WO2014066668A1 - Procédé pour récupérer des éléments d'actinide et des terres rares, extraction et séparations à partir de ressources naturelles et recyclées - Google Patents

Procédé pour récupérer des éléments d'actinide et des terres rares, extraction et séparations à partir de ressources naturelles et recyclées Download PDF

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Publication number
WO2014066668A1
WO2014066668A1 PCT/US2013/066663 US2013066663W WO2014066668A1 WO 2014066668 A1 WO2014066668 A1 WO 2014066668A1 US 2013066663 W US2013066663 W US 2013066663W WO 2014066668 A1 WO2014066668 A1 WO 2014066668A1
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WIPO (PCT)
Prior art keywords
ree
rare earth
ore
acid
elements
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PCT/US2013/066663
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English (en)
Inventor
Joseph Brewer
Neil Lawrence
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Rare Earth Salts Separation And Refining, Llc
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Publication of WO2014066668A1 publication Critical patent/WO2014066668A1/fr

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    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • 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 rare earth elements are defined as those elements having atomic numbers 57 to 71 inclusive and elements 21 and 39 which are commonly found with the rest of the rare earth elements and have similar chemical and physical properties.
  • the Actinide elements are defined as elements having atomic numbers 89 to 103, however only elements 89 to 92 of the actinides are naturally occurring in significant amounts.
  • Rare earth elements are irreplaceable chemicals used in the fabrication of a wide range of modern energy -related products such as high energy magnets, catalysts, and laser-guided military weapons.
  • REE Rare earth elements
  • the rare earth oxides are amongst the most difficult materials to refine due to their highly favorable free energies. With the exception of Sm, Eu and Yb, the rare earth metals are being conventionally refined by calciothermic reduction at temperatures exceeding 1000 °C and in an inert atmosphere.
  • Caustic fusion is undertaken by dissolving the non-silicate minerals in concentrated solutions of sodium hydroxide at temperatures of up to 600 °C. Both complex processes only result in a cake of oxide or hydroxide material that is highly concentrated with all of the rare earths present in their relative concentrations. This cake still must be refined and the elements must be separated from each other.
  • Each step in the extraction and purification results in the loss of yield, cost increase and waste chemical.
  • One object of the method is the reduction in the number of steps and chemical usage in the preparation of REE oxides, hydroxides, salts and organometallic compounds.
  • a further object of the method is the extraction and separation of REE oxides, hydroxides, salts and organometallic compounds through the use of mechanochemistry.
  • Mechanochemistry is the use of mechanical energy to overcome the energy of activation of a chemical reaction. This is in contrast to thermochemistry in which the energy to overcome the energy of activation of the reaction is provided by adding heat to the reaction.
  • Another objective of the method is to provide a method by which REE can be extracted from solid natural resources readily and economically.
  • the objective of the separation of the REE one from another after extraction from the solid source is achieved through the use of selective titration and precipitation of either the REE or the containing matrix.
  • the objective of the separation of the REE one from another is also achieved through the use of various methods of chromatography including but not limited to ion exchange, counter current, normal phase and reverse phase.
  • FIG. 1 is an overlay of x-ray powder diffraction (XRD) data of typical apatite ore before and after mechanochemical processing demonstrating some of the physical and chemical changes produced by the processing. The major differences are pointed out and lettered.
  • XRD x-ray powder diffraction
  • FIG. 2 is an offset of the same XRD data of typical apatite ore before and after mechanochemical processing which is displayed in Fig. 1.
  • the offset makes some of the physical and chemical changes produced by the processing more apparent than the overlay. The major differences are pointed out and lettered.
  • FIG. 3 is a graph of the data from a typical titration separation of REE from an ore sample in which the 1 1 most abundant REE are separated from one another.
  • FIG. 4 is XRD data taken from the cerium oxide produced by this process demonstrating the relatively high purity which is achievable by this process directly from ore to useable product.
  • FIG. 5 is a schematic of A) a granule of ore with B,C) inclusions which represent one or more REE minerals demonstrating that the desired minerals are frequently included in very small grains in the main ore body. Also shown are d) schematic representations, not to scale, of one possible ligand molecule being brought into close contact with the ore so that the reaction can occur between it and the REE mineral removing the REE from the ore.
  • FIG. 6 is a schematic of various types of mills which are suitable for the disclosed methods.
  • FIG. 7 is a schematic representation of counter current chromatography as used in the method.
  • A) is a piston driven pump that forces the B) REE compound laden mobile phase through a diffuser into C) a column containing the liquid stationary phase which is not miscible with the stationary phase finally leading to the D) extraction of the same or new REE compounds in turn from the eluent or retained in the stationary phase.
  • DETAILED DESCRIPTION is a piston driven pump that forces the B) REE compound laden mobile phase through a diffuser into C) a column containing the liquid stationary phase which is not miscible with the stationary phase finally leading to the D) extraction of the same or new REE compounds in turn from the eluent or retained in the stationary phase.
  • the disclosed methods overcome the limitations of the current technology by not requiring the entire ore to be dissolved. Elements which are not dissolved remain in solid form, thus requiring a much smaller mass of chemical to be used overall. Additionally the separation of large volumes of REE concentrate has proven to yield the more pure salts compared to the same separation technique used on small volume samples. This is likely due to the longer time allowed for equilibrium to be reached as well as the simple fact that a larger total mass of the desired element is present allowing for all 15 elements to be eluted.
  • Mechanochemistry is a field of chemistry with a long history.
  • Mechanochemistry is the use of mechanical energy to overcome the energy of activation of a chemical reaction. This is in contrast to thermochemistry in which the energy to overcome the energy of activation of the reaction is provided by adding heat to the reaction.
  • the earliest apparent reported use of mechanical energy to drive a chemical reaction was reported in a book by Theophrastus of Ephesus (371 - 286 B.C.) "De Lapidibus" translated to "on stones” in which the reaction of cinnabar (HgS) ground in a brass mortar with a brass pestle in the presence of vinegar produced metallic mercury. The reaction in modern terms would be expressed HgS + Cu ->Hg + CuS. From these beginnings
  • mechanochemistry has been utilized, sometimes without recognition, to drive many reactions.
  • the chemical reactions are thought to occur due to the deformation and fracturing of solids which in turn leads to the reactants coming into contact one with another in the appropriate orientation and with the proper energy.
  • the chemical reactions typically occur at very small sizes at the moment of impact.
  • the mechanical energy required for mechanochemistry is imparted to the reactants through the use of a mortar and pestle, or in a mill of some sort. A variety of mills which can be utilized in conjunction with the method are shown in figure 4.
  • REE compounds which are more soluble in a given solvent than the remainder of the material in the ore, or other resource can be accomplished by reacting the REE minerals within the solid with other molecules which form ligand complexes with the REE. Additionally it is possible to form covalent or ionic compounds with the REE by adding other reactants.
  • EDTA Ethylenediaminetetraacetic acid
  • Reacting a REE with a porphyrin molecule can form a metal organic framework which is very insoluble in water while becoming very soluble in dimethyl sulfoxide (DMSO).
  • Chromatography is the selective separation of a mixture by passing a compound loaded mobile phase through a stationary phase which interacts with the compound in the mobile phase.
  • Various forms of chromatography have proven useful in the method; ion exchange, counter current, normal phase and reverse phase.
  • counter current chromatography CCC
