CN101265588B - Method for low-temperature electrolysis of aluminum oxide for producing aluminum adopting ion liquid - Google Patents
Method for low-temperature electrolysis of aluminum oxide for producing aluminum adopting ion liquid Download PDFInfo
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- CN101265588B CN101265588B CN200710064331A CN200710064331A CN101265588B CN 101265588 B CN101265588 B CN 101265588B CN 200710064331 A CN200710064331 A CN 200710064331A CN 200710064331 A CN200710064331 A CN 200710064331A CN 101265588 B CN101265588 B CN 101265588B
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- ionic liquid
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- aluminum oxide
- alumina
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Abstract
The invention relates to a method for producing aluminum by adopting ionic liquid to directly electrolyze alumina at a low temperature, and is characterized in that the HSO4<-> type anionic ionic liquid dissolves alumina and is taken as a low temperature electrolyte, alumina is taken as raw material and is directly electrolyzed by the direct current, the tank voltage is higher than the decomposition voltage of alumina but lower than that of the electrochemical window of the ionic liquid, aluminum is separated out from the cathode, and CO2 is generated from the anode. The ionic liquid adopted by the invention has wide source, low price, good stability, high conductivity, and wide electrochemical window; the good stability is environmental friendly and can efficiently dissolve alumina at a low temperature; adopting the ionic liquid as the low temperature electrolyte greatly reduces the temperature of electrolysis and the tank voltage; the capacity usage ratio is high and the erosion of equipment is greatly reduced.
Description
Technical field:
The invention belongs to the Metal smelting field, relate to a kind of method that adopts the ionic liquid low-temperature electrolysis of aluminum oxide for producing aluminum specifically.
Background technology:
Aluminium industry is maximum in the world electrochemical industry, and the output of aluminium is only second to steel.Because aluminium has light weight, good thermal conductivity and electroconductibility, workability and constitute premium properties such as alloy, a large amount of aluminium is applied in aspects such as building and structured material, conveyer, beverages can, wrapping material, electric power supply line, daily necessities, mechanical means.
Modern aluminum industry is produced aluminium and is mainly adopted Hall-H é roult method, i.e. sodium aluminum fluoride-aluminum oxide molten salt electrolysis.This method is raw material with the aluminum oxide, and molten cryolitic is an ionogen, and direct current feeds electrolyzer, and in negative electrode and anode generation electrochemical reaction, the electrolysate of negative electrode is a liquid aluminium, is CO on the anode
2(about 75%～85%) and CO (20%～25%).1 ton of aluminium of the every production of this method, power consumption 14000kW.h, carbon anode 550～600kg, villiaumite 30～50kg, 2 tons in aluminum oxide, power cost accounts for 20%.Yet there are a lot of shortcomings in Hall-H é roult method: capacity usage ratio is low, less than 50%; The electrolysis temperature height generally all at 950 ℃～970 ℃, requires harsh to equipment and material; Environmental pollution is serious, has produced a large amount of CO
2, CO and fluorine-containing obnoxious flavour.And the price that continues rising and global aluminum oxide along with energy shortage, power cost is lasting high, makes aluminum electrolysis industry stride forward to edge profit industry, and the cost that reduces electrolytic aluminum is the electrolytic aluminum industry task of top priority.
Electrolytic aluminum can effectively reduce bath voltage in low-temperature electrolytes solution.Every groove reduces voltage 0.1V, 1 ton of aluminium 330kW.h that will economize on electricity; Reduce the solubleness of impurity in aluminium simultaneously, also slowed down the corrosion of counter electrode material and slot liner greatly.Current low-temperature aluminum electrolysis technology remains the method based on Hall-H é roult, makes the raw material of aluminium metallurgy with aluminum oxide, cooperate with inert cathode, inert anode and insulative sidewall, but electrolysis temperature is still more than 800 ℃.
Chinese patent (CN1664170A) has been announced the way of a kind of producing aluminium under low-temperature and aluminium alloy, has adopted AlCl
3The type ionic liquid is as low-temperature electrolytes.They are with aluminum oxide or contain aluminium silicate mineral and comprise that bauxite, coal gangue, kaolin or kaolinite, kyanite, andaluzite and sillimanite are that the raw material chlorination obtains Aluminum chloride anhydrous and further handles and obtain AlCl
3The type ionic liquid.Though reduced electrolysis temperature effectively, because AlCl
3Type ionic liquid synthesis condition harshness, character are extremely unstable, divide sensitivity to water in air, and very easily hydrolysis forms HCl smog, need prepare under vacuum or inert atmosphere and use, and can cause heavy corrosion and contaminate environment to equipment simultaneously.In addition, the existence of micro-proton and oxide impurity all can affect greatly ion liquid character, greatly reduces the purity of current efficiency and electrolytic aluminum.Make a general survey of whole flow process and belong to indirect electrolytic oxidation aluminium, long flow path, side reaction is many, and it is many to relate to operation, and chlorination process danger is bigger, and environmental pollution is serious, is not suitable for industrial mass production.
