EP0094353B1 - Matériaux mouillables par l'aluminium - Google Patents
Matériaux mouillables par l'aluminium Download PDFInfo
- Publication number
- EP0094353B1 EP0094353B1 EP83810197A EP83810197A EP0094353B1 EP 0094353 B1 EP0094353 B1 EP 0094353B1 EP 83810197 A EP83810197 A EP 83810197A EP 83810197 A EP83810197 A EP 83810197A EP 0094353 B1 EP0094353 B1 EP 0094353B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminum
- cell
- molten
- coating
- wettable
- 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
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 187
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 239000000463 material Substances 0.000 title claims abstract description 32
- 210000004027 cell Anatomy 0.000 claims abstract description 112
- 239000010936 titanium Substances 0.000 claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 210000003850 cellular structure Anatomy 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 48
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 41
- 239000000080 wetting agent Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 206010030924 Optic ischaemic neuropathy Diseases 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 238000005363 electrowinning Methods 0.000 abstract description 18
- 238000009877 rendering Methods 0.000 abstract description 2
- 229910001610 cryolite Inorganic materials 0.000 description 43
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 38
- 229910033181 TiB2 Inorganic materials 0.000 description 34
- 239000000758 substrate Substances 0.000 description 31
- 238000012856 packing Methods 0.000 description 30
- 241000264877 Hippospongia communis Species 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011819 refractory material Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910000048 titanium hydride Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011530 conductive current collector Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- -1 titanium hydride Chemical compound 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- DXNVUKXMTZHOTP-UHFFFAOYSA-N dialuminum;dimagnesium;barium(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Mg+2].[Al+3].[Al+3].[Ba+2].[Ba+2] DXNVUKXMTZHOTP-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C25C3/16—Electric current supply devices, e.g. bus bars
-
- 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
Definitions
- the present invention relates to a molten salt aluminum production cell comprising an aluminum wettable component exposed to molten aluminum in said cell, the component being essentially made of an aluminum non-wettable material rendered aluminum wettable by coating it with a compound containing the elements of a wetting agent and a solubility suppressor for said wetting agent.
- Aluminum is commonly produced by electrowinning aluminum from AI 2 0 3 (alumina) at about 900°C to 1,000°C. Aluminum oxide being electrowon frequently is dissolved in molten Na 3 AIF 6 (cryolite) that generally contains other additives helpful to the electrowinning process such as CaF z , AIF 3 and possibly LiF or MgF 2 .
- anode and cathode are arranged in vertical spaced configuration within the cell, the anode being uppermost. Reduction of aluminum oxide to aluminum occurs at the cathode which customarily is positioned at the bottom or floor of the cell. Oxygen is disassociated from A1 2 0 3 , in most commercial cells combining with carbonaceous material comprising the cell anode and being emitted from the cell as CO and CO 2 ,
- Cryolite is an aggressive chemical necessitating use of a cathode material substantially resistant to this aggressive cryolite.
- a cathode material substantially resistant to this aggressive cryolite.
- One popular choice is the use of molten aluminum as a cathode. While use of other cathodes such as bare graphite in contact with cryolite has been contemplated, formation of undesirable by-products such as aluminum carbide has discouraged use. In many commercial cells, this cathode often covers substantially the entire floor of the cell which typically can be 6 feet wide by 18 or more feet in length.
- the cathode In utilizing aluminum for cathode purposes in a cell, typically the cathode is included in an assembly of a cathodic current feeder covered by a pool of aluminum ranging in depth, depending upon the cell, from a few inches to in excess of a foot, but generally about 6 inches.
- the aluminum pool functions effectively as a cathode and also serves to protect current feeders made from materials less than fully resistant to cell contents.
- These aluminum pool type cell cathode assemblies contain conductive current collectors. Where these conductive current collectors are utilized in certain cell configurations, these collectors contribute to an electrical current flow within the cell that is not perpendicular to the cell bottom. These nonperpendicular electrical currents can interact with strong magnetic fields established around cells by current flow through busses and the like to contribute to strong electromagnetic fluxes within the cell.
- cryolite In cells employing a pool of aluminum covering the cathode floor of the cell, the cryolite, containing A1 2 0 3 to be electrolyzed, floats atop this aluminum pool.
- the cell anodes are imfnersed in this cryolite layer.
- cell anodes are generally positioned within the cryolite substantially above the normal or expected level of the interface between molten cryolite and molten aluminum within the cell. Usually, a spacing of 3.75-6.25 cm (1'2 to 2; inches) is utilized.
- drained cathodes In such cells, no pool of aluminum is maintained upon a cathode current feeder to function as a cathode; electrowon aluminum drains from the cathode at the bottom of the cell to be recovered from a collection area.
