Recovery very of critic ical al metals ls from m lamps mps and CRTs Valentina Innocenzi 1 Ida De Michelis 1 , Serena Sgarioto 2 , Daniele Gotta 2 , Bernd Kopacek 3 , Francesco Vegliò 1 1. University of L’Aquila – L’Aquila (Italy) 2. Relight Srl – Milan (Italy) 3. SAT- Austrian Society for Systems Engineering and Automation- Wien – (Austria)
In this presentation the main results of the scientific works about the development of the processes for the recovery of REEs from lamps and cathode ray tubes were presented. Activities were performed in the laboratory of chemical engineering of University of L’Aquila in Italy. Some pictures of our laboratory Laboratory of Valorization and integrated treatment of industrial waste and wastewater
HYDROWEEE ROWEEE projec jects ts Princip cipal al Aims HYDROWEEE HYDROWEEE demo (2008-2012) (2012-2016) Recycling of Realization of two WEEE industrial demo plants (stationary and mobile) Recovery of Implementation of critical and the processes preciuos metals form WEEE Study the technical, Development of European founds economical and hydrometallurgical (European FP7 framework) social feasibility processes of the processes The projects were found to support SMEs (small, medium enterprises) in research and development
HYDROWEEE ROWEEE projec jects ts Recovery very of metals ls from m WEE Printed Liquid circuit Crystal boards Display Spent Spent batteries catalysts Fluorescent lamps and cathode rays tubes (CRTs)
HYDROWEEE ROWEEE projec jects ts Recyclin cling g of WEEE E
HYDROWEEE ROWEEE projec jects ts 6 OF MOST IMPORTANT RTANT REEs s Lanthanu hanum Main application: Battery alloys Metallurgy Auto catalysts FCC Phosphors Ceramics Others..
HYDROWEEE ROWEEE projec jects ts 6 OF MOST IMPORTANT RTANT REEs s Erbium um Erbium is used to produce lasers and super fast fiber optics
HYDROWEEE ROWEEE projec jects ts 6 OF MOST IMPORTANT RTANT REEs s Neodymium ymium Main application: Magnets Battery alloys Metallurgy Auto catalysts Glass additives Ceramics Others.. Neodymium is used to produce magnets
HYDROWEEE ROWEEE projec jects ts 6 OF MOST IMPORTANT RTANT REEs s Europium pium and Yttriu rium m and Europium is an important metal used to create white light Yttrium with Europium used to create red light Other uses: alloys and ceramics
HYDROWEEE ROWEEE projec jects ts 6 OF MOST IMPORTANT RTANT REEs s Terbi bium um and Terbium is an important metal used to produce the green phoshors for the lamps Other uses: alloys and ceramics
HYDROWEEE ROWEEE projec jects ts Argus metal report ECONOMIC NOMIC VALUES UES OF REEs Terbium and Europium and dysprosium maintain a certain economic importance
HYDROWEEE ROWEEE projec jects ts Summariz arizing ing in the lamps s and CRTs s Yttrium um Europiun piun 340 $/kg g Europiun piun 90 $/kg g (oxid ide) Gadoli linu num Lantha hanu num Terbium ium 630 $/kg g Cerium ium 410 0 $/kg g (oxide ide) Terbium ium Yttrium um Yttrium um 35 $/kg g Europi piun un 4.80 0 $/kg g (oxid ide)
HYDROWEEE ROWEEE projec jects ts INITIAL MATERIALS as POWDERS were provided by RELIGTH Srl (Rho, Milan) Partner of the HydroWEEE projects Collection/Sorting Pretreatment (Dissambley and cutting) CRTs LAMPS Pretreatment (Crushing and sieving)
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs Hydrometallurgical processes developed within HydroWEEE projects In the further pages the details for the development of the hydrometallurgical process for the recycling of lamps will be presented
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs WHY TO RECOVER ALL RARE EARTHS FROM LAMPS? Economic value of the fluorescent powders RED PHOSPHORS PRICES OF € /kg kg/ton powder € /ton powders Element % METALS !! Y 15 35 150 5250 Yttrium has the greatest Eu 0,6 340 6 2040 influence on the total price OTHER PHOSPHORS Tb € /kg kg/ton powder € /ton powders 25% Element % La 0,5 5,3 5 26,5 Y Gd Ce La Ce 0,6 5,4 7 37,8 53% 1% 0% 0% Gd 0,3 44 3 132 Eu Tb 0,4 630 4 2520 21%
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs WHY TO RECYCLE THE ALL RARE EARTHS FROM LAMPS? Economic value of the fluorescent powders RED PHOSPHORS 7200 1370 € € /kg € /ton Oxide kg/ton powder powders PRICES OF Y 4.3 190 817 OXIDES !! Eu 80 6.9 552 10000 3180 € OTHER PHOSPHORS € /kg € /ton Oxide kg/ton powder powders Y 26% La 5.4 5.7 31 Tb Ce 1.7 8.2 14 54% Eu 17% Gd 15 3.5 53 Gd Ce La Tb 365 4.7 1716 2% 0% 1%
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs Hydrometallurgical processes developed within HydroWEEE projects Situation 2015 • Total recovery of yttrium and europium was 93% • Purity of the final oxide was on average 97% with 91% of Y 2 O 3 , 4% of Eu 2 O 3 , 0.5% Tb 2 O 3 , 0.11% Ce 2 O 3 , 1% Gd 2 O 3 with traces of lanthanum oxide.
