CN115784188A - Method for recycling and preparing battery-grade iron phosphate - Google Patents
Method for recycling and preparing battery-grade iron phosphate Download PDFInfo
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- CN115784188A CN115784188A CN202310075000.7A CN202310075000A CN115784188A CN 115784188 A CN115784188 A CN 115784188A CN 202310075000 A CN202310075000 A CN 202310075000A CN 115784188 A CN115784188 A CN 115784188A
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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 76
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000706 filtrate Substances 0.000 claims abstract description 39
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 13
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 238000004537 pulping Methods 0.000 claims abstract description 5
- 238000010405 reoxidation reaction Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 iron phosphorus ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- IYTVWFLTBYCNAD-UHFFFAOYSA-K O.O.O.O.O.O.O.[Fe+3].[O-]P([O-])([O-])=O Chemical compound O.O.O.O.O.O.O.[Fe+3].[O-]P([O-])([O-])=O IYTVWFLTBYCNAD-UHFFFAOYSA-K 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000010406 cathode material 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
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- 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
Abstract
The invention provides a method for recycling and preparing battery-grade iron phosphate, which comprises the following steps: (1) leaching: mixing the high-content ferric phosphate anode waste with water, acid and an oxidant, heating, stirring to fully react, filtering, and collecting filtrate as leachate. (2) precipitation: adding a precipitator into the leaching solution obtained in the step (1), carrying out liquid-solid separation after reaction, and collecting a filter cake. (3) reduction: adding water into the filter cake for pulping, adding a reducing agent into the filter cake for adding Fe 3+ Reduction to Fe 2+ . (4) removing impurities: and (4) adding an alkaline solution into the solution obtained in the step (3) to adjust the pH value, stirring to fully react, filtering, and collecting a filtrate, wherein the filtrate is an iron-rich filtrate. (5) reoxidation: adding oxidant into the iron-rich filtrate to obtain Fe 2+ Oxidation to Fe 3+ And obtaining the iron phosphate slurry. (6) preparing iron phosphate: adding phosphoric acid into the iron phosphate slurry obtained in the step (5), and heatingAnd after full reaction, washing, drying and calcining to obtain the battery-grade iron phosphate.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a method for recycling and preparing battery-grade iron phosphate.
Background
With the development and upgrade of electric vehicles and various electric vehicles, the usage of secondary batteries becomes larger and larger, and if a large amount of waste secondary batteries cannot be safely disposed and utilized, the waste of resources and serious environmental pollution problems can be caused. Therefore, the method has double meanings of economic value and social benefit for effectively recycling and reusing the waste batteries.
Patent CN108899601B proposes a method for recovering lithium and iron from lithium iron phosphate, wherein the method for purifying iron phosphate is to dissolve the slag of lithium iron phosphate with acid and add an oxidant, filter to obtain iron phosphate slag, add phosphoric acid to convert after calcining, and then prepare anhydrous iron phosphate through washing and calcining. The raw material lithium iron phosphate slag contains aluminum and copper with different degrees, and is an important element influencing the quality of the iron phosphate.
The patent CN 1116447B provides a method for recovering iron phosphate from iron phosphorus slag after lithium extraction of a lithium iron phosphate battery, the method comprises the steps of mixing the iron phosphorus slag after lithium extraction of the lithium iron phosphate battery with water, carrying out size mixing, reacting with acid, carrying out liquid-solid separation to obtain leachate containing iron phosphorus ions, carrying out iron addition displacement copper removal and resin aluminum removal to obtain purified liquid, adding iron phosphate heptahydrate and phosphoric acid to adjust the phosphorus-iron ratio to obtain a certain P: fe synthetic stock solution, adding hydrogen peroxide and ammonia water, adjusting pH to obtain iron phosphate precursor precipitate, and carrying out aftertreatment to obtain a battery-grade iron phosphate precursor product. According to the method, impurities are removed aiming at Al and Cu elements, but the Al and the Cu need to be removed respectively, and ion exchange resin needs to be additionally added as an adsorbent, so that the process flow is complex, and the cost is increased.
Disclosure of Invention
Therefore, the invention provides a method for recycling and preparing battery-grade iron phosphate, which comprises the following steps: (1) leaching: mixing the high-content ferric phosphate anode waste with water, acid and an oxidant, heating, stirring to fully react, filtering, and collecting filtrate, wherein the filtrate is leachate.
(2) And precipitation: and (2) adding a precipitator into the leachate obtained in the step (1), carrying out full reaction, carrying out liquid-solid separation, and collecting a filter cake.
(3) And reduction: adding water into the filter cake for pulping, adding a reducing agent for full reaction, and adding Fe 3+ Reduction to Fe 2+ 。
(4) And removing impurities: and (3) adding an alkaline solution into the solution obtained in the step (3) to adjust the pH, stirring to fully react, filtering, and collecting a filtrate, wherein the filtrate is an iron-rich filtrate.
(5) Reoxidation: adding the oxidant into the iron-rich filtrate for full reaction, and adding Fe again 2+ Oxidation to Fe 3+ And obtaining the iron phosphate slurry.
(6) Preparing battery-grade iron phosphate: and (4) adding phosphoric acid into the iron phosphate slurry obtained in the step (5), heating, fully reacting, washing with water, drying, and calcining to obtain the battery-grade iron phosphate.
Preferably, in the step (1), the acid for leaching is a mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid and acetic acid, and the liquid-solid ratio of the mixture of the high-content ferric phosphate positive electrode waste, the water, the acid and the oxidant is 1 to 5:1, the using amount of the acid is 120-180 wt%.
Preferably, the oxidant in the step (1) or (5) is one of hydrogen peroxide, peroxyacetic acid and ammonium persulfate, and the addition amount of the oxidant is 120-180 wt%.
Preferably, in the step (1) or (5), the oxidant is added in a slow dropwise manner, and after the addition is finished, the mixture is stirred and reacts for 0.5 to 2h.
Preferably, in the step (2), the precipitant is one of a sodium hydroxide solution, ammonia water and a potassium hydroxide solution, and the precipitant adjusts the pH to 1.5 to 3.5.
Preferably, the battery-grade iron phosphate is recovered from lithium iron phosphate, and in the step (2), after the liquid-solid separation, a filtrate is collected in addition to the filter cake, and the filtrate is a lithium-rich filtrate, and the lithium-rich filtrate can be used for further extracting lithium.
Preferably, in the step (3), the reducing agent is sodium persulfate or iron powder, and the adding amount of the reducing agent is 110-150 wt%.
Preferably, in step (4), the pH is adjusted to be greater than 3.7.
Preferably, in the step (6), the phosphoric acid is added in an amount of 5 wt% to 10wt%.
Preferably, in the step (6), the mixture is heated to 85 to 100 ℃, and the reaction is carried out for 1 to 2h under the condition of heat preservation, wherein the calcining temperature is 500 to 700 ℃.
In the process of recycling the iron phosphate, the Fe is firstly leached in the pickling process 2+ Oxidation to Fe 3+ Then Fe is added by adding a precipitant 3+ 、Al 3+ 、Cu 2+ All precipitate out, then Fe 3+ Reduction to Fe 2+ Adjusting pH to Al 3+ 、Cu 2+ Removed in the form of a precipitate, followed by removal of Fe 2+ Reoxidizing to Fe 3+ And forming iron phosphate precipitate to finally obtain the battery-grade iron phosphate. Wherein, al and Cu can be removed synchronously without adding an adsorbent additionally, and the cost is low.
Drawings
FIG. 1 is a schematic process flow diagram according to an embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The method for recycling and preparing the battery-grade iron phosphate is suitable for recycling and treating battery cathode waste with high content of iron phosphate, such as recycling and treating cathode materials such as lithium iron phosphate, lithium manganese iron phosphate, sodium iron phosphate and the like, and comprises the steps (1) to (6), which are specifically stated below.
Step (1), leaching: mixing the high-content ferric phosphate anode waste with water, acid and an oxidant, heating, stirring to fully react, filtering, and collecting filtrate, wherein the filtrate is leachate.
Wherein the acid used for leaching in the step (1) is one or a mixture of sulfuric acid, hydrochloric acid, nitric acid and acetic acid, and the liquid-solid ratio of the mixture of the high-content ferric phosphate positive electrode waste, water, acid and an oxidant is 1 to 5:1. the using amount of the acid is 120-180 wt%, that is, the mass ratio of the total mass of the high-content ferric phosphate cathode waste, water and the oxidant to the acid is 1:1.2 to 1.8. After uniform mixing, heating to 60 to 90 ℃, and stirring for reaction for 0.5 to 3h. Oxidant for using Fe in high-content anode waste of ferric phosphate 2+ Oxidation to Fe 3+ So that the iron ions can be better leached and better precipitated in the later steps.
In the step (1), the oxidant is added in a slow dropwise manner, and after the oxidant is added, the mixture is stirred and reacts for 0.5 to 2h.
The oxidant is one of hydrogen peroxide, peroxyacetic acid and ammonium persulfate, and the addition amount of the oxidant is 120-180 wt%, namely the mass ratio of the total mass of the high-content ferric phosphate cathode waste, water and acid to the oxidant is 1:1.2 to 1.8.
And (2) precipitating: and (2) adding a precipitator into the leachate obtained in the step (1), carrying out full reaction, carrying out liquid-solid separation, and collecting a filter cake.
Fe in step (2) 3+ And impurities such as Al, cu and the like are precipitated in the form of iron phosphate, and are also precipitated together with the iron phosphate in the form of compounds. Wherein the precipitant is one of sodium hydroxide solution, ammonia water and potassium hydroxide solution. The precipitator can adjust the pH to 1.5-3.5, preferably to 2.0-2.5, so that the iron phosphate is better precipitated, and the obtained filter cake mainly contains the iron phosphate and a small amount of precipitates of impurities such as Al, cu and the like. When the battery-grade iron phosphate is recovered and prepared from the lithium iron phosphate, after solid-liquid separation, collecting a filter cake and also collecting a filtrate, wherein the filtrate is a lithium-rich filtrate, and the lithium-rich filtrate can be used for further extracting lithium to prepare lithium carbonate.
Step (3)) Reduction: adding water into the filter cake for pulping, adding a reducing agent for full reaction, and adding Fe 3+ Reduction to Fe 2+ 。
The reducing agent is sodium persulfate or iron powder, the adding amount of the reducing agent is 110-150 wt%, namely the mass ratio of the beaten filter cake to the reducing agent is 1:1.1 to 1.5. Before adding the reducing agent, the pH value can be adjusted to 0.8 to 2.5, preferably 1.0 to 2.0. An acidic solution, such as a mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, may be added to adjust the pH to better dissolve the precipitate for better reduction of the iron 3.
And (4) removing impurities: and (4) adding an alkaline solution into the solution obtained in the step (3) to adjust the pH value, stirring the solution to fully react, filtering the solution, and collecting filtrate, wherein the filtrate is iron-rich filtrate.
The alkaline solution in the step (4) and the precipitant in the step (2) can be the same solvent, and the pH is adjusted to be more than 3.7, preferably between 3.7 and 5.0. Wherein, the pH value is too low, and the impurity precipitation is incomplete, so that the impurity removal is incomplete; the pH is too high, which, although it is possible to ensure thorough removal of the impurities, will lose a part of the iron.
And (5) reoxidation: adding the oxidant into the iron-rich filtrate for full reaction, and adding Fe again 2+ Oxidation to Fe 3+ And obtaining the iron phosphate slurry.
Step (5) adopts an oxidation mode similar to that of step (1).
Step (6), preparing iron phosphate: and (4) adding phosphoric acid into the iron phosphate slurry obtained in the step (5), heating, fully reacting, washing with water, drying, and calcining to obtain the battery-grade iron phosphate.
