CN117585691A - Method and system for extracting lithium from solid material - Google Patents
Method and system for extracting lithium from solid material Download PDFInfo
- Publication number
- CN117585691A CN117585691A CN202311422956.6A CN202311422956A CN117585691A CN 117585691 A CN117585691 A CN 117585691A CN 202311422956 A CN202311422956 A CN 202311422956A CN 117585691 A CN117585691 A CN 117585691A
- Authority
- CN
- China
- Prior art keywords
- lithium
- liquid
- product
- optionally
- solid
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 267
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 262
- 239000011343 solid material Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000011344 liquid material Substances 0.000 claims abstract description 97
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 238000002156 mixing Methods 0.000 claims abstract description 84
- 239000007788 liquid Substances 0.000 claims abstract description 83
- 239000012263 liquid product Substances 0.000 claims abstract description 71
- -1 sulfide ions Chemical class 0.000 claims abstract description 71
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 37
- 238000000926 separation method Methods 0.000 claims abstract description 36
- 239000012265 solid product Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims description 182
- 239000000047 product Substances 0.000 claims description 87
- 239000007789 gas Substances 0.000 claims description 73
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 49
- 238000002425 crystallisation Methods 0.000 claims description 45
- 230000008025 crystallization Effects 0.000 claims description 45
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 44
- 229910052717 sulfur Inorganic materials 0.000 claims description 42
- 239000011593 sulfur Substances 0.000 claims description 42
- 238000000605 extraction Methods 0.000 claims description 38
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 38
- 238000000197 pyrolysis Methods 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 33
- 238000002386 leaching Methods 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 238000000746 purification Methods 0.000 claims description 28
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 28
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 27
- 235000011152 sodium sulphate Nutrition 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 124
- 229910052742 iron Inorganic materials 0.000 description 71
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 70
- 239000000243 solution Substances 0.000 description 54
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 48
- 238000011084 recovery Methods 0.000 description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 35
- 230000001180 sulfating effect Effects 0.000 description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 23
- 229910052698 phosphorus Inorganic materials 0.000 description 23
- 239000011574 phosphorus Substances 0.000 description 23
- 238000005406 washing Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000010941 cobalt Substances 0.000 description 21
- 229910017052 cobalt Inorganic materials 0.000 description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 21
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 19
- 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 description 19
- 239000011572 manganese Substances 0.000 description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 17
- 229910052748 manganese Inorganic materials 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 15
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 14
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 14
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 10
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000036284 oxygen consumption Effects 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000005955 Ferric phosphate Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 229940032958 ferric phosphate Drugs 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 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
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MBUJIFHANTWAKB-UHFFFAOYSA-N [S-2].[Mn+2].[Co+2].[Ni+2].[S-2].[S-2] Chemical compound [S-2].[Mn+2].[Co+2].[Ni+2].[S-2].[S-2] MBUJIFHANTWAKB-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011549 crystallization solution Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 239000002245 particle Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/185—Preparation neither from elemental phosphorus or phosphoric anhydride nor by reacting phosphate-containing material with an acid, e.g. by reacting phosphate-containing material with an ion-exchange resin or an acid salt used alone
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- 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
Abstract
The application provides a method and a system for extracting lithium from solid materials, wherein the method comprises the following steps: mixing the liquid material with the solid material for reaction, and then carrying out solid-liquid separation to obtain a solid product and a liquid product; wherein the liquid material contains water and sulfide ions, the solid material contains iron oxide and lithium oxide, the solid product contains iron oxide, and the liquid product contains lithium ions. According to the method for extracting lithium from the solid material, provided by the embodiment of the application, the lithium element in the solid material can be economically and effectively extracted.
Description
Technical Field
The application relates to the technical field of extraction of lithium elements, in particular to a method and a system for extracting lithium from solid materials.
Background
The sales of new energy automobiles are increased to drive the output of the power battery to continuously rise, and the lithium element is used as an important raw material for manufacturing the power battery, so that the demand of the lithium element is also increased. Relying solely on extraction of lithium from mineral products results in the yield of lithium elements being severely limited by the reserves and yields of mineral resources, and therefore new directions for extraction of lithium need to be found.
Considering that part of solid materials generated in the current industrial production process contain lithium, if the extraction of lithium in the solid materials can be economically and effectively realized, the supply pressure of lithium resources can be greatly relieved.
Disclosure of Invention
The application provides a method and a system for extracting lithium from solid materials, which can economically and effectively extract lithium elements in the solid materials.
The embodiment of the application provides a method for extracting lithium from a solid material, which comprises the following steps:
mixing the liquid material with the solid material, and performing solid-liquid separation to obtain a solid product and a liquid product;
wherein the liquid material contains water and sulfide ions, the solid material contains iron oxide and lithium oxide, the solid product contains iron oxide, and the liquid product contains lithium ions.
In this embodiment, the liquid material containing water and sulfur ions is mixed with the solid material containing ferric oxide and lithium oxide to react, so that the water in the liquid material reacts with the lithium oxide in the solid material to obtain lithium ions, the ferric oxide in the solid material is almost insoluble in water, and a very small amount of iron ions generated after the dissolution of ferric oxide also react with the sulfur ions in the liquid material to generate ferrous sulfide precipitate. Therefore, after the solid-liquid separation of the reacted liquid, lithium ions enter the liquid product, and iron oxide and ferrous sulfide enter the solid product. Therefore, the method can realize the economic and effective extraction of lithium elements in the solid material, and simultaneously realize the separation of lithium and iron, thereby being beneficial to improving the purity of lithium ions in the liquid product.
In some embodiments of the present application, the liquid to solid ratio of the liquid to the solid is from 2L to 6L:1kg;
optionally, the mixing is performed in a stirring state, and the stirring speed is 120-150r/min;
optionally, the mixing time is 0.5-1.5h;
optionally, the temperature of the mixing is 65-92 ℃;
optionally, the liquid material has a sulfur ion content of 0.05-1g/L;
optionally, the liquid product has a sulfur ion content of 2.5-50mg/L;
optionally, the pH of the reaction solution is controlled to be maintained at 5-8 during the mixing process.
In some embodiments of the present application, the liquid material is obtained by performing a preconditioning lithium treatment on the first battery recycle to obtain a lithium extraction liquid, and the lithium extraction liquid is obtained by performing a purification treatment;
optionally, the preconditioning lithium treatment comprises the operation of leaching the first battery recycle by acid to obtain a lithium extraction liquid, or leaching by a leaching agent after mixing and roasting with acid or a reducing agent to obtain the lithium extraction liquid;
optionally, the leaching agent comprises any one of acid and water;
optionally, the acid comprises sulfuric acid, or the reducing agent comprises carbon and/or hydrogen;
optionally, the roasting temperature is 250-600 ℃; and/or the roasting time is 0.5-3h;
Optionally, the first battery recycle comprises at least one of a unitary lithium battery recycle, a binary lithium battery recycle, and a ternary lithium battery recycle.
In some embodiments of the present application, the solid material is obtained from the second battery recycle after calcination in an oxygen-containing atmosphere;
optionally, the temperature of the calcination is in the range 1060-1380 ℃;
optionally, the calcination time is 6-30min, preferably 12-24min;
optionally, the calcining comprises a primary calcining and a secondary calcining which are sequentially carried out, and the calcining temperature of the primary calcining is lower than that of the secondary calcining;
optionally, the oxygen-containing atmosphere has a gas excess coefficient of 1.35-1.7;
optionally, the mass ratio of the second battery recycle to the first battery recycle is from 0.8 to 4:1, preferably from 2 to 3:1;
optionally, the second battery recycle comprises a lithium iron phosphate battery recycle.
In some embodiments of the present application, the purifying treatment includes adding a precipitant into the lithium extraction liquid to perform a precipitation reaction, and performing solid-liquid separation after the reaction to obtain the liquid material;
optionally, the precipitating agent comprises a sulfide, preferably sodium sulfide;
optionally, the precipitant comprises an alkaline substance, preferably sodium hydroxide;
Optionally, the lithium content of the liquid material is 3-16g/L;
optionally, the liquid material has a sodium content of 2.5-10g/L;
optionally, the pH of the liquid feed is 5-8.
In some embodiments of the present application, prior to subjecting the first battery recycle to the preconditioning lithium treatment, the method further comprises: and carrying out pyrolysis treatment on the first battery recycle to obtain a pyrolysis material, and using the pyrolysis material for carrying out precondition lithium treatment.
In some embodiments of the present application, the method further comprises: the pH value of the liquid product is regulated to be alkaline, and then the liquid product is concentrated, cooled and crystallized to obtain cooled and crystallized liquid and cooled and crystallized product, and the cooled and crystallized liquid is subjected to aftertreatment to obtain a lithium hydroxide product;
optionally, treating the cooled crystallized product to obtain a sodium sulfate product;
optionally, the temperature of the cooling crystallization is 0-20 ℃;
optionally, the mass percentage of sodium sulfate in the cooled and crystallized liquid is less than or equal to 15%;
optionally, the lithium content of the liquid after cooling crystallization is more than or equal to 5g/L;
optionally, a base is added to the liquid product to adjust the pH to 13-14.5 prior to concentration.
The system comprises a calcination system, a precondition lithium system, a purification system and a mixing system, wherein the calcination system is connected with the mixing system, and the precondition lithium system is sequentially connected with the purification system and the mixing system;
The calcination system is used for obtaining solid materials after the second battery recycle is calcined;
the precondition lithium system and the purification system are used for sequentially carrying out precondition lithium treatment and purification treatment on the first battery recycle to obtain a liquid material;
the mixing system is used for mixing liquid materials and solid materials, and then solid-liquid separation is carried out to obtain a solid product containing ferric oxide and a liquid product containing lithium ions.
