CA2877591C - Electrolytic cell for aluminum electrolysis and electrolysis process using electrolytic cell - Google Patents
Electrolytic cell for aluminum electrolysis and electrolysis process using electrolytic cell Download PDFInfo
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- CA2877591C CA2877591C CA2877591A CA2877591A CA2877591C CA 2877591 C CA2877591 C CA 2877591C CA 2877591 A CA2877591 A CA 2877591A CA 2877591 A CA2877591 A CA 2877591A CA 2877591 C CA2877591 C CA 2877591C
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 118
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 79
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims description 68
- 230000008569 process Effects 0.000 title claims description 67
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 102
- 239000003792 electrolyte Substances 0.000 claims abstract description 97
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910052718 tin Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 5
- 210000004027 cell Anatomy 0.000 claims description 79
- 238000002844 melting Methods 0.000 claims description 51
- 230000008018 melting Effects 0.000 claims description 51
- 210000005056 cell body Anatomy 0.000 claims description 37
- 239000000155 melt Substances 0.000 claims description 36
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 2
- 238000009413 insulation Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- 239000010949 copper Substances 0.000 description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 30
- 239000002184 metal Substances 0.000 description 30
- 239000000956 alloy Substances 0.000 description 22
- 229910045601 alloy Inorganic materials 0.000 description 20
- 239000011135 tin Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 239000010405 anode material Substances 0.000 description 12
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 7
- 238000005266 casting Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910001610 cryolite Inorganic materials 0.000 description 4
- -1 NaCI Chemical compound 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 101100004392 Arabidopsis thaliana BHLH147 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- VRSRNLHMYUACMN-UHFFFAOYSA-H trilithium;hexafluoroaluminum(3-) Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[F-].[F-].[Al+3] VRSRNLHMYUACMN-UHFFFAOYSA-H 0.000 description 1
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
- C25C3/18—Electrolytes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
An electrolysis tank used for aluminum electrolysis, comprising a tank body, an anode and a cathode arranged within the tank body, also an electrolyte accommodated within the tank body, where at least a part of the anode is submerged in the electrolyte. The anode is arranged above the tank body. The cathode is arranged at the tank bottom and is covered by a certain amount of liquid aluminum. The electrolyte is provided between the anode and the cathode. The electrolyte covers the liquid aluminum. The tank body has arranged on an inner sidewall thereof an insulation layer for use in separating oxygen or the electrolyte from a carbon block. The tank is characterized in that: the constituents of the anode comprise Fe, Cu, Ni, and Sn, where Fe and Cu are the main constituents; the electrolyte consists of 30 to 38 wt% of NaF, 49 to 60 wt% of AlF3, 1 to 5 wt% of LiF, 1 to 6 wt% of KF, and 3 to 6 wt% of Al2O3, where the molar ratio of NaF to AlF3 is between 1.0 and 1.52. The electrolysis tank is applicable in industrialized production of electrolyzed aluminum.
Description
CA Application Blakes Ref.: 11878/00001
2 USING ELECTROLYTIC CELL
3 Field of the Invention
4 The present invention relates to an electrolytic cell for aluminum electrolysis and an electrolysis process using the electrolytic cell, belonging to non-ferrous metal smelting industry.
6 Background of the Invention 7 In aluminum electrolysis industry, a traditional Hall-Heroult molten salt aluminum electrolysis 8 process is typically adopted to perform electrolysis on the molten salts of cryolite-alumina in a 9 prebaked carbon anode electrolytic cell typically by adopting, that is, cryolite Na3AIF6 fluoride salt melt is taken as flux, A1203 is dissolved in the fluoride salt, a carbon body is taken as an 11 anode and vertically inserted into the electrolytic cell, a carbon body with aluminum liquid 12 covering the bottom of the electrolytic cell is taken as a cathode, electrochemical reaction is 13 carried out on the anode and cathode of the electrolytic cell at a high temperature ranging from 14 940 to 960 C after a strong direct current is introduced, and the resultant aluminum liquid product covers the cathode at the bottom of the electrolytic cell. Due to high electrolysis 16 temperature, the traditional aluminum electrolysis process has such characteristics as large 17 volatilization amount of electrolyte, large oxidization loss of a carbon anode, large energy 18 consumption and poor working environment.
19 In the prior art, in order to lower electrolysis temperature, a low temperature molten salt system for aluminum electrolysis is disclosed in Chinese patent document CN101671835A, the molten 21 salt composition of the system includes AlF3, A1203 and one or more salts selected from the 22 group consisting of KF, NaF, MgF2, CaF2, NaCI, LiF, and BaF2, and the electrolysis temperature 23 of the electrolyte can be lowered to be within a wide area from 680 to 900 C for the purpose of 24 operations.
Addition of NaCI to the aforementioned electrolyte aims at lowering the liquidus temperature of 26 the electrolyte, however, NaCI will lead to corrosion to metal parts like electrolytic cell 27 accessories at the aforementioned electrolysis temperature, furthermore, NaCI is extremely 28 liable to volatilization in the electrolysis process so as to form HCI
toxic gas, so its application is 29 difficult; in addition to addition of NaCI, decrease of the molar ratio of NaF to AlF3 can also lower the liquidus temperature of the electrolyte in light of common knowledge in this art, but in the 31 existing industry, the molar ratio of NaF to AlF3 is generally larger than 2.2, this is because, if 22653226.3 1 CA Application Blakes Ref.: 11878/00001 1 the molar ratio of NaF to AlF3 further decreases, NaF and AlF3 will lead to a 'crusting' 2 phenomenon of the cathode in the process of low-temperature electrolysis while the liquidus 3 temperature of the electrolyte is lowered, the reason for this 'crusting' phenomenon is that 4 sodium ions and aluminum ions in the electrolyte will gather at the cathode in the electrolysis process to generate sodium cryolite, which is seldom molten at a low temperature due to its 6 high melting point, as a result, the surface of the cathode is covered by a layer of refractory 7 cryolite crust to affect normal electrolysis in the electrolysis process tremendously. Due to the 8 above problems in the prior art, industrial application of the electrolyte is significantly limited, 9 and it is an unsolved problem in the prior art to find a way of avoiding corrosion to electrolysis devices and damage to human body and ensuring proper electric conductivity and alumina 11 solubility as well as no cathode 'crusting' phenomenon of the prepared electrolyte while the 12 liquidus temperature of the electrolyte is further lowered.
13 In addition to the high electrolysis temperature problem that needs to be solved, the carbon 14 anode in the traditional electrolytic cell for aluminum electrolysis is ceaselessly consumed by oxidization in the electrolysis process, thus constant replacement for the carbon anode is 16 required; moreover, carbon dioxide, carbon monoxide and other waste gases are continuously 17 generated at the anode during aluminum electrolysis. Hence, to lessen the consumption of an 18 anode material in the aluminum electrolysis process and simultaneously reduce the emission of 19 waste gases, disclosed in the prior art is plenty of documents for research on anode material, e.g. disclosed in Chinese patent document CN1443877A is an inert anode material applied to 21 aluminum, magnesium and rare earth electrolysis industries, this material is formed by binary or 22 multi-element alloy composed of chromium, nickel, ferrum, cobalt, titanium, copper, aluminum, 23 magnesium and other metals, and the preparation method thereof is a smelting or powder 24 metallurgy method. The prepared anode material is good in electric and thermal conductivity and generates oxygen in the electrolysis process, wherein in Example 1, an anode is made of 26 the alloy material composed of 37wt /0 of cobalt, 18wt% of copper, 19wt /0 of nickel, 23wt 70 of 27 ferrum and 3wt% of silver and is used for aluminum electrolysis, the anode has a current density 28 of 1.0A/cm2 in the electrolysis process at 850 C and the cell voltage is maintained within a 29 range from 4.1V to 4.5V in the electrolysis process, the prepared aluminum has a purity of 98.35%.
31 Compared with the carbon material, the alloy anode material in the technologies 32 aforementioned has higher electric conductivity and lower corrosion amount in the electrolysis 22653226.2 2 CA Application Blakes Ref.: 11878/00001 1 process and can be processed into random shapes, however, the alloy anode composed of the 2 aforementioned components is still high in overvoltage, which results in large industrial power 3 consumption and low product quality, besides, since a large quantity of expensive metal 4 materials are used, the anode material is high in cost and cannot adapt to industrial needs.
In addition, a layer of oxide film is generated on the surface of the prepared alloy anode in the = 6 prior art, and if this oxide film is destroyed, the anode material exposed to the surface will be 7 oxidized as a new oxide film. The oxide film on the surface of the alloy anode in the prior art has 8 low oxidization resistance and is further liable to oxidization reaction to generate products that 9 are likely to be corroded by the electrolyte, and the oxide film with low stability is liable to fall off the anode electrode in the electrolysis process; after the previous oxide film is corroded or falls 11 off, the material of the alloy anode exposed to the surface will create a new oxide film by 12 reaction, such replacement between new and old oxide films results in continuous consumption = 13 and poor corrosion resistance of the anode material;
furthermore, the corroded or falling oxide 14 film enters into liquid aluminum in the electrolysis process of alumina to degrade the purity of the final product aluminum, as a result, the manufactured aluminum product cannot meet the 16 demand of national standards and accordingly cannot be directly used as a finished product.
17 Summary of the Invention 18 The first technical problem to be solved by the present invention is that, the prior art is incapable 19 of avoiding corrosion to electrolysis devices and damage to human body and ensuring proper electric conductivity and alumina solubility as well as no 'crusting' phenomenon in the prepared 21 electrolyte while the liquidus temperature of the electrolyte is further lowered. Thus the present 22 invention provides an electrolytic cell, containing an electrolyte for aluminum electrolysis which 23 is low in liquidus temperature, free from metal corrosion, not liable to volatilization, proper in 24 electric conductivity and alumina solubility and free from cathode 'crusting' phenomenon.
Simultaneously, the second technical problem to be solved by the present invention is that, an 26 alloy anode composed of metal components in the prior art is high in overvoltage, power 27 consumption in the aluminum electrolysis process is large and the metal components employed 28 are high in price, resulting in cost increment of the alloy anode; in addition, an oxide film on the 29 surface of the alloy anode in the prior art is low in oxidation resistance and liable to fall off, which leads to continuous consumption of the alloy anode and poor corrosion resistance, 31 furthermore, the corroded or falling oxide film enters into liquid aluminum to degrade the purity 32 of the final product aluminum; and therefore, provided is an electrolytic cell for aluminum 22653226.2 3 =
CA Application Blakes Ref.: 11878/00001 1 electrolysis, which is low in overvoltage of the used inert anode material, low in price, strong in 2 oxidation resistance and stability of the oxide film formed on the surface thereof and resistant to 3 electrolyte corrosion.
