WO2013138900A1 - Procédés pour la récupération d'éléments terres rares et de métaux rares - Google Patents

Procédés pour la récupération d'éléments terres rares et de métaux rares Download PDF

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Publication number
WO2013138900A1
WO2013138900A1 PCT/CA2013/000226 CA2013000226W WO2013138900A1 WO 2013138900 A1 WO2013138900 A1 WO 2013138900A1 CA 2013000226 W CA2013000226 W CA 2013000226W WO 2013138900 A1 WO2013138900 A1 WO 2013138900A1
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WO
WIPO (PCT)
Prior art keywords
rare earth
earth element
organic phase
rare
loaded organic
Prior art date
Application number
PCT/CA2013/000226
Other languages
English (en)
Inventor
Richard Boudreault
Denis PRIMEAU
Heinz Krivanec
Carsten DITTRICH
Marie-Maxime LABRECQUE-GILBERT
Original Assignee
Orbite Aluminae Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/CA2012/000253 external-priority patent/WO2012126092A1/fr
Priority claimed from PCT/CA2012/000419 external-priority patent/WO2012149642A1/fr
Application filed by Orbite Aluminae Inc. filed Critical Orbite Aluminae Inc.
Priority to RU2014141795/02A priority Critical patent/RU2595178C2/ru
Priority to CA2868363A priority patent/CA2868363A1/fr
Priority to EP13764060.3A priority patent/EP2828415A4/fr
Priority to CN201380026281.1A priority patent/CN104603303A/zh
Priority to US14/386,133 priority patent/US20150104361A1/en
Priority to JP2015500721A priority patent/JP2015516507A/ja
Priority to AU2013203668A priority patent/AU2013203668A1/en
Publication of WO2013138900A1 publication Critical patent/WO2013138900A1/fr

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Classifications

    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • 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
    • C22B58/00—Obtaining gallium or indium
    • 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

Definitions

  • the present disclosure relates to improvements in the field of chemistry applied to the recovery, extraction and/or isolation of rare earth elements (REE) and rare metals (RM).
  • REE rare earth elements
  • RM rare metals
  • such processes are useful for obtaining rare earth elements from various materials and derivatives thereof such as aluminum-containing materials and derivatives, iron- containing materials and derivatives, zinc-containing materials and derivatives thereof, copper-containing materials and derivatives thereof, nickel-containing materials and derivatives thereof, and titanium-containing materials and derivatives thereof.
  • a process for recovering at least one rare earth element comprising : obtaining an acidic composition comprising (i) at least one rare earth element and optionally at least one rare metal; and reacting the composition with a precipitating agent so as to substantially selectively precipitate a first rare earth element and optionally a first rare metal.
  • a process for recovering at least one rare earth element comprising : obtaining an acidic composition comprising (i) at least one rare earth element and optionally at least one rare metal and (ii) at least one metal ion; at least partially removing, from the acidic composition, the least one metal ion by means of an extracting agent, an ion echange resin and/or by reacting the composition with a reducing agent, thereby obtaining a composition having a reduced content in the at least one metal ion; and reacting the composition having the reduced content in the at least one metal ion with a precipitating agent so as to substantially selectively precipitate a first rare earth element and optionally a first rare metal.
  • a process for recovering at least one rare earth element comprising : obtaining an acidic composition comprising (i) at least one rare earth element and optionally at least one rare metal and (ii) at least one iron ion, ; at least partially removing, from the acidic composition, the least one iron ion by means of an extracting agent, an ion echange resin and/or by reacting the composition with a reducing agent, thereby obtaining a composition having a reduced content in the at least one iron ion; and reacting the composition having the reduced content in the at least one iron ion with a precipitating agent so as to substantially selectively precipitate a first rare earth element and optionally a first rare metal.
  • a process for recovering at least one rare earth element from at least one material comprising : leaching the at least one material with at least one acid so as to obtain a leachate comprising at least one metal ion, and the at least one rare earth element ; substantially selectively precipitating, extracting and/or isolating the at least one metal ion from the leachate and optionally obtaining a precipitate; and substantially selectively precipitating, extracting and/or isolating the at least one rare earth element from the leachate and/or the precipitate.
  • a process for extracting at least one rare earth element from at least one material comprising : leaching the at least one material with at least one acid so as to obtain a leachate comprising at least one metal ion, and the at least one rare earth element; and selectively precipitating at least one member chosen from the at least one rare earth element, and the at least one metal ion.
  • a process for recovering at least one rare earth element from at least one material comprising : leaching the at least one material with at least one acid so as to obtain a leachate comprising at least one metal ion, and at least one rare earth element ; optionally substantially selectively precipitating, extracting and/or isolating the at least one rare earth element from the leachate and/or the precipitate. substantially selectively precipitating, extracting and/or isolating the at least one metal ion from the leachate and optionally obtaining a precipitate; and substantially selectively precipitating, extracting and/or isolating the at least one rare earth element from the leachate and/or the precipitate.
  • a process for recovering at least one rare earth element from at least one material comprising : leaching the at least one material with at least one acid so as to obtain a leachate comprising at least one metal ion, the at least one rare earth element, and a solid, and separating the leachate from the solid; substantially selectively removing at least one metal ion from the leachate and optionally obtaining a precipitate; and substantially selectively removing the at least one rare earth element from the leachate and/or the precipitate.
  • process for recovering at least one rare earth element from at least one material comprising : leaching the at least one material with at least one acid so as to obtain a leachate comprising at least one metal ion and the at least one rare earth element, and a solid, and separating the leachate from the solid; and substantially selectively removing at least one member chosen from the at least one rare earth element and the at least one metal ion from the leachate.
  • FIG. 1 shows a bloc diagram of an example of a process for preparing alumina and various other products including rare earth elements, according to the present disclosure
  • FIG. 2 shows a bloc diagram of another example of process for preparing alumina and various other products including rare earth elements, according to the present disclosure
  • FIGs. 2A and 2B show a bloc diagram of a process similar to the process shown in Fig. 2;
  • FIG. 3 shows a bloc diagram of another example of process for extracting rare earth elements according to the present disclosure
  • FIG. 3A shows a bloc diagram of a process similar to the process shown in Fig. 3;
  • Figs. 4A and 4B show a bloc diagram of another example of a process for extracting rare earth elements according to the present disclosure
  • Figs. 4C and 4D show a bloc diagram of processes similar to those shown in Figs. 4A and 4B; [0021] Figs. 5A, 5B, 5C, 5D show a bloc diagram of another example of a process for extracting rare earth elements according to the present disclosure;
  • Figs. 5E, 5F, 5G and 5H show a bloc diagram of processes similar to those shown in Figs. 5A, 5B, 5C, and 5D;
  • Figs. 6 to 11 represents precipitation yields (%) obtained for various rare earth elements and rare metals, during processes according to the present disclosure
  • Figs. 12 to 25 represent curves showing various results obtained when carrying out extractions of compounds, during processes according to the present disclosure.
  • Fig. 26 shows a bloc diagram of another example of process for extracting rare earth elements according to the present disclosure.
  • the rare earth element(s) recovery can be made, for example, in the processes described in the present disclosure at various stages. Moreover, it was found that such processes can be useful even if the rare earth elements are only found as traces. It was also found that such processes can be particularly useful for extracting rare earth elements from a solution that is substantially refined or purified. For example, these processes can be useful since they can be applied to solutions from which several of the main components have been removed They can also be applied to solutions before removal of several of the main components.
  • At least one metal ion refers, for example, to at least one type of ion chosen form all possible forms of ions of such a metal.
  • the metal "M” can be M 2+ or M 3+
  • the at least one metal ion for the metal M can be either M 2+ or M 3+ .
  • the metal can be chosen from aluminum, iron, zinc, copper, nickel, magnesium, titanium etc.
  • At least one aluminum ion refers, for example, to at least one type of aluminum ion chosen from all possible forms of Al ions.
  • the at least one aluminum ion can be Al 3+ .
  • At least one iron ion refers, for example, to at least one type of iron ion chosen from all possible forms of Fe ions.
  • the at least one iron ion can be Fe 2+ , Fe 3+ , or a mixture thereof.
  • At least one zinc ion refers, for example, to at least one type of zinc ion chosen from all possible forms of Zn ions.
  • the at least one zinc ion can be Zn 2+ .
  • At least one copper ion refers, for example, to at least one type of copper ion chosen from all possible forms of Cu ions.
  • the at least one copper ion can be Cu 1+ or Cu 2+ , or a mixture thereof.
  • At least one nickel ion refers, for example, to at least one type of nickel ion chosen from all possible forms of Ni ions.
  • the at least one nickel ion can be Ni 2+ or Ni 3+ , or a mixture thereof.
  • At least one magnesium ion refers, for example, to at least one type of magnesium ion chosen from all possible forms of Mg ions.
  • the at least one magnesium ion can be Mg 2+ .
  • At least one titanium ion refers, for example, to at least one type of titanium ion chosen from all possible forms of Ti ions.
  • the at least one titanium ion can be Ti 3+ or Ti 4+ , or a mixture thereof.
  • At least one rare earth element refers, for example, to at least one type of rare earth element chosen from all the rare earth elements described in the present disclosure in all their possible forms.
  • At least one rare metal refers, for example, to at least one type of rare metal chosen from all the rare metals described in the present disclosure in all their possible forms.
  • Ga-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of gallium.
  • Ce-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of cerium.
  • Sc-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of scandium.
  • Sm-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of samarium.
  • Eu-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of europium.
  • Gd-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of gadolinium.
  • Y-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of yttrium.
  • Pr-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of praseodymium.
  • Nd-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of neodymium.
  • La-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of lanthanum.
  • Er-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of erbium.
  • Dy-free solution refers, for example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of dysprosium.
  • rare earth element refers, for example, to a rare element chosen from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • REE can be used in the present disclosure as a synonym for "rare earth element”.
  • rare metal refers, for example, to a rare metal chosen from indium, zirconium, lithium, and gallium. These rare metals can be in various form such as the elemental form (or metallic form), under the form of halides (for example chlorides), oxides, sulfates, oxalates, hydroxides etc.
  • halides for example chlorides
  • RM can be used in the present disclosure as a synonym for "rare metal”.
  • REEO or REE-O refers to rare earth element oxide(s).
  • RMO or RM-O refers to rare metal oxide(s).
  • the substantially selectively removing of the at least one member chosen from the at least one rare earth element and the at least one metal from the leachate can be made in various manners.
  • the at least one metal ion (or a second metal ion) can be removed and then, a first metal ion can be removed and finally, the at least one rare earth element can be removed.
  • the first metal ion can be removed, then the second metal ion can be removed and finally, the at least one rare earth element can be removed.
  • the at least one rare earth element can be removed, then, the first metal ion can be removed, and finally the second metal ion can be removed.
  • the at least one rare earth element can be removed, then, the second metal ion can be removed, and finally the first metal ion can be removed.
  • Various other possible combinations can also be envisaged.
  • the at least one acid used for leaching the at least one material can be HCI, H 2 S0 , HNO 3 or mixtures thereof. More than one acid can be used as a mixture or separately. Solutions made with these acids can be used at various concentration. For example, concentrated solutions can be used. For example, 6 M or 12 M HCI can be used. For example, up to 98 % or 100 % wt H 2 S0 4 can be used. For example, 18 wt % or 32 wt % can be used
  • the at least one material can be leached with HCI having a concentration of about 15 to about 45 weight %, of about 20 to about 45 weight %, of about 25 to about 45 weight %, of about 26 to about 42 weight %, of about 28 to about 40 weight %, of about 30 to about 38 weight %, or between 25 and 36 weight %.
  • Leaching can also be carried out by adding dry highly concentrated acid (for example, 85 %, 90 % or 95 %) in gas phase into the aqueous solution.
  • leaching can also be carried out by using a weak acid solution (for example ⁇ 3 wt %).
  • leaching can be carried out by using HCI having a concentration of about 18 to about 32 wt % in a first reactor and then, by using HCI having concentration of about 90 to about 95 % in a second reactor.
  • the at least one material can be leached at a temperature of about 125 to about 225 °C, about 150 to about 200 °C, about 160 to about 180 °C, or about 165 to about 170 °C.
  • the leaching can be carried out under pressure.
  • the pressure can be about 100 to about 300 or about 150 to about 200 psig.
  • the leaching can be carried out for about 30 minutes to about 5 hours.
  • the leaching can be carried out at a temperature of about 60 °C to about 200 °C.
  • the leaching can be carried out under pressure into an autoclave.
  • it can be carried out at a pressure of 5 KPag to about 850 KPag, 50 KPag to about 800 KPag, 100 KPag to about 750 KPag, 150 KPag to about 700 KPag, 200 KPag to about 600 KPag, or 250 KPag to about 500 KPag.
  • the leaching can be carried out at a temperature of at least 80 °C, at least 90 °C, or about 100 °C to about 1 10 °C. In certain cases it can be done at higher temperatures so as to increase extraction yields of rare earth elements in certain ores.
  • the leaching can be carried out at a temperature of at least 100 °C, at least 120 °C, at least 130 °C, at least 140 °C, or about 140 °C to about 175 °C.
  • the at least one rare earth element in the leachate, can be in the form of an ion.
  • the at least one rare earth element can be solubilized into the solution and can be found as a soluble ion, associated to chlorine, a sulfate, a nitrate, or hydrates thereof, etc.
  • various bases can be used for raising up the pH such as KOH, NaOH, Ca(OH) 2 , CaO, MgO, Mg(OH) 2 , CaC0 3 , Na 2 C0 3 , NaHC0 3 , C0 2 , or mixtures thereof.
  • the at least one material can be chosen from aluminum-containing materials and derivatives, iron-containing materials and derivatives, zinc-containing materials and derivatives thereof, copper- containing materials and derivatives thereof, nickel-containing materials and derivatives thereof, magnesium-containing materials and derivatives thereof and titanium-containing materials and derivatives thereof.
  • the at least one aluminum-containing material can be at least one aluminum-containing ore.
