CN107541753A - A kind of removing method of the Hull cell containing lithium in lithium electrolyte - Google Patents
A kind of removing method of the Hull cell containing lithium in lithium electrolyte Download PDFInfo
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- CN107541753A CN107541753A CN201710678027.XA CN201710678027A CN107541753A CN 107541753 A CN107541753 A CN 107541753A CN 201710678027 A CN201710678027 A CN 201710678027A CN 107541753 A CN107541753 A CN 107541753A
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Abstract
A kind of removing method of the Hull cell containing lithium in lithium electrolyte, is related to a kind of non-ferrous metal separation process, is particularly used to remove method of the Hull cell containing lithium in lithium electrolyte.It is electrolysed it is characterized in that the electrolyte in Hull cell is transferred in the de- lithium fused-salt bath that negative electrode is graphite cathode, the lithium ion in electrolyte melt is preferentially embedded into graphite cathode, carries out the removing of lithium in electrolyte.The method of the present invention, the lithium ion in electrolyte melt is set to be selectively inserted into graphite cathode, after lithium content reaches requirement in negative electrode, make the anode of magnesium chloride molten-salt electrolysis with the negative electrode rich in lithium after de- lithium in other magnesium chloride fused-salt bath, lithium during magnesium chloride molten-salt electrolysis in graphite anode can be entered in molten chloride and magnesium metal, electrolytic conductivity can be improved into the lithium in magnesium eletrolysis fused salt, the magnesium containing lithium metal for being electrolysed gained can be used for producing magnesium lithium alloy.This method, which can reduce, obtains Hull cell containing lithium in lithium electrolyte, and effectively to provide condition using lithium.
Description
Technical field
A kind of removing method of the Hull cell containing lithium in lithium electrolyte, is related to a kind of non-ferrous metal separation process, particularly uses
The method of lithium in removing Hull cell is containing lithium electrolyte.
Background technology
In recent years, due to resource, lithium content increase in partial domestic aluminum oxide, the long-term use of this oxygen of electrolytic cell
After changing aluminium progress electrolysis production, lithium salt content is substantially increased in electrolyte, causes electrolysis temperature low, and bearth precipitation is more, and stove side is empty,
Electrolytic cell stability is poor, and current efficiency reduces, high energy consumption, or even rolling aluminium phenomenon occurs.Henan, Shanxi, Shaanxi, Gansu, Qinghai,
The aluminium electrolysis enterprise that the whole nation such as Inner Mongol there are about half encounters the problem of similar.
Influence of the lithium fluoride to electrolyte has two main aspects, and on the one hand it improves electrical conductivity, is advantageous to save, still
Weak point is lithium fluoride excessive concentration, to significantly reduce electrolyte primary crystal temperature.Lithium fluoride in some enterprise's electrolyte in recent years
Content has reached 5% even more high, has had a strong impact on normal aluminum electrolysis.
The content of the invention
The problem of purpose of the present invention produces aiming at the higher influence of lithium content in Hull cell electrolyte, there is provided Yi Zhongneng
The lithium in fused salt is efficiently separated, and effectively to provide removing method of the Hull cell containing lithium in lithium electrolyte of condition using lithium.
In order to solve the above problems, the present invention uses following technical scheme.
A kind of removing method of the Hull cell containing lithium in lithium electrolyte, it is characterised in that be transferred to the electrolyte in Hull cell
Negative electrode makes the lithium ion in electrolyte melt preferentially be embedded into graphite to be electrolysed in the de- lithium fused-salt bath of graphite cathode
In negative electrode, the removing of lithium in electrolyte is carried out.
A kind of method of the removing Hull cell containing lithium in lithium electrolyte of the present invention, it is characterised in that described de- lithium fused salt electricity
Solution groove uses carbon anode or inert anode, and negative electrode is graphite cathode, one group or array cathode anode it is relative vertically, be inserted in parallel into electricity
Xie Zhizhong.
A kind of method of the removing Hull cell containing lithium in lithium electrolyte of the present invention, it is characterised in that described negative electrode, anode
Surfacing, outward appearance are cuboid or approximate cuboid.
A kind of method of the removing Hull cell containing lithium in lithium electrolyte of the present invention, it is characterised in that described de- lithium fused salt electricity
Electrolytic process is carried out in solution groove, the degree of superheat of electrolyte is more than 5 DEG C.
A kind of method of the removing Hull cell containing lithium in lithium electrolyte of the present invention, it is characterised in that described de- lithium fused salt electricity
The reduction potential of solution preocess：Using being higher than 1.6V during carbon annode, using being higher than 2.1V during inert material anode.
