EP3571333B1 - Kathodenanordnung mit metallischer sammelschiene für eine elektrolysezelle, die für den hall-héroult-prozess geeignet ist - Google Patents

Kathodenanordnung mit metallischer sammelschiene für eine elektrolysezelle, die für den hall-héroult-prozess geeignet ist Download PDF

Info

Publication number
EP3571333B1
EP3571333B1 EP18741304.2A EP18741304A EP3571333B1 EP 3571333 B1 EP3571333 B1 EP 3571333B1 EP 18741304 A EP18741304 A EP 18741304A EP 3571333 B1 EP3571333 B1 EP 3571333B1
Authority
EP
European Patent Office
Prior art keywords
bar
slot
cathode
side wall
wall
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.)
Active
Application number
EP18741304.2A
Other languages
English (en)
French (fr)
Other versions
EP3571333A1 (de
EP3571333A4 (de
Inventor
Bernard JONQUA
Mustafa MUSTAFA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dubai Aluminium PJSC
Original Assignee
Dubai Aluminium PJSC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dubai Aluminium PJSC filed Critical Dubai Aluminium PJSC
Priority to PL18741304T priority Critical patent/PL3571333T3/pl
Publication of EP3571333A1 publication Critical patent/EP3571333A1/de
Publication of EP3571333A4 publication Critical patent/EP3571333A4/de
Application granted granted Critical
Publication of EP3571333B1 publication Critical patent/EP3571333B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • 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

