CN113981232A - Method for directly leaching and recovering lithium element in aluminum electrolyte waste residue by using aluminum sulfate - Google Patents
Method for directly leaching and recovering lithium element in aluminum electrolyte waste residue by using aluminum sulfate Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 68
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003792 electrolyte Substances 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 54
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000002386 leaching Methods 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000012452 mother liquor Substances 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 239000001164 aluminium sulphate Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 235000011128 aluminium sulphate Nutrition 0.000 claims 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 31
- 239000002253 acid Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 238000000197 pyrolysis Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- -1 aluminum ion Chemical class 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- BPNMMLCOFUEDKN-UHFFFAOYSA-J [Li+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Li+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BPNMMLCOFUEDKN-UHFFFAOYSA-J 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for directly leaching and recovering lithium element aluminum sulfate in aluminum electrolyte waste residue, which comprises the following steps: (1) grinding and screening the lithium-containing aluminum electrolyte waste residue, mixing the waste residue with aluminum sulfate and water for reaction, and filtering to obtain filtrate A and filter residue B; (2) adding sodium carbonate into the filtrate A for reaction, and filtering to obtain filtrate C and filter residue D; (3) adding water into the filter residue D, and introducing CO2Filtering to obtain filtrate E and filter residue F; (4) carrying out thermal decomposition, filtration and drying on the filtrate E to obtain lithium carbonate; (5) and (3) evaporating and concentrating the filtrate C to obtain a byproduct sodium sulfate, and recycling the mother liquor obtained by evaporation and concentration to the step (2). (6) And (4) reacting the filter residue F with sulfuric acid to obtain aluminum sulfate, and recycling the aluminum sulfate to the step (1). The method effectively utilizes lithium in the aluminum electrolyte waste residue, has low cost and simple steps, and does not use strong lithium in the lithium leaching processThe acid is beneficial to environmental protection and subsequent impurity removal, and also can effectively recycle resources.
Description
Technical Field
The invention belongs to the technical field of lithium recovery, and belongs to the field of aluminum sulfate direct leaching method for recovering aluminum electrolyte waste residues.
Background
Lithium resources have a very high value in the fields of batteries, ceramics, aluminum smelting industry and the like. With the increase of the consumption number of mobile devices such as mobile phones and computers, the lithium ion batteries have a larger market. China is also one of the countries with abundant lithium resources, and the lithium resources in China account for about 13% of the reserves of the lithium resources in the world. Lithium resources in China are mainly divided into lepidolite, spodumene and salt lake brine. The consumption of lithium resources in the world is also increasing year by year, and therefore the demand for lithium carbonate is also increasing year by year.
Since the raw material of the electrolytic aluminum contains a certain amount of lithium oxide and lithium fluoride as one of the additives of the aluminum electrolyte, lithium is enriched during the process of electrolyzing the aluminum. Therefore, the electrolytic aluminum waste residue contains 1 to 7% of lithium. With the increase of the capacity of the aluminum electrolysis plant, the amount of the surplus industrial electrolyte per year is also increasing, for example, the surplus electrolyte per year can reach 2800t in the aluminum electrolysis plant which produces 20 ten thousand tons per year, and thus a large amount of solid waste is produced each year. Lithium-containing aluminum electrolyte waste residue can not be effectively treated, so that site resources of a factory are occupied. Because the waste lithium-containing aluminum electrolyte slag is generated in the electrolytic process, the waste lithium-containing aluminum electrolyte generated in the production process needs to be taken out from the electrolytic cell, and then new additives or supplementary electrolyte is added to adjust the electrolyte components in the electrolytic cell, so that the cost is increased, and the economic loss is indirectly caused. The aluminum electrolyte waste residue contains a large amount of fluorine, and is a dangerous waste. Therefore, the aluminum electrolyte waste residue causes great pollution to the environment.
In the prior art, CN105293536A discloses a method for extracting lithium from electrolytic aluminum waste residues. The method comprises the steps of reacting electrolytic aluminum waste residue with concentrated sulfuric acid, adding water for leaching, and then obtaining lithium carbonate through alkaline hydrolysis reaction, causticization reaction and carbonization reaction. The method uses concentrated sulfuric acid for high-temperature roasting, and has high requirements on equipment. CN105925819A discloses a method for comprehensively recovering lithium element in aluminum electrolyte by using an acid roasting leaching method. Mixing the aluminum electrolyte with acid salt, then carrying out acid roasting, adding water to adjust the pH value, then filtering, and then adding carbonate to finally obtain the lithium carbonate. The roasting temperature of the method can reach 800 ℃ at most, and the method has extremely high requirements on equipment. CN 108569711A discloses a method for extracting lithium salt from waste of aluminum electrolysis high-lithium electrolyte to prepare lithium carbonate. Preparing lithium sulfate solution from electrolyte waste, filtering, removing impurities from filtrate, depositing lithium, filtering for the second time to obtain crude lithium carbonate, washing with water, and drying to obtain the finished lithium carbonate product. The method uses dilute sulfuric acid to react, is easy to react with other fluorides in electrolyte, is high in fluorine content in the prepared lithium sulfate solution, is not beneficial to environmental protection, and is too high in cost due to the fact that an EDTA complexing agent is used in the impurity removal process. CN 105349786A discloses a comprehensive recycling method for lithium-containing aluminum electrolyte. The method is that the lithium-containing aluminum electrolyte is mixed with water, the pH value is adjusted to be less than 2 by using inorganic acid, and then aluminum salt is added to obtain the cryolite. The method uses an acid leaching route, is not beneficial to environmental protection, uses cation exchange resin for impurity removal, and has high cost.