In some embodiments of the present application, the calcination system comprises a primary calcination system and a secondary calcination system, the primary calcination system being sequentially connected to the secondary calcination system and the mixing system;
the first-stage calcining system and the second-stage calcining system are used for enabling the second battery recycle to be subjected to first-stage calcining and second-stage calcining in sequence to obtain a solid material.
In some embodiments of the present application, the system further comprises a pyrolysis system, wherein the pyrolysis system is connected with the lithium precursor system, and the pyrolysis system is used for feeding the first battery recycle into the lithium precursor system after pyrolysis treatment.
In some embodiments of the present application, further comprising a concentration system, a cooling crystallization system, and a post-treatment system, the mixing system being sequentially connected to the concentration system, the cooling crystallization system, and the post-treatment system;
The concentrating system and the cooling crystallization system are used for concentrating and cooling and crystallizing the liquid product obtained by the mixing system in sequence to obtain cooled and crystallized liquid and cooled and crystallized product;
and the post-treatment system is used for carrying out post-treatment on the cooled and crystallized liquid to obtain a lithium hydroxide product.
Additional aspects and advantages of the application 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 application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow diagram of one embodiment of the method and system of the present application;
FIG. 2 is a schematic diagram of one embodiment of a purification system of the present application.
Detailed Description
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, unless specifically stated otherwise.
All technical features and optional technical features of the present application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise indicated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Reference herein to "comprising" and "including" means open ended, as well as closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
In this application, liquid-solid ratio refers to the ratio of the amount of liquid material to the amount of solid material.
In this application, the first battery recycle and the second battery recycle may be the same or different battery recycles.
In the present application, the battery recycle means a mixture containing a positive electrode recovered from a battery, wherein the battery may be a nickel-sulfur secondary battery, a nickel-hydrogen secondary battery, a lithium ion secondary battery, or the like. In some examples, the lithium ion secondary battery may include a lithium iron phosphate battery. In some examples, a positive electrode in a lithium ion secondary battery includes a positive electrode current collector, which may be a metal foil of aluminum, copper, nickel, or the like, and a positive electrode active material, which may include valuable metals of nickel (Ni), cobalt (Co), manganese (Mn), lithium (Li), or the like. In some specific examples, the battery recycle may be a mixture containing valuable metals such as Ni, co, mn, and Li, and carbon powder obtained through processes such as disassembly, crushing, sieving, pyrolysis, sorting, and the like.
In some embodiments of the present application, the battery recycle comprises a lithium iron phosphate battery recycle and at least one of a monobasic lithium battery recycle, a dibasic lithium battery recycle, and a tribasic lithium battery recycle.
In some embodiments of the present application, the lithium iron phosphate battery recycle is a battery recycle whose positive electrode material contains lithium iron phosphate, and the unitary lithium battery recycle refers to a battery recycle including lithium element and at least one of nickel, cobalt, manganese, aluminum and four elements in the positive electrode material, and the unitary lithium battery recycle may be a lithium manganate battery recycle or a lithium cobaltate battery recycle, for example; the binary lithium battery recycle is a battery recycle including at least two of lithium element and nickel, cobalt, manganese and aluminum in the positive electrode material, and the binary lithium battery recycle can be a nickel lithium manganate battery recycle or a nickel lithium cobaltate battery recycle by way of example; the ternary lithium battery recycle is a battery recycle including at least three of lithium element and nickel, cobalt, manganese and aluminum in the positive electrode material, and the ternary lithium battery recycle can be a nickel cobalt lithium manganate battery recycle or a nickel cobalt lithium aluminate battery recycle.
In the present application, the gas excess coefficient refers to a ratio of an actual amount of gas to a theoretical amount of gas, and may be used to represent a degree of excess of gas. Wherein the theoretical amount refers to the amount of gas required to fully react the starting materials, and in some embodiments of the present application, in evaluating the gas excess factor of the oxygen-containing atmosphere, the theoretical amount of gas refers to the amount of gas required to fully decompose lithium iron phosphate and fully oxidize graphite in the lithium iron phosphate battery recycle.
Referring to fig. 1, the present application provides a method for extracting lithium from a solid material, the method comprising: mixing the liquid material with the solid material for reaction to obtain a post-reaction liquid, and carrying out solid-liquid separation on the post-reaction liquid to obtain a solid product and a liquid product; wherein the liquid material contains water and sulfur ions, the solid material contains ferric oxide and lithium oxide, the solid product contains ferric oxide, and the liquid product contains lithium ions.
According to the method for extracting lithium from the solid material, the liquid material containing water and sulfur ions is mixed and reacted with the solid material containing ferric oxide and lithium oxide, so that the water in the liquid material reacts with the lithium oxide in the solid material to obtain lithium ions, the ferric oxide in the solid material is almost insoluble in water, and the iron ions generated after the dissolution of a few of ferric oxides react with the sulfur ions in the liquid material to generate ferrous sulfide precipitates, so that after the solid-liquid separation of the reacted liquid, the lithium ions can enter a liquid product, and the ferric oxide and a small amount of ferrous sulfide enter the solid product, lithium can be extracted from the solid material, and meanwhile, the separation of lithium and iron is realized, thereby being beneficial to improving the purity of the lithium ions in the liquid product. And after the ferric oxide is separated into a solid product, the main component of the obtained solid product is ferric oxide, so that a product containing ferric oxide can be obtained.
The solid-liquid separation method may be any method known in the art for separating a solid from a liquid, for example, the solid-liquid separation may be performed by a centrifugal separation method, an inclined method, a filtration method, or the like, and the solid-liquid separation herein may be performed by referring to the above methods.
In order to more fully convert lithium oxide in the solid material into lithium ions, the conditions of the mixing reaction should be controlled within a proper range. In some embodiments, the liquid to solid ratio is 2L-6L:1kg; and/or the mixing reaction is carried out in a stirring state, and the stirring speed is 120-150r/min; and/or the mixing reaction time is 0.5-1.5h; and/or the temperature of the mixing reaction is 65-92 ℃. By selectively controlling the dosage, stirring rate, mixing reaction time or mixing reaction temperature of the liquid material and the solid material within the above range, lithium ions can be obtained by fully reacting lithium oxide with water, and meanwhile, the reaction can prevent the reduction of lithium recovery rate caused by a small amount of lithium entrainment during the deposition of ferric oxide and ferrous sulfide in a stirring state, thereby being beneficial to improving the lithium recovery rate.
In addition, the ferric oxide is easier to dissolve under the condition of stronger acidity to generate iron ions, and the iron ions can enter the liquid product to influence the purity of lithium ions, so that the pH value of the reaction solution of the mixed reaction can be selectively regulated and controlled to realize the separation of lithium and iron as much as possible. In some embodiments, the p H value of the reaction solution is maintained at 5-8 during the mixing reaction, at which time iron oxide dissolution to produce iron ion impurities is avoided as much as possible. Specifically, when the mixing reaction is carried out, the pH of the reaction solution of the mixing reaction may be optionally monitored in real time, and the pH of the reaction solution of the mixing reaction may be adjusted within the above range by adding an appropriate amount of an acid such as sulfuric acid.
When the pH of the reaction solution of the mixed reaction is controlled to be higher than 7, that is, the reaction solution is alkaline, the reaction solution has a large amount of hydroxide ions, and a liquid product containing lithium hydroxide can be obtained.
In some embodiments, the pH of the liquid material is 5-8, i.e., the pH of the raw materials of the mixing reaction is 5-8, and it is more advantageous to maintain the pH of the reaction solution of the mixing reaction in the range of 5-8 after mixing the liquid material with the solid material.
Further, at the time when the pH of the reaction solution of the mixed reaction is 5 to 8 and under stirring, the sulfur ions in the reaction solution of the mixed reaction are converted into hydrogen sulfide and evolved, and the evolution rate of sulfur in the form of hydrogen sulfide is 50 to 95%, wherein the evolution rate=the content of sulfur ions generating hydrogen sulfide/the total content of sulfur ions.
The reactions that mainly occur during the mixing reaction include:
Li 2 O+H 2 O→2LiOH；
in addition, reactions that occur with small amounts of materials include:
Fe 2 O 3 +6H+→2Fe 3+ +3H 2 O；
2Fe 3+ +3S 2- →2FeS+S；
2Fe 3+ +4S 2- +2H + →2FeS+H 2 S+S。
through the reaction, iron ions generated by dissolution of ferric oxide can be converted into ferrous sulfide, elemental sulfur and hydrogen sulfide. The ferrous sulfide and the elemental sulfur are in a precipitation form and can be removed through solid-liquid separation, and hydrogen sulfide can escape from the reacted liquid in a gas form, so that iron ions in the reaction solution of the mixed reaction are fully removed. In addition, because the iron ions and the sulfur ions fully react, the iron ions and the sulfur ions cannot form enrichment, so that the waste water does not need to be discharged periodically to control the content of impurity ions such as the iron ions in the waste water, thereby reducing the discharge of the waste water and being beneficial to economically and effectively realizing the extraction of lithium in the solid material.
The solid product contains a small amount of ferrous sulfide and elemental sulfur besides ferric oxide, so that the ferrous sulfide and elemental sulfur are required to be separated to obtain the ferric oxide product. In some embodiments, the solid product may be treated by sequentially subjecting the solid product to a sulfur sublimation treatment, a ferrous sulfide oxidation treatment, to yield a purified iron oxide product.
In some embodiments, the liquid material has a sulfur ion content of 0.05-1g/L, which facilitates sufficient reaction of sulfur ions with iron ions to substantially remove iron ions.
