EP1982006A2 - Cathode pour la production electrolytique de poudres de titane et d'autres metaux - Google Patents

Cathode pour la production electrolytique de poudres de titane et d'autres metaux

Info

Publication number
EP1982006A2
EP1982006A2 EP07763287A EP07763287A EP1982006A2 EP 1982006 A2 EP1982006 A2 EP 1982006A2 EP 07763287 A EP07763287 A EP 07763287A EP 07763287 A EP07763287 A EP 07763287A EP 1982006 A2 EP1982006 A2 EP 1982006A2
Authority
EP
European Patent Office
Prior art keywords
titanium
cathode
metal
anode
molten 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.)
Withdrawn
Application number
EP07763287A
Other languages
German (de)
English (en)
Inventor
Aaron J. Becker
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1982006A2 publication Critical patent/EP1982006A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc

Definitions

  • electrolytic cells comprising cathodes having a non-uniform current distribution and methods of use thereof for the production of titanium and other multi-valence and high (2 or more) valence metals, in particular refractory metals such as, for example, chromium, hafnium, molybdenum, niobium, tantalum, tungsten, vanadium, and zirconium.
  • refractory metals such as, for example, chromium, hafnium, molybdenum, niobium, tantalum, tungsten, vanadium, and zirconium.
  • the simplest electrolytic cell for use in electrowinning metals consists of at least two electrodes and a molten electrolyte.
  • the electrode at which the electron producing oxidation reaction occurs is the anode.
  • the electrode at which an electron consuming reduction reaction occurs is the cathode.
  • the direction of the electron flow in the circuit is always from anode to cathode.
  • Metal particles are removed from solid cathodes by force of gravity or forced fluid flow across the face of the cathode. If the metal particles grow too large or strongly stick to the surface of the cathode, the particles are difficult to dislodge and collect.
  • Other levers that people have found to control particle size and morphology include: 1. feedstock concentration, 2. temperature, 3. electrolyte composition including special additives, and 4. current density.
  • One aspect is for electrolytic cell comprising a cathode having a non-uniform current distribution.
  • a further aspect is for a method of controlling the morphology of a metal product in an electrolytic cell comprising the steps of (a)providing an electrolytic cell comprising a molten electrolyte, a cathode having a nonuniform current distribution in contact with the molten electrolyte, and an anode in contact with the molten electrolyte; (b) providing a metal compound to the electrolyte; and (c) applying either a fixed voltage or a fixed current across the anode and the cathode thereby depositing metal on the cathode.
  • the disclosure herein while relating in particular to the production of titanium from a titanium oxide, is also applicable to the production of titanium from other titanium compounds as well as for the production of other metal compounds such as, for example, chromium, hafnium, molybdenum, niobium, tantalum, tungsten, vanadium, or zirconium from, for example, the respective oxides, halides, nitrides, or sulfides.
  • Cathode design is used to aid in controlling the cross-sectional area of electrodepositing metal particles by controlling the lines of constant potential parallel to the face of the cathode surface, lsopotential lines will be parallel to the contour of the surface of the electrode and current distribution will be orthogonal or perpendicular to these lines and with metal deposition rates proportional to current density, the areas of highest current density will have the largest metal deposition rates. Furthermore, current density is highest where the distance between cathode and anode is shortest so as particles grow from the cathode, current densities at the tip of the growing particles are highest.
  • One embodiment for producing this non-uniform current distribution relates to a cathode comprising a wire mesh screen. If a screen is used to control particle cross-sectional area, particles can only grow where there is metal mesh, so, for example if the mesh is 100 microns across, the cross- sectional area of the particles formed will have an average cross-section of 100 microns.
  • a cathode comprising a wire mesh screen.
  • additional useful cathode designs include, but are not limited to, bristles, cones, rods, combinations thereof, and combinations with mesh screens.
