CN116706302A - Lithium battery recycling method - Google Patents
Lithium battery recycling method Download PDFInfo
- Publication number
- CN116706302A CN116706302A CN202310535500.4A CN202310535500A CN116706302A CN 116706302 A CN116706302 A CN 116706302A CN 202310535500 A CN202310535500 A CN 202310535500A CN 116706302 A CN116706302 A CN 116706302A
- Authority
- CN
- China
- Prior art keywords
- lithium
- battery
- iron phosphate
- leaching
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 125
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- 238000004064 recycling Methods 0.000 title claims abstract description 30
- 238000000605 extraction Methods 0.000 claims abstract description 83
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 70
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000008569 process Effects 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 59
- 239000012535 impurity Substances 0.000 claims abstract description 56
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- 239000010941 cobalt Substances 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004090 dissolution Methods 0.000 claims abstract description 24
- 238000000197 pyrolysis Methods 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 14
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 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 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 6
- 239000010405 anode material Substances 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 239000010816 packaging waste Substances 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000002386 leaching Methods 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000006115 defluorination reaction Methods 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 14
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 230000005484 gravity Effects 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 51
- 239000007788 liquid Substances 0.000 description 29
- 239000002893 slag Substances 0.000 description 29
- 238000000926 separation method Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000005086 pumping Methods 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 239000011572 manganese Substances 0.000 description 17
- 238000003860 storage Methods 0.000 description 16
- 238000003825 pressing Methods 0.000 description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 13
- 229910052748 manganese Inorganic materials 0.000 description 13
- 239000012528 membrane Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 13
- 239000002699 waste material Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000007127 saponification reaction Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 9
- 229940044175 cobalt sulfate Drugs 0.000 description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000000428 dust Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000000909 electrodialysis Methods 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000002910 solid waste Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 241000080590 Niso Species 0.000 description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 208000028659 discharge Diseases 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000010926 waste battery Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 229910018661 Ni(OH) Inorganic materials 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- WFXRJNDIBXZNJK-KVVVOXFISA-N azanium;(z)-octadec-9-enoate Chemical compound N.CCCCCCCC\C=C/CCCCCCCC(O)=O WFXRJNDIBXZNJK-KVVVOXFISA-N 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- -1 fluoride ions Chemical class 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000010815 organic waste Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
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- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- AIKPDSWOXGWNNL-UHFFFAOYSA-N [Mn].[Mg].[Ca] Chemical compound [Mn].[Mg].[Ca] AIKPDSWOXGWNNL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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Abstract
The invention discloses a lithium battery recycling method, which comprises the following steps: a pretreatment procedure, namely detecting and decomposing a lithium battery monomer, crushing, drying and sorting the lithium battery monomer, obtaining lithium iron phosphate battery powder and ternary battery powder through pyrolysis, respectively mixing the lithium iron phosphate battery powder and the ternary battery powder into sulfuric acid, and finally roasting to obtain water-soluble lithium sulfate; the method comprises the following steps of repairing the anode material, namely, shredding, pyrolyzing, screening, removing iron, crushing, electromagnetically removing iron, mixing and packaging waste lithium iron phosphate anode sheets and leftover materials; the acid dissolution impurity removal process comprises the steps of removing impurities of a lithium iron phosphate battery and removing impurities of a ternary battery, wherein the lithium iron phosphate battery is used for removing impurities to remove copper, fluorine and aluminum, and the ternary battery is used for removing impurities to remove nickel, cobalt, manganese, copper, aluminum and iron; an extraction procedure comprising the steps of removing impurities by extraction and extracting manganese, nickel, cobalt and magnesium; and preparing lithium hydroxide. The lithium battery recycling method can improve recycling efficiency.
Description
Technical Field
The invention relates to a lithium battery recycling process, in particular to a lithium battery recycling method.
Background
With the wide application of lithium batteries, a large amount of waste lithium batteries are generated, so that the recycling of the lithium batteries is beneficial to saving resources and reducing pollution.
The existing recovery mode is as follows: the lithium battery is firstly physically crushed and then chemically separated, so that various components are gradually separated.
However, the existing recovery mode is inefficient.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a lithium battery recovery method which can improve the recovery efficiency.
According to the embodiment of the invention, the lithium battery recycling method comprises the following steps:
a pretreatment procedure, namely detecting and decomposing a lithium battery monomer, crushing, drying and sorting the lithium battery monomer, obtaining lithium iron phosphate battery powder and ternary battery powder through pyrolysis, respectively mixing the lithium iron phosphate battery powder and the ternary battery powder into sulfuric acid, and finally roasting to obtain water-soluble lithium sulfate;
the method comprises the following steps of repairing the anode material, namely, shredding, pyrolyzing, screening, removing iron, crushing, electromagnetically removing iron, mixing and packaging waste lithium iron phosphate anode sheets and leftover materials;
the acid dissolution impurity removal process comprises the steps of removing impurities of a lithium iron phosphate battery and removing impurities of a ternary battery, wherein the lithium iron phosphate battery is used for removing impurities to remove copper, fluorine and aluminum, and the ternary battery is used for removing impurities to remove nickel, cobalt, manganese, copper, aluminum and iron;
an extraction procedure comprising the steps of removing impurities by extraction and extracting manganese, nickel, cobalt and magnesium;
and preparing lithium hydroxide.
According to the lithium battery recycling method provided by the embodiment of the invention, batteries with different degrees are detected and decomposed in the pretreatment process, and battery monomers are utilized or disassembled in a gradient manner.
According to the lithium battery recycling method, in the pretreatment process, sorting comprises gravity sorting and stripping sorting.
According to the lithium battery recycling method, in the pretreatment process, the pyrolysis temperature is 450-550 ℃, and the pyrolysis time is 1-3 hours.
According to the lithium battery recovery method provided by the embodiment of the invention, in the positive electrode material repair process, permanent magnet is utilized to remove iron first, and then electromagnetic iron is utilized to remove iron.
According to the lithium battery recycling method provided by the embodiment of the invention, in the impurity removal of the lithium iron phosphate battery, hydrogen peroxide and sulfuric acid solution are used for leaching, and the PH value is controlled to be neutral.
According to the lithium battery recycling method provided by the embodiment of the invention, in the impurity removal of the lithium iron phosphate battery, the total leaching time is 3.5 hours.
According to the lithium battery recycling method provided by the embodiment of the invention, in the impurity removal of the lithium iron phosphate battery, the aluminum is removed by reversely adjusting the PH.
