WO2016171236A1 - Procédé pour récupérer des éléments des terres rares - Google Patents

Procédé pour récupérer des éléments des terres rares Download PDF

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WO2016171236A1
WO2016171236A1 PCT/JP2016/062711 JP2016062711W WO2016171236A1 WO 2016171236 A1 WO2016171236 A1 WO 2016171236A1 JP 2016062711 W JP2016062711 W JP 2016062711W WO 2016171236 A1 WO2016171236 A1 WO 2016171236A1
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rare earth
microorganism
earth elements
acid
earth element
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Japanese (ja)
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光雄 山下
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Shibaura Institute of Technology
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Shibaura Institute of Technology
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Priority to JP2017514195A priority patent/JP6793402B2/ja
Priority to BR112017022818-1A priority patent/BR112017022818B1/pt
Publication of WO2016171236A1 publication Critical patent/WO2016171236A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M1/00—Apparatus for enzymology or microbiology
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • 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
    • C22B3/02—Apparatus therefor
    • 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
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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 present invention relates to a method for recovering rare earth elements using microorganisms capable of eluting rare earth elements, and a rare earth element recovery apparatus.
  • Rare earth element is a group of 15 elements collectively called scandium (Sc) and yttrium (Y) of atomic number 21 of Group 3 of the periodic table and lanthanoids of 57 to 71. Point to. Rare earth elements have a special electron orbital atomic structure and have properties such as fluorescence, magnetism, and superconductivity at high temperatures, so they are indispensable for the Japanese industry as fluorescent materials, permanent magnets, and superconducting materials. It is a metal. In particular, the demand for dysprosium soot (Dy) is increasing as a raw material for strong magnets that can withstand high temperatures called heat-resistant neodymium (Nd) magnets.
  • Dy dysprosium soot
  • Dy not only has a limited number of producing countries, but also has an impact on environmental conservation measures, and export prices continue to fluctuate.
  • Nd magnets are used as motors in next-generation automobiles, mobile phones, and personal computers, and are produced approximately 16,000 tons annually in Japan. Recycling of 5,600 tons of polishing waste discharged from the manufacturing process has been attempted by physicochemical treatment.
  • the physicochemical recovery method cannot completely recover rare earth elements from low-concentration contents. Therefore, REE recycling recovery has a problem of recovering low-concentration residual rare earth elements.
  • the importance of environmental conservation and resource recycling society has been emphasized. As one of the new technologies for solving these problems, microbial metal metabolism has attracted attention.
  • microorganisms The metal metabolism of microorganisms is known to be converted to elemental state by specific respiration such as denitrification, and selective enrichment and accumulation of manganese.
  • respiration such as denitrification
  • selective enrichment and accumulation of manganese due to the lack of elucidation of microbial functions and the development of systems for following up on these functions, resources are hardly recycled using microorganisms.
  • Patent Document 1 describes a microorganism (accession number NITE BP-01593) belonging to the family Teratosphaeriaceae as a microorganism having the ability to solidify rare earth elements, and a method for solidifying rare earth elements using the microorganisms. Has been.
  • Patent Document 1 describes a T9 strain (Teratosphaeriaceae sp. T9) belonging to the family Teratosphaeriaceae that accumulates and solidifies REE from a solution. This microorganism can solidify and recover 90% Dy soot in an accumulation test using a low concentration Dy solution. However, in order to put it into practical use, it is necessary to increase the efficiency in a shorter time.
  • An object of the present invention is to investigate a REE metabolism mechanism by elucidating the REE metabolism mechanism, and to establish a REE collection technique using microorganisms.
  • An object of the present invention is to provide a method for solidifying and recovering a rare earth element using a microorganism having the ability to solidify the rare earth element, and a rare earth element recovery apparatus.
  • the present inventor first elucidated the REE accumulation characteristics and accumulation sites of microorganisms having the ability to solidify rare earth elements, and elucidated the chemical state of the REE solidified recovery product, which is a metabolite. . Then, optimization of the REE recovery conditions from the solution using the above-mentioned microorganisms was examined, and further a method for refining the REE solidified recovered material was studied. As a result, it was found that 100% Dy can be desorbed from the Dy solidified recovered product using EDTA or HCl, and that Dy solidified and recovered by reusing the cells after Dy desorbing has led to the completion of the present invention.
