CN111534697A - Selection-smelting combined comprehensive recovery method and device for waste lithium ion batteries - Google Patents
Selection-smelting combined comprehensive recovery method and device for waste lithium ion batteries Download PDFInfo
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- CN111534697A CN111534697A CN202010520232.5A CN202010520232A CN111534697A CN 111534697 A CN111534697 A CN 111534697A CN 202010520232 A CN202010520232 A CN 202010520232A CN 111534697 A CN111534697 A CN 111534697A
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- lithium
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- 238000011084 recovery Methods 0.000 title claims abstract description 131
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 108
- 239000002699 waste material Substances 0.000 title claims abstract description 81
- 238000003723 Smelting Methods 0.000 title claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 200
- 239000000047 product Substances 0.000 claims abstract description 200
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 199
- 238000002386 leaching Methods 0.000 claims abstract description 175
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 159
- 239000002245 particle Substances 0.000 claims abstract description 149
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 148
- 239000010439 graphite Substances 0.000 claims abstract description 148
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000012535 impurity Substances 0.000 claims abstract description 94
- 239000002893 slag Substances 0.000 claims abstract description 94
- 238000005188 flotation Methods 0.000 claims abstract description 90
- 239000000843 powder Substances 0.000 claims abstract description 85
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 50
- 239000013067 intermediate product Substances 0.000 claims abstract description 39
- 238000005406 washing Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 230000001698 pyrogenic effect Effects 0.000 claims abstract description 31
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012141 concentrate Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 133
- 238000007885 magnetic separation Methods 0.000 claims description 73
- 229910017052 cobalt Inorganic materials 0.000 claims description 68
- 239000010941 cobalt Substances 0.000 claims description 68
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 68
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- 230000008569 process Effects 0.000 claims description 66
- 229910052802 copper Inorganic materials 0.000 claims description 54
- 239000010949 copper Substances 0.000 claims description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 53
- 229910052748 manganese Inorganic materials 0.000 claims description 53
- 239000011572 manganese Substances 0.000 claims description 53
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 52
- 229910052782 aluminium Inorganic materials 0.000 claims description 51
- 238000000197 pyrolysis Methods 0.000 claims description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 37
- 239000003546 flue gas Substances 0.000 claims description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 35
- 239000011777 magnesium Substances 0.000 claims description 35
- 229910052749 magnesium Inorganic materials 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 238000000746 purification Methods 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 23
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 23
- 238000004064 recycling Methods 0.000 claims description 23
- 238000000605 extraction Methods 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 20
- 235000021110 pickles Nutrition 0.000 claims description 20
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
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- 239000000428 dust Substances 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 17
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002485 combustion reaction Methods 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 8
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 3
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 3
- -1 nickel-cobalt-aluminum Chemical compound 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 150000002739 metals Chemical class 0.000 abstract description 10
- 239000010419 fine particle Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 131
- 239000007788 liquid Substances 0.000 description 27
- 229910052731 fluorine Inorganic materials 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 17
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000002002 slurry Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000000926 separation method Methods 0.000 description 13
- 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 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- 230000002195 synergetic effect Effects 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical group [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C22B7/001—Dry processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/14—Flotation machines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
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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
- C22B1/00—Preliminary treatment of ores or scrap
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- C22B15/00—Obtaining copper
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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
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
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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
- C22B21/00—Obtaining aluminium
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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
- C22B21/00—Obtaining aluminium
- C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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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
- C22B47/00—Obtaining manganese
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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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
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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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- 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
- C22B7/007—Wet processes by acid leaching
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
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Abstract
The invention provides a method and a device for selecting and smelting combined comprehensive recovery of waste lithium ion batteries. The method comprises the following steps: s1, battery pyrogenic pretreatment; s2, washing and grading the pretreated product to obtain coarse-fraction particles, medium-fine-fraction particles, fine-fraction particles and a first part of lithium-containing solution; s3, magnetically separating the particles to obtain magnetic concentrate, wherein the obtained magnetic concentrate is a nickel-cobalt-manganese intermediate product, the magnetic tailings of coarse and medium-fine particle grade particles are copper-aluminum products, and the magnetic tailings of fine particle grade particles are graphite and black powder products; performing size mixing and graphite flotation on the graphite and black powder products to obtain graphite products and black powder; s4, carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and black powder to obtain roasted slag; extracting lithium from the roasting slag to obtain a second part of lithium-containing solution and water leaching slag; s5, combining the first part and the second part of the lithium-containing solution to prepare a lithium product; s6, acid leaching the water leaching slag, and removing impurities. The invention can effectively recover lithium element, other metals and graphite in the waste lithium ion battery.
Description
Technical Field
The invention relates to waste lithium ion battery resource recovery, in particular to a selection and metallurgy combined comprehensive recovery method and device for waste lithium ion batteries.
Background
With the coming of the abandonment tide of lithium ion batteries, a large number of recovery processes are developed and applied at a time. At present, the recovery process of the waste lithium ion battery has the following main problems: firstly, most processes pay attention to the recovery of nickel and cobalt with high content and high market price in waste lithium ion batteries, and the recovery attention of lithium with low content is low, so that the recovery rate of nickel, cobalt and manganese in most recovery processes is high, and the recovery rate of lithium is low. Secondly, the definition of the solid waste generated in the battery recycling field is not complete at present, and the treatment process of a large amount of fluorine-containing and phosphorus-containing diaphragm plastic parts is not complete, but with the maturity of the recycling industry, a large amount of solid waste is required to be treated harmlessly.
CN 109935922a discloses a method for recovering valuable metals from waste lithium ion battery positive electrode materials, which uses a mixture of low-valent sulfates such as sulfur and sulfide as a reducing agent to reduce high-valent compounds in the positive electrode materials, then uses water or weak acid to leach reduction roasting slag, recovers lithium from the leaching solution, and recovers nickel and cobalt from the leaching slag after acid leaching. The core of the method is that the low-valence sulfide is used as a reducing agent for reduction roasting, lithium is preferentially extracted after reduction, so that the recovery rate of lithium can be improved, but the reduction degree is difficult to control no matter sulfur or the reduction roasting of the sulfide, and the over-vulcanization condition is easy to occur, so that nickel cobalt is roasted into low-valence sulfate, and the difficulty in separation of lithium and nickel cobalt is increased.
CN 108264068A discloses a method for treating the positive electrode material of waste lithium ion power battery by electrochemical method, which uses sulfate and/or bisulfate as the solution electrolyte to carry out reaction, the essence of the reaction is to leach lithium in the positive electrode material by using the acidic solution decomposed by the electrolyzed water.
CN 108767354A discloses a method for processing waste lithium ion battery anode materials by using an ammonium salt roasting process, wherein the ammonium salt is roasted and then soaked in water, valuable metals Ni, Co, Mn and Li are completely transferred into a solution, and then the valuable metals are recovered from the solution.
CN 106505270a also discloses a process for treating a waste ternary lithium ion battery anode material by an ammonium salt roasting method, wherein aluminum foil is removed from roasting residues after ammonium salt roasting, acid leaching is adopted to solubilize cobalt and lithium, then a precipitation method is adopted to precipitate cobalt in a cobalt hydroxide form, and finally lithium is recovered. The method avoids the extraction process, can effectively reduce the loss of lithium, but has limited applicability to waste lithium ion batteries with complex composition and scattered and difficultly-separated models.
Therefore, the problem of low recovery rate exists in the prior art when the lithium element in the waste lithium ion battery is recovered. In addition, a method for comprehensively recovering metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in waste lithium ion batteries is lacked at present, and the method is not effective for treating phosphorus-containing fluorine-containing diaphragms and plastic parts in the batteries.
Disclosure of Invention
The invention mainly aims to provide a method and a device for the comprehensive recovery of waste lithium ion batteries by combination of dressing and smelting, so as to improve the recovery rate of lithium elements in the waste lithium ion batteries, comprehensively recover metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in the waste lithium ion batteries, and effectively treat phosphorus-containing fluorine-containing diaphragms and plastic parts in the batteries.