Definitions

  • the invention relates to the field of fused salt electrolysis using the Hall-Heroult process for making aluminium. More specifically it relates to the improvement of the cathode blocks of such an electrolysis cell, the improvement being related to the cathode drop and the current distribution along the cathode blocks. In particular, the invention relates to an improvement for cathode block provided with a cathode collector bar.
  • the Hall-Héroult process is the only continuous industrial process for producing metallic aluminium from aluminium oxide.
  • Aluminium oxide Al 2 O 3
  • molten cryolite Na 3 AlF 6
  • the resulting mixture typically at a temperature comprised between 940 °C and 970 °C acts as a liquid electrolyte in an electrolytic cell.
  • An electrolytic cell used for the Hall-Heroult process typically comprises a steel shell (so-called pot shell), a lining (comprising refractory bricks protecting said steel shell against heat, and cathode blocks usually made from graphite, anthracite or a mixture of both), and a plurality of anodes (usually made from carbon) that plunge into the liquid electrolyte contained in the volume defined by the cathode bottom and a side lining made from carbonaceous material.
  • Anodes and cathodes are connected to external busbars.
  • An electrical current is passed through the cell (typically at a voltage between 3.5 V and 5 V) which electrochemically reduces the aluminium oxide, split in the electrolyte into aluminium and oxygen ions, then into aluminium at the cathode and oxygen at the anode; said oxygen reacting with the carbon of the anode to form carbon dioxide.
  • the resulting metallic aluminium is not miscible with the liquid electrolyte, has a higher density than the liquid electrolyte and will thus accumulate as a liquid metal pad on the cathode surface below the electrolyte from where it needs to be removed from time to time, usually by suction into a crucible.
  • Industrial electrolytic cells used for the Hall-Heroult process are generally rectangular in shape and connected electrically in series, the ends of the series being connected to the positive and negative poles of an electrical rectification and control substation.
  • the general outline of these cells is known to a person skilled in the art and will not be repeated here in detail. They have a length usually comprised between 8 and 25 meters and a width usually comprised between 3 and 5 meters.
  • the cells also called “pots” are always operated in series of several tens (up to several hundreds) of pots (such a series being also called a "potline”); within each series DC currents flow from one cell to the neighbouring cell.
  • the electrical currents in most modern electrolytic cells using the Hall-Héroult process exceed 200 kA and can reach 400 kA, 450 kA or even more; in these potlines the pots are arranged side by side. Most newly installed pots operate at a current comprised between about 350 kA and 600 kA, and more often in the order of 400 kA to 500 kA. The passage of these enormous current intensities through the electrolytic cell leads to ohmic losses at various locations of the pot and its environment.
  • Cathode assemblies for use in electrolytic cells suitable for the Hall-Heroult process are industrially manufactured for more than a century, and the state of the art is summarized in the reference book " Cathodes in Aluminium Electrolysis” by M. S ⁇ rlie and H. ⁇ ye, 3rd edition (Düsseldorf 2010 ). They comprise a cathode body made from a carbon material and one or more metallic cathode bars that are fitted into slots or grooves machined into the lower surface of said carbon body. Said metallic cathode bar protrudes out of each end of the cathode block, thereby allowing to connect the cathode assembly to the cathode busbar system.
  • the metallic cathode bar is usually mode from steel; copper inserts within the steel bar can be used in order to increase the electrical conductivity of the cathode bar.
  • Said steel bars are inserted into grooves that are wider than the steel bars, and then fixed with electrically conductive glue (carbonaceous glue or cement, or ramming paste) or with cast iron that is poured into the interstitial space between the steel bar and the carbon body, as described in GB 663 763 (assigned to Compagnie de Produits Chimiques et Electrométallurgiques Alais, Froges & Camargue).
  • a cathode with a full copper cathode bar inlaid into a groove machined in the lower surface of the carbon body is known from WO 2016/079605 (Kan Nak s.a.), in particular figures 7 and 9 of said document.
  • the contact between the carbon body and the copper bar is critical for the electrical performance of the electrolysis cell. Copper has a much higher thermal expansion coefficient than the carbon material of the cathode block body, and the copper bar in direct contact with the carbon body will operate at a temperature that is probably less than 100°C lower than its melting point, leading to significant thermal expansion. As a consequence, a well-defined allowance for thermal expansion must be groove is required in order to ensure a good and reliable electrical contact between the copper bar and the carbon body over the whole length.
  • Reliability of this contact is of paramount importance, because once installed into a cell and the cell started, a cathode block cannot be repaired, and cannot be replaced without relining of the whole cell.
  • the normal lifetime of a cathode lining is comprised between five and seven years.
  • the problem addressed by the present invention is therefore to improve the quality and reliability of the electrical contact of metallic bars, in particular copper bars, inserted into grooves machined into the carbon body of a cathode block.
  • a first object of the invention is a cathode assembly suitable for a Hall-Heroult electrolysis cell, comprising
  • said cathode assembly is provided with fixation means, in particular permanent fixation means, between said tapered walls of said bar elements.
  • fixation means are advantageously welding means.
  • said welding means comprise at least one welding line, in particular several welding lines, extending over at least part of said contact line.
  • said cathode body is provided with at least one first and one second slots, each slot being provided with a blind wall defining a longitudinal end of said slot, each slot receiving a respective cathode bar.
  • said cathode bar is jammed against said longitudinal end of a respective slot.
  • one first bar element has a triangular shape and comprises a front wall, said main side wall and said tapered wall.
  • one second bar element comprises a further side wall, opposite to main side wall, said further side wall protruding with respect to main side wall of first bar element, along a transversal direction of said slot.