- drained cathode cells without wave action attendant to a molten aluminum pool, the anode and the cathode may be quite closely arranged, realizing significant electrical power savings.
- the cathode In these drained cathode cells, the cathode, particularly where non-wettable by molten aluminum, is in generally continuous contact with molten cryolite.
- This aggressive material in contact with a graphite or carbon cathode, can contribute to material loss from the cathode and can trigger formation of such undesirables as aluminum carbide.
- Particularly carbon or graphite for use as a drained cathode material of construction is therefore of quite limited utility due to possible service life constraints and carbide contaminant formation.
- the molten cryolite can contribute to TiB 2 corrosion by fluxing reaction products of a reaction between impure TiB 2 and aluminum, particularly near grain boundaries of the material. While it is known that in aluminum electrowinning cells utilizing essentially pure TiB 2 do not exhibit as substantial a corrosion susceptibility as do those employing lower purity TiB 2 , cost and availability factors seriously limit the use of TiB 2 sufficiently pure to withstand an aggressive aluminum cell environment.
- cryolite Conventionally, most cells employ construction materials that are either wettable by molten aluminum, are relatively inert to the corrosive effects of cryolite or both. Where a substance is not readily wetted by molten aluminum, even though immersed in molten aluminum the substance may contact cryolite present at the interface between the substance and the molten aluminum due to poor wetting. Where the substance is significantly soluble in cryolite, or corroded by cryolite, substantial material losses to the substrate therefore can occur.
- substrates substantially wettable by molten aluminum tend, while immersed in the molten aluminum, to be protected from the deleterious effects of contact with molten cryolite.
- a sheathing effect by the molten aluminum protects the substance.
- Aluminum wettable substances such as refractory TiB 2 have therefore been suggested for constructing components of cells which are to be immersed in molten aluminum.
- aluminum nonwettable materials particularly those such as alumina which are subject to attack/ dissolution by molten cryolite, for fabrication of cell components. This reluctance may be enhanced where dimensional stability of the component is relatively important, for example in the fabrication of electrical current feeders, weirs, sidewalls, and the like.
- an aluminum production cathode comprising a top layer of porous structure which is coated with e.g. TiB 2 .
- the porous top layer is infiltrated with molten aluminum saturated with Ti.
- TiB 2 e.g. TiB 2
- EP-A-0 069 502 also unpublished before the filing date of the present application discloses cell components of TiB 2 or comprising a coating of TiB 2 . It is known in the art that TiB 2 coatings on components which are immersed in molten aluminum render the substrate aluminum wettable. However, it is also known that TiB 2 has a certain solubility in molten aluminum and does therefore not quality for long term operation under known conditions.
- EP-A-0 021 850 discloses an aluminum cathode of carbon which comprises a coating of TiB 2 . This coating is produced by electrodeposition from an electrolyte containing titanium and boron. Long term operation of this coated cathode once produced and installed in an operating cell is impaired by the same reasons as mentioned in the preceding paragraph.
- the present invention provides a molten salt aluminum production cell as set out under the heading "Technical Field of the Invention", wherein the molten aluminum contains said wetting agent and said solubility suppressor in concentrations near saturation.
- the present invention further provides a method of maintaining aluminum wettability of a component of the above aluminum production cell.
- the present invention provides a method for making substrates used in, or components of an aluminum electrowinning cell substantially wettable and thereby at least partially filled where porous by molten aluminum where those components or substrates normally would not be aluminum wetted in the environment of the cell. Used in the electrowinning cell, these wettable components, when immersed in molten aluminum contained in the cell are stable in the cell environment even where the materials from which the substrates were fabricated would otherwise be subject to aggressive attack by materials such as cryolite contained in the cell.
- Substrates are made wettable by molten aluminum by applying to the substrate a coating of a compound containing the elements of a wetting agent and a solubility suppressor for the wetting agent prior to or while the substrate is immersed in molten aluminum, and the molten aluminum is maintained near saturation with the wetting agent and solubility suppressor by introducing the wetting agent and the solubility suppressor into the molten aluminum to maintain desired levels in the molten aluminum.
- the coating applied to the substrate is preferably quite thin.
- the coating need not be continuous.
- the method preferably is utilized to make refractory materials commonly non aluminum wettable, amenable to wetting by aluminum. Once aluminum wettable, these refractory materials can be utilized for a variety of purposes within an aluminum electrowinning cell including weirs, current feeders, packing, baffles, structural components and the like.
- Fig. 1 is a cross sectional representation of an aluminum electrowinning cell.
- Fig. 1 shows in cross section a representation of an aluminum electrowinning cell 10.
- the cell includes a base 14 and sidewalls 16, 18, generally of steel, surrounding the cell.
- the cell includes a cathodic current feeder 20 and anodes 22, 24.
