CN109930174A - The method that aluminium electrolyte takes off lithium purification and recycling lithium - Google Patents
The method that aluminium electrolyte takes off lithium purification and recycling lithium Download PDFInfo
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- CN109930174A CN109930174A CN201910155461.9A CN201910155461A CN109930174A CN 109930174 A CN109930174 A CN 109930174A CN 201910155461 A CN201910155461 A CN 201910155461A CN 109930174 A CN109930174 A CN 109930174A
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- aluminium electrolyte
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- aluminium
- purification
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 98
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 95
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 94
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000004411 aluminium Substances 0.000 title claims abstract description 88
- 239000003792 electrolyte Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000000746 purification Methods 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 84
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 44
- 238000001914 filtration Methods 0.000 claims description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 235000010344 sodium nitrate Nutrition 0.000 claims description 22
- 239000004317 sodium nitrate Substances 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003916 acid precipitation Methods 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- 238000001816 cooling Methods 0.000 claims 1
- 238000005373 pervaporation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 76
- 238000001228 spectrum Methods 0.000 description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 description 11
- 239000013078 crystal Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 229910001610 cryolite Inorganic materials 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of methods that aluminium electrolyte takes off lithium purification and recycling lithium, comprising the following steps: (1) aluminium electrolyte takes off lithium purification；(2) lithium deviate from is recycled, and specifically includes: filtrate is concentrated by evaporation, neutralizes, cleaning, recycling lithium prepares lithium salts.Aim to solve the problem that energy consumption caused by the enrichment of electrolyte lithium content increases problem in aluminum i ndustry electrolytic cell During Process of Long-term Operation.It is not more than 0.5% by this method treated aluminium electrolyte lithium content, can return to electrolytic cell and recycle；The lithium recoverable of abjection.High added value lithium salts product is prepared in the present invention, on the one hand opens new lithium resource, on the one hand alleviates existing market to the demand status of high-end lithium product, promotes China in the technological progress of new energy industry and high-end lithium application industry, social benefit is significant；Raw material sources are extensive, and overall cost is lower, simple for process, production technology clean and environmental protection, have good economical, societal benefits.
Description
Technical field
The present invention relates to aluminium electroloysis technical field of smelting, and in particular to a kind of aluminium electrolyte takes off the side of lithium purification and recycling lithium
Method.
Background technique
In recent years, with the rapid development of Aluminium Industry, the demand of alumina raw material is more and more, domestic aluminium oxide by
In mineral resources, the difference of preparation process, all contain Li to some extent2O.This kind of otide containing lighium aluminum feedstock is added in electrolytic cell,
Lithium salts is also introduced into aluminium cell together therewith, and can constantly be accumulated in the electrolyte.And with the extension in electrolytic cell age,
Lithium is gradually enriched with, and fluorination lithium content may be up to 6~10%.In aluminium electrolyte system, fluorination lithium content at 2~3%, can such as drop
The liquidus temperature of low electrolyte, advantageously reduces energy consumption；However, the electrolyte system of high lithium salt content then can not only reduce oxidation
The solubility of aluminium in the electrolyte, and electrolyte superheat degree can be made higher, energy consumption increases, shorten the service life of electrolytic cell,
Directly influence the business efficiency of Aluminium Industry.Therefore, how to reduce the lithium content of aluminium electrolyte in electrolytic cell is China's electricity
Solve aluminum i ndustry technical problem urgently to be resolved.
In aluminium electrolysis process, in order to run electrolytic cell normal table, it is necessary to be controlled to its electrolyte level and total amount
System, the electrolytic cell for running one period usually require to drain out excessive electrolyte to control its balance, and excessive electrolyte is actually
It is the byproduct of electrolytic aluminium factory.Domestic enterprise pays little attention to this resource at present, and most enterprises are all by such electrolyte
A large amount of storages, using level, there are larger gaps with foreign countries.
With the development of industrial technology, the industrial application of lithium salts constantly extends, such as lithium battery, aluminium lithium alloy, bromination
Lithium air-conditioning, atomic energy industry, organic synthesis etc., the demand to lithium salts is grown rapidly, and especially in terms of the chemical industry energy, lithium salts is made
For the basic material of new energy, supply falls short of demand for demand, holds at high price, if can will contain lithium aluminium electrolyte conduct
Lithium salts resource extracts lithium salts therein, is of great significance to China's lithium salts industrial expansion.
