EP0156744B1 - Procédé d'obtention d'un métal par électrolyse d'halogénures en bain de sels fondus comportant un double dépôt simultané et continu et dispositifs d'application - Google Patents

Procédé d'obtention d'un métal par électrolyse d'halogénures en bain de sels fondus comportant un double dépôt simultané et continu et dispositifs d'application Download PDF

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Publication number
EP0156744B1
EP0156744B1 EP85420040A EP85420040A EP0156744B1 EP 0156744 B1 EP0156744 B1 EP 0156744B1 EP 85420040 A EP85420040 A EP 85420040A EP 85420040 A EP85420040 A EP 85420040A EP 0156744 B1 EP0156744 B1 EP 0156744B1
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EP
European Patent Office
Prior art keywords
basket
bath
cathode
metal
halides
Prior art date
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Expired
Application number
EP85420040A
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German (de)
English (en)
French (fr)
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EP0156744A1 (fr
Inventor
Joseph Cohen
Gérard Lorthioir
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Pechiney SA
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Pechiney SA
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Priority to AT85420040T priority Critical patent/ATE34189T1/de
Publication of EP0156744A1 publication Critical patent/EP0156744A1/fr
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Publication of EP0156744B1 publication Critical patent/EP0156744B1/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
    • 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
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • 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