  • the at least one iron-containing material can be at least one iron-containing ore.
  • the at least one zinc-containing material can be at least one zinc-containing ore.
  • the at least one copper-containing material can be at least one copper-containing ore.
  • the at least one nickel-containing material can be at least one nickel-containing ore.
  • the at least one magnesium-containing material can be at least one magnesium-containing ore.
  • the at least one titanium-containing material can be at least one titanium-containing ore.
  • the at least one metal ion can comprise at least one aluminum ion, at least one zinc ion, at least one copper ion, at least one nickel ion, at least one magnesium ion, at least one titanium ion and/or at least one iron ion.
  • the at least one metal ion can comprise a first metal ion and a second metal ion.
  • the first metal ion can comprise at least one aluminum ion, at least one zinc ion, at least one copper ion, at least one nickel ion, at least one titanium ion and/or at least one iron ion.
  • the second metal ion can comprise at least one aluminum ion, at least one zinc ion, at least one copper ion, at least one nickel ion, at least one titanium ion and/or at least one iron ion.
  • the first metal ion can be at least one aluminum ion.
  • the second metal ion can be at least one iron ion.
  • the at least one metal ion can be removed by using an ion exchange resin or ion exchange system.
  • an ion exchange resin or system can be effective for allowing only chlorides of rare earth elements and chlorides rare metals to pass therethrough, while capturing the at least one metal ion.
  • the at least one iron ion can be precipitated.
  • it can be precipitated by means of an ionic precipitation and it can precipitate in the form of various salts, hydroxides, chlorides or hydrates thereof.
  • the at least one iron ion can be precipitated as FeCI 2 , FeCI 3 , Fe(OH) 3 , Fe(OH) 2 , hematite, geotite, jarosite or hydrates thereof.
  • the at least one rare earth element can be solubilized into the solution and can be found as a soluble ion, associated as an hydroxide or a salt, or hydrates thereof.
  • the at least aluminum ion can be precipitated.
  • it can be precipitated by means of an ionic precipitation and it can precipitate in the form of various salts, (such as chlorides, sulfates) or hydroxides or hydrates thereof.
  • the at least one aluminum ion can be precipitated as AI(OH)3, AICl3*6H 2 0, Al2(S0 )3, or hydrates thereof.
  • the at least one rare earth element can be solubilized into the solution and can be found as a an ion associated to an hydroxide or a salt or hydrates thereof.
  • the residual and substantially purified or refined solution can contain the at least one rare earth element into a mixture of residual soluble ions, such as CI " , S0 4 2" , Na + .
  • the processes of the present disclosure can be effective for treating various materials.
  • the at least one material can be an aluminum-containing material,
  • the aluminum-containing material can be an aluminum-containing ore.
  • clays, argillite, mudstone, beryl, cryolite, garnet, spinel, bauxite, or mixtures thereof can be used as starting material.
  • the aluminum- containing material can also be a recycled industrial aluminum-containing material such as slag.
  • the aluminum-containing material can also be red mud.
  • the processes of the present disclosure can be effective for treating various nickel-containing ores.
  • niccolite, kamacite, taenite, limonite, garnierite, laterite, pentlandite, or mixtures thereof can be used.
  • the processes of the present disclosure can be effective for treating various zinc-containing ores.
  • smithsonite, warikahnite, sphalerite, or mixtures thereof can be used.
  • the processes of the present disclosure can be effective for treating various copper-containing ores.
  • copper-containing oxide ores can be used.
  • chalcopyrite, chalcocite, covellite, bornite, tetrahedrite, malachite, azurite, cuprite, chrysocolla, or mixtures thereof can also be used.
  • the processes of the present disclosure can be effective for treating various magnesium-containing materials.
  • the serpentine can be treated by such processes.
  • antigorite, chrysotile and lizardite can also be treated by such processes as well as various magnesium waste meterials and reject such as industrial or mining wastes and mixtures thereof.
  • the processes of the present disclosure can be effective for treating various titanium-containing ores.
  • ecandrewsite, geikielite, pyrophanite, ilmenite, rutile or mixtures thereof can be used.
  • the at least one rare earth element can be chosen from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • the at least one rare metal can be chosen from indium, zirconium, lithium, and gallium.
  • rare earth elements can sometimes be divided into two categories, light rare earth elements (LRE) and heavy rare earth elements (HRE).
  • the light rare earth elements can comprise lanthanum, cerium, praseodymium, neodymium, and samarium (atomic numbers 57-62), and they are usually more abundant than heavy ones.
  • the at least one rare element can be extracted under the form of various salts, oxides, hydroxides, and hydrates thereof.
  • the at least one rare earth element can be chosen from scandium, gallium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium and mixtures thereof.
  • the at least one rare earth element is chosen from scandium, gallium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, dysprosium and mixtures thereof.
  • the at least one rare earth element is chosen from scandium, gallium, yttrium, cerium and mixtures thereof.
  • the at least one rare earth element can be yttrium.
  • the at least one rare earth element can be scandium.
  • the at least one rare earth element can be gallium.
  • the at least one rare earth element can be cerium.
  • the processes can comprise : leaching the at least one material with HCI so as to obtain the leachate comprising the at least one metal ion, and the at least one rare earth element, and the solid and separating the leachate from the solid; substantially selectively removing the at least one metal ion from the leachate, thereby obtaining a composition comprising the metal ion, and the at least one rare earth element; and substantially selectively at least partially removing the at least one metal ion from the composition, thereby obtaining a liquor comprising the at least one rare earth element.
  • the at least one metal ion can be substantially selectively removed from the leachate by substantially selectively precipitating it from the leachate and removing it therefrom by carrying out a solid-liquid separation.
  • the at least one metal ion can be substantially selectively removed from the leachate by substantially selectively precipitating it under the form of AICl3 « 6H 2 0 and removing it therefrom by carrying out a solid-liquid separation.
  • the composition can comprise HCI, the at least one metal ion, and the at least one rare earth element.
  • the composition can be an acidic composition that comprises, the at least one metal ion, and the at least one rare earth element.
  • the acidic composition can comprises (i) the at least one rare earth element and optionally theat least one rare metal and (ii) FeCI 3 .
  • the at least one iron ion can be substantially selectively removed from the composition by carrying out an hydrolysis so as to convert the at least one iron ion into Fe 2 0 3 and removing the precipitated Fe20 3 from the composition by carrying out a solid-liquid separation, thereby obtaining the liquor comprising the at least one rare earth element.
  • the liquor containing the at least one rare earth element is recirculated back for being further concentrated by being used in precipitating the at least one aluminum ion.
  • the liquor containing the at least one rare earth element is recirculated back for being further concentrated by being used in precipitating the at least one aluminum ion under the form of ⁇ 3 ⁇ 6 ⁇ 2 ⁇ .
  • the at least one iron ion can be Fe 3+ and it can be substantially selectively partially removed from the composition, and wherein the composition can be further treated with a reducing agent so as to convert Fe 3+ into Fe 2+ and then, Fe 2+ , under the form of FeCI 2l can be removed from the composition by carrying out a solid-liquid separation, thereby obtaining the liquor comprising the at least one rare earth element.
  • the at least one rare earth element can be substantially selectively precipitated, extracted and/or isolated from the liquor by means of a liquid-liquid extraction.
  • the at least one rare earth element can be extracted from the liquor by means of liquid-liquid extraction.
  • the at least one rare earth element can be recovered from the liquor by means of liquid-liquid extraction.
  • the at least one extracting agent can be chosen from di-(2-ethylhexyl) phosphoric acid (HDEHP), mono(2-ethylhexyl)2-ethylhexyl phosphonate (HEH/EHP), bis(2,4,4-trimethylpentyl)monothiophosphinic acid), octyl phenyl phosphate (OPAP), 2-ethylhexylphosphonic acid mono-2- ethylhexyl ester (PC88A) and optionally toluene, tributyl phosphate, di- isoamylmethyl phosphonate, 7-(4-ethyl-1-methyloctyl)-8-hydroxyquinoline, di- (2-ethylhexyl) phosphinic acid, bis(2,4,4-trimethylp
  • the at least one extracting agent can be di-(2- ethylhexyl) phosphoric acid.
  • the at least one extracting agent can be 2- ethylhexylphosphonic acid mono-2-ethylhexyl ester.
  • the at least one extracting agent can be octyl phenyl phosphate.
  • the at least one extracting agent can be tributyl phosphate.
  • the at least one extracting agent can be chosen from diethylenetriamine-penthaacetic acid (DTPA), ethylenedlaminetetraacetic (EDTA), 1 ,4,7,10-tetraazacyclododecane-1 ,4,7,10-tetraacetic acid (DOTA), bis(2,4,4-trimethylpentyl)monothiophosphinic acid and mixtures thereof.
  • DTPA diethylenetriamine-penthaacetic acid
  • EDTA ethylenedlaminetetraacetic
  • DOTA 1,4,7,10-tetraazacyclododecane-1 ,4,7,10-tetraacetic acid
  • bis(2,4,4-trimethylpentyl)monothiophosphinic acid bis(2,4,4-trimethylpentyl)monothiophosphinic acid and mixtures thereof.
  • the at least one rare earth element found as an ion in the leachate can be precipitated.
  • scandium can be precipitated in the form of Sc(OH) 3 , ScCI 3 , ScF 3 , and/or [ScF 6 ] 3" (cation), wherein the cation can be sodium, potassium, magnesium, calcium etc
  • Scandium can be precipitated at a pH of about 7 to about 9, or about 7 to about 8.
  • the leaching can be carried out at a pH of about 0.5 to about 2.5., about 0.5 to about 1.5, or about 1 ; then the second metal ion can be precipitated at a pH of at least about 9.5, 10, 10.5, 11 , or 11.5; and then the first metal ion can be precipitated at a pH of about 8 to about 9.
  • the second metal ion can be precipitated at a pH of about 10 to about 12.5, 10.5 to about 1 1.5, about 10.8 to about 1 1.2, about 1 1.5 to about 12.5, or between 10 and 1 1.
  • the precipitation of the first metal ion can be carried out at a pH of about 7 to about 1 1 , about 8 to about 10.5, about 8.5 to 10 or about 9 to about 10.
  • the precipitation of the second metal ion can be carried out at a pH of about 3 to about 6, about 3.0 to about 5.5, about 3 to about 5, about 3 to about 4, about 3.0 to about 3.5, about 3.5 to about 4.0, about 4.0 to about 5.0, about 4.0 to about 4.5, or about 4.5 to about 5.0.
  • the precipitation of the first metal ion can be carried out at a pH of about 5 to about 6, about 5.0 to about 5.5, or about 5.5 to about 6.0.
  • highly concentrated dry gaseous HCI at about 90 to about 98 % can be bubbled into the composition comprising the at least one iron ion, the at least one aluminum ion and the at least one rare earth element.
  • the pH during the hydrolysis can be about below 2.5, 2.0, 1.5 or 1.0.
  • the liquor can comprise the at least one rare earth element under the form of a chloride, and wherein the liquor can be reacted with an extracting agent in order to substantially selectively extract gallium therefrom, thereby obtaining a Ga-free solution and an extracted gallium solution, and separating the solutions from one another.
  • gallium in the liquor can be under the form of GaCI 3 .
  • the extracting agent can be octyl phenyl phosphate, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester and toluene, tri-butyl phosphate or mixtures thereof.
  • the extracted GaCI 3 can then be precipitated and then converted into Ga 2 0 3 . The latter can be further processed through a plasma torch for purification abouve 99.5 %.
  • the Ga-free solution can then be reacted with another an extracting agent in order to substantially selectively extract cerium therefrom, thereby obtaining a Ce-free solution and an extracted cerium solution, and separating the solutions from one another.
  • the cerium in the Ga-free solution can be under the form of CeCI 3 .
  • the another extracting agent can be tri-butyl phosphate, di-isoamylmethyl phosphonate, di-(2-ethylhexyl) phosphoric acid, 7-(4-ethyl-1-methyloctyl)-8- hydroxyquinoline or mixtures thereof.
  • the process can further comprise converting the extracted cerium into Ce 2 03.
  • the extracted cerium can be calcinated into Ce 2 0 3 . If the extracted cerium in under the form of a chloride, HCI can be recovered (or regenerated) from such a calcination process. For example, HCI can be regenerated at its azeotropic concentration.
  • the process can further comprise reacting the Ce-free solution with a further extracting agent in order to substantially selectively extract scandium therefrom, thereby obtaining a Sc-free solution and an extracted scandium solution, and separating the solutions from one another.
  • scandium in the Ce-free solution can be under the form of SCCI3.
  • the further extracting agent can be di-(2-ethylhexyl) phosphoric acid, di-(2-ethylhexyl) phosphinic acid or a mixture thereof.
  • the process can further comprise converting the extracted scandium into SC2O3.
  • the extracted scandium can be converted into SC2O3 by means of NaOH.
  • the extracted scandium can be calcined so as to obtain Sc 2 0 3 .
  • HCI can be recovered (or regenerated) from such a calcination process.
  • HCI can be regenerated at its azeotropic concentration.
  • the process can further comprise reacting the Sc-free solution with still a further extracting agent in order to substantially selectively extract samarium, europium or a mixture thereof, thereby obtaining a Sm-free solution and/or Eu-free solution and extracted samarium and/or europium solution, and separating the solutions from one another.
  • the still a further extracting agent can be chosen from bis(2,4,4-trimethylpentyl) phosphinic acid, di-(2-ethylhexyl) phosphoric acid and a mixture thereof.
  • the process can further comprise reacting the Sm-free solution and/or Eu-free solution with still another extracting agent in order to substantially selectively extract gadolinium, thereby obtaining a Gd-free solution and an extracted gadolinium solution, and separating the solutions from one another.
  • the still another extracting agent can be 8- hydroxyquinoline.
  • the process can further comprise reacting the Gd-free solution with yet another extracting agent in order to substantially selectively extract yttrium, thereby obtaining a Y-free solution and an extracted yttrium solution, and separating the solutions from one another.
