WO2023038401A1 - 네오디뮴 화합물을 전해 제련하는 방법 및 이에 사용되는 네오디뮴 화합물 그래뉼의 제조 방법 - Google Patents
네오디뮴 화합물을 전해 제련하는 방법 및 이에 사용되는 네오디뮴 화합물 그래뉼의 제조 방법 Download PDFInfo
- Publication number
- WO2023038401A1 WO2023038401A1 PCT/KR2022/013361 KR2022013361W WO2023038401A1 WO 2023038401 A1 WO2023038401 A1 WO 2023038401A1 KR 2022013361 W KR2022013361 W KR 2022013361W WO 2023038401 A1 WO2023038401 A1 WO 2023038401A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- neodymium
- granules
- praseodymium
- less
- anode
- Prior art date
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 209
- 238000000034 method Methods 0.000 title claims abstract description 76
- 150000002798 neodymium compounds Chemical class 0.000 title claims abstract description 74
- 238000007670 refining Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 90
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 41
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 15
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 54
- 238000003723 Smelting Methods 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- KBLRIGLPGMRISA-UHFFFAOYSA-N neodymium(3+) oxygen(2-) praseodymium(3+) Chemical compound [O-2].[Pr+3].[Nd+3].[O-2].[O-2] KBLRIGLPGMRISA-UHFFFAOYSA-N 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- PYEJXBWRVNYIFO-UHFFFAOYSA-H C(C(=O)[O-])(=O)[O-].[Nd+3].[Pr+3].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] Chemical compound C(C(=O)[O-])(=O)[O-].[Nd+3].[Pr+3].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] PYEJXBWRVNYIFO-UHFFFAOYSA-H 0.000 claims description 10
- XKCJIWHFQBSXPX-UHFFFAOYSA-H neodymium(3+) praseodymium(3+) tricarbonate Chemical compound [Nd+3].C([O-])([O-])=O.[Pr+3].C([O-])([O-])=O.C([O-])([O-])=O XKCJIWHFQBSXPX-UHFFFAOYSA-H 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- MBULCFMSBDQQQT-UHFFFAOYSA-N (3-carboxy-2-hydroxypropyl)-trimethylazanium;2,4-dioxo-1h-pyrimidine-6-carboxylate Chemical compound C[N+](C)(C)CC(O)CC(O)=O.[O-]C(=O)C1=CC(=O)NC(=O)N1 MBULCFMSBDQQQT-UHFFFAOYSA-N 0.000 claims description 6
- UTWHRPIUNFLOBE-UHFFFAOYSA-H neodymium(3+);tricarbonate Chemical compound [Nd+3].[Nd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UTWHRPIUNFLOBE-UHFFFAOYSA-H 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000011800 void material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 49
- 229910052777 Praseodymium Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001172 neodymium magnet Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- -1 CF 4 gas Chemical class 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008094 contradictory effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010079 rubber tapping Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000583 Nd alloy Inorganic materials 0.000 description 2
- 229910017555 NdF Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- RKLPWYXSIBFAJB-UHFFFAOYSA-N [Nd].[Pr] Chemical class [Nd].[Pr] RKLPWYXSIBFAJB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005563 spheronization Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910017557 NdF3 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/247—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/002—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least an electrode made of particles
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
-
- 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 electrolytic refining of neodymium compounds and a method for producing neodymium compound granules used therein, and more specifically, to a method for producing neodymium compound granules in which one or more pores are defined and using the neodymium compound granules produced thereby , It is about a method for reducing neodymium compounds in an environmentally friendly, low-cost and high-efficiency manner.
- Permanent magnets are applied in various fields, and various studies are being conducted to improve the performance of permanent magnets. In particular, from the viewpoint of energy saving or environment friendliness, research on permanent magnets is rapidly progressing in fields such as IT, automobiles, and home appliances.
- Neodymium magnets which are most widely used among permanent magnets, are permanent magnets whose main components are neodymium-iron-boron (Nd-Fe-B)-based intermetallic compounds (Nd 2 Fe 14 B). Since neodymium magnets have advantages such as excellent magnetic properties, high strength, and low production cost, they are used in various industrial products and their production volume is increasing exponentially.
- the main uses of neodymium (Nd) magnets include voice coil motors of hard disks, air conditioner compressor motors, and motors for hybrid vehicles.
- neodymium (Nd) which is a raw material of neodymium magnets, is ubiquitous in certain countries with excellent mining properties, and the price fluctuates easily due to export regulations of the countries concerned, and stable supply is becoming difficult. Therefore, an efficient process for smelting neodymium used in the manufacture of permanent magnets and the like is further required.
- thermo reduction method is also used for smelting neodymium, but since continuous smelting is not possible, it is not suitable for industrial mass production.
- the electrolyte easily evaporates at the exposed electrolyte interface, and the exposed electrode reacts with oxygen in the air to easily oxidize.
- the present invention has been proposed to solve the problems of the prior art, and an object of the present invention is to provide a method for reducing a neodymium compound in an environmentally friendly, low-cost and high-efficiency manner using a granule containing a neodymium compound and having one or more pores defined therein. do.
- an object of the present invention is to provide a method for reducing a neodymium compound that can increase the high-quality production rate of a final product compared to the prior art and has high energy efficiency, which is advantageous for commercialization.
- an object of the present invention is to provide a method for producing granules of a neodymium compound suitable for use in the above-described excellent method for reducing a neodymium compound.
- adding a binder to the neodymium compound powder or adding a binder to a mixture of neodymium compound powder and graphite powder to form a granule precursor, drying the granule precursor There is provided a method for producing neodymium compound granules used in electrolytic smelting, comprising the steps of heat treatment and sintering by applying heat of 800° C. to 1500° C. to the dried granule precursor.