In conclusion eliminating elemental lithium how by using the elemental lithium in suitable technique extraction recycling aluminium electrolyte
The high lithium salts product of added value is prepared while influence for aluminum electrolysis to be of great significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that aluminium electrolyte takes off lithium purification and recycling lithium, this method
The elemental lithium in electrolyte can be effectively extracted, the industrial electrolysis matter that purity is high is suitable for aluminium electrolyte production is obtained, reduces electricity
Solve the energy consumption of aluminium production；The lithium salts product of purity is high is prepared simultaneously, and overall cost is lower, simple for process.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of method for designing de- lithium purification of aluminium electrolyte, includes the following steps:
(1) aluminium electrolyte is crushed and is sieved, the aluminium electrolyte main component is ice crystal Na3AlF6, calcirm-fluoride CaF2, fluorine
Change lithium LiF etc.；
(2) aluminium electrolyte is slowly added into 0.5~12mol/L nitric acid, the proportionate relationship of aluminium electrolyte and nitric acid is 1g:
1mL~40mL is stirred to react 0.5~10h under the conditions of 60~120 DEG C；
(3) after reaction, by after the mixed liquor cooled to room temperature after reaction, filtering, collect respectively obtain first-time filtrate,
Residue washing to neutrality is dried to get to the aluminium electrolyte after de- lithium purification for filter residue and hydrogen fluoride gas, by
To after the purification of de- lithium, the lithium content of aluminium electrolyte is not more than 0.5%, that is, can return in electrolytic aluminium factory electrolytic cell as aluminium electroloysis
Matter is recycled；
In the step, key reaction equation are as follows:
。
Preferably, in step (1), the aluminium electrolyte crosses 50~200 meshes after ball mill grinding.
Preferably, in step (1), the concentration of nitric acid is 2~6mol/L.
Preferably, in step (2), the reaction time is 0.5~5h.
Preferably, in step (3), above-mentioned aluminium electrolyte takes off in lithium purification, can generate hydrogen fluoride gas, a part is dissolved in
Hydrofluoric acid is formed in filtrate, hydrogen fluoride gas is volatile, and the mode that condensing reflux can be used is enriched with hydrogen fluoride gas, then
Qualified discharge again after harmless treatment is carried out using lye.
It is taken off in lithium purification in above-mentioned aluminium electrolyte, in the prior art has and aluminium electrolyte to be leached using sulfuric acid, but
The study found that this Leaching way has also dissolved in electrolyte while leaching lithium salts and has needed existing ice crystal, destroyed
The structure of aluminium electrolyte, and sulfuric acid medium can not be recycled.And the present invention by a large amount of experimental study and combines
The nitric acid liquid of long-term production experience, the suitable low strength range of optimum choice mentions to carry out de- lithium to aluminium electrolyte
It is pure, while leaching lithium salts, do not destroy the structure of aluminium electrolyte substantially, and during first-time filtrate is concentrated, it can
With recovery section nitric acid recycling.
The present invention still further provides the method that lithium is recycled from aluminium electrolyte, mainly includes the following steps:
(1) lithium that above-mentioned aluminium electrolyte takes off that filtrate is deviate from after lithium purifies is used to extract elemental lithium, after first-time filtrate evaporation, concentration
Elemental lithium concentration is 3~8g/L, and cooled to room temperature filters, obtains secondary filter residue and secondary filtrate, secondary filter residue and drying obtains
To byproduct sodium nitrate；
(2) alkaline matter is added in Xiang Erci filtrate and adjusts its pH value to 6~7, cooled to room temperature, and filtering obtains three times
Filter residue and three times filtrate obtain byproduct nitrate three times after filter residue and drying；
(3) Xiang Sanci filtrate addition soluble calcium salt or calcium hydroxide remove the fluorine ion in filtrate, and four filtrates are obtained by filtration
And calcium fluoride precipitate, the calcium ion that four filtrates add oxalic acid precipitation extra again obtain five filtrates and calcium oxalate precipitation after filtering；
For the high-purity for guaranteeing the lithium salts product being prepared, fluorine removal processing need to be carried out to filtrate；
(4) five filtrates recycle lithium using solid sodium carbonate or potassium carbonate, adjust its pH value to 8~12, filter, in gained filtrate
With to neutrality, since it contains N, K element, Fertilizer application can be done；Filtering gained precipitates washed, drying to get high-purity is arrived
Lithium salts product lithium carbonate.
Preferably, in first-time filtrate evaporation, concentration process, nitric acid volatilization in part passes through condensing recovery, part nitric acid acid
Liquid is recyclable to be recycled.
