US3562135A - Electrolytic cell - Google Patents

Electrolytic cell Download PDF

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Publication number
US3562135A
US3562135A US638249A US3562135DA US3562135A US 3562135 A US3562135 A US 3562135A US 638249 A US638249 A US 638249A US 3562135D A US3562135D A US 3562135DA US 3562135 A US3562135 A US 3562135A
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US
United States
Prior art keywords
oxygen
anode
melt
electrolysis
layer
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
US638249A
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English (en)
Inventor
Borut Marincek
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.)
Alcan Holdings Switzerland AG
Original Assignee
Alusuisse Holdings AG
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Filing date
Publication date
Priority claimed from CH614567A external-priority patent/CH492795A/de
Application filed by Alusuisse Holdings AG filed Critical Alusuisse Holdings AG
Application granted granted Critical
Publication of US3562135A publication Critical patent/US3562135A/en
Anticipated expiration legal-status Critical
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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
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof

Definitions

  • an anode of any suitable conducting material we use an anode of any suitable conducting material, and lwe separate this anode from the melt being electrolysed by a layer of material which is oxygen-ions-conducting but non-permeable to and resistant to the melt at the temperature of the electrolysis, so that the oxygen ions diffuse through the layer and are then discharged at the anode with the formation of oxygen gas.
  • the anode itself preferably consists of an electron-conducting material which does not react with oxygen or at least does not form with oxygen any compound impairing the conduction of electrons.
  • Suitable materials include heat-resistant alloys, platinum or other noble metals, electron-conducting oxides, such as for example, wustite, certain materials with semi-conductor properties, and metals with a passivated surface.
  • the thickness of the oxygen-ion-conducting layer may be very small so that the voltage drop across it is also small; this reduces losses of energy during the electrolysis.
  • stabilised forms of zirconium oxide are very suitable as the material which separates the anode from the melt.
  • zirconium oxide in which is incorporated proportions of other oxides such as calcium oxide, magnesium oxide and yttrium oxide, whcih serve firstly to stabilise the cubic (fluorite) lattice of the zirconium oxide, and secondly to confer on it the necessary oxygen-ion conductivity.
  • a stabilised zirconium oxide can have a resistance as low as l0 ohmscm. at l000 C.
  • refractory oxides which have uorite lattices can be used, such as for example, rare earth oxideuranium oxide compositions, thorium oxide-uranium oxide compositions and cerium oxide suitably stabilised with calcium oxide or magnesium oxide. Substances which reduce the solubility of the oxygen-ion-conductng material may be added to the fused melt.
  • the invention will be described hereinafter with specific reference to the electrolysis of alumina for the production of aluminum.
  • the oxygen ions which are formed in accordance with the equation diffuse through the oxygen-ion-conductive layer and are discharged at the anode in accordance with the equation i.e. the oxygen ions combine to form oxygen gas and electrons are released in the process. These electrons are conducted away by the anode.
  • Other oxides such as for instance, MgO, NagO, CaO, Fe2O3, can also be electrolysed by the process according to the invention and similar equations can be formulated.
  • cells according to the invention afford the following advantages, inter alia, in comparison with the present state of the art.
  • Cells according to the invention can readily be adapted for automation of operation with for example, continuous addition of alumina to the fused melt and maintenance of constant interelectrode gap or cell voltage.
  • Cells according to the invention may be constructed in two Ways.
  • the anode is coated with or is in contact with the layer of oxygen-ion-conducting material over at least that part of its surface which is immersed in the melt; the anode must then be in such a physical state that oxygen gas can pass through it.
  • the anode may be solid, in which case it must be porous, perforated or reticulated.
  • the layer of oxygen-ion-conducting material may be applied directly to it by pressing or casting with subsequent drying and sintering or by plasma spraying.
