EP3710607A1 - Récupération sélective de métaux des terres rares à partir d'une suspension acide ou d'une solution acide - Google Patents

Récupération sélective de métaux des terres rares à partir d'une suspension acide ou d'une solution acide

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Publication number
EP3710607A1
EP3710607A1 EP18879504.1A EP18879504A EP3710607A1 EP 3710607 A1 EP3710607 A1 EP 3710607A1 EP 18879504 A EP18879504 A EP 18879504A EP 3710607 A1 EP3710607 A1 EP 3710607A1
Authority
EP
European Patent Office
Prior art keywords
solution
acidic
slurry
ppm
acid
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP18879504.1A
Other languages
German (de)
English (en)
Other versions
EP3710607A4 (fr
Inventor
Wen-Qing Xu
Shailesh PATKAR
Louie I. BEDES
Marie Ysabel R. ABELLA
Gomer M. ABRENICA
Vincent D. MATTERA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
II VI Delaware Inc
Original Assignee
II VI Delaware 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 US16/186,897 external-priority patent/US10808296B2/en
Application filed by II VI Delaware Inc filed Critical II VI Delaware Inc
Publication of EP3710607A1 publication Critical patent/EP3710607A1/fr
Publication of EP3710607A4 publication Critical patent/EP3710607A4/fr
Pending legal-status Critical Current

Links

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
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • C01F17/13—Preparation or treatment, e.g. separation or purification by using ion exchange resins, e.g. chelate resins
    • 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
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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 invention is directed to a method for selective recovery of valuable metals, specifically, rare earth metals, from an acidic slurry or acidic solution.
  • Solvent extraction is widely used for recovering valuable metals that are dissolved in an aqueous solution, as disclosed in United States Patent Nos. 4,041,125; 4,624,703; 4,718,996; 4,751,061; 4,808,384; 5,015,447; 5,030,424; 5,708,958, 6,110,433; 6,238,566; 7,138,643; 7,282,187; 7,799,294; 7,829,044; 8,062,614; 8,177,881; 8,328,900 and United States Patent Application Publication Nos. 2004/0031356; 2005/0107599; 2006/0024224; 2010/0089764; 2010/0282025; and 2012/0160061.
  • the valuable metals are typically acid- leached into the aqueous solution from ores and/or other feedstock and a clear aqueous solution containing valuable metals is separated from the acid-leached ore slurry by filtration and washing. The solvent extraction is then performed on the clear aqueous solution.
  • the feedstock may include different rare earth metal-containing ores and minerals, such as titania ore tailing, uranium ore tailing, red mud that is typically generated from an aluminum Bauxite-Bayer process, and other such materials.
  • the ore and/or feedstock that contain these valuable metals may be pre-processed for the purpose of achieving threshold leachability and commercial viability.
  • Such processing may include particle- size reduction, hydrothermal treatments involving hydrothermal reactions, high- temperature treatments involving solid phase reactions, meta-glassy-phase high temperature reactions, complete melting high temperature liquid phase reactions, etc.
  • an organic liquid or solvent phase containing extractant(s) that can chemically react with a valuable metal or multiple valuable metals is well mixed with the aqueous solution that contains such valuable metal ion(s).
  • the valuable metal ion or multiple valuable metal ions are then transferred into the organic phase of the extractive organic solvent during mixing.
  • Intensive mixing ensures a complete transfer of the valuable metal ion(s) from the aqueous phase to the organic phase.
  • the process typically undergoes a phase separation via gravitational settling or a high-g centrifugal phase separation mechanism, such as a centrifuge.
  • a continuous process using a combination of (1) mixing an organic extractive solvent and an aqueous solution containing valuable metal(s) and (2) settling the mixture of such aqueous and organic phases for phase separation by gravity is called a mixer and settler process.
  • Such a mixing and settling process can also be achieved with a batch process in a batch mixing tank in a manufacturing plant or in a beaker equipped with a magnetic stirrer or a mechanical mixer in a chemical lab.
  • the separated organic phase is the desirable product that contains the valuable metals.
  • the separated aqueous phase is called raffinate which, ideally, contains minimum amounts of the targeted valuable metal(s).
  • phase separation process may need to be extended to a level that is not economically feasible.
  • the formed emulsions might be stable enough such that economical phase separation is impossible, and, in other cases, phase separation may be incomplete, which results in a loss of valuable organic solvent and valuable metals contained in the lost organic solvent.
  • Emulsions are classified into two different forms, oil-in-water and water-in-oil, both of which are typically formed under intense mixing conditions due to the formation of oil droplets in water or water droplets in oil.
  • the droplet size of such newly formed emulsions decreases with the level of mixing. Intense mixing conditions lead to emulsions with smaller droplet sizes.
  • Lucas and Ritcey inventors of United States Patent No. 3,969,476, disclose a sieve- in-plate pulse column process, called the“solvent-in-pulp” process, in which soluble valuable metal(s) is extracted from ore slurries. Lucas and Ritcey also realize that up to the time of their patent disclosure, no process had run successfully on a plant scale for the recovery of valuable metal(s) directly from leached ore slurries. They also state that early work on mixer-settlers proved unsatisfactory because the excessive agitation caused stable emulsions and crud formation with amines (the extractant used in Lucas and Ritcey’ s disclosure).
  • any leached ore slurry has a very broad particle size distribution. Large particles may not be well-suspended and may plug the sieve holes of the column plates. Small particles might flocculate to form large particle agglomerates due to a lack of shear in the column and these large agglomerated particles might also plug the sieve holes of the column plates.
  • solids content of acid-leached ore slurries may be three to five magnitudes higher, from a few percent to as high as 50-70%.
  • the extractant molecules in the organic extractive solvent are of the amine type.
  • Organic extractive solvents of the amine type are typically cationic and react with and bond to the anionic surface sites of silicate/silica-related residues in the ore slurry. Such bonding of the amine type extractive molecules in the organic extractive solvent to the anionic surface sites of the silica/silicate- related residues leads to a significant loss of the organic extractive solvent.
  • Lucas and Ritcey’s process requires a pretreatment with organic non-ionic hydrophilic materials which are adsorbed by the gangue solids for the purposes of decreasing the affinity of the gangue solids for the amine; however, solvent loss still exists, which is a substantial cost for recovering valuable metal or metals from acid-leaching slurry that contains a very low concentration of valuable metal or metals.
  • solvent extraction process experiences more or less the problems of (1) solvent loss, (2) difficulties in achieving a complete organic-aqueous phase separation, (3) formation of emulsions, (4) crud formation, and (5) poor economics in dealing with a large volume of acid-leaching solution and/or acid-leaching slurry that contains a very low concentration of valuable metal or metals, etc.
  • an ion-exchange resin is typically considered as an ionic salt in which exchangeable ions are attached to an insoluble organic matrix.
  • Such exchangeable ions in ion-exchange resins may be cations or anions, and the resins are referred to as a cation exchange resin or an anion exchange resin, respectively.
  • Cation exchange resins may be used to uptake valuable metal ion(s) from acid-leaching solutions and/or acid-leaching slurries.
  • Typical ion exchange resins are categorized into strong resins, weak resins, and resins that lie between strong resins and weak resins.
  • Dow Chemical produces strong cation ion-exchange resins that have sulfonic acid functional groups, such as DowexTMG-26(H), and chelating cation ion-exchange resins that have iminodiacetic acid groups, such as AmberliteTM 7481.
  • Purolite ® produces a cation ion-exchange resin, Purolite ® S957, that has a phosphoric acid functional group.
  • Alkali ion forms, such as sodium forms, or proton forms of these resins may be used to uptake valuable metal or metals.
  • the exchangeable ions of the ion exchange resin may be displaced; generally, (1) an ion of higher charge displaces an ion of lower charge, (2) between similarly charged ions, the ions of a large radius displaces the one of the smaller radius, and (3) the displacement occurs according to the law of mass action.
