WO2014013929A1 - 希土類元素含有合金からの希土類回収方法 - Google Patents
希土類元素含有合金からの希土類回収方法 Download PDFInfo
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- WO2014013929A1 WO2014013929A1 PCT/JP2013/068963 JP2013068963W WO2014013929A1 WO 2014013929 A1 WO2014013929 A1 WO 2014013929A1 JP 2013068963 W JP2013068963 W JP 2013068963W WO 2014013929 A1 WO2014013929 A1 WO 2014013929A1
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- Prior art keywords
- rare earth
- earth element
- recovering
- electrolysis
- solution
- Prior art date
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 15
- 239000000956 alloy Substances 0.000 title claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 title description 30
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 229910052779 Neodymium Inorganic materials 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- 238000010828 elution Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052692 Dysprosium Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- -1 hydrofluoric acid ion Chemical class 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 229910001172 neodymium magnet Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910002065 alloy metal Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DUENOCOQRLXLKT-UHFFFAOYSA-N 5,8-diethyldodecan-6-ylphosphonic acid Chemical compound CCCCC(CC)CC(P(O)(O)=O)C(CC)CCCC DUENOCOQRLXLKT-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000828 alnico Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/045—Leaching using electrochemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- 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
- C22B5/00—General methods of reducing to metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
-
- 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
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a method for recovering rare earth elements from a rare earth element-containing alloy.
- Permanent magnets have been applied to various fields as a result of dramatic progress, and improvements in their performance and development of new devices have been made every day.
- Permanent magnet applications include voice coil motors for hard disk drives and optical pickup parts for DVD / CD for personal computers, microspeakers and vibration motors for mobile phones, and servo motors and linear motors for home appliances and industrial equipment. There is a motor.
- 100 or more permanent magnets are used for each hybrid electric vehicle such as HEV.
- a neodymium magnet usually has a ferromagnetic Nd 2 Fe 14 B intermetallic compound as a main phase, and is composed of a nonmagnetic B-rich phase, a nonmagnetic Nd-rich phase, and an oxide as an impurity. Furthermore, efforts are being made to improve magnetic properties by adding various elements to this.
- Neodymium magnets are expected to increase in demand in the future due to their high performance.
- rare earth metals such as Nd and Dy contained in neodymium magnets have a problem in resource supply, and if the demand for rare earth metals increases, the price of those metals is expected to rise rapidly.
- technological development relating to a method for recovering and separating rare earth metals from such rare earth magnets has been actively conducted.
- a rare earth element-iron-containing alloy is heated and oxidized in air, and then a rare earth element salt is generated and dissolved in a filtrate by an acid leaching method using a strong acid, and this is separated by filtration.
- an acid leaching method using a strong acid is separated by filtration.
- Patent Document 2 discloses that a rare earth element / iron-based magnet material is dissolved in a mineral acid solution, then a hydrofluoric acid ion-containing solution is added to precipitate a rare earth fluoride, and the precipitate is separated. The recovery of rare earth elements is described.
- Patent Document 3 discloses that rare earth-transition metal alloy scrap is immersed in an aqueous mineral acid ammonium salt solution, and a gas containing oxygen is circulated therein to oxidize the scrap to produce oxide and hydroxide powders. A method is described in which a precipitate is obtained, which is separated from an aqueous mineral acid ammonium salt solution, and the rare earth element is recovered from the separated precipitate.
- Patent Document 4 rare earth oxide scrap is put into a molten salt electrolytic bath, and the scrap is melted and separated into a rare earth oxide and a magnet alloy portion in the electrolytic bath, and the rare earth oxide dissolved in the electrolytic bath is electrolyzed. It is described that the magnetic alloy part is reduced to a rare earth metal by alloying it, and the magnet alloy part is alloyed with the rare earth metal to be regenerated as a rare earth metal-transition metal-boron alloy. Further, in Patent Document 5, a rare earth element-containing alloy is used as an anode, and an alloy of Co, Ni, Fe is deposited on the cathode by a direct electrolysis method, and oxalic acid is added to an electrolyte containing a rare earth element. Is separated and recovered, and fired in the atmosphere to separate and recover rare earth elements.
