EP0548498A1 - Procédé d'électrolyse de composés de néodyme en milieu fondu - Google Patents
Procédé d'électrolyse de composés de néodyme en milieu fondu Download PDFInfo
- Publication number
- EP0548498A1 EP0548498A1 EP92118082A EP92118082A EP0548498A1 EP 0548498 A1 EP0548498 A1 EP 0548498A1 EP 92118082 A EP92118082 A EP 92118082A EP 92118082 A EP92118082 A EP 92118082A EP 0548498 A1 EP0548498 A1 EP 0548498A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- neodymium
- fluoride
- melt
- magnetite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 30
- 150000003839 salts Chemical class 0.000 title description 5
- 150000002798 neodymium compounds Chemical class 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 24
- 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 24
- 239000000155 melt Substances 0.000 claims description 22
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 2
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- PXAWCNYZAWMWIC-UHFFFAOYSA-N [Fe].[Nd] Chemical compound [Fe].[Nd] PXAWCNYZAWMWIC-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000640 Fe alloy Inorganic materials 0.000 abstract description 10
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001206 Neodymium Chemical class 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
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
Definitions
- the invention relates to a process for the electrolysis of a melt containing neodymium oxide, neodymium fluoride, alkali metal fluoride and optionally alkaline earth metal fluoride with one or more anodes immersed in the melt.
- Both metallic neodymium and neodymium-iron master alloys which are becoming increasingly important as materials for the production of permanent magnet materials, such as neodymium-iron-boron alloys (DE-A1 37 29 361), can be produced by electrolytic ones Reduction of molten salts containing neodymium compounds can be produced, the neodymium-iron alloys being able to be obtained using iron cathodes.
- JP 2-4994 A1 (Chemical Abstracts Vol.112, 1990, 225539) describes the electrolysis of melts from 65.9% by weight (20 mol%) neodymium fluoride and 34.1% by weight (80 mol%) lithium fluoride or from 2% by weight of neodymium oxide, 64.6% by weight (20 mol%) of neodymium fluoride and 33.4% by weight (80 mol%) of lithium fluoride with carbon anodes and carbon or iron cathodes. To remove the carbon that accumulates on the surface of the molten bath during electrolysis, the melt is electrolyzed in an oxygen-containing atmosphere.
- EP 0 177 233 B1 also relates to the production of neodymium-iron alloys by melt flow electrolysis.
- a bath consisting of a melt of 35-76% by weight of neodymium fluoride, 20-60% by weight of lithium fluoride, 0-40% by weight of barium fluoride and 0-20% by weight of calcium fluoride is made under protective gas with at least one carbon anode and at least one Iron cathode is electrolyzed, the neodymium which deposits on the iron cathode reacts with the iron to form an alloy, and the neodymium-iron alloy which is liquid at the bath temperature drips from the cathode into a container underneath.
- the electrolysis takes place at 770 ° - 950 ° C by applying a direct current to the anode with a current density of 0.05 - 0.60 A / cm2 and to the iron cathode with a current density of 0.50 - 55 A / cm2.
- the carbon anodes used in these known processes are consumed by oxidation, so that they have to be constantly readjusted and frequently replaced.
- both the molten baths and the neodymium-iron alloys that are formed are enriched with carbon and the impurities present in the anode material and oxides and fluorides of the carbon enter the atmosphere surrounding the electrolysis cell.
- the method is intended to obtain high-purity neodymium and neodymium-iron alloys, as are required for the production of permanent magnet materials.
- the method which achieves the object is characterized in that magnetite is used as the anode material.
- the anode material can be applied as a coating on an electrically conductive carrier material, for example iron (EP 0 443 730 A1).
- anodes made entirely of magnetite can equally well be used.
- the anodes can be both in compact form and as hollow bodies. The latter proves to be favorable if a possible decomposition or the conversion of the magnetite into less conductive iron oxides is to be prevented.
- a protective gas can be pressed through the hollow body or - with dense, non-porous magnetite material - a negative pressure or positive pressure can be generated within the hollow body.
- a protective gas is also used to generate the excess pressure.
- the process has proven particularly useful when the electrolysis is carried out at a melt temperature between 750 ° C and 1100 ° C and under a protective gas.
- protective gases which form an inert protective atmosphere and thus prevent undesired reactions of the melt and the electrodes, especially with the atmospheric oxygen.
- Protective gases suitable for the process according to the invention are, for example, helium, argon and nitrogen.
- Salt melts suitable for the process consist in particular of 2-5% by weight of neodymium oxide 35-92% by weight of neodymium fluoride, 6-60% by weight of lithium fluoride, 0-40% by weight of barium fluoride and 0-20% by weight of calcium fluoride.
- Salt melts of 2-4% by weight of neodymium oxide, 78-90% by weight of neodymium fluoride and 8-20% by weight of lithium fluoride are preferred, in particular those of 2% by weight of neodymium oxide, 80% by weight of neodymium fluoride and 18% by weight of lithium fluoride.
- the process can be carried out in electrolysis cells as are known per se for the electrolysis of molten salts containing neodymium compounds, for example in the cells described by E. Morrice et al and in EP 0 177 233 B1.
- Insoluble cathodes made of heat-resistant (refractory) metals, preferably made of tungsten or molybdenum, or - to obtain the neodymium-iron alloys - consuming cathodes made of iron are suitable for the process.
- One or more cathodes can be present, which either dip into the melt or are arranged horizontally on the bottom of the electrolytic cell and are then completely covered by the melt.