Preferably, in the step (2), the alkaline matter is potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide
At least one of.
Preferably, five filtrates recycle lithium using solid sodium hydroxide or potassium hydroxide, adjust its pH value to 8~12, mistake
Filter gained precipitates washed, drying to get high-purity lithium salts product monohydrate lithium hydroxide is arrived.
Compared with prior art, the beneficial technical effect of the present invention lies in:
1. method of purification of the present invention can reduce aluminum electrolysis industry electrolytic cell aluminium electrolyte lithium content, the aluminium electrolyte after purification
Lithium content be not more than 0.5%, the aluminium electrolyte that de- lithium purifies can be recycling in Aluminium Industry, realize electrolysis
The stabilization and balance movement of slot, this method solve the technical problems of current puzzlement aluminum electrolysis industry production, improve electrolytic aluminium
The labor efficiency of production, it is energy-saving, reduce production cost.
2. high added value lithium salts product can be prepared in recovery method of the present invention, new lithium resource is on the one hand opened, one
Aspect alleviates existing market to the demand status of high-end lithium product, promotes China in new energy industry and high-end lithium application row
The technological progress of industry, social benefit are significant.
3. it is of the invention while the de- lithium purification for realizing aluminium electrolyte and recycling lithium obtain the byproduct of high added value,
The discharge of no poisonous and harmful substance, it is production technology clean and environmental protection, sustainable.
4. raw material sources of the present invention are extensive, overall cost is lower, simple for process, has good economic, society's effect
Benefit.
Detailed description of the invention
Fig. 1 is the process flow chart for the method that aluminium electrolyte of the present invention takes off lithium purification and recycling lithium；
Fig. 2 is the sodium nitrate XRD spectrum for the method that aluminium electrolyte of the present invention takes off lithium purification and recycling lithium；
Fig. 3 is the lithium carbonate XRD spectrum for the method that aluminium electrolyte of the present invention takes off lithium purification and recycling lithium.
Specific embodiment
Illustrate a specific embodiment of the invention below with reference to embodiment, but following embodiment is used only to be described in detail
The present invention does not limit the scope of the invention in any way.Related instrument and equipment is as without especially in the examples below
Illustrate, is routine instrument device；The related raw material of industry is commercially available regular industrial raw material unless otherwise instructed.
Embodiment 1
The method that the aluminium electrolyte of the present embodiment takes off lithium purification and recycling lithium, process flow is as shown in Figure 1, specifically include following step
It is rapid:
Step 1: aluminium electrolyte takes off lithium purification
(1) aluminium electrolyte containing elemental lithium is subjected to ball mill crushing, aluminium electrolyte main component is ice crystal Na3AlF6, fluorine
Change calcium CaF2, lithium fluoride LiF etc., wherein lithium fluoride LiF content is 6.5%, crosses 50~200 meshes；
(2) it is 2.5mol/L nitre that the aluminium electrolyte for weighing 100 mesh of the 30g containing 6.5% lithium fluoride LiF, which is added slowly to 110mL concentration,
In acid, 5h is stirred under the conditions of 70 DEG C；
(3) mixed liquor after completion of the reaction, is cooled to room temperature under field conditions (factors), filtering, repeatedly washing filter residue to final washing
Liquid pH value is 7, obtains first-time filtrate and a filter residue, first-time filtrate 350mL, a filter residue drying, weight 26.3g, purification
Afterwards, it is 0.75% that lithium content is fluorinated in aluminium electrolyte；
Step 2: the lithium recycling and reusing of abjection
(1) by the evaporation of 350mL first-time filtrate that above-mentioned steps 1 obtain, to be concentrated into elemental lithium concentration be 3.5g/L, in evaporation, dense
In compression process, nitric acid volatilization in part can be recycled by condensing recovery, be filtered after cooled to room temperature, obtain secondary filtrate
With secondary filter residue, secondary filter residue is sodium nitrate, and sodium nitrate XRD spectrum such as Fig. 2 is dried as 0.8g；
(2) secondary filtrate adjusts pH value to 7 using sodium carbonate, consumes sodium carbonate 20.5g, cooled and filtered obtains filtrate three times
With filter residue sodium nitrate, sodium nitrate XRD spectrum such as Fig. 2, the drying of filter residue sodium nitrate is 2.5g；
(3) filtrate adds 0.7g calcium hydroxide three times, to precipitate fluorine ion, is obtained by filtration four filtrates, then plus 0.3g oxalic acid, precipitating
Extra calcium ion obtains five filtrates and calcium oxalate after filtering；
(4) five filtrates add 3g sodium carbonate in a heated condition, adjust pH value to 9, this filtrate is heated to boiling, is reacted
30min, heat filtering, gained filtrate are neutralized to neutrality, containing N element, do Fertilizer application；Filtering gained precipitating is washed, dry
After obtain 0.8g lithium carbonate Li2CO3, lithium carbonate XRD spectrum such as Fig. 3, purity 99.5%.