  • the height to which particles can grow from the cathode surface can be controlled by adjusting the electrolyte flowrate so the fluid would shear particles as they form to the desired height.
  • mechanical means can be used to dislodge the particles as they grow toward the anode, for example, vibration.
  • Gas blowers can also be used to dislodge the particles.
  • particle size ranges, particle aspect ratio ranges and particle morphologies preferred for each powder metallurgical processing method used to make various forms of metal parts.
  • symmetric spherical powders with particles less than 45 microns are preferred.
  • press and sintering 45 to 150 micron asymmetric powder particles with aspect ratios of >1.5 are preferred.
  • Anodes useful in standard electrolytic cells can be utilized in an electrolytic cell containing a cathode having a non-uniform current distribution.
  • carbon anodes for example, carbon anodes, inert dimensionally stable anodes, or a gas diffusion anodes fed with a combustible gas are all useful in electrolytic cells containing a cathode having a non-uniform current distribution.
  • Other useful anodes include consumable anodes containing a compound of the metal, such as titanium, to be deposited at the cathode.
  • Consumable anodes are known in the art and an example of a suitable consumable anode is described in U.S. Patent No. 2,722,509 which is incorporated herein by reference.
  • One anode or multiple anodes can be employed.
  • the anode can be a molten metal anode as disclosed in U.S. Patent Publication No. 2005/0121333, incorporated herein by reference.
  • the metal compound to be electrowon is a metal oxide, for example titanium oxide or titanium dioxide. It is also possible, however, to electrowin a metal from other metal compounds that are not oxides. These compounds include, for example, halides such as, e.g., TiCI 3 , nitrides such as, e.g., titanium nitride, and carbides such as, e.g., titanium carbide.
  • the metal compound may be in the form of a rod, sheet or other artifact. If the metal compound is in the form of swarf or particulate matter, it may be held in a mesh basket. In another embodiment, the metal compound can also be solubil ⁇ zed in the electrolyte, optionally with the assistance of standard solubilizers.
  • an alloy By using more than one metal compound, it is possible to produce an alloy.
  • the metal compounds for alloy production may be incorporated into the molten electrolyte simultaneously, added stepwise, or in any other manner as is necessary to produce the desired alloy.
  • an alloy of Ti-Al-V can be produced by mixing aluminum oxide, vanadium oxide, and TiO 2 in the electrolyte thereby to produce an alloy of Ti- Al-- V in the molten zinc cathode.
  • the Eo and current density should be adjusted to deposit precise composition alloy particles.
  • the electrolyte consists of salts which are preferably more stable than the equivalent salts of the metal which is being deposited. Using salts with a low melting point, it is possible to use mixtures if a fused salt melting at a lower temperature is required, e.g. by utilizing a eutectic or near-eutectic mixture. It is also advantageous to have, as an electrolyte, a salt with as wide a difference between the melting and boiling points, since this gives a wide operating temperature without excessive vaporization.
  • Exemplary electrolytes include, but are not limited to, metal fluorides, metal chlorides, and mixtures thereof.
  • the level of metal compound provided to the molten electrolyte is continuously adjusted in order to insure continuous operating electrolysis.

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)

Abstract

La présente invention concerne des cellules électrolytiques comprenant des cathodes présentant une répartition non uniforme de courant et des procédés d'utilisation de celles-ci.
EP07763287A 2006-02-06 2007-02-06 Cathode pour la production electrolytique de poudres de titane et d'autres metaux Withdrawn EP1982006A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76556006P 2006-02-06 2006-02-06
PCT/US2007/003066 WO2007092398A2 (fr) 2006-02-06 2007-02-06 cathode pour la production Electrolytique de poudres de titane et d'autres mEtaux

Publications (1)

Publication Number Publication Date
EP1982006A2 true EP1982006A2 (fr) 2008-10-22

Family

ID=38345718

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07763287A Withdrawn EP1982006A2 (fr) 2006-02-06 2007-02-06 Cathode pour la production electrolytique de poudres de titane et d'autres metaux