  • the yet another extracting agent can be (2-ethylhexyl)phosphonic acid, di-(2- ethylhexyl)phosphonic acid or a mixture thereof.
  • the process can further comprise reacting the Y-free solution with still yet another extracting agent in order to substantially selectively extract dysprosium and/or erbium, thereby obtaining a Dy-free solution and/or an Er-free solution and an extracted dysprosium and/or erbium solution, and separating the solutions from one another.
  • the liquor can be reacted with a first extracting agent in order to substantially selectively extract gallium therefrom, thereby obtaining a Ga-free solution and an extracted gallium solution, and separating the solutions from one another.
  • gallium in the liquor can be under the form of GaC ⁇ .
  • the first extracting agent can be tri-butyl phosphate optionally in kerosene.
  • the Ga-free solution can be reacted with a precipitating agent for precipitating at least one rare earth element present in the Ga-free solution, thereby obtaining a precipitate containing the at least one rare earth element and recovering the precipitate via a solid-liquid separation.
  • the process can further comprise leaching the precipitate with at least one acid so as to obtain a leach solution comprising the at least one rare earth element.
  • the acid can be HCI.
  • the leach solution can be reacted with a second extracting agent so as to substantially selectively extract a first group of rare earth elements, thereby obtaining a solution comprising the extracted rare earth elements of the first group and a raffinate comprising a second group of rare earth elements, and separating the solution from the raffinate.
  • the first group can comprise yttrium and scandium.
  • the second group can comprise cerium, neodynium, europium and praseodymium.
  • the second extracting agent can be chosen from di-(2-ethylhexyl)phosphoric acid and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester.
  • the process can further comprise reacting the solution comprising the extracted rare earth elements of the first group with HCI at least once so as to remove impurities therefrom.
  • HCI can be at azeotropic concentration or it can be a very high concentration such as 95 wt
  • the process can further comprise stripping the solution comprising the extracted rare earth elements of the first group with at least one acid so as to obtain a first group strip liquor.
  • the at least one acid can be HCI.
  • the process can further comprise repeating at least once the extraction with the second extracting agent.
  • the first group strip liquor can be reacted with a third extracting agent so as to substantially selectively extracting at least one of scandium, erbium and dysprosium from the first group strip liquor, thereby obtaining a solution comprising the extracted at least one of scandium, erbium and dysprosium, and an yttrium raffinate, and separating the solution from the raffinate.
  • the third extracting agent can be tri-butyl phosphate.
  • the process can further comprise stripping the solution comprising the extracted at least one of scandium, erbium and dysprosium solution with at least one acid so as to obtain another first group strip liquor.
  • the at least one acid can be HCI.
  • the another first group strip liquor can be reacted with a fourth extracting agent so as to substantially selectively extracting erbium and dysprosium from the another first group strip liquor, thereby obtaining a solution comprising the extracted erbium and dysprosium, and a scandium raffinate, and separating the solution from the raffinate.
  • the another first group strip liquor can be reacted with a fourth extracting agent so as to substantially selectively extracting scandium from the another first group strip liquor, thereby obtaining a solution comprising the extracted scandium, and raffinate comprising erbium and dysprosium, and separating the solution from the raffinate.
  • the at least one rare earth element can be substantially selectively precipitated, extracted and/or isolated by means of an adsorption on activated charcoal optionally modified with tributyl phosphate or on a polyurethane polyether foam (PUF).
  • activated charcoal optionally modified with tributyl phosphate or on a polyurethane polyether foam (PUF).
  • PEF polyurethane polyether foam
  • the at least one rare earth element can be substantially selectively removed by means of a liquid-liquid extraction.
  • the liquid-liquid extraction can be carried out by using an extracting agent.
  • the process can comprise selectively precipitating at least two members chosen from the at least one rare earth element that is in the form of ions, the second metal ion and the first metal ion.
  • each of the members can be precipitated separately or together.
  • the processes can comprise : leaching the at least one material with HCI so as to obtain the leachate comprising a first metal ion a second metal ion and the at least one rare earth element, and the solid and separating the leachate from the solid; substantially selectively removing the second metal ion from the leachate, thereby obtaining a composition comprising the first metal ion, and the at least one rare earth element; and substantially selectively at least partially removing the first metal ion from the composition, thereby obtaining a liquor comprising the at least one rare earth element.
  • the processes can comprise : leaching the at least one material with HCI so as to obtain the leachate comprising a first metal ion, a second metal ion, and the at least one rare earth element, and the solid and separating the leachate from the solid; substantially selectively removing the second metal ion from the leachate, thereby obtaining a composition comprising the first metal ion, and the at least one rare earth element; and substantially selectively at least partially removing the first metal ion from the composition, thereby obtaining a liquor comprising the at least one rare earth element.
  • the leaching can be carried out at a pH of about 0.5 to about 2.5, then the second metal ion can be precipitated at a pH of at least about 9.5, then the first metal ion can be precipitated at a pH of about 8 to about 9, and then at least one scandium ion can be precipitated at a pH of about 7 to about 8.
  • the leaching can be carried out at a pH of about 0.5 to about 1.5, then the second metal ion can be precipitated at a pH of at least about 10.5, then the first metal ion can be precipitated at a pH of about 8 to about 9, and then at least one scandium ion can be precipitated at a pH of about 7 to about 8.
  • the leaching can be carried out at a pH of about 0.5 to about 1.5, then the second metal ion can be precipitated at a pH of at least about 11 , then the first metal ion can be precipitated at a pH of about 8 to about 9, and then at least one scandium ion can be precipitated at a pH of about 7 to about 8.
  • scandium can be precipitated from a by-product generated during the process.
  • scandium can be precipitated from a solution generated during the process.
  • scandium can be precipitated using HNO3.
  • the at least one rare earth element can be substantially selectively precipitated, extracted and/or isolated by at least one technique chosen from ion exchange resin, extraction by means of solvent(s) and adsorption.
  • the at least one rare earth element can be substantially selectively precipitated, extracted and/or isolated by means of an ion exchange resin.
  • the at least one rare earth element can be substantially selectively precipitated, extracted and/or isolated by means of a liquid-liquid extraction.
  • the at least one rare earth element can be substantially selectively precipitated, extracted and/or isolated by means of an electrowinning process.
  • the leaching can be carried out at a pH of about 0.5 to about 2.5, then the second metal ion can be precipitated at a pH of at least about 9.5, then the first metal ion can be precipitated at a pH of about 8 to about 9, and then and then the at least one rare earth element can be substantially selectively extracted.
  • the leaching can be carried out at a pH of about 0.5 to about 1.5, then the second metal ion can be precipitated at a pH of at least about 10.5, then the first metal ion can be precipitated at a pH of about 8 to about 9, and then the at least one rare earth element can be substantially selectively extracted.
  • the leaching can be carried out at a pH of about 0.5 to about 1.5, then the second metal ion can be precipitated at a pH of at least about 11 , then the first metal ion can be precipitated at a pH of about 8 to about 9, and then the at least one rare earth element can be substantially selectively extracted.
  • the at least one material / acid ratio can be about 1 / 10 in weight by volume.
  • the processes can further comprise at least one of at least partially removing the second metal ion from the leachate by substantially complexing the second metal ion with an extracting agent; selectively precipitating the second metal ion; selectively precipitating the first metal ion; and at least partially removing the first metal ion from the leachate by substantially complexing the first metal ion with another extracting agent.
  • the processes comprise : leaching the at least one material with HCI so as to obtain a leachate comprising a first metal ion and a second metal ion and a solid residue, and separating the leachate from the solid residue; at least partially removing the second metal ion from the leachate by substantially selectively precipitating the second metal ion by reacting the leachate with a base so as to obtain an aqueous composition rich in the first metal ion and comprising the at least one rare element and a precipitate, and removing the precipitate from the composition; purifying the aqueous composition by substantially selectively precipitating the first metal ion, thereby obtaining another composition comprising the at least one rare element and another precipitate, removing the precipitate from the composition; and substantially selectively extracting the at least one rare element from the another composition.
  • the processes can comprise : leaching the at least one material with HCI so as to obtain a leachate comprising a first metal ion and a second metal ion and a solid residue, and separating the leachate from the solid residue, at least partially removing the second metal ion from the leachate by substantially selectively precipitating the second metal ion by reacting the leachate with a base so as to obtain an aqueous composition rich in the first metal ion and comprising the at least one rare element and a precipitate, and removing the precipitate from the composition; substantially selectively extracting the first metal ion from the aqueous composition by means of a hollow fiber membrane, or by a liquid-liquid extraction, and removing the extracted first metal ion, thereby obtaining an aqueous composition depleted in the first metal ion comprising the at least one rare element; and substantially selectively extracting the at least one rare element from the aqueous composition.
  • the processes can comprise : leaching the at least one material with HCI so as to obtain a leachate comprising a first metal ion and a second metal ion and a solid residue, and separating the leachate from the solid residue; at least partially removing the second metal ion from the leachate by substantially selectively complexing the second metal ion with an extracting agent so as to obtain an aqueous composition rich in the first metal ion comprising the at least one rare earth element; purifying the aqueous composition by substantially selectively precipitating the first metal ion, thereby obtaining another composition comprising the at least one rare element and another precipitate, removing the precipitate from the composition; and substantially selectively extracting the at least one rare element from the another composition.
  • the processes can comprise : leaching the at least one material with HCI so as to obtain a leachate comprising a first metal ion and a second metal ion and a solid residue, and separating the leachate from the solid residue; at least partially removing the second metal ion from the leachate by substantially selectively complexing the second metal ion with an extracting agent so as to obtain an aqueous composition rich in the first metal ion comprising the at least one rare earth element; substantially selectively extracting the first metal ion from the aqueous composition by means of a hollow fiber membrane, or by a liquid-liquid extraction, and removing the extracted first metal ion, thereby obtaining an aqueous composition depleted in the first metal ion comprising the at least one rare element; and substantially selectively extracting the at least one rare element from the aqueous composition depleted in the first metal ion.
  • the processes can comprise : leaching the at least one material with HCI so as to obtain a leachate comprising a first metal ion and a second metal ion and a solid residue, and separating the leachate from the solid residue; at least partially removing the first metal ion from the leachate by substantially selectively precipitating the first metal ion so as to obtain an aqueous composition rich in the second metal ion comprising the at least one rare element and a precipitate, and removing the precipitate from the composition; substantially selectively precipitating the second metal ion from the aqueous composition rich in the second metal ion, and removing the precipitate therefrom, thereby obtaining thereby obtaining an aqueous composition depleted in the second metal ion and comprising the at least one rare element; and substantially selectively extracting the at least one rare element from the aqueous composition depleted in the second metal ion.
  • the first metal ion can comprises at
  • the second metal ion can comprise at least one iron ion.
  • the at least one aluminum ion can be precipitated under the form of AICl 3 *6H 2 0 in a crystallizer, for example, by sparging gaseous HCI.
  • the at least one aluminum ion can be precipitated under the form of ⁇ 3 ⁇ 6 ⁇ 2 0 in a crystallizer, for example, by adding HCI having a concentration of about 26 to about 32 wt %.
  • the at least one iron ion can be precipitated under the form of Fe 2 0 3 by means, for example, of an hydrolysis.
  • the aqueous composition rich in the first metal ion can be purified by complexing the first metal ion with an extracting agent so as to obtain a complex, separating the complex form the composition and precipitating the first metal ion.
  • the aqueous composition rich in the first metal ion can be purified by complexing impurities contained in aqueous composition rich in the first metal ion with an extracting agent, at least partially removing the complexed impurities from the composition and precipitating the first metal ion.
  • the rare earth elements and rare metals obtained by the processes of the present disclosure can be further purified by means of a plasma torch.
  • the rare earth elements and rare metals, once isolated, can be individually injected into a plasma torch so as to further purify them. Examples of such optional purification steps can be seen in Figs. 4C, 4D, 5F, 5G and 5H.
  • the acidic compositions of the present disclosure can be treated by means of an ion exchange resin prior to extraction of the at least one rare earth element and/or at least rare metal. Examples of such steps can be seen, for example, in Figs. 3A, 4C, 5E and 5F.
  • the acidic composition can be reacted with Fe(0), thereby obtaining a composition having a reduced content in Fe 3+ .
  • the first rare earth element can be scandium.
  • the acidic composition can comprise at least one rare metal.
  • the processes can comprise reacting the composition having the reduced content in the at least one iron ion with the precipitating agent so as to substantially selectively precipitate the first rare earth element and the first rare metal.
  • the first rare metal can be gallium.
  • the precipitating agent can be chosen from oxalic acid, NaOH, MgO, CaC0 3 and mixtures thereof.
  • the precipitating agent can be CaC0 3 .
  • the first rare earth element and optionally the first rare metal is/are substantially selectively precipitated by maintaining a pH value below 2, or a pH at a value of about 1 to about 2.
  • the first rare earth element and optionally the first rare metal is/are substantially selectively precipitated by maintaining Redox potential of about +380 mV.
  • the processes can comprise reacting the composition having reduced content in the at least one iron ion with the precipitating agent so as to substantially selectively precipitate a first rare earth element and first rare metal that are comprised in a so-formed precipitate, and recovering the precipitate.
  • the processes can further compriseg leaching the precipitate and obtaining a leaching solution.
  • the precipitate can be leached with HCI.
  • HCI can have a concentration of about 5 to about 15 mol/L.
  • the leaching solution can be further extracted with an extracting agent so as to substantially selectively extract the first rare earth element and the first rare metal and obtain a loaded organic phase.
  • the extracting agent can be tri-butyl phosphate, tri- butyl phosphate in kerosene or tri-butyl phosphate in kerosene and in the presence of isodecanol.
  • the processes can further comprising scrubbing the loaded organic phase with a scrubbing solution so as to recover the first rare earth element and obtained a scrubbed organic phase.
  • the scrubbing solution can be an acidic aqueous solution comprising HCI at a concentration of about 2 to about 12 mol/L.