In order to achieve the above object, according to one aspect of the present invention, there is provided a combined recycling method for waste lithium ion batteries, comprising the following steps: s1, carrying out pyrogenic pretreatment on the waste lithium ion battery to obtain a pretreatment product; s2, carrying out ore washing grading treatment on the pretreatment product to obtain coarse-grain-grade particles, medium-fine-grain-grade particles, fine-grain-grade particles and a first part of lithium-containing solution, wherein the grain size of the coarse-grain-grade particles is larger than that of the medium-fine-grain-grade particles, and the grain size of the medium-fine-grain-grade particles is larger than that of the fine-grain-grade particles; s3, respectively carrying out magnetic separation on coarse-fraction particles, medium-fine-fraction particles and fine-fraction particles to obtain magnetic separation concentrate serving as a nickel-cobalt-manganese intermediate product, magnetic separation tailings of the coarse-fraction particles and the medium-fine-fraction particles serving as a copper-aluminum product, and magnetic separation tailings of the fine-fraction particles serving as graphite and black powder products; sequentially carrying out size mixing and graphite flotation on the graphite and black powder products to obtain graphite products and black powder; s4, carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and black powder to obtain roasted slag; carrying out water leaching on the roasting slag to extract lithium, so as to obtain a second part of lithium-containing solution and water leaching slag; s5, combining the first part of lithium-containing solution and the second part of lithium-containing solution to obtain a combined solution; preparing a lithium product by adopting the combined solution; and S6, acid leaching the water leaching slag, and removing impurities to obtain a solution product containing nickel, cobalt and manganese.
Further, in step S1, the pyrometallurgical pretreatment process includes: disassembling and crushing the waste lithium ion battery to obtain a crushed material; preferably, the particle size of the crushed material is below 50 mm; carrying out low-temperature pyrolysis on the crushed material under the conditions of protective atmosphere and temperature of 400-700 ℃ to obtain a pretreatment product; preferably, the temperature of the low-temperature pyrolysis is 600-650 ℃, and more preferably 610-640 ℃; preferably, the time of low-temperature pyrolysis is 0.5-6 h; preferably, before the step of disassembling and crushing the waste lithium ion batteries, step S1 further includes a step of discharging the waste lithium ion batteries.
Further, in step S2, the particle size of the coarse-fraction particles is greater than 2mm, the particle size of the fine-fraction particles is less than 0.2mm, and the particle size of the medium-fine-fraction particles is between the particle sizes of the coarse-fraction particles and the fine-fraction particles; preferably, in step S3, the magnetic separation magnetic field strength for the coarse fraction particles, the medium and fine fraction particles and the fine fraction particles is 40 to 280kA/m respectively.
Further, the steps of sequentially carrying out size mixing and graphite flotation on the graphite and black powder products comprise: mixing graphite and black powder products into flotation ore pulp with the concentration of 5-35 wt% by using water; and adding a regulator, a graphite collector and a foaming agent into the flotation pulp to perform graphite flotation so as to obtain a graphite product and black powder.
Further, in step S4, the reducing agent used in the reducing roasting process is the graphite product obtained in step S3, or the reducing roasting process is performed in a reducing atmosphere; preferably, the reducing atmosphere consists of a reducing gas and optionally an inert gas, the reducing gas is one or more of hydrogen, ammonia, methane and sulfur dioxide, and the inert gas is nitrogen and/or argon; preferably, the temperature in the reduction roasting process is 400-700 ℃, and the reaction time is 0.5-6 h.
Further, in step S5, evaporating and crystallizing lithium in the combined solution in the form of lithium hydroxide, or introducing carbon dioxide into the combined solution or adding soluble carbonate to precipitate lithium in the form of lithium carbonate, so as to obtain a lithium product; preferably, step S5 further includes the step of removing impurity ions from the combined solution using chemical precipitation or ion exchange resin before the step of preparing a lithium product using the combined solution.
Further, in step S6, performing acid leaching on the water leaching residue to obtain an acid leaching solution; the impurity removing step comprises: adjusting the pH value of the pickle liquor to be more than 4.2, and removing iron impurities and aluminum impurities to obtain an iron and aluminum removing solution; adding fluoride into the solution without the iron and the aluminum, and removing magnesium impurities to obtain a magnesium-removed solution; preferably, the fluoride is sodium fluoride; adding sulfide salt and/or hydrogen sulfide into the magnesium-removing solution to remove copper impurities and zinc impurities to obtain a solution product containing nickel, cobalt and manganese; preferably, the sulfide salt is sodium sulfide; or, the impurity removing step comprises: extracting the pickle liquor by using an extracting agent to obtain a solution product containing nickel, cobalt and manganese; preferably, the extractant is a P204 extractant.
Further, before the step of acid leaching the water leaching slag, the step S6 further includes a step of reduction smelting the water leaching slag; preferably, the water leaching residue is subjected to reduction smelting for 0.5-5 h at the temperature of 1200-1600 ℃ to obtain a nickel-cobalt-manganese alloy, and then acid leaching and impurity removal are sequentially performed on the nickel-cobalt-manganese alloy to obtain a solution product containing nickel, cobalt and manganese.
Further, the first flue gas is obtained in the pyrogenic pretreatment step, the second flue gas is obtained in the reduction smelting step, and the recovery method further comprises the steps of secondary combustion, surface cooling, dust removal and tail gas purification of the first flue gas and the second flue gas in sequence.
Further, the waste lithium ion battery is one or more of a waste lithium cobalt oxide battery, a lithium manganate battery, a nickel-manganese binary composite lithium ion battery, a nickel-cobalt binary composite lithium ion battery, a cobalt-manganese binary composite lithium ion battery, a nickel-cobalt-manganese ternary composite lithium ion battery and a nickel-cobalt-aluminum ternary composite lithium ion battery.
According to another aspect of the present invention, there is also provided a comprehensive recovery device for dressing and smelting waste lithium ion batteries, comprising: the pyrogenic pretreatment unit is provided with a waste lithium ion battery inlet and a pretreatment product outlet and is used for pyrogenically pretreating the waste lithium ion battery to obtain a pretreatment product; the washing and grading unit is used for carrying out washing and grading treatment on the pretreated product to obtain coarse-grain-grade particles, medium-fine-grain-grade particles, fine-grain-grade particles and a first part of lithium-containing solution, wherein the grain size of the coarse-grain-grade particles is larger than that of the medium-fine-grain-grade particles, and the grain size of the medium-fine-grain-grade particles is larger than that of the fine-grain-grade particles; the magnetic separation unit is connected with an outlet of the ore washing classification unit and is used for carrying out magnetic separation on coarse-grain-level particles, medium-fine-grain-level particles and fine-grain-level particles respectively to obtain a nickel-cobalt-manganese intermediate product, coarse-grain-level particle magnetic separation tailings, medium-fine-grain-level particle magnetic separation tailings and fine-grain-level particle magnetic separation tailings, the coarse-grain-level particle magnetic separation tailings and the medium-fine-grain-level particle magnetic separation tailings serve as copper and aluminum products, and the fine-grain-level particle magnetic separation tailings serve as graphite and black powder products; the graphite recovery unit is connected with an outlet of the magnetic separation unit and comprises a size mixing unit and a flotation unit which are sequentially connected, the size mixing unit is used for mixing the size of graphite and black powder products, and the flotation unit is used for performing graphite flotation to obtain graphite products and black powder; the reduction roasting unit is respectively connected with the outlet of the magnetic separation unit and the outlet of the flotation unit and is used for carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and the black powder to obtain roasted slag; the water leaching unit is provided with a roasting slag inlet and a second water inlet, the roasting slag inlet is connected with an outlet of the reduction roasting unit, and the water leaching unit is used for performing water leaching lithium extraction on the roasting slag to obtain a second part of lithium-containing solution and water leaching slag; the inlet of the lithium recovery unit is respectively connected with the outlet of the water leaching unit and the outlet of the ore washing classification unit, and the lithium recovery unit is used for preparing a lithium product by adopting a combined solution of the first part of lithium-containing solution and the second part of lithium-containing solution; the acid leaching unit is provided with a water leaching residue inlet, an acid inlet and an acid leaching solution outlet, the water leaching residue inlet is connected with the outlet of the water leaching unit, and the acid leaching unit is used for performing acid leaching on the water leaching residue to obtain acid leaching solution; and the impurity removal unit is connected with the pickle liquor outlet and is used for removing impurities from the pickle liquor to obtain a solution product containing nickel, cobalt and manganese.