  • said front wall of first bar element is positioned against longitudinal end of said slot, and said second bar element comprises a front wall, the length of which is far inferior to that of front wall of first bar element, front wall of second bar element being remote from end of said slot.
  • said cathode bar has two portions, i.e. a first portion the width of which is equal to that of slot, as well as a second portion the width of which is superior to that of slot.
  • said cathode bar has a protrusion which extends outside said slot.
  • Said protrusion is in particular formed by said second portion and by a fraction of said first portion.
  • main side wall of each bar element protrudes outside said slot.
  • main side wall of each bar element directly contacts a respective side wall of said slot.
  • main side wall of each bar element indirectly contacts a respective side wall of said slot, an intercalary material, in particular at least one graphite foil, being interposed between said main side wall and said respective side wall of said slot.
  • an intercalary material in particular at least one further graphite foil, may be interposed between upper wall of said slot and facing walls of bar elements.
  • said side walls of said slot and said side walls of said bar elements show a slope, the value of which is in particular of about 10 degrees, so as to retain said bar elements in the inner volume of said slot.
  • Said cathode bar is advantageously made of copper.
  • said cathode bar is made of steel.
  • Another object of the present invention is a process for making a cathode assembly as described above, comprising the steps of
  • urging forward said second bar element also provokes the jamming of said first bar element against one longitudinal end of said slot.
  • said process further comprises providing said side walls of said slot and said side walls of said bar elements with a slope, the value of which is in particular of about 10 degrees, so as to retain said bar elements in the inner volume of said slot.
  • second bar element is provided with a handling portion and said second bar is urged forward manually, by handling said handling portion.
  • bar elements are provided by cutting a rough bar along a cutting line, said cutting line being tapered with respect to main axis of said rough bar.
  • said process further comprises providing fixation means, in particular permanent fixation means, between said tapered walls of said bar elements, once said tapered walls of said bar elements are in mutual contact.
  • Another object of the present invention is an electrolytic cell suitable for the Hall-Heroult electrolysis process, comprising a cathode forming the bottom of said electrolytic cell and comprising a plurality of parallel cathode assembly, each cathode assembly comprising at least one metallic cathode collector bar protruding out of each of the two ends of the cathode, a lateral lining defining together with the cathode a volume containing the liquid electrolyte and the liquid metal resulting from the Hall-Heroult electrolysis process, an outer metallic potshell containing said cathode and lateral lining, a plurality of anode assemblies suspended above the cathode, each anode assembly comprising at least one anode and at least one metallic anode rod connected to an anode beam, a cathodic bus bar surrounding said potshell, said bus bar being connected to at least part of said cathode assemblies said electrolytic cell being characterized in that at least one of said cathode assembly, and preferably more than 60%
  • Another object of the present invention is an electrolytic cell for the production of aluminium by the Hall-Heroult process, comprising at least one cathode assembly as described above.
  • Another object of the present invention is a process for making aluminium by the Hall-Héroult process, using an electrolytic cell provided with cathode assemblies as described above.
  • C Cathode assembly 1 Cathode body 11,12 Front/rear wall of cathode body 1 171, 172 Side walls of slot 17 13,14 Upper/lower wall of cathode body 1 173 Top wall of slot 17,17' 15,16 Side walls of cathode body 1 174,174' Blind wall of slot 17,17' 17, 17' Slots in cathode body 1 D174 Distance between 174 174' 3,3' Cathode bar 31,32 Front/rear wall of cathode bar 3 33,34 Side walls of cathode bar 3 37 Contact line of 3 5 Rough bar 51,52 Front / rear wall of rough bar 5 53,54 Upper / lower wall of rough bar 5 55,56 Side walls of rough bar 5 A5 Axis of rough bar 5 CL Cutting line L6 Length of slotted bar ⁇ s Angle of slotted bar ⁇ c Angle between A5 and CL A17,A17' Axis of slots 17, 17' 7, 9 Bar elements 9A Handling part of 9 9B Tip
  • a cathode assembly comprises a cathode body 1 and at least one cathode bar 3 .
  • the present invention is first applicable to cathode assemblies C comprising a cathode body 1 and at least one cathode bar 3 and 3'.
  • the invention is applicable to cathode assemblies comprising two cathode bars 3 , 3' , one 3 of which is protruding out of the front wall 11 , the other 3' protruding out of the rear wall 12 of the cathode body 1.
  • These cathode bars which are half bars, form two portions of a so-called "split bar” in the sense that they are not through bars, i.e. each cathode bar is not extending through the whole length of the cathode block.
  • the present invention is also applicable to cathode assemblies having one (or more) through bar(s) instead of above defined split bars.
  • the invention applies in particular to such through bars, which have a short length.
  • split bars is preferred, since it allows a better jamming of these bars, as will appear at reading the following description.
  • the present invention applies to cathodes used in the Hall-Heroult process that form the bottom of an electrolysis cell, said cathodes being assembled from individual cathode assemblies C , each of which bears at least one cathode bar 3 , 3'.
  • the Hall-Heroult process and the outline of an electrolysis cell (also called “pot") are known to a person skilled in the art and will not be described here in great detail.
  • the cathode assembly of the invention is designated as a whole by alphanumeric reference C. It is suitable for a Hall-Heroult electrolysis cell, but could be used in other electrolytic processes.
  • the cathode assembly C first comprises a cathode body 1 , of known type, which is made of a carbonaceous material, typically graphitized carbon or graphite.
  • This cathode body 1 which has an elongated shape, has opposite end walls, i.e. front 11 and rear 12 walls, as well as peripheral walls. The latter are formed by parallel upper and lower walls 13 and 14 , as well as parallel side walls 15 and 16.
  • its length L1 (see figure 3 ), i.e. the distance between walls 11 and 12 , is between about 3100 millimetres (mm) and about 4000 mm.
  • its width W1 see figure 2 ), i.e.
  • the distance between walls 15 and 16 is between about 400 mm and about 700 mm.