After the mixed reaction, the contents of the sulfur ions and the iron ions in the reaction liquid are reduced to extremely low values. Specifically, more than 95% of the sulfur ions are converted into ferrous sulfide, elemental sulfur and hydrogen sulfide gas during the mixing reaction, and only a small amount of the remaining sulfur ions are present in the post-reaction solution. In some embodiments, after the liquid after the reaction is subjected to solid-liquid separation, the sulfur ion content of the obtained liquid product is 2.5-50mg/L, the iron content (ferrous iron and ferric iron) can be reduced to below 1ppm, and the influence of the content of sulfur and iron impurities in the obtained liquid product on the purity of lithium ions is almost negligible. In addition, when lithium ions with very high purity are required to be prepared, the liquid product after the mixed reaction can be subjected to further sulfur removal treatment, for example, separation of sulfur can be realized by means of concentration, cooling crystallization and the like, so that the liquid product with higher purity of lithium ions is obtained.
In some embodiments, the source of the liquid feed may include: and carrying out lithium pretreatment on the first battery recycle to obtain lithium extraction liquid, and purifying the lithium extraction liquid to obtain a liquid material. The precondition lithium treatment is to convert lithium contained in the first battery recycle into a soluble lithium ion form, and specific precondition lithium means can adopt the existing modes of salinization lithium extraction, chlorination lithium extraction, nitration lithium extraction, reduction acid leaching lithium extraction, carbon reduction lithium extraction, sulfation lithium extraction and the like. After the first battery recycle is subjected to precondition lithium treatment and purification treatment, the components possibly contained in the liquid material at the moment comprise lithium ions, and the lithium ions contained in the liquid material can finally enter a liquid product in the mixing reaction process. Therefore, the lithium contained in the first battery recovery product can be fully utilized, and the purity of lithium ions in the obtained liquid product can be improved.
In some embodiments, the first battery recycle comprises at least one of a unitary lithium battery recycle, a binary lithium battery recycle, and a ternary lithium battery recycle. Since the lithium ion battery in the market mainly comprises a ternary lithium battery and a ferric phosphate lithium battery, when the liquid material is obtained, the recycled materials of the two main batteries are preferably selected as raw materials. The liquid material source of the embodiments of the present application will be described in detail below with reference to the example of the first battery recycle including a ternary lithium battery recycle.
In some embodiments, the preconditioning lithium treatment includes an operation of mixing and roasting the ternary lithium battery recycle with an acid and leaching with a leaching agent to obtain a lithium extraction solution, for example, mixing and roasting the ternary lithium battery recycle with sulfuric acid and leaching with sulfuric acid/water to obtain the lithium extraction solution, where possible reactions include:
Li 2 MeO 2 +H 2 SO 4 →Li 2 SO 4 +MeO+H 2 O。
in the above reaction, me may be a metal element such as nickel, cobalt, or manganese, and the source thereof may be a metal element such as nickel, cobalt, or manganese contained in the ternary lithium battery recycle. Through the reaction, lithium contained in the ternary lithium battery recovery material can be converted into soluble lithium sulfate, and meanwhile nickel, cobalt and manganese are converted into oxides or sulfates, so that nickel, cobalt and manganese are removed in the purification treatment process, and a liquid material mainly containing lithium is obtained.
In some embodiments, since the tail gas generated by sulfating, roasting and lithium extraction contains sulfur, the tail gas generated by sulfating, roasting and lithium extraction can be used for preparing sulfuric acid after wet scrubbing, and the prepared sulfuric acid is recycled for sulfating, so that raw material consumption is saved.
In some embodiments, the preconditioning lithium treatment may further include an operation of mixing and roasting the ternary lithium battery recycle with a reducing agent and leaching with a leaching agent to obtain a lithium extraction liquid, for example, mixing and roasting the ternary lithium battery recycle with a reducing agent such as carbon and/or hydrogen, and adding sulfuric acid/water to leach the ternary lithium battery recycle to obtain the lithium extraction liquid. The lithium in the ternary lithium battery recovery is converted into lithium carbonate/lithium hydroxide through a reducing agent, sulfuric acid/water is added for leaching, and the lithium carbonate is dissolved into lithium ions through regulating and controlling the pH value in the purification process, so that a liquid material mainly containing lithium is obtained.
In order to more fully extract lithium in the ternary lithium battery recycle, the firing conditions should be controlled within a proper range. In some embodiments, the firing temperature is 250-600 ℃; and/or the roasting time is 0.5-3h. At the moment, the method is favorable for fully roasting and extracting lithium from the ternary lithium battery recycle, so that the recovery rate of lithium is improved.
In some embodiments, the preconditioning lithium treatment may further include directly leaching the ternary lithium battery recycle with acid to obtain a lithium-extracted solution, e.g., directly leaching the elements of lithium, nickel cobalt manganese, etc., of the ternary lithium battery recycle with sulfuric acid. And removing impurity elements such as nickel, cobalt, manganese and the like through purification treatment after acid leaching, so as to obtain the liquid material with the main component of lithium.
In order to more fully extract lithium contained in the ternary lithium battery recycle, in some embodiments, the ternary lithium battery recycle is subjected to pyrolysis to obtain a pyrolysis product before the ternary lithium battery recycle is subjected to the preconditioning treatment, and the pyrolysis product is used for the preconditioning treatment. For example, the pyrolysis temperature may be controlled to be 320-480 ℃ and the pyrolysis time may be controlled to be 1-3 hours, so that the pyrolysis residue is obtained after the electrolyte contained in the ternary lithium battery recycle is removed by pyrolysis treatment, thereby facilitating the extraction of lithium from the pyrolysis residue.
In some embodiments, when the pretreatment lithium is processed by adopting a roasting mode, tail gas generated by pyrolysis treatment can be used as a heat source for roasting and extracting lithium, so that the energy utilization rate is improved. Specifically, the pyrolysis tail gas is firstly subjected to electrolyte recovery, and then most of organic matters are converted into CO through heat storage incineration/catalytic incineration 2 And water, which is then used as a heat source for extracting lithium by roasting.
Because the ternary lithium battery recovery contains metal elements such as nickel, cobalt, manganese and the like, the metal elements such as nickel, cobalt, manganese and the like can be converted into corresponding ion forms in the precondition lithium process, the metal elements such as nickel, cobalt, manganese and the like also need to be removed, and impurities are prevented from being introduced into the liquid material. In some embodiments, the purification treatment comprises adding a precipitant to the lithium extraction solution, which is the material after the lithium extraction treatment, to perform a precipitation reaction, and performing solid-liquid separation after the reaction to obtain a liquid material. In the precipitation reaction process, the precipitant can react with ions such as nickel, cobalt, manganese and the like to generate corresponding metal precipitates, and then solid-liquid separation is carried out to realize the separation of metal element impurities such as lithium ions and nickel, cobalt, manganese and the like.
In some embodiments, the precipitation agent comprises a sulfide, preferably sodium sulfide. The sulfide precipitates such as nickel sulfide, cobalt sulfide, manganese sulfide and the like can be generated by utilizing the reaction of sodium sulfide and ions such as nickel cobalt manganese sulfide and the like, and lithium ions still exist in a liquid phase, so that a liquid material mainly containing lithium ions can be obtained.
In other alternative embodiments, the precipitant may also include an alkaline substance, preferably sodium hydroxide. The hydroxide precipitate such as nickel hydroxide, cobalt hydroxide, manganese hydroxide and the like can be generated by utilizing the ion reaction of the sodium hydroxide and the metals such as nickel cobalt manganese and the like, and at the moment, the effective separation of the metals such as lithium and nickel cobalt manganese and the like can be realized.
In some embodiments, after the precondition lithium treatment and the purification treatment, the precipitate converted from the metal elements such as nickel, cobalt, manganese and the like can be further treated, so that the metals such as nickel, cobalt, manganese and the like are recovered, and the utilization rate of the ternary lithium battery recovery is improved. In the process of treating the precipitate to recover metal elements such as nickel, cobalt, manganese and the like, if tail gas containing sulfur dioxide and sulfur trioxide is generated in the treatment process, the tail gas can be used for preparing sulfuric acid to obtain sulfuric acid, so that sulfuric acid raw materials are supplemented for other processes requiring sulfuric acid such as sulfation roasting, pH adjustment of mixed reaction and the like.
In some embodiments, after the purification treatment process of removing impurities such as nickel, cobalt, manganese and the like, the lithium content of the obtained liquid material is 3-16g/L, so that the lithium contained in the ternary lithium battery recycle is fully recovered. In this case, since the lithium content of the liquid material is large, the local concentration is close to the saturation concentration, and if stirring is not performed during the mixing reaction, the lithium oxide contained in the solid material is hardly dissolved even if the liquid material and the solid material are mixed due to the homoionic effect. In this embodiment, the liquid material and the solid material are mixed and reacted with stirring, so that the liquid and the solid material can be fully mixed and contacted, and lithium oxide contained in the solid material can be dissolved as much as possible, which is beneficial to improving the recovery rate of lithium contained in the solid material.
In some embodiments, besides precipitating ions such as nickel, cobalt, manganese and the like, the purification treatment can also comprise the steps of adding a fluorine removing agent to remove fluorine, adding a heavy agent to remove calcium and magnesium, performing solid-liquid separation such as pressure filtration, removing organic matters and the like to the lithium extraction liquid which is the material subjected to the lithium pretreatment, so as to remove most of impurities such as nickel, cobalt, manganese, fluorine, organic matters and the like, and obtain a liquid material with higher lithium content. For example, after the purification treatment, the components of the liquid feed may include: 3-16g/L of lithium, less than or equal to 10mg/L of nickel, cobalt and manganese, less than or equal to 10mg/L of fluoride, less than or equal to 20mg/L of calcium ion, 2.5-10g/L of sodium ion and 0.05-1g/L of sulfur ion.
