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WO2004018734A2 - Anode en ceramique coulee destinee a la reduction electrolytique d'oxydes metalliques - Google Patents

Anode en ceramique coulee destinee a la reduction electrolytique d'oxydes metalliques Download PDF

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Publication number
WO2004018734A2
WO2004018734A2 PCT/US2003/025607 US0325607W WO2004018734A2 WO 2004018734 A2 WO2004018734 A2 WO 2004018734A2 US 0325607 W US0325607 W US 0325607W WO 2004018734 A2 WO2004018734 A2 WO 2004018734A2
Authority
WO
WIPO (PCT)
Prior art keywords
anode
nickel
molten
cast
iron
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.)
Ceased
Application number
PCT/US2003/025607
Other languages
English (en)
Other versions
WO2004018734A3 (fr
Inventor
David C. Meissner
Ashvin Srivastava
Jeffrey B. Musat
Jeffrey K. Cheetham
Abid Bengali
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.)
PEL TECHNOLOGIES LLC
Original Assignee
PEL TECHNOLOGIES LLC
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 PEL TECHNOLOGIES LLC filed Critical PEL TECHNOLOGIES LLC
Priority to AU2003262712A priority Critical patent/AU2003262712A1/en
Publication of WO2004018734A2 publication Critical patent/WO2004018734A2/fr
Publication of WO2004018734A3 publication Critical patent/WO2004018734A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/056—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using gas
    • 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
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/12—Anodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
    • B22D1/002—Treatment with gases
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides

Definitions

  • the present invention relates to a method and apparatus for producing a cast ceramic anode for metal oxide electrolytic reduction, and a cast ceramic anode product.
  • the invention provides a method for producing a cast ceramic anode for metal oxide electrolytic reduction by feeding metallic iron and metallic nickel in solid form to an oxidizing reactor; melting and oxidizing the iron and nickel and forming molten nickel ferrite; transferring the molten nickel ferrite material into a holding vessel such as a ladle or tundish, and casting the molten material into a mold to form a near net shape of the desired anode.
  • the material in the holding vessel may be blown with an oxygen- containing gas for stirring of the molten material and the oxidation of any remaining metal.
  • Metal containing compounds, especially oxides may be added to dope the ferrite, which increases the electrical conductivity and mechanical strength of the ferrite.
  • the invention also comprises apparatus for producing a cast ceramic anode for metal oxide electrolytic reduction, comprising an oxidizing reactor; means for feeding metallic iron and metallic nickel to the oxidizing reactor; a ladle or tundish positioned for receiving molten material from the reactor; means for adding metal oxide dopants to the ladle or tundish; means for blowing an oxygen-containing gas into the ladle or tundish for stirring and oxidation of any remaining metal; a mold positioned to receive molten material from the ladle or tundish; and means for discharging molten metal from the ladle or tundish into the mold to form the anode.
  • an electrical conductor rod made of nickel may be inserted into the still molten casting.
  • a further object of this invention is to provide apparatus for the manufacture of ceramic type cast inert anodes.
  • Figure 1 is a schematic diagram of the method and apparatus of the preferred embodiment of the invention.
  • Figure 2 is a schematic diagram of the method and apparatus of an alternative embodiment of the invention.
  • Figure 3 is a schematic diagram of the method and apparatus of another alternative embodiment of the invention which utilizes a melting furnace rather than an oxidizing furnace.
  • Figure 4 is a schematic diagram of alternative embodiment of the invented method utilizing a variation of feed materials to the oxidizing furnace.
  • molten metal oxide is formed by oxidizing iron and other metal(s) to form a molten ferrite of the general formula where A and B are divalent metal ions such as Mg, Ni, Mn, Co, Fe; and x can vary from 0 to 1.0.
  • the molten ferrite is then mixed with a dopant to increase its electrical conductivity.
  • the molten mixture may be blown with an oxygen containing gas for stirring and oxidation of any remaining metal or it may be stirred with an inert gas.
  • the molten mixture of ferrite and dopant is then cast, solidified and cooled. The mixture may be cast into a near net shape of the desired cermet anode.
  • An electrical connector may be attached to the cermet anode by cementing after cooling, or by insertion during the time the anode is molten in the mold. After removal from the mold the cast anode with attached electrical connector may be post-heat treated. This treatment may be an annealing step carried out in an oxygen-containing atmosphere.
  • Ni Fe Ni 2/1 .
  • a molten nickel ferrite of formula Ni Fe 2 O 4 is formed.
  • Ni Fe 2 O 4 nickel ferrite
  • Fe 3 O 4 iron ferrite
  • NiO nickel oxide
  • a dopant such as zinc oxide may be added between the melting oxidizing reactor and the tundish or ladle by introducing it into the discharge runner between the oxidizing reactor and the tundish.
  • the dopant may be added in powder form or in lump form.
  • the dopant may be added directly to the casting mold before or during filling of the mold with the molten nickel ferrite.
  • the dopant may be added in the form of powder or lump.
  • solid nickel ferrite 40, or a mixture of nickel ferrite, nickel oxide and iron ferrite, or iron-containing and nickel- containing compounds 42 are melted in a melting furnace or vessel 44, which need not be an oxidizing vessel, to form molten nickel ferrite.
  • the melting vessel can be a gas fired furnace, induction furnace, or electric arc furnace.
  • a ceramic type inert anode made from a ferrite may be used in electrolytic reduction processes besides aluminum reduction, such as electrolytic reduction of magnesium, lithium, or calcium. It is also understood that a ceramic type inert anode made from a ferrite may be used as an anode in the brine electrolysis process in the chlor-alkali industry.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Magnetic Ceramics (AREA)

