EP0253841B1 - Verfahren zur herstellung von übergangsmetallpulver durch schmelzflusselektrolyse - Google Patents

Verfahren zur herstellung von übergangsmetallpulver durch schmelzflusselektrolyse Download PDF

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Publication number
EP0253841B1
EP0253841B1 EP87900658A EP87900658A EP0253841B1 EP 0253841 B1 EP0253841 B1 EP 0253841B1 EP 87900658 A EP87900658 A EP 87900658A EP 87900658 A EP87900658 A EP 87900658A EP 0253841 B1 EP0253841 B1 EP 0253841B1
Authority
EP
European Patent Office
Prior art keywords
metal
bath
electrolysis
process according
voltage
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
Application number
EP87900658A
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English (en)
French (fr)
Other versions
EP0253841A1 (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
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
Publication of EP0253841A1 publication Critical patent/EP0253841A1/de
Application granted granted Critical
Publication of EP0253841B1 publication Critical patent/EP0253841B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts

Definitions

  • the present invention relates to the preparation of powders of transition metals by electrolysis of their halides in baths of molten salts.
  • the studies undertaken for the development of the invention were carried out in a cell comprising, on the one hand a metal tank containing the molten bath, on the other hand a also metallic cover ensuring the sealing of the system and having various orifices allowing, among other things, the sealed and isolated passage of the anode and cathode devices immersed in the bath, the supply of this bath with the halide of the metal to be produced and the extraction of the halogen released at the anode.
  • the fluorine / metal ratio is between 3 and 20. However, preferably, the best results are obtained with the range of values between 6 and 12.
  • the anode device further comprises a diaphragm which separates the bath into two compartments, an anode compartment which contains only traces of Titanium in solution, and a cathode compartment in which the content of dissolved Titanium is kept constant by a continuous supply device.
  • the bath consists of an equimolecular mixture of potassium chlorides and sodium molten at 750 ° C.
  • the halide introduced is titanium tetrachloride.
  • the content of titanium dissolved in the bath is 4%.
  • the deposition voltage of titanium measured by drawing the voltage / current curve, is 2.15 V.
  • the easiest to reduce of the alkali in this case, the sodium is 3.2 V.
  • the deposits collected on the cathode are in the form of well crystallized dendrites which can reach several centimeters and which meet the following analysis in ppm:
  • the electrical efficiency is greater than 90%.
  • the electrical efficiency is greater than 85%.
  • This example relates to Hafnium.
  • the halide introduced this time being hafnium tetrachloride, at the content of 25%, under normal conditions.
  • electrolysis i.e. with a current density of 1.0 A / cm 2
  • the deposition voltage of Hafnium is 2.2 V. and deposits are obtained in the form of relatively massive dendrites ( cauliflower appearance) with an electrical efficiency greater than 95%.
  • F- ions are introduced into the bath by means of the addition of sodium fluoride for example, so that the fluorine / Hafnium molecular ratio is equal to 12, under the same electrolysis conditions, the voltage of Hafnium deposit goes to 2.90 V and after washing the deposit, a powder is obtained which passes almost entirely through a sieve of 200 microns opening and which meets the following analysis in ppm:

Landscapes

  • 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)

Claims (6)