Summary of the invention:
The objective of the invention is to overcome current electrolytic aluminum industrial electrolysis temperature height, energy consumption is big, the cost height, defective in the environmental pollution, a kind of method that adopts the direct low-temperature electrolysis of aluminum oxide for producing aluminum of ionic liquid is provided, have the advantages that technical process is simple, electrolysis temperature is low, no fluorochemical discharges, production cost is low, can be used in the method for industrial electrolysis aluminium.
The present invention realizes by following technological step:
(1) ion liquid synthetic:
The present invention mainly adopts [emim] HSO
4[bmim] HSO
4Type ([Rmim] HSO
4) ionic liquid is as low-temperature electrolytes, its building-up reactions formula is as follows:
[mim]+RX＝[Rmim]X(R＝C
2H
5，C
4H
7，X＝Br，Cl.....)
[Rmim]X+NaHSO
4＝[Rmim]HSO
4+NaX
[emim]X+NaHSO
4＝[emim]HSO
4+NaX
[bmim]X+NaHSO
4＝[bmim]HSO
4+NaX；
Wherein mim is the N-Methylimidazole, [emim]
+Be N-ethyl-N '-methyl-glyoxaline cation, [bmim]
+Be N-butyl-N '-methyl-glyoxaline cation, [Rmim]
+Be N-alkyl-N '-methyl-glyoxaline cation.
Adopt N-Methylimidazole and halogenated alkane according to mol ratio mixed reaction in 1: 1, ionic liquid precursor [Rmim] X that 24h obtains is stirred in 50 ℃ of reactions.To the sodium pyrosulfate solid and the amount of acetone that wherein add the metering ratio, stir 24h then.The ionic liquid that obtains adopts sintered filter funnel to filter, and filtrate is adopted CH
2Cl
2Extraction.Remove CH in the filtrate through underpressure distillation and vacuum-drying again
2Cl
2And acetone, finally obtain product ion liquid.
(2) alumina eltrolysis:
Ionic liquid and aluminum oxide is evenly mixed, adopt dc electrolysis; With the high purity solid charcoal respectively as anode and negative electrode.Anode electrolytic cell and negative electrode are perpendicular to groove face, and apart from being 3～3.5cm, bath voltage is 2.0～2.5V between the two, and anodic current density is 0.65～0.70A/cm
2, 100 ℃～200 ℃ of electrolysis temperatures.Electrolyzer is concatenated into serial electrolyzer.Anode generates CO
2, negative electrode obtains aluminium, and current efficiency is greater than 95%.Direct current consumption is at 8～10KWh/kgAl.
Characteristics of the present invention:
1. to adopt the ion liquid dissolving aluminum oxide be that ionogen is produced aluminium in the present invention.Ionic liquid is as ionogen, and its stable in properties is nontoxic, the specific conductivity height, and electrochemical window is wide, and Heat stability is good is stable to water vapor, is easy to reclaim separate environmental friendliness.
2. the present invention greatly reduces electrolysis temperature, is reduced to 100 ℃～200 ℃ from 950 ℃～970 ℃, effectively reduces bath voltage, has improved the current efficiency height, has reduced energy consumption, has delayed the corrosion of equipment simultaneously.
Embodiment:
Embodiment 1
Adopt N-Methylimidazole and C
2H
5The Br reaction, two kinds of raw materials mix according to mol ratio at 1: 1, and 50 ℃ are stirred 24h and obtain [emim] Br.To the sodium pyrosulfate solid (consumption with the N-Methylimidazole is a benchmark) and the amount of acetone of mol ratios such as adding wherein, stir 24h then.The ionic liquid that obtains adopts sintered filter funnel to filter, and filtrate is adopted CH
2Cl
2Extraction removes CH in the filtrate through underpressure distillation and vacuum-drying again
2Cl
2And acetone, obtain product ion liquid [emim] HSO
4
Gained ionic liquid and commercial alumina is evenly mixed, adopt dc electrolysis.With the high purity solid charcoal as anode and cathode.Anode electrolytic cell and negative electrode are perpendicular to groove face, and both spacings are 2.0V for the 3.2cm bath voltage, and anodic current density is 0.65A/cm
2, 100 ℃ of electrolysis temperatures.Electrolyzer is concatenated into serial electrolyzer.Anode generates CO
2, negative electrode obtains aluminium, current efficiency 98%.Direct current consumption is at 8KWh/kgAl.