- the base and sidewalls enclose the cathodic current feeder 20 which in this best embodiment functions also as a cell liner. Portions 26 of the liner define a floor of the cell. Well known refractory materials and graphite are suitable for fabricating this current feeder 20, as are other suitable or conventional materials.
- a current buss 28, embedded in the feeder 20 provides electrical current for distribution within the cell 10. The buss 28 is connected to an external source of electrical current (not shown).
- the anodes 22, 24 are arranged in vertical spaced relationship with the current feeder portions 26 defining the floor of the cell.
- the anodes 22, 24 are separated from the cathodic current feeder by two pools 30, 32 of molten material.
- One pool 30 comprises essentially molten aluminum. This molten aluminum pool functions as a cathode for electrowinning of aluminum within the cell. While the pool consists essentially of molten aluminum, impurities customarily associated with aluminum produced electrolytically may be present.
- the remaining pool 32 is comprised of molten cryolite, Na 3 AIF 6 , containing dissolved A1 2 0 3 .
- a number of cryolite formulations that include additives such as CaF 2 , LiF, and AIF 3 for enhancing electrolysis of the A1 2 0 3 to aluminum are possible and are contemplated as being utilized within the scope of the invention.
- This cryolite layer being less dense than the molten aluminum, floats upon the aluminum.
- An interface 36 separates the molten aluminum 30 from the molten cryolite 32.
- An insulating layer 39 is provided to resist heat flow from the cell 10. While a variety ofwell-known structures are available for making this insulating structure, often the insulating layer 39 is crystallized contents of the electrolytic cell.
- the anodes 22, 24 are fabricated from any suitable or conventional material and immersed in a cryolite phase 32 contained in the cell. Since oxygen is released in some form at the anode, the anode material must be either resistant to attack by oxygen or should be made of a material that can be agreeably reacted with the evolving oxygen, preferably producing a lower anode half cell voltage by virtue of reactive depolarization. Typically, carbon or graphite is utilized providing a depolarized anode.
- the anodes 22, 24 should be arranged for vertical movement within the cell so that a desired spacing can be maintained between the anode and cathode notwithstanding the anode being consumed by evolving oxygen.
- a packed bed 41 of loose elements 42 is positioned in the cell, in the molten aluminum pool 30.
- These elements are formed of a substance substantially non-wettable by aluminum.
- the elements are maintained in the molten aluminum at a level at or below the interface 36 between the molten aluminum and molten cryolite, the depth to which the elements are packed being substantially uniform across the cell.
- the elements should be notfurtherthan 5 centimeters from the interface, but should not extend substantially above the interface, particularly where the elements 42 may be subject to aggressive attack by the cryolite.
- the packed bed elements can be of any shape. It is preferred that the shapes provide, when packed, interstices through the packed bed whereby aluminum can fill gaps in the packing to maintain uniform electrical conductivity through the packed pool of aluminum. Particularly, packing in the formed of berl saddles, Raschig rings, Intaox saddles, and equiaxed shapes such as cylinders and spheres are much preferred; however randomly shaped packing, blocks or bricks may be utilized.
- the packing is fabricated from a material substantially non-wettable by molten aluminum, preferably porous, with alumina, AI 2 0 3 , being much preferred. Since alumina is soluble in the molten cryolite, and since aluminum is being electrolyzed within the cell from alumina dissolved in the cryolite layer 32, it is important that the alumina packing be maintained reliably covered with aluminum to prevent consumption of the packing-covering is conveniently accomplished by maintaining the packing virtually continuously beneath the interface when the packing is non- wettable by aluminum, a substantial aluminum thickness is required to assure non-contact with cryolite. However should portions of the aluminum, non-wettable packing protrude from the molten aluminum but be coated with molten aluminum, the packing would thereby be protected. Being covered by molten aluminum shields the packing elements from aggressive attack by the cryolite.
- Shielding can be accomplished by making the normally aluminum non-wettable packing wettable by molten aluminum at operating temperatures within the cell. Wettability is accomplished by providing the otherwise nonwettable packing with a surface coating of a wetting agent and a solubility suppressor for the wetting agent. This coating can include any of a variety of elemental materials known for making aluminum non-wettable materials wettable by aluminum. As wetting agent Zr, Hf, Si, Mg, V, Cr, Nb, Ca and Ti are suitable with Ti being substantially preferred in the practice of the invention.
- Elements substantially suppressing the solubility of the wetting agents in molten aluminum are suitable for use as solubility suppressors.
- solubility suppressors typically boron, carbon and nitrogen are useful with boron being much preferred.
- the coating applied then is TiB 2 , but the practice detailed applies equally to other wetting agents and solubility suppressors.
- the surface coating can be applied to the packing by a variety of methods.
