CN115947356B - Method for selectively leaching lithium element in aluminum electrolyte by using organic acid and preparing lithium carbonate - Google Patents
Method for selectively leaching lithium element in aluminum electrolyte by using organic acid and preparing lithium carbonate Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 91
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003792 electrolyte Substances 0.000 title claims abstract description 79
- 238000002386 leaching Methods 0.000 title claims abstract description 60
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000000706 filtrate Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 13
- 159000000002 lithium salts Chemical class 0.000 abstract description 13
- 238000000605 extraction Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 229910001610 cryolite Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012535 impurity Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000001630 malic acid Substances 0.000 description 5
- 235000011090 malic acid Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method 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)
Abstract
The invention discloses a method for selectively leaching lithium element in aluminum electrolyte by using organic acid and preparing lithium carbonate, belonging to the technical field of extraction and recovery of waste aluminum electrolyte. The method comprises the following steps: crushing and screening the aluminum electrolyte to obtain aluminum electrolyte powder; mixing organic acid with water to obtain acid liquor, adding aluminum electrolyte powder into the acid liquor, heating and stirring to leach, and obtaining filter residue A and filtrate A after leaching is finished; adding alkali solution to regulate the pH value of the filtrate A to 7-9, heating and stirring, and obtaining filter residue B and filtrate B after the reaction is finished; adding water-soluble carbonate into the filtrate B, heating and stirring, filtering, washing and drying after the reaction is finished to obtain lithium carbonate. The invention utilizes the organic acid to selectively leach the lithium salt, has low leaching rate of elements such as sodium, aluminum and the like in the aluminum electrolyte, can effectively solve the problem of piling up the waste aluminum electrolyte, and realizes the harmless and recycling of the waste electrolyte.
Description
Technical Field
The invention belongs to the technical field of extraction and recovery of aluminum electrolyte, and particularly relates to a method for selectively leaching lithium element in aluminum electrolyte by using organic acid and preparing lithium carbonate.
Background
The electrolytic aluminum industry in China rapidly develops, and the demand for bauxite resources is rapidly increased. The aluminum oxide containing a large amount of lithium salt is used as a raw material for producing electrolytic aluminum, so that electrolyte components in the aluminum electrolysis cell are changed, the lithium salt is enriched in the electrolyte in a large amount, the primary crystal temperature of the electrolyte and the solubility of the aluminum oxide are reduced, the aluminum electrolysis temperature is reduced, the precipitation at the bottom of the furnace is increased, the current efficiency is reduced, the energy consumption per ton of aluminum is increased, the economic benefit of the aluminum electrolysis industry in China is directly influenced, and the problem to be solved in the aluminum electrolysis industry in China is urgently needed. Therefore, the lithium element in the aluminum electrolyte is removed, and the method has important significance for the development of the aluminum electrolysis industry in China. Meanwhile, the industrial application fields of lithium salts are continuously expanded, such as lithium batteries, aluminum-lithium alloys, atomic energy industry, organic synthesis and the like, the demand for lithium salts is rapidly increased, and lithium resources are also challenged. If the aluminum-containing electrolyte can be used as lithium salt resources, the lithium salt in the aluminum-containing electrolyte can be extracted, and the aluminum-containing electrolyte has important significance for the development of the lithium salt industry in China.
At present, inorganic acid leaching is adopted to leach lithium salt in the aluminum electrolyte, but the leaching mode not only can leach lithium salt, but also can leach all components in the aluminum electrolyte, so that the acid consumption is increased, and the subsequent lithium salt is difficult to separate from other components, so that the production cost is greatly increased.
In view of the foregoing, there is a need for a method for selectively leaching lithium salts from an aluminum electrolyte to obtain an industrial electrolyte with high purity suitable for aluminum electrolyte production, which reduces energy consumption in electrolytic aluminum production and reduces overall average extraction cost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for selectively leaching lithium element in aluminum electrolyte by using organic acid and preparing lithium carbonate, which can effectively extract the lithium element in the electrolyte, and meanwhile, the obtained organic acid leaching slag can be used as aluminum industrial electrolyte to meet the production requirement of the aluminum electrolyte, so that the energy consumption and the extraction cost of electrolytic aluminum production are reduced.