Embodiment 2
Adopt N-Methylimidazole and C
4H
9Br is according to mol ratio mixed reaction in 1: 1.2, and [bmim] Br that 48h obtains is stirred in 50 ℃ of reactions.To wherein added mol ratio 1: the 1.2 sodium pyrosulfate solid and the amount of acetone of (consumption with the N-Methylimidazole is a benchmark), 50 ℃ are stirred 12h then.The ionic liquid that obtains adopts sintered filter funnel to filter, and filtrate is adopted CH
2Cl
2Extraction.Remove CH in the filtrate through underpressure distillation and vacuum-drying again
2Cl
2And acetone, obtain product ion liquid [bmim] HSO
4
Ionic liquid and commercial alumina is evenly mixed, dc electrolysis.With the high purity solid charcoal as anode and cathode.Anode electrolytic cell and negative electrode are perpendicular to groove face, and both spacings are 2.1V for the 3cm bath voltage, and anodic current density is 0.70A/cm
2, 120 ℃ of electrolysis temperatures.Electrolyzer is concatenated into serial electrolyzer.Anode generates CO
2, negative electrode obtains aluminium, current efficiency 95%.Direct current consumption is at 9KW/kgAl.
Embodiment 3
Adopt N-Methylimidazole and C
4H
9Cl is according to mol ratio mixed reaction in 1: 1.3, and [bmim] Cl that 24h obtains is stirred in 50 ℃ of reactions.To wherein adding sodium pyrosulfate solid and the amount of acetone that mol ratio is 1: 1.3 (consumption with the N-Methylimidazole is a benchmark), 50 ℃ are stirred 24h then.The ionic liquid that obtains adopts sintered filter funnel to filter, and filtrate is adopted CH
2Cl
2Extraction.Remove CH in the filtrate through underpressure distillation and vacuum-drying again
2Cl
2And acetone, obtain product ion liquid [bmim] HSO
4
Ionic liquid and commercial alumina is evenly mixed, dc electrolysis.With the high purity solid charcoal as anode and cathode.Anode electrolytic cell and negative electrode are perpendicular to groove face, and both spacings are 2.2V for the 3.5cm bath voltage, and anodic current density is 0.68A/cm
2, 130 ℃ of electrolysis temperatures.Electrolyzer is concatenated into serial electrolyzer.Anode generates CO
2, negative electrode obtains aluminium, current efficiency 97%.Direct current consumption is at 9.2KW/kgAl.
Embodiment 4
Adopt N-Methylimidazole and C
2H
5Cl is according to mol ratio mixed reaction in 1: 1.4, and [emim] Cl that 48h obtains is stirred in 50 ℃ of reactions.To wherein added mol ratio 1: the 1.4 sodium pyrosulfate solid and the amount of acetone of (consumption with the N-Methylimidazole is a benchmark), 50 ℃ are stirred 12h then.The ionic liquid that obtains adopts sintered filter funnel to filter, and filtrate is adopted CH
2Cl
2Extraction.Remove CH in the filtrate through underpressure distillation and vacuum-drying again
2Cl
2And acetone, obtain product ion liquid [emim] HSO
4
Ionic liquid and commercial alumina is evenly mixed, dc electrolysis.With the high purity solid charcoal as anode and cathode.Anode electrolytic cell and negative electrode are perpendicular to groove face, and both spacings are 2.4V for the 3.4cm bath voltage, and anodic current density is 0.70A/cm
2, 150 ℃ of electrolysis temperatures.Electrolyzer is concatenated into serial electrolyzer.Anode generates CO
2, negative electrode obtains aluminium, current efficiency 96%.Direct current consumption is at 9.6KW/kgAl.
