CN103429792A - Cathode assembly and cathode block having a groove with a guide recess - Google Patents
Cathode assembly and cathode block having a groove with a guide recess Download PDFInfo
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- CN103429792A CN103429792A CN2012800086302A CN201280008630A CN103429792A CN 103429792 A CN103429792 A CN 103429792A CN 2012800086302 A CN2012800086302 A CN 2012800086302A CN 201280008630 A CN201280008630 A CN 201280008630A CN 103429792 A CN103429792 A CN 103429792A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- 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
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- 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
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Abstract
The present invention relates to a cathode assembly for an aluminum electrolytic cell, comprising at least one cathode block on the basis of carbon and/or graphite, which has a groove that is lined at least in some sections with a graphite film, wherein at least one busbar is provided in the at least one groove, said busbar having at least in some sections an envelope of cast iron. According to the invention, at least one recess is provided in the wall delimiting the at least one groove, and the envelope of cast iron engages in at least some sections into the at least one recess. The invention further relates to a cathode block for such a cathode assembly and to a method for producing such a cathode assembly for an aluminum electrolytic cell.
Description
Technical field
The present invention relates to a kind of cathode assembly for aluminium cell, a kind of cathode block for this cathode assembly and a kind of method for the manufacture of this cathode assembly.
Background technology
This electrolyzer is used for the electrolytic production of aluminum of usually being implemented by Hall-Heroult process (Hall-H é roult process) industrial.In Hall-Heroult process, the melts be comprised of aluminum oxide and sodium aluminum fluoride is by electrolysis.Herein, sodium aluminum fluoride Na
3[AlF
6] be used for the approximately fusing point of 950 ℃ to the mixture that comprises sodium aluminum fluoride, aluminum oxide and additive such as aluminum fluoride and Calcium Fluoride (Fluorspan) by the melting point depression of 2045 ℃ of pure alumina.
In this method, electrolyzer used has bottom, and this bottom is comprised of the cathode block of a plurality of adjacency that form negative electrode.In order to tolerate at the operating period of groove main heat condition and electrochemical conditions, cathode block is comprised of carbonaceous material usually.The bottom side of each in cathode block is provided with groove, arranges at least one bus-bar in each in groove, and by this bus-bar, the electric current of supplying with via anode is released.In this case, each wall of the restriction groove of cathode block and the space between bus-bar be cylinder iron sealing often, in order to rely on the housing that cast iron produces that utilizes of bus-bar that bus-bar is electrically connected to and is mechanically connected to cathode block.The anode formed soon by independent anode is disposed in the about 3cm to 5cm in top of the layer of molten aluminum that is positioned at the negative electrode top side, and ionogen comprises that the melts of aluminum oxide and sodium aluminum fluoride is between the surface of this anode and aluminium.During the electrolysis of approximately carrying out under 1000 ℃, the aluminum precipitation formed is under dielectric substrate, and as in the top side of cathode block and the middle layer between dielectric substrate, this is because the density of aluminium is compared relative large with electrolytical density.During electrolysis, the aluminum oxide dissolved in the sodium aluminum fluoride melts is flowed separately to form aluminium and oxygen by electric current.According to electrochemistry, layer of molten aluminum is actual negative electrode, and this is because aluminum ion is reduced into element aluminum on the surface of layer of molten aluminum.Yet hereinafter, term " negative electrode " can not be understood to mean the negative electrode according to the electrochemistry viewpoint, i.e. layer of molten aluminum, but be understood to form assembly bottom of electrolytic tank and that formed by one or more cathode block.
The significant drawback of the cathode assembly used in Hall-Heroult process is self relatively low wear resistance that the corrosion of passing through cathode block surface during electrolysis of cathode assembly embodies.In this case, due to distribution of current inhomogeneous in cathode block, the cathode block surface is not corroded equably on the length of cathode block, but the degree that is corroded and increases into the end at cathode block, therefore, after certain electrolysis time length, the surface of cathode block becomes W shape profile.As the result of the unsymmetrical corrosion on cathode block surface, there is the region limits of maximum corrosion the work-ing life of cathode block.
In order to address this problem, WO 2007/118510A2 discloses a kind of cathode block, and this cathode block has groove, and this groove is designed to receive bus-bar, and, with respect to cathode block length, this groove is large in the degree of depth of cathode block end in central depth ratio.This is in the roughly uniform vertical distribution of current realized during electrolytic cell operation on cathode block length, and result is the enhancing wearing and tearing that reduced on the cathode block end, and therefore, increases the work-ing life of negative electrode.
Another shortcoming of the cathode assembly used in Hall-Heroult process is its relatively high resistance.One of relatively high-resistance some reasons are that the contact resistance between the cathode block of bus-bar and negative electrode is relatively high, and this contact resistance is with operating time increase and the additionally increase of negative electrode.At first this be due to the fact that and cause: during electrolysis, the composition of melts is diffused in cathode block undesirably, and this causes forming for example insulation layer of beta-alumina; Next is due to the fact that and causes: after relatively long loading, the carbon of the steel of bus-bar, cast iron and cathode block starts creep, after relatively long loading, and the irreversibly creep of the carbon of the steel of bus-bar, cast iron and cathode block.
