US2915442A - Production of aluminum - Google Patents

Production of aluminum Download PDF

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Publication number
US2915442A
US2915442A US549347A US54934755A US2915442A US 2915442 A US2915442 A US 2915442A US 549347 A US549347 A US 549347A US 54934755 A US54934755 A US 54934755A US 2915442 A US2915442 A US 2915442A
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United States
Prior art keywords
bath
cryolite
potassium
aluminum
sodium
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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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US549347A
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English (en)
Inventor
Robert A Lewis
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Kaiser Aluminum and Chemical Corp
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Kaiser Aluminum and Chemical Corp
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Publication date
Application filed by Kaiser Aluminum and Chemical Corp filed Critical Kaiser Aluminum and Chemical Corp
Priority to US549347A priority Critical patent/US2915442A/en
Priority to GB34985/56A priority patent/GB814031A/en
Priority to CH3997156A priority patent/CH365224A/de
Priority to FR1165136D priority patent/FR1165136A/fr
Priority to DEK30444A priority patent/DE1130607B/de
Application granted granted Critical
Publication of US2915442A publication Critical patent/US2915442A/en
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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
    • C25C3/18—Electrolytes

Definitions

  • This invention relates to the production of aluminum by electrolytic reduction of alumina; and, more particularly, it relates to providing an improved electrolyte and electrolyzing system and an improved method of electrolysis for such production of aluminum.
  • the production of aluminum metalv by electrolysis of alumina dissolved in a fused electrolyte and deposition of aluminum metal at the cathode has long been known.
  • the fused bath employed has consisted essentially of sodium cryolite which is a double salt of sodium fluoride and aluminum uoride and is generally considered by the authorities to have the-formula Na3AlF6 or, expressed in another manner, 3NaFAlF3.
  • This compound has a melting point of about 1000 C. but the melting7 point is decreased by dissolution of alumina in the cryolte.
  • the melting point can also be decreased by addition of another compound, notably sodium iluoride, aluminum fluoride, fluorspar, or sodium chloride, but the addition of another compound or of other compounds to lower the melting point must also take into account the effect of such addition upon the surface tension or the viscosity of the bath content and upon the solubility of alumina in the bath.
  • the bath of sodium cryolite is in practice operated at a temperature of about 950 to 970 C. or higher, that is, at atemperature which is not the lowest which could be attained by such additions, if decrease in temperature were the only factor to be considered.
  • Potassium compounds have been known to be quite destructive to the ⁇ carbon cathode of an electrolytic cell as such cell normally employed in this process and, in fact, it has been recognized that even small amounts of potassium compound must be rigidly excluded from the cell bath constituents in the usual known process, because, even though the original, very small amountV thereof might not be apparently detrimental, potassium, as a compound, will accumulate in the bath and will very soon exert a deleterious effect.
  • the cell can be operated at a lower tempera- ICC ture, volatilization of bath componentsreduced, and elliciency of the operation improved by carrying out the reduction of the alumina by a process wherein alumina is dissolved in molten potassium-containing cryolite and electric current is passed through the solution yso obtained from a carbon anode to a negative current conductor which consists essentially of at least one compound chosen from the group consisting ofthe carbides of refractory hard metals andl the borides and nitrides ofthe refractory hard metals, which compounds are resistant to attack by molten aluminum, are Vresistant, to attack by molten cryolite baths, are wetted by molten aluminum and have an electrical conductivity at least greater than graphite.
  • Figure l' is a vertical sectional view of an electrolytic cell which is suitable for carrying out this invention.
  • Figure 2 is a plan view of the cell of Figure 1,"taken along line 2 2. i
  • the molten or fused electrolyte bath employed in the present invention consists essentially of from 5% to V95% of at least one potassium compound chosen from the group consisting of potassium cryolite, potassium chloride and potassium uoride and the remainder sodium cryolite, sodium chloride or fluoride, or lithium chloride or fluoride, lithium cryolite, or any desired mixture of these compounds.
  • the major component of' the bath mixture i.e. at least 50% thereof, is cryolite, either potassium cryolite, sodium cryolite or lithium cryolite or mixture of these compounds, in order to provide sulicient dissolving power for the alumina to be added.
  • potassium chloride or uoride, 'or both is used as freezing point depressant, it is preferred to add not over 30% of either compound when used alone or total, if both are employed, in order tov maintain high alumina solubility.