- the present inventors have conducted intensive research, and as a result, mixed rare earth element-containing alloy metal powder with an electrolytic solution, and electrolyzed it, thereby making the rare earth element extremely simple and efficient. It was found that it can be recovered.
- the present invention 1) A method for recovering a rare earth element, wherein the rare earth element is eluted by electrolysis in an electrolytic solution containing metal powder of a rare earth element-containing alloy, 2) The method for recovering rare earth elements according to 1) above, wherein a conductive salt is added to the electrolytic solution, 3) The method for recovering rare earth elements according to 1) or 2) above, wherein the pH of the electrolyte is 2 to 8, and the temperature of the electrolyte is 10 to 90 ° C.
- the present invention only performs electrolysis in an electrolytic solution containing metal powder of a rare earth element-containing alloy obtained from used permanent magnets or scraps (scraps) generated during production, the rare earth elements are extremely simple and efficient. It is an excellent method that can be recovered well.
- the present invention relates to a rare earth element from a rare earth element-containing alloy characterized in that a rare earth element-containing alloy metal powder contained in a permanent magnet or the like is mixed in an electrolytic solution and the rare earth element is eluted by electrolysis.
- the recovery method of the present invention can be applied to a known rare earth magnet as long as it is a rare earth permanent magnet, and the component composition is not particularly limited.
- Known rare earth magnets include, for example, Nd—Fe—B rare earth permanent magnets, which contain Nd, Fe, and B as typical components and, if necessary, Dy, Pr, Tb, Ho, Sm.
- rare earth elements such as Co, Cu, Cr, Ni and Al.
- the metal powder of the rare earth element-containing alloy of the present invention can be obtained, for example, from scraps (scrap) generated during the production of rare earth magnets. If the scrap is fine, such as pulverized powder or abrasive powder, it may be used directly. However, it is preferable to use a large-sized one such as a used permanent magnet after finely pulverizing it. Even when a part of the metal powder is an oxide, the recovery method of the present invention can be applied. Moreover, when containing organic substance, it is preferable to remove by roasting etc. in atmosphere, such as air
- atmosphere such as air
- This metal powder is mixed with an electrolyte prepared with conductive salt and pure water and electrolyzed.
- conductive salt for example, ammonium sulfate, ammonium nitrate, ammonium chloride, sodium chloride, sodium sulfate and the like can be used.
- stainless steel, Ti, graphite or the like can be used as the cathode and an insoluble anode or the like can be used as the anode.
- the pH of the electrolytic solution is preferably adjusted to 2-8. This is because if the pH is low (acidic), a large amount of Fe dissolves and the filterability of the residue deteriorates, and if the pH is high (alkaline), the elution rate of rare earth metals decreases.
- the temperature of the electrolytic solution is preferably adjusted to 10 to 90 ° C. in consideration of cost and the like. This is because when the electrolysis temperature is less than 10 ° C., the elution rate of the rare earth metal decreases, and when it exceeds 90 ° C., electrolysis becomes difficult due to evaporation of the electrolytic solution.
- the electrolysis conditions shown above vary depending on the type, nature, amount, etc. of the material, they can be selected and implemented as appropriate.
- rare earth elements are eluted as ions, while metals such as iron are eluted into the electrolytic solution and precipitated as iron hydroxide, or one of them. It can be removed from the electrolytic solution by electrodepositing the portion on the cathode.
- the metal powder is in contact with the anode as much as possible. Therefore, for example, it is effective to increase the number of contacts by stirring the electrolytic solution or to increase the contact area by increasing the area of the anode.
- the obtained rare earth element is eluted as ions, the solution from which the rare earth element is eluted is filtered and separated, and the rare earth element can be recovered by solvent extraction or crystallization.
- the solvent extraction method an organic solution in which an extractant is dissolved is added to a filtrate from which rare earth ions are eluted, so that the extractant and rare earth ions form a complex to be extracted and separated into the organic solution.
- an extractant for example, 2-ethylhexyl-2-ethylhexyl-phosphonic acid can be used.
- the solubility of the rare earth sulfate salt differs depending on the temperature of the sulfuric acid (for example, sodium sulfate, ammonium sulfate) electrolyte solution. Only the salt is crystallized and separated from the solution.