Disclosure of Invention
The invention relates to a method for directly leaching and extracting lithium element in aluminum electrolyte waste residue by using aluminum sulfate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for directly leaching and recovering lithium aluminum sulfate in aluminum electrolyte waste residue is characterized by comprising the following steps:
1) grinding the aluminum electrolyte waste residue, mixing the ground aluminum electrolyte waste residue with aluminum sulfate and water according to a certain proportion for reaction, and filtering to obtain a filtrate A and a filter residue B, wherein the filtrate A is a sulfate solution, and fluorine-containing lithium salt in the electrolyte waste residue is converted into aluminum fluoride to enter the filter residue B;
2) adding sodium carbonate into the filtrate A obtained in the step 1) for reaction, and filtering to obtain a filtrate C and a filter residue D, wherein the filtrate C is a sodium sulfate solution, and the filter residue D is lithium carbonate and aluminum hydroxide;
3) adding water into the filter residue D obtained in the step 2) to prepare slurry, and then introducing CO2Carrying out carbonization reaction, and filtering to obtain a filtrate E and a filter residue F, wherein the filtrate E is a lithium bicarbonate solution, and the filter residue F is aluminum hydroxide;
4) carrying out thermal decomposition on the filtrate E obtained in the step 3), and filtering and drying to obtain lithium carbonate.
In the step 1), the reaction temperature is 30-90 ℃, the pH value ranges from 2.5 to 3.5, and the reaction time is 1-5 h;
in the step 2), the reaction temperature is 30-100 ℃, and the reaction time is 1-3 h;
the solid-to-liquid ratio of the filter residue D to water in the step 3) is 1: 2-10,
step 3), the carbonization reaction pressure is 0-1.0 Mpa, the time is 0.5-5 h, and the temperature is less than or equal to 40 ℃;
step 4), the thermal decomposition temperature is 70-100 ℃;
concentrating the filtrate C obtained in the step 2) by evaporation to obtain a byproduct sodium sulfate.
The chemical reaction equation related to the invention is as follows:
step 1
2Na2LiAlF6+Al2(SO4)3=2Li2SO4+4AlF3+2Na2SO4
Step 2
Al2(SO4)3+3Na2CO3+3H2O=2Al(OH)3+3Na2SO4+3CO2
Li2SO4+Na2CO3=Li2CO3+Na2SO4
Step 3
Li2CO3+CO2+H2O=2LiHCO3
Step 4
2LiHCO3=Li2CO3+H2O+CO2
The invention provides a method for extracting lithium from lithium-containing aluminum electrolyte waste residue. Has the following advantages:
(1) the method directly uses the aluminum sulfate to leach the lithium in the electrolytic aluminum waste residue, is more favorable for environmental protection, and has low leaching temperature and low requirement on equipment. And the leaching rate of lithium can reach 99%.
(2) In the invention, the aluminum sulfate solution is directly used for leaching lithium without adding acid, and the pH range of the solution is 2.5-3.5, and the aluminum sulfate solution is not hydrolyzed in the pH range, so that the water and ion state is kept in the solution, and F ions are not changed into HF to volatilize. And the aluminum ion has very strong capability of combining with the F ion, and the aluminum ion in the aluminum sulfate is combined with the F ion to generate aluminum fluoride precipitate. So that F in the aluminum electrolyte waste slag can be remained in the reaction slag. Is beneficial to environmental protection and subsequent impurity removal and recovery of lithium carbonate.
(3) The invention provides a method with simpler step and lower requirement on equipment for treating the aluminum electrolyte waste residue. And the production cost is also lower.
Drawings
FIG. 1 is a process flow chart of a direct leaching and recovering method of aluminum sulfate of lithium element in aluminum electrolyte waste residue.
