CN101671835A - Low-temperature molten salt system for aluminum electrolysis and method for carrying out aluminum electrolysis by same - Google Patents
Low-temperature molten salt system for aluminum electrolysis and method for carrying out aluminum electrolysis by same Download PDFInfo
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- CN101671835A CN101671835A CN200810222100A CN200810222100A CN101671835A CN 101671835 A CN101671835 A CN 101671835A CN 200810222100 A CN200810222100 A CN 200810222100A CN 200810222100 A CN200810222100 A CN 200810222100A CN 101671835 A CN101671835 A CN 101671835A
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Abstract
The invention relates to the field of molten salt electrolysis of nonferrous metal metallurgy and provides a novel molten salt electrolyte system which can be applied to the aluminum electrolysis industry. The molten salt as an electrolyte system of aluminum electrolysis can greatly reduce the electrolysis temperature, and the electrolyte system also presents a favorable dissolving performance onAl2O3 in the process of electrolysis. The novel molten salt electrolyte system comprises ternary or multivariant salt, such as KF, KCl, NaF, NaCl, AlF3, MgF2, CaF2, LiF, BaF2, Al2O3, and the like. Theelectrolyte system has a lower primary crystal temperature and the favorable dissolving performance on the Al2O3. The problems of low Al2O3 solubility and low dissolving speed brought by reducing theelectrolyte primary crystal temperature through reducing the NaF/AlF3 ratio in a sodium cryolite system are solved. In addition, the low-temperature electrolyte system is particularly suitable for adopting an inert anode of metal ceramics or metal alloy.
Description
Technical field
Invention relates to the electrolyte system of electrolysis of aluminum, and characteristics are that lower liquidus temperature is arranged, and suitable electrolysis at low temperatures belongs to Non-ferrous Metallurgy fused salt electrolysis technical field.
Background technology
Aluminium is produced in the electrolysis of Hall-H é roult method, is to adopt sodium cryolite system dissolved oxygen aluminium down at 940～960 ℃, carries out electrolysis and obtains primary aluminum.Development through surplus 100 years, Hall-H é roult method has experienced some technical renovation, reduced energy consumption, can realize per kilogram primary aluminum power consumption 13.5kwh at present, but because service temperature is higher, differ bigger with theoretical energy consumption 6.33kwh, the service temperature that therefore reduces electrolysis of aluminum becomes researchist's common recognition.Traditional low-temperature aluminum electrolysis generally adopts and reduces NaF/AlF
3Ratio or interpolation MgF
2, CaF
2, materials such as NaCl, LiF realize.Reduce NaF/AlF
3Than can obviously reducing electrolytical primary crystal point temperature, still can bring Al
2O
3Solubleness reduces, the slow problem of dissolution rate; By adding MgF
2, CaF
2, materials such as NaCl, LiF can reduce electrolytical primary crystal point temperature to a certain extent, but can only be among a small circle effectively.Invent a kind of electrolyte system, the industrial production needs that make this system can satisfy electrolysis of aluminum have become people's common recognition.Lu Huimin is at patent " a kind of method of low-temperature electrolytic productivity and special-purpose aluminium cell thereof " (publication number: CN 1673418A; Application number: 200510011143.3) disclose the pure potassium cryolite system of employing and carried out electrolysis product aluminium, but pure potassium cryolite system is low than the specific conductivity of that cryolite-based system, and obviously decline of electrolytical specific conductivity in the low temperature system.For example, 55mol%NaF-45mol%AlF in the time of 750 ℃
3Specific conductivity is 1.27Scm in the system
-1And 55mol%KF-45mol%AlF
3Specific conductivity only is 1.05Scm in the system
-1, and electrolytical specific conductivity is about 2.8Scm in the industry now
-1Therefore can increase the bath voltage in the electrolytic process like this, develop and a kind ofly both aluminum oxide was had fine solute effect, the low-temperature electrolyte system that has suitable industrial aluminum electrolytic conductivity again is significant.
Summary of the invention
The present invention is based on the focus of present world aluminum industrial development, the successful low-temperature electrolyte system of research on a large amount of experimental study bases.The object of the present invention is to provide a kind of low-temperature molten salt system of electrolysis of aluminum, provide a kind of low-temperature electrolytes that is applicable to that Aluminium Electrolysis is used to form, purpose is to solve the Al that electrolyte system was brought based on sodium cryolite
2O
3The shortcoming that solubleness reduces, dissolution rate is slow and based on the low problem of the electrolyte system specific conductivity of pure potassium cryolite.