- the packing can be soaked in a slurry of titanium hydride and morphous, powdered boron in polyvinyl alcohol, and then fired at 800-1500 0 C for 1 to 25 hours.
- titanium can be applied by electroless metallidization techniques in a fused salt bath.
- the titanium coated packing is then packed in boron powder for 1 to 25 hours at 800 to 1200°C.
- the titanium may be sputtered onto the packing.
- boridization in boron powder may be eliminated by sputtering TiB 2 directly onto the packing.
- TiB 2 may also be applied directly to the packing by vapor deposition. Alternately a slurry of Ti0 2 and B 2 0 3 may be spray applied to the surface and reduced.
- the packing can be soaked in aluminum containing titanium and boron for 1 to 2 weeks to apply the coating.
- Titanium may be present as Ti, Ti0 2 or TiB 2 for example, while boron may be present as B Z O 3 , B°for example where the packing has been molded from a refractory material such as alumina, titanium and boron compounds such as Ti0 2 and B 2 0 1 or TiB 2 may be molded with the packing.
- the boron and titanium will tend to migrate to the surface of the packing to provide the desired coating.
- Wetting of alumina or other suitable substrate can be achieved using this procedure of soaking in aluminum containing wetting agent and solubility suppressor outside of the aluminum electrowinning cell, in which case the coated wettable packing is transferred to the cell.
- the packing or substrate can be made wettable in-situ by soaking in aluminum containing wetting agent and solubility suppressor in the aluminum electrowinning cell.
- the coating can be produced in-situ through the aluminothermic reduction of titanium oxide and boron oxide coatings on alumina or other substrates.
- the formation of a surface coating of TiB 2 combined with alumina results through this in-situ reaction and wetting by aluminum is achieved. If desired, this in-situ reaction coating can be done by contact with molten aluminum in the electrowinning cell.
- An average coating thickness of between 5.0 angstroms and 100 microns is preferable, with coatings in excess of about 10 angstroms being much preferred.
- the coating need not be continuous; continuous coatings delivering only marginally superior wettability over noncontinuous coatings.
- the inclusion of the wetting agent and solubility suppressor is intended to produce a surface effect only. Total inclusion of substances such as TiB 2 generally will not exceed about 5% and usually substantially below 1% by weight. Unless the substrate being coated is electrically conductive, the coated substrate remains relatively electrically non-conductive.
- the TiB 2 coating permits virtually instantaneous wetting of the substrate. It is further believed that the TiB 2 coating functions to provide a surfactant permitting molten aluminum to penetrate pores of a coated structure. A partially aluminum filled porous structure surface results, having advantageous physical characteristics over a mere wetted surface. Ti and B dissolving from the surface coating penetrate the pores with the molten aluminum, permitting in surfactant fashion the passage of molten aluminum into pores otherwise inaccessible to the molten aluminum by reason of surface tension. To achieve this result, both the substrate surface and the TiB 2 coating should be porous, permitting infiltration into substrate pores.
- Titanium and boron present in the coating are, together, marginally soluble in molten aluminum. Once immersed in molten aluminum, the coating therefore tends to dissolve into the molten aluminum unless the molten aluminum is near or above saturation with titanium and boron.
- titanium is soluble in molten aluminum to about 50 parts per million (ppm) and boron to about 20 ppm. Therefore it is desirable that molten aluminum present in the cell be maintained saturated with titanium and boron by the addition of compounds containing them.
- existing aluminum electrowinning cells are equipped for introducing additives, however any suitable or conventional method for introducing the Ti and B would suffice, including the introduction of TiB 2 .
- packing has been shown as the cell component being fabricated from a nonaluminum wettable material, other components are suitable candidates for fabrication using these wettability techniques.
- weirs for overflowing molten aluminum from the cell, and current feeders may be fabricated using the technique of the instant invention from aluminum nonwettable materials.
- Other applications within the cell will become apparent upon reflection.
- a number of suitable or conventional materials substantially nonwettable by aluminum are available for use in the instant invention. These materials, because of the relatively elevated temperature they must withstand in an aluminum electrolysis cell, are primarily refractory materials including alumina, aluminum nitride, AION, SiAION, boron nitride, silicon nitride, aluminum borodes such as AIB 121 silicon carbides, alkali earth metal zirconates and aluminates such as calcium zirconate, barium zirconate, and magnesium aluminate, and mixtures of these materials. Alumina is preferred.
- wettable what is meant is a contact angle between the coated substrate and molten aluminum of less than 90°; nonwettable being a contact angle in excess of 90°.
- nonwettable substrates such as alumina, coated according to the method of the instant invention allow aluminum to spread over the substrate surface, indicating a contact angle of about 30° or less.