Detailed description of the preferred embodiments
Example 1
The aluminum electrolyte waste residue is crushed to 75 meshes, and then aluminum sulfate and water are added to prepare slurry. Wherein Li in the aluminum electrolyte waste residue+With Al in aluminium sulphate3+The molar ratio of (1: 1), the solid-to-liquid ratio of 1:3, and the pH value of 3. The reaction was carried out at 40 ℃ for 3 h. Filtering to obtain a filtrate A; sodium carbonate was added to the filtrate A to adjust the pH to 8. Reacting for 1h at 60 ℃, and filtering to obtain filter residue D and filtrate C; mixing the filter residue D and water in a solid-to-liquid ratio of 1:2 to prepare slurry, and reacting for 0.5h at 0.5Mpa and 30 ℃ to obtain a filtrate E;and carrying out pyrolysis reaction on the filtrate E at the temperature of 80 ℃ to obtain lithium carbonate, wherein the total lithium yield in the aluminum electrolyte is 99.3%.
Example 2
The aluminum electrolyte waste residue is crushed to 120 meshes, and then aluminum sulfate and water are added to prepare slurry. Wherein Li in the aluminum electrolyte waste residue+With Al in aluminium sulphate3+The molar ratio of (1: 2), the solid-to-liquid ratio of 1:5 and the pH value of 2.5. The reaction was carried out at 40 ℃ for 3 h. Filtering to obtain a filtrate A; sodium carbonate was added to the filtrate A to adjust the pH to 7. Reacting for 1h at 80 ℃, and filtering to obtain filter residue D and filtrate C; mixing the filter residue D and water in a solid-to-liquid ratio of 1:3 to prepare slurry, and reacting for 1h at the temperature of 20 ℃ under 0.5Mpa to obtain filtrate E; and carrying out pyrolysis reaction on the filtrate E at the temperature of 90 ℃ to obtain lithium carbonate, wherein the total lithium yield in the aluminum electrolyte is 99.5%. .
Example 3
The aluminum electrolyte waste residue is crushed to 200 meshes, and then aluminum sulfate and water are added to prepare slurry. Wherein Li in the aluminum electrolyte waste residue+With Al in aluminium sulphate3+The molar ratio of (1: 2.5), the solid-to-liquid ratio of 1:2 and the pH value of 3. The reaction was carried out at 60 ℃ for 2 h. Filtering to obtain a filtrate A; sodium carbonate was added to the filtrate A to adjust the pH to 9. Reacting at 70 deg.C for 1h, filtering to obtain residue D and filtrate C, mixing residue D and water at a solid-to-liquid ratio of 1:4 to obtain slurry, and reacting at 0.5Mpa and 30 deg.C for 0.5h to obtain filtrate E; and carrying out pyrolysis reaction on the filtrate E at the temperature of 90 ℃ to obtain lithium carbonate, wherein the total lithium yield in the aluminum electrolyte is 99.25%.
Example 4
The aluminum electrolyte waste residue is crushed to 200 meshes, and then aluminum sulfate and water are added to prepare slurry. Wherein Li in the aluminum electrolyte waste residue+With Al in aluminium sulphate3+The molar ratio of (1: 4), the solid-to-liquid ratio of 1:5 and the pH value of 4.3. The reaction was carried out at 50 ℃ for 4 h. Filtering to obtain a filtrate A; sodium carbonate was added to the filtrate A to adjust the pH to 8. Reacting at 90 deg.C for 1h, filtering to obtain residue D and filtrate C, mixing residue D and water at a solid-to-liquid ratio of 1:4 to obtain slurry, and reacting at 30 deg.C under 0.5Mpa for 0.5h to obtain filtrate E; and carrying out pyrolysis reaction on the filtrate E at the temperature of 85 ℃ to obtain lithium carbonate, wherein the total lithium yield in the aluminum electrolyte is 99.15%.
Example 5
The aluminum electrolyte waste residue is crushed to 300 meshes, and then aluminum sulfate and water are added to prepare slurry. Wherein Li in the aluminum electrolyte waste residue+With Al in aluminium sulphate3+The molar ratio of (1: 3), the solid-to-liquid ratio of 1:5 and the pH value of 3.2. The reaction was carried out at 70 ℃ for 4 h. Filtering to obtain a filtrate A; sodium carbonate was added to the filtrate A to adjust the pH to 10. Reacting at 90 deg.C for 2h, filtering to obtain residue D and filtrate C, mixing residue D and water at a solid-to-liquid ratio of 1:5 to obtain slurry, and reacting at 0.5Mpa and 20 deg.C for 0.5h to obtain filtrate E; and carrying out pyrolysis reaction on the filtrate E at 100 ℃ to obtain lithium carbonate, wherein the total lithium yield in the aluminum electrolyte is 99.55%.