  • a body of the material may be preformed quite separately and put in Contact with the anode, if the latter is, for example, a metal network.
  • a porous layer of platinum black may be applied to a preformed body of the material, and electrically connected to one terminal of the current supply. This last proposal is found to be very satisfactory, as platinum black is particularly suitable for the discharge of oxygen ions and the formation and removal of oxygen gas.
  • FIGS. l to 2 of the accompanying drawings each of which represents a section through an electrolytic cell for the electrolysis of fused alumina-cryolite mixtures.
  • a carbon tank 4 contains the fused aluminacryolite melt indicated as 1, and the liquid, electrolytically produced aluminum, which accumulates on the bottom of the cell and at the same time acts as a cathode in the arrangements according to FIGS. l and 2 is shown as 2.
  • the fused melt is covered by a layer 3 consisting of solidified melt and alumina.
  • a bus bar 5 conducts the current from the tank.
  • the anode consists of a gas-permeable, electron-conducting body which is covered with the oxygen-ion conductive material over at least the portion of its surface immersed in the fused melt.
  • the oxygen-ion conductive material 8 is in the form of a hollow cup-shaped body, the inner surface of which is lined with a layer 9 of platinum black as anode.
  • the layer 9 is electrically connected to a terminal 7 which is itself connected to a source of direct current by means of a lead 6.
  • the oxygen ions of the electrolyte diffuse through the oxygen-ion conductive layer 8, are discharged at the surface of contact between the oxygen-ion conductive layer 8 and the layer of platinum black 9 and combine in the layer of platinum black to form gaseous oxygen which collects in the hollow space 10 and escapes through a vent 11.
  • the terminal 7 forms the upper end of the hollow space 10 and incorporates the gas vent 11.
  • the electrons that are liberated flow off by way of the anode 9, the terminal 7 and the lead 6.
  • the oxygen gas evolved can escape under atmospheric pressure, be drawn off under reduced pressure or be collected under pressure in excess of atmospheric in the space 10.
  • the oxygen-ion conductive material is in o metal oxides contained in a molten electrolytic bath, this cell comprising a container for the melt being electrolysed, a cathode for contact with the melt and a gas permeable anode resistant to the formation with oxygen of any compound impairing its conduction of electrons, a layer of oxygen-ion-conducting material in direct electric contact at one side with said anode substantially over at least that part of its area to be immersed in a melt in said container and freely exposed at its other side to said melt, said layer being non-permeable to and resistant to the melt at the temperature of the electrolysis, and a source of direct current connected between said anode and said cathode to maintain said electrolysis, said current during said electrolysis effecting the diffusion of oxygen ions through the layer and their discharge at the anode with the formation of oxygen gas which escapes through the gas-permeable anode which is uncovered on its other side.
  • a cell according to claim 1 in which the anode is in contact with the layer of oxygen ion-conducting material over at least that part of the surface which is immersed in the melt and is in such a physical state that oxygen gas can pass through it.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrolytic Production Of Metals (AREA)
US638249A 1966-05-17 1967-05-15 Electrolytic cell Expired - Lifetime US3562135A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH727566A CH441776A (de) 1966-05-17 1966-05-17 Verfahren zur Herstellung von Metallen durch Schmelzflusselektrolyse von Oxiden
CH614567A CH492795A (de) 1967-04-28 1967-04-28 Verfahren und Vorrichtung zur Herstellung von Metallen durch Schmelzflusselektrolyse von Oxiden

Publications (1)

Publication Number Publication Date
US3562135A true US3562135A (en) 1971-02-09

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Family Applications (2)

Application Number Title Priority Date Filing Date
US638249A Expired - Lifetime US3562135A (en) 1966-05-17 1967-05-15 Electrolytic cell
US675881A Expired - Lifetime US3578580A (en) 1966-05-17 1967-10-17 Electrolytic cell apparatus

Family Applications After (1)

Application Number Title Priority Date Filing Date
US675881A Expired - Lifetime US3578580A (en) 1966-05-17 1967-10-17 Electrolytic cell apparatus

Country Status (10)

