CN101824631A - Composite alloy inert anode for aluminum electrolysis and aluminum electrolysis method utilizing same - Google Patents
Composite alloy inert anode for aluminum electrolysis and aluminum electrolysis method utilizing same Download PDFInfo
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Abstract
The invention relates to a composite alloy inert anode for aluminum electrolysis. The composition of the matrix of the composite alloy inert anode for aluminum electrolysis is (x)A(y)B, wherein X is the content of A in percentage by weight, y is the content of B in percentage by weight, X is 40-100%, and y is 0-60%; A consists of one or multiple elements of Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Sn and Zn; and B consists of one or multiple elements of Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb, Si, N, C and rare-earth. A compact protective film is coated on the matrix, and is an oxide film and or a permeator. The composite alloy inert anode is adopted in the process of electrolysis, thus solving the problems of poor conductivity and thermal shock stability of ceramic anodes; the composite alloy inert anode has better corrosion resistance as compared with a single alloy anode; and in addition, the composite alloy inert anode is especially suitable for being applied in a low-temperature aluminum electrolysis system and can also be applied in the field of fusion-electrolysis metallurgy of rare earth, Mg and the like.
Description
Technical field
The present invention relates to the anode material of electrolysis of aluminum; adopt composite alloy as inert anode material; characteristics are by forming fine and close protective membrane on the alloy substrate surface; these composite alloy inert anodic characteristics are to be better than the ceramic-like inert anode aspect conductivity and the thermal shock resistance; aspect anticorrosive, be better than the alloy anode material, the composite alloy inert anode be applied to the electrolysis of aluminum industry can avoid a large amount of greenhouse gases CO
2With the discharging of perfluorinated hydrocarbon, belong to Non-ferrous Metallurgy fused salt electrolysis technical field.
Background technology
Traditional Hall-H é roult method electrolysis is produced needs to consume a large amount of high-quality carbon sources and frequent replacing anode in the aluminium process, but also can discharge a large amount of greenhouse gases CO
2Reach pollutions such as perfluor class carbide, carry out technological revolution and become the research focus.The carbon anode that inert anode substitutes in the existing technology becomes the hot issue that people study.In the electrolysis of aluminum, because the electrochemical oxidation zone of anode in the cryolite fused salt system, so the corrosion resistance nature of inert anode material becomes the key of research.At present, the development to the inert anode novel material mainly is divided into ceramic anode, sintering metal anode and metal anode three class electrodes with exploitation.Wherein, ceramic anode and sintering metal anode are owing at the needs that are difficult to satisfy aluminium electrolytic industry aspect heat-conductivity conducting performance and the thermal shock resistance, will significantly improve energy consumption if adopt the low-temperature electrolyte system conductivity also can reduce significantly.Nineteen ninety Sadoway proposes to adopt alloy as the used for aluminium electrolysis inert anode first, from then on alloy anode is considered to a class electrode more likely, because its electrical and thermal conductivity performance is good, the machining property excellence especially is suitable as the inert anode material in the low temperature system.Invent a kind of novel alloy material, the production needs that make this material can satisfy aluminium electrolytic industry have become people's common recognition.Shi Zhongning is at patent " metal matrix aluminum electrolysis inertia anode and preparation method thereof " (mandate publication number: CN 1203217C; Application number: 03111484.9) disclose employing binary or multi-element metal alloy and constituted inert anode; but simple metal alloy or only carry out the inert anode that simple pre-oxidation treatment obtains and carry out electrolysis of aluminum; electrode surface easily forms loose metal protective film; this can make the fluorochemical in the ionogen corrode alloy easily; be unfavorable for suppressing corrosion of metal; therefore develop and a kind ofly form fine and close oxide film on the alloy base surface, and this protective membrane should to have a good corrosion resistance nature significant for the technology progress of electrolysis of aluminum.