Further, the pyrometallurgical pretreatment unit includes: disassembling the crushing unit, wherein the crushing unit is provided with a waste lithium ion battery inlet and a crushed material outlet; the low-temperature pyrolysis unit is provided with a crushed material inlet, an inert gas inlet and a pretreatment product outlet, and the crushed material inlet is connected with the crushed material outlet.
Furthermore, the pyrogenic pretreatment unit also comprises a discharge unit, wherein the discharge unit is positioned at the upstream of the disassembly crushing unit and is connected with an inlet of the waste lithium ion battery, and the discharge unit is used for carrying out discharge treatment on the waste lithium ion battery.
Further, the graphite recovery unit further comprises: a conditioning agent supply unit connected to the flotation unit for supplying conditioning agent thereto; the graphite collector supply unit is connected with the flotation unit and is used for supplying a graphite collector to the flotation unit; a frother supply unit coupled to the flotation unit for supplying frother thereto.
Furthermore, the reduction roasting unit is also provided with a first reducing agent inlet, and the first reducing agent inlet is connected with an outlet of the flotation unit and is used for taking a graphite product obtained in the graphite flotation process as a reducing agent in the reduction roasting process; or the reduction roasting unit is also provided with a reducing gas inlet, and the recovery device also comprises a reducing gas supply unit which is connected with the reducing gas inlet.
Further, the recovery device further comprises an inert gas supply unit, and the inert gas supply unit is respectively connected with the reducing gas inlet and the inert gas inlet of the low-temperature pyrolysis unit.
Further, the lithium recovery unit includes: an impurity removing agent supply unit for supplying an impurity removing agent; the inlet of the impurity removal and purification unit is respectively connected with the outlet of the water leaching unit, the outlet of the ore washing and classifying unit and the impurity removing agent supply unit, and the impurity removal and purification unit is used for carrying out impurity removal reaction on the combined solution of the first part of lithium-containing solution and the second part of lithium-containing solution to obtain an impurity-removed lithium solution; and the lithium product preparation unit is connected with the outlet of the impurity removal and purification unit and is used for carrying out evaporation crystallization on the impurity removal lithium solution or depositing lithium carbonate to obtain a lithium product.
Further, the impurity removing unit includes: the pH adjusting unit is connected with the pickle liquor outlet and is used for adjusting the pH value of the pickle liquor to be more than 4.2 so as to obtain an aluminum-removed solution; the magnesium removing unit is provided with a fluoride inlet and an deironing solution inlet, the deironing solution inlet is connected with the outlet of the pH adjusting unit, and the magnesium removing unit is used for removing magnesium impurities in the deironing solution to obtain a magnesium removing solution; the copper and zinc removing unit is provided with a magnesium removing solution inlet and a sulfide inlet, the magnesium removing solution inlet is connected with an outlet of the magnesium removing unit, the sulfide inlet is used for introducing sulfide salt and/or hydrogen sulfide, and the copper and zinc removing unit is used for removing copper impurities and zinc impurities in the magnesium removing solution to obtain a solution product containing nickel, cobalt and manganese; or the impurity removal unit is an extraction impurity removal unit.
Furthermore, the recovery device further comprises a reduction smelting unit, the reduction smelting unit is arranged on a flow path connecting the water leaching slag inlet and the water leaching unit, the reduction smelting unit is also provided with a flux inlet, the reduction smelting unit is used for carrying out reduction smelting on the water leaching slag to obtain nickel-cobalt-manganese alloy, and the acid leaching unit is used for carrying out acid leaching on the nickel-cobalt-manganese alloy to obtain acid leaching liquid.
Furthermore, the pyrogenic process pretreatment unit is also provided with a first flue gas outlet, the reduction smelting unit is also provided with a second flue gas outlet, and the recovery device further comprises a flue gas treatment unit which is respectively connected with the first flue gas outlet and the second flue gas outlet.
The invention provides a combined comprehensive recovery method for selecting and smelting waste lithium ion batteries, which can more effectively recover lithium elements in the waste lithium ion batteries in a shorter process, comprehensively recover metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in the waste lithium ion batteries, and effectively remove phosphorus-containing fluorine-containing diaphragms and plastic parts in the batteries by a pyrogenic process.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a flow chart of a combined recycling method for dressing and smelting of waste lithium ion batteries according to an embodiment of the invention; and
fig. 2 shows a block diagram of a combined recycling device for dressing and metallurgy of waste lithium ion batteries according to an embodiment of the invention.
Wherein the figures include the following reference numerals:
10. a pyrogenic pretreatment unit; 11. disassembling the crushing unit; 12. a low temperature pyrolysis unit; 13. a discharge unit; 20. a washing and grading unit; 30. a magnetic separation unit; 40. a graphite recovery unit; 41. a size mixing unit; 42. a flotation unit; 43. a conditioning agent supply unit; 44. a graphite collector supply unit; 45. a foaming agent supply unit; 50. a reduction roasting unit; 60. a water immersion unit; 70. a lithium recovery unit; 71. an impurity removal agent supply unit; 72. an impurity removal and purification unit; 73. a lithium product preparation unit; 80. an acid leaching unit; 90. an impurity removal unit; 91. a pH adjusting unit; 92. a magnesium removal unit; 93. a copper and zinc removal unit; 100. an inert gas supply unit; 110. a reduction smelting unit; 120. a flue gas treatment unit.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background section, there is a problem in the prior art that the recovery rate is low when recovering lithium element from the used lithium ion battery as a whole. In addition, a method for comprehensively recovering metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in waste lithium ion batteries is lacked at present, and the method is not effective for treating phosphorus-containing fluorine-containing diaphragms and plastic parts in the batteries.
In order to solve the above problems, the present invention provides a comprehensive recovery method for selecting and smelting waste lithium ion batteries, as shown in fig. 1, the recovery method comprises the following steps: s1, carrying out pyrogenic pretreatment on the waste lithium ion battery to obtain a pretreatment product; s2, carrying out ore washing grading treatment on the pretreatment product to obtain coarse-grain-grade particles, medium-fine-grain-grade particles, fine-grain-grade particles and a first part of lithium-containing solution, wherein the grain size of the coarse-grain-grade particles is larger than that of the medium-fine-grain-grade particles, and the grain size of the medium-fine-grain-grade particles is larger than that of the fine-grain-grade particles; s3, respectively carrying out magnetic separation on coarse-fraction particles, medium-fine-fraction particles and fine-fraction particles to obtain magnetic separation concentrate serving as a nickel-cobalt-manganese intermediate product, magnetic separation tailings of the coarse-fraction particles and the medium-fine-fraction particles serving as a copper-aluminum product, and magnetic separation tailings of the fine-fraction particles serving as graphite and black powder products; sequentially carrying out size mixing and graphite flotation on the graphite and black powder products to obtain graphite products and black powder; s4, carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and black powder to obtain roasted slag; carrying out water leaching on the roasting slag to extract lithium, so as to obtain a second part of lithium-containing solution and water leaching slag; s5, combining the first part of lithium-containing solution and the second part of lithium-containing solution to obtain a combined solution; preparing a lithium product by adopting the combined solution; and S6, acid leaching the water leaching slag, and removing impurities to obtain a solution product containing nickel, cobalt and manganese.
