CN112079395A - Method for preparing high-purity cobalt sulfate crystal - Google Patents
Method for preparing high-purity cobalt sulfate crystal Download PDFInfo
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- CN112079395A CN112079395A CN202010981112.5A CN202010981112A CN112079395A CN 112079395 A CN112079395 A CN 112079395A CN 202010981112 A CN202010981112 A CN 202010981112A CN 112079395 A CN112079395 A CN 112079395A
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- cobalt sulfate
- leaching
- lithium cobaltate
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- cobalt
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- 229940044175 cobalt sulfate Drugs 0.000 title claims abstract description 55
- 229910000361 cobalt sulfate Inorganic materials 0.000 title claims abstract description 55
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 title claims abstract description 55
- 239000013078 crystal Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 44
- 238000002386 leaching Methods 0.000 claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000004090 dissolution Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 229910052782 aluminium Inorganic materials 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 35
- 239000002244 precipitate Substances 0.000 claims description 32
- 239000011888 foil Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 16
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- -1 isooctyl Chemical group 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 229960004887 ferric hydroxide Drugs 0.000 claims description 8
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of preparation of cobalt sulfate crystals, and particularly discloses a method for preparing high-purity cobalt sulfate crystals, which comprises 1) raw material treatment, 2) lithium cobaltate leaching, 3) acid dissolution, 4) primary iron removal, 5) secondary iron removal, 6) cobalt precipitation and 7) cobalt sulfate crystals. The method for recycling and producing the cobalt sulfate crystals from the waste lithium ion batteries is environment-friendly, few in steps, mild in reaction, low in cost and high in purity of the obtained cobalt sulfate crystals.
Description
Technical Field
The invention belongs to the field of preparation of cobalt sulfate crystals, and particularly discloses a method for preparing high-purity cobalt sulfate crystals.
Background
The new energy automobile is a model for the development of the current new technology, wherein the battery material technology is one of the key cores of the new technology, the demand of the cobalt sulfate for manufacturing the battery material is greatly increased, and meanwhile, the quality of the cobalt sulfate has a great influence on the performance of the battery material due to the improvement of the quality requirement of the battery, and the quality requirement of the cobalt sulfate is continuously improved. Lithium cobaltate is simple to synthesize, stable in electrochemical performance, mature upstream and downstream of an industrial chain, widely used as a positive electrode material of a lithium ion secondary battery, and capable of predicting that a lot of waste batteries are generated every year with the vigorous popularization of new energy automobiles in China. The content of cobalt in the lithium cobaltate waste materials reaches more than one third, the traditional extraction method is used for recovering the cobalt, the operation is complex, the flow is long, the alkali dissolution method is used for pretreatment, the aluminum in the battery can not be completely removed, and the cobalt content of filter residue generated by later aluminum removal is higher, thereby causing waste.
Disclosure of Invention
Based on the method, the method for preparing the high-purity cobalt sulfate crystal is green and environment-friendly, few in steps, mild in reaction, low in cost and high in purity of the obtained cobalt sulfate crystal.
The technical scheme of the invention is as follows:
a method for preparing high-purity cobalt sulfate crystals comprises the following steps:
1) raw material treatment: collecting the positive electrode of the waste lithium ion battery, and crushing the positive electrode into small aluminum foil pieces adhered with lithium cobaltate;
2) leaching lithium cobaltate: leaching lithium cobaltate in the aluminum foil chip by using a solvent capable of dissolving an adhesive in the battery, wherein the leaching temperature is 130-150 ℃, and the solid-liquid ratio of the aluminum foil chip to the solvent is 0.1-0.5 g/ml; the leaching time is 2-4 h; after leaching, sieving the solution by a sieve of 50 to 100 meshes, and evaporating the solvent in the sieved solution to obtain crude lithium cobaltate;
3) acid dissolution: dissolving the crude lithium cobaltate obtained in the step 3 by using concentrated sulfuric acid, and adding a reducing agent;
4) iron removal for the first time: adding sodium hydroxide, adjusting the pH of the solution in the step 3 to 5-6 to generate ferric hydroxide precipitate, filtering and collecting filtrate;
5) and (3) secondary iron removal: adding an extracting agent into the filtrate obtained in the step (4), separating the filtrate into an iron-containing organic phase, removing the iron-containing organic phase, and reserving an inorganic phase;
6) cobalt precipitation: continuously adding sodium hydroxide into the inorganic phase obtained in the step 5, adjusting the pH value to 9-11 to obtain cobalt hydroxide precipitate, filtering and collecting the precipitate;
7) cobalt sulfate crystallization: and (4) reacting the cobalt hydroxide precipitate obtained in the step (6) with dilute sulfuric acid, and concentrating and crystallizing to obtain a cobalt sulfate crystal.
