CN118221082A - Method for recycling iron and phosphorus in waste lithium iron phosphate battery - Google Patents
Method for recycling iron and phosphorus in waste lithium iron phosphate battery Download PDFInfo
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- CN118221082A CN118221082A CN202410232610.8A CN202410232610A CN118221082A CN 118221082 A CN118221082 A CN 118221082A CN 202410232610 A CN202410232610 A CN 202410232610A CN 118221082 A CN118221082 A CN 118221082A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 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 39
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002699 waste material Substances 0.000 title claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000011574 phosphorus Substances 0.000 title claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000002386 leaching Methods 0.000 claims abstract description 45
- 239000000919 ceramic Substances 0.000 claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000706 filtrate Substances 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 238000001728 nano-filtration Methods 0.000 claims abstract description 29
- 239000002893 slag Substances 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 8
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- -1 (mercapto) methyl siloxane Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 5
- SIXCVGPRIOVMFR-UHFFFAOYSA-M lithium;2-hydroxyethanesulfonate Chemical compound [Li+].OCCS([O-])(=O)=O SIXCVGPRIOVMFR-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- HQLSVOWNWRZPBW-UHFFFAOYSA-N [Li].CCOC(=O)C=C Chemical compound [Li].CCOC(=O)C=C HQLSVOWNWRZPBW-UHFFFAOYSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- SCMOGELHJOYZSW-UHFFFAOYSA-N [Li]CCO Chemical compound [Li]CCO SCMOGELHJOYZSW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000197 pyrolysis Methods 0.000 description 10
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- RDXARWSSOJYNLI-UHFFFAOYSA-N [P].[K] Chemical compound [P].[K] RDXARWSSOJYNLI-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000007885 magnetic separation Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005262 decarbonization Methods 0.000 description 3
- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling iron and phosphorus in waste lithium iron phosphate batteries, and belongs to the technical field of lithium battery recycling. The invention provides a salt assisted carbothermic reduction-water leaching method, which is a process for efficiently separating phosphorus and iron elements in phosphorus-iron slag and recovering Fe products from the phosphorus-iron slag, wherein the comprehensive recovery rate of iron is up to 99.3 percent by utilizing the process. According to the invention, lithium sulfonate and ferrocene are led into the chip zirconia ceramic nanofiltration membrane through chemical reaction, so that in the filtration of water leaching filtrate, the compatibility with fine lithium-containing and iron-suspending particles is improved, the content of metal impurities in the filtrate is reduced, the efficient separation of iron and phosphorus in ferrophosphorus slag is improved, and the metal content in the filtrate is lower than 8%, and the minimum content can reach 0.06%.
Description
Technical Field
The invention belongs to the technical field of lithium battery recycling, and particularly relates to a method for recycling iron and phosphorus in waste lithium iron phosphate batteries.
Background
Lithium ion batteries are widely regarded as environment-friendly and pollution-free green batteries, but the recycling of the lithium ion batteries is incorrect and pollution is generated. Although the lithium ion battery does not contain toxic heavy metals such as mercury, cadmium, lead and the like, the influence of anode and cathode materials, electrolyte and the like of the battery on the environment and human bodies is still large. If common garbage treatment methods are adopted to treat lithium ion batteries (landfill, incineration, composting and the like), metals such as cobalt, nickel, lithium, manganese and the like in the batteries, and various organic and inorganic compounds can cause metal pollution, organic matter pollution, dust pollution, acid-base pollution. Lithium ion electrolyte machine transformants such as LiPF 6, lithium hexafluoroarsenate (LiAsF 6), lithium triflate (LiCF 3SO3), hydrofluoric acid (HF), and the like, solvents and hydrolysates such as ethylene glycol dimethyl ether (DME), methanol, formic acid, and the like are toxic substances. Therefore, the waste lithium ion batteries need to be recycled, so that the harm to the natural environment and the health of human bodies is reduced.
The positive electrode powder is subjected to gas reduction roasting according to the patent application with the publication number of CN 117013128A; adding the reduction roasting material into sulfuric acid for dissolution and filtration to obtain first filtrate and filter residues, concentrating the first filtrate, adding carbonate to form precipitate, and filtering and drying the precipitate to obtain lithium carbonate; adding filter residues into an acid solution, adding a reducing agent, heating, stirring and leaching to obtain a leaching solution; adding a copper removing agent after regulating the pH value of the leaching solution, adding an oxidizing agent, and removing impurities after heat preservation to obtain a nickel-cobalt-manganese mixed solution; evaporating and crystallizing to obtain nickel-cobalt-manganese mixed salt and enriched mother liquor; adding fluoride into the enriched mother solution, preserving heat to enable calcium and magnesium to form calcium and magnesium fluoride precipitate, filtering to obtain second filtrate, returning most of the second filtrate to the acid solution in the previous step, and discharging a small part of the second filtrate.