According to the lithium battery recovery method provided by the embodiment of the invention, in the process of removing impurities of the ternary battery, lithium sulfate is obtained by leaching water at normal temperature, and the slag is subjected to nickel-cobalt-manganese precipitation and reduction acid leaching.
According to the lithium battery recovery method provided by the embodiment of the invention, the prepared lithium hydroxide further comprises chemical defluorination and resin defluorination.
The lithium battery recycling method provided by the embodiment of the invention has at least the following beneficial effects:
according to the invention, the recovered batteries are detected, so that gradient utilization or scrapping recovery is performed according to the degree of the batteries, the recovery efficiency is improved, unnecessary scrapping is avoided, the recovery cost is reduced, and the environment protection is facilitated.
Meanwhile, the lithium iron phosphate battery and the ternary battery are subjected to distinguishing treatment, so that lithium can be recovered in a targeted manner, process compatibility is less considered, and process difficulty is reduced.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 is a pretreatment flow chart of a lithium battery recycling method according to an embodiment of the invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, it should be understood that references to orientation descriptions such as upper, lower, front, rear, left, right, etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description of the present invention and to simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, a number means one or more, a number means two or more, and greater than, less than, exceeding, etc. are understood to not include the present number, and above, below, within, etc. are understood to include the present number. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
A lithium battery recycling method according to an embodiment of the present invention is described below with reference to the accompanying drawings.
Referring to fig. 1, the present invention is directed to an embodiment of a lithium battery recycling method.
Specifically, the method takes waste lithium ion batteries as raw materials for recycling, and the whole production process comprises the following steps: pretreatment, positive electrode material repair, acid dissolution and impurity removal (lithium iron phosphate acid dissolution and impurity removal and ternary battery acid dissolution and impurity removal), extraction and lithium hydroxide preparation.
Pretreatment process for waste batteries
According to the method, 2 dismantling and crushing lines are arranged in total, lithium iron phosphate batteries and ternary batteries respectively enter respective pretreatment production lines, waste gas generated by the two pretreatment lines enters respective pyrolysis furnace incineration systems to remove organic waste gas after being dedusted by respective dedusters, and the waste gas after incineration is collected into 1 alkali spray towers to be treated and then is discharged by 1 exhaust pipe.
The pretreatment process comprises residual energy detection, charge and discharge, battery pack splitting, battery module detection, battery module disassembly, crushing, drying, gravity separation, stripping separation and pyrolysis, wherein lithium iron phosphate battery powder generated by pyrolysis enters an acid dissolution workshop for further treatment; and (3) carrying out acid mixing and roasting on the ternary battery powder after pyrolysis, and enabling the battery powder generated by roasting to enter an acid dissolution workshop for further treatment.
Detailed description of pretreatment procedure the process flow:
1. and (3) residual energy detection: according to the specification in the detection of residual energy of recycling of a power battery for a vehicle (GB/T34015-2017), the main content of residual energy detection and recycling of a waste battery comprises appearance inspection, information acquisition, voltage discrimination, primary discharge current determination, discharge capacity determination, material discrimination and residual energy detection, the residual energy detection is carried out according to the specification in the technical requirement of a power storage battery for an electric automobile and the electric performance of a test method (GB/T31486-2015), and the residual energy detection is mainly to carry out a charge and discharge test on a battery module by using a charge and discharge instrument, and no chemical reaction is involved.
2. Charging and discharging: the discharging process does not involve soaking and discharging of sodium chloride solution, the power battery is generally selected to be 1-3 ℃, the discharging multiplying power is too small, the working efficiency is affected, and the battery is discharged to be lower than 2V to finish the operation.
3. Splitting a battery pack: different splitting modes are adopted according to different battery pack shells. After the shell is removed, battery parts are detached respectively, and the battery parts comprise a bracket, a partition plate, a high-voltage wire harness, a circuit board, a battery management system, a high-voltage safety box and the like. In the disassembling process of the power storage battery pack (pack), the contact between the disassembled metal parts such as bolts and the positions of the high-low voltage connecting contacts is avoided so as to avoid short circuit and fire, and meanwhile, a special magnetic tool is needed for taking out the metal parts falling in the gaps.
4. And (3) detecting a battery module: and detecting the battery modules detached from the battery pack, transferring the power storage battery modules meeting the standard requirement of the 'power battery recycling echelon utilization requirement' to an echelon utilization enterprise, and enabling the battery modules not meeting the echelon utilization requirement to enter a battery module disassembly procedure.
5. Disassembling a battery module: and lifting the power storage battery module to a disassembly tool table by a special insulating lifting appliance for the unqualified battery module, and adopting different disassembly modes according to different battery module shells.
After the shell is removed, connecting parts such as a wire, a connecting sheet and the like are removed by a tool, and the battery monomer is separated.
The process flow of the battery monomer comprises the following specific steps:
6. crushing the single battery: according to different specifications and sizes of the waste batteries and different shell materials, the waste batteries are added into a special anaerobic crusher through a belt conveyor to disintegrate and crush the battery shells in batches, and the size of crushed materials is about 3 cm to 5cm.
7. And (3) drying: the crushed battery waste is sent to an electric heating drying system through a closed conveying system for the thermal volatilization of electrolyte, the volatilization temperature is 120 ℃, and the flow of drying carrier gas (nitrogen) is 300m 3 And/h. A fully-closed exhaust hood is arranged at the charging port of the crusher, the air outlet of the thermal volatilization system and the like.
8. Gravity separation: the method comprises the steps of respectively producing shells, diaphragms and waste pole pieces from dried battery fragments by utilizing the specific gravity difference of various materials through a physical separation method, cleaning the separated battery shells and diaphragms, selling the battery shells and diaphragms as common solid waste, and enabling the waste pole pieces to enter a high-speed decomposer.
9. Stripping and sorting: after the waste pole piece is decomposed and stripped by a high-speed decomposer, the negative pole piece is broken and agglomerated into copper particles with the granularity of about 0.2mm, the positive pole piece is rubbed and agglomerated into aluminum particles with the granularity of about 0.5mm, the pole piece active substance coating is decomposed into battery powder with the granularity of less than 50 mu m, the copper aluminum particles and the battery powder are further screened and produced respectively, and the battery powder is sent to the next working procedure. Copper and aluminum particles are separated into copper particles and aluminum particles through a specific gravity separator, and the copper particles and the aluminum particles are sold as common solid waste.