The solid material source of the present application will be described in detail below with reference to the example of a second battery recycle including lithium iron phosphate battery recycle.
In some embodiments, the sources of solid material may include: calcining the lithium iron phosphate battery recycle under an oxygen-containing atmosphere to obtain a solid material; the oxygen-containing atmosphere can comprise oxygen, oxygen-enriched air or air atmosphere, and the like, and can supplement fuel natural gas or hydrogen-containing tail gas and the like to support combustion during calcination, and the fuel consumption can be adjusted according to the combustion temperature. Chemical reactions that may occur during calcination include:
2LiFePO 4 +1/2O 2 →Li 2 O+Fe 2 O 3 +P 2 O 5 ；
3C+O 2 →2CO+CO 2 。
By calcining the resultant P 2 O 5 、CO、CO 2 、N 2 Surplus O 2 The calcination tail gas is introduced, and the rest solid materials comprise lithium oxide and ferric oxide, so that the separation of lithium and iron can be realized by mixing the solid materials with the liquid materials obtained in the embodiment, and the liquid products containing lithium ions and the solid products containing ferric oxide are prepared.
In order to improve the calcination efficiency, the lithium iron phosphate battery recycle is fully converted into a solid material containing lithium oxide and iron oxide, and the calcination conditions can be controlled within a proper range. In some embodiments, the temperature of calcination is 1060-1380 ℃; and/or calcination for a period of time of 6 to 30 minutes, preferably 12 to 24 minutes. For example, the calcination temperature may be 1060 ℃, 1080 ℃, 1100 ℃, 1120 ℃, 1140 ℃, 1160 ℃, 1180 ℃, 1200 ℃, 1220 ℃, 1240 ℃, 1250 ℃, 1260 ℃, 1280 ℃, 1300 ℃, 1320 ℃, 1340 ℃, 1360 ℃, 1380 ℃ or any value between 1060-1380 ℃; the calcination time may be any number between 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min, 30min, or 6-30 min.
In some embodiments, calcining comprises subjecting the lithium iron phosphate battery recycle to a first calcination for a period of time, a second calcination for a period of time, and a calcination temperature of the first calcination being lower than a calcination temperature of the second calcination, in sequence, in an oxygen-containing atmosphere. The two-stage calcination is carried out in stages, so that lithium iron phosphate can be decomposed as much as possible, the subsequent recovery of lithium oxide, ferric oxide and phosphoric acid with higher purity is facilitated, and meanwhile, the concentration of nitrogen oxides in the calcination tail gas is facilitated to be reduced, so that the denitration cost is reduced, and the quality of phosphoric acid (the concentration of nitric acid in phosphoric acid) is also facilitated to be improved.
In some embodiments, the calcination temperature of the primary calcination is in the range of 1060-1250 ℃, preferably in the range of 1100-1250 ℃; and/or calcination time is 4 to 20min, preferably 8 to 16min. The reactions that occur during the primary calcination include:
4LiFePO 4 +3O 2 +2C→2Li 2 CO 3 +2Fe 2 O 3 +2P 2 O 5 ；
Li 2 CO 3 →Li 2 O+CO 2 ；
C+O 2 →CO 2 。
after primary calcination, most of the lithium iron phosphate battery recycle is converted into CO/CO 2 、Fe 2 O 3 、P 2 O 5 . In addition, as graphite can affect the decomposition of lithium iron phosphate, the graphite can wrap the lithium iron phosphate, and simultaneously adsorb oxygen, so that the decomposition effect of the lithium iron phosphate is reduced. By a secondary at a higher temperatureThe first stage calcination is performed before the calcination step, so that a part of graphite is oxidized, for example, in some embodiments, the conversion rate of graphite to carbon dioxide is 30-70% in the first stage calcination process, so that the situation that lithium iron phosphate is wrapped by graphite can be reduced, the decomposition of the lithium iron phosphate is facilitated, and the recovery rate of each component including lithium, iron and phosphorus of the recovered lithium iron phosphate battery is improved. After the primary calcination, most of the lithium iron phosphate is decomposed, and then the secondary calcination is carried out to enable the rest lithium iron phosphate to be approximately completely decomposed.
It should be noted that too low a temperature of the primary calcination is not conducive to achieving effective decomposition of lithium iron phosphate, resulting in a decrease in lithium recovery rate; too high a temperature can result in high calcination fuel consumption and high nitrogen oxide concentration, thereby reducing the quality of phosphoric acid obtained by subsequent recovery and increasing the tail gas treatment cost. And under the proper temperature range of the embodiment of the application, the lithium iron phosphate can be fully decomposed, so that the recovery rate of each component including lithium, iron and phosphorus of the lithium iron phosphate battery recovery product is improved, the calcining fuel consumption can be reduced, the concentration of nitrogen oxides in tail gas is reduced, and the production cost is saved.
In some embodiments, the calcination temperature of the secondary calcination is in the range of 1250-1380 ℃, preferably in the range of 1280-1350 ℃; and/or calcination time is 2 to 10min, preferably 4 to 8min. By performing the secondary calcination at a higher temperature and/or for the above-described suitable calcination temperature and/or calcination time, the lithium iron phosphate battery recycle (including lithium iron phosphate, graphite) remaining from the primary calcination process can be substantially completely decomposed and converted to CO, CO 2 、Fe 2 O 3 、P 2 O 5 Thereby improving the recovery rate of lithium, iron and phosphorus.
As the two-stage calcination is adopted, the calcination conditions of the first-stage calcination and the second-stage calcination can be reasonably regulated and controlled according to the decomposition difficulty of the recovered matters of the lithium iron phosphate battery under the actual calcination working condition, so as to realize the effects of reducing pollution, improving the recovery rate of phosphorus, iron and lithium and the purity of phosphoric acid of the product and reducing the peroxidation problem in the calcination process. In addition, as the primary calcination time is longer and the temperature is relatively lower, compared with the whole process adopting high-temperature calcination, the two-stage calcination can reduce the reaction of nitrogen and oxygen at high temperature and reduce the generation of nitrogen oxides, thereby reducing the concentration of nitrogen oxides in the tail gas, and being beneficial to obtaining phosphoric acid with higher purity (nitric acid concentration reduction) after absorbing the tail gas in the subsequent step.
In some embodiments, the rate of temperature rise of the primary and secondary calcination is 1-3 ℃/min, where the rate of temperature rise refers to the rate of temperature rise during the rise from the temperature of the primary calcination to the temperature required for the secondary calcination. Because the calcination process is carried out at a higher temperature, if the temperature rising rate of the calcination temperature is too small, the temperature rising time is too long, or the temperature rising rate is too large, the calcination equipment is easy to generate thermal strain, so that the equipment becomes brittle, and even fracture occurs. In the embodiment, the temperature rising rate of the calcination temperature is controlled to be 1-3 ℃/min, so that the full calcination can be realized, the damage to calcination equipment can be reduced, and the service life of the equipment is prolonged.
In addition, the control of the gas excess coefficient of the oxygen-containing atmosphere in a proper range also contributes to the effect of calcination. In some embodiments, the oxygen-containing atmosphere has a gas excess factor of 1.35 to 1.7. For example, the gas excess factor of the oxygen-containing atmosphere may be any number between 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, or 1.35-1.7.
In some embodiments, the oxygen consumption of the primary calcination is 80-95% of the total oxygen consumption of the primary and secondary calcination. The reasonable allocation of the consumption of the calcinations oxygen of the primary calcination and the secondary calcination is beneficial to the full decomposition of the recovered matters of the lithium iron phosphate battery through the staged calcination, thereby improving the recovery rate of phosphorus, iron and lithium.
The tail gas generated by calcination contains P 2 O 5 The part P can be 2 O 5 The method is used for preparing phosphoric acid, so that the recovery of the phosphorus is realized, and the utilization rate of the recovered lithium iron phosphate battery is improved. In some embodiments, the lithium iron phosphate battery recycle may be calcined to obtain a gas stream for acid washing to obtain a phosphoric acid product to effect recovery of phosphorus from the lithium iron phosphate battery recycle. For example, a quality score may be usedThe washing is performed with 75-95% phosphoric acid, at which time the phosphorus can be recovered sufficiently and a phosphoric acid product can be obtained. The reaction occurring during the pickling process includes:
3H 2 O+P 2 O 5 →2H 3 PO 4 。
in some embodiments, the temperature of the acid wash is 45-162 ℃; and/or the pressure of the acid washing is 0.05-0.6Mpa, which is favorable for fully recovering phosphorus pentoxide. The temperature of the acid to be used means the temperature of the acid to be used, and the pressure of the acid to be used means the pressure of the acid to be used, for example, the pressure of spraying when the acid to be used is sprayed.
In some embodiments, the calcined product of the first stage calcination may be directly subjected to acid washing without secondary calcination, in which case P contained in the calcined product of the first stage calcination may also be utilized 2 O 5 Preparing a phosphoric acid product.
In some embodiments, the tail gas generated in the acid washing process can be mixed with the tail gas of the sulfating roasting lithium to be used as a heat source of the sulfating roasting lithium, in particular, organic combustible substances contained in the tail gas and a small amount of hydrogen are used as a roasting heat source, thus being beneficial to reducing SO of the tail gas of the sulfating roasting lithium 2 And acid mist concentration, and simultaneously energy consumption is saved. The waste residue generated in the acid washing process can be recycled and used as a roasting raw material for sulfating roasting, so that lithium is further fully extracted.