Embodiment 2
The method that the aluminium electrolyte of the present embodiment takes off lithium purification and recycling lithium, process flow is as shown in Figure 1, specifically include following step
It is rapid:
Step 1: aluminium electrolyte takes off lithium purification
(1) aluminium electrolyte containing elemental lithium is subjected to ball mill crushing, aluminium electrolyte main component is ice crystal Na3AlF6, fluorine
Change calcium CaF2, lithium fluoride LiF etc., wherein lithium fluoride LiF content is 8.5%, crosses 50~200 meshes；
(2) it is 7mol/L nitre that the aluminium electrolyte for weighing 200 mesh of the 100g containing 8.5% lithium fluoride LiF, which is added slowly to 1000mL concentration,
In acid, 3h is stirred under the conditions of 115 DEG C；
(3) mixed liquor after completion of the reaction, cooled to room temperature, filtering, repeatedly washing filter residue to final cleaning solution pH are 7,
First-time filtrate and a filter residue are obtained, first-time filtrate 2230mL, one time filter residue is dried, weight 80g, after purification, aluminium electrolyte
Middle lithium fluoride LiF content is 0.35%；
Step 2: the lithium recycling and reusing of abjection
(1) by the evaporation of 2230mL first-time filtrate that above-mentioned steps 1 obtain, to be concentrated into elemental lithium concentration be 8g/L, in concentration process,
The volatilization of part nitric acid, condensing recovery recycle, are cooled to room temperature filtering, obtain secondary filtrate and secondary filter residue, secondary filter residue is
Sodium nitrate, sodium nitrate XRD spectrum such as Fig. 2, is dried as 3.5g；
(2) secondary filtrate using sodium carbonate adjust pH to 7, consume sodium carbonate 68.7g, cooled and filtered, obtain three times filtrate and
Filter residue sodium nitrate, sodium nitrate XRD spectrum such as Fig. 2, the drying of filter residue sodium nitrate are 12g；
(3) filtrate adds 3.2g calcium chloride three times, to precipitate fluorine ion, is obtained by filtration four filtrates, then plus 2g oxalic acid, it is extra to precipitate
Calcium ion, five filtrates and calcium oxalate are obtained after filtering；
(4) five times filtrate adds 10g sodium hydroxide in a heated condition, adjusts its pH value to 12, this filtrate is heated to boiling, instead
45min, heat filtering are answered, gained filtrate is neutralized to neutrality, containing N element, does Fertilizer application；Filtering gained precipitating is washed, dry
10g monohydrate lithium hydroxide LiOHH is obtained after dry2O, purity 99.5%.
Embodiment 3
The method that the aluminium electrolyte of the present embodiment takes off lithium purification and recycling lithium, process flow is as shown in Figure 1, specifically include following step
It is rapid:
Step 1: aluminium electrolyte takes off lithium purification
(1) aluminium electrolyte containing elemental lithium is subjected to ball mill crushing, aluminium electrolyte main component: ice crystal Na3AlF6, fluorination
Calcium CaF2, lithium fluoride LiF etc., wherein lithium fluoride LiF content is 7.5%, crosses 50~200 meshes；
(2) it is 12mol/L nitric acid that the aluminium electrolyte for weighing 50 mesh of the 20g containing 7.5% lithium fluoride LiF, which is added slowly to 400mL concentration,
In, 9h is stirred under the conditions of 70 DEG C；
(3) mixed liquor after completion of the reaction, cooled to room temperature, filtering, repeatedly washing filter residue to final cleaning solution pH value is
7, first-time filtrate and a filter residue are obtained, first-time filtrate 750mL, one time filter residue is dried, weight 16.5g, after purification, aluminium electroloysis
Lithium fluoride LiF content is 1.5% in matter；
Step 2: the lithium recycling and reusing of abjection
(1) by the evaporation of 750mL first-time filtrate that above-mentioned steps 1 obtain, to be concentrated into elemental lithium concentration be 6g/L, in concentration process,
The volatilization of part nitric acid, condensing recovery recycle, are cooled to room temperature filtering, obtain secondary filtrate and secondary filter residue, secondary filter residue is
Sodium nitrate, sodium nitrate XRD spectrum such as Fig. 2, is dried as 0.5g；
(2) secondary filtrate adjusts its pH value to 7 using potassium carbonate, consumes potassium carbonate 12.5g, cooled and filtered is filtered three times
Liquid and filter residue potassium nitrate, the drying of filter residue potassium nitrate are 1.5g；
(3) filtrate adds 0.62g calcium hydroxide three times, to precipitate fluorine ion, is obtained by filtration four filtrates, then plus 0.18g oxalic acid, sink
Form sediment extra calcium ion, and five filtrates and calcium oxalate are obtained after filtering；
(4) five times filtrate adds 3g potassium carbonate in a heated condition, adjusts its pH value to 9, this filtrate is heated to boiling, is reacted
30min, heat filtering, gained filtrate are neutralized to neutrality, containing N, K element, do Fertilizer application；Filtering gained precipitating is washed, dry
0.76g lithium carbonate Li is obtained after dry2CO3, lithium carbonate XRD spectrum such as Fig. 3, purity 99.7%.