10. And (3) pyrolysis: the battery powder is added into a rotary kiln which takes natural gas as an energy source for pyrolysis, and the main purpose is to remove binder, electrolyte and the like in the battery cell. Firstly, heat treatment is carried out for 1-3 h at the temperature of 450-550 ℃, and organic matters, HF and CO2 are generated by thermal decomposition of high boiling point electrolyte organic matters and binder polyvinylidene fluoride (PVDF) under non-oxidizing atmosphere. The lithium iron phosphate battery powder is conveyed to an acid dissolution workshop through a pipeline after pyrolysis to carry out wet lithium extraction in the acid dissolution workshop; and (3) pyrolyzing the ternary battery powder, and then, entering a mixed acid roasting procedure.
11. Acid mixing: and after pyrolysis, the ternary battery powder is directly conveyed into a slurrying device by a metering screw conveyor arranged below a storage bin and slurried by 50% sulfuric acid metered by a metering pump, and the slurried ternary battery powder is conveyed to an electric heating drying system for heating by a closed conveying system.
12. Roasting: the dried material is sent to a rotary roasting furnace through a belt conveyor to carry out lithium removal reaction at the temperature of 200 ℃ (electric heating), so that lithium in the battery powder is removed from the lattice structure of the anode material and reacts to generate water-soluble lithium sulfate, and elements such as nickel, cobalt, manganese and the like exist in the form of oxide. After roasting for 4 hours, the materials are conveyed to a storage bin through a roasting kiln material outlet end pipe chain conveyor, and then conveyed to an acid dissolution workshop through a pipeline for carrying out wet lithium extraction in the acid dissolution workshop.
Repair process for positive electrode material
The process flow of the positive electrode material repairing procedure is as follows:
1. shredding: the waste lithium iron phosphate anode plates and scraps are put into a lower hopper of a shredder through a manual feeding station, the pole pieces are shredded into sheet materials of about 2-5 cm after being extruded, rubbed and sheared by a double-stick of the shredder in the shredder, and the shredded sheet materials are conveyed into a bin of a pyrolysis furnace for standby through a screw conveyor. And negative pressure dust removal is adopted above the feeding station and the storage bin, a pipeline is connected to the bag-type dust remover in a sealing manner, and the waste gas is processed by the bag-type dust remover and then is converged into an organic waste gas processing system.
2. And (3) pyrolysis: the shredded flaky materials are uniformly added into the pyrolysis furnace through a feeder, and the pyrolysis time of the materials is controlled by adjusting the rotating speed of the pyrolysis furnace. And in the thermal pyrolysis process, the binder on the positive plate is subjected to anaerobic pyrolysis under the protection of nitrogen, decomposed and volatilized into gas, and the waste gas is connected to a waste gas treatment system through a closed pipeline.
3. And (3) screening: after the pole piece pyrolysis is finished, the positive pole powder is peeled off from the aluminum foil, and the aluminum foil and the positive pole powder are completely separated through screening by a vibrating screen. And packaging the aluminum foil by a packaging machine, and entering an iron removal procedure by the anode powder.
4. Iron removal: and (3) carrying out first iron removal on the sieved material through a permanent magnet iron remover, taking out the magnetic rod of the iron remover periodically, cleaning magnetic foreign matters on the magnetic rod, and collecting and packaging the magnetic foreign matters.
5. Crushing: the positive electrode powder is continuously fed into the crushing cavity of the crusher through spiral feeding, the materials in the crushing cavity are rubbed and collided with the high-speed rotary millstone, the crushing purpose is realized through the collision friction between the materials, the crushed materials are brought to the classifying impeller area through the ascending air flow, and the coarse and fine particle separation is realized under the action of the classifying impeller and the induced draft fan which rotate at high speed. The coarse particles are blocked by the classifying impeller and return to the crushing cavity to be continuously crushed under the action of gravity. Qualified materials enter a buffering bin after passing through a cloth bag collector along with air flow. The equipment air outlet is connected to an exhaust gas pipeline in a sealing way through soft connection, and the pipeline is connected to the bag-type dust remover in a sealing way.
6. Electromagnetic iron removal: the material is crushed and then needs to be deironing for the second time, and the procedure adopts an electromagnetic iron remover, so that ferromagnetic foreign matters in the anode material can be effectively removed. The magnetic foreign matters are automatically discharged through the magnetic discharging port, and the magnetic foreign matters are collected and packed.
7. And (5) mixing and packaging: the materials after the demagnetization directly enter a mixer through pipeline connection, are uniformly mixed by the mixer and enter a packaging bin, and the whole process is in pipeline airtight connection.
The acid dissolution and impurity removal process is divided into acid dissolution and impurity removal of lithium iron phosphate batteries and acid dissolution and impurity removal of ternary batteries.
1. Acid dissolution impurity removal for lithium iron phosphate battery
1.1 acid leaching section of lithium iron phosphate battery powder
The main component of the lithium iron phosphate battery powder after the binder is removed by anaerobic pyrolysis in a pretreatment workshop is LiFePO 4 . The process uses hydrogen peroxide as oxidant, adopts sulfuric acid solution with proper concentration (ensuring that the PH of the leaching end solution is close to neutral) to carry out selective oxidation leaching, can lead lithium in the raw materials to be selectively leached into leaching solution, and other elements are FePO 4 The form remains in the leaching residue. The raw material feeding, paddle adjusting, material pumping, water adding and steam introducing and heating time is 1 hour, the time for adding sulfuric acid at multiple points is 2 hours, the stirring is continued for 30 minutes after the adding, and the total leaching time is 3.5 hours. The relevant reaction equation is shown below:
4LiFePO 4 +2H 2 SO 4 +2H 2 O 2 →2Li 2 SO 4 +4FePO 4 ↓+2H 2 O+O 2 ↑
after leaching, the pH value of the solution is nearly neutral, a mortar pump is adopted to pump the feed liquid into a filter press to carry out liquid-solid separation, the filter pressing time is 1 hour, the total control of the leaching process and the filter pressing time is 5 hours, the water washing time of the filter press is 0.5 hour, the squeezing time is 20 minutes, and the slag discharging time is 40 minutes. The leached filtrate automatically flows into an intermediate temporary storage tank and then is sent to a impurity removing process, and iron phosphate slag and graphite slag are temporarily stored. Acid mist generated in the leaching process is conveyed to a spray tower for treatment through a gas pipeline in negative pressure which is hermetically connected to the top cover of the reaction tank, and then is discharged.