Summary of the invention
The present invention is based on the focus of present world aluminum industrial development, the successful composite alloy inert anode of research on a large amount of experimental study bases.The purpose of this invention is to provide a kind of inert anode that is applicable to that Aluminium Electrolysis is used, it is the greenhouse gases CO that anode was brought that purpose is to solve in the existing technology with the charcoal element
2, the perfluorinated hydrocarbon emission problem, and the frequent substitution anode makes problems such as the continuous production of electrolysis of aluminum is forced to stop.
A further object of the present invention provides a kind of composite alloy inert anodic method for preparing used for aluminium electrolysis.
When the present invention proposes a kind of inert anode that is applicable to electrolysis of aluminum, also provide the operational condition that is applicable to this inert anode.The method that another object of the present invention is to provide a kind of novel electrolysis system and uses inert anode to carry out electrolysis of aluminum.
The present invention comes to be realized by the following technical programs:
A kind of composite alloy inert anode of used for aluminium electrolysis, the composite alloy inert anodic matrix of this used for aluminium electrolysis consists of (x) A (y) B, and wherein x is the mass percentage content of A, and y is the mass percentage content of B, and x is 40～100%, y is 0～60%; A single or multiple elementary composition by among Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Sn and the Zn, B single or multiple elementary composition by in Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb, Si, N, C and the rare earth element.
The composite alloy inert anode of electrolysis of aluminum provided by the present invention is to select to have the alloy of certain corrosion resistance nature as composite alloy inert anodic matrix.
The present invention and the oxide film that obtains at self-generating or preoxidation on the present alloy anode surface are more loose, and the problem of poor corrosion resistance provides a kind of composite alloy inert anode with fine and close protective membrane.This densification protective membrane is oxide film and/or infiltration layer.
In the composite alloy inert anode of used for aluminium electrolysis of the present invention, be coated with the oxide film layer on the described composite alloy inert anodic matrix, this oxide film layer is made up of the oxide compound of D, D is the single or multiple element in Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb and the rare earth element, and the thickness of oxide film is 0.1 μ m～5mm.
In the composite alloy inert anode of used for aluminium electrolysis of the present invention, on described composite alloy inert anodic matrix, ooze a kind of element or several element among N, C, B, F, Si, P and the S, alloying layer thickness is μ m～5mm O.1.
In the composite alloy inert anode of used for aluminium electrolysis of the present invention, on the oxide film surface of described composite alloy inert anodic matrix, ooze a kind of element or several element among N, C, B, F, Si, P and the S, alloying layer thickness is 0.1 μ m～5mm.
In the composite alloy inert anode of used for aluminium electrolysis of the present invention, described used for aluminium electrolysis composite alloy inert anode shape is tabular, column, ring-type, netted or groove shape.
A kind of composite alloy inert anodic method for preparing used for aluminium electrolysis of the present invention, this method comprises the steps:
(1), according to chemical expression (x) A (y) B of composite alloy inert anodic matrix of the present invention, be equipped with powdery A and B material, or block A and B material;
(2), powdery A and B are expected that the mode of mixing or employing mechanical ball milling mixes, and adopts the method for powder metallurgy or melting to make composite alloy inert anodic body material then, and is processed into required composite alloy inert anodic base shape;
Or block A and B material is carried out melting obtains composite alloy inert anodic body material, and is processed into needed composite alloy inert anodic base shape.
Can coat fine and close protective membrane on above-mentioned composite alloy inert anodic matrix, this densification protective membrane is oxide film and/or infiltration layer.
In the composite alloy inert anodic method of above-mentioned preparation used for aluminium electrolysis of the present invention, on matrix, directly carry out oxide treatment, on matrix, coating oxide film, promptly the composite alloy inert anodic method of used for aluminium electrolysis of the present invention also comprises the steps:
(3), on the surface of the composite alloy inert anodic matrix that step (2) obtains, carry out oxide treatment, obtain the composite alloy inert anode that oxidized thin film layer coats, the thickness of oxide film is 0.1 μ m～5mm.