  • the aspect of the present invention relates to the following.
  • a step of solidifying a rare earth element by culturing a microorganism having the ability to solidify the rare earth element in a solution containing the rare earth element, and a treatment of the microorganism containing the solidified rare earth element with a chelating agent or an acid.
  • a method for recovering rare earth elements comprising a step of recovering rare earth elements.
  • the microorganism has the ability to solidify one or more rare earth elements selected from yttrium (Y), praseodymium (Pr), neodymium (Nd), europium (Eu), and dysprosium (Dy). The method described.
  • the microorganism has a scientific property that the colony has a black, rod-like shape (major axis 10 ⁇ m, minor axis 2 ⁇ m), spore (spherical 1 ⁇ m), pH 2 to 4 and optimal growth, any of [1] to [4] The method of crab.
  • the reaction proceeds at room temperature and pressure, so that an energy saving and low cost recycling process can be provided.
  • FIG. 1 shows a Dy desorption test from a Dy soot solidified product.
  • FIG. 2 shows a Dy accumulation test using the T9 strain after desorption of Dy.
  • FIG. 3 shows the 7th day of culture in the Dy accumulation test using the cells after the desorption test.
  • FIG. 4 shows a continuous REE straw collection system using T9 strain.
  • the method for recovering rare earth elements according to the present invention includes a step of solidifying a rare earth element by culturing a microorganism having the ability to solidify the rare earth element in a solution containing the rare earth element, and a chelate of the microorganism containing the solidified rare earth element. It is a method including the process of collect
  • the microorganism used in the present invention is a microorganism having an ability to solidify rare earth elements.
  • rare earth elements include Sc (scandium), Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), There are 17 species of Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium) and Lu (lutetium).
  • the microorganism of the present invention only needs to have the ability to solidify at least one of the rare earth elements described above.
  • the microorganism of the present invention is a microorganism having the ability to solidify one or more rare earth elements selected from yttrium (Y), praseodymium (Pr), neodymium (Nd), europium (Eu) and dysprosium (Dy).
  • the microorganism has the ability to solidify dysprosium (Dy).
  • the microorganism has the ability to solidify all of yttrium (Y), praseodymium (Pr), neodymium (Nd), europium (Eu) and dysprosium (Dy).
  • solidification means that a rare earth element dissolved in a solution is insolubilized (mineralized).
  • a microorganism-containing medium to which a rare earth chloride solution (for example, DyCl 3 solution) is added is inoculated with a sample containing microorganisms, cultured under conditions that allow the microorganisms to grow, and then the supernatant of the sampling sample.
  • a rare earth chloride solution for example, DyCl 3 solution
  • Microorganisms having the ability to solidify rare earth elements of the present invention can be isolated and collected by screening from wild strains, mutant strains and the like by the method described above or a method equivalent thereto.
  • the genus to which the microorganism having the ability to solidify rare earth elements of the present invention is not particularly limited.
  • a method of classifying microorganisms (identification of genus species) based on 16S rRNA information and the like for microorganisms collected from environmental samples and the like is known.
  • the microorganism used in the present invention may be any microorganism such as a wild-type strain, a mutant strain, and a recombinant produced by genetic engineering techniques.
  • the genus to which the microorganisms capable of solidifying rare earth elements of the present invention belong preferably belongs to the family Teratosphaeriaceae (for example, Penidiella genus) or Dosideales Microorganisms (eg, Mycosphaerellaceae family microorganisms).
  • the microorganism has been found to have a homology of 95% or more in the base sequences of 18SrDNA, 28SrDNA-D1 / D2, and ITS-5.8SrDNA.
  • a microorganism having 95% or more homology with a microorganism belonging to the family Teratosphaeriaceae in the nucleotide sequences of 18SrDNA, 28SrDNA-D1 / D2, and ITS-5.8SrDNA can be used.
  • the T9 strain (Teratosphaeriaceae sp. T9) used in the examples of the present specification can be cited (see International Publication WO2014 / 178360) .
  • the T9 strain under the accession number NITE BP-01593, was established on April 15, 2013 by the National Institute of Technology and Evaluation, Microorganisms Deposit Center (Zip code 292-0818, 2-5 Kazusa Kamashichi, Kisarazu City, Chiba Prefecture, Japan). 8 Room 122).
  • the T9 strain has a scientific property that the colonies are black and rod-shaped (major axis 10 ⁇ m, minor axis 2 ⁇ m), spores (spherical 1 ⁇ m), pH 2 to 4 and optimal for growth.