  • the majority of rare earth metal ions have chemical valences of 3+ in acid-leaching solutions and/or slurries; however, such acid-leaching solutions and/or slurries contain very low concentrations of rare earth metal ions or valuable metal ions, while the majority of the soluble cations are Fe 3+ , Ti 4+ , Zr 4+ , etc., plus alkali and alkali earth cations such as Na + , Ca 2+ , Mg 2+ , etc.
  • 4,816,233 discloses a process of reducing Mn 4+ and Fe 3+ ions into Mn 2+ and Fe 2+ , respectively, by hydrazine hydrate, followed by adjusting the pH to about 2.0 and contacting the solution with AmberliteTM IRC-718, a chelating cation ion-exchange resin with iminodiacetic acid functional groups.
  • AmberliteTM IRC-718 a chelating cation ion-exchange resin with iminodiacetic acid functional groups.
  • such an acid- leaching solution has a ratio of iron to scandium of 173:1 and a ratio of manganese to scandium of 278:1, therefore, a large amount of hydrazine hydrate per unit of scandium (289 L/kg scandium) is used in the process.
  • Hydrazine hydrate is a very expensive chemical, so the step of hydrazine hydrate reduction alone is costly, not to mention the other chemicals that are used in the leaching process and purification steps.
  • feedstock such as Ni/Co-containing ores (such as laterite) and red muds from aluminum bauxite process, only contain scandium at a level of less than 100 ppm, in most cases, or less than 200 ppm, in some cases, which makes this process cost-prohibitive due to the requirement for a large amount of hydrazine hydrate for reduction of ferric ions to ferrous ions.
  • the present invention addresses the practical need for a new material/composition that allows a new process to extract valuable metals, such as rare earth metals, more particularly, scandium, from an acid- leaching slurry/solution that contains a very low concentration of valuable metal ions (rare earth metals, more particularly, scandium) and a very high concentration of ferric/titanium ions or other trivalent/tetravalent cations.
  • valuable metals such as rare earth metals, more particularly, scandium
  • the embodiments of the present invention enable the economic recovery of valuable metals (rare earth metals, particularly, scandium) from feedstock that contains very low concentrations of said valuable metals without suffering the shortcomings of solvent extraction including solvent loss, difficulties in achieving a complete solvent-aqueous phase separation, formation of emulsions, crud formation, etc.
  • valuable metals rare earth metals, particularly, scandium
  • the invention is directed to a method for extracting rare earth metals from an acidic slurry or acidic solution.
  • the method comprises providing an acidic slurry or acidic solution, adding a composite comprising an extractant and a polymer resin, mixing the composite with the acidic slurry or acidic solution to form a mixture slurry or solution, and separating the mixture slurry or solution into a rare-earth-metal-loaded composite and a raffinate slurry or solution.
  • the acidic slurry or acidic solution comprises at least one rare earth metal (scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), Samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu)) and at least one early transition metal (titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn) and rhenium (Re)) and/or at least one act
  • Each of the early transition metal(s) may be present in the acidic slurry or acidic solution in an amount up to 50,000 ppm and/or each of the actinide metal(s) may be in the acidic slurry or acidic solution in an amount up to 5,000 ppm.
  • the acidic slurry or acidic solution may be an acidic slurry or acidic solution generated during processing of an ore containing at least one rare earth metal and at least one early transition metal and/or at least one actinide metal, and may be a titanium tailing waste liquor from processing of titanium ores such as the chloride process employed in the production of titanium tetrachloride or titanium dioxide from rutile and the sulfate process employed in the production of titanium dioxide from ilmenite.
  • the rare earth metal may be scandium.
  • the method may further comprise raising the pH of the acidic slurry or acidic solution to form a precipitate of at least a portion of at least one early transition metal and/or at least one actinide metal, for example titanium, thorium, or both.
  • the precipitate may be filtered from the acidic slurry or acidic solution prior to adding the composite.
  • the method may further comprise stripping the rare earth metals from the rare- earth-metal-loaded composite and regenerating the composite for reuse.
  • the composite may be regenerated using a solution generated during the processing of ores containing at least one rare earth metal and at least one early transition metal and/or at least one actinide metal.
  • the regeneration solution may be an acid scrubber solution or a spent processing waste solution, and may be an acid scrubber solution from processing of titanium ores such as the chloride process employed in the production of titanium tetrachloride or titanium dioxide from rutile and the sulfate process employed in the production of titanium dioxide from ilmenite.
  • the polymer resin may have at least one phosphoric acid functional group and/or the extractant may comprise a cation extractant.
  • the extractant may be di(2ethylhexyl)phosphoric acid (DEHPA).
  • FIG. 1 is a graph comparing scandium recovery when using a polymer resin having phosphoric acid functional groups and when using a composite extractant-enhanced polymer resin according to the present invention in a column process for extracting rare earth metals from an acid-leaching solution that contains a large amount of ferric ions (Example 31);
  • FIG. 2 is a graph showing scandium recovery when using a composite extractant- enhanced polymer resin according to the present invention in a column process for extracting rare earth metals from an acid-leaching solution that contains a large amount of ferric ions (Example 32);
  • FIG. 3 is a graph showing scandium recovery when using a composite extractant- enhanced polymer resin according to the present invention in a column process for extracting rare earth metals from an acid-leaching solution that contains a large amount of ferric ions (Example 33);
  • FIG. 4 is a graph showing scandium recovery when using a composite extractant- enhanced polymer resin according to the present invention in a column process for extracting rare earth metals from an acid-leaching solution that contains a large amount of ferric ions (Example 34);
  • FIG. 5 is a graph showing breakthrough curves comparing the adsorption of scandium onto the composite extractant-enhanced polymer resin from a titanium tailing waste liquor and a pH-adjusted titanium tailing waste liquor (Examples 36 and 37);
  • FIG. 6 is a graph showing the co-extraction of early transition metals, such as titanium, niobium, and zirconium, with scandium into a composite extractant-enhanced polymer resin from an un-adjusted titanium tailing waste liquor (Example 36); and
  • FIG. 7 is a graph showing scandium and titanium uptake onto a composite extractant-enhanced polymer resin in a cyclic operation using an acid scrubber solution from titanium processing as regeneration solution (Example 38).
  • any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • a range of“1 to 10” is intended to include any and all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10, that is, all subranges beginning with a minimum value equal to or greater than 1 and ending with a maximum value equal to or less than 10, and all subranges in between, e.g., 1 to 6.3, or 5.5 to 10, or 2.7 to 6.1.
  • the present invention is directed to a composite comprising an extractant and a polymer resin.
  • any suitable extractant may be used to prepare the composite extractant-enhanced polymer resin.
  • the extractant may be anionic, cationic, or non-ionic.
  • Such extractants include, but are not limited to, a cation exchange extractant such as organophosphorous acids, sulfonic acids, and carboxylic acids, a neutral extractant such as tri-n-butyl-phosphate, and an anion exchange extractant such as the amines.
  • a primary industrial extractant comprises di- (2-ethylhexyl)-phosphoric acid (DEHPA), 2-ethyl-hexyl-2-ethyl-hexyl-phosphoric acid (EHEHPA), tributyl-phosphate (TBP), versatic acid, versatic 10, Alamine® 336, and Aliquat 336.
  • DEHPA di- (2-ethylhexyl)-phosphoric acid
  • EHEHPA 2-ethyl-hexyl-2-ethyl-hexyl-phosphoric acid
  • TBP tributyl-phosphate
  • versatic acid versatic 10
  • Alamine® 336 Alamine® 336
  • Aliquat 336 Aliquat 336
  • phosphorus-containing molecules may be used as the extractant to enhance the ability of the polymer resin to extract valuable metals such as rare earth metals
  • di-(2-ethylhexyl)-phosphoric acid (DEHPA) may be used as the extractant
  • the extractant may be used in its original form for preparation of a composite extractant-enhanced polymer resin, or may optionally be diluted by a solvent or modified by a modifier prior to use.
