EP0394154B1 - Vorrichtung zur fortlaufenden Herstellung eines mehrwertigen Metalls durch Elektrolyse eines in einem Schmelzbad aufgelösten Halogenids - Google Patents

Vorrichtung zur fortlaufenden Herstellung eines mehrwertigen Metalls durch Elektrolyse eines in einem Schmelzbad aufgelösten Halogenids Download PDF

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Publication number
EP0394154B1
EP0394154B1 EP90420196A EP90420196A EP0394154B1 EP 0394154 B1 EP0394154 B1 EP 0394154B1 EP 90420196 A EP90420196 A EP 90420196A EP 90420196 A EP90420196 A EP 90420196A EP 0394154 B1 EP0394154 B1 EP 0394154B1
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EP
European Patent Office
Prior art keywords
cathode
cell
bath
halide
metal
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
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EP90420196A
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English (en)
French (fr)
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EP0394154A1 (de
Inventor
Airy-Pierre Lamaze
Patrick Paillere
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Compagnie Europeenne du Zirconium Cezus SA
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Compagnie Europeenne du Zirconium Cezus SA
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Priority to AT90420196T priority Critical patent/ATE90741T1/de
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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

Definitions

  • the present invention relates to a device for the continuous production of a multivalent metal by electrolysis of a halide of said metal dissolved in a bath of at least one molten salt.
  • Multivalent is understood here to mean any metal the halide of which is capable of presenting in solution in a bath of molten salts several stable valence states. It can be, for example, titanium, zirconium, niobium, uranium, hafnium, vanadium, tantalum or even 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 so-called igneous electrolysis technique has been the subject of numerous studies which have led to the design of various processes which are distinguished between them by the composition of the bath, its halide concentration, the physical and chemical state of the halide set. in use, the values of current density applied to the electrodes and to the production of numerous models of devices which differ from one another by their structure and their shape, in particular at the level of the electrodes, of the halide injection and recovery systems. deposited metal.
  • the introduction of the halide into the cell is done by means of complicated dissolving means and / or difficult to exploit industrially.
  • the operating conditions are such that the bath is completely saturated with an halide of intermediate valence.
  • Complex agitation systems and strict temperature control must then be used to avoid any spontaneous precipitation or disproportionation of said halide. It also happens that certain reduced halides decompose with the formation of sludge so that the cell must be stopped periodically to clean it.
  • the metal deposit becomes spongy and very fine.
  • this valence is less than or equal to 2 and the metal has a concentration by weight in the bath greater than or equal to 5%, then sludge is formed.
  • This process uses a bath in which, after reduction, the salt formed is at a concentration greater than its solubility. Although this supersaturation is theoretically advised, it is practically observed that it ultimately leads to decomposition of the salt or disproportionation during which titanium precipitates so that there is formation of sludge. This disproportionation changes both the concentration of the salt in the bath and the value of its average valence so that one can find oneself in the conditions of a deposit of poor quality as has been indicated above.
  • the mechanical displacement of the salt from the cathode requires mechanical means of difficult operation.
  • the dispersion of said salt in the bath requires vigorous stirring means to have a suitable homogeneity.
  • the halogen MA x content of the solvent is chosen so that the dissolution is complete and there is therefore no local variation which would cause the formation of sludge.
  • the conditions of the electrodismutation are obtained by an adjustment of the anodic current density in particular in a range of values such that at the anode there is no release of halogen, but an increase in the value of the metal. Under these conditions, a deposit of well crystallized, homogeneous metal is obtained, which does not trap either solvent or halide. In addition, there is thus no risk of spontaneous disproportionation of the halides and of sludge formation in the disproportionation cell, because due to the very principle of electrodismutation, the bath is always maintained in a state of concentration and valence in thermodynamic equilibrium or slightly oxidized with respect to this equilibrium.
  • anodic current densities of less than 0.2 A / cm2 are used.
  • the quantity of metal released is generally limited as a function of the concentration that there is in the bath. This amount does not exceed 25% and more particularly is between 1 and 10%. This makes it possible to better conduct the electrolysis under industrial operating conditions. It is also preferable to subject the bath to stirring, for example using an inert gas in order to homogenize the bath and ensure circulation of the bath relative to the electrodes.