A kind of method of the removing Hull cell containing lithium in lithium electrolyte of the present invention, it is characterised in that described contains lithium electrolyte
In lithium by it is one or many electrolysis be removed to required concentration.
A kind of method of the removing Hull cell containing lithium in lithium electrolyte of the present invention, it is characterised in that described graphite cathode makes
With one or many.
A kind of method of the removing Hull cell containing lithium in lithium electrolyte of the present invention, it is characterised in that described to be obtained by de- lithium
To graphite cathode containing lithium make the anode of the electrolysis of magnesium chloride, obtain magnesium containing lithium metal.
A kind of method of the removing Hull cell containing lithium in lithium electrolyte of the present invention, utilize graphite crystal category hexagonal crystal system, tool
There is special layer structure feature, its graphite crystal interlamellar spacing is 0.34nm, and this size is more than the diameter 0.29nm of lithium atom,
Less than sodium atom（Atomic diameter 0.44nm）And potassium atom（Atomic diameter 0.45nm）Diameter.After cathodic polarization effect, lithium, sodium
Intercalation compound can be formed with graphite with chemistry and electrochemical means with potassium.Because lithium atom diameter is small, lithium is easier to enter stone
Intercalation compound is formed between layer of ink.And potassium sodium diameter is big, it is necessary to which intercalation compound, difficulty phase could can be formed by destroying graphite-structure
To bigger.Lithium is low compared with sodium potassium reduction potential simultaneously, it is easier to reduces.Therefore make negative electrode with graphite material, control reduction potential, can
So that lithium is preferentially entered in graphite-structure, intercalation compound is formed, so as to realize that removing Hull cell contains lithium in lithium electrolyte.
The method of the present invention, the theory based on more than, the electrolyte in Hull cell is transferred to negative electrode as graphite cathode
It is electrolysed in de- lithium fused-salt bath, the anode of de- lithium fused-salt bath is carbon anode or inert anode, and negative electrode is that graphite is cloudy
Pole.By controlling reduction potential, the lithium ion in electrolyte melt is set to be selectively inserted into graphite cathode, when lithium contains in negative electrode
After amount reaches requirement, make magnesium chloride molten-salt electrolysis with the negative electrode rich in lithium after de- lithium in other magnesium chloride fused-salt bath
Anode, lithium during magnesium chloride molten-salt electrolysis in graphite anode can be entered in molten chloride and magnesium metal, into magnesium eletrolysis
Method, which can reduce, obtains Hull cell containing lithium in lithium electrolyte, and the magnesium containing lithium metal for being electrolysed gained can be used for producing magnesium lithium alloy.
Brief description of the drawings
Fig. 1 is the de- lithium molten-salt electrolysis slot structure schematic diagram that the inventive method uses.
1 is anode in figure, and 2 be negative electrode, and 3 be electrolytic cell, and 4 be electrolyte.
Embodiment
A kind of removing method of the Hull cell containing lithium in lithium electrolyte, it is graphite that the electrolyte in Hull cell is transferred into negative electrode
It is electrolysed in the de- lithium fused-salt bath of negative electrode, the lithium ion in electrolyte melt is preferentially embedded into graphite cathode, enter
The removing of lithium in row electrolyte.
Further explaination is of the invention with reference to embodiments, but is not intended to limit present disclosure.
Embodiment 1
Electrolyte is 3% Al in Hull cell2O3, 3% CaF2, 1% MgF2, 3% KF, 7 %LiF, 45% NaF, 38% AlF3, will
Electrolyte in Hull cell is transferred in de- lithium fused-salt bath, and de- lithium is carried out in de- lithium fused-salt bath.Using common carbon
Plain block is anode, and graphite material is negative electrode, and electrolyte superheat degree is 15 DEG C, reduction potential 1.75V when taking off lithium, and is continuously added
Al2O3, keep alumina concentration in electrolyte to maintain 2%-4%.After once taking off lithium, LiF contents are reduced to 5.9% in electrolyte,
The graphite cathode containing lithium obtained by taking off lithium makees the anode of the electrolysis of magnesium chloride.During the electrolysis of magnesium chloride, electrolyte Initial Composition（Quality
Fraction）MgCl210% ~ 20%, CaCl235% ~ 40%, NaCl 40% ~ 45%, KCl 5% ~ 10%, 710 DEG C of electrolysis temperature, iron conduct
Negative electrode, cathode-current density 0.5A/cm2.After LiCl mass fractions are enriched to 1%, the electrical conductivity of electrolyte improves 1%, electrolysis production
Lithium content 0.01% in thing magnesium liquid.During the electrolysis of magnesium chloride after containing in lithium graphite anode lithium content and being less than 0.01%, the anode is again
Return to the negative electrode for being used as de- lithium fused-salt bath, lithium content is reduced to 2.5% in Hull cell electrolyte after 5 de- lithiums.