  • the freezing point can be advantageously decreased by the addition of 10% to 15% of sodium chloride, lithium chloride, lithium uoride or any desired mixture of these compounds.
  • One bath composition which is quite advantageous, according to this invention consists essentially of to 70% sodium cryolite and from 10% to 30% potassium cryolte.
  • Another suitable bath composition consists essentially of V80% to 95% sodium cryolite and from 5% to 20% of potassium iluoride or chloride.
  • a further bath composition consists essentially of from 70% to 95% potassium cryolite and from 5% to 30% sodium chloride. It ⁇ will be understood that the compositions set forth herein are those of the base baths but that other modifying agents can alsobe, and usually are, admixed therewith. For instance, infoperation the bath will always contain a few percent of alumina, that is, usually and preferably up to the limit of solubility of alumina in the bath, or, in other words, up to a saturated solution of alumina ⁇ in the bath. Also there can be added if desired, a small amount, up to 5% of uorspar. Electrolyte baths can be prepared according to the present invention having melting points of less than 950 C., enabling operation of the reduction process at temperatures lower than those required in the processes of the prior art.
  • the reduction cell or system of the present invention consists essentially, at the time when operation ofthe reduction process is to be carried out, of an anode, preferably of carbon, a fused electrolyte bath consisting essen tially of from 5% to 95% of at least one potassium compound chosen from the group consisting of potassium cryolite, potassium chloride and potassium uoride and the remainder sodium cryolite, sodium chloride or uoride, lithium cryolite, lithium chloride or fluoride, or any desired mixture of these compounds, and a negative current conductor consisting essentially of at least one subor the current conductor can'be a series of plates disposed within the bath in any desired manner and connected in any desired manner to the negative pole of the current ⁇ supply.
  • a bath receptacle can be provided with a coating, which can be quite thin or of any thickness desired, of the compound or compounds herein described as suitable, this electric current-conductive coating being connected to a suitable current supply.
  • the compounds useful as conductor materials in the process and cell of this invention include titanium carbide, titanium boridetitanium nitride, zirconium carbide, 'zirconium boride, zirconium nitride, vanadium carbide, va-
  • the current conductor is a solid mass of the compound or mixture defined, and can be of any fdesired size and shape, for instance, as described above.
  • a conductor of the composition described has excellent resistance to attack by a potassiumcontaining electrolytic bath under the conditions of operation of an aluminum reduction cell.
  • the presence of such conductor enables, in an etiicient and inexpensive manner, the operation of an aluminum reduction cell containing in the bath an etfective amount of potassium compound.
  • the alumina employed as reactant in the method of this invention can be derived from any source. However, the alumina produced by the well known Bayer process is advantageously employed as reactant.
  • FIG. 1 One embodiment of a cell according to the present invention and suitable for carrying out the process of this invention is shown schematically in Figure 1.
  • a cell-containing shell suitably of steel, within which is disposed in the usual manner an insulating lining 11 which can be any desired insulating material, such as alumina, bauxite, clay, or aluminum silicate bricks, and in this instance is a packing of granular alumina.
  • bath lining 12 which can beof any desired material, for instance, carbon,
  • alumina, fused alumina, silicon carbide, silicon nitride, or otherk desired material and in this instance is high alumina brick.
  • the electrolyte bath 13 containing a potassium compound as described.
  • a pad 14 of aluminum metal At the base or bottom of bath 13 is a pad 14 of aluminum metal.
  • bath 13 and metal pad 14 are both in molten or fused state.
  • the anode 15 is of the conventional carbon type and can be either pre-baked or of the self-baking type known to the art, or of any desired sort.
  • the electrolyte bath is covered by a solid crust or cake 16, which consists essentially of frozen bath constituents'and addi- ,tional alumina, in the usual way. As alumina is consumed inthe bath 13, the frozen crust is broken and more alumina fed into the bath in known manner.
  • a sealing material 20 is packed in around rods 18 within apertures 17 to seal oi the apertures and prevent leakage of the fused bath.
  • Any suitable sealing material can be employed.
  • the lining 12 is of carbon or silicon carbide, a carbonaceous paste which cokes upon heating can be advantageously employed.
  • the bath can also flow into the apertures around the rods and will freeze there and effectively seal these openings.
  • the rods can be sealed in with calcium aluminate cement, for instance.
  • the current conductors according to this invention can be plates extending within the bath and connected to metallic connectors leading to the bus bars or other conductors; or the conductor rods can be connected at their-outer ends to metallic connectors leading to bus bars or other conductors.
  • vthe electrolyte bath has a melting point lower than the electrolytes heretofore useful, and therefore the reaction can be carried out at lower temperatures, for instance, at temperatuers below 950 C.