In order to achieve the above purpose, the present invention proposes the following technical scheme:
a method for selectively leaching lithium element in an aluminum electrolyte and preparing lithium carbonate by using an organic acid, comprising the following steps:
1) Crushing and screening the waste aluminum electrolyte to obtain aluminum electrolyte powder;
2) Mixing organic acid with water to obtain acid liquor, adding aluminum electrolyte powder into the acid liquor, heating and stirring to leach, and obtaining filter residue A and filtrate A after leaching is finished;
3) Adding alkali solution to regulate the pH value of the filtrate A to 7-9, heating and stirring, and filtering after the reaction is finished to obtain filter residue B and filtrate B;
4) Adding water-soluble carbonate into the filtrate B, heating and stirring, filtering, washing and drying after the reaction is finished to obtain lithium carbonate.
Further, in step 1), the particle size of the aluminum electrolyte powder is-180 mesh to +300 mesh.
Further, in the step 2), the organic acid is at least one of malonic acid, malic acid, oxalic acid, citric acid and aspartic acid; the concentration of the acid liquor is 0.5-5mol/L; the solid-liquid ratio of the aluminum electrolyte powder to the acid liquid is 1g to (5-40) mL.
Further, in the step 2), the leaching temperature is 60-90 ℃ and the leaching time is 1-3h.
The filter residue A obtained in the step 2) is insoluble matters after leaching, namely leaching residues, and belongs to low-lithium cryolite electrolyte (containing additives of calcium fluoride and magnesium fluoride) capable of being returned to an aluminum electrolysis system.
Further, in the step 3), the alkali liquor is sodium hydroxide solution or sodium carbonate solution; the heating temperature is 50-90 ℃ and the heating time is 0.5-2h.
The filter residue B obtained in the step 3) is a cryolite product, and can be returned to the aluminum electrolysis cell for use after washing and drying.
Further, in step 4), the water-soluble carbonate is sodium carbonate or potassium carbonate. The addition amount of the water-soluble carbonate is 1.0-1.3 times of the theoretical reaction amount of the lithium carbonate.
Further, in the step 4), the heating temperature is 50-100 ℃ and the heating time is 0.5-3h.
The invention also provides lithium carbonate prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides a method for selectively leaching lithium element in an aluminum electrolyte by using organic acid and preparing lithium carbonate. Compared with the traditional inorganic acid leaching, the method only leaches the lithium element in the aluminum electrolyte, but does not leach or leaches other elements in the aluminum electrolyte very little, so that the subsequent impurity removal process is simplified, and the cost is saved. Compared with inorganic acid, the organic acid has the advantages of good biodegradability, low acidity, low corrosiveness, recycling, environmental friendliness and the like, and is more environment-friendly.
The invention can also obtain cryolite with low lithium content, and return the cryolite to the electrolytic tank, so that the lithium salt content in the aluminum electrolytic tank can be reduced, thereby effectively solving the adverse effect of the current high-lithium electrolyte system on the production of electrolytic aluminum and realizing the efficient and stable operation of the aluminum electrolytic tank; meanwhile, the recycling problem of lithium in the high-lithium aluminum electrolyte is effectively solved, the harmless and recycling treatment of the waste high-lithium aluminum electrolyte is realized, and the environment protection is facilitated.
In summary, the invention provides a method for selectively leaching lithium element in aluminum electrolyte and preparing lithium carbonate by using organic acid, which is a clean and green production technology, has remarkable economic benefit, social benefit and environmental protection benefit, and is beneficial to realizing sustainable development of electrolytic aluminum industry in China.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of embodiments 1-4 of the present invention;
FIG. 2 is an XRD pattern of the aluminum electrolyte leaching residue in example 1 of the present invention;
FIG. 3 is an XRD pattern of cryolite as a purified and impurity-removed product obtained in example 1 of the present invention;
Fig. 4 is an XRD pattern of the lithium carbonate product obtained in example 1 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the invention are high lithium aluminum electrolyte from a certain domestic aluminum electrolysis enterprise, and the chemical reagents used in the invention are all analytically pure reagents purchased in the market.
