EP2989234A1 - Cathode block having a slot with a varying depth and a filled intermediate space - Google Patents
Cathode block having a slot with a varying depth and a filled intermediate spaceInfo
- Publication number
- EP2989234A1 EP2989234A1 EP14720118.0A EP14720118A EP2989234A1 EP 2989234 A1 EP2989234 A1 EP 2989234A1 EP 14720118 A EP14720118 A EP 14720118A EP 2989234 A1 EP2989234 A1 EP 2989234A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode block
- groove
- steel
- cathode
- busbar
- 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.)
- Withdrawn
Links
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 33
- 239000010959 steel Substances 0.000 claims abstract description 33
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 229910001018 Cast iron Inorganic materials 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910001610 cryolite Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000009626 Hall-Héroult process Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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 cathode block for an aluminum electrolysis cell, its use and a cathode comprising this.
- Electrolysis cells are used, for example, for the electrolytic production of aluminum, which is usually carried out industrially by the Hall-Heroult process.
- a melt composed of alumina and cryolite is electrolyzed.
- the cryolite, Na 3 [AIF 6 ] serves to lower the melting point from 2045 ° C. for pure aluminum oxide to approximately 950 ° C. for a mixture containing cryolite, aluminum oxide and additives such as aluminum fluoride and calcium fluoride.
- the electrolytic cell used in this method has a cathode bottom, which is composed of a plurality of, for example, up to 28 adjacent cathode blocks forming the cathode.
- the spaces between the cathode blocks are usually filled with a carbon-containing ramming mass to seal the cathode against molten components of the electrolytic cell, and to compensate for mechanical stresses that occur during commissioning of the electrolysis cell.
- the cathode blocks are usually composed of a carbonaceous material, such as graphite.
- each of the cathode blocks On the undersides of the cathode blocks are usually provided in each case grooves, in each of which at least one or two bus bars are arranged, through which the current supplied via the anodes is dissipated.
- the gaps between the individual walls delimiting the grooves of the cathode blocks and the busbars are often poured with cast iron to to thereby electrically and mechanically connect the bus bars to the cathode blocks by the covering of the bus bars with cast iron produced thereby.
- layer of liquid aluminum is arranged, in particular from individual anode blocks, anode, between the and the surface of the aluminum, the electrolyte, ie the Alumina and cryolite-containing melt is located.
- the aluminum formed is deposited below the electrolyte layer due to its greater density compared to that of the electrolyte, ie as an intermediate layer between the upper side of the cathode and the electrolyte layer.
- the dissolved in the melt aluminum oxide is split by electric current flow to aluminum and oxygen. From an electrochemical point of view, the layer of liquid aluminum is the actual cathode, since aluminum ions are reduced to elemental aluminum on its surface.
- cathode will not be understood below to mean the cathode from an electrochemical point of view, ie the layer of liquid aluminum, but rather the component forming the base of the electrolytic cell, for example composed of one or more cathode blocks.
- a major disadvantage of the cathode assemblies used in the Hall-Heroult method is their relatively low wear resistance, which manifests itself by a removal of the cathode block surfaces during the electrolysis.
- the removal of the cathode block surfaces due to an inhomogeneous current distribution within the cathode blocks is not uniform over the length of the cathode blocks, but to an increased extent at the cathode block ends, so that the surfaces of the cathode blocks change after a certain electrolysis time to a W-shaped profile. Due to the uneven removal of the cathode block surfaces, the service life of the cathode blocks is limited by the locations with the greatest removal.
- a cathode block has been proposed in WO 2007/1 18510 A2, which has a greater depth in the middle in relation to the cathode block length in the center than at the cathode block ends for receiving one or more busbars.
- the busbar (s) is or are wrapped in a conventional manner with cast iron, which sheathing is done by pouring liquid cast iron in the space between the groove and the or the busbar (s).
- Such a cathode block is subject to disadvantages.
- the cathode block is comparatively large Subjected to temperature changes, which lead to expansion or shrinkage of the cast iron and the bus bar (s) relative to the cathode block. This effect of expansion or shrinkage can be enhanced by occurring temperature gradients.