In order to reduce the contact resistance between bus-bar and cathode block, and thereby improve the energy efficiency of electrolytic process, in WO 2007/071392 A2, proposed at least in some zone, to be lined with graphite foil in the groove based on carbon or cathode block based on graphite.Be reduced in bus-bar except graphite foil due to graphite foil good form fit on both sides or embed the curing cast iron layer of graphite foil and the fact of the contact resistance between cathode block, the elasticity of graphite foil also means that this elasticity of the latter also reduces particularly that operating time along with negative electrode increases and this contact resistance of increasing, and this is because graphite foil has been filled the wall of the formed groove limiting cathode block during the negative electrode creep of the steel of bus-bar and cathode block and the gap between bus-bar.
Yet graphite foil has the smooth surface with very good sliding.At cathode block, have in the situation of groove of the graphite foil of being lined with, therefore the risk existed is, if for example cathode block is raised or because other reason is moved when cathode block is mounted, the bus-bar that is contained in the weight that usually has the length of some meters and hundreds of kilogram in this groove subsequently can be by the depth direction superior displacement at slot opening in uncontrolled mode, or even can drop out from groove.This risk particularly exists in groove has the situation of rectangular cross section, and for the groove with the depth of groove changed on the length of groove of cathode block, this rectangular cross section is actually unique applicable form.In addition, because bus-bar slides in groove, and lost the accurate cooperation contact between groove and cast iron, and this causes the poor current delivery from the bus-bar to the cathode block, and therefore cause energy efficiency to reduce.Finally, graphite foil can not be connected to cast iron, perhaps only can be connected to cast iron by the degree with very little, and therefore by liquid cast iron is poured in the gap between bus-bar and graphite foil, fills this gap and make subsequently the cast iron sclerosis or solidify the connection be not created between graphite foil and cast iron, but only making bus-bar be embedded by cast iron.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of cathode assembly, the aluminium cell of the type that this cathode assembly is mentioned for foreword, this cathode assembly has low resistance, this resistance is also permanent low especially on during the prolongation electrolysis, and particularly also between bus-bar and cathode block, there is low contact resistance, and in this cathode assembly, prevented reliably bus-bar in the groove of cathode block the longitudinal direction with cathode block vertically on the depth direction at groove do not expect with retrodisplacement, and particularly prevented that bus-bar from dropping out from groove, with definitely particularly in the situation of the groove with the square-section usually be used in the cathode block with the depth of groove changed on cathode block length in.
According to the present invention, this purpose realizes by the cathode assembly of the aluminium cell for having at least one cathode block based on carbon and/or graphite, this cathode block has at least one groove that at least in some zone, is lined with graphite foil, wherein, at least one bus-bar is arranged in this at least one groove and at least in some zone, has the housing of cast iron, wherein, at least one recess is arranged in the wall of this at least one groove of restriction of cathode block, and the housing of cast iron at least joins in this at least one recess in some part.
This solution is based on following and realizes: if at least one wall of the restriction groove of cathode block, at least one recess is set, and the bus-bar will be at least cylinder iron embedded in some zone makes in being introduced in groove during the housing of cast iron at least joins recess in some part, at bus-bar with have between the cathode block of groove of the graphite foil of being lined with and realized that the just locking of the accurate cooperation of the displacement on the opposing direction vertical at the longitudinal direction with cathode block is connected.According to the present invention, it has been determined that, irrelevant with the high sliding of utilized graphite foil, this has realized having the solid mechanical vertical with the longitudinal direction of cathode block between the bus-bar of cast iron and cathode block to be connected in embedding, this solid mechanical connects and hinders the displacement of not expecting and the particularly bus-bar that bus-bar makes progress the party and drop out from the groove that is lined with graphite foil, definitely particularly even in the situation of the groove with rectangular cross section in the cathode block as be preferred for having the depth of groove changed on cathode block length.Therefore, due to the electrical characteristic of graphite foil with mechanical characteristics and to groove to form lining by graphite foil relevant, cathode assembly according to the present invention has the following advantages: improve the current delivery between bus-bar and cathode block and therefore improve energy efficiency, and prevent the following shortcoming relevant to the high sliding of graphite simultaneously: bus-bar in groove at the longitudinal direction with cathode block the uncontrolled movability on vertical direction, and be operated in the situation of relatively long time at electrolyzer, the possibility of following of the electrical connection of infringement between bus-bar and cathode block.
In addition, the present invention can utilize the sliding of graphite foil to guarantee optionally vertical shift in groove of bus-bar by mode targetedly, in the situation of the movement particularly caused in the temperature variation by between the starting period.
In addition, can enough extremely low cost manufactures there is the cathode assembly of above-mentioned advantage and there is no complicated additional operation according to of the present invention.Therefore, fill filling recess with cast iron at least in part and realizing of cathode block during the mechanical connection arranged between bus-bar and cathode block can be only by the casting needed of the bus-bar with cast iron.Realize contact very closely between this housing at bus-bar, cast iron, graphite foil and cathode block, thereby contributed to the low especially contact resistance between bus-bar and cathode block.In addition, graphite foil is absorbed in the mechanical pressure that the plane of operating period of cathode assembly and paper tinsel vertically produces.
In situation of the present invention, in the restriction with respect to pure surfaceness, " recess " is understood to refer to otch, the surface of the restriction groove based on wall, and the degree of depth of this otch is at least 0.05mm and preferably 0.5mm.
In addition, in situation of the present invention, " graphite foil " is understood to refer to be not only thin graphite flake, also particularly Partial shrinkage base or the flexible board of expanded graphite.
In situation of the present invention, " cathode assembly " is understood to refer to have the cathode block of at least one groove, and wherein, at least one bus-bar that may be embedded by cast iron is received within each groove at least one groove.Similarly, this term refers to all to have the device of a plurality of cathode blocks of at least one groove, and wherein, at least one bus-bar that may be embedded by cast iron is received within each groove at least one groove.
