CN103443330B - Graphitization cathode block with wear-resistant surface - Google Patents
Graphitization cathode block with wear-resistant surface Download PDFInfo
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- CN103443330B CN103443330B CN201280015194.1A CN201280015194A CN103443330B CN 103443330 B CN103443330 B CN 103443330B CN 201280015194 A CN201280015194 A CN 201280015194A CN 103443330 B CN103443330 B CN 103443330B
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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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Abstract
A kind of cathode block for aluminium cell, it includes basic unit and the cap rock being disposed thereon, graphite is contained in wherein described basic unit, and the cap rock is made up of graphite composite material, and the graphite composite material contains 1 to the hard material that the fusing point less than 50 weight % is at least 1000 DEG C.
Description
Invention field
The present invention relates to the cathode block for aluminium cell.
Background technology
Such electrolytic cell is used for the electrolysis production of aluminium, and it is generally entered by Hall-H é roult methods in the industry
OK.In Hall-H é roult methods, the melt being made up of aluminum oxide and ice crystal is electrolysed.Herein, ice crystal Na3
[AlF6] be used to 2045 DEG C of fusing point of pure alumina being reduced to containing ice crystal, aluminum oxide and additive such as aluminum fluoride and
About 950 DEG C of the mixture of calcirm-fluoride.
The electrolytic cell used in this approach has the bottom being made up of the multiple cathode blocks adjoined for forming negative electrode.For
The thermally and chemically environment of generally existing during electrolytic cell operation is subjected to, cathode block is generally made up of carbonaceous material.Each negative electrode
The bottom surface of block is provided with groove, is disposed with least one bus in each recess, and the electric current through anode feed passes through the bus
Outflow.In this case, the space between each wall and bus of the restriction groove of cathode block, is generally cylinder iron sealed,
So as to which bus is electrically and mechanically connected with cathode block with the obtained bus sheath with cast iron.Formed by each anode block
Anode be disposed at about 3 to 5cm above the layer of molten aluminum on negative electrode top surface, and electrolyte contains aluminum oxide
With the melt of ice crystal, between the anode and aluminium surface.During being electrolysed at about 1000 DEG C, the aluminium of formation due to
The fact that its density is relatively large compared with electrolyte density and be deposited in below dielectric substrate, i.e. the top surface as cathode block
Intermediate layer between dielectric substrate.During electrolysis, the Current Decomposition that the aluminum oxide being dissolved in cryolite melts is flowed through
Into aluminium and oxygen.According to electrochemistry, layer of molten aluminum is actual negative electrode, because aluminium ion is reduced into element aluminum in its surface.
However, hereinafter term " negative electrode " will be not understood to refer to from the negative electrode for electrochemistry viewpoint, i.e. layer of molten aluminum, but
The component that finger-type is formed into bottom of electrolytic tank and by one or more cathode blocks.
The notable defect of Hall-H é roult methods is the big energy of its needs.In order to produce 1kg aluminium need about 12 to
15kWh electric energy, it accounts for up to the 40% of production cost.Therefore, in order to reducing production cost, it is desirable to reduce as much as possible
The ratio energy expenditure of this method.
Therefore, graphite cathode has been used more and more recently, i.e., by containing cathode block system of the graphite as main component
Into negative electrode.Here, using graphite as the graphite cathode block that raw material produces with using carbon containing graphite precursor as raw material
Differentiation is made between the graphitization cathode block of production, the graphite precursor is turned by the then heat treatment at 2100 to 3000 DEG C
It is melted into graphite.Compared with amorphous carbon, graphite is characterised by much lower ratio resistance rate and considerably higher thermal conductivity, because
This, can reduce the ratio energy expenditure of electrolysis first using graphite cathode during electrolysis, secondly can be under higher current strength
It is electrolysed, so as to improve the productivity ratio of single electrolytic cell.However, during electrolysis, due to surface erosion, the negative electrode of graphite
Or cathode block, particularly graphitization cathode block experience high wear, it is more much higher than the abrasion that amorphous carbon cathode block is undergone.It is cloudy
This erosion on pole block surface is equably occurred on the longitudinal direction of cathode block, but is being occurred most during cathode block operates
Degree increase at the borderline region of the cathode block of big local current densities.This is due to that bus is fed with the electric current in borderline region
Element is in contact, based on this reason, obtain from electric current feed element up to the resistance of cathode block surface, flowing through negative electrode
It is lower than in the situation at center of cathode block is flowed through in the situation of the borderline region of block.Due to this uneven current density
Distribution, and with the increase of running time, when being looked up in cathode block vertical, the surface of cathode block becomes approximate W type
Profile, this uneven erosion means that the service life of cathode block being limited by the point corroded with maximum.No matter
How is this point, and mechanical influence both increases the abrasion of cathode block during electrolysis.Due to the high magnetic of generally existing during electrolysis
Field and caused electromagnetic interaction, layer of molten aluminum are among continuous moving, therefore are occurred significantly on cathode block surface
Particle wears, and in the situation of graphite cathode block, this causes much higher mill compared with the cathode block made of amorphous carbon
Damage degree.
In addition, the C2 of DE 197 14 433 disclose the cated cathode block of tool, the coating contains at least 80 weight %'s
Titanium diboride, and by will produce on titanium diboride plasma jet to cathode block surface.This coating is intended to improve the moon
The wear resistence of pole block.However, such pure titanium diboride or with very high titanium diboride content coating it is extremely fragile, and
Therefore it is easy to ftracture.In addition, the specific thermic dilatation of these coatings is about the high twice of the specific thermic dilatation of carbon, therefore such cathode block
Coating only has short service life when being used in molten-salt electrolysis.
The content of the invention
It is therefore an object of the present invention to provide a kind of following cathode block, it has low ratio resistance rate, can be preferably
Fully soaked with aluminum melt, and especially for the abrasion of generally existing, chemically and thermally environment during molten-salt electrolysis operation
With high wear resistence and wearability.