  • the scrubbing solution can be used in a ratio scrubbing solution : loaded organic phase of about 1 : 1.
  • the processes can further comprise stripping the scrubbed organic phase with a stripping solution so as to recover the first rare metal.
  • the stripping solution can be water.
  • the stripping solution can be used in a ratio stripping solution : loaded organic phase of about 1 : 2.
  • the composition having a reduced content in the at least one iron ion can be reacted with the precipitating agent so as to obtain a liquid comprising at least one further rare earth element and the precipitate comprising the first rare earth element and the first rare metal, the process further comprising separating the liquid from the precipitate.
  • the process can further comprise reacting the liquid with another precipitating agent so as to obtain another precipitate, and recovering the another precipitate.
  • the liquid can be reacted with the another precipitating agent at a pH of about 7.8 to about 8.2 or about 7.9 to about 8.1.
  • the liquid can be reacted with the another precipitating agent by maintaining Redox potential at about +340 mV or at about +380 mV.
  • the liquid can be reacted with the another precipitating agent by maintaining a temperature of about 50 to about 70 °C.
  • the another precipitating agent can be chosen from oxalic acid, NaOH, MgO, CaC0 3 and mixtures thereof.
  • the another precipitating agent can be CaC0 3 .
  • the processes can further comprise leaching the another precipitate and obtaining a leaching solution comprising a second rare earth element.
  • the another precipitate can be leached with HCI.
  • the leaching solution comprising the second rare earth element can be extracted with an extracting agent so as to substantially selectively extract the second rare earth element and obtain a loaded organic phase comprising the second rare earth element and an aqueous phase comprising at least one light rare earth element.
  • the extracting agent di(ethylhexyl)phosphonic acid or di(ethylhexyl)phosphonic acid in kerosene.
  • the processes can further comprise at least partially removing a third rare earth element from the loaded organic phase comprising the second rare earth element.
  • the processes can further comprise at least partially removing a third rare earth element from the loaded organic phase comprising the second rare earth element by treating the loaded organic phase with an acidic scrubbing solution.
  • the scrubbing solution can comprise 1 N HCI.
  • the third rare earth element can cerium.
  • the processes can further comprise treating the loaded organic phase comprising the second rare earth element with an acidic stripping solution so as to obtain a strip liquor comprising the second rare earth element and recovering the strip liquor.
  • the strip liquor can comprise 3.5 N HCI.
  • the processes can comprise treating the strip liquor comprising the second rare earth element with an extracting agent so as to substantially selectively extract a fourth rare earth element and optionally a fifth rare earth element from the strip liquor and obtaining a raffinate comprising the second rare earth element.
  • the extracting agent can be tri-butyl phosphate or tri-butyl phosphate in kerosene.
  • the fourth rare earth element can be dysprosium.
  • the fifth rare earth element is erbium.
  • the processes can further comprise reacting an organic phase comprising the fourth rare earth element and optionally the fifth rare earth element with a strip solution so as to obtain a strip liquor comprising the fifth rare earth element and optionally the fifth rare earth element.
  • a strip solution can be water.
  • the second rare earth element is yttrium.
  • the leaching solution comprising the second rare earth element can be extracted with an extracting agent so as to substantially selectively extract the second rare earth element and obtain a loaded organic phase comprising the second rare earth element and a raffinate comprising at least one light rare earth element.
  • the extracting agent can be di(ethylhexyl)phosphonic acid or di-(2-ethylhexyl) phosphoric acid.
  • the processes can further comprise at least partially removing a third rare earth element from the loaded organic phase comprising the second rare earth element.
  • the processes can further comprise at least partially removing a third rare earth element from the loaded organic phase comprising the second rare earth element by treating the loaded organic phase with an acidic scrubbing solution.
  • the scrubbing solution comprises about 1 N to about 2 N HCI.
  • the processes can further comprise treating the loaded organic phase comprising the second rare earth element with a stripping solution so as to obtain a strip liquor comprising the second rare earth element.
  • the stripping solution can comprise about 3 M to about 4M HCI.
  • the strip liquor comprising the second rare earth element can be extracted with an extracting agent so as to remove a fourth rare earth element and optionally a fifth rare earth element, thereby obtaining a raffinate comprising the second rare earth element and a loaded organic phase comprising the fourth rare earth element and optionally the fifth rare earth element.
  • the extracting agent is tri-butyl phosphate or tri- butyl phosphate in kerosene.
  • the processes can comprise recovering the raffinate comprising the second rare earth element.
  • the second rare earth element can be yttrium.
  • the fourth rare earth element can be dysprosium.
  • the fifth rare earth element can be erbium.
  • the processes can further comprise reacting the loaded organic phase comprising the fourth rare earth element and the fifth rare earth element with a stripping solution so as to obtain strip liquor comprising the fourth rare earth element and the fifth rare earth element.
  • a stripping solution can be water.
  • the processes can further comprise reacting the strip liquor with an extracting agent so as to substantially selectively extract the fifth rare earth element from the strop liquor, thereby obtaining a raffinate comprising the fourth rare earth element and a loaded organic phase comprising the fifth rare earth element.
  • the extracting agent can be di(ethylhexyl)phosphonic acid or di-(2-ethylhexyl) phosphoric acid.
  • the proceses can further comprise separating the raffinate from the loaded organic phase comprising the fifth rare earth element, treating the loaded organic phase with a scrubbing solution so as to remove impurities therefrom and then treating the loaded organic phase with a stripping solution so as to obtain a strip liquor comprising the fifth rare earth element.
  • the scrubbing solution can comprise about 2 M to about 4 M HCI.
  • the raffinate can be reacted with an oxidation agent so as to oxidize the third rare earth element.
  • the oxidation agent can comprise sodium hypochlorite.
  • the raffinate can be reacted with an oxidation agent at a pH of about 0.5 to about 1 .5.
  • the processes can further comprise removing, from the raffinate, the oxidized third rare earth element that is under the form of a precipitate, thereby obtaining a filtrate comprising a sixth rare earth element.
  • the processes can further comprise reacting the filtrate with an extracting agent so as to substantially selectively extracting the sixth rare earth element from the filtrate, thereby obtaining a loaded organic phase comprising the sixth rare earth element and another raffinate comprising a seventh rare earth element and an eight rare earth element, and separating the loaded organic phase comprising the sixth rare earth element from the raffinate.
  • the extracting agent can be di(ethylhexyl)phosphonic acid or di-(2-ethylhexyl) phosphoric acid.
  • the processes can further comprise treating the loaded organic phase with a scrubbing solution so as to remove impurities therefrom and then treating the loaded organic phase with a stripping solution so as to obtain a strip liquor comprising the sixth rare earth element.
  • a scrubbing solution can comprise about 0.5 M to about 1.5 M HCI.
  • the stripping solution can comprise about 2 M to about 3 M HCI.
  • the sixth rare earth element can europium.
  • the seventh rare earth element can be praseodymium.
  • the eigth rare earth element can be neodymium.
  • the processes can further comprise reducing the sixth rare earth element by means of a reducing agent.
  • the reducing agent can be zinc (0).
  • the processes can further comprise reacting the sixth rare earth element with sodium sulphate so as to obtain a sulphate derivative thereof under the form of a precipitate and recovering the precipitate.
  • the processes can further comprise reacting the raffinate comprising the seventh rare earth element and the eight rare earth element with an extracting agent so as to substantially selectively extracting the eight rare earth element from the raffinate, thereby obtaining a loaded organic phase comprising the eight rare earth element a raffinate comprising the seventh rare earth element, and separating the loaded organic phase comprising the eight rare earth element from the raffinate.
  • the extracting agent can be di(ethylhexyl)phosphonic acid or di-(2-ethylhexyl) phosphoric acid.
  • the processes can further comprise treating the loaded organic phase with a scrubbing solution so as to remove impurities therefrom and then treating the loaded organic phase with a stripping solution so as to obtain a strip liquor comprising the eight rare earth element.
  • a scrubbing solution can comprise about 2 M to about 3 M HCI.
  • the stripping solution can comprise about 3 M to about 4 M HCI.
  • the processes can further comprise, pre-treating or treating the acidic composition with an ion exchange resin so as to remove impurities.
  • the processes can further comprise, before extracting at least one rare earth element and optionally at least one rare metal from the acidic composition, treating the acidic composition with an ion exchange resin so as to at least partially remove impurities therefrom.
  • the processes can further comprise treating the at least one rare earth element and optionally the at least one rare metal extracted by the process by means of a plasma torch so as to further purify the at least one rare earth element and optionally the at least one rare metal.
  • the processes can comprise :
  • leaching argillite with at least one acid for example a solution of HCI or gaseous HCI (for example at pH of about 0.5 to about 1.5 or about 0.8 to about 1.2).
  • the leaching can also be carried out under pressure ;
  • 5- precipitating, extracting and/or isolating at least one rare earth element can be carried out after at least one of steps 1 , 2, 3 and 4.
  • the processes can comprise :
  • leaching argillite with an acid for example a solution of HCI 18-32 wt%.
  • the leaching can also be carried out under pressure such as about 350 KPag to about 500 KPag during about 4 to about 7 hours ;
  • the processes can involve the following steps (the reference numbers in Fig. 1 correspond to the following steps) :
  • the aluminum-containing material is reduced to an average particle size of about 50 to about 80 ⁇ .
  • the reduced and classified material is treated with hydrochloric acid which allows for dissolving, under a predetermined temperature and pressure, the aluminum with other elements like iron, magnesium and other metals including rare earth.
  • the silica (and optionally titanium) remains totally undissolved.
  • the mother liquor from the leaching step then undergoes a separation, a cleaning stage in order to separate the purified silica from the metal chloride in solution.
  • the purified silica can then undergo one or two additional leaching stages (for example at a temperature of about 150 to about 160 °C) so as to increase the purity of silica above 99.9 %.
  • Ti0 2 contained in silica can be separated from silica through a leach made by using HCI and MgCI 2 as a lixiviant composition.
  • step 4 The spent acid (leachate) obtained from step 1 is then brought up in concentration with dry and highly concentrated gaseous hydrogen chloride by sparging this one into a crystallizer. This results into the crystallization of aluminum chloride hexahydrate (precipitate) with a minimum of other impurities. Depending on the concentration of iron chloride at this stage, further crystallization step(s) can be required. The precipitate is then separated from the liquid.
  • the aluminum chloride hexahydrate is then calcined (for example by means of a rotary kiln, fluid bed, etc) at high temperature in order to obtain the desired alumina.
  • Highly concentrated gaseous hydrogen chloride is then recovered and excess is brought in aqueous form to the highest concentration possible so as to be used (recycled) in the acid leaching step.
  • Acid can also be directly sent in gas phase to the acid purification stage to increase HCI concentration from about 30 wt % to about 95 wt %. This can be done, for example, during drying stage or distillation.
  • 6- Iron chloride, rare earth elements and rare metals (the liquid obtained from step 4) is then pre-concentrated and hydrolyzed at low temperature in view of the Fe 2 0 3 (hematite form) extraction and acid recovery from its hydrolysis. All heat recovery from the calcination step (step 5), the leaching part exothermic reaction (step 1) and other section of the process is being recovered into the pre-concentrator.
  • a solution rich in rare earth elemants can be processed by using any one of the processes described in the present disclosure for recovering rare earth elements from aluminum-containing materials.
  • the recovered rare earth elements can be in various forms such oxides, chlorides, hydroxides etc.
  • the expression "rare earth element” can also encompass “rare metal” and thus, in step 10, rare metals can also be recovered.
  • rare metals can be under the form of rare metals oxides.
  • the step 10 can be, for example, the processes shown in Fig. 3 or in Figs. 4a and 4b.
  • MgCI 2 non-hydrolyzable metal chlorides
  • Me-CI undergo a standard pyrohydrolysis step where mixed oxides can be produced and hydrochloric acid at the azeotropic point (20.2% wt.) is regenerated.
  • the liquid can be concentrated to a concentrated liquid having an iron chloride concentration of at least 26% by weight; and then the iron chloride can be hydrolyzed at a temperature of about 155 to about 350 °C while maintaining a ferric chloride concentration at a level of at least 65% by weight, to generate a composition comprising a liquid and precipitated hematite, and recovering the hematite.
  • the liquid can be concentrated to a concentrated liquid having an iron chloride concentration of at least 26% by weight; and then the iron chloride can be hydrolyzed at a temperature of about 155 to about 350 °C while maintaining a ferric chloride concentration at a level of at least 65% by weight, to generate a composition comprising a liquid and precipitated hematite; recovering the hematite; and recovering rare earths from the liquid.
  • the process can further comprise, after recovery of the rare earths, reacting the liquid with HCI so as to cause precipitation of MgCI 2 , and recovering same.
  • step 1 the mineral, whether or not thermally treated is crushed, milled, dried and classified to have an average particle size of about 50 to about 80 ⁇ .
  • step 2 the milled raw material is introduced into the reactor and will undergo the leaching phase.
  • the leaching hydrochloric acid used in step 2 is a recycled or regenerated acid from steps 5, 6, 8 and 9 and its concentration can vary from 15% to 45% weight, percent. Higher concentration can be obtained using a membrane separation, a cryogenic and/or high pressure approach.
  • the acid leaching can be carried out under pressure and at temperature close to its boiling point thus, allowing a minimal digestion time and extended reaction extent (90%-100%).
  • Leaching (step 2) can be accomplished in a semi- continuous mode where spent acid with residual free hydrochloric acid is replaced by highly concentrated acid at a certain stage of the reaction or allowing a reduced acid/mineral ratio, thereby reducing reaction time and improving reaction kinetics.
  • kinetic constant k can be : 0.5 - 0.75 g/mole.L, or 0.75-1.10 g/mole.L.
  • alkali metals, iron, magnesium, calcium, potassium, rare earth elements and other elements will also be in a chloride form at different stages.