Further, in the above method for preparing high-purity cobalt sulfate crystals, in the step 1, the volume of the aluminum foil piece is 1-10cm3In the meantime.
Further, in the above method for preparing high-purity cobalt sulfate crystal, in the step 2, the solvent is an organic solvent.
Further, in the above method for preparing high-purity cobalt sulfate crystals, the organic solvent is a mixed solvent of DCM and DMF.
Further, in the above method for preparing high purity cobalt sulfate crystal, the molar ratio of DCM to DMF is 1: 1.
Further, in the above method for preparing high-purity cobalt sulfate crystals, the reducing agent in step 3 is sodium thiosulfate.
Further, in the above method for preparing high-purity cobalt sulfate crystals, the extractant in step 5 is isooctyl acid amine phosphate salt.
Further, the method for preparing the high-purity cobalt sulfate crystal comprises the following steps:
1) raw material treatment: collecting the positive electrode of the waste lithium ion battery, and crushing the positive electrode into small aluminum foil pieces adhered with lithium cobaltate;
2) leaching lithium cobaltate: leaching lithium cobaltate in the aluminum foil chip by using a solvent capable of dissolving an adhesive in the battery, wherein the leaching temperature is 140 ℃, and the solid-liquid ratio of the aluminum foil chip to the solvent is 0.25 g/ml; the leaching time is 3 h; after leaching, sieving the solution by a sieve of 80 meshes, and evaporating the solvent in the sieved solution to obtain crude lithium cobaltate;
3) acid dissolution: dissolving the crude lithium cobaltate obtained in the step 3 by using concentrated sulfuric acid, and adding a reducing agent;
4) iron removal for the first time: adding sodium hydroxide, adjusting the pH of the solution in the step 3 to 5.5 to generate ferric hydroxide precipitate, filtering and collecting filtrate;
5) and (3) secondary iron removal: adding an extracting agent into the filtrate obtained in the step (4), separating the filtrate into an iron-containing organic phase, removing the iron-containing organic phase, and reserving an inorganic phase;
6) cobalt precipitation: continuously adding sodium hydroxide into the inorganic phase obtained in the step 5, adjusting the pH value to 10 to obtain cobalt hydroxide precipitate, filtering and collecting the precipitate;
7) cobalt sulfate crystallization: and (4) reacting the cobalt hydroxide precipitate obtained in the step (6) with dilute sulfuric acid, and concentrating and crystallizing to obtain a cobalt sulfate crystal.
Compared with the prior art, the invention has the beneficial effects that:
the method recovers and produces the cobalt sulfate crystal from the waste lithium ion battery, and efficiently removes metal impurities such as aluminum, iron and the like through the steps of 1) raw material treatment, 2) lithium cobaltate leaching, 3) acid dissolution, 4) primary iron removal, 5) secondary iron removal, 6) cobalt precipitation, 7) cobalt sulfate crystallization and the like, and simultaneously aluminum can be recovered; the method is green and environment-friendly, has few steps, mild reaction and low cost, and the obtained cobalt sulfate crystal has high purity.