  • the pre-reduction therefore makes it possible to bring the metal of the oxidized halide during the production of the metal as well as possibly that of the halide top-up to the valence state existing in the cell before electrolysis and to maintain thus balancing said state. This reduction is carried out electrolytically.
  • top-up can also be done with TiCl4 in which case the electrical conditions such as: TiCl4 - ⁇ TiCl2 + Cl2.
  • valence states are obtained by adjusting in particular the cathodic current density in a range of values such that there is no metal formation but nevertheless sufficient to achieve the desired valence state. It is then possible to add at this time the supplement of halide to readjust the metal concentration of the bath, since the latter being suitably reduced and unsaturated spontaneously dissolves the halide introduced. Hence a very reduced supply device limited to means for simple contacting of said halide with the bath without the need for very vigorous stirring.
  • the pre-reduction can only be carried out in a cell where the electrodes are separated by a diaphragm in order to avoid the recombination of the halogen with the halide reduced at the cathode but the conduct of electrolysis is then less critical than when the release of halogen takes place near a deposition cathode, more or less significant variations in valence in the bath not having the same consequences as reoxidation of the deposited metal .
  • the electrolytic pre-reduction is preferably carried out in a cell where the cathodic density is less than 0.5 A / cm2 per molarity of dissolved metal in order to avoid any formation of metal.
  • This cell is equipped with a halide supply feed device and a diaphragm around the anode and the electrodes subjected to suitable current densities.
  • the pre-reduction cell and the disproportionation cell are arranged contiguously and have a common wall in the form of a grid through which the bath circulates.
  • This grid electrically insulated from the cell walls is negatively polarized so as to constitute the pre-reduction cathode.
  • This circulation is produced by forced convection which is achieved by bubbling neutral gas with respect to the halide bath such as argon for example; this gas is introduced with the addition of halide so that the bath moves up and down in the disproportionation cell and from bottom to top in the pre-reduction cell with a speed parallel to the plane of the electrodes between 1 and 10 cm / sec, the interval in which the concentration of the halide bath is kept within limits favorable to a good quality deposit.
  • neutral gas such as argon for example
  • the production process thus becomes continuous and makes it possible to maintain the concentration and valence values within relatively narrow ranges.
  • the metal deposited on the cathode of the disproportionation cell can be recovered at any time after interrupting the flow of current and removing the cathode from the bath.
  • Figure 1 a sectional view along a vertical plane BB of a metal processing device with electrolytic pre-reduction formed of two contiguous cells and Figure 2 a view in section along a horizontal plane AA of the same cell.
  • the tank is generally made of bare stainless steel, polarized or not, possibly cooled to form a self-filling or else provided internally with a refractory lining.
  • the grid is made of electrically conductive material and in particular metal; it is provided with slots and leaves a space with the bottom and the level of the bath allowing to facilitate the flow of the bath.
  • the cathodes are made of steel, the anodes and the graphite supply tubes, the metal diaphragm is polarizable.
  • the metal is deposited on the cathode 4 while in the vicinity of the anodes 5, the oxidized halide at a higher valence state is entrained with the bath by forced convection by argon down through the grid in the reduction cell where an additional halide and argon are introduced through the tubes 9; the oxidized halide and make-up are reduced at the grid 3 and recycled to the deposition cell passing through the top of the grid while the halogen is released on the anode 8 surrounded by the diaphragm 7 which limits bath oxidation reactions.
  • This tank contained about 150 kg of a molten salt bath consisting of sodium chloride at 800-850 ° C in which was dissolved 5% by weight of titanium chloride of average valence 2.1 or about 7.8 kg.
  • a continuous electric current of 1000 Amperes so as to create current densities on the anode of 0.18 A / cm2 and on the cathode of 0.5 A / cm2 and ensure circulation bath using an argon flow of 100 l / h so as to have 5 rotations per hour towards the pre-reduction cell in which also passed a current of 1000 A and where the current densities were of 1 A / cm2 on the anode and 0.2 A / cm2 on the cathode.
  • a current of 165A was passed through the dismutation cell and a cathode 400 mm high and 100 mm wide was used so as to have a cathodic density of 0.2 A / cm2 while the anodic density was 0.06 A / cm2.
  • Example 2 Two contiguous cells identical to those of Example 1 were used.
  • the bath consisted of NaCl containing 2% by weight of NaF and 5% by weight of ZrCl 3.3 (ie 1/3 of ZrCl4 and 2/3 ZrCl3).
  • a direct current of 275A circulated in the dismutation cell so as to have a cathodic density of 0.33 A / cm2 and anodic density of 0.10 A / cm2.