  • Silica and titanium can remain undissolved and will undergo (step 3) a liquid/solid separation and cleaning stage,
  • the processes of the present disclosure tend to recover maximum amount of free hydrochloric acid left and chlorides in solution in order to maximize hydrochloric acid recovery yield, using techniques such as rake classifying, filtration with band filters, centrifugation, and others.
  • Mother liquor free of silica is then named as spent acid (various metal chlorides and water) and goes to the crystallization step (step 4).
  • step 4 the spent acid (or leachate) with a substantial amount of aluminum chloride is then saturated with dry and highly concentrated gaseous hydrogen chloride obtained or recycled from step 5, which results in the precipitate of aluminum chloride hexahydrate (AICI 3 ⁇ 6H 2 0).
  • the precipitate retained is then filtered or centrifuged before being fed to the calcination stage (step 5).
  • the remaining of the spent acid from step 4 is then processed to acid recovery system (steps 6 to 8) where pure secondary products will be obtained.
  • step 5 aluminum oxide (alumina) is directly obtained from high temperature conditions.
  • the highly concentrated hydrogen chloride in gaseous form obtained can be fed to steps 4 and 7 for crystallization.
  • the excess hydrogen chloride is absorbed and used as regenerated acid to the leaching step 2 as highly concentrated acid, higher than the concentration at the azeotropic point (>20.2%).
  • concentration at the azeotropic point >20.2%
  • Acid can also be redirected in gas phase directly (> 30 wt %) to acid purification.
  • step 4 various chlorides derivatives of (mainly iron chlorides, magnesium chloride and rare earth element in the form of chlorides) are next subjected to an iron extraction step.
  • an iron extraction step can be carried out for example by using the technology disclosed in WO 2009/153321 , which is hereby incorporated by reference in its entirety.
  • hematite can be seeded for crystal growth.
  • step 6 a hydrolysis at low temperature (155-350°C) is carried out and pure Fe 2 03 (hematite) is being produced and hydrochloric acid of at least 15% concentration is being regenerated.
  • the method as described in WO 2009/153321 is processing the solution of ferrous chloride and ferric chloride, possible mixtures thereof, and free hydrochloric acid through a series of steps pre-concentration step, oxidation step where ferrous chloride is oxidized into ferric form, and finally through an hydrolysis step into an operational unit called hydrolyser where the ferric chloride concentration is maintained at 65 weight % to generate a rich gas stream where concentration ensures a hydrogen chloride concentration of 15-20.2% and a pure hematite that will undergo a physical separation step. Latent heat of condensation is recovered to the pre-concentration and used as the heating input with excess heat from the calcination stage (step 5).
  • the mother liquor left from the hydrolyser (step 6), after iron removal, is rich in other non-hydrolysable elements and mainly comprises magnesium chloride or possible mixture of other elements (various chlorides) and rare earth elements.
  • Rare earth elements in form of chlorides are highly concentrated in percentage into the hydrolyser operational unit (step 6) and are extracted from the mother liquor (step 10) where the processes defined in the present disclosure for recovering rare earth elements from aluminum-containing materials can be employed.
  • rare earth elements under various forms can thus be extracted.
  • it can be under the form of oxides. REO.
  • the processes of the present disclosure for recovering rare earth elements can allow, for example, to concentrate to a high concentration the following rare earth elements, within the hydrolyser recirculation loop: scandium (Sc), galium (Ga), yttrium (Y), dysperosium (Dy), cerium (Ce), praseodynium (Pr), neodynium (Nd), europium (Eu), samarium (Sm), gadolinium (Gd), lanthanum (La), erbium (Er).
  • the at least one rare earth element that will be recovered will depend upon the nature of the starting material (aluminum-containing material).
  • step 7 The spent acid liquor from steps 6 and 10 rich in value added metals, mainly magnesium, is processed to step 7.
  • the solution is saturated with dry and highly concentrated gaseous hydrogen chloride from step 5, which results in the precipitation of magnesium chloride hexahydrate.
  • the precipitate retained is fed to a calcination stage step 8 where pure MgO (>98% wt.) is obtained and highly concentrated hydrochloric acid (for example of at least 38 %) is regenerated and diverted to the leaching step (step 2).
  • An alternative route for step 7 is using dry gaseous hydrochloric acid from step 8.
  • step 9 metal chlorides unconverted are processed to a pyrohydrolysis step (700-900°C) to generate mixed oxides and where hydrochloric acid from 15-20.2% wt. concentration can be recovered.
  • the processes can be similar to the example shown in Fig, 1 but can comprise some variants as below discussed.
  • the process can comprise (after step 6 or just before step 10) an internal recirculation back to the crystallization step 4.
  • the mother liquor from the hydrolyser (step 6) can be recirculated fully or partially to the crystallization of step 4 where a concentration increase will occur with respect to the non-hydrolyzable elements including rare earth elements.
  • Such a step can be useful for significantly increasing the concentration of rare earth elements, thereby facilitating their extraction in step 10.
  • step 7 the solution rich in magnesium chloride and other non-hydrolyzable products at low temperature is, as previously discussed, then brought up in concentration with dry and highly concentrated gaseous hydrogen chloride by sparging it into a crystallizer. This can result into the precipitation of magnesium chloride as an hexahydrate (for example after sodium and potassium chloride removal).
  • an extra step 11 can be added.
  • Sodium chloride can undergo a chemical reaction with sulfuric acid so as to obtain sodium sulfate and regenerate hydrochloric acid at the azeotropic point.
  • Potassium chloride can undergo a chemical reaction with sulfuric acid so as to obtain potassium sulfate and regenerate hydrochloric acid at the azeotropic point.
  • the process shown in Fig. 2A is similar to the process shown in Fig. 2, with the exception of the fact that it comprises an additional step between stage 12 and stage 2 for using the purified acid obtained.
  • the process shown in Fig. 2B is similar to the process shown in Fig. 2, with the exception of the fact that it comprises an additional step of Si0 2 purification by separating Ti0 2 therefrom and an optional step 5a in which a low temperature decomposition of alumina chloride can be carried out.
  • steps 6 and 10 and/or steps 7 and 10 in Figs. 1 and 2 it is possible to further purify the composition comprising rare earth elements and/or rare metals.
  • a composition can be treated with an ion exchange column so as to remove impurities that are not rare earth elements and rare metals.
  • such a composition that comprises chlorides of rare earth elements and/or rare metals will be treated so as to remove impurities such as iron, aluminum or other metals. Then, once the treatment with such columns is done, the earth elements and/or rare metals can be extracted as indicated in the processes of the present disclosure.
  • Certain examples are hereby provided in the present disclosure for substantially selectively recovering, precipitating, extracting and/or isolating at least one rare earth element. This can be done, for example from the leachate and/or the precipitate and any other downstream derivatives, solutions, precipitates, compositions or liquors.
  • recovering, precipitating, extracting and/or isolating at least one rare earth element can be carried out by :
  • a liquid-liquid extraction can be carried out using di-(2-ethylhexyl) phosphoric acid (HDEHP (also called DEHPA or D2EHPA)), mono(2-ethylhexyl)2-ethylhexyl phosphonate (HEH/EHP), octyl phenyl phosphate (OPAP), 2- ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A)and optionally toluene (for example as described in Kao et al.
  • HDEHP di-(2-ethylhexyl) phosphoric acid
  • HHEH/EHP mono(2-ethylhexyl)2-ethylhexyl phosphonate
  • OPAP octyl phenyl phosphate
  • PC88A 2- ethylhexylphosphonic acid mono-2-ethylhexyl ester
  • an extracting agent for example using bis(2,4,4- trimethylpentyl)monothiophosphinic acid or a derivative thereof
  • activated charcoal activated carbon adsorption
  • PAF polyurethane polyether foam
  • scandium can be precipitated (optionally using HNO 3 ) from a residual solution generated during the process (for example when iron is precipitated and/or when aluminum is precipitated).
  • the mixture in a mixture or liquor comprising HCI, water and rare elements in the form of chlorides, the mixture can be treated with an extracting agent in order to extract GaCl3 therefrom, thereby obtaining a Ga-free solution.
  • an extracting agent can be, for example, octyl phenyl phosphate (OPAP)or 2-ethylhexylphosphonic acid mono-2- ethylhexyl ester (PC88A)and toluene.
  • OPAP octyl phenyl phosphate
  • PC88A 2-ethylhexylphosphonic acid mono-2- ethylhexyl ester
  • GaCI 3 can then be precipitated and then converted into Ga 2 03 by heating it, while, optionally recovering HCI.
  • the Ga-free solution can be treated with an extracting agent (for example SME 529TM, tri-butyl phosphate or di-isoamylmethyl phosphonate, di-(2-ethylhexyl) phosphoric acid, 7-(4-ethyl-1-methyloctyl)-8- hydroxyquinoline (Kelex 100TM) in n-heptane with the addition of 10% n- decanol.) for substantially selectively extracting cerium chloride therefrom so as to obtain a Ce-free solution.
  • CeCI 3 can be eventually converted into Ce20 3 , while, optionally recovering HCI.
  • the Ce-free solution can be treated with an extracting agent such as di-(2-ethylhexyl) phosphoric acid or di-(2-ethylhexyl) phosphinic acid so as substantially selectively extract Sc and to provide a Sc-free solution.
  • the extracted Sc can be treated with an oxidizer (such as NaOH) so as to provide SC2O3.
  • the various remaining rare earth elements (Pr, Nd, Sm, Eu, La, Gd, Y, Dy, Er etc.) in the Sc-free solution can be extracted in different possible orders.
  • the process schematized in Fig. 3 can be used as a component of various other processes such as the process schematized in Fig. 1 or in Fig. 2.
  • the step 10 of Figs. 1 and 2 can be the process schematized in Fig. 3.
  • Fig. 3A The process shown in Fig. 3A is similar to the process shown in Fig. 3, with the exception that it comprises an extra purification step by using an ion exchange column.
  • the process for extracting rare earth elements can comprise :
  • Figs. 4C and 4D are similar to the processes shown in Figs. 4A and 4B, with the exception that they can comprise an extra purification step by using an ion exchange column, an optional plasma purification step, an extra acid regenerations step, and an extra calcination step.
  • the reduction of ferric to ferrous with a reducing agent can be used so as to prevent iron coextraction or iron precipitation.
  • a reducing agent such as metallic iron, starch
  • the reaction time can be very short and it can generate heat.
  • the general chemical reaction for reduction of iron(lll) is shown below.
  • the ferric chloride feed solution 101 can be fed to an agitated reaction tank and a reducing agent (for example metallic iron 102 ) can added so as to allow for converting ferric chloride to ferrous chloride (see "Ferric Removal").
  • a reducing agent for example metallic iron 102
  • the resulting filtrate 103 can be further treated in a gallium extraction circuit.
  • a filter cake, containing solid material and iron, can be dewatered and the resulting slurry can then be prepared for disposal.
  • Gallium can then be extracted with an organic solution containing an extracting agent (for example tri-butyl phosphate (TBP) dissolved in kerosene) (see “Gallium Recovery”).
  • an extracting agent for example tri-butyl phosphate (TBP) dissolved in kerosene
  • TBP tri-butyl phosphate
  • the rare earth elements and iron can thus be left in the raffinate.
  • the extraction can vary as a function of the chloride ion concentration. For example, the higher chloride ion concentration, the stronger tendency for gallium complex formation and the better extraction.
  • reagents such as tri-butyl phosphate or tertiary amines (e.g. Alamine 336) can be used.
  • HCI hydrochloric acid
  • gallium extraction can rise to a maximum and can then decrease again.
  • HCI concentration can be increased up to about 4 M HCI for the gallium extraction.
  • gallium can be present in the form of HGaCI 4 complex and TBP extracted gallium as a trisolvate (HGaCI 4 *3TBP) (for example when the extracting agent is TBP).
  • the extracted species is GaCI 3 in the form of a hydrated solvate.
  • Co-extracted iron, accumulated in the organic phase can be scrubbed with hydrochloric acid (see "Gallium Strip Liquor").
  • the resulting organic solution, containing gallium can be fed to a stripping circuit where gallium is stripped with water 104.
  • the raffinate 106, containing ferrous chloride and the rare earth elements, can then be fed to the rare earth precipitation section.
  • the final strip liquor 105 contains gallium.
  • oxalate precipitation of rare earth elements result in very low solubility of the compounds in aqueous solution.
  • the precipitation of rare earth oxalates can be achieved by addition of a precipitation reagent 107.
  • oxalic acid 107 can be used for the precipitation.
  • precipitating agent that are effective for precipitating rare earth elements of the trivalent such as oxalate (from oxalic acid)
  • oxalate from oxalic acid
  • such precipitating agents can have provide a very low solubility in aqueous solution to so-formed precipitate.
  • An overflow from the primary rare earth elements precipitation 109 can be fed to a ferrous treatment circuit. After filtration, the filter cake, containing the rare earth elements, can be fed to a washing and dewatering unit. A resulting slurry 108 can then be prepared for re-leaching (see “REE- Re-leaching"). Re-leaching of the rare earth filter cake can be carried out using hydrochloric acid 1 10.
  • rare earth elements yttrium, scandium and the heavy rare earth (HRE) are extracted (see “Primary REE Recovery") with an extracting agent (for example (di-(2- ethylhexyl)phosphoric acid (D2EHPA) or 2-ethylhexylphosphonic acid mono- 2-ethylhexyl ester (PC88A (also called lonquestTM 801) in kerosene)).
  • D2EHPA di-(2- ethylhexyl)phosphoric acid
  • PC88A also called lonquestTM 801 in kerosene
  • a loaded organic phase can then be selectively scrubbed with hydrochloric acid (2 M HCI) to remove the co-extracted LRE.
  • a secondary scrubbing section can remove europium by using weak hydrochloric acid (1 to 1.5 M HCI).
  • the extract, containing yttrium, scandium and the HRE, can then be stripped with strong acid (3.5 M HCI) 112.
  • the HRE strip liquor 114 containing yttrium and scandium, can be treated further to obtain more than 90 % Y 2 0 3 and Sc 2 0 3 in a first circuit of a double solvent extraction purification process.
