WO2014071510A1 - Procédé pour récupérer des oxydes de terre rare à partir de luminophores, de lampes fluorescentes et d'ampoules électriques, de tubes cathodiques et d'autres déchets industriels - Google Patents

Procédé pour récupérer des oxydes de terre rare à partir de luminophores, de lampes fluorescentes et d'ampoules électriques, de tubes cathodiques et d'autres déchets industriels Download PDF

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WO2014071510A1
WO2014071510A1 PCT/CA2013/000954 CA2013000954W WO2014071510A1 WO 2014071510 A1 WO2014071510 A1 WO 2014071510A1 CA 2013000954 W CA2013000954 W CA 2013000954W WO 2014071510 A1 WO2014071510 A1 WO 2014071510A1
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alkali
europium
iii
rare earths
caustic
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PCT/CA2013/000954
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English (en)
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Francois Cardarelli
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Electrochem Technologies & Materials Inc.
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Priority to CA2878486A priority Critical patent/CA2878486C/fr
Publication of WO2014071510A1 publication Critical patent/WO2014071510A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/70—Lamps with low-pressure unconstricted discharge having a cold pressure < 400 Torr
    • H01J61/72—Lamps with low-pressure unconstricted discharge having a cold pressure < 400 Torr having a main light-emitting filling of easily vaporisable metal vapour, e.g. mercury
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/01—Recovery of luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • the present disclosure relates to the combination of pyrometallurgical and hydrometallurgical processes for recovering rare earths oxides from phosphors, fluorescent lamps and light bulbs, cathode ray tubes, and other industrial wastes containing rare earths elements in the form of halophosphates, tri-band phosphors and other fluorescent materials.
  • REEs rare earth elements
  • the spent fluorescent lamps and light bulbs collected by hazardous wastes recyclers in North America and Europe are all sent to specialized processing facilities for the removal of mercury that poses environment, health, and safety issues for their disposal.
  • the spent fluorescent lamps and light bulbs are crushed by means of roller mill followed by screening and sizing using for instance vibrating screens of various size apertures.
  • the coarse fraction (ca. 70 wt.%) consists mostly of soda-lime glass from slivers together with metals (e.g., filaments, electrodes, caps), plastics (caps, seals) and cement, while the remaining fine fraction (ca. 30 wt.%) contains phosphors dusts and glass fines.
  • mercury-free fine fraction consists essentially of soda-lime glass fines together with halophosphates, tri-band phosphors and other fluorescent materials that contains most of the valuable rare earths elements mixed with an inert matrix made of silicates, together with phosphates, aluminates, and lesser extent borates, sulfates, vanadates, fluorides and chlorides compounds based on the typical composition described previously.
  • rare earth oxides ranges usually from 10 to 20 wt.%.
  • concentration of yttrium (III) oxide ranges from 70 wt.% to 80 wt.% with the remaining 20-30 wt.% consisting of oxides of lanthanum, cerium, europium, gadolinium, terbium, and erbium.
  • This complex chemistry renders the extraction and recovery of rare earths troublesome as some of these materials are refractory to most chemical treatments especially silicates and aluminates or they generate large volume of wastes upon chemical treatment that poses disposal issues because they contains deleterious compounds such as barium, lead, antimony, phosphates, and fluorides.
  • the final REOs product obtained that will contain in addition to the light rare earths elements (LREEs) such as lanthanum, cerium and europium, the heavy rare earths elements (HREEs) present (i.e., Y, Gd, Tb, and Er) will yield a heavy rare earths oxides (HREOs) product with a much higher commercial value than most of the REOs concentrates currently obtained from natural ores (e.g., monazite and bastnaesite) and it might even compete with other naturally occurring HREE- sources mentioned previously such as ion exchange clays, and xenotime.
  • LREEs light rare earths elements
  • HREEs heavy rare earths elements
  • the alkaline pregnant leach solution contains mostly all phosphates and fluoride anions and sodium cations, while the rare earths are precipitated as metal hydroxides and recovered by solid-liquid separation. Finally, the rare earths hydroxides are dissolved in nitric acid in order to be separated by common solvent extraction techniques that are currently used commercially. [0013] In US patent 7,796,798 to OSRAM GmbH, the treatment of spent fluorescent light bulbs starts also with an acid leaching step that selectively dissolves the rare earths compounds based on their different dissolution behavior in various acidic and alkaline reagents.
  • the aims is to recover the critical rare earths elements especially europium, gadolinium, terbium and erbium that are the most valuable.
  • the present disclosure broadly relates to a novel process for recovering rare earths oxides from phosphors, fluorescent lamps and light bulbs, cathode ray tubes and other electronic wastes containing rare earths elements in the form of halophosphates, tri-band phosphors and fluorescent materials.