  • Titration is the stepwise addition of one chemical compound to a solution containing one or more chemical compounds to effect a change in the solution.
  • titration is used by adding a solution stepwise which contains a precipitating compound such as sodium hydroxide, or oxalic acid to a solution containing REE compound.
  • a precipitating compound such as sodium hydroxide, or oxalic acid
  • a variety of other acids may be used including nitric acid, hydrochloric acid, sufuric acid, trichloroacetic acid, phosphoric acid, formic acid, acetic acid, propionic acid, carbonic acid mixtures of these or other suitable acids.
  • base dissolution may be carried out to extract the REE.
  • the base may be selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium bicarbonate, calcium carbonate, ammonium hydroxide, potassium carbonate, lithium hydroxide, mixtures of these, or other suitable bases.
  • the method comprises several parts which when combined allow for the extraction of well separated rare earth elements (REE) from a wide variety of solid sources including but not limited to ore, tailings, slag, sludge, recycled magnets, and or recycled electronics.
  • This process is unique in that it combines mechanochemical synthesis of soluble REE compounds as a method of extracting the REE from the solid source with titrimetric and chromatographic techniques for the green separation of each of the elements into a highly pure useable REE compound, oxide, or salt without the need for the use of metallic calcium or heating to temperatures above 200 °C.
  • This process utilizes ball-milling to impart the energy to induce a wide variety of solid-solid chemical reactions.
  • iodobenzenediacetate L-ascorbic acid, tetraethylammoniumiodide, sodium laureth sulfate, terephthalic acid, toluene or 2,2-bipyridine-4,4-dicarboxylic acid
  • Other potentially suitable ligands include those disclosed in U.S. Pat. No. 6,060,614, to Orvig, the disclosure of which is hereby incorporated herein by reference in its entirety, and which discusses various chelating ligands that may be useful in the process disclosed herein. These products can then be removed by solvation, leaving behind the undesired elements such as calcium and iron for further traditional processing.
  • Mechanochemical REE refinement process is unique and innovative over the present industrial processes because it combines four processes: acid or base dissolution of REE ore, refining, alloying, and powder manufacture, into a cost effective, low temperature process. Since the kinetics of such mechanically activated reactions depend on milling parameters such as collision energy and frequency, as well as the thermodynamic properties of the reaction, this allows mechanical activation via mechanical milling processes to induce a wide range of chemical reactions. The process has been shown to extract > 90% of the REE from both simulate and actual ore samples. The REE from the simulated and actual ore samples have been recovered as individual salts, oxides, hydroxides, and organometallic compounds with purity in excess of 95%. The separation of the most abundant 1 1 REE from an actual ore sample have been recovered in approximately relative concentrations, the other elements were not present in high enough concentrations to be detected using our equipment.
  • solubility constants of each compound is dependent upon the concentrations of each of the free ions.
  • concentration of H + and OH " are logarithmically proportional to the pH or pOH value as seen in equation 1.3 and 1.4:
  • the H + concentration is 10 times more than at pH of 2.
  • the OH- concentration at a pH of 1 is 10 less than at pH of 2:
  • REE were extracted from a number of ore and tailing samples.
  • the ore or tailings samples were preground to 200 mesh size (-75 ⁇ ) particle size.
  • Stoichiometric amounts of ligands i.e., EDTA and DTP A
  • 50 ⁇ ⁇ of acid i.e., nitric or sulfuric acid
  • the mixture of ligands, acid and ore/tailings was then further ground to 2400 mesh particle size (6 ⁇ ).
  • the mixture of ground ligands, acid and ore/tailings was then washed with acid (i.e., 1M nitric acid) and filtered.
  • acid i.e., 1M nitric acid
  • Thet pH of filtered acid washed solution was adjusted to 1.
  • the pH 1 adjusted solution was then titrated with a base (i.e., NaOH or KOH) to various pH end points. At those end points, specific materials precipitated and the solution was centrifuged to separate the precipitated solid material from the solution. At each endpoint, the solution was decanted from the solid precipitate and titrated to the next end point.
  • a base i.e., NaOH or KOH
  • Synthetic ore was prepared having a combination of REE oxides in ratios approximately the same as those found in the elk creek deposit in southeaster California combined with calcite (calcium carbonate, CaCCb).
  • This simulated ore was processed in a liquid assisted mechanochemical method in a vibratory mill with a combination of ligands a small amount of solvent ( ⁇ ⁇ L/g mixture) for several hours.
  • the resulting mixture was then mixed with water which had been pH adjusted to 1.
  • the CaCCb from the original solid was filtered from the rest of the solution as it was not soluble under these conditions.
  • the resulting aqueous solution was then titrated with ammonium hydroxide. As the pH of the solution increased each REE element precipitated selectively and was collected for further verification of the purity and identity of the REE present.
  • the resulting precipitates from each even were calcined at 400 °C and were then examined utilizing x-ray powder diffraction (XRD) to verify the identity of the oxide.
  • the powders were also examined utilizing electron microscopy (SEM) with coupled with energy dispersive x-ray spectroscopy (EDX) and the crystallite were found to vary from between 100 nm to 1 mm with the average being about 300 ⁇ .
  • SEM electron microscopy
  • EDX energy dispersive x-ray spectroscopy
  • the elemental composition and absence of grains of impurities was verified.
  • the samples were digested in acid and were analyzed by inductively coupled argon plasma optical emission spectroscopy (ICP-OES) and the purity was verified.
  • ICP-OES inductively coupled argon plasma optical emission spectroscopy
  • Apatite tailings from the pea ridge mine in central Missouri were processed using a liquid assisted mechanochemical method in a ball mill.
  • the ore was mixed with a combination of salts, and organic solids with an organic solvent being used for the assist.
  • the resulting mixture was ball milled for several hours and the powder was then mixed with n-butanol and filtered.
  • the filtrate contained the original Cas(P04)3 from the ore.
  • the remaining solution was then processed utilizing CCC and divided into 4 fractions which were individually titrated utilizing oxalic acid producing 10 clean precipitations of REE and a liquid solution containing a high concentration of iron and other transition metals.
  • the resulting precipitates from each even were calcined at 400 °C and were then examined utilizing XRD to verify the identity of the oxide.
  • the powders were also examined utilizing SEM and EDX and the crystallite were found to vary from between 100 nm to 1 mm with the average being about 500 ⁇ .
  • the elemental composition and absence of grains of impurities was verified. Additionally the samples were digested in acid and were analyzed by ICP-OES and the purity was verified.
  • Apatite tailings the same as used in Example 2 were processed in the same manner as the simulated ore in Example 1. Most of the resulting precipitations were equally pure as those in Example 2 with the exception of the last to precipitate which was contaminated, co-precipitated, with iron hydroxide.
  • the resulting precipitates from each even were calcined at 400 °C and were then examined utilizing XRD to verify the identity of the oxide.
  • the powders were also examined utilizing SEM and EDX and the crystallite were found to vary from between 100 nm to 1 mm with the average being about 500 ⁇ .
  • the elemental composition and absence of grains of impurities was verified. Additionally the samples were digested in acid and were analyzed by ICP-OES and the purity was verified.
  • Example 2 A sample of the same simulated ore as used in Example 1 was processed in an identical manner but excluded the use of any ligands or other reacting materials. The resulting solution when titrated produced no detectable precipitation events. ICP analysis verified that only trace amounts of REE and Ca were present in the solution.
  • first and second are used herein to describe various features, elements, regions, layers and/or sections, these features, elements, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one feature, element, region, layer or section from another feature, element, region, layer or section. Thus, a first feature, element, region, layer or section discussed below could be termed a second feature, element, region, layer or section, and similarly, a second without departing from the teachings of the present invention.