In some embodiments, the solid material may be treated with an abrasive and then mixed with the liquid material prior to the mixing reaction. For example, the solid material can be mixed with the liquid material for reaction after being cooled and ball-milled to smaller particle size, which is beneficial to the full reaction of the solid material and the liquid material.
In order to extract as much lithium as possible from the ternary lithium battery recycle and the lithium iron phosphate lithium battery recycle, the raw material usage ratio of the ternary lithium battery recycle and the lithium iron phosphate lithium battery recycle may be controlled within a proper range. In some embodiments, the mass ratio of lithium iron phosphate battery recycle to ternary lithium battery recycle is 0.8-4:1, preferably 2-3:1. In the relative dosage range, lithium and iron contained in the ternary lithium battery recycle and the ferric phosphate lithium battery recycle can be fully extracted, and meanwhile, the auxiliary material consumption in the lithium extraction process is reduced.
In the process of obtaining a liquid material from a ternary lithium battery recycle, when sodium sulfide or sodium hydroxide is used as a precipitant for purification treatment, in order to ensure sufficient precipitation of metals such as nickel cobalt manganese, an excessive amount of sodium sulfide or sodium hydroxide is generally selected to be added, and therefore, a part of sodium ions may be contained in the liquid material. In some embodiments, the liquid material has a sodium content of 2.5-10g/L, and the liquid material contains sodium that eventually enters the liquid product, so that it is also necessary to remove sodium ions from the liquid product in order to obtain a liquid product with higher lithium ion purity.
In some embodiments, the method of extracting lithium from a solid material further comprises: and (3) regulating the pH value of the liquid product to be alkaline, concentrating, cooling and crystallizing to obtain a cooled and crystallized liquid and a cooled and crystallized product, and performing aftertreatment on the cooled and crystallized liquid to obtain the lithium hydroxide product. For example, a base such as sodium hydroxide may be added to the liquid product to adjust the pH to be alkaline, at which time the liquid product contains a relatively large amount of hydroxide ions, and then the liquid product is concentrated, for example, by evaporation, to a salt (possibly containing sodium sulfate, lithium sulfate, etc.) content of 10-22% (wt%) and a lithium content of 0.5-10g/L, and then the cooled crystallization product is obtained by controlling the temperature of the cooled crystallization, for example, in the range of 0-20 ℃, so that sodium ions, sulfur ions, sulfate ions in the liquid product crystallize out to obtain the cooled crystallization product, which may be further processed to obtain the sodium sulfate product. And lithium ions and hydroxyl ions contained in the liquid product can enter into the liquid after cooling crystallization, for example, in some embodiments, the lithium content of the liquid after cooling crystallization is more than or equal to 5g/L, and the lithium hydroxide product can be obtained by post-treating the liquid after cooling crystallization. Thus, the byproduct sodium sulfate can be prepared at the same time of preparing the lithium hydroxide product.
In some embodiments, the mass percent of sodium sulfate in the cooled crystallized solution is 15% or less. In order to further remove impurities such as sodium ions and sulfate radicals, the solution after cooling crystallization can be subjected to post-treatment steps such as evaporation crystallization, centrifugal separation, drying packaging and the like, so that a lithium hydroxide product with higher purity can be obtained.
In some embodiments, a base such as sodium hydroxide is added to the liquid product to adjust the pH to 13-14.5 prior to concentration. If anions such as sulfate are introduced in the solid material and the liquid material in the mixing reaction or in the step before the mixing reaction, the liquid product contains sulfate, and lithium ions in the liquid product may exist in the form of lithium sulfate. In this embodiment, the pH of the liquid product is adjusted to be strongly alkaline, which is advantageous for increasing the hydroxide ion concentration in the liquid product, thereby increasing the yield of lithium hydroxide.
Referring to fig. 1, the application further provides a system for extracting lithium from solid materials, which comprises a calcination system, a precondition lithium system, a purification system and a mixing system, wherein the calcination system is connected with the mixing system, and the precondition lithium system is sequentially connected with the purification system and the mixing system. Wherein the calcination system is used for performing the calcination steps described in the above embodiments, so that the second battery recycle is calcined to obtain a solid material; the precondition lithium system and the purification system are respectively used for performing the precondition lithium step and the purification step described in the above embodiments, so that the first battery recycle is subjected to the precondition lithium treatment and the purification treatment in sequence to obtain a liquid material; the mixing system is used for carrying out the mixing reaction step in the embodiment, so that the solid material and the liquid material are mixed to react to obtain a reacted liquid, and the reacted liquid is subjected to solid-liquid separation to obtain a solid product containing ferric oxide and ferrous sulfide and a liquid product containing lithium ions.
In this embodiment, the calcination system is used to calcine the battery recycle, so that the second battery recycle is decomposed as much as possible, which is beneficial to separating and recovering lithium, iron and other elements contained in the second battery recycle, so as to obtain a solid material containing ferric oxide and lithium oxide, and is beneficial to reducing the concentration of nitrogen oxides in the calcination tail gas, thereby reducing pollution and reducing denitration cost. The first battery recycle is treated by the precondition lithium system and the purification system, so that a liquid material containing water and sulfur ions can be obtained, and lithium contained in the first battery recycle can be fully utilized. The liquid material and the solid material are supplied to react in a mixing way through the mixing system, so that water in the liquid material and lithium oxide in the solid material react to obtain lithium ions, the lithium ions can enter a liquid product, iron oxide in the solid material is almost insoluble in water, and then the separation of lithium and iron can be realized through solid-liquid separation. In addition, a small amount of iron ions entering the solution can fully react with sulfur ions to form ferrous sulfide precipitates, sulfur simple substance precipitates and hydrogen sulfide gas, so that enrichment of iron ions and sulfur ions can not be formed, and the waste water does not need to be discharged periodically to control the content of impurity ions such as iron ions and sulfur ions in the waste water, thereby reducing the discharge of the waste water. Therefore, the method can realize the economic and effective extraction of lithium elements in the solid material, and is beneficial to improving the purity of lithium ions in the liquid product.
In some embodiments, the calcination system comprises a primary calcination system and a secondary calcination system, the primary calcination system being sequentially connected to the secondary calcination system and the mixing system; the first-stage calcining system and the second-stage calcining system are respectively used for performing the first-stage calcining step and the second-stage calcining step in the embodiment, so that the second battery recycle material is subjected to first-stage calcining and second-stage calcining in sequence to obtain a solid material.
In some embodiments, the system for extracting lithium from a solid material further comprises a pyrolysis system connected to the lithium precursor system, the pyrolysis system configured to perform the pyrolysis step described in the above embodiments, such that the first battery recycle is sent to the lithium precursor system after pyrolysis.
Referring to fig. 2, in some embodiments, the purifying system includes a nickel-cobalt depositing device, a fluorine removing device, a heavy device, and the like, which are sequentially connected, and the purifying system is used for performing the steps of removing nickel-cobalt-manganese plasma, adding a fluorine removing agent to remove fluorine, adding a heavy agent to remove calcium and magnesium, and the like in the precipitation reaction described in the above embodiments, so as to obtain a liquid material with higher lithium content.
In some embodiments, the system for extracting lithium from the solid material further comprises a concentration system, a cooling crystallization system and a post-treatment system, wherein the mixing system is sequentially connected with the concentration system, the cooling crystallization system and the post-treatment system; the concentration system and the cooling crystallization system are respectively used for carrying out the concentration step and the cooling crystallization step in the embodiment, so that liquid products obtained by the mixing system are concentrated and cooled and crystallized in sequence to obtain cooled and crystallized liquid and cooled and crystallized products; the post-treatment system is used for carrying out the steps of evaporation crystallization, centrifugal separation, drying and packaging and the like in the embodiment, so that the lithium hydroxide product is obtained by post-treatment of the cooled and crystallized liquid.
The following examples more particularly describe the disclosure of the present application, which are intended as illustrative only, since numerous modifications and variations within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by mass, and all reagents and materials used in the examples are commercially available or are obtained synthetically according to conventional methods, as well as the instruments used in the examples.
Example 1
The embodiment provides a method for extracting lithium from solid materials, which comprises the following steps:
1) Adding ternary lithium battery recycle (lithium content 4% and total nickel cobalt manganese content 40%) into pyrolysis equipment according to the flow of 0.4kg/h, and carrying out pyrolysis to remove electrolyte, wherein the pyrolysis temperature is 320 ℃, and the pyrolysis time is 3h; the pyrolysis tail gas is sent to step 2) to be used as a heat source for sulfating roasting.
2) And adding the pyrolyzed ternary lithium battery recycle into roasting equipment, and adding concentrated sulfuric acid for roasting, wherein the roasting temperature is 250 ℃ and the roasting time is 3 hours.
3) Wet washing the sulfating roasting tail gas, removing acid to obtain sulfuric acid, using the sulfuric acid as a raw material for sulfating roasting, recycling waste residue obtained by wet washing to roasting equipment, and repeatedly performing sulfating roasting;
4) And (3) ball milling the sulfated roasting product, leaching with water, filtering, adding sodium sulfide into the filtrate to perform precipitation reaction, filtering again to obtain a lithium sulfate solution, wherein the obtained lithium sulfate solution is used as a liquid material for the mixing reaction in the step (8), the lithium content in the liquid material is 9.5g/L, the lithium sulfate mass content is 10.8%, the sulfur ion content is 0.06g/L, the sodium content is 5g/L, the sodium sulfate mass content is 3.9%, and the pH value of the liquid material is 6.