Country Status (4)

Country Link
US (1) US20090045070A1 (fr)
EP (1) EP1982006A2 (fr)
AU (1) AU2007212481A1 (fr)
WO (1) WO2007092398A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201208698D0 (en) * 2012-05-16 2012-06-27 Metalysis Ltd Electrolytic method,apparatus and product
WO2018096769A1 (fr) * 2016-11-22 2018-05-31 住友電気工業株式会社 Procédé de production de solution de placage en titane et procédé de production de produit à placage en titane
CA3046585A1 (fr) * 2016-12-08 2018-06-14 Metoxs Pte, Ltd. Recuperation d'or et d'argent de solides contenant des metaux precieux

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FR1066602A (fr) * 1951-11-23 1954-06-08 Ici Ltd Perfectionnements à la fabrication de métaux
US2722509A (en) * 1952-11-12 1955-11-01 Horizons Titanium Corp Production of titanium
US2974092A (en) * 1955-12-16 1961-03-07 Horizons Titanium Corp Production of titanium
US2975111A (en) * 1958-03-19 1961-03-14 New Jersey Zinc Co Production of titanium
DE1115033B (de) * 1958-03-19 1961-10-12 New Jersey Zinc Co Verfahren zur Herstellung von Titan durch Schmelzflusselektrolyse
US3030753A (en) * 1958-04-10 1962-04-24 Koppers Co Inc Rapper
AU419537B2 (en) * 1966-08-26 1971-12-03 Titanium Metals Corporation Of America Electrolytic cell
US3860509A (en) * 1973-02-20 1975-01-14 Envirotech Corp Continuous electrowinning cell
US4655825A (en) * 1982-11-08 1987-04-07 Occidental Research Corporation Metal powder and sponge and processes for the production thereof
US5102451A (en) * 1990-11-08 1992-04-07 Dynamet Technology, Inc. Titanium aluminide/titanium alloy microcomposite material
US6832735B2 (en) * 2002-01-03 2004-12-21 Nanoproducts Corporation Post-processed nanoscale powders and method for such post-processing
GB9812169D0 (en) * 1998-06-05 1998-08-05 Univ Cambridge Tech Purification method
AUPR317201A0 (en) * 2001-02-16 2001-03-15 Bhp Innovation Pty Ltd Extraction of Metals
AUPR443801A0 (en) * 2001-04-10 2001-05-17 Bhp Innovation Pty Ltd Removal of oxygen from metal oxides and solid metal solutions
AUPR602901A0 (en) * 2001-06-29 2001-07-26 Bhp Innovation Pty Ltd Removal of oxygen from metals oxides and solid metal solutions
AUPR712101A0 (en) * 2001-08-16 2001-09-06 Bhp Innovation Pty Ltd Process for manufacture of titanium products
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
AUPS117002A0 (en) * 2002-03-13 2002-04-18 Bhp Billiton Innovation Pty Ltd Minimising carbon transfer in an electrolytic cell
GB0222382D0 (en) * 2002-09-27 2002-11-06 Qinetiq Ltd Improved process for removing oxygen from metal oxides by electrolysis in a fused salt
AU2002952181A0 (en) * 2002-10-21 2002-11-07 Intec Ltd Electrolysis process and cell for use in same
US6958115B2 (en) * 2003-06-24 2005-10-25 The United States Of America As Represented By The Secretary Of The Navy Low temperature refining and formation of refractory metals
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CN1664173A (zh) * 2004-12-24 2005-09-07 北京科技大学 一种熔盐电解二氧化钛制备海绵钛的方法

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Title
See references of WO2007092398A2 *

Also Published As

Publication number Publication date
WO2007092398A2 (fr) 2007-08-16
AU2007212481A1 (en) 2007-08-16
US20090045070A1 (en) 2009-02-19
WO2007092398A3 (fr) 2008-02-28

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