EP0289434B1 - Procédé de préparation d'alliages mères de fer et de néodyme par électrolyse de sels oxygénés en milieu fluorures fondus - Google Patents

Procédé de préparation d'alliages mères de fer et de néodyme par électrolyse de sels oxygénés en milieu fluorures fondus Download PDF

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Publication number
EP0289434B1
EP0289434B1 EP88420124A EP88420124A EP0289434B1 EP 0289434 B1 EP0289434 B1 EP 0289434B1 EP 88420124 A EP88420124 A EP 88420124A EP 88420124 A EP88420124 A EP 88420124A EP 0289434 B1 EP0289434 B1 EP 0289434B1
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EP
European Patent Office
Prior art keywords
neodymium
process according
iron
anode
mixture
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.)
Expired - Lifetime
Application number
EP88420124A
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German (de)
English (en)
French (fr)
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EP0289434A1 (fr
Inventor
Yves Bertaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rio Tinto France SAS
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Aluminium Pechiney SA
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Publication date
Application filed by Aluminium Pechiney SA filed Critical Aluminium Pechiney SA
Priority to AT88420124T priority Critical patent/ATE70569T1/de
Publication of EP0289434A1 publication Critical patent/EP0289434A1/fr
Application granted granted Critical
Publication of EP0289434B1 publication Critical patent/EP0289434B1/fr
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    • 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
    • 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 preparation of master alloys of iron - neodymium by electrolysis of a neodymium salt containing oxygen in a medium containing mainly molten fluorides, using an iron cathode and d 'a carbon-based anode.
  • the present invention relates to a very efficient process combining the advantages of the electrolysis of ions containing oxygen, dissolved in a molten fluoride, on a consumable depolarizing anode and the judicious use of oxygenated salts with high kinetics of dissolution.
  • These compounds are very specially chosen and / or prepared or can result from in situ reactions of previously chosen species. Their behavior on electrolysis is fundamentally different from that of conventional calcined oxides.
  • the molten electrolyte bath can also be constituted, with or without the presence of NdF3 and / or LiF, by at least one fluoride whose decomposition potential is close to or more negative than that of NdF3, such as for example MgF2, ScF3, YF3 , CeF3, LaF3, BaF2, CaF2, SrF2 and allowing the complexing effect to solubilize the oxides.
  • Certain additives such as CaCl2, MgCl2, BaCl2 and LiCl can favorably modify certain physicochemical properties of fluoride mixtures, for example viscosity and / or density and / or resistivity electric.
  • the solute to be electrolyzed must dissolve very quickly in the solvent otherwise there may be in the vicinity of the positive electrode a depletion of oxide ions which causes polarization of the electrode.
  • impedance measurements such as those described in the publication of G. PICARD et al. Light Metals (1987) p. 507 that commercially available calcined neodymium oxides are long to dissolve which causes sludge at the bottom of the electrolysis cell and quickly leads to a blockage of production.
  • neodymium oxide very reactive because poorly crystallized, obtained by controlled under-calcination of carbonate or oxalate or other neodymium salts of organic acids, carbonate, oxalate, nitrate, sulfate , neodymium oxychloride and oxyfluoride behave quite differently and can be used without problems with amazing results.
  • the level of under-calcination is thus chosen and controlled after analysis of the thermogravimetric curve of the starting compound.
  • the dissolution of boron in the alloy can also be carried out by additions of ferro-boron, mixed or not mixed with the salt to be electrolyzed, in a proportion ranging up to 12% of boron.
  • One of the principles of the process is based on the reaction of dissolved oxyfluorinated species and adsorbed on the carbon anode, which makes it possible to lower the electrolysis voltage.
  • the current density at the anode that is to say the speed at which the oxide ions are "consumed” is adjusted in such a way that the speed of "production” of these ions by solvolysis is at least as great as the speed of "consumption” otherwise a polarization of the electrode is observed.
