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 present invention relates to a cathode block for an aluminum electrolytic cell.
• Such electrolysis cells are used 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 2,045 ° 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 electrolysis cell used in this method has a bottom which is conventionally composed of a plurality of adjacent cathode blocks forming the cathode.
• the cathode blocks are usually composed of a carbonaceous material.
• grooves are provided on the lower sides of the cathode blocks, in each of which at least one bus bar is arranged, through which the current supplied via the anodes is removed.
• the gaps between the individual walls delimiting the grooves of the cathode blocks and the busbars are often poured with cast iron in order to electrically and mechanically connect the busbars to the cathode blocks through the cast iron busbars produced thereby.
• anode formed of individual anode blocks between which and the surface of the aluminum is the electrolyte, ie the melt containing alumina and cryolite.
• the electrolyte ie the melt containing alumina and cryolite.
• 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 blocks and the electrolyte layer.
• the aluminum oxide dissolved in the cryolite melt is split by the flow of electrical current into aluminum and oxygen.
• the layer of molten aluminum is the actual cathode because aluminum ions are reduced to elemental aluminum on its surface. Nevertheless, the term cathode will not be understood below to mean the cathode from an electrochemical point of view, ie the layer of molten aluminum, but rather the component forming the electrolytic cell bottom and composed of one or more cathode blocks.
• a major disadvantage of the Hall-Heroult process is that it is very energy intensive. To produce 1 kg of aluminum about 12 to 15 kWh of electrical energy is needed, which accounts for up to 40% of the manufacturing cost. In order to reduce the manufacturing costs, it is therefore desirable to reduce the specific energy consumption in this process as much as possible.
• graphite cathodes are increasingly used in recent times, ie cathode blocks containing graphite as the main component.
• graphite is characterized by a considerably lower specific electrical resistance as well as by a significantly higher thermal conductivity, which means that the use of graphite cathodes during electrolysis reduces the specific energy consumption of the electrolysis and also the electrolysis can be performed at a higher current, which allows an increase in the production of aluminum per electrolytic cell.
• cathode blocks made of graphite have a very low and in particular a lower resistance compared to the occurring during operation of the electrolytic cell abrasive wear processes and thus a shorter service life than consisting of amorphous carbon cathode blocks.
• undissolved alumina sludge readily deposits on the surface of graphite cathode blocks, which, on the one hand, significantly reduces the wear resistance of the cathode block due to the particle abrasion resulting from the sludge formation and, on the other hand, hinders the flow of current at the cathode block surface due to the reduction of the effective cathode surface. which results in an increase in the specific energy consumption during the electrolysis. As a result, the current density is additionally increased, which can lead to a shorter life of the electrolytic cell.
• the object of the present invention is therefore to provide a cathode block which has a low electrical resistivity, which is characterized by a high thermal conductivity, which is well wettable with molten aluminum, which has a high wear resistance against the abrasive in the operation in a fused-salt electrolysis , chemical and thermal conditions, and which is special also distinguished by the fact that when carrying out a melt electrolysis no sludge deposited on the surface or at most deposit small amounts of sludge.
• a cathode block for an aluminum electrolytic cell having a base layer and a cover layer, wherein the base layer contains graphite and the cover layer of a 15 to less than 50 wt .-% hard material having a melting point of at least 1, 000 ° C containing carbon composite material is composed.
• This solution is based on the finding that by providing a cover layer of a carbon composite material which contains not less than 15 wt .-%, but not more than less than 50 wt .-% hard material having a melting point of at least 1, 000 ° C. a graphite-containing base layer, a cathode block is obtained, which has a sufficiently low for an energy-efficient operation of a fused-salt electrolysis resistivity and also very resistant to wear prevailing in the melt electrolysis, abrasive, chemical and thermal conditions.
• the cathode block according to the present invention is characterized by the provision of graphite in the base layer of the cathode block.
