EP1481115A2 - Graphitierte kathodenblöcke - Google Patents
Graphitierte kathodenblöckeInfo
- Publication number
- EP1481115A2 EP1481115A2 EP02796687A EP02796687A EP1481115A2 EP 1481115 A2 EP1481115 A2 EP 1481115A2 EP 02796687 A EP02796687 A EP 02796687A EP 02796687 A EP02796687 A EP 02796687A EP 1481115 A2 EP1481115 A2 EP 1481115A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode blocks
- cathode
- parts
- blocks
- graphitized
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910001610 cryolite Inorganic materials 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000005087 graphitization Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000007704 transition Effects 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
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
Definitions
- the invention relates to graphitized cathode blocks, a process for their production and their use in particular for the electrolytic production of aluminum.
- electrolysis cells which comprise a base composed of a multiplicity of blocks, which acts as a cathode.
- the electrolyte is a melt, essentially a solution of aluminum oxide in cryolite.
- the working temperature is around 1000 ° C, for example.
- the electrolytically deposited molten aluminum collects on the bottom of the cell under a layer of the electrolyte.
- Around the cells is a metallic housing (preferably steel) with a lining made of high temperature resistant material.
- the material of the cathode blocks is preferably carbon because of the required chemical and thermal resistance, which can be partially or completely graphitized by thermal treatment.
- mixtures of pitches, cokes, anthracite and / or graphite in selected particle sizes or particle size distributions for the solids are mixed, shaped and fired and optionally (partially) graphitized.
- the firing (carbonization) usually takes place at temperatures of approx. 1200 ° C, the graphitization usually at temperatures of over 2400 ° C.
- While graphitized cathodes are preferred because of their higher electrical conductivity, they show greater wear during operation, corresponding to an average annual decrease in their thickness of up to 80 mm. This wear is not evenly distributed over the length of the cathode blocks (corresponding to the width of the cell), but changes the surface of the cathode blocks into a W-shaped profile. Due to the uneven removal, the service life of the cathode blocks is limited by the places with the greatest removal.
- One way to equalize the removal over the length of the cathode block and thus to extend the service life is to design the cathode blocks so that their electrical resistance varies over the length such that the current density (and thus the Wear) is uniform over its length or at least exhibits the smallest possible deviation over the length from its mean value.
- a solution is described in DE 20 61 263, in which composite cathodes are formed either from several carbon blocks with different electrical conductivity, which are arranged in such a way that a uniform or approximately uniform current distribution results, or from carbon blocks, the electrical resistances of which are in the direction of the cathodic Derivatives increase continuously.
- the number of carbon blocks and their electrical resistance depend on the cell size and type, they must be recalculated for each case.
- Cathode blocks made of a large number of individual carbon blocks require a great deal of effort in the construction; the joints must also be properly sealed to prevent the liquid aluminum from flowing out at the joints.
- WO 00/46426 describes a graphite cathode which consists of a single block which has an electrical conductivity which is variable over its length, the conductivity at the ends of the block being lower than in the middle. This uneven distribution of electrical conductivity is achieved, while during the graphitization the end zones are brought to a temperature of 2200 to 2500 ° C, while the other zone is exposed to a temperature of 2700 to 3000 ° C.
- This different heat treatment can be achieved according to this teaching in two ways: first, the heat dissipation in the graphitization furnace can be limited differently, or heat sinks can be introduced in the vicinity of the end zones, which increase the heat loss.
- the density of the heat-insulating bed is changed so that the heat loss becomes uneven over the length of the cathodes and the desired temperatures are thus set.
- the heat loss in the vicinity of the ends can be increased by different designs of the heat-insulating bed, or heat-dissipating bodies made of graphite, which cause a greater heat outflow to the furnace wall, are preferably introduced for this purpose.
- the difference in the heat treatment can be done by locally changing the current density, with the result of different heat development.
- the current density can be changed by different resistances of the conductive bed between two cathodes in an Acheson furnace (cross-graphing); no solution of this type is specified for a longitudinal graphitization process.
- cathode blocks are graphitized using the longitudinal graphitization method, an electrical transition with an increased resistance compared to the resistance inside the individual cathode blocks or the connecting element results at the joints between the individual cathode blocks with one another or with electrically conductive connecting elements arranged between them.
- This increased resistance leads to increased heat development and thus to a higher temperature, that is to say an acceleration of the graphitization reaction. Therefore, the electrical resistance in longitudinal graphitization at the ends of the cathode blocks is usually lower than that in the center of the cathode blocks. This distribution of the resistance or the electrical conductivity over the length of the cathode block is precisely the opposite of the desired course.
- cathode blocks with the desired course can be produced in a simple manner by placing the cathode blocks described above in the middle cut apart and reassembled in the opposite direction. This results in a profile of the electrical resistance in the form of an N. rounded on the legs.
- the present invention therefore relates to graphitized cathode blocks for the production of aluminum by electrolytic reduction of aluminum oxide in a bath of molten cryolite, characterized in that the cathode blocks are composed of at least two parts and have a V-shaped profile of their electrical resistance over their length, wherein the resistance in the center of the cathode blocks has a discontinuity and increases steadily towards the ends, such that the resistance at the ends of the parts is at least 1.05: 1 to that in the center.
- the cathode blocks are preferably composed of at least two parts, the electrical resistance of which increases continuously over their length, such that the resistance at the ends of the parts is at least 1.15: 1 in relation to that in the middle. This ratio is particularly preferably 1.3: 1.
- FIG. 2 shows a side view of a cathode block which has been separated and reversed in the middle, a connecting layer of ramming mass being introduced in the middle,
- Fig. 3 is a side view of a cathode block which has been separated in the middle and reversed '' ', with an adhesive joint connecting the two parts in the middle
- Fig. 4 is a side view of a cathode block separated in the middle and assembled in reverse, the two parts being merely flush with one another.
- FIG. 1 shows the course of the specific electrical resistance p shown in the interior of the side view of a cathode block 4, calculated as (R & /), where R is the electrical resistance of a cuboid test specimen, a its cross-sectional area, and 6 its length, along the length of the cathode block.
- R is the electrical resistance of a cuboid test specimen, a its cross-sectional area, and 6 its length, along the length of the cathode block.
- the ends of the block are marked with A.
- the cathode block is cut apart along the line BB, the end faces at A being designated as 4-1, and the separating surface along the line BB in the side section is called 4-2.
- the separated cathode block is now assembled as shown in FIGS. 2 to 4, that the ends A and the end faces 4-1 are in the middle of the assembled cathode block.
- Fig. 2 shows an embodiment, wherein between the two ends A now located in the middle with the end surfaces 4-line position of the ramming mass 5, which is otherwise also used to seal the contact surfaces between the individual cathode blocks on the bottom of the tub of the electrolytic cell becomes.
- Ramming compounds based on anthracite and graphite with a density of approx. 1700 kg / m 3 such as BST 17/1 from SGL Carbon AG, are suitable for this.
- the areas 4-2 that were previously inside have now become outside areas.
- the course of the specific electrical resistance p is now such that the lowest value lies in the center of the cathode block, and the specific electrical resistance now rises symmetrically towards the center towards the ends.
- the course of the electrical conductivity is then reversed, namely descending from a peak in the middle of the cathode block to the ends.
- FIG. 3 A further preferred embodiment is shown in which case the two half-blocks are each joined together with ends A by a layer of adhesive 6 with the required temperature resistance.
- FIG. 4 shows an embodiment in which an adhesive or intermediate layer has been dispensed with and the two half blocks have only been joined together with their ends A.
- the required surface pressure is applied due to the thermal expansion of the half-blocks, which after flush installation are pressed together during heating in the electrolysis cells. It has been shown that the pressing force is large enough to ensure a secure and tight connection of the two half blocks if the end faces were sufficiently flat before the division.
- the graphitized cathode blocks according to the invention show in the production of aluminum by electrolytic reduction of aluminum oxide in a bath of molten cryolite a more uniform wear over the length of the cathode compared to the conventional ones with homogeneous distribution of the electrical conductivity and therefore a significantly increased service life.
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)
Abstract
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10164008 | 2001-12-28 | ||
| DE2001164008 DE10164008C1 (de) | 2001-12-28 | 2001-12-28 | Graphitierte Kathodenblöcke |
| PCT/EP2002/014548 WO2003056068A2 (de) | 2001-12-28 | 2002-12-19 | Graphitierte kathodenblöcke |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1481115A2 true EP1481115A2 (de) | 2004-12-01 |
| EP1481115B1 EP1481115B1 (de) | 2005-12-07 |
Family
ID=7710902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02796687A Expired - Lifetime EP1481115B1 (de) | 2001-12-28 | 2002-12-19 | Graphitierte kathodenblöcke |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1481115B1 (de) |
| AR (1) | AR037912A1 (de) |
| AU (1) | AU2002361174A1 (de) |
| BR (1) | BR0215323A (de) |
| CA (1) | CA2470753A1 (de) |
| DE (2) | DE10164008C1 (de) |
| PL (1) | PL201672B1 (de) |
| WO (1) | WO2003056068A2 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011076302A1 (de) | 2011-05-23 | 2013-01-03 | Sgl Carbon Se | Elektrolysezelle und Kathode mit unregelmäßiger Oberflächenprofilierung |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2728109A (en) * | 1952-06-06 | 1955-12-27 | Savoie Electrodes Refract | Method of making cathodic electrodes for electrolysis furnaces |
| US4194959A (en) * | 1977-11-23 | 1980-03-25 | Alcan Research And Development Limited | Electrolytic reduction cells |
| NO157462C (no) * | 1985-10-24 | 1988-03-23 | Hydro Aluminium As | Laminert karbonkatode for celler til smelte-elektrolytisk fremstilling av aluminium. |
| US4795540A (en) * | 1987-05-19 | 1989-01-03 | Comalco Aluminum, Ltd. | Slotted cathode collector bar for electrolyte reduction cell |
| FR2789091B1 (fr) * | 1999-02-02 | 2001-03-09 | Carbone Savoie | Cathode graphite pour l'electrolyse de l'aluminium |
| EP1233083A1 (de) * | 2001-02-14 | 2002-08-21 | Alcan Technology & Management AG | Kohleboden einer Elektrolysezelle zur Gewinnung von Aluminium |
-
2001
- 2001-12-28 DE DE2001164008 patent/DE10164008C1/de not_active Expired - Fee Related
-
2002
- 2002-12-18 AR ARP020104963 patent/AR037912A1/es unknown
- 2002-12-19 WO PCT/EP2002/014548 patent/WO2003056068A2/de not_active Ceased
- 2002-12-19 EP EP02796687A patent/EP1481115B1/de not_active Expired - Lifetime
- 2002-12-19 DE DE50205232T patent/DE50205232D1/de not_active Expired - Fee Related
- 2002-12-19 BR BR0215323-8A patent/BR0215323A/pt not_active IP Right Cessation
- 2002-12-19 PL PL369969A patent/PL201672B1/pl not_active IP Right Cessation
- 2002-12-19 AU AU2002361174A patent/AU2002361174A1/en not_active Abandoned
- 2002-12-19 CA CA002470753A patent/CA2470753A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03056068A3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2470753A1 (en) | 2003-07-10 |
| BR0215323A (pt) | 2004-10-19 |
| DE50205232D1 (de) | 2006-01-12 |
| DE10164008C1 (de) | 2003-04-30 |
| AU2002361174A1 (en) | 2003-07-15 |
| PL201672B1 (pl) | 2009-04-30 |
| EP1481115B1 (de) | 2005-12-07 |
| AR037912A1 (es) | 2004-12-22 |
| WO2003056068A3 (de) | 2004-09-30 |
| PL369969A1 (en) | 2005-05-02 |
| WO2003056068A2 (de) | 2003-07-10 |
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