4 Simultaneously, the present invention provides a process for aluminum electrolysis using the above electrolytic cell.
6 To solve the aforementioned technical problems, the present invention provides an electrolytic 7 cell for aluminum electrolysis, comprising a cell body, wherein an anode and a cathode are 8 arranged inside the cell body, the cell body is further filled with an electrolyte; the anode is 9 arranged above the cell body, and at least a part of the anode is immersed in the electrolyte; the cathode is arranged at the bottom of the electrolytic cell and covered by a certain amount of 11 aluminum liquid; the electrolyte is located between the anode and the cathode; the anode 12 contains the components including Fe, Cu, Ni and Sn, wherein Fe and Cu serve as primary 13 components; the electrolyte is composed of 30-38wV/0 of NaF, 49-60wV/0 of AlF3, 1-5wt% of LiF, 14 1-6wr/o of KF and 3-6wr/0 of A1203, wherein the molar ratio of NaF to AlF3 is 1.0-1.52.
The bottom surface of the anode is kept parallel to the cell body, and an insulating layer is = 16 arranged on the inner sidewall of the cell body and is used for isolating oxygen or the electrolyte 17 from a carbon block.
18 A cell cover is arranged at the upper end of the cell body and is provided with a vent and a 19 feeding hole; a cathode bar is arranged inside the cathode, one end of the anode penetrates through the cell cover and is connectedly provided with a binding post for connection with a 21 power supply.
22 The mass ratio of Fe to Cu to Sn is (23-40): (36-60): (0.2-5).
23 The components of the anode further include Ni.
24 The anode is composed of Fe, Cu, Ni and 'Sn, wherein the content of Fe is 23-40wt%, the content of Cu is 36-60%, the content of Ni is 14-28wt% and the content of Sn is 0.2-5wt%.
26 The components of the anode further include Al and Y.
27 The anode is composed of Fe, Cu, Ni, Sn, Al and Y, wherein the content of Fe is 23-40wr/o, the 28 content of Cu is 36-60wt%, the content of Ni is 14-28wr/o, the content of Al is more than zero 22653226.2 4 CA Application Blakes Ref.: 11878/00001 1 and less than or equal to 4wt /0, the content of Y is more than zero and less than or equal to 2 2wV/0, and the content of Sn is 0.2-5wr/o.
3 The molar ratio of NaF to AlF3 is 1.12-1.52.
4 The liquidus temperature of the electrolyte is 620-670 C.
An electrolysis process using the electrolytic cell comprises the steps of:
6 (1) adding specified amounts of NaF, AlF3, LiF, KF and A1203 to a melting furnace for mixing and 7 melting to form a melt; or adding specified amounts of NaF, AlF3, LiF and KF to a melting 8 furnace for mixing and melting, and then adding A1203 to obtain a melt;
and 9 (2) raising the temperature of the melt prepared in step (1) to above 720-760 C, and then, pouring the melt into the electrolytic cell and carrying out electrolysis while the temperature is 11 maintained at 720-760 C.
12 The electrolysis temperature is 730-750 C.
13 A1203 is quantitatively supplied in the electrolysis process.
14 The electrolysis process using the electrolytic cell comprises the steps of:
(1) adding specified amounts of NaF, AlF3, LiF, KF and A1203 to a melting furnace for mixing and 16 melting to form a melt; or adding specified amounts of NaF, AlF3, LiF
and KF to a melting 17 furnace for mixing and melting, and then adding A1203 to obtain a melt;
and 18 (2) raising the temperature of the melt prepared in step (1) to above 720-760 C, and then, 19 pouring the melt into the electrolytic cell and carrying out electrolysis while the temperature is maintained at 720-760 C.
21 The electrolysis temperature is 730-750 C.
22 A1203 is quantitatively supplied in the electrolysis process.
23 The electrolytic cell and the electrolysis process using the electrolytic cell in the present 24 invention have the advantages below:
22653226.2 5 =
CA Application Blakes Ref.: 11878/00001 1 (1) The electrolytic cell for aluminum electrolysis in the present invention comprises a cell body, 2 wherein an anode and a cathode are arranged inside the cell body, and the cell body is further 3 filled with an electrolyte; the anode is arranged above the cell body, and at least a part of the 4 anode is immersed in the electrolyte; the cathode is arranged at the bottom of the electrolytic cell and covered by a certain amount of aluminum liquid; the electrolyte is located between the 6 anode and the cathode; the anode contains the components including Fe, Cu, Ni and Sn, 7 wherein Fe and Cu serve as primary components; the electrolyte is composed of 30-38wt% of 8 NaF, 49-60wr/0 of AlF3, 1-5wr/o of LiF, 1-6wtcY0 of KF and 3-6wr/0 of A1203, wherein the molar 9 ratio of NaF to AlF3 is 1.0-1.52.
The anode containing metal Sn and composed of the aforementioned metal components is high 11 in electric conductivity and low in overvoltage, the cell voltage in the electrolysis process of the 12 electrolytic cell is about 3.1-3.4V, power consumption in the aluminum electrolysis process is 13 small, the power consumption for per ton of aluminum is not more than 11000kw=h, so the 14 process cost is low; the anode material is alloy composed of Fe, Cu and Sn, so an oxide film formed on the surface of the anode in the electrolysis process is high in oxidation resistance 16 and is hardly corroded by the electrolyte, and the formed oxide film is stable and not liable to fall 17 off, therefore, the anode is imparted with quite high oxidation resistance and strong corrosion 18 resistance so as to ensure the purity of aluminum products, that is, the purity of the produced 19 aluminum can reach 99.8%. The following problems in the prior art are avoided: the alloy anode has high overvoltage, the oxide film on the alloy surface is low in oxidation resistance and liable 21 to fall off, which leads to continuous consumption of the alloy anode and poor corrosion 22 resistance, furthermore, the corroded or falling oxide film enters into liquid aluminum to degrade 23 the purity of the final product aluminum. In addition, Fe and Cu serve as primary components of 24 the alloy anode and their content proportions are quite high, and accordingly, the manufacturing cost of the anode material is lowered.
26 The used electrolyte employs a pure fluoride system, substance composition in the electrolyte is 27 defined, the contents of these substances are further defined and the molar ratio of NaF to AlF3 28 is 1.0-1.52, so that the liquidus temperature of the electrolyte is lowered to 640-670 C, as a 29 result, electrolysis can be carried out at 720-760 C according to the electrolysis process, which reduces volatilization loss of fluoride salt, avoids corrosion to electrolysis devices and damage 31 to human body, improves working environment, greatly reduces energy consumption in the 32 electrolysis process and achieves the aim of energy saving and emission reduction; meanwhile, 22653226.2 6 CA Application Blakes Ref.: 11878/00001 1 in the present invention, proper amounts of LiF and KF are added and can be combined with 2 sodium ions and aluminum ions in the electrolyte to form lithium cryolite and potassium cryolite 3 with low melting points, thus the crusting phenomenon is avoided in the electrolysis process;
4 compared with the existing industry, the electrolyte for aluminum electrolysis in the present invention has no CaF2 and MgF2 added therein, instead, KF in an appropriate proportion, which 6 has the function of increasing alumina solubility and dissolution velocity, is added to a system in 7 which the molar ratio of NaF to AlF3 is 1.0-1.52, therefore, the shortcoming of low alumina 8 solubility in the low-molar-ratio electrolyte is improved; in general, the electric conductivity of the = 9 electrolyte decreases as the temperature decreases, so typically, the electric conductivity at a low electrolysis temperature hardly meets the demand in a normal electrolysis process; the 11 electrolysis temperature is lowered by lowering the liquidus temperature of the electrolyte in the 12 present invention, however, the electric conductivity of the electrolyte at a low temperature can 13 still meet the demand in the electrolysis process because LiF with a larger electric conductivity 14 is added and component proportions in the electrolyte are optimized, thus enhancing the current efficiency in the electrolysis process. According to the invention, the content of LiF is defined as = 16 1-5%, this is because too low content of LiF fails to improve electric conductivity and to prevent 17 crusting, and too high content of LiF results in decrease of the alumina solubility, and the above 18 two situations are effectively avoided by defining the content of LiF as 1-5% in the present 19 invention; and there is no corrosion to a metal device when the electrolyte with the above proportions in the present invention is used, in this way, the service life of the electrolysis device 21 is prolonged.
22 (2) In the electrolytic cell for aluminum electrolysis in the present invention, the anode is 23 composed of Fe, Cu, Ni, Sn, Al and Y, wherein the content of Fe is 23-40wr/o, the content of Cu 24 is 36-60wr/o, the content of Ni is 14-28wr/o, the content of Al is less than or equal to 4wV/0, the content of Y is less than or equal to 2wr/o, and the content of Sn is 0.2-5wV/0.
26 Similarly, the aforementioned inert alloy anode has the advantages of low material cost and high 27 electric conductivity, in addition, the metal Al contained in the aforementioned inert alloy anode 28 plays a role of oxidization resistance and can serve as a reducing agent for metallothermic = 29 reduction reaction with metal oxides in the inert anode alloy, thus preventing the metals in the inert alloy anode, i.e. primary components, from being oxidized, and causing reduction of the 31 electric conductivity of the alloy anode; meanwhile, the metal Y added can be used for 22653226.2 7 CA Application Blakes Ref.: 11878/00001 1 controlling a crystal structure for anode material formation in the preparation process of the inert 2 anode, achieving the anti-oxidization purpose.
3 (3) In the electrolytic cell for aluminum electrolysis in the present invention, specified amounts of 4 NaF, AlF3, LiF, KF and A1203 are mixed, the resultant mixture is heated to form a melt; or specified amounts of NaF, AlF3, LiF and KF are mixed, the resultant mixture is heated until the 6 mixture is molten, and then A1203 is added to obtain a melt; afterwards, the melt prepared is 7 electrolyzed at 720-760 C. Electrolysis temperature is directly associated with volatilization of 8 the electrolyte, cathode crusting phenomenon, energy consumption of the process, electric 9 conductivity and a. lumina solubility, and the inventor of the present invention, by long search, set the electrolysis temperature within a range from 720-760 C in a matching way based on the 11 components and content characteristics of the electrolyte in the present invention, thus the 12 cathode crusting phenomenon is prevented and volatilization of the electrolyte and energy 13 consumption of the electrolysis process are remarkably reduced while both the electric 14 conductivity and the alumina solubility are increased, and the economic efficiency of the process is improved. Preferably, the electrolysis temperature is further set within a range from 730-16 750 C in the present invention.
17 Brief Description of the Drawings 18 For more easily understanding the contents of the present invention, further description will be = 19 made below to the technical solution of the present invention in conjunction with the drawing and the embodiments.