In the composite alloy inert anodic method of above-mentioned preparation used for aluminium electrolysis of the present invention, on matrix, coating earlier metallic film, again metallic film is carried out oxide treatment, make and coating oxide film on the matrix, be i.e. the composite alloy inert anodic method of used for aluminium electrolysis of the present invention or also comprise the steps:
(3), the surface of the composite alloy inert anodic matrix that step (2) is obtained polish and carrying out washing treatment after, adopt method, the method for metallize, the method for sputter and any one method in the sedimentary method of gas phase of layering electrodip process, codeposition electrodip process, hot dipping stain, on the surface of composite alloy inert anodic matrix, be coated with the metallic film of the single or multiple element in Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb and the rare earth element;
(4), metallic film that step (3) is obtained carries out oxide treatment, makes the metallic film that coats on the surface of composite alloy inert anodic matrix become oxide film, the thickness of oxide film is 0.1 μ m～5mm.
In above-mentioned oxide treatment, the temperature of described oxide treatment is 300 ℃～1500 ℃, and the time of oxide treatment is 0.5h～30h.
In the composite alloy inert anodic method of above-mentioned preparation used for aluminium electrolysis of the present invention, direct metallize oxide compound on matrix, make and coating oxide film on the matrix, be i.e. the composite alloy inert anodic method of used for aluminium electrolysis of the present invention or also comprise the steps:
(3), the surface of the composite alloy inert anodic matrix that step (2) is obtained polish and carrying out washing treatment after, adopt the method for metallize oxide compound, on the surface of composite alloy inert anodic matrix, be coated with the metal oxide film of the single or multiple element in Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb and the rare earth element.
In the composite alloy inert anodic method of above-mentioned preparation used for aluminium electrolysis of the present invention, on matrix, directly ooze N etc., make and form infiltration layer on the matrix, be i.e. the composite alloy inert anodic method of used for aluminium electrolysis of the present invention or also comprise the steps:
(3), the surface of composite alloy inert anodic matrix that step (2) is obtained imposes a kind of element or several element that oozes among N, C, B, F, Si, P and the S, the thickness of infiltration layer is 0.1 μ m～5mm.
In the composite alloy inert anodic method of above-mentioned preparation used for aluminium electrolysis of the present invention, made and coated oxide film on the matrix, ooze N etc. on the oxide film surface again, make and form infiltration layer in the oxide film.The composite alloy inert anodic method that is used for aluminium electrolysis of the present invention also comprises the steps: the oxide film surface that obtains is imposed a kind of element or several element that oozes among N, C, B, F, Si, P and the S, and the thickness of infiltration layer is 0.1 μ m～5mm.
A kind of method of electrolysis of aluminum, the composite alloy inert anode that adopts used for aluminium electrolysis of the present invention is as anode; Negative electrode adopts carbon, TiB
2, or surface-coated 1 μ m～5cm thickness T iB
2Carbon, negative electrode and anodic pole span are 0.5～15cm; Electrolytic current density is controlled at 0.1～5A/cm
2Ionogen is sodium cryolite system or potassium cryolite system; Electrolysis temperature is 670 ℃～980 ℃.
The invention provides a kind of anode material that can be used as electrolysis of aluminum, the present invention has effectively changed the performance of aluminium electrolysis anode material, has improved the physical and chemical performance of anode material.The invention solves aluminium electrolysis process percent of greenhouse gases CO
2Emission problem with the obnoxious flavour perfluoro-carbon, solved ceramic-like inert anode thermal shock resistance difference and machining property difference shortcoming, have better corrosion resistance nature than alloy anode, this composite alloy inert anode has service temperature widely, is fit to 670～980 ℃.
Advantage of the present invention not only can overcome the above problems, and following advantage is arranged:
(1) cooperates wettable negative electrode and insulation slot liner can significantly reduce energy consumption, can reduce the anode and cathode pole span, reduce bath voltage.
(2) this composite alloy inert anode is particularly suitable for low-temperature electrolyte system, and carrying out electrolysis of aluminum under cold condition can further cut down the consumption of energy.
