Classifications

• • 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

• This invention relates to a slurry for coating anodes for use in cells for the electrowinning of metals from their oxides dissolved in molten salts, and to methods for their fabrication and reconditioning, as well as aluminium electrowinning cells containing coated anodes and their use to produce aluminium.
• the surface of the anode must be electrochemically active, substantially insoluble in the electrolyte and resistant to attacks by the nascent monoatomic oxygen and by the subsequently formed molecular oxygen gas which are anodically produced. Since monoatomic oxygen is far more aggressive than biatomic molecular gaseous oxygen, the constituents of the active surface of the anode should contain electro-catalytic materials for the reaction which forms molecular oxygen from the monoatomic oxygen to reduce monatomic oxygen attack.
• the materials having the greatest resistance to oxidation are metal oxides which are all to some extent soluble in cryolite. Oxides are also poorly electrically conductive, therefore, to avoid substantial ohmic losses and high cell voltages, the use of oxides should be minimal in the manufacture of anodes. Whenever possible, a good conductive material should be utilised for the anode core, whereas the surface of the anode is preferably made of an oxide having a high electrocatalytic activity.
• An object of the invention is to provide a method for coating an anode for metal electrowinning cells, in particular aluminium electrowinning cells, which substantially reduces the consumption of the active anode surface that is attacked by nascent monoatomic oxygen by enhancing the reaction of nascent oxygen to gaseous molecular gaseous oxygen.
• Another object of the invention is to provide a slurry for coating anodes for metal electrowinning cells, in particular aluminium electrowinning cells, which provides a coating with high electrolytic activity, a long life and which can be re-coated onto the anode as soon as such activity decreases or when the coating is worn out .
• a major object of the invention is to provide an anode for metal electrowinning cells, in particular aluminium electrowinning cells, which has no carbon so as to eliminate carbon-generated pollution and reduce the cell voltage and the high cost of cell operation.
• the present invention concerns a method of applying a slurry onto a conductive, heat resistant anode substrate to form an oxide coating on those parts of the substrate which are exposed to oxidising or corrosive cell environments .
• the invention in particular relates to a method of coating an electronically conductive and heat resistant substrate of a non-carbon metal-based anode of a cell for the electrowinning of metals from their oxides dissolved in molten salt, to protect and make the surface of the anode substrate active for the oxidation of the oxygen ions present in the electrolyte.
• the method comprises applying onto the substrate a slurry comprising at least one oxide or a precursor thereof as a non-dispersed but suspended particulate in a colloidal and/or inorganic polymeric carrier, the slurry is then solidified and made adherent to the substrate upon heat treatment to form an adherent, protective, predominantly oxide-containing coating.
• An oxide may be present in the oxide-containing coating as such, or in a multi-compound mixed oxide and/or in a solid solution of oxides.
• the oxide may be in the form of a simple, double and/or multiple oxide, and/or in the form of a stoichiometric or non- stoichiometric oxide.
• a typical application for this method is the coating of anodes for the electrowinning of aluminium by the electrolysis of alumina dissolved in a molten fluoride- containing electrolyte, such as a cryolite-based electrolyte or cryolite.
• the colloidal and/or inorganic polymeric carrier may be selected from alumina, ceria, lithia, magnesia, silica, thoria, yttria, zirconia, tin oxide, zinc oxide and mixtures thereof .
• the colloidal and/or inorganic polymeric carrier forms upon heat treatment the same chemical compound as the non-dispersed particulate.
• the oxides which may be used as a non-dispersed particulate and/or as a carrier may be in the form of spinels and/or perovskites or precursors thereof.
• Spinels may be doped, non-stoichiometric and/or partially substituted spinels, the doped spinels comprising dopants selected from the group consisting of Ti 4+ , Zr 4+ , Sn 4+ , Fe 4+ , Hf 4+ , Mn + , Fe 3+ , Ni 3+ , Co 3+ , Mn 3+ , Al 3+ , Cr 3+ , Fe 2+ , Ni 2+ , Co 2+ , Mg 2+ , Mn 2+ , Cu 2+ , Zn 2+ and Li + .
• the spinels may comprise a ferrite which can be selected from cobalt, copper, chromium, manganese, nickel and zinc ferrite, and mixtures and precursors thereof.
• the ferrites may also be doped with at least one oxide selected from chromium, titanium, tin, zinc and zirconium.
• Nickel-ferrite is a preferred compound for an electrochemically active coating for its high chemical resistance and may be present as such or partially substituted with Fe 2+ .
• the spinels may also comprise a chromite which can be selected from iron, cobalt, copper, manganese, beryllium, calcium, strontium, barium, yttrium, magnesium, nickel and zinc chromite, and mixtures and precursors thereof.
• the slurry advantageously comprises one or more electrocatalysts or a precursor thereof, however such a constituent is not always necessary.
• an electrocatalyst it may be advantageously selected from iridium, palladium, platinum, rhodium, ruthenium, silicon, tin, zinc, Mischmetal oxides and metals of the Lanthanide series, and mixtures and compounds thereof.
• the oxide constituents of the slurry may react among themselves.
• the constituents of the slurry may react with constituents of the electronically conductive and heat resistant substrate.
• a reaction is not always necessary for the formation of the coating from the slurry.
• the slurry may be applied onto the substrate by conventional techniques such as brushing, spraying dipping, electrodeposition or by using rollers.
• the substrate can be chosen among metals, alloys, intermetallics, cermets, and conductive ceramics. It may for instance comprise at least one of chromium, cobalt, hafnium, iron, molybdenum, nickel, copper, niobium, platinum, silicon, tantalum, titanium, tungsten, vanadium, yttrium and zirconium, and their combinations and compounds.
• the substrates may advantageously have a self- healing effect, i.e. when exposed to electrolyte the substrate passivates under the effect of the electrical current and becomes substantially inert to the electrolyte.
• the adherence of the coating on the substrate may be enhanced by applying onto the substrate a pre-coat before applying the slurry.
• a pre-coat before applying the slurry.
• Several methods are known to obtain an oxide pre-coat on a metal substrate, e.g. heating in air for prolonged periods at high temperatures (>1000°C) .
• a preferred pre-coat can be formed by applying a metal oxide in a colloidal or polymeric solution onto a clean metal substrate, drying and heat- treating the pre-coat at 500°C.
• Oxides for the pre-coat may be selected from Si ⁇ 2 , AI 2 O 3 , Th0 2 , Zr ⁇ 2 , Sn ⁇ 2 , Ti0 and Ce ⁇ 2 .
• the colloid/polymer contains cerium oxide having a crystallite size of about 5 to 10 nanometer and a N0 3 " /Ce0 2 mole ratio of approximately
• the pre-coat can be applied from a colloidal dispersion having a concentration between 25 and 250 g/1. Conventional techniques such as dipping, brushing or spraying can be used prior to drying and/or heat-treating the pre-coat.
• the invention also relates to an anode coating slurry for coating an electronically conductive and heat resistant substrate of a non-carbon metal-based anode for the electrowinning of metals from their oxides dissolved in molten salts, to form an adherent, protective, predominantly oxide-containing coating after heat treatment and to make the surface of the anode active for the oxidation of the oxygen ions present in the electrolyte.
• the slurry comprises at least one oxide or oxide precursor as a non-dispersed but suspended or suspendable particulate in a colloidal and/or inorganic polymeric carrier.
• This method may also be applied for reconditioning a non-carbon metal-based anode with a slurry as described hereabove, the active coating of which anode has become non-active or worn out.
• the method comprises clearing and restoring the surface of the conductive substrate before applying the slurry onto the substrate as described hereabove .
• Another aspect of the invention is an anode of a cell for the electrowinning of a metal, in particular of an aluminium electrowinning cell, comprising an electronically conductive substrate and a protective electrochemically active coating obtained from a slurry as described hereabove .
• a further aspect of the invention is a cell for the production of a metal by the electrolysis of its oxide dissolved in a molten salt, in particular for the electrowinning of aluminium or a lanthanide such as neodymium, having at least one anode comprising an electronically conductive substrate and a protective electrochemically active coating obtained from a slurry as described hereabove .
• An aluminium electrowinning cell may advantageously comprise at least one aluminium-wettable cathode.
• the cell may be in a drained configuration by having at least one drained cathode on which aluminium is produced and from which aluminium continuously drains.
• the cell may be of monopolar, multi-monopolar or bipolar configuration.
• a bipolar cell may comprise the anodes as described above as a terminal anode or as the anode part of a bipolar electrode.
• the aluminium electrowinning cell comprises means to improve the circulation of the electrolyte between the anodes and facing cathodes and/or means to facilitate dissolution of alumina in the electrolyte.
• Such means can for instance be provided by the geometry of the cell as described in co-pending application PCT/IB98/00161 (de Nora/Duruz) or by periodically moving the anodes as described in co-pending application PCT/IB98/00162 (Duruz/Bell ⁇ ) .
• the aluminium electrowinning cell may be operated with the electrolyte at conventional temperatures, such as 950 to 970°C, or at reduced temperatures as low as 750°C.
• Yet another aspect of the invention is a method of electrowinning aluminium in a cell comprising at least one coated non-carbon metal-based anode as described hereabove, the method comprising dissolving alumina in the electrolyte and then electrolysing the dissolved alumina to produce aluminium.
• the slurry as described hereabove can be used for coating a non-carbon metal-based anode for the production of aluminium in a cell for the electrowinning of aluminium by the electrolysis of alumina dissolved in a fluoride-containing electrolyte, on which anode oxygen ions in the electrolyte are oxidised and released as biatomic molecular gaseous oxygen by the electrochemically active anode slurry-obtained coating.
• a polymeric slurry was prepared from: a non- dispersable but suspendable particulate consisting of a nickel-ferrite powder and a nickel aluminate (iOAl ⁇ 3 ) precursor material acting as a polymeric carrier and binder for the nickel ferrite powder.
• the nickel-ferrite powder was specially prepared; however, commercially- available products could also have been used.
• the precursor NiOAl 2 0 3 materials, solution and gel powder reacted to form the spinel NiAl 0 4 at ⁇ 1000°C.
• this slurry When applied to a suitably prepared substrate such as nickel, this slurry produced an oxide coating made from the pre-formed or the in-situ formed nickel ferrite which adhered well onto the substrate and formed a coherent coating when dried and heated.
• the slurry could be applied by a simple technique such as brushing or dipping to give a coating of pre-determined thickness .
• a carrier consisting of a nickel aluminate polymeric solution containing a non-dispersed but suspended particulate of nickel aluminate was made by heating 75 g of Al(N0 3 ) 3 .9 H 2 0 (0.2 moles Al) at 80°C to give a concentrated solution which readily dissolved 12 g of NiC0 3 (0.1 moles).
• the viscous solution (50 ml) contained 200 g/1 Al 2 0 3 and 160 g/1 NiO (total oxide, >350 g/1) .
• This nickel-rich polymeric concentrated anion deficient solution was compatible with commercially- available alumina sols e.g. NYACOLTM.
• NiO.Al 0 3 mixture was prepared by adding 5 ml of the anion deficient solution to 2.0 ml of a 150 g/1 alumina sol; this mixture was stable ' to gelling and could be applied to smooth metal and ceramic surfaces by a dip-coating technique. When heated to 450-500°C, X-ray diffraction showed nickel- aluminate had formed in the coating.
• non-dispersable particulate than nickel aluminate could be suspended in the anion-deficient nickel aluminate precursor solution and applied as coatings which when heat-treated would form nickel- aluminate containing the added oxides .
• a colloidal solution containing a metal ferrite precursor (as required for NiONiFe 2 0 ) was prepared by mixing 20.7 g Ni(N0 3 ) 2 .6 H 2 0 (5.17 g NiO) with 18.4 g Fe(N0 3 ) 3 .9 H 2 0 (4.8 g Fe 2 0 3 ) and dissolving the salts in water to a volume of 30 ml.
• the solution was stable to viscosity changes and to precipitation when aged for several days at 20°C.
• An organic solvent such as PRIMENETM JMT (R 3 CNH 2 molecular weight ⁇ 350) is immiscible with water and extracts nitric acid from acid and metal nitrate salt solutions.
• the spherical droplets of feed were converted to a mixed oxide gel; they were filtered off, washed with acetone and dried to a free-flowing powder.
• nickel-ferrite formed at ⁇ 800°C and the powder could be used as a non-dispersable but suspended particulate in colloidal and/or inorganic polymeric slurries as described in Example 1 or 2.
• Commercially-available nickel-ferrite powder could also have been used.
• NiFe20 4 (40 ml) having the composition required for the formation of NiFe20 4 .
• the solution was converted to gel particles by solvent extracting the nitrate with PRIMENETM JMT as described in Example 3.
• the nickel-ferrite precursor gel was calcined in air to give a non-dispersable but suspended particulate in the form of a nickel-ferrite powder, which could be hosted into nickel-aluminate carrier for coating applications from colloidal and/or polymeric slurries.
• the magnesium chromite particulate was suspended in the polymer carrier to form a slurry suitable for coating treated metal substrates .
• Example 6 An amount of 150 g of Fe(N ⁇ 3 ) 3 .9 H 2 O was heated to dissolve the salt in its own water of crystallisation to form a solution containing 29 g Fe 2 U 3 . The solution was heated to 120°C and 18.9 g of magnesium hydroxy-carbonate dissolved in the hot solution to form 7.5 g MgO in form of an inorganic polymer together with Fe 2 ⁇ 3 . An amount of
• the ferrite powder was ground in a pestle and mortar and then suspended as a non- dispersable particulate in the same inorganic polymer acting as a carrier to give a slurry that was used to coat a treated metal substrate.
• a cleaned surface of an InconelTM billet (typically comprising 76 weight% nickel - 15.5 weight% chromium - 8 weight% iron) was pre-coated with a ceria colloid as described in US Patent 4,356,106 (Woodhead/Raw) , dried and heated in air at 500°C.
• the pre-coated billet was then further coated with the polymeric slurry described in Example 1 or 2 , dried and heated in air at 500°C.
• the ferrite coating was very adherent and successive layers of the slurry could be applied to build up a coating of ferrite/aluminate having a thickness above 100 micron.
• Example 1 A similar untreated InconelTM billet was coated with a 10 micron thick layer using the polymeric slurry described in Example 1 or 2 but without pre-coating the billet with ceria colloid. After heat-treatment the coating was cracked and easily broke away from the substrate, which demonstrated the effect of the ceria pre-coat .

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• 1999
  • 1999-01-19 ES ES99900109T patent/ES2274613T3/es not_active Expired - Lifetime
  • 1999-01-19 AU AU17797/99A patent/AU747903B2/en not_active Ceased
  • 1999-01-19 CA CA002317802A patent/CA2317802C/en not_active Expired - Fee Related
  • 1999-01-19 DE DE69933854T patent/DE69933854T2/de not_active Expired - Lifetime
  • 1999-01-19 EP EP99900109A patent/EP1049817B1/de not_active Expired - Lifetime
  • 1999-01-19 WO PCT/IB1999/000081 patent/WO1999036593A1/en active IP Right Grant
• 2000
  • 2000-07-19 NO NO20003702A patent/NO326358B1/no not_active IP Right Cessation

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