Then evenly mixing the nickel cobalt lithium manganate waste, carbon powder and silicon dioxide to obtain a mixed material according to the patent application with the publication number of CN 116903003A; the mixed material is subjected to gradient temperature dynamic calcination, the temperature is gradually increased in the calcination process, and the calcination is sequentially carried out at each calcination temperature stage; adding water into the calcined material for size mixing, adding sodium hydroxide, and carrying out solid-liquid separation to obtain a mixed solid; adding pure water into the mixed solid to prepare slurry, performing solid-liquid separation after carbonization to obtain a mixture of lithium bicarbonate solution and nickel cobalt manganese oxide, and purifying the lithium bicarbonate solution to obtain a purified solution; and pyrolyzing the purified solution, and carrying out solid-liquid separation to obtain crude lithium carbonate.
Another patent application with publication number CN116903002a discloses a full-element recovery method of nickel cobalt lithium manganate waste, belongs to the field of waste lithium battery recovery, and solves the problems of large medicament consumption, complex process and production influence caused by a large amount of sodium sulfate decahydrate in the existing recovery method. The method comprises the following steps: mixing and calcining the materials and carbon powder; pulping and carbonizing; pyrolyzing; and (3) circulating acid leaching, and separating out different sulfates by fractional crystallization through temperature control by utilizing solubility characteristics.
At present, the proportion of the lithium iron phosphate battery in the retired lithium battery is gradually increased, and a large amount of ferrophosphorus slag can be remained and piled up while the lithium of the battery is extracted, so that the ferrophosphorus slag has complex components and high impurity content, and the recycling is needed urgently.
Disclosure of Invention
The invention aims to provide a method for recovering iron and phosphorus in a waste lithium iron phosphate battery, which aims at solving the problems that the residual ferrophosphorus slag in the lithium iron phosphate positive electrode material after lithium recovery does not exist in an effective treatment method, so that a salt assisted carbothermic reduction-water leaching separation method is adopted, fePO 4 is firstly converted into Fe and a phosphorus-containing compound under the combined action of metal carbonate and carbothermic reduction, and then the Fe and the phosphorus are separated in a water leaching mode, so that Fe products are recovered. The process is simple to operate, does not use strong inorganic acid, is efficient to recover and has industrial application prospect.
The invention aims to solve the technical problems: realizing the high-efficiency separation of iron and phosphorus in the ferrophosphorus slag.
The aim of the invention can be achieved by the following technical scheme:
in one aspect, the invention provides a method for recovering iron and phosphorus in a waste lithium iron phosphate battery, which comprises the following steps:
(1) Discharging, crushing and screening the waste lithium iron phosphate battery to obtain a diaphragm, al, cu, lithium iron phosphate powder, graphite powder and a shell, and performing heat treatment on the lithium iron phosphate powder;
(2) Leaching the lithium iron phosphate powder subjected to the heat treatment in the step (1) by using acid, and filtering and washing to obtain ferrophosphorus slag;
(3) Uniformly mixing the ferrophosphorus slag, carbon and metal carbonate obtained in the step (2), and roasting under inert gas to obtain a roasting product;
(4) Leaching the roasting product in the step (3) to obtain slurry, and performing solid-liquid separation on the slurry to obtain leaching residues and leaching filtrate;
(5) And magnetically separating the water leaching residues to obtain iron, and filtering the water leaching filtrate by using a modified ceramic membrane to obtain the phosphorus-containing compound.
Specifically, in the step (5), the preparation method of the modified ceramic membrane comprises the following steps:
generating ferrocene-containing lithium ethyl acrylate sulfonate from 2-hydroxyethyl lithium sulfonate, ferrocenyl methyl alcohol and isocyanate ethyl acrylate, and then carrying out a sulfhydryl-acrylic acid addition reaction with sulfhydryl groups of the sulfhydryl ceramic nanofiltration membrane to obtain the modified ceramic membrane.
