CN114988381B - Method for preparing ferric phosphate by using waste lithium iron phosphate battery - Google Patents
Method for preparing ferric phosphate by using waste lithium iron phosphate battery Download PDFInfo
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- CN114988381B CN114988381B CN202210578802.5A CN202210578802A CN114988381B CN 114988381 B CN114988381 B CN 114988381B CN 202210578802 A CN202210578802 A CN 202210578802A CN 114988381 B CN114988381 B CN 114988381B
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- iron
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 92
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 87
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 87
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 87
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007788 liquid Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 238000002386 leaching Methods 0.000 claims abstract description 40
- 229910052742 iron Inorganic materials 0.000 claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 18
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000010413 mother solution Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims description 70
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 241000242583 Scyphozoa Species 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 26
- 239000012452 mother liquor Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 8
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 230000002431 foraging effect Effects 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 dihydrate ferric phosphate Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Primary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing ferric phosphate by using waste lithium iron phosphate batteries, and belongs to the technical field of waste lithium battery recovery. The method comprises the following steps: firstly, acid leaching is carried out on waste lithium iron phosphate battery powder to obtain leaching liquid and tailings; heating the leaching solution in water bath to regulate pH for precipitating lithium to obtain crude lithium carbonate; and (3) drying, roasting and acid leaching the tailings to obtain an iron phosphate mother solution, adding an iron source into the iron phosphate mother solution for reaction, heating, adding alkali to adjust pH, oxidizing and ageing to obtain ferric phosphate dihydrate, and calcining at a high temperature to obtain the anhydrous ferric phosphate. The invention effectively solves the problem that a large amount of waste residues generated by the existing wet recovery process of the waste lithium iron phosphate batteries cannot be fully utilized, and the anhydrous ferric phosphate prepared by the waste lithium iron phosphate batteries has high purity, moderate iron-phosphorus ratio and high product quality.
Description
Technical Field
The invention belongs to the technical field of waste lithium batteries, and particularly relates to a method for preparing ferric phosphate by using waste lithium iron phosphate batteries.
Background
The lithium iron phosphate battery has the advantages of low cost, long cycle life, good safety and the like, and is widely applied to the field of various new energy automobiles. The lithium battery consumption of China is large, and with the rapid development of new energy automobiles in recent years, the demand of the lithium iron phosphate battery is rapidly increased, but the scrapping amount is increased year by year. If the waste lithium iron phosphate battery is improperly treated, not only can great resource waste be caused, but also great pollution can be caused to the environment.
At present, the recovery and utilization of the waste lithium iron phosphate battery mainly adopts a wet process to recover valuable metal components, the waste lithium iron phosphate battery is crushed to a certain granularity, and valuable metals in the anode material are recovered in the form of lithium carbonate by acid dissolution. The method can effectively recycle lithium element in the lithium iron phosphate positive electrode material, but can generate a large amount of tailings which cannot be continuously utilized, and has the defect of insufficient resource recycling.
In view of this, there is a need to develop a method capable of more fully recycling the waste lithium iron phosphate batteries.
Disclosure of Invention
Aiming at the technical defect that the existing wet recycling process generates a large amount of unusable tailings in the background art, the invention aims to provide a method for preparing ferric phosphate by using waste lithium iron phosphate batteries, and aims to provide a method capable of recycling the waste lithium iron phosphate batteries more fully, thereby protecting the environment and reducing resource waste.
The invention is realized by the following technical scheme:
the invention provides a method for preparing ferric phosphate by using waste lithium iron phosphate batteries, which comprises the following steps:
1) Crushing waste lithium iron phosphate batteries to obtain mixed powder, adding acid into the powder, uniformly mixing and leaching for 1-5h at normal temperature, and filtering to obtain leaching liquid and tailings;
2) Heating the leaching solution obtained in the step 1) to 70-95 ℃ in a water bath, adding alkali liquor to adjust the pH to 9-12, and filtering to obtain solid and lithium jellyfish solution; heating lithium jellyfish solution in 70-95 deg.c water bath, adding sodium carbonate to regulate pH to 9-12, and filtering to obtain white coarse lithium carbonate;
3) Drying and roasting the tailings obtained in the step 1), adding acid, uniformly mixing for 2-5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor;
4) Adding an iron source into the ferric phosphate mother solution at normal temperature, and reacting for 0.5-2h to obtain a solution A; heating the solution A, adding alkali to adjust the pH to 2-3, and reacting for 1-2h to obtain a solution B; adding an oxidant into the solution B for aging for 2-6 hours to obtain a solution C; and finally, filtering, washing and drying the obtained solution C to obtain ferric phosphate dihydrate, and further calcining at high temperature to obtain anhydrous ferric phosphate.
Further, the acid in the step 1) and the step 3) is at least one of sulfuric acid, hydrochloric acid and phosphoric acid, and the concentration is 0.1-0.2mol/L; the solid-to-liquid ratio of the acid is 1 (2-6).