  • the aqueous solution containing about 25 g / L (of rare earth elements in the form of oxides) and 0.4 M HCI, can be brought into contact with an extracting agent (for example (di-(2-ethylhexyl)phosphoric acid (D2EHPA) or 2- ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A (also called lonquestTM 801) in kerosene)) (see “Secondary REE Recovery").
  • D2EHPA di-(2-ethylhexyl)phosphoric acid
  • PC88A 2- ethylhexylphosphonic acid mono-2-ethylhexyl ester
  • the loaded organic phase is then scrubbed with diluted hydrochloric acid. Scandium, yttrium and HRE can be extracted by the reagent and finally stripped with strong hydrochloric acid 1 15 at a high oxide / acid ratio.
  • the final strip liquor would have a concentration in rare earth elements oxides of about 40 g/L and about 1 M HCI. This solution is partially neutralized.
  • This pre-treated strip liquor 116 can be further extracted with an extracting agent (for example tri-butyl phosphate (TBP) in kerosene).
  • TBP tri-butyl phosphate
  • the treatment can be done in a multi stage procedure, and ending up in a final stripping of the loaded organic with water 117. All HRE and scandium can thus extracted, leaving yttrium in a raffinate 1 19.
  • various possible extracting agents can be used such as di-(2-ethylhexyl) phosphoric acid.
  • Yttrium can also removed from the strip liquor obtained from the primary extraction step.
  • the separation can be carried out at pH 3 after addition of ammonium thiocyanate as complexion reagent.
  • the procedure can results in an yttrium rich raffinate, when extracting heavy rare earth elements with tri-butyl phosphate, Alamine 336 or Aliquat 336.
  • the separation of scandium from other HRE, can be carried out using a further solvent extraction purification circuit, similar to the yttrium separation and purification process and previously described.
  • the extracting agent can be the same or a different one (for example (di-(2-ethylhexyl)phosphoric acid (D2EHPA); 2- ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A (also called lonquestTM 801) in kerosene) or Bis (2,4,4-Trimethylpentyl) Phosphonic acid (lonquestTM 290)),
  • the strip solution 120 can be the same than 117, thereby providing a scandium raffinate 121 and a strip liquor 122 comprising europium and erbium.
  • yttrium can be extracted as described in US 3,751 ,553 (hereby incorporated by reference in its entirety).
  • yttrium can be extracted starting from a xenotime concentrate. It can be done by using three solvent extraction circuits.
  • DEHPA can be used to separate yttrium.
  • tri (caprylmethyl) ammonium nitrate Aliquat 336) can be used to extract and separate cerium and leave yttrium in the raffinate.
  • Tm, Yb, and Lu can be extracted by means of tri (caprylmethyl) ammonium thio cyanate.
  • yttrium behaves like a cerium element. From this step, high-purity of yttrium oxide can be obtained.
  • yttrium oxide can be extracted in two steps i.e. tri (caprylmethyl) ammonium nitrate can be used to separate a mixture La - Er/Y - Lu and then, a purification of yttrium is carried out using versatic acid.
  • tri (caprylmethyl) ammonium nitrate can be used to separate a mixture La - Er/Y - Lu and then, a purification of yttrium is carried out using versatic acid.
  • Solvent extraction is a selective separation procedure for isolating and concentrating valuable elements from an aqueous solution with the aid of an organic solution.
  • the aqueous solution containing the element of interest often at a low concentration and together with other dissolved substances (pollutants), is mixed (extraction) with an organic solvent containing a reagent.
  • the element of interest reacts with the reagent to form a chemical compound that is more soluble in the organic than in the aqueous solution. As a consequence, the element of interest is transferred to the organic solution.
  • the organic solution is mixed (stripping) with an aqueous solution whose composition is such that the chemical compound between the element and the reagent is split and, thus, the element is recovered in the "new" aqueous solution, in a pure form.
  • concentration of the element in the "new" aqueous solution may be increased, often to 10-100 times that of the original aqueous solution, through adjustment of the liquid flow rates.
  • the organic solution is returned for further extraction, either directly or after a fraction of it has been cleansed of impurities.
  • Important factors that govern this solvent extraction process can be, for example, the number of extraction, scrubbing and stripping stages, organic solvent concentration and diluent.
  • the aqueous phase containing the rare earth elements
  • the organic phase comprises an extracting agent as those recited in the present disclosure or alternatives in an organic solvent such as an aliphatic diluent.
  • Solvent extraction technique can be used as separation and purification procedure for the rare earth elements. Some of the following properties are particularly relevant when selecting an extracting agent or chemical extractant:
  • precipitation denotes the removal of the rare earth elements from solution by the addition of a chemical reagent to form a new, less soluble (solid) compound.
  • a complete precipitation can be carried out by oxalate, hydroxide, or other compounds.
  • Hydroxide precipitation and double sulphate can also be used.
  • ammonia can be used for carrying out hydroxide precipitation from nitrate or chloride solutions.
  • the double sulphates RE2(S0 4 )3*Na 2 S0 4 *nH 2 0 can be precipitated by either addition of sodium sulphate to the solution containing rare earth elements.
  • the precipitation reaction of trivalent rare earth elements in aqueous solution is according to the following equation:
  • the extraction can be highly dependent on the chloride ion concentration. In fact, the higher chloride ion concentration, the stronger tendency for iron(lll) complex formation and the better extraction. Iron(ll) also forms similar chloride complexes (FeCI 4 "2 ), however, the FeCI 4 "2 -organic complex is less inclined for extraction at prevailing conditions.
  • the organic solvent can be washed with pure water (for example nano water purity ). Iron(lll) can then be transferred to the water (strip solution) according to the expression:
  • Iron can be stripped as iron chloride. An equivalent amount of hydrochloric acid can also be washed out. The chloride concentration increases and the stripping of iron stops. Thus, the concentration of iron in the strip solution is limited by the simultaneous transfer of chloride ions. [00319] The below presented examples are non-limitative and are used to better exemplify the processes of the present disclosure.
  • the aluminum-containing material for example argillite
  • the aluminum-containing material can be finely crushed in order to help along during the following steps. For example, micronization can shorten the reaction time by few hours (about 2 to 3 hours).
  • a leaching step at room temperature is optionally carried out between the crushing step and the calcination step. This operation is, for example, carried out with hydrochloric acid HCI (32 wt%) and an argillite / acid ratio (weight / volume) of 1 :5 is used.
  • HCI hydrochloric acid
  • argillite / acid ratio weight / volume
  • about 65 % to about 93 % of the iron can then be dissolved.
  • the last step of the preparation of argillite comprises calcining the pretreated argillite. This can be accomplished at a calcinating temperature greater than 550 °C for a period of about 1 to 2 hours. For example, a heat treatment makes it possible to increase the quantity of extracted aluminum by about 30 % to about 40 % for the same period of time. In others words, the quantity of extracted aluminum is doubled.
  • a phase separation before calcination can be made in order to recover the acid and reduce heating costs.
  • Acid leaching can comprise reacting the crushed and roasted argillite with at least one acid solution (for example HCI) at elevated temperature during a given period of time.
  • the argillite / acid ratio can be of about of 1 :10 (weight / volume)
  • the HCI concentration can be of about 6 M or about 18 to 20 wt%
  • the temperature can be of about 100 °C to about 1 10 °C
  • the reaction time can be of about 30 minutes to about 7 hours. Under such conditions, more than about 90 % of the aluminum and about 100 % of the iron can be extracted in addition to impurities.
  • the leaching can be carried out at a temperature of about 150 °C to about 175 °C at a pressure of about 350 KPag to about 500 KPag during about 4 to about 7 hours.
  • the acid recovered can be re-utilized after having adjusted its titer either by adding either gaseous HCI, or by adding concentrated HCI (12 M).
  • the titer of the acid can vary from about 4 M to about 6 M depending on experimental conditions. With respect to the solid, it represents about 65 % to about 75 % of the initial mass of argillite, it can be valorized and be used again either as an ion exchange resin, or as an adsorbent.
  • the HCI leaching can be carried out under pressure (so to increase the reaction temperature) into an autoclave.
  • the rare earth element(s) recovery can be made, for example, at this stage, after carrying out the above mentioned acid leaching.
  • iron removal can be carried out by substantially selectively precipitating iron ions at certain pH values.
  • some extracting agents can be used as described in WO20081 1423.
  • a membrane can also be used in combination with such extracting agents
  • removal of iron can be carried out by ionic precipitation of the latter in basic medium for example at a pH of at least 10 or at a pH of about 11.5 to about 12.5.
  • the pH can also be about 3 to about 6, or about 3 to about 5 or about 3 to about 4.
  • Such a step can be made by adding a solution of NaOH, for example at a concentration of 10 M.
  • Other bases such as KOH can also be used.
  • a diluted base such as a solution of NaOH (for example NaOH at a concentration of 0.01 M to 0.02 M).
  • the liquid portion comprises aluminum and alkaline-earths
  • a substantially complete removal of the iron and of nearly all the impurities (other metals) can thus be achieved as insoluble and washed hydroxides.
  • it is possible to recover iron by using a refining step by liquid-liquid extraction through a hollow fiber membrane.
  • removal of iron can be carried out by using an extracting agent and a hollow fiber membrane.
  • Various extracting agents that could substantially selectively complex iron ions over aluminum ions (or aluminum ions over iron ions) could be used in such a step depending an Al / Fe ratio.
  • extraction can be carried out by using HDEHP (or DEHPA) di(2-ethylhexyl)phosphoric acid) as an extracting agent adapted to complex iron ions.
  • a concentration of about 1 M of HDEHP can be used in an organic solvent, such as heptane or any hydrocarbon solvent. Such an extraction can require relatively short contact times (few minutes).
  • aqueous phase / organic phase ratio can be of about 1 :1. It was observed that is possible to extract from 86 % to 98 % iron under such conditions. It will be understood that in the present case, iron is trapped in the organic phase.
  • a reverse extraction with hydrochloric acid (2 M or 6 M) and organic phase / acidic phase ratio of about 1 :0.5 can then be carried out. In such a case, the resulting aqueous phase is rich in Fe 3+ ions.
  • the rare earth element(s) recovery can be made, for example, at this stage, after carrying out the above mentioned iron recovery.
  • This step can also be carried in various ways.
  • aluminum ions can be precipitated under the form of AI(OH) 3 (for example an hydrated form of AI(OH) 3 ) at a pH of about 7 to about 9 or about 7.5 to about 8.5 or about 8.
  • the aluminum ions can be reacted with an extracting agent as descried in WO2008141423.
  • the solution obtained from the previous step using either the precipitation or the extraction technique is relatively clean and mainly contains aluminum for example about 90 % to about 95 % or even as high as about 90 % to about 99.8 % (without the alkaline-earths in the case of precipitation).
  • Recovery of the latter can be carried out by liquid-liquid extraction for example by using a same hollow fiber membrane and an extracting agent that is adapted to complex at least substantially selectively aluminum over other metals or residues.
  • an extracting agent that is adapted to complex at least substantially selectively aluminum over other metals or residues.
  • bis(2,4,4-trimethylpentyl) phosphinic acid such as the one sold under the name CyanexTM 272
  • CyanexTM 272 can be used as an extracting agent specific to aluminum.
  • this extracting agent can be used at a concentration of about 20 % v/v in an organic solvent such as heptane.
  • the ratios between the aqueous phase and the organic phase can be of about 1 :1 to about 1 :3.
  • the extraction temperatures can be of about 40 °C and the pH can be maintained at about 2.5 to about 3.5. It was observed that such a technique makes it possible to extract more than 70 - 90 % of the aluminum.
  • the reverse extraction can be carried out at a temperature of about 40 °C with hydrochloric acid (for example at a concentration of 6 M). Under this condition, more than 90 % of aluminum can be recovered.
  • the rare earth element(s) recovery can be made, for example, at this stage, after carrying out the above mentioned aluminum recovery.
  • Al 3+ can be converted into aluminum hydroxide (for example an hydrated form of AI(OH) 3 by addition of a base such as NaOH.
  • AI(OH) 3 can be converted into alumina (alumina Al 2 0 3 ) by calcinating AI(OH) 3 for example at a temperature of about 800 °C to1200 °C.
  • Al 3+ can also be converted into AICl3»6H 2 0 and upon quenation HCI can be recovered and Al 2 0 3 be produced
  • Rare earth elements recovery can then be made, for example, at this stage by using any of the technology previously mentioned in the present disclosure for doing so. For example, it can be carried out by using a technology as defined in any one of Figs. 3, 3A 4A, 4B, 4C, 4D, 5A, 5B, 5C, 5D, 5E, 5F, 5G, 5H and 26.
  • the processes shown in Figs. 5E, 5F, 5G and 5H are similar to the processes shown in Figs. 5A, 5B, 5C and 5D, with the exception that they can comprise an extra purification step by using an ion exchange column, an optional plasma purification step, an extra acid regeneration step, and an extra calcination step.
  • the at least one rare earth element contained in the residual solutions obtained from the above-mentioned process can be in low concentration for example at a concentration of less than about 50, about 25, 15, 10, 5, 4, 3, 2 or 1 ppm in the lixiviate or leachate or a solution obtained during the process .
  • the rare earth elements can be concentrated in the latter stage of the process prior to extraction with solvent(s). It was demonstrated that through an internal concentration loop, concentration can be significantly increased (for example from 100 to 1000 times) thereby providing more effective conditions for substantially selectively precipitating, extracting and/or isolating at least one rare earth element.
  • This material was thereafter leached in a two-stage procedure at 140-170 °C with 18-32 weight % HCI.
  • the HCI solution was used in a stoichiometric excess of 10-20% based on the stoichiometric quantity required for the removal of the acid leachable constituents of the clay.
  • the clay was contacted for 2.5 hours with required amount or certain proportion of the total amount of hydrochloric acid. After removal of the spent acid, the clay was contacted again with a minimum 18 weight % hydrochloric acid solution for about 1.5 hour at same temperature and pressure.