Further, the modified ceramic membrane is a lithium-loaded sheet type zirconia ceramic nanofiltration membrane, and the specific preparation method comprises the following steps:
S1, performing S1; placing 100-120 parts of a sheet zirconia ceramic nanofiltration membrane with an average pore diameter of 2-8nm, 2-4 parts of (mercapto) methyl siloxane and 600-1000 parts of petroleum ether into a stirring kettle, stirring and modifying for 2-5 hours at the temperature of 30-42 ℃, taking out and airing; obtaining a sulfhydrylation sheet type zirconia ceramic nanofiltration membrane;
S2: adding 0.6-3 parts of lithium 2-hydroxyethyl sulfonate, 10-20 parts of ferrocenyl methyl alcohol, 14-28 parts of isocyanate ethyl acrylate, 2-5 parts of dibutyl tin dilaurate, 500-800 parts of petroleum ether, stirring for 2-5 hours at 50-60 ℃, adding 100-120 parts of thiolated sheet type zirconia ceramic nanofiltration membrane, 5-10 parts of potassium tert-butoxide, stirring for 30-100 minutes at 50-60 ℃, taking out and drying to obtain the lithium-loaded sheet type zirconia ceramic nanofiltration membrane.
2-Lithium isethionate, ferrocenyl methyl alcohol and isocyanate ethyl acrylate to generate ferrocene-containing lithium ethyl acrylate sulfonate; carrying out a sulfhydryl-acrylic acid addition reaction with sulfhydryl of the sulfhydryl-type zirconia ceramic nanofiltration membrane; lithium sulfonate and ferrocene are led into the chip zirconia ceramic nanofiltration membrane through chemical reaction, so that the compatibility with fine lithium-containing and iron-containing suspended particles can be improved in the filtration of water leaching filtrate.
Specifically, in the step (1), the conditions of the heat treatment are as follows: and (3) performing anaerobic pyrolysis on organic matters of the waste lithium iron phosphate battery in a high-temperature pyrolysis furnace under the condition of 450-600 ℃ for 2-5 hours by adopting nitrogen protection. Part of the impurities can be removed by heat treatment.
Specifically, in the step (2), the acid is hydrochloric acid, the concentration of the acid is 1-3mol/L,
The mass ratio of the lithium iron phosphate powder to the acid is 3-4:4-5.
Preferably, in the step (3), the carbon is at least one of graphite, activated carbon and coke, and graphite is preferred in the present invention,
The metal carbonate is at least one of potassium carbonate, sodium bicarbonate and magnesium carbonate, preferably potassium carbonate in the invention,
The mass ratio of the ferrophosphorus slag to the carbon to the metal carbonate is 1:0.1-0.5:0.6-1.
Preferably, in the step (3), the roasting temperature is 800-1000 ℃ and the roasting time is 3-5h.
Preferably, in the step (4), the water immersion time is 0.8-1.5h.
The invention has the beneficial effects that:
(1) In order to realize the aim of recycling the ferrophosphorus slag, a salt assisted carbothermic reduction-water leaching method is innovatively developed, the phosphorus and iron elements in the ferrophosphorus slag are efficiently separated, and Fe products are recovered from the ferrophosphorus slag, and the comprehensive recovery rate of iron by using the process disclosed by the invention is as high as 99.3%.
(2) According to the invention, lithium sulfonate and ferrocene are led into the chip zirconia ceramic nanofiltration membrane through chemical reaction, so that in the filtration of water leaching filtrate, the compatibility with fine lithium-containing and iron-suspending particles is improved, the content of metal impurities in the filtrate is reduced, the efficient separation of iron and phosphorus in ferrophosphorus slag is improved, and the metal content in the filtrate is lower than 8%, and the minimum content can reach 0.06%.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
1. Modified ceramic membrane
S1: 110g of a sheet zirconia ceramic nanofiltration membrane with an average pore diameter of 5nm, 408.6g of (mercapto) methyl siloxane and 4080g of petroleum ether are put into a stirring kettle, stirred and modified for 4 hours at the temperature of 35 ℃, taken out and dried; obtaining a mercapto-type zirconia ceramic nanofiltration membrane;
S2: in a reaction kettle, 254g of lithium 2-hydroxyethyl sulfonate, 3240.9g of ferrocenyl methyl alcohol, 2963.52g of ethyl isocyanate acrylate, 2526.24g of dibutyltin dilaurate, 3250g of petroleum ether and stirring for 4 hours at the temperature of 55 ℃, then 110g of a mercapto-chip zirconia ceramic nanofiltration membrane and 785.47g of potassium tert-butoxide are added, stirring is carried out for 65 minutes at the temperature of 55 ℃, and the lithium-loaded chip zirconia ceramic nanofiltration membrane is obtained after taking out and drying.