The waste lithium ion battery is treated by the process, the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the waste lithium ion battery can be effectively decomposed by pyrogenic pretreatment, and nickel, cobalt and manganese can be converted from non-magnetism to magnetism. The lithium ion battery material after the pyrogenic pretreatment mainly comprises nickel-cobalt-manganese, copper, aluminum, iron and black powder (the black powder comprises graphite which is the original cathode material of the battery, carbon generated in the pyrogenic pretreatment process and a part of lithium). The pre-treatment product is divided into coarse fraction particles, medium and fine fraction particles through ore washing and classification, and a part of soluble lithium salt can enter water to form a first part of lithium-containing solution. The black powder has small particle size and is mainly enriched in fine-fraction particles, and the rest components have large particle size and are enriched in coarse-fraction particles and medium-fine-fraction particles. Magnetic nickel, cobalt and manganese in each grain size fraction can be separated through magnetic separation, and a part of lithium elements can be carried in the magnetic separation, so that a nickel, cobalt and manganese intermediate product is obtained, the main components of magnetic tailings of coarse grain size fractions and medium fine grain size fractions are copper and aluminum which can be used as copper and aluminum products, and the magnetic tailings of the fine grain size fractions are graphite and black powder products. And (3) after the graphite and the black powder product are sequentially subjected to size mixing and graphite flotation, the graphite can be enriched to obtain a graphite product, and the flotation tailings are the black powder. And secondly, carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and the black powder, and then carrying out water leaching to extract lithium, wherein due to different reducibility of the lithium, the nickel, the cobalt and the manganese, the lithium can be preferentially extracted by utilizing the reduction roasting-water leaching to enrich the lithium, so that a second part of lithium-containing solution is formed. After the first part of lithium-containing solution and the second part of lithium-containing solution are combined, lithium can be extracted by methods such as chemical precipitation, evaporative crystallization and the like to form a lithium product. And (4) carrying out acid leaching and impurity removal on the residual water leaching residue after water leaching to obtain a solution product containing nickel, cobalt and manganese.
From the lithium recovery process, the traditional waste lithium ion battery is a process for recovering lithium after recovering nickel, cobalt and manganese, the lithium loss is serious (the lithium recovery rate is less than 90 percent or even lower), the flow of an extraction and separation process is long, and the material flux is large. According to the invention, the reduction roasting-leaching is adopted to preferentially extract lithium according to the different reducibility of lithium, nickel, cobalt and manganese, so that the recovery rate of lithium in the waste battery can be effectively improved (more than 98 percent), the extraction flux is reduced, and the process advantage is obvious. In the invention, the beneficiation-metallurgy combined process is adopted to comprehensively recover the metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in the waste lithium ion battery. Due to the characteristics of the beneficiation process, the beneficiation process is adopted to separate valuable components in the waste batteries, the comprehensive cost is low, and the separation effect is obvious. In addition, the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the battery can be decomposed by pyrogenic pretreatment, and the obtained flue gas is subjected to post-treatment.
In a preferred embodiment, in step S1, the pyrometallurgical pretreatment process includes: disassembling and crushing the waste lithium ion battery to obtain a crushed material; preferably, the particle size of the crushed material is below 50 mm; carrying out low-temperature pyrolysis on the crushed material under the conditions of protective atmosphere and temperature of 400-700 ℃ to obtain a pretreatment product; preferably, the temperature of the low-temperature pyrolysis is 600-650 ℃, and more preferably 610-640 ℃; preferably, the time of low-temperature pyrolysis is 0.5-6 h. By adopting the process, on one hand, the pyrolysis effect of the plastic shell and the phosphorus-containing fluorine-containing diaphragm can be improved, and on the other hand, the nickel, cobalt and manganese can be more fully converted into magnetism, so that the nickel, cobalt and manganese can be more effectively separated in the subsequent magnetic separation process. The specific method for disassembling and crushing adopts a common method in the field, preferably, nitrogen is introduced in the disassembling and crushing process as shielding gas to prevent the electric core from firing in the crushing process; tail gas generated in the crushing process can be treated by a tail gas purification system, and the tail gas is discharged after reaching the standard.
Preferably, before the step of disassembling and crushing the waste lithium ion batteries, step S1 further includes a step of discharging the waste lithium ion batteries. When the battery is scrapped, the residual electric quantity has explosion danger in the storage and crushing processes, the explosion danger can be reduced by utilizing the discharging step, and the problems of fire and the like caused by the residual electric quantity in the crushing process are avoided being disassembled.
In a preferred embodiment, in step S2, the coarse fraction has a particle size of greater than 2mm, the fine fraction has a particle size of less than 0.2mm, and the medium-fine fraction has a particle size between the particle sizes of the coarse fraction and the fine fraction. The size of each grade of particles is controlled within the range, so that the black powder is more favorably separated from metal components (copper, aluminum, nickel, cobalt, manganese and the like), the graphite is in a fine grade of particles as much as possible, and the copper, the aluminum, the nickel, cobalt, manganese and the like are enriched in coarse grade particles and middle and fine grade particles.
In order to remove magnetic impurities such as nickel, cobalt, manganese and the like more fully, in a preferred embodiment, in step S3, the magnetic separation magnetic field strength of the coarse fraction particles, the medium and fine fraction particles and the fine fraction particles is 40 to 280kA/m respectively.
In order to further improve the recovery effect of graphite, in a preferred embodiment, the steps of sequentially carrying out size mixing and graphite flotation on the graphite and the black powder product comprise: mixing graphite and black powder products into flotation ore pulp with the concentration of 5-35 wt% by using water; and sequentially adding a regulator, a graphite collector and a foaming agent into the flotation pulp to perform graphite flotation so as to obtain a graphite product and black powder. Preferably, the graphite collector is a hydrocarbon oil collector, and the hydrocarbon oil collector is kerosene and/or diesel oil; preferably, the foaming agent is terpineol oil and/or methyl isobutyl carbinol; preferably, the modifier is one or more of sodium hydrosulfide, sodium sulfide and ammonium sulfide. The reagents are selected, so that the recovery effect of graphite is better.
Preferably, in step S4, the reducing agent used in the reduction roasting process is the graphite product obtained in step S3, which is favorable for full utilization of resources. Or the reduction roasting process is carried out in a reducing atmosphere. Preferably, the reducing atmosphere consists of a reducing gas and optionally an inert gas, the reducing gas is one or more of hydrogen, ammonia, methane and sulfur dioxide, and the inert gas is nitrogen and/or argon; preferably, the temperature in the reduction roasting process is 400-700 ℃, and the reaction time is 0.5-6 h.
In a preferred embodiment, in step S5, lithium in the combined solution is recovered as lithium hydroxide or lithium carbonate to obtain a lithium product; during the specific operation, carbon dioxide or soluble carbonate (such as sodium carbonate and the like) can be introduced into the combined solution, and lithium element can be precipitated in the form of lithium carbonate. Or the lithium hydroxide product can be prepared by an evaporation crystallization mode, the recovery rate of lithium is higher, and the treatment efficiency is higher.
In addition, in order to obtain a relatively pure lithium product, the content of impurities (Al, Cu, F, P, etc.) in the combined solution may be analyzed first, if the content of impurities is qualified, a lithium hydroxide or lithium carbonate product is prepared from the leachate, if the content of impurities is unqualified, a lithium hydroxide or lithium carbonate product is prepared after a purification process, and the purification process may be a chemical precipitation method or an ion exchange resin method for removing impurities.
In a preferred embodiment, in step S6, the water leaching residue is subjected to acid leaching to obtain a pickle liquor; the impurity removing step comprises: adjusting the pH value of the pickle liquor to be more than 4.2, and removing iron impurities and aluminum impurities to obtain an iron and aluminum removing solution; adding fluoride into the solution without the iron and the aluminum, and removing magnesium impurities to obtain a magnesium-removed solution; preferably, the fluoride is sodium fluoride; adding sulfide salt and/or hydrogen sulfide into the magnesium-removing solution to remove copper impurities and zinc impurities to obtain a solution product containing nickel, cobalt and manganese; preferably, the sulfide salt is sodium sulfide; or, the impurity removing step comprises: extracting the pickle liquor by using an extracting agent to obtain a solution product containing nickel, cobalt and manganese; preferably, the extractant is a P204 extractant.
