CN114597530B - Recovery method of phosphate positive electrode material - Google Patents
Recovery method of phosphate positive electrode material Download PDFInfo
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- CN114597530B CN114597530B CN202210211892.4A CN202210211892A CN114597530B CN 114597530 B CN114597530 B CN 114597530B CN 202210211892 A CN202210211892 A CN 202210211892A CN 114597530 B CN114597530 B CN 114597530B
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- ion exchange
- filtrate
- exchange medium
- lithium
- acid
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 39
- 239000010452 phosphate Substances 0.000 title claims abstract description 38
- 238000011084 recovery Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 28
- 238000005342 ion exchange Methods 0.000 claims abstract description 76
- 239000000706 filtrate Substances 0.000 claims abstract description 67
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000007787 solid Substances 0.000 claims abstract description 46
- 239000002002 slurry Substances 0.000 claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011574 phosphorus Substances 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000002378 acidificating effect Effects 0.000 claims abstract description 22
- 239000010405 anode material Substances 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000003456 ion exchange resin Substances 0.000 claims description 20
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 20
- 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 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 230000001172 regenerating effect Effects 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011973 solid acid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 25
- 238000002386 leaching Methods 0.000 abstract description 20
- 239000000047 product Substances 0.000 abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 78
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 63
- 229910052742 iron Inorganic materials 0.000 description 33
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 21
- 238000000498 ball milling Methods 0.000 description 18
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 16
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical group [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 7
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010926 waste battery Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000001994 activation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RZSRVBMQQGDAIS-UHFFFAOYSA-K potassium;iron(2+);phosphate Chemical compound [K+].[Fe+2].[O-]P([O-])([O-])=O RZSRVBMQQGDAIS-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 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
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B25/18—Phosphoric acid
-
- 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
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
-
- 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a recovery method of a phosphate positive electrode material, which comprises the following steps: s1) mixing a phosphate anode material with a solvent to obtain slurry; the solvent is water and/or the filtrate in the step S2); s2) mixing the slurry with a solid acidic ion exchange medium, and filtering after reaction to obtain filtrate and insoluble solids; S3A) repeating the step S1) by taking the filtrate as a solvent until the phosphorus content in the filtrate reaches 100-500 g/L, and treating the filtrate by a solid acidic ion exchange medium to obtain phosphoric acid. Compared with the prior art, the invention adopts the recyclable solid acidic ion exchange medium to replace the traditional liquid acid, realizes the efficient simultaneous leaching of metal ions in the waste phosphate anode material, realizes the separation of phosphorus and metal ions, and can obtain the high-concentration pure phosphoric acid solution with high added value; the process does not use high-cost oxidants such as hydrogen peroxide, and the like, and has low process cost and high added value of products.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a recovery method of a phosphate positive electrode material.
Background
In recent years, as a lithium iron phosphate positive electrode material commonly used in an automobile power battery, the lithium iron phosphate positive electrode material has the characteristics of safety, environmental protection, long service life, high cost performance and the like, is widely applied in the fields of energy storage, electric automobiles and the like, and occupies the market output of the positive electrode material of 73% at most in 2016. Although the output of the lithium iron phosphate anode material in China is reduced in proportion to all anode materials from 2017, the output is increased year by year, and particularly the output reaches 14.2 ten thousand tons at the highest in 2020, the same proportion is increased by 40.9%, and the market scale reaches 45 hundred million yuan. However, after long-term charge and discharge cycles, the internal structure of the lithium ion battery is irreversibly changed, so that the lithium ion battery fails. A large amount of waste batteries are expected to enter the market, and the waste batteries contain residual electric energy, so that potential safety hazards exist; meanwhile, the waste batteries contain a large amount of heavy metals and organic matters, which may cause harm to the environment and related personnel. Therefore, recovery of waste power batteries is imperative.
Currently, the recovery methods of waste lithium iron phosphate batteries can be classified into pyrogenic recovery and wet recovery. The fire recovery process is simple and widely applied, but has relatively large energy consumption, wastes a large amount of reusable resources, and generates a large amount of polluting gases or substances in the production process. The wet recovery process is relatively stable, the recovery efficiency of the precious metal lithium is higher, but a large amount of liquid alkali and oxidant are consumed in the wet recovery process, the later waste liquid is required to be further treated, and the recovery cost is higher.
The Chinese patent with publication number CN109554545B discloses a method for leaching lithium iron phosphate waste by introducing strong acid, regulating the pH value of a system to 2-4, and obtaining a lithium-rich solution and ferrophosphorus slag after solid-liquid separation to realize selective leaching of lithium. The method is only aimed at recycling lithium components in lithium iron phosphate waste, and high-value recycling of iron and phosphorus components is omitted.
