WO2016171236A1 - Method for recovering rare-earth elements - Google Patents
Method for recovering rare-earth elements Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
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- 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
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- 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, e.g. protozoa; 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
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- 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
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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
- C22B3/02—Apparatus therefor
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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
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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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
- C22B59/00—Obtaining rare earth metals
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- 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
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- 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
Description
[1]希土類元素を固化する能力を有する微生物を、希土類元素を含む溶液中で培養することによって希土類元素を固化する工程、及び固化した希土類元素を含む微生物をキレート剤又は酸で処理することによって希土類元素を回収する工程を含む、希土類元素を回収する方法。
[2]微生物が、イットリウム(Y)、プラセオジム(Pr)、ネオジム(Nd)、ユウロピウム(Eu)及びジスプロシウム(Dy)から選択される1以上の希土類元素を固化する能力を有する、[1]に記載の方法。
[3]微生物が、イットリウム(Y)、プラセオジム(Pr)、ネオジム(Nd)、ユウロピウム(Eu)及びジスプロシウム(Dy)の全てを固化する能力を有する、[1]又は[2]に記載の方法。
[4]微生物が、テラトスファエリアセアエ(Teratosphaeriaceae)科に属する、[1]から[3]の何れかに記載の方法。
[5]微生物が、コロニーは黒色、棒状の形態(長径10μm、短径2μm)、胞子(球形1μm)、pH2~4で増殖最適という科学的性質を有する、[1]から[4]の何れかに記載の方法。
[6]微生物が、受託番号NITE BP-01593を有する微生物である、[1]から[5]の何れかに記載の方法。 That is, the aspect of the present invention relates to the following.
[1] 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.
[2] 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.
[3] The method according to [1] or [2], wherein the microorganism has an ability to solidify all of yttrium (Y), praseodymium (Pr), neodymium (Nd), europium (Eu), and dysprosium (Dy). .
[4] The method according to any one of [1] to [3], wherein the microorganism belongs to the family Teratosphaeriaceae.
[5] The microorganism has a scientific property that the colony has a black, rod-like shape (major axis 10 μm,
[6] The method according to any one of [1] to [5], wherein the microorganism is a microorganism having a deposit number of NITE BP-01593.
[8]キレート剤が3mMから1000mMのEDTAであり、酸が30mMから1000mMの塩酸である、[1]から[7]の何れかに記載の方法。
[9]微生物が担体上に固定されている、[1]から[8]の何れかに記載の方法。
[10](i)[1]から[9]の何れかに記載の方法により希土類元素を回収する工程;
(ii)上記工程(i)においてキレート剤又は酸で処理された微生物を回収する工程、及び
(iii)上記工程(ii)において回収した微生物を用いて[1]から[9]の何れかに記載の方法により希土類元素を回収する工程を含む、希土類元素を回収する方法。
[11](a)希土類元素を固化する能力を有する微生物を固定した担体;及び
(b)希土類元素を含む溶液中で上記担体上の微生物を培養するための培養槽;及び
(c)キレート剤又は酸を収容するための溶離槽;
を含む、[1]から[10]の何れかに記載の方法により希土類元素を回収するための装置。 [7] The method according to any one of [1] to [6], wherein the chelating agent is EDTA and the acid is hydrochloric acid.
[8] The method according to any one of [1] to [7], wherein the chelating agent is 3 mM to 1000 mM EDTA, and the acid is 30 mM to 1000 mM hydrochloric acid.
[9] The method according to any one of [1] to [8], wherein the microorganism is immobilized on a carrier.
[10] (i) A step of recovering rare earth elements by the method according to any one of [1] to [9];
(Ii) a step of recovering a microorganism treated with a chelating agent or an acid in the step (i), and (iii) any one of [1] to [9] using the microorganism recovered in the step (ii) A method for recovering rare earth elements, comprising a step of recovering rare earth elements by the method described.
[11] (a) a carrier on which microorganisms having the ability to solidify rare earth elements are fixed; and (b) a culture vessel for culturing microorganisms on the carrier in a solution containing rare earth elements; and (c) a chelating agent. Or an elution tank for containing acid;
An apparatus for recovering rare earth elements by the method according to any one of [1] to [10].
本発明による希土類元素を回収する方法は、希土類元素を固化する能力を有する微生物を、希土類元素を含む溶液中で培養することによって希土類元素を固化する工程、及び固化した希土類元素を含む微生物をキレート剤又は酸で処理することによって希土類元素を回収する工程を含む方法である。 Embodiments of the present invention will be described below.
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 | recovering rare earth elements by processing with an agent or an acid.