2. A method for recovering iron and phosphorus in waste lithium iron phosphate batteries comprises the following steps:
(1) Discharging, disassembling, crushing and sorting the lithium battery to respectively obtain a diaphragm, al, cu, iron lithium powder, graphite powder and a shell;
(2) Performing heat treatment on the lithium iron powder, performing anaerobic pyrolysis on organic matters of the waste lithium iron phosphate battery in a high-temperature pyrolysis furnace under the condition of 450 ℃ for 2 hours by adopting nitrogen protection, and removing part of impurities through heat treatment;
adding 54.75g of hydrochloric acid solution for leaching; the concentration of the acid is 1mol/L; the mass ratio of the lithium iron phosphate powder to the acid is 3:4;
(3) Filtering, washing and removing impurities to obtain a lithium product and ferrophosphorus slag;
(4) The mass ratio of K 2CO3 to the ferrophosphorus slag is 0.7, the mass ratio of graphite powder to the ferrophosphorus slag is 0.3, and the mixture is placed in a tube furnace for roasting for 4 hours at 900 ℃ in an argon atmosphere after being uniformly mixed;
(5) Soaking the roasting product in water for 1h at room temperature to obtain slurry;
(6) Then carrying out solid-liquid separation on the slurry to obtain water leaching residues and water leaching filtrate;
(7) The water leaching residue is subjected to magnetic separation and decarbonization to obtain an iron product, and the water leaching filtrate is filtered by adopting a modified ceramic membrane and evaporated and concentrated to obtain a phosphorus-potassium compound.
The detection result shows that: the overall recovery of iron in this example was 99.3% and the metal content in the filtrate was 0.06%.
Example 2
1. Modified ceramic membrane
S1: 100g of a sheet zirconia ceramic nanofiltration membrane with an average pore diameter of 5nm, 272.4g of (mercapto) methyl siloxane and 3060g of petroleum ether are put into a stirring kettle, stirred and modified for 2 hours at the temperature of 30 ℃, taken out and dried; obtaining a mercapto-type zirconia ceramic nanofiltration membrane;
S2: 76.2g of lithium 2-hydroxyethyl sulfonate, 2160.6g of ferrocene methanol, 1975.68g of ethyl isocyanate acrylate, 1684.16g of dibutyltin dilaurate, 2550g of petroleum ether and stirring at 50 ℃ for 2 hours, 100g of a mercapto-plate zirconia ceramic nanofiltration membrane and 561.05g of potassium tert-butoxide are added, stirring is carried out at 50 ℃ for 30 minutes, and the obtained mixture is taken out and dried to obtain the lithium-loaded plate zirconia ceramic nanofiltration membrane.
2. A method for recovering iron and phosphorus in waste lithium iron phosphate batteries comprises the following steps:
(1) Discharging, disassembling, crushing and sorting the lithium battery to respectively obtain a diaphragm, al, cu, iron lithium powder, graphite powder and a shell;
(2) Performing heat treatment on the lithium iron powder, performing anaerobic pyrolysis on organic matters of the waste lithium iron phosphate battery in a high-temperature pyrolysis furnace under the condition of 500 ℃ for 3 hours by adopting nitrogen protection, and removing part of impurities through heat treatment;
Adding 36.5g of hydrochloric acid solution for leaching; the concentration of the acid is 1.8mol/L; the mass ratio of the lithium iron phosphate powder to the acid is 3.5:4.5;
(3) Filtering, washing and removing impurities to obtain a lithium product and ferrophosphorus slag;
(4) The mass ratio of K 2CO3 to the ferrophosphorus slag is 0.6, the mass ratio of graphite powder to the ferrophosphorus slag is 0.1, and the mixture is placed in a tube furnace for roasting for 3 hours at 800 ℃ in an argon atmosphere after being uniformly mixed;
(5) Soaking the roasting product in water for 0.8h at room temperature to obtain slurry;
(6) Then carrying out solid-liquid separation on the slurry to obtain water leaching residues and water leaching filtrate;
(7) The water leaching residue is subjected to magnetic separation and decarbonization to obtain an iron product, and the water leaching filtrate is filtered by adopting a modified ceramic membrane and evaporated and concentrated to obtain a phosphorus-potassium compound.
