US3718550A - Process for the electrolytic production of aluminum - Google Patents

Process for the electrolytic production of aluminum Download PDF

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Publication number
US3718550A
US3718550A US00094581A US3718550DA US3718550A US 3718550 A US3718550 A US 3718550A US 00094581 A US00094581 A US 00094581A US 3718550D A US3718550D A US 3718550DA US 3718550 A US3718550 A US 3718550A
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US
United States
Prior art keywords
bath
aluminum
ceramic material
anode
fluoride
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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
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US00094581A
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English (en)
Inventor
H Klein
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Rio Tinto Switzerland AG
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Alusuisse Holdings AG
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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
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in 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
    • C25C3/06—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

Definitions

  • the oxygen produced at the anode by the decomposition of the alumina reacts completely with the carbon to carbon dioxide and carbon monoxide.
  • the carbon anode is consumed and must be lowered from time to time to the same level in the bath, and it must be exchanged before full consumption.
  • To produce one kg. of aluminum 450 g. anode carbon are consumed in practice.
  • My object in this invention is to provide anodes which do not react with the oxygen during the fused-bath electrolysis of aluminum and accordingly are not consumed.
  • the part of the anode in contact with the bath consists of an oxidic electron-conducting ceramic material (oxidic semiconductor) chemically resistant to the fused fluoride bath in which the aluminum oxide is dissolved.
  • This oxidic ceramic material preferably consists predominantly of S1102-
  • the anodes can be made by the conventional processes used in the ceramic industry, a powdered mixture being shaped and burned. The mixture should be homogenised and may advantageously be pre-burned, for example at a temperature between 700 and 1500 C. during 24 to hours, before being shaped and finally burned at a temperature between 800 and 1600 C. during 24 to 10 hours. The preburning step may be omitted if the mixture is hot-pressed.
  • a carrier of the shape desired for the anode may be provided with a coating of the ceramic material, for example by flame-spraying or plasma-spraying with subsequent densification by thermal treatment.
  • a carrier may be of wire mesh, a hollow or solid metal body, or a shaped body of electron-conducting carbide, nitride or boride.
  • Anodes for use in the production of aluminum from fluoride baths preferably contain at least 80% 8110;.
  • Percent SnO 94-83 F5203 2-6 ZnO 3-7 T3205 1"4 A very suitable composition of the ceramic material for use in a fluoride bath for the production of aluminum, taking into account both the electrical conductivity and the resistance to attack by the bath, is:
  • This composition may be pre-burned for example at a temperature between 1000 and 1100 C. during 15 to 12 hours and finally burned between 1350 and 1450" C. during 20 to 15 hours, the longer durations corresponding to the lower temperatures and reversely.
  • Another suitable composition comprises 98% SnO 1.5% Sb O 0.3% 'Fe O and 0.2% ZnO, and may be prepared under similar conditions.
  • the invention specifically includes anodes consisting of bodies shaped from or of carriers coated with ceramic materials consisting of at least SnO' together with one or more of Fe O Sb O ZnO, Cr O Bi203 and V 0 and one or more of Ta O Nbgos and W0
  • the anodes must of course not only be in contact with the bath, the discharge of ions taking place at the interface between the bath and the ceramic material and the gas that is evolved escaping through the bath, but must also be in such connection with the source of current supply; that electrons can flow from this interface.
  • FIG. 1 is a purely diagrammatic vertical section through one electrolytic cell, is not to scale and shows only those parts required to illustrate the invention
  • FIG. 2 is a similar section illustrating three different ways of connecting the anodes to the current supply.
  • FIG. 3 is a similar section showing an anode formed by coating a carrier.
  • the cells shown in the drawings are all intended for the production of aluminum, and are conventional except for the anodes.
  • the cell 1 comprises a pot 2 of carbonaceous material in which iron bars 3 are embedded as cathode conductors and which contains a bath 4 of alkali aluminum fluoride with alurniua dissolved in it.
  • a bath 4 of alkali aluminum fluoride with alurniua dissolved in it On the application of direct current liquid aluminum 5 separates on the bottom of the pot.
  • a slag crust consisting of solidified bath and undissolved alumina, which is covered by a layer 7 of alumina.
  • One or more anodes 8 dip into the bath 4.
  • Each such anode consists of a crucible, rectangular in horizontal section, with rounded edges and corners which holds liquid silver 9.
  • One or more rods 10 of titanium diboride dip into this liquid silver and are connected to cathodic conductors 11.
  • the crucible 8 is made of a ceramic electron-conducting material, preferably having one of the compositions described in detail above.
  • FIG. 2 shows anodes 12 of a different shape, being in tubes with closed and rounded lower ends, each again being made of the suitable ceramic material described above.
  • This figure shows three ways by which such anodes may be connected to the current supply.
  • the left-hand tube 12 there is molten silver 13 into which a rod 14 of titanium carbide projects, this rod being connected to the conductor 11.
  • a hollow cylinder 15 of nickel-alloy wire mesh is inserted and is connected by nickel-alloy wires 16 to the conductor 11.
  • a rod 18 of zirconium diboride is used to connect nickel powder 17 to the conductor 11.
  • FIG. 3 shows an anode consisting of an essentially rectangular body 19 of a conducting material, for example ZrB TiB or TiC, carrying a coating 20 of ceramic material as described above, applied by spraying and subsequently densified by heat-treatment.
  • a metal bell 21 is embedded in the body 19 to make connection with the conductor 11.