Country Link
US (2) US3562135A (fr)
CH (1) CH441776A (fr)
ES (1) ES340590A1 (fr)
GB (1) GB1152124A (fr)
GR (1) GR33087B (fr)
NL (1) NL156759B (fr)
OA (1) OA02678A (fr)
PL (1) PL79100B1 (fr)
SE (1) SE342848B (fr)
YU (1) YU34911B (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4614569A (en) * 1983-01-14 1986-09-30 Eltech Systems Corporation Molten salt electrowinning method, anode and manufacture thereof
US4804448A (en) * 1987-06-24 1989-02-14 Eltron Research, Inc. Apparatus for simultaneous generation of alkali metal species and oxygen gas
US5942097A (en) * 1997-12-05 1999-08-24 The Ohio State University Method and apparatus featuring a non-consumable anode for the electrowinning of aluminum
US6187168B1 (en) 1998-10-06 2001-02-13 Aluminum Company Of America Electrolysis in a cell having a solid oxide ion conductor
US6299742B1 (en) 1997-01-06 2001-10-09 Trustees Of Boston University Apparatus for metal extraction
US20060191408A1 (en) * 2004-11-23 2006-08-31 Trustees Of Boston University Composite mixed oxide ionic and electronic conductors for hydrogen separation
WO2007011669A2 (fr) * 2005-07-15 2007-01-25 Trustees Of Boston University Anodes inertes produisant de l'oxygene pour un processus som
US20090071841A1 (en) * 2005-06-16 2009-03-19 Boston University Waste to hydrogen conversion process and related apparatus
US20100015014A1 (en) * 2005-09-29 2010-01-21 Srikanth Gopalan Mixed Ionic and Electronic Conducting Membrane
US20100126875A1 (en) * 2007-04-20 2010-05-27 Mitsui Chemicals Inc, Electrolyzer, electrodes used therefor, and electrolysis method

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH576005A5 (fr) * 1972-03-21 1976-05-31 Alusuisse
US3909375A (en) * 1972-04-17 1975-09-30 Conzinc Riotinto Ltd Electrolytic process for the production of metals in molten halide systems
CH587929A5 (fr) * 1973-08-13 1977-05-13 Alusuisse
NO801818L (no) * 1979-07-20 1981-01-21 Conradty Nuernberg Regenererbar, formstabil elektrode for hoeytemperaturanvendelse
US4351057A (en) * 1980-06-09 1982-09-21 Biuro Projektow Przemyslu Metali Niezelaznych "Bipromet" Electric installation for heating of molten metals and/or salts and solutions
US4622111A (en) * 1983-04-26 1986-11-11 Aluminum Company Of America Apparatus and method for electrolysis and inclined electrodes
US4664760A (en) * 1983-04-26 1987-05-12 Aluminum Company Of America Electrolytic cell and method of electrolysis using supported electrodes
US4504366A (en) * 1983-04-26 1985-03-12 Aluminum Company Of America Support member and electrolytic method
US4596637A (en) * 1983-04-26 1986-06-24 Aluminum Company Of America Apparatus and method for electrolysis and float
AU616638B2 (en) * 1986-08-21 1991-11-07 Moltech Invent S.A. Cerium oxycompound, stable anode for molten salt electrowinning and method of production
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
US6419813B1 (en) 2000-11-25 2002-07-16 Northwest Aluminum Technologies Cathode connector for aluminum low temperature smelting cell
US6419812B1 (en) 2000-11-27 2002-07-16 Northwest Aluminum Technologies Aluminum low temperature smelting cell metal collection
US6811676B2 (en) * 2002-07-16 2004-11-02 Northwest Aluminum Technologies Electrolytic cell for production of aluminum from alumina
US6866768B2 (en) * 2002-07-16 2005-03-15 Donald R Bradford Electrolytic cell for production of aluminum from alumina
BRPI0513992A (pt) * 2004-07-30 2008-05-20 Bhp Billiton Innovation Pty processo para minimização da re-oxidação de material reduzido e processo para redução eletroquìmica de um material de alimentação de óxido metálico
US8764962B2 (en) 2010-08-23 2014-07-01 Massachusetts Institute Of Technology Extraction of liquid elements by electrolysis of oxides
US9206516B2 (en) * 2011-08-22 2015-12-08 Infinium, Inc. Liquid anodes and fuels for production of metals from their oxides by molten salt electrolysis with a solid electrolyte
US9234288B2 (en) 2011-09-01 2016-01-12 Infinium, Inc. Conductor of high electrical current at high temperature in oxygen and liquid metal environment
GB201223375D0 (en) * 2012-12-24 2013-02-06 Metalysis Ltd Method and apparatus for producing metal by electrolytic reduction
US10087539B2 (en) * 2013-06-12 2018-10-02 Infinium, Inc. Liquid metal electrodes for gas separation
WO2016061577A1 (fr) * 2014-10-17 2016-04-21 Infinium, Inc. Procédé et appareil pour une connexion d'électrode métallique liquide dans la production ou le raffinage de métaux
CN110760887B (zh) * 2019-11-27 2020-07-31 镇江慧诚新材料科技有限公司 氧铝联产电解用的电极结构