  • the present specification relates to a process for recovering rare earths oxides from spent fluorescent lamps and light bulbs, the process comprising: a) submitting the mercury-free phosphors dusts and glass fines that contains the rare earths elements to a caustic fusion or an alkali fusion using a melt comprising at least one salt of an alkali metal to produce a solidified melt; b) submitting the solidified melt to hot alkaline leaching step either under atmospheric conditions or under pressure to produce insoluble solid residues and a barren leaching solution comprising mostly the phosphates anions and in a lesser extent silicates, aluminates, borates, vanadates, sulfates, chlorides, and fluorides anions;
  • the caustic fusion can be omitted and the mercury-free phosphors dusts and glass fines undergoing directly a hot alkaline leaching step either under atmospheric conditions or under pressure to produce insoluble solid residues and an alkaline barren leaching solution comprising mostly the phosphates anions and in a lesser extent silicates, aluminates, borates, vanadates, sulfates, chlorides, and fluorides anions.
  • REEs rare earth elements
  • R(OH) 3 with R Sc, Y, and lanthan
  • the process further comprises recovering the crystals of tri-sodium phosphate (Na 3 P0 4 ) by evaporation, followed by crystallization and solid-liquid separation from the barren alkaline leach solution produced after the caustic leaching.
  • the process comprises recycling the spent and depleted solution after the crystallization and separation of tri- sodium phosphate.
  • This step consists by performing the causticization by adding calcium hydroxide or calcium oxide for precipitating the residual phosphates anions together with silicates, sulfates, borates and fluorides anions as insoluble calcium salts.
  • the replenished and strong alkaline solution is suitable for performing the caustic leaching step.
  • the process further comprises oven-drying or calcining in air the insoluble solid residues from the alkaline leaching to oxidize all the cerium (III) into cerium (IV) while the oxidation state of the remaining rare earths elements remains unaffected as trivalent cations (R 3+ ), together with the oxides and/or hydroxides of alkali-earths metals.
  • the process further comprises performing the acid leaching of the oven-dried or calcined solids.
  • the process further comprises separating by solid-liquid separation techniques the cerium (IV) compounds [e.g., Ce(OH) 4 and Ce0 2 ] as insoluble solids.
  • the process further comprises calcining the cerium (IV) compounds to yield pure cerium (IV) oxide (Ce0 2 ).
  • the process further comprises reducing the trivalent europium (III) cations into divalent europium (II) cations in the acidic filtrate by adding a reducing agent such as zinc, magnesium or aluminum metals or their alloys.
  • a reducing agent such as zinc, magnesium or aluminum metals or their alloys.
  • the process further comprises adding barium chloride and then sulfuric acid or a soluble alkali-metal sulfate in order to co-precipitate barium and europium sulfates [(Ba,Eu)S0 4 ].
  • the process further comprises separating the co-precipitate of barium and europium sulfates by solid-liquid separation techniques.
  • the process further comprises performing an oxidative acid leaching of the co-precipitate of barium and europium sulfates by for instance with nitric acid to fully oxidize europium (II) to europium (III).
  • the process further comprises separating by solid-liquid separation the insoluble barium sulfate from the acidic solution containing all the soluble europium (III) cations.
  • the process further comprises precipitating the europium (III) hydroxide from the acidic solution by neutralizing and adjusting the pH by adding for instance a neutralizing agent such as ammonia or sodium hydroxide.
  • a neutralizing agent such as ammonia or sodium hydroxide.
  • the process further comprises performing the calcination of the europium (III) hydroxide [Eu(OH) 3 ] to yield europium (III) oxide (Eu 2 0 3 ).
  • the process further comprises precipitating the remaining rare earths elements from the cerium-free and europium-free acidic pregnant leach solution as rare earths oxalates by adjusting the pH and by adding a solution of containing oxalic acid or an alkali-metal oxalate;
  • the process further comprises separating by solid-liquid separation and performing the calcination of the precipitate of rare earths oxalates to yield cerium-free and europium-free mixture of rare earths oxides (REOs) containing mostly scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium as rare earths (III) oxides (e.g., Y 2 0 3 , Ln 2 0 3 ) or complex rare earths oxides (e.g., Pr 6 On, Tb 4 0 7 ).
  • rare earths III
  • the process further comprises dissolving the cerium-free and europium-free mixture of rare earths oxides in hot hydrochloric or hot nitric acid and performing the selective separation of yttrium, gadolinium, terbium and erbium by means of ion exchange (IX) or solvent extraction (SX).
  • IX ion exchange
  • SX solvent extraction
  • the process further comprises precipitating from each individual stream the oxalates of yttrium, gadolinium, terbium and erbium followed by the calcination of each single oxalates to yield pure yttrium (III) oxide (Y 2 0 3 ), pure gadolinium (III) oxide (Gd 2 0 3 ), pure erbium (III) oxide (Er 2 0 3 ), and pure terbium (III, IV) oxides (Tb 4 0 7 ).
  • the caustic fusion or alkali fusion comprises using a molten alkali-metal hydroxide of formula MOH, wherein M is selected from the group consisting of Li, Na and K.
  • the molten alkali-metal hydroxide is selected from the group consisting of potassium hydroxide, sodium hydroxide, lithium hydroxide and mixtures thereof.
  • FIG. 1 is an illustration of a flowchart in accordance with an embodiment of the present specification.
  • the mercury-free dusts and glass fines undergo a caustic fusion with molten alkali-metal hydroxides.