According to the present invention, this purpose realizes that the cathode block has by following cathode blocks for aluminium cell
Basic unit simultaneously has cap rock, wherein graphite is contained in the basic unit, and the cap rock is made up of graphite composite material, and the graphite is compound
Material contains 1 to the hard material that the fusing point less than 50 weight % is at least 1000 DEG C.
This solution is to be based upon an insight, i.e. is provided in the basic unit containing graphite by containing no less than 1 weight
The cap rock that the graphite composite material for the hard material that amount % but the fusing point for being at most less than 50 weight % are at least 1000 DEG C is formed, is produced
Following cathode block, the cathode block have the sufficiently low ratio resistance rate for being used for high energy efficiency molten-salt electrolysis operation, and to fused salt
The abrasion of generally existing during electrolysis, chemically and thermally environment are also with very high wear resistence and therefore with wearability.
Herein, especially make us unexpected, this prevents or at least significantly reduced the W shape profiles appeared in following situation
Formation, i.e. in the situation of conventional cathode blocks made of graphite, during electrolysis due to the uneven mill on cathode block longitudinal direction
Lose and W shape profiles occur.
Therefore, cathode block of the present invention is characterised by providing the advantages of graphite is related in cathode block basic unit and cap rock,
Such as the particularly low resistance of cathode block, but the shortcomings that in the absence of by being caused using graphite, such as lack and the profit of aluminum melt
Moist and particularly low wear resistence and wearability.Conversely, because the lid containing hard material provided in cathode block of the present invention
Layer, obtains the outstanding wear resistence of cathode block and therefore have also obtained wearability.However, because this hard material is only deposited
It is being not present in cap rock in basic unit, therefore is avoiding the shortcomings that possible as caused by addition hard material, such as negative electrode
The reduction of block conductance.In addition, although the fact that using cap rock containing hard material, but the surface of the cathode block of the present invention
Cracking is surprisingly not inclined to, does not also have the adversely high fragility of characteristic particularly.Sum it up, the present invention
Cathode block has long-time stability in terms of molten-salt electrolysis is carried out using the melt containing aluminum oxide and ice crystal to produce aluminium, and
And molten-salt electrolysis can be made to be carried out with low-down than energy expenditure.
In the context of the present invention, the usual definition with the term in the art is consistent, and " hard material " is managed
Solve for refer to by particularly even at 1000 DEG C and it is higher at a high temperature of with the material characterized by extra high hardness.
The fusing point of used hard material is preferably more much higher than 1000 DEG C, wherein particularly fusing point is at least 1500 DEG C
Hard material, preferably fusing point is at least 2000 DEG C of hard material, and particularly preferably fusing point is at least 2500 DEG C
Hard material, have been demonstrated to be particularly suitable.
Generally, all hard materials can be used in the cap rock of the cathode block of the present invention.However, especially with Knoop
Hardness is at least 1000N/mm2, preferably at least 1500N/mm2, particularly preferably at least 2000N/mm2It is and very especially excellent
Selection of land at least 2500N/mm2Hard material when, obtain good result, described value is measured according to DIN EN843-4.
According to the embodiment of the first of the invention very particularly preferably, the cap rock of cathode block of the invention contains Knoop
Hardness is at least 1000N/mm2, preferably at least 1500N/mm2, particularly preferably at least 2000N/mm2It is and very especially excellent
Selection of land at least 2500N/mm2Hard carbon material as hard material, described value is measured according to DIN EN843-4.Herein
Place, carbon material, which is understood to mean, particularly to be contained higher than 60 weight %, is preferably higher than 70 weight %, particularly preferably higher than 80
Weight % and the material for being very particularly preferably higher than 90 weight % carbon.
The carbon material is selected from coke, anthracite, carbon black, vitreous carbon and two or more above-mentioned materials
Mixture material, and be particularly preferred that coke.Hereinafter, this group of compound is also referred to as " not graphitisable
Carbon ", this can not be graphitized or be at least accurate in the meaning of the bad carbon of graphitization, and it is dependent on reference in this regard
German patent application DE 10 2,010 029 538.8.The bad coke of graphitization particularly hard coke, such as acetylene coke.
Especially for the basic unit being made up of graphitized carbon and the cathode block of cap rock, in the development of concept of the present invention
It is proposed, the cap rock of cathode block of the present invention, which contains, is preferably selected from coke, anthracite, vitreous carbon and carbon black, the tool of particularly preferred coke
There is the carbon material of low graphitizability as the hard material.Graphitization cathode block produces as follows：By carbon containing stone
Black precursor mixes with binding agent and to mixture shaping in the form of providing cathode block, is then carbonized and most its stone at last
Mo Hua.Due to containing carbon material of the mixture of the graphite precursor and binding agent addition with low graphitizability then to this
As the hard material, therefore during final graphitization, the destruction of hard material additive or the hard material are to phase
Conversion to soft graphite is prevented from or is at least greatly reduced, therefore the hard material can complete its task after graphitization,
Improve the wear resistence of cathode block.In the context of the present invention, " carbon material with low graphitizability " is understood to
Refer to that degree of graphitization is at most 0.50 carbon material, the degree of graphitization is after being heat-treated at 2800 DEG C, according to Maire and
Mehring method（J.Maire, J.Mehring, Proceedings of the4th Conference on Carbon（The
The progress of four carbon meetings）, Pergamon Press1960, page 345 to 350）Calculated from average interlamellar spacing c/2.Particularly
If the carbon material for being preferably chosen from coke, anthracite, carbon black and vitreous carbon has at most 0.4 and particularly preferably at most
During 0.3 degree of graphitization, good result is obtained.
In order that the cap rock of cathode block, particularly cathode block obtains sufficiently high conductance, the lid of cathode block of the invention
Layer is preferably containing 1 to 25 weight %, particularly preferably 10 to 25 weight % and very particularly preferably 10 to 20 weight %
Carbon material is as the hard material.Therefore, obtained between the high-wearing feature and sufficiently high conductance of the cap rock special
The balance of optimization.