  • the T9 strain belongs to the genus Penidiella.
  • a rare earth element is solidified by culturing a microorganism having the ability to solidify the rare earth element of the present invention in a solution containing the rare earth element.
  • the kind of rare earth element to be solidified is not particularly limited, but is preferably one or more selected from yttrium (Y), praseodymium (Pr), neodymium (Nd), europium (Eu), and dysprosium (Dy), particularly preferably. Is dysprosium (Dy).
  • the method for culturing the microorganism of the present invention is not particularly limited as long as the rare earth element can be solidified, and suitable culture conditions can be appropriately selected according to the properties of the microorganism to be used.
  • the culture is performed at a temperature of 25 to 40 ° C., preferably at a temperature of 25 to 35 ° C., particularly preferably at 28 to 32 ° C. under aerobic conditions such as pH 2 to 4 of the medium and shaking culture. be able to.
  • the rare earth element solidification ability of the microorganism may be improved.
  • the rare earth element can be solidified by the above method, and then the solidified rare earth element can be recovered.
  • the solidified rare earth element can be recovered by treating the microorganism containing the solidified rare earth element with a chelating agent or an acid to elute the rare earth element from the microorganism.
  • the chelating agent is not particularly limited as long as it can elute rare earth elements from microorganisms.
  • ethylenediaminetetraacetic acid (EDTA), L-aspartic acid diacetic acid (ASDA), L-glutamic acid diacetic acid (GLDA), ethylenediamine -N, N'-disuccinic acid (EDDS), (diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), etc. can be used.
  • the acid is not particularly limited as long as it can elute rare earth elements from microorganisms.
  • inorganic acids hydroochloric acid, sulfuric acid, nitric acid, etc.
  • organic acids formic acid, acetic acid, citric acid, oxalic acid, etc.
  • the concentration of the chelating agent and the acid is not particularly limited as long as the rare earth element can be eluted from the microorganism, and can be set as appropriate.
  • 3 mM to 1000 mM is preferable, 3 mM to 500 mM is more preferable, 10 mM to 500 mM is further preferable, 30 mM to 500 mM is further preferable, and 30 mM to 300 mM is further preferable.
  • hydrochloric acid 3 mM to 1000 mM is preferable, 30 mM to 1000 mM is more preferable, 30 mM to 500 mM is further preferable, and 50 mM to 500 mM is further preferable.
  • the recovery of rare earth elements can be performed by a known method such as centrifugation, filter filtration, or a combination thereof.
  • a microorganism immobilized on a carrier can be used.
  • the carrier for immobilizing microorganisms is not particularly limited, and the shape, structure, size, material and the like can be appropriately selected.
  • the shape of the bag carrier examples include a spherical shape, a granular shape, a lump shape (pellet shape), a sheet shape, a column shape, a net shape, and a capsule shape.
  • the structure of the carrier it may be formed of one type of member or two or more types of members.
  • the carrier may be a single layer structure or a laminated structure.
  • the fine structure of the carrier is not particularly limited as long as it is a structure in which a microorganism and a solution containing a rare earth element can be contacted, and examples thereof include a porous structure and a network structure. Such a structure is advantageous because the contact area between the microorganisms immobilized on the carrier and the solution containing the rare earth element can be increased.
  • the size of the carrier can be appropriately selected according to the size of the container that accommodates the carrier.
  • the material of the cocoon carrier is preferably a polysaccharide, protein, synthetic polymer, inorganic material, etc., but is not particularly limited.
  • the polysaccharide include cellulose, dextran, agarose, sodium alginate, agar, and carrageenan.
  • the protein include gelatin, albumin, collagen and the like.
  • the synthetic polymer include acrylamide, polyvinyl alcohol, polyethylene glycol, sodium polyacrylate, polyvinyl chloride, polystyrene, and polyurethane.
  • the inorganic substance include silica gel, activated carbon, sand, zeolite, porous glass, anthracite, zeolite, foamed brick, and molten slag.
  • the method for immobilizing microorganisms on the carrier is not particularly limited, and can be performed according to a conventional method.
  • a carrier binding method, a crosslinking method, a comprehensive method and the like are preferable.
  • the carrier binding method is a method of immobilizing microorganisms on the surface of a water-insoluble carrier.
  • the crosslinking method is a method of crosslinking with a reagent having two or more functional groups.
  • the inclusion method is a method in which microorganisms are encapsulated in a gel lattice (lattice type) or coated with a polymer film (microcapsule).
  • the carrier on which the microorganisms are fixed is accommodated in a container when contacting with a solution containing a rare earth element. Since the carrier is accommodated in the container, the contact between the carrier and the solution containing the rare earth element can be efficiently and controlled.