Further, the solid obtained by filtering the leaching solution in the step 2) is mainly nickel, magnesium, aluminum and other substances. Adding acid into lithium iron phosphate battery powder to dissolve magnesium, aluminum, lithium and other elements into leaching liquid, regulating pH of the leaching liquid, filtering and removing solid generated by nickel, magnesium, aluminum and other substances in the solution in a chemical precipitation mode, and adding sodium carbonate into lithium jellyfish solution obtained by filtering to prepare crude lithium carbonate.
Further, the roasting temperature in the step 3) is 350-600 ℃, and the roasting time is 2-5h.
Further, the iron source in the step 4) is at least one of iron powder, ferric sulfate, ferric oxide and ferrous sulfate; the addition amount of the iron source is calculated by the ratio (1-2) of the iron to the phosphorus substances in the feed liquid to be 1.
Further, the temperature of the solution A in the step 4) is raised to 50-90 ℃ before the pH is regulated.
Further, in the step 4), the alkali is at least one of alkali metal hydroxide, alkali metal carbonate solution and ammonia water.
Further, the oxidant in the step 4) is at least one of chlorate, peroxide, oxygen and ozone; the addition amount of the oxidant is 1-2 times of the amount of the iron substances in the feed liquid.
Further, the high-temperature calcination temperature in the step 4) is 500-800 ℃ and the calcination time is 2-5h.
The method comprises the steps of firstly, carrying out high-temperature treatment on acid leaching and filtering tailings to remove substances such as a binder, then adding acid and filtering to obtain an iron phosphate mother solution, adding an iron source into the mother solution, adjusting pH to generate a dihydrate iron phosphate complex precipitate, and continuously adding an oxidant for aging to completely oxidize ferrous ions in the solution into ferric ions; and finally, calcining the obtained dihydrate ferric phosphate at high temperature to remove crystal water, thereby obtaining the battery-grade pure anhydrous ferric phosphate.
Compared with the prior art, the invention has the beneficial effects that:
firstly, acid leaching is carried out on waste lithium iron phosphate battery powder to obtain leaching liquid and tailings; heating the leaching solution in water bath to regulate pH for precipitating lithium to obtain crude lithium carbonate; and (3) drying, roasting and acid leaching the tailings to obtain an iron phosphate mother solution, adding an iron source into the iron phosphate mother solution for reaction, heating, adding alkali to adjust pH, oxidizing and ageing to obtain ferric phosphate dihydrate, and calcining the ferric phosphate dihydrate at a high temperature to obtain anhydrous ferric phosphate. The invention effectively solves the problem that a large amount of waste residues can not be fully utilized in the existing wet recovery process of the waste lithium iron phosphate batteries, and the anhydrous ferric phosphate prepared by using the waste lithium iron phosphate batteries has high purity, proper iron-phosphorus ratio and high product quality.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in the following examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Unless defined otherwise, 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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding iron powder (the ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature for reacting for 1.4h; then heating the mixture to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding hydrogen peroxide with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Example 2
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:5.5, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:5.8, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding iron powder (the ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature for reacting for 1.4h; then heating the mixture to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding hydrogen peroxide with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Example 3
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.20mol/L is added according to the solid-to-liquid ratio of 1:2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then leaching liquid and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.14mol/L according to the solid-to-liquid ratio of 1:2.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding ferric sulfate (the ratio of iron to phosphorus substances in the feed liquid is 1.8:1) at normal temperature for reacting for 1.4h; then heating the mixture to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding hydrogen peroxide with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Example 4
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding ferric sulfate (the ratio of iron to phosphorus substances in the feed liquid is 1.2:1) at normal temperature for reacting for 1.8h; then heating the mixture to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding hydrogen peroxide with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Example 5
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding ferric oxide (the ratio of iron to phosphorus substances in the feed liquid is 2:1) at normal temperature for reacting for 1.2h; then heating the mixture to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding sodium chlorate with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Example 6
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding ferric oxide (the ratio of iron to phosphorus substances in the feed liquid is 1.8:1) at normal temperature for reacting for 1.4h; then heating the mixture to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding sodium chlorate with the mass 1.5 times that of iron in the feed liquid into the feed liquid, and aging for 3 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Example 7
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding ferrous sulfate (the ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature for reacting for 1.4h; then heating the mixture to 85 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding sodium chlorate with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Example 8
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding ferrous sulfate (the ratio of iron to phosphorus substances in the feed liquid is 2:1) at normal temperature to react for 1.6h; then heating the mixture to 75 ℃ in water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8h; adding sodium chlorate with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
The pure anhydrous ferric phosphate product prepared in the above example was tested and the results are shown in table 1.
TABLE 1
Comparative example 1
The preparation method and the step parameters of reference example 1 were different in that the iron source addition amount was changed.
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding iron powder (the ratio of iron to phosphorus in the feed liquid is 2.5:1) at normal temperature for reacting for 1.4h; then heating the mixture to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding hydrogen peroxide with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Comparative example 2
The preparation method and the step parameters of reference example 1 are different in that the treatment process of adding alkali to adjust the pH by heating the ferric phosphate mother liquor is changed.