Example 6
The aluminum electrolyte waste residue is crushed to 400 meshes, and then aluminum sulfate and water are added to prepare slurry. Wherein Li in the aluminum electrolyte waste residue+With Al in aluminium sulphate3+The molar ratio of (1: 4), the solid-to-liquid ratio of 1:5 and the pH value of 3.3. The reaction was carried out at 65 ℃ for 5 h. Filtering to obtain a filtrate A; sodium carbonate was added to the filtrate A to adjust the pH to 10. Reacting at 80 deg.C for 3h, filtering to obtain residue D and filtrate C, mixing residue D and water at a solid-to-liquid ratio of 1:6 to obtain slurry, and reacting at 30 deg.C under 0.5Mpa for 0.5h to obtain filtrate E; and carrying out pyrolysis reaction on the filtrate E at the temperature of 90 ℃ to obtain lithium carbonate, wherein the total lithium yield in the aluminum electrolyte is 99.05%.
The above embodiments are illustrative of the present invention, but the present invention is not limited to the above embodiments, and any changes, modifications, substitutions, combinations, and simplifications made without departing from the scope of the present invention shall be considered as equivalent replacements within the scope of the present invention.
Claims (10)
1. A method for directly leaching and recovering lithium element aluminum sulfate in aluminum electrolyte waste residue is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) crushing and grinding the aluminum electrolyte waste residue, mixing the crushed and ground aluminum electrolyte waste residue with aluminum sulfate and water for reaction to obtain filtrate A and filter residue B;
(2) the filtrate A obtained in the step (1) is a mixed sulfate solution of lithium sulfate, sodium sulfate and aluminum sulfate, sodium carbonate is added into the sulfate solution for reaction, and filtrate C and filter residue D are obtained after filtration;
(3) adding water into the filter residue D in the step (2) to prepare slurry, and then introducing CO2Carrying out carbonization reaction, and filtering to obtain filtrate E and filter residue F;
(4) and (4) carrying out thermal decomposition, filtration and drying on the filtrate E obtained in the step (3) to obtain lithium carbonate.
2. The method for directly leaching and recovering the aluminum sulfate of the lithium element in the aluminum electrolyte waste residue according to claim 1, which is characterized in that: in the step (1), the aluminum electrolyte waste residue is crushed and ground to 75-400 meshes, and Li in the aluminum electrolyte waste residue+With Al in aluminium sulphate3 +The molar ratio of (A) to (B) is 1: 0.5-5, the solid-to-liquid ratio is 1: 2-15, and the pH value ranges from 2.5 to 3.5.
3. The method for directly leaching and recovering the aluminum sulfate of the lithium element in the aluminum electrolyte waste residue according to claim 1, which is characterized in that: in the step (1), the reaction temperature is 30-90 ℃, and the reaction time is 1-5 h.
4. The method for directly leaching and recovering the aluminum sulfate of the lithium element in the aluminum electrolyte waste residue according to claim 1, which is characterized in that: adding sodium carbonate into the step (2) to adjust the pH value to 6-12, wherein the obtained filter residue D is a mixture of lithium carbonate and aluminum hydroxide.
5. The method for directly leaching and recovering the aluminum sulfate of the lithium element in the aluminum electrolyte waste residue according to claim 1, which is characterized in that: in the step (2), the reaction temperature is 30-100 ℃, and the reaction time is 1-3 h.
6. The method for directly leaching and recovering the aluminum sulfate of the lithium element in the aluminum electrolyte waste residue according to claim 1, which is characterized in that: and (4) the solid-to-liquid ratio of the filter residue D to water in the step (3) is 1: 2-10.
7. The method for directly leaching and recovering the aluminum sulfate of the lithium element in the aluminum electrolyte waste residue according to claim 1, which is characterized in that: the carbonization reaction pressure in the step (3) is 0-1.0 Mpa, the time is 0.5-5 h, and the temperature is less than or equal to 40 ℃.
8. The method for directly leaching and recovering the aluminum sulfate of the lithium element in the aluminum electrolyte waste residue according to claim 1, which is characterized in that: the thermal decomposition temperature in the step (4) is 70-100 ℃.
9. The method for directly leaching and recovering the aluminum sulfate as the lithium element in the aluminum electrolyte waste residue according to claim 1, characterized in that: and (3) evaporating and concentrating the filtrate C obtained in the step (2) to obtain a byproduct sodium sulfate, and recycling the evaporation and concentration mother liquor to the step (2).
10. The method for directly leaching and recovering the aluminum sulfate as the lithium element in the aluminum electrolyte waste residue according to claim 1, characterized in that: and (4) reacting the filter residue F obtained in the step (3) with sulfuric acid to obtain aluminum sulfate, and recycling the aluminum sulfate to the step (1).
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