  • the cell lining in contact with the electrolyte bath can be carbon and that the carbon will not be disintegrated because the path of the current is through the current conductors as defined herein. Carbon is disrupted and disintegrated when it acts as a current conductor in contact with an appreciable amount of potassium compound but the present cell system and process avoid this disadvantage.
  • cell bath 13 consists essentially of a mixture of 73% sodium cryolite, 22% potassium cryolite (3KF-AlFg) and 5% alumina and the furnace temperature is maintained at 940 C. while electric current is passed through the bath from the anode to the cathode, the current density being maintained at an average value of S amperes per square centimeter.
  • the conductor rods 18 are composed of zirconium boride and lining 12 is of'high alumina brick.
  • A Reduction bath electrolyte as used in prior art commercial production of aluminum, and containing 88% sodium cryolite (NaaAlF), 8% uorspar CaF2) and 4% alumina (A1203).
  • the negative current leads or cathodes employed in the various tests are identified in Table I below, the carbon cathodes being prepared from arc-welding electrodes, and the other cathodes being zirconium boride rods and titanium carbide rods.
  • Each current lead is disposed vertically over the crucible and immersed about 1.5 inch in the molten bath, and electric current is turned on, being applied at a cathodic current density of 5 amperes per square inch.
  • Bath A which corresponds to commercial practice of the known art, is maintained at 970 C.; and baths B, at 940 C. Table I sets forth the eiect of the electrolyte upon the respective current leads, in each test.
  • a negative current ⁇ conductor consisting essentially of at least one substance chosen from the group consisting of the borides, carbides and nitrides of titanium, zirconium, vanadium, tantalum, niobium and hafnium.
  • the current conductor rods can pass upwardly through the bottom of the cell lining, and extend substantially vertically into the bottom portion of the bath.
  • the current conductor can be a plate or plates disposed in the bath at an angle to the horizontal axis of the bath, the plate or plates being suitably connected to a bus bar or other electrical conductor, in the manner known to the art.
  • potassium cryolite and sodium cryolite refer respectively to composition of the general formulae, BKF-AlFa and SNaF-AIF3, but it will be understood that an excess of the alkali metal fluoride or the aluminum fluoride can be present as desired.
  • alumina is a reactant in this system and when added as such dissolves in the fused bath, alumina brick or grog can be used as cell lining because a protective layer of bath freezes on the side walls thereof and prevents further substantial dissolution, the aluminum pad protecting the bottom of the cell.
  • alumina in a fused bath of electrolyte consisting essentially of from 5% to 95% of at least one potassium compound chosen from the group consisting of potassium cryolite, potassium chloride and potassium uoride, and from 95% to 5% of at least one substance chosen from the group consisting of sodium cryolite, sodium chloride, sodium lluoride, lithium cryolite, lithium chloride and lithium uoride, and containing at least 50% of cryolite, and passing an electric 7.
  • a process for the electrolytic production of aluminum the steps which comprise dissolving alumina in a fused electrolyte bath consisting essentially of about 77% sodium cryolite and 23% potassium cryolite and passing an electric current through said bath from a carbon anode to a negative current conductor consisting essentially of zirconium boride.
  • a process for the electrolytic production of aluminum the steps which comprise dissolving alumina in a fused electrolyte bath consisting essentially of from 5% to of at least one substance chosen from the group consisting of potassium cryolite, potassium chloride and potassium fluoride and from 95% to 5% of at least one substance chosen from the group consisting of sodium cryolite, sodium chloride, sodium fluoride, lithium cryolite, lithium chloride and lithium iluoride, and containing at least 50% cryolite, and passing an electric current through said bath and a molten aluminum cathode to a negative current conductor consisting essentially of at least one substance chosen from the group consisting of the borides, carbides and nitrides of titanium, zirconium, vanadium, tantalum, niobium and hafnium.
  • alumina in a fused bath of electrolyte consisting essentially of from to.95% of'at least onepotassium compound chosen from the group consisting of potassium cryolite, potassium chloride and potassium fluoride, and from 95% to 5% of at least one substance chosen from the group consisting of sodium cryolite, sodium chloride, ,Sodium uoride lithium cryolite, lithium chloride and lithium fluoride, and containing at least 50% of cryolite, and passing an electric current through said bathtrom an anode to at least one negative current conductorfconsisting essentially of at least one substance chosen from the group consisting of the borides, carbides and nitrides of titanium, zirconium, vanadium, tantalum, niobium and lhafnium the temperature of said bath beingfbelowabout 950 C.
  • said negative current conductor consisting essentially of atleast one substance chosenfromthe group consisting of the borides and carbides of titanium and zirconium, said fused bath of electrolyte being at a temperature below about 950 C.