- FIG. 1 is a view schematically showing a cross section of an electrolytic cell in which an electrolytic refining process is in progress.
- FIG. 2 is a diagram showing granules of a neodymium compound, specifically neodymium oxide.
- Nd 2 O 3 powder and graphite powder mixing steps (a to c), granule formation steps, and granule spheronization steps (d).
- Example 4 is a view showing granules of neodymium oxide of Example 1;
- Example 5 is a view showing granules of neodymium oxide in Example 2.
- Figure 6a is a view showing a piece of the granule of Example 1.
- Figure 6b is an enlarged view showing the granules of Example 1 magnified 1000 times.
- Figure 6c is an enlarged view showing the granules of Example 1 magnified 5000 times.
- FIGS. 1 and 2 a method for obtaining reduced pure neodymium (ND) metal by electrolytically refining the neodymium compound according to the present invention will be described in detail with reference to FIGS. 1 and 2 .
- the electrolytic smelting method is described for each step, it does not specify the order of the process.
- each step according to the method of the present invention may not proceed in the order described unless contradictory, and each step may proceed concurrently.
- 1 is a view schematically showing a cross section of an electrolytic cell (EB) in which an electrolytic refining process is in progress.
- 2 is a view showing granules (GR) of neodymium oxide among neodymium compounds.
- a fluoride-based electrolyte (EL) through an opening (EB-O) defined on an electrolytic cell equipped with a cathode (CT) and an anode (AN); providing granules (GR) comprising a neodymium compound through defined openings (EB-O) on an electrolytic cell (EB) and having one or more pores (CV) defined therein; dissolving at least a part of the granules (GR) in the molten salt of the electrolyte (EL); and reducing neodymium (ND) at a cathode (CT), wherein the pores are defined inside or outside the granules (GR), and the apparent density of the granules (GR) is less than the density of the molten salt.
- the electrolytic cell EB may include a lower part EB-B and a side part EB-S.
- an opening EB-O may be defined in the electrolytic cell EB.
- Electrolytes EL and/or granules GR may be provided through openings EB-O during the process.
- a basket BS accommodating neodymium ND reduced by a reaction between the electrolyte EL and the cathode CT may be provided at the lower end EB-B of the electrolytic cell EB.
- the basket BS may be provided under the cathode CT to correspond to the location of the cathode CT, but the embodiment is not limited thereto.
- the basket BS may include a tap furnace for easily recovering the reduced neodymium (ND).
- the tapping furnace can be opened or closed through a separate device, and the reduced neodymium (ND) in a molten state can be recovered through the tapping furnace.
- the embodiment is not limited thereto, and the reduced neodymium (ND) may be recovered through the opening (EB-O) defined in the electrolytic cell (EB).
- the fluoride-based electrolyte (EL) may include a mixed salt of a fluoride compound of an alkali metal or alkaline earth metal and NdF 3 .
- the fluoride-based electrolyte (EL) may be provided in the form of a molten salt of a fluoride compound of an alkali metal or alkaline earth metal and NdF 3 .
- Fluoride compounds of alkali metals or alkaline earth metals included in the fluoride-based electrolyte EL may be one or two or more. Examples of the alkali metal or alkaline earth metal in the alkali metal or alkaline earth metal fluoride compound include Li, Mg, Na, K or Ca.
- Fluoride compounds of alkali metals or alkaline earth metals may be used without particular limitation as long as they are compounds used in the art, such as LiF or CaF 2 .
- the fluoride-based electrolyte EL may include, for example, a mixed salt of LiF and NdF 3 . Due to the high melting point of NdF 3 , it is difficult to perform electrolytic smelting using NdF 3 alone, but a eutectic composition having a low melting point can be used in the process by using a fluorinated alkali compound such as LiF together.
- the fluoride-based electrolyte (EL) may include 5 to 50 wt% or 10 to 50 wt% of LiF and 20 to 95 wt% of NdF 3 based on the total weight of the electrolyte (EL). or 20 to 80% by weight.
- LiF and NdF 3 may be included in a weight ratio of about 40:60 to 5:95, about 40:60 to 20:80, for example, about 30:70.
- the cathode CT and the anode AN may be spaced apart by a predetermined distance.
- the cathode CT and the anode AN may be electrically connected to a power supply unit PO that supplies power.
- each of the cathode CT and the anode AN may be electrically connected to the power supply unit PO through the power supply line PL.
- neodymium is reduced at the cathode CT to obtain pure neodymium (ND) metal.
- At least a portion of the cathode CT and/or the anode AN may be immersed in molten salt. At least a portion of the cathode CT and/or the anode AN, particularly the anode AN, may be exposed to air. That is, the cathode CT and/or the anode AN may include a contact portion immersed in the electrolyte EL to contact the electrolyte and an exposed portion exposed to air.
- one cathode (CT) and two anodes (AN) are provided in an electrolytic cell (EB), but the embodiment is not limited thereto.
- the cathode (CT) and/or the anode (AN) may each independently have 1 or more and 5 or less, 1 or more and 4 or less, 1 or more and 3 or less, or 1 or more and 2 or less.
- one cathode CT may be provided, and one, two, or four anodes AN may be provided.
- the anode AN is shown as being arranged to surround the cathode CT, but the embodiment is not limited thereto, and any electrode arrangement conventional in the art can be applied to the present invention without limitation. there is.
- CT cathode
- AN anode
- EB electrolytic cell
- the powder containing neodymium oxide was introduced into the electrolytic cell (EB) to proceed with the process. Therefore, the powder containing neodymium oxide is scattered in the air, resulting in loss of raw materials and difficulties in the process. In particular, since very high heat is applied to the electrolytic smelting process, powder is very actively scattered by thermal convection generated by the heat, resulting in loss of raw materials and a great problem in process safety.