1.2 lithium iron phosphate feed liquid impurity removing work section
The main component in the leaching solution obtained by acid leaching of the lithium iron phosphate battery powder is lithium sulfate, but a small amount of copper, aluminum and fluoride ions still exist, so that the leaching solution is pumped to an acid dissolution workshop for purification and impurity removal, and the main equipment is a reaction kettle.
1.2.1 copper removal
Pumping acid leaching solution of lithium iron phosphate battery powder to a copper removal reaction kettle, adding self-produced lithium hydroxide solution of a bipolar membrane system for precipitation and impurity removal, and thus obtaining copper hydroxide slag. The pumping time of the process is 0.5 hour, the alkali adding time is 0.5 hour, the normal pressure reaction is carried out for 1 hour, the pH value of the system is controlled to be 12-13, cu in the feed liquid is less than or equal to 0.1g/L, and copper hydroxide sediment is generated.
CuSO 4 +2LiOH→Li 2 SO 4 +Cu(OH) 2 ↓
After the reaction is finished, a mortar pump is adopted to pump the feed liquid into a filter press for liquid-solid separation, the filter pressing time is 1 hour, the total of the leaching process and the filter pressing time is controlled to be 5 hours, the water washing time of the filter press is 0.5 hour, the squeezing time is 20 minutes, and the slag discharging time is 40 minutes. The leached filtrate automatically flows into an intermediate temporary storage tank and then is sent to a defluorination process, and copper slag is temporarily stored.
1.2.2 chemical defluorination
The lithium iron leach solution after copper removal contains fluoride ion impurities, which affect both the end product and the equipment and therefore need to be removed. Pumping the copper-removed liquid into a defluorination reaction kettle, adding lime powder to generate calcium fluoride precipitate to remove fluoride ions, controlling the pH value in the process to be 12-13, pumping for 0.5 hour, adding calcium oxide for 0.5 hour, and reacting for 1 hour under normal pressure.
2F - +Ca 2+ →CaF 2 ↓
After the reaction is finished, a mortar pump is adopted to pump the feed liquid into a filter press for liquid-solid separation, the filter pressing time is 1 hour, the total of the leaching process and the filter pressing time is controlled to be 5 hours, the water washing time of the filter press is 0.5 hour, the squeezing time is 20 minutes, and the slag discharging time is 40 minutes. The leached filtrate automatically flows into an intermediate temporary storage tank and then is sent to an aluminum removal process, and calcium slag is temporarily stored.
1.2.3 reverse pH adjustment to remove aluminum
Pumping the chemical defluorination solution into an aluminum removal reaction kettle, adding 50% sulfuric acid produced by a bipolar membrane system, adjusting the pH value to 7-8, and precipitating aluminum ions in the form of aluminum hydroxide. The pumping time of the process is 0.5 hour, the calcium oxide adding time is 0.5 hour, and the normal pressure reaction time is 2-3 hours.
After the reaction is finished, a mortar pump is adopted to pump the feed liquid into a filter press for liquid-solid separation, the filter pressing time is 1 hour, the total of the leaching process and the filter pressing time is controlled to be 5 hours, the water washing time of the filter press is 0.5 hour, the squeezing time is 20 minutes, and the slag discharging time is 40 minutes. And after the leaching filtrate automatically flows into the intermediate temporary storage tank, pumping the intermediate temporary storage tank and the defluorinated ternary lithium liquid into a resin defluorination system, and temporarily storing the calcium slag.
2. Ternary battery powder water immersion impurity removal
2.1 ternary battery acid dissolution section
2.1.1 Water leaching Process
The lithium in the ternary waste after acidification and roasting mainly exists in the form of lithium sulfate, and more than 95% of lithium sulfate can be leached into the solution by normal-temperature water leaching, and most of metal elements such as nickel, cobalt, manganese and the like are reserved in the leaching slag in the form of oxides. After leaching, a pulp pump is adopted to pump the feed liquid into a filter press for liquid-solid separation, a filtrate pump is used for removing impurities in a nickel-cobalt-manganese precipitation tank of an acid-leaching workshop, and water leaching residues are sent to a ternary acid leaching process.
2.1.2 Nickel cobalt manganese precipitation procedure
And pumping the ternary water into a nickel-cobalt-manganese precipitation tank of an acid dissolution workshop, adding a self-produced lithium hydroxide solution of a bipolar membrane system, and precipitating nickel-cobalt-manganese in the form of hydroxide so as to achieve the purpose of removing nickel-cobalt-manganese. The PH is controlled to be about 12-13, the temperature is less than or equal to 60 ℃, and the normal pressure reaction time is about 2 hours. And returning the cobalt nickel hydroxide slag after filter pressing to a ternary lithium battery powder low-acid leaching process of an acid-soluble secondary workshop, and filtering to a defluorination process.