In the step (6), the phosphoric acid is added in an amount of 5 wt% to 10wt%, that is, the mass ratio of the iron phosphate slurry to the phosphoric acid is 1: and (3) 0.05 to 0.1, adding phosphoric acid to carry out an aging reaction of the iron phosphate so as to promote the crystal form conversion of the iron phosphate. Heating to 85-100 ℃, and reacting for 1-2h under the condition of heat preservation, wherein the calcining temperature is 500-700 ℃.
The process flow in the embodiment of the invention is schematically shown in fig. 1.
For a further understanding of the present invention, preferred embodiments of the present invention are described below with reference to the following examples. In this embodiment, the preparation of battery-grade iron phosphate recovered from lithium iron phosphate is taken as an example.
Example 1
(1) Leaching: mixing the lithium iron phosphate powder with water, dilute sulfuric acid and hydrogen peroxide, and stirring and reacting for 1h at 75 ℃; wherein the liquid-solid ratio is 2; and after the reaction is finished, filtering, and collecting leaching filtrate.
(2) And (3) precipitation: adding sodium hydroxide solution as precipitant, regulating pH to 2.5, and oxidizing in step (1) to obtain Fe 3+ Precipitating in the form of ferric phosphate, precipitating impurities such as Al, cu and the like together with the ferric phosphate in the form of compounds, reacting for 1h, filtering after the reaction is finished, and taking filtrate as a lithium-rich solution for subsequent lithium extraction to prepare lithium carbonate; and the filter cake is used for recovering and preparing the battery-grade iron phosphate.
(3) Reduction: adding water into the filter cake for pulping, adjusting the liquid-solid ratio to be 5, adjusting the pH value to be 2.0, adding sodium persulfate, wherein the addition of the sodium persulfate is 120wt% of the theoretical addition, and reducing Fe 3+ Is Fe 2+ The reaction was stirred for 2h.
(4) Removing impurities: and (4) adding a sodium hydroxide solution into the solution obtained in the step (3), adjusting the pH value of the slurry to be 4.5, stirring for reaction for 1 hour, filtering, and collecting an iron-rich filtrate.
(5) Reoxidation (reprecipitation): and (5) adding hydrogen peroxide diluted by pure water into the filtrate obtained in the step (4) dropwise slowly, immediately combining oxidized ferric iron with phosphate radicals in the solution to generate iron phosphate precipitate, and stirring and reacting for 1 hour after the addition is finished.
(6) Preparing anhydrous iron phosphate: and (3) adding 7wt% of phosphoric acid into the slurry obtained in the step (5), heating to 98 ℃, preserving heat, reacting for 2 hours, filtering after the reaction is finished, washing with water, drying, and calcining at 600 ℃ to obtain the battery-grade anhydrous iron phosphate.
The index results of the iron phosphate prepared by the method are shown in table 1, and as can be seen from table 1, the iron phosphate prepared by the embodiment of the invention has an Al content of less than 50ppm and a Cu content of less than 20ppm, and the specific surface, the median diameter D50, the tap density and the water content of the iron phosphate reach a battery level.
TABLE 1
The method for recycling and preparing the battery-grade iron phosphate has the following advantages: 1. the recovery rate of the ferric phosphate is high. 2. The Al, cu and other impurities are removed effectively, and the prepared iron phosphate material has high purity and narrow particle size distribution. 3. The recovery process flow is simple, the production cost is low, and the environment is friendly.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The method for recycling and preparing the battery-grade iron phosphate is characterized by comprising the following steps of:
(1) Leaching: mixing the high-content ferric phosphate positive electrode waste with water, acid and an oxidant, heating, stirring to fully react, filtering, and collecting filtrate, wherein the filtrate is leachate;
(2) And precipitating: adding a precipitator into the leachate obtained in the step (1), carrying out liquid-solid separation after full reaction, and collecting a filter cake;
(3) And reduction: adding water into the filter cake for pulping, adding a reducing agent for full reaction, and adding Fe 3+ Reduction to Fe 2+ ；
(4) And removing impurities: adding an alkaline solution into the solution obtained in the step (3) to adjust the pH value, stirring the solution to fully react, filtering the solution, and collecting filtrate, wherein the filtrate is iron-rich filtrate;
(5) Reoxidation: adding the oxidant into the iron-rich filtrate for full reaction, and adding Fe again 2+ Oxidation to Fe 3+ Obtaining iron phosphate slurry;
(6) And preparing iron phosphate: and (4) adding phosphoric acid into the iron phosphate slurry obtained in the step (5), heating, fully reacting, washing with water, drying, and calcining to obtain the battery-grade iron phosphate.