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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)
  • Compositions Of Oxide Ceramics (AREA)
US00094581A 1969-12-05 1970-12-02 Process for the electrolytic production of aluminum Expired - Lifetime US3718550A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1797569A CH520779A (de) 1969-12-05 1969-12-05 Anode für die Schmelzflusselektrolyse von Metalloxiden

Publications (1)

Publication Number Publication Date
US3718550A true US3718550A (en) 1973-02-27

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Family Applications (1)

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US00094581A Expired - Lifetime US3718550A (en) 1969-12-05 1970-12-02 Process for the electrolytic production of aluminum

Country Status (12)

Country Link
US (1) US3718550A (cs)
AT (1) AT301894B (cs)
BE (1) BE759874A (cs)
CA (1) CA931901A (cs)
CH (1) CH520779A (cs)
DE (1) DE2059866A1 (cs)
FR (1) FR2068784B1 (cs)
GB (1) GB1295117A (cs)
IS (1) IS875B6 (cs)
NL (1) NL7016660A (cs)
NO (1) NO126034B (cs)
ZA (1) ZA708010B (cs)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930967A (en) * 1973-08-13 1976-01-06 Swiss Aluminium Ltd. Process for the electrolysis of a molten charge using inconsumable bi-polar electrodes
US3960678A (en) * 1973-05-25 1976-06-01 Swiss Aluminium Ltd. Electrolysis of a molten charge using incomsumable electrodes
US3974046A (en) * 1973-10-16 1976-08-10 Swiss Aluminium Ltd. Process for the electrolysis of a molten charge using inconsumable anodes
JPS5230790A (en) * 1975-09-04 1977-03-08 Kyocera Corp Anode made of ceramics for electrolysis
US4039401A (en) * 1973-10-05 1977-08-02 Sumitomo Chemical Company, Limited Aluminum production method with electrodes for aluminum reduction cells
US4098651A (en) * 1973-12-20 1978-07-04 Swiss Aluminium Ltd. Continuous measurement of electrolyte parameters in a cell for the electrolysis of a molten charge
US4098669A (en) * 1976-03-31 1978-07-04 Diamond Shamrock Technologies S.A. Novel yttrium oxide electrodes and their uses
US4173518A (en) * 1974-10-23 1979-11-06 Sumitomo Aluminum Smelting Company, Limited Electrodes for aluminum reduction cells
US4272354A (en) * 1978-03-28 1981-06-09 Diamond Shamrock Technologies, S.A. Electrodes for electrolytic processes
WO1981002027A1 (en) * 1980-01-17 1981-07-23 Diamond Shamrock Corp Cell with cermet anode for fused salt electrolysis
US4379033A (en) * 1981-03-09 1983-04-05 Great Lakes Carbon Corporation Method of manufacturing aluminum in a Hall-Heroult cell
US4450061A (en) * 1982-12-20 1984-05-22 Aluminum Company Of America Metal stub and ceramic body electrode assembly
US4457811A (en) * 1982-12-20 1984-07-03 Aluminum Company Of America Process for producing elements from a fused bath using a metal strap and ceramic electrode body nonconsumable electrode assembly
US4468300A (en) * 1982-12-20 1984-08-28 Aluminum Company Of America Nonconsumable electrode assembly and use thereof for the electrolytic production of metals and silicon
US4468299A (en) * 1982-12-20 1984-08-28 Aluminum Company Of America Friction welded nonconsumable electrode assembly and use thereof for electrolytic production of metals and silicon