CoSO 4 +2LiOH＝Co(OH) 2 ↓+Li 2 SO 4
NiSO 4 +2LiOH＝Ni(OH) 2 ↓+Li 2 SO 4
MnSO 4 +2LiOH＝Mn(OH) 2 ↓+Li 2 SO 4
2.1.3 reduction acid leaching
The materials such as nickel cobalt manganese leaching slag, nickel cobalt manganese precipitation slag and the like are conveyed to an acid leaching reaction kettle in a sealing way through a conveying device, sulfuric acid and sodium sulfite are added for two-stage countercurrent acid reduction leaching, the first-stage leaching is low-acid leaching, the PH of a leaching end point is controlled between 1.5 and 2, the second-stage leaching is high-acid leaching, the PH of the leaching end point is 1 to 1.5, the low-acid leaching slag enters high-acid leaching, and the leaching liquid of the high-acid leaching returns to the low-acid leaching to be used as a leaching agent. The two-stage leaching is carried out, the reaction temperature is controlled to be 60-90 ℃, the liquid-solid ratio is controlled to be (3-5), the acid-base acidity of the high-acid leaching is controlled to be 200-220 g/L, and the good leaching effect of nickel, cobalt, manganese, copper and the leaching effect is ensured through the first two-stage leaching, and meanwhile, the leaching liquid is ensured to be suitable for the next process treatment. The valuable metals such as nickel, cobalt, manganese, copper, aluminum, iron and the like are dissolved into leaching liquid through reduction leaching, high-valence nickel, cobalt, manganese and the like are reduced into divalent metal ions under the action of sodium sulfite, most ternary materials after acidification roasting are changed into suboxide (NixMnyCo 1-x-yO), sulfuric acid is adopted for direct leaching, a small part of the ternary materials still exist in the form of the suboxide (NixMnyCo 1-x-yOz,1< z < 2), a reducing agent is required to be added for reduction leaching, and the leaching process mainly generates the following reactions:
Ni(OH) 2 +H 2 SO4→NiSO 4 +2H 2 O
NixMnyCo1-x-yOz+H 2 SO 4 +H 2 O 2 →NiSO 4 +MnSO 4 +CoSO 4 +H 2 O+O 2 ↑
NixMnyCo1-x-yO+H 2 SO 4 →xNiSO 4 +yMnSO 4 +(1-x-y)CoSO 4 +H 2 O
Ni(OH) 2 +H 2 SO 4 →NiSO 4 +2H 2 O
Co(OH) 2 +H 2 SO 4 →CoSO 4 +2H 2 O
Mn(OH) 2 +H 2 SO 4 →MnSO 4 +2H 2 O
Cu(OH) 2 +H 2 SO 4 →CuSO 4 +2H 2 O
2Al(OH) 3 +3H 2 SO 4 →Al 2 (SO 4 ) 3 +3H 2 O
2Fe(OH) 3 +3H 2 SO 4 →Fe 2 (SO 4 ) 3 +3H 2 O
after the leaching time is reached, pumping the low-acid leached ore pulp into a filter press to carry out liquid-solid separation, wherein the filter pressing time is 2 hours, the total time of deslagging and squeezing is 1 hour, the low-acid leached liquid automatically flows into an intermediate tank and then pumping the intermediate tank into a subsequent copper removal process, and pumping the high-acid leached slag after pulping the low-acid leached slag. And (3) leaching the high acid for 3-5 hours, then performing liquid-solid separation by a pulp pumping filter press, wherein the filter pressing time is 2 hours, the pressing and deslagging time is 1 hour, the high leaching liquid automatically flows into an intermediate storage tank and returns to the low acid leaching process, and the high leaching slag (carbon black slag) is sent to a factory dangerous waste temporary storage for temporary storage after being washed for many times. And (3) managing and storing the high-acid leaching slag (graphite) according to dangerous wastes, and treating according to the category after the toxicity identification result of the dangerous wastes is obtained. Acid mist generated in the reduction acid leaching process is conveyed to a spray tower through a gas pipeline in a closed connection on the top cover of the reaction tank under negative pressure, and is discharged through an exhaust funnel of an acid dissolving workshop after being treated.
2.2 Tri-element battery impurity removing work section
2.2.1 copper recovery Process
The copper recovery system of the method adopts a leaching-extraction-electrodeposition process and mainly comprises three main links: (1) the dissolution leaching of copper in sulfuric acid medium (acid-dissolution second shop), (2) extraction of copper with Lix984 extractant (extraction shop), (3) electro-deposition of copper on cathode (acid-dissolution first shop).
Leaching: in the acid leaching process, the copper is leached together with cobalt, nickel and manganese, and the diameter of the low-acid leaching solution is conveyed to a Lix984 copper extraction procedure to extract and separate copper in advance.
Extraction: the extractant of the copper extraction process adopts domestic Lix984 (aldoxime+modifier) with high acidity, which is suitable for high-concentration solution extraction, and adopts 25% extractant concentration, normal temperature and normal pressure, reaction time and clarification time of about 5 minutes. The method is provided with a 6-level extraction tank (3-level extraction and 3-level back extraction), the extraction process is carried out in a mixing and clarifying extractor, and the extractor consists of a mixing chamber, a clarifying chamber, a submerged chamber and a stirrer. And (3) carrying out countercurrent contact between the mixed sulfuric acid metal solution (water phase) generated in the acid leaching process and the organic solvent (organic phase) in an extractor, and finally completing the extraction-back extraction operation.
Extracting copper from the leaching solution into an organic phase by adopting an extractant, and then back-extracting the copper from the organic phase into the electrolyte. Pumping the leaching solution to a flowmeter, feeding the leaching solution into an extraction tank, performing three-stage extraction, feeding copper into an organic phase, when the copper concentration in the leaching solution is high (more than 15 g/l), adding alkali liquor into a second-stage aqueous-phase liquid to neutralize and partially acid in order to reduce the copper concentration (less than 0.3 g/l) of the raffinate, feeding the raffinate into the next process, and enabling the organic phase to flow to a back-extraction copper extraction tank. Copper loaded in the organic phase after back extraction enters back extraction liquid, the back extraction liquid is CuSO4 solution, and the CuSO4 solution is sent to an acid dissolution workshop.
The copper substitution process is reacted as follows:
2RH+Cu 2+ ＝R 2 Cu+2H +
wherein: RH is a displacer, R 2 Cu is sponge copper formed by extractant and copper.
2.2.2 ammonium bicarbonate to remove iron and aluminum
The main components of the raffinate after copper extraction are cobalt sulfate nickel manganese and the like, the liquid enters an acid-soluble two-car purification process, the main purification purpose is to remove impurities such as aluminum, a small amount of iron and the like contained in the solution, and the main equipment is a purification tank. Heating nickel cobalt manganese low-acid leaching solution after copper removal for 1 hour by steam to be heated to more than 90 ℃, adding ammonium bicarbonate solution, stirring for 2-3 hours, controlling the pH value of a system to be in the range of 1.5-1.7, adding ammonium bicarbonate solution, stirring for 2-3 hours, adjusting the pH value to 3.5-4.0, and enabling Fe in feed liquid to be less than or equal to 0.1g/l and Al to be less than or equal to 0.20g/l, thereby generating iron aluminum alum slag precipitation, and cooling time and waiting for test time to be 1 hour:
H 2 SO 4 +2NH 4 HCO 3 →(NH 4 ) 2 SO 4 +2H 2 O+2CO 2 ↑
3Fe 2 (SO 4 ) 3 +(NH 4 ) 2 SO 4 +12H 2 O→2NH 4 Fe 3 (SO 4 ) 2 (OH) 6 ↓+6H 2 SO 4
3Al 2 (SO 4 ) 3 +(NH 4 ) 2 SO 4 +12H 2 O→2NH 4 Al 3 (SO 4 ) 2 (OH) 6 ↓+6H 2 SO 4
a small amount of carbon dioxide gas is generated in the iron and aluminum removing process and is discharged through workshop micro negative pressure. After the reaction is finished, the slurry is pumped into a filter press through an ore pulp pump to carry out liquid-solid separation, the filter pressing time is 4-5 hours, and the total time of slag discharging and squeezing is 2 hours. The filtrate automatically flows into an intermediate storage tank, is cooled to 40 ℃ by a heat exchanger, is stored and is finely filtered by a precise filter, so that trace suspended matters in the feed liquid are removed, the generation of three phases in the subsequent extraction process is reduced, filter residues are iron-aluminum alum residues, the general industrial solid waste is treated according to dangerous waste before an identification conclusion, and corresponding disposal measures are adopted according to the identification conclusion.