  • the shape, structure, size, and material of the container are not particularly limited, and can be appropriately selected according to the purpose. Suitable examples of the shape of the container include a cylindrical shape. Examples of the material of the container include glass, resin, and stainless steel.
  • the microorganism treated with the chelating agent or the acid can be recovered.
  • the rare earth element can be solidified and recovered by culturing again in the solution containing the rare earth element using the recovered microorganism.
  • An example of the continuous REE soot recovery system described above is shown in FIG. A carrier on which a microorganism having the ability to solidify rare earth elements is introduced into a culture tank containing a solution containing rare earth elements, and the microorganisms solidify the rare earth elements (first figure from the left).
  • carrier with which the microorganisms containing the solidified rare earth element were fixed is taken out from the said culture tank (2nd figure from the left).
  • the carrier on which the solidified microorganism containing the rare earth element is fixed is introduced into an elution tank containing a chelating agent or an acid to elute the rare earth element (third figure from the left).
  • the carrier on which the microorganisms eluting the rare earth elements are fixed can be taken out from the elution tank and reused (fourth figure from the left).
  • a carrier on which microorganisms having the ability to solidify rare earth elements are fixed (b) a culture vessel for culturing microorganisms on the carrier in a solution containing rare earth elements; and (c) An apparatus is provided for recovering rare earth elements including an elution tank containing a chelating agent or acid.
  • a chelating agent or acid Specific examples of the microorganism, the carrier, the chelating agent, and the acid having the ability to solidify rare earth elements in the above apparatus are as described above in the present specification.
  • Example 1 Dy desorption test from REE solidified material (1) Method ⁇ Medium and culture conditions Liquid culture is performed using inorganic salt minimum medium (BSM) (distilled water, NH4Cl 0.24 g / L, MgSO4 ⁇ 7H2O 0.12 g / L, CaCl2 ⁇ 2H2O 0.2 g / L, KH2PO4 0.05 g / L L, K2HPO4 0.05 g / L, NaCl 0.1 g / L, Yeast Extract 0.1 g / L, Glucose 2 g / L, H3BO3 0.6 mg / L, CoCl2 ⁇ 6H2O 0.16 mg / L, CuCl2 0.067 mg / L, MnCl2 0.63 mg / L, ZnCl2 0.22 mg / L) was sterilized by autoclave (121 ° C, 15 minutes), temperature 30 ° C, rotary shaking 120 rpm. The culture pH was adjusted with
  • BSM adjusted to pH 2.5 with 20 mM potassium hydrogen phthalate-HCl buffer was used. 50 mL of BSM was dispensed into a 100 mL Erlenmeyer flask, and DyCl3 solution was added at a final concentration of 100 mg / L. The BSM after addition of Dy was inoculated with 0.5 mL of the T9 strain culture solution on the 4th day of preculture, and cultured for 7 days under conditions of 30 ° C and rotary shaking (120 rpm).
  • a Dy desorption test was conducted to recover Dy with high purity from the Dy solidified product derived from the T9 strain.
  • the Dy solidified recovery used in the test the Dy solidified recovered 3 days after the Dy accumulation test was used. The collected material was dried overnight at a room temperature of about 25 ° C., and then the dry weight was measured. The Dy concentration in the Dy collection was calculated from the Dy decrease in the accumulation test. The dried Dy solidified recovered product was added to the desorption solution to a final concentration of 500 mg / L Dy (about 3 mM).
  • EDTA ethylenediaminetetraacetic acid
  • HCl hydrochloric acid
  • the concentration of the desorption solution was 300 mM, 30 mM, and 3 mM, respectively.
  • the Dy desorption reaction was performed at 30 ° C. for 3 hours with 120 rpm shaking.
  • the desorption reaction solution was sampled every 0.5 mL in a timely manner, and the element concentration in the supernatant was quantified by ICP-AES.
  • Results Fig. 1 shows the results of the Dy desorption test from the Dy solidified recovered material.
  • EDTA dissolved more than 90% Dy at 3 hours of reaction at all concentrations tested.
  • the EDTA concentration with the highest desorption rate was 30 mM, and 100% of Dy was desorbed after 3 hours of reaction.
  • 100% Dy was desorbed after 30 minutes of reaction at 300 mM.
  • 30 mM and 3 mM HCl concentrations little Dy was desorbed.
  • the solution pH for EDTA was 300 mM for 7.8, 30 mM and 3 mM, 8.2, and for HCL, 300 mM was 0.9, 30 mM was 1.7, and 3 mM was 2.4.
  • Example 2 Reuse of T9 strain after Dy desorption (1) Method The T9 strain after Dy desorption was cultured for reuse, and a Dy accumulation test was performed. After Dy desorption, the solidified product containing T9 strain viable bacteria was recovered with a 0.2 ⁇ m filter. Similar to the Dy accumulation test, the culture was carried out for 7 days by inoculating 1% (v / v) in BSM (pH 2.5) containing 100 mg / L Dy. 1.0 mL of the culture solution was sampled in a timely manner, and the element concentration in the supernatant was quantified by ICP-AES.