Moreover it is preferred that it is used as hard material in the cap rock of cathode block of the present invention and is preferably chosen from coke, smokeless
The carbon material of coal, carbon black and vitreous carbon and particularly preferably coke, there is highest 3mm and preferably up to 2mm crystal grain
Degree.
In other embodiments, the single particle has onion skin structure, its in the context of the present invention, quilt
Sandwich construction is understood as referring to, wherein the internal layer with the spherical particle to ellipsoidal shape is completely or at least partially by least
One intermediate layer and outer layer covering.
In addition, have been demonstrated advantageously, used hard material be preferably chosen from coke, anthracite, carbon black and
Apparent piling height after the carbon material of vitreous carbon and particularly preferred coke, the wherein carbon material are heat-treated at 2800 DEG C is excellent
Selection of land is less than 20nm, and the BET specific surface area of the particle of the carbon material is preferably 10 to 40m2/ g, and particularly preferably
20 to 30m2/g。
The preferred embodiment of the above-mentioned coke with low degree of graphitization, made during unsaturated hydro carbons particularly acetylene production
The coke obtained for accessory substance, it is hereinafter referred to as acetylene coke, with obtaining the coke during unsaturated hydrocarbons is produced
The unsaturated hydrocarbons property it is unrelated.It can be used to reacting gas be quenched from the synthesis in unsaturated hydro carbons particularly acetylene
The acetylene coke obtained in crude oil fractions or steam crack resid, has been demonstrated particularly suitable for this purpose.In order to produce this
Kind of coke, quenching oil or black stock are fed to and are heated to about 500 DEG C of coking plant.In coking plant, quenching oil
Liquid component volatilization, and coke is gathered on the bottom of coking plant.Corresponding process is described in such as DE 29 47
In 005 A1.The shot coke with onion-skin form is derived from, it preferably has at least 96 weight % carbon content, and
Content of ashes with most 0.05 weight %, preferably up to 0.01 weight %.
The acetylene coke preferably has the c directions crystallite dimension L less than 20nmc, and preferably less than 50nm, spy
Not You Xuandi little Yu 40nm a directions crystallite dimension La。
Substitute in addition to acetylene coke or as acetylene coke, can be used as the hard material coke it is other
Preferred embodiment, it is the coke produced in the following manner, this method is bed process, such as the spirit developed by Exxon Mobil
Coking method living, a kind of method for thermal cracking using fluidized-bed reactor.This method production has spherical to ellipsoidal shape
The coke with onion skin structure.
In addition to above-mentioned acetylene coke and/or the coke obtained by flexicoking method or it is used as their replacement
Product, the again other preferable example that may be used as the coke of the hard material is Ballet Shop coke, and it passes through " delayed coking "
To produce.The particle of this coke has spherical morphology.
Except being preferably selected from coke, anthracite, carbon black and vitreous carbon and particularly preferably Jiao as the hard material
Outside the carbon material of charcoal, the cap rock of cathode block of the present invention also contains graphite, preferably graphited carbon, and, if be adapted to, carbon
Change and/or graphited binding agent, such as pitch particularly coal tar asphalt and/or asphalt, tar, pitch, phenolic aldehyde tree
Fat or furane resins.If hereinafter mention pitch, it means that the pitch of all kinds well known by persons skilled in the art.
Here, together with carbonization and/or graphited binding agent, formation wherein embeds described hard for graphite or preferably graphited carbon
The matrix of material.Particularly if the cap rock contains 99 to 50 weight %, preferably 99 to 75 weight %, particularly preferably 90
To 75 weight %, very particularly preferably 90 to 80 weight % carbon, then good result is obtained.
According to second of embodiment very particularly preferably of the present invention, the cap rock of cathode block of the present invention contains non-oxide
Ceramics are used as the hard material, and the non-oxidation ceramic preferably belongs to the transition group of the periodic table of elements the 4th to 6 by least one
Metal and at least one element for belonging to the periodic table of elements the 3rd or 4 main groups form.These particularly include following metal carbon
Compound, metal boride, metal nitride and carbonitride, its include belong to the 4th to 6 transition group metal such as titanium,
Zirconium, vanadium, niobium, tantalum, chromium or tungsten.
The instantiation of suitable representative from these set is following compound, and it is selected from titanium diboride, two boron
Change zirconium, tantalum diboride, titanium carbide, boron carbide, titanium carbonitride, carborundum, tungsten carbide, vanadium carbide, titanium nitride, boron nitride, nitridation
Silicon, zirconium dioxide, aluminum oxide, and any required chemical combination and/or mixture of two or more above-claimed cpds.
Especially in the case of titanium diboride, titanium carbide, titanium carbonitride and/or titanium nitride, good result is obtained.Most preferably, this hair
The cap rock of bright cathode block contains titanium diboride as the hard material.All above-mentioned hard materials can be used alone, Huo Zheke
To use any required chemical combination and/or mixture of two or more above-claimed cpds.
In the development of idea of the invention, it is proposed that according to described second embodiment very particularly preferably
Hard material present in cathode block cap rock has monomodal grit distribution, wherein passing through according to international standard ISO 13320-1 quiet
The average external volume weighted PSD of state determination of light scattering（d3,50）For 10 to 20 μm.
