CN115448279B - Method for preparing battery grade ferric phosphate material by recycling lithium-extracted ferrophosphorus slag - Google Patents
Method for preparing battery grade ferric phosphate material by recycling lithium-extracted ferrophosphorus slag Download PDFInfo
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- CN115448279B CN115448279B CN202211312361.0A CN202211312361A CN115448279B CN 115448279 B CN115448279 B CN 115448279B CN 202211312361 A CN202211312361 A CN 202211312361A CN 115448279 B CN115448279 B CN 115448279B
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- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 75
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 75
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 75
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 72
- 239000002893 slag Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- 235000021110 pickles Nutrition 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000002244 precipitate Substances 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 16
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000010790 dilution Methods 0.000 claims abstract description 7
- 239000012895 dilution Substances 0.000 claims abstract description 7
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 7
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000001630 malic acid Substances 0.000 claims description 14
- 235000011090 malic acid Nutrition 0.000 claims description 14
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- -1 dihydrate ferric phosphate Chemical class 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229940116007 ferrous phosphate Drugs 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 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
-
- 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)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for preparing a battery-grade ferric phosphate material by recycling ferrophosphorus slag after lithium extraction, and relates to the technical field of resource recycling of waste lithium iron phosphate batteries. The method comprises the steps of adding concentrated sulfuric acid into the ferrophosphorus slag after lithium extraction after pulp mixing, adding iron powder for reduction, adding complexing agent into pickle liquor, adjusting pH for impurity removal to obtain ferrous sulfate solution, adding hydrogen peroxide into the ferrous sulfate solution after filtration, adding water for dilution, precipitating ferric phosphate dihydrate at high temperature, adding phosphoric acid solution to convert entrained ferric hydroxide into ferric phosphate dihydrate, and roasting the ferric phosphate dihydrate precipitate at high temperature after filtration to remove the entrained complexing agent, so that the ferric phosphate obtained by the method can ensure higher purity and realize the recycling of ferrophosphorus slag resources.
Description
Technical Field
The invention relates to the technical field of resource recovery of waste lithium iron phosphate batteries, in particular to a method for preparing a battery-grade ferric phosphate material by recovering phosphorus iron slag after lithium extraction.
Background
Along with the development of technology, the new energy automobile is promoted in a large amount due to the environment-friendly, safe and easy-to-charge characteristics of the lithium battery, but a large amount of waste lithium batteries are generated. The lithium iron phosphate battery has the characteristics of high reliability, no toxicity and the like due to the characteristic low cost, and the share of the lithium iron phosphate battery in the power lithium battery is continuously increased. According to statistics, the output of the lithium iron phosphate battery is accumulated to 125.4GWh in 2021 for 1-12 months, the total output is 57.1%, the same ratio is accumulated to 262.9%, and the retirement amount of the lithium battery power lithium battery in 2025 is expected to exceed 134GWh due to the limited service life of the lithium battery.
In the waste lithium iron phosphate battery, the mass of the lithium iron phosphate accounts for 30-35%, and the content of metals such as Li, fe, cu and the like is far higher than that of common minerals, so that the waste lithium ion battery has extremely high resource and value, and therefore, the recovery of the waste lithium ion battery is particularly important.
At present, the recovery of the waste lithium iron phosphate battery is mainly performed by a wet process, and lithium in the waste lithium iron phosphate is mainly recovered by adding carbonate after leaching to form high-value lithium carbonate. The treatment of the ferrophosphorus slag is to form phosphate fertilizer and iron oxide red or directly discard the ferrophosphorus slag, and the present method has reports on regenerated ferric phosphate, but the related process has the problems of low purity, poor applicability and the like of the generated ferric phosphate. Therefore, development of a green and efficient recycling technology for ferrophosphorus slag is imperative.