- the density of the powder containing neodymium oxide is greater than the density of the electrolyte EL, the powder settles on the bottom of the electrolytic cell EB.
- the precipitated neodymium oxide powder is poorly soluble in the electrolyte and does not participate in the reaction.
- a periodic stirring process is required to treat the settled neodymium oxide powder.
- various process problems occurred, such as an increase in the difficulty of the process and a decrease in yield.
- granules (GR) comprising neodymium compounds are provided in an electrolytic cell. Therefore, the granules GR can be easily injected without scattering in the air.
- the density of the granules (GR) is smaller than the density of the electrolyte (EL), they can continuously float on the interface (EL-S) of the electrolyte (EL), so the granules (GR) are precipitated at the bottom of the electrolytic cell (EB). It doesn't work.
- the neodymium compound may be continuously supplied to the electrolyte EL while the granules GR remain at the interface EL-S of the electrolyte EL. Since continuous electrolytic smelting is possible for a long time, the process speed is increased, and the cost used in the process can also be reduced.
- the concentration of the neodymium compound in the electrolyte EL may be maintained constant.
- the concentration of the neodymium compound in the electrolyte EL may be maintained at about 0.1 to 5 wt%, about 0.5 to 3 wt%, about 1 to 3 wt%, or about 2 wt%.
- the providing of the granules GR may include covering the exposed portion of the anode AN and the interface EL-S of the electrolyte EL with the granules GR.
- the interface EL-S of the electrolyte EL is defined as an interface where the electrolyte EL and air come into contact.
- the cathode CT and the anode AN may include materials commonly used in the art.
- the cathode CT may include tungsten or molybdenum, and the anode AN may include graphite.
- the cathode CT may be a tungsten electrode made of tungsten, and the anode AN may be a graphite electrode made of graphite.
- the cathode CT may include, for example, iron (Fe).
- Fe iron
- neodymium may be smelted in an alloy form (NdFe) with iron.
- one or more anodes AN in the electrolytic cell EB may be disposed, for example, two or more, but is not limited thereto.
- neodymium metal may be reduced by a reaction according to Reaction Formula 1 below.
- carbon dioxide gas is generated by a reaction according to Reaction Formula 2 below, and gases such as carbon tetrafluoride may be generated by a reaction according to Reaction Formula 3 below when process conditions are not maintained.
- the process temperature of the electrolytic smelting process may be higher than the temperature at which the neodymium compound is reduced by melting the electrolyte.
- the electrolytic smelting process may be performed by selecting the most reasonable temperature from the viewpoint of thermal efficiency among temperatures of about 800 to 1300 °C, about 800 to 1100 °C, about 800 to 900 °C, or about 1200 °C.
- the cathode CT and/or the anode AN may be heated to a high temperature. At this time, exposed portions of the cathode CT and/or the anode AN may be oxidized by contact with air.
- the anode AN when the anode AN includes graphite, carbon in an exposed portion of the anode AN reacts with oxygen in the air to form carbon dioxide. In this case, since the consumption rate due to oxidation of the anode AN increases, the replacement cycle of the anode AN may be very frequent.
- high-temperature heat is applied to the electrolyte (EL)
- EL electrolyte
- a process of continuously replenishing the electrolyte (EL) is required. Therefore, there is a problem in that the process speed is delayed and the process cost is increased.
- the interface EL-S of the electrolyte EL and the exposed portion of the anode AN is prevented from being exposed to air.
- the granules GR covers the interface of the molten salt and at least a portion of the exposed portion of the anode AN so that the anode AN and the molten salt come into contact with the gas. can be blocked or reduced.
- the granules GR may cover both the interface of the molten salt and the exposed portion of the anode AN.
- oxidation of the anode AN by reaction with air can be prevented or reduced, and vaporization of the electrolyte EL into the air can also be prevented or reduced. Therefore, since the interval between replacing the anode AN or replenishing the electrolyte EL is minimized, continuous electrolytic smelting is possible for a long time and material costs can be reduced. Thus, according to one embodiment, excellent process speed and cost reduction can be achieved.
- fluorocarbon gas such as CF 4 or C 2 F 6 , which is a greenhouse gas
- CF 4 has a warming potential about 6,500 times higher than CO 2 and takes about 50,000 years to naturally decompose in the atmosphere.
- C 2 F 6 has a warming potential about 9,200 times higher than CO 2 Since the period is about 10,000 years, it can cause fatal environmental pollution. Therefore, according to the existing process, a lot of cost may be consumed to equip facilities for treating fluorocarbon gas.
- CF 4 gas is discharged while contacting the granules GR of the neodymium compound, for example, A chemical reaction may be performed according to Scheme 4 below.
- the shape of the granules (GR) may be spherical, or may be quasi-spherical with curves on the spherical surface.
- the embodiment is not limited thereto, and the granules (GR) may be defined in various forms depending on the manufacturing process and manufacturing method.
- the diameter of the granules (GR) is about 1 mm or more and 50 mm or less, about 1 mm or more and 30 mm or less, about 1 mm or more and 15 mm or less, about 1 mm or more and 10 mm or less, about 1 mm or more and 5 mm or less, or about may be 1 mm.
- the diameter of the granule GR may mean the average length of lines connecting two points on the circumference of the granule GR in a straight line passing through the center of gravity of the granule GR. .
- the aforementioned diameter of the granules (GR) may mean an individual diameter of each granule (GR) or an average diameter of a plurality of granules (GR). In one embodiment, the diameter of each of the plurality of granules (GR) may be substantially the same as or different from each other.
- the diameter of the granules (GR) is not limited to the above-mentioned length, but when the diameter of the granules (GR) is within the above-mentioned range, the exposed portion of the anode (AN) and the electrolyte (EL) interface (EL-S) are separated from the air. While sufficiently blocked, the volume can be appropriately maintained.