In principle, the housing of cast iron at least can directly contact with graphite foil or with cathode block self in the zone of recess.Although this is preferred according to the present invention, this is not indispensable.In fact primary for the mechanical connection that produces expectation between bus-bar and cathode block is the following fact: the housing of cast iron at least joins at least one recess in some part, that is, at least in some zone, fill the hollow space formed by least one recess.
According to a preferred embodiment of the invention, the part joined at least one recess of cast housing is configured to and the recess complementation.This makes it possible to achieve cast housing and engages to the good especially just locking in recess, therefore realize by cast housing and the bus-bar that is connected to cast housing especially effectively machine riveting to cathode block.
In order to realize good especially just cooperation between cast housing and cathode block, in the development of concept of the present invention, propose, if housing join to part in this at least one recess and the suitable bus-bar embedded by this housing fill recess at least 70%, preferably at least 80%, particularly preferably be at least 90%, be very particularly preferably at least 95% and be most preferably 100%.Therefore can prevent especially reliably the displacement of not expecting on direction that bus-bar is vertical at the longitudinal direction with cathode block and prevent that particularly bus-bar drops out from groove.
Be advantageously, at least 20%, preferably at least 40% of each the whole length at groove at least one recess, particularly preferably at least 60%, be very particularly preferably at least 80% and optimum be at least about being to extend continuously on the whole length of groove.This can prevent that bus-bar from may skid off groove between erecting stage.In addition; if recess extends on the suitable major part of groove length, as mentioned above, may guarantee the good displaceability of bus-bar on the longitudinal direction of groove; in this case, still prevented reliably the bus-bar displacement do not expected parallel with the depth direction of groove.
In principle, cathode block also can have a plurality of recesses, the plurality of recess on the longitudinal direction of groove one by one and the part without recess by groove separated from one another.Vertical shift when bus-bar in cathode block be do not expect the time, this embodiment is particularly advantageous.
In order to ensure cast housing and bus-bar, be fixed on reliably in cathode block, the degree of depth of this at least one recess preferably 2mm to 40mm, particularly preferably be 5mm to 30mm and be very particularly preferably 10mm to 20mm.
For the same reason, the height of the A/F of this at least one recess based on cathode block preferably 2mm to 40mm, particularly preferably be 5mm to 30mm and be very particularly preferably 10mm to 20mm.
As a result, the cross-sectional area of this at least one recess 1.5mm preferably
2To 1600mm
2, particularly preferably be 10mm
2To 900mm
2And 40mm very particularly preferably
2To 400mm
2.Especially for the recess with Polygons cross section and particularly for the recess with rectangular cross section, these values are preferred.If this at least one recess has crooked cross section, such as for example semi-circular cross-section roughly, the cross-sectional area of this at least one recess is 1.5mm preferably
2To 630mm
2, particularly preferably be 10mm
2To 350mm
2, be very particularly preferably 40mm
2To 160mm
2.
In principle, this at least one recess can have any Polygons cross section or crooked cross section.If especially the cross section of this at least one recess is at least roughly semicircle, trilateral, rectangle or trapezoidal, with regard to regard to cast housing just is being lock bonded at least one recess well and obtain good result with regard to the reliable and no problem filling of cylinder iron carrying out of recess during casting simultaneously.
In the development of concept of the present invention, proposed in the wall of restriction groove that at least one recess generally perpendicularly extends to cathode block.This brings fixed action especially reliably on the depth direction of groove.
According to the present invention,---while considering on the depth direction at this groove---this at least one recess is limited by the transitional region between the contiguous sections in recess and groove walls in each end of its end.If this transitional region has angled structure, as while observing from the inside of cathode block, the angle between the wall of the contiguous sections of groove walls and recess is for preferably 90 spending to 160 degree, particularly preferably be 90 degree to 135 degree and be very particularly preferably 100 degree to 120 degree.If this transitional region has curved configuration, can but needn't be picture crooked structure circularly ideally, the radius-of-curvature of transitional region is for maximum 50mm preferably, particularly preferably be maximum 20mm and be very particularly preferably maximum 5mm.
According to a further advantageous embodiment of the invention, the wall that limits groove comprises diapire and two sidewalls, and each sidewall has at least one recess, the recess preferably extended with the Surface Vertical of respective side walls.By this way, bus-bar is remained on the both sides of groove, result, bus-bar can be fixed in the position of expectation especially effectively.In principle, can also be that a plurality of recesses are arranged in one or two in sidewall, for example, at least 1, at least 2, at least 3 or at least 4 recesses are arranged in each sidewall, and the cast housing of bus-bar at least joins in each in this recess in some part.As a result of, realized especially firmly connecting between bus-bar and cathode block.In the time of preferably in more recesses are arranged on groove, the degree of depth and/or the volume of each all recesses are all less.
Preferably this at least one recess on the length of groove the diapire in the distance groove at least constant the distance and with the diapire of groove, extend abreast.In this structure, guaranteed the bus-bar displacement parallel with bottom portion of groove.
According to a further advantageous embodiment of the invention, each in this at least one recess at least is lined with graphite foil in some zone and preferably on the four corner of recess, in this case, much less, all the other zones of groove also preferably are lined with graphite foil on their gamut.As a result, even also between cast iron and cathode block, produce low especially contact resistance in the zone of recess.In addition; the sliding of graphite foil refers to: if the surface of the restriction groove of wall most of and preferably at least about whole surface, be lined with graphite foil can guarantee that bus-bar is as described above on the longitudinal direction of at least one recess and thereby at the longitudinal direction superior displacement of cathode block.In this case, graphite foil can press by the cast housing of bus-bar the border of recess, to bring good especially electrically contacting, and brings especially and effectively just coordinates.Especially at the heating electrolyzer between the starting period, this effect becomes important, this is because the concrete thermal expansivity of steel or iron is about three times of the particular thermal coefficient of expansion of conventional cathode material.