In the context of the present invention, it is determined that there is monomodal grit as defined above as the hard material
The non-oxidation ceramic of distribution, especially particularly non-oxide titanium ceramics and titanium diboride, not only causes cathode block surface
Extraordinary wetability, its be slurry formation and slurry the reason for the deposition on cathode block surface is reliably prevented, and
And it is particularly the wear resistence for also resulting in cathode block protrusion and therefore caused wearability.In addition, in the context of the present invention,
Surprisingly determine, the ceramic hard material, excellent of the relatively small amount less than 50 weight % is provided particularly in the cap rock
Elect titanium diboride as, and when the amount particularly preferably even provided is only 10 to 20 weight %, can also realize this effect.Cause
This, can not use the high concentration ceramic hard material for causing cathode block surface frangible in the cap rock.In addition, with as above
The ceramic hard material of the monomodal grit distribution of definition is further characterized in that very good machinability.Particularly, it is such
The tendentiousness that hard material forms dust for example when being directed in blending tank or when hard material powder transports is sufficiently low,
And such as the agglomerate of small degree at most occurs during mixing and is formed.In addition, such hard material powder have it is sufficiently high
Mobility and opourability, therefore it can for example using routine conveyer and be sent to mixing arrangement.This not only all leads
The simple and cost-effective productivity of cathode block of the present invention has been caused, and has particularly resulted in the hard material in the moon
Highly uniform distribution in the block cap rock of pole.
It is hard present in the cap rock of the cathode block according to second of embodiment very particularly preferably of the present invention
Material, preferably titanium diboride, it is therefore preferred to have monomodal grit distribution, wherein the average external volume weighted PSD determined as described above
（d3,50）For 12 to 18 μm, and particularly preferably 14 to 16 μm.
As the alternative of above-mentioned embodiment, ceramic hard material can have present in the cathode block cap rock
Monomodal grit distribution, wherein the average external volume weighted PSD determined according to international standard ISO13320-1 by static light scattering
（d3,50）For 3 to 10 μm, and preferably 4 to 6 μm.In this embodiment, non-oxide titanium is also particularly preferably used
Ceramics, and most preferably with there is the titanium diboride of monomodal grit distribution as defined above.
Itd is proposed in the development of idea of the invention, the ceramic hard material has 20 to 40 μm, preferably 25 to 30 μm
Measure as described above volume weighting d3,90Granularity.The ceramic hard material preferably has such d3,90It is worth and above
The d of restriction3,50The combination of value.In this embodiment, the ceramic hard material is also preferably non-oxide titanium ceramics,
And it is particularly preferred that titanium diboride.As a result, or even to a greater degree realize the advantages of being mentioned to above-mentioned embodiment and
Effect.
As the alternative of above-mentioned embodiment, ceramic hard material can have present in the cathode block cap rock
The volume weighting d of 10 to 20 μm, preferably 12 to 18 μm of measure as described above3,90Granularity.The ceramic hard material is preferred
Ground has such d3,90The d for being worth and being defined above3,50The combination of value.In this embodiment, also particularly preferably using non-oxygen
The titanium ceramics of change, and most preferably with there is the titanium diboride for the monomodal grit distribution being defined above.
According to the other preferred embodiment of the present invention, the ceramic hard material has 2 to 7 μm, preferably 3 to 5 μm
The volume weighting d as above determined3,10Granularity.The hard material preferably has such d3,10It is worth and is defined above
d3,90Value and/or d3,50The combination of value.In this embodiment, the hard material is also preferably non-oxide titanium ceramics,
And it is particularly preferred that titanium diboride.As a result, or even to a greater degree realize the advantages of being mentioned to embodiment above
And effect.
As the alternative of above-mentioned embodiment, the ceramic hard material present in cathode block cap rock can have 1 to 3
μm, the volume weighting d of preferably 1 to 2 μm of measure as described above3,10Granularity.The hard material preferably has such
d3,10The d for being worth and being defined above3,90Value and/or d3,50The combination of value.In this embodiment, also particularly preferably using non-
The titanium ceramics of oxidation, and most preferably with there is the titanium diboride for the monomodal grit distribution being defined above.
In addition, non-oxidation ceramic as the hard material, particularly non-oxide titanium are ceramic and particularly preferred two
Titanium boride, preferably with following size distribution, the size distribution be characterised by according to following equation calculate 0.65 to
3.80th, particularly preferably 1.00 to 2.25 span value：
Span=(d3,90-d3,10)/d3,50。
The hard material preferably has such span value and the d being defined above3,90Value and/or d3,50Value and/or
d3,10The combination of value.As a result, or even to a greater degree realize the advantages of being mentioned to embodiment above and effect.
As described above, non-oxide titanium ceramics, such as preferred titanium carbide, titanium carbonitride, titanium nitride and most preferably two
Titanium boride, particularly suitable as the non-oxidation ceramic hard material in the cap rock of cathode block of the present invention.For this reason, in this hair
Itd is proposed in the development of bright concept, it is ceramic and particularly preferred that the hard material includes non-oxidation ceramic, preferably non-oxide titanium
Titanium diboride, reach at least 80 weight % degree, preferably at least 90 weight % degree, particularly preferably at least 95 weight %
Degree, very particularly preferably at least 99 weight % degree, and most preferably fully by non-oxidation ceramic, it is preferably non-oxygen
The titanium ceramics of change and particularly preferably titanium diboride composition.
According to the present invention, the total amount of the ceramic hard material in the cap rock is at least 1 weight %, but at most low
In 50 weight %.When the amount of hard material is in the number range, the cap rock contains enough hard materials, to be first
Cap rock provides excellent hardness and wear resistence to improve wearability, secondly provides cap rock surface and the sufficiently high of liquid aluminium is moistened
It is moist, deposited with avoiding slurry from being formed with slurry, as a result the wearability of cathode block further improves, and during molten-salt electrolysis
Reduction further than energy expenditure；However, simultaneously, the cap rock contains hard material a small amount of enough, to cause the cap rock
Surface does not have too high fragility because of the addition of hard material, to obtain sufficiently high long-time stability.
In this case, particularly if in second of embodiment very particularly preferably of the invention, the lid
Layer contains 5 to 40 weight %, particularly preferably 10 to 30 weight % and very particularly preferably 10 to 20 weight % non-oxide pottery
Porcelain, preferably non-oxide titanium ceramics and particularly preferred titanium diboride then will as the hard material that fusing point is at least 1000 DEG C
Obtain good result.