- neodymium compound may be defined as including one or more selected from the group consisting of neodymium oxide, praseodymium-neodymium oxide, neodymium oxalate, praseodymium-neodymium oxalate, neodymium carbonate, and praseodymium-neodymium carbonate. there is.
- neodymium oxide may include Nd 2 O 3
- neodymium oxalate may include Nd 2 (C 2 O 4 ) 3
- neodymium carbonate may include Nd 2 (CO 3 ) 3
- the theoretical decomposition potential of Nd 2 O 3 is about 2.4 to 2.6 V, which is lower than about 4.6 to 5.6 V, which is the decomposition potential of NdF 3 . Therefore, it is possible to selectively smelt Nd 2 O 3 in the electrolyte EL by applying a current in the decomposition potential region of Nd 2 O 3 .
- praseodymium-neodymium oxide, praseodymium-neodymium oxalate, and praseodymium-neodymium carbonate are respectively Nd 2 O 3 and Pr 6 O 11 , Nd 2 (C 2 O 4 ) 3 and Pr 2 (C 2 O 4 ) 3 and Nd 2 (CO 3 ) 3 and Pr 2 (CO 3 ) 3 may be physically mixed or chemically combined.
- Nd 2 O 3 is praseodymium-neodymium oxide based on the total weight. greater than 70 wt% (Nd 2 O 3 >70%), greater than 75 wt%, greater than 80 wt%, greater than 85 wt%, greater than 90 wt%, greater than 95 wt%, and Pr 6 O 11 is It may include less than 30% by weight, less than 25% by weight, less than 20% by weight, less than 15% by weight, less than 10% by weight, or less than 5% by weight.
- the mole ratio of praseodymium based on the total number of moles of the elements praseodymium and neodymium in the praseodymium-neodymium oxide is less than about 30%, less than 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5% can be
- Nd 2 (C 2 O 4 ) 3 and Pr 2 (C 2 O 4 ) 3 are chemically bonded praseodymium-neodymium oxalate (Nd 2 (C 2 O 4 ) 3 +Pr 2 (C 2 Nd 2 (C 2 O 4 ) 3 in O 4 ) 3 ) greater than 70% by weight (Nd 2 (C 2 O 4 ) 3 >70%), greater than 75% by weight based on the total weight of praseodymium-neodymium oxalate , greater than 80% by weight, greater than 85% by weight, greater than 90% by weight, greater than 95% by weight, and Pr 2 (C 2 O 4 ) 3 is less than 30% by weight, less than 25% by weight, 20% by weight less than, less than 15% by weight, less than 10% by weight, or less than 5% by weight.
- the mole ratio of praseodymium based on the total number of moles of the elements praseodymium and neodymium in the praseodymium-neodymium oxalate is less than about 30%, less than 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5% may be below.
- Nd 2 (CO 3 ) 3 and Pr 2 (CO 3 ) 3 are chemically bonded praseodymium-neodymium carbonate (Nd 2 (CO 3 ) 3 +Pr 2 (CO 3 ) 3 ) to Nd 2 ( CO 3 ) 3 greater than 70% by weight (Nd 2 (CO 3 ) 3 >70%), greater than 75%, greater than 80%, greater than 85%, greater than 90% by weight of praseodymium-neodymium carbonate greater than or equal to 95 wt%, and Pr 2 (CO 3 ) 3 is less than 30 wt%, less than 25 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt% can be included as
- the mole ratio of praseodymium based on the total number of moles of the elements praseodymium and neodymium in the praseodymium-neodymium carbonate is less than about
- electrolytic smelting it can be smelted in the form of a praseodymium-neodymium alloy.
- a permanent magnet may be manufactured from a praseodymium-neodymium alloy smelted according to an embodiment. For example, when the molar ratio of praseodymium is less than about 30%, less than 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5%, it is possible to manufacture a permanent magnet exhibiting excellent effects.
- the voids (CV) may be defined inside the granules (GR) or on the surface of the granules (GR).
- the voids (CV) may be defined as hemispherical or quasi-hemispherical.
- the diameter of the void (CV) may be defined as greater than or equal to 1 ⁇ m and less than or equal to 100 ⁇ m.
- the void CV is shown in more detail in FIGS. 6A to 6C to be described later.
- the volume ratio of the pores CV in the neodymium compound granules GR may be defined such that the density of the granules GR has a smaller value than the density of the electrolyte EL.
- the volume ratio of pores (CV) defined in the neodymium compound granules (GR) (volume of pores/volume of granules, hereinafter, porosity) is defined as greater than or equal to the value (unit: %) calculated by Equation 1 below It can be.
- the porosity may be greater than about 15%, greater than about 35%, greater than about 40%, greater than about 45%, greater than about 50%, or greater than about 37.55%.
- the apparent density of the granules (GR) may be smaller than the density of the molten salt.
- the porosity is calculated based on the volume defined by all the pores (CV) defined in the granules (GR).
- the apparent density of the granules (GR) is 2.0 g/cm 3 or more and 6.0 g/cm 3 or less, 2.0 g/cm 3 or more and 5.0 g/cm 3 or less, 2.5 g/cm 3 or more and 5.0 g/cm 3 Less than 3.0 g/cm 3 5.0 g/cm 3 or less or 3.0 g/cm 3 or more 4.5 g/cm 3 or less, and the density of the molten salt is 3.0 g/cm 3 or more and 6.0 g/cm 3 or less, 3.0 g/cm 3 or more and 5.0 g/cm 3 or less, 3.5 g/cm 3 or more and 5.0 g/cm 3 or less, 4.1 g/cm 3 or more and 5.0 g/cm 3 or less, 3.5 g/cm 3 or more and 4.5 g/cm 3 or less, or 4.1 g/cm 3 or more and 4.5 g/
- the fluoride-based electrolyte (EL) includes LiF and NdF 3 in a weight ratio of 30:70 and neodymium oxide is Nd 2 O 3
- the porosity is 37.55% or more
- the apparent density of the granules (GR) is may be less than or equal to about 4.52.