(3) use this composite alloy inert anode, can produce a large amount of by product O
2If, recycle and have certain economic and be worth, can further reduce the production cost of electrolysis of aluminum.
Embodiment
The invention will be further described below by embodiment, but claim protection domain of the present invention is not constituted any limitation.
Embodiment 1
Getting mass percent is: 60% bronze medal (Cu): 25% nickel (Ni): 15% iron (Fe) bulk, make the sheet material alloy by melting, and obtain groove shape anode by processing, anodic current density is 0.5A/cm
2, adopt tabular TiB
2Negative electrode, anode and cathode pole span are 2.0cm, in 800 ℃, constitute electrolysis system in the potassium cryolite system, and the electrolytic process bath voltage steadily is 3.7～3.9V, and electrolysis obtains primary aluminum purity and reaches 99.1%.
Embodiment 2
Getting mass percent is: 92% bronze medal (Cu): 8% aluminium (Al) powder mixes is even, make cylindric alloy by melting, the method of alloy surface being polished, adopted after the cleaning, drying treatment galvanic deposit electrode surface form 50 μ m films (85wt% copper (Cu): 15wt% aluminium (Al)), under 700 ℃ at 10vt% oxygen (O
2): 90vt% nitrogen (N
2) atmosphere under handle 3h, make that the thickness of surface film oxide is 200 μ m, obtain required anode, anodic current density is 0.7A/cm
2, adopt circular arc TiB
2Coated cathode, anode and cathode pole span are 1.5cm, in 940 ℃, constitute electrolysis system in the sodium cryolite system, and the electrolytic process bath voltage steadily is 3.6～3.8V, and electrolysis obtains primary aluminum purity and reaches 98.3%.
Embodiment 3
Getting mass percent is: 10% bronze medal (Cu): 45% tin (Sn): 45% iron (Fe) powder mixes is even, is making board-like material by melting, to the surface polish, clean, dry back under 650 ℃ at 15vt% oxygen (O
2): 85vt% nitrogen (N
2) atmosphere under handle 3h, make that the thickness of surface film oxide is 300 μ m, obtain required anode, anodic current density is 0.6A/cm
2, adopting the C negative electrode, the anode and cathode pole span is 2.5cm, in 900 ℃, constitutes electrolysis system in the sodium cryolite system, and the electrolytic process bath voltage steadily is 3.7～3.9V, and electrolysis obtains primary aluminum purity and reaches 99.1%.
Embodiment 4
Getting mass percent is: 85% titanium (Ti): 10% chromium (Cr): 5% silver medal (Ag) powder mixes is even, under 500Mpa pressure, obtain ingot, obtain alloy at 1500 ℃ of following sintering 4h, to alloy surface polish, clean, dry back is at alloy surface spraying 55wt% ferric oxide (Fe
2O
3): 45wt% nickel oxide (NiO), sintering 4h in 900 ℃ of following air makes that the thickness of surface film oxide is 100 μ m then, obtains required anode, anodic current density is 0.8A/cm
2, adopt TiB
2Coated cathode, anode and cathode pole span are 2.5cm, in 940 ℃, constitute electrolysis system in the sodium cryolite system, and the electrolytic process bath voltage steadily is 3.8～4.0V, and electrolysis obtains primary aluminum purity and reaches 98.6%.
Embodiment 5
Getting mass percent is: 50% iron (Fe): 38% nickel (Ni): 8% cobalt (Co): 4% neodymium (Nd) powder mixes is even, make ring-like alloy by melting, to alloy surface polish, clean, dry back carries out C, N to alloy and oozes altogether, alloying layer thickness is 500 μ m, obtain required anode, anodic current density is 1.0A/cm
2, adopt cylindricality TiB
2Coated cathode, anode and cathode pole span are 2.0cm, in 750 ℃, constitute electrolysis system in the potassium cryolite system, and the electrolytic process bath voltage steadily is 3.4～3.6V, and electrolysis obtains primary aluminum purity and reaches 99.3%.
