CN114597530A - Recovery method of phosphate anode material - Google Patents
Recovery method of phosphate anode material Download PDFInfo
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- CN114597530A CN114597530A CN202210211892.4A CN202210211892A CN114597530A CN 114597530 A CN114597530 A CN 114597530A CN 202210211892 A CN202210211892 A CN 202210211892A CN 114597530 A CN114597530 A CN 114597530A
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- ion exchange
- filtrate
- exchange medium
- lithium
- acid
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 41
- 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
- 239000010405 anode material Substances 0.000 title claims abstract description 26
- 238000011084 recovery Methods 0.000 title claims description 36
- 238000005342 ion exchange Methods 0.000 claims abstract description 74
- 239000000706 filtrate Substances 0.000 claims abstract description 69
- 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 52
- 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
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 239000011574 phosphorus Substances 0.000 claims abstract description 38
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 230000002378 acidificating effect Effects 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000002609 medium Substances 0.000 claims description 72
- 229910052744 lithium Inorganic materials 0.000 claims description 70
- 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
- 229910052742 iron Inorganic materials 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000003456 ion exchange resin Substances 0.000 claims description 20
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000007774 positive electrode material 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 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
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000012500 ion exchange media Substances 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
- 229910052749 magnesium Inorganic materials 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen 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
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims 2
- 239000002699 waste material Substances 0.000 abstract description 25
- 239000000047 product Substances 0.000 abstract description 20
- 239000010406 cathode material Substances 0.000 abstract description 15
- 238000002386 leaching Methods 0.000 abstract description 12
- 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 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 63
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 29
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 22
- 238000000498 ball milling Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 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 16
- 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
- 238000003756 stirring Methods 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 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
- 238000005406 washing Methods 0.000 description 7
- 238000004537 pulping Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000002441 X-ray diffraction Methods 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940116007 ferrous phosphate Drugs 0.000 description 3
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 3
- 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 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010926 waste battery Substances 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 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
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 230000002427 irreversible effect Effects 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
- 239000000203 mixture Substances 0.000 description 1
- 235000021110 pickles Nutrition 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
- 238000012216 screening Methods 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
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
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
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- 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 method for recovering a phosphate cathode material, which comprises the following steps: s1) mixing the 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, reacting and filtering to obtain a 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 using a solid acidic ion exchange medium to obtain phosphoric acid. Compared with the prior art, the method adopts the recyclable solid acidic ion exchange medium to replace the traditional liquid acid, realizes the high-efficiency simultaneous leaching of metal ions in the waste phosphate anode material, realizes the separation of phosphorus and the metal ions, and can obtain 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 method for recovering a phosphate anode material.
Background
In recent years, as a lithium iron phosphate cathode material commonly used in automobile power batteries, the lithium iron phosphate cathode 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 73% of the maximum market sales of the cathode material in 2016. Although the output of lithium iron phosphate cathode materials in China is reduced in proportion to all cathode materials from 2017, the output is increased year by year, particularly in 2020, the output reaches 14.2 million tons at the maximum, the on-line increase is 40.9%, and the market scale reaches 45 million yuan. However, after a lithium ion battery undergoes a long-term charge-discharge cycle, the internal structure undergoes irreversible transformation, resulting in failure. A large amount of waste batteries are expected to enter the market, and the waste batteries contain residual electric energy and have potential safety hazards; meanwhile, the waste battery contains a large amount of heavy metals and organic matters, which may cause harm to the environment and related personnel. Therefore, the recovery of the waste power battery is imperative.
Currently, the recovery method of waste ferrous phosphate lithium batteries can be divided into pyrogenic recovery and wet recovery. The pyrogenic process recovery process is simple and widely applied, but has relatively large energy consumption, wastes a large amount of recyclable 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 high, but a large amount of liquid alkali and oxidant are consumed in the wet recovery process, the later-stage waste liquid needs to be further treated, and the recovery cost is also high.
Chinese patent with publication number CN109554545B discloses a method for realizing selective leaching of lithium by introducing strong acid to leach lithium iron phosphate waste, adjusting the pH value of a system to be 2-4, and performing solid-liquid separation to obtain a lithium-rich solution and ferrophosphorus slag. The method only aims at the recovery of the lithium component in the lithium iron phosphate waste material, and ignores the high-value recovery of the iron and phosphorus components.
