EP0053567B1 - Zelle zur Herstellung mehrwertiger Metalle, z.B. Zr oder Hf, durch Elektrolyse geschmolzener Halogenide und Verfahren, um diese Zelle in Betrieb zu setzen - Google Patents

Zelle zur Herstellung mehrwertiger Metalle, z.B. Zr oder Hf, durch Elektrolyse geschmolzener Halogenide und Verfahren, um diese Zelle in Betrieb zu setzen Download PDF

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Publication number
EP0053567B1
EP0053567B1 EP81420175A EP81420175A EP0053567B1 EP 0053567 B1 EP0053567 B1 EP 0053567B1 EP 81420175 A EP81420175 A EP 81420175A EP 81420175 A EP81420175 A EP 81420175A EP 0053567 B1 EP0053567 B1 EP 0053567B1
Authority
EP
European Patent Office
Prior art keywords
cell
metal
electrolysis
collector
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
EP81420175A
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English (en)
French (fr)
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EP0053567A1 (de
Inventor
Marcel Armand
Philippe Moinard
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 AT81420175T priority Critical patent/ATE20608T1/de
Publication of EP0053567A1 publication Critical patent/EP0053567A1/de
Application granted granted Critical
Publication of EP0053567B1 publication Critical patent/EP0053567B1/de
Expired legal-status Critical Current

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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
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the 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 new electrolysis cell which is the subject of the invention relates to the preparation by electrolysis of Zr or Hf.
  • FIG. 1 represents an electrolysis cell for the preparation of zirconium, which is described in report R18125 from the USBM: "Investigation of a cell design for electrowinning zirconium metal from zirconium tetrachloride", G.M. Martinez et al, (1976).
  • a graphite anode (3) is connected to the positive pole of a current source not shown and an annular cathode (4) of nickel surrounds the anode and is connected to the negative pole of the current source.
  • a graphite collector (5) collects the chlorine which is released at the anode and directs it towards the gas evacuation pipe (6).
  • the lower part of the collector penetrates a little below the surface of the electrolyte so as to form a hydraulic seal.
  • the new electrolysis cell which is the subject of the invention, makes it possible to resolve these difficulties. It includes above the electrolyte an anode space delimited by a graphite collector or coated with graphite, the lower end of which penetrates a little below the surface of the electrolyte to form a hydraulic seal. This end is extended in the electrolyte by a solid or perforated or porous metal wall open downwards made in metal to be deposited or coated with the metal to be deposited.
  • the invention consists, as shown in FIG. 3, of placing in a cell similar to that described in FIG. 1, a collector (15) of graphite or of metal which cannot be attacked by the electrolyte coated with graphite on the anode side.
  • the coating of graphite can be carried out for example by means of a felt based on expanded graphite.
  • the end of this collector only enters the electrolyte over a shallow depth; it is extended into the electrolyte by an annular wall (16) of polyvalent metal to be deposited (zirconium or hafnium).
  • This wall (16) of limited height may or may not be perforated. It can be produced, for example, by means of a perforated sheet or not, of a profile, or even of a deployed sheet.
  • Such a device which eliminates the release of chlorine from the cathode side, makes it possible to avoid any phenomenon of corrosion in this area of the cell and also makes it possible to very significantly increase the yields of the amps as well as regards the yield. in chlorine as the yield in Zr or Hf.
  • the use in the cell of only metallic materials, and of graphite makes it possible to obtain deposits of Zr or Hf of high purity, the oxygen contents of which are particularly low.
  • this wall is maintained slightly cathodic with respect to the anode by deriving a current 1 1 , fraction of current 1, through this wall.
  • the wall is covered with polyvalent metal and, provided that the current 1 1 is sufficient, it is this constantly renewed deposit which serves as a sacrificial anode.
  • Such a device has over the previous one, the advantage of not requiring any intervention on the cell to replace the sacrificial wall which is, in this case, self-healing.

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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)
  • Secondary Cells (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Claims (2)

1. Elektrolysezelle zur Herstellung von Zr oder Hf durch Elektrolyse ihrer Chloride in einem Bad geschmolzener Alkali- und/oder Erdalkalihalogenide,
die oberhalb des Elektrolyten einen Anodenraum aufweist, der durch eine mit Graphit beschichtete oder aus Graphit bestehende Sammeleinrichtung begrenzt ist, deren unteres Ende unter Bildung einer hydraulischen Verbindung ein wenig unterhalb der Oberfläche des Elektrolyten eintaucht,
dadurch gekennzeichnet, daß
das untere Ende der Sammeleinrichtung mit einer ringförmigen vollen oder Perforierten oder Porösen metallischen Wand verlängert ist, die nach unten offen ist und aus dem abzuscheidenden Metall besteht oder mit ihm beschichtet ist.
2. Elektrolysezelle nach Anspruch 1, dadurch gekennzeichnet, daß die Wand mittels der Sammeleinrichtung mit dem negativen Pol einer Stromquelle verbunden ist, deren positiver Pol an die Anode der Elektrolysezelle angeschlossen ist.
EP81420175A 1980-11-27 1981-11-25 Zelle zur Herstellung mehrwertiger Metalle, z.B. Zr oder Hf, durch Elektrolyse geschmolzener Halogenide und Verfahren, um diese Zelle in Betrieb zu setzen Expired EP0053567B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81420175T ATE20608T1 (de) 1980-11-27 1981-11-25 Zelle zur herstellung mehrwertiger metalle, z.b. zr oder hf, durch elektrolyse geschmolzener halogenide und verfahren, um diese zelle in betrieb zu setzen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8025507 1980-11-27
FR8025507A FR2494727A1 (fr) 1980-11-27 1980-11-27 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