Chinese patent publication No. CN112331949a discloses a method of adding lithium iron phosphate powder after aluminum removal into a mixed solution of sulfuric acid and hydrogen peroxide, and heating and leaching to obtain an pickle liquor; regulating the pH value of the pickle liquor to obtain crude ferric phosphate; dissolving, precipitating and calcining crude ferric phosphate to obtain battery grade ferric phosphate; evaporating and concentrating the filtrate containing lithium, and adding an alkali solution to obtain lithium carbonate precipitate. According to the method, a large amount of oxidant (hydrogen peroxide) is introduced, so that the treatment cost of lithium iron phosphate waste is increased; although this process achieves recovery of lithium, iron and phosphorus components in lithium iron phosphate waste, the value of the phosphorus components present in the iron phosphate is severely diminished.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a recovery method of phosphate anode material, which has low process cost and high added value of products.
The invention provides a recovery method of a phosphate positive electrode material, which comprises the following steps:
s1) mixing a phosphate anode material with a solvent to obtain slurry; the solvent is water and/or the filtrate in the step S2);
s2) mixing the slurry with a solid acidic ion exchange medium, and filtering after reaction to obtain filtrate and insoluble solids;
S3A) repeating the step S1) by taking the filtrate as a solvent until the phosphorus content in the filtrate reaches 100-500 g/L, and treating the filtrate by a solid acidic ion exchange medium to obtain phosphoric acid.
Preferably, the phosphate positive electrode material is Q 1-zMaNbPO4; wherein Q is one or more of Li, na and K; m is one or more of Li, na, K, ca, al, mg, cu, F, B, ni, co, mn, ti, nb, sn, mo, W and N is one or more of Fe, mn, co, ni; -0.1.ltoreq.z.ltoreq.0.1, 0.ltoreq.a.ltoreq. 0.1,0.9.ltoreq.b.ltoreq.1;
The mass ratio of the phosphate positive electrode material to the solvent is (1-4): (1-10);
the granularity of the phosphate positive electrode material is 10 nm-1000 mu m.
Preferably, the method further comprises:
S3B) separating the insoluble solids to obtain graphite and an ion exchange medium after exchange;
Regenerating the ion exchange medium after exchange by acid, and filtering to obtain a solution containing metal ions;
the pH value of the solution containing metal ions is regulated to 6-10 for reaction, and then the solution is filtered to obtain metal precipitate and filtrate containing Q;
Roasting the metal precipitate to obtain a metal oxide;
The S3A) and the S3B) are not separated in sequence.
Preferably, the concentration of the acid is 1-5 mol/L; the acid is selected from one or more of sulfuric acid, nitric acid and hydrochloric acid;
adjusting the pH value of the solution containing the metal ions to 6-10 by using sodium hydroxide solution and/or sodium carbonate solution; the reaction time is 1-4 h;
The roasting temperature is 400-800 ℃; the roasting time is 0.5-5 h.
Preferably, when Q is Li, the step S3B) further includes:
Concentrating the filtrate containing Q, adding alkali liquor to adjust the pH value to 6-13, and adding a lithium precipitating agent under the heating condition to obtain lithium salt.
Preferably, the filtrate containing Q is concentrated to 20-40 g/L; the alkali liquor is selected from sodium hydroxide solution and/or sodium carbonate solution; the concentration of the alkali liquor is 1-3 mol/L; the heating condition is 60-100 ℃; the lithium precipitating agent is selected from carbonate or phosphate.
Preferably, the temperature of the concentration is 70-100 ℃; adding alkali liquor to regulate pH value to 8-12.
Preferably, the solid acidic ion exchange medium comprises one or more of sulfonic acid groups, carboxylic acid groups, hydroxyl groups, tertiary amine groups, and quaternary amine groups;
Preferably, the solid acidic ion exchange medium is selected from polystyrene sulfonic acid type ion exchange resins and/or polyacrylic acid sulfonic acid type ion exchange resins;
preferably, the mass ratio of the solid acidic ion exchange medium to the slurry is preferably (2 to 30): 1.
Preferably, the flow rate of the filtrate when being treated by the ion exchange medium is 0.1-20 B.V.