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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)

Claims (2)

  1. Vorrichtung zum fortlaufenden Herstellen eines in mehreren Wertigkeitsstufen vorkommenden Metalls durch Elektrolyse eines Halogenids in einem Bad (2) aus wenigstens einem geschmolzenen Salz,
    dadurch gekennzeichnet,
    daß sie aufgebaut ist aus
    - einer Zelle (a) zur Elektrowertigkeitsdismutation, in deren Bad wenigstens eine Abscheidekathode (4) und wenigstens zwei Anoden (5) eintauchen, die mit einer wenigstens teilweise Gleichstrom liefernden Stromquelle verbunden sind, die zum einen an den Anoden eine Stromdichte mit einem Wert entwickelt, der kleiner ist als der zur Freisetzung des dem Halogenid entsprechenden Halogens führende, aber ausreicht, um wenigstens eine Teil des Metalls des Halogenids in eine höhere Wertigkeitsstufe übergehen zu lassen, und zum anderen an der Kathode eine Stromdichte entwickelt, die zur Abscheidung von Metall des Halogenids führt,
    und
    - einer Zelle (b) zur Vorreduktion, die mit einem System (9) zum Zuführen von Halogenid ausgestattet ist und in deren Bad wenigstens eine Anode (6) und eine Kathode (3) eintauche, die durch ein Diaphragma (7) voneinander getrennt und mit einer wenigstens teilweise Gleichstrom lieferenden Stromquelle verbunden sind, an der zum einen die Dichte des Kathodenstroms auf einen Wert geregelt wird, der kleiner ist als der, bei dem sich das Metall an der Kathode abscheiden würde, aber ausreicht, um wenigstens einen Teil dieses Metalls in eine höhere Wertigkeitsstufe übergehen zu lassen, und zum anderen die Dichte des Anodenstroms auf einen Wert geregelt wird, der zur Freisetzung des Halogens führt,
    wobei
    - die Zellen (a) und (b) nebeneinander liegen und ihre gemeinsame Wand durch ein Gitter gebildet wird, das von den Wänden der Zellen (a) und (b) elektrisch isoliert und negativ polarisiert ist und das die Kathode (3) bildet, durch die hindurch das Bad zirkuliert, eine Einrichtung vorgesehen ist, die für eine Bewegung des Bades durch erzwungene Konverktion von oben nach unten in der Zelle zur Elektrowertigkeitsdismutation und von unten nach oben in der Zelle zur Vorreduktion sorgt und die Kathode (3) vom Zellenboden und von der Badoberfläche einen Abstand aufweist, der ein Strömen des Bades vom Boden der Zelle (a) zur Zelle (b) und umgekehrt von der Oberfläche der Zelle (b) in die Zelle (a) erlaubt.
  2. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet,
    daß die erzwungene Konvektion durch in das System zum Zuführen von Halogenid eingeführte Blasen eines Gases gewährleistet wird.
EP90420196A 1989-04-21 1990-04-19 Vorrichtung zur fortlaufenden Herstellung eines mehrwertigen Metalls durch Elektrolyse eines in einem Schmelzbad aufgelösten Halogenids Expired - Lifetime EP0394154B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90420196T ATE90741T1 (de) 1989-04-21 1990-04-19 Vorrichtung zur fortlaufenden herstellung eines mehrwertigen metalls durch elektrolyse eines in einem schmelzbad aufgeloesten halogenids.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8906134 1989-04-21
FR8906134 1989-04-21

Publications (2)

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EP0394154A1 EP0394154A1 (de) 1990-10-24
EP0394154B1 true EP0394154B1 (de) 1993-06-16

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US (1) US5013413A (de)
EP (1) EP0394154B1 (de)
JP (1) JPH0823077B2 (de)
AT (1) ATE90741T1 (de)
DE (1) DE69001949T2 (de)
NO (1) NO179014C (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015098626A (ja) * 2013-11-19 2015-05-28 住友電気工業株式会社 精製金属の製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1135670A (fr) * 1954-11-30 1957-05-02 Horizons Titanium Corp Procédé d'obtention de métaux de transition
US2955078A (en) * 1956-10-16 1960-10-04 Horizons Titanium Corp Electrolytic process
US4338177A (en) * 1978-09-22 1982-07-06 Metallurgical, Inc. Electrolytic cell for the production of aluminum
US4521281A (en) * 1983-10-03 1985-06-04 Olin Corporation Process and apparatus for continuously producing multivalent metals

Also Published As

Publication number Publication date
JPH0823077B2 (ja) 1996-03-06
NO179014B (no) 1996-04-09
NO901757L (no) 1990-10-22
NO179014C (no) 1996-07-17
US5013413A (en) 1991-05-07
JPH0394088A (ja) 1991-04-18
ATE90741T1 (de) 1993-07-15
DE69001949T2 (de) 1993-10-07
EP0394154A1 (de) 1990-10-24
DE69001949D1 (de) 1993-07-22
NO901757D0 (no) 1990-04-20

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