Definitions

  • the present invention relates to a process for obtaining a metal by electrolysis of halides in a bath of molten salts comprising a simultaneous and continuous double deposition and to devices for applying said process.
  • metals concerned there are all those which have a melting point above 1000 ° C. and, preferably, several valence states such as in particular titanium, zirconium, hafnium, thorium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, plutonium as well as rare earth metals.
  • a metal can be deposited by introducing one of its derivatives such as a halide, for example, into a bath of molten salts and by subjecting it in its simplest principle. by the action of two electrodes connected to the poles of a direct current source: at the anode the halogen is released and at the cathode the metal is deposited.
  • This diaphragm can be made of ceramic or by depositing a refractory metal on a suitably polarized metal mesh.
  • the present invention uses a basket-shaped metal cathode which, while being able to serve as a diaphragm, serves above all as the first receiver of the metal to be deposited.
  • the documents GB 781.311, EP-A-0053567 and US-A-3.282.822 describe methods which could be compared to our invention.
  • the first of them describes a cell of parallelepiped shape containing a bath of chlorides; it is divided by a vertical partition into two compartments which communicate with each other by a space located between the bottom of the partition and the bottom of the cell.
  • a metal log constituting the anode and in the other a cathode assembly, in perforated sheet, composed of a tubular cathode and a concentric cathode basket supplied with halide of the metal to be deposited.
  • This cell operates according to two chloride supply regimes. In a first stage, it is quickly fed so as to have a mole TiC1 4 for 10 to 20 Faradays. This results in the formation on the inner walls of the box of fine titanium crystals which develop to form a more or less spongy deposit. Then, the amount of TiC1 4 is increased so as to have one mole of TiC1 4 for 4.5 to 6.5 Faradays. Under these conditions, a concentration of TiC1 2 occurs and titanium metal is preferably deposited on the cathode bars in the form of branched crystals.
  • the supply of TiC1 4 is interrupted, the current extended for a few moments to exhaust the soluble titanium, then the cathode box is taken out of the bath and cooled away from the atmosphere. The metal is then separated from the box, then washed with a dilute acid solution and dried.
  • the product obtained contains between 50 and 80% of metal having a Brinell hardness of around 120.
  • the product obtained is heterogeneous since the initial deposit of metal on the walls of the box, at the moment when the quantity of current admitted is large, is spongy in nature, while the subsequent deposit on cathode bars, at reduced quantity of current, has larger crystals;
  • EP-A-0053567 relates to a cell for the preparation by discontinuous electrolysis of zirconium or hafnium from a molten mixture of chlorides and alkali or alkaline earth fluorides.
  • a simultaneous and continuous double deposition of metal is brought into play on the one hand on a basket-shaped diaphragm maintained cathode relative to a central anode and on the other hand on cathodes outside this diaphragm.
  • a direct current Il is circulated between the anode and the diaphragm and simultaneously a current 1-1 1 between the diaphragm and the external cathodes from which the metal is recovered.
  • the invention is inspired by the technique taught in EP-A-0053567 and consists in a process for obtaining a metal by electrolysis of halides in a bath of molten halides contained in a tank comprising a simultaneous double deposition and continuous, in which a direct electrical current 1 1 is first circulated from an anode assembly to a cathode in the shape of a double-walled basket, both being immersed in the bath, by supplying the basket with a metal halogen to deposit, until the quantity of electricity delivered corresponds to the filling of 1/3 to 2/3 of the volume of the basket with the metal, then introduced into the compartment delimited by the interior walls of the tank and the external walls of the basket, the halide of the metal so as to have in the bath contained in said compartment a content of combined metal comprised between 1 and 7% by weight, and then is circulated, simultaneously with current 1 1, a current 1 2 from the basket to at least one cathode com while continuing to supply the basket with halides, and periodically extracted said complementary ca
  • a current 1 1 and a current 1 2 are passed simultaneously while continuing to supply the basket with halide.
  • the cell thus acquires its cruising speed. It then only remains to regularly remove the cathode (s) from the bath to recover the metal and to replace them with blank cathodes.
  • n cathodes the procedure is as follows: a single cathode having been placed in the bath during start-up, the n-1 others are successively immersed at regularly spaced times so that at the time of immersion of the nth, the first is covered by the quantity of refined metal desired.
  • the process according to the invention allows the supply of halide in a form which is not only liquid but also solid, which is different from the process of USP 3,282,822 which only admitted in the case of titanium tetrachloride and preferably gas.
  • This enlargement to the three physical states of matter results from the production of a deposit in two stages which frees the process from the quality constraints of the metal present in the basket since the latter constitutes only a transitory phase of its obtaining.
  • the process is applicable to most halides of type M (halogen) ,, where M is a metal such as titanium, zirconium, hafnium, thorium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, plutonium, rare earth metals and X one of the valences of the metal considered. It can also be applied to metals which are difficult to obtain directly in a correct crystalline state.
  • Subchlorides have the advantage over TiC1 4 of being soluble in the bath of molten salts and therefore of giving a more homogeneous bath. They also allow better control of the quantity of homogenides introduced and therefore of being able to limit the content of combined titanium in the basket and thus reduce the diffusion of titanium ions towards the anode and, consequently, losses due to anodic reoxidation.
  • the molten salt bath used is chosen according to the metal to be deposited.
  • titanium a mixture of calcium, barium and sodium chlorides is preferably taken, in suitable proportions.
  • This bath has the advantage of having a composition similar to that of the bath used for the electrolytic production of sodium: it is thus possible to design a loop comprising the pre-reduction of TiC1 4 to TiCl x by sodium and the recirculation of the bath from the anode compartment to the sodium electrolysis cell.
  • the current intensities applied they mainly depend on the metals to be deposited, the type of halide and the speed of supply and are therefore subject to specific adaptations.