HYDROWEEE ROWEEE projec jects ts Situation 2015 The processes were tested on mobile and stationary plants realized within HYDROWEEE projects From Gennary 2014 The research activities were focused on the recovery of red phosphors (Y and Eu)
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs Hydrometallurgical processes developed within HydroWEEE projects Considering the high economic value of terbium the further activities were concentrated on the dissolution of the other phosphors containing terbium The low percentage of recovery for rare earths was mainly due to high acid resistance of green phosphors that contain terbium, lanthanum and cerium. To leach green phosphors: strong leaching conditions or a pre- treatment at high temperature to transform the phosphates in oxides that can be leached with weak leaching conditions. In our research activities the second approach was chosen to improve the leaching of terbium
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs Hydrometallurgical processes developed within HydroWEEE projects The trasformation of phosphates in oxides by thermal treatment XRD analysis were showed in the following figures REPO 4 + AM RE 2 O 3 + AP + H 2 O RE = rare earths (La, Ce, Tb) AM = alkaline material.
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs Hydrometallurgical processes developed within HydroWEEE projects Leaching process Several acids were tested Sulfuric acid was chosen to perform leaching The leaching reaction RE 2 O 3 + 3 H 2 SO 4 RE 2 (SO 4 ) 3 + 3 H 2 O Fluorescent Sulfuric acid lamps powders Water Investigated factors o Alkaline concentration o Acid concentration o Powder concentration o Reaction time o Temperature
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs Hydrometallurgical processes developed within HydroWEEE projects Precipitation process after leaching Oxalic acid Dissolution Filtration Recovery of Filtration Calcination REEs by precipitation 2RE(SO 4 ) 3 + 3H 2 C 2 O 4 RE 2 (C 2 O 4 ) 3 + 6H 2 SO 4
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - LAMPs LAMPs Hydrometallurgical processes developed within HydroWEEE projects Precipitation process after leaching Grade of the oxides (98.62): 82.22% Y 2 O 3 , 8.38% Eu 2 O 3 , 2.43% Ce 2 O 3 , 2.29% Gd 2 O3, 1.77% La 2 O 3 and 1.52% Tb 2 O 3 . Other impurities were 0.62% phosphor oxide, 0.48% calcium oxide and 0.28% silica. The total recoveries are 70% Y, 100% Eu, 60% Tb, 40% Ce, La and Gd.
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - CRTs CRTs Only the red phosphor of color television tubes contains a rare earth, i.e. europium. The first red phosphor, YVO4:Eu3+, was replaced by Y2O2S:Eu3+ due to the increased brightness of the latter phosphor. The blue and green phosphors in CRTs are based on zinc sulfide: the green phosphor is ZnS:Cu while the blue phosphor is ZnS:Ag
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - CRTs CRTs WHY TO RECOVER RARE EARTHS (Y and Eu) FROM CRTs? Economic value of the fluorescent powders Fluorescent powders from CRTs € /kg € /ton Element % kg/ton PRICES OF powder powders METALS !! Y 14 35 140 4900 Eu 0.9 340 6 3060 Fluorescent powders from CRTs € /kg € /ton Element kg/ton PRICES OF powder powders OXDES !! Y 4.3 1177 761 Eu 80 10 800
HYDROWEEE ROWEEE projec jects ts Details ils of our research arch - CRTs CRTs Hydrometallurgical processes developed within HydroWEEE projects • Total recovery of yttrium and europium was 90% • Purity of the final oxide was on average 96% New activities are focused on the valorization of the residual cake after leaching rich in zinc
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