  • the cathode When the cathode is made up or covered with a metal giving an alloy with the neodymium, like for example iron, nickel or cobalt, the reduced neodymium diffuses in the cathode, is combined and if the temperature allows it, alloy formed melts and flows. In the latter case, a sufficient local temperature in the vicinity of the cathode makes it possible to obtain a liquid film and the simultaneous diffusion in this liquid of the metal constituting the cathode substrate and of the neodymium produced by reduction.
  • a metal giving an alloy with the neodymium like for example iron, nickel or cobalt
  • Neodymium is very soluble in this cathode liquid film. This solubility, by decreasing the absolute value of the actual decomposition voltage of neodymium salts (action on the activity of the reduced metal in the cathode alloy) promotes the reduction of neodymium to the detriment of other cations present in the solvent and poorly soluble in the liquid film and improves selectivity.
  • a cathodic current density is chosen which makes it possible to supply the sufficient quantity of neodymium to ally with all the iron which diffuses and to form the alloy in liquid form. Otherwise the metal obtained must be remelted later.
  • a cell such as that shown in FIG. 1 consisting of a cylindrical crucible 8 made of boron nitride with an internal diameter of 10 cm, a cathode 3 consisting of a soft iron rod with a diameter of 0.4 cm and d 'an anode 14 consisting of a carbon tube with an internal diameter of 7 cm, concentric with the cathode, and obtained from a mixture of coke of Gilsonite and 2% Fe2O3 as electrocatalyst.
  • the electrodes sink 3 cm into the electrolyte.
  • the cell is equipped with a cover 9 maintained under slight overpressure of neutral gas intended to entrain the anodic gases through the orifices 5 and 6 and to prevent the entry of air.
  • the whole is carried in an electric oven which can reach temperatures close to 1100 ° C.
  • the salt bath 2 used is a mixture (by weight) of LiF 13%, BaF2 31%, NdF3 56% melted at 870 ° C.
  • the cell is supplied via tube 4 using “cigarettes” with a diameter of 6 mm, length 30 mm, mass 3 g of neodymium oxalate previously calcined at 500 ° C. so that the transformation into oxide is not not complete.
  • the residual volatile compounds which escape suddenly on contact with the molten bath allow the powder to disperse and the particles to dissolve more quickly in the molten salt.
  • the intensity of the current flowing through the cell is 45 A, which corresponds to a cathode density of 11.9 A / cm2 and an anode density of 0.68 A / cm2.
  • the terminal voltage is kept constant (9V) thanks to a potentiostatic mounting.
  • the intensity of the "ripples" corresponding to the formation and flow of the drops towards the bottom of the crucible is then observed on the recording.
  • the electrolysis is continued for 32 h thanks to regular introductions of under-calcined oxalate cigarettes and, if necessary, NdF3 and to regular introduction of the cathode iron rods into the molten salt at the rate of their consumption.
  • the liquid metal contained in the bottom of the crucible is drawn up via an iron tube and it is siphoned off under an argon atmosphere in a boron nitride container fitted with a lid. .
  • a cell slightly different from that described in example 1 is used.
  • the cylindrical anode 15 of striated carbon obtained from coal pitch pitch coke, of diameter 7 cm is full and animated by a slow rotational movement (6 revolutions per minute). It is surrounded by 4 cylindrical cathodes 3 made of soft iron with a diameter of 0.2 cm.
  • the electrodes immerse 2 cm in the electrolyte obtained by melting and maintaining at 850 ° C in an electric oven of 78% NdF3, 17% LiF and 5% boron oxide by weight.
  • cigarettes with a diameter of 4 mm, length 30 mm, mass 6 g, of neodymium carbonate under-calcined at 500 ° C. are used as regular supply of electrolyte so that the residual volatile species disperse the powder in the electrolyte whose height in the cell and the composition of NdF3 and B2O3 are kept constant by additions after regular analyzes of the bath.
  • the cell is supplied at 8.4 volts and 39 A, which corresponds to a cathode density of 7.8 A / cm2 and an anode density of 0.89 A / cm2.
  • the wear of the anode leads to an increase in the anode density which requires before the end of the experiment a change of the latter before the appearance of an irreversible polarization.
  • the geometry of the cell is identical to that of Example 2. (fig. 2), with a crucible 10 made of molybdenum. But this time the composition of the anode is different. It is in fact obtained from a mixture (by weight) of 74% coal pitch coke, 11% neodymium oxide and 15% coal pitch; the mixture is kneaded at 150 ° C, pressed at 100 ° C and calcined at 1150 ° C.