  • the purity of the silica was 99.67 % through an extra leaching step.
  • AICI 3 15-20%; FeCIs : 4-6%; FeCI 2 : 0.5-2.0%; MgCI 2 : 0.5-2.0 %; REE-CI : 0.1 - 2 % Free HCI : 5-50 g/l
  • Spent acid was then crystallized using about 90 to about 98% pure dry hydrochloric acid in gas phase in two stages with less than 25 ppm iron in the aluminum chloride hexahydrate formed.
  • concentration of HCI in solution was about 22 to about 32 % allowing 95.3 % of Al 2 0 3 recovery.
  • the recovered crystallized material (hydrate form of AICI 3 having a minimum purity of 99.8 %) was then calcined at 930°C or 1250°C, thus obtaining the a form of the alumina (1250 °C). The ⁇ form being obtained at 930 °C.
  • HCI concentration in gas phase exiting the calcination stage was having a concentration of about 21 to about 32 % by weight and was used (recycled) for crystallization of the AICI 3 and MgC . Excess of hydrochloric acid is absorbed at the required and targeted concentration for the leaching steps.
  • Iron chloride (about 90% to about 95% in ferric form) is then sent to a hydrothermal process in view of its extraction as pure hematite (Fe 2 0 3 ). This can be done by using the technology described in WO 2009/153321 of low temperature hydrolysis with full heat recovery from calcining, pyrohydrolysis and leaching stage.
  • step 10 in both processes of Figs. 1 and 2) it was demonstrated that about 90 to about 98 % by weight of the elements (Al, Fe, Mg and rare earths elements such as (Sc, Ga, Y, Ce) found in the starting material were recovered. It can be estimated that the processes for recovering rare earth elements from an aluminum-containing material disclosed in the present disclosure can be efficient for recovering about 90 % of the rare earth elements. Thus, with respect to the examples of processes provided in Figs. 1 and 2, it can be estimated that the overall yield for recovering the at least one rare earth element from the aluminum-containing material would be about 80 % to about 90 %.
  • Rare earth elements can be extracted from the mother liquor of the hydrolyzer (where silica, aluminum, iron and a great portion of water have been removed) following pre-concentration from crystallization to the hydrolyzer.
  • the rare earth elements In the form of chlorides the rare earth elements (RECI) are considerably concentrated and ready to be extracted. Rare earth elements have demonstrated to concentrate by a factor 5 to 10 in average within the hydrolyzer itself on a single pass through it (without any concentration loop).
  • concentration factors obtained for certain elements within the hydrolyser were as follows :
  • Remaining magnesium chloride is sparged with dry and highly concentrated hydrochloric acid and then calcinated to MgO while recovering acid at its azeotropic point.
  • a similar feed material (bauxite instead of clay) was processed as per in example 2 up to the leaching stage and revealed to be easily leachable under the conditions established in example 2. It provided an extraction percentage of 100% for the iron and over 95 % for aluminum. The process was found to be economically viable and no harmful by-products (red mud) were generated. A rare earth elements recovery (as a mixture) of about 90 to about 95 % or about 91 % (by weight as compared to the starting material) was observed Samples tested had various concentrations of Al 2 0 3 (up to 51%), Fe 2 0 3 (up to 27%) and MgO (up to 1.5%). Gallium extraction of 97.0 % was observed. Scandium extraction was 95 %.
  • Gallium chloride and rare earth chloride hydrates from Alfa Aesar GmbH & Co KG, Düsseldorf, Germany were used in the experiments.
  • the products are of chemically pure quality (99.9 %). Chemicals were dissolved in tap water to obtain a stock solution.
  • Aluminum chloride and iron chloride are of technical grade.
  • Fig. 6 show the dependency of gallium and rare earth precipitation yields as a function of the pH.
  • An increase in the pH increases the gallium and scandium precipitation yield and approaches 98 % for gallium and scandium at a pH around 2.0.
  • Fig. 6 also shows that there is an increase in aluminum co-precipitation at pH levels higher than 2.0. No cerium and yttrium precipitate under these conditions. Therefore, it was shown that if the pH in the precipitation process is maintained at or below 2.0, gallium and scandium precipitates with minimizing aluminum, iron(ll) and rare earth elements co-precipitation.
  • iron(ll) chloride in the order of 100 g/L Fe was added to the gallium and scandium feed solution.
  • the following test parameters were defined:
  • Fig. 7 shows, for the precipitation of gallium - the influence of iron(ll) (aqueous solution (270 mg/L Ga, 90 mg/L Sc and 35 g/L HCI, Eh +380 mV). Fig. 7 above shows that the iron(ll) concentration did not have significant effect on the precipitation of gallium.
  • Fig. 8 show the influence of iron(ll) contamination of scandium precipitation as a function of pH (aqueous solution (270 mg/L Ga, 90 mg/L Sc and 35 g/L HCI, Eh +380 mV).
  • aqueous solution 270 mg/L Ga, 90 mg/L Sc and 35 g/L HCI, Eh +380 mV.
  • the conditions are the same than in Fig. 7
  • the precipitation pH of scandium increased from about pH 2 to about pH 3.5 which may have been due to the absence of iron in the aqueous feed solution.
  • the final concentration of scandium at pH around 4 achieved 18 mg/L Sc, equivalent to a precipitation yield of 80 %.
  • Precipitation reagent magnesium oxide and caustic soda
  • Fig. 9 shows that the precipitation of the rare earth hydroxides starts at pH 6 and have their maximum at pH around 8.0.ln Fig. 9, an aqueous solution in which the initial pH was 1 and the Eh was +340 mV.
  • a pre-neutralized aqueous solution from the hydroxide precipitation tests containing 1.8 g/L Ce, 2.3 g/L Y, 1.8 g/L Er, 2 g/L Nd and 0.5 g/L Pr was heated up to 50 to 60 °C. Oxalic acid slurry was added. The pH value was then adjusted by adding drop wise ammonia solution to precipitate and remove the rare earth elements. To investigate the influence on the amount of precipitation reagent, the following test parameters were defined:
  • Precipitation reagent oxalic acid as di-hydrate
  • Fig.10 shows the solubility of the rare earth oxalates with increasing oxalic acid concentration at constant acidity (pH 1.2).
  • the precipitation concentration ranged from 0 .06 mol/L to 1 mol/L oxalic acid, (aqueous solution (LRE and HRE, final pH 1.2, Eh +340 mV).
  • the solubility of the rare earth oxalates decreases as oxalic acid concentration increase and reached a precipitation yield of more than 99 % all of the investigated rare earth elements if the added oxalic acid concentration is 0.15 mol/L or more.
  • Iron(ll) concentration 100 g/l
  • Fig. 1 1 shows the rare earth elements and iron precipitation as a function of oxalic acid concentration at constant acidity (pH 1.2). The figure indicates that precipitation of the rare earth elements do not proceed at high iron(ll) contamination.
  • Table 3 The results of the rare earth elements removal tests are summarised in table 3.
  • reagent tri-butyl phosphate (TBP) was chosen.
  • iron(lll) was being co-extracted with TBP.
  • iron(lll) was removed either by solvent extraction or pre-treated by metallic iron in order to remove of iron(lll) by the reduction.
  • Fig. 12 shows equilibrium data for extraction of iron from a iron(lll) chloride solution.
  • the organic solution contained 90 vol.-% TBP in aromatic kerosene (Solvesso150).
  • Co-extracted gallium can be partially removed by scrubbing with water at high phase ratio. This scrubbing reduces the gallium losses from the loaded organic solution.
  • Equilibrium data for scrubbing of gallium from the loaded organic solution is shown in Fig. 13 (equilibrium curve, org. solution (90 vol.-% TBP, containing 110 g/L Fe, 0.13 g/L Ga) aqueous solution (water).
  • Fig. 14 org. solution (90 vol.-% TBP, containing 110 g/L Fe, 0.13 g/L Ga) Aqueous solution (water).
  • the gallium and scandium feed solution was prepared by dissolution of the gallium/scandium precipitate from a hydrochloric acid solution, containing 10 mol/L HCI.
  • the experiments were carried out with 50 vol.-% TBP diluted in aliphatic kerosene (D85). Isodecanol was used in the experiments as modifier to prevent third phase formation. Equilibrium data for gallium and scandium extraction is shown in Fig. 15 (org. solution (50 vol.-% TBP in kerosene; aq. solution 6 g/L Ga, 2.2 g/L Sc and 10 mol/L HCI).
  • Fig. 16 shows the co-extraction of hydrochloric acid during the gallium and scandium extraction (org. solution (50 vol.-% TBP in kerosene; aq. solution (6 g/L Ga, 2.2 g/L Sc and 10 mol/L HCI).
  • the organic solvent is then further loaded with gallium and scandium for conducting scandium scrubbing and gallium stripping experiments.
  • To remove scandium from the loaded organic solution 5 mol/L, 6 mol/l and 7 mol/L HCI solutions at O/A ratio of 1 to 1 were used. This scrubbing significantly reduces the quantity of scandium from the loaded organic solution.
  • the influence on the hydrochloric acid scrub solution of scandium scrubbing efficiency is shown in table 5.
  • Fig. 18 Equilibrium data for gallium stripping from the loaded organic solution is shown in Fig. 18 (org. solution (7.5 % TBP in kerosene, 0.4 g/L Ga; aqueous solution (water).
  • composition of aqueous feed and raffinate during the solvent extraction tests are summarised in Table 6.
  • organo- phosphorus extractants are pH dependent extractants.
  • Commercial reagents available such as di(ethylhexyl)phosphoric acid (D2EHPA), di(ethylhexyl)phosphonic acid (lonquest 801) can be used.
  • the selectivity is calculated as the quotient of the distribution factors of yttrium to that of cerium.
  • Fig. 19 org. solution (10 vol.-% reagent in kerosene; aq. solution (6.4 g/L Y, 107 g/L Ce, initial pH 1.5, Eh +430 mV. below, the yttrium/cerium selectivity for lonquest 801 is raising until pH 1 and then falling.
  • reagent di(ethylhexyl)phosphonic acid (lonquest 801) was chosen.
  • the experiments were carried out with 10 vol.-% lonquest 801 diluted in aliphatic kerosene (D85). No modifier was used in the experiments.
  • the pH value during the yttrium extraction was kept constant at pH 1.4 by adjusted drop wise with sodium hydroxide solution (2 mol/L NaOH).
  • Equilibrium data for yttrium extraction from an aqueous solution containing yttrium and cerium is shown in Fig. 21 (org. solution (10 vol.-% lonquest 801 in kerosene; aq. solution (6.4 g/L Y, 107 g/L Ce, initial pH 1.5, Eh +430 mV).
  • the yttrium recovery rate was more than 99 %.
  • the maximum yttrium loading of 10 % vol.-% lonquest 801 reagent was about 10 g/L yttrium.
  • Feed solution (6,4 ⁇ -' ⁇ Y » 107 g/l Ce, initial pH 1.5, Eh +430 mV)
  • Fig. 23 Equilibrium data for yttrium stripping from loaded organic solution is shown in Fig. 23 (org. solution (10 vol.-% lonquest 801 in kerosene, containing 1 g/L Y); aqueous solution (3.5 mol/L HCI) .
  • the feed solution was prepared by dissolution of dysprosium chloride, erbium chloride and yttrium chloride in tap water.
  • the experiments were carried out with tri-butyl phosphate (TBP), Alamine® 336 and Aliquat® 336 diluted in aliphatic kerosene (D85).
  • TBP tri-butyl phosphate
  • Alamine® 336 Alamine® 336
  • Aliquat® 336 diluted in aliphatic kerosene
  • the pH value was adjusted at pH 3 by drop wise addition of ammonia solution (25 %).
  • the organic solutions were contacted for about 10 to 15 minutes in stirred beakers.
  • the organic to aqueous (O/A) ratio was 1/1.
  • the separation and purification of dysprosium and erbium by TBP, Alamine® 336 and Aliquat® is shown in Table 8.
  • Table 11 Selected conditions for extraction of gallium and scandium.
  • Gallium was calcined and the purity of the obtained Ga 2 03 was 99.99 +%.
  • the impurities were CI at 8.9 ppm and Al at 1.1 ppm.
  • Section 1 Iron(lll) Removal. Removal of iron(lll) from feed solution by solvent extraction using tri-butyl phosphate (TBP) in kerosene;
  • TBP tri-butyl phosphate
  • Section 2 Final Iron Removal. Removal of iron by reduction using metallic iron;
  • Section 3 Gallium and Scandium Precipitation. Removal of gallium and scandium using limestone or magnesium oxide;
  • Section 4 Gallium and Scandium Separation. Separation and recovery of gallium and scandium from re-leach solution containing 10 mol/l hydrochloric acid and based on solvent extrcation using the tri-butyl phosphate (TBP) in kerosene;
  • TBP tri-butyl phosphate
  • Section 5 Yttrium and other rare earth precipitation. Removal of yttrium and other rare earth elements by neutralization and precipitation using limestone, followed by re-leaching in diluted hydrochloric acid;
  • Section 6 Yttrium Recovery. Separation and recovery of yttrium from the resulting solution in section 5 by solvent extraction using di(ethylhexyl) phosphonic acid (lonquest 801); and
  • Section 7 Yttrium Separation from HRE. Separation and recovery of yttrium from heavy rare earth, mainly dysprosium and erbium by solvent extraction using tri-butyl phosphate (TBP) in kerosene.
  • TBP tri-butyl phosphate
  • the prepared aqueous feed solution containing 40 % iron(lll) chloride and 270 mg/L of gallium (201) was fed to the iron removal circuit. Iron was counter-currently extracted with an organic solution containing 90 % TBP dissolved in aromatic kerosene (Solvesso150) (202). The achieved iron extraction yield was 90 %. Co-extracted gallium was accumulated in the organic phase to 0.13 g/L gallium. The resulting organic solution (203), containing iron and small amounts of gallium, was fed to the scrubbing circuit. Here, gallium was counter-currently scrubbed with an aqueous water solution (204) at high phase ratio. The organic solvent was then sent to a stripping circuit. Here, iron (206) is counter-currently stripped with water (207) before the organic solution (205) was returned back to the extraction circuit.