The method that another object of the present invention is to provide a kind of new type low temperature molten salt system that uses electrolysis of aluminum to carry out electrolysis of aluminum.
The present invention proposes a kind of electrolyte system simultaneously, and the cathode and anode that is applicable to this electrolyte system material also is provided, and a further object of the present invention is to provide a kind of new type low temperature electrolysis of aluminum system.
For achieving the above object, the present invention takes following technical scheme:
1, a kind of molten salt system of electrolysis of aluminum, molten salt system consist of (x) A (y) AlF
3(z) Al
2O
3, wherein x is the mole percent level of A, y is AlF
3Mole percent level, z is Al
2O
3Mole percent level, x is 25～77%, y is 22～50%, z is 1～25%; A is by KF, NaF, MgF
2, CaF
2, NaCl, LiF, BaF
2Single or multiple salt form.
2, the molten salt system of another kind of electrolysis of aluminum, molten salt system consist of (x) A (y) AlF
3(z) Al
2O
3, wherein x is the mole percent level of A, y is AlF
3Mole percent level, z is Al
2O
3Mole percent level, x is 30～76%, y is 22～50%, z is 2～20%; A is by KF, KCl, NaF, MgF
2, CaF
2, NaCl, LiF, BaF
2Single or multiple salt form.
The method that a kind of molten salt system that uses electrolysis of aluminum of the present invention carries out electrolysis of aluminum, this method comprises the steps:
(1), with flour A, AlF
3And Al
2O
3Respectively behind the thermal dehydration, levigate;
(2), mix A, AlF according to mole percent level in the molten salt system of of the present invention 1 or 2 electrolysis of aluminum
3And Al
2O
3, heating up and obtaining melt is electrolytic solution; Or mix A and AlF according to mole percent level in the molten salt system of of the present invention 1 or 2 electrolysis of aluminum
3, heating up and obtaining melt is electrolytic solution, adds Al according to mole percent level in the molten salt system of of the present invention 1 or 2 electrolysis of aluminum again
2O
3, it is electrolytic solution that the stirring fusion obtains melt;
(3), the electrolytic solution that obtains in the step (2) being controlled at 680～900 ℃ carries out electrolysis and obtains primary aluminum.
In the method for electrolysis of aluminum of the present invention, in electrolytic process, replenish the number of dropouts of the electrolytic solution that causes along with consumption in the electrolytic process or volatilization continuously or regularly.
A kind of electrolysis of aluminum system, this electrolyte system comprise the molten salt system of of the present invention 1 or 2 electrolysis of aluminum, and anode and negative electrode, and described anode is the inert anode of sintering metal or metal alloy, and described negative electrode is TiB
2Coated cathode.
In electrolysis of aluminum system of the present invention, described sintering metal consists of (x ') A ' (y ') B ', and A ' is by Ni
aFe
3-aO
4, and 0＜a＜1, Ni
bFe
1-bO and 0＜b＜1, NiFe
2O
4, ZnFe
2O
4In one or more mix to form, B ' is made up of one or more mixing among Cu, Fe, Ni, the Ag, x ' is the mass percentage content of A ', y ' is the mass percentage content of B ', x ' is 40～98%, y ' is 2～60%; Described metal alloy is made of two or more alloys formed among Cu, Ni, Fe, Al, Mg, Zn, Mn, Ti, Ta, the W.
In electrolysis of aluminum system of the present invention, described TiB
2Coated cathode is at the thick TiB of carbon materials surface-coated 0.1mm～28mm
2Coating.
The new type low temperature molten salt system of electrolysis of aluminum provided by the present invention, be to improve electrolytical performance by improving electrolytical composition, mainly be by in existing system, adding KF or KCl, partly or entirely replace NaF, the content of other material in the adjustment system simultaneously makes new system adapt to the industry needs of electrolysis of aluminum more.