According to second of embodiment very particularly preferably of the present invention, except as the non-oxide of the hard material
Outside ceramics, the cap rock of cathode block of the present invention also containing graphite or preferred graphited carbon, and, if be adapted to, carbonization and/or
Graphited binding agent, such as pitch particularly coal tar asphalt and/or asphalt, tar, pitch, phenolic resin or furans
Resin.Here, together with optional binding agent, formation wherein embeds the hard material for the graphite or preferably graphited carbon
The matrix of material.Particularly if the cap rock contains 99 to higher than 50 weight %, preferably 95 to 60 weight %, particularly preferably 90
To 70 weight %, very particularly preferably 90 to 80 weight % graphite, then good result is obtained.
In the development of idea of the invention, proposed for the cathode block cap rock containing graphite, the cap rock has at 950 DEG C
It is down 5 to 20 Ω μm and preferably 9 to 13 Ω μm of vertical ratio resistance rates.This corresponds at room temperature for 5 to 25 Ω μm and 10
To 15 Ω μm of vertical ratio resistance rates.Within a context, " vertical ratio resistance rate " is understood to mean when the cathode block to hang down
Nogata to installation when ratio resistance rate.
In principle, the thickness of the cap rock should be as small as possible, so as to by expensive hard material in ceramic situation
Cost be kept as it is as low as possible, but also should be sufficiently large so that the cap rock has sufficiently high wearability and service life.
In the situation of all hard materials, the superperformance of cathode body should be damaged by minimum possible cap rock as few as possible
Evil.For these reasons, particularly if the thickness of the cap rock reaches the 1 to 50% of the cathode block total height, preferably 5
To 40%, particularly preferably 10 to 30% and very particularly preferably 15 to 25%, e.g., from about 20%, then good result is obtained.
For example, the cap rock can have 50 to 400mm, preferably 50 to 200mm, particularly preferably 70 to 180mm, very
Particularly preferably 100 to 170mm and most preferably about 150mm thickness or height.Here, " thickness or height " is understood
To refer to the distance of the highest protuberance point from the bottom surface of the cap rock to the cap rock.
According to other embodiment very particularly preferably of the invention, the basic unit includes graphite and binding agent such as carbon
Change or Graphitized pitch mixture, reach at least 80 weight % degree, preferably at least 90 weight % degree, particularly preferably
Ground at least 95 weight % degree, very particularly preferably at least 99 weight % degree, and most preferably fully by graphite with
Binding agent is for example carbonized or the mixture of Graphitized pitch is formed.Such basic unit has appropriate low ratio resistance rate.Here,
This mixture is preferably made up of 70 to 95 weight % graphite and 5 to 30 weight % binding agent, and particularly preferably by
80 to 90 weight % graphite and 10 to 20 weight % binding agent are formed, such as the carbonization of the graphite and 15 weight % by 85 weight %
Or Graphitized pitch is formed.
The bottom surface of top surface and the cap rock for the basic unit, and therefore also for the basic unit and the cap rock it
Between interface, all preferably there is substantially planar form.Two layers of the cathode block by method for oscillating or can pass through pressure
Method processed is connected to each other in green state.Within a context, " substantially planar " is understood to mean the basic unit and not had
Heteromorphosis, and the section is provided with cap rock.
Although being not preferred, intermediate layer can be set between the basic unit and the cap rock, the intermediate layer has
Such as it is that the intermediate layer has hard material concentration relatively low compared with the cap rock with the cap rock identical structure, difference.
Itd is proposed in the development of concept of the present invention, the basic unit have at 950 DEG C for 13 to 18 Ω μm, preferably 14 to
16 Ω μm of vertical resistivitys.It is at room temperature 14 to 20 Ω μm and 16 to 18 Ω μm of vertical ratio resistance rates that this is corresponding.
The invention further relates to the negative electrode containing at least one above-mentioned cathode block, wherein the cathode block is basic unit and cap rock
There is at least one groove on opposite side, wherein be provided with least one bus at least one groove, so as to
During electrolysis electric current is fed to negative electrode.
In order to which at least one bus is regularly linked into the cathode block, and in order to avoid in bus and negative electrode
The hollow space of increase resistance between block, it is additionally preferred to which at least one bus is at least in some regions and special
Preferably there is cast iron shell throughout the circumferential.Can be by the way that at least one bus to be inserted into the groove of the cathode block
In, then cast iron is imported into the space between bus and the wall for defining groove, this shell is made.
Molten-salt electrolysis is carried out the invention further relates to above-mentioned cathode block or above-mentioned negative electrode to produce metal, for example be particularly aluminium
Purposes.
The cathode block or the negative electrode be preferably used for using the melt of ice crystal and aluminum oxide carry out molten-salt electrolysis with
Aluminium is produced, the molten-salt electrolysis is particularly preferably carried out using Hall-H é roult methods.
Hereinafter, on the basis of Advantageous embodiments and referring to the drawings, only the present invention is retouched by embodiment
State.
Brief description of the drawings
In the drawing：
Fig. 1 shows the schematic cross-section of the details of following aluminium cell, and the aluminium cell is included according to this hair
The cathode block of bright illustrative embodiments.
Embodiment
Fig. 1 shows the cross section of the details of the aluminium cell 10 with negative electrode 12, and the negative electrode 12 is formed simultaneously
The bottom of following tank, the tank are used for the aluminum melt 14 produced during electrolytic cell 10 is run and for being located at aluminum melt 14
The Cryolite-alumina Melt 16 of side.The anode 18 of electrolytic cell 10 contacts with Cryolite-alumina Melt 16.By aluminium cell
The tank that 10 bottom is formed is at side by carbon and/or graphite liner（It is not shown in Fig. 1）Define.