US4468298A (en) * 1982-12-20 1984-08-28 Aluminum Company Of America Diffusion welded nonconsumable electrode assembly and use thereof for electrolytic production of metals and silicon
US4491510A (en) * 1981-03-09 1985-01-01 Great Lakes Carbon Corporation Monolithic composite electrode for molten salt electrolysis
US4504369A (en) * 1984-02-08 1985-03-12 Rudolf Keller Method to improve the performance of non-consumable anodes in the electrolysis of metal
US4552630A (en) * 1979-12-06 1985-11-12 Eltech Systems Corporation Ceramic oxide electrodes for molten salt electrolysis
US5279715A (en) * 1991-09-17 1994-01-18 Aluminum Company Of America Process and apparatus for low temperature electrolysis of oxides
US5378325A (en) * 1991-09-17 1995-01-03 Aluminum Company Of America Process for low temperature electrolysis of metals in a chloride salt bath
US5565144A (en) * 1994-08-18 1996-10-15 E. I. Du Pont De Nemours And Company Tin oxide based conductive powders and coatings
US6248227B1 (en) * 1998-07-30 2001-06-19 Moltech Invent S.A. Slow consumable non-carbon metal-based anodes for aluminium production cells
US20050164871A1 (en) * 2003-04-02 2005-07-28 Latvaitis J. D. Nickel foam pin connections for inert anodes
WO2006124742A3 (en) * 2005-05-19 2007-04-12 Saint Gobain Ceramics Tin oxide-based electrodes having improved corrosion resistance
RU2452797C2 (ru) * 2009-11-30 2012-06-10 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Способ производства металлов с керамическим анодом
EP2853621A1 (en) * 2003-04-02 2015-04-01 Alcoa Inc. Mechanical attachment of electrical current conductor to inert anodes
US11668017B2 (en) 2018-07-30 2023-06-06 Water Star, Inc. Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5536074B2 (cs) * 1973-10-05 1980-09-18
DD137365A5 (de) * 1976-03-31 1979-08-29 Diamond Shamrock Techn Elektrode
EP0022921B1 (de) * 1979-07-20 1983-10-26 C. CONRADTY NÜRNBERG GmbH & Co. KG Regenerierbare, formstabile Elektrode für Hochtemperaturanwendungen
DE2929346C2 (de) * 1979-07-20 1985-10-17 C. Conradty Nürnberg GmbH & Co KG, 8505 Röthenbach Regenerierbare formstabile Faserwerkstoff-Elektrode für schmelzflußelektrolytische Prozesse
US4374050A (en) 1980-11-10 1983-02-15 Aluminum Company Of America Inert electrode compositions
US4374761A (en) 1980-11-10 1983-02-22 Aluminum Company Of America Inert electrode formulations
US4399008A (en) 1980-11-10 1983-08-16 Aluminum Company Of America Composition for inert electrodes
CA1181616A (en) * 1980-11-10 1985-01-29 Aluminum Company Of America Inert electrode compositions
US4478693A (en) * 1980-11-10 1984-10-23 Aluminum Company Of America Inert electrode compositions
US4454015A (en) * 1982-09-27 1984-06-12 Aluminum Company Of America Composition suitable for use as inert electrode having good electrical conductivity and mechanical properties
BR8306968A (pt) * 1982-12-20 1984-07-24 Aluminum Co Of America Montagem de eletrodo nao-consumivel e processo para produzir um metal por reducao eletrolitica
CA2061391C (en) * 1991-02-26 2002-10-29 Oronzio De Nora Ceramic anode for oxygen evolution, method of production and use of the same