The novel method of realization low-temperature aluminum electrolysis of the present invention, its step is as follows: with flour A, AlE
3And Al
2O
3Respectively behind the thermal dehydration, levigate, according to certain mixed, heating up obtains melt, after rest on required temperature and carry out the electrolysis production primary aluminum, can regularly or add electrolysis Al continuously in the electrolytic process
2O
3And because the electrolyte losses that volatilization or side reaction cause.
Also can be with flour A and AlF
3Respectively behind the thermal dehydration, levigate, according to certain mixed, heating up obtains melt, the back adds through the Al after dehydration and the refinement by proportioning
2O
3Powder rests on required temperature and carries out the electrolysis production primary aluminum, needs equally regularly or continuous supplementation electrolysis Al in the electrolytic process
2O
3And because the electrolyte losses that volatilization or side reaction cause.
The present invention has effectively changed the electrolysis of aluminum system electrolyte and has formed, electrolytical physicochemical property have been improved, electrolytical fusing point is reduced, electrolysis temperature can drop to 680～900 ℃ extensive operating area, ionogen is to the bigger improvement of solubility property of aluminum oxide, and the also suitable industrial production of electrolytical specific conductivity can reduce the energy consumption in the production process greatly.
Characteristics of the present invention are to solve Al in the electrolyte system of sodium cryolite
2O
3The low problem of specific conductivity in shortcoming that solubleness is low, dissolution rate is slow and the pure potassium cryolite electrolyte system.The present invention proposes a kind of electrolyte system simultaneously, and the cathode and anode that is applicable to this electrolyte system material also is provided.
Advantage and effect: advantage of the present invention not only can overcome the above problems, and also has following advantage:
(1) cooperates inert anode, wettable negative electrode and insulation slot liner can significantly reduce energy consumption, can reduce the anode and cathode pole span, reduce bath voltage.
(2) cooperate inert anode, wettable negative electrode and insulation slot liner can realize not having greenhouse gases CO
2And obnoxious flavour CF
4Deng discharging, discharge a large amount of green gases O
2
Embodiment
The invention will be further described below by embodiment, but scope of the present invention is not constituted any limitation.
Embodiment 1
Getting the amount of substance ratio is: 55% Potassium monofluoride (KF): 40% aluminum fluoride (AlF
3): 5% aluminum oxide (Al
2O
3), powder mixes after removing water treatment, is warmed up to 750 ℃, adopts alloy anode ((90 quality %) Cu (10 quality %) Al) and TiB
2Coated cathode constitutes electrolysis system, carries out electrolysis and obtains primary aluminum.
Embodiment 2
Getting the amount of substance ratio is: 45% Potassium monofluoride (KF): 10% Sodium Fluoride (NaF): 40% aluminum fluoride (AlF
3): 5% aluminum oxide (Al
2O
3), powder mixes after removing water treatment, is warmed up to 770 ℃, adopts sintering metal anode ((88 quality %) NiFe
2O
4(12 quality %) Cu) and TiB
2Coated cathode constitutes electrolysis system, carries out electrolysis and obtains primary aluminum.
Embodiment 3
Getting the amount of substance ratio is: 45% Potassium monofluoride (KF): 3% lithium fluoride (LiF): 5% sodium-chlor (NaCl): 5% Repone K (KCl): 37% aluminum fluoride (AlF
3): 5% aluminum oxide (Al
2O
3), powder mixes after removing water treatment, is warmed up to 740 ℃, adopts sintering metal anode ((40 quality %) ZnFe
2O
4(45 quality %) Ni
aFe
3-aO
4(9 quality %) Cu (6 quality %) Ag) and TiB
2Coated cathode constitutes electrolysis system, carries out electrolysis and obtains primary aluminum.
Embodiment 4
Getting the amount of substance ratio is: 25% Potassium monofluoride (KF): 28% Sodium Fluoride (NaF): 3% lithium fluoride (LiF): 2% Calcium Fluoride (Fluorspan) (CaF
2): 1% magnesium fluoride (CaF
2): 1% barium fluoride (BaF
2): 35% aluminum fluoride (AlF
3): 5% aluminum oxide (Al
2O
3), powder mixes after removing water treatment, is warmed up to 820 ℃, adopts metal alloy anode and TiB
2Coated cathode constitutes electrolysis system, carries out electrolysis and obtains primary aluminum.
