EP0053565B1 - Nouveau dispositif et procédé pour l'alimentation en TiCl4 des cellules d'électrolyse pour la préparation du titane - Google Patents

Nouveau dispositif et procédé pour l'alimentation en TiCl4 des cellules d'électrolyse pour la préparation du titane Download PDF

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Publication number
EP0053565B1
EP0053565B1 EP81420173A EP81420173A EP0053565B1 EP 0053565 B1 EP0053565 B1 EP 0053565B1 EP 81420173 A EP81420173 A EP 81420173A EP 81420173 A EP81420173 A EP 81420173A EP 0053565 B1 EP0053565 B1 EP 0053565B1
Authority
EP
European Patent Office
Prior art keywords
cathode
diaphragm
titanium
tic1
electrolyte
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
Application number
EP81420173A
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German (de)
English (en)
French (fr)
Other versions
EP0053565A1 (fr
Inventor
Marcel Armand
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.)
Pechiney SA
Original Assignee
Pechiney SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Pechiney SA filed Critical Pechiney SA
Priority to AT81420173T priority Critical patent/ATE15080T1/de
Publication of EP0053565A1 publication Critical patent/EP0053565A1/fr
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Publication of EP0053565B1 publication Critical patent/EP0053565B1/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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • 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
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium

Definitions

  • the device and the method which are the subject of the invention relate to the preparation of titanium by electrolysis in a bath of molten halides. They relate more particularly to the method of supplying the cell with TiCl 4 .
  • FIG. 1 represents such an electrolysis cell of the type described in FR 2 423 55 which comprises a metal envelope (1) containing the molten electrolysis (2).
  • An anode (3) is placed inside an anode compartment (4).
  • a diaphragm (5) separates this compartment from the rest of the cell in which the deposition (6) and supply (7) cathodes are located.
  • the supply cathode (7) is tubular in shape. It is, for example, in wire mesh and connected to the negative pole of a current source.
  • This metallic fabric can be, for example, carbon steel or another metal such as nickel or stainless steel optionally coated with cobalt.
  • a supply of TiC1 4 is carried out inside the supply cathode (7) by means of the tube (8) placed in the vicinity of its axis. This tube is insulated from the cathode. Under these conditions, it can be seen that the TiC1 4 which leaves through the orifice (9) of the tube (8) is reduced at least partially to titanium subchloride which dissolves in the bath.
  • reaction (1) diffuses in the electrolyte and come to reduce at the supply cathode according to the reaction:
  • q is the mass of TiC1 4 introduced into the electrolyte in g / h and I 1 the intensity of the current in amperes.
  • the total current I which flows through the anode is such that:
  • the object of the invention is a device for supplying TiC1 4 to an electrolysis cell for the preparation of titanium in which the cover is traversed by a tube which allows the introduction of TiC1 4 and by a cathode of feed formed by two steel rods arranged on either side of the tube connected to the negative pole of a current source, electrically isolated from the cover, the tube and the rods immersed in the molten electrolyte characterized in that the tube and the cathode are surrounded by a diaphragm electrically isolated from the cathode.
  • Another object of the invention is a method for supplying TiC1 4 to an electrolysis cell equipped with the device described above and in which a current of intensity I 1 is passed through the supply cathode the ratio of the activities of the Ti 3+ and Ti 3+ ions is the same on both sides of the diaphragm.
  • This value can be given by equipping the supply device with two measurement electrodes placed on either side of the diaphragm.
  • FIG. 2 represents, by way of nonlimiting example, a feed cathode device according to the invention.
  • This device is placed inside a cell (10) for the preparation by electrolysis of titans from a molten electrolyte (11).
  • This cell comprises, like that of FIG. 1, an anode (12) surrounded by a diaphragm (13) and, at least, a deposition cathode (14): Only the supply device according to the invention is described from in detail. It comprises a tube (15) which makes it possible to introduce the TiC1 4 which leaves the electrolyte through the orifice (16).
  • the feed cathode consists of two steel rods (17) and (18) arranged on either side of the tube (15). They pass through the cover (19) of the cell through insulating joints and are connected to the negative pole of a current source not shown.
  • the diaphragm (20) which constitutes one of the objects of the invention, is made of a metal having sufficient resistance to the electrolyte under the temperature conditions in which it is operated. It is possible, for example, to use unalloyed nickel, or nickel-based alloys or else steels, preferably stainless.
  • This diaphragm is connected to the upper part of the cover (19) of the electrolyser by means of a sealed metallic annular wall (21) which is fixed to the cover (19) by insulating and waterproof annular seals (22) and (23 ).
  • the annular wall (21) penetrates through its lower part into the electrolyte and thus obstructs the circulation of the gases present above the level of the electrolyte on either side of the diaphragm (20).
  • the essential role of the latter is to obstruct the diffusion of TiC1 3 formed according to reaction (2) by the action of TiC1 4 on TiCl 2 , outside the space delimited by this diaphragm.
  • the electrolyte zone located in the immediate vicinity of the rods (17) and (18), which constitute the supply cathode, is enriched in TiCl 3 , which allows a very rapid redissolution of the titanium formed in the contact of these rods by discharge of bivalent titanium ions.
  • the structure of the diaphragm (20) can be produced, for example, in the form of a metallic cloth such as a nickel cloth, or of a sheet obtained perfitting a metallic powder, for example based on stainless steel , and having sufficient residual porosity.
  • the potential of this diaphragm (20) relative to the electrolyte in which it is immersed can be calculated by one of the following two equations, considering either the potential of the internal face of this diaphragm relative to the electrolyte (24) which is inside this diaphragm, that is to say the potential of the external face of the same diaphragm with respect to the electrolyte (25) situated outside this diaphragm.
  • e 0 Ti3 + / Ti2 + represents the normal potential for the reaction (6)
  • a 1 Ti3 + and a 1 Ti2 + represent the respective activities of the Ti2 + ions in the volume of electrolyte (24) contained in the space surrounded through the diaphragm (20).
  • a 2 Ti3 + and a 2 Ti2 + represent the respective activities of the Ti 2+ ions in the electrolyte (25) with which the external face of the diaphragm (20) is in contact.
  • this drop in potential is relatively difficult to achieve. It is however possible to measure a value very close to this potential difference by having on either side of the diaphragm, but without contact with it, two reference electrodes, for example electrodes sensitive to chlorine ions (26 ) and (27) such as Ag / AgCI electrodes immersed in the electrolyte: the ends of these electrodes pass through the cell cover by insulating seals and are connected to a means of measuring the potential difference which will be used to control the current I 1 or what amounts to the same, the ratio I 2 / I 1 .
  • two reference electrodes for example electrodes sensitive to chlorine ions (26 ) and (27)
  • Ag / AgCI electrodes immersed in the electrolyte the ends of these electrodes pass through the cell cover by insulating seals and are connected to a means of measuring the potential difference which will be used to control the current I 1 or what amounts to the same, the ratio I 2 / I 1 .