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding iron powder (the ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature for reacting for 1.4h; then heating the water bath to 100 ℃, adding sodium hydroxide to adjust the pH of the solution to 4, and continuing the reaction for 1.8h; adding hydrogen peroxide with the mass twice that of iron in the feed liquid into the mixture, and aging for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 4 hours at 650 ℃ to obtain pure anhydrous ferric phosphate.
Comparative example 3
The preparation method and the step parameters of reference example 1 are different in that the iron source addition amount and the oxidant aging treatment process are changed.
1. 1000g of crushed powder of waste lithium iron phosphate batteries is taken, sulfuric acid aqueous solution with the concentration of 0.16mol/L is added according to the solid-to-liquid ratio of 1:4.2, and the mixture is uniformly mixed and leached for 3.5 hours at normal temperature, and then the leaching solution and tailings are obtained through filtration.
2. Heating the leaching solution to 85 ℃ in a water bath, adding alkali to adjust the pH to 11, and filtering to obtain solid and lithium jellyfish solution; and (3) heating the lithium jellyfish solution in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And taking and drying tailings, roasting for 4 hours at 520 ℃, then adding sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor.
4. Placing the obtained ferric phosphate mother liquor in a water bath, and adding iron powder (the ratio of iron to phosphorus in the feed liquid is 2.5:1) at normal temperature for reacting for 1.4h; then heating the mixture to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing the reaction for 1.8 hours; adding hydrogen peroxide with the mass 3.5 times that of iron in the feed liquid into the mixture for ageing for 4 hours; filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and placing the ferric phosphate dihydrate into a high-temperature furnace for calcining for 5 hours at 750 ℃ to obtain pure anhydrous ferric phosphate.
The anhydrous iron phosphate product prepared in the above comparative example was tested and the results are shown in table 1.
TABLE 2
The embodiments described above represent only a few preferred embodiments of the present invention, which are described in more detail and are not intended to limit the present invention. It should be noted that various changes and modifications can be made to the present invention by those skilled in the art, and any modifications, equivalent substitutions, improvements, etc. which are within the spirit and principle of the present invention are included in the scope of the present invention.
Claims (7)
1. The method for preparing the ferric phosphate by using the waste lithium iron phosphate battery is characterized by comprising the following steps of:
1) Crushing waste lithium iron phosphate batteries to obtain mixed powder, adding acid into the powder, uniformly mixing and leaching for 1-5h at normal temperature, and filtering to obtain leaching liquid and tailings;
2) Heating the leaching solution obtained in the step 1) to 70-95 ℃ in a water bath, adding alkali liquor to adjust the pH to 9-12, and filtering to obtain solid and lithium jellyfish solution; heating lithium jellyfish solution in 70-95 deg.c water bath, adding sodium carbonate to regulate pH to 9-12, and filtering to obtain white coarse lithium carbonate;
3) Drying and roasting the tailings obtained in the step 1), adding acid, uniformly mixing for 2-5 hours at normal temperature, and filtering to obtain carbon powder and ferric phosphate mother liquor;
4) Adding an iron source into the ferric phosphate mother solution at normal temperature, and reacting for 0.5-2h to obtain a solution A; heating the solution A, adding alkali to adjust the pH to 2-3, and reacting for 1-2h to obtain a solution B; adding an oxidant into the solution B for aging for 2-6 hours to obtain a solution C; finally, filtering, washing and drying the obtained solution C to obtain ferric phosphate dihydrate, and further calcining at high temperature to obtain anhydrous ferric phosphate; wherein the iron source is at least one of iron powder, ferric sulfate, ferric oxide and ferrous sulfate; the addition amount of the iron source is calculated by the ratio (1-2) of the iron to the phosphorus substances in the feed liquid to be 1.
2. The method for preparing ferric phosphate by using the waste lithium iron phosphate battery as claimed in claim 1, wherein the acid in the step 1) and the step 3) is at least one of sulfuric acid, hydrochloric acid and phosphoric acid, and the concentration is 0.1-0.2mol/L; the solid-to-liquid ratio of the acid is 1 (2-6).
3. The method for preparing ferric phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the roasting temperature in the step 3) is 350-600 ℃ and the roasting time is 2-5h.
4. The method for preparing ferric phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the solution A in the step 4) is heated to 50-90 ℃ before the pH is adjusted.
5. The method for preparing ferric phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein in the step 4), the alkali is at least one of alkali metal hydroxide, alkali metal carbonate solution and ammonia water.
6. The method for preparing ferric phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the oxidant in the step 4) is at least one of chlorate, peroxide, oxygen and ozone; the addition amount of the oxidant is 1-2 times of the amount of the iron substances in the feed liquid.
7. The method for preparing ferric phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the high-temperature calcination temperature in the step 4) is 500-800 ℃ and the calcination time is 2-5h.
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