At present, a small amount of technology relates to regenerated ferric phosphate, such as CN114394581A and CN112551498A, wherein CN114394581A is characterized in that acid is used for obtaining a ferric phosphate solution by using iron in pyrite through a complexing agent and a phosphoric acid solution, and ferric phosphate dihydrate precipitate is obtained after dilution. While CN112551498A is prepared by adding alkali liquor to keep phosphate radicals in filtrate, adding acid liquor to regulate pH, and adding phosphoric acid solution to obtain battery grade ferric phosphate, wherein the pH value is regulated to 8-10, and the generated ferric phosphate still contains a large amount of aluminum ions.
Disclosure of Invention
The invention aims to provide a method for preparing a battery grade ferric phosphate material by recycling lithium-extracted ferrophosphorus slag, which mainly aims to reduce impurity ions carried in the current ferric phosphate regeneration and improve the purity of the recycled ferric phosphate.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for preparing a battery grade ferric phosphate material by recycling ferrophosphorus slag after lithium extraction, comprising the following steps:
(1) Mixing the ferrophosphorus slag after lithium extraction, and adding concentrated sulfuric acid to obtain a first pickle liquor;
(2) Adding iron powder into the first pickle liquor for reduction to obtain a second pickle liquor; reducing ferric iron in the slurry into ferrous iron by using iron powder, filtering after the reaction is finished, and recycling excessive iron powder;
(3) Adding a complexing agent into the second pickle liquor; adding a complexing agent to prevent ferrous phosphate from generating when the pH value is subsequently increased;
(4) Adding alkali liquor to adjust pH, removing impurities, and filtering to obtain ferrous sulfate solution;
(5) Adding hydrogen peroxide into the ferrous sulfate solution, adding water for dilution, and precipitating ferric phosphate dihydrate at high temperature to obtain ferric phosphate dihydrate precipitate 1;
(6) Adding a phosphoric acid solution to convert ferric hydroxide carried in the ferric phosphate dihydrate precipitate 1 into ferric phosphate dihydrate, and filtering to obtain a ferric phosphate dihydrate precipitate 2;
(7) Roasting the dihydrate ferric phosphate precipitate 2 at high temperature, and removing complexing agent carried in the precipitation to obtain the battery grade dihydrate ferric phosphate.
The further technical proposal is that the solid-liquid ratio in the step (1) is 1:2-5, the molar quantity of the concentrated sulfuric acid is 0.5-2 times of the molar quantity of iron in the ferrophosphorus slag, the leaching temperature is 50-80 ℃, and the leaching time is 0.5-3 h.
The further technical proposal is that the iron usage amount in the step (2) is 1-2 times of the mole amount of iron in the ferrophosphorus slag, and the reaction time is 10-60 min.
The further technical scheme is that in the step (3), the complexing agent is selected from one or more of malic acid, dicarboxylic acid and oxalic acid, and the added molar quantity of the complexing agent is 0.5-2 times of the molar quantity of iron in the second pickle liquor.
The further technical proposal is that the alkali liquor in the step (4) is selected from one or more of sodium hydroxide, lithium hydroxide and sodium carbonate, and the pH value is adjusted to be 3-6.
The further technical proposal is that the molar quantity of hydrogen peroxide used in the step (5) is 1-2 times of the molar quantity of iron in the ferrous sulfate solution, the mass ratio of water added in the diluted solution to the ferrous sulfate solution is 5:1-5, and the temperature is 80-100 ℃.
The reaction equation is: fe (Fe) m 3+ L n +2mH 2 O+mPO 4 3- →m(FePO 4 ·2H 2 O)↓+nL
The further technical proposal is that the molar quantity of phosphoric acid used in the step (6) is 5 to 10 percent of the molar quantity of iron in the ferric phosphate dihydrate sediment 1.
The further technical proposal is that the high temperature roasting temperature in the step (7) is 200-600 ℃, and the roasting time is 3-7 hours.
Compared with the prior art, the invention has the following technical effects:
according to the invention, iron powder and a complexing agent are added into the ferrophosphorus slag pickle liquor, so that the generation of ferrous phosphate or ferric hydroxide during the impurity removal at the elevated pH is inhibited, and the loss of phosphate radical and iron ion during the impurity removal is reduced. The complexing agent mixed in the dihydrate ferric phosphate during aging treatment is removed through roasting, so that the purity of the ferric phosphate is further improved. The method has good applicability to raw materials, consumes less acid liquor compared with the traditional method for recycling the ferrophosphorus slag to generate ferric phosphate, and simultaneously increases the purity and the recycling rate of the ferric phosphate.