Chinese patent publication No. CN112331949A discloses a method for producing a pickling solution by adding aluminum-removed lithium iron phosphate powder to a mixed solution of sulfuric acid and hydrogen peroxide, and heating and leaching the mixture to obtain a pickling solution; adjusting the pH value of the pickle liquor to obtain crude iron phosphate; dissolving, precipitating and calcining the rough ferric phosphate to obtain battery-grade ferric phosphate; evaporating and concentrating the lithium-containing filtrate, and adding an alkali solution to obtain a lithium carbonate precipitate. The method introduces a large amount of oxidant (hydrogen peroxide), which increases the treatment cost of the lithium iron phosphate waste; although this method achieves the recovery of lithium, iron and phosphorus components from lithium iron phosphate waste, the value of the phosphorus components present in the iron phosphate is severely devalued.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for recovering a phosphate positive electrode material, wherein the recovery method has low process cost and high added value of the product.
The invention provides a method for recovering a phosphate anode material, which comprises the following steps:
s1) mixing the 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, reacting and filtering to obtain a 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 using a solid acidic ion exchange medium to obtain phosphoric acid.
Preferably, the phosphate cathode material is Q1-zMaNbPO4(ii) a 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 and W, and N is one or more of Fe, Mn, Co and Ni; z is more than or equal to-0.1 and less than or equal to 0.1, a is more than or equal to 0 and less than or equal to 0.1, and b is more than or equal to 0.9 and less than or equal to 1;
the mass ratio of the phosphate anode material to the solvent is (1-4): (1-10);
the granularity of the phosphate anode material is 10 nm-1000 mu m.
Preferably, the method further comprises the following steps:
S3B) separating the insoluble solid to obtain graphite and an exchanged ion exchange medium;
regenerating the exchanged ion exchange medium by acid, and filtering to obtain a solution containing metal ions;
adjusting the pH value of the solution containing the metal ions to 6-10, reacting, and filtering to obtain a metal precipitate and a filtrate containing Q;
roasting the metal precipitate to obtain metal oxide;
the S3A) and the S3B) are not ordered sequentially.
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 a sodium hydroxide solution and/or a 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:
and concentrating the filtrate containing Q, adding alkali liquor to adjust the pH value to 6-13, and adding a lithium precipitation 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 concentration temperature is 70-100 ℃; adding alkali liquor to adjust the pH value to 8-12.
Preferably, the solid acidic ion exchange media 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 (2-30): 1.
Preferably, the flow rate of the filtrate treated by the ion exchange medium is 0.1-20 B.V.
The invention provides a method for recovering a phosphate anode material, which comprises the following steps: s1) mixing the 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, reacting and filtering to obtain a 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 using a solid acidic ion exchange medium to obtain phosphoric acid. Compared with the prior art, the method adopts the recyclable solid acidic ion exchange medium to replace the traditional liquid acid, realizes the high-efficiency simultaneous leaching of metal ions in the waste phosphate anode material, realizes the separation of phosphorus and the metal ions, and can obtain 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 diagram of a method for recovering a phosphate cathode material according to the present 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 in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 invention.
The invention provides a method for recovering a phosphate anode material, which comprises the following steps: s1) mixing the 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, reacting and filtering to obtain a 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 using 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 a phosphate cathode material provided by the present invention.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
In the present invention, the phosphate cathode material is not particularly limited as long as it is a waste phosphate cathode material to be recovered, which is well known to those skilled in the art, and in the present invention, Q is preferable1-zMaNbPO4(ii) a 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 and W, and N is one or more of Fe, Mn, Co and Ni; z is more than or equal to 0.1 and less than or equal to 0.1, a is more than or equal to 0 and less than or equal to 0.1, and b is more than or equal to 0.9 and less than or equal to 1; in the invention, it is further preferable that the phosphate positive electrode material is a ferrous phosphate positive electrode material, and it is further preferable 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 cathode material is preferably 10 nm-1000 μm.