For the extraction working procedure, the extraction working section of the method comprises the working procedures of impurity removal by extraction, manganese extraction, nickel-cobalt extraction and separation, cobalt extraction, magnesium extraction and the like, and the detailed procedures for realizing the separation of nickel, cobalt and manganese are as follows:
1. extracting and removing impurities
The nickel cobalt manganese sulfate solution after fine filtration is pumped to an extraction process through a pipeline pump to carry out deep impurity removal, an extractant and 260# solvent oil are added into an extraction tank to prepare an extraction organic phase with the concentration of the extractant of 20 percent, ammonia water is added to carry out saponification reaction on the extractant and the liquid ammonia, and NH4+ in the ammonia water is replaced by H+ ions in the extractant. The extractant after ammonia soap and nickel cobalt manganese sulfate feed liquid are subjected to multistage countercurrent extraction, and elements such as manganese, copper, zinc, calcium, iron, aluminum and the like in the water phase and NH4 < + > ions in the extractant are subjected to displacement reaction and enter an organic phase by controlling the pH value of the water phase to be in the range of 3.0-3.5. After extraction, clarifying and layering separation is carried out, a water phase is deoiled, then a pipeline is used for pumping the solution to a nickel-cobalt separation process, a manganese precipitation tank is pumped after the loaded organic phase is reversely extracted by adopting a low-concentration sulfuric acid solution to obtain a manganese sulfate mixed solution, deep iron reflection is carried out on the manganese reflection organic phase through high-concentration hydrochloric acid, the organic phase returns to a saponification process for recycling after iron reflection, an iron reflection water phase is continuously recycled after deoiling, ferric chloride in the ferric chloride water phase is precipitated through liquid alkali in an open circuit after 15-20 days, and sodium chloride waste liquid is obtained after liquid-solid separation of a filter press. The precipitation mode of the iron vitriol and the iron vitriol slag in the purifying and impurity removing process is the same and the components are similar, and the iron vitriol slag are sold as common solid waste.
The reaction equation related to this procedure is as follows:
saponification: HA (org) +NH 4 OH→NH 4 A(org)+H 2 O
Extraction: 2NH 4 A(org)+MeSO 4 →MeA 2 (org)+(NH 4 ) 2 SO 4
Back extraction of hydrochloric acid: meA (MeA) 2 (org)+2HCl→2HA(org)+MeCl 2 Wherein: me is Mn 2+ 、Fe 3+ 、Ca 2+ Equal metal
2. Manganese extraction
Pumping the raffinate after impurity removal to a manganese extraction process through a pipeline, adding an extractant and 260# solvent oil into an extraction tank, preparing an extraction organic phase with the concentration of the extractant of 20%, and then adding ammonia water to enable the extractant to perform saponification reaction with liquid ammonia, wherein NH4+ in the ammonia water is replaced by H+ ions in the extractant. The extractant after ammonia soap and raffinate of the impurity removal line are subjected to multistage countercurrent extraction, and manganese in the water phase and NH4 < + > ions in the extractant are subjected to displacement reaction by controlling the pH value of the water phase within a range of 3.0-3.5 so as to enter an organic phase, and impurity elements such as calcium, magnesium, manganese and the like are left in the water phase.
The reaction equation related to this procedure is as follows:
saponification: HA (org) +NH 4 OH→NH 4 A(org)+H 2 O
Extraction: 2NH 4 A(org)+MeSO 4 →MeA 2 (org)+(NH 4 ) 2 SO 4
Back extraction of hydrochloric acid: meA (MeA) 2 (org)+2HCl→2HA(org)+MeCl 2 Wherein: me is Mn 2+ 、Mg 2+ 、Ca 2+ Equal metal
3. Extraction separation of nickel and cobalt and refined cobalt
The raffinate in the process of extracting and removing impurities adopts an extractant (concentration of 25%) after ammonia soap to carry out multistage countercurrent cobalt extraction, and Co < 2+ > and trace Cu < 2+ > in the feed liquid are replaced with NH < 4+ > in an organic phase by controlling the pH value of a water phase to be 4.5, and nickel, magnesium and other ions are reserved in the raffinate. After extraction, clarifying and layering separation is carried out, a water phase is deoiled and then pumped to a magnesium extraction process through a pipeline, a loaded organic phase is subjected to multistage countercurrent washing by dilute sulfuric acid, sulfuric acid is used for back extraction to obtain a cobalt-rich solution, an extractant is used for deep purification and impurity removal, cobalt is reserved in raffinate, a loaded organic phase in the fine extraction impurity removal process is subjected to multistage countercurrent washing by dilute sulfuric acid and then is subjected to sulfuric acid back extraction regeneration, the organic phase is returned to the extraction process for recycling, and the back extraction liquid is pumped to a nickel-cobalt acid leaching process.
The reaction equation related to saponification, extraction and back extraction processes is as follows:
saponification: HA (org) +NH 3 ·H 2 O→NH 4 A(org)+H 2 O
Cobalt extraction: 2NH 4 A(org)+CoSO 4 →CoA 2 (org)+(NH 4 ) 2 SO 4
Sulfuric acid back extraction: coA 2 (org)+H 2 SO 4 →2HA(org)+CoSO 4
The reaction equation related to saponification, extraction and back extraction processes is as follows:
saponification: 2HA (org) +CoSO 4 →CoA(org)+H 2 SO 4
Cobalt extraction: coA (org) +CuSO 4 →CuA 2 (org)+CoSO 4
Sulfuric acid back extraction: cuA (CuA) 2 (org)+H 2 SO 4 →2HA(org)+CuSO 4
4. Extracting magnesium
And (3) pumping the raffinate from the nickel-cobalt separation line to a magnesium extraction process through a pipeline to remove magnesium, washing the magnesium-rich organic phase by adopting dilute sulfuric acid in a multistage countercurrent manner, and carrying out back extraction by adopting sulfuric acid to obtain a magnesium-rich solution. Adding liquid alkali into the magnesium-rich strip liquor after degreasing treatment to neutralize and precipitate magnesium, pumping the slurry into a filter press to carry out liquid-solid separation, and selling the magnesium hydroxide as common solid waste.