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  • 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)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Catalysts (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP88420124A 1987-04-21 1988-04-19 Procédé de préparation d'alliages mères de fer et de néodyme par électrolyse de sels oxygénés en milieu fluorures fondus Expired - Lifetime EP0289434B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88420124T ATE70569T1 (de) 1987-04-21 1988-04-19 Verfahren zur herstellung von vorlegierungen aus eisen und neodym durch elektrolyse von sauerstoff enthaltenden salzen in geschmolzenen fluoriden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8705954 1987-04-21
FR8705954A FR2614319B1 (fr) 1987-04-21 1987-04-21 Procede de preparation d'alliages mere de fer et de neodyme par electrolyse de sels oxygenes en milieu fluorures fondus.

Publications (2)

Publication Number Publication Date
EP0289434A1 EP0289434A1 (fr) 1988-11-02
EP0289434B1 true EP0289434B1 (fr) 1991-12-18

Family

ID=9350528

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88420124A Expired - Lifetime EP0289434B1 (fr) 1987-04-21 1988-04-19 Procédé de préparation d'alliages mères de fer et de néodyme par électrolyse de sels oxygénés en milieu fluorures fondus

Country Status (16)

Country Link
US (1) US4828658A (zh)
EP (1) EP0289434B1 (zh)
JP (1) JPS63282287A (zh)
KR (1) KR880012798A (zh)
CN (1) CN1040631A (zh)
AT (1) ATE70569T1 (zh)
AU (1) AU1478588A (zh)
BR (1) BR8801885A (zh)
CA (1) CA1325194C (zh)
DE (1) DE3866939D1 (zh)
DK (1) DK214188D0 (zh)
ES (1) ES2028344T3 (zh)
FR (1) FR2614319B1 (zh)
NO (1) NO176190C (zh)
SG (1) SG39692G (zh)
ZA (1) ZA882769B (zh)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993013247A1 (en) * 1986-12-23 1993-07-08 Hideo Tamamura Process for producing neodymium or alloy thereof
US4966661A (en) * 1986-12-23 1990-10-30 Showa Denko Kabushiki Kaisha Process for preparation of neodymium or neodymium alloy
JPH0243391A (ja) * 1988-08-01 1990-02-13 Japan Metals & Chem Co Ltd Ｎｄ−Ｆｅ母合金の製造方法
US5118396A (en) * 1989-06-09 1992-06-02 The Dow Chemical Company Electrolytic process for producing neodymium metal or neodymium metal alloys
FR2661425B1 (fr) * 1990-04-27 1992-12-04 Pechiney Recherche Procede de preparation electrolytique, en milieu de fluorures fondus, de lanthane ou de ses alliages avec le nickel.
US5188711A (en) * 1991-04-17 1993-02-23 Eveready Battery Company, Inc. Electrolytic process for making alloys of rare earth and other metals
DE4142160C1 (zh) * 1991-12-20 1993-03-11 Heraeus Elektrochemie Gmbh, 6450 Hanau, De
WO1997015701A1 (fr) * 1995-10-25 1997-05-01 Santoku Metal Industry Co., Ltd. Procede pour produire des metaux de terres rares
US5810993A (en) * 1996-11-13 1998-09-22 Emec Consultants Electrolytic production of neodymium without perfluorinated carbon compounds on the offgases
EP2143827A1 (en) * 2008-07-11 2010-01-13 Université Libre de Bruxelles Process for the production of copper from sulphide compounds
WO2012078524A1 (en) * 2010-12-05 2012-06-14 Metal Oxygen Separation Technologies, Inc. Methods and apparatus for processing of rare earth metal ore
JP5853826B2 (ja) * 2012-03-30 2016-02-09 日立金属株式会社 希土類元素の金属および合金の製造方法
KR101556774B1 (ko) * 2014-08-20 2015-10-05 서울대학교산학협력단 전해채취법을 이용한 티타늄의 제조방법
DE102014218369A1 (de) * 2014-09-12 2016-03-31 Siemens Aktiengesellschaft Elektrochemische Abscheidung von Neodym zur Vergrößerung der Koerzitivfeldstärke von Seltenerddauermagneten
CN106835205A (zh) * 2016-12-16 2017-06-13 包头稀土研究院 镨钕铁合金及其制备方法
FR3069253B1 (fr) * 2017-07-21 2019-08-30 Commissariat A L'energie Atomique Et Aux Energies Alternatives Utilisation de la chronopotentiometrie inverse pour la production d'elements chimiques a l'etat metallique ou d'alliages de ceux-ci par reduction electrolytique en milieux de sels fondus
CN108950605A (zh) * 2018-08-27 2018-12-07 王福刚 一种四元熔盐体系电解制备稀土金属或合金的方法
CN112813463A (zh) * 2020-04-26 2021-05-18 虔东稀土集团股份有限公司 一种制备稀土金属或稀土合金的方法
CN116024607A (zh) * 2022-12-27 2023-04-28 昆明理工大学 一种铁镍或铁铜电解水制氢催化剂的制备和使用方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3383294A (en) * 1965-01-15 1968-05-14 Wood Lyle Russell Process for production of misch metal and apparatus therefor
US3524800A (en) * 1968-04-04 1970-08-18 Us Interior Method for the production of samarium alloys
US3729397A (en) * 1970-09-25 1973-04-24 Molybdenum Corp Method for the recovery of rare earth metal alloys
US4235692A (en) * 1972-01-24 1980-11-25 Townsend Douglas W Electrolytic apparatus
JPS5347332B2 (zh) * 1972-08-01 1978-12-20
US4747924A (en) * 1984-10-03 1988-05-31 Sumitomo Light Metal Industries, Ltd. Apparatus for producing neodymium-iron alloy
US4684448A (en) * 1984-10-03 1987-08-04 Sumitomo Light Metal Industries, Ltd. Process of producing neodymium-iron alloy

Also Published As

Publication number Publication date
JPS63282287A (ja) 1988-11-18
KR880012798A (ko) 1988-11-29
FR2614319A1 (fr) 1988-10-28
CN1040631A (zh) 1990-03-21
NO881703L (no) 1988-10-24
NO176190C (no) 1995-02-15
NO176190B (no) 1994-11-07
EP0289434A1 (fr) 1988-11-02
BR8801885A (pt) 1988-11-22
DE3866939D1 (de) 1992-01-30
AU1478588A (en) 1988-10-27
SG39692G (en) 1992-06-12
CA1325194C (fr) 1993-12-14
ZA882769B (en) 1988-10-21
ES2028344T3 (es) 1992-07-01
US4828658A (en) 1989-05-09
DK214188D0 (da) 1988-04-20
FR2614319B1 (fr) 1989-06-30
NO881703D0 (no) 1988-04-20
ATE70569T1 (de) 1992-01-15

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