  • a first device comprising a cylindrical tank designed to contain said bath sheltered from the atmosphere, an anode assembly comprising at least one anode of cylindrical shape placed in the center of the cell immersed in the bath, a metal cathode surrounding completely and symmetrically the anode assembly, means for connecting the upper parts of the anode assembly and of the cathode respectively to the positive and negative poles of a direct current source, at least one complementary cathode placed outside the cathode connected to a source of potential current which is more strongly negative than that of the cathode and characterized in that the cathode has the shape of a lattice basket, suspended in the bath, constituted by two vertical coaxial cylinders integral with a perforated bottom extending up to the axis of the tank so as to share the volume of the bath in three compartments, that it comprises a halide supply system placed at the upper part of the cathode and between the two cylinders, means for suction
  • This device differs from that of EP-A-0053567 in particular by the presence of a double-walled basket-shaped cathode.
  • the anode assembly occupies a central position in the electrolysis cell and is symmetrically surrounded by the cathode basket, so that the whole of the inner side wall and the whole of the outer side wall of said basket are each equidistant from the anode.
  • Such an arrangement creates in the anolyte a regularly distributed electric field which avoids local diffusions of titanium ions towards the anode and promotes the channeling of the released halogen.
  • the basket consists of a nickel metal mesh preferably with mesh sizes that prevent too easy passage of the metal particles without being a cause of clogging.
  • the upper part of the basket emerges from the bath and can be opened to closed. In both cases, it is in relation, on the one hand with the halide supply system, on the other hand with the negative pole of a current source by means of sealed passages made in the cover of the cell.
  • the central anode assembly preferably consists of a cylindrical piece of graphite, sculpted longitudinally in order to promote the release of gas, connected to the positive pole of a current source and placed inside d 'A bell tightly attached to the cell cover and through which the halide is sent to an external capture.
  • cathodes preferably of iron, nickel, titanium or metal to be deposited, which serve to receive the final metal.
  • This arrangement allows a regular distribution of the second deposit current and obtaining a uniform deposit of metal. It also contributes to facilitating the recovery of the metal due to good accessibility of said cathodes. By using a sufficient number of cathodes, the cathode current density is reduced and the quality of the deposit is improved.
  • anode compartment where the titanium content of the bath is practically zero
  • a compartment constituted by the basket where the bath is very rich in titanium ions
  • a cathode compartment delimited by the inner walls of the cell and the outer walls of the basket, where the titanium content of the bath is relatively low and of the order of a few percent by weight.
  • a device comprising a cylindrical tank designed to contain the bath sheltered from the atmosphere, a cathode in the shape of a metal perforated basket with vertical side wall secured to a bottom suspended in the bath, a set anode comprising at least one cylindrical anode immersed in the bath placed outside the basket, means for connecting the upper parts of the anode assembly and the cathode respectively to the positive and negative poles of a direct current source , at least one additional cathode placed inside the basket in a symmetrical manner, a halide supply device through the upper part of the cathode, means for suctioning the released halogen, characterized in that the side wall of the basket is in lattice, in the form of a cylinder, that the basket is internally equipped with a second lateral wall in metallic trellis parallel and coaxial with the first and fixed on the bottom so as to share the volume of the bath in three compartments, that the complementary cathode is connected by its upper part and by a means of
  • This device makes it possible to group the cathodes in the center of the cell, which has the result, in particular, of reducing the number of devices for extracting said cathodes. It resembles in this the device of US-A-3 282 822, but is distinguished by a polarization of the basket and its supply between two walls forming a space separate from the complementary cathodes hence the possibility of obtaining on these last a homogeneous and non-spongy metal deposit.
  • the bottom of the cell is equipped with a nozzle for extracting the bath which opens into the anode compartment.
  • the bath is then continuously recycled to the basket after having been properly recharged with the metal halide to be deposited.
  • FIG. 1 a section along an axial plane of an example cell according to the invention and in FIG. 2 a section of the same cell according to a horizontal plane of layout XX 'in FIG. 1.
  • Hastelloy C cell with an internal diameter of 235 mm and a height of 700 mm, equipped with a heating system, and inside which is placed a cylindrical nickel tank with a diameter of 220 mm and a height of 300 mm, we have loaded with 13.7 kg of a BaCI 2 -CaCI 2 -NaCI eutectic (16.3 - 46.9 - 36.7% in moles).
  • the cell was evacuated at around 550 ° C. to eliminate the humidity, then treatment with HCl to remove the oxides, hydroxides, and other impurities contained in the bath, then electrolysis at a DC voltage of 2.2 V until the residual current stabilizes.
  • the cover was then removed and an annular cylindrical basket made by means of a 3 mm diameter nickel wire frame covered with a metallic fabric made with 0.28 mm diameter nickel wire braided according to the bath was introduced. 35 mesh. Then, the cover was replaced with a central anode and its bell, its complementary cathodes, the various gas inlet and outlet pipes and the halide supply system.
  • the atmosphere of the cell was purged under vacuum, then under argon, then warmed to 550 ° C.
  • the bath being liquid, the various electrodes were immersed in it.
  • the height of the bath in the cell was then 150 mm.
  • TiCl x was prepared in a bath of molten salts, where X was 2.3 by oxidation of titanium powder with titanium tetrachloride. This solution contained about 10% by weight of titanium in the form of halide.
  • This TiCl x was introduced at the rate of 6 g / hour into the cell and a voltage of 3.5 V was applied. Current 1, then had the value 2 A.
  • the compartment delimited by the interior walls of the cell and the exterior walls of the basket was then supplied with TiCl x until a composition of between 1.5 and 2% by weight of titanium was reached and a voltage of -0 was imposed. , 9 V between cathode and basket. A current 1 2 with an average value of 1.5 A has been established.