Claims (7)
1, a kind of molten salt system of electrolysis of aluminum is characterized in that: molten salt system consists of (x) A (y) AlF
3(z) Al
2O
3, wherein x is the mole percent level of A, y is AlF
3Mole percent level, z is Al
2O
3Mole percent level, x is 25～77%, y is 22～50%, z is 1～25%; A is by KF, NaF, MgF
2, CaF
2, NaCl, LiF, BaF
2Single or multiple salt form.
2, a kind of molten salt system of electrolysis of aluminum is characterized in that: molten salt system consists of (x) A (y) AlF
3(z) Al
2O
3, wherein x is the mole percent level of A, and y is the mole percent level of AlF3, and z is Al
2O
3Mole percent level, x is 30～76%, y is 22～50%, z is 2～20%; A is by KF, KCl, NaF, MgF
2, CaF
2, NaCl, LiF, BaF
2Single or multiple salt form.
3, a kind of molten salt system that uses the electrolysis of aluminum of claim 1 or 2 method of carrying out electrolysis of aluminum, it is characterized in that: this method comprises the steps:
(1), with flour A, AlF
3And Al
2O
3Respectively behind the thermal dehydration, levigate;
(2), mix A, AlF according to mole percent level in the molten salt system of the electrolysis of aluminum of claim 1 or 2
3And Al
2O
3, heating up and obtaining melt is electrolytic solution; Or mix A and AlF according to mole percent level in the molten salt system of the electrolysis of aluminum of claim 1 or 2
3, heating up and obtaining melt is electrolytic solution, adds Al according to mole percent level in the molten salt system of the electrolysis of aluminum of claim 1 or 2 again
2O
3, it is electrolytic solution that the stirring fusion obtains melt;
(3), the electrolytic solution that obtains in the step (2) being controlled at 680～900 ℃ carries out electrolysis and obtains primary aluminum.
4, the method for electrolysis of aluminum according to claim 3 is characterized in that: the number of dropouts of replenishing the electrolytic solution that causes along with consumption in the electrolytic process or volatilization in electrolytic process continuously or regularly.
5, a kind of electrolysis of aluminum system, it is characterized in that: this electrolyte system comprises the molten salt system of claim 1 or 2 described electrolysis of aluminum, and anode and negative electrode, and described anode is the inert anode of sintering metal or metal alloy, and described negative electrode is TiB
2Coated cathode.
6, electrolysis of aluminum system according to claim 5 is characterized in that: described sintering metal consists of (x ') A ' (y ') B ', and A ' is by Ni
aFe
3-aO
4, and 0＜a＜1, Ni
bFe
1-bO and 0＜b＜1, NiFe
2O
4, ZnFe
2O
4In one or more mix to form, B ' is made up of one or more mixing among Cu, Fe, Ni, the Ag, x ' is the mass percentage content of A ', y ' is the mass percentage content of B ', x ' is 40～98%, y ' is 2～60%; Described metal alloy is made of two or more alloys formed among Cu, Ni, Fe, Al, Mg, Zn, Mn, Ti, Ta, the W.
7, electrolysis of aluminum system according to claim 5 is characterized in that: described TiB
2Coated cathode is at the thick TiB of carbon materials surface-coated 0.1mm～28mm
2Coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810222100A CN101671835A (en) | 2008-09-09 | 2008-09-09 | Low-temperature molten salt system for aluminum electrolysis and method for carrying out aluminum electrolysis by same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810222100A CN101671835A (en) | 2008-09-09 | 2008-09-09 | Low-temperature molten salt system for aluminum electrolysis and method for carrying out aluminum electrolysis by same |
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|---|---|
| CN101671835A true CN101671835A (en) | 2010-03-17 |
Family
ID=42019245
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|---|---|---|---|
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Cited By (12)
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|---|---|---|---|---|
| CN101857961A (en) * | 2010-06-13 | 2010-10-13 | 中国铝业股份有限公司 | Method for reducing per-unit production energy consumption of aluminium electrolytic bath |