  • the melt once solidified is submitted to the caustic leaching with an aqueous solution of alkali-metal hydroxides; afterwards the recovery of tri-sodium phosphate by crystallization, the regeneration of the spent and depleted alkaline solution by causticization, and the recovery of rare earths oxides is performed.
  • FIG. 2 is an illustration of a flowchart in accordance with an embodiment of the present specification.
  • the mercury-free dusts and glass fines undergo directly a hot caustic leaching either at atmospheric pressure or under pressure with an aqueous solution of alkali-metal hydroxides; afterwards the recovery of tri-sodium phosphate by crystallization, the regeneration of the spent and depleted alkaline solution by causticization, and the recovery of rare earths oxides product is performed.
  • FIG. 3 is an illustration of a flowchart in accordance with an embodiment of the present specification.
  • the first separation and recovery of cerium (IV) oxide, the second separation recovery of europium (III) oxide and finally the separation of other rare earths oxides especially yttrium (III) oxide, gadolinium (III) oxide, terbium (III, IV) oxides, and erbium (III) oxide is performed from the rare earth oxides product obtained from the oven-dried or calcined solid residues obtained at the end of STEP 1A or 1 B.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), having (and any form of having, such as “have” and “has”), "including” (and any form of including, such as “include” and “includes”), or “containing” (and any form of containing, such as “contain” and “contains”), are inclusive and open-ended and do not exclude additional, unrecited elements or process steps.
  • dusts and glass fines refers to the intimate mixture of dusts of spent phosphors and glass fines obtained after the crushing and screening the spent fluorescent lamps and light bulbs, or cathode ray tubes that consists essentially of soda-lime glass fines together with halophosphates, tri-band phosphors and other fluorescent materials that contains most of the rare earths elements values.
  • the term "mercury-free dusts and glass fines” refers to the previously described “dusts and glass fines" by-produced after the vacuum retorting for removing the mercury. In the following description, all the processed wastes will be assumed to be mercury-free materials.
  • the present specification broadly relates to a process for recovering rare earths oxides from spent luminophors and phosphors, spent fluorescent lamps and light bulbs, cathode ray tubes and other electronic wastes containing halophosphates, tri-band phosphors and other fluorescent materials that contain most of the rare earths elements.
  • the present specification relates to a process for recovering rare earths oxides from spent fluorescent lamps and light bulbs, by submitting the mercury-free dusts and glass fines, to a molten caustic fusion or an alkali fusion using a melt comprising at least one alkali metal hydroxides;
  • the process comprises a high temperature caustic fusion or alkali fusion step followed by a hydrometallurgical alkaline or caustic leaching step with the production of insoluble solid residues containing most of the rare earth elements and alkali-metals together with a barren alkaline leach solution containing mostly sodium phosphate and other sodium salts such as silicates, borates, aluminates, vanadates, chlorides and fluorides.
  • the process further comprises precipitation steps, leaching steps, ion exchange steps and calcination steps ultimately yielding substantially cerium oxide, europium oxide, yttrium oxide, erbium oxide and terbium oxides or mixtures of these oxides.
  • the process comprises steps for the recovery of sodium phosphate and the regeneration of at least some of the reactants such as the spent alkaline leaching solution by performing a causticization with calcium oxide or calcium hydroxide.
  • the caustic fusion can be omitted and the mercury-free dusts and glass fines undergo directly a hot alkaline leaching step either under atmospheric pressure or under pressure inside an autoclave in order to produce insoluble solid residues and an alkaline barren leaching solution comprising mostly the sodium and phosphates anions and in a lesser extent silicates, aluminates, sulfates, borates, vanadates, chlorides and fluorides anions;
  • the process comprises a high temperature caustic fusion or alkali fusion step.
  • This high temperature pyrometallurgical step includes subjecting the mercury- free dusts and glass fines to a molten caustic fusion or a molten alkali fusion using a melt comprising an alkali-metal hydroxide.
  • the alkali-metal hydroxide has the general formula MOH, wherein M is selected from the group consisting of Li, Na and K. Accordingly, non-limiting examples of alkali-metal hydroxides include potassium hydroxide, sodium hydroxide, lithium hydroxide and mixtures thereof. Eventually, alkali metal peroxide is added to the melt.
  • the alkali-metal peroxide has the general formula M 2 0 2 , wherein M is selected from the group consisting of Li, Na and K.
  • M is selected from the group consisting of Li, Na and K.
  • the alkali- metal hydroxide and peroxide typically have the same M value (i.e. both are either Li, Na or K).
  • the addition of the peroxide ensures that essentially all the cerium content is oxidized to its tetravalent oxidation state (Ce 4+ ).
  • an alkali- metal carbonate of formula M 2 C0 3 or an alkali-metal nitrate of formula MN0 3 are added to the melt, wherein M is selected from the group consisting of Li, Na and K.
  • the addition of the alkali-metal carbonate or alkali-metal nitrate improves the fluxing properties of the melt by lowering the melting temperature of the alkali mixture and by increasing the fluidity of the melt.
  • the melt comprises more than one alkali-metal hydroxide (alkali-metal hydroxide blend).