Detailed Description
A method for preparing high-purity cobalt sulfate crystals comprises the following steps:
1) raw material treatment: collecting the positive electrode of the waste lithium ion battery, and crushing the positive electrode into small aluminum foil pieces adhered with lithium cobaltate; preferably, the volume of the aluminum foil small piece is 1-10cm3Between
2) Leaching lithium cobaltate: leaching lithium cobaltate in the aluminum foil chip by using a solvent capable of dissolving an adhesive in the battery, wherein the leaching temperature is 130-150 ℃, and the solid-liquid ratio of the aluminum foil chip to the solvent is 0.1-0.5 g/ml; the leaching time is 2-4 h; after leaching, sieving the solution by a sieve of 50 to 100 meshes, and evaporating the solvent in the sieved solution to obtain crude lithium cobaltate; preferably, the solvent is an organic solvent, and further, the organic solvent is a mixed solvent of DCM and DMF; further preferably, the molar ratio of DCM to DMF is 1: 1.
3) Acid dissolution: dissolving the crude lithium cobaltate obtained in the step 3 by using concentrated sulfuric acid, and adding a reducing agent; preferably, the reducing agent is sodium thiosulfate.
4) Iron removal for the first time: adding sodium hydroxide, adjusting the pH of the solution in the step 3 to 5-6 to generate ferric hydroxide precipitate, filtering and collecting filtrate;
5) and (3) secondary iron removal: adding an extracting agent into the filtrate obtained in the step (4), separating the filtrate into an iron-containing organic phase, removing the iron-containing organic phase, and reserving an inorganic phase; preferably, the extractant is isooctyl acid amine phosphate salt.
6) Cobalt precipitation: continuously adding sodium hydroxide into the inorganic phase obtained in the step 5, adjusting the pH value to 9-11 to obtain cobalt hydroxide precipitate, filtering and collecting the precipitate;
7) cobalt sulfate crystallization: and (4) reacting the cobalt hydroxide precipitate obtained in the step (6) with dilute sulfuric acid, and concentrating and crystallizing to obtain a cobalt sulfate crystal.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
A method for preparing high-purity cobalt sulfate crystals comprises the following steps:
1) raw material treatment: collecting the positive electrode of the waste lithium ion battery, and crushing the positive electrode into small aluminum foil pieces adhered with lithium cobaltate; the average volume of the aluminum foil small piece is 1cm3。
2) Leaching lithium cobaltate: leaching lithium cobaltate in the aluminum foil chip by using a solvent capable of dissolving an adhesive in the battery, wherein the leaching temperature is 130 ℃, and the solid-liquid ratio of the aluminum foil chip to the solvent is 0.1 g/ml; the leaching time is 2 h; after leaching, sieving the solution by a 50-mesh sieve, and evaporating the solvent in the sieved solution to obtain crude lithium cobaltate; the solvent is a mixed solvent of DCM and DMF; the molar ratio of DCM to DMF was 1: 2.
3) Acid dissolution: dissolving the crude lithium cobaltate obtained in the step 3 by using concentrated sulfuric acid, and adding a reducing agent; the reducing agent is sodium thiosulfate.
4) Iron removal for the first time: adding sodium hydroxide, adjusting the pH of the solution in the step 3 to 5 to generate ferric hydroxide precipitate, filtering and collecting filtrate;
5) and (3) secondary iron removal: adding an extracting agent into the filtrate obtained in the step (4), separating the filtrate into an iron-containing organic phase, removing the iron-containing organic phase, and reserving an inorganic phase; the extractant is isooctyl acid amine phosphate.
6) Cobalt precipitation: continuously adding sodium hydroxide into the inorganic phase obtained in the step 5, adjusting the pH value to 9 to obtain cobalt hydroxide precipitate, filtering and collecting the precipitate;
7) cobalt sulfate crystallization: and (4) reacting the cobalt hydroxide precipitate obtained in the step (6) with dilute sulfuric acid, and concentrating and crystallizing to obtain a cobalt sulfate crystal.
Example 2
A method for preparing high-purity cobalt sulfate crystals comprises the following steps:
1) raw material treatment: collecting the positive electrode of the waste lithium ion battery, and crushing the positive electrode into small aluminum foil pieces adhered with lithium cobaltate; preferably, the average volume of the aluminum foil pieces is 5cm3。
2) Leaching lithium cobaltate: leaching lithium cobaltate in the aluminum foil chip by using a solvent capable of dissolving an adhesive in the battery, wherein the leaching temperature is 140 ℃, and the solid-liquid ratio of the aluminum foil chip to the solvent is 0.25 g/ml; the leaching time is 3 h; after leaching, sieving the solution by a sieve of 80 meshes, and evaporating the solvent in the sieved solution to obtain crude lithium cobaltate; the solvent is a mixed solvent of DCM and DMF; the molar ratio of DCM to DMF was 1: 1.