The detection result shows that: the overall recovery of iron in this example was 98.1% and the metal content in the filtrate was 3.5%.
Example 3
1. Modified ceramic membrane
S1: 120g of a sheet zirconia ceramic nanofiltration membrane with an average pore diameter of 5nm, 544.8g of (mercapto) methyl siloxane and 5100g of petroleum ether are put into a stirring kettle, stirred and modified for 5 hours at the temperature of 42 ℃, taken out and dried; obtaining a mercapto-type zirconia ceramic nanofiltration membrane;
S2: in a reaction kettle, 4321.2g of lithium 2-hydroxyethyl sulfonate, 4321.2g of ferrocenyl methyl alcohol, 3951.36g of ethyl isocyanate acrylate, 4210.4g of dibutyltin dilaurate, 4080g of petroleum ether and stirring at 60 ℃ for 5 hours, then 120g of a mercapto-plate zirconia ceramic nanofiltration membrane and 1122.1g of potassium tert-butoxide are added, stirring is carried out at 60 ℃ for 100 minutes, and the obtained product is taken out and dried to obtain the lithium-loaded plate zirconia ceramic nanofiltration membrane.
2. A method for recovering iron and phosphorus in waste lithium iron phosphate batteries comprises the following steps:
(1) Discharging, disassembling, crushing and sorting the lithium battery to respectively obtain a diaphragm, al, cu, iron lithium powder, graphite powder and a shell;
(2) Performing heat treatment on the lithium iron powder, performing anaerobic pyrolysis on organic matters of the waste lithium iron phosphate battery in a high-temperature pyrolysis furnace under the condition of 600 ℃ for 5 hours by adopting nitrogen protection, and removing part of impurities through heat treatment;
Adding 73g of hydrochloric acid solution for leaching; the concentration of the acid is 3mol/L; the mass ratio of the lithium iron phosphate powder to the acid is 4:5;
(3) Filtering, washing and removing impurities to obtain a lithium product and ferrophosphorus slag;
(4) The mass ratio of K 2CO3 to the ferrophosphorus slag is 1.0, the mass ratio of graphite powder to the ferrophosphorus slag is 0.5, and the mixture is placed in a tube furnace for roasting for 5 hours at 1000 ℃ in an argon atmosphere after being uniformly mixed;
(5) Soaking the roasting product in water for 1.5 hours at room temperature to obtain slurry;
(6) Then carrying out solid-liquid separation on the slurry to obtain water leaching residues and water leaching filtrate;
(7) The water leaching residue is subjected to magnetic separation and decarbonization to obtain an iron product, and the water leaching filtrate is filtered by adopting a modified ceramic membrane and evaporated and concentrated to obtain a phosphorus-potassium compound.
The detection result shows that: the overall recovery of iron in this example was 97.5% and the metal content in the filtrate was 7.85%.
Comparative example 1
The filtering of the water leaching filtrate adopts a 5nm chip zirconia ceramic nanofiltration membrane for separation. The other steps are the same as in example 1.
The detection result shows that: the overall recovery of iron in this example was 85% and the metal content in the filtrate was 36.85%.
Comparative example 2
A method for recovering iron and phosphorus in waste lithium iron phosphate batteries comprises the following steps:
(1) Discharging, disassembling, crushing and sorting the lithium battery to respectively obtain a diaphragm, al, cu, iron lithium powder, graphite powder and a shell;
(2) Performing heat treatment on the lithium iron powder, performing anaerobic pyrolysis on organic matters of the waste lithium iron phosphate battery in a high-temperature pyrolysis furnace under the condition of 450 ℃ for 2 hours by adopting nitrogen protection, and removing part of impurities through heat treatment;
adding 36.5g of hydrochloric acid solution for leaching; the concentration of the acid is 1mol/L; the mass ratio of the lithium iron phosphate powder to the acid is 3:4;
(3) Filtering, washing and removing impurities to obtain a lithium product and ferrophosphorus slag;
(4) The mass ratio of K 2CO3 to the ferrophosphorus slag is 1.0, and the mass ratio of graphite powder to the ferrophosphorus slag is 0.5, and the mixture is placed in a tube furnace for roasting for 4 hours at 300 ℃ in an argon atmosphere after being uniformly mixed;
(5) Leaching the roasting product in water at room temperature to obtain slurry;
(6) Then carrying out solid-liquid separation on the slurry to obtain water leaching residues and water leaching filtrate;
(7) And (3) carrying out magnetic separation on the water leaching residues to remove carbon to obtain an iron product, filtering the water leaching filtrate by a filter, and evaporating and concentrating to obtain the phosphorus-potassium compound.