- the bus bar (s) are movable in the space between the groove and the bus bar (s) both in the vertical and in the horizontal direction before pouring the molten cast iron so that they are poured of the molten cast iron and during the subsequent cooling and solidification of the cast iron can move uncontrollably in the groove, which can also lead to a non-uniform electrical contact between busbar, cast iron and cathode block. This also leads to an increased electrical resistance of the arrangement and thus to a poor energy efficiency of the electrolysis process.
- the cast iron ramming mass can also be used.
- ramming mass ramming compounds based on anthracite, graphite and any mixtures thereof can be used.
- a ramming mass based on graphite is used.
- cathode block which is suitable, in particular, for use with an aluminum electrolysis cell, with which a substantially homogeneous vertical current distribution is achieved over the cathode block length during operation of the electrolysis cell, which also has a low and, in particular, high temperature changes it also has permanently low resistivity and low contact resistance between the bus bar and the cathode block over an extended period of electrolysis, and which is stable to mechanical damage such as cracking at high temperature changes.
- a cathode block for an aluminum electrolysis cell based on carbon and / or graphite having at least one groove extending in the longitudinal direction of the cathode block, at least one of the at least one groove extending over the length of the Seen cathode block, varying depth and in the at least one groove at least one bus bar is provided, wherein the gap between the at least one bus bar and the at least one groove of varying depth limiting wall is at least partially filled with steel.
- steel and other suitable material such as other metals such as
- Copper or silver, alloys, composites of the above materials, such as steel core with copper core, composites such as metal-infiltrated graphite or carbon materials or electrically conductive materials may be used.
- metal in the above-mentioned metal-infiltrated graphite or carbon materials all metals can be considered, which have a melting point above the operating temperature of the electrolytic cell, which is about 1,000 ° C. Copper with a melting point of 1080 ° C is a preferred metal.
- the proportion of metal in the composite may be between 40 and 90 weight percent.
- the carbon in the composite may be anthracite and the graphite composite may include graphitized graphite or graphitic carbon.
- steel is used synonymously in this context for all these materials.
- a cathode assembly is created, which is due to the groove of varying depth over the length of the cathode assembly by a substantially homogeneous vertical current distribution and at the same time despite the groove of varying depth has a permanently low electrical resistance and low contact resistance between the busbar and the cathode block, and which at large Temperature changes to mechanical damage, such as cracking, is stable.
- the intermediate space is filled with steel, ie the material from which conventional busbars are made, this material behaves in the event of temperature changes and in particular also at rapid temperatures. Changes in the temperature such as the busbar, so that a net shrinkage reliably prevented and thereby a bad electrical contact in the gap is reliably prevented.
- the filling of the gap may be achieved by one or more steel packings, which may be made separately by casting, rolling, milling, or other suitable molding techniques.
- At least 50%, preferably at least 75%, more preferably at least 90%, most preferably at least 95%, most preferably at least 98%, and most preferably 100% of the gap is filled with steel.
- the steel, with which the intermediate space is at least partially filled preferably the same, from which the at least one busbar is composed.
- the thermal expansion coefficients of both materials are the same, so that mechanical stresses between the bus bar and the steel, with which the gap is at least partially filled, are reliably minimized in the heating for adjusting the operating temperature of the electrolytic cell.
- steel with a very high electrical conductivity is used here as the material for the busbars and the shaped body filling the intermediate space.
- This is characterized, for example, by a low carbon content of ⁇ 0.1%, a silicon content of ⁇ 0.1% and a phosphorus content of ⁇ 0.05%.
- at least 50%, preferably at least 75%, more preferably at least 90%, most preferably at least 95%, and most preferably at least 98% of the space is filled with steel and is between the steel and the at least one groove with varying depth limiting wall provided cast iron.
- the cast iron achieves a good mechanical connection of the steel, with which the intermediate space is at least partially filled, and the at least one bus bar with the cathode block of the cathode arrangement, wherein at least 50%, and preferably, due to the steel, with which the intermediate space At least 90% is filled, comparatively small amounts of cast iron are needed, so that the disadvantages described above in terms of filling the gap completely made of cast iron, at least as far as possible.