1. Verfahren zur Herstellung von Pulvern mit Körnern von Abmessungen unter 200 pm aus zu den Gruppen IVa, Va und Vla gehörenden Übergangsmetallen durch Elektrolyse ihrer in einem Bad geschmolzener Salze auf Basis von Alkali- und/oder Erdalkalihalogeniden gelösten Halogenide, bei dem man Stromdichten im bereich von 0,3 bis 1,0 A/cm2 verwendet, dadurch gekennzeichnet, daß man die Elektrolyse in der Weise durchführt, daß die Abscheidespannung des Übergangsmetalls um 0,1 bis 0,4 Volt niedriger als die des am leichtesten reduzierbaren Alkali- oder Erdalkalimetalls ist.
2. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die Abscheidespannung um 0,2 bis 0,3 Volt niedriger als die des am leichtesten reduzierbaren Alkali- oder Erdalkalimetalls ist.
3. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man diese Spannung durch Senken des Gehalts an im kathodischen Bad gelöstem Metall erhält.
4. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man diese Spannung durch Änderung der Komplexbildung der Ionen des gelösten Metalls erhält.
5. Verfahren nach dem Ansprüchen 1 und 4, dadurch gekennzeichnet, daß das verwendet Bad von Salzen ein bei 750°C geschmolzenes, äquimolekulares NaCI/KCI-Gemisch ist, das Halogenid des abzuscheidenden Metalls ein Chlorid ist und das komplexbildende Mittel in das Bad eingeführtes Fluor in Form von NaF in solcher Menge ist, daß das molekulare Verhältnis Fluor/Metall im bereich von 3 bis 20 ist.
6. Verfahren nach dem Anspruch 5, dadurch gekennzeichnet, daß das molekulare Verhältnis Fluor/ Metall im Bereich von 6 bis 12 ist.
EP87900658A 1986-01-06 1987-01-05 Verfahren zur herstellung von übergangsmetallpulver durch schmelzflusselektrolyse Expired - Lifetime EP0253841B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8600390 1986-01-06
FR8600390A FR2592664B1 (fr) 1986-01-06 1986-01-06 Procede d'elaboration de poudres de metaux de transition par electrolyse en bains de sels fondus

Publications (2)

Publication Number Publication Date
EP0253841A1 EP0253841A1 (de) 1988-01-27
EP0253841B1 true EP0253841B1 (de) 1990-05-23

Family

ID=9331054

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87900658A Expired - Lifetime EP0253841B1 (de) 1986-01-06 1987-01-05 Verfahren zur herstellung von übergangsmetallpulver durch schmelzflusselektrolyse

Country Status (7)

Country Link
US (1) US4770750A (de)
EP (1) EP0253841B1 (de)
JP (1) JPS63500187A (de)
CA (1) CA1287814C (de)
DE (1) DE3762890D1 (de)
FR (1) FR2592664B1 (de)
WO (1) WO1987004193A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991001942A1 (en) * 1989-08-01 1991-02-21 Australian Copper Company Pty. Ltd. Production of copper compounds
DE60130322T2 (de) * 2000-02-22 2008-06-12 Metalysis Ltd., Wath-Upon-Dearne Verfahren zur herstellung von metallschaum durch elektrolytische reduktion poröser oxidischer vorformen
WO2005111272A1 (ja) * 2004-04-06 2005-11-24 Iox Co., Ltd. プラズマ誘起電解による微粒子の製造方法
PL377451A1 (pl) * 2005-10-05 2007-04-16 Instytut Wysokich Ciśnień PAN Sposób prowadzenia reakcji i reaktor chemiczny
WO2013096893A1 (en) 2011-12-22 2013-06-27 Universal Technical Resource Services, Inc. A system and method for extraction and refining of titanium
JP7096235B2 (ja) 2016-09-14 2022-07-05 ユニバーサル アケメタル タイタニウム リミテッド ライアビリティ カンパニー チタン－アルミニウム－バナジウム合金の製造方法
WO2018186922A2 (en) 2017-01-13 2018-10-11 Universal Technical Resource Services, Inc. Titanium master alloy for titanium-aluminum based alloys

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2951021A (en) * 1952-03-28 1960-08-30 Nat Res Corp Electrolytic production of titanium
GB736567A (en) * 1952-07-03 1955-09-07 Horizons Titanium Corp Improvements in production of metallic titanium
FR1265427A (fr) * 1960-06-03 1961-06-30 Ciba Geigy Procédé d'élaboration électrolytique des métaux niobium et tantale

Also Published As

Publication number Publication date
EP0253841A1 (de) 1988-01-27
WO1987004193A1 (fr) 1987-07-16
US4770750A (en) 1988-09-13
JPH0312156B2 (de) 1991-02-19
FR2592664B1 (fr) 1990-03-30
JPS63500187A (ja) 1988-01-21
FR2592664A1 (fr) 1987-07-10
DE3762890D1 (de) 1990-06-28
CA1287814C (fr) 1991-08-20

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