• advantages include, in particular, low electrical resistance of the cathode block and high thermal conductivity of the cathode block, without, however, the disadvantages resulting from the use of graphite, such as low wear resistance and lack of wettability due to aluminum melt. Rather, good wettability of the cathode block surface with molten aluminum is achieved on account of the cover layer provided in the cathode block according to the invention, which is why sludge formation or sludge deposition on the surface of the cathode block is reliably prevented.
• the movement of the molten aluminum is significantly reduced thereby, so that the distance between the surface of the molten aluminum layer and the anode in the electrolytic cell is reduced, for example, to 2.5 to 4.0 cm, and preferably to 3 to 3.5 cm which further reduces the specific energy consumption of the electrolysis process.
• the surface of the cathode block according to the invention surprisingly does not tend to crack despite the use of a cover layer containing hard material and in particular is not distinguished by a disadvantageously high brittleness.
• the cathode block according to the invention is long-term stable with respect to the performance of a fused-salt electrolysis with a melt containing aluminum oxide and cryolite for the production of aluminum and allows melt electrolysis to be carried out with a very low specific energy consumption.
• This is achieved by the above-mentioned combination of a graphite-containing base layer and a hard layer in an amount of less than 50 wt .-% containing top layer based on a carbon composite material.
• This was particularly surprising because the known from the prior art cathode blocks containing a titanium diboride coating necessarily contain relatively high amounts of titanium diboride, which makes the known coatings brittle.
• hard material in accordance with the definition of this term in the art is understood to be a material which is characterized by a particularly high hardness, especially at high temperatures of 1 000 ° C. and higher.
• the melting point of the hard material used is considerably higher than 1 .000 ° C, in particular hard materials having a melting point of at least 1, 500 ° C, preferably hard materials having a melting point of at least 2000 ° C and more preferably hard materials having a melting point of at least 2,500 ° C have been found to be particularly suitable.
• all hard materials can be used in the cover layer of the cathode block according to the invention.
• hard materials which have a Knoop hardness of at least 1 000 N / mm 2 , preferably of at least 1 500 N / mm 2 , particularly preferably of at least 2000 N / mm, measured according to DIN EN 843-4 2 and most preferably of at least 2,500 N / mm 2 .
• suitable hard materials are metal carbides, metal borides, metal nitrides and metal carbonitrides having a sufficiently high hardness at 1, 000 ° C.
• suitable representatives from these groups are titanium diboride, zirconium diboride, tantalum boride, titanium carbide, boron carbide, titanium carbonitride, silicon carbide, tungsten carbide, vanadium carbide, titanium nitride, boron nitride and silicon nitride.
• a non-oxidic titanium ceramic as the hard material in the cover layer of the cathode block according to the invention, preferably titanium diboride, titanium carbide, titanium carbonitride and / or titanium nitride.
• the cover layer of the cathode block according to the invention most preferably contains titanium diboride as the hard material. All of the aforementioned hard materials can be used alone or any chemical combination and / or mixture of two or more of the aforementioned compounds may be used.
• the hard material contained in the cover layer of the cathode block has a monomodal particle size distribution, wherein the determined by static light scattering according to International Standard ISO 13320-1 mean volume-weighted particle size (d 3 , 5 o) 10 bis 20 pm.
• a non-oxidic titanium ceramic and most preferably titanium diboride having a monomodal particle size distribution as defined above.
• a hard material in particular non-oxidic titanium ceramic and especially titanium diboride, having a monomodal particle size distribution as defined above not only results in very good wettability of the surface of the cathode block, and therefore sludge formation and sludge deposition on the surface of the cathode block is reliably prevented , increases the wear resistance of the cathode block and reduces the specific energy consumption during electrolysis.
• this effect is achieved even in the case of comparatively small amounts of titanium diboride of less than 50% by weight and more preferably even of amounts of titanium diboride of only 15 to 20% by weight in the top layer.
• hard material in particular non-oxidic titanium ceramic and especially titanium diboride, with a monomodal particle size distribution as defined above, is also distinguished by very good processability.