  • alkali-metal hydroxide blend the individual alkali-metal hydroxide can be melted individually and then combined, or melted together to produce the melt to be used in the fusion step. This prior melting drives-off all residual moisture and hydration water.
  • the alkali-metal hydroxide blend is allowed to cool prior to be used in the fusion step.
  • the mercury-free dust and glass fines are fed directly into the melt once the desired operating temperature is reached and subsequently continuously stirred.
  • the mercury-free dusts and fines are added on top of a solidified melt comprising at least one alkali-metal hydroxide followed by raising the temperature until melting of the mixture has occurred.
  • the mercury-free dusts and glass fines are mixed with at least one alkali- metal hydroxide that has been previously ground followed by raising the temperature until melting of the mixture has occurred.
  • the caustic or alkali fusion step is performed using a dimensionless mass ratio of dusts and fines (F) to mass of melt material (i.e. mass of molten hydroxide salt) (M) denoted as F:M or F/M ranging from 1 :1 to 1 :20.
  • F:M or F/M mass of melt material
  • the caustic or alkali fusion step is performed using a dimensionless mass ratio maintaining a low melt viscosity and allowing for substantially complete dissolution of the products.
  • the caustic or alkali fusion step is performed using a dimensionless mass ratio ranging from 1 : 1 to 1 : 15.
  • the caustic or alkali fusion step is performed using a dimensionless mass ratio ranging from 1 : 1 to 1 :10. In an embodiment of the present specification, the caustic or alkali fusion step is performed using a dimensionless mass ratio ranging from 1 : 1 to 1 :6.
  • the caustic or alkali fusion step is performed at a temperature of at least the melting point of the alkali metal salt (i.e. alkali metal hydroxide). In cases where the melt comprises more than one alkali- metal hydroxide, the caustic or alkali fusion step is performed at a temperature of at least the eutectic temperature of the alkali mixture.
  • the melt temperature ranges from about 200°C to about 1200°C. In a further embodiment of the present disclosure, the melt temperature ranges from about 300°C to about 1000°C. In a further embodiment of the present disclosure, the melt temperature ranges from about 300°C to about 1000°C.
  • the melt temperature ranges from about 400°C to about 900°C.
  • the operating temperature is sometimes increased in order to compensate for heat losses and to keep the charge fully liquid.
  • the maximum operating temperatures are typically dictated so as to prevent losses in molten salts by intense evaporation of caustic fumes and by the limited number of corrosion resistant materials commercially available in which to perform the fusion reaction.
  • the caustic or alkali fusion step is performed over a period of time ranging from 5 minutes to 6 hours. In a further embodiment of the present disclosure, the caustic or alkali fusion step is performed over a period of time ranging from 10 minutes to 4 hours. In a further embodiment of the present disclosure, the caustic or alkali fusion step is performed over a period of time ranging from 15 minutes to 2 hours. In a further embodiment of the present disclosure, the caustic or alkali fusion step is performed over a period of time ranging from 15 minutes to 1 hour.
  • the caustic or alkali fusion step is performed either batch wise using a crucible furnace or a muffle furnace or in continuous mode using a rotary kiln or a rotary heart furnace.
  • the caustic or alkali fusion step is performed by means of direct flame heating, gas fired burners, radiant gas heaters, external electrical heaters, Joule heating by immersed AC or DC electrodes, or by induction heating of the crucible used as susceptor.
  • Other suitable heating means for performing the caustic or alkali fusion step are known in the art, and are within the capacity of a skilled technician.
  • the caustic or alkali fusion step is performed using a containment vessel or crucible comprising a construction material capable of withstanding both the high operating temperatures as well as the inherent corrosiveness of the molten alkali-metal hydroxide(s) without contaminating the melt by releasing deleterious metallic impurities.
  • Suitable materials include metals such as pure nickel (Ni) and nickel alloys, pure zirconium (Zr) and zirconium alloys, and their alloys; pure iron (Fe), nickel cast iron, cast irons; mild steels; and non-metals such as graphite and carbon-based materials.
  • suitable materials include metallic composite materials comprising inexpensive bulk commercial alloys such as heat resistant stainless steels; copper-nickel and high nickel-alloys coated with an inert, protective and impervious metal lining composed of a highly corrosion resistant pure metal or alloy.
  • Protective lining materials include gold (Au), gold alloys, silver (Ag), silver alloys, nickel (Ni), nickel alloys, iron (Fe), iron alloys, zirconium (Zr), and zirconium alloys, hafnium (Hf), hafnium alloys and combinations thereof.
  • the protective lining materials can be applied by various techniques such as electroplating, electroless plating, physical or chemical vapor deposition, mechanical cladding, loose lining and explosion bonding.
  • Ceramic materials useful as refractory brick linings, castables and coatings.
  • Non-limiting examples of such ceramic materials include graphite, diamond like carbon (DLC), carbon-carbon composites, silicon carbide (SiC,), fused zirconia (Zr0 2 ), fused magnesia (MgO), fused ceria (Ce0 2 ), fused calcia (CaO) and combinations thereof.
  • the melt produced following the caustic or alkali fusion step is subsequently subjected to a hot alkaline leaching step.