- at least 50%, preferably at least 75%, and more preferably at least 90% of the space is filled with steel, wherein between the bus bar and the wall defining the at least one groove of varying depth, one or more plates or balls Steel are provided.
- At least one of the at least one groove and preferably all of the grooves of varying depth have or have a smaller depth at their longitudinal ends than in their middle (s).
- a uniform distribution of the electric current supplied in the electrolysis operation is achieved over the entire length of the cathode block, whereby an excessive electric current density at the longitudinal ends of the cathode block and thus premature wear at the ends of the cathode block is avoided.
- each of the at least one groove has an at least substantially perpendicular rectangular, preferably rectangular, cross-section.
- the at least one bus bar is at least substantially parallelepiped-shaped or barren-shaped, preferably parallelepiped-shaped or barren-shaped.
- the cathode block according to the invention is obtainable thereby and is particularly preferably obtained by providing a cathode block with at least one groove, which has a varying depth over the length of the cathode block, into which at least one groove at least a preferably bar renförmigen busbar is used, the gap between the at least one busbar and the at least one groove of varying depth limiting wall is at least partially filled with one or more moldings made of steel.
- the gap such as at least 50%, preferably at least 75% and more preferably at least 90% of the gap, are filled with one or more moldings made of steel, and between these and the at least one groove with varying the depth-limiting wall of the cathode block cast iron melt is introduced and the molten cast iron is allowed to solidify.
- Another object of the present invention is a cathode assembly comprising at least one previously described cathode block.
- the present invention relates to the use of a previously described cathode arrangement for carrying out a fused-salt electrolysis for the production of metal, preferably for the production of aluminum.
- Fig. 1 is a longitudinal section of a cathode assembly according to an embodiment of the present invention.
- Fig. 1 shows a cathode assembly 12 'according to an embodiment of the present invention shown in longitudinal section, standing upside down.
- the cathode assembly 12 ' includes a cathode block 20, in the bottom of which a groove 26 is provided whose depth varies along the length of the groove 26, such that the groove 26 has a smaller depth at its longitudinal ends than at its center.
- the difference between the groove depth at the longitudinal ends of the groove 26 and in the center of the groove 26 in the present embodiment is about 5 cm, with respect to the longitudinal direction of the cathode block.
- the depth of the groove 26 at the two longitudinal ends of the groove 26 is about 16 cm, whereas the depth of the groove 26 in the - relative to the longitudinal direction of the cathode block - center of the groove 26 is about 21 cm.
- the width 44 each groove 26 is substantially constant over the entire groove length and is about 15 cm, whereas the width 46 of the cathode blocks 20 is about 42 cm each.
- a barrenformig trained and a rectangular longitudinal section having bus bar 28 is arranged, wherein between the busbar 28 and the groove bottom 34 to the middle of the groove 26 toward increasing interspace 56 consists.
- this intermediate space 56 is filled at least partially and in the case shown in FIG. 1 completely with steel, specifically with the same steel from which the bus bar 28 is made.
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)
- Tires In General (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102013207738.6A DE102013207738A1 (en) | 2013-04-26 | 2013-04-26 | Cathode block with a groove of varying depth and filled gap |
PCT/EP2014/058554 WO2014174108A1 (en) | 2013-04-26 | 2014-04-28 | Cathode block having a slot with a varying depth and a filled intermediate space |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2989234A1 true EP2989234A1 (en) | 2016-03-02 |
Family
ID=50624578
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14720118.0A Withdrawn EP2989234A1 (en) | 2013-04-26 | 2014-04-28 | Cathode block having a slot with a varying depth and a filled intermediate space |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP2989234A1 (en) |
JP (1) | JP6612737B2 (en) |
CN (1) | CN105247110A (en) |
CA (1) | CA2910088C (en) |
DE (1) | DE102013207738A1 (en) |
RU (1) | RU2642815C2 (en) |
UA (1) | UA118349C2 (en) |
WO (1) | WO2014174108A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2017302066B2 (en) * | 2016-07-26 | 2020-07-09 | Tokai Cobex Gmbh | Cathode assembly for the production of aluminum |
GB2595460A (en) * | 2020-05-26 | 2021-12-01 | Dubai Aluminium Pjsc | Cathode assembly with metallic collector bar systems for electrolytic cell suitable for the Hall-Héroult process |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012027809A1 (en) * | 2010-09-03 | 2012-03-08 | Incotep Indústria E Comércio De Tubos Especiais De Precisão Ltda. | Low-carbon steel composition for the purpose of electrical conduction in electrolytic reduction cells and the like |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2318244A1 (en) * | 1975-07-17 | 1977-02-11 | Savoie Electrodes Refactaires | PROCESS FOR JOINING METAL BARS WITH CARBON BLOCKS |
JPS55141587A (en) * | 1979-04-24 | 1980-11-05 | Nikkei Giken:Kk | Jointing method of current-collecting bar to cathode carbon block of aluminum electrolysis furnace |
GB8331769D0 (en) * | 1983-11-29 | 1984-01-04 | Alcan Int Ltd | Aluminium reduction cells |
RU2060303C1 (en) * | 1994-02-05 | 1996-05-20 | Акционерное общество открытого типа "Братский алюминиевый завод" | Hearth section of aluminum electrolyzer |
CA2199288C (en) * | 1994-09-08 | 2008-06-17 | Vittorio De Nora | Aluminium electrowinning cell with improved carbon cathode blocks |
JP3806653B2 (en) * | 2002-02-06 | 2006-08-09 | 株式会社神戸製鋼所 | Steel for electrical parts excellent in cold forgeability and electrical conductivity, electrical parts excellent in electrical conductivity, and manufacturing method thereof |
RU2303654C2 (en) * | 2005-10-07 | 2007-07-27 | Общество с ограниченной ответственностью "Русская инжиниринговая компания" | Mounting method for cathode section |
ATE500356T1 (en) * | 2006-04-13 | 2011-03-15 | Sgl Carbon Se | CATHODE FOR ALUMINUM ELECTROLYSIS WITH NON-FLAT GROOVE DESIGN |
DE102010039638B4 (en) * | 2010-08-23 | 2015-11-19 | Sgl Carbon Se | Cathode, apparatus for aluminum extraction and use of the cathode in aluminum production |
DE102010041082A1 (en) * | 2010-09-20 | 2012-03-22 | Sgl Carbon Se | Cathode for electrolysis cells |
DE102011004011A1 (en) * | 2011-02-11 | 2012-08-16 | Sgl Carbon Se | Cathode assembly having a surface profiled cathode block with a graphite foil-lined groove of variable depth |
-
2013
- 2013-04-26 DE DE102013207738.6A patent/DE102013207738A1/en not_active Withdrawn
-
2014
- 2014-04-28 CN CN201480023606.5A patent/CN105247110A/en active Pending
- 2014-04-28 EP EP14720118.0A patent/EP2989234A1/en not_active Withdrawn
- 2014-04-28 JP JP2016509497A patent/JP6612737B2/en active Active
- 2014-04-28 RU RU2015150377A patent/RU2642815C2/en active
- 2014-04-28 WO PCT/EP2014/058554 patent/WO2014174108A1/en active Application Filing
- 2014-04-28 UA UAA201511662A patent/UA118349C2/en unknown
- 2014-04-28 CA CA2910088A patent/CA2910088C/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012027809A1 (en) * | 2010-09-03 | 2012-03-08 | Incotep Indústria E Comércio De Tubos Especiais De Precisão Ltda. | Low-carbon steel composition for the purpose of electrical conduction in electrolytic reduction cells and the like |
Non-Patent Citations (1)
Title |
---|
See also references of WO2014174108A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102013207738A1 (en) | 2014-10-30 |
RU2015150377A (en) | 2017-06-02 |
CA2910088A1 (en) | 2014-10-30 |
CN105247110A (en) | 2016-01-13 |
JP2016520720A (en) | 2016-07-14 |
JP6612737B2 (en) | 2019-11-27 |
RU2642815C2 (en) | 2018-01-26 |
UA118349C2 (en) | 2019-01-10 |
WO2014174108A1 (en) | 2014-10-30 |
CA2910088C (en) | 2018-01-23 |
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