During the manufacture of cathode assembly, can only by being inserted in groove, graphite foil make graphite foil fill recess and then cast iron is poured in groove, make graphite foil be extruded in recess, wherein specifically graphite foil is directly pressed to the cathode block material that limits recess, make this at least one recess of groove be lined with graphite foil.
In order to realize the uniformly vertical electric current distribution on cathode block length, in the development of concept of the present invention, propose, the degree of depth of at least one groove changes on the length of the length of groove or cathode block, and is particularly preferably large for the degree of depth of two vertical side ends of the depth ratio groove of the central authorities with respect to longitudinal direction of groove.This realizes being uniformly distributed of the electric current supplied with by cathode assembly on the whole length of cathode block, as a result of, has prevented the super-high-current density in the end of vertical side of cathode block, thereby has prevented the too early wearing and tearing in the end of cathode block.In the present embodiment, in fact unique shape of cross section applicatory of groove, be rectangle, therefore, effect of the present invention, specifically prevent that bus-bar from dropping out from slot opening reliably, obvious especially herein.
This uniform electric current distribution on the length of cathode block prevents that the aluminium melts that the interaction by electromagnetic field causes from moving, and thus, can be above the aluminium melt surface, than low height, to arrange anode.This reduces the resistance between anode and aluminium melts, and increases the energy efficiency of the fused salt electrolysis be performed.
In addition, at cathode block, have in above-described embodiment of groove of variable depth, at least one recess of cathode block is preferably configured as makes this at least one recess distance in the bottom of distance groove constant on the whole length of groove, in order to therefore make the bus-bar that can be shifted as required along the longitudinal direction of cathode block.
Also be particularly suitable for without doubt using the geometrical shape of conventional groove and/or bus-bar according to cathode assembly of the present invention.By the mode of example, groove and/or bus-bar can have the cross section of essentially rectangular usually.Preferably, if particularly the degree of depth of groove changes in a longitudinal direction.Particularly bus-bar can also be formed from steel usually.
In the development of concept of the present invention, proposed at least in some zone, for groove forms the graphite foil served as a contrast, to comprise expanded graphite, and be particularly preferably compressed expanded graphite, this compressed expanded graphite is particularly preferably containing binding agent.Be very particularly preferably at least in some zone, for groove, form lining graphite foil by expanded graphite and be particularly preferably not form containing the compressed expanded graphite of binding agent.As described above, in principle, paper tinsel can also be formed by roughly tabular base, this base comprises expanded graphite, and in this case, this base has enough elasticity to be made it allow the above-mentioned filling of being undertaken by cast housing of recess by recoverable deformation, and in can between the wall at cast iron and restriction groove, being inserted into this recess during this period.
The content of graphite of graphite foil is preferably at least 70%, particularly preferably preferably at least 60%, further at least 80%, especially preferably at least 90% and is very particularly preferably at least about 100%.
If particularly the thickness of graphite foil is between 0.2mm and 3mm, preferably between 0.2mm and 1mm and be particularly preferably between 0.3mm and 0.5mm, obtained the good result with regard to the optimum development of the mechanical property of graphite and electrical property.
The performance that depends on expectation, can insert graphite foil or be glued onto in groove.If particularly only with relatively little degree, graphite foil is pressed to the surface of recess, or if prevent the no matter how little displacement of graphite foil on the longitudinal direction of cathode block, it is preferred graphite foil being glued onto in groove.
According to a further advantageous embodiment of the invention, cathode block has one or two groove, and this groove is for receiving in each case at least one bus-bar.In principle, passable in situation of the present invention is that a groove of cathode block is received a bus-bar just, but also can receive under special circumstances two bus-bars in the different piece of the length of inserting groove.In this case, bus-bar can be arranged such that bus-bar placement relative to one another on the surface of bus-bar.
The invention still further relates to a kind of cathode block of the cathode assembly for aluminium cell, this cathode assembly is based on carbon and/or graphite, and this cathode block has at least one groove, and this groove is for receiving bus-bar, wherein, at least one recess is arranged in the wall of this at least one groove of restriction of cathode block.This cathode block can be advantageously used for the building block of above-mentioned cathode assembly.Can construct cathode block by any required mixture based on decolorizing carbon, graphite carbon, graphitized carbon or above carbon herein.
The invention still further relates to a kind of method for the manufacture of the cathode assembly for aluminium cell, the method comprises the following steps:
Cathode block based on carbon and/or graphite is provided, and this cathode block has at least one groove, and this groove is for receiving bus-bar, and wherein, at least one recess is arranged in the wall of this at least one groove of restriction of cathode block,
Make at least one zone of this at least one groove be lined with graphite foil,
Bus-bar is inserted in this at least one groove,
In between graphite foil and bus-bar, liquid cast iron being poured into at least a portion between graphite foil and bus-bar of this at least one recess, and
Permission cast iron solidifies.
The graphite foil that the static pressure of cast iron post will be arranged in groove is advanced to this at least one recess, and in this at least one recess, graphite foil particularly is pressed against the cathode block that limits this at least one recess.Thus, can especially easily manufacture and have the cathode assembly that partially or even wholly by graphite foil, is formed the recess of lining, this cathode assembly has the low especially contact resistance between bus-bar and cathode block.For between the starting period, by the different heat expansion of steel or iron and cathode material, realize exceptionally close the contact at the heating electrolyzer.
