CN104937144A - An electrode for aluminium production and a method of making same - Google Patents

An electrode for aluminium production and a method of making same Download PDF

Info

Publication number
CN104937144A
CN104937144A CN201480005438.7A CN201480005438A CN104937144A CN 104937144 A CN104937144 A CN 104937144A CN 201480005438 A CN201480005438 A CN 201480005438A CN 104937144 A CN104937144 A CN 104937144A
Authority
CN
China
Prior art keywords
electrode
blocking layer
electrode according
conductive compositions
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201480005438.7A
Other languages
Chinese (zh)
Other versions
CN104937144B (en
Inventor
E·哈根
B·欧叶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Norsk Hydro ASA
Original Assignee
Norsk Hydro ASA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Norsk Hydro ASA filed Critical Norsk Hydro ASA
Publication of CN104937144A publication Critical patent/CN104937144A/en
Application granted granted Critical
Publication of CN104937144B publication Critical patent/CN104937144B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/12—Anodes
    • 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
    • C25C3/12—Anodes
    • C25C3/125—Anodes based on carbon
    • 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

Abstract

An electrode for production of aluminium metal by electrolysis of an aluminium containing compound dissolved in a molten electrolyte, where the electrowinning process is performed in smelting cells of conventional Hall-Heroult design. The electrode comprises a calcinated carbon containing body being integrated with at least one composite metallic conductor comprising conducting elements of a Fe containing material and conducting elements of a Cu containing material. The composite conductor comprises a barrier layer material at the interface between the two conducting materials. Barrier materials of ceramic, Refractory Hard Materials (RHM), and of metallic types are proposed as well as methods for their application.