  • Suitable optional solvents used for dilution include, but are not limited to, water, alcohol, ester, ether, ketone, hydrocarbon, and combinations thereof.
  • Suitable optional modifiers include, but are not limited to, isodecanol, coconut alcohol, octanol, ethylhexyl alcohol, alcohol(s) containing six or more carbons, and combinations thereof.
  • any suitable polymer resin may be used for the preparation of the composite extractant-enhanced polymer resin.
  • the polymer resin may be synthetic or natural.
  • the polymer resin may be non-functional and porous.
  • non-functional and porous polymers include, but are not limited to, Dow’s AmberliteTM XAD7HP, AmberliteTM XAD1180N, AmberliteTM XAD2, AmberliteTM XAD4, and AmberliteTM XAD 16N.
  • the polymer resin may also be functional.
  • the functional group may include, but is not limited to, sulfonic acid, iminodiacetic acid, carboxylic acid, phosphoric acid, and amine.
  • Functional polymer resins that have sulfonic acid functional group(s) include, but are not limited to, Dow’s AmberliteTM IRC- 120 and DowexTM G-26(H).
  • Functional polymer resins that have carboxylic acid functional groups include, but are not limited to, AmberliteTM FPC-3500 and AmberliteTM IRC-86SB.
  • Functional polymer resins that have phosphoric acid functional groups include, but are not limited to, Purolite ® S957, Monophosphonix, and Diphosphonix.
  • Functional polymer resins that have amine functional groups include, but are not limited to, Amberlite ® IRA96 and Dowex ® Marathon.
  • the composite extractant-enhanced polymer resin may contain 80 wt.% or less of the extractant, for example, 60 wt.% or less of the extractant, or 50 wt.% or less of the extractant.
  • the composite extractant-enhanced polymer resin may be prepared by soaking the polymer resin in a pure extractant liquid or in a mixture solution comprising extractant and organic solvent, followed by filtration and washing.
  • the solvent may be a low carbon alcohol such as ethanol and isopropanol or may be ketone, ether, and/or another organic solvent.
  • the wet extractant-enhanced polymer resin may have a density of at least 0.3 g/ml and up to 1.30 g/ml, for example, 0.3- 1.3 g/ml, 0.4- 1.1 g/ml, or 00.5-1.1 g/ml.
  • the prepared composite extractant-enhanced polymer resin in a wet form, may be used directly for extracting the valuable metals from an acid-leaching slurry or an acid- leaching solution, or may be dried in air or in an oven at a temperature that is not detrimental to the resin and extractant and then used for extraction.
  • the drying temperature may be ⁇ 200°C, ⁇ 150°C, ⁇ 120°C, ⁇ 100°C, ⁇ 80°C, or room temperature.
  • Direct extraction of rare earth metals including scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) using the composite extractant-enhanced polymer resin may be carried out in a batch operation or continuously.
  • An aqueous acid-leaching slurry or solution containing one or more rare earth metals is combined in a mixing tank with the composite extractant-enhanced polymer resin prepared as described above.
  • An aqueous acid-leaching solution is the liquid resulting from filtration of an acid-leaching slurry or from the separation of the liquid and solid components of an acid leaching slurry using any liquid-solid separation method.
  • the feedstock for the slurry is any ore, mineral, or residues that contain rare earth metals in trace amounts up to 50,000 ppm, for example up to 10,000 ppm, up to 1,000 ppm, up to 500 ppm, or up to 500 ppm.
  • Feedstock materials include, but are not limited to, rare earth-metal-containing minerals such as thorteveitite, bastrasite, monazite, xenotime, Allanite, apatite, brannerite, eudialyte, euxenite, Fergusonite, Florencite, gadolinite, laparite, perovskite, pyrochlore, zircon, Wolframite, tungste, Kolbeckite, jervisite, cascandite, juonnite,elle, scandiobingtonite, Kristiansenite, red mud, titanium tailing, tungsten tailing, uranium tailing, and cobalt and nickel minerals, such as laterites.
  • rare earth-metal-containing minerals such as thorteveitite, bastrasite, monazite, xenotime, Allanite, apatite, brannerite, eudialyte, euxenite, Fergusonite
  • the feedstock may be ground into a fine particulate and mixed with water and at least one suitable acid for dissolving metals in the ore.
  • suitable acids may include, but are not limited to, mineral acids including sulfuric acid, hydrochloric acid, and nitric acid.
  • the leaching may be carried out at a temperature equal to or less than the boiling point of water, for example, l00°C or below or 80-l00°C, or under hydrothermal conditions at a temperature of up to 300°C, while the solution is thoroughly mixed, for example, at 145-150 rpm, or under static conditions.
  • the aqueous acid-leaching slurry may have a viscosity of 400 centipoise or less, for example, a viscosity of 100 centipoise or less or a viscosity of 20 centipoise or less.
  • the pH of the aqueous acid-leaching slurry and/or acid-leaching solution is not limited, but should be sufficient to prevent partial or complete precipitation of the rare earth metals.
  • the pH of the aqueous acid-leached ore slurry or solution therefore, may be up to 6.5, for example, up to 4.0.
  • the aqueous acid-leaching slurry and/or solution may comprise iron in the form of ferric ions and/or ferrous ions.
  • Feedstock such as red mud, titanium tailing, uranium tailing, cobalt and nickel minerals such as laterites, and other such rare earth metal-containing ores or minerals may contain a certain level of iron, and sometimes, iron may even be a major component of the feedstock, such as red mud from an aluminum Bauxite-Bayer process.
  • iron is dissolved by the acid to form ferric ions, which compete with the rare earth metal ions for the extractant molecules in the composite extractant-enhanced polymer resin.
  • Ferric ions may be chemically reduced to ferrous ions prior to adding the composite extractant-enhanced polymer resin.
  • the amount of composite extractant-enhanced polymer resin used may be dictated by the targeted recovery of the targeted valuable metal ion(s).
  • the ratio of the volume of the acid-leaching slurry or solution to the volume of composite extractant-enhanced polymer resin may vary accordingly to the properties of the slurry or solution, particularly, the concentrations of ferric ions, titanium ions, and the targeted valuable metal ions.
  • the ratio of the volume of the acid-leaching slurry or solution to the volume of composite extractant- enhanced polymer resin may be at least 0.5 and up to 3000, for example, at least 1 and up to 2000.
  • the combination of the composite extractant-enhanced polymer resin and the acid- leaching slurry or solution is then mixed for at least a few minutes, for example, one hour or longer.
  • Mixing may be accomplished using any suitable method including, but not limited to, a mixing bar, a paddle stirrer, a pump, and air-bubbling.
  • the direct extraction of the rare earth metals may be carried out at room temperature or at an elevated temperature up to the boiling point of water, for example, l00°C. When elevated temperatures are used the extraction rate is accelerated.
  • the composite extractant-enhanced polymer resin may be loaded with at least 2,000 wt. ppm, for example, at least 1,800 wt. ppm, at least 1,600 wt. ppm, at least 1,400 wt. ppm, at least 1,200 wt. ppm, at least 1,000 wt. ppm, at least 800 wt. ppm, at least 600 wt. ppm, at least 400 wt. ppm, or at least 200 wt. ppm of rare earth metal, such as scandium.
  • the composite extractant-enhanced polymer resin may be loaded with at least 0.2 grams of rare earth metal, for example, scandium, per liter of wet composite extractant-enhanced polymer resin, for example, at least 0.4 grams of rare earth metal per liter of wet composite extractant-enhanced polymer resin, at least 0.8 grams of rare earth metal per liter of wet composite extractant-enhanced polymer resin, at least 1.2 grams of rare earth metal per liter of wet composite extractant-enhanced polymer resin, or at least 1.4 grams of rare earth metal per liter of wet composite extractant-enhanced polymer resin.