- an alumina substrate normally subject to some aggressive attack by molten cryolite even when immersed in an aluminum pool within an aluminum electrowinning cell, can be coated and immersed in molten aluminum within the cell with small concern for its dimensional integrity.
- Titanium diboride was coated onto Diamonite@ alumina balls. These balls were supplied by Diamonite Products Manufacturing Incorporated and were comprised of approximately 1 to 3 percent silicon dioxide and the balance alumina. These balls were first etched in a molten salt mixture of 49 percent NaOH, 49 percent KOH, and 2 percent NaF at 180°C for approximately 1 hour. Following etching, these balls were solvent degreased and coated with titanium by immersion in a molten salt mixture of 203.6 grams of KCI, 165.2 grams of NaCI, 15.2 grams of CaCI 2 and 16.7 grams of TiH2. Coating was conducted at approximately 1000°C for four hours.
- the balls were then washed and dried. Following drying the balls were packed into a boron powder bed and boridized using well known techniques at 1000°C for 48 hours in an argon atmosphere scrubbed of residual oxygen by passage over hot titanium. Following boridization, the balls were placed in a ball mill including alumina beads and agitated to remove excess surface boron from the balls by abrasion.
- the balls were then each placed in an alumina crucible with 30 grams of aluminum and 3-5 grams cryolite.
- the crucible was evacuated and heated to 1000°C for 4-8 weeks. While under heat the crucible was maintained under an argon purge, the argon being scrubbed of oxygen by passage over hot titanium at 800-900°C.
- the balls were inspected and found to be wetted by aluminum. Only extremely limited grain boundary corrosion was noted in a TiB 2 coating that averaged only 10-20 micrometers in thickness. Additionally, trace amounts of titanium were found in the alumina crucible, primarily in the pores. These pores were also found to be at least partially wetted by aluminum with a small quantity of the aluminum being found in pores of the alumina crucible. Specifically with respect to the balls, the interface between the TiB 2 coating and the alumina substrate was found to be intact, and showing no evidence of grain boundary corrosion of TiB 2 was observed. In the balls, a contrast gradation was observed in the alumina substrate which was attributed to filling of the pores with aluminum.
- Example 1 was repeated with the exception that the balls were not solvent degreased. The results were essentially identical.
- the etched alumina materials were rinsed in distilled water and stored in methyl alcohol. Each was then coated with titanium for four hours at approximately 1000°C under an argon atmosphere scrubbed of oxygen by passage over hot titanium in a bath comprising 796 grams of KCI, 640 grams of NaCI, 59 grams of CaCI, and 65 grams of TiH 2 .
- honeycombs and balls surrounded by the treated alumina tube sections and encased in aluminum were subjected to 10 hour polarization tests.
- Each honeycomb or ball in its alumina tube section was placed on a carbon disc 6 centimeters in diameter by 0.7 centimeters thick resting on a 6 centimeter diameter alumina pallet positioned in the bottom of a 750 milliliter alumina crucible.
- a molybdenum rod encased in boron nitride was employed as a cathodic current feeder connecting to the carbon disc and alumina pallet to the negative pole of a source of electrical current.
- the cell was completed by positioning a carbon cylinder 3 centimeters in diameter and 3; centimeters in length into the crucible for employ as an anode.
- the cell was charged with 600 grams of 10 percent alumina in cryolite. 4.81 amperes were passed between anode and cathode for 10 hours. 3 centimeters of molten aluminum was maintained in the cell so that the honeycombs or balls remained immersed at all time.
- each aluminum cathode was disassembled and the coating alumina honeycomb or ball was examined.
- the surrounding alumina tube section had fractured. Examination of the honeycomb revealed that the aluminum surrounding the honeycomb had protected the alumina honeycomb from attack while under polarization.
- the cell voltage was approximately 2.47 volts, and the spacing between the anode and the aluminum cryolite interface within the cell was 2.5 to 2.7 centimeters.
- Example 3 was repeated except that provision was made for draining aluminum from the crucible as it formed so that the honeycomb or ball were bathed in cryolite, the carbon disc was replaced with a titanium diboride disc of equal dimension, and the honeycomb or balls were placed directly on the titanium diboride disc without benefit of the surrounding treated tube section.
- the honeycomb or ball were each encased in aluminum upon insertion into the cell. That aluminum melted upon cell start-up and was withdrawn from the crucible.
- the cryolite charged to the cell was electrolyzed to produce molten aluminum under electrolysis conditions identical to Example 3 except that the anode was maintained at approximately 2.5 centimeters distance from upper portions of the honeycomb or ball as arranged in the crucible cell.
- each cell was cooled and each honeycomb or ball was removed for examination.
- These objects notwithstanding their direct contact with molten cryolite during electrolysis, were found to have a 100 to 500 micron film upon all surfaces.
- the alumina substrates of each honeycomb or ball were not attacked.