5) Controlling the mass ratio of the lithium iron phosphate battery recycle to the ternary lithium battery recycle in the step 1) to be 2.5:1, namely adding the lithium iron phosphate battery recycle (the lithium content is 3%, the phosphorus content is 15% and the iron content is 25%) into the calcining equipment according to the flow of 1kg/h, and adding oxygen to sequentially perform primary calcining and secondary calcining; wherein the temperature of the primary calcination is 1100 ℃ and the time is 10min; the temperature of the secondary calcination is 1300 ℃ and the time is 6min; the total oxygen consumption of the first-stage calcination and the second-stage calcination satisfies that the oxygen excess coefficient is 1.7, the oxygen consumption of the first-stage calcination accounts for 80% of the total oxygen consumption, and the rest oxygen is supplied to the second-stage calcination.
The gas material and the solid material are obtained after the secondary calcination, wherein the solid material comprises lithium oxide and ferric oxide, and the gas material comprises phosphorus pentoxide, CO and CO 2 Gas feed and surplus O 2 The nitrogen oxides generated by calcination enter the calcination tail gas, and the emission concentration of the nitrogen oxides is 210mg/Nm 3 The mass rate was 1.15g/h.
6) Recovering waste heat from the calcined tail gas, and circularly washing and absorbing P in the calcined tail gas by using concentrated phosphoric acid solution with the mass fraction of 95 percent 2 O 5 And obtaining a phosphoric acid product; wherein the temperature of the washed concentrated phosphoric acid solution is 162 ℃, and the pressure of the washed concentrated phosphoric acid solution is 0.6MPa; the yield of the phosphoric acid product was 0.444kg/h, the purity was 99.7%, and the recovery rate of phosphorus was 90%.
7) The washing tail gas is sent into roasting equipment to be used as a heat source for sulfating roasting, and SO of the sulfating roasting tail gas is reduced 2 Concentration of acid mist.
8) And (3) carrying out a cooling ball milling on the solid material obtained after the secondary calcination, mixing the solid material with the liquid material obtained in the step (4), wherein the liquid-solid ratio of the liquid material to the solid material is 4L/kg, the stirring rate in the mixing reaction process is 120r/min, the time is 1h, the temperature is 72 ℃, the pH value is maintained to be 6, the solid product and the liquid product are obtained through filter pressing after the mixing reaction is finished, the lithium sulfate content in the liquid product is 7.6%, the lithium hydroxide content is 8.9%, the sulfur ion content is 6mg/L, the iron (ferrous iron+ferric iron) content is less than 1ppm, the leaching rate of iron in the solid material is 0.05%, and the leaching rate of lithium is 93.2%.
9) The solid product mainly contains ferric oxide, can be directly used as ferric oxide product, and has the yield of 0.161kg/h and the iron recovery rate of 92 percent.
10 The pH value of the liquid product is adjusted to 14 by using solid alkali or liquid alkali, the mixture is further concentrated until the total content of sodium sulfate and lithium sulfate in the solution is 16 percent (wt%), the content of lithium is 5.5g/L, then liquid ammonia is used as a cooling medium for cooling crystallization at the temperature of 0 ℃ to obtain cooled crystallization liquid and cooled crystallization product, the concentration of sodium sulfate in the cooled crystallization liquid is 12 percent, the content of lithium is 5.3g/L, and the cooled crystallization product is subjected to sodium sulfate post-treatment to obtain the sodium sulfate product.
11 The cooled and crystallized liquid is subjected to evaporation and crystallization, centrifugal separation, drying and packaging and the like to obtain the product lithium hydroxide monohydrate, wherein the yield of the product lithium hydroxide monohydrate is 0.253kg/h, and the comprehensive recovery rate of the lithium is 91 percent, thereby meeting the judgment standard of GB/T26008-2020 battery grade lithium hydroxide monohydrate.
Example 2
This example provides a method for extracting lithium from a solid material, which differs from example 1 in that: the parameter conditions of each step are different, and the pyrolysis step is not carried out, and the method specifically comprises the following steps:
1) Ternary lithium battery recycle (lithium content 4%, total nickel cobalt manganese content 40%) is added into roasting equipment according to the flow of 0.4kg/h, concentrated sulfuric acid is added for roasting, the roasting temperature is 425 ℃, and the roasting time is 1.7h.
2) And (3) wet washing the sulfating roasting tail gas, removing acid to obtain sulfuric acid, wherein the sulfuric acid is used as a raw material for sulfating roasting, and waste residues obtained by wet washing are recycled to roasting equipment for repeated sulfating roasting.
3) And (3) ball milling the sulfated roasting product, leaching with water, filtering, adding sodium sulfide into the filtrate to perform precipitation reaction, and filtering to obtain a lithium sulfate solution, wherein the obtained lithium sulfate solution is used as a liquid material for the mixing reaction in the step (7), the lithium content in the liquid material is 7g/L, the sulfur ion content is 0.05g/L, and the pH value of the liquid material is 6.
4) Controlling the mass ratio of the lithium iron phosphate battery recycle to the ternary lithium battery recycle in the step 1) to be 2.5:1, namely adding the lithium iron phosphate battery recycle (3% of lithium, 15% of phosphorus and 25% of iron) into the calcining equipment according to the flow of 1kg/h, and adding oxygen-enriched air to sequentially perform primary calcination and secondary calcination; wherein the temperature of the primary calcination is 1100 ℃ and the time is 8min; the temperature of the secondary calcination is 1280 ℃ and the time is 5min; the total consumption of the oxygen-enriched air of the first-stage calcination and the second-stage calcination meets the requirement that the excess coefficient of the oxygen-enriched air is 1.53, the consumption of the oxygen-enriched air of the first-stage calcination accounts for 87.5 percent of the total consumption of the oxygen-enriched air, and the residual oxygen is supplied to the second-stage calcination.
The gas material and the solid material are obtained after the secondary calcination, wherein the solid material comprises lithium oxide and ferric oxide, and the gas material comprises phosphorus pentoxide, CO and CO 2 Gas feed and surplus O 2 The nitrogen oxides generated by calcination enter the calcination tail gas, and the emission concentration of the nitrogen oxides is 209mg/Nm 3 The mass rate was 1.14g/h.
5) Recovering waste heat from the calcined tail gas, and circularly washing and absorbing P in the calcined tail gas by using concentrated phosphoric acid solution with the mass fraction of 95 percent 2 O 5 And obtaining a phosphoric acid product; wherein the temperature of the washed concentrated phosphoric acid solution is 103 ℃, and the pressure of the washed concentrated phosphoric acid solution is 0.325MPa; the yield of the phosphoric acid product was 0.499kg/h, the purity was 99.7%, and the recovery rate of phosphorus was 89.5%.
6) The washing tail gas is sent into roasting equipment to be used as a heat source for sulfating roasting, and SO of the sulfating roasting tail gas is reduced 2 Concentration of acid mist.
7) And (3) carrying out a cooling ball milling on the solid material obtained after the secondary calcination, mixing the solid material with the liquid material obtained in the step (3) for reaction, wherein the liquid-solid ratio of the liquid material to the solid material is 4L/kg, the stirring rate in the mixing reaction process is 120r/min, the time is 0.7h, the temperature is 70 ℃, the pH value is maintained to be 6, the solid product and the liquid product are obtained through filter pressing after the mixing reaction is finished, the content of sulfide ions in the liquid product is 7mg/L, the content of iron (ferrous iron and ferric iron) is less than 1ppm, the leaching rate of iron in the solid material is 0.07%, and the leaching rate of lithium is 90.4%.
8) The solid product mainly contains ferric oxide, can be directly used as ferric oxide product, and has the yield of 0.16kg/h and the iron recovery rate of 91.5%.
9) The pH value of the liquid product is regulated to 14 by using solid alkali or liquid alkali, the solution is further concentrated until the total content of sodium sulfate and lithium sulfate in the solution is 10 percent (wt%), the content of lithium is 4g/L, cooling crystallization is carried out by using chilled water as a cooling medium at the temperature of 10 ℃ to obtain cooled crystallization liquid and cooled crystallization product, the concentration of sodium sulfate in the cooled crystallization liquid is 12 percent, the content of lithium is 5.1g/L, and the cooled crystallization product is subjected to sodium sulfate post-treatment to obtain the sodium sulfate product.
10 The cooled and crystallized liquid is subjected to evaporation and crystallization, centrifugal separation, drying and packaging and the like to obtain the product lithium hydroxide monohydrate, wherein the yield of the product lithium hydroxide monohydrate is 0.219kg/h, and the comprehensive recovery rate of lithium is 90.5 percent, thereby meeting the judgment standard of GB/T26008-2020 battery level lithium hydroxide monohydrate.
Example 3
This example provides a method for extracting lithium from a solid material, which differs from example 1 in that: the parameter conditions of each step are different, and the pyrolysis step is not carried out, and the method specifically comprises the following steps:
1) Ternary lithium battery recycle (lithium content 4% and total nickel cobalt manganese content 40%) is added into roasting equipment according to the flow of 0.4kg/h, concentrated sulfuric acid is added for roasting, the roasting temperature is 600 ℃, and the roasting time is 0.5h.
2) And (3) wet washing the sulfating roasting tail gas, removing acid to obtain sulfuric acid, wherein the sulfuric acid is used as a raw material for sulfating roasting, and waste residues obtained by wet washing are recycled to roasting equipment for repeated sulfating roasting.
3) And (3) ball milling the sulfated roasting product, leaching with water, filtering, adding sodium sulfide into the filtrate to perform precipitation reaction, and filtering to obtain a lithium sulfate solution, wherein the obtained lithium sulfate solution is used as a liquid material for the mixing reaction in the step (7), the lithium content in the liquid material is 16g/L, the mass content of sulfide ions is 10%, the content of sulfide ions is 0.08g/L, and the pH value of the liquid material is 6.