The reaction equation related to this procedure is as follows:
saponification: HA (org) +NH 3 ·H 2 O→NH 4 A(org)+H 2 O
Extracting magnesium: 2NH 4 A(org)+MgSO 4 →MgA 2 (org)+(NH 4 ) 2 SO 4
Sulfuric acid back extraction: mgA (MgA) 2 (org)+H 2 SO 4 →2HA(org)+MgSO 4
Neutralizing and precipitating magnesium: mgSO (MgSO) 4 +(NH 4 ) 2 CO 3 →MgCO 3 ↓+(NH 4 ) 2 SO 4
The waste gas in the extraction process (removing impurities, separating nickel and cobalt, finely extracting cobalt, extracting magnesium and extracting manganese) is mainly organic waste gas volatilized by an extracting agent, and hydrochloric acid, sulfuric acid mist and ammonia gas generated by adding ammonia water, hydrochloric acid and sulfuric acid. The extraction tank and the auxiliary storage tank are all sealed negative pressure pipelines for waste gas collection, and the waste gas is discharged after acid spraying, alkali liquor spraying, water spraying and activated carbon adsorption.
Through the fine extraction separation engineering, the nickel-cobalt mixed solution can be separated into nickel sulfate solution, cobalt sulfate and ammonium sulfate solution, and nickel salt and cobalt salt solution are evaporated and crystallized to obtain nickel sulfate crystals and cobalt sulfate crystals.
The reaction equation in this procedure is as follows:
scale formation of ammonium sulfate solution: (NH 4) 2 SO 4 +Ca(OH) 2 →CaSO 4 ↓+NH 3 ↑+H 2 O
Ammonia absorption: NH (NH) 3 +H 2 O→NH 3 ·H 2 O
The ammonia-containing gas generated by the ammonia absorption tower is discharged after being absorbed by ammonia.
For the process of preparing lithium hydroxide
1. Hydrogen-producing lithium oxide and lithium carbonate
1.1 chemical defluorination
And (3) delivering the solution of the ternary lithium solution after cobalt and nickel are precipitated to a fluorine precipitation reaction tank, adding lime powder, controlling the PH between 12 and 13, controlling the temperature to be less than or equal to 60 ℃ and reacting for 1 hour at normal pressure. Precipitating to obtain calcium fluoride slag, press-filtering the calcium fluoride slag, storing in a comprehensive warehouse, pumping the filtrate into a mixed solution storage tank, and pumping into a resin defluorination process. The defluorination process is as follows:
2LiF+Ca(OH) 2 ＝CaF 2 ↓+2LiOH
1.2 resin defluorination
And mixing the ternary lithium sulfate solution and the lithium iron phosphate solution, and then pumping the mixture to an acid-dissolution workshop resin defluorination process. The lithium sulfate solution is firstly added with a certain amount of sulfuric acid to adjust the pH value to be acidic (the pH value is approximately equal to 4), then a precise filter is adopted for treatment, suspended matters and fine particles in the solution are trapped, and impurities are prevented from entering an adsorption material to influence the adsorption performance. And (3) the filtered feed liquid enters an adsorption tower filled with special adsorption materials for adsorption, the adsorption materials are subjected to desorption regeneration treatment after adsorption saturation, and the adsorption materials can be reused after regeneration. The lithium solution is defluorinated by resin to obtain relatively pure lithium sulfate solution, and the relatively pure lithium sulfate solution is conveyed to a bipolar membrane electrolysis system.
1.3 bipolar Membrane electrodialysis System
The PH of the lithium liquid is regulated to 11-11.5 by adding self-produced lithium hydroxide, and divalent metal ions such as cobalt, manganese, calcium, magnesium and the like in the leaching liquid are formed into hydroxide precipitates, and the hydroxide precipitates are subjected to plate-type filter pressing filtration and then are subjected to precise filtration. The filtered effluent is filtered by active carbon to remove COD, so that the COD is prevented from being enriched in the system. The effluent filtered by the activated carbon is treated by chelating resin to remove divalent cations in the solution so as to meet the water inlet requirement of the bipolar membrane.
The resin effluent enters bipolar membrane electrodialysis to carry out acid-base conversion, and enters three paths, namely an acid chamber, an alkali chamber and a salt chamber, and is converted by the bipolar membrane, the acid is recycled continuously after reaching 98g/L, namely the concentration of lithium hydroxide is less than 48g/L, and the concentration of lithium hydroxide is increased to 72g/L by alkali concentration electrodialysis and enters a nanofiltration system to carry out purification, so that sulfate ions in the lithium hydroxide are removed, and the lithium hydroxide with higher purity is obtained. The fresh water of the alkali concentration electrodialysis is returned to the alkali chamber of the bipolar membrane for recycling. The concentrated nanofiltration water contains a certain amount of lithium sulfate and is refluxed to a front-end precipitation section for adjusting the pH. The dilute brine of the bipolar membrane is required to be concentrated through salt concentration electrodialysis and then enters bipolar membrane equipment for repeated treatment, fresh water of the salt concentration electrodialysis enters reverse osmosis for desalination, one part of desalted water enters a bipolar membrane system for water supplementing, and the other part of desalted water is required to be sent out for being used as pure water.
The dilute sulfuric acid produced by the bipolar membrane system is evaporated and concentrated to obtain 30% sulfuric acid and condensed water, and the 30% sulfuric acid is concentrated to obtain 50% sulfuric acid and distilled water, wherein the 50% sulfuric acid is recycled in the ternary battery powder mixed acid process and the leaching process of the lithium iron phosphate battery powder. And concentrating, evaporating and crystallizing the lithium hydroxide solution to obtain lithium hydroxide monohydrate and condensed water, and roasting the lithium hydroxide monohydrate in a carbon dioxide atmosphere to obtain refined lithium carbonate.