  • its height H1 (see figure 3 ) , i.e. the distance between walls 13 and 14 , is between about 375 mm and about580 mm.
  • the lower wall 14 of cathode body 1 is provided with two housings, each being formed by a respective longitudinal slot 17 and 17' , the longitudinal main axis of which is referenced A17 , A17'.
  • Figure 2 shows cathode body "upside down", with reference to its above defined industrial use position.
  • Each slot 17 , 17' is provided with opposite side walls 171 , 171' and 172 , 172' (see figure 2 ), parallel to said main axis A17 , A17' , whereas its top wall is referenced 173 , 173' (see figure 3 ).
  • each slot 17 , 17' is provided with a respective rear wall, or blind wall 174 , 174' (see figure 2 ), each defining a respective longitudinal end of said slot.
  • the distance D174 (see figure 3 ) between these two walls is typically between 200 millimetres (mm) and 600 mm. Viewed from bottom, blind wall 174 , 174' is rounded, which makes it possible to ease the slot machining.
  • First slot 17 does lead to front wall 11 of this cathode body, whereas second slot 17' does lead to rear wall 12 of this cathode body.
  • width W17 or W17' (see figure 2 ) of each slot 17 , 17 ', i.e. the distance between side walls, is between about 50 mm and about 250 mm.
  • each side wall 171 and 172 shows a slope, the value as of which is typically of about 10 degrees. Therefore the above defined width W17 or W17' decreases from top wall 173 , 173' of this slot to lower wall 14 of cathode body. As will be described hereafter, these slopes make it possible to maintain the bar elements in the inner volume of the slot, when turning over the cathode assemblies. For sake of clarity, the value of as is exaggerated on this figure 11 .
  • depth D17 or D17' of each slot 17, 17' is between about 50 mm and about 150 mm.
  • its length L17 or L17' is between about 1200 mm and about 1850 mm. This length is taken from the junction of rounded portion of said blind wall with rectilinear part of side walls 171 , 171' and 172, 172'.
  • the cathode assembly C also comprises two cathode bars 3 and 3' (schematically shown on figure 1 ), each of which is accommodated in a respective slot 17 and 17'.
  • Each cathode bar 3 or 3' is made of a conductive material, typically able to conduct the current from the cathode to the exterior Bus Bar.
  • the material of these cathode bars is copper.
  • the invention encompasses cathode bars made of other materials, such as for example steel, or other materials usually installed inside the cathode assemblies.
  • the first step of said insertion process is the provision of a so called rough bar, which is shown on figure 5 and is referenced 5 as a whole.
  • the dimensions of said rough bar 5 are globally analogous to those of final cathode bar 3, but slightly different.
  • This bar 5, which has an elongated shape, is not shown with its real scale on figure 4 , in order to clearly illustrate the insertion process.
  • the same remark applies to mechanical elements of figures 5 to 10 : slot 17, cathode bar 3 and bar elements 7 and 9, formed from rough bar 5.
  • the width of these mechanical elements is far exaggerated with respect to their length.
  • top views of figures 6 to 10 have been hatched to clearly distinguish the different mechanical elements.
  • Rough bar 5 has front 51 and rear 52 walls, parallel upper and lower walls 53 and 54 , as well as parallel side walls 55 and 56. Respective length L5 , width W5 and height H5 of rough bar 5 are defined the same way as above length L1, width W1 and height H1 of cathode body 1 .
  • Length L5 of rough bar is far superior to that L17 of slot 17 , so that final cathode bar 3 will protrude outside slot 17, above front wall 11.
  • the value of the difference ( L5 - L17 ) implies the length of the protrusion of final cathode bar 3.
  • this difference ( L5 - L17 ) is between 400 and 700 mm.
  • Side walls 55 and 56 show slopes, the angle of which is similar to that aS of the side walls of the slot.
  • the lengths of slotted parts of these side walls are referred L6 and L6' on figure 4 . Both L6 and L6' are superior to the length L17 of the cathode slot.
  • the difference (L6 - L17) or (L6' - L17) is between 150 and 200 mm.
  • width W5 of rough bar 5 is slightly superior to that W17 of slot 17 , which enables a steady jamming of final cathode bar 3 in the slot 17 .
  • the difference ( W5 - W17 ) is between 5 to 10 mm.
  • height H5 of rough bar 5 is equal or slightly inferior to depth D17 of cathode slot, so as to prevent final cathode bar from protruding outside the slot 17 , above lower wall 14.
  • the difference ( D17 - H5 ) is between 0 and 4 mm.
  • the insertion process then implies cutting rough bar 5, so as to form two cathode bar elements, or so called bar elements 7 and 9.
  • Rough bar 5 is cut along a cutting line referenced CL, shown on figure 4 .
  • This line CL forms an angle, noted ac, with the main longitudinal axis A5 of rough bar 5.
  • this angle ac is between 1° and 4°, typically of about 2°.
  • the cutting operation can be carried out by water jet cutting following a machining of the two surfaces, since the cut cannot be straight and the roughness will not be good enough to get a good contact between the two parts.
  • Another way is cutting the two parts directly by machining using a circular cutting blade, typically of 3 to 6 mm of thickness. The latest way is preferred, since the cutting surface will present a good roughness and machining the cut surfaces will therefore not be necessary.
  • first bar element 7 has a triangular shape. It has a front wall 71 , a main side wall 73 , as well as a tapered wall 77. It has neither a rear wall, nor a second side wall, since wall 77 directly connects both walls 71 and 73. Side wall 73 shows a slope, which corresponds to that of side wall 55 of rough bar 5.
  • Width W7 is inferior to that W5 of rough bar 5, and is also slightly inferior to that W17 of the slot, so as to enable an insertion without jamming of said bar element 7 into slot 17 .
  • the difference ( W17 - W7 ) is between 10 and 40 mm.
  • Length L7 is far inferior to that L5 of rough bar 5, but is slightly superior to that L17 of slot, so as to enable a protrusion of said bar element 7 outside slot 17.
  • the difference ( L7 - L17 ) is between 20 and 100 mm.
  • height H7 of bar element 7 is equal to that H5 of rough bar 5.
  • second bar element 9 has a shape which is different from a triangle. It has a short front wall 91 , a long rear wall 92 , a main side wall 93, a short side wall 94, as well as a tapered wall 97. Side wall 93 shows a slope, which corresponds to that of side wall 56 of rough bar 5.
  • This second bar element can therefore be divided into two parts, namely a handling part 9A with constant width, as well as an insertion part or tip 9B , with a tapered shape.
  • Tip 9B is ended by a shoulder 9C , formed adjacent front wall 91 , which eases the jamming of bars 7 and 9 into the slot.
  • the respective dimensions of above defined walls and parts of bar element 9 are as follows:
  • first bar element 7 is inserted into slot 17. It is to be noted that this step is carried out with a cathode block upside down. In other words, during said insertion, access to slot 17 is permitted from the end of the cathode block groove, whereas so called lower wall of cathode body is in an upper position.
  • bar element 7 rests by gravity against wall 173 of this slot. Since W7 is inferior to W17 of slot, this insertion can be carried out easily, without jamming of said bar element 7 into slot 17.
  • Bar element 7 is positioned in the slot, so that its front wall 71 is close to the end of the slot, and its main side wall 73 is adjacent side wall 172 of the slot. End of the slot is defined by the transition between rectilinear side walls 171 , 172 and rounded wall 174.
  • main side wall 73 of first bar element 7 is urged against facing side wall 172 of slot 17 , along arrow F73
  • main side wall 93 of second bar element 9 is urged against facing opposite side wall 171 of slot 17, along arrow F93.
  • At least one and, preferably several welding lines are provided along the above defined contact line 37.
  • four welding lines 21 to 24 are provided.
  • L21 to L24 the length of each of these lines, as well as Lw the so called welding length, which corresponds to the sum ( L21 + L22 +L23 + L24 ) of the lengths of these lines.
  • Each of L21 to L24 is typically between 50 and 100 mm, whereas the welding ratio, i.e ( Lw / L37 ) is between 10 and 40 %.
  • Said global cathode bar has front 31 and rear 32 walls, as well as side walls 33 and 34.
  • Said figure 8 also illustrates above described tapered line 37 , separating walls 77 and 97 of bar elements 7 and 9.
  • First, rear wall 32 and side wall 34 are respectively constituted by those 92 and 94 of bar element 9.
  • front wall 31 is formed by front wall 71 and front wall 91, as well as by a linking portion 77' of tapered wall 77.
  • Front wall 91 is remote from end of slot, whereas front wall 71 is positioned against said end, as explained above.
  • side wall 33 is formed by side wall 73 and side wall 93 , as well as by a linking portion 97' of tapered wall 97.
  • Side wall 93 protrudes laterally, with respect to side wall 73 .
  • Cathode can be decomposed into two portions, i.e. a first portion 3A the width of which W3A is equal to that W17 of slot 17 , as well as a second portion 3B the width of which W3B is equal to that W5 of rough bar 5 .
  • This cathode defines a protrusion 3C , which extends outside slot 17 .
  • This protrusion which is formed by portion 3B as well as by a fraction of portion 3A, has a typical length L3C between 400 and 700 mm.
  • cathode bars 3 and 3' are positioned and jammed in their respective slot 17 and 17', the whole cathode assembly is turned upside down, so as to be in its final position of figure 1 . Due to the slopes of side walls of both the slots and the bar elements, as above described in reference to figure 11 , cathode bars cannot escape from their slots due to gravity, so that they are firmly retained therein.
  • each side wall of cathode bar 3 directly contacts facing side walls of the slot 17 , i.e. without any intercalary material.
  • the invention also encompasses alternative embodiments, wherein side walls of cathode bar indirectly contacts facing side walls of the slot. In this respect, a thin sheet of an intercalary material is interposed between said facing walls of slot and cathode bar.
  • said intercalary material is a graphite foil, inserted between said facing side walls.
  • This graphite foil is typically placed against the side walls of the slot, before insertion of bar elements.
  • a further intercalary material, in particular at least one further graphite foil, may also be interposed between upper wall 173 of said slot and facing walls of the bar elements 7 and 9.
  • one single intercalary graphite foil may recover both side walls and upper wall of the slot. The adjustment will be set, so that no substantial gap or space is left between bar elements, graphite foil and cathode body.
  • Said graphite foil can be a flexible graphite foil of compressed expanded graphite.
  • Said foil is available from various suppliers under different trademarks, such as PAPYEX® by MERSEN.
  • the density of the foil is typically 0.7 and it may have 0.5 mm of thickness.
  • graphite material is compressible to cope with the thermal expansion of bar elements.
  • the selected electrolysis cell was provided with new cathode blocks; seventeen cathode assemblies were used, and the assembly n° 2,7,11, and 16 had copper cathode bars according to the invention, whereas the other ones were provided with conventional steel cathode bars.
  • Cathode assemblies n° 2 and 7 had a sheet of graphite foil between the cathode bar and the cathode block, whereas assemblies n° 11 and 16 had a direct contact between the copper cathode bar and the cathode material. All cathode bars were half bars. Contact tabs were made from copper.
  • the cell was started up according to conventional practice and run for about 3.5 months under production conditions (211 kA). Its overall performance was slightly better than that of the other cells with 100 % conventional cathode assemblies: as an example, compared to conventional D18 cells of the same potline, the average net voltage was slightly lower (60 mV), the aluminium purity was identical (99.873 %), aluminium production was slightly higher, specific energy consumption was lower (approximately 300 kW/h per ton), bath height and metal height as well as bath temperature (958 °C) were comparable, cell stability was comparable, base resistance set point and cathode voltage drop were slightly lower (approximately 20 mV).
  • cathode assemblies with copper bars according to the invention were pulling about 40 % more current than cathode assemblies with steel bars in the same cell. This demonstrates that a significant gain can be obtained by constructing a pot equipped with all cathodes having full copper bars. At the beginning of the operations, a small difference was observed between copper cathode bars in direct contact with the cathode block and copper cathodes bars with an intercalary graphite foil, giving the benefit to the latest.
  • the cell was then autopsied; the copper bars could be easily cut out, and it was found that for each half bar the two bar elements were firmly welded together at their tapered interface and did not separate upon removal. This shows that the electrical contact at the tapered interface between the two bar elements was excellent. No melting of the copper bar was observed, no significant visual change was observed. Slight remains of graphite foil were visible on the collector bar side for the two bars that had been in contact with graphite foil. The copper could be fully recovered for recycling.

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)

Claims (15)

  1. Kathodenanordnung (C), die für eine Hall-Heroult-Elektrolysezelle geeignet ist, umfassend
    - einen Kathodenkörper (1), der aus einem kohlenstoffhaltigen Material besteht, wobei der Kathodenkörper mit mindestens einem Schlitz (17, 17') versehen ist, wobei der Schlitz mit Seitenwänden (171, 172, 171', 172') versehen ist, die zu einer Längsrichtung (A17, A17') des Schlitzes parallel verlaufen;
    - mindestens eine Kathodenkollektorstange (3, 3'), die aus einem metallischen Material besteht, wobei die Kathodenstange mit Seitenwänden (33, 34) versehen ist, die sich mit den Seitenwänden des Schlitzes in Berührung befinden;
    dadurch gekennzeichnet, dass die Kathodenstange zwei Stangenelemente (7, 9) umfasst, wobei jedes Stangenelement mit einer Hauptseitenwand (73, 93), die sich mit einer jeweiligen Seitenwand (171, 172) des Schlitzes in Berührung befindet, sowie einer schrägen Wand (77, 97) versehen ist, wobei die zwei schrägen Wände der Stangenelemente eine Berührungslinie (37) zwischen diesen zwei Stangenelementen bilden.
  2. Kathodenanordnung nach Anspruch 1, dadurch gekennzeichnet, dass sie mit Befestigungsmitteln, insbesondere dauerhaften Befestigungsmitteln (21-24), wie etwa Verschweißungsmitteln, zwischen den schrägen Wänden (77, 97) der Stangenelemente (7, 9) versehen ist.
  3. Kathodenanordnung nach Anspruch 2, dadurch gekennzeichnet, dass die Verschweißungsmittel mindestens eine Schweißnaht, insbesondere mehrere Schweißnähte (21-24) umfassen, die sich über mindestens einen Teil der Berührungslinie (37) erstrecken.
  4. Kathodenanordnung nach einem obigen Anspruch, dadurch gekennzeichnet, dass ein erstes Stangenelement (7) eine dreieckige Form aufweist und eine Vorderwand (71), die Hauptseitenwand (73) und die schräge Wand (77) umfasst.
  5. Kathodenanordnung nach einem obigen Anspruch, dadurch gekennzeichnet, dass ein zweites Stangenelement (9) Hauptseitenwand (93) gegenüberliegend eine weitere Seitenwand (94) umfasst, wobei die weitere Seitenwand in Bezug auf Hauptseitenwand (73) des ersten Stangenelements (7) entlang einer Querrichtung des Schlitzes übersteht.
  6. Kathodenanordnung nach einem obigen Anspruch, dadurch gekennzeichnet, dass die Kathodenstange (3) zwei Abschnitte aufweist, d. h. einen ersten Abschnitt (3A), dessen Breite (W3A) gleich der von Schlitz (17) ist, sowie einen zweiten Abschnitt (3B), dessen Breite (W3B) größer als die des Schlitzes ist.
  7. Kathodenanordnung nach Anspruch 6, dadurch gekennzeichnet, dass die Kathodenstange einen Überstand (3C) aufweist, der sich außerhalb des Schlitzes (17) erstreckt.
  8. Kathodenanordnung nach Anspruch 7, dadurch gekennzeichnet, dass der Überstand (3C) vom zweiten Abschnitt (3C) und von einem Bruchteil des ersten Abschnitts (3A) gebildet wird.
  9. Kathodenanordnung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Hauptseitenwand jedes Stangenelements eine jeweilige Seitenwand des Schlitzes indirekt berührt, wobei ein Zwischenlagematerial, insbesondere mindestens eine Graphitfolie, zwischen der Hauptseitenwand und der jeweiligen Seitenwand des Schlitzes eingefügt ist, und gegebenenfalls ein weiteres Zwischenlagematerial, insbesondere mindestens eine weitere Graphitfolie, zwischen der oberen Wand (173) des Schlitzes und zugewandten Wänden der Stangenelemente (7, 9) eingefügt ist.
  10. Kathodenanordnung nach einem obigen Anspruch, dadurch gekennzeichnet, dass die Seitenwände (171, 171', 172, 172') des Schlitzes und die Seitenwände (73, 93) der Stangenelemente (7, 9) eine Steigung aufweisen, deren Wert (αs) insbesondere 10 Grad beträgt, um die Stangenelemente im Innenvolumen des Schlitzes zu halten.
  11. Verfahren zur Herstellung einer Kathodenanordnung (C) nach einem der obigen Ansprüche, das die Schritte umfasst des
    a) Bereitstellens eines Kathodenkörpers (1), der aus einem kohlenstoffhaltigen Material besteht;
    b) Bereitstellens mindestens eines Schlitzes (17, 17') in dem Kathodenkörper, wobei der Schlitz mit Seitenwänden (171, 171', 172, 172') versehen ist, die zu einer Längsrichtung des Schlitzes parallel verlaufen;
    c) Bereitstellens von mindestens zwei Stangenelementen (7, 9), die aus einem metallischen Material bestehen, wobei jedes Stangenelement mit einer Hauptseitenwand (73, 93) und einer schrägen Wand (77, 97) versehen ist,
    d) Anbringens eines ersten Stangenelements (7) im Schlitz, mit seiner Hauptseitenwand (73) an die zugewandte erste Seitenwand (172) des Schlitzes angrenzend;
    e) Vordrückens des zweiten Stangenelements (9) entlang der Längsrichtung des Schlitzes, um Hauptseitenwand (73) des ersten Stangenelements an die zugewandte erste Seitenwand (172) des Schlitzes zu drücken, um Hauptseitenwand (93) des zweiten Stangenelements (9) an die zugewandte, gegenüberliegende zweite Seitenwand (171) des Schlitzes zu drücken, und um die zwei schrägen Wände (77, 97) der Stangenelemente entlang einer Berührungslinie (37) in Berührung zu bringen.
  12. Verfahren nach Anspruch 11, das weiter das Versehen der Seitenwände (171, 171', 172, 172') des Schlitzes und der Seitenwände (73, 93) der Stangenelemente (7, 9) mit einer Steigung umfasst, deren Wert (αs) insbesondere 10 Grad beträgt, um die Stangenelemente im Innenvolumen des Schlitzes zu halten.
  13. Verfahren nach einem der Ansprüche 11 bis 12, wobei das zweite Stangenelement (9) mit einem Handhabungsabschnitt (9A) versehen ist, und wobei das zweite Stangenelement manuell, durch Handhaben des Handhabungsabschnitts, vorgedrückt wird.
  14. Verfahren nach einem der Ansprüche 11 bis 13, wobei die Stangenelemente durch Schneiden einer Rohstange (5) entlang einer Schnittlinie (CL) bereitgestellt werden, wobei die Schnittlinie in Bezug auf Hauptachse (A5) der Rohstange schräg verläuft.
  15. Verfahren zur Herstellung von Aluminium nach dem Hall-Heroult-Prozess unter Verwendung einer elektrolytischen Zelle, die mit Kathodenanordnungen nach einem der Ansprüche 1 bis 10 versehen ist.
EP18741304.2A 2017-01-23 2018-01-18 Kathodenanordnung mit metallischer sammelschiene für eine elektrolysezelle, die für den hall-héroult-prozess geeignet ist Active EP3571333B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL18741304T PL3571333T3 (pl) 2017-01-23 2018-01-18 Zespół katodowy z metalowym prętem kolektorowym do ogniwa elektrolitycznego odpowiedni do procesu halla-héroulta

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1701067.9A GB2558936A (en) 2017-01-23 2017-01-23 Cathode assembly with metallic collector bar for electrolytic cell suitable for the Hall-Héroult process
PCT/IB2018/050300 WO2018134754A1 (en) 2017-01-23 2018-01-18 Cathode assembly with metallic collector bar for electrolytic cell suitable for the Hall-Héroult process

Publications (3)

Publication Number Publication Date
EP3571333A1 EP3571333A1 (de) 2019-11-27
EP3571333A4 EP3571333A4 (de) 2020-09-09
EP3571333B1 true EP3571333B1 (de) 2021-08-18

Family

ID=58462950

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18741304.2A Active EP3571333B1 (de) 2017-01-23 2018-01-18 Kathodenanordnung mit metallischer sammelschiene für eine elektrolysezelle, die für den hall-héroult-prozess geeignet ist

Country Status (5)

Country Link
EP (1) EP3571333B1 (de)
CA (1) CA3049822C (de)
GB (1) GB2558936A (de)
PL (1) PL3571333T3 (de)
WO (1) WO2018134754A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2023119802A1 (ja) 2021-12-23 2023-06-29 Ｓｅｃカーボン株式会社 カソードアセンブリ
JP2024024213A (ja) * 2022-08-09 2024-02-22 Ｓｅｃカーボン株式会社 カソードアセンブリ

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1065080A (en) * 1964-06-30 1967-04-12 Reynolds Metals Co Improvements in or relating to aluminium reduction pots
US4795540A (en) * 1987-05-19 1989-01-03 Comalco Aluminum, Ltd. Slotted cathode collector bar for electrolyte reduction cell
US5976333A (en) * 1998-01-06 1999-11-02 Pate; Ray H. Collector bar
US6294067B1 (en) * 2000-03-30 2001-09-25 Alcoa Inc. 3 component cathode collector bar
US6866768B2 (en) * 2002-07-16 2005-03-15 Donald R Bradford Electrolytic cell for production of aluminum from alumina
DE10261745B3 (de) * 2002-12-30 2004-07-22 Sgl Carbon Ag Kathodensystem zur elektrolytischen Aluminiumgewinnung
CN2892888Y (zh) * 2006-03-20 2007-04-25 贵阳铝镁设计研究院 改善铝电解槽阴极电流密度的钢棒结构
DE602006020410D1 (de) * 2006-04-13 2011-04-14 Sgl Carbon Se Kathode zur Aluminiumelektrolyse mit nicht ebenen Rilledesign
EP2756114A1 (de) * 2011-09-12 2014-07-23 Alcoa Inc. Aluminiumelektrolysezelle mit verdichtungsvorrichtung und verfahren
CN202246908U (zh) * 2011-09-23 2012-05-30 高伟 铜钢复合结构阴极钢棒
GB2536901A (en) * 2015-03-30 2016-10-05 Dubai Aluminium Pjsc Cathode block for electrolytic cell suitable for the Hall-Héroult process
CN105671592B (zh) * 2016-03-14 2018-08-03 中冶天工集团有限公司 一种铝电解槽阴极钢棒等距分段的方法

Also Published As

Publication number Publication date
CA3049822A1 (en) 2018-07-26
CA3049822C (en) 2024-03-26
EP3571333A1 (de) 2019-11-27
PL3571333T3 (pl) 2021-12-27
GB2558936A (en) 2018-07-25
WO2018134754A1 (en) 2018-07-26
EP3571333A4 (de) 2020-09-09
GB201701067D0 (en) 2017-03-08

Similar Documents

Publication Publication Date Title
EP1146146B1 (de) Mit versenkten Nuten drainierte horizontale Kathodenoberfläche für die Aluminium Elektrogewinnung
US8628646B2 (en) Grooved anode for electrolysis cell
US7618519B2 (en) Cathode element for use in an electrolytic cell intended for production of aluminum
CA2347858C (en) Cathode collector bar with spacer for improved heat balance
EP3277864B1 (de) Kathodenblock für elektrolysezelle für hall-héroult-prozess
EP3571333B1 (de) Kathodenanordnung mit metallischer sammelschiene für eine elektrolysezelle, die für den hall-héroult-prozess geeignet ist
WO2008062318A2 (en) Electrolysis cell for the production of aluminium comprising means to reduce the voltage drop
US5597461A (en) Method of manufacturing an anode bar from a metal sleeve, a metal rod and a metal ring
AU755103B2 (en) Nickel-iron alloy-based anodes for aluminium electrowinning cells
WO2021240353A1 (en) Cathode assembly with metallic collector bar systems for electrolytic cell suitable for the hall-héroult process
EP3523463B1 (de) Kathodenanordnung für elektrolysezelle für hall-héroult-prozess
EP3347509B1 (de) Kathodenanordnung für elektrolysezelle für hall-héroult-prozess
WO2017168310A1 (en) Cathode block with copper-aluminium insert for electrolytic cell suitable for the hall-héroult process
EP4394089A1 (de) Kathodenkollektorstab und kathodenanordnung für hall-heroult-verfahren mit geringem spannungsabfall und geringem wärmeverlust
WO2016088001A1 (en) Electrolytic pot for hall-heroult process, having a cathode formed of high and low cathode blocks
JPS5741393A (en) Electrolytic furnace for production of aluminum
US20040016639A1 (en) Interlocking wettable ceramic tiles
CA2354120C (en) Aluminium electrowinning cell with improved carbon cathode blocks
EP0613504B1 (de) Zelle für die elektrolyse von tonerde,vorzugsweise bei niedrigeren temperaturen
AU6551901A (en) Horizontal drained cathode surface with recessed grooves for aluminium electrowinning
CN114182303A (zh) 电解槽、特别是用于生产铝的电解槽

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190823

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20200810

RIC1 Information provided on ipc code assigned before grant

Ipc: C25C 3/16 20060101ALI20200804BHEP

Ipc: C25C 3/08 20060101AFI20200804BHEP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602018022075

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C25C0003060000

Ipc: C25C0003080000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C25C 3/16 20060101ALI20210409BHEP

Ipc: C25C 3/08 20060101AFI20210409BHEP

INTG Intention to grant announced

Effective date: 20210510

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018022075

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Ref country code: AT

Ref legal event code: REF

Ref document number: 1421719

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210915

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20210818

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210818

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1421719

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211118

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018022075

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

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

Effective date: 20220519

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220131

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: 20220118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20180118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210818

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20251219

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20260122

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NO

Payment date: 20260127

Year of fee payment: 9

Ref country code: DE

Payment date: 20260223

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20260123

Year of fee payment: 9

Ref country code: IS

Payment date: 20260127

Year of fee payment: 9