Drawings
FIG. 1 is a flow chart of the process for regenerating ferrophosphorus slag into ferric phosphate after lithium extraction.
Detailed Description
The invention is further illustrated and described below with reference to examples.
Example 1
A method for regenerating ferrophosphorus slag into ferric phosphate after lithium extraction, the method comprising the steps of
(1) Mixing the lithium-extracted ferrophosphorus slag with pure water according to a solid-to-liquid ratio of 1:4, adding concentrated sulfuric acid into the slurry, wherein the molar quantity of the concentrated sulfuric acid is 1.5 times that of iron in the ferrophosphorus slag, the temperature is 65 ℃, and the leaching time is 1h, so as to obtain pickle liquor 1;
(2) Adding iron powder into the pickle liquor 1, wherein the use amount of the iron powder is 1.2 times of the molar amount of iron in the ferrophosphorus slag, filtering after the reaction is finished to obtain pickle liquor 2, and the reaction temperature is 65 ℃ and the reaction time is 20min;
(3) Adding oxalic acid into the pickle liquor 2 to generate ferrous oxalate complex, wherein the use amount of the oxalic acid is 1.1 times of the molar amount of iron in the pickle liquor 2;
(4) Adding sodium hydroxide solution into the pickle liquor 2 added with oxalic acid to adjust the pH value to remove impurities from the pickle liquor 2, adjusting the pH value to 4.0, and filtering to obtain ferrous sulfate solution;
(5) Adding hydrogen peroxide into the ferrous sulfate solution, wherein the molar quantity of the hydrogen peroxide is 1.2 times of that of iron in the ferrous sulfate solution, adding water for dilution, and aging at 90 ℃ to precipitate ferric phosphate dihydrate, and filtering to obtain ferric phosphate dihydrate precipitate 1;
(6) Adding phosphoric acid solution into the ferric phosphate dihydrate precipitate 1, wherein the phosphoric acid consumption is 7% of the molar amount of iron in the ferric phosphate dihydrate precipitate, so that entrained ferric hydroxide is converted into ferric phosphate dihydrate, and filtering to obtain ferric phosphate dihydrate precipitate 2;
(7) Roasting the ferric phosphate dihydrate precipitate 2 at 300 ℃ for 5 hours, and removing oxalic acid entrained during precipitation to obtain the battery grade ferric phosphate dihydrate. The composition of the ferric phosphate dihydrate is shown in table 1.
Example 2
(1) Mixing the lithium-extracted ferrophosphorus slag with pure water according to a solid-to-liquid ratio of 1:5, adding concentrated sulfuric acid into the slurry, wherein the molar quantity of the concentrated sulfuric acid is 1.3 times that of iron in the ferrophosphorus slag, the temperature is 70 ℃, and the leaching time is 0.8h, so as to obtain pickle liquor 1;
(2) Adding iron powder into the pickle liquor 1, wherein the use amount of the iron powder is 1.3 times of the molar amount of iron in the ferrophosphorus slag, filtering after the reaction is finished to obtain pickle liquor 2, and the reaction temperature is 65 ℃ and the reaction time is 20min;
(3) Adding malic acid into the pickle liquor 2 to generate a malic acid iron complex, wherein the using amount of the malic acid is 1.7 times of the iron molar amount in the pickle liquor 2;
(4) Adding sodium hydroxide solution into the pickle liquor 2 added with malic acid to adjust the pH value to remove impurities from the pickle liquor 2, adjusting the pH value to 3.7, and filtering to obtain ferrous sulfate solution;
(5) Adding hydrogen peroxide into the ferrous sulfate solution, wherein the molar quantity of the hydrogen peroxide is 1.4 times of the molar quantity of iron in the ferrous sulfate solution, adding water for dilution, and aging at 90 ℃ to precipitate ferric phosphate dihydrate, and filtering to obtain ferric phosphate dihydrate precipitate 1;
(6) Adding phosphoric acid solution into the ferric phosphate dihydrate precipitate 1, wherein the phosphoric acid consumption is 7% of the molar amount of iron in the ferric phosphate dihydrate precipitate, so that entrained ferric hydroxide is converted into ferric phosphate dihydrate, and filtering to obtain ferric phosphate dihydrate precipitate 2;
(7) Roasting the ferric phosphate dihydrate precipitate 2 at 500 ℃ for 5 hours, and removing malic acid entrained during precipitation to obtain the battery grade ferric phosphate dihydrate. The composition of the ferric phosphate dihydrate is shown in table 1.
Comparative example 1
Comparative example 1 the procedure for preparing ferric phosphate dihydrate is as follows
(1) Mixing ferrophosphorus slag according to a solid-to-liquid ratio of 1:5, adding concentrated sulfuric acid, wherein the molar quantity of the concentrated sulfuric acid used is 1.3 times of that of iron in the ferrophosphorus slag, the temperature is 70 ℃, and the leaching time is 0.8h, so as to obtain pickle liquor 1;
(2) Adding liquid alkali into the pickle liquor 1 to adjust the pH value to 1.6, reacting for 1h at the temperature of 70 ℃, and filtering the precipitate to obtain the ferric phosphate dihydrate precipitate. The composition of the ferric phosphate dihydrate is shown in table 1.
Comparative example 2
Comparative example 2 the procedure for preparing ferric phosphate dihydrate is as follows:
(1) Mixing the lithium-extracted ferrophosphorus slag with pure water according to a solid-to-liquid ratio of 1:5, adding concentrated sulfuric acid into the slurry, wherein the molar quantity of the concentrated sulfuric acid is 1.3 times that of iron in the ferrophosphorus slag, the temperature is 70 ℃, and the leaching time is 0.8h, so as to obtain pickle liquor 1;
(2) Adding iron powder into the pickle liquor 1, wherein the use amount of the iron powder is 1.3 times of the molar amount of iron in the ferrophosphorus slag, filtering after the reaction is finished to obtain pickle liquor 2, and the reaction temperature is 65 ℃ and the reaction time is 20min;
(3) Adding malic acid into the pickle liquor 2 to generate a malic acid iron complex, wherein the using amount of the malic acid is 1.7 times of the iron molar amount in the pickle liquor 2;
(4) Adding hydrogen peroxide into the pickle liquor 2 after the malic acid is added, wherein the molar quantity of the hydrogen peroxide is 1.4 times of the molar quantity of iron in the pickle liquor 2 after the malic acid is added, adding water for dilution, the mass ratio of water to the pickle liquor 2 after the malic acid is added is 3:1, aging at 90 ℃ to precipitate ferric phosphate dihydrate, and filtering to obtain ferric phosphate dihydrate precipitate 1;
(5) Adding phosphoric acid solution into the ferric phosphate dihydrate precipitate 1, wherein the phosphoric acid consumption is 7% of the molar amount of iron in the ferric phosphate dihydrate precipitate, so that entrained ferric hydroxide is converted into ferric phosphate dihydrate, and filtering to obtain ferric phosphate dihydrate precipitate 2;
(6) Roasting the ferric phosphate dihydrate precipitate 2 at 500 ℃ for 5 hours, and removing malic acid entrained during precipitation to obtain the battery grade ferric phosphate dihydrate. The composition of the ferric phosphate dihydrate is shown in table 1.
The iron phosphate dihydrate components prepared in examples 1 and 2 and comparative examples 1 and 2 are shown in table 1, wherein the iron and phosphorus contents and the ratio of the iron and phosphorus in examples 1 and 2 are relatively high, and aluminum in the products is much lower than that in comparative examples 1 and 2, which indicates that the iron phosphate dihydrate prepared in the examples of the application has high purity and meets the requirements.
TABLE 1 composition table of iron phosphate synthesized
Although the invention has been described herein with reference to the above-described illustrative embodiments thereof, the above-described embodiments are merely preferred embodiments of the present invention, and the embodiments of the present invention are not limited by the above-described embodiments, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure.
Claims (5)
1. The method for preparing the battery grade ferric phosphate material by recycling the lithium-extracted ferrophosphorus slag is characterized by comprising the following steps of:
(1) Mixing the ferrophosphorus slag after lithium extraction, and adding concentrated sulfuric acid to obtain a first pickle liquor; the solid-liquid ratio in the step (1) is 1:2-5, the molar quantity of the concentrated sulfuric acid is 0.5-2 times of the molar quantity of iron in the ferrophosphorus slag, the leaching temperature is 50-80 ℃, and the leaching time is 0.5-3 h;
(2) Adding iron powder into the first pickle liquor for reduction to obtain a second pickle liquor; the iron usage amount in the step (2) is 1-2 times of the iron mole amount in the ferrophosphorus slag, and the reaction time is 10-60 min;
(3) Adding a complexing agent into the second pickle liquor; in the step (3), the complexing agent is selected from one or more of malic acid, dicarboxylic acid and oxalic acid, and the added molar quantity of the complexing agent is 0.5-2 times of the molar quantity of iron in the second pickle liquor;
(4) Adding alkali liquor to adjust pH, removing impurities, and filtering to obtain ferrous sulfate solution;
(5) Adding hydrogen peroxide into the ferrous sulfate solution, adding water for dilution, and precipitating ferric phosphate dihydrate at high temperature to obtain ferric phosphate dihydrate precipitate 1;
(6) Adding a phosphoric acid solution to convert ferric hydroxide carried in the ferric phosphate dihydrate precipitate 1 into ferric phosphate dihydrate, and filtering to obtain a ferric phosphate dihydrate precipitate 2;
(7) Roasting the dihydrate ferric phosphate precipitate 2 at high temperature to obtain the battery grade dihydrate ferric phosphate.
2. The method for preparing the battery grade ferric phosphate material by recycling the lithium-extracted phosphorus iron slag, which is disclosed in claim 1, is characterized in that alkali liquor in the step (4) is selected from one or more of sodium hydroxide, lithium hydroxide and sodium carbonate, and the pH value is adjusted to be 3-6.
3. The method for preparing the battery grade ferric phosphate material by recycling the lithium-extracted ferrophosphorus slag according to claim 1, wherein the molar quantity of hydrogen peroxide used in the step (5) is 1-2 times of the molar quantity of iron in the ferrous sulfate solution, the mass ratio of water added into the diluted solution to ferrous sulfate is 5:1-5, and the temperature is 80-100 ℃.
4. The method for preparing a battery grade iron phosphate material by recycling lithium-extracted ferrophosphorus slag according to claim 1, wherein the molar amount of phosphoric acid used in the step (6) is 5-10% of the molar amount of iron in the iron phosphate dihydrate precipitate 1.
5. The method for preparing battery grade ferric phosphate dihydrate by recycling lithium-extracted ferrophosphorus slag according to claim 1, wherein the high-temperature roasting temperature in the step (7) is 200-600 ℃, and the roasting time is 3-7 hours.
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| CN112093785A (en) * | 2020-09-08 | 2020-12-18 | 北京科技大学 | Method for efficiently recycling lithium in lithium iron phosphate cathode waste and preparing iron phosphate for battery |
| CN112661129A (en) * | 2021-01-27 | 2021-04-16 | 四川大学 | Preparation method of iron phosphate |
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| WO2022127323A1 (en) * | 2020-12-15 | 2022-06-23 | 广东邦普循环科技有限公司 | Battery-grade iron phosphate, preparation method therefor, and application thereof |
| CN114988381A (en) * | 2022-05-25 | 2022-09-02 | 赣州赛可韦尔科技有限公司 | Method for preparing iron phosphate by using waste lithium iron phosphate battery |
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| CN112093785A (en) * | 2020-09-08 | 2020-12-18 | 北京科技大学 | Method for efficiently recycling lithium in lithium iron phosphate cathode waste and preparing iron phosphate for battery |
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