4) Controlling the mass ratio of the lithium iron phosphate battery recycle to the ternary lithium battery recycle in the step 1) to be 2.5:1, namely adding the lithium iron phosphate battery recycle (the lithium content is 3%, the phosphorus content is 15% and the iron content is 25%) into the calcining equipment according to the flow of 1kg/h, and adding air to sequentially perform primary calcining and secondary calcining; wherein the temperature of the primary calcination is 1100 ℃ and the time is 8min; the temperature of the secondary calcination is 1300 ℃ and the time is 10min; the total air consumption of the first-stage calcination and the second-stage calcination satisfies that the air excess coefficient is 1.35, the air consumption of the first-stage calcination accounts for 95% of the total air consumption, and the residual oxygen is supplied to the second-stage calcination.
The gas material and the solid material are obtained after the secondary calcination, wherein the solid material comprises lithium oxide and ferric oxide, and the gas material comprises phosphorus pentoxide, CO and CO 2 Gas feed and surplus O 2 The nitrogen oxides generated by calcination enter the calcination tail gas, and the emission concentration of the nitrogen oxides is 224mg/Nm 3 The mass rate was 1.21g/h.
5) Recovering waste heat from the calcined tail gas, and circularly washing and absorbing P in the calcined tail gas by using concentrated phosphoric acid solution with the mass fraction of 95 percent 2 O 5 And obtaining a phosphoric acid product; wherein the temperature of the washed concentrated phosphoric acid solution is 45 ℃, and the pressure of the washed concentrated phosphoric acid solution is 0.6MPa; the yield of the phosphoric acid product was 0.469kg/h, the purity was 99.5%, and the recovery of phosphorus was 90%.
6) The washing tail gas is sent into roasting equipment to be used as a heat source for sulfating roasting, and SO of the sulfating roasting tail gas is reduced 2 Concentration of acid mist.
7) And (3) carrying out a cooling ball milling on the solid material obtained after the secondary calcination, mixing the solid material with the liquid material obtained in the step (3) for reaction, wherein the liquid-solid ratio of the liquid material to the solid material is 6L/kg, the stirring rate in the mixing reaction process is 150r/min, the time is 0.5h, the temperature is 65 ℃, the pH value is maintained to be 6, the solid product and the liquid product are obtained through filter pressing after the mixing reaction is finished, the content of sulfide ions in the liquid product is 4mg/L, the content of iron (ferrous iron and ferric iron) is less than 1ppm, the leaching rate of iron in the solid material is 0.06%, and the leaching rate of lithium is 93.4%.
8) The solid product mainly contains ferric oxide, can be directly used as ferric oxide product, and has the yield of 0.159kg/h and the iron recovery rate of 91%.
9) The pH value of the liquid product is regulated to 14 by using solid alkali or liquid alkali, the solution is further concentrated until the total content of sodium sulfate and lithium sulfate in the solution is 22 percent (wt%), the content of lithium is 10g/L, propylene is adopted as a cooling medium for cooling crystallization at the temperature of 20 ℃ to obtain cooled crystallization liquid and cooled crystallization product, the concentration of sodium sulfate in the cooled crystallization liquid is 10 percent, the content of lithium is 5.8g/L, and the cooled crystallization product is subjected to sodium sulfate post-treatment to obtain the sodium sulfate product.
10 The cooled and crystallized liquid is subjected to evaporation and crystallization, centrifugal separation, drying and packaging and the like to obtain the product lithium hydroxide monohydrate, wherein the yield of the product lithium hydroxide monohydrate is 0.254kg/h, and the comprehensive recovery rate of the lithium is 92 percent, thereby meeting the judgment standard of GB/T26008-2020 battery grade lithium hydroxide monohydrate.
Example 4
This example provides a method for extracting lithium from a solid material, which differs from example 1 in that: the composition of the raw materials of the battery recycle is different, the parameter conditions of each step are different, and the battery recycle does not undergo a pyrolysis step, and the method specifically comprises the following steps:
1) Ternary lithium battery recycle (lithium content 3% and nickel cobalt manganese total content 31%) is added into roasting equipment according to the flow of 0.4kg/h, concentrated sulfuric acid is added for roasting, the roasting temperature is 310 ℃, and the roasting time is 2.1h.
2) And (3) wet washing the sulfating roasting tail gas, removing acid to obtain sulfuric acid, wherein the sulfuric acid is used as a raw material for sulfating roasting, and waste residues obtained by wet washing are recycled to roasting equipment for repeated sulfating roasting.
3) And (3) ball milling the sulfated roasting product, leaching with water, filtering, adding sodium sulfide into the filtrate to perform precipitation reaction, and filtering to obtain a lithium sulfate solution, wherein the obtained lithium sulfate solution is used as a liquid material for the mixing reaction in the step (7), the lithium content in the liquid material is 7.6g/L, the mass content of the sulfide ions is 0.08g/L, and the pH value of the liquid material is 7.
4) Controlling the mass ratio of the lithium iron phosphate battery recycle to the ternary lithium battery recycle in the step 1) to be 2.5:1, namely adding the lithium iron phosphate battery recycle (the lithium content is 3%, the phosphorus content is 15% and the iron content is 25%) into the calcining equipment according to the flow of 1kg/h, and adding oxygen to sequentially perform primary calcining and secondary calcining; wherein the temperature of the primary calcination is 1250 ℃ and the time is 8min; the temperature of the secondary calcination is 1350 ℃ and the time is 8min; the total oxygen consumption of the first-stage calcination and the second-stage calcination satisfies that the oxygen excess coefficient is 1.5, and the oxygen consumption of the first-stage calcination accounts for 83% of the total oxygen consumption, and the remaining oxygen is supplied to the second-stage calcination.
The gas material and the solid material are obtained after the secondary calcination, wherein the solid material comprises lithium oxide and ferric oxide, and the gas material comprises phosphorus pentoxide, CO and CO 2 Gas feed and surplus O 2 The nitrogen oxides generated by calcination enter the calcination tail gas, and the emission concentration of the nitrogen oxides is 218mg/Nm 3 The mass rate was 1.18g/h.
5) Recovering waste heat from the calcined tail gas, and circularly washing and absorbing P in the calcined tail gas by using concentrated phosphoric acid solution with the mass fraction of 95 percent 2 O 5 And obtaining a phosphoric acid product; wherein the temperature of the washed concentrated phosphoric acid solution is 58 ℃, and the pressure of the washed concentrated phosphoric acid solution is 0.27MPa; the yield of the phosphoric acid product was 0.495kg/h, the purity was 99.7%, and the recovery rate of phosphorus was 88%.
6) The washing tail gas is sent into roasting equipment to be used as a heat source for sulfating roasting, and SO of the sulfating roasting tail gas is reduced 2 Concentration of acid mist.
7) And (3) carrying out a cooling ball milling on the solid material obtained after the secondary calcination, mixing the solid material with the liquid material obtained in the step (3) for reaction, wherein the liquid-solid ratio of the liquid material to the solid material is 2L/kg, the stirring rate in the mixing reaction process is 120r/min, the time is 1h, the temperature is 92 ℃, the pH value is maintained to be 7, the solid product and the liquid product are obtained through filter pressing after the mixing reaction is finished, the content of sulfide ions in the liquid product is 10mg/L, the content of iron (ferrous iron and ferric iron) is less than 1ppm, the leaching rate of iron in the solid material is 0.04%, and the leaching rate of lithium is 90.2%.
8) The solid product mainly contains ferric oxide, can be directly used as ferric oxide product, and has the yield of 0.164kg/h and the iron recovery rate of 90 percent.
9) The pH value of the liquid product is regulated to 14 by using solid alkali or liquid alkali, the solution is further concentrated until the total content of sodium sulfate and lithium sulfate in the solution is 17 percent (wt%), the content of lithium is 8.2g/L, then the solution and the cooled crystallization product are obtained by cooling and crystallizing with R410a as a cooling medium at the temperature of 6 ℃ to obtain the cooled crystallization solution with the sodium sulfate concentration of 15 percent and the lithium content of 3g/L, and the sodium sulfate product is obtained by performing sodium sulfate post-treatment on the cooled crystallization product.
10 The cooled and crystallized liquid is subjected to evaporation and crystallization, centrifugal separation, drying and packaging and the like to obtain the product lithium hydroxide monohydrate, wherein the yield of the product lithium hydroxide monohydrate is 0.292kg/h, and the comprehensive recovery rate of the lithium is 90 percent, thereby meeting the judgment standard of GB/T26008-2020 battery grade lithium hydroxide monohydrate.
Example 5
This example provides a method for extracting lithium from a solid material, which differs from example 1 in that: during the mixing reaction of the liquid material and the solid material, stirring is not performed.
In this example, after the primary calcination and the secondary calcination, the emission concentration of nitrogen oxides was 210mg/Nm 3 The mass rate is 1.15g/h, the yield of phosphoric acid product is 0.444kg/h, the purity is 99.7%, the recovery rate of phosphorus is 90%, the yield of ferric oxide product is 0.161kg/h, the recovery rate of iron is 91%, the yield of lithium hydroxide monohydrate product is 0.253kg/h, and the comprehensive recovery rate of lithium is 91%.
Comparative example 1
This comparative example provides a method of extracting lithium from a solid material, which differs from example 1 in that the liquid material is directly made from a mixed solution of lithium sulfate and sodium sulfate, rather than from a ternary lithium battery recycle.
The comparative example showed a nitrogen oxide emission concentration of 210mg/Nm after the primary and secondary calcination 3 The mass rate is 1.15g/h, the yield of phosphoric acid product is 0.444kg/h, the purity is 99.7%, the recovery rate of phosphorus is 90%, the yield of ferric oxide product is 0.154kg/h, the recovery rate of iron is 89%, the yield of lithium hydroxide monohydrate product is 0.253kg/h, and the comprehensive recovery rate of lithium is 91%.