Abstract

L'invention concerne un procédé de production d'une anode en céramique coulée destinée à la réduction électrolytique d'oxydes métalliques. Ledit procédé consiste : à fournir à un réacteur d'oxydation du fer métallique et du nickel métallique sous forme solide ; à fondre et à oxyder le fer et le nickel, et à former de la ferrite de nickel en fusion ; à mélanger la ferrite de nickel en fusion avec un dopant dans un récipient tel qu'une poche ou un panier de coulée, afin d'augmenter la conductivité électrique du mélange ; et à couler le mélange dans un moule, de façon à former une anode de grande précision dimensionnelle. L'invention a également trait à un appareil permettant de mettre en oeuvre ledit procédé, ainsi qu'au produit obtenu.
PCT/US2003/025607 2002-08-21 2003-08-15 Anode en ceramique coulee destinee a la reduction electrolytique d'oxydes metalliques Ceased WO2004018734A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003262712A AU2003262712A1 (en) 2002-08-21 2003-08-15 Cast ceramic anode for metal oxide electrolytic reduction

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40502102P 2002-08-21 2002-08-21
US60/405,021 2002-08-21

Publications (2)

Publication Number Publication Date
WO2004018734A2 true WO2004018734A2 (fr) 2004-03-04
WO2004018734A3 WO2004018734A3 (fr) 2004-09-30

Family

ID=31946802

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US2003/025607 Ceased WO2004018734A2 (fr) 2002-08-21 2003-08-15 Anode en ceramique coulee destinee a la reduction electrolytique d'oxydes metalliques
PCT/US2003/025597 Ceased WO2004018082A1 (fr) 2002-08-21 2003-08-15 Anode en cermet moule pour reduction electrolytique d'un oxyde metallique

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US2003/025597 Ceased WO2004018082A1 (fr) 2002-08-21 2003-08-15 Anode en cermet moule pour reduction electrolytique d'un oxyde metallique

Country Status (3)

Country Link
US (2) US20040038805A1 (fr)
AU (2) AU2003262706A1 (fr)
WO (2) WO2004018734A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6915838B2 (en) * 2002-08-21 2005-07-12 Pel Technologies Llc Cast ceramic anode for metal oxide electrolytic reduction
CN102149853B (zh) 2008-09-08 2014-01-08 力拓艾尔坎国际有限公司 用于铝还原电解槽的在高电流密度下运行的金属析氧阳极
WO2016189570A1 (fr) * 2015-05-26 2016-12-01 Tdk Corporation Corps formant ensemble et électrode pour électrolyse
CN109811368B (zh) * 2019-03-20 2021-03-16 武汉大学 用于熔盐电解体系的锂离子强化型惰性阳极及其制备方法
CN110265170B (zh) * 2019-06-25 2022-12-09 华东理工大学 电化学合成铁氧体资源化处理钢铁酸洗废液的方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4173518A (en) * 1974-10-23 1979-11-06 Sumitomo Aluminum Smelting Company, Limited Electrodes for aluminum reduction cells
BR8207776A (pt) * 1981-07-01 1983-05-31 Diamond Shamrock Corp Producao eletrolitica de aluminio
US4443314A (en) * 1983-03-16 1984-04-17 Great Lakes Carbon Corporation Anode assembly for molten salt electrolysis
US4495049A (en) * 1983-05-03 1985-01-22 Great Lakes Carbon Corporation Anode for molten salt electrolysis
US4541912A (en) * 1983-12-12 1985-09-17 Great Lakes Carbon Corporation Cermet electrode assembly
US4999097A (en) * 1987-01-06 1991-03-12 Massachusetts Institute Of Technology Apparatus and method for the electrolytic production of metals
US5284562A (en) * 1992-04-17 1994-02-08 Electrochemical Technology Corp. Non-consumable anode and lining for aluminum electrolytic reduction cell
US6423204B1 (en) * 1997-06-26 2002-07-23 Alcoa Inc. For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals
US6372119B1 (en) * 1997-06-26 2002-04-16 Alcoa Inc. Inert anode containing oxides of nickel iron and cobalt useful for the electrolytic production of metals
US5865980A (en) * 1997-06-26 1999-02-02 Aluminum Company Of America Electrolysis with a inert electrode containing a ferrite, copper and silver
US6416649B1 (en) * 1997-06-26 2002-07-09 Alcoa Inc. Electrolytic production of high purity aluminum using ceramic inert anodes
US6217739B1 (en) * 1997-06-26 2001-04-17 Alcoa Inc. Electrolytic production of high purity aluminum using inert anodes
US6083362A (en) * 1998-08-06 2000-07-04 University Of Chicago Dimensionally stable anode for electrolysis, method for maintaining dimensions of anode during electrolysis
US6146513A (en) * 1998-12-31 2000-11-14 The Ohio State University Electrodes, electrolysis apparatus and methods using uranium-bearing ceramic electrodes, and methods of producing a metal from a metal compound dissolved in a molten salt, including the electrowinning of aluminum
US6440279B1 (en) * 2000-12-28 2002-08-27 Alcoa Inc. Chemical milling process for inert anodes

Also Published As

Publication number Publication date
US20050262964A1 (en) 2005-12-01
AU2003262712A8 (en) 2004-03-11
AU2003262712A1 (en) 2004-03-11
AU2003262706A1 (en) 2004-03-11
WO2004018734A3 (fr) 2004-09-30
WO2004018082A1 (fr) 2004-03-04
US20040038805A1 (en) 2004-02-26

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