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960678A (en) * 1973-05-25 1976-06-01 Swiss Aluminium Ltd. Electrolysis of a molten charge using incomsumable electrodes
US3930967A (en) * 1973-08-13 1976-01-06 Swiss Aluminium Ltd. Process for the electrolysis of a molten charge using inconsumable bi-polar electrodes
US4039401A (en) * 1973-10-05 1977-08-02 Sumitomo Chemical Company, Limited Aluminum production method with electrodes for aluminum reduction cells
US3974046A (en) * 1973-10-16 1976-08-10 Swiss Aluminium Ltd. Process for the electrolysis of a molten charge using inconsumable anodes
US4098651A (en) * 1973-12-20 1978-07-04 Swiss Aluminium Ltd. Continuous measurement of electrolyte parameters in a cell for the electrolysis of a molten charge
US4173518A (en) * 1974-10-23 1979-11-06 Sumitomo Aluminum Smelting Company, Limited Electrodes for aluminum reduction cells
JPS5230790A (en) * 1975-09-04 1977-03-08 Kyocera Corp Anode made of ceramics for electrolysis
US4098669A (en) * 1976-03-31 1978-07-04 Diamond Shamrock Technologies S.A. Novel yttrium oxide electrodes and their uses
US4272354A (en) * 1978-03-28 1981-06-09 Diamond Shamrock Technologies, S.A. Electrodes for electrolytic processes
US4552630A (en) * 1979-12-06 1985-11-12 Eltech Systems Corporation Ceramic oxide electrodes for molten salt electrolysis
WO1981002027A1 (en) * 1980-01-17 1981-07-23 Diamond Shamrock Corp Cell with cermet anode for fused salt electrolysis
US4491510A (en) * 1981-03-09 1985-01-01 Great Lakes Carbon Corporation Monolithic composite electrode for molten salt electrolysis
US4379033A (en) * 1981-03-09 1983-04-05 Great Lakes Carbon Corporation Method of manufacturing aluminum in a Hall-Heroult cell
US4450061A (en) * 1982-12-20 1984-05-22 Aluminum Company Of America Metal stub and ceramic body electrode assembly
US4457811A (en) * 1982-12-20 1984-07-03 Aluminum Company Of America Process for producing elements from a fused bath using a metal strap and ceramic electrode body nonconsumable electrode assembly
US4468300A (en) * 1982-12-20 1984-08-28 Aluminum Company Of America Nonconsumable electrode assembly and use thereof for the electrolytic production of metals and silicon
US4468299A (en) * 1982-12-20 1984-08-28 Aluminum Company Of America Friction welded nonconsumable electrode assembly and use thereof for electrolytic production of metals and silicon
US4468298A (en) * 1982-12-20 1984-08-28 Aluminum Company Of America Diffusion welded nonconsumable electrode assembly and use thereof for electrolytic production of metals and silicon
US4504369A (en) * 1984-02-08 1985-03-12 Rudolf Keller Method to improve the performance of non-consumable anodes in the electrolysis of metal
US5279715A (en) * 1991-09-17 1994-01-18 Aluminum Company Of America Process and apparatus for low temperature electrolysis of oxides
US5378325A (en) * 1991-09-17 1995-01-03 Aluminum Company Of America Process for low temperature electrolysis of metals in a chloride salt bath
US5415742A (en) * 1991-09-17 1995-05-16 Aluminum Company Of America Process and apparatus for low temperature electrolysis of oxides
US5569412A (en) * 1994-08-18 1996-10-29 E. I. Du Pont De Nemours And Company Tin oxide based conductive powders and coatings
US5571456A (en) * 1994-08-18 1996-11-05 E. I. Du Pont De Nemours And Company Tin oxide based conductive powders and coatings
US5776373A (en) * 1994-08-18 1998-07-07 E. I. Du Pont De Nemours And Company Tin oxide based conductive powders and coatings
US5565144A (en) * 1994-08-18 1996-10-15 E. I. Du Pont De Nemours And Company Tin oxide based conductive powders and coatings
US6248227B1 (en) * 1998-07-30 2001-06-19 Moltech Invent S.A. Slow consumable non-carbon metal-based anodes for aluminium production cells
EP2853621A1 (en) * 2003-04-02 2015-04-01 Alcoa Inc. Mechanical attachment of electrical current conductor to inert anodes
US20050164871A1 (en) * 2003-04-02 2005-07-28 Latvaitis J. D. Nickel foam pin connections for inert anodes
EP1609215A4 (en) * 2003-04-02 2006-05-17 Alcoa Inc NICKEL FOAM PENCIL LINKS FOR INERTE ANODES
US7316577B2 (en) 2003-04-02 2008-01-08 Alcoa, Inc. Nickel foam pin connections for inert anodes
WO2006124742A3 (en) * 2005-05-19 2007-04-12 Saint Gobain Ceramics Tin oxide-based electrodes having improved corrosion resistance
US8431049B2 (en) 2005-05-19 2013-04-30 Saint-Gobain Ceramics & Plastics, Inc. Tin oxide-based electrodes having improved corrosion resistance
RU2452797C2 (ru) * 2009-11-30 2012-06-10 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Способ производства металлов с керамическим анодом
US11668017B2 (en) 2018-07-30 2023-06-06 Water Star, Inc. Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes
US12305300B2 (en) 2018-07-30 2025-05-20 Water Star, Inc. Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes

Also Published As

Publication number Publication date
ZA708010B (en) 1971-08-25
DE2059866A1 (de) 1971-06-09
IS875B6 (is) 1974-07-02
FR2068784A1 (cs) 1971-09-03
GB1295117A (cs) 1972-11-01
IS1963A7 (is) 1971-06-06
CA931901A (en) 1973-08-14
AT301894B (de) 1972-09-25
BE759874A (fr) 1971-05-17
CH520779A (de) 1972-03-31
NO126034B (cs) 1972-12-11
FR2068784B1 (cs) 1974-07-26
NL7016660A (cs) 1971-06-08

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