• the dust tendency of such a hard material is sufficient, for example, when it is filled into a mixing container or during the transport of the hard material powder low and occurs, for example, when mixing at most a small agglomeration.
• such a hard material powder has a sufficiently high flowability and flowability, so that it can be conveyed for example with a conventional conveying device to a mixing device. For all this, not only follows a simple and cost-effective manufacturability of the cathode blocks according to the invention, but in particular also follows a very homogeneous distribution of the hard material in the top layer of the cathode blocks.
• the hard material contained in the cover layer of the cathode block preferably titanium diboride, preferably has a monomodal particle size distribution, the average volume-weighted particle size (d 3 5 o) determined above being from 12 to 18 ⁇ m and particularly preferably from 14 to 16 ⁇ m.
• the hard material contained in the cover layer of the cathode block may have a monomodal particle size distribution, wherein the average volume-weighted particle size (d 3 , 5 o) determined by static light scattering according to International Standard ISO 13320-1 is 3 to 10 ⁇ m and preferably 4 to 6 pm.
• the average volume-weighted particle size (d 3 , 5 o) determined by static light scattering according to International Standard ISO 13320-1 is 3 to 10 ⁇ m and preferably 4 to 6 pm.
• the hard material has a volume-weighted d 3 9 o particle size of from 20 to 40 ⁇ m, and preferably from 25 to 30 ⁇ m, as determined above.
• the hard material has such a d 3 9 o value in combination with a d 3 50 value defined above.
• the hard material is preferably a non-oxidic titanium ceramic and more preferably titanium diboride.
• the hard material contained in the cover layer of the cathode block may have a volume-weighted d 3 9 o particle size of from 10 to 20 ⁇ m, and preferably from 12 to 18 ⁇ m, as determined above.
• the hard material preferably has such a d 3 9 o value in combination with a d 3 5 o value as defined above.
• the hard material has a volume-weighted one as determined above
• the hard material preferably has such a d 3 -m value in combination with a d 3 9 o value and / or d 3 5 o value as defined above. Also in this embodiment, the hard material is preferably a non-oxidic titanium ceramic and more preferably titanium diboride.
• the hard material contained in the cover layer of the cathode block may have a volume-weighted d 3 io particle size of from 1 to 3 ⁇ m, and preferably from 1 to 2 ⁇ m, as determined above.
• the hard material preferably has such a d 3 -m value in combination with a d 3 9 o value and / or d 3 5 o value as defined above.
• the hard material in particular a non-oxidic titanium ceramic and particularly preferably titanium diboride, has a particle size distribution which is calculated by a span value calculated according to the following equation:
• Span (d 3 , 9o - d 3 , io) is characterized d3,5o from 0.65 to 3.80 and more preferably from 1, 00 to 2.25.
• the hard material has such a span value in combination with a d 3 9 o value and / or d 3 5 o value and / or d 3 -m value as defined above.
• non-oxidic titanium ceramics such as titanium carbide, titanium carbonitride, titanium nitride and most preferably titanium diboride
• the hard material to at least 80 wt .-%, preferably at least 90 wt .-%, more preferably at least 95 wt .-%, most preferably at least 99 wt. % and most preferably entirely consists of non-oxide titanium ceramic and in particular of titanium diboride.
• the total amount of the hard material in the cover layer is according to the invention at least 15 wt .-%, but at most less than 50 wt .-%.
• the cover layer contains sufficient hard material to impart on the one hand the cover layer to increase the wear resistance excellent hardness and abrasion resistance, and on the other hand to give a sufficiently high wettability of the cover layer surface with liquid aluminum to avoid sludge formation and sludge deposition whereby the wear resistance of the cathode block is further increased and the specific energy consumption during a fused-salt electrolysis is further reduced; at the same time, however, the topcoat contains sufficient low amount of hard material, so that the surface of the cover layer due to the addition of hard material does not have too high a brittleness for a sufficiently high long-term stability.