| CN102134728A (en) * | 2011-03-01 | 2011-07-27 | 哈尔滨工程大学 | Method for separating praseodymium oxide and dysprosium oxide through fused salt electrolytic deposition |
| CN102312252A (en) * | 2011-09-09 | 2012-01-11 | 东北大学 | Method for improving alumina dissolution rate in aluminium electrolysis process |
| CN102373484A (en) * | 2010-08-10 | 2012-03-14 | 乔卫林 | Novel low temperature, low carbon and energy-saving technology for refining high purity aluminum by electrolytic aluminum and primary aluminum |
| CN102817044A (en) * | 2012-07-27 | 2012-12-12 | 中国铝业股份有限公司 | Aluminium electrolyte and using method thereof |
| WO2013174065A1 (en) * | 2012-05-23 | 2013-11-28 | 深圳市新星轻合金材料股份有限公司 | Cryolite with low molecular ratio used in aluminum electrolysis industry and preparation method thereof |
| WO2013185538A1 (en) | 2012-06-11 | 2013-12-19 | 内蒙古联合工业有限公司 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
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| CN103484897A (en) * | 2012-06-11 | 2014-01-01 | 内蒙古联合工业有限公司 | Electrolyte for aluminium electrolysis and electrolysis technology using same |
| KR20170010232A (en) * | 2015-07-17 | 2017-01-26 | 재단법인 포항산업과학연구원 | Method for producing aluminum-scandium alloy with high purity |
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| CN101857961A (en) * | 2010-06-13 | 2010-10-13 | 中国铝业股份有限公司 | Method for reducing per-unit production energy consumption of aluminium electrolytic bath |
| CN102373484A (en) * | 2010-08-10 | 2012-03-14 | 乔卫林 | Novel low temperature, low carbon and energy-saving technology for refining high purity aluminum by electrolytic aluminum and primary aluminum |
| CN102134728A (en) * | 2011-03-01 | 2011-07-27 | 哈尔滨工程大学 | Method for separating praseodymium oxide and dysprosium oxide through fused salt electrolytic deposition |
| CN102312252A (en) * | 2011-09-09 | 2012-01-11 | 东北大学 | Method for improving alumina dissolution rate in aluminium electrolysis process |
| CN102312252B (en) * | 2011-09-09 | 2013-11-13 | 东北大学 | Method for improving alumina dissolution rate in aluminium electrolysis process |
| WO2013174065A1 (en) * | 2012-05-23 | 2013-11-28 | 深圳市新星轻合金材料股份有限公司 | Cryolite with low molecular ratio used in aluminum electrolysis industry and preparation method thereof |
| 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 |
| WO2013185538A1 (en) | 2012-06-11 | 2013-12-19 | 内蒙古联合工业有限公司 | Electrolysis tank used for aluminum electrolysis and electrolysis process using the electrolyzer |
| WO2013185540A1 (en) | 2012-06-11 | 2013-12-19 | 内蒙古联合工业有限公司 | Electrolyte used for aluminum electrolysis and electrolysis process using the electrolyte |
| CN103484897A (en) * | 2012-06-11 | 2014-01-01 | 内蒙古联合工业有限公司 | Electrolyte for aluminium electrolysis and electrolysis technology using same |
| CN103484897B (en) * | 2012-06-11 | 2016-05-11 | 内蒙古联合工业有限公司 | A kind of electrolgtic aluminium electrolyte and use this electrolytical electrolysis process |
| AU2013275997B2 (en) * | 2012-06-11 | 2016-06-16 | Inner Mongolia United Industrial Co., Ltd. | Electrolyte used for aluminum electrolysis and electrolysis process using the electrolyte |
| CN102817044A (en) * | 2012-07-27 | 2012-12-12 | 中国铝业股份有限公司 | Aluminium electrolyte and using method thereof |
| KR101724288B1 (en) | 2015-07-17 | 2017-04-10 | 재단법인 포항산업과학연구원 | Method for producing aluminum-scandium alloy with high purity |
| KR20170010232A (en) * | 2015-07-17 | 2017-01-26 | 재단법인 포항산업과학연구원 | Method for producing aluminum-scandium alloy with high purity |
| CN108950603A (en) * | 2018-08-31 | 2018-12-07 | 营口忠旺铝业有限公司 | A kind of method for electrolyzing aluminum improving electrolyte dissolution degree |
| CN114410975A (en) * | 2022-01-25 | 2022-04-29 | 东北大学 | Method for recovering waste aluminum/waste aluminum alloy |
| CN114410975B (en) * | 2022-01-25 | 2023-01-03 | 东北大学 | Method for recovering waste aluminum/waste aluminum alloy |
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Application publication date: 20100317 |