The detection result shows that: the overall recovery of iron in this example was 83.5% and the metal content in the filtrate was 33.77%.
Claims (8)
1. The method for recycling the iron and the phosphorus in the waste lithium iron phosphate battery is characterized by comprising the following steps of:
(1) Discharging, crushing, disassembling and sorting the waste lithium iron phosphate battery to obtain a diaphragm, al, cu, lithium iron phosphate powder, graphite powder and a shell, and performing heat treatment on the lithium iron phosphate powder;
(2) Leaching the lithium iron phosphate powder subjected to the heat treatment in the step (1) by using acid, and filtering and washing to obtain ferrophosphorus slag;
(3) Uniformly mixing the ferrophosphorus slag, carbon and metal carbonate obtained in the step (2), and roasting under inert gas to obtain a roasting product;
(4) Leaching the roasting product in the step (3) to obtain slurry, and performing solid-liquid separation on the slurry to obtain leaching residues and leaching filtrate;
(5) And magnetically separating the water leaching residues to obtain iron, and filtering the water leaching filtrate by using a modified ceramic membrane to obtain the phosphorus-containing compound.
2. The method for recovering iron and phosphorus in a waste lithium iron phosphate battery according to claim 1, wherein in the step (5), the preparation method of the modified ceramic film is as follows:
generating ferrocene-containing lithium ethyl acrylate sulfonate from 2-hydroxyethyl lithium sulfonate, ferrocenyl methyl alcohol and isocyanate ethyl acrylate, and then carrying out a sulfhydryl-acrylic acid addition reaction with sulfhydryl groups of the sulfhydryl ceramic nanofiltration membrane to obtain the modified ceramic membrane.
3. The method for recovering iron and phosphorus in the waste lithium iron phosphate battery as claimed in claim 2, wherein the modified ceramic membrane is a lithium-loaded sheet type zirconia ceramic nanofiltration membrane, and the specific preparation method comprises the following steps:
S1, performing S1; placing 100-120 parts of a sheet zirconia ceramic nanofiltration membrane with an average pore diameter of 2-8nm, 2-4 parts of (mercapto) methyl siloxane and 600-1000 parts of petroleum ether into a stirring kettle, stirring and modifying for 2-5 hours at the temperature of 30-42 ℃, taking out and airing; obtaining a sulfhydrylation sheet type zirconia ceramic nanofiltration membrane;
S2: adding 0.6-3 parts of lithium 2-hydroxyethyl sulfonate, 10-20 parts of ferrocenyl methyl alcohol, 14-28 parts of isocyanate ethyl acrylate, 2-5 parts of dibutyl tin dilaurate, 500-800 parts of petroleum ether, stirring for 2-5 hours at 50-60 ℃, adding 100-120 parts of thiolated sheet type zirconia ceramic nanofiltration membrane, 5-10 parts of potassium tert-butoxide, stirring for 30-100 minutes at 50-60 ℃, taking out and drying to obtain the lithium-loaded sheet type zirconia ceramic nanofiltration membrane.
4. The method for recovering iron and phosphorus from a waste lithium iron phosphate battery according to claim 1, wherein in the step (1), the heat treatment conditions are as follows: heat treating at 450-600deg.C for 2-5h.
5. The method for recovering iron and phosphorus in a waste lithium iron phosphate battery according to claim 1, wherein in the step (2), the acid is hydrochloric acid, the concentration of the acid is 1-3mol/L,
The mass ratio of the lithium iron phosphate powder to the acid is 3-4:4-5.
6. The method for recycling iron and phosphorus in waste lithium iron phosphate batteries according to claim 1, wherein in the step (3), the carbon is at least one of graphite, activated carbon and coke, the metal carbonate is at least one of potassium carbonate, sodium bicarbonate and magnesium carbonate,
The mass ratio of the ferrophosphorus slag to the carbon to the metal carbonate is 1:0.1-0.5:0.6-1.
7. The method for recovering iron and phosphorus in a waste lithium iron phosphate battery according to claim 1, wherein in the step (3), the roasting temperature is 800-1000 ℃ and the roasting time is 3-5h.
8. The method for recovering iron and phosphorus in a waste lithium iron phosphate battery according to claim 1, wherein in the step (4), the water immersion time is 0.8-1.5h.
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