Publications (2)

Publication Number Publication Date
EP0053567A1 EP0053567A1 (de) 1982-06-09
EP0053567B1 true EP0053567B1 (de) 1986-07-02

Family

ID=9248547

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81420175A Expired EP0053567B1 (de) 1980-11-27 1981-11-25 Zelle zur Herstellung mehrwertiger Metalle, z.B. Zr oder Hf, durch Elektrolyse geschmolzener Halogenide und Verfahren, um diese Zelle in Betrieb zu setzen

Country Status (7)

Country Link
US (1) US4443306A (de)
EP (1) EP0053567B1 (de)
JP (1) JPS5834553B2 (de)
AT (1) ATE20608T1 (de)
DE (1) DE3174903D1 (de)
FR (1) FR2494727A1 (de)
NO (1) NO157025C (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2257426C1 (ru) * 2003-11-06 2005-07-27 Открытое акционерное общество "Чепецкий механический завод" (ОАО ЧМЗ) Способ получения циркония
RU2400568C2 (ru) * 2008-08-08 2010-09-27 Открытое акционерное общество "Высокотехнологический научно-исследовательский институт неорганических материалов имени академика А.А.Бочвара" Способ получения циркония электролизом расплавленного электролита (варианты)
RU2654397C2 (ru) * 2016-09-06 2018-05-17 Акционерное общество "Высокотехнологический научно-исследовательский институт неорганических материалов имени академика А.А. Бочвара" Способ получения циркония электролизом расплавленного электролита (варианты)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2560896B1 (fr) * 1984-03-12 1989-10-20 Pechiney 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
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
IT1219222B (it) * 1988-04-19 1990-05-03 Ginatta Spa Procedimento per la produzione elettrolitica di un metallo polivalente ed apparecchiatura per l'attuazione del procedimento
US4865694A (en) * 1988-09-12 1989-09-12 Westinghouse Electric Corp. Electrochemical decomposition of complexes of zirconium or hafnium
US4874475A (en) * 1988-09-12 1989-10-17 Westinghouse Electric Corp. Molten salt extractive distillation process for zirconium-hafnium separation
RU2140465C1 (ru) * 1997-03-20 1999-10-27 Открытое акционерное общество "Чепецкий механический завод" Способ утилизации хлора, фтора из анодного газа и отработанного электролита, образующихся в процессе электролитического получения циркония
GB9812169D0 (en) * 1998-06-05 1998-08-05 Univ Cambridge Tech Purification method
CN115896875A (zh) * 2022-11-22 2023-04-04 南京佑天金属科技有限公司 海绵锆、铪在电子束熔炼过程中挥发物的回收装置及方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2789943A (en) * 1955-05-05 1957-04-23 New Jersey Zinc Co Production of titanium
FR2423555A1 (fr) * 1978-04-21 1979-11-16 Dow Chemical Co Appareil et procede pour l'obtention par electrolyse de metaux polyvalents

Family Cites Families (7)

* 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
DE1201567B (de) * 1953-11-06 1965-09-23 Titanium Metals Corp Verfahren und Vorrichtung zur elektrolytischen Herstellung von reinem Titan oder Zirkonium
US3345278A (en) * 1963-03-25 1967-10-03 Hooker Chemical Corp Anodic passivation of metals
US3622491A (en) * 1969-04-23 1971-11-23 Us Interior Electrolytic apparatus for molten salt electrolysis
US4116801A (en) * 1974-10-24 1978-09-26 The Dow Chemical Company Apparatus for electrowinning multivalent metals
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
JPS5914556B2 (ja) * 1978-04-28 1984-04-05 ザ ダウ ケミカル カンパニ− チタン電解製造用金属性隔膜および該隔膜を使用する電解槽と該電解槽中でのチタン製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2789943A (en) * 1955-05-05 1957-04-23 New Jersey Zinc Co Production of titanium
FR2423555A1 (fr) * 1978-04-21 1979-11-16 Dow Chemical Co Appareil et procede pour l'obtention par electrolyse de metaux polyvalents

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2257426C1 (ru) * 2003-11-06 2005-07-27 Открытое акционерное общество "Чепецкий механический завод" (ОАО ЧМЗ) Способ получения циркония
RU2400568C2 (ru) * 2008-08-08 2010-09-27 Открытое акционерное общество "Высокотехнологический научно-исследовательский институт неорганических материалов имени академика А.А.Бочвара" Способ получения циркония электролизом расплавленного электролита (варианты)
RU2654397C2 (ru) * 2016-09-06 2018-05-17 Акционерное общество "Высокотехнологический научно-исследовательский институт неорганических материалов имени академика А.А. Бочвара" Способ получения циркония электролизом расплавленного электролита (варианты)

Also Published As

Publication number Publication date
NO157025B (no) 1987-09-28
NO814031L (no) 1982-05-28
NO157025C (no) 1988-01-20
DE3174903D1 (en) 1986-08-07
ATE20608T1 (de) 1986-07-15
FR2494727A1 (fr) 1982-05-28
JPS5834553B2 (ja) 1983-07-27
FR2494727B1 (de) 1982-12-10
EP0053567A1 (de) 1982-06-09
JPS57116792A (en) 1982-07-20
US4443306A (en) 1984-04-17

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