21 Fig.1 is a structure diagram of the electrolytic cell for aluminum electrolysis in the present 22 invention;
23 In this drawing, reference signs are as follows: 1 refers to cell body, 2 refers to anode, 3 refers 24 to cathode, 4 refers to electrolyte, 5 refers to insulating layer, 6 refers to cell cover, 7 refers to vent, 8 refers to feeding hole, 9 refers to binding post, 10 refers to cathode bar and 11 refers to 26 aluminum liquid.
27 Detailed Description of the Embodiments 28 The electrolytic cell for aluminum electrolysis in the present invention is as shown in Fig.1 and 29 comprises a cell body 1, wherein an anode 2 and a cathode 3 are arranged inside the cell body 1, the anode 2 and the cathode 3 can be arranged in random ways in accordance with the = 31 actual need, in this embodiment, the anode 2 is arranged above the cell body 1, the bottom 22653226.2 8 =
CA Application Blakes Ref.: 11878/00001 1 surface of the anode 2 is kept parallel to the cell body 1, the cathode 3 is arranged at the bottom 2 of the electrolytic cell and covered by a certain amount of aluminum liquid 11; the cell body 1 is 3 further filled with an electrolyte 4, immersion of the anode 2 and the cathode 3 in the electrolyte 4 4 depends on the selected electrolytic cell structure, in this embodiment, at least a part of the anode 2 is immersed in the electrolyte 4; the cathode 3 is arranged at the bottom of the 6 electrolytic cell and covered by a certain amount of aluminum liquid 11;
the electrolyte 4 is 7 located between the anode 2 and the cathode 3 and covers the aluminum liquid 11; the anode 2 8 contains the components including Fe, Cu, Ni and Sn, wherein Fe and Cu serve as primary 9 components, and the molar ratio of Fe to Cu to Sn is (23-40): (36-60):
(0.2-5); the electrolyte 4 is composed of 30-38wt% of NaF, 49-60wt% of AlF3, 1-5wt /0 of LiF, 1-6wt /0 of KF and 3-6wt /0 11 of A1203, wherein the molar ratio of NaF to AIF3 is 1.0-1.52, preferably 1.12-1.52, and the 12 liquidus temperature of the electrolyte 4 is 620-670 C, preferably 640-670 C.
13 As a variable embodiment on this basis, in order to isolate the inner sidewall of the cell body 1 14 from the electrolyte 4 and oxygen to prevent transfer of electrons between the sidewall of the cell body 1 and th.e electrolyte 4 and corrosion of the electrolyte 4 to the sidewall of the cell body 16 1, an insulating lay.er 5 is arranged on the inner sidewall of the cell body 1 and is made of any 17 commercially available insulating material that is resistant to high temperature and corrosion of 18 the electrolyte 4, e.g. corundum, aluminate spinel refractory and the like. In this embodiment, a 19 carbon block is arranged between the inner sidewall of the cell body 1 and the insulating layer 5, and the carbon block and the cathode 3 are integrally formed. Undoubtedly, the carbon block 21 and the cathode 3 can also be arranged in a separated manner.
22 On this basis, in order to isolate the electrolysis environment for the electrolytic cell from outside = 23 without impediment to exhaust and feeding, a cell cover 6 is arranged at the upper end of the 24 cell body 1 and is provided with a vent 7 and a feeding hole 8 thereon, the sizes and positions of the vent 7 and the feeding hole can be randomly determined in accordance with the actual 26 need, and in this embodiment, the vent 7 is arranged next to the anode 2.
27 Further, in order to facilitate connection of the anode 2 and the cathode 3 with a power supply, a 28 cathode bar 10 is arranged on the cathode 3 at the bottom of the electrolytic cell and is used for 29 connection with the power supply of the cathode 3; one end of the anode 2 penetrates through the cell cover 6 and is connected and provided with a binding post 9 for connection with the 31 power supply of the anode 2; and the cathode 10 and the binding post 9 can be made of any 32 material with good electric conductivity, including steel, iron and alloy materials, etc.
22653226.2 9 CA Application Blakes Ref.: 11878/00001 1 On this basis, in order to improve the combination firmness among metals Fe, Cu and Sn, the 2 components of the anode 2 further include Ni, preferably the anode 2 is composed of Fe, Cu, Ni 3 and Sn, wherein the content Fe is 23-40wr/o, the content of Cu is 36-60wt%, the content of Ni is 4 14-28wt% and the content of Sn is 0.2-5wr/o.
The anode 2 may be preferably composed of Fe, Cu, Ni, Sn, Al and Y, the added Al can prevent 6 other primary metal components of the anode 2 from oxidation and improve the oxidization 7 resistance, the component Y can be used for regulating and controlling the structure of the 8 prepared alloy crystal in order to achieve the anti-oxidization purpose, wherein the content of Fe 9 is 23-40wt%, the content of Cu is 36-60wV/0, the content of Ni is 14-28wt /0, the content of Al is less than or equal to 4wt%, the content of Y is less than or equal to 2wt%, and the content of Sn 11 is 0.2-5wV/0.
12 The electrolysis temperature is 720-760 C when the aforementioned electrolytic cell is used for = 13 aluminum electrolysis, preferably 730-750 C.
14 Description is made below in conjunction with the embodiments.
Embodiment 1 16 Fe, Cu, Ni and Sn metal blocks are mixed based on 23wt /0 of Fe, 60wt /0 of Cu, 14wt /0 of Ni 17 and 3wt /0 of Sn, the mixture is molten by heating at high temperature and then subjected to 18 casting to obtain an anode 1. The anode 1 has a density of 8.3/cm3, a specific resistivity of 19 68pD=cm and a melting point of 1360 C.
The components of the electrolyte in this embodiment are as follows: 32% of NaF, 57% of AlF3, 21 3% of LiF, 4% of KF and 4% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 22 is 1.12. The liquidus temperature of the electrolyte in this embodiment is 640 C according to 23 measurement. The electrolyte has an electric conductivity of about 1.70-1.cm-1, a density of 24 about 2.03g/cm3 and an alumina saturation concentration of 5%.
The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
26 (1) by means of the anode 1 and the carbon body cathode, melting the aforementioned amounts 27 of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 28 (2) raising the temperature of the melt prepared in step (1) to above 720 C in the melting 29 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 22653226.2 10 CA Application Blakes Ref.: 11878/00001 1 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 2 maintained at 720 C, wherein A1203is quantitatively supplied in the electrolysis process.
3 There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 4 electrolytic cell is 3.1V, the power consumption for per ton of aluminum is 10040kw=h in the electrolysis process, and the prepared aluminum has a purity of 99.85%.
6 Embodiment 2 7 Fe,. Cu, Ni and Sn metal blocks are mixed based on 40wt /0 of Fe, 36wt%
of Cu, 19wt% of Ni 8 and 5wt% of Sn, the mixture is molten by heating at high temperature and then subjected to 9 casting to obtain an anode 2. The anode has a density of 8.1/cm3, a specific resistivity of 76.8p0=cm and a melting point of 1386 C.
11 The components of the electrolyte in this embodiment are as follows: 38%
of NaF, 50% of AlF3, 12 2% of LiF, 5% of KF and 5% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 13 is 1.52.
14 The performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 670 C. The = 16 electrolyte has an electric conductivity of about 1.80-1.cm-1, a density of about 2.05g/cm3 and an 17 alumina saturation concentration of 6%.
18 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
19 (1) by means of the anode 2 and the carbon body cathode, melting the aforementioned amounts of NaF, AlF3, LiF and KF in a melting furnace, and then adding the aforementioned amount of 21 A1203 to obtain a melt by melting; and 22 (2) raising the temperature of the melt prepared in step (1) to above 760 C in the melting 23 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 24 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is maintained at 760 C.
26 There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 27 electrolytic cell is 3.39V, the power consumption for per ton of aluminum is 10979kw.h in the 28 electrolysis process, and the prepared aluminum has a purity of 99.82%.
22653226.2 1 1 CA Application Blakes Ref.: 11878/00001 1 Embodiment 3 = 2 Fe, Cu, Ni and Sn metal blocks are mixed based on 25wr/o of Fe, 46.8wt% of Cu, 28wr/0 of Ni 3 and 0.2wt% of Sn, the mixture is molten by heating at high temperature and then subjected to 4 casting to obtain an anode 3. The anode has a density of 8.2/cm3, a specific resistivity of 72p0=cm and a melting point of 1350 C.
6 The components of the electrolyte in this embodiment are as follows: 32%
of NaF, 57% of AlF3, 7 3% of LiF, 4% of KF and 4% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 8 is 1.12.
9 The performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640 C. The 11 electrolyte has an electric conductivity of about 1.6Q-1-cm-1, a density of about 2.03g/cm3 and an 12 alumina saturation concentration of 5%.
13 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
14 (1) by means of the anode 3 and the carbon body cathode, melting the aforementioned amounts of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 16 (2) raising the temperature of the melt prepared in step (1) to above 730 C in the melting 17 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 18 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 19 maintained at 730 C, wherein A1203 is quantitatively supplied in the electrolysis process.
There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 21 electrolytic cell is 3.15V, the power consumption for per ton of aluminum is 10202kw.h in the 22 electrolysis process, and the prepared aluminum has a purity of 99.85%.
23 Embodiment 4 24 Fe, Cu, Ni and Sn metal blocks are mixed based on 24.2w% of Fe, 60wt% of Cu, 14wV3/0 of Ni and 0.2wt% of Sn, the mixture is molten by heating at high temperature, 1.8wr/o of Al metal 26 block is then added for continuous melting and mixing, and finally, 0.8wt% of Y metal block is 27 added for melting and mixing and an anode 4 is obtained by casting of the mixture. The anode 28 has a density of 8.3/cm3, a specific resistivity of 68pQ=cm and a melting point of 1360 C.
22653226.2 12 CA Application Blakes Ref.: 11878/00001 1 The components of the electrolyte in this embodiment are as follows: 32%
of NaF, 57% of AlF3, 2 3% of LiF, 4% of KF and 4% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 3 is 1.12.
4 The performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640 C. The 6 electrolyte has an electric conductivity of about 1.80-1.cm-1, a density of about 2.04g/cm3 and an 7 alumina saturation concentration of 6%.
8 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
9 (1) by means of the anode 4 and the carbon body cathode, melting the aforementioned amounts of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 11 (2) raising the temperature of the melt prepared in step (1) to above 750 C in the melting 12 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 13 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 14 maintained at 750 C, wherein A1203 is quantitatively supplied in the electrolysis process.
There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 16 electrolytic cell is 3.12V, the power consumption for per ton of aluminum is 10105kw-h in the 17 electrolysis process, and the prepared aluminum has a purity of 99.8%.
