italy SAT, Austria University of Ancona, Italy University of Rome, La Sapienza, Italy; Pupin Institute, Serbia; Relight Srl, Rho, Italy; Greentronics, Romania; SET-Trade, Serbia. MAIN HYDROMETALLURGICAL PROCESSES FOR lamps CRT PCB Li-ion spent batteries LCD panels Spent catalysts

6 3 Characterization of initial materials, experimental tests (leaching, purification and recovery of rare earths) FIRST PHASE OF THE PROJECT LAB ACTIVTIES 1 HYDROWEEE project DEVELOPMENT OF THE HYDROMETALLURGICAL PROCESSES (base schemes) Implementations of the processes PILOT TESTS 3 Implementations of the processes LAB ACTIVTIES 1 DEVELOPMENT OF THE IMPLEMENTED HYDROMETALLURGICAL PROCESSES (Implemented scheme) SECOND PHASE OF THE PROJECT FURTHER Implementations of the processes In progress INDUSTRIAL SCALE TESTS HYDROWEEE demo project In progress PILOT TESTS DESIGN, REALIZATION OF THE INDUSTRIAL PLANTS

7 3 In the FIRST PHASE OF THE PROJECT BASE SCHEME Note in the first phase of the projects only Y was considered 3 In the SECOND PHASE OF THE PROJECT MAIN IMPLEMENTATIONS TO BASE SCHEME Recovery of other rare earths (Eu, Gd,..) Reduction of the reagents amount (H2O2, sulfurici acid,..) Removal of purification step (no use of Na2S and NaOH) (only for CRT) (only for CRT) Wastewater treatments and recycle of the solutions into processes % NEW CHARACTERIZATION OF THE INITIAL MATERIALS Y La Ce Eu Gd Tb 14 0,001 0,002 0,88 0,001 0,013 FOR CRT FOR LAMPS % La Ce Eu Gd Tb Y 0,57 0,60 0,49 0,46 0,26 8,00

8 3 In the SECOND PHASE OF THE PROJECT IMPLEMENTED SCHEME FOR CRT RECOVERIES YIELDS = 70 % Y, Eu PURITY OF OXIDES = 96% 75% OF RECYCLE OF SOLUTIONS Y2O3 Eu2O3 Tb4O7 La2O3 Ce2O3 Gd2O3 % 90, ,0021 0,0028 Composition of final product from CRTs 3 In the SECOND PHASE OF THE PROJECT IMPLEMENTED SCHEME FOR LAMPS RECOVERIES YIELDS = 93 % Y, Eu PURITY OF OXIDES = 97% 88% OF RECYCLE OF SOLUTIONS Y2O3 Eu2O3 Tb4O7 La2O3 Ce2O3 Gd2O3 % Composition of final product from CRTs

4 Discussion: Further implementations of the processes Activities in progress -Industrial scale tests (Stationary plant in Relight SRL) - LAB ACTIVITIES FOR increase the total recovery of the rare

9 4 Discussion: Further implementations of the processes Activities in progress -Industrial scale tests (Stationary plant in Relight SRL) - LAB ACTIVITIES FOR increase the total recovery of the rare earths, increase the % of water recycle, reduce the wastewater discharge, study the recovery of other metals (like zinc presents in CRT) STUDY NEW HYDROMETALLURGICAL PROCESS WITH SOLVENT EXTRACTION OPERATIONS TO SEPARATE YTTRIUM FROM EUROPOIUM The processes will be tested in the industrial mobile plant 5 Conclusions ACKNOWLEDGMENTS The financial support provided by the European Commission within the FP7 Work Program and all partners of the HYDROWEEE and of the HYDROWEEE-DEMO are acknowledged: University of L Aquila, Italy; SAT, Austria; University of Ancona, Italia; University of Rome, La Sapienza, Italy; Pupin Institute, Serbia; Relight Srl, Rho, Italy; Greentronics, Romania; SET-Trade, Serbia.

10 5 Conclusions For more informations... I. De Michelis, F. Ferella, E. Fioravante Varelli, F. Vegliò, Treatment of exhaust fluorescent lamps to recover yttrium: Experimental and process analyses. Waste Management 31, V. Innocenzi, I. De Michelis, F. Ferella, F.Beolchini, B. Kopacek, F. Veglio, Recovery of yttrium from fluorescent powder of cathode ray tube, CRT: Zn removal by sulphide precipitation. Waste Management 33, V.Innocenzi, I. De Michelis, F. Ferella, F. Vegliò, Experimental results and economic simulations for the processes of recovery of yttrium from fluorescent powders of cathode and lamps. Waste management 33, F. Beolchini, L. Rocchetti, P. Altimari, I. De Michelis, L. Toro, F. Pagnanelli, E. Moscardini, B. Kopacek, B. Bibiana, V. Innocenzi, F. Vegliò, Urban mining: a successful experience of the EU-FP7 HydroWEEE project. Environmental Engineering and Management Journal 12, V.Innocenzi, I.De Michelis, B. Kopacek, F.Vegliò, Yttrium recovery from primary and secondary sources: a review of main hydrometallurgical processes. Waste Management 33, V.Innocenzi, I.De Michelis, F.Vegliò, Process development for the recovery of yttrium by solvent extraction from sulfate leach liquor coming from treatment of fluorescent powders of lamps, submitted. V.Innocenzi, I. De Michelis, F. Vegliò, Rare earths from secondary sources: hydrometallurgical process to recover yttrium from fluorescent powders of spent lamps using solvent extraction. Economical feasibility study, submitted. V. Innocenzi, I. De Michelis, F. Vegliò, Recovery of metals from WEEE: Design and Construction of a Industrial - Mobile Plant, submitted. CONTACTS PhD VALENTINA INNOCENZI UNIVERSITY OF L AQUILA ITALY DEPARTMENT OF INDUSTRIAL ENGINEERING, INFORMATION AND ECONOMY valentina.innocenzi1@univaq.it Responsible Prof. Francesco Vegliò UNIVERSITY OF L AQUILA ITALY DEPARTMENT OF INDUSTRIAL ENGINEERING, INFORMATION AND ECONOMY francesco.veglio@univaq.it TEL:

The HydroWEEE strategy: a case study of efficient flexibility for the recovery of critical metals

The HydroWEEE strategy: a case study of efficient flexibility for the recovery of critical metals Dipartimento di Scienze della Vita e dell Ambiente Ancona - Italy THE FP7 PROJECTs Innovative Hydrometallurgical