The invention provides a recovery method of a phosphate positive electrode material, which comprises the following steps: s1) mixing a phosphate anode material with a solvent to obtain slurry; the solvent is water and/or the filtrate in the step S2); s2) mixing the slurry with a solid acidic ion exchange medium, and filtering after reaction to obtain filtrate and insoluble solids; S3A) repeating the step S1) by taking the filtrate as a solvent until the phosphorus content in the filtrate reaches 100-500 g/L, and treating the filtrate by a solid acidic ion exchange medium to obtain phosphoric acid. Compared with the prior art, the invention adopts the recyclable solid acidic ion exchange medium to replace the traditional liquid acid, realizes the efficient simultaneous leaching of metal ions in the waste phosphate anode material, realizes the separation of phosphorus and metal ions, and can obtain the high-concentration pure phosphoric acid solution with high added value; the process does not use high-cost oxidants such as hydrogen peroxide, and the like, and has low process cost and high added value of products.
Drawings
FIG. 1 is a schematic flow chart of a method for recovering phosphate positive electrode materials provided by the invention;
FIG. 2 is an XRD diffraction pattern of iron oxide obtained in example 1 of the present invention;
fig. 3 is an XRD diffractogram of lithium carbonate obtained in example 1 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a recovery method of a phosphate positive electrode material, which comprises the following steps: s1) mixing a phosphate anode material with a solvent to obtain slurry; the solvent is water and/or the filtrate in the step S2); s2) mixing the slurry with a solid acidic ion exchange medium, and filtering after reaction to obtain filtrate and insoluble solids; S3A) repeating the step S1) by taking the filtrate as a solvent until the phosphorus content in the filtrate reaches 100-500 g/L, and treating the filtrate by a solid acidic ion exchange medium to obtain phosphoric acid.
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for recovering phosphate cathode materials provided by the invention.
The source of all the raw materials is not particularly limited, and the raw materials are commercially available.
In the present invention, the phosphate positive electrode material is a waste phosphate positive electrode material to be recovered, which is well known to those skilled in the art, and is not particularly limited, and Q 1-zMaNbPO4 is preferred in the present invention; wherein Q is one or more of Li, na and K; m is one or more of Li, na, K, ca, al, mg, cu, F, B, ni, co, mn, ti, nb, sn, mo, W and N is one or more of Fe, mn, co, ni; -0.1.ltoreq.z.ltoreq.0.1, 0.ltoreq.a.ltoreq. 0.1,0.9.ltoreq.b.ltoreq.1; in the present invention, it is further preferred that the phosphate positive electrode material is a ferrous phosphate positive electrode material, and it is further preferred that the phosphate positive electrode material is one or more of lithium iron phosphate, sodium iron phosphate and potassium iron phosphate; the particle size of the phosphate positive electrode material is preferably 10nm to 1000 μm.
Mixing a phosphate anode material with a solvent to obtain slurry; the solvent is water or the filtrate obtained in the step S2); the mass ratio of the phosphate positive electrode material to the solvent is preferably (1-4): (1 to 10), more preferably (1 to 4): (1 to 6), more preferably (1 to 3): (1 to 4), most preferably 1: (2-3); the amount of the solvent can influence the subsequent steps, and too little solvent can lead to insufficient reaction between the subsequent solid acid ion exchange medium and the slurry, and too much solvent can lead to excessive dilution of the concentration of the exchanged phosphate ions; the method of mixing is preferably mechanical stirring or ball milling, more preferably ball milling; the rotation speed of the ball milling is preferably 200-800 r/min, more preferably 400-600 r/min, and still more preferably 500r/min; the mixing time is preferably 0.5 to 8 hours, more preferably 1 to 6 hours, still more preferably 2 to 4 hours; the phosphate positive electrode material can be activated by ball milling, and the time is short, so that the subsequent reaction time is correspondingly increased, and the activation process can be accelerated by both prolonging the time and increasing the rotating speed.
Mixing the slurry with a solid acidic ion exchange medium, and filtering after reaction to obtain filtrate and insoluble solids; the solid acidic ion exchange medium preferably comprises one or more of sulfonic acid groups, carboxylic acid groups, hydroxyl groups, tertiary amine groups, and quaternary amine groups; in the present invention, it is further preferable that the solid acidic ion exchange medium is a polystyrene sulfonic acid type ion exchange resin and/or a polyacrylic acid type sulfonic acid type ion exchange resin, which may be a gel type resin or a macroporous type resin; the solid acid ion exchange medium is preferably pretreated and then mixed with the slurry; the pretreatment process is a process well known to those skilled in the art, and is not particularly limited, and the present invention is preferably specifically: soaking a solid acid ion exchange medium by using deionized water, and replacing the deionized water every 10-20 min until the deionized water shows insignificant color and less foam; the mass ratio of the solid acid ion exchange medium to the slurry is preferably (2-30): 1; the reaction temperature is preferably 5-120 ℃, more preferably 10-80 ℃, still more preferably 15-60 ℃, still more preferably 20-40 ℃, and most preferably 25-30 ℃; the ion exchange medium is easy to deactivate when the reaction temperature is too high, and the volume of the water in the gaps of the ion exchange medium expands after solidification to cause the collapse and deactivation of the structure; the reaction time is preferably 0.1 to 10 hours, more preferably 0.5 to 8 hours, still more preferably 0.5 to 6 hours, and most preferably 0.5 to 2 hours.