3) Acid dissolution: dissolving the crude lithium cobaltate obtained in the step 3 by using concentrated sulfuric acid, and adding a reducing agent; the reducing agent is sodium thiosulfate.
4) Iron removal for the first time: adding sodium hydroxide, adjusting the pH of the solution in the step 3 to 5.5 to generate ferric hydroxide precipitate, filtering and collecting filtrate;
5) and (3) secondary iron removal: adding an extracting agent into the filtrate obtained in the step (4), separating the filtrate into an iron-containing organic phase, removing the iron-containing organic phase, and reserving an inorganic phase; the extractant is isooctyl acid amine phosphate;
6) cobalt precipitation: continuously adding sodium hydroxide into the inorganic phase obtained in the step 5, adjusting the pH value to 10 to obtain cobalt hydroxide precipitate, filtering and collecting the precipitate;
7) cobalt sulfate crystallization: and (4) reacting the cobalt hydroxide precipitate obtained in the step (6) with dilute sulfuric acid, and concentrating and crystallizing to obtain a cobalt sulfate crystal.
Example 3
A method for preparing high-purity cobalt sulfate crystals comprises the following steps:
1) raw material treatment: collecting the positive electrode of the waste lithium ion battery, and crushing the positive electrode into small aluminum foil pieces adhered with lithium cobaltate; preferably, the average volume of the aluminum foil pieces is 10cm3；
2) Leaching lithium cobaltate: leaching lithium cobaltate in the aluminum foil chip by using a solvent capable of dissolving an adhesive in the battery, wherein the leaching temperature is 150 ℃, and the solid-liquid ratio of the aluminum foil chip to the solvent is 0.5 g/ml; the leaching time is 4 h; after leaching, sieving the solution by a 100-mesh sieve, and evaporating the solvent in the sieved solution to obtain crude lithium cobaltate; the solvent is a mixed solvent of DCM and DMF; the molar ratio of DCM to DMF is 2: 1;
3) acid dissolution: dissolving the crude lithium cobaltate obtained in the step 3 by using concentrated sulfuric acid, and adding a reducing agent; the reducing agent is sodium thiosulfate;
4) iron removal for the first time: adding sodium hydroxide, adjusting the pH of the solution in the step 3 to 6 to generate ferric hydroxide precipitate, filtering and collecting filtrate;
5) and (3) secondary iron removal: adding an extracting agent into the filtrate obtained in the step (4), separating the filtrate into an iron-containing organic phase, removing the iron-containing organic phase, and reserving an inorganic phase; the extractant is isooctyl acid amine phosphate;
6) cobalt precipitation: continuously adding sodium hydroxide into the inorganic phase obtained in the step 5, adjusting the pH value to 11 to obtain cobalt hydroxide precipitate, filtering and collecting the precipitate;
7) cobalt sulfate crystallization: and (4) reacting the cobalt hydroxide precipitate obtained in the step (6) with dilute sulfuric acid, and concentrating and crystallizing to obtain a cobalt sulfate crystal.
Test example
The three cobalt sulfate crystals prepared in examples 1, 2, 3, etc. were subjected to moisture removal and composition measurement, and the results are shown in table 1.
TABLE 1 component detection
| Example 1 | Example 2 | Example 3 | |
| Cobalt sulfate% | 98.4 | 99.3 | 97.7 |
| Aluminum% | 0.74 | 0.21 | 0.59 |
| Iron% | 0.22 | 0.10 | 0.17 |
| Zinc% | 0.04 | 0.02 | 0.05 |
According to the data in the table 1, the method is green and environment-friendly, has few steps, mild reaction and low cost, and the obtained cobalt sulfate crystal has high purity.