In a preferred embodiment, step S6 further includes the step of reduction smelting the water leached slag before the step of acid leaching the water leached slag. Like this, the reduction smelting process can be with the more abundant reduction enrichment of nickel cobalt manganese in the water immersion sediment, and utilize the reduction smelting process still to solve the dispersion of puzzlement power battery recovery in-process fluorine and be difficult to open a way the problem, can obtain the smelting slag that contains F, realizes that the part of F element is opened a way, when the recovery resource, has also taken into account the processing of harmful substance. Preferably, the first flue gas generated in the pyrogenic pretreatment process is subjected to post-treatment to obtain fluorine-containing gypsum slag, and the fluorine-containing gypsum slag is fed into the reduction smelting process for synergistic treatment, so that the environmental protection of the process is improved. Preferably, the water leaching residue is subjected to reduction smelting for 0.5-5 h at the temperature of 1200-1600 ℃ to obtain a nickel-cobalt-manganese alloy, and then acid leaching and impurity removal are sequentially performed on the nickel-cobalt-manganese alloy to obtain a solution product containing nickel, cobalt and manganese.
In the actual reduction smelting process, the water-immersed slag, the flux and the reducing agent are mixed and then subjected to reduction smelting in the smelting furnace, wherein the specific flux preferably adopts quartz sand, limestone, dolomite, calcite and the like, and the specific reducing agent preferably adopts coal, coke, petroleum coke, activated carbon and the like. The specific dosage of each reagent can be adjusted according to the actual conditions such as the amount of the water-immersed slag and the like, and is not described in detail herein.
In a preferred embodiment, the first flue gas is obtained in the pyrogenic pretreatment step, the second flue gas is obtained in the reduction smelting step, the recovery method further comprises the steps of secondary combustion, surface cooling, dust removal and tail gas purification of the first flue gas and the second flue gas in sequence, and the tail gas purification is discharged after reaching the standard. The dust removal process can adopt a high-temperature bag-type dust remover, and the specific tail gas purification step can adopt one or more combinations of common waste gas treatment devices such as an alkali absorption device, an active carbon device, a UV photolysis device, a biological filtration and purification device and the like.
Preferably, when the solution product containing nickel, cobalt and manganese is obtained, the nickel, cobalt and manganese elements can be further separated through wet processing.
The waste lithium ion battery refers to a waste lithium ion battery obtained after safe discharge and/or a waste product generated in the production process of the lithium ion battery. In a preferred embodiment, the waste lithium ion battery is one or more of a waste lithium cobalt oxide battery, a waste lithium manganese oxide battery, a nickel-manganese binary composite lithium ion battery, a nickel-cobalt binary composite lithium ion battery, a cobalt-manganese binary composite lithium ion battery, a nickel-cobalt-manganese ternary composite lithium ion battery, and a nickel-cobalt-aluminum ternary composite lithium ion battery.
According to another aspect of the present invention, there is also provided a dressing and smelting combined comprehensive recovery device for waste lithium ion batteries, as shown in fig. 2, the recovery device includes a pyrogenic pretreatment unit 10, an ore washing and classifying unit 20, a magnetic separation unit 30, a graphite recovery unit 40, a reduction roasting unit 50, a water leaching unit 60, a lithium recovery unit 70, an acid leaching unit 80, and an impurity removal unit 90, the pyrogenic pretreatment unit 10 has a waste lithium ion battery inlet and a pretreated product outlet, and the pyrogenic pretreatment unit 10 is configured to pyrogenically pretreat the waste lithium ion batteries to obtain pretreated products; the ore washing grading unit 20 is provided with a pretreatment product inlet and a first water inlet, the pretreatment product inlet is connected with the pretreatment product inlet, the ore washing grading unit 20 is used for carrying out ore washing grading treatment on the pretreatment product to obtain coarse-grain-grade particles A, medium-fine-grain-grade particles B, fine-grain-grade particles C and a first part of lithium-containing solution D, the grain size of the coarse-grain-grade particles A is larger than that of the medium-fine-grain-grade particles B, and the grain size of the medium-fine-grain-grade particles B is larger than that of the fine-grain-grade particles C; the magnetic separation unit 30 is connected with an outlet of the ore washing classification unit 20, the magnetic separation unit 30 is used for respectively carrying out magnetic separation on coarse-grain-level particles A, medium-fine-grain-level particles B and fine-grain-level particles C to obtain a nickel-cobalt-manganese intermediate product G, coarse-grain-level particle magnetic separation tailings, medium-fine-grain-level particle magnetic separation tailings and fine-grain-level particle magnetic separation tailings, the coarse-grain-level particle magnetic separation tailings and the medium-fine-grain-level particle magnetic separation tailings are used as copper-aluminum products E, and the fine-grain-level particle magnetic separation tailings are used as graphite and; the graphite recovery unit 40 is connected with an outlet of the magnetic separation unit 30, the graphite recovery unit 40 comprises a size mixing unit 41 and a flotation unit 42 which are sequentially connected, the size mixing unit 41 is used for mixing the graphite and the black powder product F, and the flotation unit 42 is used for performing graphite flotation to obtain a graphite product H and black powder J; the reduction roasting unit 50 is respectively connected with the outlet of the magnetic separation unit 30 and the outlet of the flotation unit 42, and the reduction roasting unit 50 is used for carrying out reduction roasting on the nickel-cobalt-manganese intermediate product G and the black powder J to obtain roasted slag; the water leaching unit 60 is provided with a roasting slag inlet and a second water inlet, the roasting slag inlet is connected with the outlet of the reduction roasting unit 50, and the water leaching unit 60 is used for performing water leaching lithium extraction on the roasting slag to obtain a second part of lithium-containing solution K and water leaching slag L; an inlet of the lithium recovery unit 70 is connected to an outlet of the water leaching unit 60 and an outlet of the ore washing classification unit 20, respectively, and the lithium recovery unit 70 is configured to perform lithium recovery processing on a combined solution of the first part of lithium-containing solution D and the second part of lithium-containing solution K to obtain a lithium product M; the acid leaching unit 80 is provided with a water leaching residue inlet, an acid inlet and an acid leaching solution outlet, the water leaching residue inlet is connected with the outlet of the water leaching unit 60, and the acid leaching unit 80 is used for performing acid leaching on the water leaching residue to obtain acid leaching solution; the impurity removal unit 90 is connected with the pickle liquor outlet, and the impurity removal unit 90 is used for removing impurities from the pickle liquor to obtain a solution product N containing nickel, cobalt and manganese.
The device is used for treating the waste lithium ion battery, the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the waste lithium ion battery can be effectively decomposed through pyrogenic pretreatment, and the nickel, cobalt and manganese can be converted from non-magnetism to magnetism. The lithium ion battery material after the pyrogenic pretreatment mainly comprises nickel-cobalt-manganese, copper, aluminum, iron and black powder (the black powder comprises graphite which is the original cathode material of the battery, carbon generated in the pyrogenic pretreatment process and a part of lithium). The pre-treatment product is divided into coarse fraction particles, medium and fine fraction particles through ore washing and classification, and a part of soluble lithium salt can enter water to form a first part of lithium-containing solution. The black powder has small particle size and is mainly enriched in fine-fraction particles, and the rest components have large particle size and are enriched in coarse-fraction particles and medium-fine-fraction particles. Magnetic nickel, cobalt and manganese in each grain size fraction can be separated through magnetic separation, and a part of lithium elements can be carried in the magnetic separation, so that a nickel, cobalt and manganese intermediate product is obtained, the main components of magnetic tailings of coarse grain size fractions and medium fine grain size fractions are copper and aluminum which can be used as copper and aluminum products, and the magnetic tailings of the fine grain size fractions are graphite and black powder products. And (3) after the graphite and the black powder product are sequentially subjected to size mixing and graphite flotation, the graphite can be enriched to obtain a graphite product, and the flotation tailings are the black powder. And secondly, carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and the black powder, and then carrying out water leaching to extract lithium, wherein due to different reducibility of the lithium, the nickel, the cobalt and the manganese, the lithium can be preferentially extracted by utilizing the reduction roasting-water leaching to enrich the lithium, so that a second part of lithium-containing solution is formed. After the first part of lithium-containing solution and the second part of lithium-containing solution are combined, lithium can be extracted by a chemical precipitation or evaporative crystallization method to form a lithium product. And (4) carrying out acid leaching and impurity removal on the residual water leaching residue after water leaching to obtain a solution product containing nickel, cobalt and manganese.