A method for selectively leaching lithium element in an aluminum electrolyte and preparing lithium carbonate by using an organic acid, comprising the following steps:
1) Crushing and screening lithium-containing waste aluminum electrolyte to obtain aluminum electrolyte powder;
2) Mixing organic acid with water to obtain acid liquor, adding aluminum electrolyte powder into the acid liquor, stirring and heating to leach, and obtaining filter residue A and filtrate A after leaching is finished;
3) Adding alkali solution to adjust pH of filtrate A to 7-9 (the purpose of adjusting pH is to remove Al, na and F in the solution to make them generate cryolite), preferably 7, 8 and 9, stirring and heating, and filtering after reaction to obtain filter residue B and filtrate B; the filter residue B is a cryolite product, and can be returned to the aluminum electrolysis cell for use after washing and drying;
4) Adding water-soluble carbonate into the filtrate B, heating and stirring for reaction (lithium precipitation reaction), filtering, washing and drying after the reaction is finished to obtain lithium carbonate.
In some embodiments, step 1), the aluminum electrolyte powder has a particle size of-180 mesh to +300 mesh. Preferably-200 mesh to +250 mesh. The content of lithium element in the lithium-containing aluminum electrolyte is not more than 5%, preferably 1.21-1.88%, more preferably 1.21%, 1.54%, 1.66%, 1.88%.
In some embodiments, step 2), the organic acid is at least one of malonic acid, malic acid, oxalic acid, citric acid, and aspartic acid, preferably malonic acid, malic acid; the concentration of the acid solution is 0.5-5mol/L, preferably 1.25-3mol/L, and more preferably 2.5mol/L; the solid-liquid ratio of the aluminum electrolyte powder to the acid solution is 1g to (5-40) mL, preferably 1g to (15-30) mL, and more preferably 1g to 25mL.
In some embodiments step 2), the leaching temperature is 60-90 ℃, preferably 60-85 ℃, more preferably 85 ℃; the leaching time is 1-3 hours, preferably 1.5-2 hours, more preferably 2 hours.
In some examples step 2), the residue a obtained is the insoluble after the leaching, i.e. the leached residue, belonging to the low-lithium cryolite electrolyte (containing the additives calcium fluoride and magnesium fluoride) that can be returned to the aluminium electrolysis system.
In some embodiments step 3), the lye is sodium hydroxide solution or sodium carbonate solution, preferably sodium hydroxide solution; the heating temperature is 50-90 ℃, preferably 70-75 ℃, more preferably 75 ℃; the time is 0.5 to 2 hours, preferably 1.5 to 2 hours, more preferably 1.5 hours.
In some embodiments, step 4), the water-soluble carbonate is sodium carbonate or potassium carbonate. The addition amount of the water-soluble carbonate is 1.0-1.3 times of the theoretical reaction amount of the lithium carbonate.
In some embodiments, step 4), the heating is at a temperature of 50-100 ℃, preferably 90-95 ℃, more preferably 90 ℃; the time is 0.5 to 3 hours, preferably 1 to 2 hours, more preferably 2 hours.
The invention also provides lithium carbonate prepared by the method.
FIG. 1 is a flow chart of examples 1-4 of the present invention.
Example 1
1) Crushing and screening 30g of lithium-containing waste aluminum electrolyte (lithium element content is 1.21%) to obtain aluminum electrolyte powder with-180 meshes accounting for 100%;
2) Preparing 600mL of acid liquor with the concentration of 2mol/L by using malonic acid and water, adding the aluminum electrolyte powder treated in the step 1) into the acid liquor, heating and stirring for leaching by using a constant-temperature water bath kettle for 2 hours at the leaching temperature of 80 ℃, and filtering after the leaching is finished to obtain filter residue A and filtrate A;
3) Regulating the pH value of the filtrate A obtained in the step 2) to 7 by using a sodium hydroxide solution, heating and reacting for 1.5 hours by using a constant-temperature water bath kettle, wherein the reaction temperature is 75 ℃, and filtering after the reaction is finished to obtain filter residues B and filtrate B;
4) Washing and drying the filter residue B obtained in the step 3) to obtain 1.63g of cryolite product;
5) Adding 2.59g of sodium carbonate into the filtrate B obtained in the step 3), heating and reacting for 1h by using a constant-temperature water bath kettle, wherein the reaction temperature is 90 ℃, and filtering, washing and drying after the reaction is finished to obtain 1.48g of lithium carbonate.