Repeating the step S1) until the phosphorus content in the filtrate reaches 100-500 g/L, preferably 200-500 g/L, more preferably 300-500 g/L, still more preferably 400-500 g/L and most preferably 420-442 g/L, and treating the filtrate by a solid acid ion exchange medium to obtain phosphoric acid; the solid acidic ion exchange medium is the same as described above and is not described in detail herein; the flow rate of the filtrate when being treated by the ion exchange medium is preferably 0.1-20 B.V, more preferably 1-20 B.V, still more preferably 3-15 B.V, still more preferably 3-10 B.V, and most preferably 4-5 B.V; if the flow rate is too high, the target ions may not be intercepted, and the failure of the ion exchange medium may be accelerated, and if the flow rate is too low, the production efficiency may be low.
According to the present invention, it is preferable that: separating the insoluble solid to obtain graphite and an ion exchange medium after exchange; the separation method is a method well known to those skilled in the art, and is not particularly limited, and it is preferable in the present invention to separate by sieving or centrifugation in an aqueous system; the screen mesh used for the screening separation is preferably 50 to 500 mesh, more preferably 50 to 300 mesh; the insoluble solid is placed in a screen, washed in a water system, small-particle graphite can be screened, and then filtered to obtain graphite, the mesh number of the screen is lower than 50 meshes, exchange media easily pass through the screen, and the problem of low graphite separation efficiency occurs due to the excessive mesh number of the screen.
Regenerating the ion exchange medium after exchange by acid, and filtering to obtain a solution containing metal ions; the concentration of the acid is preferably 1 to 5mol/L, more preferably 2 to 3mol/L; the acid is preferably one or more of sulfuric acid, nitric acid and hydrochloric acid, more preferably sulfuric acid; the adoption of sulfuric acid to regenerate the ion exchange medium does not introduce other elements, such as low acidity, which can lead to low concentration of metal ions in the solution containing the metal ions; the regenerated solid acidic ion exchange medium can be reused to carry out mixed exchange with slurry.
The pH value of the solution containing the metal ions is regulated to 6-10 for reaction, and then the solution is filtered to obtain a metal precipitate and a filtrate containing Q; in the present invention, it is preferable to adjust the concentration to 6 to 10 using a sodium hydroxide solution; preferably, the pH is adjusted to 8 to 10, more preferably to 9; too low pH iron ions have residues, and too high pH can increase raw material cost; the reaction time is 1 to 4 hours, more preferably 2 to 4 hours; in the invention, since the phosphate positive electrode material is preferably ferrous phosphate positive electrode material, the obtained metal precipitate is ferrous hydroxide and/or ferric hydroxide, and other metal ions such as lithium ions can be selectively leached in a stable region of the ferrous hydroxide.
Roasting the metal precipitate to obtain a metal oxide; the roasting temperature is preferably 400-800 ℃, more preferably 500-700 ℃ and still more preferably 600 ℃; the time for the calcination is preferably 0.5 to 5 hours, more preferably 1 to 4 hours, still more preferably 2 to 3 hours.
According to the present invention, when Q is Li, it is preferable to further include: concentrating the filtrate containing Q, then adding alkali liquor to adjust the pH value to 6-13, and adding a lithium precipitating agent under the heating condition to obtain lithium salt; the temperature of the concentration is preferably 40-100 ℃, more preferably 70-100 ℃; in the present invention, the Q-containing filtrate is preferably concentrated to 20 to 40g/L, more preferably 25 to 35g/L, still more preferably 30g/L; the alkali liquor is preferably sodium hydroxide solution and/or sodium carbonate solution; the concentration of the alkali liquor is preferably 1-3 mol/L; adding alkali liquor to adjust the pH value to 8-12, 10-12, 11-12; the heating conditions are preferably 60-100 ℃, more preferably 80-100 ℃, still more preferably 90-100 ℃ and most preferably 95 ℃; the lithium precipitating agent is preferably carbonate or phosphate, more preferably sodium carbonate; in the invention, saturated sodium carbonate solution is preferably used as a lithium precipitating agent; the amount of the lithium precipitating agent added is preferably 1 to 1.5 times the standard amount, more preferably 1.1 to 1.3 times.