  • Co-extraction of iron(lll) can be prevented and/or by prior reduction to iron(ll) using iron (0).
  • the resulting raffinate (209), containing aluminum, gallium, scandium, rare earth elements and extracted iron(lll) was treated with stoichiometric amounts of iron powder (210) to eliminate the iron(lll) ions. Starch can also be used for carrying out the reduction.
  • the resulting filtrate (215) from the gallium and scandium re- leaching step was fed to the gallium and scandium separation circuit.
  • Gallium and scandium are counter-currently extracted with an organic solution containing 50 vol.-% TBP dissolved in aliphatic kerosene (D85) (216).
  • the achieved gallium and scandium extraction yield was more than 99 %.
  • Co-extracted iron was accumulated in the organic phase to 0.2 g/L Fe.
  • the resulting organic solution (218), containing gallium and scandium and small amounts of iron was fed to the scrubbing circuit.
  • scandium was counter-currently scrubbed with an aqueous water (219) solution at high phase ratio so as to provide product (221).
  • the organic solvent (220) was then sent to a stripping unit where gallium was counter-currently stripped with water (222) before the organic solution (223) is returned back to the extraction circuit and gallium (224) is recovered.
  • a raffinate of hydrochloric acid is also recovered (217).
  • the filtrate (225) from the gallium and scandium precipitation step was fed to a further neutralization circuit.
  • rare earth elements are precipitated with limestone (226) by raising the pH to 8 during 60 min under controlled RedOx potential and at elevated (60 °C) temperature. A precipitation of more than 99 % of the investigated rare earth elements was achieved. Remaining iron(ll) will precipitate together with the rare earth elements.
  • the precipitate (227) was then prepared for re-leaching in concentrated hydrochloric acid solution (228).
  • the resulting product (229) from the gallium and scandium precipitation step will be fed to the extraction circuit for yttrium.
  • Yttrium is counter-currently extracted with an organic solution (230) containing 10 vol.-% lonquest 801 dissolved in aliphatic kerosene (D85).
  • the achieved yttrium extraction yield was more than 99 %.
  • Co-extracted cerium was accumulated in the organic phase to 0.1 g/L Ce.
  • the organic phase (232) can be treated with a scrub solution (233) such as 1 N HCI so as to remove cerium and obtain composition (234).
  • a scrub solution such as 1 N HCI so as to remove cerium and obtain composition (234).
  • the raffinate of LRE (Ce, Nd, Eu, Pr) (231) can eventually be treated so as to separatethem from one another and optionally purifify them (see Fig. 5G).
  • dysprosium and erbium are removed from the yttrium strip liquor (237) after neutralization.
  • Dysprosium and erbium are counter-currently extracted with an organic solution containing 80 vol.-% tri-butyl phosphate (TBP) , dissolved in aliphatic kerosene (D85) (238), thereby yielding the raffinate of yttrium (239).
  • TBP tri-butyl phosphate
  • D85 aliphatic kerosene
  • a heavy rare earth extraction yield of more than 99 % is achieved under controlled pH conditions.
  • the resulting organic solution (240), containing heavy rare earth and small amounts of yttrium, is fed to the scrubbing function.
  • the yttrium (242) is scrubbed with water (241) at high phase ratio, counter- currently in multistage mixersettler equipment.
  • the scrubbing liquor (242) is returned to the feed solution.
  • the organic solvent, depleted from yttrium (243) is stripped with water (244) and returned to the extraction loop.
  • the dysprosium and erbium strip liquor (245) is the feed solution for dysprosium and erbium separation.
  • the obtained yttrium was calcined into Y2O3 and a purity of 99.9 +% was obtained.
  • the impurities were Si at 26 ppm, Dy at 51 ppm and Al at 6.2 ppm.
  • the pregnant leach solution (329) (after fine filtration) was the feed solution to the rare earth separation steps.
  • the present aqueous feed solution comprises cerium, praseodymium, neodymium, europium, dysprosium, erbium and yttrium is contacted with D2EHPA or lonquest 801 in kerosene. Alkali is used to adjust the pH during the extraction procedure.
  • Dysprosium, erbium and also yttrium (HRE) are extracted and leaving cerium, praseodymium, neodymium and europium (LRE) in the raffinate (331).
  • the loaded organic phase is then selectively scrubbed with hydrochloric acid (1 to 2 M HCI) to remove the co-extracted LRE.
  • the extract contained dysprosium, erbium and yttrium, is then stripped with hydrochloric acid (3 to 4 M HCI) (336).
  • the separation of yttrium from the strip liquor (337) can be done by extracting it with tri-butyl phosphate (TBP) in kerosene.
  • TBP tri-butyl phosphate
  • the treatment can be done in a multi stage procedure, and ending up in a final stripping of the loaded organic with water (344). All HRE substantially selectively extracted, leaving yttrium in the raffinate (339).
  • the strip liquor (345), containing HRE, forms the source for further separation of the heavy rare earth elements (HRE).
  • the final strip liquor from the yttrium separation process (345) containing dysprosium and erbium was treated by solvent extraction using D2EHPA or lonquest 801 in kerosene, leaving dysprosium in the raffinate (347). Alkali is used to adjust the pH during the extraction circuit.
  • the loaded organic phase is then scrubbed with hydrochloric acid (2 to 3 M HCI) to remove the co-extracted dysprosium.
  • the extract, containing erbium is then stripped with hydrochloric acid (3 to 4 M HCI) (346) so as to yield the strip liquor of erbium (348).
  • the so-obtained dysprosium was calcined in order to produce Dy 2 0 3 having a purity of 99.9 + %.
  • Other impurities were mainly Yb at 440 ppm and Ca at 100 ppm.
  • the so-obtained erbium was calcined in order to produce Er 2 0 3 having a purity of 99.9 + %.
  • Other impurities were mainly Y at 390 ppm and Al at 140 ppm.
  • the raffinate (331 A) from the primary separation is fed to oxidation and cerium precipitation unit.
  • the oxidation of cerium is achieved by addition of an oxidation reagent.
  • an oxidation reagent for example, sodium hypochlorite (349) can be used.
  • the precipitation of cerium hydroxide can be carried at a pH of about 0.5 to about 1.5 or pH of about 1 after adding of alkali (350).
  • the outflow from the cerium oxidation (352) is fed to the europium separation circuit.
  • the filter cake (351), containing cerium hydroxide was washed with acidic water, dewatered and stored for further processing.
  • the resulting filtrate (352) from the cerium recovery step was used to separate europium from praseodymium and neodymium.
  • the aqueous feed solution was contacted with D2EHPA or lonquest 801 in kerosene.
  • Europium was extracted and leaving praseodymium, neodymium in the raffinate (354).
  • Alkali was used to adjust the pH during the extraction circuit.
  • a scrubbing section removed co-extracted praseodymium and neodymium by using weak hydrochloric acid (0.5 to 1.5 M HCI).
  • the extract, containing europium was then stripped with hydrochloric acid (2 to 3 M HCI) (353).
  • the reduction of europium(lll) was achieved by addition of an reduction reagent.
  • europium (355) can be reduced by zinc powder or alternatives (361).
  • the precipitation of europium sulphate can be carried out after addition of sodium sulphate (362).
  • the outflow from the europium reduction circuit was fed to the effluent treatment.
  • the filter cake (363), containing europium sulphate was washed with acidic water, dewatered and stored for further processing.
  • the raffinate (354) from the europium separation consists mainly of praseodymium and neodymium.
  • the separation of praseodymium and neodymium was carried out with D2EHPA or lonquest 801 in kerosene. Neodymium was extracted, leaving praseodymium in the raffinate (357). Alkali was used to adjust the pH during the extraction circuit.
  • the loaded organic phase was then scrubbed with hydrochloric acid (2 to 3 M HCI) (356) to remove the co-extracted praseodymium.
  • hydrochloric acid 3 to 4 M HCI
  • the so-obtained neodymium was calcined into Nd 2 0 3 and a purity of 99.9 +% was obtained.
  • the impurities were K at 330 ppm, Pr at 280 ppm and Y at 50 ppm.
  • Another starting material has been used for preparing acidic compositions comprising various components.
  • a material that is a concentrate of rare earth elements and rare metals (particularly rich in zirconium) has been tested.
  • Table 14 shows the results of the leaching carried out on such a starting material using a similar process as shown in Figs. 1 and 2 and as detailed in Examples 1-3. It can thus be inferred from the results shown in Table 14 that the rare earth elements and rare metals extracted and present in the obtained leaching composition can eventually be isolated by the processes of the present disclosure such as, for example, by those presented in Examples 4 and 5.
  • the results obtained were superior by at least 20 % as compared to leaching carried out with H 2 S0 4 .
  • the initial composition measured was:
  • the samples were leached in batch mode at about 150 to about 160°C for a 6 hour duration with 18.0 wt % HCI + 5% excess.
  • Iron powder 0 - Fe 2 0 3 removed from hydrolysis
  • HCI (2% wt): 0.75 Kg/h as a strip solution ion REE 5x separation and releaching ree oxalates;
  • Nano water 10 kg/h for solution strip and washing of precipitation
  • Oxalic acid 325 g/h for precipitation of ree oxalates
  • TBP 5x organic solution 6.5 g/h for gallium records and yttrium separation; Kerosene: ⁇ 5 g/h.
  • any compositions comprising at least one rare earth element and/or at least one rare earth metal can be used as a starting material.
  • any compositions comprising at least one iron ion and at least one rare earth element can be used as a starting material.

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Abstract

L'invention porte sur des procédés pour la récupération d'au moins un élément terre rare. De tels procédés comprennent l'obtention d'une composition acide comprenant (i) au moins un élément terre rare et éventuellement au moins un métal rare ; et la réaction de la composition avec un agent précipitant afin de faire précipiter pratiquement sélectivement un premier élément terre rare et éventuellement un premier métal rare. Par exemple, divers éléments terres rares (tels que le scandium, l'yttrium, le lanthane, le cérium, le praséodyme, le néodyme, le prométhium, le samarium, l'europium, le gadolinium, le terbium, le dysprosium, l'holmium, l'erbium, le thulium, l'ytterbium, le lutétium, etc.) et divers métaux rares (tels que l'indium, le zirconium, le lithium, le gallium, etc.) peuvent être extraits à l'aide de tels procédés.
PCT/CA2013/000226 2012-03-19 2013-03-13 Procédés pour la récupération d'éléments terres rares et de métaux rares WO2013138900A1 (fr)

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CN103924078A (zh) * 2014-03-18 2014-07-16 包头稀土研究院 料液中添加氯化铵提高钐和锌萃取分离因素的方法
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US20140353164A1 (en) * 2013-05-28 2014-12-04 Korea Institute Of Geoscience And Mineral Resources Device for electrowinning europium with channeled cell and method thereof
CZ305491B6 (cs) * 2013-12-19 2015-10-29 Vysoká škola chemicko-technologická v Praze Koncentrační separace india a galia z roztoků obsahujících měď srážením kyselinou šťavelovou
CN103924079A (zh) * 2014-03-18 2014-07-16 包头稀土研究院 提高有机皂化度增大钐和锌在氯化铵体系中萃取分离因素的方法
CN103924078A (zh) * 2014-03-18 2014-07-16 包头稀土研究院 料液中添加氯化铵提高钐和锌萃取分离因素的方法
CN104046803A (zh) * 2014-06-04 2014-09-17 吉林吉恩镍业股份有限公司 从含钪物料中采用矿浆萃取方式回收钪的方法
US11345977B2 (en) * 2014-10-10 2022-05-31 Rare Element Resources Ltd. Processing for the extraction of rare earth elements
US11286170B2 (en) 2015-01-27 2022-03-29 Reed Advanced Materials Pty Ltd Processing of lithium containing material including HCl sparge
RU2582404C1 (ru) * 2015-02-06 2016-04-27 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) Способ очистки скандия от циркония, тория и железа
RU2603418C1 (ru) * 2015-07-24 2016-11-27 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Способ извлечения скандия и редкоземельных элементов из красных шламов
RU2674717C2 (ru) * 2016-11-28 2018-12-12 Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" Способ получения концентрата скандия из скандийсодержащего раствора
WO2018223192A1 (fr) * 2017-06-08 2018-12-13 Urban Mining Pty Ltd Procédé de récupération de lithium
CN107419098A (zh) * 2017-08-25 2017-12-01 广东省稀有金属研究所 一种从稀土磷酸盐矿物的硫酸浸出液中萃取稀土的方法
RU2694866C1 (ru) * 2019-02-18 2019-07-17 Акционерное Общество "Группа компаний "Русредмет" (АО "ГК "Русредмет") Способ извлечения скандия из скандийсодержащего сырья
CN110004292A (zh) * 2019-04-19 2019-07-12 湖南雅城新材料有限公司 一种废弃硫酸锰溶液净化降低钙镁含量的工艺
CN110004292B (zh) * 2019-04-19 2020-12-29 湖南雅城新材料有限公司 一种废弃硫酸锰溶液净化降低钙镁含量的工艺
US20210347652A1 (en) * 2020-05-11 2021-11-11 University Of Wyoming Methods and apparatus for separation of rare earth elements from coal ash
US11814299B2 (en) * 2020-05-11 2023-11-14 University Of Wyoming Method for separation of rare earth elements from coal ash using supercritical carbon dioxide
CN111778413A (zh) * 2020-07-03 2020-10-16 神华准能资源综合开发有限公司 一种基于树脂法从粉煤灰中提取镓的方法
CN114150167A (zh) * 2020-09-08 2022-03-08 中国科学院过程工程研究所 一种膜过程强化的无皂化稀土萃取分离新技术

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US20150104361A1 (en) 2015-04-16
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