18 Embodiment 5 19 Fe, Cu, Ni and Sn metal blocks are mixed based on 40wr/0 of Fe, 36wt% of Cu, 14.9wV/0 of Ni and 5wt(3/0 of Sn, the mixture is molten by heating at high temperature, 0.1wr/0 of Al metal block 21 is then added for continuous melting and mixing, and finally, 0.1wt% of Y metal block is added 22 for melting and mixing and an anode 5 is obtained by casting of the mixture. The anode has a = 23 density of 8.1/cm3, a specific resistivity of 76.8pQ=cm and a melting point of 1386 C.
24 The components of the electrolyte in this embodiment are as follows: 30%
of NaF, 60% of AlF3, 1% of LiF, 6% of KF and 3% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 26 is 1Ø
27 The performances of the electrolyte in this embodiment are measured and the measurement 28 result is that the liquidus temperature of the electrolyte in this embodiment is 620 C. The 22653226.2 13 CA Application Blakes Ref.: 11878/00001 1 electrolyte has an electric conductivity of about 1.60-1-cm-1, a density of about 2.03g/cm3 and an 2 alumina saturation concentration of 5%.
3 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
4 (1) by means of the anode 5 and the carbon body cathode, melting the aforementioned amounts of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 6 (2) raising the temperature of the melt prepared in step (1) to above 720 C in the melting 7 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 8 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 9 maintained at 720 C, wherein A1203 is quantitatively supplied in the electrolysis process.
There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 11 electrolytic cell is 3.27V, the power consumption for per ton of aluminum is 10591kw.h in the 12 electrolysis process, and the prepared aluminum has a purity of 99.81%.
13 Embodiment 6 14 Fe, Cu, Ni and Sn metal blocks are mixed based on 25wt% of Fe, 38wr/0 of Cu, 28wt% of Ni and 4wt /0 of Sn, the mixture is molten by heating at high temperature, 4wr/0 of Al metal block is 16 then added for continuous melting and mixing, and finally, 1wt(3/0 of Y
metal block is added for 17 melting and mixing and an anode 6 is obtained by casting of the mixture.
The anode has a 18 density of 8.2/cm3, a specific resistivity of 70p0=cm and a melting point of 1365 C.
19 The components of the electrolyte in this embodiment are as follows: 38%
of NaF, 54% of AlF3, = 20 4% of LiF, 1% of KF and 3% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 21 is 1.4.
22 The performances of the electrolyte in this embodiment are measured and the measurement 23 result is that: the liquidus temperature of the electrolyte in this embodiment is 670 C. The 24 electrolyte has an electric conductivity of about 1.8D-1.cm-1, a density of about 2.05g/cm3 and an alumina saturation concentration of 6%.
26 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
27 (1) by means of the anode 6 and the carbon body cathode, melting the aforementioned amounts 28 of NaF, AlF3, LiF, KF and A1203in a melting furnace so as to form a melt; and 22653226.2 14 CA Application Blakes Ref.: 11878/00001 1 (2) raising the temperature of the melt prepared in step (1) to above 760 C in the melting 2 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 3 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 4 maintained at 760 C, wherein A1203 is quantitatively supplied in the electrolysis process.
There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 6 electrolytic cell is 3.35V, the power consumption for per ton of aluminum is 10850kw-h in the 7 electrolysis process, and the prepared aluminum has a purity of 99.83%.
8 Embodiment 7 9 Fe, Cu, Ni and Sn metal blocks are mixed based on 40wt /0 of Fe, 36.5wt%
of Cu, 18wt% of Ni and 3wt /0 of Sn, the mixture is molten by heating at high temperature, 1.5wt%
of Al metal block 11 is then added for continuous melting and mixing, and finally, 1wV/0 of Y
metal block is added for 12 melting and mixing and an anode 7 is obtained by casting of the mixture.
The anode has a 13 density of 8.1/cm3, a specific resistivity of 76.8pD=cm and a melting point of 1386 C.
14 The components of the electrolyte in this embodiment are as follows: 34%
of NaF, 49% of AlF3,
6 Background of the Invention 7 In aluminum electrolysis industry, a traditional Hall-Heroult molten salt aluminum electrolysis 8 process is typically adopted to perform electrolysis on the molten salts of cryolite-alumina in a 9 prebaked carbon anode electrolytic cell typically by adopting, that is, cryolite Na3AIF6 fluoride salt melt is taken as flux, A1203 is dissolved in the fluoride salt, a carbon body is taken as an 11 anode and vertically inserted into the electrolytic cell, a carbon body with aluminum liquid 12 covering the bottom of the electrolytic cell is taken as a cathode, electrochemical reaction is 13 carried out on the anode and cathode of the electrolytic cell at a high temperature ranging from 14 940 to 960 C after a strong direct current is introduced, and the resultant aluminum liquid product covers the cathode at the bottom of the electrolytic cell. Due to high electrolysis 16 temperature, the traditional aluminum electrolysis process has such characteristics as large 17 volatilization amount of electrolyte, large oxidization loss of a carbon anode, large energy 18 consumption and poor working environment.
19 In the prior art, in order to lower electrolysis temperature, a low temperature molten salt system for aluminum electrolysis is disclosed in Chinese patent document CN101671835A, the molten 21 salt composition of the system includes AlF3, A1203 and one or more salts selected from the 22 group consisting of KF, NaF, MgF2, CaF2, NaCI, LiF, and BaF2, and the electrolysis temperature 23 of the electrolyte can be lowered to be within a wide area from 680 to 900 C for the purpose of 24 operations.
Addition of NaCI to the aforementioned electrolyte aims at lowering the liquidus temperature of 26 the electrolyte, however, NaCI will lead to corrosion to metal parts like electrolytic cell 27 accessories at the aforementioned electrolysis temperature, furthermore, NaCI is extremely 28 liable to volatilization in the electrolysis process so as to form HCI
toxic gas, so its application is 29 difficult; in addition to addition of NaCI, decrease of the molar ratio of NaF to AlF3 can also lower the liquidus temperature of the electrolyte in light of common knowledge in this art, but in the 31 existing industry, the molar ratio of NaF to AlF3 is generally larger than 2.2, this is because, if 22653226.3 1 CA Application Blakes Ref.: 11878/00001 1 the molar ratio of NaF to AlF3 further decreases, NaF and AlF3 will lead to a 'crusting' 2 phenomenon of the cathode in the process of low-temperature electrolysis while the liquidus 3 temperature of the electrolyte is lowered, the reason for this 'crusting' phenomenon is that 4 sodium ions and aluminum ions in the electrolyte will gather at the cathode in the electrolysis process to generate sodium cryolite, which is seldom molten at a low temperature due to its 6 high melting point, as a result, the surface of the cathode is covered by a layer of refractory 7 cryolite crust to affect normal electrolysis in the electrolysis process tremendously. Due to the 8 above problems in the prior art, industrial application of the electrolyte is significantly limited, 9 and it is an unsolved problem in the prior art to find a way of avoiding corrosion to electrolysis devices and damage to human body and ensuring proper electric conductivity and alumina 11 solubility as well as no cathode 'crusting' phenomenon of the prepared electrolyte while the 12 liquidus temperature of the electrolyte is further lowered.
13 In addition to the high electrolysis temperature problem that needs to be solved, the carbon 14 anode in the traditional electrolytic cell for aluminum electrolysis is ceaselessly consumed by oxidization in the electrolysis process, thus constant replacement for the carbon anode is 16 required; moreover, carbon dioxide, carbon monoxide and other waste gases are continuously 17 generated at the anode during aluminum electrolysis. Hence, to lessen the consumption of an 18 anode material in the aluminum electrolysis process and simultaneously reduce the emission of 19 waste gases, disclosed in the prior art is plenty of documents for research on anode material, e.g. disclosed in Chinese patent document CN1443877A is an inert anode material applied to 21 aluminum, magnesium and rare earth electrolysis industries, this material is formed by binary or 22 multi-element alloy composed of chromium, nickel, ferrum, cobalt, titanium, copper, aluminum, 23 magnesium and other metals, and the preparation method thereof is a smelting or powder 24 metallurgy method. The prepared anode material is good in electric and thermal conductivity and generates oxygen in the electrolysis process, wherein in Example 1, an anode is made of 26 the alloy material composed of 37wt /0 of cobalt, 18wt% of copper, 19wt /0 of nickel, 23wt 70 of 27 ferrum and 3wt% of silver and is used for aluminum electrolysis, the anode has a current density 28 of 1.0A/cm2 in the electrolysis process at 850 C and the cell voltage is maintained within a 29 range from 4.1V to 4.5V in the electrolysis process, the prepared aluminum has a purity of 98.35%.
31 Compared with the carbon material, the alloy anode material in the technologies 32 aforementioned has higher electric conductivity and lower corrosion amount in the electrolysis 22653226.2 2 CA Application Blakes Ref.: 11878/00001 1 process and can be processed into random shapes, however, the alloy anode composed of the 2 aforementioned components is still high in overvoltage, which results in large industrial power 3 consumption and low product quality, besides, since a large quantity of expensive metal 4 materials are used, the anode material is high in cost and cannot adapt to industrial needs.
In addition, a layer of oxide film is generated on the surface of the prepared alloy anode in the = 6 prior art, and if this oxide film is destroyed, the anode material exposed to the surface will be 7 oxidized as a new oxide film. The oxide film on the surface of the alloy anode in the prior art has 8 low oxidization resistance and is further liable to oxidization reaction to generate products that 9 are likely to be corroded by the electrolyte, and the oxide film with low stability is liable to fall off the anode electrode in the electrolysis process; after the previous oxide film is corroded or falls 11 off, the material of the alloy anode exposed to the surface will create a new oxide film by 12 reaction, such replacement between new and old oxide films results in continuous consumption = 13 and poor corrosion resistance of the anode material;
furthermore, the corroded or falling oxide 14 film enters into liquid aluminum in the electrolysis process of alumina to degrade the purity of the final product aluminum, as a result, the manufactured aluminum product cannot meet the 16 demand of national standards and accordingly cannot be directly used as a finished product.
17 Summary of the Invention 18 The first technical problem to be solved by the present invention is that, the prior art is incapable 19 of avoiding corrosion to electrolysis devices and damage to human body and ensuring proper electric conductivity and alumina solubility as well as no 'crusting' phenomenon in the prepared 21 electrolyte while the liquidus temperature of the electrolyte is further lowered. Thus the present 22 invention provides an electrolytic cell, containing an electrolyte for aluminum electrolysis which 23 is low in liquidus temperature, free from metal corrosion, not liable to volatilization, proper in 24 electric conductivity and alumina solubility and free from cathode 'crusting' phenomenon.
Simultaneously, the second technical problem to be solved by the present invention is that, an 26 alloy anode composed of metal components in the prior art is high in overvoltage, power 27 consumption in the aluminum electrolysis process is large and the metal components employed 28 are high in price, resulting in cost increment of the alloy anode; in addition, an oxide film on the 29 surface of the alloy anode in the prior art is low in oxidation resistance and liable to fall off, which leads to continuous consumption of the alloy anode and poor corrosion resistance, 31 furthermore, the corroded or falling oxide film enters into liquid aluminum to degrade the purity 32 of the final product aluminum; and therefore, provided is an electrolytic cell for aluminum 22653226.2 3 =
CA Application Blakes Ref.: 11878/00001 1 electrolysis, which is low in overvoltage of the used inert anode material, low in price, strong in 2 oxidation resistance and stability of the oxide film formed on the surface thereof and resistant to 3 electrolyte corrosion.
4 Simultaneously, the present invention provides a process for aluminum electrolysis using the above electrolytic cell.
6 To solve the aforementioned technical problems, the present invention provides an electrolytic 7 cell for aluminum electrolysis, comprising a cell body, wherein an anode and a cathode are 8 arranged inside the cell body, the cell body is further filled with an electrolyte; the anode is 9 arranged above the cell body, and at least a part of the anode is immersed in the electrolyte; the cathode is arranged at the bottom of the electrolytic cell and covered by a certain amount of 11 aluminum liquid; the electrolyte is located between the anode and the cathode; the anode 12 contains the components including Fe, Cu, Ni and Sn, wherein Fe and Cu serve as primary 13 components; the electrolyte is composed of 30-38wV/0 of NaF, 49-60wV/0 of AlF3, 1-5wt% of LiF, 14 1-6wr/o of KF and 3-6wr/0 of A1203, wherein the molar ratio of NaF to AlF3 is 1.0-1.52.
The bottom surface of the anode is kept parallel to the cell body, and an insulating layer is = 16 arranged on the inner sidewall of the cell body and is used for isolating oxygen or the electrolyte 17 from a carbon block.
18 A cell cover is arranged at the upper end of the cell body and is provided with a vent and a 19 feeding hole; a cathode bar is arranged inside the cathode, one end of the anode penetrates through the cell cover and is connectedly provided with a binding post for connection with a 21 power supply.
22 The mass ratio of Fe to Cu to Sn is (23-40): (36-60): (0.2-5).
23 The components of the anode further include Ni.
24 The anode is composed of Fe, Cu, Ni and 'Sn, wherein the content of Fe is 23-40wt%, the content of Cu is 36-60%, the content of Ni is 14-28wt% and the content of Sn is 0.2-5wt%.
26 The components of the anode further include Al and Y.
27 The anode is composed of Fe, Cu, Ni, Sn, Al and Y, wherein the content of Fe is 23-40wr/o, the 28 content of Cu is 36-60wt%, the content of Ni is 14-28wr/o, the content of Al is more than zero 22653226.2 4 CA Application Blakes Ref.: 11878/00001 1 and less than or equal to 4wt /0, the content of Y is more than zero and less than or equal to 2 2wV/0, and the content of Sn is 0.2-5wr/o.
3 The molar ratio of NaF to AlF3 is 1.12-1.52.
4 The liquidus temperature of the electrolyte is 620-670 C.
An electrolysis process using the electrolytic cell comprises the steps of:
6 (1) adding specified amounts of NaF, AlF3, LiF, KF and A1203 to a melting furnace for mixing and 7 melting to form a melt; or adding specified amounts of NaF, AlF3, LiF and KF to a melting 8 furnace for mixing and melting, and then adding A1203 to obtain a melt;
and 9 (2) raising the temperature of the melt prepared in step (1) to above 720-760 C, and then, pouring the melt into the electrolytic cell and carrying out electrolysis while the temperature is 11 maintained at 720-760 C.
12 The electrolysis temperature is 730-750 C.
13 A1203 is quantitatively supplied in the electrolysis process.
14 The electrolysis process using the electrolytic cell comprises the steps of:
(1) adding specified amounts of NaF, AlF3, LiF, KF and A1203 to a melting furnace for mixing and 16 melting to form a melt; or adding specified amounts of NaF, AlF3, LiF
and KF to a melting 17 furnace for mixing and melting, and then adding A1203 to obtain a melt;
and 18 (2) raising the temperature of the melt prepared in step (1) to above 720-760 C, and then, 19 pouring the melt into the electrolytic cell and carrying out electrolysis while the temperature is maintained at 720-760 C.
21 The electrolysis temperature is 730-750 C.
22 A1203 is quantitatively supplied in the electrolysis process.
23 The electrolytic cell and the electrolysis process using the electrolytic cell in the present 24 invention have the advantages below:
22653226.2 5 =
CA Application Blakes Ref.: 11878/00001 1 (1) The electrolytic cell for aluminum electrolysis in the present invention comprises a cell body, 2 wherein an anode and a cathode are arranged inside the cell body, and the cell body is further 3 filled with an electrolyte; the anode is arranged above the cell body, and at least a part of the 4 anode is immersed in the electrolyte; the cathode is arranged at the bottom of the electrolytic cell and covered by a certain amount of aluminum liquid; the electrolyte is located between the 6 anode and the cathode; the anode contains the components including Fe, Cu, Ni and Sn, 7 wherein Fe and Cu serve as primary components; the electrolyte is composed of 30-38wt% of 8 NaF, 49-60wr/0 of AlF3, 1-5wr/o of LiF, 1-6wtcY0 of KF and 3-6wr/0 of A1203, wherein the molar 9 ratio of NaF to AlF3 is 1.0-1.52.
The anode containing metal Sn and composed of the aforementioned metal components is high 11 in electric conductivity and low in overvoltage, the cell voltage in the electrolysis process of the 12 electrolytic cell is about 3.1-3.4V, power consumption in the aluminum electrolysis process is 13 small, the power consumption for per ton of aluminum is not more than 11000kw=h, so the 14 process cost is low; the anode material is alloy composed of Fe, Cu and Sn, so an oxide film formed on the surface of the anode in the electrolysis process is high in oxidation resistance 16 and is hardly corroded by the electrolyte, and the formed oxide film is stable and not liable to fall 17 off, therefore, the anode is imparted with quite high oxidation resistance and strong corrosion 18 resistance so as to ensure the purity of aluminum products, that is, the purity of the produced 19 aluminum can reach 99.8%. The following problems in the prior art are avoided: the alloy anode has high overvoltage, the oxide film on the alloy surface is low in oxidation resistance and liable 21 to fall off, which leads to continuous consumption of the alloy anode and poor corrosion 22 resistance, furthermore, the corroded or falling oxide film enters into liquid aluminum to degrade 23 the purity of the final product aluminum. In addition, Fe and Cu serve as primary components of 24 the alloy anode and their content proportions are quite high, and accordingly, the manufacturing cost of the anode material is lowered.
26 The used electrolyte employs a pure fluoride system, substance composition in the electrolyte is 27 defined, the contents of these substances are further defined and the molar ratio of NaF to AlF3 28 is 1.0-1.52, so that the liquidus temperature of the electrolyte is lowered to 640-670 C, as a 29 result, electrolysis can be carried out at 720-760 C according to the electrolysis process, which reduces volatilization loss of fluoride salt, avoids corrosion to electrolysis devices and damage 31 to human body, improves working environment, greatly reduces energy consumption in the 32 electrolysis process and achieves the aim of energy saving and emission reduction; meanwhile, 22653226.2 6 CA Application Blakes Ref.: 11878/00001 1 in the present invention, proper amounts of LiF and KF are added and can be combined with 2 sodium ions and aluminum ions in the electrolyte to form lithium cryolite and potassium cryolite 3 with low melting points, thus the crusting phenomenon is avoided in the electrolysis process;
4 compared with the existing industry, the electrolyte for aluminum electrolysis in the present invention has no CaF2 and MgF2 added therein, instead, KF in an appropriate proportion, which 6 has the function of increasing alumina solubility and dissolution velocity, is added to a system in 7 which the molar ratio of NaF to AlF3 is 1.0-1.52, therefore, the shortcoming of low alumina 8 solubility in the low-molar-ratio electrolyte is improved; in general, the electric conductivity of the = 9 electrolyte decreases as the temperature decreases, so typically, the electric conductivity at a low electrolysis temperature hardly meets the demand in a normal electrolysis process; the 11 electrolysis temperature is lowered by lowering the liquidus temperature of the electrolyte in the 12 present invention, however, the electric conductivity of the electrolyte at a low temperature can 13 still meet the demand in the electrolysis process because LiF with a larger electric conductivity 14 is added and component proportions in the electrolyte are optimized, thus enhancing the current efficiency in the electrolysis process. According to the invention, the content of LiF is defined as = 16 1-5%, this is because too low content of LiF fails to improve electric conductivity and to prevent 17 crusting, and too high content of LiF results in decrease of the alumina solubility, and the above 18 two situations are effectively avoided by defining the content of LiF as 1-5% in the present 19 invention; and there is no corrosion to a metal device when the electrolyte with the above proportions in the present invention is used, in this way, the service life of the electrolysis device 21 is prolonged.
22 (2) In the electrolytic cell for aluminum electrolysis in the present invention, the anode is 23 composed of Fe, Cu, Ni, Sn, Al and Y, wherein the content of Fe is 23-40wr/o, the content of Cu 24 is 36-60wr/o, the content of Ni is 14-28wr/o, the content of Al is less than or equal to 4wV/0, the content of Y is less than or equal to 2wr/o, and the content of Sn is 0.2-5wV/0.
26 Similarly, the aforementioned inert alloy anode has the advantages of low material cost and high 27 electric conductivity, in addition, the metal Al contained in the aforementioned inert alloy anode 28 plays a role of oxidization resistance and can serve as a reducing agent for metallothermic = 29 reduction reaction with metal oxides in the inert anode alloy, thus preventing the metals in the inert alloy anode, i.e. primary components, from being oxidized, and causing reduction of the 31 electric conductivity of the alloy anode; meanwhile, the metal Y added can be used for 22653226.2 7 CA Application Blakes Ref.: 11878/00001 1 controlling a crystal structure for anode material formation in the preparation process of the inert 2 anode, achieving the anti-oxidization purpose.
3 (3) In the electrolytic cell for aluminum electrolysis in the present invention, specified amounts of 4 NaF, AlF3, LiF, KF and A1203 are mixed, the resultant mixture is heated to form a melt; or specified amounts of NaF, AlF3, LiF and KF are mixed, the resultant mixture is heated until the 6 mixture is molten, and then A1203 is added to obtain a melt; afterwards, the melt prepared is 7 electrolyzed at 720-760 C. Electrolysis temperature is directly associated with volatilization of 8 the electrolyte, cathode crusting phenomenon, energy consumption of the process, electric 9 conductivity and a. lumina solubility, and the inventor of the present invention, by long search, set the electrolysis temperature within a range from 720-760 C in a matching way based on the 11 components and content characteristics of the electrolyte in the present invention, thus the 12 cathode crusting phenomenon is prevented and volatilization of the electrolyte and energy 13 consumption of the electrolysis process are remarkably reduced while both the electric 14 conductivity and the alumina solubility are increased, and the economic efficiency of the process is improved. Preferably, the electrolysis temperature is further set within a range from 730-16 750 C in the present invention.
17 Brief Description of the Drawings 18 For more easily understanding the contents of the present invention, further description will be = 19 made below to the technical solution of the present invention in conjunction with the drawing and the embodiments.
21 Fig.1 is a structure diagram of the electrolytic cell for aluminum electrolysis in the present 22 invention;
23 In this drawing, reference signs are as follows: 1 refers to cell body, 2 refers to anode, 3 refers 24 to cathode, 4 refers to electrolyte, 5 refers to insulating layer, 6 refers to cell cover, 7 refers to vent, 8 refers to feeding hole, 9 refers to binding post, 10 refers to cathode bar and 11 refers to 26 aluminum liquid.
27 Detailed Description of the Embodiments 28 The electrolytic cell for aluminum electrolysis in the present invention is as shown in Fig.1 and 29 comprises a cell body 1, wherein an anode 2 and a cathode 3 are arranged inside the cell body 1, the anode 2 and the cathode 3 can be arranged in random ways in accordance with the = 31 actual need, in this embodiment, the anode 2 is arranged above the cell body 1, the bottom 22653226.2 8 =
CA Application Blakes Ref.: 11878/00001 1 surface of the anode 2 is kept parallel to the cell body 1, the cathode 3 is arranged at the bottom 2 of the electrolytic cell and covered by a certain amount of aluminum liquid 11; the cell body 1 is 3 further filled with an electrolyte 4, immersion of the anode 2 and the cathode 3 in the electrolyte 4 4 depends on the selected electrolytic cell structure, in this embodiment, at least a part of the anode 2 is immersed in the electrolyte 4; the cathode 3 is arranged at the bottom of the 6 electrolytic cell and covered by a certain amount of aluminum liquid 11;
the electrolyte 4 is 7 located between the anode 2 and the cathode 3 and covers the aluminum liquid 11; the anode 2 8 contains the components including Fe, Cu, Ni and Sn, wherein Fe and Cu serve as primary 9 components, and the molar ratio of Fe to Cu to Sn is (23-40): (36-60):
(0.2-5); the electrolyte 4 is composed of 30-38wt% of NaF, 49-60wt% of AlF3, 1-5wt /0 of LiF, 1-6wt /0 of KF and 3-6wt /0 11 of A1203, wherein the molar ratio of NaF to AIF3 is 1.0-1.52, preferably 1.12-1.52, and the 12 liquidus temperature of the electrolyte 4 is 620-670 C, preferably 640-670 C.
13 As a variable embodiment on this basis, in order to isolate the inner sidewall of the cell body 1 14 from the electrolyte 4 and oxygen to prevent transfer of electrons between the sidewall of the cell body 1 and th.e electrolyte 4 and corrosion of the electrolyte 4 to the sidewall of the cell body 16 1, an insulating lay.er 5 is arranged on the inner sidewall of the cell body 1 and is made of any 17 commercially available insulating material that is resistant to high temperature and corrosion of 18 the electrolyte 4, e.g. corundum, aluminate spinel refractory and the like. In this embodiment, a 19 carbon block is arranged between the inner sidewall of the cell body 1 and the insulating layer 5, and the carbon block and the cathode 3 are integrally formed. Undoubtedly, the carbon block 21 and the cathode 3 can also be arranged in a separated manner.
22 On this basis, in order to isolate the electrolysis environment for the electrolytic cell from outside = 23 without impediment to exhaust and feeding, a cell cover 6 is arranged at the upper end of the 24 cell body 1 and is provided with a vent 7 and a feeding hole 8 thereon, the sizes and positions of the vent 7 and the feeding hole can be randomly determined in accordance with the actual 26 need, and in this embodiment, the vent 7 is arranged next to the anode 2.
27 Further, in order to facilitate connection of the anode 2 and the cathode 3 with a power supply, a 28 cathode bar 10 is arranged on the cathode 3 at the bottom of the electrolytic cell and is used for 29 connection with the power supply of the cathode 3; one end of the anode 2 penetrates through the cell cover 6 and is connected and provided with a binding post 9 for connection with the 31 power supply of the anode 2; and the cathode 10 and the binding post 9 can be made of any 32 material with good electric conductivity, including steel, iron and alloy materials, etc.
22653226.2 9 CA Application Blakes Ref.: 11878/00001 1 On this basis, in order to improve the combination firmness among metals Fe, Cu and Sn, the 2 components of the anode 2 further include Ni, preferably the anode 2 is composed of Fe, Cu, Ni 3 and Sn, wherein the content Fe is 23-40wr/o, the content of Cu is 36-60wt%, the content of Ni is 4 14-28wt% and the content of Sn is 0.2-5wr/o.
The anode 2 may be preferably composed of Fe, Cu, Ni, Sn, Al and Y, the added Al can prevent 6 other primary metal components of the anode 2 from oxidation and improve the oxidization 7 resistance, the component Y can be used for regulating and controlling the structure of the 8 prepared alloy crystal in order to achieve the anti-oxidization purpose, wherein the content of Fe 9 is 23-40wt%, the content of Cu is 36-60wV/0, the content of Ni is 14-28wt /0, the content of Al is less than or equal to 4wt%, the content of Y is less than or equal to 2wt%, and the content of Sn 11 is 0.2-5wV/0.
12 The electrolysis temperature is 720-760 C when the aforementioned electrolytic cell is used for = 13 aluminum electrolysis, preferably 730-750 C.
14 Description is made below in conjunction with the embodiments.
Embodiment 1 16 Fe, Cu, Ni and Sn metal blocks are mixed based on 23wt /0 of Fe, 60wt /0 of Cu, 14wt /0 of Ni 17 and 3wt /0 of Sn, the mixture is molten by heating at high temperature and then subjected to 18 casting to obtain an anode 1. The anode 1 has a density of 8.3/cm3, a specific resistivity of 19 68pD=cm and a melting point of 1360 C.
The components of the electrolyte in this embodiment are as follows: 32% of NaF, 57% of AlF3, 21 3% of LiF, 4% of KF and 4% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 22 is 1.12. The liquidus temperature of the electrolyte in this embodiment is 640 C according to 23 measurement. The electrolyte has an electric conductivity of about 1.70-1.cm-1, a density of 24 about 2.03g/cm3 and an alumina saturation concentration of 5%.
The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
26 (1) by means of the anode 1 and the carbon body cathode, melting the aforementioned amounts 27 of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 28 (2) raising the temperature of the melt prepared in step (1) to above 720 C in the melting 29 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 22653226.2 10 CA Application Blakes Ref.: 11878/00001 1 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 2 maintained at 720 C, wherein A1203is quantitatively supplied in the electrolysis process.
3 There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 4 electrolytic cell is 3.1V, the power consumption for per ton of aluminum is 10040kw=h in the electrolysis process, and the prepared aluminum has a purity of 99.85%.
6 Embodiment 2 7 Fe,. Cu, Ni and Sn metal blocks are mixed based on 40wt /0 of Fe, 36wt%
of Cu, 19wt% of Ni 8 and 5wt% of Sn, the mixture is molten by heating at high temperature and then subjected to 9 casting to obtain an anode 2. The anode has a density of 8.1/cm3, a specific resistivity of 76.8p0=cm and a melting point of 1386 C.
11 The components of the electrolyte in this embodiment are as follows: 38%
of NaF, 50% of AlF3, 12 2% of LiF, 5% of KF and 5% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 13 is 1.52.
14 The performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 670 C. The = 16 electrolyte has an electric conductivity of about 1.80-1.cm-1, a density of about 2.05g/cm3 and an 17 alumina saturation concentration of 6%.
18 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
19 (1) by means of the anode 2 and the carbon body cathode, melting the aforementioned amounts of NaF, AlF3, LiF and KF in a melting furnace, and then adding the aforementioned amount of 21 A1203 to obtain a melt by melting; and 22 (2) raising the temperature of the melt prepared in step (1) to above 760 C in the melting 23 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 24 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is maintained at 760 C.
26 There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 27 electrolytic cell is 3.39V, the power consumption for per ton of aluminum is 10979kw.h in the 28 electrolysis process, and the prepared aluminum has a purity of 99.82%.
22653226.2 1 1 CA Application Blakes Ref.: 11878/00001 1 Embodiment 3 = 2 Fe, Cu, Ni and Sn metal blocks are mixed based on 25wr/o of Fe, 46.8wt% of Cu, 28wr/0 of Ni 3 and 0.2wt% of Sn, the mixture is molten by heating at high temperature and then subjected to 4 casting to obtain an anode 3. The anode has a density of 8.2/cm3, a specific resistivity of 72p0=cm and a melting point of 1350 C.
6 The components of the electrolyte in this embodiment are as follows: 32%
of NaF, 57% of AlF3, 7 3% of LiF, 4% of KF and 4% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 8 is 1.12.
9 The performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640 C. The 11 electrolyte has an electric conductivity of about 1.6Q-1-cm-1, a density of about 2.03g/cm3 and an 12 alumina saturation concentration of 5%.
13 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
14 (1) by means of the anode 3 and the carbon body cathode, melting the aforementioned amounts of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 16 (2) raising the temperature of the melt prepared in step (1) to above 730 C in the melting 17 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 18 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 19 maintained at 730 C, wherein A1203 is quantitatively supplied in the electrolysis process.
There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 21 electrolytic cell is 3.15V, the power consumption for per ton of aluminum is 10202kw.h in the 22 electrolysis process, and the prepared aluminum has a purity of 99.85%.
23 Embodiment 4 24 Fe, Cu, Ni and Sn metal blocks are mixed based on 24.2w% of Fe, 60wt% of Cu, 14wV3/0 of Ni and 0.2wt% of Sn, the mixture is molten by heating at high temperature, 1.8wr/o of Al metal 26 block is then added for continuous melting and mixing, and finally, 0.8wt% of Y metal block is 27 added for melting and mixing and an anode 4 is obtained by casting of the mixture. The anode 28 has a density of 8.3/cm3, a specific resistivity of 68pQ=cm and a melting point of 1360 C.
22653226.2 12 CA Application Blakes Ref.: 11878/00001 1 The components of the electrolyte in this embodiment are as follows: 32%
of NaF, 57% of AlF3, 2 3% of LiF, 4% of KF and 4% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 3 is 1.12.
4 The performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640 C. The 6 electrolyte has an electric conductivity of about 1.80-1.cm-1, a density of about 2.04g/cm3 and an 7 alumina saturation concentration of 6%.
8 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
9 (1) by means of the anode 4 and the carbon body cathode, melting the aforementioned amounts of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 11 (2) raising the temperature of the melt prepared in step (1) to above 750 C in the melting 12 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 13 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 14 maintained at 750 C, wherein A1203 is quantitatively supplied in the electrolysis process.
There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 16 electrolytic cell is 3.12V, the power consumption for per ton of aluminum is 10105kw-h in the 17 electrolysis process, and the prepared aluminum has a purity of 99.8%.
18 Embodiment 5 19 Fe, Cu, Ni and Sn metal blocks are mixed based on 40wr/0 of Fe, 36wt% of Cu, 14.9wV/0 of Ni and 5wt(3/0 of Sn, the mixture is molten by heating at high temperature, 0.1wr/0 of Al metal block 21 is then added for continuous melting and mixing, and finally, 0.1wt% of Y metal block is added 22 for melting and mixing and an anode 5 is obtained by casting of the mixture. The anode has a = 23 density of 8.1/cm3, a specific resistivity of 76.8pQ=cm and a melting point of 1386 C.
24 The components of the electrolyte in this embodiment are as follows: 30%
of NaF, 60% of AlF3, 1% of LiF, 6% of KF and 3% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 26 is 1Ø
27 The performances of the electrolyte in this embodiment are measured and the measurement 28 result is that the liquidus temperature of the electrolyte in this embodiment is 620 C. The 22653226.2 13 CA Application Blakes Ref.: 11878/00001 1 electrolyte has an electric conductivity of about 1.60-1-cm-1, a density of about 2.03g/cm3 and an 2 alumina saturation concentration of 5%.
3 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
4 (1) by means of the anode 5 and the carbon body cathode, melting the aforementioned amounts of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 6 (2) raising the temperature of the melt prepared in step (1) to above 720 C in the melting 7 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 8 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 9 maintained at 720 C, wherein A1203 is quantitatively supplied in the electrolysis process.
There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 11 electrolytic cell is 3.27V, the power consumption for per ton of aluminum is 10591kw.h in the 12 electrolysis process, and the prepared aluminum has a purity of 99.81%.
13 Embodiment 6 14 Fe, Cu, Ni and Sn metal blocks are mixed based on 25wt% of Fe, 38wr/0 of Cu, 28wt% of Ni and 4wt /0 of Sn, the mixture is molten by heating at high temperature, 4wr/0 of Al metal block is 16 then added for continuous melting and mixing, and finally, 1wt(3/0 of Y
metal block is added for 17 melting and mixing and an anode 6 is obtained by casting of the mixture.
The anode has a 18 density of 8.2/cm3, a specific resistivity of 70p0=cm and a melting point of 1365 C.
19 The components of the electrolyte in this embodiment are as follows: 38%
of NaF, 54% of AlF3, = 20 4% of LiF, 1% of KF and 3% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 21 is 1.4.
22 The performances of the electrolyte in this embodiment are measured and the measurement 23 result is that: the liquidus temperature of the electrolyte in this embodiment is 670 C. The 24 electrolyte has an electric conductivity of about 1.8D-1.cm-1, a density of about 2.05g/cm3 and an alumina saturation concentration of 6%.
26 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
27 (1) by means of the anode 6 and the carbon body cathode, melting the aforementioned amounts 28 of NaF, AlF3, LiF, KF and A1203in a melting furnace so as to form a melt; and 22653226.2 14 CA Application Blakes Ref.: 11878/00001 1 (2) raising the temperature of the melt prepared in step (1) to above 760 C in the melting 2 furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 3 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 4 maintained at 760 C, wherein A1203 is quantitatively supplied in the electrolysis process.
There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 6 electrolytic cell is 3.35V, the power consumption for per ton of aluminum is 10850kw-h in the 7 electrolysis process, and the prepared aluminum has a purity of 99.83%.
8 Embodiment 7 9 Fe, Cu, Ni and Sn metal blocks are mixed based on 40wt /0 of Fe, 36.5wt%
of Cu, 18wt% of Ni and 3wt /0 of Sn, the mixture is molten by heating at high temperature, 1.5wt%
of Al metal block 11 is then added for continuous melting and mixing, and finally, 1wV/0 of Y
metal block is added for 12 melting and mixing and an anode 7 is obtained by casting of the mixture.
The anode has a 13 density of 8.1/cm3, a specific resistivity of 76.8pD=cm and a melting point of 1386 C.
14 The components of the electrolyte in this embodiment are as follows: 34%
of NaF, 49% of AlF3,
5% of LiF, 6% of KF and 6% of A1203, wherein the molar ratio of NaF to aluminum fluoride AlF3 16 is 1.39.
17 The performances of the electrolyte in this embodiment are measured and the measurement 18 result is that the liquidus temperature of the electrolyte in this embodiment is 660 C. The 19 electrolyte has an electric conductivity of about 1.8D-1.cm-1, a density of about 2.05g/cm3 and an alumina saturation concentration of 6%.
21 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
22 (1) by means of the anode 7 and the carbon body cathode, melting the aforementioned amounts 23 of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 24 (2) raising the temperature of the melt prepared in step (1) to above 760 C in the melting furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 26 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 27 maintained at 760 C, wherein A1203 is quantitatively supplied in the electrolysis process.
22653226.2 15 CA Application Blakes Ref.: 11878/00001 1 There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 2 electrolytic cell is 3.38V, the power consumption for per ton of aluminum is 10947kw.h in the 3 electrolysis process, and the prepared aluminum has a purity of 99.8%.
4 The electrolytic cell in the aforementioned embodiments is any of the electrolytic cells in the present invention.
17 The performances of the electrolyte in this embodiment are measured and the measurement 18 result is that the liquidus temperature of the electrolyte in this embodiment is 660 C. The 19 electrolyte has an electric conductivity of about 1.8D-1.cm-1, a density of about 2.05g/cm3 and an alumina saturation concentration of 6%.
21 The process using the electrolyte in the present invention for aluminum electrolysis is as follows:
22 (1) by means of the anode 7 and the carbon body cathode, melting the aforementioned amounts 23 of NaF, AlF3, LiF, KF and A1203 in a melting furnace so as to form a melt; and 24 (2) raising the temperature of the melt prepared in step (1) to above 760 C in the melting furnace, then pouring the melt into the electrolytic cell, switching on the power supplies of the 26 anode and the cathode, and carrying out electrolysis for 40 hours while the temperature is 27 maintained at 760 C, wherein A1203 is quantitatively supplied in the electrolysis process.
22653226.2 15 CA Application Blakes Ref.: 11878/00001 1 There is no crust at the bottom of the cell body in the electrolysis process, the cell voltage of the 2 electrolytic cell is 3.38V, the power consumption for per ton of aluminum is 10947kw.h in the 3 electrolysis process, and the prepared aluminum has a purity of 99.8%.
4 The electrolytic cell in the aforementioned embodiments is any of the electrolytic cells in the present invention.
6 Detailed description has been made to the specific contents of the present invention in the
7 aforementioned embodiments, and it should be understood by those skilled in this art that
8 modifications and detail variations in any form based upon the present invention pertain to the
9 contents that the present invention seeks to protect.
22653226.2 16
22653226.2 16
Claims (13)
1. An electrolytic cell for aluminum electrolysis, comprising:
a cell body (1), an anode (2) and a cathode (3) being arranged inside the cell body (1), the cell body (1) being further filled with an electrolyte (4);
the anode (2) being arranged above the cell body (1), and at least a part of the anode (2) being immersed in the electrolyte (4);
the cathode (3) being arranged at the bottom of the electrolytic cell and covered by a certain amount of aluminum liquid (11);
the electrolyte (4) being located between the anode (2) and the cathode (3);
characterized in that the anode (2) contains the components including Fe, Cu, Ni and Sn, wherein Fe and Cu serve as primary components; and the electrolyte (4) is composed of 30-38wt% of NaF, 49-60wt% of AlF3, 1-5wt%
of LiF, 1-6wt% of KF and 3-6wt% of Al2O3, wherein the molar ratio of NaF to AlF3 is 1.0-1.52.
a cell body (1), an anode (2) and a cathode (3) being arranged inside the cell body (1), the cell body (1) being further filled with an electrolyte (4);
the anode (2) being arranged above the cell body (1), and at least a part of the anode (2) being immersed in the electrolyte (4);
the cathode (3) being arranged at the bottom of the electrolytic cell and covered by a certain amount of aluminum liquid (11);
the electrolyte (4) being located between the anode (2) and the cathode (3);
characterized in that the anode (2) contains the components including Fe, Cu, Ni and Sn, wherein Fe and Cu serve as primary components; and the electrolyte (4) is composed of 30-38wt% of NaF, 49-60wt% of AlF3, 1-5wt%
of LiF, 1-6wt% of KF and 3-6wt% of Al2O3, wherein the molar ratio of NaF to AlF3 is 1.0-1.52.
2. The electrolytic cell according to claim 1, characterized in that the bottom surface of the anode (2) is kept parallel to the cell body (1), and an insulating layer (5) is arranged on the inner sidewall of the cell body (1) and is used for isolating oxygen or the electrolyte (4) from a carbon block.
3. The electrolytic cell according to claim 1 or 2, characterized in that a cell cover (6) is arranged at the upper end of the cell body (1) and is provided with a vent (7) and a feeding hole (8); a cathode bar (10) is arranged inside the cathode (3), one end of the anode (2) penetrates through the cell cover (6) and is connected and provided with a binding post (9) for connection with a power supply.
4. The electrolytic cell according to any of claims 1-3, characterized in that the mass ratio of Fe to Cu to Sn is (23-40): (36-60): (0.2-5).
5. The electrolytic cell according to any of claims 1-4, characterized in that the components of the anode (2) further include Ni.
6. The electrolytic cell according to claim 5, characterized in that the anode (2) is composed of Fe, Cu, Ni and Sn, wherein the content of Fe is 23-40wt%, the content of Cu is 36-60wt%, the content of Ni is 14-28wt% and the content of Sn is 0.2-5wt%.
7. The electrolytic cell according to any of claims 1-6, characterized in that the components of the anode (2) further include Al and Y.
8. The electrolytic cell according to claim 7, characterized in that the anode (2) is composed of Fe, Cu, Ni, Sn, Al and Y, wherein the content of Fe is 23-40wt%, the content of Cu is 36-60wt%, the content of Ni is 14-28wt%, the content of Al is more than zero and less than or equal to 4wt%, the content of Y is more than zero and less than or equal to 2wt%, and the content of Sn is 0.2-5wt%.
9. The electrolytic cell according to any of claims 1-8, characterized in that the molar ratio of NaF to AlF3 is 1.12-1.52.
10. The electrolytic cell according to any of claims 1-9, characterized in that the liquidus temperature of the electrolyte (4) is 620-670°C.
11. An electrolysis process using the electrolytic cell according to any of claims 1-10, comprising the steps of:
(1) adding specified amounts of NaF, AlF3, LiF, KF and Al2O3 to a melting furnace for mixing and melting to form a melt; or adding specified amounts of NaF, AlF3, LiF and KF to a melting furnace for mixing and melting, and then adding Al2O3 to obtain a melt; and (2) raising the temperature of the melt prepared in step (1) to above 720-760°C, and then, pouring the melt into the electrolytic cell and carrying out electrolysis while the temperature is maintained at 720-760°C.
(1) adding specified amounts of NaF, AlF3, LiF, KF and Al2O3 to a melting furnace for mixing and melting to form a melt; or adding specified amounts of NaF, AlF3, LiF and KF to a melting furnace for mixing and melting, and then adding Al2O3 to obtain a melt; and (2) raising the temperature of the melt prepared in step (1) to above 720-760°C, and then, pouring the melt into the electrolytic cell and carrying out electrolysis while the temperature is maintained at 720-760°C.
12. The electrolysis process according to claim 11, characterized in that the electrolysis temperature is 730-750°C.
13. The electrolysis process according to claim 11 or 12, characterized in that Al2O3 is quantitatively supplied in the electrolysis process.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210188436.9 | 2012-06-11 | ||
| CN201210188436.9A CN103484891B (en) | 2012-06-11 | 2012-06-11 | A kind of electrolgtic aluminium electrolyzer and use the electrolysis process of this electrolyzer |
| PCT/CN2013/076440 WO2013185538A1 (en) | 2012-06-11 | 2013-05-30 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2877591A1 CA2877591A1 (en) | 2013-12-19 |
| CA2877591C true CA2877591C (en) | 2016-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CA2877591A Expired - Fee Related CA2877591C (en) | 2012-06-11 | 2013-05-30 | Electrolytic cell for aluminum electrolysis and electrolysis process using electrolytic cell |
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| US (1) | US20150122664A1 (en) |
| EP (1) | EP2860290B1 (en) |
| KR (1) | KR101684813B1 (en) |
| CN (1) | CN103484891B (en) |
| AP (1) | AP2015008184A0 (en) |
| AU (1) | AU2013275995B2 (en) |
| CA (1) | CA2877591C (en) |
| EA (1) | EA030419B1 (en) |
| HR (1) | HRP20190669T1 (en) |
| HU (1) | HUE042500T2 (en) |
| IN (1) | IN2015DN00216A (en) |
| PL (1) | PL2860290T3 (en) |
| WO (1) | WO2013185538A1 (en) |
| ZA (1) | ZA201409512B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EA032047B1 (en) * | 2012-06-11 | 2019-03-29 | Иннер Монголия Юнайтед Индастриал Ко., Лтд. | Electrolyte used for aluminum electrolysis and electrolysis process using the electrolyte |
| CN103952722A (en) * | 2014-05-06 | 2014-07-30 | 肖凯云 | Method for dipping carbon block in aluminium |
| CN103952723B (en) * | 2014-05-16 | 2016-03-30 | 北方工业大学 | A method for replacing anodes in aluminum electrolysis process |
| CN104593828A (en) * | 2014-12-18 | 2015-05-06 | 东北大学 | Preparation method of low-boron-phosphorus metallurgical grade silicon |
| WO2016171589A1 (en) * | 2015-04-22 | 2016-10-27 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Method for producing aluminium-scandium alloy and reactor for implementing the method |
| KR102438142B1 (en) * | 2015-12-11 | 2022-09-01 | 재단법인 포항산업과학연구원 | Electrolytic cell for the electroceparation of aluminium-scandium alloys and electrolytic method using the electrolytic cell |
| CN105543894B (en) * | 2016-02-26 | 2018-07-10 | 贵州铝城铝业原材料研究发展有限公司 | The anode carbon block structure that a kind of pre-calcining electrolytic cell non-residual electrode generates |
| CN105780053B (en) * | 2016-04-27 | 2018-08-17 | 新疆大学 | A kind of aluminum electrolysis method using aluminium as cathode |
| CN105780056B (en) * | 2016-04-27 | 2018-04-20 | 新疆大学 | Double-layer aluminum cathode aluminium electrolytic cell |
| CN105780054B (en) * | 2016-04-27 | 2018-04-20 | 新疆大学 | The aluminium electrolytic cell cathode of cathode is used as using aluminium |
| CN105780055B (en) * | 2016-04-27 | 2018-04-20 | 新疆大学 | The aluminium cell of cathode is used as using aluminium |
| CN105780057B (en) * | 2016-04-27 | 2018-04-20 | 新疆大学 | Double-layer aluminum cathode aluminium electrolytic cell cathode |
| CN107881531B (en) * | 2017-11-03 | 2019-08-30 | 党建平 | A kind of composite anode of aluminium cell |
| CN108950604A (en) * | 2018-08-31 | 2018-12-07 | 营口忠旺铝业有限公司 | A kind of aluminum electrolysis technology |
| CN113557313A (en) * | 2019-03-22 | 2021-10-26 | 株式会社Uacj | Manufacturing method and manufacturing apparatus of aluminum material |
| CN113957485A (en) * | 2020-07-20 | 2022-01-21 | 武汉市德成科技工程研究院有限责任公司 | Fixing seat frame device for continuous anode on aluminum electrolytic cell |
| CN114410975B (en) * | 2022-01-25 | 2023-01-03 | 东北大学 | Method for recovering waste aluminum/waste aluminum alloy |
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| FR2139648B1 (en) * | 1971-05-28 | 1973-08-10 | Prat Daniel Poelman | |
| US5006209A (en) * | 1990-02-13 | 1991-04-09 | Electrochemical Technology Corp. | Electrolytic reduction of alumina |
| US5284562A (en) * | 1992-04-17 | 1994-02-08 | Electrochemical Technology Corp. | Non-consumable anode and lining for aluminum electrolytic reduction cell |
| US6258247B1 (en) * | 1998-02-11 | 2001-07-10 | Northwest Aluminum Technology | Bath for electrolytic reduction of alumina and method therefor |
| US6723222B2 (en) * | 2002-04-22 | 2004-04-20 | Northwest Aluminum Company | Cu-Ni-Fe anodes having improved microstructure |
| US7077945B2 (en) * | 2002-03-01 | 2006-07-18 | Northwest Aluminum Technologies | Cu—Ni—Fe anode for use in aluminum producing electrolytic cell |
| US7431812B2 (en) * | 2002-03-15 | 2008-10-07 | Moitech Invent S.A. | Surface oxidised nickel-iron metal anodes for aluminium production |
| US6719889B2 (en) * | 2002-04-22 | 2004-04-13 | Northwest Aluminum Technologies | Cathode for aluminum producing electrolytic cell |
| US6719890B2 (en) * | 2002-04-22 | 2004-04-13 | Northwest Aluminum Technologies | Cathode for a hall-heroult type electrolytic cell for producing aluminum |
| CA2498622C (en) * | 2002-10-18 | 2011-09-20 | Moltech Invent S.A. | Aluminium electrowinning cells with metal-based anodes |
| CN1203217C (en) * | 2003-04-18 | 2005-05-25 | 石忠宁 | Metal base aluminium electrolytic inert anode and its preparation method |
| US20070278107A1 (en) * | 2006-05-30 | 2007-12-06 | Northwest Aluminum Technologies | Anode for use in aluminum producing electrolytic cell |
| CN101368282B (en) * | 2007-08-14 | 2012-07-11 | 北京有色金属研究总院 | Lower cathode rare earth metal electrolytic cell and electrolysis process using the electrolytic cell |
| CN101671835A (en) | 2008-09-09 | 2010-03-17 | 北京有色金属研究总院 | Low-temperature molten salt system for aluminum electrolysis and method for carrying out aluminum electrolysis by same |
| CN102011144A (en) | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Nickel-based alloy material suitable for inert anode of metal molten salt electrolyzer |
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2013
- 2013-05-30 PL PL13804286T patent/PL2860290T3/en unknown
- 2013-05-30 US US14/407,289 patent/US20150122664A1/en not_active Abandoned
- 2013-05-30 AU AU2013275995A patent/AU2013275995B2/en not_active Ceased
- 2013-05-30 CA CA2877591A patent/CA2877591C/en not_active Expired - Fee Related
- 2013-05-30 WO PCT/CN2013/076440 patent/WO2013185538A1/en not_active Ceased
- 2013-05-30 KR KR1020157000519A patent/KR101684813B1/en not_active Expired - Fee Related
- 2013-05-30 HR HRP20190669TT patent/HRP20190669T1/en unknown
- 2013-05-30 HU HUE13804286A patent/HUE042500T2/en unknown
- 2013-05-30 EP EP13804286.6A patent/EP2860290B1/en active Active
- 2013-05-30 EA EA201492226A patent/EA030419B1/en not_active IP Right Cessation
- 2013-05-30 AP AP2015008184A patent/AP2015008184A0/en unknown
- 2013-05-30 IN IN216DEN2015 patent/IN2015DN00216A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| AP2015008184A0 (en) | 2015-01-31 |
| CN103484891B (en) | 2016-06-15 |
| ZA201409512B (en) | 2016-08-31 |
| CA2877591A1 (en) | 2013-12-19 |
| EP2860290A1 (en) | 2015-04-15 |
| US20150122664A1 (en) | 2015-05-07 |
| EA201492226A1 (en) | 2015-05-29 |
| HRP20190669T1 (en) | 2019-06-14 |
| IN2015DN00216A (en) | 2015-06-12 |
| KR101684813B1 (en) | 2016-12-08 |
| AU2013275995A1 (en) | 2015-01-22 |
| EP2860290A4 (en) | 2016-02-10 |
| KR20150022993A (en) | 2015-03-04 |
| AU2013275995B2 (en) | 2016-05-12 |
| EA030419B1 (en) | 2018-08-31 |
| EP2860290B1 (en) | 2019-01-09 |
| HUE042500T2 (en) | 2019-07-29 |
| CN103484891A (en) | 2014-01-01 |
| PL2860290T3 (en) | 2019-07-31 |
| WO2013185538A1 (en) | 2013-12-19 |
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