  • the melt produced as a result of the caustic or alkali fusion step is transferred while hot into alkaline water.
  • the transfer may be accomplished by either pouring or scoping the melt into the cold alkaline water.
  • the melt, once cooled and still in the crucible is demoulded onto a hard surface acting as a heat sink and is subsequently transferred into alkaline water.
  • the crucible comprising the melt is cooled after which alkaline water is added to the crucible.
  • the solidified melt is subjected to a hot alkaline leaching step either under atmospheric conditions or under pressure.
  • the alkaline leaching step is performed using an aqueous solution of alkali-metal hydroxide (MOH) with M being an alkali-metal such as sodium, potassium or lithium, or a mixture thereof.
  • M alkali-metal hydroxide
  • the aqueous alkaline solution comprises a concentration ranging from 5 mass percent up to 50 mass percent MOH.
  • the temperature of the alkali-metal hydroxide solution ranges from room temperature to the boiling point of the solution.
  • the pH of the alkaline solution is at least 13.
  • the first caustic fusion step can be omitted and the mercury-free spent dusts and glass fines can be directly treated by hot alkaline leaching step either under atmospheric conditions or under pressure performed inside an autoclave in order to produce insoluble solid residues and an alkaline barren leaching solution comprising mostly sodium phosphate and in a lesser extent silicates, aluminates, borates, sulfates, vanadates, chlorides, and fluoride salts.
  • the hot alkaline leaching step performed directly on the mercury-free dusts and glass fines using a concentrated aqueous solution of alkali-metal hydroxide (MOH) with M being an alkali-metal such as sodium, potassium or iithium, or a mixture thereof.
  • MOH alkali-metal hydroxide
  • the aqueous alkaline solution comprises a concentration ranging from 5 mass percent MOH up to 50 mass percent of MOH.
  • the temperature of the alkali-metal hydroxide solution ranges from room temperature to the boiling point of the solution.
  • the hot alkaline leaching step is performed either batch wise or in continuous mode.
  • the caustic fusion and/or alkaline leaching step are performed using a containment vessel or autoclave comprising a construction material capable of withstanding both the high operating temperatures as well as the inherent corrosiveness of the concentrated alkali-metal hydroxide(s) solution without contaminating the liquor by releasing deleterious metallic impurities.
  • Suitable materials include metals such as pure nickel (Ni) and nickel alloys, pure zirconium (Zr) and zirconium alloys, and their alloys; pure iron (Fe), nickel cast iron, cast irons; mild steels; and non-metals such as graphite and carbon-based materials.
  • suitable materials include metallic composite materials comprising inexpensive bulk commercial alloys such as heat resistant stainless steels; copper- nickel and high nickel-alloys coated with an inert, protective and impervious metal lining composed of a highly corrosion resistant pure metal or alloy.
  • Protective lining materials include gold (Au), gold-alloys, silver (Ag), silver-alloys, nickel (Ni), nickel- alloys, iron (Fe), iron-alloys, zirconium (Zr), zirconium-alloys, hafnium (Hf), hafnium- alloys and combinations thereof.
  • the protective lining materials can be applied by various techniques such as electroplating, electroless plating, physical or chemical vapor deposition, mechanical cladding, loose lining and explosion bonding.
  • Ceramic materials useful as refractory brick linings, castables and coatings.
  • Non-limiting examples of such ceramic materials include graphite, diamond like carbon (DLC), carbon-carbon composites, silicon carbide (SiC), fused zirconia (Zr0 2 ), fused magnesia (MgO), fused ceria (Ce0 2 ), fused calcia (CaO) and combinations thereof.
  • the alkaline leach solution together with a suspension of non-dissolved solids and particulates produced by the hot alkaline leaching is subjected to common solid-liquid separation techniques, such as gravity settling, filtration or centrifugation.
  • the solid residues obtained following solid-liquid separation consist essentially of insoluble compounds rare earths (i.e., Y, Sc, and lanthanides), alkali-earths metals, and in a lesser extent iron if present as an impurity. These solid residues are typically insoluble under the strongly alkaline conditions prevailing in the pregnant leach solution.
  • non-soluble compounds found in the solid residues are oxides and hydroxides of rare earth elements (REEs) [e.g., R(OH) 3 ], rare earths elements carbonates [e.g., R 2 (C0 3 )2], alkali-earth metals hydroxides [e.g., M(OH) 2 ], alkali-earth metals carbonates [e.g., MC0 3 ] and iron oxides, hydroxides and carbonates [e.g., Fe 2 0 3 , Fe(OH) 3 , FeC0 3 , etc.] and eventually insoluble alkali-earth metals sulfates [MS0 4 ] with M being an alkali-earth metal such as calcium, barium or strontium.
  • REEs rare earth elements
  • R(OH) 3 rare earths elements carbonates
  • M(OH) 2 alkali-earth metals carbonates
  • MC0 3 alkali-earth
  • the wet filter cake obtained following solid-liquid separation is thoroughly washed with a hot aqueous solution of alkali metal hydroxides.
