EP0053565A1 - Vorrichtung und Verfahren zur Zufuhr von TiCl4 in Elektrolysezellen für die Titanherstellung - Google Patents

Vorrichtung und Verfahren zur Zufuhr von TiCl4 in Elektrolysezellen für die Titanherstellung Download PDF

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Publication number
EP0053565A1
EP0053565A1 EP81420173A EP81420173A EP0053565A1 EP 0053565 A1 EP0053565 A1 EP 0053565A1 EP 81420173 A EP81420173 A EP 81420173A EP 81420173 A EP81420173 A EP 81420173A EP 0053565 A1 EP0053565 A1 EP 0053565A1
Authority
EP
European Patent Office
Prior art keywords
diaphragm
ticl
cathode
titanium
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.)
Granted
Application number
EP81420173A
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English (en)
French (fr)
Other versions
EP0053565B1 (de
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
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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/de
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Publication of EP0053565B1 publication Critical patent/EP0053565B1/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
    • 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 .
  • a feed device makes it possible to continuously introduce, as the electrolysis takes place, titanium tetrachloride into a bath of molten alkali or alkaline earth halides.
  • FIG. 1 represents such an electrolysis cell of the type described in FR 2,423,555 which comprises a metal casing (1) containing the molten electrolyte (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 TiCl 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 TiCl 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 TiCl 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 allowing the supply of TiCl 4 to an electrolysis cell for the preparation of titanium comprising at least one deposition cathode and a supply cathode; this device is a metallic diaphragm which surrounds the insulating cathode and which is insulated from it.
  • 'reference electrodes disposed on either side of the diaphgrame are connected to a means for measuring the voltage difference therebetween.
  • Another object of the invention is a method for supplying an electrolysis cell for the preparation of titanium, comprising at least one supply cathode for TiCl 4 surrounded by a diaphragm isolated from it, in which the intensity of current 1 which flows through the supply cathode is adjusted so as to maintain a drop in potential weak but not zero in the electrolyte which permeates the diaphragm.
  • this adjustment is carried out by controlling the intensity of the current flowing through the supply cathode to the drop in potential in the electrolyte impregnating the diaphragm or to a variable linked to this drop in potential.
  • the diaphragm (20) which constitutes one of the objects of the invention, is made of a metal having sufficient strength vis-à-vis the elec - trolyte in the temperature conditions in which one operates. 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 diaphgram (20).
  • the essential role of this is to obstruct the diffusion of TiCl3 formed according to reaction (2) by the action of TiC1 4 on TiCl 2 , outside the space delimited by this diaphragm.
  • the electrolyte area 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 contact with 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 by sintering a metallic powder, for example based on steel. stainless, 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) located outside this diaphragm.
  • e o Ti 3+ / Ti 2+ represents the normal potential for reaction (6)
  • a Ti 3+ and a Ti 2+ represent the respective activities of the Ti 3+ and Ti2 + ions in the volume of electrolyte (24) contained in the space surrounded by the diaphragm (20).
  • n ° I which meets the best operating conditions of the cell, the solution, and this is the object of the invention, consists in regulating the current I 1 so that 'there is a drop in potential as small as possible, but not zero, in the bath permeating the diaphragm.
  • the porosity of it is not critical. It must be large enough not to overly brake the flow of electrolyte which passes through the diaphragm. It should be low enough to allow easy detection of a potential drop in the electrolyte permeating the diaphragm.
  • 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 / AgCl electrodes immersed in the electrolyte: the ends of these electrodes pass through the cell cover by insulating joints 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) such as Ag / AgCl electrodes immersed in the electrolyte: the ends of these electrodes pass through the cell cover by insulating joints 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 Vorrichtung und Verfahren zur Zufuhr von TiCl4 in Elektrolysezellen für die Titanherstellung Expired EP0053565B1 (de)

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 true EP0053565A1 (de) 1982-06-09
EP0053565B1 EP0053565B1 (de) 1985-08-21

Family

ID=9248545

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81420173A Expired EP0053565B1 (de) 1980-11-27 1981-11-25 Vorrichtung und Verfahren zur Zufuhr von TiCl4 in Elektrolysezellen für die Titanherstellung

Country Status (7)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2579629A1 (fr) * 1985-03-28 1986-10-03 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

Families Citing this family (6)

* 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
WO2003046258A2 (en) * 2001-11-22 2003-06-05 Qit - Fer Et Titane Inc. A 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
EP2794943B8 (de) 2011-12-22 2019-07-10 Universal Achemetal Titanium, LLC Verfahren zur extraktion und reinigung von titan
CA3047102C (en) 2016-09-14 2023-12-05 Universal Achemetal Titanium, Llc A method for producing titanium-aluminum-vanadium alloy
CA3049769C (en) 2017-01-13 2023-11-21 Universal Achemetal Titanium, Llc Titanium master alloy for titanium-aluminum based alloys

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2760930A (en) * 1952-01-31 1956-08-28 Nat Lead Co Electrolytic cell of the diaphragm type
US4219401A (en) * 1978-08-07 1980-08-26 The D-H Titanium Company Metal electrowinning feed cathode

Family Cites Families (2)

* 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
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2760930A (en) * 1952-01-31 1956-08-28 Nat Lead Co Electrolytic cell of the diaphragm type
US4219401A (en) * 1978-08-07 1980-08-26 The D-H Titanium Company Metal electrowinning feed cathode

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2579629A1 (fr) * 1985-03-28 1986-10-03 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
EP0198775A1 (de) * 1985-03-28 1986-10-22 Pechiney Verfahren zur kontinuierlichen Überwachung des Gehalts eines in einem geschmolzenen Salzbad aufgelösten Metalls und dessen Anwendung zur kontinuierlichen Zufuhr dieser Metallsalze in einer Elektrolysezelle

Also Published As

Publication number Publication date
US4396472A (en) 1983-08-02
JPS57116790A (en) 1982-07-20
EP0053565B1 (de) 1985-08-21
NO156171B (no) 1987-04-27
NO814029L (no) 1982-05-28
FR2494725B1 (de) 1982-12-10
FR2494725A1 (fr) 1982-05-28
NO156171C (no) 1987-08-12
DE3171944D1 (en) 1985-09-26
ATE15080T1 (de) 1985-09-15
JPS5833314B2 (ja) 1983-07-19

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