Embodiment 4
The method that the aluminium electrolyte of the present embodiment takes off lithium purification and recycling lithium, process flow is as shown in Figure 1, specifically include following step
It is rapid:
Step 1: aluminium electrolyte takes off lithium purification
(1) aluminium electrolyte containing elemental lithium is subjected to ball mill crushing, aluminium electrolyte main component: ice crystal Na3AlF6, fluorination
Calcium CaF2, lithium fluoride LiF etc., wherein lithium fluoride LiF content is 9.5%, crosses 50~200 meshes；
(2) weigh 60g containing 9.5% lithium fluoride 180 mesh aluminium electrolyte be added slowly to 300mL concentration be 1mol/L nitric acid in,
2h is stirred under the conditions of 80 DEG C；
(3) mixed liquor after completion of the reaction, cooled to room temperature, filtering, repeatedly washing filter residue to final cleaning solution pH are 7,
First-time filtrate and a filter residue are obtained, first-time filtrate 620mL, one time filter residue is dried, weight 51.3g, after purification, aluminium electrolyte
Middle lithium fluoride LiF content is 1.1%；
Step 2: the lithium recycling and reusing of abjection
(1) evaporating the 620mL first-time filtrate that above-mentioned steps 1 obtain, being concentrated into elemental lithium concentration is 4.7g/L, concentration process
In, part nitric acid volatilization, condensing recovery recycles, is cooled to room temperature filtering, obtains secondary filtrate and secondary filter residue, secondary filter residue
For sodium nitrate, sodium nitrate XRD spectrum such as Fig. 2 is dried as 1.3g；
(2) secondary filtrate adjusts its pH value to 7 using potassium hydroxide, consumes potassium hydroxide 26.8g, cooled and filtered obtains three
Secondary filtrate and filter residue potassium nitrate, the drying of filter residue potassium nitrate are 8g；
(3) filtrate adds 1.5g calcium hydroxide three times, to precipitate fluorine ion, is obtained by filtration four filtrates, then plus 0.45g oxalic acid, sink
Form sediment extra calcium ion, and five filtrates and calcium oxalate are obtained after filtering；
(4) five filtrates add 3g potassium carbonate in a heated condition, adjust pH to 9, this filtrate is heated to boiling, and react 30min,
Heat filtering, gained filtrate are neutralized to neutrality, containing N, K element, do Fertilizer application；Filtering gained obtains after precipitating washed, drying
To 0.8g lithium carbonate Li2CO3, lithium carbonate XRD spectrum such as Fig. 3, purity 99.5%.
Comparative examples
The method that the aluminium electrolyte of comparative examples takes off lithium purification and recycling lithium, specifically includes the following steps:
Step 1: aluminium electrolyte takes off lithium purification
(1) aluminium electrolyte containing elemental lithium is subjected to ball mill crushing, aluminium electrolyte main component: ice crystal Na3AlF6, fluorination
Calcium CaF2, lithium fluoride LiF etc., wherein lithium fluoride LiF content is 8%, crosses 50~200 meshes；
(2) it is 0.5mol/L nitric acid that the aluminium electrolyte for weighing 150 mesh of the 40g containing 8% lithium fluoride LiF, which is added slowly to 650mL concentration,
In, 0.5h is stirred under the conditions of 110 DEG C；
(3) mixed liquor after completion of the reaction, cooled to room temperature, filtering, repeatedly washing to filter residue pH are 7, are once filtered
Liquid and a filter residue, first-time filtrate 1000mL, a filter residue drying, weight 35.7g, after purification, lithium fluoride in aluminium electrolyte
LiF content is 1.65%.