From the lithium recovery process, the traditional waste lithium ion battery is a process for recovering lithium after recovering nickel, cobalt and manganese, the lithium loss is serious (the lithium recovery rate is less than 90 percent or even lower), the flow of an extraction and separation process is long, and the material flux is large. According to the invention, the reduction roasting-leaching is adopted to preferentially extract lithium according to the different reducibility of lithium, nickel, cobalt and manganese, so that the recovery rate of lithium in the waste battery can be effectively improved (more than 98 percent), the extraction flux is reduced, and the process advantage is obvious. In the invention, the beneficiation-metallurgy combined process is adopted to comprehensively recover the metals such as lithium, nickel, cobalt, manganese, copper, aluminum and the like and graphite in the waste lithium ion battery. Due to the characteristics of the beneficiation process, the beneficiation process is adopted to separate valuable components in the waste batteries, the comprehensive cost is low, and the separation effect is obvious. In addition, the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the battery can be decomposed by pyrogenic pretreatment, and the obtained flue gas is subjected to post-treatment.
In a preferred embodiment, the pyrogenic pretreatment unit 10 comprises a dismantling crushing unit 11 and a low-temperature pyrolysis unit 12, wherein the dismantling crushing unit 11 has a waste lithium ion battery inlet and a crushed material outlet; and the low-temperature pyrolysis unit 12 is provided with a crushed material inlet, an inert gas inlet and a pretreatment product outlet, wherein the crushed material inlet is connected with the crushed material outlet. In this way, the waste lithium ion battery is disassembled and crushed and then pyrolyzed at low temperature, so that the plastic shell and the phosphorus-containing fluorine-containing diaphragm in the battery can be pyrolyzed and removed, and preferably, the low-temperature pyrolysis unit 12 is used for pyrolyzing the crushed material discharged by the disassembling and crushing unit 11 at low temperature of 400-700 ℃ to obtain a pretreated product.
In a preferred embodiment, the pyrometallurgical pretreatment unit 10 further comprises a discharge unit 13, the discharge unit 13 is located upstream of the dismantling and crushing unit 11 and is connected with the inlet of the waste lithium ion battery, and the discharge unit 13 is used for discharging the waste lithium ion battery. When the battery is scrapped, the residual electric quantity has explosion danger in the storage and crushing processes, the explosion danger can be reduced by utilizing the discharging step, and the problems of fire and the like caused by the residual electric quantity in the crushing process are avoided being disassembled.
In a preferred embodiment, as shown in fig. 1, the graphite recovery unit 40 further includes a modifier supply unit 43, a graphite collector supply unit 44, and a foaming agent supply unit 45; a conditioning agent supply unit 43 connected to the flotation unit 42 for supplying a graphite conditioning agent thereto; a graphite collector supply unit 44 is connected to the flotation unit 42 for supplying a collector thereto; a frother supply unit 45 is connected to the flotation unit 42 for supplying frother thereto. Therefore, the graphite product and the black powder after size mixing can be subjected to graphite flotation under the action of the graphite collecting agent, the foaming agent and the regulator, so that the graphite can be recovered and separated more fully.
In a preferred embodiment, the reducing roasting unit 50 also has a first reducing agent inlet connected to the outlet of the flotation unit 42 for using the graphite product from the graphite flotation process as a reducing agent in the reducing roasting process; alternatively, the reduction roasting unit 50 further has a reducing gas inlet, and the recovery apparatus further includes a reducing gas supply unit connected to the reducing gas inlet. Preferably, the recycling apparatus further includes an inert gas supply unit 100, and the inert gas supply unit 100 is connected to the reducing gas inlet and the inert gas inlet of the low-temperature pyrolysis unit 12, respectively. Thus, the inert gas may be introduced into the reduction roasting unit 50 to form a reduction atmosphere together with the first reducing gas, so that the black powder and the nickel-cobalt-manganese intermediate are subjected to reduction roasting.
In a preferred embodiment, the lithium recovery unit 70 includes: an impurity removing agent supply unit 71 for supplying an impurity removing agent; an impurity removal purification unit 72, an inlet of which is connected with an outlet of the water leaching unit 60, an outlet of the ore washing classification unit 20 and the impurity removal agent supply unit 71 respectively, wherein the impurity removal purification unit 72 is used for performing impurity removal purification reaction on the combined solution of the first part of lithium-containing solution and the second part of lithium-containing solution to obtain an impurity removal lithium solution; and the lithium product preparation unit 73 is connected with the outlet of the impurity removal and purification unit 72, and the lithium product preparation unit 73 is used for performing evaporation crystallization on the impurity-removed lithium solution or depositing lithium carbonate to obtain a lithium product. Preferably, the magnesium removing agent is sodium hydroxide, calcium hydroxide or sodium fluoride, and preferably, the calcium removing agent is sodium carbonate or sodium fluoride.
In a preferred embodiment, the impurity removing unit 90 includes: the pH adjusting unit 91 is connected with the pickle liquor outlet, and the pH adjusting unit 91 is used for adjusting the pH value of the pickle liquor to be more than 4.2 so as to obtain an aluminum-removed solution; the magnesium removing unit 92 is provided with a fluoride inlet and an deironing solution inlet, the deironing solution inlet is connected with the outlet of the pH adjusting unit 91, and the magnesium removing unit 92 is used for removing magnesium impurities in the deironing solution to obtain a magnesium removing solution; and the copper and zinc removing unit 93 is provided with a magnesium removing solution inlet and a sulfide inlet, the magnesium removing solution inlet is connected with an outlet of the magnesium removing unit 92, the sulfide inlet is used for introducing sulfide salt and/or hydrogen sulfide, and the copper and zinc removing unit 93 is used for removing copper impurities and zinc impurities in the magnesium removing solution to obtain a solution product containing nickel, cobalt and manganese. Alternatively, the impurity removal unit 90 is an extraction impurity removal unit. When an extraction and impurity removal unit is adopted, the extracting agent is preferably a P204 extracting agent.
In a preferred embodiment, the recycling device further includes a reduction smelting unit 110, the reduction smelting unit 110 is disposed on a flow path connecting the water leaching slag inlet and the water leaching unit 60, and the reduction smelting unit 110 further has a flux inlet, the reduction smelting unit 110 is configured to perform reduction smelting on the water leaching slag to obtain nickel-cobalt-manganese alloy, and the acid leaching unit 80 is configured to perform acid leaching on the nickel-cobalt-manganese alloy to obtain acid leaching solution. Like this, the reduction smelting process can be with the more abundant reduction enrichment of nickel cobalt manganese in the water immersion sediment, and utilize the reduction smelting process still to solve the dispersion of puzzlement power battery recovery in-process fluorine and be difficult to open a way the problem, can obtain the smelting slag that contains F, realizes that the part of F element is opened a way, when the recovery resource, has also taken into account the processing of harmful substance. Preferably, the first flue gas generated in the pyrogenic pretreatment process is subjected to post-treatment to obtain fluorine-containing gypsum slag, and the fluorine-containing gypsum slag is fed into the reduction smelting process for synergistic treatment, so that the environmental protection of the process is improved.
More preferably, the reduction smelting unit 110 further has a second reducing agent inlet for introducing a reducing agent into the reduction smelting unit 110 to complete the reduction smelting of the water leached slag.