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  • Environmental & Geological Engineering (AREA)
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  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne des procédés pour récupérer et séparer des éléments des terres rares à partir de minerai, de produits de queue ou d'une autre source quelconque solide. Le procédé précité met en œuvre des procédés mécanochimiques pour créer des composés et des complexes chimiques qui sont appropriés pour séparer les matériaux d'origine. Les composés des éléments des terres rares créés à partir des solides sont ensuite extraits du reste des matériaux par utilisation de solvants. Enfin, l'utilisation de titrages sélectifs, de la chromatographie à contre-courant et de la chromatographie à phase inverse permet de séparer les éléments les uns des autres et de les transformer en oxydes, hydroxydes, sels et composés organométalliques.
PCT/US2013/066663 2012-10-24 2013-10-24 Procédé pour récupérer des éléments d'actinide et des terres rares, extraction et séparations à partir de ressources naturelles et recyclées WO2014066668A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014211289A1 (de) 2014-06-12 2015-12-17 Fne Entsorgungsdienste Freiberg Gmbh Vorrichtung und Verfahren zur Abtrennung und Konzentration von Bestandteilen mit magnetischem Verhalten aus einer ionenhaltigen Lösung
WO2016025928A1 (fr) * 2014-08-15 2016-02-18 Rare Earth Salts Separation And Refining, Llc Procédé d'extraction et de séparation d'éléments de terres rares
CN110639689A (zh) * 2019-10-14 2020-01-03 广东省资源综合利用研究所 一种从稀土尾矿中综合回收稀土、锶和钼的选矿方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02179835A (ja) * 1988-12-28 1990-07-12 Unitika Ltd 希土類元素の分離法
JPH05147931A (ja) * 1991-11-25 1993-06-15 Shin Etsu Chem Co Ltd 希土類酸化物の製造方法
JPH1171111A (ja) * 1997-08-25 1999-03-16 Fumiyoshi Saito 希土類金属化合物の抽出方法
KR20110058054A (ko) * 2009-11-25 2011-06-01 한국지질자원연구원 모나자이트 내 희토류 추출방법
US8263028B1 (en) * 2011-06-17 2012-09-11 Vierheilig Albert A Methods of recovering rare earth elements