Negative electrode 12 includes multiple cathode blocks 20,20', 20'', and it is connected with each other each via ramming mass 24,24', described to smash
Dnockout 24,24', which have been inserted into, is arranged on cathode block 20, the ramming mass joint 22 between 20', 20'', in 22'.Similarly, it is positive
Pole 18 include multiple anode blocks 26,26', the anode block 26,26' each have cathode block 20,20', 20'' close to twice
Width and the length close to half.In this case, anode block 26,26' be arranged on as follows cathode block 20,
Above 20', 20'', which to be arranged side by side each other on width in every kind of situation Anodic block 26,26' coverings two
Cathode block 20,20', 20'', and cathode block 20,20', 20'' cover two and set side by side each other in length in every kind of situation
Anode block 26, the 26' put.
Each cathode block 20,20', 20'' by the basic unit 30 of lower section, 30', 30'' and are disposed thereon and are secured to phase
Cap rock 32 even, 32', 32'' are formed.Basic unit 30,30', 30'' and cap rock 32, the interface between 32', 32'' are planes.So
And cathode block 20,20', 20'' basic unit 30,30', 30'' each have graphite material structure, it is for example, by by petroleum coke
The mixture of charcoal and coal tar asphalt is moulded and then is heat-treated at up to 3000 DEG C to produce, and cap rock 32,32', 32'' are each
Freely the graphite composite material containing acetylene coke is formed, and the graphite composite material contains 20 weight % acetylene coke, graphite
With the carbonization as binding agent or Graphitized pitch.The acetylene coke present in cap rock 32,32', 32'' has 0.2 to 1mm
Grain size.
Each cathode block 20,20', 20'' have 650mm width and 550mm total height, basic unit 30,30', 30''
Each there is 450mm height, and cap rock 32,32', 32'' each have 100mm height.Anode block 26,26' and negative electrode
The distance between block 20,20', 20'' are about 200 to about 350mm, the layer tool for the Cryolite-alumina Melt 16 being disposed there between
Have about 50mm thickness, set aluminum melt 14 thereunder layer similarly have about 150 to about 300mm thickness.
Finally, each cathode block 20,20', 20'' include two grooves 38,38' on its bottom surface, therein each to have
The cross section of rectangle, particularly substantial rectangular, wherein the steel bus of the cross section equally with rectangle or substantial rectangular
40th, 40' is accommodated in each groove 38,38'.In this case, by bus 40,40' and the wall for defining groove 38,38'
Between space each cylinder iron seal（It is not shown）, as a result, bus 40,40' be fixedly connected to define groove 38,
38' wall.Preferably, in forming process, definitely for example by swing die and/or stamping machine, by groove 38,38' and
Depression 34,34' are all placed in cap rock 32,32', 32'' top surface.
Reference numerals list
10 aluminium cells
12 negative electrodes
14 aluminum melts
16 Cryolite-alumina Melts
18 anodes
20,20', 20'' cathode block
22,22' ramming mass joints
24,24' ramming masses
26,26' anode blocks
30,30', 30'' basic unit
32,32', 32'' cap rock
38,38' grooves
40,40' buses
Claims (28)
1. a kind of cathode block (20,20', 20 ") for aluminium cell, it has basic unit (30,30', 30 ") and has cap rock
(32,32', 32 "), wherein graphite is contained in the basic unit (30,30', 30 "), the cap rock (32,32', 32 ") is answered containing graphite
Condensation material, the graphite composite material contain 1 to the hard material that the fusing point less than 50 weight % is at least 1000 DEG C, and its
Described in cap rock have 50 to 400mm thickness.
2. cathode block (20,20', 20 ") according to claim 1,
It is characterized in that
The hard material being present in the cap rock (32,32', 32 ") has at least 1000N/mm2Knoop hardness, it is described
Value is measured according to DIN EN 843-4.
3. cathode block (20,20', 20 ") according to claim 1 or 2,
It is characterized in that
The hard material being present in the cap rock (32,32', 32 "), it is the material containing the carbon for having more than 60 weight %.
4. cathode block (20,20', 20 ") according to claim 3,
It is characterized in that
The carbonaceous material is selected from any required of coke, anthracite, carbon black, vitreous carbon and two or more above-mentioned materials
Chemical combination and/or any required mixture.
5. cathode block (20,20', 20 ") according to claim 3,
It is characterized in that
The hard material being present in the cap rock (32,32', 32 ") is following carbonaceous material, the carbonaceous material tool
Have at most 0.50 degree of graphitization, the degree of graphitization be after being heat-treated at 2800 DEG C according to Maire and Mehring methods from
What average interlamellar spacing c/2 was calculated.
6. cathode block (20,20', 20 ") according to claim 3,
It is characterized in that
The cap rock (32,32', 32 ") contains 1 to 25 weight % carbonaceous material as the hard material.
7. cathode block (20,20', 20 ") according to claim 3,
It is characterized in that
As the carbonaceous material existing for the hard material in the cap rock (32,32', 32 "), have at most 3mm's
Grain size.
8. cathode block (20,20', 20 ") according to claim 3,
It is characterized in that
As the carbonaceous material existing for the hard material in the cap rock (32,32', 32 "), have at least
0.339nm average interlamellar spacing c/2, the numerical value are to interfere to determine by X-ray diffraction.
9. cathode block (20,20', 20 ") according to claim 3,
It is characterized in that
As the carbonaceous material existing for the hard material in the cap rock (32,32', 32 "), have 0.340 to
0.344nm average interlamellar spacing c/2, the numerical value are to interfere to determine by X-ray diffraction.
10. cathode block (20,20', 20 ") according to claim 3,
It is characterized in that
As the carbonaceous material existing for the hard material in the cap rock (32,32', 32 "), by BET specific surface area
For 10 to 40m2/ g particle composition.
11. cathode block (20,20', 20 ") according to claim 1 or 2,
It is characterized in that
The hard material being present in the cap rock (32,32', 32 ") is non-oxidation ceramic, and the non-oxidation ceramic is by extremely
A kind of few metal for belonging to the transition group of the periodic table of elements the 4th to 6 and at least one member for belonging to the periodic table of elements the 3rd or 4 main groups
Element is formed.
12. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
The hard material being present in the cap rock (32,32', 32 "), selected from titanium diboride, zirconium diboride, two boronations
Tantalum, titanium carbide, boron carbide, titanium carbonitride, carborundum, tungsten carbide, vanadium carbide, titanium nitride, boron nitride, silicon nitride, zirconium dioxide,
Any required chemical combination and/or mixture of aluminum oxide and two or more above-claimed cpds.
13. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
The hard material being present in the cap rock (32,32', 32 ") has monomodal grit distribution, wherein according to ISO
Average external volume weighted PSD (the d that 13320-1 is determined by static light scattering3,50) it is 10 to 20 μm.
14. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
The hard material being present in the cap rock (32,32', 32 ") has monomodal grit distribution, wherein according to ISO
Average external volume weighted PSD (the d that 13320-1 is determined by static light scattering3,50) it is 3 to 10 μm.
15. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
According to the d of the ISO 13320-1 hard materials determined by static light scattering3,90Granularity is 20 to 40 μm.
16. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
According to the d of the ISO 13320-1 hard materials determined by static light scattering3,90Granularity is 10 to 20 μm.
17. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
According to the d of the ISO 13320-1 hard materials determined by static light scattering3,10Granularity is 2 to 7 μm.
18. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
According to the d of the ISO 13320-1 hard materials determined by static light scattering3,10Granularity is 1 to 3 μm.
19. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
The hard material is non-oxide titanium ceramics, and with being calculated according to following equation, span value be 0.65 to
3.80 monomodal grit distribution：
Span=(d3,90-d3,10)/d3,50,
Wherein d3,90、d3,10And d3,50It is the grain according to the ISO 13320-1 hard materials determined by static light scattering
Degree.
20. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
The hard material contains at least 80 weight % non-oxidation ceramic.
21. cathode block (20,20', 20 ") according to claim 11,
It is characterized in that
The hard material that the fusing point of the cap rock (32,32', 32 ") containing 5 to 40 weight % is at least 1000 DEG C.
22. cathode block (20,20', 20 ") according to claim 1 or 2,
It is characterized in that
The cap rock (32,32', 32 ") is containing 99 to the graphite higher than 50 weight %.
23. cathode block (20,20', 20 ") according to claim 1 or 2,
It is characterized in that
The cap rock (32,32', 32 ") has at 950 DEG C for 5 to 20 Ω μm of vertical ratio resistance rates.
24. cathode block (20,20', 20 ") according to claim 1 or 2,
It is characterized in that
The thickness of the cap rock (32,32', 32 ") reaches the 1 to 50% of the total height of the cathode block (20,20', 20 ").
25. cathode block (20,20', 20 ") according to claim 1 or 2,
It is characterized in that
The basic unit (30,30', 30 ") includes graphite and binding agent, reaches at least 80 weight % degree.
26. cathode block (20,20', 20 ") according to claim 1 or 2,
It is characterized in that
The basic unit (30,30', 30 ") has at 950 DEG C for 13 to 18 Ω μm of vertical ratio resistance rates.
27. a kind of negative electrode (12), its contain it is at least one according to one of preceding claims cathode block (20,20',
20 "), wherein the cathode block (20,20', 20 ") is in the basic unit (30,30', 30 ") and institute cap rock (32,32', 32 ") phase
There is at least one groove (38,38'), wherein being provided with least one at least one groove (38,38') on anti-side
Individual bus (40,40 '), to feed electric current to the negative electrode (12) during electrolysis.
28. cathode block (20,20', 20 ") according to any one of claim 1 to 26 or according to claim 27 institute
The purposes for the negative electrode (12) stated, it is used to carry out molten-salt electrolysis to produce metal.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011004013A DE102011004013A1 (en) | 2011-02-11 | 2011-02-11 | Graphitized cathode block with an abrasion resistant surface |
| DE102011004013.7 | 2011-02-11 | ||
| PCT/EP2012/051959 WO2012107400A2 (en) | 2011-02-11 | 2012-02-06 | Graphitized cathode block having an abrasion-proof surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103443330A CN103443330A (en) | 2013-12-11 |
| CN103443330B true CN103443330B (en) | 2018-01-02 |
Family
ID=45558749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280015194.1A Expired - Fee Related CN103443330B (en) | 2011-02-11 | 2012-02-06 | Graphitization cathode block with wear-resistant surface |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP2673396A2 (en) |
| JP (1) | JP5963779B2 (en) |
| CN (1) | CN103443330B (en) |
| CA (1) | CA2826599A1 (en) |
| DE (1) | DE102011004013A1 (en) |
| RU (1) | RU2586381C2 (en) |
| UA (1) | UA110511C2 (en) |
| WO (1) | WO2012107400A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013202437A1 (en) * | 2013-02-14 | 2014-08-14 | Sgl Carbon Se | Cathode block with a wettable and abrasion resistant surface |
| CN104120454B (en) * | 2014-07-01 | 2016-08-17 | 湖南创元铝业有限公司 | Prebaked anode non-oxidizability ceramic base coating and painting method thereof |
| RU2682732C1 (en) * | 2018-02-06 | 2019-03-21 | федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" | Method for production of a cathode pack for an aluminum electrolytic cell |
| CN111364061B (en) * | 2018-12-25 | 2021-03-16 | 中南大学 | Wettable carbon cathode for aluminum electrolysis and preparation method and application thereof |
| CN113897639B (en) * | 2021-11-19 | 2024-06-07 | 河南世源铝业科技有限公司 | Aluminum-oxygen-separating electrode for electrolytic aluminum and preparation method thereof |
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| FR1303788A (en) * | 1961-10-13 | 1962-09-14 | Union Carbide Corp | Carbon parts plating process |
| DE2947005C2 (en) | 1979-11-22 | 1983-08-04 | Basf Ag, 6700 Ludwigshafen | Process for the production of acetylene from hydrocarbons |
| US4333813A (en) * | 1980-03-03 | 1982-06-08 | Reynolds Metals Company | Cathodes for alumina reduction cells |
| US4308114A (en) * | 1980-07-21 | 1981-12-29 | Aluminum Company Of America | Electrolytic production of aluminum using a composite cathode |
| US4376029A (en) * | 1980-09-11 | 1983-03-08 | Great Lakes Carbon Corporation | Titanium diboride-graphite composits |
| EP0085093A4 (en) * | 1981-07-27 | 1984-04-27 | Great Lakes Carbon Corp | Sintered refractory hard metals. |
| US4526669A (en) * | 1982-06-03 | 1985-07-02 | Great Lakes Carbon Corporation | Cathodic component for aluminum reduction cell |
| US4466995A (en) * | 1982-07-22 | 1984-08-21 | Martin Marietta Corporation | Control of ledge formation in aluminum cell operation |
| US4544469A (en) * | 1982-07-22 | 1985-10-01 | Commonwealth Aluminum Corporation | Aluminum cell having aluminum wettable cathode surface |
| US4481052A (en) * | 1983-01-28 | 1984-11-06 | Martin Marietta Corporation | Method of making refractory hard metal containing tiles for aluminum cell cathodes |
| US4582553A (en) * | 1984-02-03 | 1986-04-15 | Commonwealth Aluminum Corporation | Process for manufacture of refractory hard metal containing plates for aluminum cell cathodes |
| FR2566002B1 (en) * | 1984-06-13 | 1986-11-21 | Pechiney Aluminium | MODULAR CATHODE BLOCK AND LOW VOLTAGE DROP CATHODE FOR HALL-HEROULT ELECTROLYSIS TANKS |
| DE3534750A1 (en) * | 1985-09-28 | 1987-04-16 | Krupp Gmbh | FLOOR OF AN ELECTRICALLY HEATED MELTING STOVE, ESPECIALLY A DC STOVE |
| US5250324A (en) * | 1990-06-25 | 1993-10-05 | Lanxide Technology Company, L.P. | Method for forming a surface coating using powdered solid oxidants and parent metals |
| US5364513A (en) * | 1992-06-12 | 1994-11-15 | Moltech Invent S.A. | Electrochemical cell component or other material having oxidation preventive coating |
| CA2152048C (en) * | 1992-12-17 | 2004-06-29 | Kevin Drew Watson | Electrolysis cell for metal production |
| EP1146146B1 (en) * | 1994-09-08 | 2003-10-29 | MOLTECH Invent S.A. | Horizontal drained cathode surface with recessed grooves for aluminium electrowinning |
| DE19714433C2 (en) | 1997-04-08 | 2002-08-01 | Celanese Ventures Gmbh | Process for producing a coating with a titanium boride content of at least 80% by weight |
| CA2350814C (en) * | 1998-11-17 | 2006-01-10 | Alcan International Limited | Wettable and erosion/oxidation-resistant carbon-composite materials |
| CN1091471C (en) * | 2000-05-08 | 2002-09-25 | 新化县碳素厂 | Carbon block as cathode with compound titanium boride-carbon layer and its preparing process |
| CN100491600C (en) * | 2006-10-18 | 2009-05-27 | 中国铝业股份有限公司 | Method for preparing carbon block of cathode capable of being humidified |
| ATE486355T1 (en) * | 2007-02-15 | 2010-11-15 | Sgl Carbon Se | POROUS COKE |
| CN101158048A (en) * | 2007-08-03 | 2008-04-09 | 中国铝业股份有限公司 | Graphitized wetable cathode carbon block for aluminium electrolysis bath and production method thereof |
| RU2371523C1 (en) * | 2008-06-23 | 2009-10-27 | Федеральное государственное образовательное учреждение высшего профессионального образования "Сибирский федеральный университет" | Composite material for moistened cathode of aluminium electrolytic cell |
| CN201261809Y (en) * | 2008-08-12 | 2009-06-24 | 高德金 | Cathode inner lining with molten aluminum magnetic vortex stream adjustment device |
| DE102010029538A1 (en) | 2010-05-31 | 2011-12-01 | Sgl Carbon Se | Carbon body, process for producing a carbon body and its use |
| DE102010038669A1 (en) * | 2010-07-29 | 2012-02-02 | Sgl Carbon Se | Cathode block for an aluminum electrolysis cell and a method for its production |
-
2011
- 2011-02-11 DE DE102011004013A patent/DE102011004013A1/en not_active Ceased
-
2012
- 2012-02-06 JP JP2013552923A patent/JP5963779B2/en not_active Expired - Fee Related
- 2012-02-06 CN CN201280015194.1A patent/CN103443330B/en not_active Expired - Fee Related
- 2012-02-06 CA CA2826599A patent/CA2826599A1/en not_active Abandoned
- 2012-02-06 WO PCT/EP2012/051959 patent/WO2012107400A2/en active Application Filing
- 2012-02-06 RU RU2013141536/02A patent/RU2586381C2/en not_active IP Right Cessation
- 2012-02-06 EP EP12701928.9A patent/EP2673396A2/en not_active Withdrawn
- 2012-06-02 UA UAA201310891A patent/UA110511C2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012107400A2 (en) | 2012-08-16 |
| UA110511C2 (en) | 2016-01-12 |
| RU2586381C2 (en) | 2016-06-10 |
| CA2826599A1 (en) | 2012-08-16 |
| EP2673396A2 (en) | 2013-12-18 |
| DE102011004013A1 (en) | 2012-08-16 |
| JP2014505176A (en) | 2014-02-27 |
| CN103443330A (en) | 2013-12-11 |
| RU2013141536A (en) | 2015-03-20 |
| WO2012107400A3 (en) | 2013-01-10 |
| JP5963779B2 (en) | 2016-08-03 |
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