  • rare earth metal for example, scandium
  • wet composite extractant-enhanced polymer resin for example, at least 0.4 grams of rare earth metal per liter of wet composite extractant-enhanced polymer resin, at least 0.8 grams of rare earth metal per liter of wet composite extractant-enhanced polymer resin, at least 1.2 grams of rare earth metal per
  • Separation of the valuable-metal-loaded composite extractant-enhanced polymer resin from the raffinate slurry and/or solution may be accomplished by gravitational settling, screening, filtering, or other appropriate processes.
  • the valuable-metals from the loaded extractant-enhanced polymer resin may be stripped from the composite extractant-enhanced polymer using a stripping solution comprising an acid, a base, a salt, or a chelating agent to form a solution or slurry that contains valuable metals such as rare earth metals.
  • the acid may comprise a typical mineral acid and/or an organic acid, or a mixture of mineral acids and/or organic acids, for example, the acid may be, but is not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, citric acid, oxalic acid, acetic acid, formic acid, and the like.
  • the base may comprise a typical alkali metal base (such as, but not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like), an alkali earth metal base (such as, but not limited to, magnesium hydroxide, calcium hydroxide, barium hydroxide, and the like), an ammonium hydroxide, an organic amine which may be a primary amine, a secondary amine, a tertiary amine, and/or mixtures thereof.
  • a typical alkali metal base such as, but not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like
  • an alkali earth metal base such as, but not limited to, magnesium hydroxide, calcium hydroxide, barium hydroxide, and the like
  • an ammonium hydroxide an organic amine which may be a primary amine, a secondary amine, a tertiary amine, and/or mixtures thereof.
  • the salt may comprise any type of salt, for example, a salt that allows the dissolution of the rare earth metal in an aqueous solution, such as, a carbonate salt, for example, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
  • a carbonate salt for example, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
  • the salt, the base, and/or the acid may be used together, separately, or as a mixture.
  • a carbonate or bicarbonate salt may be used with a hydroxide base, such as, a mixture of sodium carbonate and sodium hydroxide, sodium carbonate and potassium carbonate, potassium carbonate and sodium carbonate, potassium carbonate and potassium hydroxide, and ammonium carbonate and ammonium hydroxide.
  • the acid, the base, and/or the salt may be included in the stripping solution at a concentration of at least one gram per liter and up to the saturated solubility of the acid, base, or salt in the stripping solution, for example, up to 350 grams per liter.
  • the concentration of sodium carbonate may be at least 1 gram per liter and up to the solubility of sodium carbonate.
  • the solubility of sodium carbonate increases with temperature and is about 164 grams per liter at 15°C and 340 gram per liter at 27°C.
  • the stripping process may be performed at any suitable temperature as long as the rare earth metal can be removed from the resin.
  • the process may be carried out at room temperature or at an elevated temperature up to the boiling point of the stripping solution, for example, 100°C. Stropping may also be carried out at a temperature below room temperature, but the process will be slower and less economical.
  • the stripping process may be carried out in a batch process or in a continuous process, ex-situ or in-situ.
  • the stripping process may be repeated as many times as is needed to achieve the desired objective.
  • the stripping of rare earth metal from the loaded resin can be partial and does not have to be complete.
  • the valuable metals and other impurities in the stripping solution may be precipitated with an acid such as, but not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or an organic acid, such as oxalic acid or tartaric acid, followed by filtration, centrifugation, or decantation to produce a filtered cake.
  • the filtered cake may be further purified to a scandium chemical or metal that has a purity greater than 30%, for example, greater than 50%, greater than 70%, greater than 90%, greater than 95%, greater than 99%, greater than 99.9%, greater than 99.99%, or greater than 99.999%.
  • the chemical may be hydroxide, oxide, oxalate, carbonate, fluoride, phosphate, chloride, or other valuable chemicals.
  • Scandium metal may be used to produce an alloy with aluminum, copper, or other metal(s). Scandium-contained materials may be used in ceramics for fiiel-cells, optics, catalysts, pharmaceuticals, automobiles, aerospace, etc.
  • the composite extractant-enhanced polymer resin after stripping may be used directly or may be regenerated with a solution comprising an acid or a mixture of acids, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and/or an organic acid, such as citric acid, oxalic acid, and tartaric acid, and recycled for use in the next batch or cycle.
  • the regeneration solution may have an acid concentration of at least 1 gram per liter and up to 500 grams per liter, or may be a pure concentrated acid (such as concentrated hydrochloric acid, typically 36-37 wt.%, concentrated nitric acid, 68-70 wt.%, or concentrated sulfuric acid, up to 98 wt.%).
  • the regeneration process may be carried out in-situ or ex-situ.
  • the regeneration process may be a batch process or a continuous process.
  • the regeneration process may be performed more than once.
  • different type of acids may be used.
  • the regeneration solution may comprise an additive, such as, but not limited to, a surfactant, a reducing agent, a chelating agent, or an oxidizing agent.
  • a continuous process may be used.
  • the composite extractant- enhanced polymer resin may be placed in a column to form a resin bed.
  • Acid-leaching slurry or solution may be continuously pumped through the resin bed at a flow rate ranging from at least one tenth of a bed volume per hour up to 30 bed volumes per hour, for example, from one bed volume per hour to 100 bed volumes per hour.
  • the raffinate solution exiting the resin bed may be monitored to determine when the composite extractant-enhanced polymer resin begins to lose its efficiency for extracting the valuable metals.
  • the valuable-metals from the loaded extractant-enhanced polymer resin may be removed as described above.
  • the above described method may also be used to extract the valuable metals from an acidic slurry or an acidic solution.
  • the acidic slurry or acidic solution may be aqueous and may be any acidic slurry or acidic solution that comprises at least one rare earth metal (scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), Samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu)), and at least one early transition metal (titanium (Ti), zirconium (Zr), hafnium (HQ, vanadium (V), niobium (Nb), tantalum (
  • the acidic slurry or acidic solution may comprise at least one rare earth metal and at least one early transition metal or may comprise at least one rare earth metal and at least one actinide metal or may comprise at least one rare earth metal, at least one early transition metal, and at least one actinide metal.
  • the acidic slurry or acidic solution may be an acidic slurry or an acidic solution created during processing of materials containing at least one rare earth metal and at least one early transition metal and/or at least one actinide metal.
  • materials include thortevetite, bastnasite, monazite, xenotime, Allanite, apatite, brannerite, eudialyte, euxenite, Fergusonite, Florencite, gadolinite, laparite, perovskite, pyrochlore, zircon, Wolframite, apelzite, Kolbeckite, jervisite, cascandite, juonnite, Amsterdamite, scandiobingtonite, Kristiansenite, red mud, titanium ores such as ilminite and rutile, titanium tailings, tungsten ores, tungsten tailings, uranium ores, uranium tailings, thorium ores,
  • the acidic slurry or acidic solution may also be a waste stream created during such processing.
  • a waste stream or other acidic slurry or acidic solution created during such processing valuable rare earth metals, early transition metals, and/or actinide metals may be recovered that would otherwise be lost.
  • the acidic slurry or acidic solution may be titanium tailing waste liquor from processing of titanium ores such as the chloride process employed in the production of titanium tetrachloride or titanium dioxide from rutile and the sulfate process employed in the production of titanium dioxide from ilmenite.
  • the valuable metal may be scandium.
  • the acidic slurry or acidic solution may comprise rare earth metals in trace amounts up to 50,000 ppm, for example, up to 10,000 ppm, up to 1,000 ppm, up to 500 ppm, or up to 50 ppm.
  • the aqueous acidic slurry or acidic solution may also comprise early transition metals, such as titanium, zirconium, vanadium, and niobium, in amounts up to 50,000 ppm, for example up to 10,000 ppm, up to 1,000 ppm, or up to 500 ppm, and actinide metals, such as thorium, up to 5,000 ppm, for example up to 1,000 ppm, up to 500 ppm, up to 100 ppm.