Step 2: the lithium recycling and reusing of abjection
(1) evaporating the 1000mL first-time filtrate that above-mentioned steps 1 obtain, being concentrated into elemental lithium concentration is 7g/L, and cold filtration obtains
To secondary filtrate and secondary filter residue, secondary filter residue is sodium nitrate, and sodium nitrate XRD spectrum such as Fig. 2 is dried as 2.6g；
(2) secondary filtrate using sodium carbonate adjust pH to 7, consume sodium carbonate 20.5g, cooled and filtered, obtain three times filtrate and
Filter residue sodium nitrate, sodium nitrate XRD spectrum such as Fig. 2, the drying of filter residue sodium nitrate are 2.5g；
(3) fluorine removal, direct reinforcing body sodium carbonate 5g, tune pH value to 9 are not heated to boiling filtrate three times, react 50min, hot mistake
Filter, washing, obtain 1.5g lithium carbonate Li after dry2CO3, purity 85.7%, wherein fluorine content is 12.5%.
The present invention is described in detail above in conjunction with embodiment and attached drawing, still, those of skill in the art
Member is it is understood that without departing from the purpose of the present invention, can also carry out each design parameter in above-described embodiment
The equivalent substitute of change and material, forms multiple specific embodiments, is common variation range of the invention, herein no longer
It is described in detail one by one.
Claims (9)
1. a kind of method that aluminium electrolyte takes off lithium purification, which comprises the steps of:
(1) aluminium electrolyte to be processed is crushed and is sieved；
(2) aluminium electrolyte is slowly added into 0.5~12mol/L nitric acid, the adding proportion relationship of aluminium electrolyte and nitric acid is
1g:1mL~40mL is stirred to react, 0.5~10h of reaction time under the conditions of 40~120 DEG C；
(3) after reaction, by after the mixed liquor cooled to room temperature after reaction, filtering collects obtain filtrate, filter residue respectively
And hydrogen fluoride gas, it is dry by residue washing to neutrality,.
2. the method that aluminium electrolyte according to claim 1 takes off lithium purification, which is characterized in that in the step (1), to
Process aluminum electrolytic matter crosses 50~200 meshes after ball mill grinding.
3. the method that aluminium electrolyte according to claim 1 takes off lithium purification, which is characterized in that in step (2), the nitre
Acid concentration is 2~6mol/L.
4. the method that aluminium electrolyte according to claim 1 takes off lithium purification, which is characterized in that described anti-in step (2)
It is 0.5~5h between seasonable.
5. the method that aluminium electrolyte according to claim 1 takes off lithium purification, which is characterized in that in step (3), further include
Harmless treatment step is carried out to hydrogen fluoride gas.
6. a kind of method for recycling lithium from aluminium electrolyte, which comprises the steps of:
(1) by the evaporation of filtrate obtained by the step of claim 1 (3), concentration, cooled to room temperature, filtering obtains secondary filter residue
With secondary filtrate, secondary filter residue and drying obtains byproduct sodium nitrate；
(2) secondary filtrate pH value to 6~7, natural cooling is adjusted using alkaline matter to filter, obtain filter residue three times and filter three times
Liquid obtains byproduct nitrate three times after filter residue and drying；
(3) Xiang Sanci filtrate addition soluble calcium salt or calcium hydroxide remove the fluorine ion in filtrate, and four filtrates are obtained by filtration
And calcium fluoride precipitate, the calcium ion that four filtrates add oxalic acid precipitation extra again obtain five filtrates and calcium oxalate precipitation after filtering；
(4) Xiang Wuci filtrate adds alkaline matter, adjusts its pH value to 8~12, filtering, filtrate is neutralized to neutrality, filtering gained
Sediment is washed, dries to get high-purity lithium salts product or/and lithium hydroxide product is arrived.
7. the method according to claim 6 for recycling lithium from aluminium electrolyte, which is characterized in that in the step (1),
First-time filtrate through pervaporation, be concentrated into elemental lithium concentration be 3~8g/L.
8. the method according to claim 6 for recycling lithium from aluminium electrolyte, which is characterized in that in the step (2),
Alkaline matter is at least one of potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide.
9. the method according to claim 6 for recycling lithium from aluminium electrolyte, which is characterized in that in the step (4),
Alkaline matter is at least one of potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide.
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