In order to further increase the degree of harmlessness of the process, in a preferred embodiment the pyrometallurgical pretreatment unit 10 further has a first flue gas outlet, the reduction smelting unit 110 further has a second flue gas outlet, and the recovery apparatus further comprises a flue gas treatment unit 120, the flue gas treatment unit 120 being connected to the first flue gas outlet and the second flue gas outlet, respectively. Preferably, the flue gas treatment unit 120 includes a secondary combustion unit, a surface cooling unit, a dust removal unit, and a tail gas purification unit, which are connected in sequence, and the secondary combustion unit is connected to the first flue gas outlet and the second flue gas outlet respectively.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
The battery adopted in the embodiment is a square ternary lithium ion battery in a factory in Hunan.
(1) The waste ternary lithium ion battery is treated by chemical discharge, and the discharged battery is subjected to multistage crushing under the nitrogen atmosphere until the size is below 50 mm. And carrying out pyrolysis pretreatment on the crushed battery for 2h at 500 ℃ in a nitrogen atmosphere to obtain a pyrolysis product, and discharging generated pyrolysis smoke after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) And washing and grading the pyrolysis product into three size fractions of more than 2mm, 0.15-2 mm and less than 0.15mm and a lithium-rich solution, wherein the three size fractions are respectively subjected to magnetic separation at the magnetic field intensity of 240kA/m to obtain a nickel-cobalt-manganese intermediate product. The magnetic separation tailings with grain sizes of >2mm and 0.15-2 mm are used as copper and aluminum products, and the recovery rates are 90.41% and 89.51% respectively. The magnetic separation tailings with the size fraction below 0.15mm are black powder and graphite products, the black powder and the graphite products are mixed with water to form flotation slurry with the concentration of 30 wt%, 500g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to perform graphite flotation, graphite with the C grade of 91.36% and the recovery rate of 88.59% is obtained through the graphite flotation, and the flotation tailings are black powder.
(3) And carrying out reduction roasting on the black powder and the nickel-cobalt-manganese intermediate product for 1h at 500 ℃ in a hydrogen reduction atmosphere to obtain reduction roasting slag. Using water as a leaching agent, leaching the roasting slag at the liquid-solid ratio of 3:1 and 80 ℃ for 1h, and performing solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. Mixing the lithium-containing solution obtained in the concentrating step with the lithium-containing leachate obtained by leaching with water, and introducing CO2Evaporating and crystallizing to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 98.6%.
(4) Reducing and smelting the water leaching slag, the flux quartz sand, the limestone and the reducing agent coke at 1600 ℃ for 2 hours to obtain the nickel-cobalt-manganese alloy and smelting slag, wherein the smelting slag belongs to harmless slag after high-temperature curing treatment and can be directly buried. And (3) discharging the smoke generated by reduction smelting after secondary combustion, a waste heat boiler, surface cooling, high-temperature cloth bag dust collection and tail gas purification and absorption.
(5) 5.5mol/L sulfuric acid is adopted, the liquid-solid ratio is 5:1, the temperature is 90 ℃, 1h is adopted to leach the nickel-cobalt-manganese alloy, the acid leaching solution obtained by leaching is subjected to P204 extraction and impurity removal, and the obtained nickel-cobalt-manganese purification solution can be used as a raw material of downstream lithium ion battery material production enterprises.
(6) After the comprehensive recovery treatment of the dressing and smelting, the purity of the obtained product is as follows: the recovery rate of copper and aluminum in the copper and aluminum product can reach 90.41 percent and 89.51 percent, the recovery rate of graphite reaches 88.59 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.7 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 98.6 percent, 99.1 percent, 99.3 percent and 98.7 percent.
Example 2
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Jiangsu.
(1) The waste ternary lithium ion battery is treated by chemical discharge, and the discharged battery is subjected to multistage crushing under the nitrogen atmosphere until the size is below 50 mm. And carrying out pyrolysis pretreatment on the crushed battery for 3h at 600 ℃ in a nitrogen atmosphere to obtain a pyrolysis product, and discharging generated pyrolysis smoke after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) And washing and grading the pyrolysis product into three size fractions of more than 3mm, 0.2-3 mm and less than 0.2mm and a lithium-rich solution, wherein the three size fractions are respectively subjected to magnetic separation at the magnetic field intensity of 200kA/m to obtain a nickel-cobalt-manganese intermediate product. The magnetic separation tailings with grain sizes of >3mm and 0.2-3 mm are used as copper and aluminum products, and the recovery rates are 89.29% and 90.88% respectively. The magnetic separation tailings with the size fraction below 0.2mm are black powder and graphite products, the black powder and the graphite products are mixed with water to form flotation slurry with the concentration of 15 wt%, 400g/t of sodium sulfide, 150g/t of diesel oil and 45g/t of pine oil are added into the flotation slurry to perform graphite flotation, graphite with the carbon grade of 92.87% and the recovery rate of 87.46% is obtained through the graphite flotation, and the flotation tailings are black powder.
(3) And carrying out reduction roasting on the black powder and the nickel-cobalt-manganese intermediate product for 1.5h at the temperature of 450 ℃ in a hydrogen reduction atmosphere to obtain reduction roasting slag. Water is used as a leaching agent, hydrogen reduction roasting slag is leached out under the conditions of the liquid-solid ratio of 5:1 and 60 ℃ for 1h, and the water leaching slag and lithium-containing leaching liquid are obtained through solid-liquid separation treatment. Mixing the lithium-containing solution obtained in the concentrating step with the lithium-containing leachate obtained by leaching with water, and introducing CO2Evaporating and crystallizing to obtain lithium carbonateThe comprehensive recovery rate of lithium of the product is 99.6%.
(4) Reducing and smelting the water leaching slag, the flux quartz sand, the limestone and the reducing agent coal at 1500 ℃ for 3h to obtain nickel-cobalt alloy and smelting slag, wherein the smelting slag belongs to harmless slag after high-temperature curing treatment and can be directly buried. And (3) discharging the smoke generated by reduction smelting after secondary combustion, a waste heat boiler, surface cooling, high-temperature cloth bag dust collection and tail gas purification and absorption.
(5) 5mol/L sulfuric acid is adopted, the liquid-solid ratio is 6:1, the temperature is 90 ℃, the time is 1 hour, the nickel-cobalt alloy is leached out, the acid leaching solution obtained by leaching is subjected to P204 extraction to remove impurities, and the obtained nickel-cobalt-manganese purifying solution can be used as a raw material of downstream lithium ion battery material production enterprises.
(6) After the comprehensive recovery treatment of the dressing and smelting, the purity of the obtained product is as follows: the recovery rate of copper and aluminum in the copper and aluminum product can reach 89.29 percent and 90.88 percent, the recovery rate of graphite reaches 87.46 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 99.6 percent, 99.3 percent, 99.4 percent and 98.9 percent.
Example 3
The difference from example 1 is that: the reduction smelting step is not needed, the specific process is as follows,
(1) the waste ternary lithium ion battery is treated by chemical discharge, and the discharged battery is subjected to multistage crushing under the nitrogen atmosphere until the size is below 50 mm. And carrying out pyrolysis pretreatment on the crushed battery for 2h at 500 ℃ in a nitrogen atmosphere to obtain a pyrolysis product, and discharging generated pyrolysis smoke after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) And washing and grading the pyrolysis product into three size fractions of more than 2mm, 0.15-2 mm and less than 0.15mm and a lithium-rich solution, wherein the three size fractions are respectively subjected to magnetic separation at the magnetic field intensity of 240kA/m to obtain a nickel-cobalt-manganese intermediate product. The magnetic separation tailings with grain sizes of >2mm and 0.15-2 mm are used as copper and aluminum products, and the recovery rates are 90.37% and 89.15% respectively. The magnetic separation tailings with the size fraction below 0.15mm are black powder and graphite products, the black powder and the graphite products are mixed with water to form flotation slurry with the concentration of 30 wt%, 200g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to perform graphite flotation, graphite with the C grade of 91.42% and the recovery rate of 88.93% is obtained through the graphite flotation, and the flotation tailings are black powder.