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02179835A (ja) * 1988-12-28 1990-07-12 Unitika Ltd 希土類元素の分離法
JPH05147931A (ja) * 1991-11-25 1993-06-15 Shin Etsu Chem Co Ltd 希土類酸化物の製造方法
JPH1171111A (ja) * 1997-08-25 1999-03-16 Fumiyoshi Saito 希土類金属化合物の抽出方法
KR20110058054A (ko) * 2009-11-25 2011-06-01 한국지질자원연구원 모나자이트 내 희토류 추출방법
US8263028B1 (en) * 2011-06-17 2012-09-11 Vierheilig Albert A Methods of recovering rare earth elements

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014211289A1 (de) 2014-06-12 2015-12-17 Fne Entsorgungsdienste Freiberg Gmbh Vorrichtung und Verfahren zur Abtrennung und Konzentration von Bestandteilen mit magnetischem Verhalten aus einer ionenhaltigen Lösung
DE102014211289B4 (de) 2014-06-12 2024-04-25 Fne Entsorgungsdienste Freiberg Gmbh Vorrichtung und Verfahren zur Abtrennung und Konzentration von Bestandteilen mit magnetischem Verhalten aus einer ionenhaltigen Lösung
WO2016025928A1 (fr) * 2014-08-15 2016-02-18 Rare Earth Salts Separation And Refining, Llc Procédé d'extraction et de séparation d'éléments de terres rares
EA036195B1 (ru) * 2014-08-15 2020-10-13 Рэа Ёрз Солтс Сепарейшн Энд Рефайнинг, Ллс Способ экстракции и выделения редкоземельных элементов
CN110639689A (zh) * 2019-10-14 2020-01-03 广东省资源综合利用研究所 一种从稀土尾矿中综合回收稀土、锶和钼的选矿方法

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