- the sulfuric acid for example, sodium sulfate, ammonium sulfate
- Example 1 A rare earth-containing scrap containing Fe (containing rare earth elements: Nd, Dy, Pr) was slurried with 1 L of pure water containing sodium chloride to prepare an electrolytic solution for electrolysis. At this time, the electrolysis conditions were pH: 2 to 3, electrolysis temperature: 20 ° C., current: 10 A, and electrolysis time of 20 hours. As a result, the elution rate of Nd was 95%, the elution rate of Dy was 98%, and the elution rate of Pr was 94%. About Fe, it precipitated as iron hydroxide.
- Example 2 A rare earth-containing scrap containing Fe (rare earth elements: containing Nd, Dy, Pr) was slurried with 1 L of pure water containing sodium sulfate to prepare an electrolytic solution for electrolysis.
- the electrolysis conditions were pH: 4, electrolysis temperature: 20 ° C., current: 5 A, and electrolysis time of 20 hours.
- the elution rate of Nd was 98%
- the elution rate of Dy was 99%
- the elution rate of Pr was 95%.
- Fe was electrodeposited on the cathode.
- the residue in the solution was removed by filtration to obtain a rare earth-containing post-filtration solution.
- the rare earth-containing scrap was added again to form a slurry, and electrolysis was performed again under the same conditions as described above, and the Nd concentration in the liquid was increased to about 100 g / l (solubility). Thereafter, the residue in the solution was removed by filtration, and the filtrate was heated to 60 ° C. to crystallize the rare earth sulfate of Nd, and this salt was recovered. At this time, the recovery rate was 69%.
- the liquid after crystallization still contains rare earth, but since this liquid can be reused in the electrolytic cell, the loss of rare earth ions can be considered to be basically zero. When such electrolysis is repeated, the concentration of Dy increases.
- the subsequent heating treatment at 60 ° C. causes crystallization of Dy sulfate.
- Dy can be recovered simultaneously with Nd.
- the recovery rate of Dy was 70%.
- the concentration of Pr increases, and when it rises to about 130 g / l, Pr sulfate crystallizes by the subsequent heat treatment at 60 ° C.
- Pr can be recovered together with Dy and Nd.
- the recovery rate of Pr was 68%.
- Nd, Dy and Pr rare earth metals can be efficiently recovered from the rare earth-containing scrap, and good filterability can be obtained. And this Nd, Dy, Pr could be used as a raw material of a reproduction