Mixing a phosphate anode material with a solvent to obtain slurry; the solvent is water or the filtrate obtained in step S2); the mass ratio of the phosphate positive electrode material to the solvent is preferably (1-4): (1-10), more preferably (1-4): (1-6), more preferably (1-3): (1-4), most preferably 1: (2-3); the amount of the solvent can influence the subsequent steps, too little solvent can cause the subsequent solid acidic ion exchange medium to react with the slurry insufficiently, and too much solvent can cause the concentration of the exchanged phosphate ions to be diluted excessively; the mixing method is preferably mechanical stirring or ball milling, and more preferably ball milling; the rotation speed of the ball milling is preferably 200-800 r/min, more preferably 400-600 r/min, and further preferably 500 r/min; the mixing time is preferably 0.5-8 h, more preferably 1-6 h, and further preferably 2-4 h; the short time period for activating the phosphate cathode material by ball milling results in a corresponding increase in the subsequent reaction time, and both the time period and the rotational speed increase can accelerate the activation process.
Mixing the slurry with a solid acidic ion exchange medium, reacting, and filtering to obtain a filtrate and insoluble solids; the solid acidic ion exchange media 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 sulfonic acid type ion exchange resin, which may be a gel type resin or a macroporous type resin; the solid acidic ion exchange medium is preferably pre-treated and then mixed with the slurry; the pretreatment process is a process known to those skilled in the art, and is not particularly limited, and in the present invention, specifically: soaking the solid acidic ion exchange medium in deionized water, and replacing the deionized water every 10-20 min until the deionized water shows an unobvious color and has less foam; the mass ratio of the solid acidic ion exchange medium to the slurry is preferably (2-30): 1; the reaction temperature is preferably 5-120 ℃, more preferably 10-80 ℃, further preferably 15-60 ℃, further preferably 20-40 ℃, and most preferably 25-30 ℃; the reaction temperature is too high, the ion exchange medium is easy to inactivate, the reaction temperature is too low, and the volume of water in the gaps of the ion exchange medium is expanded after the water is solidified, so that the structure is collapsed and inactivated; the reaction time is preferably 0.1-10 hours, more preferably 0.5-8 hours, even more preferably 0.5-6 hours, and most preferably 0.5-2 hours.
Repeating the step S1) by taking the obtained filtrate as a solvent until the phosphorus content in the filtrate reaches 100-500 g/L, preferably 200-500 g/L, more preferably 300-500 g/L, further preferably 400-500 g/L, and most preferably 420-442 g/L, and treating the filtrate with a solid acidic ion exchange medium to obtain phosphoric acid; the solid acidic ion exchange medium is the same as that described above and is not described herein again; the flow rate of the filtrate treated by the ion exchange medium is preferably 0.1-20 B.V, more preferably 1-20 B.V, further preferably 3-15 B.V, further preferably 3-10 B.V, and most preferably 4-5 B.V; if the flow rate is too high, target ions may not be intercepted, and failure of the ion exchange medium may be accelerated, and if the flow rate is too low, production efficiency may be low.
According to the present invention, it is preferable to further include: separating the insoluble solid to obtain graphite and an exchanged ion exchange medium; the method of the separation is a method well known to those skilled in the art, and is not particularly limited, and in the present invention, it is preferable to separate by sieving or centrifugation in an aqueous system; the screen mesh used for screening separation is preferably 50-500 meshes, and more preferably 50-300 meshes; the insoluble solid is placed in a screen mesh and is cleaned in a water system, the small-particle graphite can be sieved and then filtered to obtain graphite, the mesh number of the screen mesh is less than 50 meshes, an exchange medium easily passes through the screen mesh, and the problem of low graphite separation efficiency can occur when the mesh number of the screen mesh is too large.
Regenerating the exchanged ion exchange medium by acid, and filtering to obtain a solution containing metal ions; the concentration of the acid is preferably 1-5 mol/L, and more preferably 2-3 mol/L; the acid is preferably one or more of sulfuric acid, nitric acid and hydrochloric acid, and is more preferably sulfuric acid; the regeneration of the ion exchange medium by using sulfuric acid without introducing other elements, such as low acidity, can result in low metal ion concentration in the solution containing metal ions; the solid acid ion exchange medium obtained after regeneration can be reused and mixed with the slurry for exchange.
Adjusting the pH value of the solution containing the metal ions to 6-10, reacting, and filtering to obtain a metal precipitate and a filtrate containing Q; in the invention, the sodium hydroxide solution is preferably used for adjusting the pH value to 6-10; preferably, the pH value is adjusted to 8-10, and more preferably, the pH value is adjusted to 9; too low pH iron ions still remain, and too high pH increases the cost of raw materials; the reaction time is 1-4 h, and more preferably 2-4 h; in the invention, because the treated phosphate cathode material is preferably a ferrous phosphate cathode 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 metal oxide; the roasting temperature is preferably 400-800 ℃, more preferably 500-700 ℃, and further preferably 600 ℃; the roasting time is preferably 0.5-5 h, more preferably 1-4 h, and still more preferably 2-3 h.
According to the present invention, when Q is Li, it preferably further comprises: concentrating the Q-containing filtrate, adding alkali liquor to adjust the pH value to 6-13, and adding a lithium precipitation agent under the heating condition to obtain a lithium salt; the concentration temperature is preferably 40-100 ℃, and more preferably 70-100 ℃; in the invention, the filtrate containing Q is preferably concentrated to 20-40 g/L, more preferably 25-35 g/L, and still more preferably 30 g/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, preferably adjusting the pH value to 8-12, more preferably 10-12, and further preferably 11-12; the heating condition is preferably 60-100 ℃, more preferably 80-100 ℃, further preferably 90-100 ℃, and most preferably 95 ℃; the lithium precipitating agent is preferably carbonate or phosphate, and is more preferably sodium carbonate; in the invention, saturated sodium carbonate solution is preferably used as a lithium precipitation agent; the addition amount of the lithium precipitation agent is preferably 1-1.5 times of standard amount, and more preferably 1.1-1.3 times.
The method adopts the recyclable solid acidic ion exchange medium to replace the traditional liquid acid, realizes the high-efficiency leaching of the waste phosphate anode material, obtains the high-concentration pure phosphoric acid solution, does not use high-cost oxidants such as hydrogen peroxide and the like, can obtain the high-concentration pure phosphoric acid solution with high added value, and has low process cost and high added value of products.
Furthermore, the invention can also obtain a battery-grade lithium carbonate product and an iron oxide product.
In order to further illustrate the present invention, the following will describe in detail a method for recovering a phosphate positive electrode material according to the present invention with reference to examples.
The reagents used in the following examples are all commercially available.
Example 1
Adding water into the lithium iron phosphate anode material, and carrying out ball milling to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to the water is 1: 3; the ball milling speed is 500r/min, and the time is 0.5 h;
putting the slurry into pretreated gel polystyrene (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 exchanged ion exchange medium; the filtrate is used as a lithium iron phosphate waste pulping solvent again, and when the phosphorus content in the filtrate reaches 442g/L, high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with an ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium by using 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 2h, and selectively leaching lithium components in a stable area 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 leachate at high temperature until the lithium content is 30g/L, adjusting the pH value to 12 by using 1mol/L sodium hydroxide solution, controlling the temperature to be 95 ℃, and adding 1.1 times of saturated sodium carbonate solution (taking twice of the molar amount of the lithium in the solution as a standard) 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 as follows: 442g/L, the concentration of phosphoric acid is calculated to reach: 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 rate of the ion exchange medium after 10 cycles is 99.12%, and the comprehensive recovery efficiencies of lithium, iron and phosphorus components are 96.4%, 99.9% and 99.8%, respectively.
The iron oxide and lithium carbonate obtained in example 1 were analyzed by X-ray diffraction to obtain an XRD diffractogram of the iron oxide, as shown in fig. 2; the XRD diffractogram of lithium carbonate was obtained as shown in fig. 3.
Example 2
Adding water into the lithium iron phosphate anode material, and carrying out 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 speed is 500r/min, and the time is 0.5 h;
putting 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 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 exchanged ion exchange medium; the filtrate is used as a lithium iron phosphate waste pulping solvent again, and when the phosphorus content in the filtrate reaches 442g/L, high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with an ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium by using 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 2h, and selectively leaching lithium components in a stable area 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 leachate at high temperature until the lithium content is 30g/L, adjusting the pH value to 12 by using 1mol/L sodium hydroxide solution, controlling the temperature to be 95 ℃, and adding 1.1 times of saturated sodium carbonate solution (taking twice of the molar amount of the lithium in the solution as a standard) 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 as follows: 442g/L, the concentration of phosphoric acid is calculated to reach: 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 rate of the ion exchange medium after 10 cycles is 99.8%, and the comprehensive recovery efficiencies of the lithium, iron and phosphorus components are 95.8%, 99.8% and 99.5%, respectively.
Example 3
Adding water into the lithium iron phosphate anode material, and carrying out 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 speed is 500r/min, and the time is 0.5 h;
putting 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 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 exchanged ion exchange medium; the filtrate passes through a reaction column filled with ion exchange medium at the flow rate of 4B.V to obtain pure phosphoric acid; regenerating the exchanged ion exchange medium by using 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 2h, and selectively leaching lithium components in a stable area 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 leachate at high temperature until the lithium content is 30g/L, adjusting the pH value to 12 by using 1mol/L sodium hydroxide solution, controlling the temperature to be 95 ℃, and adding 1.1 times of saturated sodium carbonate solution (taking twice of the molar amount of the lithium in the solution as a standard) 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 as follows: 101.5g/L, and the concentration of phosphoric acid is calculated to reach the following concentration: 30% by mass.
The recovery efficiencies for the lithium, iron and phosphorus components were 80.9%, 99.8% and 99.5%, respectively.
The capacity retention rate of the ion exchange medium after 10 cycles is 99.1%, and the comprehensive recovery efficiencies of lithium, iron and phosphorus components are 96.4%, 99.7% and 99.8%, respectively.
Example 4
Adding water into the lithium iron phosphate anode material, and performing ball milling to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to the water is 1: 3; the ball milling speed is 500r/min, and the time is 0.5 h;
putting 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 exchanged ion exchange medium; the filtrate is used as a lithium iron phosphate waste pulping solvent again, and when the phosphorus content in the filtrate reaches 442g/L, high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with an ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium by using 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 a lithium component in a stable area 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 leachate at high temperature until the lithium content is 30g/L, adjusting the pH value to 12 by using 1mol/L sodium hydroxide solution, controlling the temperature to be 95 ℃, and adding 1.1 times of saturated sodium carbonate solution (taking twice of the molar amount of the lithium in the solution as a standard) 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 as follows: 442g/L, the concentration of phosphoric acid is calculated to reach: 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 rate of the ion exchange medium after 10 cycles is 99.4%, and the comprehensive recovery efficiencies of the lithium, iron and phosphorus components are 97.4%, 99.7% and 99.5%, respectively.
Example 5
Adding water into the lithium iron phosphate anode material, and carrying out ball milling to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to the water is 1: 3; the ball milling speed is 500r/min, and the time is 0.5 h;
putting 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 exchanged ion exchange medium; the filtrate is used as a lithium iron phosphate waste pulping solvent again, and when the phosphorus content in the filtrate reaches 442g/L, high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with an ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium by using 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 2h, and selectively leaching lithium components in a stable area 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 leachate at high temperature until the lithium content is 30g/L, adjusting the pH value to 12 by using 1mol/L sodium hydroxide solution, controlling the temperature to be 95 ℃, and adding 1.1 times of saturated sodium carbonate solution (taking twice of the molar amount of the lithium in the solution as a standard) 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 as follows: 442g/L, the concentration of phosphoric acid is calculated to reach: 83% by mass.
The recovery efficiencies for the lithium, iron and phosphorus components were 80.2%, 99.5% and 99.7%, respectively.
The capacity retention rate of the ion exchange medium after 10 cycles is 99.12%, and the comprehensive recovery efficiencies of the lithium, iron and phosphorus components are 96.9%, 99.9% and 99.9%, respectively.
Comparative example 1
Adding water into the lithium iron phosphate anode material, and carrying out 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 speed is 500r/min, and the time is 0.5 h;
putting 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 exchanged ion exchange medium; the filtrate is used as a lithium iron phosphate waste pulping solvent again, and pure phosphoric acid is obtained after the phosphorus content in the filtrate reaches 442g/L and the filtrate passes through a reaction column filled with an ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium by using 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 2h, and selectively leaching lithium components in a stable area 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 leachate at high temperature until the lithium content is 30g/L, adjusting the pH value to 12 by using 1mol/L sodium hydroxide solution, controlling the temperature to be 95 ℃, and adding 1.1 times of saturated sodium carbonate solution (taking twice of the molar amount of the lithium in the solution as a standard) 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 as follows: 442g/L, the concentration of phosphoric acid is calculated to reach: 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 rate of the ion exchange medium after 10 cycles is 99.5%, and the comprehensive recovery efficiencies of the lithium, iron and phosphorus components are 60.3%, 81.6% and 99.6%, respectively.
Comparative example 2
Adding water into the lithium iron phosphate anode material, and carrying out ball milling to obtain slurry, wherein the mass ratio of the lithium iron phosphate anode waste to the water is 1: 3; the ball milling speed is 500r/min, and the time is 0.5 h;
putting 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 20:1, stirring for 0.5h at 120 ℃, fully reacting, and filtering to obtain filtrate and insoluble solids; separating insoluble solid to obtain graphite and exchanged ion exchange medium; the filtrate is used as a lithium iron phosphate waste pulping solvent again, and when the phosphorus content in the filtrate reaches 442g/L, high-concentration pure phosphoric acid is obtained after the filtrate passes through a reaction column filled with an ion exchange medium at the flow rate of 4 B.V; regenerating the exchanged ion exchange medium by using 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 2h, and selectively leaching lithium components in a stable area 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 leachate at high temperature until the lithium content is 30g/L, adjusting the pH value to 12 by using 1mol/L sodium hydroxide solution, controlling the temperature to be 95 ℃, and adding 1.1 times of saturated sodium carbonate solution (taking twice of the molar amount of the lithium in the solution as a standard) to obtain a lithium carbonate product.
The regeneration efficiency of the ion exchange medium reaches 16.8 percent,
the content of phosphorus element in the phosphoric acid is detected by ICP-OES as follows: 3.4g/L, and the concentration of the phosphoric acid is calculated to reach the following concentration: 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 rate of the ion exchange medium after 10 cycles is 0.8%, and the comprehensive recovery efficiencies of the lithium, iron and phosphorus components are 7.3%, 11.3% and 19.6%, respectively.
Claims (10)
1. A method for recovering a phosphate positive electrode material, characterized by comprising the steps of:
s1) mixing the 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, reacting, and filtering to obtain a 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 using a solid acidic ion exchange medium to obtain phosphoric acid.
2. The recovery method according to claim 1, wherein the phosphate positive electrode material is Q1-zMaNbPO4(ii) a 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 and W, and N is one or more of Fe, Mn, Co and Ni; z is more than or equal to 0.1 and less than or equal to 0.1, a is more than or equal to 0 and less than or equal to 0.1, and b is more than or equal to 0.9 and less than or equal to 1;
the mass ratio of the phosphate anode material to the solvent is (1-4): (1-10);
the granularity of the phosphate anode material is 10 nm-1000 mu m.
3. The recycling method according to claim 2, further comprising:
S3B) separating the insoluble solid to obtain graphite and an exchanged ion exchange medium;
regenerating the exchanged ion exchange medium by acid, and filtering to obtain a solution containing metal ions;
adjusting the pH value of the solution containing the metal ions to 6-10, reacting, and filtering to obtain a metal precipitate and a filtrate containing Q;
roasting the metal precipitate to obtain metal oxide;
the S3A) and the S3B) are not ordered sequentially.
4. The recovery method according to claim 3, wherein the concentration of the acid is 1 to 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 a sodium hydroxide solution or/and a sodium carbonate solution;
adjusting the reaction time to 6-10, and reacting for 1-4 h;
the roasting temperature is 400-800 ℃; the roasting time is 0.5-5 h.
5. The recycling method according to claim 3, wherein when Q is Li, the step S3B) further includes:
and concentrating the Q-containing filtrate, adding alkali liquor to adjust the pH value to 6-13, and adding a lithium precipitation agent under the heating condition to obtain a lithium salt.
6. The recovery method according to claim 5, characterized in that 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.
7. The recovery method according to claim 5, wherein the temperature of the concentration is 70 ℃ to 100 ℃; adding alkali liquor to adjust the pH value to 8-12.
8. The recovery method of claim 1, wherein the solid acidic ion exchange media comprises one or more of sulfonic acid groups, carboxylic acid groups, hydroxyl groups, tertiary amine groups, and quaternary amine groups.
9. The recovery process according to claim 1, characterized in that 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; the mass ratio of the solid acidic ion exchange medium to the slurry is preferably (2-30): 1.
10. The recovery method according to claim 1, wherein the flow rate of the filtrate treated with the ion exchange medium is 0.1 to 20 B.V.
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