- the granules (GR) may float well on the molten salt.
- the granules (GR) are not easily broken by impact during transportation, storage and transportation convenience may be improved.
- neodymium compound granules GR
- the sequence of the process is not specified. It goes without saying that each step according to the method of the present invention may not proceed in the order described unless contradictory, and each step may proceed concurrently.
- the description of the neodymium compound granules (GR) used in the above-described neodymium compound electrolytic refining method is as it is for the neodymium compound granules (GR) produced by the manufacturing method according to the present invention. Of course, it can be applied.
- GR neodymium compound granules
- a granule precursor by adding a binder to the neodymium compound powder or adding a binder to a mixture of neodymium compound powder and graphite powder; drying the granule precursor; and applying heat of 800° C. to 1500° C. to the dried granule precursor for 30 minutes to 90 minutes to perform heat treatment and sintering.
- Mixing the neodymium compound powder and graphite powder may include providing the neodymium compound powder and graphite powder to a mixing device and rotating the mixing device.
- Forming the granule precursor may include adding a binder to a rotating mixing device.
- the binding agent allows the neodymium compounds or the neodymium compound and the graphite powder to be well bonded to each other so that the granule precursor is easily formed.
- the binder may be provided in the form of a solution in which the binder is dissolved in an aqueous solvent such as distilled water.
- the proportion of the binder based on the total weight of the binder solution may be about 1% to about 10%, about 3% to about 7% or about 4% by weight.
- Non-limiting examples of binders include water, methanol, ethanol, propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, polyvinylalcohol, polyvinylpyrrolidone, polyacrylic acid or polymethyl methacrylate.
- the mixing device may rotate at about 50 rpm to about 200 rpm, about 50 rpm to about 150 rpm, about 80 rpm to about 120 rpm, such as about 100 rpm.
- the mixing may include spraying a volatile organic compound.
- volatile organic compounds include, for example, organic compounds having a boiling point of 80° C. or less.
- organic compound having a boiling point of 80° C. or less include alcohol compounds such as methanol and ethanol, compounds commonly used in the art, such as n-hexane and ethyl acetate.
- the sintering step includes applying heat of about 800 ° C to about 1500 ° C, about 1100 ° C to about 1400 ° C, about 1200 ° C to about 1400 ° C, about 1250 ° C to about 1350 ° C or about 1300 ° C to the dried granule precursor.
- the above-described step of applying heat may be performed for about 30 to 90 minutes.
- the sintering may include heating of about 800 ° C to about 1500 ° C, about 1100 ° C to about 1400 ° C, about 1200 ° C to about 1400 ° C, about 1250 ° C to about 1350 ° C or about 1300 ° C for about 30 minutes to about 1300 ° C It may include applying for 90 minutes.
- the sintering degree and density of the manufactured neodymium compound granules may be suitable for use in the above-described electrolytic smelting process.
- the weight ratio of the neodymium compound and the graphite powder used to prepare the granule precursor may be 60:40 to 90:10, 70:30 to 80:20 or 75:25 to 85:15.
- the binder may be added in an amount of about 0.5% to about 3% by weight, about 1% to about 2% by weight, or about 1.5% by weight based on the total weight of the neodymium compound and the graphite powder.
- neodymium oxide may be Nd 2 O 3
- neodymium oxalate may be Nd 2 (C 2 O 4 ) 3
- neodymium carbonate may be Nd 2 (CO 3 ) 3
- neodymium oxide may be praseodymium-neodymium oxide.
- the neodymium compound granules (GR) may have one or more pores defined.
- the voids (CV) may be defined while graphite is burned or the binder evaporates, and the voids (CV) may be defined while the neodymium compound is sintered.
- the apparent density of the granules (GR) is 2.0 g/cm 3 or more and 6.0 g/cm 3 or less, 3.0 g/cm 3 or more and 5.0 g/cm 3 or less, or 3.0 g/cm 3 or more and 4.5 g/cm 3 or less, and the density of the molten salt is 3.0 g/cm 3 or more and 6.0 g/cm 3 or less, 3.0 g/cm 3 or more and 5.0 g/cm 3 or less, 3.5 g/cm 3 or more and 5.0 g/cm 3 or less, 4.1 g/cm 3 or more.
- the porosity may be greater than about 15%, greater than about 35%, greater than about 40%, greater than about 45%, greater than about 50%, or greater than about 37.55%.
- the neodymium compound granules (GR) prepared by the manufacturing method of an embodiment may be used in the above-described neodymium electrolytic smelting process.
- the prepared neodymium compound granules (GR) may be pulverized into two or more pieces and used in a neodymium electrolytic smelting process.
- neodymium compound granules (GR) are defined as comprising pulverized products of neodymium compound granules (GR).
- Nd 2 O 3 powder Prepare 78.5 g of Nd 2 O 3 powder, 20.0 g of graphite powder, and 37.5 g of polyvinyl alcohol (PVA) at a concentration of about 4% by weight.
- PVA polyvinyl alcohol
- Nd 2 O 3 powder and graphite powder were put into a raw material granulator as a mixing device and rotated at a rotational speed of 100 rpm for about 30 minutes. Thereafter, the PVA solution was added little by little to form granules, and about 10 ml of ethanol was sprayed to sphericalize the granules. Then, it was recovered after drying in a fan heater at 50 °C.
- the prepared dry granules were heated at about 1300° C. for 1 hour to burn (oxidize) or evaporate graphite and PVA, and sinter Nd 2 O 3 to prepare granules of Example 1.