Embodiment 2
Electrolyte is 3% Al in Hull cell2O3, 3% KF, 5 %LiF, 49% NaF, 40%AlF3, the electrolyte in Hull cell is turned
Move on in de- lithium fused-salt bath, de- lithium is carried out in de- lithium fused-salt bath.Inert cermet is used as anode, graphite material
Expect for negative electrode.Electrolyte superheat degree is 10 DEG C, reduction potential 2.41V during de- lithium, and is continuously added Al2O3, keep oxygen in electrolyte
Change aluminum concentration and maintain 2%-4%.After once taking off lithium, LiF contents are reduced to 4% in electrolyte, the graphite containing lithium obtained by taking off lithium
Negative electrode makees the anode of the electrolysis of magnesium chloride.During the electrolysis of magnesium chloride, electrolyte ingredient（Mass fraction）MgCl23 ~ 7%, LiCl 8% ~
15%, KCl 80% ~ 90%, 705 DEG C of electrolysis temperature, iron is as negative electrode, cathode-current density 0.6A/cm2, in electrolysate magnesium liquid
Lithium content 1.95%.After lithium content is less than 0.01% in graphite anode containing lithium during the electrolysis of magnesium chloride, the anode is again returned to as de-
The negative electrode of lithium fused-salt bath, lithium content is reduced to 2.2% in Hull cell electrolyte after 4 de- lithiums.
Claims (8)
1. a kind of removing method of the Hull cell containing lithium in lithium electrolyte, it is characterised in that the electrolyte in Hull cell is transferred to the moon
Extremely it is electrolysed in the de- lithium fused-salt bath of graphite cathode, the lithium ion in electrolyte melt is preferentially embedded into graphite the moon
In extremely, the removing of lithium in electrolyte is carried out.
2. a kind of removing method of the Hull cell containing lithium in lithium electrolyte according to claim 1, it is characterised in that described
De- lithium fused-salt bath uses carbon anode or inert anode, and negative electrode is graphite cathode, one group or array cathode anode it is relative vertically,
It is inserted in parallel into electrolyte.
3. a kind of removing method of the Hull cell containing lithium in lithium electrolyte according to claim 2, it is characterised in that described
Negative electrode, anode surface are smooth, and outward appearance is cuboid or approximate cuboid.
4. a kind of removing method of the Hull cell containing lithium in lithium electrolyte according to claim 1, it is characterised in that described
Electrolytic process is carried out in de- lithium fused-salt bath, the degree of superheat of electrolyte is more than 5 DEG C.
5. a kind of removing method of the Hull cell containing lithium in lithium electrolyte according to claim 1, it is characterised in that described
The reduction potential of de- lithium Molten：Using being higher than 1.6V during carbon annode, using being higher than 2.1V during inert material anode.
6. a kind of removing method of the Hull cell containing lithium in lithium electrolyte according to claim 1, it is characterised in that described
Containing the lithium in lithium electrolyte required concentration is removed to by one or many electrolysis.
7. a kind of removing method of the Hull cell containing lithium in lithium electrolyte according to claim 1, it is characterised in that described
Graphite cathode uses one or many.
8. a kind of removing method of the Hull cell containing lithium in lithium electrolyte according to claim 1, it is characterised in that described
The graphite cathode containing lithium obtained by taking off lithium makees the anode of the electrolysis of magnesium chloride, obtains magnesium containing lithium metal.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110129830A (en) * | 2019-05-17 | 2019-08-16 | 中国铝业股份有限公司 | A kind of cathode carbon material and preparation method thereof for lithium in deintercalation richness lithium electrolyte |
| CN113430578A (en) * | 2021-07-15 | 2021-09-24 | 浙江睿曦绿业新材料科技有限公司 | Sodium and lithium removing device and method for aluminum electrolysis electrolyte |
| CN114479767A (en) * | 2020-10-27 | 2022-05-13 | 武汉大学 | Embedded graphite-based composite material and preparation method and application thereof |
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| CN110129830A (en) * | 2019-05-17 | 2019-08-16 | 中国铝业股份有限公司 | A kind of cathode carbon material and preparation method thereof for lithium in deintercalation richness lithium electrolyte |
| CN114479767A (en) * | 2020-10-27 | 2022-05-13 | 武汉大学 | Embedded graphite-based composite material and preparation method and application thereof |
| CN113430578A (en) * | 2021-07-15 | 2021-09-24 | 浙江睿曦绿业新材料科技有限公司 | Sodium and lithium removing device and method for aluminum electrolysis electrolyte |
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