Embodiment 5
Adopt N-Methylimidazole and [emim] Br to mix reaction at 1: 1.5 according to mol ratio, the ionic liquid precursor that 24h obtains is stirred in 50 ℃ of reactions.To wherein added mol ratio 1: the 1.5 sodium pyrosulfate solid and the amount of acetone of (based on the consumption of N-Methylimidazole), 50 ℃ are stirred 24h then.The ionic liquid that obtains adopts sintered filter funnel to filter, and filtrate is adopted CH
2Cl
2Extraction.Remove CH in the filtrate through underpressure distillation and vacuum-drying again
2Cl
2And acetone, obtain product ion liquid [emim] HSO
4
Ionic liquid and commercial alumina is evenly mixed, dc electrolysis.With the high purity solid charcoal as anode and cathode.Anode electrolytic cell and negative electrode are perpendicular to groove face, and both spacings are 2.5V for the 3.5cm bath voltage, and anodic current density is 0.66A/cm
2, 200 ℃ of electrolysis temperatures.Electrolyzer is concatenated into serial electrolyzer.Anode generates CO
2, negative electrode obtains aluminium, current efficiency 97%.Direct current consumption is at 10KWh/kgAl.
Claims (2)
1. a method that adopts the ionic liquid low-temperature electrolysis of aluminum oxide for producing aluminum is characterized in that directly being the electrolysis raw material with the aluminum oxide, and positively charged ion is that the imidazoles positively charged ion of alkyl replacement, the ionic liquid that negatively charged ion is hydrogen sulfate ion are ionogen; This ionic liquid and commercial alumina are mixed, adopt dc electrolysis, bath voltage is higher than the aluminum oxide decomposition voltage and is lower than this ion liquid electrochemical window during electrolysis; Anode generates CO
2, negative electrode obtains aluminium.
2. the method for an employing ionic liquid low-temperature electrolysis of aluminum oxide for producing aluminum as claimed in claim 1 is characterized in that being raw material with the technical grade aluminum oxide directly, is anode and cathode with the high purity solid charcoal; Current density is 0.65～0.70A/cm
2, bath voltage is 2.0～2.5V, pole span is 3～3.5cm, 100～200 ℃ of electrolysis temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710064331A CN101265588B (en) | 2007-03-12 | 2007-03-12 | Method for low-temperature electrolysis of aluminum oxide for producing aluminum adopting ion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710064331A CN101265588B (en) | 2007-03-12 | 2007-03-12 | Method for low-temperature electrolysis of aluminum oxide for producing aluminum adopting ion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101265588A CN101265588A (en) | 2008-09-17 |
| CN101265588B true CN101265588B (en) | 2010-05-19 |
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|---|---|---|---|
| CN200710064331A Expired - Fee Related CN101265588B (en) | 2007-03-12 | 2007-03-12 | Method for low-temperature electrolysis of aluminum oxide for producing aluminum adopting ion liquid |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634817A (en) * | 2011-02-15 | 2012-08-15 | 中国科学院过程工程研究所 | Ionic liquid low-temperature aluminum electrolysis method with glassy carbon as inert anode |
| CN102154661A (en) * | 2011-03-22 | 2011-08-17 | 中国科学院过程工程研究所 | Method for preparing aluminum ingot by low-temperature electrolysis of metal monocrystal surface electrodes |
| CN102888630B (en) * | 2011-07-20 | 2015-11-18 | 中国科学院过程工程研究所 | A kind of ionic liquid/additive system Low-temperature electro-deposition prepares the method for nano aluminum or nano aluminum coating |
| CN102517608A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Method for electrodepositing zinc and zinc alloy at low temperature by ionic liquor |
| CN104499002A (en) * | 2014-12-10 | 2015-04-08 | 上海大学 | Method for preparing copper-iron nano plated layer from low-grade sulfide ore through direct electro-deposition |
| CN108441886A (en) * | 2018-05-09 | 2018-08-24 | 东北大学 | A method of preparing metal using ionic liquid electrolytic metal oxide |
| CN110534847B (en) * | 2019-09-26 | 2021-04-13 | 清华大学 | Rechargeable aluminum-air battery and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664170A (en) * | 2004-12-24 | 2005-09-07 | 北京科技大学 | Method for producing aluminium and aluminium alloy by low temperature electrolysis |
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- 2007-03-12 CN CN200710064331A patent/CN101265588B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664170A (en) * | 2004-12-24 | 2005-09-07 | 北京科技大学 | Method for producing aluminium and aluminium alloy by low temperature electrolysis |
Non-Patent Citations (2)
| Title |
|---|
| Andrew P. Abbott,etal.Selective Extration of Metals from MixedOxideMatrixesUsingCholine-Based ionic Liquids.Inorganic Chemistry44 19.2005,44(19),6497. |
| Andrew P.Abbott,etal.Selective Extration of Metals from MixedOxideMatrixesUsingCholine-Based ionic Liquids.Inorganic Chemistry44 19.2005,44(19),6497. * |
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