- a cylindrical solid section of AIB 12 was split longitudinally to yield a solid half cylinder.
- the half cylinder was degreased with propanol.
- the degreased half of the cylinder was immersed in a mixture of 20.36 grams KCI, 16.52 grams NaCI, 1.52 grams CaC1 2 , and 2 grams of titanium hydride at approximately 1000°C under an argon inerted atmosphere scrubbed of oxygen by passage over hot titanium. Immersion was contained for four hours.
- the half cylinder was then boridized in a manner identical to that of Example 1. Upon inspection, a 15 micron coating of titanium diboride was found to be present on the surface of the half cylinder.
- the half cylinder was placed in a 750 milliliter alumina crucible, containing a titanium diboride ring filled with aluminum. The half cylinder was inserted into the ring so that a portion of the half cylinder protruded above the aluminum contained within the titanium diboride ring. The balance of the crucible was filled with cryolite. The crucible was heated to 1000°C for 2 hours. After 2 hours the treated half cylinder was found to be coated uniformly with aluminum, even those portions protruding from the titanium diboride ring, into cryolite floating atop molten aluminum contained in the TiB 2 ring.
- Example 5 was repeated for BN with essentially identical results.
Landscapes
- 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)
- Cultivation Of Seaweed (AREA)
- Electroplating Methods And Accessories (AREA)
- Cookers (AREA)
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83810197T ATE32107T1 (de) | 1982-05-10 | 1983-05-09 | Aluminium benetzbare materialien. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US37662982A | 1982-05-10 | 1982-05-10 | |
US376629 | 1982-05-10 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0094353A2 EP0094353A2 (fr) | 1983-11-16 |
EP0094353A3 EP0094353A3 (en) | 1984-03-07 |
EP0094353B1 true EP0094353B1 (fr) | 1988-01-20 |
Family
ID=23485808
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83810197A Expired EP0094353B1 (fr) | 1982-05-10 | 1983-05-09 | Matériaux mouillables par l'aluminium |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0094353B1 (fr) |
JP (1) | JPS58207385A (fr) |
AT (1) | ATE32107T1 (fr) |
AU (1) | AU572092B2 (fr) |
CA (1) | CA1233781A (fr) |
DE (1) | DE3375409D1 (fr) |
NO (1) | NO831651L (fr) |
Families Citing this family (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3472973D1 (en) * | 1983-08-16 | 1988-09-01 | Alcan Int Ltd | Method of filtering molten metal |
AU4095185A (en) * | 1984-04-27 | 1985-10-31 | Aluminium Company Of America | Refractory hard metal interwoven matrix cathode for electrolytic production of aluminum |
BR8707792A (pt) * | 1986-08-21 | 1989-08-15 | Moltech Invent Sa | Eletrodo para eletroproducao de sal em fusao processo e celula |
US4828008A (en) * | 1987-05-13 | 1989-05-09 | Lanxide Technology Company, Lp | Metal matrix composites |
US5277989A (en) * | 1988-01-07 | 1994-01-11 | Lanxide Technology Company, Lp | Metal matrix composite which utilizes a barrier |
US5141819A (en) * | 1988-01-07 | 1992-08-25 | Lanxide Technology Company, Lp | Metal matrix composite with a barrier |
US4935055A (en) * | 1988-01-07 | 1990-06-19 | Lanxide Technology Company, Lp | Method of making metal matrix composite with the use of a barrier |
US5303763A (en) * | 1988-11-10 | 1994-04-19 | Lanxide Technology Company, Lp | Directional solidification of metal matrix composites |
US5119864A (en) * | 1988-11-10 | 1992-06-09 | Lanxide Technology Company, Lp | Method of forming a metal matrix composite through the use of a gating means |
US5287911A (en) * | 1988-11-10 | 1994-02-22 | Lanxide Technology Company, Lp | Method for forming metal matrix composites having variable filler loadings and products produced thereby |
US5163499A (en) * | 1988-11-10 | 1992-11-17 | Lanxide Technology Company, Lp | Method of forming electronic packages |
US5301738A (en) * | 1988-11-10 | 1994-04-12 | Lanxide Technology Company, Lp | Method of modifying the properties of a metal matrix composite body |
US5040588A (en) * | 1988-11-10 | 1991-08-20 | Lanxide Technology Company, Lp | Methods for forming macrocomposite bodies and macrocomposite bodies produced thereby |
US5016703A (en) * | 1988-11-10 | 1991-05-21 | Lanxide Technology Company, Lp | Method of forming a metal matrix composite body by a spontaneous infiltration technique |
US5240062A (en) * | 1988-11-10 | 1993-08-31 | Lanxide Technology Company, Lp | Method of providing a gating means, and products thereby |