Description

For electrode that aluminium is produced and preparation method thereof
The present invention relates to electrode produced for aluminium and preparation method thereof.
Carry out production aluminum metal by the electrolysis being dissolved in the aluminum contained compound in fused electrolyte at present, and carry out electrolytic metallurgy technique in the melting groove designed at the Hall-Heroult of routine.Equip these electrolyzers with the electrode of horizontally embarking on journey, the electrical conductivity anode of wherein current groove and negative electrode are prepared by carbon material.Ionogen is the mixture based on Sodium Fluoride and aluminum fluoride, and adds alkali and alkaline earth metal halide.Cause aluminum ion when negative electrode discharge by ionogen to the electric current of negative electrode along with from anode, this electrolytic metallurgy technique occurs, produce aluminum metal.
Usually, for fixing steel collector rod in cathode block, there is preformed groove in the block, this groove allows this rod to enter wherein.Can space or the space between the wall of this groove and this rod be filled with the cast iron of fusing and/or can electrocondution slurry be applied.
In a similar fashion, the carbon anode of prebake is fixed to steel bolt, this steel bolt is a part for anode carrier.This anode has preformed hole, and it allows steel bolt to enter wherein.Usually fixing of this bolt and anode is carried out by the cast iron of pouring molten in the annular space between hole corresponding in each single bolt and anode.
In alternative mode, conductive particle can be applied with rodding, as shown in the patent application WO09/099335 of applicant oneself.
In the chasing of the low specific energy consumption of producing for aluminium, one known and effective means are objects is to reduce negative electrode and/or anode drop.In fact, reduction cathode drop reduces ohm energy waste in negative electrode, allows operator increase potline current intensity and/or reduce bath voltage, finally causes the reduction that the specific energy producing aluminium per ton consumes.
Employ the reduction that many methods go to realize cathode drop, and a kind of usually known method uses copper insert to improve the specific conductivity of conventional steel collector rod.Many publications demonstrate side or the surface that this copper insert or element have at least one outside, and this side or surface lean against on surface corresponding to of this steel collector rod.
In WO04031452, give example, it discloses the steel collector rod with copper core, US5976333A and WO0163014 all discloses the copper bar of the various different designs inserted in steel pipe, and this steel pipe embeds in the groove of cathode block.
Demonstrating the copper insert in steel collector rod in testing can make cathode drop reduce about 60mV relative to the steel collector rod of routine.
Use in the cathode copper as another benefit of high connductivity composition be with such design realize evenly cathode current density.Especially for graphitization cathode, evenly current density reduce maximum erosion rate, thereby increase cathode life.
But each mV saved to comprise the solution of inserting high connductivity composition is expensive, because except the expensive copper bar used, assembling (boring of collector rod and copper rod insertion) is almost three times of independent copper cost.
In addition, contriver observes under the high temperature existing for such composite conductor, and the Fe in steel collector rod can diffuse in the Cu metal of contiguous copper insert.
This diffusion can cause the increase of the ohmic resistance rate of composite current collector rod, and causes cathode drop to increase along with the time subsequently.
When applying this Fe-Cu type composite conductor for anode, similar impact can be there is about ohmic resistance rate.
The present invention relates to the electrode, male or female and preparation method thereof with composite conductor, wherein can reduce or avoid these adverse influences.
More specifically, the present invention relates to the electrode carrying out production aluminum metal for the electrolysis by being dissolved in the aluminum contained compound in fused electrolyte, in the melting groove wherein designed at the Hall-Heroult of routine, carrying out electrolytic metallurgy technique.This electrode package is containing the body containing calcining carbon, and should have at least one composition metal conductor fixing with it containing the body of calcining carbon, this at least one composition metal conductor comprises the conductive compositions containing Fe material and the conductive compositions containing Cu material.The interface of this composite conductor between two kinds of electro-conductive materials comprises diffusion barrier material.Obtain several material for diffusion impervious layer and the method for applying this layer.
At least two free-revving engines of the present invention can be mentioned;
1) in the life period resistivity minimally of groove, and
2) in composite conductor, thinner Cu-part is used, i.e. Cu plate, to increase quality and the Cost Status of this composite conductor.
These and more advantage can be realized according to such as required in the appended claims the present invention.
Hereinafter, the present invention will be further described by chart, wherein:
Fig. 1 is the phasor that exposure Fe is diffused in Cu,
Fig. 2 is the chart of display increase of resistivity when Fe is diffused in Cu,
Fig. 3 is the chart of display for composite conductor Fe concentration in Cu when not having and have various baffle element material.
The present invention relates generally to electrode, but when relating to negative electrode, usually there is a problem for collector rod, and this problem is that their working temperature is far above 900 DEG C, and other composition contact with this collector rod can be diffused in this material and the resistivity of this material deteriorated.For common steel collector rod, carbon (C) is diffused in steel and resistivity increases.
For composite current collector rod (i.e. Cu and Fe), there is extra phase mutual diffusion.Fe will be diffused into the content provided to phasor in FIG in Cu.Vice versa, and Cu also will be diffused in Fe, but this resistivity for assembly is not too crucial.