- Figures 3 and 4 show views according to the steps of each process.
- 3 is Nd 2 O 3 powder and graphite powder mixing steps (a to c), granule formation steps, and granule spheronization steps (d).
- 4 is a view showing neodymium oxide granules (GR) of Example 1 prepared by applying heat to dry granules.
- GR neodymium oxide granules
- Example 2 The granules of Example 2 were prepared in the same manner as in Preparation Example 1, except that 83.5 g of Nd 2 O 3 powder, 15.0 g of graphite powder, and 37.5 g of polyvinyl alcohol (PVA) at a concentration of about 4% by weight were used.
- the granules of Example 2 prepared in FIG. 5 are shown.
- 5 is a view showing neodymium oxide granules (GR) of Example 2 prepared by applying heat to dry granules.
- GR neodymium oxide granules
- FIGS. 6A to 6C Figure 6a is a view showing a piece of granules (GR) of Example 1.
- 6B is an enlarged view showing granules (GR) of Example 1 magnified 1000 times.
- 6C is an enlarged view showing granules (GR) of Example 1 magnified 5000 times.
- gaps (CV) defined as graphite particles are burned are confirmed.
- a void (CV) defined as neodymium oxide is sintered is confirmed.
- the density of the granules GR can be smaller than that of the electrolyte EL by defining pores CV in the granules GR by combustion of graphite particles and sintering of neodymium oxide. do.
- the strength of the granules (GR) is strengthened by sintering, so that they are not easily broken and thus the transportability is excellent.
- the sintering proceeded well to the inside of the prepared granules (GR) so that the Nd 2 O 3 particles were well connected and had strength that was not easily broken by external impact. do.
- the density of the granules (GR) was also formed very suitable for the electrolytic smelting process of neodymium compounds using a fluoride-based electrolyte. Therefore, the granules (GR) containing neodymium compounds prepared according to one embodiment are very suitable for use in neodymium electrolytic smelting processes.
- the raw material contained in the ton bag was put into each storage hopper using a hoist.
- the NdF3 + LiF raw material (electrolyte) mixed in the storage hopper was put into the electrolytic smelting furnace using a shuttle car and a screw conveyor.
- the electrolyte was melted using a graphite electrode connected to an AC power supply to create a molten salt, and an additional electrolyte was added to melt it to an appropriate height.
- the electrolytic smelting furnace was connected to a DC power supply with a graphite anode and a tungsten cathode, and Nd oxide was injected while applying a current.
- the Nd metal generated in the tungsten crucible at the bottom of the electrolytic furnace was scooped out using a titanium ladle or recovered using a tapping furnace at the bottom.
- the recovered metal was solidified using a chain conveyor and an argon chamber to obtain reduced neodymium.
- neodymium is electrolytically smelted using granules containing a neodymium compound and having one or more pores defined, so that the powder is prevented from scattering or precipitated in an electrolytic cell during the process, thereby achieving excellent process efficiency and industrial mass production.
- a suitable electrolytic smelting process of neodymium is provided.
- oxidation of the electrode provided in the electrolytic cell is prevented, vaporization of the electrolyte is prevented, and emission of greenhouse gases is reduced, thereby achieving excellent process efficiency, suitable for industrial mass production, and eco-friendly electrolytic smelting of neodymium. process is provided.
- a process for producing neodymium compound granules suitable for use in an electrolytic smelting process of neodymium which achieves excellent process efficiency and is suitable for industrial mass production.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Claims (16)
- 캐소드 및 애노드가 구비된 전해조 상에 정의된 개구부를 통해 불화물계 전해질을 제공하는 단계;상기 전해조 상에 정의된 개구부를 통해 네오디뮴 화합물을 포함하고 1 이상의 공극이 정의된 그래뉼을 제공하는 단계;상기 전해질의 용융염에 상기 그래뉼의 적어도 일부가 용해되는 단계; 및상기 캐소드에서 네오디뮴이 환원되는 단계를 포함하고,상기 공극은 상기 그래뉼의 내부 또는 외부에 정의되며, 상기 그래뉼의 겉보기 밀도는 상기 용융염의 밀도보다 작은 것인, 네오디뮴 화합물을 전해 제련하는 방법.
- 제1 항에 있어서,상기 캐소드 및 애노드의 적어도 일부는 상기 용융염에 침지된 것인, 방법.
- 제2 항에 있어서,상기 애노드의 적어도 일부는 공기 중에 노출되어 있으며,상기 그래뉼을 제공하는 단계에서, 상기 그래뉼은 상기 용융염의 계면 및 상기 애노드의 노출부의 적어도 일부를 덮어 상기 애노드 및 상기 용융염이 기체와 접촉하는 것을 차단 또는 감소시키는 것인, 방법.
- 제1 항에 있어서,상기 캐소드는 텅스텐, 몰리브덴 또는 철을 포함하고,상기 애노드는 그래파이트를 포함하는 것인, 방법.
- 제1 항에 있어서,상기 그래뉼의 직경은 1mm 이상 50mm 이하인 것인, 방법.
- 제1 항에 있어서,상기 그래뉼은, 겉보기 밀도가 2.0 g/cm3 이상 6.0 g/cm3 이하이고, 공극률이 15% 이상인 것인, 방법.
- 제1 항에 있어서,상기 불화물계 전해질은 LiF 및 NdF3을 포함하는 것인, 방법.
- 제1 항에 있어서,상기 불화물계 전해질은 LiF 및 NdF3를 40:60 내지 5:95의 중량 비율로 포함하는 것인, 방법.
- 제1 항에 있어서,상기 용융염의 밀도는 3.0 g/cm3 이상 6.0 g/cm3 이하인 것인, 방법.
