WO2024021233A1 - 一种含锂废水综合回收制取磷酸铁锂的方法及应用 - Google Patents
一种含锂废水综合回收制取磷酸铁锂的方法及应用 Download PDFInfo
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- WO2024021233A1 WO2024021233A1 PCT/CN2022/117482 CN2022117482W WO2024021233A1 WO 2024021233 A1 WO2024021233 A1 WO 2024021233A1 CN 2022117482 W CN2022117482 W CN 2022117482W WO 2024021233 A1 WO2024021233 A1 WO 2024021233A1
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- Prior art keywords
- lithium
- filtrate
- containing wastewater
- solid
- iron phosphate
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 86
- 239000002351 wastewater Substances 0.000 title claims abstract description 70
- 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 47
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000011084 recovery Methods 0.000 title abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical group [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 9
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- 239000002893 slag Substances 0.000 claims description 34
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 238000004064 recycling Methods 0.000 claims description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 8
- 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
- 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
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005189 flocculation Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
- 230000001502 supplementing effect 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
- 238000001704 evaporation Methods 0.000 description 11
- 230000008020 evaporation Effects 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 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
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 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
- 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen 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
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910018119 Li 3 PO 4 Inorganic materials 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
- 239000010406 cathode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 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
- 239000011777 magnesium Substances 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000006467 substitution reaction 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
- 239000002699 waste material Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 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
- MWHIIOLMYXRIBZ-UHFFFAOYSA-N bis(2-butyloctyl) hydrogen phosphate Chemical compound CCCCCCC(CCCC)COP(O)(=O)OCC(CCCC)CCCCCC MWHIIOLMYXRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 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
- 238000005265 energy consumption Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 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
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 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
- 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
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test 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
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation 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
- 239000002904 solvent Substances 0.000 description 1
- 230000009469 supplementation Effects 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
Images
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
Definitions
- the invention belongs to the technical field of wastewater treatment, and particularly relates to a method and application for comprehensively recovering lithium-containing wastewater to produce lithium iron phosphate.
- Lithium-ion batteries have the advantages of high voltage, good cycleability, high energy density, small self-discharge, and no memory effect. They have been widely used in the electronics and wireless communication industries, and are also the first choice for light and high-capacity batteries for electric vehicles in the future. As various types of electronic products have gradually become popular and maintained a rapid replacement rate, the demand for lithium-ion batteries is growing day by day, and the amount of used lithium-ion batteries and lithium-ion battery production waste is also increasing day by day. These wastes containing valuable metals belong to Hazardous waste, resource recycling and reuse is the best way to solve this problem.
- the raffinate contains a large amount of lithium, which needs to be removed separately, and sodium carbonate is commonly used to precipitate lithium. Since the solubility product constant of lithium carbonate is 8.15 ⁇ 10 -4 , the Li recovery rate is low, and part of the lithium in the wastewater is not recovered. In addition, wastewater also contains some fluoride ions and residual transition metal ions.
- the method for recovering lithium from wastewater is mainly to recover lithium in the form of lithium carbonate.
- the solubility of lithium carbonate in water is inversely proportional to temperature.
- the solubility of lithium carbonate is greater at 20°C. 1.33g of lithium carbonate can be dissolved per 100g of water. Therefore, this method can only be used to heat low-concentration lithium-containing wastewater to Only by precipitating lithium carbonate at 90°C can a higher recovery efficiency be achieved, which usually requires a large amount of energy consumption.
- related technologies can also recycle lithium, alkali and other resources in lithium-containing wastewater, the overall process is long and the recovery equipment occupies a large area. At the same time, it does not reduce and concentrate the solution before evaporation, which consumes a lot of energy and does not meet the requirements of energy conservation and emission reduction.
- the present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a method and application for comprehensive recovery of lithium-containing wastewater to produce lithium iron phosphate. This method can recover lithium in lithium-containing wastewater to the greatest extent and prepare high-value add-ons.
- a method for comprehensively recycling lithium-containing wastewater to produce lithium iron phosphate including the following steps:
- step (3) Separate the solid liquid from the solid slag obtained in step (1) after ammonia leaching to obtain filtrate D, mix the filtrate D with the lithium-containing phosphorus iron slag obtained in step (2), and add a lithium source After mixing with the phosphorus source, a mixture is obtained, which is subjected to a hydrothermal reaction, dried, and sintered to obtain a finished lithium iron phosphate product.