Measure the increase of the resistivity when Fe is diffused in Cu, and shown in Figure 2.When Cu become saturated have a Fe time, the resistivity of Cu adds almost 100%.Therefore the baffle element with the phase mutual diffusion preventing Fe in Cu is needed.
The character required for baffle element preventing Fe to be diffused in Cu in composite current collector rod is:
1) low solubility of compound in Fe and Cu
2) be stable under the working temperature of groove
3) electricity specific conductivity is kept
4) easily apply in thin layer
In first experiment, apply TiB to Cu-bar 2the shallow layer of powder, and effect is tested in diffusion experiment.At TiB 2flood Cu bar in slurry and be applied with the layer of 100 micron thickness.In hollow steel, put into this bar and this device heats to 950 DEG C is continued 14 days.
In next one experiment, test Mo and the W paper tinsel of 100 microns in the same way, namely apply each paper tinsel in the surface of Cu bar, to put it into subsequently in hollow steel and correspondingly to heat.
Show concentration profile in figure 3.Observe the obvious reduction of diffusion.For TiB 2coating, observes diffusion with 10 times of reductions.Mo and W paper tinsel seems in fact to prevent diffusion in the period (14 days) of test.
Other composition/compound may be had to be that more (cost) is effective and do not have tested, and baffle element is not limited to the compound mentioned here.Meeting other conducting metal of standard, intermetallic compound or material is potential baffle element.
When selecting to have the material of low spread coefficient, low solubility is also important character.The specific conductivity of copper very depends on impurity level, and therefore the solubleness of material defines the upper limit of the infringement that this material can be made.This baffle element material should be able to stop Fe, and this baffle element material itself must can not enter copper phase simultaneously.
Usually, with compared with crystals, spread and more promptly occur along crystal boundary with on free surface, namely impurity will be diffused in this metal more quickly along crystal boundary.As long as solubleness is low, just also should expects that the accumulation in copper is low, and therefore will limit the potential reduction of specific conductivity.Except low diffusivity, good diffusion barrier block body also must have low solubleness in copper, and has enough electricity specific conductivity.
the choice criteria of metal barrier body material
Hume-Rothery (reference: Lee J.D.: " Concise Inorganic Chemistry ", 4th edition, Chapman & Hall, London 1991,136th page) found a series of simple rule, if the condition that will meet should appear sosoloid in a large number, in this rule description between metal:
Atomic query rule: the relative difference between two class atomic diameters (radius) should be less than 15%.If this difference >15%, then limit this solubleness.
Crystalline structure rule: for considerable solid solubility, the crystalline structure of two kinds of elements must be identical.
Valency rule: with lower valent metallographic phase ratio, a kind of metal will dissolve higher valent metal to larger degree.Solute and solvent atom should typically have identical valency, to realize maxima solubility.
Electronegativity rule: electronegativity difference produces maxima solubility close to 0.A kind of element more positive polarity and another kind more electronegativity, they are by larger for the possibility forming intermetallic compound instead of substitutional solid solution.Solute and solvent should be positioned at relative close position in the electrochemical series.
Baffle element metal according to the present invention should fall into outside above-mentioned rule as compared to Cu with Fe, because it should not disturb them.
for the choice criteria of ceramic baffle element material
When such as refractory hard material (RHM) is as baffle element material for applying pottery, if can hold less atom between the atom in metal lattice, so interval type sosoloid can be formed.According to rule (seeing below), only has the atomic radius of two kinds of compositions to compare r l/ r m<0.59, just forms interval type sosoloid.
Reference: g.: in Kristallbau by Hydriden, Boriden, Carbiden und Nitriden " der ü bergangselemente ", S.Phys.Chem.B12 (1931) 33-56and g.: " Eigenschaften der Phasen vonUbergangselementen in bin'aren Systemen mit Bor, Kolestoff undStickstoff ", Z.Phys.Chem.B12 (1931) 221-232.
Based on these standards, evaluate and contact with Cu, metal such as Ta, Mo and W appear to have hope.The good candidate preventing baffle element material from entering Cu is looked like containing B pottery.In addition, refractory hard material (RHM) also can provide good material standed for, such as nitride and boride, more specifically TiN, TaN, ZrN and ZrB 2, TiB 2and possible boride usually.
Stop the ability of Fe about baffle element material, find that W seems to be hopeful most, and Mo and Ru is possible.Come from CRC handbook the 58th edition, the W diffusion data of 1977-1978, F-63-F-71 shows that Fe is diffused in W and is diffused into slow four orders of magnitude in Cu than it.
As mentioned above, the interface of the composite conductor in electrode between two kinds of electro-conductive materials comprises diffusion barrier material.Demonstrate;
This diffusion impervious layer can be prepared by stupalith or RHM material.
Nitride or boride (such as TiN, TaN, ZrN, ZrB can also be applied 2or TiB 2) diffusion impervious layer.
Method for applying these diffusion barrier material can comprise and prepares diffusion barrier material in a form of slurry, and by flood in described slurry in two conductive compositions at least one then drying be applied to conductive compositions, or can be applied by powder coated.
In addition, the method for applying diffusion barrier block body material can comprise and applies this blocking layer by plasma coating techniques.
Preferred metallic alloy blocking layer comprises: Mo, W, Ta or Ru.
These diffusion impervious layers can be prepared by chemical vapour deposition or plating with the form of paper tinsel, and before making the associating of these parts, these diffusion impervious layers are applied at least one of two conductive compositions.
The thickness on blocking layer can preferably in the scope of 1-1000 μm.

Claims (14)

1. the electrode of production aluminum metal is carried out for the electrolysis by being dissolved in the aluminum contained compound in fused electrolyte, electrolytic metallurgy technique is carried out in the melting groove wherein designed at the Hall-Heroult of routine, wherein this electrode package is containing the body containing calcining carbon, the at least one composition metal conductor fixing with it should be had containing the body of calcining carbon, this at least one composition metal conductor comprises the conductive compositions containing Fe material and the conductive compositions containing Cu material, it is characterized in that: the interface of this composite conductor between two kinds of electro-conductive materials comprises diffusion barrier material.
2. electrode according to claim 1, is characterized in that: this blocking layer is stupalith.
3. electrode according to claim 2, is characterized in that: this blocking layer is made up of RHM material.
4. electrode according to claim 3, is characterized in that: this blocking layer such as, by nitride or boride, TiN, TaN, ZrN, ZrB 2or TiB 2obtained.
5. according to the electrode of Claims 2 or 3, it is characterized in that: apply this blocking layer with the state of slurry or by plasma coated.
6. electrode according to claim 1, is characterized in that: this blocking layer is metallic substance.
7. electrode according to claim 6, is characterized in that: this blocking layer is made up of Mo.
8. electrode according to claim 6, is characterized in that: this blocking layer is made up of W.
9. electrode according to claim 6, is characterized in that: this blocking layer is made up of Ta.
10. electrode according to claim 6, is characterized in that: this blocking layer is made up of Ru.
11. electrodes according to claim 6, is characterized in that: blocking layer during applying is paper tinsel shape, or is applied by other method, such as chemical vapour deposition, plating or similar method.
12., according to the electrode of any one aforementioned claim, is characterized in that: the thickness on this blocking layer is in the scope of 1-1000 μm.
13. according to the preparation method of the electrode of claim 1-5, it is characterized in that: prepare this diffusion impervious layer in a form of slurry, and then dry or by powder coated, this diffusion impervious layer is applied to conductive compositions by least one of flooding two conductive compositions in described slurry.
14. according to the preparation method of the electrode of claim 6-11, it is characterized in that: prepare this diffusion impervious layer by chemical vapour deposition or plating with the form of paper tinsel, and before making the associating of these parts, this diffusion impervious layer is applied at least one of two conductive compositions.
CN201480005438.7A 2013-01-22 2014-01-20 Electrode and preparation method thereof for aluminium production Expired - Fee Related CN104937144B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO20130123 2013-01-22
NO20130123A NO338410B1 (en) 2013-01-22 2013-01-22 An electrode for making aluminum and a method for forming the same
PCT/NO2014/000002 WO2014116117A1 (en) 2013-01-22 2014-01-20 An electrode for aluminium production and a method of making same

Publications (2)

Publication Number Publication Date
CN104937144A true CN104937144A (en) 2015-09-23
CN104937144B CN104937144B (en) 2019-09-03

Family

ID=51227824

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480005438.7A Expired - Fee Related CN104937144B (en) 2013-01-22 2014-01-20 Electrode and preparation method thereof for aluminium production

Country Status (10)

Country Link
EP (1) EP2948577B1 (en)
CN (1) CN104937144B (en)
AU (1) AU2014210417B2 (en)
BR (1) BR112015017071A2 (en)
CA (1) CA2896472C (en)
EA (1) EA028191B1 (en)
NO (1) NO338410B1 (en)
NZ (1) NZ709857A (en)
SA (1) SA515360744B1 (en)
WO (1) WO2014116117A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5704993A (en) * 1995-10-10 1998-01-06 The Regents Of The Univerisity Of California, Office Of Technology Transfer High conductivity composite metal
US6231745B1 (en) * 1999-10-13 2001-05-15 Alcoa Inc. Cathode collector bar
US20060151333A1 (en) * 2002-12-30 2006-07-13 Sgl Carbon Ag Cathode systems for electrolytically obtaining aluminum
EP1927679A1 (en) * 2006-11-22 2008-06-04 Alcan International Limited Electrolysis cell for the production of aluminium comprising means to reduce the voltage drop
WO2009055844A1 (en) * 2007-10-29 2009-05-07 Bhp Billiton Innovation Pty Ltd Composite collector bar

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6528185B2 (en) * 2001-02-28 2003-03-04 Hong Kong Polytechnic University Cobalt-tungsten-phosphorus alloy diffusion barrier coatings, methods for their preparation, and their use in plated articles
DE10227034A1 (en) * 2002-06-17 2003-12-24 Km Europa Metal Ag Copper casting mold
AU2003274399A1 (en) * 2002-10-18 2004-05-04 Moltech Invent S.A. Anode current feeding connection stem

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5704993A (en) * 1995-10-10 1998-01-06 The Regents Of The Univerisity Of California, Office Of Technology Transfer High conductivity composite metal
US6231745B1 (en) * 1999-10-13 2001-05-15 Alcoa Inc. Cathode collector bar
US20060151333A1 (en) * 2002-12-30 2006-07-13 Sgl Carbon Ag Cathode systems for electrolytically obtaining aluminum
EP1927679A1 (en) * 2006-11-22 2008-06-04 Alcan International Limited Electrolysis cell for the production of aluminium comprising means to reduce the voltage drop
WO2009055844A1 (en) * 2007-10-29 2009-05-07 Bhp Billiton Innovation Pty Ltd Composite collector bar

Also Published As

Publication number Publication date
EP2948577A4 (en) 2016-04-20
SA515360744B1 (en) 2018-12-10
NO338410B1 (en) 2016-08-15
AU2014210417B2 (en) 2017-06-29
EP2948577A1 (en) 2015-12-02
EP2948577B1 (en) 2018-12-05
NZ709857A (en) 2019-07-26
EA028191B1 (en) 2017-10-31
EA201500763A1 (en) 2015-11-30
CN104937144B (en) 2019-09-03
CA2896472C (en) 2020-04-14
CA2896472A1 (en) 2014-07-31
NO20130123A1 (en) 2014-07-23
WO2014116117A1 (en) 2014-07-31
AU2014210417A1 (en) 2015-07-16
BR112015017071A2 (en) 2017-07-11

Similar Documents

Publication Publication Date Title
Sokhanvaran et al. Electrochemistry of molten sulfides: copper extraction from BaS-Cu2S
AU2017203090B2 (en) Systems and methods of protecting electrolysis cells
Yang et al. Selective electrodeposition of dysprosium in LiCl-KCl-GdCl3-DyCl3 melts at magnesium electrodes: application to separation of nuclear wastes
RU2642782C2 (en) Systems and methods for protection of electrolyser side walls
US6719889B2 (en) Cathode for aluminum producing electrolytic cell
Mohammadi et al. Anodic behavior and corrosion resistance of the Pb-MnO2 composite anodes for metal electrowinning
Cao et al. Electrochemical oxidation of Fe–Ni alloys in cryolite–alumina molten salts at high temperature
JP6802255B2 (en) Conductive material and its manufacturing method
US20190323135A1 (en) Methods of forming alloys by reducing metal oxides
RU2683683C2 (en) Anode device
US11519090B2 (en) Method and apparatus for producing electrolytic aluminum foil
Los et al. Laboratory and pilot scale tests of a new potential-controlled method of copper industrial electrolysis
RU2692759C1 (en) Lead-carbon metal composite material for electrodes of lead-acid batteries and a method for synthesis thereof
CN104937144A (en) An electrode for aluminium production and a method of making same
Saevarsdottir et al. Anodic Behaviour of Ni42Fe38Cu20 Electrode in Molten Fluoride Salts
SE425804B (en) PROCEDURE FOR ELECTROLYST OF A LIQUID ELECTROLYT BETWEEN AN ANOD AND A CATHOD
Meirbekova et al. Influence of phosphorus on current efficiency in aluminum electrolysis at different current densities
Chen et al. Study on the electrochemical Co-reduction of Gd (III) and Al (III) in LiF-CaF2 melt
Xianxi Aluminum electrolytic inert anode
TW201518560A (en) Electrolyte for electrodepositing molybdenum and method for forming molybdenum-containing layer
Rolseth et al. Studies on the possible presence of an aluminum carbide layer or bath film at the bottom of aluminum electrolysis cells
Sokhanvaran et al. Cyclic Voltammetry Study of Anodic and Cathodic Reactions on Graphite in Cryolite-Silica Melt
Zheng et al. Electrochemical migration of sintered nanosilver under chloride-containing thin electrolyte layer for power electronic packaging
Zhang et al. Electrochemical preparation of Mg-Li-Y alloys by codeposition from LiCl-KCl-MgCl2-YCl3 melts
Sequeira Electrodeposition of Ti from K2TiF6 in NaCl‐KCl‐NaF Melts

Legal Events

Date Code Title Description
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190903

Termination date: 20220120

CF01 Termination of patent right due to non-payment of annual fee