  • the barren alkaline leach solution that contains mostly sodium phosphate together with silicates, aluminates, sulfates, borates, vanadates, chlorides and fluorides salts is subjected to a concentration step performed by evaporation, followed by the crystallization for separating the crystals of tri-sodium phosphate (Na 3 P0 4 ) by solid-liquid separation.
  • the process further comprises recycling the spent alkaline solution remaining after the crystallization and separation of tri-sodium phosphate.
  • the regeneration consists to perform the causticization by adding calcium hydroxide or calcium oxide in order to precipitate all the residual phosphates anions together with silicates, aluminates, sulfates, borates, vanadates, and fluorides anions as insoluble calcium salts and to obtain a replenished and concentrated alkaline solution of alkali-metal hydroxide suitable to be reused for the caustic leaching step.
  • the washed insoluble solid residues obtained after alkaline leaching are subsequently either oven-dried in air between 60°C and 200°C or calcined in air high temperature ranging from 300°C until 1200°C.
  • the purpose of these steps is to completely oxidize all the cerium (III) to its tetravalent oxidation state as cerium (IV) which forms insoluble compounds such as cerium (IV) hydroxide or cerium (IV) oxide.
  • the oven-dried product consists mainly of a mixture of hydroxides of rare earth elements (REEs) [e.g., Ce(OH) 4 , R(OH) 3 ], rare earths elements carbonates [e.g., R 2 (C0 3 )2] , alkali-earth metals hydroxides [e.g., M(OH) 2 ], alkali-earth metals carbonates [e.g., MC0 3 ] and iron oxides, hydroxides and carbonates [e.g., Fe 2 0 3 , Fe(OH) 3 , FeC0 3 , etc.] and eventually insoluble alkali-earth metals sulfates [MS0 4 ] with M being an alkali-earth metal such as calcium, barium or strontium.
  • REEs rare earth elements
  • M(OH) 2 alkali-earth metals hydroxides
  • alkali-earth metals carbonates e.g., MC0 3
  • the calcined product comprises substantially all of the cerium oxidized to cerium (IV) [e.g., Ce0 2 ] along with other rare earths oxides (REOs) [e.g., R 2 0 3 ] with R being a lanthanide element from La up to Lu together with complex lanthanide oxides [e.g., Pr 6 On, Tb 4 0 7 ], alkali-earth metals oxides [e.g., MO], and iron oxides [e.g., Fe 2 0 3 , Fe 3 0 4 ] and eventually alkali- earth metals sulfates [MS0 4 ] with M being an alkali-earth metal such as calcium, barium or strontium.
  • IV cerium oxidized to cerium
  • REOs rare earths oxides
  • the oven-dried or calcined solids are then subjected to acid leaching performed with dilute acid at a pH ranging between 0 and 4, for dissolving most of the rare earths elements (REEs) values yielding an acidic pregnant leach solution (PLS) and an insoluble solid residue containing all the cerium values as cerium (IV) compounds [e.g., Ce(OH) 4 , Ce0 2 ].
  • REEs rare earths elements
  • the acid leaching is performed using either hydrochloric acid or nitric acid or a mixture thereof.
  • the insoluble solid residues containing all the cerium values as cerium (IV) compounds is separated by usual solid liquid separation such as gravity settling, filtration, or centrifugation, thoroughly washed with diluted acid and then with deionized water.
  • the washed cerium (IV) compound is oven-dried between 60°C and 150°C and then calcined in air between 300°C and 1200°C to yield pure cerium (IV) oxide [e.g., CeOJ.
  • the cerium-free acidic solution that contains all the other lanthanides is then contacted with a reducing agent such as metallic zinc, aluminum or magnesium or alloys thereof (e.g., shot, flakes, chunks, or powder) in order to reduce substantially all the europium (III) to europium (II).
  • a reducing agent such as metallic zinc, aluminum or magnesium or alloys thereof (e.g., shot, flakes, chunks, or powder) in order to reduce substantially all the europium (III) to europium (II).
  • an aqueous solution of barium chloride (BaCI 2 ) is then added to the reduced solution and a stoichiometric amount of dilute sulfuric acid or alkali-metal sulfate is subsequently added in order to co-precipitate the insoluble barium and europium sulfates [(Ba,Eu)S0 4 ].
  • the completion of the europium precipitation is verified by visible spectrophotometry by measuring the absorbance of the supernatant at the characteristic wavelength of 394 nm [i.e., peak of maximum absorption for Eu(ll)].
  • the process further comprises separating the co-precipitate of barium and europium sulfates by solid-liquid separation techniques.
  • the process further comprises performing an oxidative acid leaching of the co-precipitate of barium and europium sulfates for instance with hot nitric acid to fully oxidize europium (II) to europium (III) cations that are soluble.
  • the process further comprises separating by solid-liquid separation the insoluble barium sulfate from the acidic solution containing all the soluble europium (III) cations.
  • the process further comprises neutralizing the acidic solution containing the europium (III) and precipitating europium as europium (III) hydroxide by adding a neutralizing agent such as ammonia, or alkali-metal hydroxide (e.g., NaOH, KOH, LiOH).
  • a neutralizing agent such as ammonia, or alkali-metal hydroxide (e.g., NaOH, KOH, LiOH).