Table 1, product comparison in each example and comparative example
In table 1, the leaching rate of iron in the solid material=iron in the liquid product/iron contained in the solid material, the leaching rate of lithium in the solid material=lithium in the liquid product/lithium contained in the solid material, the comprehensive recovery rate of lithium=lithium in the lithium hydroxide product/lithium in the battery recycle raw material, the recovery rate of phosphorus=phosphorus contained in the phosphorus/lithium iron phosphate battery recycle in the phosphoric acid product, and the recovery rate of iron=iron contained in the iron/lithium iron phosphate battery recycle in the iron oxide product.
According to the data about the above examples and comparative examples in table 1, after the method for extracting lithium from solid materials provided in the examples of the present application is adopted, the comprehensive recovery rate of lithium can reach more than 90%, and thus, the method in the examples of the present application can effectively extract lithium elements in the solid materials. In addition, because the iron ions and the sulfur ions fully react in the mixing reaction process, the iron ions and the sulfur ions cannot form enrichment, so that the waste water does not need to be discharged periodically to control the content of impurity ions such as iron ions in the waste water, thereby reducing the discharge of the waste water and being beneficial to economically and effectively realizing the extraction of lithium in the solid material. Specifically, after the solid material and the liquid material are mixed and reacted, the content of iron (ferrous iron and ferric iron) in the obtained liquid product is less than 1ppm, so that the content of iron in the liquid product is extremely low, and the effective separation of lithium and iron can be basically realized. And then further processing the liquid product to prepare lithium hydroxide, thus respectively obtaining a lithium hydroxide product and an iron oxide product.
Further, the source of the liquid material and the solid material may be from a battery recycle, for example, in embodiments of the present application, the source of the liquid material may be from a ternary lithium battery recycle, and the source of the solid material may be from a lithium iron phosphate battery recycle. After the ternary lithium battery recycle and the ferric phosphate lithium battery recycle are treated by the lithium extraction method in the embodiment of the application, lithium, iron and phosphorus elements in the ternary lithium battery recycle and the ferric phosphate lithium battery recycle can be effectively extracted and separated, the phosphorus recovery rate can be more than 88%, the iron recovery rate can be more than 90%, and corresponding lithium hydroxide products, ferric oxide products and phosphoric acid products can be prepared and obtained, so that the comprehensive utilization of the battery recycle can be realized.
Comparing experimental data of example 5 with experimental data of example 1, example 5 was not stirred during the mixing reaction of the liquid material and the solid material, and at this time, iron ions generated by dissolution of iron oxide were not sufficiently reacted with sulfur ions contained in the liquid material, resulting in that a small amount of iron ions could not be precipitated and exist in the liquid product, and eventually, the iron recovery rate was reduced. In the embodiment 1, the liquid material and the solid material are mixed and reacted while stirring, so that the reaction rate can be increased, and meanwhile, the iron ions and the sulfur ions are ensured to fully react to generate ferrous sulfide precipitates, so that iron enters the solid product, and the recovery rate of the iron is further improved.
Comparing the experimental data of comparative example 1 with those of example 1, the mixed solution of lithium sulfate and sodium sulfate was directly used as the liquid material in comparative example 1, i.e., the liquid material did not contain sulfide ions, which resulted in some iron (ferrous+ferric) entering the liquid product, resulting in a reduction in iron recovery rate. In example 1, the ternary lithium battery recycle is treated to obtain a liquid material, wherein the liquid material contains sulfur ions, and the sulfur ions can react with ferrous iron/ferric iron to generate ferrous sulfide precipitate, so that the iron content in a liquid product is reduced.
The technical features described above may be arbitrarily combined. Although not all possible combinations of features are described, any combination of features should be considered to be covered by the description provided that such combinations are not inconsistent.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (11)
1. A method for extracting lithium from a solid material, comprising the steps of:
mixing the liquid material with the solid material, and performing solid-liquid separation to obtain a solid product and a liquid product;
wherein the liquid material contains water and sulfide ions, the solid material contains iron oxide and lithium oxide, the solid product contains iron oxide, and the liquid product contains lithium ions.
2. The method for extracting lithium from solid material according to claim 1, wherein,
the liquid-solid ratio of the liquid material to the solid material is 2L-6L:1kg;
optionally, the mixing is performed in a stirring state, and the stirring speed is 120-150r/min;
optionally, the mixing time is 0.5-1.5h;
optionally, the temperature of the mixing is 65-92 ℃;
optionally, the liquid material has a sulfur ion content of 0.05-1g/L;
optionally, the liquid product has a sulfur ion content of 2.5-50mg/L;
optionally, the pH of the reaction solution is controlled to be maintained at 5-8 during the mixing process.
3. The method for extracting lithium from a solid material according to claim 1, wherein the liquid material is obtained by subjecting a first battery recycle to a preconditioning treatment to obtain a lithium extraction liquid, and subjecting the lithium extraction liquid to a purification treatment;
optionally, the preconditioning lithium treatment comprises the operation of leaching the first battery recycle by acid to obtain a lithium extraction liquid, or leaching by a leaching agent after mixing and roasting with acid or a reducing agent to obtain the lithium extraction liquid;
optionally, the leaching agent comprises any one of acid and water;
optionally, the acid comprises sulfuric acid, or the reducing agent comprises carbon and/or hydrogen;
Optionally, the roasting temperature is 250-600 ℃; and/or the roasting time is 0.5-3h;
optionally, the first battery recycle comprises at least one of a unitary lithium battery recycle, a binary lithium battery recycle, and a ternary lithium battery recycle.
4. A method of extracting lithium from a solid material according to claim 3, wherein the solid material is obtained by calcining a second battery recycle in an oxygen-containing atmosphere;
optionally, the temperature of the calcination is in the range 1060-1380 ℃;
optionally, the calcination time is 6-30min, preferably 12-24min;
optionally, the calcining comprises a primary calcining and a secondary calcining which are sequentially carried out, and the calcining temperature of the primary calcining is lower than that of the secondary calcining;
optionally, the oxygen-containing atmosphere has a gas excess coefficient of 1.35-1.7;
optionally, the mass ratio of the second battery recycle to the first battery recycle is from 0.8 to 4:1, preferably from 2 to 3:1;
optionally, the second battery recycle comprises a lithium iron phosphate battery recycle.
5. The method for extracting lithium from solid material according to claim 3, wherein the purification treatment comprises adding a precipitant into the lithium extraction liquid to perform precipitation reaction, and obtaining the liquid material through solid-liquid separation after the reaction;
Optionally, the precipitating agent comprises a sulfide, preferably sodium sulfide;
optionally, the lithium content of the liquid material is 3-16g/L;
optionally, the liquid material has a sodium content of 2.5-10g/L;
optionally, the pH of the liquid feed is 5-8.
6. A method of extracting lithium from a solid material as claimed in claim 3, wherein prior to subjecting the first battery recycle to the preconditioning lithium treatment, the method further comprises: and carrying out pyrolysis treatment on the first battery recycle to obtain a pyrolysis material, and using the pyrolysis material for carrying out precondition lithium treatment.
7. The method of extracting lithium from a solid material of claim 5, further comprising: the pH value of the liquid product is regulated to be alkaline, and then the liquid product is concentrated, cooled and crystallized to obtain cooled and crystallized liquid and cooled and crystallized product, and the cooled and crystallized liquid is subjected to aftertreatment to obtain a lithium hydroxide product;
optionally, treating the cooled crystallized product to obtain a sodium sulfate product;
optionally, the temperature of the cooling crystallization is 0-20 ℃;
optionally, the mass percentage of sodium sulfate in the cooled and crystallized liquid is less than or equal to 15%;
optionally, the lithium content of the liquid after cooling crystallization is more than or equal to 5g/L;
Optionally, a base is added to the liquid product to adjust the pH to 13-14.5 prior to concentration.
8. The system for extracting lithium from the solid material is characterized by comprising a calcination system, a precondition lithium system, a purification system and a mixing system, wherein the calcination system is connected with the mixing system, and the precondition lithium system is sequentially connected with the purification system and the mixing system;
the calcination system is used for obtaining solid materials after the second battery recycle is calcined;
the precondition lithium system and the purification system are used for sequentially carrying out precondition lithium treatment and purification treatment on the first battery recycle to obtain a liquid material;
the mixing system is used for mixing liquid materials and solid materials, and then solid-liquid separation is carried out to obtain a solid product containing ferric oxide and a liquid product containing lithium ions.
9. The system for extracting lithium from a solid material according to claim 8, wherein the calcination system comprises a primary calcination system and a secondary calcination system, and the primary calcination system is sequentially connected with the secondary calcination system and the mixing system;
the first-stage calcining system and the second-stage calcining system are used for enabling the second battery recycle to be subjected to first-stage calcining and second-stage calcining in sequence to obtain a solid material.
10. The system for extracting lithium from a solid material of claim 8, further comprising a pyrolysis system, wherein the pyrolysis system is connected to the lithium precursor system, and wherein the pyrolysis system is configured to pyrolyse the first battery recycle and send the first battery recycle to the lithium precursor system.
11. The system for extracting lithium from a solid material according to claim 8, further comprising a concentration system, a cooling crystallization system and a post-treatment system, wherein the mixing system is sequentially connected with the concentration system, the cooling crystallization system and the post-treatment system;
the concentrating system and the cooling crystallization system are used for concentrating and cooling and crystallizing the liquid product obtained by the mixing system in sequence to obtain cooled and crystallized liquid and cooled and crystallized product;
and the post-treatment system is used for carrying out post-treatment on the cooled and crystallized liquid to obtain a lithium hydroxide product.
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