  • early transition metals such as titanium, zirconium, vanadium, and niobium
  • actinide metals such as thorium, up to 5,000 ppm, for example up to 1,000 ppm, up to 500 ppm, up to 100 ppm.
  • the aqueous acidic slurry or acidic solution may also comprise iron in the form of ferric ions and/or ferrous ions, which may even be a major component. Since the ferric ions may compete with the rare earth metal ions for the extractant molecules in the composite extractant-enhanced polymer resin, the ferric ions may be chemically reduced to ferrous ions prior to contacting the acidic slurry or acidic solution with the composite extractant-enhanced polymer resin.
  • the acidic slurry or acidic solution may comprise one or more acids, for example, hydrochloric acid, sulfuric acid, nitric acid, or mixtures thereof, and may have a free acid concentration of 400 gpL or less, for example, a free acid of 200 gpL or less, or a free acid of 100 gpL or less.
  • the acidic slurry or acidic solution may be treated to remove all or a portion of these ions prior to contacting the composite extractant-enhanced resin.
  • the early transition metal ions and/or actinide metal ions may be preferentially chemically precipitated by adjusting the pH of the acidic slurry or acidic solution with a base to form a pH-adjusted slurry or solution.
  • bases include, but are not limited to, sodium hydroxide, calcium hydroxide, hydrated lime, calcium carbonate, magnesium hydroxide, or a combination thereof.
  • the pH of the resulting pH-adjusted slurry or solution may be at a pH value of at least 0 and up to 6, for example at least 0.2 and up to 4, at least 0.3 and up to 2, or at least 0.4 and up to 1.
  • the pH adjustment may be carried out at a temperature equal to or less than the boiling point of water, for example, 100°C or less, 80°C or less, 60°C or less, or 40°C or less.
  • the pH- adjusted slurry that is formed will comprise a precipitate and a pH-adjusted solution which may be separated into a wet precipitate and a pH-adjusted solution by suitable separation techniques including, but not limited to, filtering, decantation, and centrifugation.
  • the resulting pH-adjusted solution may contain early transition metal ions, such as titanium, zirconium, vanadium, and niobium each in amounts up to 10,000 ppm, for example, up to 5,000 ppm, up to 1,000 ppm, or up to 100 ppm, and actinide metal ions such as thorium in amounts up to 1,000 ppm, for example, up to 500 ppm, up to 100 ppm, or up to 10 ppm.
  • early transition metal ions such as titanium, zirconium, vanadium, and niobium each in amounts up to 10,000 ppm, for example, up to 5,000 ppm, up to 1,000 ppm, or up to 100 ppm
  • actinide metal ions such as thorium in amounts up to 1,000 ppm, for example, up to 500 ppm, up to 100 ppm, or up to 10 ppm.
  • the regeneration solution used to regenerate the composite after stripping may be a fresh preparation of a mineral acid such as hydrochloric acid, sulfuric acid, and/or nitric acid
  • the regeneration solution may also be a solution created during the processing of materials such as thortevetite, bastnasite, monazite, xenotime, Allanite, apatite, brannerite, eudialyte, euxenite, Fergusonite, Florencite, gadolinite, laparite, perovskite, pyrochlore, zircon, Wolframite, cabzite, Kolbeckite, jervisite, cascandite, juonnite, »ite, scandiobingtonite, Kristiansenite, red mud, titanium ores such as ilminite and rutile, titanium tailings, tungsten ores, tungsten tailings, uranium ores, uranium tailings,
  • the regeneration solution may be an acid scrubber solution and may be an acid scrubber solution from the processing of titanium ores such as the chloride process employed in the production of titanium tetrachloride or titanium dioxide from rutile and the sulfate process employed in the production of titanium dioxide from ilmenite.
  • the regeneration solution may also be a previously used regeneration solution.
  • Acid-leached ore slurries containing valuable metals, in this case, scandium and other rare earth metals, which may be completely water-soluble or may be chemically bonded to ion-exchangeable sites of inorganic residues in the feedstock, are typically produced in 7000-liter fiber glass-reinforced plastic (FRP) reactors, according to the general disclosures in the previously referenced patents.
  • the feedstock, the water, and the acid in this case, sulfuric acid or hydrochloric acid, are mixed at 144 rpm with 12” triple blades that pump the slurry downwards at a temperature of 80-l00°C.
  • Such leaching slurries have a pH between 0.0 and 0.5.
  • the composition of the acid-leaching slurry was analyzed (inductively coupled plasma-optical emission spectroscopy (ICP-OES) method) by (1) concentrated hydrochloric acid digestion, (2) volumetric dilution, and (3) filtration for residue removal, and the obtained elemental results are tabulated in Table 1.
  • ICP-OES inductively coupled plasma-optical emission spectroscopy
  • Table 1 the composition of the acid-leaching slurry was analyzed (inductively coupled plasma-optical emission spectroscopy (ICP-OES) method) by (1) concentrated hydrochloric acid digestion, (2) volumetric dilution, and (3) filtration for residue removal, and the obtained elemental results are tabulated in Table 1.
  • the analytical results for sodium, potassium, aluminum, silicon, and indium are not precise; however, it is believed that the sample does contain these elements.
  • the acid-leaching slurry in this example contains a substantial amount of trivalent and tetravalent cations, particularly Fe 3+ and Ti 4+ , as compared
  • the aqueous acid-leached slurry undergoes a normal solid-liquid separation process and filtration to produce a liquid filtrate which contains the rare earth metals and solid filter cakes of the leaching residues, which are generally waste material.
  • the filter cakes of the leaching residues are typically washed by fresh water in a volume that is equivalent to one volume of the filter press volume.
  • the filtrate stream and washing stream are then combined into a product stream. Additional washing with fresh water in a volume that is equivalent to four volumes of the filter press leads to the formation of very large amounts of the washing filtrate that has such low concentrations of rare earth metals that it is not economically viable.
  • the conventional process of acid-leaching followed by filtration and washing may recover 60% to 80%, or less, of the rare earth metals.
  • solvent extraction of the filtrate is needed to recover the rare earth metals.
  • Comparative Example 2 Direct Extraction of Scandium from an Aqueous Acid- Leaching Slurry with a Strong Cation Ion-Exchange Resin Containing a Sulfonic Acid Functional Group.
  • the concentration of scandium was only reduced from 95.9 ppm in the feedstock slurry to 90.5 ppm in the raffinate filtrate, with a recovery of only about 5.6%.
  • the strong cation ion-exchange resin having sulfonic acid groups was quickly saturated by the ferric ions and other high-valance metal ions (Ti 4+ ), and the resin became inactive for selective uptake of scandium ions from the acid-leaching slurry.
  • Comparative Example 3 Direct Extraction of Scandium from an Aqueous Acid- Leaching Slurry with a Weak Cation Ion-Exchange Resin. AmberliteTM IRC-7481
  • Example 4 Direct Extraction of Scandium from an Aqueous Acid-Leaching Slurry with an Ion-Exchange Resin Having Phosphoric Functional Groups.
  • Purolite ® S957
  • DEHPA di-2-ethylhexyl phosphoric acid
  • a hydrocarbon solvent such as diesel, kerosene, or mineral spirits
  • solvent extraction with a liquid organic extractant suffers shortcomings such as solvent loss, crud formation, emulsions, and difficulty in achieving a complete organic-aqueous phase separation.
  • the present invention utilizes an immobilized extractant that has functional groups that are similar to those of DEHPA.
  • Purolite S957 is one commercial product that contains phosphoric acid functional groups which are chemically bonded to the polymer matrix.
  • the immobilized phosphoric acid functional groups in the cation exchange resin, Purolite ® S957, have been found to perform similarly in extracting valuable metal(s), such as rare earth metals, without suffering the aforementioned shortcomings of solvent extraction involving liquid organic solvent.