  • the process further comprises performing the separation of the precipitated europium (III) hydroxide, washing, oven-drying between 60°C and 200°C, calcining between 300°C and 1200°C the europium (III) hydroxide [Eu(OH) 3 )] to yield europium (III) oxide (Eu 2 0 3 );
  • the cerium- and europium- free acidic solution that contains the remaining lanthanides especially all the yttrium, gadolinium, terbium and erbium values is subjected to a precipitation of the rare earths as rare earths oxalates by adding a saturated solution of oxalic acid (ca. 10 wt.% H 2 C 2 0 4 ) or an alkali-metal oxalate in order to separate them from impurities such as magnesium, sodium, sulfates, etc.
  • oxalic acid ca. 10 wt.% H 2 C 2 0 4
  • an alkali-metal oxalate in order to separate them from impurities such as magnesium, sodium, sulfates, etc.
  • the pH of the cerium- and europium-free acidic solution is subsequently adjusted to a range from about 0.5 to 2.5.
  • the pH of the solution is adjusted to a range from about 1.0 to 2.0.
  • the pH of the acid leachate is adjusted to about 1.5.
  • a saturated solution of oxalic acid ca.
  • the rare earths oxalates precipitate is then oven dried at 100-110°C and subsequently calcined between 300°C and 1200°C to yield a product containing the rare earth oxides (REOs) product containing mostly yttrium, lanthanum, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium as rare earths (III) oxides (e.g., Y 2 0 3 , Ln 2 0 3 ) or mixed rare earths oxides (e.g., Pr 6 On, Tb 4 0 7 ).
  • rare earth oxides e.g., Y 2 0 3 , Ln 2 0 3
  • mixed rare earths oxides e.g., Pr 6 On, Tb 4 0 7
  • the process further comprises dissolving the cerium-free and europium-free calcined rare earths oxides in hot hydrochloric acid or hot nitric acid and performing the selective separation of heavy rare earths such as yttrium, gadolinium, terbium and erbium by means of ion exchange (IX) or solvent extraction (SX).
  • IX ion exchange
  • SX solvent extraction
  • the process further comprises precipitating the individual oxalates of yttrium, gadolinium, terbium and erbium from the individual solutions, separating them by solid-liquid separation techniques, and finally calcining the individual oxalates between 300°C and 1200°C to yield separately pure yttrium (III) oxide (Y 2 0 3 ), gadolinium (III) oxide (Gd 2 0 3 ), erbium (III) oxide (Er 2 0 3 ), and terbium (III, IV) oxides (Tb 4 0 7 ).
  • Example 1 A sample of 10 grams of mercury-free dusts and glass fines that consists essentially of soda-lime glass fines together with halophosphates, tri-band phosphors and other fluorescent materials that contains most of the rare earths elements values with the composition breakdown reported in Table 2 was weighed using a precision scale. Separately, 60 grams of flakes of sodium hydroxide technical grade were pre-melted inside a tall 200 mL pure zirconium crucible. The heating was provided by means of propane burners. Once the residual moisture was driven off and the melt surface became quiet, the heating was stopped and the melt was cooled.
  • the dusts and glass fines sample was subsequently poured on top of the solidified melt and heating was resumed to bring the crucible temperature to red-dull heat (ca. 800°C) over a period of 30 minutes in order to perform the molten caustic fusion.
  • red-dull heat ca. 800°C
  • the effervescence or apparent boiling ceased after about 10 minutes indicating that all the chemical reactions were completed.
  • the caustic fusion was continued for an additional 25 minutes.
  • the heating was stopped and the molten mass was allowed to solidify.
  • 100 mL of an aqueous solution of sodium hydroxide (5 wt.% NaOH) was then poured directly into the crucible containing 4
  • the solidified melt As a result of the strong heat generation due to the dissolution reaction, the temperature of the solution increased.
  • the temperature of the alkaline solution was subsequently maintained at about 80°C by heating the zirconium crucible directly onto a hot plate equipped with a magnetic stirrer.
  • the resulting strong alkaline leach solution contained a suspension of non-dissolved solids and particulates. After cooling to room temperature, the solution was filtered. The insoluble solid residues were subsequently washed thoroughly with deionized water, oven-dried at 120°C and then calcined at 800°C for one hour inside a platinum crucible to yield 2.060 grams of calcined materials.
  • the calcined mass was transferred into a 250-mL round borosilicate glass flask containing 150 mL of hydrochloric acid (20 wt.% HCI) connected to a condenser. The residue was then acid leached boiling the solution under reflux conditions at atmospheric pressure during 60 minutes. Once the hot acid leaching was completed, the leachate was cooled and filtered; the isolated insoluble residue was oven-dried and then calcined at 800°C during one hour to yield 0.060 gram of cerium (IV) oxide (Ce0 2 ). Afterwards, 0.5 gram of zinc metal powder was added to the acidic solution.