Example 2
1) Crushing and screening 25g of lithium-containing waste aluminum electrolyte (lithium element content is 1.54%) to obtain aluminum electrolyte powder with the mesh of-200 accounting for 99%;
2) Preparing 625mL of acid liquor with malonic acid and water, wherein the concentration of the acid liquor is 2.5mol/L, adding the aluminum electrolyte powder treated in the step 1) into the acid liquor, heating and stirring for leaching by using a constant-temperature water bath kettle for 1.5h at the leaching temperature of 85 ℃, and filtering after the leaching is finished to obtain filter residue A and filtrate A;
3) Regulating the pH value of the filtrate A obtained in the step 2) to 8 by using a sodium hydroxide solution, heating and reacting for 2 hours by using a constant-temperature water bath kettle, and filtering after the reaction is finished at the reaction temperature of 70 ℃ to obtain filter residues B and a filtrate B;
4) Washing and drying the filter residue B obtained in the step 3) to obtain 1.45g of cryolite product;
5) Adding 2.49g of sodium carbonate into the filtrate B obtained in the step 3), heating and reacting for 1.5 hours by using a constant-temperature water bath kettle, wherein the reaction temperature is 95 ℃, and filtering, washing and drying after the reaction is finished to obtain 1.57g of lithium carbonate.
Example 3
1) Crushing and screening 10g of lithium-containing waste aluminum electrolyte (lithium element content is 1.66%) to obtain aluminum electrolyte powder with-200 meshes accounting for 97%;
2) Preparing 250mL of acid liquor with malic acid and water, wherein the concentration of the acid liquor is 1.25mol/L, adding the aluminum electrolyte powder treated in the step 1) into the acid liquor, heating and stirring for leaching by using a constant-temperature water bath kettle for 1.5h at the leaching temperature of 60 ℃, and filtering after the leaching is finished to obtain filter residue A and filtrate A;
3) Regulating the pH value of the filtrate A obtained in the step 2) to 7 by using a sodium hydroxide solution, heating and reacting for 1.5 hours by using a constant-temperature water bath kettle, wherein the reaction temperature is 75 ℃, and filtering after the reaction is finished to obtain filter residues B and filtrate B;
4) Washing and drying the filter residue B obtained in the step 3) to obtain 0.55g of cryolite product;
5) And 3) adding 1.19g of sodium carbonate into the filtrate B obtained in the step 3), heating and reacting for 2 hours by using a constant-temperature water bath kettle, wherein the reaction temperature is 90 ℃, and filtering, washing and drying after the reaction is finished to obtain 0.75g of lithium carbonate.
Example 4
1) Crushing and screening 16.67g of lithium-containing waste aluminum electrolyte (lithium element content is 1.88%) to obtain aluminum electrolyte powder with the mesh of-200 accounting for 95%;
2) Preparing 250mL of acid liquor with malic acid and water, wherein the concentration of the acid liquor is 3mol/L, adding the aluminum electrolyte powder treated in the step 1) into the acid liquor, heating and stirring for leaching for 2 hours by using a constant-temperature water bath kettle, and filtering after the leaching is finished at the leaching temperature of 80 ℃ to obtain filter residue A and filtrate A;
3) Regulating the pH value of the filtrate A obtained in the step 2) to 9 by using a sodium hydroxide solution, heating and reacting for 2 hours by using a constant-temperature water bath kettle, and filtering after the reaction is finished at the reaction temperature of 75 ℃ to obtain filter residues B and a filtrate B;
4) Washing and drying the filter residue B obtained in the step 3) to obtain 0.91g of cryolite product;
5) Adding 1.68g of sodium carbonate into the filtrate B obtained in the step 3), heating and reacting for 1h by using a constant-temperature water bath kettle, wherein the reaction temperature is 95 ℃, and filtering, washing and drying after the reaction is finished to obtain 0.96g of lithium carbonate.
FIG. 2 is an XRD pattern of the aluminum electrolyte leaching residue in example 1 of the present invention; from the figure, no lithium compound is found in the organic acid leaching slag, which shows that most of the phase containing lithium is leached into solution, and the main components in the leaching slag are Na 3AlF6 and CaF 2, so that the leaching slag can be used as aluminum electrolysis return aluminum electrolysis cell.
FIG. 3 is an XRD pattern of cryolite obtained in step 4 of example 1 of the present invention; the diffraction peak of the product is sharp, no obvious impurity phase exists, the unit cell structure is complete, and the crystallinity is good.