• the top layer contains 15 to 40 wt .-% and particularly preferably 15 to 30 wt .-% of a hard material having a melting point of at least 1 000 ° C.
• the cover layer contains carbon and optionally binder, such as pitch, in particular bituminous and / or petroleum pitch. If pitch is mentioned below, it means all pitches known to those skilled in the art.
• the carbon forms together with the optional binder, the matrix in which the hard material is embedded. Good results are obtained, in particular, if the cover layer 85 contains more than 50% by weight, preferably 85 to 60% by weight and particularly preferably 85 to 70% by weight of carbon.
• the carbon contained in the cover layer may be amorphous carbon, graphite or a mixture of amorphous carbon and graphite.
• the cover layer of the cathode block according to the invention contains as carbon exclusively amorphous carbon or a mixture of amorphous carbon and graphite. If a mixture of amorphous carbon and graphite is used, this mixture preferably contains 10 to 99 wt .-%, particularly preferably 30 to 95 wt .-% and most preferably 60 to 90 wt .-% amorphous carbon and the balance graphite, wherein as graphite both natural graphite and synthetic graphite can be used.
• Anthracite is preferably used as the starting material for the amorphous carbon, which is then calcined at a temperature of 800 and 2,200 ° C., and more preferably between 1,200 and 2,000 ° C.
• the cathode block cover layer containing amorphous carbon it is proposed for the cathode block cover layer containing amorphous carbon that the cover layer has a vertical electrical resistivity at 950 ° C. of from 20 to 32 ⁇ pm and preferably from 22 to 28 ⁇ pm. This corresponds to a vertical resistivity at room temperature of 23 to 40 ⁇ m or from 25 to 30 ⁇ pm.
• vertical specific electrical resistance is understood as meaning the specific electrical resistance in the installation situation in the vertical direction of the cathode block.
• the thickness of the cover layer should be as low as possible in order to keep the cost of the expensive hard material as low as possible, but sufficiently large for the cover layer to have sufficiently high wear resistance and service life. Good results are obtained in this regard in particular if the thickness of the cover layer is 1 to 50%, preferably 5 to 40%, more preferably 10 to 30% and most preferably 15 to 25%, for example about 20%, of the total height of the cathode block.
• the cover layer may have a thickness or height of from 50 to 400 mm, preferably from 50 to 200 mm, particularly preferably from 70 to 130 mm, very particularly preferably from 90 to 110 mm and most preferably about 100 mm. Under thickness or height is understood to mean the distance from the bottom of the cover layer to the point of the highest elevation of the cover layer.
• the base layer may have a thickness or height of from 100 to 550 mm, preferably from 300 to 500 mm, more preferably from 400 to 500 mm, most preferably from 425 to 475 mm and most preferably about 450 mm.
• the cover layer of the cathode block has an at least partially profiled surface. Due to a profiled surface, the movement of the molten aluminum caused by the electromagnetic interaction in the electrolysis is reduced, resulting in less corrugation and bulging of the aluminum layer. For this reason, by using surface-profiled cathode blocks, the distance between the molten aluminum and the anode can be further reduced so that the cell electrical resistance is further reduced due to the reduction of the ohmic resistance and thus the specific energy consumption.
• a profiled surface is understood to mean a surface which has at least one depression extending transversely, longitudinally or in any other direction, such as in a direction extending at an acute or obtuse angle to the longitudinal direction, of the cathode block or arranged chaotically
• the depression or at least a depth or height of 0.05 mm and preferably of 0.5 mm can be the least restrict a depression and / or elevation exclusively to the cover layer or the at least one depression and / or elevation may extend into the base layer.
• the at least one depression and / or elevation extends exclusively in the cover layer.