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4614569A (en) * 1983-01-14 1986-09-30 Eltech Systems Corporation Molten salt electrowinning method, anode and manufacture thereof
US4804448A (en) * 1987-06-24 1989-02-14 Eltron Research, Inc. Apparatus for simultaneous generation of alkali metal species and oxygen gas
US6299742B1 (en) 1997-01-06 2001-10-09 Trustees Of Boston University Apparatus for metal extraction
US5942097A (en) * 1997-12-05 1999-08-24 The Ohio State University Method and apparatus featuring a non-consumable anode for the electrowinning of aluminum
US6187168B1 (en) 1998-10-06 2001-02-13 Aluminum Company Of America Electrolysis in a cell having a solid oxide ion conductor
US20060191408A1 (en) * 2004-11-23 2006-08-31 Trustees Of Boston University Composite mixed oxide ionic and electronic conductors for hydrogen separation
US7588626B2 (en) 2004-11-23 2009-09-15 Trustees Of Boston University Composite mixed oxide ionic and electronic conductors for hydrogen separation
US20090071841A1 (en) * 2005-06-16 2009-03-19 Boston University Waste to hydrogen conversion process and related apparatus
US8758949B2 (en) 2005-06-16 2014-06-24 The Trustees Of Boston University Waste to hydrogen conversion process and related apparatus
US20090000955A1 (en) * 2005-07-15 2009-01-01 Trustees Of Boston University Oxygen-Producing Inert Anodes for Som Process
WO2007011669A3 (fr) * 2005-07-15 2007-09-27 Univ Boston Anodes inertes produisant de l'oxygene pour un processus som
US8658007B2 (en) 2005-07-15 2014-02-25 The Trustees Of Boston University Oxygen-producing inert anodes for SOM process
WO2007011669A2 (fr) * 2005-07-15 2007-01-25 Trustees Of Boston University Anodes inertes produisant de l'oxygene pour un processus som
US20100015014A1 (en) * 2005-09-29 2010-01-21 Srikanth Gopalan Mixed Ionic and Electronic Conducting Membrane
US20100126875A1 (en) * 2007-04-20 2010-05-27 Mitsui Chemicals Inc, Electrolyzer, electrodes used therefor, and electrolysis method
US8771497B2 (en) * 2007-04-20 2014-07-08 Mitsui Chemicals, Inc. Electrolyzer, electrodes used therefor, and electrolysis method

Also Published As

Publication number Publication date
OA02678A (fr) 1970-12-15
DE1558760B2 (de) 1976-03-18
GR33087B (el) 1967-11-01
SE342848B (fr) 1972-02-21
NL156759B (nl) 1978-05-16
US3578580A (en) 1971-05-11
GB1152124A (en) 1969-05-14
ES340590A1 (es) 1968-09-01
CH441776A (de) 1967-08-15
YU97267A (en) 1979-10-31
DE1558760A1 (de) 1970-04-23
YU34911B (en) 1980-04-30
NL6706830A (fr) 1967-11-20
PL79100B1 (fr) 1975-06-30

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