- the present invention uses rare earth element-containing alloy metal powder obtained from scraps such as used permanent magnets or scraps generated during production, and only electrolyzes an electrolytic solution containing this metal powder. There is a great industrial advantage in that it can be easily and efficiently collected.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
永久磁石の用途として、パソコンでは、ハードディスクドライブ用ボイスコイルモーターやDVD/CDの光ピックアップ用部品、携帯電話では、マイクロスピーカーやバイブレーションモーター、家電や産業機器関連では、サーボモーターやリニアモーターなどの各種モーターがある。また、HEVなどのハイブリッド電気自動車には、1台当たり100個以上の永久磁石が使用されている。
ネオジム磁石は、通常、強磁性のNd2Fe14B金属間化合物を主相とし、非磁性のBリッチ相、非磁性のNdリッチ相、さらに不純物としての酸化物などから構成されている。さらに、これに種々の元素を添加するなどして、磁気特性を改善させる取り組みが行われている。
例えば、特許文献1には、希土類元素-鉄含有合金を加熱して空気酸化した後、強酸を用いた酸浸出法により、希土類元素塩を生成して濾液中に溶解し、これを濾別して分離して、希土類元素を回収することが記載されている。
また、特許文献3には、希土類-遷移金属合金スクラップを、鉱酸アンモニウム塩水溶液に浸漬し、これに酸素を含む気体を流通させて、スクラップを酸化させて酸化物及び水酸化物の粉末を含む沈殿物を得て、これを鉱酸アンモニウム塩水溶液から分離して、この分離した沈殿物から希土類元素を回収する方法が記載されている。
また、特許文献4には、溶融塩電解浴に希土類酸化物スクラップを投入し、電解浴中にこのスクラップを希土類酸化物と磁石合金部に溶融分離させ、電解浴に溶解した希土類酸化物を電解により希土類金属に還元し、磁石合金部を希土類金属と合金化させ、希土類金属-遷移金属-ボロン合金として再生することが記載されている。
また、特許文献5には、希土類元素含有合金を陽極として、直接電解法により陰極にCo、Ni、Feの合金を析出させるとともに、希土類元素を含有する電解液に蓚酸を添加することで蓚酸塩を沈殿分離し、これを大気中で焼成して、希土類元素を分離回収することが記載されている。
1)希土類元素含有合金の金属粉を含有する電解液中で電解して、希土類元素を溶出させることを特徴とする希土類元素の回収方法、
2)電解液に電導塩を添加することを特徴とする上記1)記載の希土類元素の回収方法、
3)電解液のpHを2~8、電解液の液温を10~90℃とすることを特徴とする上記1)又は2)に記載の希土類元素の回収方法、
4)攪拌しながら電解を行うことを特徴とする上記1)~3)のいずれか一に記載の希土類元素の回収方法、
5)希土類元素が溶出した溶液から、希土類元素を回収することを特徴とする上記1)~4)のいずれか一に記載の希土類元素の回収方法、
6)希土類元素が溶出した溶液から、溶媒抽出あるいは結晶化法により希土類元素を回収することを特徴とする上記1)~5)のいずれか一に記載の希土類元素の回収方法、
本発明の回収方法は、希土類永久磁石であれば、公知の希土類磁石に適用することができ、その成分組成に特に制限はない。公知の希土類磁石としては、例えば、Nd-Fe-B系希土類永久磁石があり、これは、Nd、Fe、Bを典型的な成分とし、必要に応じて、Dy、Pr、Tb、Ho、Smなどの希土類元素や、Co、Cu、Cr、Ni、Alなどの遷移金属元素を含むものである。
但し、上記で示した電解条件は材料の種類、性質、量などによって異なるため、適宜選択して実施することができる。
このような電気的化学的な反応を効率的に進めるために、金属粉がアノードとできるだけ接触するようにすることが大切である。したがって、例えば、電解液を攪拌することで接触回数を増やしたり、アノードの面積を大きくして接触面積を広げたり、することが有効である。
溶媒抽出法は、希土類イオンが溶出した濾液に、抽出剤を溶解させた有機溶液を添加することで、抽出剤と希土類イオンが錯体を形成して有機溶液中に抽出、分離するものである。抽出剤として、例えば、2-エチルヘキシル-2-エチルヘキシル-ホスホン酸[2-ethylhexyl-2-ethylhexyl-phosphonic acid]を用いることができる。
また、結晶化法は、硫酸系(例えば硫酸ナトリウム、硫酸アンモニウム)の電解液に対して、温度の違いによって硫酸希土類塩の溶解度が異なるので、電解液の液温を高温にすることで、硫酸希土類塩のみを結晶化させ、溶液から分離するものである。
Feを含有する希土類含有スクラップ(希土類元素:Nd、Dy、Pr含有)を、塩化ナトリウムを含有する純水1Lでスラリー化して電解液とし、電解を行った。このとき電解条件は、pH:2~3、電解温度:20℃、電流:10A、電解時間20時間とした。この結果、Ndの溶出率は95%、Dyの溶出率は98%、Prの溶出率は94%であった。Feについては、水酸化鉄として沈殿した。
