CN115321505B - Method for preparing lithium iron phosphate by comprehensively recycling lithium-containing wastewater and application - Google Patents
Method for preparing lithium iron phosphate by comprehensively recycling lithium-containing wastewater and application Download PDFInfo
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- CN115321505B CN115321505B CN202210897000.0A CN202210897000A CN115321505B CN 115321505 B CN115321505 B CN 115321505B CN 202210897000 A CN202210897000 A CN 202210897000A CN 115321505 B CN115321505 B CN 115321505B
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- lithium
- filtrate
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- containing wastewater
- slag
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 83
- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004064 recycling Methods 0.000 title description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 86
- 239000002893 slag Substances 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 230000001105 regulatory effect Effects 0.000 claims description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 230000001502 supplementing effect Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000005189 flocculation Methods 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 229920002401 polyacrylamide Polymers 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 239000006012 monoammonium phosphate Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- -1 fluoride ions Chemical class 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TWYAWLYZDNVYPT-UHFFFAOYSA-N dihexan-2-yl hydrogen phosphate Chemical compound CCCCC(C)OP(O)(=O)OC(C)CCCC TWYAWLYZDNVYPT-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 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
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/20—Magnesium hydroxide by precipitation from solutions of magnesium salts with ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/28—Fluorides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater, which comprises the following steps: (1) Adding a soluble magnesium salt into the lithium-containing wastewater, and carrying out solid-liquid separation to obtain a filtrate A, and after adding alkali, carrying out solid-liquid separation to obtain a solid slag and a filtrate B; (2) Adding soluble phosphate into the filtrate B, adding acid, performing Fenton reaction, and performing solid-liquid separation after flocculation to obtain lithium-containing phosphorus iron slag and filtrate C; (3) And (3) carrying out solid-liquid separation on the solid slag after ammonia leaching to obtain a filtrate D, mixing the filtrate D with lithium-containing phosphorus iron slag, adding a lithium source and a phosphorus source to obtain a mixture, carrying out hydrothermal reaction on the mixture, drying, and sintering to obtain a lithium iron phosphate finished product. The method can recover lithium in the lithium-containing wastewater to the greatest extent and prepare high-value additional products.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for preparing lithium iron phosphate by comprehensively recycling lithium-containing wastewater and application thereof.
Background
The lithium ion battery has the advantages of high voltage, good circularity, high energy density, small self-discharge, no memory effect and the like, is widely applied to the electronic and wireless communication industry, and is also a preferred power supply of the light high-capacity battery of the electric automobile in the future. As various electronic products have been gradually popularized and kept at a faster updating speed, the demands of lithium ion batteries are increasing, and the number of waste lithium ion batteries and lithium ion battery production waste materials is increasing, and the waste materials containing valuable metals belong to dangerous waste materials, so that the recycling and reutilization are the best way for solving the problem.
At present, many researches are carried out on the recovery of valuable metals in waste lithium ion batteries, and a more traditional recovery method is to leach the valuable metals in the electrode materials by adopting an acid leaching process, namely sulfuric acid, nitric acid, hydrochloric acid and other acids. In the existing leachate purification process, iron and aluminum are removed by adjusting pH through oxidation, and then D is adopted 2 EHPA (di- (2-hexyl) phosphoric acid) extracts Ni, co, mn from impurity ions and finally, carbonate is added to the raffinate to precipitate lithium for lithium recovery. The raffinate contains a large amount of lithium, which needs to be removed separately, and common sodium carbonate is used for precipitating lithium, because the solubility product constant of the lithium carbonate is 8.15 multiplied by 10 -4 The recovery rate of Li is low, and part of lithium in the wastewater is not recovered. In addition, the wastewater contains a part of fluoride ions and residual transition metal ions.