希土類元素とは、具体的には、Sc(スカンジウム)、Y(イットリウム)、La(ランタン)、Ce(セリウム)、Pr(プラセオジム)、Nd(ネオジム)、Pm(プロメチウム)、Sm(サマリウム)、Eu(ユウロピウム)、Gd(ガドリニウム)、Tb(テルビウム)、Dy(ジスプロシウム)、Ho(ホルミウム)、Er(エルビウム)、Tm(ツリウム)、Yb(イッテルビウム)及びLu(ルテチウム)の17種である。本発明の微生物は、上記した希土類元素のうちの少なくとも1種以上を固化する能力を有すればよい。好ましくは、本発明の微生物は、イットリウム(Y)、プラセオジム(Pr)、ネオジム(Nd)、ユウロピウム(Eu)及びジスプロシウム(Dy)から選択される1以上の希土類元素を固化する能力を有する微生物であり、好ましくは、微生物は、ジスプロシウム(Dy)を固化する能力を有する。特に好ましくは、微生物は、イットリウム(Y)、プラセオジム(Pr)、ネオジム(Nd)、ユウロピウム(Eu)及びジスプロシウム(Dy)の全てを固化する能力を有する。 The microorganism used in the present invention is a microorganism having an ability to solidify rare earth elements.
Specific examples of 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. Preferably, 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). Yes, preferably the microorganism has the ability to solidify dysprosium (Dy). Particularly preferably, the microorganism has the ability to solidify all of yttrium (Y), praseodymium (Pr), neodymium (Nd), europium (Eu) and dysprosium (Dy).
固化された希土類元素の回収は、固化した希土類元素を含む微生物をキレート剤又は酸で処理することによって、希土類元素を微生物から溶離させることにより行うことができる。 In the present invention, 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.
酸としては、希土類元素を微生物から溶離できるものであれば特に限定されないが、例えば、無機酸(塩酸、硫酸、硝酸など)又は有機酸(ギ酸、酢酸、クエン酸、シュウ酸など)を使用することができる。 The chelating agent is not particularly limited as long as it can elute rare earth elements from microorganisms. For example, 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. For example, inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, etc.) or organic acids (formic acid, acetic acid, citric acid, oxalic acid, etc.) are used. be able to.
微生物を固定するための担体としては、特に限定されず、形状、構造、大きさ、材質等を適宜選択することができる。 In the present invention, preferably, 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.
容器の形状、構造、大きさ、材質は特に限定されず、目的に応じて適宜選択することができる。容器の形状としては、例えば、円筒状などが好適に挙げられる。容器の材質としては、例えば、ガラス、樹脂、ステンレスなどが挙げられる。 It is preferable that 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.
(1) 方法
・ 培地および培養条件
液体培養は、無機塩最少培地(BSM) (蒸留水、NH4Cl 0.24 g/L、MgSO4・7H2O 0.12 g/L、CaCl2・2H2O 0.2 g/L、KH2PO4 0.05 g/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) をオートクレーブ殺菌 (121°C、15 分) を行い、温度30°C、回転振とう 120rpm の条件で行われた。培養pHは、実験に合わせて HCl または NaOH溶液を用いて調整された。 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),
20mMフタル酸水素カリウム-HCl緩衝液で pH2.5 に調製したBSMを用いた。100 mL三角フラスコにBSMを50mL分注し、DyCl3溶液を終濃度100 mg/Lで添加した。Dy添加後のBSMに前培養 4 日目のT9株培養液を 0.5 mL 接種し、30°C、回転振とう (120rpm)の条件下で 7 日間培養した。 -Dy accumulation test 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).
T9株由来のDy 固化回収物から高純度でDy を回収するために、Dy脱着試験を行った。試験に用いたDy固化回収物は、Dy蓄積試験3日後のDy固化回収物を用いた。回収物は、25°C程度の常温で一昼夜乾燥され、その後乾燥重量が測定された。Dy 回収物中のDy濃度は、蓄積試験のDy減少量から算出した。乾燥したDy固化回収物を、終濃度500 mg/L Dy(約 3 mM)となるように脱着液に添加した。脱着液として、エチレンジアミン四酢酸 (EDTA)溶液および塩酸(HCl)溶液を使用した。脱着液の濃度は、それぞれ300 mMおよび30 mM、3 mM の終濃度を実施した。Dy脱着反応は、30°C、3時間、120rpm振とうで行われた。脱着反応液は適時0.5 mL ごとにサンプリングされ、上清中の元素濃度は、ICP-AES により定量された。 -Dy Desorption Test A Dy desorption test was conducted to recover Dy with high purity from the Dy solidified product derived from the T9 strain. As 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). As the desorption liquid, ethylenediaminetetraacetic acid (EDTA) solution and hydrochloric acid (HCl) solution were used. 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.