- the lithium content in the lithium-containing wastewater in step (1) is less than 8g/L.
- the magnesium ion content in the lithium-containing wastewater is 0.03-0.15 mol/L.
- the magnesium ion content in the lithium-containing wastewater is 0.05-0.10 mol/L.
- the soluble magnesium salt is at least one of magnesium sulfate, magnesium chloride or magnesium nitrate, more preferably magnesium sulfate.
- adjusting the pH to alkaline in step (1) means adjusting the pH to 10-13.
- adjusting the pH to alkaline in step (1) means adjusting the pH to 11.5-12.
- the phosphorus content in the filtrate B is 0.01-0.50 mol/L.
- step (2) after adding soluble phosphate to the filtrate B, the phosphorus content in the filtrate B is 0.01-0.20 mol/L.
- the soluble phosphate is at least one of sodium phosphate or potassium phosphate, more preferably sodium phosphate.
- adjusting the pH to acidic means adjusting the pH to 3-5.5.
- adjusting the pH to acidic means adjusting the pH to 3-4.
- step (2) the molar ratio of Fe 2+ and H 2 O 2 added is (1-3):1.
- step (2) the molar ratio of Fe 2+ and H 2 O 2 added is (1-1.5):1.
- the phosphorus content in filtrate B is less than 10 -5 mol/L, and the chemical oxygen demand is less than 200 mg/L.
- the addition amount of the flocculant is not less than 0.005g/L.
- the added amount of the flocculant is not less than 0.008g/L.
- the flocculant is a non-ionic polymer flocculant, more preferably polyacrylamide.
- the filtrate C can be directly discharged after adjusting the pH, or enter the MVR system for evaporation and crystallization to prepare Yuanming powder and pure water.
- the solid-liquid ratio of the solid residue to ammonia water is 50-500g/L.
- step (3) when the solid residue is leached with ammonia, the solid-liquid ratio of the solid residue to ammonia water is 50-300g/L.
- the concentration of ammonia water used in the ammonia leaching of the solid residue is 4-10 mol/L, and the ammonia leaching time is 1-3 hours.
- step (3) the concentration of ammonia water used in the ammonia leaching of the solid residue is 4-6 mol/L, and the ammonia leaching time is 1-2 hours.
- the ratio of lithium, phosphorus and iron elements in the mixture is (1.0-1.1): (0.95-1.0): (0.95-1.0).
- the ratio of lithium, phosphorus and iron elements in the mixture is (1.0-1.05): (0.98-1.0): (0.98-1.0).
- the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate.
- the phosphorus source is at least one of ammonium monohydrogen phosphate, lithium phosphate, ammonium dihydrogen phosphate or phosphoric acid.
- the temperature of the hydrothermal reaction is 100-200°C and the time is 1-20 h.
- step (3) the temperature of the hydrothermal reaction is 150-180°C and the time is 3-15h.
- step (3) the hydrothermal reaction is carried out in a sealed environment.
- step (3) the drying is heated at 80-100°C until the liquid phase is completely evaporated, and the ammonia water is recovered and returned to the ammonia leaching process for use.
- step (3) the sintering is performed in an inert atmosphere, the sintering temperature is 300-1000°C, and the sintering time is 5-15 hours.
- step (3) the sintering is performed in an inert atmosphere, the sintering temperature is 500-850°C, and the sintering time is 8-12 hours.
- step (3) after sintering, the obtained material is also subjected to crushing, screening and iron removal treatment.
- a method for comprehensively recovering lithium-containing wastewater to produce lithium iron phosphate includes the following steps:
- soluble magnesium salts are first used to remove fluoride ions in the wastewater, and then the pH is adjusted to alkaline to remove magnesium ions and nickel-cobalt-manganese transition metals therein, and then By adding excess phosphate, the lithium in the wastewater is further precipitated, reducing the lithium content. Through the Fenton reaction, the chemical oxygen demand of the wastewater is reduced, and the excess phosphate is removed to form iron phosphate precipitation. Finally, After further flocculation and sedimentation by the flocculant, while purifying the wastewater, lithium phosphate, iron phosphate, etc. are separated from the wastewater, and a carbon source is provided for the next step of preparing lithium iron phosphate;
- the solid slag is leached with ammonia water to dissolve the nickel, cobalt and manganese in it, and then an ammonia-containing nickel-cobalt-manganese solution is obtained and mixed with the lithium-containing iron phosphorus slag.
- ammonia water is recovered, using nickel, cobalt and manganese as doping elements, and calcined to prepare transition metal-doped lithium iron phosphate finished products, which not only recovers lithium, transition metals, etc. in wastewater, but also further obtains high-added value of lithium iron phosphate cathode material.
- the mixture is subjected to hydrothermal reaction, dried and sintered: 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.
- Figure 1 is a schematic flow chart of Embodiment 1 of the present invention.
- Figure 2 is an SEM image of lithium iron phosphate obtained in Example 1 of the present invention.
- the water quality of the lithium-containing wastewater used in Examples 1-3 and Comparative Example 1 is as follows: sodium sulfate 105.6g/L, sodium chloride 2.3g/L, and lithium content 5.9 g/L, total nickel, cobalt and manganese content is 5.2mg/L, fluorine content is 185.5mg/L, COD: 17000mg/L.
- a method for comprehensively recycling lithium-containing wastewater to produce lithium iron phosphate including the following steps:
- a method for comprehensively recycling lithium-containing wastewater to produce lithium iron phosphate including the following steps:
- a method for comprehensively recycling lithium-containing wastewater to produce lithium iron phosphate including the following steps:
- a method for comprehensively recycling lithium-containing wastewater to produce lithium iron phosphate including the following steps:
- the Li content in the wastewater discharged during the comprehensive recovery of lithium iron phosphate using the method of the present invention for comprehensive recovery of lithium-containing wastewater to produce lithium iron phosphate does not exceed 10.2 mg/L, which is much less than the comparative example.
- the nickel, cobalt, manganese and iron in the wastewater discharged during the process of comprehensive recovery of lithium iron phosphate are not found. detected, and F does not exceed 7.8mg/L.
- lithium iron phosphate cathode material obtained in Examples 1-3 and Comparative Example 1 acetylene black as the conductive agent, and PVDF as the binder, mix them in a mass ratio of 8:1:1, and add a certain amount of organic solvent NMP is stirred and then coated on aluminum foil to make a positive electrode sheet.
- the negative electrode is a metal lithium sheet;
- the separator is Celgard2400 polypropylene porous membrane;
- the solvent in the electrolyte is a solution composed of EC, DMC and EMC in a mass ratio of 1:1:1.
- the solute is LiPF 6 , and the concentration of LiPF 6 is 1.0 mol/L; a 2023 button battery is assembled in the glove box.
- the charge and discharge cycle performance of the battery was tested, and the discharge specific capacity of 0.2C and 1C was tested in the cut-off voltage range of 2.2-4.3V; the test electrochemical performance results are shown in Table 2.
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Abstract
本发明公开了一种含锂废水综合回收制取磷酸铁锂的方法,包括以下步骤:(1)向含锂废水中加入可溶性镁盐,固液分离,得到滤液A,加碱后,固液分离得到固体渣和滤液B;(2)向滤液B中加入可溶性磷酸盐后,加酸,进行芬顿反应,絮凝后,固液分离得到含锂磷铁渣和滤液C;(3)将固体渣氨浸后固液分离,得到滤液D,将滤液D与含锂磷铁渣混合,补加锂源和磷源后得到混合料,将混合料进行水热反应,干燥,烧结得到磷酸铁锂成品。该方法能最大程度的回收含锂废水中的锂,并制备高价值的附加品。
Description
本发明属于废水处理技术领域,特别涉及一种含锂废水综合回收制取磷酸铁锂的方法及应用。
锂离子电池具有电压高,循环性好,能量密度大,自放电小,无记忆效应等优点,已广泛应用于电子、无线通讯产业,也是未来电动汽车轻型高能力电池的首选电源。由于各类电子产品已经逐渐普及并保持着较快的更新换代速度,锂离子电池的需求日益增长,废旧锂离子电池以及锂离子电池生产废料的数量也是与日俱增,这些含有有价金属的废弃物属于危险废物,资源化回收再利用才是解决这一问题的最佳途径。
目前,针对废旧锂离子电池中有价金属的回收已经做了很多研究,较为传统的回收办法是采用酸浸工艺,即采用硫酸、硝酸、盐酸等酸将电极材料中的有价金属浸出。现有的浸出液净化工艺中,多采用氧化调节pH去除铁铝,然后采用D
2EHPA(二-(2-已基己基)磷酸)萃取Ni、Co、Mn与杂质离子分离,最后,为了将锂回收,在萃余液中加入碳酸盐沉淀锂。萃余液含有大量锂,需单独去除,且常用碳酸钠沉锂,由于碳酸锂溶度积常数为8.15×10
-4,Li回收率低,废水还有一部分锂没有回收。除此之外,废水中还含有一部分氟离子以及残留的过渡金属离子。
相关技术中,针对废水中锂的回收方法,主要是将锂以碳酸锂的方式进行回收。但是,碳酸锂在水中的溶解度与温度呈反比,碳酸锂在20℃时的溶解度较大,每100g水可以溶解碳酸锂1.33g,因此该方法对于低浓度的含锂废水,只能采取加热至90℃使碳酸锂析出,才能获得较高的回收效率,这通常需要消耗大量的能耗。且相关技术中虽然还可以对含锂废水中的锂、碱等资源进行回收利用,但是其整体工艺较长,回收仪器占地面积大。同时,其在蒸发前未对溶液进行减量浓缩,能量消耗较大,不符合节能减排的要求。
综上,需要针对含锂废水开发一种更加合理的回收方法。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此,本发明提出一种含锂废水综合回收制取磷酸铁锂的方法及应用,该方法能最大程度的回收含锂废水中的锂,并制备高价值的附加品。
本发明的上述技术目的是通过以下技术方案得以实现的:
一种含锂废水综合回收制取磷酸铁锂的方法,包括以下步骤:
(1)向含锂废水中加入可溶性镁盐,固液分离,得到滤液A和氟化镁渣,调节所述滤液A的pH为碱性,固液分离得到固体渣和滤液B;
(2)向所述滤液B中加入可溶性磷酸盐后,调节所述滤液B的pH为酸性,再加入Fe
2+和H
2O
2进行芬顿反应,再加入絮凝剂,固液分离得到含锂磷铁渣和滤液C;
(3)将步骤(1)得到的所述固体渣氨浸后固液分离,得到滤液D,将所述滤液D与步骤(2)得到的所述含锂磷铁渣混合,补加锂源和磷源后得到混合料,将所述混合料进行水热反应,干燥,烧结得到磷酸铁锂成品。
优选的,步骤(1)中向所述含锂废水中锂含量小于8g/L。
优选的,步骤(1)中向所述含锂废水中加入可溶性镁盐后,所述含锂废水中镁离子含量为0.03-0.15mol/L。
进一步优选的,步骤(1)中向所述含锂废水中加入可溶性镁盐后,所述含锂废水中镁离子含量为0.05-0.10mol/L。
优选的,所述可溶性镁盐为硫酸镁、氯化镁或硝酸镁中的至少一种,更优选硫酸镁。
优选的,步骤(1)中所述调节pH为碱性是指调节pH为10-13。
进一步优选的,步骤(1)中所述调节pH为碱性是指调节pH为11.5-12。
优选的,步骤(2)中,向所述滤液B中加入可溶性磷酸盐后,所述滤液B中的磷含量为0.01-0.50mol/L。
进一步优选的,步骤(2)中,向所述滤液B中加入可溶性磷酸盐后,所述滤液B中的磷含量为0.01-0.20mol/L。
优选的,步骤(2)中,所述可溶性磷酸盐为磷酸钠或磷酸钾中的至少一种,更优选磷酸钠。
优选的,步骤(2)中,所述调节pH为酸性是指调节pH为3-5.5。
进一步优选的,步骤(2)中,所述调节pH为酸性是指调节pH为3-4。
优选的,步骤(2)中,加入Fe
2+和H
2O
2的摩尔比为(1-3):1。
进一步优选的,步骤(2)中,加入Fe
2+和H
2O
2的摩尔比为(1-1.5):1。
优选的,步骤(2)中,进行芬顿反应后,所述滤液B中的磷含量低于10
-5mol/L,化学需氧量低于200mg/L。
优选的,步骤(2)中,所述絮凝剂的加入量不低于0.005g/L。
进一步优选的,步骤(2)中,所述絮凝剂的加入量不低于0.008g/L。
优选的,所述絮凝剂为非离子型高分子絮凝剂,更优选聚丙烯酰胺。
优选的,步骤(2)中,所述滤液C可经调控pH后直接排放,或进入MVR系统蒸发结晶,制备元明粉和纯水。
优选的,步骤(3)中,所述固体渣氨浸时,所述固体渣与氨水的固液比为50-500g/L。
进一步优选的,步骤(3)中,所述固体渣氨浸时,所述固体渣与氨水的固液比为50-300g/L。
优选的,步骤(3)中,所述固体渣氨浸时用到的氨水的浓度为4-10mol/L,氨浸的时间为1-3h。
进一步优选的,步骤(3)中,所述固体渣氨浸时用到的氨水的浓度为4-6mol/L,氨浸的时间为1-2h。
优选的,步骤(3)中,所述混合料中锂、磷及铁元素之比为(1.0-1.1):(0.95-1.0):(0.95-1.0)。
进一步优选的,步骤(3)中,所述混合料中锂、磷及铁元素之比为(1.0-1.05):(0.98-1.0):(0.98-1.0)。
优选的,步骤(3)中,所述锂源为碳酸锂、氢氧化锂或草酸锂中的至少一种。
优选的,步骤(3)中,所述磷源为磷酸一氢铵、磷酸锂、磷酸二氢铵或磷酸中的至少一种。
优选的,步骤(3)中,所述水热反应的温度为100-200℃,时间为1-20h。
进一步优选的,步骤(3)中,所述水热反应的温度为150-180℃,时间为3-15h。
优选的,步骤(3)中,所述水热反应是在密封环境下进行。
优选的,步骤(3)中,所述干燥是在80-100℃加热至液相完全蒸发,并回收氨水返回至氨浸环节使用。
优选的,步骤(3)中,所述烧结是于惰性气氛下进行,烧结温度为300-1000℃,时间为5-15h。
进一步优选的,步骤(3)中,所述烧结是于惰性气氛下进行,烧结温度为500-850℃,时间为8-12h。
优选的,步骤(3)中,烧结后还对得到的物料进行了粉碎、过筛及除铁处理。
优选的,一种含锂废水综合回收制取磷酸铁锂的方法,包括如下步骤:
(1)向含锂废水中加入硫酸镁,使废水中镁离子含量为0.05-0.10mol/L;
(2)固液分离,得到氟化镁渣和滤液A;
(3)使用氢氧化钠调节滤液A的pH为11.5-12,固液分离,得到固体渣和滤液B;
(4)向滤液B中加入磷酸钠,使滤液B中的磷含量为0.01-0.20mol/L;
(5)调节滤液B的pH为3-4,加入Fe
2+和H
2O
2,投加的Fe
2+/H
2O
2摩尔比为(1.0-1.5):1,对滤液B进行芬顿反应处理,直至滤液B中的磷含量低于10-5mol/L,COD低于200mg/L,其中COD是指化学需氧量;
(6)向滤液B中加入PAM,PAM的加入量不低于0.008g/L,其中PAM是指聚丙烯酰胺;
(7)固液分离,得到含锂磷铁渣和滤液C,滤液C经调控pH后可直接排放,或进入MVR系统蒸发结晶,制备元明粉和纯水;
(8)将步骤(3)所得固体渣按照固液比50-300g/L加入到4-6mol/L 的氨水中,浸泡1-2h,固液分离,得到氢氧化镁渣和滤液D;
(9)将滤液D与步骤(7)所得含锂磷铁渣混合后,补加锂源和磷源,使混合料中Li:P:Fe=(1.0-1.05):(0.98-1.0):(0.98-1.0);锂源为碳酸锂、氢氧化锂、草酸锂,磷源为磷酸一氢铵、磷酸锂、磷酸二氢铵、磷酸;
(10)将混合料移至反应釜中密封,于150-180℃下水热反应3-15h;
(11)水热反应结束后,打开反应釜密封,继续在80-100℃加热至液相完全蒸发,并回收氨水;
(12)将蒸发残留的固体物料于惰性气氛500-850℃下烧结8-12h,经粉碎、过筛、除铁,即得磷酸铁锂成品。
上述方法在制备磷酸铁锂或锂电池中的应用。
本发明的有益效果是:
1、本发明含锂废水综合回收制取磷酸铁锂的方法中,首先采用可溶性镁盐去除废水中的氟离子,再经调节pH为碱性去除镁离子以及其中的镍钴锰过渡金属,再通过过量磷酸盐的加入,使废水中的锂得到了进一步沉淀,降低了锂含量,通过芬顿反应,降低废水化学需氧量的同时,将多余的磷酸根去除,形成磷酸铁沉淀,最后,经絮凝剂进一步絮凝沉降,净化废水的同时,使磷酸锂、磷酸铁等从废水中脱离,并为下一步制备磷酸铁锂提供了碳源;
2、本发明含锂废水综合回收制取磷酸铁锂的方法中,通过氨水对固体渣进行浸出,使其中的镍钴锰溶解后,得到含氨镍钴锰溶液与含锂磷铁渣混合,通过原料补充,水热反应并蒸发回收氨水,使镍钴锰作为掺杂元素,并煅烧制备掺杂过渡金属的磷酸铁锂成品,不但回收了废水中的锂、过渡金属等,进一步得到高附加值的磷酸铁锂正极材料。
反应原理如下:
向含锂废水中加入可溶性镁盐:Mg
2++2F
-→MgF
2↓。
调节滤液A的pH为碱性:Mg
2++2OH
-→Mg(OH)
2↓Me
2++2OH
-→Me(OH)
2↓(Me为Ni、Co及Mn中的至少一种)。
向滤液B中加入可溶性磷酸盐:3Li
++PO
4
3-→Li
3PO
4↓。
加入Fe
2+和H
2O
2进行芬顿反应:Fe
3++PO
4
3-→FePO
4↓ Fe
3++3OH
-→Fe(OH)
3↓。
将固体渣氨浸:Me(OH)
2+6NH
3→[Me(NH
3)
6](OH)
2。
将混合料进行水热反应,干燥烧结:Li
3PO
4+3NH
3·H
2O→3LiOH+(NH
4)
3PO
4[Me(NH
3)
6]
2++PO
4
3-→Me
3(PO
4)
2+6NH
34LiOH+4FePO
4+C→4LiFePO
4+CO
2+2H
2O。
图1为本发明实施例1的流程示意图;
图2为本发明实施例1得到的磷酸铁锂的SEM图。
下面结合具体实施例对本发明做进一步的说明,其中实施例1-3和对比例1用到的含锂废水的水质如下:硫酸钠105.6g/L,氯化钠2.3g/L,锂含量5.9g/L,镍钴锰总含量5.2mg/L,氟含量185.5mg/L,COD:17000mg/L。
实施例1:
一种含锂废水综合回收制取磷酸铁锂的方法,如图1所示,包括如下步骤:
(1)向含锂废水中加入硫酸镁,使废水中镁离子含量为0.05mol/L;
(2)固液分离,得到氟化镁渣和滤液A;
(3)使用氢氧化钠调节滤液A的pH为11.5,固液分离,得到固体渣和滤液B;
(4)向滤液B中加入磷酸钠,使滤液B中的磷含量为0.20mol/L;
(5)调节滤液B的pH为3.5,并对滤液B进行芬顿反应处理,加入Fe
2+和H
2O
2,投加的Fe
2+/H
2O
2摩尔比为1.5:1,直至滤液B中的磷含量低于10
-5mol/L,COD低于200mg/L;
(6)向滤液B中加入PAM,PAM的加入量为0.008g/L;
(7)固液分离,得到含锂磷铁渣和滤液C,滤液C经调控pH后可直接排放,或进入MVR系统蒸发结晶,制备元明粉和纯水;
(8)将步骤(3)所得固体渣按照固液比50g/L加入到4mol/L的氨水中,浸泡1h,固液分离,得到氢氧化镁渣和滤液D;
(9)将滤液D与步骤(7)所得含锂磷铁渣混合后,补加碳酸锂和磷酸一氢铵,使混合料中Li:P:Fe=1.05:1.0:1.0;
(10)将混合料移至反应釜中密封,于180℃下水热反应3h;
(11)水热反应结束后,打开反应釜密封,继续在100℃加热至液相完全蒸发,并回收氨水;
(12)将蒸发残留的固体物料于惰性气氛850℃下烧结8h,经粉碎、过筛、除铁,即得磷酸铁锂成品,制得的磷酸铁锂成品的SEM图如图2所示。
实施例2:
一种含锂废水综合回收制取磷酸铁锂的方法,包括如下步骤:
(1)向含锂废水中加入硫酸镁,使废水中镁离子含量为0.08mol/L;
(2)固液分离,得到氟化镁渣和滤液A;
(3)使用氢氧化钠调节滤液A的pH为11.8,固液分离,得到固体渣和滤液B;
(4)向滤液B中加入磷酸钠,使滤液B中的磷含量为0.10mol/L;
(5)调节滤液B的pH为3,并对滤液B进行芬顿反应处理,加入Fe
2+和H
2O
2,投加的Fe
2+/H
2O
2摩尔比为1.3:1,直至滤液B中的磷含量低于10
-5mol/L,COD低于200mg/L;
(6)向滤液B中加入PAM,PAM的加入量为0.009g/L;
(7)固液分离,得到含锂磷铁渣和滤液C,滤液C经调控pH后可直接排放,或进入MVR系统蒸发结晶,制备元明粉和纯水;
(8)将步骤(3)所得固体渣按照固液比150g/L加入到5mol/L的氨水中,浸泡1.5h,固液分离,得到氢氧化镁渣和滤液D;
(9)将滤液D与步骤(7)所得含锂磷铁渣混合后,补加氢氧化锂和磷酸二氢铵,使混合料中Li:P:Fe=1.03:0.99:0.99;
(10)将混合料移至反应釜中密封,于170℃下水热反应9h;
(11)水热反应结束后,打开反应釜密封,继续在90℃加热至液相完全蒸发,并回收氨水;
(12)将蒸发残留的固体物料于惰性气氛700℃下烧结10h,经粉碎、 过筛、除铁,即得磷酸铁锂成品。
实施例3:
一种含锂废水综合回收制取磷酸铁锂的方法,包括如下步骤:
(1)向含锂废水中加入硫酸镁,使废水中镁离子含量为0.10mol/L;
(2)固液分离,得到氟化镁渣和滤液A;
(3)使用氢氧化钠调节滤液A的pH为12,固液分离,得到固体渣和滤液B;
(4)向滤液B中加入磷酸钠,使滤液B中的磷含量为0.01mol/L;
(5)调节滤液B的pH为4,并对滤液B进行芬顿反应处理,加入Fe
2+和H
2O
2,投加的Fe
2+/H
2O
2摩尔比为1.0:1,直至滤液B中的磷含量低于10
-5mol/L,COD低于200mg/L;
(6)向滤液B中加入PAM,PAM的加入量为0.01g/L;
(7)固液分离,得到含锂磷铁渣和滤液C,滤液C经调控pH后可直接排放,或进入MVR系统蒸发结晶,制备元明粉和纯水;
(8)将步骤(3)所得固体渣按照固液比300g/L加入到6mol/L的氨水中,浸泡2h,固液分离,得到氢氧化镁渣和滤液D;
(9)将滤液D与步骤(7)所得含锂磷铁渣混合后,补加草酸锂和磷酸,使混合料中Li:P:Fe=1.0:0.98:0.98;
(10)将混合料移至反应釜中密封,于150℃下水热反应15h;
(11)水热反应结束后,打开反应釜密封,继续在80℃加热至液相完全蒸发,并回收氨水;
(12)将蒸发残留的固体物料于惰性气氛500℃下烧结12h,经粉碎、过筛、除铁,即得磷酸铁锂成品。
对比例1:
一种含锂废水综合回收制取磷酸铁锂的方法,包括如下步骤:
(1)向含锂废水中加入碳酸钠,使废水中的碳酸根含量为0.20mol/L,固液分离,得到碳酸盐;
(2)调节废水pH为4,并对废水进行芬顿反应处理,加入Fe
2+和H
2O
2,投加的Fe
2+/H
2O
2摩尔比为1.5:1,加入量与实施例1相同;
(3)向废水中加入PAM,PAM的加入量为0.008g/L;
(4)固液分离,废水铁含量较高、pH为4.6较低无法达标排放,固体进入下一工序;
(5)将得到的固体与碳酸锂、磷酸一氢铵、氢氧化铁混合,混合料中Li:P:Fe=1.05:1.0:1.0;
(6)将混合料研磨2h后,在150℃下干燥4h;
(7)将干燥后的物料在惰性气氛850℃下烧结9h;
(8)经粉碎、过筛、除铁,即得磷酸铁锂成品。
试验例:
1.对实施例1-3及对比例1在综合回收制取磷酸铁锂的过程中排放的废水(滤液C)的水质进行检测,检测结果如表1所示。
表1:废水水质检测结果:
由表1可知,利用本发明的含锂废水综合回收制取磷酸铁锂的方法在综合回收制取磷酸铁锂的过程中排放的废水中Li的含量不超过10.2mg/L,远小于对比例1中排放的废水中Li的含量,同时利用本发明的含锂废水综合回收制取磷酸铁锂的方法在综合回收制取磷酸铁锂的过程中排放的废水中的镍钴锰及铁均未检出,且F不超过7.8mg/L。
2.以实施例1-3及对比例1得到的磷酸铁锂正极材料,乙炔黑为导电剂,PVDF为粘结剂,按质量比8:1:1进行混合,并加入一定量的有机溶剂NMP,搅拌后涂覆于铝箔上制成正极片,负极采用金属锂片;隔膜为Celgard2400聚丙烯多孔膜;电解液中溶剂为EC、DMC和EMC按质量比1:1:1组成的溶液,溶质为LiPF
6,LiPF
6的浓度为1.0mol/L;在手套箱内组装2023型扣式电池。对电池进行充放电循环性能测试,在截止电压2.2-4.3V范围内,测试0.2C、1C放 电比容量;测试电化学性能结果如表2所示。
表2:电池的电化学性能测试结果:
0.2C放电容量mAh/g | 1C放电容量mAh/g | |
实施例1 | 150.2 | 141.8 |
实施例2 | 147.6 | 140.1 |
实施例3 | 149.7 | 142.2 |
对比例1 | 127.2 | 109.4 |
由表2可知,利用本发明的含锂废水综合回收制取磷酸铁锂的方法制备得到的磷酸铁锂在组装成电池后,0.2C放电容量能达到147.6mAh/g以上,1C放电容量能达到140.1mAh/g以上,电化学性能优于对比例1含锂废水综合回收制取磷酸铁锂的方法制备得到的磷酸铁锂。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
- 一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:包括以下步骤:(1)向含锂废水中加入可溶性镁盐,固液分离,得到滤液A和氟化镁渣,调节所述滤液A的pH为碱性,固液分离得到固体渣和滤液B;(2)向所述滤液B中加入可溶性磷酸盐后,调节所述滤液B的pH为酸性,再加入Fe 2+和H 2O 2进行芬顿反应,再加入絮凝剂,固液分离得到含锂磷铁渣和滤液C;(3)将步骤(1)得到的所述固体渣氨浸后固液分离,得到滤液D,将所述滤液D与步骤(2)得到的所述含锂磷铁渣混合,补加锂源和磷源后得到混合料,将所述混合料进行水热反应,干燥,烧结得到磷酸铁锂成品。
- 根据权利要求1所述的一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:步骤(1)中向所述含锂废水中加入可溶性镁盐后,所述含锂废水中镁离子含量为0.03-0.15mol/L。
- 根据权利要求1所述的一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:步骤(1)中所述调节pH为碱性是指调节pH为10-13。
- 根据权利要求1所述的一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:步骤(2)中,向所述滤液B中加入可溶性磷酸盐后,所述滤液B中的磷含量为0.01-0.50mol/L。
- 根据权利要求1所述的一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:步骤(2)中,所述调节pH为酸性是指调节pH为3-5.5。
- 根据权利要求1所述的一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:步骤(2)中,加入Fe 2+和H 2O 2的摩尔比为(1-3):1。
- 根据权利要求1所述的一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:步骤(2)中,进行芬顿反应后,所述滤液B中的磷含量低于10 -5mol/L,化学需氧量低于200mg/L。
- 根据权利要求1所述的一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:步骤(2)中,所述絮凝剂的加入量不低于0.005g/L。
- 根据权利要求1所述的一种含锂废水综合回收制取磷酸铁锂的方法,其特征在于:步骤(3)中,所述固体渣氨浸时,所述固体渣与氨水的固液比为50-500g/L。
- 权利要求1-9任一项所述的方法在制备磷酸铁锂或锂电池中的应用。
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