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Abstract

L'invention concerne un procédé de solidification et de récupération d'éléments des terres rares à l'aide de micro-organismes qui ont la capacité de solidifier des éléments des terres rares, et un dispositif de récupération d'éléments des terres rares. L'invention concerne un procédé de récupération d'éléments des terres rares, comprenant : une étape de culture de micro-organismes qui ont la capacité de solidifier des éléments des terres rares, les microorganismes étant cultivés dans une solution qui contient un élément des terres rares, ce qui permet de solidifier l'élément des terres rares; et une étape de traitement des micro-organismes comprenant l'élément des terres rare solidifié à l'aide d'un agent de chélation ou d'un acide, ce qui permet de récupérer l'élément des terres rares.
PCT/JP2016/062711 2015-04-24 2016-04-22 Procédé pour récupérer des éléments des terres rares Ceased WO2016171236A1 (fr)

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CA2982716A CA2982716C (fr) 2015-04-24 2016-04-22 Procede pour recuperer des elements des terres rares
JP2017514195A JP6793402B2 (ja) 2015-04-24 2016-04-22 希土類元素の回収方法
BR112017022818-1A BR112017022818B1 (pt) 2015-04-24 2016-04-22 Método e aparelho para recuperar elementos de terras raras

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CN113046554A (zh) * 2021-03-09 2021-06-29 中南大学 一种利用微生物的代谢产物浸出风化壳淋积型稀土矿的方法

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CN115491490A (zh) * 2022-09-23 2022-12-20 中南大学 一种强化离子型稀土矿浸出过程中生物浸出剂渗透性的方法

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JPH01133920A (ja) * 1987-09-11 1989-05-26 Gte Lab Inc スカンジウム回収のためのイオン交換方法
JPH01502976A (ja) * 1987-04-23 1989-10-12 ジーティーイー・プロダクツ・コーポレイション スカンジウムとトリウムの分離のためのイオン交換方法
WO2014178360A1 (fr) * 2013-05-01 2014-11-06 学校法人 芝浦工業大学 Micro-organisme ayant la capacité d'éluer un élément de terres rares, procédé d'élution associé, micro-organisme ayant la capacité de solidifier un élément de terres rates et procédé de solidification associé
JP2015045041A (ja) * 2013-08-27 2015-03-12 京セラ株式会社 タングステン化合物の回収方法

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JPS5989733A (ja) * 1982-11-11 1984-05-24 Agency Of Ind Science & Technol イオン交換法によるサマリウム−コバルト合金粉末よりサマリウムおよびコバルトの回収方法
JPH01502976A (ja) * 1987-04-23 1989-10-12 ジーティーイー・プロダクツ・コーポレイション スカンジウムとトリウムの分離のためのイオン交換方法
JPH01133920A (ja) * 1987-09-11 1989-05-26 Gte Lab Inc スカンジウム回収のためのイオン交換方法
WO2014178360A1 (fr) * 2013-05-01 2014-11-06 学校法人 芝浦工業大学 Micro-organisme ayant la capacité d'éluer un élément de terres rares, procédé d'élution associé, micro-organisme ayant la capacité de solidifier un élément de terres rates et procédé de solidification associé
JP2015045041A (ja) * 2013-08-27 2015-03-12 京セラ株式会社 タングステン化合物の回収方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113046554A (zh) * 2021-03-09 2021-06-29 中南大学 一种利用微生物的代谢产物浸出风化壳淋积型稀土矿的方法
CN113046554B (zh) * 2021-03-09 2022-03-11 中南大学 一种利用微生物的代谢产物浸出风化壳淋积型稀土矿的方法

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