2. The method for recycling and preparing battery-grade iron phosphate according to claim 1, wherein in the step (1), the acid for leaching is one or more of sulfuric acid, hydrochloric acid, nitric acid and acetic acid, and the liquid-solid ratio of the mixture of the high-content positive electrode waste of iron phosphate, the water, the acid and the oxidant is 1-5: 1, the using amount of the acid is 120-180 wt%.
3. The method for recycling and preparing battery-grade iron phosphate according to claim 1, wherein the oxidant in step (1) or (5) is one of hydrogen peroxide, peroxyacetic acid and ammonium persulfate, and the addition amount of the oxidant is 120-180 wt%.
4. The method for recycling and preparing battery-grade iron phosphate according to claim 3, wherein in the step (1) or (5), the oxidant is added in a slowly dropwise manner, and after the addition is finished, the mixture is stirred and reacted for 0.5 to 2h.
5. The method for recycling and preparing battery-grade iron phosphate according to claim 1, wherein in the step (2), the precipitant is one of sodium hydroxide solution, ammonia water and potassium hydroxide solution, and the precipitant adjusts the pH to 1.5 to 3.5.
6. The method for recycling battery-grade iron phosphate according to claim 1, wherein the battery-grade iron phosphate is recycled from lithium iron phosphate, and in the step (2), after the liquid-solid separation, a filtrate is collected in addition to the filter cake, wherein the filtrate is a lithium-rich filtrate, and the lithium-rich filtrate can be used for further extracting lithium.
7. The method for recycling battery grade ferric phosphate as claimed in claim 1, wherein in the step (3), the reducing agent is sodium persulfate or iron powder, and the addition amount of the reducing agent is 110wt% to 150wt%.
8. The method for recycling battery grade iron phosphate according to claim 1, wherein in step (4), the pH is adjusted to be greater than 3.7.
9. The method for recycling and preparing battery-grade iron phosphate according to claim 1, wherein in the step (6), the phosphoric acid is added in an amount of 5 wt% to 10wt%.
10. The method for recycling and preparing the battery-grade iron phosphate according to claim 1, wherein in the step (6), the mixture is heated to 85-100 ℃, and is subjected to heat preservation reaction for 1-2h, and the calcining temperature is 500-700 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116864851A (en) * | 2023-09-05 | 2023-10-10 | 赣州市力道新能源有限公司 | Process for deeply removing phosphorus from retired battery recovery feed liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584901A (en) * | 2018-05-30 | 2018-09-28 | 重庆太锦环保科技有限公司 | A method of recycling ceramic grade ferric phosphate from more metal hazardous wastes |
| CN112331949A (en) * | 2020-11-12 | 2021-02-05 | 郑州中科新兴产业技术研究院 | Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584901A (en) * | 2018-05-30 | 2018-09-28 | 重庆太锦环保科技有限公司 | A method of recycling ceramic grade ferric phosphate from more metal hazardous wastes |
| CN112331949A (en) * | 2020-11-12 | 2021-02-05 | 郑州中科新兴产业技术研究院 | Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116864851A (en) * | 2023-09-05 | 2023-10-10 | 赣州市力道新能源有限公司 | Process for deeply removing phosphorus from retired battery recovery feed liquid |
| CN116864851B (en) * | 2023-09-05 | 2023-11-21 | 赣州市力道新能源有限公司 | Process for deeply removing phosphorus from retired battery recovery feed liquid |
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