• a depression is understood to be a recess directed inwards from the surface of the cathode block, whereas the term elevation means an elevation directed outward from the surface of the cathode block. It may, for example, in the case of rectangular recesses or elevations each have the same depth or height depend on the viewer, whether they are regarded as depressions or surveys. This blurring between the terms indentation and survey should be taken into account in the formulation of "deepening and / or survey”.
• the at least one depression and / or elevation, seen in the transverse direction of the cathode block can have any desired geometry.
• the at least one recess or elevation, seen in the transverse direction of the cathode block convex, concave or polygonal, such as trapezoidal, triangular, rectangular or square, may be formed.
• the surface profiling comprises at least one depression, the ratio of depth to width of the at least one depression being 1: 3 to 1: 1 and preferably 1: 2 to 1: 1.
• Good results are obtained, in particular, if the depth of the at least one recess is 10 to 90 mm, preferably 40 to 90 mm and particularly preferably 60 to 80 mm, for example about 70 mm.
• the width of the at least one recess is 100 to 200 mm, more preferably 120 to 180 mm and most preferably 140 to 160 mm, such as about 150 mm.
• the at least one depression viewed in the longitudinal direction of the cathode block, to extend only in regions.
• the at least one recess extend the entire length of the cathode block to achieve the effect of reducing or completely reducing the formation of waves of liquid aluminum.
• the depth and / or width of the at least one recess varies over the length of the cathode block.
• the geometry of the recess can vary over the length of the cathode block.
• the surface profiling comprises at least one projection
• the height of the at least one elevation is 10 to 150 mm, preferably 40 to 90 mm and particularly preferably 60 to 80 mm, for example about 70 mm.
• the width of the at least one protrusion is 50 to 150 mm, more preferably 55 to 100 mm and most preferably 60 to 90 mm, such as about 75 mm.
• the at least one elevation viewed in the longitudinal direction of the cathode block, extends only in regions.
• the at least one protrusion extend the entire length of the cathode block to achieve the effect of reducing or completely reducing waviness of liquid aluminum.
• the height and / or width of the at least one bump varies over the length of the cathode block.
• the geometry of the survey can vary over the length of the cathode block.
• the ratio of the width of the at least one recess to the width of the at least one projection is preferably 4: 1 to 1: 1, such as about 2: 1.
• any angled and in particular rectangular regions in the profiled surface For example, if a substantially rectangular cross-section of the at least one recess and / or bump is selected, it is preferred in accordance with a preferred embodiment of the present invention to round off the rectangular areas.
• the radius of curvature of these roundings may be, for example, 5 to 50 mm, preferably 10 to 30 mm and particularly preferably about 20 mm.
• any geometry is conceivable in principle, all fall under the term rounding.
• the present invention is not limited. Good results are obtained, for example, when the cathode block has in its transverse direction 1 to 3 wells and preferably 2 wells.
• the base layer is at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, most preferably at least 99% by weight. and most preferably completely composed of a mixture of graphite and binder, such as carbonized pitch (graphite cathode body).
• a base layer has a suitably low electrical resistivity and a sufficiently high specific thermal conductivity.
• this mixture is preferably from 70 to 95 wt .-% graphite and 5 to 30 wt .-% binder and more preferably from 80 to 90 wt .-% graphite and 10 to 20 wt .-% binder, such as 85 wt % Graphite and 15% by weight carbonized pitch, composed.
• both the upper side of the base layer and the underside of the cover layer and thus also the interface between the base layer and the cover layer are made planar.
• an intermediate layer may be provided between the base layer and the cover layer which, for example, is constructed like the cover layer, except that the intermediate layer has a lower concentration of hard material than the cover layer.
• the base layer has a vertical electrical resistivity at 950 ° C of 13 to 18 ⁇ ⁇ and preferably from 14 to 16 ⁇ ⁇ . This corresponds to vertical kalen electrical resistivities at room temperature of 14 to 20 ⁇ pm or 16 to 18 ⁇ m.
• a further subject of the present invention is a cathode which contains at least one cathode block described above, wherein the cathode block has at least one groove on the side of the base layer opposite the cover layer, wherein at least one bus bar is provided in the at least one groove in order to move the cathode during to supply electricity to the electrolysis.
• the at least one busbar at least partially, and particularly preferably full circumferential surface has a sheath of cast iron .
• This enclosure can be made by inserting the at least one bus bar into the groove of the cathode block and then filling the space between the bus bar and the walls defining the groove cast iron.
• Another object of the present invention is the use of a previously described cathode block or a previously described cathode for performing a fused-salt electrolysis for the production of metal, in particular of aluminum.
• the cathode block or the cathode is used for carrying out a fused-salt electrolysis with a melt of cryolite and aluminum oxide for the production of aluminum, wherein the fused-salt electrolysis is particularly preferably carried out as a Hall-Heroult process.
• the present invention will be described purely by way of example with reference to advantageous embodiments and with reference to the accompanying drawings.
• FIG. 1 shows a schematic cross section of a section of a
• An aluminum electrolytic cell comprising a cathode block according to an embodiment of the present invention.
• FIG. 1 shows a cross-section of a section of an aluminum electrolysis cell 10 with a cathode 12, which at the same time forms the bottom of a trough for aluminum melt 14 produced during operation of the electrolysis cell 10 and for a cryolite-alumina melt located above the aluminum melt 14 16 forms.
• the cryolite-alumina melt 16 is an anode 18 of the electrolytic cell 10 in contact.
• the trough formed by the lower part of the aluminum electrolytic cell 10 is limited by a lining of carbon and / or graphite, not shown in FIG. 1.
• the cathode 12 comprises a plurality of cathode blocks 20, 20 ', 20 ", which are each connected to one another via a ramming mass 24, 24' inserted into a ramming mass gap 22, 22 'arranged between the cathode blocks 20, 20', 20".
• the anode 18 includes a plurality of anode blocks 26, 26 ', with the anode blocks 26, 26' being each about twice as wide and about half as long as the cathode blocks 20, 20 ', 20 ", with the anode blocks 26, 26' being such arranged above the cathode blocks 20, 20 ', 20 "such that one anode block 26, 26' in width covers two adjacent cathode blocks 20, 20 ', 20" and one cathode block 20, 20', 20 "in length two adjacent anode blocks 26, 26 'covers.
• Each cathode block 20, 20 ', 20 consists of a lower base layer 30, 30', 30" and a covering layer 32, 32 ', 32 "arranged above it and firmly connected therewith.
• the titanium diboride contained in the cover layers 32, 32 ', 32 "has an average volume-weighted particle size (d 3 5 o) of 15 ⁇ m, determined by static light scattering according to standard ISO 13320-1, a d 3 9 o particle size of 27 pm and a d 3 i o particle size of 4 pm.
• Each cathode block 20, 20 ', 20 has a width of 650 mm and a height of 550 mm in total, wherein the base layers 30, 30', 30" each have a height of 450 mm and the cover layers 32, 32 ', 32nd each have a height of 100 mm.
• the distance between the anode blocks 26, 26 'and the cathode blocks 20, 20', 20 " is about 200 to about 350 mm, wherein the interposed layer of cryolite-alumina melt 16th has a thickness of about 50 mm and the underlying layer of molten aluminum 14 also has a thickness of about 150 to about 300 mm.
• each cathode block 20, 20 ', 20 on its underside in each case two grooves 38, 38', each having a rectangular, namely substantially rectangular cross-section, wherein in each groove 38, 38 'in each case a busbar 40, 40' made of steel a rectangular or substantially rectangular cross-section.
• NEN 40, 40 'and the grooves 38, 38' delimiting walls are each cast with cast iron (not shown), whereby the busbars 40, 40 'fixed to the grooves 38, 38' bounding walls are connected.
• both the grooves 38, 38 'and the depressions 34, 34' are applied to the top of the cover layers 32, 32 ', 32 "during the molding process, for example, by vibratory molding and / or stamping.

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