Embodiment 6
Getting mass percent is: 60% bronze medal (Cu): 30% nickel (Ni): 8% aluminium (Al): 2% cerium (Ce) powder mixes is even, under 400Mpa pressure, obtain ingot, obtain the column alloy at 1050 ℃ of following sintering 4h, alloy surface is polished, adopted CVD (Chemical Vapor Deposition) method that alloy is carried out C, N after the cleaning, drying treatment to ooze altogether, alloying layer thickness is 500 μ m, obtain required anode, anodic current density is 1.0A/cm
2, adopt ring-like TiB
2Coated cathode, anode and cathode pole span are 2.0cm, in 750 ℃, constitute electrolysis system in the potassium cryolite system, and the electrolytic process bath voltage steadily is 3.4～3.6V, and electrolysis obtains primary aluminum purity and reaches 99.3%.
Embodiment 7
Getting mass percent is: 50% nickel (Ni): 40% iron (Fe): 8% bronze medal (Cu): 2% chromium (Cr) powder mixes is even, make ring-like alloy by melting, to alloy surface polish, after the cleaning, drying treatment in air atmosphere in 900 ℃ of oxidation 3h, make alloy surface form oxide film, adopting CVD (Chemical Vapor Deposition) method that oxide film is carried out Si, N oozes altogether, alloying layer thickness is 400 μ m, obtains required anode, and anodic current density is 0.8A/cm
2, adopt column TiB
2Coated cathode, anode and cathode pole span are 2.0cm, in 840 ℃, constitute electrolysis system at sodium, potassium cryolite mixed system, and the electrolytic process bath voltage steadily is 3.4～3.6V, and electrolysis obtains primary aluminum purity and reaches 99.0%.
Embodiment 8
Getting mass percent is: 50% nickel (Ni): 45% iron (Fe): 5% bronze medal (Cu) powder mixes is even, make board-like material by melting, to the surface polish, clean, dry back adopts the codeposition electrodip process to form the thick 45wt% nickel (Ni) of 1.0mm on alloy collective surface: 40wt% iron (Fe): 10wt% cobalt (Co): 5wt% silver (Ag) film, in air atmosphere in 920 ℃ of oxidation 2h, make alloy surface form oxide film, obtain required anode, anodic current density is 1.2A/cm
2, adopt template TiB
2Coated cathode, anode and cathode pole span are 2.5cm, in 800 ℃, constitute electrolysis system at sodium, potassium cryolite mixed system, and the electrolytic process bath voltage steadily is 3.8～4.0V, and electrolysis obtains primary aluminum purity and reaches 99.5%.
Claims (14)
1. the composite alloy inert anode of a used for aluminium electrolysis, it is characterized in that: the composite alloy inert anodic matrix of this used for aluminium electrolysis consists of (x) A (y) B, and wherein x is the mass percentage content of A, and y is the mass percentage content of B, x is 40～100%, and y is 0～60%; A single or multiple elementary composition by among Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Sn and the Zn, B single or multiple elementary composition by in Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb, Si, N, C and the rare earth element.
2. the composite alloy inert anode of used for aluminium electrolysis according to claim 1, it is characterized in that: be coated with the oxide film layer on the described composite alloy inert anodic matrix, this oxide film layer is made up of the oxide compound of D, D is the single or multiple element in Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb and the rare earth element, and the thickness of oxide film is 0.1 μ m～5mm.
3. the composite alloy inert anode of used for aluminium electrolysis according to claim 1, it is characterized in that: ooze a kind of element or several element among N, C, B, F, Si, P and the S on described composite alloy inert anodic matrix, alloying layer thickness is 0.1 μ m～5mm.
4. the composite alloy inert anode of used for aluminium electrolysis according to claim 2, it is characterized in that: ooze a kind of element or several element among N, C, B, F, Si, P and the S on the oxide film surface of described composite alloy inert anodic matrix, alloying layer thickness is 0.1 μ m～5mm.