US5518061A (en) * | 1988-11-10 | 1996-05-21 | Lanxide Technology Company, Lp | Method of modifying the properties of a metal matrix composite body |
US5526867A (en) * | 1988-11-10 | 1996-06-18 | Lanxide Technology Company, Lp | Methods of forming electronic packages |
US5267601A (en) * | 1988-11-10 | 1993-12-07 | Lanxide Technology Company, Lp | Method for forming a metal matrix composite body by an outside-in spontaneous infiltration process, and products produced thereby |
US5172747A (en) * | 1988-11-10 | 1992-12-22 | Lanxide Technology Company, Lp | Method of forming a metal matrix composite body by a spontaneous infiltration technique |
US5165463A (en) * | 1988-11-10 | 1992-11-24 | Lanxide Technology Company, Lp | Directional solidification of metal matrix composites |
US5224533A (en) * | 1989-07-18 | 1993-07-06 | Lanxide Technology Company, Lp | Method of forming metal matrix composite bodies by a self-generated vaccum process, and products produced therefrom |
US5188164A (en) * | 1989-07-21 | 1993-02-23 | Lanxide Technology Company, Lp | Method of forming macrocomposite bodies by self-generated vacuum techniques using a glassy seal |
US5247986A (en) * | 1989-07-21 | 1993-09-28 | Lanxide Technology Company, Lp | Method of forming macrocomposite bodies by self-generated vacuum techniques, and products produced therefrom |
US5329984A (en) * | 1990-05-09 | 1994-07-19 | Lanxide Technology Company, Lp | Method of forming a filler material for use in various metal matrix composite body formation processes |
US5851686A (en) * | 1990-05-09 | 1998-12-22 | Lanxide Technology Company, L.P. | Gating mean for metal matrix composite manufacture |
US5505248A (en) * | 1990-05-09 | 1996-04-09 | Lanxide Technology Company, Lp | Barrier materials for making metal matrix composites |
ATE151470T1 (de) * | 1990-05-09 | 1997-04-15 | Lanxide Technology Co Ltd | Verfahren mit sperrwerkstoffe zur herstellung eines verbundwerkstoffes mit metallmatrix |
JPH05507319A (ja) * | 1990-05-09 | 1993-10-21 | ランキサイド テクノロジー カンパニー,リミティド パートナーシップ | 金属マトリックス複合物用硬化フィラー材料 |
WO1991017129A1 (fr) * | 1990-05-09 | 1991-11-14 | Lanxide Technology Company, Lp | Corps macrocomposites et procedes de production |
US5487420A (en) * | 1990-05-09 | 1996-01-30 | Lanxide Technology Company, Lp | Method for forming metal matrix composite bodies by using a modified spontaneous infiltration process and products produced thereby |
CA2081553A1 (fr) * | 1990-05-09 | 1991-11-10 | Marc Stevens Newkirk | Composites a matrice metallique mince, et methode de production |
US5361824A (en) * | 1990-05-10 | 1994-11-08 | Lanxide Technology Company, Lp | Method for making internal shapes in a metal matrix composite body |
US5652723A (en) * | 1991-04-18 | 1997-07-29 | Mitsubishi Denki Kabushiki Kaisha | Semiconductor memory device |
CA2152048C (fr) * | 1992-12-17 | 2004-06-29 | Kevin Drew Watson | Cellule electrolytique pour la production du metal |
US5848349A (en) * | 1993-06-25 | 1998-12-08 | Lanxide Technology Company, Lp | Method of modifying the properties of a metal matrix composite body |
US5560809A (en) * | 1995-05-26 | 1996-10-01 | Saint-Gobain/Norton Industrial Ceramics Corporation | Improved lining for aluminum production furnace |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0069502A2 (fr) * | 1981-06-25 | 1983-01-12 | Alcan International Limited | Améliorations dans les cellules de réduction électrolytique |
WO1983001465A1 (fr) * | 1981-10-23 | 1983-04-28 | Alusuisse | Cathode de cellule d'electrolyse de masse en fusion pour la preparation d'aluminium |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1172991A (fr) * | 1979-07-02 | 1984-08-21 | Richard H. Biddulph | Cellule de reduction de l'alumine, avec cathode au carbone et surface de diborure de titane |
CH643600A5 (de) * | 1979-12-05 | 1984-06-15 | Alusuisse | Elektrolysezelle zur herstellung von aluminium. |
GB2069530B (en) * | 1980-01-28 | 1984-05-16 | Diamond Shamrock Corp | Packed cathode bed for electrowinning metals from fused salts |
US4349427A (en) * | 1980-06-23 | 1982-09-14 | Kaiser Aluminum & Chemical Corporation | Aluminum reduction cell electrode |
US4308115A (en) * | 1980-08-15 | 1981-12-29 | Aluminum Company Of America | Method of producing aluminum using graphite cathode coated with refractory hard metal |
-
1983
- 1983-05-09 EP EP83810197A patent/EP0094353B1/fr not_active Expired