Can be by the graphite foil insertion and/or being glued onto groove before inserting bus-bar.The loosening insertion section of the graphite foil in groove can be enough to as pre-fixing section, and this is because graphite foil preferably is pressed against at least one wall of the restriction groove of cathode block during casting by cast iron.
In order to manufacture cathode block, the mixture of the parent material of carbon containing or graphitiferous or multiple manufactured materials can be incorporated in mould, then to this material or this mixture compacted to form the green compact body.Parent material in this case preferably exists with particulate or granular form.Then, thus if can be by green compact body heating carbonization and the suitable greying of carrying out.In situation of the present invention, can use carbonized cathode piece and graphitization cathode piece, this carbonized cathode piece is understood to refer to following cathode block: this cathode block has experienced until 1500 ℃ and the preferably thermal treatment between 800 ℃ and 1200 ℃ at the most at the production period of this cathode block, and the decolorizing carbon of high-content is arranged; This graphitization cathode piece is understood to refer to following cathode block: this cathode block has experienced over 2000 ℃ and the preferably thermal treatment between 2300 ℃ and 2700 ℃ at the production period of this cathode block, and has the class graphite carbon of high-content.Finally, can use the cathode block based on graphite carbon, not by those cathode blocks graphited but that add graphite as parent material.
As the initial substance for the carbonized cathode piece, for example use the mixture of calcined anthracite, graphite and coal-tar pitch and/or petroleum pitch, thereby graphite cathode block is for example made by the mixture that contains graphite and coal-tar pitch and/or petroleum pitch.Herein, graphite refers to natural graphite and synthetic graphite.
According to the favourable development of method, during the manufacture of cathode block, the parent material that will contain carbon and/or graphite is incorporated in mould, and this mould has the projection complementally formed with this at least one recess.
The cathode block material of at least one wall of the restriction groove that similarly, this at least one recess can be by removing and/or eliminated cathode block is subsequently manufactured.Can specifically for recess, by milling process, introduce subsequently, in this case, preferably corresponding with recess for the cross section of the milling head of introducing recess.
The invention still further relates to a kind of cathode assembly, this cathode assembly obtains by aforesaid method.
The accompanying drawing explanation
Hereinafter, the embodiment based on favourable with reference to accompanying drawing, by example, present invention is described fully.
In figure:
Fig. 1 illustrates the cross-sectional view had according to the details of the aluminium cell of the cathode assembly of exemplary embodiment of the present invention,
Fig. 2 illustrates the longitudinal section of the cathode assembly of the aluminium cell shown in Fig. 1, and
Fig. 3 a to Fig. 3 d is illustrated in the exemplary cross-sectional of the recess arranged in the groove according to cathode block of the present invention.
Embodiment
Fig. 1 illustrates the cross-sectional view of the details of the aluminium cell 10 with cathode assembly 12, this cathode assembly 12 be formed for simultaneously the aluminium melts 14 that produces in operating period of aluminium cell 10 and for be positioned at aluminium melts 14 above the bottom of groove of sodium aluminum fluoride-aluminum oxide melts 16.Anode 18 contacts with sodium aluminum fluoride-aluminum oxide melts 16.At sidepiece, the groove formed by the bottom of aluminium cell 10 limits by carbon and/or graphite lining (not shown in Fig. 1).
Cathode assembly 12 comprises a plurality of cathode blocks 20, and this cathode block 20 all is connected to each other by being inserted into the ramming mass piece (ramping composition) 24 in the ramming mass piece joint 22 be arranged between cathode block 20.Cathode block 20 in this case comprises two grooves 26, and this groove 26 is disposed in the downside of cathode block 20 and has the particularly cross section of essentially rectangular of rectangle, and wherein, the steel bus-bar 28 that has equally rectangular cross section is received within each groove 26.Each wall 32,34 that limits groove 26 herein, uses the graphite foil 30 shown in dotted line to form lining in Fig. 1.
Groove 26 all limits by two sidewalls 32 and the diapire 34 of cathode block 20, wherein generally perpendicularly extends in sidewall 32 and have the roughly recess 36 in semicircular cross section to be arranged in each sidewall 32 in sidewall 32.Each recess 36 limits by the transitional region up and down 37 of cathode block 20.In this exemplary embodiment, transitional region 37 has angled structure, and wherein the angle [alpha] between the contiguous sections of groove walls and recess wall is 90 degree.In this case, pour out cast iron 38 at bus-bar 28 and the gap that is lined with between the groove 26 of graphite foil 30 in each situation, so graphite foil 30 is fixed between cast iron 38 and cathode block 20.In this case, graphite foil 30 is pressed against the wall 32,34 that limits corresponding recesses 26 by cast iron 38.In this exemplary embodiment, recess 36 also all forms lining by graphite foil 30, and in this case, cast iron 38 just is being filled with the recess 36 of lining and graphite foil 30 is being pressed to the cathode block 20 that limits recess 36.By this way, guarantee the low contact resistance between bus-bar 28 and cathode block 20 on the whole cross section of groove 26.Cast iron 38 is formed for the housing 39 of bus-bar 28, and is integrally connected to bus-bar 28.
In addition, form and just lock connection together with the material of the cast iron 38 in being received in recess 36 in every kind of situation and the restriction recess 36 of cathode block 20, and this prevents that the bus-bar 28 that is connected to cast iron 38 from moving on the direction of arrow 40.This prevents the movement do not expected of bus-bar 28 on the depth direction of groove 26, or even prevents that bus-bar 28 from dropping out from groove 26.
Fig. 1 specifically illustrates the cross section of the vertical side at cathode block 20 of cathode assembly 10.In this case, the degree of depth of the groove 26 of cathode block 20 changes on the length of groove 26.Be illustrated in the groove cross section in the zone of central authorities of groove 26 with dotted line 42 in Fig. 1.In this example embodiment, the difference between the depth of groove of the end of vertical side of groove 26 and the depth of groove in the centre of groove 26 is about 10cm.The width 44 of each groove 26 is roughly constant on whole groove length, and is about 15cm, thereby each the width 46 in cathode block 20 is about 65cm.
In this example embodiment, a plurality of anodes 18 and a plurality of cathode block 20 are arranged to the top that one is positioned at another one, two cathode blocks 20 that make each anode 18 cover on width to be juxtaposed to each other also cover half cathode block 20, the length of two anode 18 covered cathode pieces 20 that are juxtaposed to each other in this case on length.
Fig. 2 is the longitudinal section that the cathode block 20 shown in Fig. 1 is shown.As can be seen from Figure 2, in the longitudinal section of groove 26, consider, with leg-of-mutton form, the central authorities towards cathode block 20 are tapered groove 26, and result is to guarantee roughly uniformly vertical current density on whole cathode length.As used as shown in dotted line in Fig. 2, recess 36 extends with bottom portion of groove 34 herein abreast, and has apart from the constant distance of bottom portion of groove 34 on the length of groove 26.In this exemplary embodiment, there is bar form for former thereby unshowned bus-bar 28 more clearly and there is the vertical section of rectangle in Fig. 2, in order to be formed on the gap between bus-bar and bottom portion of groove 34, this gap increases towards the central authorities of groove 26 dimensionally, and can fill by cast iron 38 or by the additional metal sheet that is connected to bus-bar 28.Similarly, can also utilize the bus-bar 28 mated with the triangular-shaped profile of groove 26 in the vertical section of bus-bar 28.
Finally, Fig. 3 a to Fig. 3 d is illustrated in the groove according to cathode block 20 of the present invention the exemplary recess 36 arranged with cross section.Herein, recess 36 all have semicircular cross section roughly (Fig. 3 a), roughly trapezoidal cross section (Fig. 3 b) or the cross section (Fig. 3 c) of general triangular.As the inside from cathode block 20, the angle [alpha] of the transitional region 37 between the contiguous sections of the wall of recess 36 and groove walls 32 in Fig. 3 a, be in this case approximately 90 the degree, in Fig. 3 b, be approximately 120 the degree, in Fig. 3 c, be approximately 125 the degree.Fig. 3 d illustrates following structure, and in this structure, a plurality of recesses 36 with the trilobal(cross)section as shown in Fig. 3 c are arranged on the depth direction at groove 26 continuously, keep reliably the bus-bar 28 inserted so that special.In this case, as the inside from cathode block 20, at two, in abutting connection with the transitional region 48 between recess 36, have at two in abutting connection with the approximately angle beta of 70 degree between the wall of recess 36.Recess 36 shown in Fig. 3 a to Fig. 3 d all extends vertically up in the sidewall 32 of restriction groove 26 of cathode block 20, so that recess 36 forms fixed part with together with cast iron in being received in recess 36, this effectively and at bus-bar 28 is cylinder iron prevented the movement of not expecting that bus-bar 28 is parallel at the depth direction with groove 26 after 38 castings.
Reference numerals list
10 aluminium cells
12 cathode assemblies
14 aluminium melts
16 sodium aluminum fluorides-aluminum oxide melts
18 anodes
20 cathode blocks
22 ramming mass piece joints
24 ramming mass pieces
26 grooves
28 bus-bars
30 graphite foil
32 sidewalls
34 diapires
36 recesses
Transitional region between the wall of 37 recesses and the contiguous sections of groove
38 cast irons
39 housings
40 arrows
42 dotted lines
The width of 44 grooves 26
The width of 46 cathode blocks 20
48 at two in abutting connection with the transitional region between recess
The angle of α between the contiguous sections of the wall of recess and groove walls
The angle of β between the wall of the recess of two adjacency
Claims (29)
1. the cathode assembly for aluminium cell (10), described cathode assembly has at least one cathode block (20) based on carbon and/or graphite, described cathode block (20) has at least one groove (26), described at least one groove (26) at least is lined with graphite foil (30) in some zone, wherein, at least one bus-bar (28) is arranged in described at least one groove (26) and at least in some zone, has the housing (39) of cast iron (38)
It is characterized in that,
At least one recess (36) is arranged in wall described cathode block (20), that limit described at least one groove (26) (32,34), and the housing (39) of described cast iron (38) at least joins in described at least one recess (36) in some part.
2. cathode assembly according to claim 1,
It is characterized in that,
The part that joins the housing (39) of the described cast iron (38) in described at least one recess (36) to is configured to and described recess (36) complementation.
3. cathode assembly according to claim 1 and 2,
It is characterized in that
Join described housing (39) in described at least one recess (36) to if part and the suitable bus-bar by described shell encapsulated (28) fill at least 70%, preferably at least 80%, particularly preferably at least 90%, very particularly preferably at least 95% and most preferably at least 100% of described recess (36).
4. according at least one the described cathode assembly in aforementioned claim,
It is characterized in that,
Each recess in described at least one recess (36) the length of described groove (26) at least 20%, preferably at least 40%, particularly preferably be at least 60%, be very particularly preferably to extend continuously and most preferably at least be similar on the whole length of described groove (26) at least 80% to extend continuously.
5. according at least one the described cathode assembly in aforementioned claim,
It is characterized in that,
The degree of depth of each recess in described at least one recess (36) is 2mm to 40mm, 5mm to 30mm and be particularly preferably 10mm to 20mm preferably.
6. according at least one the described cathode assembly in aforementioned claim,
It is characterized in that,
Height based on described cathode block, the A/F of each recess in described at least one recess (36) is 2mm to 40mm, 5mm to 30mm and be particularly preferably 10mm to 20mm preferably.
7. according at least one the described cathode assembly in aforementioned claim,
It is characterized in that,
The cross-sectional area of each recess in described at least one recess (36) is 1.5mm preferably
2To 1600mm
2, 10mm preferably
2To 900mm
2And be particularly preferably 40mm
2To 400mm
2.
8. according at least one the described cathode assembly in aforementioned claim,
It is characterized in that,
Described at least one recess (36) has at least roughly semicircle, trilateral, rectangle or trapezoidal cross section.
9. according at least one the described cathode assembly in aforementioned claim,
It is characterized in that,
Described recess (36) is substantially vertical to be extended in wall described cathode block (20), that limit described groove (26) (32,34).
10. according at least one the described cathode assembly in aforementioned claim,
It is characterized in that,
While considering on the depth direction in described groove (26), described at least one recess (36) each end in its end is by described recess (36) and described groove walls (32, 34) transitional region between contiguous sections (37) limits, wherein, each transitional region in described transitional region (37) has angled structure, wherein, when the inside from described cathode block is seen, wall and described groove walls (32 at described recess (36), 34) angle between contiguous sections (α) is 90 degree to 160 degree, preferably 90 degree are to 135 degree and be particularly preferably 100 degree to 120 degree.
11. according at least one described cathode assembly in claim 1 to 9,
It is characterized in that,
While considering on the depth direction in described groove (26), described at least one recess (36) each end in its end is limited by the transitional region (37) between the contiguous sections in described recess (36) and described groove walls (32,34), wherein, each transitional region in described transitional region (37) has curved configuration, wherein, the radius-of-curvature of described transitional region is maximum 50mm, maximum 20mm and be particularly preferably maximum 5mm preferably.
12. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
The described wall (32,34) that limits described groove (26) comprises diapire (34) and two sidewalls (32), and each sidewall (32) has at least one recess (36).
13. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
Described at least one recess (36) is the distance in described diapire (34) constant apart from described groove (26) on the length of described groove (26).
14. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
Each recess in described at least one recess (36) is at least in some zone and preferably on its four corner, be lined with described graphite foil (30), and each groove in described at least one groove (26) preferably is lined with described graphite foil (30) on its four corner.
15. cathode assembly according to claim 14,
It is characterized in that,
Described graphite foil (30) is pressed to the border of described recess (36) by the housing (39) of the cast iron (38) of described bus-bar (28).
16. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
The degree of depth of described groove (26) changes on the length of described groove (26).
17. cathode assembly according to claim 16,
It is characterized in that,
The degree of depth of the central authorities of the described groove of depth ratio (26) of vertical side end of described groove (26) is little.
18. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
Each groove in described at least one groove (26) has at least cross section of essentially rectangular.
19. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
Each bus-bar in described at least one bus-bar (28) has the cross section of essentially rectangular.
20. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
Described graphite foil (30) comprises expanded graphite or consists of expanded graphite, the expanded graphite that described expanded graphite preferably compresses at least partly.
21. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
The thickness of described graphite foil (30) is between 0.2mm and 3mm, preferably between 0.2mm and 1mm and be particularly preferably between 0.3mm and 0.5mm.
22. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
Described graphite foil (30) is inserted into and/or is glued onto in described groove (26).
23. according at least one described cathode assembly in aforementioned claim,
It is characterized in that,
Described cathode block (20) has one or two groove (26) for every kind of situation, receiving at least one bus-bar (28).
24. the cathode block of the cathode assembly for aluminium cell (10) (12), described cathode block is based on carbon and/or graphite, and has at least one groove (26), and described groove (26) is for receiving bus-bar (28),
It is characterized in that,
At least one recess (36) is arranged in wall described cathode block (20), that limit described at least one groove (26) (32,34).
25. the method for the manufacture of the cathode assembly for aluminium cell (10) (12) said method comprising the steps of:
-cathode block based on carbon and/or graphite (20) is provided, described cathode block (20) has at least one groove (26), described groove (26) is for receiving bus-bar (28), wherein, at least one recess (36) is arranged in wall described cathode block (20), that limit described at least one groove (26) (32,34)
-make at least one zone of described at least one groove (26) be lined with graphite foil (30),
-bus-bar (28) is inserted in described at least one groove (26),
-liquid cast iron is poured at least a portion described at least one recess (36), between described graphite foil (36) and described bus-bar (28), and
-described cast iron (38) is solidified.
26. method according to claim 25,
It is characterized in that,
Described graphite foil (30) is inserted and/or is glued onto in described groove (26).
27. according to the described method of claim 25 or 26,
It is characterized in that,
During the manufacture of described cathode block (20), the material that will contain carbon and/or graphite is incorporated in mould, and described mould has the projection formed with described at least one recess (36) complementation.
28. according at least one described method in claim 25 to 27,
It is characterized in that,
Described at least one recess (36) is manufactured by the material that removes and/or eliminate described wall described cathode block (20), that limit described groove (26) (32,34).
29. a cathode assembly, described cathode assembly obtains by least one the described method according in claim 25 to 28.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011004009.9 | 2011-02-11 | ||
| DE201110004009 DE102011004009A1 (en) | 2011-02-11 | 2011-02-11 | Cathode arrangement and cathode block with a guide groove having a groove |
| PCT/EP2012/051979 WO2012107412A2 (en) | 2011-02-11 | 2012-02-06 | Cathode assembly and cathode block having a groove with a guide recess |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103429792A true CN103429792A (en) | 2013-12-04 |
Family
ID=45563049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012800086302A Pending CN103429792A (en) | 2011-02-11 | 2012-02-06 | Cathode assembly and cathode block having a groove with a guide recess |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20130319853A1 (en) |
| EP (1) | EP2673400A2 (en) |
| CN (1) | CN103429792A (en) |
| AU (1) | AU2012215568A1 (en) |
| BR (1) | BR112013020197A2 (en) |
| CA (1) | CA2825785A1 (en) |
| DE (1) | DE102011004009A1 (en) |
| RU (1) | RU2013141549A (en) |
| WO (1) | WO2012107412A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109689938A (en) * | 2016-06-15 | 2019-04-26 | Cobex有限责任公司 | Cathode block with slot geometry |
| CN110379649A (en) * | 2019-06-06 | 2019-10-25 | 邵阳学院 | A kind of processing unit of unleaded electrolytic capacitor etched foil |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2506442B (en) | 2012-10-01 | 2014-09-24 | Tunstall Group Ltd | A social alarm system and method of monitoring a fall detector unit in a social alarm system |
| GB2507787B (en) | 2012-11-09 | 2014-09-24 | Tunstall Group Ltd | A fall detector and method of determining a fall in a social alarm system |
| NO347208B1 (en) * | 2012-11-13 | 2023-07-03 | Obshchestvo S Ogranichennoy Otvetstvennostyu Obedinennaya Kompaniya Rusal Inzhenerno Tekh Tsenter | Lining for an aluminum electrolyzer having inert anodes |
| DE102013207737A1 (en) * | 2013-04-26 | 2014-10-30 | Sgl Carbon Se | Cathode block with a groove of varying depth and a fixing device |
| DE102015011952A1 (en) * | 2015-09-18 | 2017-03-23 | Sgl Carbon Se | Cathode bottom, method for producing a cathode bottom and use thereof in an electrolytic cell for the production of aluminum |
| US11975972B2 (en) * | 2018-08-03 | 2024-05-07 | Sekisui Chemical Co., Ltd. | Carbon material and method for producing same, electrode material for electrical storage device, and electrical storage device |
| WO2023119802A1 (en) * | 2021-12-23 | 2023-06-29 | Ｓｅｃカーボン株式会社 | Cathode assembly |
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| SU665023A1 (en) * | 1977-10-11 | 1979-05-30 | Иркутский алюминиевый завод | Aluminium electrolyzer cathode section |
| CH663624A5 (en) * | 1985-01-25 | 1987-12-31 | Alusuisse | Cathode element of a cathode vessel for producing aluminium |
-
2011
- 2011-02-11 DE DE201110004009 patent/DE102011004009A1/en not_active Withdrawn
-
2012
- 2012-02-06 AU AU2012215568A patent/AU2012215568A1/en not_active Abandoned
- 2012-02-06 RU RU2013141549/02A patent/RU2013141549A/en not_active Application Discontinuation
- 2012-02-06 CA CA 2825785 patent/CA2825785A1/en not_active Abandoned
- 2012-02-06 EP EP12702548.4A patent/EP2673400A2/en not_active Withdrawn
- 2012-02-06 CN CN2012800086302A patent/CN103429792A/en active Pending
- 2012-02-06 WO PCT/EP2012/051979 patent/WO2012107412A2/en active Application Filing
- 2012-02-06 BR BR112013020197A patent/BR112013020197A2/en not_active Application Discontinuation
-
2013
- 2013-08-12 US US13/964,268 patent/US20130319853A1/en not_active Abandoned
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|---|---|---|---|---|
| US3867562A (en) * | 1973-02-09 | 1975-02-18 | Alusuisse | Anchoring for an electrically conductive bar in a groove in an electrode made out of a carbon block |
| US4031615A (en) * | 1975-07-17 | 1977-06-28 | Societe Des Electrodes Et Refractaires Savoie | Method of making cathodes |
| EP0052577A1 (en) * | 1980-11-19 | 1982-05-26 | Schweizerische Aluminium AG | Anchorage for a cathode bar |
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| CN109689938A (en) * | 2016-06-15 | 2019-04-26 | Cobex有限责任公司 | Cathode block with slot geometry |
| CN110379649A (en) * | 2019-06-06 | 2019-10-25 | 邵阳学院 | A kind of processing unit of unleaded electrolytic capacitor etched foil |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2825785A1 (en) | 2012-08-16 |
| WO2012107412A2 (en) | 2012-08-16 |
| BR112013020197A2 (en) | 2016-11-08 |
| DE102011004009A1 (en) | 2012-08-16 |
| RU2013141549A (en) | 2015-03-20 |
| EP2673400A2 (en) | 2013-12-18 |
| WO2012107412A3 (en) | 2012-10-11 |
| US20130319853A1 (en) | 2013-12-05 |
| AU2012215568A1 (en) | 2013-05-09 |
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Application publication date: 20131204 |