5. according to any described used for aluminium electrolysis composite alloy inert anode among the claim 1-4, it is characterized in that: described used for aluminium electrolysis composite alloy inert anode shape is tabular, column, ring-type, netted or groove shape.
6. composite alloy inert anodic method for preparing the used for aluminium electrolysis of claim 1, it is characterized in that: this method comprises the steps:
(1), according to chemical expression (x) A (y) B of the composite alloy inert anodic matrix in the claim 1, be equipped with powdery A and B material, or block A and B material;
(2), powdery A and B are expected that the mode of mixing or employing mechanical ball milling mixes, and adopts the method for powder metallurgy or melting to make composite alloy inert anodic body material then, and is processed into required composite alloy inert anodic base shape;
Or block A and B material is carried out melting obtains composite alloy inert anodic body material, and is processed into needed composite alloy inert anodic base shape.
7. the composite alloy inert anodic method of preparation used for aluminium electrolysis according to claim 6, it is characterized in that: this method also comprises the steps:
(3), on the surface of the composite alloy inert anodic matrix that step (2) obtains, carry out oxide treatment, obtain the composite alloy inert anode that oxidized thin film layer coats, the thickness of oxide film is 0.1 μ m～5mm.
8. the composite alloy inert anodic method of preparation used for aluminium electrolysis according to claim 6, it is characterized in that: this method also comprises the steps:
(3), the surface of the composite alloy inert anodic matrix that step (2) is obtained polish and carrying out washing treatment after, adopt method, the method for metallize, the method for sputter and any one method in the sedimentary method of gas phase of layering electrodip process, codeposition electrodip process, hot dipping stain, on the surface of composite alloy inert anodic matrix, be coated with the metallic film of the single or multiple element in Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb and the rare earth element;
(4), metallic film that step (3) is obtained carries out oxide treatment, makes the metallic film that coats on the surface of composite alloy inert anodic matrix become oxide film, the thickness of oxide film is 0.1 μ m～5mm.
9. according to the composite alloy inert anodic method of claim 7 or 8 described preparation used for aluminium electrolysis, it is characterized in that: the temperature of described oxide treatment is 300 ℃～1500 ℃, and the time of oxide treatment is 0.5h～30h.
10. the composite alloy inert anodic method of preparation used for aluminium electrolysis according to claim 6, it is characterized in that: this method also comprises the steps:
(3), the surface of the composite alloy inert anodic matrix that step (2) is obtained polish and carrying out washing treatment after, adopt the method for metallize oxide compound, on the surface of composite alloy inert anodic matrix, be coated with the metal oxide film of the single or multiple element in Cu, Ni, Fe, Co, Al, Mn, W, Cr, Ti, Mo, Pd, Ag, Cd, Au, Pt, Sb, Mg, Ir, Bi, Pb and the rare earth element.
11. the composite alloy inert anodic method of preparation used for aluminium electrolysis according to claim 6, it is characterized in that: this method also comprises the steps:
(3), the surface of composite alloy inert anodic matrix that step (2) is obtained imposes a kind of element or several element that oozes among N, C, B, F, Si, P and the S, the thickness of infiltration layer is 0.1 μ m～5mm.
12. the composite alloy inert anodic method of preparation used for aluminium electrolysis according to claim 7, it is characterized in that: this method also comprises the steps:
(4), oxide film surface that step (3) is obtained imposes a kind of element or several element that oozes among N, C, B, F, Si, P and the S, the thickness of infiltration layer is 0.1 μ m～5mm.
13. the composite alloy inert anodic method of preparation used for aluminium electrolysis according to claim 8, it is characterized in that: this method also comprises the steps:
(5), oxide film surface that step (4) is obtained imposes a kind of element or several element that oozes among N, C, B, F, Si, P and the S, the thickness of infiltration layer is 0.1 μ m～5mm.