  • the concentration of scandium was reduced from 95.9 ppm in the feedstock slurry to 38.1 ppm in the raffinate filtrate, for a recovery of about 60.3%, much better than DowexTM G-26(H) and AmberliteTM IRC-7481. Without reduction of ferric ions to ferrous ions, the cation ion-exchange resin of Purolite S957 that has phosphoric acid groups can selectively uptake scandium from the acid- leaching slurry, although not completely.
  • Examples 5 and 6 detail the preparation of a composite extractant-enhanced polymer resin.
  • DEHPA is used as the extractant
  • Dow Chemical’s AmberliteTM XAD7HP and XAD1180N are used as the polymer resins. These resins have no specific functional groups.
  • 50 grams of AmberliteTM XAD7HP polymer resin was weighed into a l50-mL beaker. About 75 mL of the mixture solution of DEHPA and ethanol was added to the beaker. The polymer resin was soaked in the mixture solution for about 3 hours to produce the composite. The composite was filtered from the mixture solution by gravity and washed with 30 mL of ethanol.
  • the obtained composite is designated as AmberliteTM XAD7HP-DEHPA-Wet. About one half of the wet composite was oven-dried at about 1 l0°C for at least two hours. The obtained sample is designated as AmberliteTM XAD7HP-DEHPA- Dry. The same procedure was repeated to prepare AmberliteTM XADl l80N-DEHPA-Wet and AmberliteTM XAD 1180N-DEHPA-Dry.
  • Examples 7 to 9 detail the preparation of other composite extractant-enhanced functional ion-exchange resins.
  • DEHPA was used as the extractant while DowexTM G-26(H), AmberliteTM IRC-7841, and Purolite ® S957 were used as the functional ion-exchange resin.
  • Examples 10-17 Direct Extraction of Scandium from an Aqueous Acid-Leaching Slurry Containing a High Concentration of Non-Reduced Ferric Ions Using a Composite Extractant-Enhanced Polymer Resin
  • DEHPA-Wet containing sulfonic acid functional groups and DEHPA, was weighed into a l50-mL beaker having a magnetic bar stirrer. 25 mL of feedstock acid- leaching slurry from Comparative Example 1 was added to the beaker. The composite and slurry mixture was agitated with the magnetic stirrer for about one hour. The composite and slurry mixture was then filtered to produce a raffinate filtrate. The filtrate was then analyzed with ICP-OES, and the results are tabulated in Table 3, Example 10.
  • Example 11 DowexTM G-26(H)-DEHP A-Dry was used, and the scandium concentration was reduced from 95.9 ppm to 86.9 ppm, for a recovery of 9.4% which is enhanced from 5.6% in Comparative Example 2 where only DowexTM G-26(H) resin was used.
  • the recovery of scandium by the composite extractant-enhanced DowexTM G-26(H) was still somewhat low, mainly because of the excess of trivalent cations, like ferric ions (Fe 3+ ) and tetravalent cations like Ti 4+ ions, ([Fe 3+ ] + [Ti 4+ ]) / [Sc 3+ ] > 75.3, present in the feedstock slurry.
  • Examples 12 and 13 show that composite extractant-enhanced porous resins, AmberliteTM XAD7HP-DEHPA-Dry and XADH80N-DEHPA-Dry, reduced the scandium concentration from 92.1 ppm to 63.3 ppm and 60.1 ppm, respectively, which translates into recoveries of 31.3% and 34.7%, respectively.
  • the resins of AmberliteTM XAD7HP and AmberliteTM XAD1180N without the addition of an extractant show no propensity for uptaking scandium ions.
  • these composite extractant-enhanced porous resins have enhanced capability in the uptake of scandium ions from an acid-leaching slurry having a ratio of ([Fe 3+ ] + [Ti 4+ ]) to [Sc 3+ ] greater than 231:1.
  • the composite extractant-enhanced polymer resin, Purolite ® S957-DEHPA-Dry reduced the scandium concentration from 92.1 ppm to 15.07 ppm (Example 15), a 83.6% scandium recovery with a ratio of ([Fe 3+ ] + [Ti 4+ ]) to [Sc 3+ ] greater than 231:1 in the feedstock slurry, which is enhanced from the 60.3% scandium recovery in Example 4 where only Purolite S957 resin was used.
  • Examples 10 to 17 demonstrate that a composite extractant-enhanced polymer resin enhances the capability in uptake of scandium ions from an acid-leaching slurry that contains a large amount of excess trivalent ions such as ferric ions and tetravalent ions such as titanium ions.
  • Table 3 Elemental Analysis for Direct Extraction of Scandium from Non-Reduced Acid-
  • Purolite ® S957 extraction overcomes the shortcomings of solvent extraction, such as solvent loss, difficulties in achieving a complete organic-aqueous phase separation, emulsion formation, and crud formation.
  • Example 21 shows that the composite extractant-enhanced polymer resin, DowexTM G-26(H)-DEHPA, reduces scandium ion concentration from 125.4 ppm to 15.89 ppm, an 87.3% scandium recovery (Example 22), which is enhanced from the 62.4% recovery in Example 18 where only a DowexTM G-26(H) resin was used.
  • the composite extractant- enhanced polymer resin shows a complete uptake of scandium from 125.4 ppm to ⁇ 0.0037 ppm (Example 23), which is enhanced from a recovery of 77.4% in Example 20 where only AmberliteTM IRC-7481 was used.
  • the composite extractant-enhanced polymer resin, Purolite ® S957-DEHPA has a complete uptake of scandium ions from an acid-leaching solution that has a ratio of ([Fe 3+ ] + [Ti 4+ ]) to [Sc 3+ ] of 8.2:1, since Purolite ® S957 uptakes 100% scandium by itself (Example 19).
  • Examples 18 to 25 further show that a composite extractant-enhanced polymer resin, in this case, DEHPA-enhanced polymer resin, is capable of a direct extraction of valuable metals such as scandium ions from an acid-leaching solution or slurry and, at the same time, overcomes the shortcomings of solvent extractions in solvent loss, difficulties in achieving a complete solvent-aqueous phase separation, emulsions, crud formation, etc.
  • Table 4 Direct Extraction of Scandium from an Aqueous Acid-Leaching Solution having a
  • Examples 26-29 Direct Extraction of Scandium from an Aqueous Acid-Leaching Solution in which Ferric Ions Were Reduced into Ferrous Ions with a Composite Extractant-Enhanced Polymer Resin
  • Examples 26 to 29 further illustrate that a composite extractant-enhanced polymer resin uptakes scandium ions and overcomes the shortcomings of solvent extraction in solvent loss, difficulties in achieving a complete solvent and aqueous separation, emulsions, crud formation, etc.
  • Table 5 Direct Extraction of Scandium from an Aqueous Acid-Leaching Solution having a
  • Example 30 Direct Extraction of Scandium from an Aqueous Acid-Leaching Solution Containing a High Concentration of Non-Reduced Ferric Ions with a Cation Ion- Exchange Resin with Phosphoric Acid Functional Groups (a Column Process)
  • the acid-leaching solution was pumped through the resin bed at a flow rate of 0.75 mL/min (4.5 bed volumes per hour) and the raffinate effluent samples were collected at 30 minute intervals. Analysis of the raffinate effluents and the extraction results are tabulated in Table 6 and shown in FIG. 1.
  • Table 6 Analysis of the raffinate effluents and the extraction results are tabulated in Table 6 and shown in FIG. 1.
  • 98% of scandium ions were taken up by the Purolite S957 resin, with a loading of about 368 ppm Sc on the Purolite ® S957 resin.
  • about 91% ferric ions were also taken up by the resin, which results in a 353:1 ratio of [Fe]/[Sc] in the effluent.
  • Example 31 Direct Extraction of Scandium from an Aqueous Acid-Leaching Solution Containing a High Concentration of Non-Reduced Ferric Ions with a Composite Extractant-Enhanced Polymer Resin with Phosphoric Acid Functional Groups
  • DEHPA-Dry was added into an analytical glass burette. After contacting water, the volume of the analytical glass burette (resin bed) was about 23 mL. The bottom of the analytical glass burette was connected to a Masterflex ® Tubing (L/S 14). The resin bed was filled with DI water, and the air bubbles were removed from the resin bed. An acid-leaching solution was added into the analytical glass burette.