FIG. 4 is an XRD pattern of lithium carbonate obtained as a product in example 1 of the present invention; the diffraction peak of the product is sharp, no obvious impurity phase exists, the unit cell structure is complete, and the crystallinity is good. And compared with the XRD standard spectrum of lithium carbonate, the diffraction peak of the product is consistent with the standard peak, so that the product can be determined to be lithium carbonate and has higher purity.
Comparative example 1
The difference from example 1 is that in step 2), the acid concentration is 1.5mol/L (the acid concentration is higher, the leaching effect is not deteriorated, the leaching effect is stable or increased to some extent, and high acid is not used from the viewpoint of cost).
Comparative example 2
The only difference from example 1 is that in step 2), the leaching temperature 50 ℃ (temperature becomes low and the leaching effect becomes poor).
Comparative example 3
The only difference from example 1 is that in step 2) malonic acid is replaced by acetic acid.
Comparative example 4
The only difference from example 1 is that in step 3), the pH was adjusted to 11.
Comparative example 5
The only difference from example 1 is that in step 4), the reaction temperature is 40 ℃.
Table 1 shows the leaching rates obtained after analysis and detection in examples 1 to 4 and comparative examples 1 to 5, and the loss rate of lithium at the time of neutralization and impurity removal (step 3) and the precipitation rate of lithium at the time of lithium precipitation.
TABLE 1
As can be seen from Table 1, examples 1-4 can leach out most of lithium elements in the waste aluminum electrolyte, but have very low leaching rates for elements such as sodium, aluminum and the like in the aluminum electrolyte, which shows that the invention can selectively extract lithium, simplifies the subsequent impurity removal process, saves cost, and has very little loss of lithium in the subsequent impurity removal process. As can be seen from comparison of comparative examples 1 to 3 and example 1, changing the acid concentration, leaching temperature and kind of organic acid all reduced the leaching rate of lithium. As is clear from a comparison between comparative example 4 and example 1, too high a pH at the time of neutralization and impurity removal causes lithium loss. As is clear from a comparison between comparative example 5 and example 1, too low a temperature at the time of lithium precipitation results in a low lithium precipitation rate. Therefore, the conditions are optimal within the scope of the present invention.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (7)
1. A method for selectively leaching lithium element in an aluminum electrolyte and preparing lithium carbonate by using an organic acid, comprising the following steps:
1) Crushing and screening the waste aluminum electrolyte to obtain aluminum electrolyte powder;
2) Mixing organic acid with water to obtain acid liquor, adding aluminum electrolyte powder into the acid liquor, heating and stirring to leach, and obtaining filter residue A and filtrate A after leaching is finished; the organic acid is malonic acid;
3) Adding alkali solution to regulate the pH value of the filtrate A to 7-9, heating and stirring, and filtering after the reaction is finished to obtain filter residue B and filtrate B;
4) Adding water-soluble carbonate into the filtrate B, heating and stirring, filtering, washing and drying after the reaction is finished to obtain lithium carbonate.
2. The method for selectively leaching lithium element in an aluminum electrolyte and preparing lithium carbonate using an organic acid according to claim 1, wherein in the step 1), the particle size of the aluminum electrolyte powder is-180 mesh to +300 mesh.
3. The method for selectively leaching lithium element in aluminum electrolyte and preparing lithium carbonate by using organic acid according to claim 1, wherein in the step 2), the concentration of the acid solution is 0.5-5mol/L; the solid-liquid ratio of the aluminum electrolyte powder to the acid liquid is 1g to (5-40) mL.
4. The method for selectively leaching lithium element in aluminum electrolyte and preparing lithium carbonate by using organic acid according to claim 1, wherein in the step 2), the leaching temperature is 60-90 ℃ and the leaching time is 1-3h.
5. The method for selectively leaching lithium element in aluminum electrolyte and preparing lithium carbonate by using organic acid according to claim 1, wherein in the step 3), the alkali liquor is sodium hydroxide solution or sodium carbonate solution; the heating temperature is 50-90 ℃ and the heating time is 0.5-2h.
6. The method for selectively leaching lithium element in an aluminum electrolyte and preparing lithium carbonate using an organic acid according to claim 1, wherein in the step 4), the water-soluble carbonate is sodium carbonate or potassium carbonate.
7. The method for selectively leaching lithium element in aluminum electrolyte and preparing lithium carbonate by using organic acid according to claim 1, wherein in the step 4), the heating temperature is 50-100 ℃ for 0.5-3h.
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