次に、電解終了後、溶液中の残渣をろ過除去して、この濾液を抽出剤:2-エチルヘキシル-2-エチルヘキシル-ホスホン酸[2-ethylhexyl-2-ethylhexyl-phosphonic acid] (大八化学工業社製、商品名「PC88A」)を用いて、溶媒抽出法により、希土類元素分離して、Nd、Dy、Prの希土類金属を回収した。この回収率は98%であった。
以上より、希土類含有スクラップからNd、Dy、Prの希土類金属を、効率的に回収することができ、また、良好なろ過性を得ることができた。そして、このNd、Dy、Prは再生永久磁石の原料として使用可能であった。
なお、溶出率(%)とは、スクラップ中の金属含有重量:A、電解後の残渣中の金属含有重量:Bとし、該金属が溶液中に溶け出した割合を示すものであり、溶出率(%)=(A-B)/ A×100で計算される(以下、実施例、比較例も同様とする)。
Feを含有する希土類含有スクラップ(希土類元素:Nd、Dy、Pr含有)を、硫酸ナトリウムを含有する純水1Lでスラリー化して電解液とし、電解を行った。このとき電解条件は、pH:4、電解温度:20℃、電流:5A、電解時間20時間とした。この結果、Ndの溶出率は98%、Dyの溶出率は99%、Prの溶出率は95%であった。Feについては、カソードに電着していた。
次に、電解終了後、溶液中の残渣をろ過除去して、希土類含有のろ過後液を得た。このろ過後液を用い、再度希土類含有スクラップを添加スラリー化し、上記と同条件で再度電解し、液中のNd濃度をおよそ100g/l(溶解度)まで上昇させた。
その後、溶液中の残渣をろ過除去し、この濾液60℃まで加温して、Ndの希土類硫酸塩が結晶化させ、この塩を回収した。このとき回収率は69%であった。なお、結晶化後の液にはまだ希土類を含んでいるが、電解槽にこの液を再利用できるので、希土類イオンの損失は基本的にゼロと考えることができる。
また、このような電解を繰り返していくと、Dyの濃度が上昇し、およそ100g/l(溶解度)まで上昇すると、その後の60℃の加温処理によりDyの硫酸塩が結晶化する。これによりDyはNdと同時に回収できる。このときDyの回収率は70%であった。
さらに、このようなろ過電解を繰り返していくと、Prの濃度が上昇し、およそ130g/lまで上昇すると、その後の60℃加熱処理によりPrの硫酸塩が結晶化する。これによりPrもDyやNdとともに回収できる。このときPrの回収率は68%であった。
以上より、希土類含有スクラップからNd、Dy、Prの希土類金属を、効率的に回収することができ、また、良好なろ過性を得ることができた。そして、このNd、Dy、Prは再生永久磁石の原料として使用可能であった。
Feを含有する希土類含有スクラップ(希土類元素:Nd、Dy、Pr含有)を、多量の塩酸を用いて酸浸出を行った。その結果、Nd,Dy,Prの溶出率は70~80%であったが、Feも80%溶出していた。さらに、酸浸出では、残渣のろ過性が非常に悪く、溶け出したFeの処理も問題となった。
Claims (6)
- 希土類元素含有合金の金属粉を含有する電解液中で電解して、希土類元素を溶出させることを特徴とする希土類元素の回収方法。
- 電解液に電導塩を添加することを特徴とする請求項1記載の希土類元素の回収方法。
- 電解液のpHを2~8、電解液の液温を10~90℃とすることを特徴とする請求項1又は2に記載の希土類元素の回収方法。
- 攪拌しながら電解を行うことを特徴とする請求項1~3のいずれか一項に記載の希土類元素の回収方法。
- 希土類元素が溶出した溶液から、希土類元素を回収することを特徴とする請求項1~4のいずれか一項に記載の希土類元素の回収方法。
- 希土類元素が溶出した溶液から、溶媒抽出あるいは結晶化法により希土類元素を回収することを特徴とする請求項1~5のいずれか一項に記載の希土類元素の回収方法。
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JP7076149B2 (ja) | 2020-02-04 | 2022-05-27 | 北京科技大学 | Nd-Fe-Bスクラップ溶液の電解再生方法 |
JP7213386B1 (ja) | 2022-06-13 | 2023-01-26 | ▲カン▼州晨光希土新材料有限公司 | 希土類金属又は希土類合金用浄化材料及びその製造方法、希土類金属又は希土類合金の浄化方法 |
JP2023181957A (ja) * | 2022-06-13 | 2023-12-25 | ▲カン▼州晨光希土新材料有限公司 | 希土類金属又は希土類合金用浄化材料及びその製造方法、希土類金属又は希土類合金の浄化方法 |
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JP5647750B2 (ja) | 2015-01-07 |
EP2781623A1 (en) | 2014-09-24 |
TWI567241B (zh) | 2017-01-21 |
EP2781623B1 (en) | 2017-04-05 |
US20150047469A1 (en) | 2015-02-19 |
EP2781623A4 (en) | 2015-11-11 |
CN104169471A (zh) | 2014-11-26 |
TW201413058A (zh) | 2014-04-01 |
JPWO2014013929A1 (ja) | 2016-06-30 |
KR20140108298A (ko) | 2014-09-05 |
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