- 제1 항에 있어서,상기 네오디뮴 화합물은 네오디뮴 산화물, 프라세오디뮴-네오디뮴 산화물, 네오디뮴 옥살레이트, 프라세오디뮴-네오디뮴 옥살레이트, 네오디뮴 카보네이트, 및 프라세오디뮴-네오디뮴 카보네이트로 이루어지는 군으로부터 선택되는 하나 이상을 포함하는 것인, 방법.
- 제10 항에 있어서,상기 프라세오디뮴-네오디뮴 산화물은 Nd2O3+Pr6O11(Nd2O3>70%)을 포함하고, 상기 프라세오디뮴-네오디뮴 옥살레이트는 Nd2(C2O4)3+Pr2(C2O4)3(Nd2(C2O4)3>70%)을 포함하며, 상기 프라세오디뮴-네오디뮴 카보네이트는 Nd2(CO3)3+Pr2(CO3)3(Nd2(CO3)3>70%)를 포함하는 것인, 방법.
- 네오디뮴 화합물의 분말에 결합제를 첨가하거나, 네오디뮴 화합물의 분말과 흑연 분말을 혼합한 혼합물에 결합제를 첨가하여 그래뉼 전구체를 형성하는 단계;상기 그래뉼 전구체를 건조하는 단계; 및상기 건조된 그래뉼 전구체에 800℃ 내지 1500℃의 열을 가하여 열처리 및 소결하는 단계를 포함하는, 전해 제련에 사용되는 네오디뮴 화합물 그래뉼의 제조 방법.
- 제12 항에 있어서,상기 네오디뮴 화합물은 네오디뮴 산화물, 프라세오디뮴-네오디뮴 산화물, 네오디뮴 옥살레이트, 프라세오디뮴-네오디뮴 옥살레이트, 네오디뮴 카보네이트 및 프라세오디뮴-네오디뮴 카보네이트로 이루어지는 군으로부터 선택되는 하나 이상을 포함하는 것인, 방법.
- 제13 항에 있어서,상기 프라세오디뮴-네오디뮴 산화물은 Nd2O3+Pr6O11(Nd2O3>70%)을 포함하고, 상기 프라세오디뮴-네오디뮴 옥살레이트는 Nd2(C2O4)3+Pr2(C2O4)3(Nd2(C2O4)3>70%)을 포함하며, 상기 프라세오디뮴-네오디뮴 카보네이트는 Nd2(CO3)3+Pr2(CO3)3(Nd2(CO3)3>70%)를 포함하는 것인, 방법.
- 제12 항에 있어서,상기 네오디뮴 화합물 그래뉼의 내부 또는 외부에는 1 이상의 공극이 정의된 것인, 방법.
- 제12 항에 있어서,상기 그래뉼은, 겉보기 밀도가 2.0 g/cm3 이상 6.0 g/cm3 이하이고, 공극률이 15% 이상인 것인, 방법.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280009843.0A CN116710405A (zh) | 2021-09-10 | 2022-09-06 | 用于对钕化合物进行电解提取的方法及用于该方法的钕化合物颗粒的制造方法 |
US18/263,109 US20240093399A1 (en) | 2021-09-10 | 2022-09-06 | Method for electrowinning neodymium compound and manufacturing method for neodymium compound granules used thereof |
JP2023541096A JP2024502451A (ja) | 2021-09-10 | 2022-09-06 | ネオジム化合物を電解精錬する方法およびこれに使用されるネオジム化合物グラニュールの製造方法 |
AU2022343390A AU2022343390A1 (en) | 2021-09-10 | 2022-09-06 | Electrolytic refining method for neodymium compound and preparation method for neodymium compound granule used therefor |
CA3203655A CA3203655A1 (en) | 2021-09-10 | 2022-09-06 | Method for electrowinning neodymium compound and manufacturing method for neodymium compound granules used thereof |
EP22867670.6A EP4257733A1 (en) | 2021-09-10 | 2022-09-06 | Electrolytic refining method for neodymium compound and preparation method for neodymium compound granule used therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2021-0120861 | 2021-09-10 | ||
KR1020210120861A KR102433224B1 (ko) | 2021-09-10 | 2021-09-10 | 네오디뮴 산화물을 전해 제련하는 방법 및 이에 사용되는 네오디뮴 산화물 그래뉼의 제조 방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023038401A1 true WO2023038401A1 (ko) | 2023-03-16 |
Family
ID=83112367
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2022/013361 WO2023038401A1 (ko) | 2021-09-10 | 2022-09-06 | 네오디뮴 화합물을 전해 제련하는 방법 및 이에 사용되는 네오디뮴 화합물 그래뉼의 제조 방법 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20240093399A1 (ko) |
EP (1) | EP4257733A1 (ko) |
JP (1) | JP2024502451A (ko) |
KR (1) | KR102433224B1 (ko) |
CN (1) | CN116710405A (ko) |
AU (1) | AU2022343390A1 (ko) |
CA (1) | CA3203655A1 (ko) |
WO (1) | WO2023038401A1 (ko) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102433224B1 (ko) * | 2021-09-10 | 2022-08-18 | 주식회사 케이에스엠테크놀로지 | 네오디뮴 산화물을 전해 제련하는 방법 및 이에 사용되는 네오디뮴 산화물 그래뉼의 제조 방법 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0748688A (ja) * | 1994-07-26 | 1995-02-21 | Sumitomo Light Metal Ind Ltd | ネオジム−鉄合金の製造装置 |
JPH10176296A (ja) * | 1996-11-13 | 1998-06-30 | Usa Government | 廃ガス中に過フッ化炭素化合物をともなわないネオジムの電解生成 |
KR20070001137A (ko) | 2004-01-23 | 2007-01-03 | 베리 스몰 파티클 컴파니 피티와이 리미티드 | 금속 산화물의 제조 방법 |
KR20160116429A (ko) * | 2015-03-30 | 2016-10-10 | 충남대학교산학협력단 | 전해제련법을 이용한 네오디뮴금속 회수장치 |
JP2020158730A (ja) | 2019-03-28 | 2020-10-01 | タテホ化学工業株式会社 | 化学蓄熱用造粒体及びその製造方法 |