In the related art, in the method for recovering lithium from wastewater, lithium is mainly recovered as lithium carbonate. However, the solubility of lithium carbonate in water is inversely proportional to the temperature, and the solubility of lithium carbonate at 20 ℃ is relatively high, and 1.33g of lithium carbonate can be dissolved in every 100g of water, so that the method can only obtain high recovery efficiency by heating to 90 ℃ to precipitate lithium carbonate for low-concentration lithium-containing wastewater, which generally requires a large amount of energy consumption. In addition, in the related technology, the resources such as lithium, alkali and the like in the lithium-containing wastewater can be recycled, but the whole process is longer, and the occupied area of a recycling instrument is large. Meanwhile, the solution is not subjected to decrement concentration before evaporation, so that the energy consumption is high, and the requirements of energy conservation and emission reduction are not met.
In summary, there is a need to develop a more rational recovery method for lithium-containing wastewater.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a method for comprehensively recovering and preparing lithium iron phosphate from lithium-containing wastewater and application thereof.
The technical aim of the invention is realized by the following technical scheme:
a method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater comprises the following steps:
(1) Adding a soluble magnesium salt into the lithium-containing wastewater, performing solid-liquid separation to obtain filtrate A and magnesium fluoride slag, adjusting the pH value of the filtrate A to be alkaline, and performing solid-liquid separation to obtain solid slag and filtrate B;
(2) After adding soluble phosphate to the filtrate B, adjusting the pH of the filtrate B to be acidic, and then adding Fe 2+ And H 2 O 2 Fenton reaction is carried out, then flocculant is added, and solid-liquid separation is carried out to obtain lithium-containing phosphorus iron slag and filtrate C;
(3) And (3) carrying out solid-liquid separation on the solid slag obtained in the step (1) after ammonia leaching to obtain a filtrate D, mixing the filtrate D with the lithium-containing phosphorus iron slag obtained in the step (2), adding a lithium source and a phosphorus source to obtain a mixture, carrying out hydrothermal reaction on the mixture, drying, and sintering to obtain a lithium iron phosphate finished product.
Preferably, the lithium content in the lithium-containing wastewater in the step (1) is less than 8g/L.
Preferably, after adding the soluble magnesium salt to the lithium-containing wastewater in the step (1), the magnesium ion content in the lithium-containing wastewater is 0.03-0.15mol/L.
It is further preferred that the magnesium ion content in the lithium-containing wastewater is 0.05-0.10mol/L after adding the soluble magnesium salt to the lithium-containing wastewater in the step (1).
Preferably, the soluble magnesium salt is at least one of magnesium sulfate, magnesium chloride or magnesium nitrate, more preferably magnesium sulfate.
Preferably, the adjusting the pH to be alkaline in the step (1) means adjusting the pH to 10-13.
Further preferably, the adjusting of the pH to be alkaline in the step (1) means adjusting the pH to 11.5 to 12.
Preferably, in the step (2), after adding the soluble phosphate to the filtrate B, the phosphorus content in the filtrate B is 0.01-0.50mol/L.
Further preferably, in the step (2), after adding the soluble phosphate to the filtrate B, the phosphorus content in the filtrate B is 0.01-0.20mol/L.
Preferably, in step (2), the soluble phosphate is at least one of sodium phosphate or potassium phosphate, more preferably sodium phosphate.
Preferably, in the step (2), the step of adjusting the pH to be acidic means adjusting the pH to 3 to 5.5.
Further preferably, in the step (2), the adjustment of the pH to be acidic means that the pH is adjusted to 3 to 4.
Preferably, in step (2), fe is added 2+ And H 2 O 2 The molar ratio of (1-3): 1.
further preferably, in the step (2), fe is added 2+ And H 2 O 2 The molar ratio of (1-1.5): 1.
preferably, in step (2), after Fenton reaction, the phosphorus content in the filtrate B is lower than 10 -5 The mol/L and the chemical oxygen demand is lower than 200mg/L.
Preferably, in the step (2), the addition amount of the flocculant is not less than 0.005g/L.
Further preferably, in the step (2), the addition amount of the flocculant is not less than 0.008g/L.
Preferably, the flocculant is a nonionic polymeric flocculant, more preferably polyacrylamide.
Preferably, in the step (2), the filtrate C can be directly discharged after regulating and controlling the pH value, or enter an MVR system for evaporative crystallization to prepare anhydrous sodium sulfate and pure water.