14. the method for an electrolysis of aluminum is characterized in that: the composite alloy inert anode that adopts the described used for aluminium electrolysis of claim 5 is as anode; Negative electrode adopts carbon, TiB
2, or surface-coated 1 μ m～5cm thickness T iB
2Carbon, negative electrode and anodic pole span are 0.5～15cm; Electrolytic current density is controlled at 0.1～5A/cm
2Ionogen is sodium cryolite system or potassium cryolite system; Electrolysis temperature is 670 ℃～980 ℃.
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| WO2011072545A1 (en) * | 2009-12-18 | 2011-06-23 | 中国铝业股份有限公司 | Alloy suitable for making inert anode used in molten electrolytic bath to produce metals |
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| WO2013185539A1 (en) * | 2012-06-11 | 2013-12-19 | 内蒙古联合工业有限公司 | Inert alloy anode used for aluminum electrolysis and preparation method therefor |
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| US6162334A (en) * | 1997-06-26 | 2000-12-19 | Alcoa Inc. | Inert anode containing base metal and noble metal useful for the electrolytic production of aluminum |
| US5865980A (en) * | 1997-06-26 | 1999-02-02 | Aluminum Company Of America | Electrolysis with a inert electrode containing a ferrite, copper and silver |
| US6551476B1 (en) * | 2002-01-08 | 2003-04-22 | Emil S. Scherba | Noble-metal coated inert anode for aluminum production |
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| CN101935853A (en) * | 2010-10-11 | 2011-01-05 | 济南澳海炭素有限公司 | Alloy oxygen evolving anode for aluminum electrolysis |
| CN102489700A (en) * | 2011-12-23 | 2012-06-13 | 长沙理工大学 | Cu-Ni-Al alloy powder and preparation method thereof |
| CN102489700B (en) * | 2011-12-23 | 2013-06-19 | 长沙理工大学 | Cu-Ni-Al alloy powder and preparation method thereof |
| EA030951B1 (en) * | 2012-06-11 | 2018-10-31 | Иннер Монголия Юнайтед Индастриал Ко., Лтд. | Inert alloy anode used for aluminum electrolysis and preparation method therefor |
| WO2013185539A1 (en) * | 2012-06-11 | 2013-12-19 | 内蒙古联合工业有限公司 | Inert alloy anode used for aluminum electrolysis and preparation method therefor |
| CN103938080A (en) * | 2013-01-23 | 2014-07-23 | 内蒙古联合工业有限公司 | Inert alloy anode used for electrolyzing aluminum and preparing method thereof |
| CN104060298A (en) * | 2014-06-27 | 2014-09-24 | 中国铝业股份有限公司 | Ceramic alloy inert anode with equipotential plane and preparation method thereof |
| CN104313642A (en) * | 2014-11-17 | 2015-01-28 | 中南大学 | Method for reducing voltage drop of aluminum electrolysis anode gas film |
| CN106906491A (en) * | 2017-04-06 | 2017-06-30 | 东北大学 | A kind of ferronickel base is anti-oxidant and corrosion resisting alloy inert anode material |
| CN109763146A (en) * | 2019-03-27 | 2019-05-17 | 贵州省过程工业技术研究中心 | A kind of titanium composite material anode preparation method used for aluminium electrolysis |
| CN109763146B (en) * | 2019-03-27 | 2021-03-26 | 贵州省过程工业技术研究中心 | Preparation method of titanium-based composite material anode for aluminum electrolysis |
| RU2763059C1 (en) * | 2021-01-26 | 2021-12-27 | Сергей Владимирович Кидаков | Production of aluminium with a moving electrolyte in an electrolyser |
| WO2022164344A1 (en) * | 2021-01-26 | 2022-08-04 | Сергей Владимирович КИДАКОВ | Production of aluminum with a moving electrolyte in an electrolysis cell |
| CN113897639A (en) * | 2021-11-19 | 2022-01-07 | 河南世源铝业科技有限公司 | Aluminum-separating oxygen-evolution electrode for electrolytic aluminum and preparation method thereof |
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