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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)
  • Crystals, And After-Treatments Of Crystals (AREA)
EP81420173A 1980-11-27 1981-11-25 Nouveau dispositif et procédé pour l'alimentation en TiCl4 des cellules d'électrolyse pour la préparation du titane Expired EP0053565B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81420173T ATE15080T1 (de) 1980-11-27 1981-11-25 Vorrichtung und verfahren zur zufuhr von ticl4 in elektrolysezellen fuer die titanherstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8025505A FR2494725A1 (fr) 1980-11-27 1980-11-27 Nouveau dispositif et procede pour l'alimentation en ticl4 des cellules d'electrolyse pour la preparation du titane
FR8025505 1980-11-27

Publications (2)

Publication Number Publication Date
EP0053565A1 EP0053565A1 (fr) 1982-06-09
EP0053565B1 true EP0053565B1 (fr) 1985-08-21

Family

ID=9248545

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81420173A Expired EP0053565B1 (fr) 1980-11-27 1981-11-25 Nouveau dispositif et procédé pour l'alimentation en TiCl4 des cellules d'électrolyse pour la préparation du titane

Country Status (7)

Country Link
US (1) US4396472A (enrdf_load_stackoverflow)
EP (1) EP0053565B1 (enrdf_load_stackoverflow)
JP (1) JPS5833314B2 (enrdf_load_stackoverflow)
AT (1) ATE15080T1 (enrdf_load_stackoverflow)
DE (1) DE3171944D1 (enrdf_load_stackoverflow)
FR (1) FR2494725A1 (enrdf_load_stackoverflow)
NO (1) NO156171C (enrdf_load_stackoverflow)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4521281A (en) * 1983-10-03 1985-06-04 Olin Corporation Process and apparatus for continuously producing multivalent metals
FR2579629B1 (fr) * 1985-03-28 1987-05-07 Pechiney Procede de controle en continu de la teneur en metal dissous dans un bain de sels fondus et son application a l'alimentation continue d'une cellule d'electrolyse en sels dudit metal
US7504017B2 (en) * 2001-11-22 2009-03-17 Qit-Fer Et Titane Inc. Method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state
WO2006084318A1 (en) * 2005-02-08 2006-08-17 Bhp Billiton Innovation Pty Ltd Supplying solid electrolyte to an electrolytic cell
AU2012358205B2 (en) 2011-12-22 2017-10-12 Universal Achemetal Titanium, Llc A system and method for extraction and refining of titanium
CA3047102C (en) 2016-09-14 2023-12-05 Universal Achemetal Titanium, Llc A method for producing titanium-aluminum-vanadium alloy
AU2018249909B2 (en) 2017-01-13 2023-04-06 Universal Achemetal Titanium, Llc Titanium master alloy for titanium-aluminum based alloys

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2712523A (en) * 1951-06-12 1955-07-05 Nat Lead Co Purification of titanium tetrachloride
US2760930A (en) * 1952-01-31 1956-08-28 Nat Lead Co Electrolytic cell of the diaphragm type
US4113584A (en) * 1974-10-24 1978-09-12 The Dow Chemical Company Method to produce multivalent metals from fused bath and metal electrowinning feed cathode apparatus
US4219401A (en) * 1978-08-07 1980-08-26 The D-H Titanium Company Metal electrowinning feed cathode

Also Published As

Publication number Publication date
ATE15080T1 (de) 1985-09-15
NO814029L (no) 1982-05-28
EP0053565A1 (fr) 1982-06-09
FR2494725A1 (fr) 1982-05-28
NO156171B (no) 1987-04-27
US4396472A (en) 1983-08-02
JPS5833314B2 (ja) 1983-07-19
DE3171944D1 (en) 1985-09-26
FR2494725B1 (enrdf_load_stackoverflow) 1982-12-10
JPS57116790A (en) 1982-07-20
NO156171C (no) 1987-08-12

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