  • the wet co-precipitate was transferred into a 250 mL Erlenmeyer flask containing 50 mL of nitric acid (50 wt.% HN0 3 ) and acid leached at the boiling point during 30 minutes under reflux. Then once the solution cooled, the insoluble barium sulfate residue left behind was separated by filtration and discarded. The acidic filtrate containing the Eu(ll) was neutralized with an aqueous ammonia solution added drop wise until the precipitate of europium (III) hydroxide was completed. The europium (III) hydroxide was separated by filtration, oven-dried, and calcined inside a platinum crucible at 800°C during one hour.
  • the mass of europium (III) oxide recovered was 0.055 grams.
  • the pH of cerium-free and europium-free pregnant leach solution was adjusted to about 1.5 by the drop wise addition of an aqueous solution of sodium hydroxide, then a saturated solution of oxalic acid (ca. 10 wt.% H 2 C 2 0 4 ) was added and the solution was left stand overnight in order to precipitate all the insoluble rare earths oxalates.
  • the precipitate was subsequently thoroughly rinsed using a solution containing 2 wt.% oxalic acid and then oven-dried at 1 10°C and calcined at 800°C during two hours in a platinum crucible.
  • the calcined heavy rare earths oxides produced weighed 0.840 gram and contained a mixture of yttrium (III) oxide (Y 2 0 3 ), lanthanum (III) oxide (La 2 0 3 ), gadolinium (III) oxide (Gd 2 0 3 ), and terbium (III, IV) oxides (Tb 4 0 7 ).
  • the filtered alkaline barren leach solution obtained after alkaline leaching was evaporated to reduce its volume by half and left to stand overnight to allow the crystallization and settling of crystals of tri-sodium phosphate.

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Abstract

La présente invention concerne de manière générale un nouveau procédé pour la récupération d'oxydes de terre rare à partir de luminophores, de lampes fluorescentes et d'ampoules électriques, de tubes cathodiques et d'autres déchets industriels comprenant des éléments des terre rare sous forme d'halogénophosphates, de luminophores à trois bandes et d'autres matériaux fluorescents, le procédé consistant à : a) soumettre les déchets ou matériaux usagés à une fusion caustique ou une lixiviation alcaline à chaud ; b) soumettre la masse fondue solidifiée à une étape de lixiviation alcaline à chaud pour produire des résidus solides insolubles et une solution stérile de lixiviation alcaline ; c) cristalliser le phosphate trisodique à partir de la solution stérile ; d) sécher au four ou calciner les résidus ; e) réaliser une lixiviation acide des solides séchés au four ou calcinés ; f) récupérer l'oxyde de cérium (IV) à partir des solides insolubles ; g) réduire la solution exempte de cérium, précipiter, réaliser une lixiviation acide, précipiter, calciner et récupérer l'oxyde d'europium (III) ; h) précipiter les terres rares résiduelles sous forme d'oxalates ; i) calciner les oxalates de terres rares et dissoudre les oxydes de terres rares dans de l'acide ; j) séparer l'yttrium, le gadolinium, le terbium et l'erbium par échange d'ions (IX) ou par extraction au solvant (SX) ; h) précipiter et calciner afin d'obtenir de l'oxyde d'yttrium (III), de l'oxyde de gadolinium (III), des oxydes de terbium (III, IV) et de l'oxyde d'erbium (III) purs ; i)régénérer et recycler la solution alcaline usagée après caustification par de l'oxyde ou de l'hydroxyde de calcium.
PCT/CA2013/000954 2012-11-08 2013-11-08 Procédé pour récupérer des oxydes de terre rare à partir de luminophores, de lampes fluorescentes et d'ampoules électriques, de tubes cathodiques et d'autres déchets industriels WO2014071510A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4432948A (en) * 1982-07-30 1984-02-21 U.S. Philips Corporation Recovery of yttrium and europium from contaminated solutions
WO1996000698A1 (fr) * 1994-06-28 1996-01-11 Pure Etch Co. Procede de recuperation des terres rares
WO2010118967A1 (fr) * 2009-04-14 2010-10-21 Rhodia Operations Procede de recuperation des terres rares a partir d'un melange solide contenant un halophosphate et un compose d'une ou plusieurs terres rares
US20110206580A1 (en) * 2010-02-23 2011-08-25 General Electric Company Rare earth recovery from fluorescent material and associated method
US20120027651A1 (en) * 2006-06-02 2012-02-02 Osram Gesellschaft Mit Beschraenkter Haftung Method for recovery of rare earths from fluorescent lamps

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4432948A (en) * 1982-07-30 1984-02-21 U.S. Philips Corporation Recovery of yttrium and europium from contaminated solutions
WO1996000698A1 (fr) * 1994-06-28 1996-01-11 Pure Etch Co. Procede de recuperation des terres rares
US20120027651A1 (en) * 2006-06-02 2012-02-02 Osram Gesellschaft Mit Beschraenkter Haftung Method for recovery of rare earths from fluorescent lamps
WO2010118967A1 (fr) * 2009-04-14 2010-10-21 Rhodia Operations Procede de recuperation des terres rares a partir d'un melange solide contenant un halophosphate et un compose d'une ou plusieurs terres rares
US20110206580A1 (en) * 2010-02-23 2011-08-25 General Electric Company Rare earth recovery from fluorescent material and associated method

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