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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)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP85420040A 1984-03-12 1985-03-11 Procédé d'obtention d'un métal par électrolyse d'halogénures en bain de sels fondus comportant un double dépôt simultané et continu et dispositifs d'application Expired EP0156744B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85420040T ATE34189T1 (de) 1984-03-12 1985-03-11 Verfahren zur gewinnung eines metalls durch elektrolyse von geschmolzenen halogeniden mit gleichzeitigem und fortlaufendem doppelniederschlag und vorrichtung dafuer.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8403967A FR2560896B1 (fr) 1984-03-12 1984-03-12 Procede d'obtention d'un metal par electrolyse d'halogenures en bain de sels fondus comportant un double depot simultane et continu et dispositifs d'application
FR8403967 1984-03-12

Publications (2)

Publication Number Publication Date
EP0156744A1 EP0156744A1 (fr) 1985-10-02
EP0156744B1 true EP0156744B1 (fr) 1988-05-11

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ID=9302050

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EP85420040A Expired EP0156744B1 (fr) 1984-03-12 1985-03-11 Procédé d'obtention d'un métal par électrolyse d'halogénures en bain de sels fondus comportant un double dépôt simultané et continu et dispositifs d'application

Country Status (11)

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US (1) US4588485A (ja)
EP (1) EP0156744B1 (ja)
JP (1) JPS60211092A (ja)
AT (1) ATE34189T1 (ja)
AU (1) AU571661B2 (ja)
BR (1) BR8501063A (ja)
CA (1) CA1251160A (ja)
DE (1) DE3562632D1 (ja)
ES (2) ES541142A0 (ja)
FR (1) FR2560896B1 (ja)
NO (1) NO167308C (ja)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES8609513A1 (es) * 1985-06-21 1986-09-01 Hermana Tezanos Enrique Nuevo diseno de catodo para beneficio electroquimico de me- tales
JPH0633476B2 (ja) * 1987-05-27 1994-05-02 三菱原子燃料株式会社 融解塩電解によるジルコニユウムとハフニユウムの分離方法
JPH0624982B2 (ja) * 1988-01-12 1994-04-06 三菱原子燃料株式会社 四塩化ジルコニュウムと四塩化ハフニユウムを分離する方法
JPH02285087A (ja) * 1989-04-26 1990-11-22 Osaka Titanium Co Ltd 電解浴塩の浄化方法
US5324394A (en) * 1992-10-05 1994-06-28 The United States Of America As Represented By The Secretary Of The Interior Recovery of Li from alloys of Al- Li and Li- Al using engineered scavenger compounds
US5380406A (en) * 1993-10-27 1995-01-10 The United States Of America As Represented By The Department Of Energy Electrochemical method of producing eutectic uranium alloy and apparatus
US6086745A (en) * 1997-07-03 2000-07-11 Tsirelnikov; Viatcheslav I. Allotropic modification of zirconium and hafnium metals and method of preparing same
US6911134B2 (en) * 2002-09-06 2005-06-28 The University Of Chicago Three-electrode metal oxide reduction cell
US7097747B1 (en) * 2003-08-05 2006-08-29 Herceg Joseph E Continuous process electrorefiner
US7011736B1 (en) * 2003-08-05 2006-03-14 The United States Of America As Represented By The United States Department Of Energy U+4 generation in HTER
JP3949620B2 (ja) * 2003-08-06 2007-07-25 核燃料サイクル開発機構 酸化物電解法用の電解装置
US8460535B2 (en) 2009-04-30 2013-06-11 Infinium, Inc. Primary production of elements
WO2014004610A1 (en) * 2012-06-27 2014-01-03 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona, Acting For And On Behalf Of Arizona State University System and method for electrorefining of silicon
WO2014201207A2 (en) 2013-06-14 2014-12-18 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona, Acting For And On Behalf Of Arizona State University System and method for purification of electrolytic salt
CN108728870B (zh) * 2017-08-07 2021-02-12 南京佑天金属科技有限公司 晶条铪的生产系统及其方法
CN110079834B (zh) * 2019-06-10 2020-03-17 永嘉县纳海川科技有限公司 一种用于稀土金属制备用的熔盐电解装置及其使用方法

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
FR1146248A (fr) * 1956-03-20 1957-11-07 Soberti Fabrication électrolytique du titane et du zirconium par raffinage de leurs alliages
FR1221991A (fr) * 1958-03-19 1960-06-07 New Jersey Zinc Co Procédé de fabrication de titane
US3282822A (en) * 1963-05-20 1966-11-01 Titanium Metals Corp Electrolytic cell for the production of titanium
FR2494728A1 (fr) * 1980-11-27 1982-05-28 Armand Marcel Procede de controle de la permeabilite des diaphragmes dans la preparation de metaux polyvalents par electrolyse et cellule d'electrolyse pour la mise en oeuvre de ce procede
FR2494727A1 (fr) * 1980-11-27 1982-05-28 Armand Marcel Cellule pour la preparation de metaux polyvalents tels que zr ou hf par electrolyse d'halogenures fondus et procede de mise en oeuvre de cette cellule

Also Published As

Publication number Publication date
EP0156744A1 (fr) 1985-10-02
ES542730A0 (es) 1985-12-16
NO167308B (no) 1991-07-15
DE3562632D1 (en) 1988-06-16
FR2560896B1 (fr) 1989-10-20
ATE34189T1 (de) 1988-05-15
ES8602967A1 (es) 1985-12-01
AU571661B2 (en) 1988-04-21
CA1251160A (fr) 1989-03-14
FR2560896A1 (fr) 1985-09-13
ES8603590A1 (es) 1985-12-16
US4588485A (en) 1986-05-13
BR8501063A (pt) 1985-10-29
JPS6353275B2 (ja) 1988-10-21
NO850950L (no) 1985-09-13
NO167308C (no) 1991-10-23
ES541142A0 (es) 1985-12-01
JPS60211092A (ja) 1985-10-23
AU3970785A (en) 1985-09-19

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