  • the composition of acid-leaching solution is listed in Table 7, and its ratio of ([Fe 3+ ] + [Ti 4+ ]) to [Sc 3+ ] is about 83:1.
  • the acid-leaching solution was pumped through the resin bed at a flow rate of 0.75 mL/min ( ⁇ 2 bed volumes per hour).
  • Raffinate effluent samples were collected at 30 minute intervals. Analysis of the raffinate effluents and the extraction results are tabulated in Table 7 and illustrated in FIG. 1.
  • Table 7 Analysis of the raffinate effluents and the extraction results are tabulated in Table 7 and illustrated in FIG. 1.
  • 98% or more of the scandium ions were taken up by the Purolite S957-DEHPA, with a loading of as high as 2249 ppm Sc on the Purolite ® S957-DEHPA, which is 6.4 times more efficient than Purolite ® S957 resin used alone.
  • the percentage of ferric ions that were loaded onto the resin decreased from 100% (30 min), to 93% (60 min), to 67% (90 min), to 39% (120 min), and to 26% (150 min).
  • the ratio of [Fe]/[Sc] in the effluent was extremely high, about 30,000 or higher for the first 90 minutes and decreased to about 3000 at 120 and 150 minutes.
  • the loading of an extractant, DEHPA, onto the Purolite ® S957 resin enhanced the capability of the Purolite ® S957 resin to achieve selective and complete uptake of scandium ions from the acid-leaching slurry containing a high concentration of ferric ions. This is particularly useful for extracting a low concentration of scandium from an acid-leaching slurry or solution that contains a high concentration of trivalent cations such as ferric ions and tetravalent cations like titanium.
  • composite extractant-enhanced polymer resins are highly suitable for economical extraction of rare earth metal ions from a stream of acid- leaching slurry or solution, even if the stream of aqueous slurry or solution contains large amounts of ferric ions, without reducing the ferric ions to ferrous ions.
  • the composite extractant-enhanced polymer resin allows enhanced extraction of rare earth metals from a stream of acid-leaching slurry or solution and overcomes the shortcomings of solvent extraction in solvent loss, difficulties of achieving a complete organic-aqueous phase separation, formation of emulsions, and crud formation.
  • Example 32 Direct Extraction of Scandium from a Synthetic Solution Containing about 3.000 ppm Iron Ions with a Composite Extractant-Enhanced Polymer Resin with Phosphoric Acid Functional Groups (regenerated with multi-pass of acids, less cost effective)
  • a synthetic stream containing 24.9 ppm scandium along with 4,302 ppm nickel, 246 ppm cobalt, 2,988 ppm iron, 2,598 ppm aluminum, 207 ppm chromium, and other divalent cations, such as calcium (>20,000 ppm), copper, magnesium (>11,000 ppm), manganese, zinc, silicon, etc. was passed through a PVC column filled with about 4.25 liters of a composite extractant-enhanced polymer resin, Purolite ® S957-DEHPA.
  • the composite extractant-enhanced polymer resin (Purolite ® S957-DEHPA) was used in the previous runs in which it was loaded with scandium ions along with other undesirable cations.
  • the scandium ions were stripped from the loaded resin using a sodium carbonate solution (about 16 liters) heated to about 80°C for about one hour under mixing conditions.
  • the carbonate solution that was used as a stripping solution contained about 200 grams of sodium carbonate per liter. The stripping procedure was repeated a second time.
  • the Sc-stripped resin was then regenerated using 10 liters sulfuric acid solution (440 grams per liter) that contained about 5% hydrogen peroxide for one hour under mixing conditions.
  • the resin was then regenerated using a 10 liter hydrochloric acid solution (200 grams per liter) under mixing conditions for another hour.
  • the resin was then loaded onto a PVC column and a stream of 10 liters of sulfuric acid solution (440 grams per liter) and a stream of 10 liters of hydrochloric acid (200 grams per liter) were passed through the column consecutively. After rinsing with water, the column was then used for the run described below.
  • the loaded resin was then stripped with a first sodium carbonate solution using the same procedures described above.
  • the first stripping solution contained 1,013 ppm Sc, 2.3 ppm Al, 291 ppm Ca, 1.7 ppm Co, 0.9 ppm Cr, 2.6 ppm Cu, 45 ppm Fe, 106 ppm Mg, 1.6 ppm Mn, ⁇ 0.2 ppm Ni, 164 ppm Si, and 1.8 ppm Zn. Scandium and other impurities in the stripping solution were then precipitated with hydrochloric acid, followed by filtration, to produce a filtered cake.
  • the resin was then stripped with a second sodium carbonate solution and the stripping solution contained a lower concentration of scandium; the second stripping solution may be used as a first stripping solution in the next cycle.
  • Example 33 Direct Extraction of Scandium from a Synthetic Solution Containing about 16.000 ppm Iron Ions with a Composite Extractant-Enhanced Polymer Resin with Phosphoric Acid Functional Groups (regenerated with multi-pass of acids, less cost effective), and followeded by Stripping and Low Cost Ex-situ Regeneration with One Pass of Hydrochloric Acid
  • a composite extractant-enhanced polymer resin Purolite ® S957-DEHPA
  • the loaded resin was removed from the column and was stripped at 80°C with a first sodium carbonate solution (10.5 liters, 200 grams sodium carbonate per liter) under mixing conditions for one hour.
  • the first stripping solution contained 905 ppm Sc, 29 ppm Al, 295 ppm Ca, ⁇ 0.7 ppm Co, ⁇ 0.2 ppm Cr, ⁇ 0.1 ppm Cu, 78 ppm Fe, 218 ppm Mg, 3.2 ppm Mn, ⁇ 0.7 ppm Ni, 258 ppm Si, and ⁇ 0.5 ppm Zn. Scandium and other impurities in the stripping solution were then precipitated with hydrochloric acid, followed by filtration, to produce a filtered cake.
  • the loaded resin was then stripped at 80°C with a second sodium carbonate solution (10 liters, 200 grams sodium carbonate per liter) under mixing conditions for one hour.
  • the second stripping solution contained 326 ppm Sc, 7 ppm Al, 114 ppm Ca, ⁇ 0.1 ppm Co, ⁇ 0.1 ppm Cr, ⁇ 0.04 ppm Cu, 20 ppm Fe, 88 ppm Mg, 0.6 ppm Mn, ⁇ 0.3 ppm Ni, 79 ppm Si, and ⁇ 0.2 ppm Zn.
  • the second stripping solution may be used as the first stripping solution in the next cycle.
  • the resin was then regenerated by flowing a hydrochloric acid solution (200 grams per liter, 9 liters) through the column.
  • the used hydrochloric acid solution contained 0.1 ppm Sc, 228 ppm Al, 179 ppm Ca, 0.4 ppm Co, 35 ppm Cr, 0.5 ppm Cu, 3,222 ppm Fe, 752 ppm Mg, 101 ppm Mn, ⁇ 0.7 ppm Ni, 84 ppm Si, and 5.6 ppm Zn.
  • the regenerated resin was ready for the next cycle.
  • Example 34 Direct Extraction of Scandium from a Synthetic Solution Containing about 15.000 ppm Iron Ions with a Composite Extractant-Enhanced Polymer Resin with Phosphoric Acid Functional Groups (regenerated ex-situ with a single-pass of acids, very economic), and Followed by In-situ Stripping and In-situ Regeneration with One Pass of Hydrochloric Acid.
  • a composite extractant-enhanced polymer resin Purolite ® S957-DEHPA
  • the loaded resin was then stripped in-situ at 60°C with a first sodium carbonate solution (which was the second stripping solution from Example 33, about 8.5 liters) by flowing through the column.