Preferably, in the step (3), the solid slag and the ammonia water have a solid-to-liquid ratio of 50-500g/L when the solid slag is immersed in ammonia.
Further preferably, in the step (3), the solid slag and ammonia water have a solid-to-liquid ratio of 50-300g/L when the solid slag is immersed in ammonia.
Preferably, in the step (3), the concentration of the ammonia water used in the ammonia leaching of the solid slag is 4-10mol/L, and the ammonia leaching time is 1-3h.
Further preferably, in the step (3), the concentration of the ammonia water used in the ammonia leaching of the solid slag is 4-6mol/L, and the ammonia leaching time is 1-2h.
Preferably, in the step (3), the ratio of lithium, phosphorus and iron elements in the mixture is (1.0-1.1): 0.95-1.0.
Further preferably, in the step (3), the ratio of lithium, phosphorus and iron elements in the mixture is (1.0-1.05): 0.98-1.0.
Preferably, in step (3), the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate.
Preferably, in the step (3), the phosphorus source is at least one of monoammonium phosphate, lithium phosphate, monoammonium phosphate or phosphoric acid.
Preferably, in the step (3), the temperature of the hydrothermal reaction is 100-200 ℃ and the time is 1-20h.
Further preferably, in the step (3), the temperature of the hydrothermal reaction is 150-180 ℃ and the time is 3-15h.
Preferably, in step (3), the hydrothermal reaction is performed in a sealed environment.
Preferably, in the step (3), the drying is performed by heating at 80-100 ℃ until the liquid phase is completely evaporated, and recycling the ammonia water for return to an ammonia leaching link.
Preferably, in the step (3), the sintering is performed under an inert atmosphere, the sintering temperature is 300-1000 ℃ and the sintering time is 5-15h.
Further preferably, in the step (3), the sintering is performed under an inert atmosphere, the sintering temperature is 500-850 ℃, and the sintering time is 8-12h.
Preferably, in the step (3), the obtained material is further subjected to crushing, sieving and iron removal treatment after sintering.
Preferably, the method for preparing the lithium iron phosphate by comprehensively recycling the lithium-containing wastewater comprises the following steps of:
(1) Adding magnesium sulfate into the lithium-containing wastewater to ensure that the magnesium ion content in the wastewater is 0.05-0.10mol/L;
(2) Solid-liquid separation is carried out to obtain magnesium fluoride slag and filtrate A;
(3) Adjusting the pH of the filtrate A to 11.5-12 by using sodium hydroxide, and carrying out solid-liquid separation to obtain solid slag and filtrate B;
(4) Adding sodium phosphate into the filtrate B to ensure that the phosphorus content in the filtrate B is 0.01-0.20mol/L;
(5) Regulating pH of filtrate B to 3-4, adding Fe 2+ And H 2 O 2 Added Fe 2+ /H 2 O 2 The molar ratio is 1.0-1.5:1, carrying out Fenton reaction treatment on the filtrate B until the phosphorus content in the filtrate B is lower than 10 < -5 > mol/L and COD is lower than 200mg/L, wherein the COD refers to chemical oxygen demand;
(6) PAM is added into the filtrate B, wherein the addition amount of the PAM is not less than 0.008g/L, and the PAM refers to polyacrylamide;
(7) Solid-liquid separation is carried out to obtain lithium-containing ferrophosphorus slag and filtrate C, and the filtrate C can be directly discharged after regulating and controlling the pH value or enters an MVR system for evaporative crystallization to prepare anhydrous sodium sulfate and pure water;
(8) Adding the solid slag obtained in the step (3) into 4-6mol/L ammonia water according to a solid-liquid ratio of 50-300g/L, soaking for 1-2h, and carrying out solid-liquid separation to obtain magnesium hydroxide slag and filtrate D;
(9) Mixing the filtrate D with the lithium-containing phosphorus iron slag obtained in the step (7), and then supplementing a lithium source and a phosphorus source to ensure that the mixture contains 0.98-1.0% of Li: P and 0.98-1.0% of Fe= (1.0-1.05); the lithium source is lithium carbonate, lithium hydroxide and lithium oxalate, and the phosphorus source is monoammonium phosphate, lithium phosphate, monoammonium phosphate and phosphoric acid;
(10) Transferring the mixture into a reaction kettle for sealing, and performing hydrothermal reaction for 3-15h at 150-180 ℃;
(11) After the hydrothermal reaction is finished, opening the reaction kettle for sealing, continuously heating at 80-100 ℃ until the liquid phase is completely evaporated, and recovering ammonia water;
(12) Sintering the solid material remained by evaporation for 8-12h under the inert atmosphere of 500-850 ℃, and obtaining the finished product of lithium iron phosphate through crushing, sieving and deironing.