- the advantages of the method according to the invention characterized by the use of magnetite instead of the carbon which is consumed as anode material are a simpler operation and a longer operating time since the anodes have to be readjusted less frequently and replaced less frequently.
- the impurities caused by the carbon anodes are avoided both in the melt and in the alloys obtained and in the exhaust air. Because of their purity, the neodymium-iron alloys produced by the process according to the invention are very well suited for the production of permanent magnet materials.
- a melt of 2% by weight neodymium oxide, 80% by weight neodymium fluoride and 18% by weight lithium fluoride is prepared in the graphite crucible of a cell, corresponding to that described by E. Morrice et al, and at 980 ° C. under argon on an anode electrolyzed from magnetite and an iron cathode.
- the current is 55 A, the cell voltage 29 V, the anodic current density 0.8 A / dm2, the cathodic current density 7 A / dm2 and the duration of the electrolysis 2 hours.
- the alloy dripping from the iron cathode into the container underneath consists of 72% by weight of neodymium and 28% by weight of iron.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4142160A DE4142160C1 (fr) | 1991-12-20 | 1991-12-20 | |
| DE4142160 | 1991-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0548498A1 true EP0548498A1 (fr) | 1993-06-30 |
| EP0548498B1 EP0548498B1 (fr) | 1995-09-06 |
Family
ID=6447603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92118082A Expired - Lifetime EP0548498B1 (fr) | 1991-12-20 | 1992-10-22 | Procédé d'électrolyse de composés de néodyme en milieu fondu |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5346608A (fr) |
| EP (1) | EP0548498B1 (fr) |
| JP (1) | JP2577172B2 (fr) |
| AT (1) | ATE127539T1 (fr) |
| AU (1) | AU654419B2 (fr) |
| DE (2) | DE4142160C1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025038994A1 (fr) * | 2023-08-17 | 2025-02-20 | Samy Ashkar | Systèmes et procédés d'extraction de métaux de terres rares à partir de déchets |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0289434A1 (fr) * | 1987-04-21 | 1988-11-02 | Aluminium Pechiney | Procédé de préparation d'alliages mères de fer et de néodyme par électrolyse de sels oxygénés en milieu fluorures fondus |
| WO1990001078A1 (fr) * | 1988-07-28 | 1990-02-08 | Massachusetts Institute Of Technology | Procede et appareil de production de metaux par electrolyse |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088548A (en) * | 1973-05-15 | 1978-05-09 | Townsend Douglas W | Electrolytic method and apparatus for refractory metals using a hollow carbon electrode |
| US4684448A (en) * | 1984-10-03 | 1987-08-04 | Sumitomo Light Metal Industries, Ltd. | Process of producing neodymium-iron alloy |
| JPS63166987A (ja) * | 1986-12-27 | 1988-07-11 | Asahi Chem Ind Co Ltd | 希土類金属の製造方法 |
| DE3729361A1 (de) * | 1987-09-02 | 1989-03-16 | Max Planck Gesellschaft | Optimierung der gefuegestruktur des fe-nd-b-basis sintermagneten |
| GB8804859D0 (en) * | 1988-03-01 | 1988-03-30 | Ici Plc | Electrode & construction thereof |
| JP2596976B2 (ja) * | 1988-06-22 | 1997-04-02 | 昭和電工株式会社 | ネオジム又はネオジム合金の製造方法 |
| JPH03229888A (ja) * | 1990-02-05 | 1991-10-11 | Tokai Carbon Co Ltd | マグネタイト被覆電極の製造方法 |
-
1991
- 1991-12-20 DE DE4142160A patent/DE4142160C1/de not_active Expired - Fee Related
-
1992
- 1992-10-22 EP EP92118082A patent/EP0548498B1/fr not_active Expired - Lifetime
- 1992-10-22 DE DE59203579T patent/DE59203579D1/de not_active Expired - Fee Related
- 1992-10-22 AT AT92118082T patent/ATE127539T1/de not_active IP Right Cessation
- 1992-12-18 JP JP4338591A patent/JP2577172B2/ja not_active Expired - Lifetime
- 1992-12-18 AU AU30288/92A patent/AU654419B2/en not_active Ceased
- 1992-12-18 US US07/992,691 patent/US5346608A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0289434A1 (fr) * | 1987-04-21 | 1988-11-02 | Aluminium Pechiney | Procédé de préparation d'alliages mères de fer et de néodyme par électrolyse de sels oxygénés en milieu fluorures fondus |
| WO1990001078A1 (fr) * | 1988-07-28 | 1990-02-08 | Massachusetts Institute Of Technology | Procede et appareil de production de metaux par electrolyse |
Non-Patent Citations (1)
| Title |
|---|
| Section Ch, Week 8833, 11. Juli 1988 Derwent Publications Ltd., London, GB; Class M28, AN 88-232370 & JP-A-63 166 987 (ASAHI CHEMICAL IND. KK) * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU654419B2 (en) | 1994-11-03 |
| US5346608A (en) | 1994-09-13 |
| DE4142160C1 (fr) | 1993-03-11 |
| EP0548498B1 (fr) | 1995-09-06 |
| JPH0688279A (ja) | 1994-03-29 |
| ATE127539T1 (de) | 1995-09-15 |
| AU3028892A (en) | 1993-06-24 |
| DE59203579D1 (de) | 1995-10-12 |
| JP2577172B2 (ja) | 1997-01-29 |
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