Dy 固化回収物からのDy 脱着試験の結果を図1に示す。EDTAは、試験したすべての濃度において反応3時間で90%以上のDyを溶解した。最も脱着率の高かった EDTA濃度は、30 mMで、反応時間3時間で 100%のDyを脱着した。HClの場合は、300 mMで、反応30分後に 100%のDyを脱着した。30mMおよび3mMのHCl濃度では、Dyをほとんど脱着しなかった。溶液 pH は、EDTAでは 300 mMが7.8、30 mM および3 mMが8.2、HCLでは 300 mM が 0.9、30 mM が 1.7、3 mM が 2.4 であった。このpH の結果から、溶液のpHに関わらずDyを脱着できることがわかった。以上の結果から、Dy固化回収物から30 mM EDTA または 300 mM HCl を用いてすべての Dy を再溶解させることが可能と示された。 (2) 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. In the case of HCl, 100% Dy was desorbed after 30 minutes of reaction at 300 mM. At 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. From this pH result, it was found that Dy can be desorbed regardless of the pH of the solution. From the above results, it was shown that it was possible to redissolve all Dy from the Dy solidified collection using 30 mM EDTA or 300 mM HCl.
(1) 方法
Dy 脱着後のT9 株を、再度利用するために培養し、Dy蓄積試験を行った。Dy脱着後にT9株生菌を含む固化物を0.2 μmフィルターにより回収された。Dy蓄積試験と同様に、培養は、100 mg/L Dy を含む BSM (pH2.5) に 1% (v/v) を植菌して7日間行われた。培養液は適時 1.0 mL をサンプリングされ、上清中の元素濃度は、ICP-AES により定量された。 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 μm 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.
T9株をDy 蓄積回収に繰り返して使用可能かどうかを明らかにするために、Dy 脱着後の菌体を用いてDy蓄積試験を行った。その結果を図2に示す。T9株は、脱着液の種類や濃度に関係なく、培養3 日目に溶存Dyを 40-50 mg/L まで減少した。Dy 蓄積試験により増殖した培養液を図3に示す。EDTAおよびHClによりDyを脱着された菌体は、BSMに比べて暗緑色の培養物が増加していることから、菌体が増殖していることがわかる。さらに、HClによりDyを脱着された菌体は、EDTAによる脱着菌体よりも培養液の色が濃いことから、増殖が活発であると考えられた。以上の結果から、EDTAおよびHClによりDy 脱着されたT9株菌体は、BSMで再度増殖し、Dy 蓄積回収に再使用可能 であることが示された。 (2) Results In order to clarify whether the T9 strain can be repeatedly used for Dy accumulation and recovery, a Dy accumulation test was performed using the cells after Dy desorption. The result is shown in FIG. The T9 strain decreased the dissolved Dy to 40-50 mg / L on the third day of culture regardless of the type and concentration of the desorption solution. The culture solution grown by the Dy accumulation test is shown in FIG. The microbial cells desorbed by EDTA and HCl have an increased dark green culture compared to BSM, indicating that the microbial cells are growing. Furthermore, the bacterial cells from which Dy was desorbed by HCl were thought to be actively proliferating because the culture solution had a darker color than the desorbed cells by EDTA. From the above results, it was shown that T9 strain cells Dy-desorbed by EDTA and HCl grew again in BSM and could be reused for Dy accumulation and recovery.
Dy固化回収物からのDy脱着試験では、30 mM EDTA溶液を用いて3時間、300 mM HCl を用いて30分でDyを100%脱離できた (図1)。また、HClによる脱着試験で得られたDyを含む溶液に、炭酸ナトリウム溶液と加えることで、炭酸塩としてDyの沈殿回収が可能であった。さらに、EDTAおよびHClで脱離処理された後の菌体は、再度、増 殖およびDy蓄積が可能であることが明らかとなった (図3)。このことは、応用開発に向けた大きな利点である。 (Consideration of Examples)
In the Dy desorption test from the Dy solidified product, 100% Dy could be desorbed in 3 hours using 30 mM EDTA solution and 30 minutes using 300 mM HCl (FIG. 1). Further, by adding a sodium carbonate solution to a solution containing Dy obtained by the desorption test with HCl, precipitation recovery of Dy as a carbonate was possible. Furthermore, it was revealed that the cells after detachment treatment with EDTA and HCl can again grow and accumulate Dy (FIG. 3). This is a great advantage for application development.