The invention adopts the recyclable solid acidic ion exchange medium to replace the traditional liquid acid, realizes the efficient leaching of the waste phosphate anode material, obtains the high-concentration pure phosphoric acid solution, and can obtain the high-concentration pure phosphoric acid solution with high added value without using high-cost oxidants such as hydrogen peroxide and the like, and has low process cost and high added value of products.
Further, the invention can also obtain battery grade lithium carbonate products and ferric oxide products.
In order to further illustrate the present invention, a method for recovering a phosphate positive electrode material according to the present invention will be described in detail with reference to examples.
The reagents used in the examples below are all commercially available.
Example 1
Adding water into the lithium iron phosphate anode material for ball milling to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to water is 1:3; the ball milling rotating speed is 500r/min, and the time is 0.5h;
Placing the slurry into pretreated gel-type polystyrene (hydrogen-type) sulfonic acid ion exchange resin, stirring for 0.5h at 25 ℃ with the mass ratio of the ion exchange resin to the slurry being 20:1, and filtering after full reaction to obtain filtrate and insoluble solids; separating insoluble solid to obtain graphite and ion exchange medium after exchange; the filtrate is taken as a pulping solvent of lithium iron phosphate waste again, and when the phosphorus content in the filtrate reaches 442g/L, the high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium with 2mol/L sulfuric acid, and filtering to obtain a solution containing lithium and iron; adding 1mol/L sodium hydroxide solution into the solution containing lithium and iron, adjusting the pH value of the solution to 9, reacting for 2 hours, and selectively leaching lithium components in a stable region of ferrous hydroxide; filtering and washing after the reaction is finished to obtain a ferrous hydroxide precursor, and roasting at 600 ℃ for 2 hours to obtain an iron oxide product;
Concentrating the leaching solution at high temperature until the lithium content is 30g/L, regulating the pH value to 12 by using a sodium hydroxide solution with the concentration of 1mol/L, controlling the temperature to 95 ℃, and adding a saturated sodium carbonate solution with the standard quantity of 1.1 times (based on twice the molar quantity of lithium in the solution) to obtain a lithium carbonate product.
The regeneration efficiency of the ion exchange medium reaches 99.8 percent,
The content of phosphorus element in the phosphoric acid is detected by ICP-OES: 442g/L, the concentration of phosphoric acid reaches: 83% by mass.
The recovery efficiencies of the lithium, iron and phosphorus components were 80.01%, 99.8% and 99.5%, respectively.
The capacity retention of the ion exchange medium after 10 cycles was 99.12%, and the comprehensive recovery efficiencies of lithium, iron and phosphorus components were 96.4%, 99.9% and 99.8%, respectively.
The iron oxide obtained in example 1 was analyzed with lithium carbonate by X-ray diffraction to obtain an XRD diffractogram of iron oxide, as shown in fig. 2; an XRD diffraction pattern of lithium carbonate was obtained as shown in FIG. 3.
Example 2
Adding water into the lithium iron phosphate anode material for ball milling or stirring to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to the water is 1:3; the ball milling rotating speed is 500r/min, and the time is 0.5h;
Placing the slurry into pretreated macroporous polystyrene (hydrogen type) sulfonic acid ion exchange resin, stirring for 0.5h at 25 ℃ with the mass ratio of the ion exchange resin to the slurry being 20:1, and filtering after full reaction to obtain filtrate and insoluble solids; separating insoluble solid to obtain graphite and ion exchange medium after exchange; the filtrate is taken as a pulping solvent of lithium iron phosphate waste again, and when the phosphorus content in the filtrate reaches 442g/L, the high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium with 2mol/L sulfuric acid, and filtering to obtain a solution containing lithium and iron; adding 1mol/L sodium hydroxide solution into the solution containing lithium and iron, adjusting the pH value of the solution to 9, reacting for 2 hours, and selectively leaching lithium components in a stable region of ferrous hydroxide; filtering and washing after the reaction is finished to obtain a ferrous hydroxide precursor, and roasting at 600 ℃ for 2 hours to obtain an iron oxide product;
Concentrating the leaching solution at high temperature until the lithium content is 30g/L, regulating the pH value to 12 by using a sodium hydroxide solution with the concentration of 1mol/L, controlling the temperature to 95 ℃, and adding a saturated sodium carbonate solution with the standard quantity of 1.1 times (based on twice the molar quantity of lithium in the solution) to obtain a lithium carbonate product.