2. Preparation of manganese sulfate
After the manganese extraction is completed, the water phase is pumped to a calcium-magnesium-manganese precipitation tank through a pipeline after the oil removal, and calcium-magnesium-manganese slag is obtained after the precipitation of ammonium bicarbonate and is used as common solid waste for sale. The loaded organic phase is reversely extracted by adopting low-concentration sulfuric acid solution to obtain manganese sulfate solution, the manganese sulfate solution is deoiled, then pumped into an MVR evaporator and a cooling crystallization kettle to be concentrated and crystallized, and manganese sulfate crystals are centrifugally dehydrated, dried and packaged to produce manganese sulfate (MnSO) 4 ·H 2 And O) obtaining a finished product. The lithium battery industry has extremely high requirements on the impurity content of manganese sulfate, and the multi-stage extraction can realize the refined separation of various metals, so the section adopts a multi-stage extraction procedure to realize the preparation of refined cobalt sulfate.
3. Preparation of cobalt sulfate
The pure cobalt sulfate solution obtained by the fine extraction is treated by degreasing and then pumped into an MVR evaporator and a cooling crystallization kettle for concentration and crystallization, and cobalt sulfate crystals are centrifugally dehydrated, dried and packaged to produce cobalt sulfate (CoSO) 4 ·7H 2 And O) obtaining a finished product. Lithium battery industryThe impurity content of the cobalt sulfate is extremely high, and the refined separation of various metals can be realized by multistage extraction, so the preparation of the refined cobalt sulfate is realized by adopting multistage extraction procedures in the section.
4. Preparation of nickel sulfate
The raffinate in the magnesium extraction process is clarified and separated in layers, the aqueous phase is pumped to an ammonia water regeneration and recovery workshop through a pipeline after oil removal, lime causticization is carried out, stripping ammonia distillation regenerated ammonia water is returned to the saponification process for recycling, and ammonia distillation mother liquor is periodically pumped to a centrifuge for liquid-solid separation to obtain gypsum slag; the loaded organic phase is subjected to multistage countercurrent washing by dilute sulfuric acid, then is subjected to back extraction by sulfuric acid to obtain a nickel-rich solution, is subjected to deoiling treatment, is pumped into an MVR evaporator and a cooling crystallization kettle to be respectively concentrated and crystallized, and is subjected to centrifugal dehydration, drying, screening and packaging to obtain nickel sulfate (NiSO) 4 ·6H 2 And O) obtaining a finished product. The air outlet of the drying device is connected to a workshop dust removing device in a sealing way through a pipeline, and a small amount of dust and water vapor generated in the drying process are conveyed in a sealing way under negative pressure, condensed and then treated by the dust removing device and discharged.
The impurity content of nickel sulfate in the lithium battery industry is extremely high, and the refined separation of various metals can be realized by multistage extraction, so that the preparation of refined nickel sulfate is realized by multistage extraction procedures in the section.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention.
Claims (10)
1. A lithium battery recycling method, characterized by comprising:
a pretreatment procedure, namely detecting and decomposing a lithium battery monomer, crushing, drying and sorting the lithium battery monomer, obtaining lithium iron phosphate battery powder and ternary battery powder through pyrolysis, respectively mixing the lithium iron phosphate battery powder and the ternary battery powder into sulfuric acid, and finally roasting to obtain water-soluble lithium sulfate;
the method comprises the following steps of repairing the anode material, namely, shredding, pyrolyzing, screening, removing iron, crushing, electromagnetically removing iron, mixing and packaging waste lithium iron phosphate anode sheets and leftover materials;
the acid dissolution impurity removal process comprises the steps of removing impurities of a lithium iron phosphate battery and removing impurities of a ternary battery, wherein the lithium iron phosphate battery is used for removing impurities to remove copper, fluorine and aluminum, and the ternary battery is used for removing impurities to remove nickel, cobalt, manganese, copper, aluminum and iron;
an extraction procedure comprising the steps of removing impurities by extraction and extracting manganese, nickel, cobalt and magnesium;
and preparing lithium hydroxide.
2. The method according to claim 1, wherein the batteries of different degrees are detected and decomposed in the pretreatment process, and the battery cells are used in a ladder or disassembled.
3. The method of claim 1, wherein in the pretreatment step, the sorting includes gravity sorting and stripping sorting.
4. The method according to claim 1, wherein in the pretreatment step, the pyrolysis temperature is 450 to 550 degrees celsius, and the pyrolysis time is 1 to 3 hours.
5. The method according to claim 1, wherein in the positive electrode material repairing process, permanent magnet is used to remove iron, and then electromagnetic is used to remove iron.
6. The method for recycling lithium batteries according to claim 1, wherein in the impurity removal of the lithium iron phosphate battery, hydrogen peroxide and sulfuric acid solution are used for leaching, and the PH value is controlled to be neutral.
7. The method according to claim 1, wherein the total leaching time in the lithium iron phosphate battery impurity removal is 3.5 hours.
8. The method for recycling lithium batteries according to claim 1, wherein aluminum is removed by reversely adjusting PH in the impurity removal of the lithium iron phosphate battery.
9. The method according to claim 1, wherein lithium sulfate is obtained by leaching the ternary battery with water at normal temperature, and the residue is subjected to nickel-cobalt-manganese precipitation and reductive acid leaching.
10. The method according to claim 1, wherein in the preparation of lithium hydroxide, chemical defluorination and resin defluorination are further included.
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| CN117416974A (en) * | 2023-09-28 | 2024-01-19 | 安徽天铄锂电新材料科技有限公司 | Method for recycling lithium iron phosphate lithium battery to prepare lithium carbonate |
| CN118017064A (en) * | 2024-04-08 | 2024-05-10 | 江苏杰成新能源科技有限公司 | Method for repairing lithium iron phosphate positive pole piece material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117416974A (en) * | 2023-09-28 | 2024-01-19 | 安徽天铄锂电新材料科技有限公司 | Method for recycling lithium iron phosphate lithium battery to prepare lithium carbonate |
| CN118017064A (en) * | 2024-04-08 | 2024-05-10 | 江苏杰成新能源科技有限公司 | Method for repairing lithium iron phosphate positive pole piece material |
| CN118017064B (en) * | 2024-04-08 | 2024-06-11 | 江苏杰成新能源科技有限公司 | Method for repairing lithium iron phosphate positive pole piece material |
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