  • a first sodium carbonate solution which was the second stripping solution from Example 33, about 8.5 liters
  • Such first stripping solution contained 1,277 ppm Sc, 9.4 ppm Al, 88 ppm Ca, ⁇ 0.3 ppm Co, ⁇ 0.2 ppm Cr, 1.0 ppm Cu, 63 ppm Fe, 41 ppm Mg, ⁇ 0.1 ppm Mn, 4.1 ppm Ni, 140 ppm Si, and 10 ppm Zn. Scandium and other impurities in the stripping solution were then precipitated with hydrochloric acid, followed by filtration, to produce a filtered cake.
  • the resin was then stripped in-situ with a second sodium carbonate solution (fresh solution, 200 gram sodium carbonate per liter, 10 liters) at 60°C by flowing through the column.
  • the second stripping solution contained 326 ppm Sc, 31 ppm Al, 116 ppm Ca, ⁇ 0.3 ppm Co, ⁇ 0.2 ppm Cr, ⁇ 0.1 ppm Cu, 42 ppm Fe, 57 ppm Mg, ⁇ 0.1 ppm Mn, ⁇ 0.7 ppm Ni, 180 ppm Si, and ⁇ 0.5 ppm Zn; the second stripping solution may be used as a first stripping solution in the next cycle.
  • the resin was then regenerated in-situ by flowing a hydrochloric acid solution (200 grams per liter, 10 liters) through the column.
  • the used hydrochloric acid solution contained 0.1 ppm Sc, 111 ppm Al, 44 ppm Ca, ⁇ 0.03 ppm Co, ⁇ 18.5 ppm Cr, ⁇ 0.008 ppm Cu, >5,552 ppm Fe, >190 ppm Mg, 38 ppm Mn, 0.7 ppm Ni, 22 ppm Si, and 0.9 ppm Zn.
  • the regenerated resin was ready for the next cycle.
  • Example 35 Extraction of Scandium from Un-Adiusted Titanium Tailing Waste Liquor Using Composite Extractant-Enhanced Polymer Resin - Batch Method
  • Titanium tailing waste liquor was analyzed with ICP-OES (Inductively-Coupled Plasma-Optical Emission Spectroscopy) for metals content, and the results are shown in Table 8.
  • ICP-OES Inductively-Coupled Plasma-Optical Emission Spectroscopy
  • Example 36 Extraction of Scandium from Un-Adiusted Titanium Tailing Waste Liquor Using Composite Extractant-Enhanced Polymer Resin - Column Method
  • the breakthrough point for scandium was attained very early after the passage of about the first bed-volume (BV) through the column with a calculated scandium loading on the composite extractant-enhanced polymer resin of about 98 mg/L composite. Consequently, the exhaustion point was achieved at about the nineteenth bed volume with a calculated cumulated scandium loading on the composite extractant-enhanced polymer resin of about 977.2 mg/L composite.
  • the reason for such a behavior was due to the co-adsorption of interfering metal ions such as titanium, niobium, and zirconium with the scandium as shown in FIG. 6.
  • Example 37 Extraction of Scandium from pH-Adiusted Titanium Tailing Waste Liquor Using Composite Extractant-Enhanced Polymer Resin
  • a sufficient volume of the titanium tailing waste liquor to generate at least 1,000 mL of filtrate was transferred into a 4000-mL beaker and, while agitating using an overhead stirrer, hydrated lime was slowly added to adjust the pH to between 0.80 and 0.90. After an hour of equilibration, the pH-adjusted slurry was filtered using a Buchner funnel with the aid of a vacuum pump. The pH-adjusted solution was analyzed with ICP-OES for metals content as shown in Table 11.
  • Table 11 Elemental Composition of pH-Adjusted Solution (pH 0.80-0.90) from
  • Example 38 Use of the Acid Scrubber Solution from a Carbothermal Chlorination Process of Treating Titanium Ores as a Regeneration Solution for the Stripped Composite Extractant-Enhanced Polymer Resin in a Cyclic Operation
  • Step 1 About 720 mL of the pH-adjusted solution was measured and added to a 1,000-mL beaker with 30 mL of the composite extractant-enhanced polymer resin of Example 35. With the aid of an overhead stirrer, the resulting mixture was mixed at 100 rpm for 2 hours. The composite extractant-enhanced polymer resin was separated by decantation. The loaded composite extractant-enhanced polymer resin was then mixed with a sufficient amount of deionized water to ensure removal of entrained raffinate and again separated by decantation. The raffinate and the washing were analyzed with ICP-OES for metals content and the scandium and titanium loading on the composite extractant-enhanced polymer resin was calculated. The results are shown in Table 14.
  • Step 2 The washed, loaded composite extractant-enhanced polymer resin was transferred into a 250-mL beaker for the stripping step.
  • For the first stripping stage about 75 mL of 200 gpL sodium carbonate solution was added into to the loaded composite extractant-enhanced polymer resin, and the mixture was agitated with the aid of an overhead stirrer for about 30 minutes at about 80°C. The mixture was allowed to cool to room temperature and then the composite extractant-enhanced polymer resin was separated by decantation.
  • the second stripping stage about 75 mL of 200 gpL sodium carbonate solution was added to the composite extractant-enhanced polymer resin obtained after the first stripping and the agitation and decantation was repeated.
  • the resulting composite extractant-enhanced polymer resin was mixed with a sufficient amount of deionized water to ensure removal of entrained stripping solution and again separated by decantation.
  • the stripping solutions from the first and second stripping stages and the washing were analyzed with ICP-OES for metals content.
  • Step 3 The water- washed stripped composite from Step 2 was then mixed with about 75 mL of the acid scrubbing solution as a regeneration solution and mixed with the aid of an overhead stirrer for about 30 minutes.
  • the composite extractant-enhanced polymer resin was separated by decantation, mixed with a sufficient amount of deionized water to ensure removal of entrained regeneration solution, and again separated by decantation.
  • the spent regeneration solution and washing were analyzed with ICP-OES for metals content. The regenerated composite was recovered and weighed for the next cycle.
  • Steps 1 through 3 were repeated 12 times (Cycles 2 to 13).
  • the regeneration solution used was a 200 gpL hydrochloric acid solution prepared from technical grade concentrated hydrochloric acid.
  • Steps 1 and 2 were performed.

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Abstract

La présente invention concerne un procédé d'extraction de métaux des terres rares à partir d'une suspension acide ou d'une solution acide. Le procédé comprend l'obtention d'une suspension acide ou d'une solution acide; l'ajout d'un composite comprenant un agent d'extraction et une résine polymère; le mélange du composite avec la suspension acide ou la solution acide pour former une suspension ou solution de mélange; et la séparation de la suspension ou solution de mélange en un composite chargé de métaux des terres rares et une suspension ou solution de raffinat. La suspension acide ou la solution acide comprend au moins un métal des terres rares et au moins un métal de transition précoce et/ou au moins un métal actinide.
EP18879504.1A 2017-11-17 2018-11-16 Récupération sélective de métaux des terres rares à partir d'une suspension acide ou d'une solution acide Pending EP3710607A4 (fr)

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US16/186,897 US10808296B2 (en) 2015-10-30 2018-11-12 Selective recovery of rare earth metals from an acidic slurry or acidic solution
PCT/US2018/061561 WO2019099859A1 (fr) 2017-11-17 2018-11-16 Récupération sélective de métaux des terres rares à partir d'une suspension acide ou d'une solution acide

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CN113667843B (zh) * 2020-05-13 2023-04-18 厦门稀土材料研究所 一种采用低共熔溶剂分离钍的方法
CN113151697A (zh) * 2021-03-09 2021-07-23 中南大学 一种浸出风化壳淋积型稀土矿的方法
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JP5367862B2 (ja) * 2012-03-13 2013-12-11 国立大学法人九州大学 スカンジウム抽出剤およびこの抽出剤を用いたスカンジウム抽出方法
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