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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)
US549347A 1955-11-28 1955-11-28 Production of aluminum Expired - Lifetime US2915442A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US549347A US2915442A (en) 1955-11-28 1955-11-28 Production of aluminum
GB34985/56A GB814031A (en) 1955-11-28 1956-11-15 Improvements in or relating to the electrolytic production of aluminium
CH3997156A CH365224A (de) 1955-11-28 1956-11-26 Verfahren zur elektrolytischen Herstellung von Aluminium und Einrichtung zur Durchführung desselben
FR1165136D FR1165136A (fr) 1955-11-28 1956-11-26 Fabrication de l'aluminium
DEK30444A DE1130607B (de) 1955-11-28 1956-11-28 Verfahren und Zelle zur elektrolytischen Herstellung von Aluminium

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US549347A US2915442A (en) 1955-11-28 1955-11-28 Production of aluminum

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CH (1) CH365224A (de)
DE (1) DE1130607B (de)
FR (1) FR1165136A (de)
GB (1) GB814031A (de)

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3018233A (en) * 1960-02-09 1962-01-23 Manganese Chemicals Corp Producing manganese by fused salt electrolysis, and apparatus therefor
US3081254A (en) * 1958-06-24 1963-03-12 Kaiser Aluminium Chem Corp Electrolytic cell structure
US3088906A (en) * 1959-12-07 1963-05-07 Norton Co Cathode bar for aluminum reduction cell
US3093570A (en) * 1959-10-20 1963-06-11 Reynolds Metals Co Refractory lining for alumina reduction cells
US3151053A (en) * 1958-06-12 1964-09-29 Kaiser Aluminium Chem Corp Metallurgy
US3156639A (en) * 1961-08-17 1964-11-10 Reynolds Metals Co Electrode
US3161579A (en) * 1961-03-06 1964-12-15 Kaiser Aluminium Chem Corp Electrolytic cell for the production of aluminum
US3256173A (en) * 1960-10-28 1966-06-14 Alusuisse Electrolytic furnace with lined cathode pots for the production of aluminum
US3256696A (en) * 1962-01-29 1966-06-21 Monsanto Co Thermoelectric unit and process of using to interconvert heat and electrical energy
US3287247A (en) * 1962-07-24 1966-11-22 Reynolds Metals Co Electrolytic cell for the production of aluminum
US3314876A (en) * 1960-11-28 1967-04-18 British Aluminium Co Ltd Method for manufacturing solid current conducting elements
US3330756A (en) * 1951-05-04 1967-07-11 British Aluminum Company Ltd Current conducting elements
US3330637A (en) * 1963-08-19 1967-07-11 Pilkington Brothers Ltd Method of removing impurities in a molten metal bath for glass sheet making
US3372107A (en) * 1964-01-17 1968-03-05 Klein Alfred Electrode material for electrolytic processes
US3392092A (en) * 1963-08-30 1968-07-09 Isaac M. Diller Activation of cryolite-alumina compositions
US3459515A (en) * 1964-03-31 1969-08-05 Du Pont Cermets of aluminum with titanium carbide and titanium and zirconium borides
US3479274A (en) * 1967-03-27 1969-11-18 Nalco Chemical Co Electrochemical cell having ceramic-lined tubular cathodes
US4181583A (en) * 1978-12-06 1980-01-01 Ppg Industries, Inc. Method for heating electrolytic cell
EP0042658A3 (de) * 1980-06-23 1982-03-10 KAISER ALUMINUM & CHEMICAL CORPORATION Elektrode für eine Elektrolysezelle für die Gewinnung von Aluminium