The method is applied to the preparation of lithium iron phosphate or lithium batteries.
The beneficial effects of the invention are as follows:
1. in the method for preparing lithium iron phosphate by comprehensively recycling lithium-containing wastewater, firstly, fluoride ions in the wastewater are removed by adopting a soluble magnesium salt, then, magnesium ions and nickel cobalt manganese transition metals in the magnesium ions are removed by adjusting the pH value to be alkaline, and then, lithium in the wastewater is further precipitated by adding excessive phosphate, so that the lithium content is reduced, the chemical oxygen demand of the wastewater is reduced by Fenton reaction, and meanwhile, the excessive phosphate is removed to form ferric phosphate precipitation, and finally, the flocculating agent is used for further flocculating and settling, so that lithium phosphate, ferric phosphate and the like are separated from the wastewater while the wastewater is purified, and a carbon source is provided for preparing lithium iron phosphate in the next step;
2. in the method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater, solid slag is leached by ammonia water, nickel cobalt manganese in the solid slag is dissolved, ammonia-containing nickel cobalt manganese solution is obtained and mixed with lithium-containing phosphorus iron slag, the ammonia water is recovered by supplementing raw materials, carrying out hydrothermal reaction and evaporation, nickel cobalt manganese is used as doping element, and the doping transition metal-doped lithium iron phosphate finished product is prepared by calcining, so that lithium, transition metal and the like in the wastewater are recovered, and the lithium iron phosphate anode material with high added value is further obtained.
The reaction principle is as follows:
adding soluble magnesium salt into lithium-containing wastewater: mg of 2+ +2F - →MgF 2 ↓。
The pH of filtrate A was adjusted to alkaline: mg of 2+ +2OH - →Mg(OH) 2 ↓Me 2+ +2OH - →Me(OH) 2 And ∈ (Me is at least one of Ni, co and Mn).
Adding soluble phosphate to filtrate B: 3Li + +PO 4 3- →Li 3 PO 4 ↓。
Adding Fe 2+ And H 2 O 2 Fenton reaction was performed: fe (Fe) 3+ +PO 4 3- →FePO 4 ↓Fe 3+ +3OH - →Fe(OH) 3 ↓。
Ammonia leaching the solid slag: me (OH) 2 +6NH 3 →[Me(NH 3 ) 6 ](OH) 2 。
Carrying out hydrothermal reaction on the mixture, drying and sintering: li (Li) 3 PO 4 +3NH 3 ·H 2 O→3LiOH+(NH 4 ) 3 PO 4 [Me(NH 3 ) 6 ] 2+ +PO 4 3- →Me 3 (PO 4 ) 2 +6NH 3 4LiOH+4FePO 4 +C→4LiFePO 4 +CO 2 +2H 2 O。
Drawings
FIG. 1 is a schematic flow chart of embodiment 1 of the present invention;
fig. 2 is an SEM image of lithium iron phosphate obtained in example 1 of the present invention.
Detailed Description
The invention is further illustrated below with reference to specific examples, wherein examples 1-3 and comparative example 1 use the following lithium-containing wastewater with the following water qualities: 105.6g/L sodium sulfate, 2.3g/L sodium chloride, 5.9g/L lithium content, 5.2mg/L total nickel cobalt manganese content, 185.5mg/L fluorine content, COD 17000mg/L.
Example 1:
a method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater is shown in figure 1, and comprises the following steps:
(1) Adding magnesium sulfate into the lithium-containing wastewater to enable the magnesium ion content in the wastewater to be 0.05mol/L;
(2) Solid-liquid separation is carried out to obtain magnesium fluoride slag and filtrate A;
(3) Adjusting the pH value of the filtrate A to 11.5 by using sodium hydroxide, and carrying out solid-liquid separation to obtain solid slag and filtrate B;
(4) Adding sodium phosphate into the filtrate B to ensure that the phosphorus content in the filtrate B is 0.20mol/L;
(5) Regulating pH of filtrate B to 3.5, performing Fenton reaction on filtrate B, and adding Fe 2+ And H 2 O 2 Added intoFe 2+ /H 2 O 2 The molar ratio is 1.5:1 until the phosphorus content in the filtrate B is lower than 10 -5 mol/L, COD is lower than 200mg/L;
(6) PAM is added into the filtrate B, wherein the addition amount of the PAM is 0.008g/L;
(7) Solid-liquid separation is carried out to obtain lithium-containing ferrophosphorus slag and filtrate C, and the filtrate C can be directly discharged after regulating and controlling the pH value or enters an MVR system for evaporative crystallization to prepare anhydrous sodium sulfate and pure water;
(8) Adding the solid slag obtained in the step (3) into 4mol/L ammonia water according to a solid-to-liquid ratio of 50g/L, soaking for 1h, and carrying out solid-liquid separation to obtain magnesium hydroxide slag and filtrate D;
(9) Mixing the filtrate D with the lithium-containing phosphorus iron slag obtained in the step (7), and then supplementing lithium carbonate and monoammonium phosphate to ensure that Li: P in the mixture is Fe=1.05:1.0:1.0;
(10) Transferring the mixture into a reaction kettle for sealing, and performing hydrothermal reaction for 3 hours at 180 ℃;
(11) After the hydrothermal reaction is finished, opening the reaction kettle for sealing, continuously heating at 100 ℃ until the liquid phase is completely evaporated, and recovering ammonia water;
(12) Sintering the evaporated solid material for 8 hours at 850 ℃ in an inert atmosphere, and crushing, sieving and removing iron to obtain a finished lithium iron phosphate product, wherein an SEM (scanning electron microscope) diagram of the finished lithium iron phosphate product is shown in figure 2.
Example 2:
a method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater comprises the following steps:
(1) Adding magnesium sulfate into the lithium-containing wastewater to enable the magnesium ion content in the wastewater to be 0.08mol/L;
(2) Solid-liquid separation is carried out to obtain magnesium fluoride slag and filtrate A;
(3) Adjusting the pH value of the filtrate A to 11.8 by using sodium hydroxide, and carrying out solid-liquid separation to obtain solid slag and filtrate B;
(4) Adding sodium phosphate into the filtrate B to ensure that the phosphorus content in the filtrate B is 0.10mol/L;
(5) Regulating pH of filtrate B to 3, performing Fenton reaction on filtrate B, and adding Fe 2+ And H 2 O 2 Added Fe 2 + /H 2 O 2 The molar ratio is 1.3:1 until the phosphorus content in the filtrate B is lower than 10 -5 mol/L, COD is lower than 200mg/L;
(6) PAM is added into the filtrate B, wherein the addition amount of the PAM is 0.009g/L;
(7) Solid-liquid separation is carried out to obtain lithium-containing ferrophosphorus slag and filtrate C, and the filtrate C can be directly discharged after regulating and controlling the pH value or enters an MVR system for evaporative crystallization to prepare anhydrous sodium sulfate and pure water;
(8) Adding the solid slag obtained in the step (3) into 5mol/L ammonia water according to a solid-to-liquid ratio of 150g/L, soaking for 1.5h, and carrying out solid-liquid separation to obtain magnesium hydroxide slag and filtrate D;
(9) Mixing the filtrate D with the lithium-containing phosphorus iron slag obtained in the step (7), and then supplementing lithium hydroxide and ammonium dihydrogen phosphate to ensure that the Li:P in the mixture is Fe=1.03:0.99:0.99;
(10) Transferring the mixture into a reaction kettle for sealing, and performing hydrothermal reaction for 9 hours at 170 ℃;
(11) After the hydrothermal reaction is finished, opening the reaction kettle for sealing, continuously heating at 90 ℃ until the liquid phase is completely evaporated, and recovering ammonia water;
(12) Sintering the solid material remained by evaporation for 10 hours under the inert atmosphere of 700 ℃, and obtaining the finished product of lithium iron phosphate through crushing, sieving and deironing.
Example 3:
a method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater comprises the following steps:
(1) Adding magnesium sulfate into the lithium-containing wastewater to enable the magnesium ion content in the wastewater to be 0.10mol/L;
(2) Solid-liquid separation is carried out to obtain magnesium fluoride slag and filtrate A;
(3) Adjusting the pH value of the filtrate A to 12 by using sodium hydroxide, and carrying out solid-liquid separation to obtain solid slag and filtrate B;
(4) Adding sodium phosphate into the filtrate B to ensure that the phosphorus content in the filtrate B is 0.01mol/L;
(5) Regulating pH of filtrate B to 4, performing Fenton reaction on filtrate B, and adding Fe 2+ And H 2 O 2 Added Fe 2 + /H 2 O 2 The molar ratio is 1.0:1 until the phosphorus content in the filtrate B is lower than10 -5 mol/L, COD is lower than 200mg/L;
(6) PAM is added into the filtrate B, wherein the addition amount of the PAM is 0.01g/L;
(7) Solid-liquid separation is carried out to obtain lithium-containing ferrophosphorus slag and filtrate C, and the filtrate C can be directly discharged after regulating and controlling the pH value or enters an MVR system for evaporative crystallization to prepare anhydrous sodium sulfate and pure water;
(8) Adding the solid slag obtained in the step (3) into 6mol/L ammonia water according to a solid-to-liquid ratio of 300g/L, soaking for 2 hours, and carrying out solid-liquid separation to obtain magnesium hydroxide slag and filtrate D;
(9) Mixing the filtrate D with the lithium-containing phosphorus iron slag obtained in the step (7), and then adding lithium oxalate and phosphoric acid to ensure that the Li: P, fe=1.0:0.98:0.98 in the mixture;
(10) Transferring the mixture into a reaction kettle for sealing, and performing hydrothermal reaction for 15 hours at 150 ℃;
(11) After the hydrothermal reaction is finished, opening the reaction kettle for sealing, continuously heating at 80 ℃ until the liquid phase is completely evaporated, and recovering ammonia water;
(12) Sintering the solid material remained by evaporation for 12 hours under the inert atmosphere of 500 ℃, and obtaining a lithium iron phosphate finished product through crushing, sieving and deironing.
Comparative example 1:
a method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater comprises the following steps:
(1) Adding sodium carbonate into the lithium-containing wastewater to ensure that the carbonate content in the wastewater is 0.20mol/L, and carrying out solid-liquid separation to obtain carbonate;
(2) Regulating pH of the wastewater to 4, performing Fenton reaction treatment on the wastewater, and adding Fe 2+ And H 2 O 2 Added Fe 2+ /H 2 O 2 The molar ratio is 1.5:1, the addition amount was the same as in example 1;
(3) PAM is added into the wastewater, wherein the addition amount of the PAM is 0.008g/L;
(4) Solid-liquid separation, wherein the iron content of the wastewater is higher, the pH value is 4.6, the wastewater cannot reach the standard, and the solid enters the next working procedure;
(5) Mixing the obtained solid with lithium carbonate, monoammonium phosphate and ferric hydroxide, wherein in the mixture, li is P, fe=1.05:1.0:1.0;
(6) Grinding the mixture for 2 hours, and drying the mixture at 150 ℃ for 4 hours;
(7) Sintering the dried material for 9 hours at 850 ℃ in inert atmosphere;
(8) And crushing, sieving and removing iron to obtain a finished product of lithium iron phosphate.
Test example:
1. the water quality of the wastewater (filtrate C) discharged in the process of comprehensively recovering and producing lithium iron phosphate in examples 1 to 3 and comparative example 1 was examined, and the examination results are shown in Table 1.
Table 1: wastewater quality detection results:
as is clear from Table 1, the content of Li in the wastewater discharged in the process of comprehensively recovering and preparing lithium iron phosphate by the method for comprehensively recovering and preparing lithium iron phosphate by the invention is not more than 10.2mg/L, which is far less than the content of Li in the wastewater discharged in comparative example 1, and meanwhile, the nickel, cobalt, manganese and iron in the wastewater discharged in the process of comprehensively recovering and preparing lithium iron phosphate by the method for comprehensively recovering and preparing lithium iron phosphate by the invention are not detected, and F is not more than 7.8mg/L.
2. Mixing the lithium iron phosphate anode materials obtained in the examples 1-3 and the comparative example 1 with acetylene black as a conductive agent and PVDF as a binder according to a mass ratio of 8:1:1, adding a certain amount of organic solvent NMP, stirring, coating on an aluminum foil to prepare an anode sheet, and adopting a metal lithium sheet as an anode; the separator is a Celgard2400 polypropylene porous membrane; the electrolyte is prepared from EC, DMC and EMC in a mass ratio of 1:1:1, and the solute is LiPF 6 ，LiPF 6 The concentration of (2) is 1.0mol/L; inside the glove box, 2023 type button cell was assembled. Performing charge-discharge cycle performance test on the battery, and testing the discharge specific capacities of 0.2C and 1C within the range of 2.2-4.3V of cut-off voltage; the results of the electrochemical properties are shown in Table 2.
Table 2: electrochemical performance test results of the cell:
as can be seen from Table 2, after the lithium iron phosphate prepared by the method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater of the invention is assembled into a battery, the 0.2C discharge capacity can reach more than 147.6mAh/g, the 1C discharge capacity can reach more than 140.1mAh/g, and the electrochemical performance of the lithium iron phosphate prepared by the method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater of comparative example 1 is superior.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. A method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding a soluble magnesium salt into the lithium-containing wastewater, performing solid-liquid separation to obtain filtrate A and magnesium fluoride slag, adjusting the pH value of the filtrate A to be alkaline, and performing solid-liquid separation to obtain solid slag and filtrate B;
(2) After adding soluble phosphate to the filtrate B, adjusting the pH of the filtrate B to be acidic, and then adding Fe 2+ And H 2 O 2 Fenton reaction is carried out, then flocculant is added, and solid-liquid separation is carried out to obtain lithium-containing phosphorus iron slag and filtrate C;
(3) Carrying out solid-liquid separation on the solid slag obtained in the step (1) after ammonia leaching to obtain a filtrate D, mixing the filtrate D with the lithium-containing phosphorus iron slag obtained in the step (2), supplementing a lithium source and a phosphorus source to obtain a mixture, carrying out hydrothermal reaction on the mixture, drying and sintering to obtain a lithium iron phosphate finished product;
the lithium content in the lithium-containing wastewater in the step (1) is less than 8g/L;
in the step (2), after adding soluble phosphate into the filtrate B, the phosphorus content in the filtrate B is 0.01-0.50mol/L, the pH is regulated to be acidic, namely, the pH is regulated to be 3-5.5, and Fe is added 2+ And H 2 O 2 The molar ratio of (1-3): 1, after Fenton reaction, the phosphorus content in the filtrate B is lower than 10 -5 The mol/L and the chemical oxygen demand is lower than 200mg/L.
2. The method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater according to claim 1, which is characterized in that: after adding soluble magnesium salt into the lithium-containing wastewater in the step (1), the magnesium ion content in the lithium-containing wastewater is 0.03-0.15mol/L.
3. The method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater according to claim 1, which is characterized in that: the step (1) of adjusting the pH to be alkaline means that the pH is adjusted to 10-13.
4. The method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater according to claim 1, which is characterized in that: in the step (2), the addition amount of the flocculating agent is not less than 0.005g/L.
5. The method for preparing lithium iron phosphate by comprehensively recovering lithium-containing wastewater according to claim 1, which is characterized in that: in the step (3), the solid-liquid ratio of the solid slag to the ammonia water is 50-500g/L when the solid slag is immersed in the ammonia water.
6. Use of the method of any one of claims 1-5 for the preparation of lithium iron phosphate or lithium batteries.
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