The regeneration efficiency of the ion exchange medium reaches 99.9 percent,
The content of phosphorus element in the phosphoric acid is detected by ICP-OES: 442g/L, the concentration of phosphoric acid reaches: 83% by mass.
The recovery efficiencies of the lithium, iron and phosphorus components were 79.86%, 99.9% and 99.4%, respectively.
The capacity retention of the ion exchange medium after 10 cycles was 99.8%, and the comprehensive recovery efficiencies of lithium, iron and phosphorus components were 95.8%, 99.8% and 99.5%, respectively.
Example 3
Adding water into the lithium iron phosphate anode material for ball milling or stirring to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to the water is 1:3; the ball milling rotating speed is 500r/min, and the time is 0.5h;
Placing the slurry into pretreated macroporous polystyrene (hydrogen type) sulfonic acid ion exchange resin, stirring for 0.5h at 25 ℃ with the mass ratio of the ion exchange resin to the slurry being 20:1, and filtering after full reaction to obtain filtrate and insoluble solids; separating insoluble solid to obtain graphite and ion exchange medium after exchange; the filtrate passes through a reaction column filled with ion exchange medium at a flow rate of 4B.V to obtain pure phosphoric acid; regenerating the exchanged ion exchange medium with 2mol/L sulfuric acid, and filtering to obtain a solution containing lithium and iron; adding 1mol/L sodium hydroxide solution into the solution containing lithium and iron, adjusting the pH value of the solution to 9, reacting for 2 hours, and selectively leaching lithium components in a stable region of ferrous hydroxide; filtering and washing after the reaction is finished to obtain a ferrous hydroxide precursor, and roasting at 600 ℃ for 2 hours to obtain an iron oxide product;
Concentrating the leaching solution at high temperature until the lithium content is 30g/L, regulating the pH value to 12 by using a sodium hydroxide solution with the concentration of 1mol/L, controlling the temperature to 95 ℃, and adding a saturated sodium carbonate solution with the standard quantity of 1.1 times (based on twice the molar quantity of lithium in the solution) to obtain a lithium carbonate product.
The regeneration efficiency of the ion exchange medium reaches 99.8 percent,
The content of phosphorus element in the phosphoric acid is detected by ICP-OES: 101.5g/L, and the concentration of phosphoric acid reaches the following value: 30% by mass.
The recovery efficiencies of the lithium, iron and phosphorus components were 80.9%, 99.8% and 99.5%, respectively.
The capacity retention of the ion exchange medium after 10 cycles was 99.1%, and the comprehensive recovery efficiencies of lithium, iron and phosphorus components were 96.4%, 99.7% and 99.8%, respectively.
Example 4
Adding water into the lithium iron phosphate anode material for ball milling to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to water is 1:3; the ball milling rotating speed is 500r/min, and the time is 0.5h;
Placing the slurry into pretreated gel type polyacrylic acid (hydrogen type) sulfonic acid ion exchange resin, wherein the mass ratio of the ion exchange resin to the slurry is 20:1, stirring for 0.5h at 25 ℃, fully reacting, and filtering to obtain filtrate and insoluble solids; separating insoluble solid to obtain graphite and ion exchange medium after exchange; the filtrate is taken as a pulping solvent of lithium iron phosphate waste again, and when the phosphorus content in the filtrate reaches 442g/L, the high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium with 2mol/L sulfuric acid, and filtering to obtain a solution containing lithium and iron; adding 1mol/L sodium hydroxide solution into the solution containing lithium and iron, adjusting the pH value of the solution to 9, reacting for 2 hours, and selectively leaching lithium components in a stable region of ferrous hydroxide; filtering and washing after the reaction is finished to obtain a ferrous hydroxide precursor, and roasting at 600 ℃ for 2 hours to obtain an iron oxide product;
Concentrating the leaching solution at high temperature until the lithium content is 30g/L, regulating the pH value to 12 by using a sodium hydroxide solution with the concentration of 1mol/L, controlling the temperature to 95 ℃, and adding a saturated sodium carbonate solution with the standard quantity of 1.1 times (based on twice the molar quantity of lithium in the solution) to obtain a lithium carbonate product.
The regeneration efficiency of the ion exchange medium reaches 99.9 percent,
The content of phosphorus element in the phosphoric acid is detected by ICP-OES: 442g/L, the concentration of phosphoric acid reaches: 83% by mass.
The recovery efficiencies of the lithium, iron and phosphorus components were 81.6%, 99.8% and 99.1%, respectively.
The capacity retention of the ion exchange medium after 10 cycles was 99.4%, and the comprehensive recovery efficiencies of lithium, iron and phosphorus components were 97.4%, 99.7% and 99.5%, respectively.
Example 5
Adding water into the lithium iron phosphate anode material for ball milling to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to water is 1:3; the ball milling rotating speed is 500r/min, and the time is 0.5h;
Placing the slurry into pretreated macroporous polyacrylic acid (hydrogen type) sulfonic acid ion exchange resin, wherein the mass ratio of the ion exchange resin to the slurry is 20:1, stirring for 0.5h at 25 ℃, fully reacting, and filtering to obtain filtrate and insoluble solids; separating insoluble solid to obtain graphite and ion exchange medium after exchange; the filtrate is taken as a pulping solvent of lithium iron phosphate waste again, and when the phosphorus content in the filtrate reaches 442g/L, the high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium with 2mol/L sulfuric acid, and filtering to obtain a solution containing lithium and iron; adding 1mol/L sodium hydroxide solution into the solution containing lithium and iron, adjusting the pH value of the solution to 9, reacting for 2 hours, and selectively leaching lithium components in a stable region of ferrous hydroxide; filtering and washing after the reaction is finished to obtain a ferrous hydroxide precursor, and roasting at 600 ℃ for 2 hours to obtain an iron oxide product;
Concentrating the leaching solution at high temperature until the lithium content is 30g/L, regulating the pH value to 12 by using a sodium hydroxide solution with the concentration of 1mol/L, controlling the temperature to 95 ℃, and adding a saturated sodium carbonate solution with the standard quantity of 1.1 times (based on twice the molar quantity of lithium in the solution) to obtain a lithium carbonate product.
The regeneration efficiency of the ion exchange medium reaches 99.8 percent,
The content of phosphorus element in the phosphoric acid is detected by ICP-OES: 442g/L, the concentration of phosphoric acid reaches: 83% by mass.
The recovery efficiencies of the lithium, iron and phosphorus components were 80.2%, 99.5% and 99.7%, respectively.
The capacity retention of the ion exchange medium after 10 cycles was 99.12%, and the comprehensive recovery efficiencies of lithium, iron and phosphorus components were 96.9%, 99.9% and 99.9%, respectively.
Comparative example 1
Adding water into the lithium iron phosphate anode material for ball milling or stirring to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to the water is 1:3; the ball milling rotating speed is 500r/min, and the time is 0.5h;
Placing the slurry into pretreated macroporous polystyrene (hydrogen type) sulfonic acid ion exchange resin, wherein the mass ratio of the ion exchange resin to the slurry is 2:1, stirring for 0.5h at 25 ℃, fully reacting, and filtering to obtain filtrate and insoluble solids; separating insoluble solid to obtain graphite and ion exchange medium after exchange; the filtrate is taken as a pulping solvent of lithium iron phosphate waste again, and when the phosphorus content in the filtrate reaches 442g/L, pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium with 2mol/L sulfuric acid, and filtering to obtain a solution containing lithium and iron; adding 1mol/L sodium hydroxide solution into the solution containing lithium and iron, adjusting the pH value of the solution to 9, reacting for 2 hours, and selectively leaching lithium components in a stable region of ferrous hydroxide; filtering and washing after the reaction is finished to obtain a ferrous hydroxide precursor, and roasting at 600 ℃ for 2 hours to obtain an iron oxide product;
Concentrating the leaching solution at high temperature until the lithium content is 30g/L, regulating the pH value to 12 by using a sodium hydroxide solution with the concentration of 1mol/L, controlling the temperature to 95 ℃, and adding a saturated sodium carbonate solution with the standard quantity of 1.1 times (based on twice the molar quantity of lithium in the solution) to obtain a lithium carbonate product.
The regeneration efficiency of the ion exchange medium reaches 99.9 percent,
The content of phosphorus element in the phosphoric acid is detected by ICP-OES: 442g/L, the concentration of phosphoric acid reaches: 83% by mass.
The recovery efficiencies of the lithium, iron and phosphorus components were 50.4%, 76.2% and 99.5%, respectively.
The capacity retention of the ion exchange medium after 10 cycles was 99.5%, and the comprehensive recovery efficiencies of lithium, iron and phosphorus components were 60.3%, 81.6% and 99.6%, respectively.
Comparative example 2
Adding water into the lithium iron phosphate anode material for ball milling to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to water is 1:3; the ball milling rotating speed is 500r/min, and the time is 0.5h;
Placing the slurry into pretreated macroporous polystyrene (hydrogen type) sulfonic acid ion exchange resin, stirring for 0.5h at the temperature of 120 ℃ with the mass ratio of the ion exchange resin to the slurry being 20:1, and filtering after full reaction to obtain filtrate and insoluble solids; separating insoluble solid to obtain graphite and ion exchange medium after exchange; the filtrate is taken as a pulping solvent of lithium iron phosphate waste again, and when the phosphorus content in the filtrate reaches 442g/L, the high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium with 2mol/L sulfuric acid, and filtering to obtain a solution containing lithium and iron; adding 1mol/L sodium hydroxide solution into the solution containing lithium and iron, adjusting the pH value of the solution to 9, reacting for 2 hours, and selectively leaching lithium components in a stable region of ferrous hydroxide; filtering and washing after the reaction is finished to obtain a ferrous hydroxide precursor, and roasting at 600 ℃ for 2 hours to obtain an iron oxide product;
Concentrating the leaching solution at high temperature until the lithium content is 30g/L, regulating the pH value to 12 by using a sodium hydroxide solution with the concentration of 1mol/L, controlling the temperature to 95 ℃, and adding a saturated sodium carbonate solution with the standard quantity of 1.1 times (based on twice the molar quantity of lithium in the solution) to obtain a lithium carbonate product.
The regeneration efficiency of the ion exchange medium reaches 16.8%,
The content of phosphorus element in the phosphoric acid is detected by ICP-OES: 3.4g/L, and the concentration of phosphoric acid reaches the following value: 1% by mass.
The recovery efficiencies of the lithium, iron and phosphorus components were 6.9%, 10.9% and 18.9%, respectively.
The capacity retention of the ion exchange medium after 10 cycles was 0.8% and the comprehensive recovery efficiencies of lithium, iron and phosphorus components were 7.3%, 11.3% and 19.6%, respectively.
Claims (2)
1. The recovery method of the phosphate positive electrode material is characterized by comprising the following steps of:
s1) mixing a phosphate anode material with a solvent to obtain slurry; the solvent is water and/or the filtrate in the step S2);
s2) mixing the slurry with a solid acidic ion exchange medium, and filtering after reaction to obtain filtrate and insoluble solids;
S3A) taking the filtrate as a solvent, repeating the step S1) until the phosphorus content in the filtrate reaches 100-500 g/L, and treating the filtrate by a solid acidic ion exchange medium to obtain phosphoric acid;
the phosphate positive electrode material is lithium iron phosphate;
The mass ratio of the phosphate positive electrode material to the solvent is (1-4): (1-10);
The granularity of the phosphate anode material is 10 nm-1000 mu m;
Further comprises:
S3B) screening and separating or centrifuging the insoluble solids to obtain graphite and an ion exchange medium after exchange;
Regenerating the ion exchange medium after exchange by acid, and filtering to obtain a solution containing metal ions;
Adjusting the pH value of the solution containing the metal ions to 8-10 by using a sodium hydroxide solution, reacting for 1-4 hours, and filtering to obtain a metal precipitate and a filtrate containing Li;
Roasting the metal precipitate to obtain a metal oxide;
The S3A) and the S3B) are not sequentially divided;
the concentration of the acid is 1-5 mol/L; the acid is selected from one or more of sulfuric acid, nitric acid and hydrochloric acid;
The roasting temperature is 400-800 ℃; the roasting time is 0.5-5 h;
The step S3B) further includes:
concentrating the filtrate containing Li, then adding alkali liquor to adjust the pH value to 8-12, and adding a lithium precipitating agent under the heating condition to obtain lithium salt;
Concentrating the Li-containing filtrate to 20-40 g/L; the alkali liquor is selected from sodium hydroxide solution and/or sodium carbonate solution; the concentration of the alkali liquor is 1-3 mol/L; the heating condition is 80-100 ℃; the lithium precipitating agent is selected from carbonate or phosphate;
the concentration temperature is 70-100 ℃;
The solid acid ion exchange medium is selected from polystyrene sulfonic acid type ion exchange resin and/or polyacrylic acid type sulfonic acid type ion exchange resin, and is gel type or macroporous resin type; the mass ratio of the solid acid ion exchange medium to the slurry is 20:1, and the reaction temperature in the step S2) is 25-30 ℃.
2. The recovery method of claim 1, wherein the solid acidic ion exchange medium comprises one or more of sulfonic acid groups, carboxylic acid groups, hydroxyl groups, tertiary amine groups, and quaternary amine groups.
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