- 1983-05-09 AT AT83810197T patent/ATE32107T1/de not_active IP Right Cessation
- 1983-05-09 DE DE8383810197T patent/DE3375409D1/de not_active Expired
- 1983-05-10 CA CA000427851A patent/CA1233781A/fr not_active Expired
- 1983-05-10 NO NO831651A patent/NO831651L/no unknown
- 1983-05-10 JP JP58081616A patent/JPS58207385A/ja active Pending
- 1983-05-10 AU AU14390/83A patent/AU572092B2/en not_active Ceased
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0069502A2 (fr) * | 1981-06-25 | 1983-01-12 | Alcan International Limited | Améliorations dans les cellules de réduction électrolytique |
WO1983001465A1 (fr) * | 1981-10-23 | 1983-04-28 | Alusuisse | Cathode de cellule d'electrolyse de masse en fusion pour la preparation d'aluminium |
Also Published As
Publication number | Publication date |
---|---|
CA1233781A (fr) | 1988-03-08 |
EP0094353A2 (fr) | 1983-11-16 |
DE3375409D1 (en) | 1988-02-25 |
JPS58207385A (ja) | 1983-12-02 |
AU1439083A (en) | 1983-11-17 |
EP0094353A3 (en) | 1984-03-07 |
NO831651L (no) | 1983-11-11 |
AU572092B2 (en) | 1988-05-05 |
ATE32107T1 (de) | 1988-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0094353B1 (fr) | Matériaux mouillables par l'aluminium | |
US4560448A (en) | Aluminum wettable materials for aluminum production | |
EP0072043B1 (fr) | Procédé de production d'aluminium par électrolyse | |
US5279715A (en) | Process and apparatus for low temperature electrolysis of oxides | |
US6692631B2 (en) | Carbon containing Cu-Ni-Fe anodes for electrolysis of alumina | |
RU2318924C2 (ru) | Электролизеры для получения алюминия электролизом с анодами на основе металлов | |
US4544457A (en) | Dimensionally stable drained aluminum electrowinning cathode method and apparatus | |
RU2281987C2 (ru) | Пористый керамический материал, смачиваемый алюминием | |
US5534119A (en) | Method of reducing erosion of carbon-containing components of aluminum production cells | |
EP0092525A1 (fr) | Corps de remplissage non-mouillables destinés à une cellule électrolytique pour l'obtention d'aluminium | |
EP0843745B1 (fr) | Maintien de surfaces de protection sur des cathodes en carbone dans des cellules d'extraction electrolytique d'aluminium | |
EP0096001B1 (fr) | Cathode dimensionellement stable à drainage pour l'obtention électrolytique d'aluminium, méthode et appareil pour sa fabrication | |
WO1990001078A1 (fr) | Procede et appareil de production de metaux par electrolyse | |
RU2283372C2 (ru) | Электролизер для электрохимического получения алюминия, работающий с анодами на основе металла | |
EP1608798A2 (fr) | Cellules d'extraction electrolytique de l'aluminium a anodes a base de metal | |
AU2004213650B2 (en) | Aluminium electrowinning cells with metal-based anodes | |
AU615596B2 (en) | Supersaturation plating of aluminum wettable cathode coatings during aluminum smelting in drained cathode cells | |
AU2002247933A1 (en) | Metal-based anodes for aluminum production cells | |
EP1392893A2 (fr) | Fonctionnement de cellules a extraction electrolytique d'aluminium pourvues d'anodes a base de metal | |
WO2002083990A1 (fr) | Anodes a base de metal pour des cellules de production d'aluminium | |
AU2002236142A1 (en) | Metal-based anodes for aluminium production cells | |
WO2002070786A1 (fr) | Anodes a base de metal pour cellules de production d'aluminium | |
AU2002310576A1 (en) | Operation of aluminium electrowinning cells having metal-based anodes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
17P | Request for examination filed |
Effective date: 19840830 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ELTECH SYSTEMS CORPORATION |
|
ITF | It: translation for a ep patent filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19880120 Ref country code: LI Effective date: 19880120 Ref country code: CH Effective date: 19880120 Ref country code: BE Effective date: 19880120 Ref country code: AT Effective date: 19880120 |
|
REF | Corresponds to: |
Ref document number: 32107 Country of ref document: AT Date of ref document: 19880215 Kind code of ref document: T |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19880131 |
|
REF | Corresponds to: |
Ref document number: 3375409 Country of ref document: DE Date of ref document: 19880225 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19880531 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19890509 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19900131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19900201 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |