CN103484891B - A kind of electrolgtic aluminium electrolyzer and use the electrolysis process of this electrolyzer - Google Patents
A kind of electrolgtic aluminium electrolyzer and use the electrolysis process of this electrolyzer Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 86
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000004411 aluminium Substances 0.000 title claims abstract description 62
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims description 61
- 230000008569 process Effects 0.000 title claims description 48
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- 229910052718 tin Inorganic materials 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000009413 insulation Methods 0.000 claims abstract description 7
- 239000002075 main ingredient Substances 0.000 claims abstract description 7
- 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
- 238000002844 melting Methods 0.000 claims description 42
- 230000008018 melting Effects 0.000 claims description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 36
- 229910052593 corundum Inorganic materials 0.000 claims description 32
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 31
- 238000005516 engineering process Methods 0.000 claims description 13
- 239000013589 supplement Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000013022 venting Methods 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 41
- 239000010949 copper Substances 0.000 description 37
- 239000011135 tin Substances 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 229910052751 metal Inorganic materials 0.000 description 30
- 239000002184 metal Substances 0.000 description 30
- 239000000956 alloy Substances 0.000 description 23
- 229910045601 alloy Inorganic materials 0.000 description 21
- 239000010405 anode material Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 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
- 238000004090 dissolution Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 229910001610 cryolite Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- -1 sodium aluminum fluoride Chemical compound 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 230000008901 benefit Effects 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
- 230000000694 effects Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-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-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- CTWSQXCNHFQOOK-UHFFFAOYSA-M [F-].[Al+3].[Na+].[O-2].[Al+3] Chemical compound [F-].[Al+3].[Na+].[O-2].[Al+3] CTWSQXCNHFQOOK-UHFFFAOYSA-M 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007769 metal material 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 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
- 229920001187 thermosetting polymer Polymers 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
- 230000003245 working effect Effects 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
Abstract
The present invention discloses the electrolyzer of a kind of electrolgtic aluminium, comprises groove body, is provided with anode and negative electrode in described groove body, in described groove body, ionogen is also housed, and at least part of described anode soaks in described ionogen; Described anode is arranged on the top of groove body, and described negative electrode is arranged on bottom land and is covered by a certain amount of aluminium liquid, and described ionogen is in the middle of anode and negative electrode, and described ionogen covers on described aluminium liquid; Described groove body inner side-wall is provided with insulation layer, for by isolated to oxygen or ionogen and carbon block. Its feature is, the component of described anode comprises Fe, Cu, Ni and Sn, wherein taking described Fe and Cu as main ingredient; Described ionogen is by the AlF of NaF, 49-60wt% of 30-38wt%3, 1-5wt% the Al of KF and 3-6wt% of LiF, 1-6wt%2O3Composition, wherein said NaF and AlF3Mol ratio be 1.0-1.52. This electrolyzer can be used for industrialization Aluminum Electrolysis Production.
Description
Technical field
The present invention relates to a kind of electrolgtic aluminium electrolyzer and use the electrolysis process of this electrolyzer, belong to non-ferrous metal metallurgy industry.
Background technology
Electrolytic aluminum industry adopts traditional Hall-Heroult fused salt electrolysis aluminium technique, in prebake carbon annode electrolyzer, the salt that melts of sodium aluminum fluoride-aluminum oxide is carried out electrolysis usually, namely with sodium aluminum fluoride Na3AlF6Fluoride salt melt is flux, by Al2O3It is dissolved in fluoride salt, vertically insert in electrolyzer using carbon body as anode, the carbon body being coated with aluminium liquid using bottom of electrolytic tank is as negative electrode, after leading to powerful direct current, under the hot conditions of 940-960 DEG C, carrying out electrochemical reaction at the two poles of the earth of electrolyzer, the aluminium liquid product produced covers on the negative electrode of bottom of electrolytic tank. The shortcomings such as traditional aluminum electrolysis technology, due to electrolysis temperature height, therefore exists ionogen volatile quantity big, poor working environment, and carbon annode oxidation loss is big, energy consumption is big.
In order to reduce electrolysis temperature, in prior art, Chinese patent literature CN101671835A discloses the low-temperature molten salt system of a kind of electrolysis of aluminum, and the fused salt of this system consists of AlF3And Al2O3, and KF, NaF, MgF2、CaF2、NaCl、LiF、BaF2In one or more salt, the extensive region that the electrolysis temperature of this ionogen can drop to 680-900 DEG C operates.
Adding NaCl in above-mentioned ionogen is to reduce electrolyte primary crystal temperature, but the metal objects such as such as electrolyzer accessory can be corroded by NaCl under above-mentioned electrolysis temperature, and NaCl highly volatile HCl toxic gas in electrolytic process, therefore, it is difficult to application; Except adding NaCl, according to the common practise of this area, reduce NaF and AlF3Mol ratio also can reduce the liquidus temperature of ionogen, but in applicable industry, NaF and AlF3Mol ratio be normally greater than 2.2, if this is because reducing NaF and AlF further3Mol ratio, with the reduction of electrolyte primary crystal temperature, NaF and AlF3Negative electrode " crust " phenomenon can be there is in low-temperature electrolytic process, the sodium ion that the reason of this kind of negative electrode " crust " phenomenon is in electrolytic process in ionogen and aluminum ion can be gathered in negative electrode, generate sodium cryolite, the fusing point of sodium cryolite is higher, it is difficult to melting under cryogenic, this just causes cathode surface can cover the molten sodium aluminum fluoride housing of lid layer difficulty, thus greatly have impact on the normal electrolysis of electrolytic process.In above-mentioned technology, Problems existing makes the industrial applications of ionogen be limited by very large, how while reducing electrolyte primary crystal temperature further, the corrosion to electrolyzer and the harm to human body can also be avoided, can also ensure that the ionogen prepared has suitable specific conductivity and alumina dissolution degree and do not produce negative electrode " crust " phenomenon simultaneously, be the difficult problem not yet solved in prior art.
Except needing to solve except the high problem of electrolysis temperature, in the electrolyzer of traditional electrolyte aluminium, carbon annode is continuous oxidized consumption in electrolytic process, thus needs constantly to change carbon annode; And with the process of electrolysis of aluminum, constantly produce the waste gas such as carbonic acid gas, carbon monoxide at anode. Therefore, in order to reduce the consumption of aluminium electrolysis process anode material, reduce the discharge of waste gas simultaneously, prior art discloses the document that many antianode materials carry out studying, as Chinese patent literature CN1443877A discloses a kind of inert anode material being applied to the electrolytic industries such as aluminium, magnesium and rare earth, the binary that it is made up of metals such as chromium, nickel, iron, cobalt, titanium, copper, aluminium, manganese or multicomponent alloy are formed, and its preparation method is the method for melting or powder metallurgy. Preparation-obtained anode material electrical and thermal conductivity is good, in electrolytic process, anode produces oxygen, the alloy material that wherein example one is made up of the nickel of the copper of the cobalt of 37wt%, 18wt%, 19wt%, the iron of 23wt%, the silver of 3wt% is made into anode for electrolytic aluminum, in the electrolytic process of 850 DEG C, anodic current density is 1.0A/cm2, and stablize in electrolytic process middle slot pressure and remain on 4.1-4.5V, the purity being produced aluminium is 98.35%.
Although carbon materials compared by the alloy anode material of above-mentioned technology has higher electric conductivity, electrolytic process has lower etching extent, and arbitrary shape can be processed into. But, the superpotential of the alloy anode being made up of above-mentioned metal component is still higher, and electric power consumed by industry amount is big, and quality product is low, and owing to employing metallic substance expensive in a large number, causes the with high costs of anode material, cannot adapt to industrialization needs.
In addition, alloy anode surface prepared in prior art all can produce one layer of sull, and this layer of sull destroyed after, the anode material being exposed to surface can oxidized supplement again as new sull. Alloy anode oxide on surface film oxidation-resistance in above-mentioned technology is low, it is easy to occur oxidizing reaction to generate the product being easily corroded from an electrolyte further, and this sull stability is low, easily comes off from anode electrode in the process of electrolysis; Original sull corrosion or after coming off, the material that alloy anode is exposed to surface can react and form new sull, and the new and old replacement of this kind of sull causes anode material to be constantly consumed, corrosion-resistant; And corroding or the sull that comes off can enter into liquid aluminium along with the electrolytic process of aluminum oxide, thus reduce the purity of the finished product aluminium, the requirement making the aluminium product produced not be up to state standards, directly cannot use as finished product.
Summary of the invention
First technical problem to be solved by this invention lacks in prior art reducing electrolyte primary crystal temperature further while, the corrosion to electrolyzer and the harm to human body can also be avoided, can also ensure that the ionogen prepared has suitable specific conductivity and alumina dissolution degree and do not produce the ionogen of negative electrode " crust " phenomenon simultaneously, the present invention provides a kind of low containing liquidus temperature, to had no corrosive effect on metals, not easily volatilize, there is suitable specific conductivity and alumina dissolution degree and do not produce the electrolyzer of the electrolgtic aluminium ionogen of negative electrode " crust " phenomenon.
The present invention simultaneously the 2nd technical problem to be solved be the alloy anode superpotential height being made up of metal component in prior art, the current consumption of aluminum electrolysis technology is big, and the metal component used is expensive, causes the cost of alloy anode to increase; In addition, in prior art the oxidation-resistance of alloy anode oxide on surface film low, easily come off, cause alloy anode to be constantly consumed, corrosion-resistant, and corrode or the sull that comes off enters into the purity that liquid aluminium reduces the finished product aluminium; And then propose that a kind of used inert anode material superpotential is low, price cheap, the sull oxidation-resistance that surface is formed is strong, stability strong, the electrolgtic aluminium electrolyzer of electrolyte-resistant corrosion.
Invention also provides the technique using above-mentioned electrolyzer to carry out electrolytic aluminum.
For solving the problems of the technologies described above, the present invention provides a kind of electrolgtic aluminium electrolyzer, comprises groove body, is provided with anode and negative electrode in described groove body, in described groove body, ionogen is also housed; Described anode is arranged on the top of described groove body, and at least part of described anode is immersed in described ionogen; Described negative electrode is arranged on bottom land and is covered by a certain amount of aluminium liquid; Described ionogen is in the middle of described anode and negative electrode; The component of described anode comprises Fe, Cu and Sn, wherein taking described Fe and Cu as main ingredient; Described ionogen is by the AlF of NaF, 49-60wt% of 30-38wt%3, 1-5wt% the Al of KF and 3-6wt% of LiF, 1-6wt%2O3Composition, wherein said NaF and AlF3Mol ratio be 1.0-1.52.
The bottom surface of described anode and described groove body keep parallel, and the inner side-wall of described groove body is provided with insulation layer, for by isolated to oxygen and described ionogen and carbon block.
Described groove body upper end is provided with groove lid, and described groove covers and is provided with venting hole and feed port; Being provided with cathode bar in described negative electrode, one end of described anode is through described groove lid and is connected with terminal stud, for jointed anode power supply.
The mass ratio of described Fe, Cu and Sn is (23～40): (36～60): (0.2～5).
The component of described anode also comprises Ni.
Described anode is made up of Fe, Cu, Ni and Sn, and the content of wherein said Fe is 23～40wt%, and the content of described Cu is 36～60wt%, and the content of described Ni is 14～28wt%, and the content of described Sn is 0.2～5wt%.
The component of described anode also comprises Al and Y.
Described anode is made up of Fe, Cu, Ni, Sn, Al and Y, the content of wherein said Fe is 23～40wt%, the content of described Cu is 36～60wt%, the content of described Ni is 14～28wt%, the content of described Al is for being greater than zero and be less than or equal 4wt%, the content of described Y is for being greater than zero and be less than or equal 2wt%, and the content of described Sn is 0.2～5wt%.
Described NaF and AlF3Mol ratio be 1.12-1.52.
The liquidus temperature of described ionogen is 620-670 DEG C.
Use the aluminum electrolysis technology of described electrolyzer, comprise the steps:
(1) by NaF, AlF of specified quantitative3、LiF、KF、Al2O3Join mixed melting in melting furnace and become melt; Or, by NaF, AlF of specified quantitative3, LiF, KF join in melting furnace after mixed melting, then add Al2O3Obtain melt;
(2) melt that step (1) prepares is warming up in melting furnace pours in electrolyzer after more than 720-760 DEG C and maintain the temperature at 720-760 DEG C and carry out electrolysis.
The temperature of described electrolysis is 730-750 DEG C.
Electrolytic process quantitatively supplements Al2O3。
The aluminum electrolysis technology of described electrolyzer, comprises the steps:
(1) by NaF, AlF of specified quantitative3、LiF、KF、Al2O3Join mixed melting in melting furnace and become melt; Or, by NaF, AlF of specified quantitative3, LiF, KF join in melting furnace after mixed melting, then add Al2O3Obtain melt;
(2) melt that step (1) prepares is warming up in melting furnace pours in electrolyzer after more than 720-760 DEG C and maintain the temperature at 720-760 DEG C and carry out electrolysis.
The temperature of described electrolysis is 730-750 DEG C.
Electrolytic process quantitatively supplements Al2O3。
Electrolyzer of the present invention and use the advantage of the electrolysis process of this electrolyzer to be:
(1) electrolgtic aluminium electrolyzer of the present invention, comprises groove body, is provided with anode and negative electrode in described groove body, in described groove body, ionogen is also housed; Described anode is arranged on the top of groove body, and at least part of described anode is immersed in described ionogen; Described negative electrode is arranged on described bottom land and is covered by a certain amount of aluminium liquid, and described ionogen is in the middle of anode and negative electrode; The component of described anode comprises Fe, Cu and Sn, wherein taking described Fe and Cu as main ingredient; Described ionogen is by the AlF of NaF, 49-60wt% of 30-38wt%3, 1-5wt% the Al of KF and 3-6wt% of LiF, 1-6wt%2O3Composition, wherein said NaF and AlF3Mol ratio be 1.0-1.52.
Electric conductivity height, superpotential containing metal Sn and the anode that is made up of above-mentioned metal component are low, and the bath voltage in electrolyzer electric solution preocess is about 3.1～3.4V, and the current consumption of aluminum electrolysis technology is little, every ton of aluminum consumption amount≤11000kw h, and technique cost is low; Owing to anode material is the alloy of Fe, Cu and Sn composition, the sull oxidation-resistance height that anode surface is formed in electrolytic process, not easily it is corroded from an electrolyte, and the sull formed is stablized, it is not easy to come off, so that anode has very high oxidation-resistance and erosion resistance is strong. Also just due to oxidation-resistance and the erosion resistance of above-mentioned anode, anode material because corrosion occurring or comes off to produce the impurity being mixed in liquid aluminium, thus can not ensure that the purity of aluminium product, and the aluminium purity produced can reach 99.8%. Avoid the superpotential height of alloy anode in prior art, the oxidation-resistance of alloy surface sull is low, easily come off, cause alloy anode to be constantly consumed, corrosion-resistant, and corrode or the sull that comes off enters into the problem that liquid aluminium reduces the purity of the finished product aluminium. In addition, described alloy anode is using Fe, Cu as main ingredient, and shared content ratio is higher, reduces the manufacturing cost of anode material.
The ionogen used adopts pure fluoride salt system, by limiting the composition of material in ionogen, and limits the content of these materials further, and described NaF and AlF3Mol ratio be 1.0-1.52, the liquidus temperature of ionogen is made to be reduced to 640-670 DEG C, so that electrolysis process can carry out electrolysis under 720-760 DEG C of condition, decrease the volatilization loss of fluoride salt, avoid the corrosion to electrolyzer and the harm to human body, improve Working environment, greatly reduce the energy consumption of electrolytic process, reach the object of energy-saving and emission-reduction; The present invention simultaneously is by adding LiF and KF of suitable content, it is possible to combines with the sodium ion in ionogen and aluminum ion and forms low-melting cryolithionite and potassium cryolite, thus ensures can not produce in electrolytic process the phenomenon of crust; The electrolgtic aluminium ionogen of the present invention is compared with applicable industry, it does not have additional CaF2And MgF2, but at NaF and AlF3Mol ratio be 1.0-1.52 system in, with the addition of suitable proportion, there is the KF increasing alumina dissolution degree and dissolution rate function, thus improve the shortcoming that low mole prop0rtion ionogen al dissolution degree is low;In general, the specific conductivity of ionogen reduces with the reduction of temperature, therefore the specific conductivity under low electrolysis temperature is difficult to meet the needs of normal electrical solution preocess usually, the present invention makes electrolysis temperature also corresponding reduction by reducing the liquidus temperature of ionogen, but the present invention has by adding increases the big LiF of electric conductivity, and the proportioning of component in ionogen is optimized, make the described ionogen specific conductivity at low temperatures also can to meet the needs of electrolytic process, it is to increase the current efficiency of electrolytic process. It is 1-5% that the present invention limits the content of LiF, reason is, the content of LiF is too low, then cannot play the effect improving specific conductivity and preventing crust, and the too high levels of LiF, the solubleness of aluminum oxide can be caused again to decrease, and the present invention is 1-5% by limiting the content of LiF, effectively prevent above-mentioned two situations; Use the ionogen of said ratio in the present invention to carry out electrolysis, metal device is not had corrosive nature, thus improves the work-ing life of electrolyzer.
(2) electrolgtic aluminium electrolyzer of the present invention, described anode is made up of Fe, Cu, Ni, Sn, Al and Y, the content of wherein said Fe is 23～40wt%, the content of described Cu is 36～60wt%, the content of described Ni is 14～28wt%, the content of described Al is for being less than or equal 4wt%, and the content of described Y is for being less than or equal 2wt%, and the content of described Sn is 0.2～5wt%.
Above-mentioned inert alloy anode has the advantage that material cost is low, electric conductivity is high equally, in addition, the metal A l contained in above-mentioned inert alloy anode has antioxygenation, and can react as the metal oxide generation metallothermic reduction in reductive agent and inert anode alloy, prevent the metal of main ingredient in inert alloy anode oxidized, cause the specific conductivity of alloy anode to reduce; Meanwhile, the metal Y added can control the shaping crystalline structure of anode material in process prepared by inert anode, reaches anti-oxidant object.
(3) electrolgtic aluminium electrolyzer of the present invention, by NaF, AlF of certain content3、LiF、KF、Al2O3Mix, the mixture obtained is added thermosetting melt; Or by NaF, AlF of certain content3, LiF, KF mix, the mixture obtained is heated until adding Al after melting again2O3Obtain melt; Then the melt prepared is carried out electrolysis under 720-760 DEG C of condition. The solubleness of the energy consumption of the volatilization of electrolysis temperature and ionogen, negative electrode crust phenomenon, technique, specific conductivity and aluminum oxide has direct impact, the present inventor is by long-term research, based on component and the content characteristic of ionogen of the present invention, set electrolysis temperature matchingly and it is 720-760 DEG C, while increasing specific conductivity and alumina dissolution degree, prevent negative electrode crust phenomenon, also considerably reduce the volatilization of ionogen and the energy consumption of electrolysis process, it is to increase the economic performance of technique. As preferably, the present invention also arranges described electrolysis temperature further and is 730-750 DEG C.
Accompanying drawing explanation
In order to make content of the present invention more easily be understood, below in conjunction with the drawings and specific embodiments, technical solutions according to the invention are further elaborated.
Fig. 1 is the structural representation of electrolgtic aluminium electrolyzer of the present invention;
Reference numeral wherein is: 1-groove body, 2-anode, 3-negative electrode, 4-ionogen, 5-insulation layer, 6-groove lid, 7-venting hole, 8-feed port, 9-terminal stud, 10-cathode bar, 11-aluminium liquid.
Embodiment
Electrolgtic aluminium electrolyzer of the present invention is as shown in Figure 1, comprise groove body 1, anode 2 and negative electrode 3 it is provided with in described groove body 1, described anode 2 and negative electrode 3 can select any set-up mode according to actual needs, in the present embodiment, described anode 2 is arranged on the top of groove body 1, and the bottom surface of described anode 2 keeps parallel with described groove body 1, and described negative electrode 3 is arranged on described bottom land and is covered by a certain amount of aluminium liquid 11; Described groove body 1 is also equipped with ionogen 4, described anode 2 and the negative electrode 3 dipping situation in described ionogen 4 is depending on selected cell construction, in the present embodiment, at least part of described anode 2 is immersed in described ionogen 4, and described negative electrode 3 is placed in bottom land and is covered by a certain amount of aluminium liquid 11; Described ionogen 4 is in the middle of described anode 2 and negative electrode 3, and described ionogen 4 covers on described aluminium liquid 11; The component of described anode 2 comprises Fe, Cu and Sn, and wherein taking described Fe and Cu as main ingredient, the mass ratio of described Fe, Cu and Sn is (23～40): (36～60): (0.2～5); Described ionogen 4 is by the AlF of NaF, 49-60wt% of 30-38wt%3, 1-5wt% the Al of KF and 3-6wt% of LiF, 1-6wt%2O3Composition, wherein said NaF and AlF3Mol ratio be 1.0-1.52, it is preferable to 1.12-1.52, the liquidus temperature of above-mentioned ionogen 4 is 620-670 DEG C, it is preferable to 640-670 DEG C.
On this basis, as the enforcement mode of alterable, in order to by described groove body 1 inner side-wall and described ionogen 4 and oxygen gases separated, to prevent electronics transmits between groove body 1 sidewall and ionogen 4, and groove body 1 sidewall is formed corrosion by ionogen 4, being provided with insulation layer 5 on described groove body 1 inner side-wall, the insulating material that described insulation layer 5 is corroded by commercially available any high temperature resistant and electrolyte-resistant 4 is made, such as corundum, aluminate spinel refractory materials etc. In the present embodiment, between described groove body 1 inner side-wall and described insulation layer 5, it is provided with carbon block, the material that described carbon block and described negative electrode 3 are formed in one. Certain described carbon block can also be separated setting with described negative electrode 3.
On above-mentioned basis, in order to the electrolytic environments of electrolyzer and the external world are separated, do not hinder again exhaust with reinforced simultaneously, described groove body 1 upper end is provided with groove lid 6, described groove lid 6 is provided with venting hole 7 and feed port 8, size and the position of described venting hole 7 and charge cavity can be selected arbitrarily according to actual needs, and in the present embodiment, described venting hole 7 is arranged near described anode 2.
Further, it is connected with power supply for the ease of anode 2 and negative electrode 3, the described negative electrode 3 of described bottom land is provided with cathode bar 10, for connecting negative electrode 3 power supply; One end of described anode 2 is through described groove lid 6 and is connected with terminal stud 9, for jointed anode 2 power supply; Described cathode bar 10 and terminal stud 9 can be made up of the material that any electroconductibility is good, comprise steel, iron and alloy material etc.
On this basis, the stability combined to improve between metal Fe, Cu and Sn, described anode 2 component also comprises Ni, preferably, described anode 2 is made up of Fe, Cu, Ni and Sn, and the content of wherein said Fe is 23～40wt%, and the content of described Cu is 36～60wt%, the content of described Ni is 14～28wt%, and the content of described Sn is 0.2～5wt%.
Described anode 2 can preferably be made up of Fe, Cu, Ni, Sn, Al and Y, it is oxidized and improve antioxidant property that the Al added is possible to prevent other main body metal components of anode 2, Y composition can the structure of alloy crystal for preparing of regulation and control, to reach anti-oxidant object, the content of wherein said Fe is 23～40wt%, the content of described Cu is 36～60wt%, the content of described Ni is 14～28wt%, the content of described Al is for being less than or equal 4wt%, the content of described Y is for being less than or equal 2wt%, and the content of described Sn is 0.2～5wt%.The electrolysis temperature of above-mentioned electrolyzer when electrolytic aluminum is used to be 720-760 DEG C, it is preferable that 730-750 DEG C.
It is described below in conjunction with specific embodiment.
Embodiment 1
After being mixed according to the ratio of the Sn of Ni and 3wt% of Cu, 14wt% of Fe, 60wt% of 23wt% by Fe, Cu, Ni and Sn metal block, after heat to molten state, casting obtains anode 1. The density of anode 1 is 8.3g/cm3, ratio resistance is 68 μ Ω cm, and fusing point is 1360 DEG C.
The composition of the ionogen in the present embodiment is: NaF, 32%; AlF3, 57%; LiF, 3%; KF, 4%; Al2O3, 4%, wherein NaF and aluminum fluoride AlF3Mol ratio be 1.12. The liquidus temperature measuring ionogen in the present embodiment is 640 DEG C. Specific conductivity ≈ 1.7 Ω of ionogen-1·cm-1, density ≈ 2.03g/cm3, aluminum oxide saturation concentration 5%.
The technique of electrolytic tank electrolysis aluminium of the present invention is used to be:
(1) anode 1 and carbon body negative electrode is adopted, by NaF, AlF of above-mentioned amount3、LiF、KF、Al2O3First in melting furnace, dissolve formation melt;
(2) melt that step (1) prepares is warming up to more than 720 DEG C in melting furnace, then pours in electrolyzer, connect the power supply of anode and negative electrode, at remaining on 720 DEG C, carry out electrolysis 40 hours, electrolytic process quantitatively supplements Al2O3。
Not crusting bottom electrolytic process middle slot body, the bath voltage of electrolyzer is 3.1V, and in electrolytic process, the current consumption of every ton of aluminium is 10040kw h, and the purity being produced aluminium is 99.85%.
Embodiment 2
After being mixed according to the ratio of the Sn of Ni and 5wt% of Cu, 19wt% of Fe, 36wt% of 40wt% by Fe, Cu, Ni and Sn metal block, after heat to molten state, casting obtains anode 2. The density of this anode is 8.1g/cm3, ratio resistance is 76.8 μ Ω cm, and fusing point is 1386 DEG C.
The composition of the ionogen in the present embodiment is: NaF, 38%; AlF3, 50%; LiF, 2%; KF, 5%; Al2O3, 5%, wherein NaF and aluminum fluoride AlF3Mol ratio be 1.52.
The performance of the ionogen described in the present embodiment being measured, result is: in the present embodiment, the liquidus temperature of ionogen is 670 DEG C. Electrolytic conductivity ≈ 1.8 Ω-1·cm-1, density ≈ 2.05g/cm3, aluminum oxide saturation concentration 6%.
The technique of electrolytic tank electrolysis aluminium of the present invention is used to be:
(1) anode 2 and carbon body negative electrode is adopted, by NaF, AlF of above-mentioned amount3, LiF, KF add and first dissolve in melting furnace, then add the Al of above-mentioned amount2O3Melting obtains melt;
(2) melt that step (1) prepares is warming up to more than 760 DEG C in melting furnace, then pours in electrolyzer, connect the power supply of anode and negative electrode, at remaining on 760 DEG C, carry out electrolysis 40 hours.
Not crusting bottom electrolytic process middle slot body, the bath voltage of electrolyzer is 3.39V, and in electrolytic process, the current consumption of every ton of aluminium is 10979kw h, and the purity being produced aluminium is 99.82%.
Embodiment 3
After being mixed according to the ratio of the Sn of Ni and 0.2wt% of Cu, 28wt% of Fe, 46.8wt% of 25wt% by Fe, Cu, Ni and Sn metal block, after heat to molten state, casting obtains anode 3. The density of this anode is 8.2g/cm3, ratio resistance is 72 μ Ω cm, and fusing point is 1350 DEG C.
The composition of the ionogen in the present embodiment is: NaF, 32%; AlF3, 57%; LiF, 3%; KF, 4%; Al2O3, 4%, wherein NaF and aluminum fluoride AlF3Mol ratio be 1.12.
The performance of the ionogen described in the present embodiment being measured, result is: in the present embodiment, the liquidus temperature of ionogen is 640 DEG C.Specific conductivity ≈ 1.6 Ω of ionogen-1·cm-1, density ≈ 2.03g/cm3, aluminum oxide saturation concentration 5%.
The technique of electrolytic tank electrolysis aluminium of the present invention is used to be:
(1) anode 3 and carbon body negative electrode is adopted, by NaF, AlF of above-mentioned amount3、LiF、KF、Al2O3First in melting furnace, dissolve formation melt;
(2) melt that step (1) prepares is warming up to more than 730 DEG C in melting furnace, then pours in electrolyzer, connect the power supply of anode and negative electrode, at remaining on 730 DEG C, carry out electrolysis 40 hours, electrolytic process quantitatively supplements Al2O3。
Not crusting bottom electrolytic process middle slot body, the bath voltage of electrolyzer is 3.15V, and in electrolytic process, the current consumption of every ton of aluminium is 10202kw h, and the purity being produced aluminium is 99.85%.
Embodiment 4
After Fe, Cu, Ni and Sn metal block is mixed according to the ratio of the Sn of Ni and 0.2wt% of Cu, 14wt% of Fe, 60wt% of 24.2wt%, after heat to molten state, the Al metal block adding 1.8wt% again continues melting mixing, and after finally adding the Y metal block melting mixing of 0.8wt%, casting obtains anode 4. The density of this anode is 8.3g/cm3, ratio resistance is 68 μ Ω cm, and fusing point is 1360 DEG C.
The composition of the ionogen in the present embodiment is: NaF, 32%; AlF3, 57%; LiF, 3%; KF, 4%; Al2O3, 4%, wherein NaF and aluminum fluoride AlF3Mol ratio be 1.12.
The performance of the ionogen described in the present embodiment being measured, result is: in the present embodiment, the liquidus temperature of ionogen is 640 DEG C. Specific conductivity ≈ 1.8 Ω of ionogen-1·cm-1, density ≈ 2.04g/cm3, aluminum oxide saturation concentration 6%.
The technique of electrolytic tank electrolysis aluminium of the present invention is used to be:
(1) anode 4 and carbon body negative electrode is adopted, by NaF, AlF of above-mentioned amount3、LiF、KF、Al2O3First in melting furnace, dissolve formation melt;
(2) melt that step (1) prepares is warming up to more than 750 DEG C in melting furnace, then pours in electrolyzer, connect the power supply of anode and negative electrode, at remaining on 750 DEG C, carry out electrolysis 40 hours, electrolytic process quantitatively supplements Al2O3。
Not crusting bottom electrolytic process middle slot body, the bath voltage of electrolyzer is 3.12V, and in electrolytic process, the current consumption of every ton of aluminium is 10105kw h, and the purity being produced aluminium is 99.8%.
Embodiment 5
After Fe, Cu, Ni and Sn metal block is mixed according to the ratio of the Sn of Ni and 5wt% of Cu, 14.9wt% of Fe, 36wt% of 40wt%, after heat to molten state, the Al metal block adding 0.1wt% again continues melting mixing, and after finally adding the Y metal block melting mixing of 0.1wt%, casting obtains anode 5. The density of this anode is 8.1g/cm3, ratio resistance is 76.8 μ Ω cm, and fusing point is 1386 DEG C.
The composition of the ionogen in the present embodiment is: NaF, 30%; AlF3, 60%; LiF, 1%; KF, 6%; Al2O3, 3%, wherein NaF and aluminum fluoride AlF3Mol ratio be 1.0.
The performance of the ionogen described in the present embodiment being measured, result is: in the present embodiment, the liquidus temperature of ionogen is 620 DEG C. Specific conductivity ≈ 1.6 Ω of ionogen-1·cm-1, density ≈ 2.03g/cm3, aluminum oxide saturation concentration 5%.
The technique of electrolytic tank electrolysis aluminium of the present invention is used to be:
(1) anode 5 and carbon body negative electrode is adopted, by NaF, AlF of above-mentioned amount3、LiF、KF、Al2O3First in melting furnace, dissolve formation melt;
(2) melt that step (1) prepares is warming up to more than 720 DEG C in melting furnace, then pours in electrolyzer, connect the power supply of anode and negative electrode, at remaining on 720 DEG C, carry out electrolysis 40 hours, electrolytic process quantitatively supplements Al2O3。
Not crusting bottom electrolytic process groove body, the bath voltage of electrolyzer is 3.27V, and in electrolytic process, the current consumption of every ton of aluminium is 10591kw h, and the purity being produced aluminium is 99.81%.
Embodiment 6
After Fe, Cu, Ni and Sn metal block is mixed according to the ratio of the Sn of Ni and 4wt% of Cu, 28wt% of Fe, 38wt% of 25wt%, after heat to molten state, the Al metal block adding 4wt% again continues melting mixing, and after finally adding the Y metal block melting mixing of 1wt%, casting obtains anode 6. The density of this anode is 8.2g/cm3, ratio resistance is 70 μ Ω cm, and fusing point is 1365 DEG C.
The composition of the ionogen in the present embodiment is: NaF, 38%; AlF3, 54%; LiF, 4%; KF, 1%; Al2O3, 3%, wherein NaF and aluminum fluoride AlF3Mol ratio be 1.4.
The performance of the ionogen described in the present embodiment being measured, result is: in the present embodiment, the liquidus temperature of ionogen is 670 DEG C. Specific conductivity ≈ 1.8 Ω of ionogen-1·cm-1, density ≈ 2.05g/cm3, aluminum oxide saturation concentration 6%.
The technique of electrolytic tank electrolysis aluminium of the present invention is used to be:
(1) anode 6 and carbon body negative electrode is adopted, by NaF, AlF of above-mentioned amount3、LiF、KF、Al2O3First in melting furnace, dissolve formation melt;
(2) melt that step (1) prepares is warming up to more than 760 DEG C in melting furnace, then pours in electrolyzer, connect the power supply of anode and negative electrode, at remaining on 760 DEG C, carry out electrolysis 40 hours, electrolytic process quantitatively supplements Al2O3.
Not crusting bottom electrolytic process middle slot body, the bath voltage of electrolyzer is 3.35V, and in electrolytic process, the current consumption of every ton of aluminium is 10850kw h, and the purity being produced aluminium is 99.83%.
Embodiment 7
After Fe, Cu, Ni and Sn metal block is mixed according to the ratio of the Sn of Ni and 3wt% of Cu, 18wt% of Fe, 36.5wt% of 40wt%, after heat to molten state, the Al metal block adding 1.5wt% again continues melting mixing, and after finally adding the Y metal block melting mixing of 1wt%, casting obtains anode 7. The density of this anode is 8.1g/cm3, ratio resistance is 76.8 μ Ω cm, and fusing point is 1386 DEG C.
The composition of the ionogen in the present embodiment is: NaF, 34%; AlF3, 49%; LiF, 5%; KF, 6%; Al2O3, 6%, wherein NaF and aluminum fluoride AlF3Mol ratio be 1.39.
The performance of the ionogen described in the present embodiment being measured, result is: in the present embodiment, the liquidus temperature of ionogen is 660 DEG C. Specific conductivity ≈ 1.8 Ω of ionogen-1·cm-1, density ≈ 2.05g/cm3, aluminum oxide saturation concentration 6%.
The technique of electrolytic tank electrolysis aluminium of the present invention is used to be:
(1) anode 7 and carbon body negative electrode is adopted, by NaF, AlF of above-mentioned amount3、LiF、KF、Al2O3First in melting furnace, dissolve formation melt;
(2) melt that step (1) prepares is warming up to more than 760 DEG C in melting furnace, then pours in electrolyzer, connect the power supply of anode and negative electrode, at remaining on 760 DEG C, carry out electrolysis 40 hours, electrolytic process quantitatively supplements Al2O3。
Not crusting bottom electrolytic process middle slot body, the bath voltage of electrolyzer is 3.38V, and in electrolytic process, the current consumption of every ton of aluminium is 10947kw h, and the purity being produced aluminium is 99.8%.
Electrolyzer in above-described embodiment is any one in electrolyzer of the present invention.
The particular content of the present invention is elaborated by above-described embodiment, and those skilled in the art are it is to be appreciated that the variation in any type of improvement done on the basis of the present invention and details all belongs to the claimed content of the present invention.
Claims (8)
1. an electrolgtic aluminium electrolyzer, comprises
Groove body (1), is provided with anode (2) and negative electrode (3) in described groove body (1), in described groove body (1), ionogen (4) is also housed;
Described anode (2) is arranged on the top of described groove body (1), and at least part of described anode (2) is immersed in described ionogen (4);
Described negative electrode (3) is arranged on bottom land and is covered by a certain amount of aluminium liquid (11);
Described ionogen (4) is in the middle of described anode (2) and negative electrode (3);
It is characterized in that,
The component of described anode (2) comprises Fe, Cu, Sn, Ni, Al and Y, wherein taking described Fe and Cu as main ingredient;
Described ionogen (4) is by the AlF of NaF, 49-60wt% of 30-38wt%3, 1-5wt% the Al of KF and 3-6wt% of LiF, 1-6wt%2O3Composition, wherein said NaF and AlF3Mol ratio be 1.0-1.52;
The bottom surface of described anode (2) keeps parallel with described groove body (1), and the inner side-wall of described groove body (1) is provided with insulation layer (5), for by isolated with carbon block to oxygen and described ionogen (4);
Described groove body (1) upper end is provided with groove lid (6), and described groove lid (6) is provided with venting hole (7) and feed port (8); Being provided with cathode bar (10) in described negative electrode (3), one end of described anode (2) is through described groove lid (6) and is connected with terminal stud (9), for connecting power supply.
2. electrolyzer according to claim 1, it is characterised in that, the mass ratio of described Fe, Cu and Sn is (23～40): (36～60): (0.2～5).
3. electrolyzer according to claim 1 and 2, it is characterized in that, described anode (2) is made up of Fe, Cu, Ni, Sn, Al and Y, the content of wherein said Fe is 23～40wt%, the content of described Cu is 36～60wt%, and the content of described Ni is 14～28wt%, and the content of described Al is for being greater than zero and be less than or equal 4wt%, the content of described Y is for being greater than zero and be less than or equal 2wt%, and the content of described Sn is 0.2～5wt%.
4. electrolyzer according to claim 3, it is characterised in that, described NaF and AlF3Mol ratio be 1.12-1.52.
5. electrolyzer according to claim 1,2 or 4, it is characterised in that, the liquidus temperature of described ionogen (4) is 620-670 DEG C.
6. use the aluminum electrolysis technology of the claim 1-5 described electrolyzer of arbitrary item, comprise the steps:
(1) by NaF, AlF of specified quantitative3、LiF、KF、Al2O3Join mixed melting in melting furnace and become melt; Or, by NaF, AlF of specified quantitative3, LiF, KF join in melting furnace after mixed melting, then add Al2O3Obtain melt;
(2) melt that step (1) prepares is warming up in melting furnace pours in electrolyzer after more than 720-760 DEG C and maintain the temperature at 720-760 DEG C and carry out electrolysis.
7. aluminum electrolysis technology according to claim 6, it is characterised in that, the temperature of described electrolysis is 730-750 DEG C.
8. aluminum electrolysis technology according to claim 6 or 7, it is characterised in that, electrolytic process quantitatively supplements Al2O3。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210188436.9A CN103484891B (en) | 2012-06-11 | 2012-06-11 | A kind of electrolgtic aluminium electrolyzer and use the electrolysis process of this electrolyzer |
| US14/407,289 US20150122664A1 (en) | 2012-06-11 | 2013-05-30 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
| PL13804286T PL2860290T3 (en) | 2012-06-11 | 2013-05-30 | Electrolytic cell for aluminium electrolysis and electrolysis process using the electrolytic cell |
| HUE13804286A HUE042500T2 (en) | 2012-06-11 | 2013-05-30 | Electrolytic cell for aluminium electrolysis and electrolysis process using the electrolytic cell |
| EP13804286.6A EP2860290B1 (en) | 2012-06-11 | 2013-05-30 | Electrolytic cell for aluminium electrolysis and electrolysis process using the electrolytic cell |
| IN216DEN2015 IN2015DN00216A (en) | 2012-06-11 | 2013-05-30 | |
| CA2877591A CA2877591C (en) | 2012-06-11 | 2013-05-30 | Electrolytic cell for aluminum electrolysis and electrolysis process using electrolytic cell |
| AP2015008184A AP2015008184A0 (en) | 2012-06-11 | 2013-05-30 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
| PCT/CN2013/076440 WO2013185538A1 (en) | 2012-06-11 | 2013-05-30 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
| KR1020157000519A KR101684813B1 (en) | 2012-06-11 | 2013-05-30 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
| AU2013275995A AU2013275995B2 (en) | 2012-06-11 | 2013-05-30 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
| EA201492226A EA030419B1 (en) | 2012-06-11 | 2013-05-30 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
| ZA2014/09512A ZA201409512B (en) | 2012-06-11 | 2014-12-23 | Electrolysis cell used for aluminum electrolysis and electrolysis process using the electrolytic cell |
| HRP20190669TT HRP20190669T1 (en) | 2012-06-11 | 2019-04-09 | Electrolytic cell for aluminium electrolysis and electrolysis process using the electrolytic cell |
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| EP (1) | EP2860290B1 (en) |
| KR (1) | KR101684813B1 (en) |
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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 | Anode replacement method 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 |
| US11186897B2 (en) * | 2015-04-22 | 2021-11-30 | United Company RUSAL Engineering and Technology Centre LLC | Method for producing aluminum-scandium alloy and reactor for implementing the method |
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Also Published As
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| IN2015DN00216A (en) | 2015-06-12 |
| AU2013275995B2 (en) | 2016-05-12 |
| EA201492226A1 (en) | 2015-05-29 |
| EP2860290A4 (en) | 2016-02-10 |
| HUE042500T2 (en) | 2019-07-29 |
| CN103484891A (en) | 2014-01-01 |
| AP2015008184A0 (en) | 2015-01-31 |
| US20150122664A1 (en) | 2015-05-07 |
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| ZA201409512B (en) | 2016-08-31 |
| HRP20190669T1 (en) | 2019-06-14 |
| KR101684813B1 (en) | 2016-12-08 |
| EP2860290B1 (en) | 2019-01-09 |
| WO2013185538A1 (en) | 2013-12-19 |
| EA030419B1 (en) | 2018-08-31 |
| KR20150022993A (en) | 2015-03-04 |
| AU2013275995A1 (en) | 2015-01-22 |
| CA2877591C (en) | 2016-08-23 |
| EP2860290A1 (en) | 2015-04-15 |
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