US4353885A (en) * 1979-02-12 1982-10-12 Ppg Industries, Inc. Titanium diboride article and method for preparing same
US4377463A (en) * 1981-07-27 1983-03-22 Great Lakes Carbon Corporation Controlled atmosphere processing of TiB2 /carbon composites
US4439382A (en) * 1981-07-27 1984-03-27 Great Lakes Carbon Corporation Titanium diboride-graphite composites
US4465581A (en) * 1981-07-27 1984-08-14 Great Lakes Carbon Corporation Composite of TiB2 -graphite
US4612103A (en) * 1983-11-29 1986-09-16 Alcan International Limited Aluminium reduction cells
US4617053A (en) * 1985-09-20 1986-10-14 Great Lakes Carbon Corporation Metal reinforced porous refractory hard metal bodies
US5310476A (en) * 1992-04-01 1994-05-10 Moltech Invent S.A. Application of refractory protective coatings, particularly on the surface of electrolytic cell components
US5378325A (en) * 1991-09-17 1995-01-03 Aluminum Company Of America Process for low temperature electrolysis of metals in a chloride salt bath
US5534130A (en) * 1994-06-07 1996-07-09 Moltech Invent S.A. Application of phosphates of aluminum to carbonaceous components of aluminum production cells
US5534119A (en) * 1992-06-12 1996-07-09 Sekhar; Jainagesh A. Method of reducing erosion of carbon-containing components of aluminum production cells
US5560809A (en) * 1995-05-26 1996-10-01 Saint-Gobain/Norton Industrial Ceramics Corporation Improved lining for aluminum production furnace
US5618403A (en) * 1995-08-07 1997-04-08 Moltech Invent S.A. Maintaining protective surfaces on carbon cathodes in aluminium electrowinning cells
US5651874A (en) * 1993-05-28 1997-07-29 Moltech Invent S.A. Method for production of aluminum utilizing protected carbon-containing components
US5683559A (en) * 1994-09-08 1997-11-04 Moltech Invent S.A. Cell for aluminium electrowinning employing a cathode cell bottom made of carbon blocks which have parallel channels therein
US5728466A (en) * 1995-08-07 1998-03-17 Moltech Invent S.A. Hard and abrasion resistant surfaces protecting cathode blocks of aluminium electrowinning cells
US5753163A (en) * 1995-08-28 1998-05-19 Moltech. Invent S.A. Production of bodies of refractory borides
US6001236A (en) * 1992-04-01 1999-12-14 Moltech Invent S.A. Application of refractory borides to protect carbon-containing components of aluminium production cells
US6187168B1 (en) 1998-10-06 2001-02-13 Aluminum Company Of America Electrolysis in a cell having a solid oxide ion conductor
US20100122903A1 (en) * 2008-11-17 2010-05-20 Kennametal, Inc. Readily-Densified Titanium Diboride and Process for Making Same
WO2012042075A1 (es) * 2010-10-01 2012-04-05 Asturiana De Aleaciones, S.A. Composición de electrolito para la obtención de aluminio metálico
US8211278B2 (en) 2009-07-28 2012-07-03 Alcoa Inc. Composition for making wettable cathode in aluminum smelting
EP3075886A1 (de) * 2015-04-02 2016-10-05 Shenzhen Sunxing Light Alloys Materials Co., Ltd Verfahren zur herstellung von elektrolytischem aluminium unter verwendung von kaliumkryolith als zusatzsystem
US9738983B2 (en) 2014-12-01 2017-08-22 KCL Enterprises, LLC Method for fabricating a dense, dimensionally stable, wettable cathode substrate in situ

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH404012A (de) * 1962-03-05 1965-12-15 Elektrokemisk As Anordnung zur Stromzuführung in einem Ofen zur schmelzelektrolytischen Herstellung von Aluminium
DE1209303B (de) * 1962-06-26 1966-01-20 Reynolds Metals Co Aluminiumelektrolysezelle und Verfahren zur Herstellung einer Auskleidung fuer eine solche Zelle

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US400664A (en) * 1886-07-09 1889-04-02 M Hall Charles Process of reducing aluminium from its fluoride salts by electrolysis
FR1064743A (fr) * 1951-08-03 1954-05-17 British Aluminium Co Ltd Perfectionnements aux cuves électrolytiques pour la production de l'aluminium

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1039442A (fr) * 1950-07-14 1953-10-07 Aluminum Co Of America Perfectionnements à la fabrication de l'aluminium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US400664A (en) * 1886-07-09 1889-04-02 M Hall Charles Process of reducing aluminium from its fluoride salts by electrolysis
FR1064743A (fr) * 1951-08-03 1954-05-17 British Aluminium Co Ltd Perfectionnements aux cuves électrolytiques pour la production de l'aluminium

Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330756A (en) * 1951-05-04 1967-07-11 British Aluminum Company Ltd Current conducting elements
US3151053A (en) * 1958-06-12 1964-09-29 Kaiser Aluminium Chem Corp Metallurgy
US3081254A (en) * 1958-06-24 1963-03-12 Kaiser Aluminium Chem Corp Electrolytic cell structure
US3093570A (en) * 1959-10-20 1963-06-11 Reynolds Metals Co Refractory lining for alumina reduction cells
US3088906A (en) * 1959-12-07 1963-05-07 Norton Co Cathode bar for aluminum reduction cell
US3018233A (en) * 1960-02-09 1962-01-23 Manganese Chemicals Corp Producing manganese by fused salt electrolysis, and apparatus therefor
US3256173A (en) * 1960-10-28 1966-06-14 Alusuisse Electrolytic furnace with lined cathode pots for the production of aluminum
US3314876A (en) * 1960-11-28 1967-04-18 British Aluminium Co Ltd Method for manufacturing solid current conducting elements
US3161579A (en) * 1961-03-06 1964-12-15 Kaiser Aluminium Chem Corp Electrolytic cell for the production of aluminum
US3156639A (en) * 1961-08-17 1964-11-10 Reynolds Metals Co Electrode
US3256696A (en) * 1962-01-29 1966-06-21 Monsanto Co Thermoelectric unit and process of using to interconvert heat and electrical energy
US3287247A (en) * 1962-07-24 1966-11-22 Reynolds Metals Co Electrolytic cell for the production of aluminum
US3330637A (en) * 1963-08-19 1967-07-11 Pilkington Brothers Ltd Method of removing impurities in a molten metal bath for glass sheet making
US3330635A (en) * 1963-08-19 1967-07-11 Pilkington Brothers Ltd Method and apparatus for decontaminating a glass sheet making molten metal bath
US3392092A (en) * 1963-08-30 1968-07-09 Isaac M. Diller Activation of cryolite-alumina compositions
US3372107A (en) * 1964-01-17 1968-03-05 Klein Alfred Electrode material for electrolytic processes
US3459515A (en) * 1964-03-31 1969-08-05 Du Pont Cermets of aluminum with titanium carbide and titanium and zirconium borides
US3479274A (en) * 1967-03-27 1969-11-18 Nalco Chemical Co Electrochemical cell having ceramic-lined tubular cathodes
US4181583A (en) * 1978-12-06 1980-01-01 Ppg Industries, Inc. Method for heating electrolytic cell
US4353885A (en) * 1979-02-12 1982-10-12 Ppg Industries, Inc. Titanium diboride article and method for preparing same
EP0042658A3 (de) * 1980-06-23 1982-03-10 KAISER ALUMINUM & CHEMICAL CORPORATION Elektrode für eine Elektrolysezelle für die Gewinnung von Aluminium
US4377463A (en) * 1981-07-27 1983-03-22 Great Lakes Carbon Corporation Controlled atmosphere processing of TiB2 /carbon composites
US4439382A (en) * 1981-07-27 1984-03-27 Great Lakes Carbon Corporation Titanium diboride-graphite composites
US4465581A (en) * 1981-07-27 1984-08-14 Great Lakes Carbon Corporation Composite of TiB2 -graphite
US4612103A (en) * 1983-11-29 1986-09-16 Alcan International Limited Aluminium reduction cells
US4617053A (en) * 1985-09-20 1986-10-14 Great Lakes Carbon Corporation Metal reinforced porous refractory hard metal bodies
US5378325A (en) * 1991-09-17 1995-01-03 Aluminum Company Of America Process for low temperature electrolysis of metals in a chloride salt bath
US5310476A (en) * 1992-04-01 1994-05-10 Moltech Invent S.A. Application of refractory protective coatings, particularly on the surface of electrolytic cell components
US5527442A (en) * 1992-04-01 1996-06-18 Moltech Invent S.A. Refractory protective coated electroylytic cell components
US6001236A (en) * 1992-04-01 1999-12-14 Moltech Invent S.A. Application of refractory borides to protect carbon-containing components of aluminium production cells
US5534119A (en) * 1992-06-12 1996-07-09 Sekhar; Jainagesh A. Method of reducing erosion of carbon-containing components of aluminum production cells
US5651874A (en) * 1993-05-28 1997-07-29 Moltech Invent S.A. Method for production of aluminum utilizing protected carbon-containing components
US5534130A (en) * 1994-06-07 1996-07-09 Moltech Invent S.A. Application of phosphates of aluminum to carbonaceous components of aluminum production cells
US5888360A (en) * 1994-09-08 1999-03-30 Moltech Invent S.A. Cell for aluminium electrowinning
US5683559A (en) * 1994-09-08 1997-11-04 Moltech Invent S.A. Cell for aluminium electrowinning employing a cathode cell bottom made of carbon blocks which have parallel channels therein
US5876584A (en) * 1995-05-26 1999-03-02 Saint-Gobain Industrial Ceramics, Inc. Method of producing aluminum
US5560809A (en) * 1995-05-26 1996-10-01 Saint-Gobain/Norton Industrial Ceramics Corporation Improved lining for aluminum production furnace
US5728466A (en) * 1995-08-07 1998-03-17 Moltech Invent S.A. Hard and abrasion resistant surfaces protecting cathode blocks of aluminium electrowinning cells
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GB814031A (en) 1959-05-27
FR1165136A (fr) 1958-10-20
CH365224A (de) 1962-10-31

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