KR102433224B1 (ko) * | 2021-09-10 | 2022-08-18 | 주식회사 케이에스엠테크놀로지 | 네오디뮴 산화물을 전해 제련하는 방법 및 이에 사용되는 네오디뮴 산화물 그래뉼의 제조 방법 |
-
2021
- 2021-09-10 KR KR1020210120861A patent/KR102433224B1/ko active IP Right Grant
-
2022
- 2022-09-06 AU AU2022343390A patent/AU2022343390A1/en active Pending
- 2022-09-06 US US18/263,109 patent/US20240093399A1/en active Pending
- 2022-09-06 WO PCT/KR2022/013361 patent/WO2023038401A1/ko active Application Filing
- 2022-09-06 CA CA3203655A patent/CA3203655A1/en active Pending
- 2022-09-06 CN CN202280009843.0A patent/CN116710405A/zh active Pending
- 2022-09-06 EP EP22867670.6A patent/EP4257733A1/en active Pending
- 2022-09-06 JP JP2023541096A patent/JP2024502451A/ja active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0748688A (ja) * | 1994-07-26 | 1995-02-21 | Sumitomo Light Metal Ind Ltd | ネオジム−鉄合金の製造装置 |
JPH10176296A (ja) * | 1996-11-13 | 1998-06-30 | Usa Government | 廃ガス中に過フッ化炭素化合物をともなわないネオジムの電解生成 |
KR20070001137A (ko) | 2004-01-23 | 2007-01-03 | 베리 스몰 파티클 컴파니 피티와이 리미티드 | 금속 산화물의 제조 방법 |
KR20160116429A (ko) * | 2015-03-30 | 2016-10-10 | 충남대학교산학협력단 | 전해제련법을 이용한 네오디뮴금속 회수장치 |
JP2020158730A (ja) | 2019-03-28 | 2020-10-01 | タテホ化学工業株式会社 | 化学蓄熱用造粒体及びその製造方法 |
KR102433224B1 (ko) * | 2021-09-10 | 2022-08-18 | 주식회사 케이에스엠테크놀로지 | 네오디뮴 산화물을 전해 제련하는 방법 및 이에 사용되는 네오디뮴 산화물 그래뉼의 제조 방법 |
Also Published As
Publication number | Publication date |
---|---|
JP2024502451A (ja) | 2024-01-19 |
CN116710405A (zh) | 2023-09-05 |
EP4257733A1 (en) | 2023-10-11 |
CA3203655A1 (en) | 2023-03-16 |
US20240093399A1 (en) | 2024-03-21 |
KR102433224B1 (ko) | 2022-08-18 |
AU2022343390A1 (en) | 2023-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2023038401A1 (ko) | 네오디뮴 화합물을 전해 제련하는 방법 및 이에 사용되는 네오디뮴 화합물 그래뉼의 제조 방법 | |
JP5526207B2 (ja) | 金属チタンの製造方法およびこの方法を用いて得られた金属チタン | |
CN103380218A (zh) | 有价金属的回收方法 | |
WO2012015278A2 (ko) | 원광 금속환원 및 전해정련 일관공정에 의한 원자로급 지르코늄 친환경 신 제련공정 | |
KR20080074092A (ko) | 금속 제조를 위한 열적 및 전기화학적 방법 | |
CN87102206A (zh) | 稀土氯化物的金属热还原 | |
WO2022019172A1 (ja) | 有価金属を回収する方法 | |
EA011796B1 (ru) | Способ и установка для извлечения цветных металлов из отходов производства цинка | |
JP7400589B2 (ja) | 廃リチウムイオン電池からの有価金属の回収方法 | |
WO2019201070A1 (zh) | 采用废弃铝材生产氢氧化铝的方法 | |
CN106884110B (zh) | 一种高真空电弧炉制备镍基高温合金的方法 | |
CN100532653C (zh) | 一种熔盐电解提取钛的方法 | |
JP2002060855A (ja) | Nd系希土類磁石スクラップのリサイクル方法 | |
CN112921360B (zh) | 一种熔盐电解制备稀土金属的方法 | |
CN101509139A (zh) | 一种由钛铁矿制备钛铁合金的方法 | |
Bian et al. | Recovery of rare earth elements from NdFeB magnet scraps by pyrometallurgical processes | |
JPH0790411A (ja) | 高純度希土類金属の製造方法 | |
WO2018008850A1 (ko) | 전해채취법을 이용한 환원철 제조방법 및 이에 따라 제조된 환원철 | |
JPH0559199B2 (ko) | ||
JP4574826B2 (ja) | テルルを回収する方法 | |
JP3109290B2 (ja) | 箔スクラップからのアルミニウム回収方法 | |
CN113445080B (zh) | 一种基于液态阴极-可溶性含钛阳极直接电解制备钛合金的方法 | |
WO2022108007A1 (ko) | 불화물계 전해질을 이용한 고융점 금속 산화물의 환원 방법 및 시스템 | |
JP7487510B2 (ja) | 有価金属を回収する方法及びマグネシア耐火物 | |
CN112921362B (zh) | 一种熔盐电解制备稀土合金的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22867670 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 3203655 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023541096 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280009843.0 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2022343390 Country of ref document: AU Date of ref document: 20220906 Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2022867670 Country of ref document: EP Effective date: 20230705 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18263109 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |