CN115583641A - Method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores - Google Patents
Method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores Download PDFInfo
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- CN115583641A CN115583641A CN202211437917.9A CN202211437917A CN115583641A CN 115583641 A CN115583641 A CN 115583641A CN 202211437917 A CN202211437917 A CN 202211437917A CN 115583641 A CN115583641 A CN 115583641A
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- iron
- iron phosphate
- lithium
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- pyrite cinder
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 50
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000011028 pyrite Substances 0.000 title claims abstract description 38
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 38
- 239000003818 cinder Substances 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 107
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000002386 leaching Methods 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 8
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical group Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims 1
- 235000019799 monosodium phosphate Nutrition 0.000 claims 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims 1
- 239000000243 solution Substances 0.000 description 30
- 239000005955 Ferric phosphate Substances 0.000 description 20
- 229940032958 ferric phosphate Drugs 0.000 description 20
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 20
- 238000003756 stirring Methods 0.000 description 16
- 239000010431 corundum Substances 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229940116007 ferrous phosphate Drugs 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- -1 inorganic acid hydrogen peroxide Chemical class 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
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-
- 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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores, which comprises the following steps: (1) Crushing and roasting the waste lithium iron phosphate cores, screening by using a vibrating screen, and uniformly mixing undersize products with pyrite cinder; (2) Roasting the mixture at high temperature, leaching with sulfuric acid, and filtering to obtain a leachate; (3) Adding iron powder into the leaching solution to reduce ferric iron into bivalent iron, adding sodium hydroxide to remove impurities, and filtering to obtain a purified solution; (4) Adding phosphoric acid into the purified solution to adjust the iron-phosphorus ratio, and adjusting the pH value by using sulfuric acid; (5) Adding hydrogen peroxide for reaction, filtering, and carrying out the next lithium extraction process on the filtrate; and (3) carrying out secondary washing on the filter cake by using pure water, and carrying out the working procedures of drying, roasting, crushing and the like to obtain the battery-grade anhydrous iron phosphate. The method effectively combines the extraction of the iron source in the pyrite cinder and the extraction of the iron, the phosphorus and the lithium in the lithium iron phosphate black powder, has simple process flow, and is easy to realize industrialization.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a method for extracting iron in iron-containing waste materials and regenerating ferric phosphate in waste lithium iron phosphate cores.
Background
The high-speed development of new energy automobiles promotes the price of upstream raw materials of power batteries to greatly rise, and the recycling of waste power batteries is an effective way for relieving the shortage of upstream raw materials. At present, the power battery recycling industry in China is still in a starting stage, and with continuous rising of the permeability of new energy automobiles, the power battery recycling industry has huge future development space and is expected to become the next tuyere industry. The waste lithium iron phosphate batteries are disassembled and reconstructed on a large scale only in recent years, the lithium carbonate price is rapidly increased, and the original lithium iron phosphate batteries which do not have disassembling value can be profitable, however, most of the waste lithium iron phosphate battery recycling enterprises only carry out lithium extraction at present, the iron phosphate is not recycled, and the waste lithium iron phosphate batteries are completely stockpiled or sold at a low price (200-300 yuan/ton), and the full-component recycling of the waste lithium iron phosphate batteries is not realized.
Four recyclable useful components, namely copper foil, aluminum foil, graphite powder and lithium iron phosphate black powder, can be obtained after the waste lithium iron phosphate battery is disassembled (the lithium iron phosphate black powder contains the graphite powder during integral crushing), and in order to further remove electrolyte impurities which are not completely removed from the lithium iron phosphate black powder, the waste lithium iron phosphate battery usually needs to be further roasted at high temperature. Chinese patent CN112811404A (jiujiang tianci) discloses a recycling method of waste lithium iron phosphate cathode powder, adding inorganic acid and complexing agent to the cathode powder for dealumination, then adding inorganic acid hydrogen peroxide for reaction to obtain coarse iron phosphate, continuously adding inorganic acid for dissolution, and then adjusting pH with alkali to obtain iron phosphate. Chinese patent CN113912032A discloses a method for recovering and preparing battery-grade lithium carbonate and iron phosphate from waste lithium iron phosphate battery positive electrode powder, which adopts oxidation acid leaching to selectively leach lithium, the leaching solution is used for preparing lithium carbonate, the lithium leaching slag is leached again by sulfuric acid phosphoric acid, and simultaneously iron powder is added to reduce ferric iron into bivalent iron, and iron phosphate is obtained after removing aluminum and heavy metals.
Pyrite cinder is a byproduct after pyrite is used for preparing sulfuric acid, iron generally exists in a high-price ferric oxide form, the leaching rate is low (less than 30%) by directly leaching with sulfuric acid (no matter how high the concentration and the temperature is), reduction treatment is generally required, and the lithium iron phosphate black powder contains 3% -5% of carbon (about 20% of carbon when the whole is crushed), and can play a role in reduction at high temperature. According to the invention, through the synergistic effect among the raw material components, the synchronous extraction of iron in the pyrite cinder and the recovery of lithium, iron and phosphorus in the lithium iron phosphate black powder can be realized, the repeated construction of the device is avoided, in addition, the full-component leaching process of iron, phosphorus and lithium is creatively adopted in the wet-process leaching process, the secondary leaching of the lithium leaching slag after the selective lithium leaching is avoided, and the process flow is shortened.
Disclosure of Invention
The core technical problems to be solved by the invention are three: firstly, carbon in the lithium iron phosphate black powder is fully utilized to carry out reduction treatment on high-valence iron in pyrite cinder, so that the leaching rate of iron in acid leaching is improved; secondly, the leaching rates of three elements such as lithium, iron, phosphorus and the like in the mixture of the lithium iron phosphate black powder and the pyrite cinder are ensured to be more than 90%; and thirdly, removing impurities from the leaching solution in a targeted manner according to the quality of the iron phosphate product (the quality when the impurities are not removed).
The technical scheme of the invention is a method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores, which mainly comprises the following steps:
(1) Crushing and roasting the waste lithium iron phosphate cores, screening by using a vibrating screen, and uniformly mixing undersize products (lithium iron phosphate black powder) and pyrite cinder in a spiral belt mixer according to the proportion of 2;
(2) Roasting the mixture at high temperature in a tubular atmosphere furnace, leaching the mixture by using sulfuric acid after roasting is finished, and filtering to obtain leachate containing phosphorus, iron, lithium and partial impurities;
(3) Adding iron powder into the leachate to reduce ferric iron into bivalent iron, adding sodium hydroxide, controlling the pH of the solution to remove impurities, and filtering to obtain a purified solution mainly containing phosphorus, iron and lithium;
(4) Adding industrial wet-process purified phosphoric acid into the purified solution to adjust the iron-phosphorus ratio, and further adjusting the pH value of the solution by using sulfuric acid;
(5) Adding hydrogen peroxide for oxidation reaction, filtering after the reaction is finished, and performing the next lithium extraction process on the filtrate, wherein the main component of the filtrate is lithium sulfate; and (3) carrying out secondary washing on the filter cake by using pure water, and carrying out the working procedures of drying, roasting, crushing, demagnetizing and the like to obtain the battery-grade anhydrous iron phosphate.
According to the method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores, in the step (1), the crushing process is performed in a closed box (N) 2 Atmosphere) is completed; the roasting temperature is 300-350 ℃, and the roasting time is 1.5-2 h; cooling after roasting, and then performing high-frequency vibration screening, wherein the undersize is lithium iron phosphate black powder; the content of iron in the pyrite cinder is 45-55%, the particle size is not more than 150 mu m and not more than 70%, and all the iron passes through a standard sieve of 1 mm.
According to the method for preparing battery-grade iron phosphate by cooperation of the pyrite cinder and the waste lithium iron phosphate cores, in the step (2), the roasting temperature is 600-1000 ℃, the roasting time is 0.5-3 hours, preferably 800-850 ℃, and the roasting time is 1.5-2 hours; the molar ratio of sulfuric acid to iron in the mixture in acid leaching is 1.3-1.7, preferably 1.5-1.55. The concentration of the sulfuric acid used is 15 to 40 percent, preferably 20 to 25 percent. The acid leaching temperature is 70-95 ℃, and the acid leaching time is 0.5-3 h.
According to the method for preparing battery-grade iron phosphate by cooperation of the pyrite cinder and the waste lithium iron phosphate cores, in the step (3), the addition amount of the reduced iron powder is controlled in a mode that the reduced iron powder is added until bubbles (hydrogen) appear in the solution, the sodium hydroxide is added at a concentration of 30%, and the final pH value is controlled to be 3.5-5.5, preferably 4.0-4.5.
According to the method for preparing battery-grade iron phosphate by synergy of pyrite cinder and waste lithium iron phosphate cores, industrial wet-process purified phosphoric acid (with the phosphoric acid concentration of 85%) is added in the step (4) to adjust the iron-phosphorus ratio of the solution to be 0.94-0.95, and then industrial-grade concentrated sulfuric acid is used to adjust the pH value of the solution to be 1.5-2.1, preferably 1.7-1.8.
According to the method for preparing the battery-grade iron phosphate by the cooperation of the pyrite cinder and the waste lithium iron phosphate cores, the concentration of hydrogen peroxide used in the step (5) is 1% -10%, preferably 3% -5%, and the molar ratio of hydrogen peroxide to iron is 0.6-0.65. The oxidation reaction is controlled under the condition that hydrogen peroxide is added at room temperature for 15-20 min, the temperature is raised to 80-95 ℃ after the hydrogen peroxide is added, and the reaction is carried out for 0.5-1 h after the color of the slurry turns from yellow to white (after 2-3 h). The volume ratio of the washing water consumption to the slurry quantity before filtration is 1-1.2 in the second-stage washing, the drying temperature is 200-250 ℃, the drying time is 1-2 h, the roasting temperature is 600-700 ℃, and the roasting time is 1.5-2 h.
After oxidation reaction, lithium-containing filtrate is obtained by filtering, the main component of the lithium-containing filtrate is lithium sulfate, and a small part of impurities such as iron, nickel, cobalt, manganese, magnesium and the like are also obtained, the impurities can be removed by adjusting the pH value to 10-11, then sodium carbonate is added for precipitating lithium, and pure water is used for multi-stage washing, so that battery-grade lithium carbonate can be obtained.
The invention mixes and roasts the lithium iron phosphate black powder and the pyrite cinder, and when the roasted product is subjected to acid leaching, the leaching rates of iron, phosphorus and lithium are all more than 93 percent. The key points of the invention are the impurity removal of the pickle liquor and the preparation of battery-grade iron phosphate. After the ferric phosphate is taken out of the system by adding hydrogen peroxide, the process for preparing the lithium carbonate by removing impurities from the residual lithium-containing filtrate is relatively simple, because the lithium hydroxide has higher solubility (12.8 g/100g of water, 20 ℃), and most metal ion impurities can be removed when the pH is adjusted to 10-11. The purpose of adding iron powder during impurity removal and purification is to remove copper on one hand, reduce a small part of ferric iron into divalent iron on the other hand, and remove aluminum (Fe) by using a precipitation method better under a divalent iron system 3+ Begins to precipitate at pH > 1.5, while Fe 2+ At pH > 6.5Precipitation is started at the moment), iron powder is preferentially mixed with Cu 2+ And Fe 3+ Reacted with H + The reaction can therefore be controlled by the phenomenon that the solution starts to bubble. The purpose of adding sodium hydroxide is to remove aluminum (Al) 3+ Precipitation starts at pH > 3.3). In addition, in a ferrous system, because the solution contains more phosphate radicals, the ferrous phosphate colloid has a very good adsorption effect on tetravalent titanium ions, and the removal rate of titanium can reach more than 98%.
Compared with the existing lithium iron phosphate black powder recovery process, the invention has the following advantages:
(1) Creatively and synergistically utilizing the pyrite cinder and the waste lithium iron phosphate batteries, introducing the pyrite cinder powder in the roasting process of the lithium iron phosphate black powder, and reducing iron oxide in the pyrite cinder into FeO (containing part of Fe) by utilizing carbon in the lithium iron phosphate black powder 3 O 4 ) The leaching rate of iron is high, and the source approach of the iron source in the iron phosphate production is widened (most of the existing iron sources are the byproduct ferrous sulfate heptahydrate of titanium dioxide).
(2) The acid leaching process adopts a full-component leaching process, and hydrogen peroxide is added after the elements of phosphorus and iron are leached, so that the secondary acid leaching of the iron phosphate black slag after lithium extraction by the existing acid leaching oxidation process is avoided, and the process flow is shortened.
(3) After the roasted mixture is acid-leached by sulfuric acid, the iron is mainly divalent, and a small amount of iron powder is added to obtain a small amount of Fe 3+ All reduced to Fe 2+ The impurities can be removed more easily in a ferrous system, and the removal rate of the aluminum and the titanium is high and is over 95 percent.
(4) The iron phosphate is prepared by adopting a one-step method, and the process flow is simple. The invention slowly adds hydrogen peroxide into the ferrous phosphate purification solution, then raises the temperature, and the reaction and the aging crystal transformation (turning from yellow to white in appearance) are carried out in the same kettle, the process is simple, and the process is easy to control.
Drawings
FIG. 1 is a block diagram of the process flow of the present invention.
Detailed Description
The electric core of the waste lithium iron phosphate power battery after being disassembled isN 2 Crushing in a protective closed box, transferring the crushed material to a rotary tubular furnace for calcination at 300 ℃ for 1.5h. Then sorting by a high-frequency vibrating screen, wherein the undersize is lithium iron phosphate black powder (positive and negative electrode powder). And crushing, winnowing, reselecting and the like on oversize products to respectively obtain the copper foil and the aluminum foil. The main chemical composition of the lithium iron phosphate black powder is shown in table 1,
TABLE 1 main chemical composition of lithium iron phosphate black powder (unit:%)
| Name (R) | Fe | P | Li | Mn | Mg | Al | Na | K | Cu |
| Content (c) of | 26.56 | 14.8 | 3.80 | 0.0502 | 0.0005 | 0.0174 | 0.0077 | 0.0021 | 0.0112 |
| Name (R) | Ti | Ni | Co | Zn | As | Pb | Cr | ||
| Content (c) of | 0.0050 | 0.0156 | 0.0246 | Not detected out | 0.0046 | 0.001 | 0.0021 |
The main chemical composition of the pyrite cinder used in the invention is shown in table 2,
table 2 main chemical composition of pyrite cinder (unit:%)
| Name (R) | Fe 2 O 3 | SiO 2 | SO 3 | CaO | Al 2 O 3 | MgO | TiO 2 | K 2 O | P 2 O 5 |
| Content (wt.) | 70.68 | 12.75 | 7.81 | 3.17 | 2.34 | 0.69 | 0.14 | 0.55 | 0.06 |
And respectively weighing 20kg of the lithium iron phosphate black powder and 10kg of pyrite cinder powder in a ribbon mixer, and intermittently mixing for 1 hour to obtain a uniformly distributed mixture.
Example 1
Weighing 200g of mixture in a square corundum crucible, placing the crucible in a tubular atmosphere furnace, vacuumizing, and introducing N 2 To normal pressure, then continuously introducing N at the rate of 10mL/min 2 . Setting the temperature of the tube furnace at 1000 ℃, heating rate of 10 ℃/min, constant temperature period time of 1h, and cooling to obtain the roasting material. Placing the roasted material in a 2L glass jacket reaction kettle, adding 950.6g of 17% sulfuric acid (diluted by industrial-grade sulfuric acid), starting stirring, starting jacket circulating water for heating (an external constant temperature tank), setting the temperature at 92 ℃, reacting for 1h, and filtering after the reaction is finished. 6.6g of reduced iron powder was added to the filtrate (controlled in such a manner that the solution was added until bubbles began to appear), the pH of the solution was adjusted to 4.9 with 20% sodium hydroxide, 15g of 0.1% polyacrylamide solution was added thereto, followed by stirring for 2min and filtration. 82.3g of technical grade phosphoric acid (85%) was added to the filtrate, and the iron-phosphorus ratio of the solution was measured to be 0.973.
Transferring the solution into a 2L glass jacket reaction kettle, starting stirring (the stirring speed is 400 r/min), adding industrial-grade concentrated sulfuric acid to adjust the pH value of the solution to 1.65, slowly adding 775.8g of 3.5% hydrogen peroxide (the molar ratio of hydrogen peroxide to iron is 0.62. Transferring the filter cake into a 2000ml beaker, adding 1408g of pure water for repulping, filtering after stirring for 10min (the stirring speed is 400 r/min), repeating the processes (secondary repulping and washing of the filter cake and recycling of washing water) to obtain ferric phosphate dihydrate with the water content of 49.6%, transferring the ferric phosphate dihydrate into a tray, placing the tray in a blast drying oven at 200 ℃, drying for 2h, cooling, crushing, transferring the ferric phosphate dihydrate into a square corundum crucible, placing the square corundum crucible in a box-type resistance furnace at 630 ℃, and calcining for 2h to obtain 191.3g of anhydrous ferric phosphate, wherein the recovery rate of iron in the mixture of the ferric phosphate black powder and the pyrite cinder is 91.72%, the recovery rate of phosphorus is 88.18%, and the analysis index of the anhydrous ferric phosphate is shown in table 3.
Example 2
Weighing 200g of mixture in a square corundum crucible, placing the crucible in a tubular atmosphere furnace, and vacuumizingIntroduction of N 2 To normal pressure, then continuously introducing N at the rate of 10mL/min 2 . Setting the temperature of the tubular furnace to 850 ℃, heating rate to 10 ℃/min, keeping the temperature for 2h in a constant-temperature period, and cooling to obtain the roasted material. Placing the roasted material in a 2L glass jacket reaction kettle, adding 843.3g of 22% sulfuric acid (industrial-grade sulfuric acid for dilution), starting stirring, starting jacket circulating water for heating (an external constant temperature tank), setting the temperature at 75 ℃, reacting for 2h, and filtering after the reaction is finished. 6.5g of reduced iron powder was added to the filtrate (by controlling the addition until bubbles began to appear in the solution), the pH of the solution was adjusted to 4.3 with 20% sodium hydroxide, 15g of 0.1% polyacrylamide solution was added thereto, and the mixture was stirred for 2min and filtered. 81.8g of technical grade phosphoric acid (85%) was added to the filtrate, and the iron-phosphorus ratio of the solution was measured to be 0.975.
Transferring the solution into a 2L glass jacket reaction kettle, starting stirring (the stirring speed is 400 r/min), adding industrial-grade concentrated sulfuric acid to adjust the pH value of the solution to be 1.95, slowly adding 612.3g of hydrogen peroxide with the concentration of 4.5% (the molar ratio of hydrogen peroxide to iron is 0.63. Transferring the filter cake into a 2000ml beaker, adding 1137.5g of pure water for repulping, stirring for 10min (stirring speed is 400 r/min), filtering, repeating the processes (secondary repulping and washing of the filter cake, and recycling of washing water) to obtain ferric phosphate dihydrate with the water content of 47.3%, transferring the ferric phosphate dihydrate into a tray, placing the tray in a forced air drying oven at 250 ℃, drying for 1h, cooling, crushing, transferring the crushed ferric phosphate into a square corundum crucible, placing the square corundum crucible in a box-type resistance furnace at 680 ℃, and calcining for 1.5h to obtain 188.9g of anhydrous ferric phosphate, wherein the recovery rate of iron in the mixture of the ferric phosphate black powder and the pyrite cinder is 90.95%, the recovery rate of phosphorus is 86.03%, and the analysis index of the anhydrous ferric phosphate is shown in Table 3.
Example 3
Weighing 200g of mixture in a square corundum crucible, placing the crucible in a tubular atmosphere furnace, vacuumizing, and introducing N 2 To normal pressure, then N is continuously introduced at a rate of 10mL/min 2 . Setting the temperature of the tubular furnace to 900 ℃, heating rate to 10 ℃/min, constant temperature period time to 2.5h, and cooling to obtain the roasting material. Placing the roasting material in705.4g of 28 percent sulfuric acid (diluted by industrial-grade sulfuric acid) is added into a 2L glass jacket reaction kettle, stirring is started, jacket circulating water is started for heating (an external constant temperature tank), the temperature is set to 83 ℃, the reaction time is 2 hours, and filtering is carried out after the reaction is finished. 6.9g of reduced iron powder was added to the filtrate (by controlling the addition until bubbles began to appear in the solution), the pH of the solution was adjusted to 3.9 with 20% sodium hydroxide, 15g of 0.1% polyacrylamide solution was added thereto, and the mixture was stirred for 2min and filtered. 82.1g of technical grade phosphoric acid (85%) was added to the filtrate, and the iron-phosphorus ratio of the solution was measured to be 0.978.
Transferring the solution into a 2L glass jacket reaction kettle, starting stirring (the stirring speed is 400 r/min), adding industrial-grade concentrated sulfuric acid to adjust the pH value of the solution to 1.83, slowly adding 714.6g of hydrogen peroxide with the concentration of 4% (the molar ratio of hydrogen peroxide to iron is 0.65. And transferring the filter cake into a 2000ml beaker, adding 1102.3g of pure water for repulping, stirring for 10min (stirring speed is 400 r/min), filtering, repeating the processes (secondary repulping washing and washing of the filter cake, recycling of washing water) to obtain ferric phosphate dihydrate with the water content of 47.9%, transferring the ferric phosphate dihydrate into a tray, placing the tray into a blast drying oven at 230 ℃, drying for 2h, cooling, crushing, transferring the crushed ferric phosphate into a square corundum crucible, placing the square corundum crucible into a box-type resistance furnace at 650 ℃, calcining for 2h to obtain 190.8g of anhydrous ferric phosphate, wherein the recovery rate of iron in the mixture of the ferric phosphate black powder and the pyrite cinder is 90.71%, the recovery rate of phosphorus is 88.46%, and the analysis indexes of the anhydrous ferric phosphate are shown in Table 3.
Table 3 indexes of anhydrous iron phosphate products of examples 1 to 3
| Name (R) | Example 1 | Example 2 | Example 3 | Some downstream customer index |
| Fe (%) | 36.25 | 36.37 | 36.14 | 36.0～36.6 |
| P (%) | 20.65 | 20.61 | 20.71 | 20.6～21.0 |
| Fe/P | 0.972 | 0.977 | 0.966 | 0.960～0.980 |
| Na（ppm） | 37 | 29 | 35 | ≤50 |
| Mg（ppm） | 32 | 33 | 26 | ≤250 |
| K（ppm） | 19 | 14 | 11 | ≤50 |
| Ca（ppm） | 43 | 47 | 29 | ≤50 |
| Zn（ppm） | 2 | 3 | 3 | ≤30 |
| Cu（ppm） | Not detected out | Undetected | Not detected out | ≤20 |
| Al（ppm） | 49 | 43 | 37 | ≤150 |
| Mn（ppm） | 117 | 103 | 97 | ≤200 |
| Ni（ppm） | 2 | 2 | 1 | ≤10 |
| Pb （ppm） | 16 | 15 | 21 | ≤30 |
| S（ppm） | 192 | 279 | 213 | ≤350 |
| Ti（ppm） | 12 | 12 | 17 | ≤150 |
| Magnetic foreign matter (ppm) | 0.8 | 0.6 | 0.6 | ≤1 |
| Moisture (ppm) | 2601 | 2414 | 2219 | ≤5000 |
| pH | 2.99 | 3.13 | 3.07 | 2.7～3.6 |
| Particle size D 50 μm | 2.92 | 3.25 | 3.13 | ≤5 |
| Specific surface area m 2 /g | 4.25 | 4.32 | 4.56 | 4～8 |
| Tap density g/cm 3 | 0.809 | 0.827 | 0.833 | ≥0.6 |
Claims (7)
1. A method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores is characterized by comprising the following steps:
(1) Crushing and roasting the waste lithium iron phosphate cores, screening by using a vibrating screen, and uniformly mixing undersize products and pyrite cinder in a spiral belt mixer according to the proportion of 2;
(2) Roasting the mixture in a tubular atmosphere furnace at high temperature, leaching the mixture by using sulfuric acid after roasting is finished, and filtering to obtain leachate containing phosphorus, iron, lithium and part of impurities;
(3) Adding iron powder into the leachate to reduce ferric iron into bivalent iron, adding sodium hydroxide, controlling the pH of the solution to remove impurities, and filtering to obtain a purifying solution mainly containing phosphorus, iron and lithium;
(4) Adding industrial wet-process purified phosphoric acid into the purified solution to adjust the iron-phosphorus ratio, and further adjusting the pH value of the solution by using sulfuric acid;
(5) Adding hydrogen peroxide for oxidation reaction, filtering after the reaction is finished, and performing the next lithium extraction process on the filtrate, wherein the main component of the filtrate is lithium sulfate; and (3) carrying out secondary washing on the filter cake by using pure water, and carrying out the working procedures of drying, roasting, crushing and the like to obtain the battery-grade anhydrous iron phosphate.
2. The method for preparing battery-grade iron phosphate by using the cooperation of pyrite cinder and waste lithium iron phosphate cores according to claim 1, wherein the crushing process in the step (1) is performed under N 2 The protection is finished in a closed box; the roasting temperature is 300-350 ℃, and the roasting time is 1.5-2 h; cooling after roasting, and then performing high-frequency vibration screening, wherein the undersize is lithium iron phosphate black powder; the content of the pyrite cinder iron is 45-55%, the particle size is not more than 150 mu m and not more than 70%, and all the pyrite cinder iron passes through a standard sieve with the size of 1 mm.
3. The method for preparing battery-grade iron phosphate by the cooperation of the pyrite cinder and the waste lithium iron phosphate cores according to claim 1, wherein the roasting temperature in the step (2) is 600-1000 ℃, and the time is 0.5-3 h; the mol ratio of the sulfuric acid to the iron in the mixture during acid leaching is 1.3-1.7, the concentration of the used sulfuric acid is 15% -40%, the acid leaching temperature is 70-95 ℃, and the acid leaching time is 0.5-3 h.
4. The method for preparing battery-grade iron phosphate by cooperation of the pyrite cinder and the waste lithium iron phosphate cores according to claim 1, wherein in the step (3), the adding amount of the iron powder is controlled in a manner that the adding amount of the iron powder is controlled until bubbles appear in the solution, the adding amount of the sodium hydroxide is configured to be 30%, and the final pH value is controlled to be 3.5-5.5.
5. The method for the synergistic utilization of the pyrite cinder and the waste lithium iron phosphate batteries according to claim 1, characterized in that the industrial wet-process purified phosphoric acid with the phosphoric acid concentration of 85% is added in the step (4), the iron-phosphorus ratio of the solution is adjusted to 0.94-0.95, and then the pH value of the solution is adjusted to 1.5-2.1 by using industrial-grade concentrated sulfuric acid.
6. The method for preparing battery-grade iron phosphate by the cooperation of the pyrite cinder and the waste lithium iron phosphate cores according to claim 1, wherein the concentration of hydrogen peroxide used in the step (5) is 1-10%, and the molar ratio of hydrogen peroxide to iron is 0.6-0.65; the oxidation reaction is controlled under the condition that hydrogen peroxide is added at room temperature for 15-20 min, the temperature is raised to 80-95 ℃ after the hydrogen peroxide is added, and the reaction lasts for 0.5-1 h after the color of the slurry turns from yellow to white; and removing impurities and purifying lithium sulfate filtrate, and then adding sodium carbonate/sodium dihydrogen phosphate to obtain a lithium carbonate/lithium dihydrogen phosphate product.
7. The method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores according to claim 1, characterized in that the volume ratio of the amount of washing water to the amount of slurry before filtration in the secondary washing in step (5) is 1-1.2, the drying temperature is 200-250 ℃, the drying time is 1-2 h, the roasting temperature is 600-700 ℃, and the roasting time is 1.5-2 h.
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