Claims (11)
- 希土類元素を固化する能力を有する微生物を、希土類元素を含む溶液中で培養することによって希土類元素を固化する工程、及び固化した希土類元素を含む微生物をキレート剤又は酸で処理することによって希土類元素を回収する工程を含む、希土類元素を回収する方法。 A step of solidifying the 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 treating the rare earth element by treating 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.
- 微生物が、イットリウム(Y)、プラセオジム(Pr)、ネオジム(Nd)、ユウロピウム(Eu)及びジスプロシウム(Dy)から選択される1以上の希土類元素を固化する能力を有する、請求項1に記載の方法。 The method according to claim 1, wherein 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). .
- 微生物が、イットリウム(Y)、プラセオジム(Pr)、ネオジム(Nd)、ユウロピウム(Eu)及びジスプロシウム(Dy)の全てを固化する能力を有する、請求項1又は2に記載の方法。 The method according to claim 1 or 2, wherein the microorganism has the ability to solidify all of yttrium (Y), praseodymium (Pr), neodymium (Nd), europium (Eu) and dysprosium (Dy).
- 微生物が、テラトスファエリアセアエ(Teratosphaeriaceae)科に属する、請求項1から3の何れか1項に記載の方法。 The method according to any one of claims 1 to 3, wherein the microorganism belongs to the family Teratosphaeriaceae.
- 微生物が、コロニーは黒色、棒状の形態(長径10μm、短径2μm)、胞子(球形1μm)、pH2~4で増殖最適という科学的性質を有する、請求項1から4の何れか1項に記載の方法。 5. The microorganism according to any one of claims 1 to 4, wherein the microorganism has a scientific property that the colonies are black, rod-shaped (major axis 10 μm, minor axis 2 μm), spores (spherical 1 μm), pH 2 to 4 and optimal for growth. the method of.
- 微生物が、受託番号NITE BP-01593を有する微生物である、請求項1から5の何れか1項に記載の方法。 The method according to any one of claims 1 to 5, wherein the microorganism is a microorganism having a deposit number of NITE BP-01593.
- キレート剤がEDTAであり、酸が塩酸である、請求項1から6の何れか1項に記載の方法。 The method according to any one of claims 1 to 6, wherein the chelating agent is EDTA and the acid is hydrochloric acid.
- キレート剤が3mMから1000mMのEDTAであり、酸が30mMから1000mMの塩酸である、請求項1から7の何れか1項に記載の方法。 The method according to any one of claims 1 to 7, wherein the chelating agent is 3 mM to 1000 mM EDTA, and the acid is 30 mM to 1000 mM hydrochloric acid.
- 微生物が担体上に固定されている、請求項1から8の何れか1項に記載の方法。 The method according to any one of claims 1 to 8, wherein the microorganism is immobilized on a carrier.
- (i)請求項1から9の何れか1項に記載の方法により希土類元素を回収する工程;
(ii)上記工程(i)においてキレート剤又は酸で処理された微生物を回収する工程、及び
(iii)上記工程(ii)において回収した微生物を用いて請求項1から9の何れか1項に記載の方法により希土類元素を回収する工程を含む、希土類元素を回収する方法。 (I) recovering rare earth elements by the method according to any one of claims 1 to 9;
(Ii) The step of recovering the microorganism treated with the chelating agent or acid in the step (i), and (iii) The microorganism recovered in the step (ii) is used in any one of claims 1 to 9. A method for recovering rare earth elements, comprising a step of recovering rare earth elements by the method described. - (a)希土類元素を固化する能力を有する微生物を固定した担体;及び
(b)希土類元素を含む溶液中で上記担体上の微生物を培養するための培養槽;及び
(c)キレート剤又は酸を収容するための溶離槽;
を含む、請求項1から10の何れか1項に記載の方法により希土類元素を回収するための装置。 (A) a carrier on which microorganisms having the ability to solidify rare earth elements are fixed; and (b) a culture vessel for culturing microorganisms on the carrier in a solution containing rare earth elements; and (c) a chelating agent or acid. An elution tank for containment;
The apparatus for collect | recovering rare earth elements by the method of any one of Claim 1 to 10 containing this.
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CN113046554A (en) * | 2021-03-09 | 2021-06-29 | 中南大学 | Method for leaching weathering crust elution-deposited rare earth ore by using metabolite of microorganism |
CN113046554B (en) * | 2021-03-09 | 2022-03-11 | 中南大学 | Method for leaching weathering crust elution-deposited rare earth ore by using metabolite of microorganism |
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JPWO2016171236A1 (en) | 2018-02-22 |
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CA2982716A1 (en) | 2016-10-27 |
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