The foregoing is only a preferred embodiment of the present invention. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for preparing high-purity cobalt sulfate crystals is characterized by comprising the following steps:
1) raw material treatment: collecting the positive electrode of the waste lithium ion battery, and crushing the positive electrode into small aluminum foil pieces adhered with lithium cobaltate;
2) leaching lithium cobaltate: leaching lithium cobaltate in the aluminum foil chip by using a solvent capable of dissolving an adhesive in the battery, wherein the leaching temperature is 130-150 ℃, and the solid-liquid ratio of the aluminum foil chip to the solvent is 0.1-0.5 g/ml; the leaching time is 2-4 h; after leaching, sieving the solution by a sieve of 50 to 100 meshes, and evaporating the solvent in the sieved solution to obtain crude lithium cobaltate;
3) acid dissolution: dissolving the crude lithium cobaltate obtained in the step 3 by using concentrated sulfuric acid, and adding a reducing agent;
4) iron removal for the first time: adding sodium hydroxide, adjusting the pH of the solution in the step 3 to 5-6 to generate ferric hydroxide precipitate, filtering and collecting filtrate;
5) and (3) secondary iron removal: adding an extracting agent into the filtrate obtained in the step (4), separating the filtrate into an iron-containing organic phase, removing the iron-containing organic phase, and reserving an inorganic phase;
6) cobalt precipitation: continuously adding sodium hydroxide into the inorganic phase obtained in the step 5, adjusting the pH value to 9-11 to obtain cobalt hydroxide precipitate, filtering and collecting the precipitate;
7) cobalt sulfate crystallization: and (4) reacting the cobalt hydroxide precipitate obtained in the step (6) with dilute sulfuric acid, and concentrating and crystallizing to obtain a cobalt sulfate crystal.
2. The method for preparing high-purity cobalt sulfate crystals as claimed in claim 1, wherein the volume of the aluminum foil pieces in step 1 is 1-10cm 3.
3. The method for preparing high-purity cobalt sulfate crystals as claimed in claim 1, wherein in the step 2, the solvent is an organic solvent.
4. The method for preparing high-purity cobalt sulfate crystals as claimed in claim 3, wherein the organic solvent is a mixed solvent of DCM and DMF.
5. The method of claim 4, wherein the molar ratio of DCM to DMF is 1: 1.
6. The method for preparing high-purity cobalt sulfate crystals as claimed in claim 1, wherein the reducing agent in step 3 is sodium thiosulfate.
7. The method for preparing high-purity cobalt sulfate crystals according to claim 1, wherein the extractant in the step 5 is isooctyl acid amine phosphate.
8. The method for preparing high-purity cobalt sulfate crystals according to claim 1, comprising the steps of:
1) raw material treatment: collecting the positive electrode of the waste lithium ion battery, and crushing the positive electrode into small aluminum foil pieces adhered with lithium cobaltate;
2) leaching lithium cobaltate: leaching lithium cobaltate in the aluminum foil chip by using a solvent capable of dissolving an adhesive in the battery, wherein the leaching temperature is 140 ℃, and the solid-liquid ratio of the aluminum foil chip to the solvent is 0.25 g/ml; the leaching time is 3 h; after leaching, sieving the solution by a sieve of 80 meshes, and evaporating the solvent in the sieved solution to obtain crude lithium cobaltate;
3) acid dissolution: dissolving the crude lithium cobaltate obtained in the step 3 by using concentrated sulfuric acid, and adding a reducing agent;
4) iron removal for the first time: adding sodium hydroxide, adjusting the pH of the solution in the step 3 to 5.5 to generate ferric hydroxide precipitate, filtering and collecting filtrate;
5) and (3) secondary iron removal: adding an extracting agent into the filtrate obtained in the step (4), separating the filtrate into an iron-containing organic phase, removing the iron-containing organic phase, and reserving an inorganic phase;
6) cobalt precipitation: continuously adding sodium hydroxide into the inorganic phase obtained in the step 5, adjusting the pH value to 10 to obtain cobalt hydroxide precipitate, filtering and collecting the precipitate;
7) cobalt sulfate crystallization: and (4) reacting the cobalt hydroxide precipitate obtained in the step (6) with dilute sulfuric acid, and concentrating and crystallizing to obtain a cobalt sulfate crystal.
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