(3) And carrying out reduction roasting on the black powder and the nickel-cobalt-manganese intermediate product for 1h at 500 ℃ in a hydrogen reduction atmosphere to obtain reduction roasting slag. Using water as a leaching agent, leaching the roasting slag at the liquid-solid ratio of 3:1 and 80 ℃ for 1h, and performing solid-liquid separation treatment to obtain water leaching slag and lithium-containing leaching liquid. Mixing the lithium-containing solution obtained in the concentrating step with the lithium-containing leachate obtained by leaching with water, and introducing CO2Evaporating and crystallizing to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 98.6%.
(4) And (4) leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 4.6mol/L to obtain a leaching solution containing nickel, cobalt and manganese. Neutralizing, precipitating and removing iron and aluminum (the pH value is 4.4), removing copper and zinc by using sodium sulfide, and removing magnesium by using sodium fluoride to obtain a purified liquid, wherein the purified liquid is a solution product containing nickel, cobalt and manganese.
(5) After the comprehensive recovery treatment of the dressing and smelting, the purity of the obtained product is as follows: the recovery rate of copper and aluminum in the copper and aluminum product can reach 90.37% and 89.15%, the recovery rate of graphite can reach 88.93%, the purity of lithium carbonate obtained by wet lithium extraction is 99.7%, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 98.5%, 98.9%, 98.2% and 98.1%.
Example 4
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) The waste ternary lithium ion battery is treated by chemical discharge, and the discharged battery is subjected to multistage crushing in a nitrogen atmosphere. And carrying out pyrolysis pretreatment on the crushed battery for 3h at 600 ℃ in a nitrogen atmosphere to obtain a pyrolysis product, and discharging generated pyrolysis smoke after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) Washing and grading the pyrolysis product into three size fractions of more than 5mm, 0.45-5 mm and less than 0.45mm and a lithium-rich solution, carrying out magnetic separation on the three size fractions respectively at the magnetic field intensity of 220kA/m to obtain a nickel-cobalt-manganese intermediate product, using magnetic tailings of more than 5mm and 0.45-5 mm as copper-aluminum products, and respectively obtaining the recovery rates of 92.47% and 90.37%. The magnetic separation tailings with the grain size of below 0.45mm are black powder and graphite products, the black powder and the graphite products are mixed with water to form flotation slurry with the concentration of 10 wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to perform graphite flotation, graphite with the carbon grade of 91.17% and the recovery rate of 88.10% is obtained through the graphite flotation, and the flotation tailings are black powder and nickel-cobalt-manganese intermediate products and enter a subsequent reduction roasting process.
(3) And carrying out reduction roasting on the black powder nickel-cobalt-manganese intermediate product for 1.5h at the temperature of 450 ℃ in a hydrogen reduction atmosphere to obtain reduction roasting slag. Water is used as a leaching agent, hydrogen reduction roasting slag is leached out under the conditions of liquid-solid ratio of 4:1 and 80 ℃ and leaching for 1h, and water leaching slag and lithium-containing leaching liquid are obtained through solid-liquid separation treatment. Mixing the lithium-rich solution and the lithium-containing leaching solution, and introducing CO2Evaporating and crystallizing to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 99.6%.
(4) And (4) leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 5mol/L to obtain leaching solution containing nickel, cobalt and manganese. Neutralizing, precipitating and removing iron and aluminum (the pH value is 4.6), removing copper and zinc by using sodium sulfide, and removing magnesium by using sodium fluoride to obtain a purified liquid, wherein the purified liquid is a solution product containing nickel, cobalt and manganese.
(5) After the comprehensive recovery treatment of the dressing and smelting, the purity of the obtained product is as follows: the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent and 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 98.6 percent, 99.3 percent, 99.5 percent and 99.2 percent.
Example 5
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) The waste ternary lithium ion battery is treated by chemical discharge, and the discharged battery is subjected to multistage crushing in a nitrogen atmosphere. And carrying out pyrolysis pretreatment on the crushed battery for 6h at 400 ℃ in a nitrogen atmosphere to obtain a pyrolysis product, and discharging generated pyrolysis smoke after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) Washing and grading the pyrolysis product into three size fractions of more than 5mm, 0.2-5 mm and less than 0.20mm and a lithium-rich solution, carrying out magnetic separation on the three size fractions respectively at the magnetic field intensity of 280kA/m to obtain a nickel-cobalt-manganese intermediate product, using magnetic tailings of two size fractions of more than 20mm and 0.2-5 mm as copper-aluminum products, and respectively obtaining the recovery rates of 93.19% and 91.42%. The magnetic separation tailings with the size fraction below 0.20mm are black powder and graphite products, the black powder and the graphite products are mixed with water to form flotation slurry with the concentration of 5 wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to perform graphite flotation, graphite with the carbon grade of 92.82% and the recovery rate of 87.36% is obtained through the graphite flotation, and the flotation tailings are black powder and nickel-cobalt-manganese intermediate products and enter a subsequent reduction roasting process.
(3) And carrying out reduction roasting on the black powder nickel-cobalt-manganese intermediate product for 1.5h at the temperature of 750 ℃ in a hydrogen reduction atmosphere to obtain reduction roasting slag. Water is used as a leaching agent, hydrogen reduction roasting slag is leached out under the conditions of liquid-solid ratio of 4:1 and 80 ℃ and leaching for 1h, and water leaching slag and lithium-containing leaching liquid are obtained through solid-liquid separation treatment. Mixing the lithium-rich solution and the lithium-containing leaching solution, and introducing CO2Evaporating and crystallizing to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 69.6%.
(4) And (4) leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 5mol/L to obtain leaching solution containing nickel, cobalt and manganese. Neutralizing, precipitating and removing iron and aluminum (the pH value is 4.6), removing copper and zinc by using sodium sulfide, and removing magnesium by using sodium fluoride to obtain a purified liquid, wherein the purified liquid is a solution product containing nickel, cobalt and manganese.
(5) After the comprehensive recovery treatment of the dressing and smelting, the purity of the obtained product is as follows: the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent and 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are 69.6 percent, 99.3 percent, 99.5 percent and 99.2 percent respectively.
Example 6
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) The waste ternary lithium ion battery is treated by chemical discharge, and the discharged battery is subjected to multistage crushing in a nitrogen atmosphere. And carrying out pyrolysis pretreatment on the crushed battery for 0.5h at 700 ℃ in a nitrogen atmosphere to obtain a pyrolysis product, and discharging generated pyrolysis smoke after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) Washing and grading the pyrolysis product into three size fractions of more than 3mm, 0.20-3 mm and less than 0.20mm and a lithium-rich solution, carrying out magnetic separation on the three size fractions at the magnetic field intensity of 40kA/m to obtain a nickel-cobalt-manganese intermediate product, using magnetic tailings of the two size fractions of more than 3mm and 0.20-3 mm as copper-aluminum products, and respectively carrying out recovery rates of 93.98% and 92.13%. The magnetic separation tailings with the grain size of below 0.20mm are black powder and graphite products, the black powder and the graphite products are mixed with water to form flotation slurry with the concentration of 35 wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to perform graphite flotation, graphite with the carbon grade of 87.05% and the recovery rate of 87.29% is obtained through the graphite flotation, and the flotation tailings are black powder and nickel-cobalt-manganese intermediate products and enter a subsequent reduction roasting process.
(3) And carrying out reduction roasting on the black powder nickel-cobalt-manganese intermediate product for 7 hours at the temperature of 650 ℃ in a hydrogen reduction atmosphere to obtain reduction roasting slag. Water is used as a leaching agent, hydrogen reduction roasting slag is leached out under the conditions of liquid-solid ratio of 4:1 and 80 ℃ and leaching for 1h, and water leaching slag and lithium-containing leaching liquid are obtained through solid-liquid separation treatment. Mixing the lithium-rich solution and the lithium-containing leaching solution, and introducing CO2Evaporating and crystallizing to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 77.6%.
(4) And (4) leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 5mol/L to obtain leaching solution containing nickel, cobalt and manganese. Neutralizing, precipitating and removing iron and aluminum (the pH value is 4.6), removing copper and zinc by using sodium sulfide, and removing magnesium by using sodium fluoride to obtain a purified liquid, wherein the purified liquid is a solution product containing nickel, cobalt and manganese.
(5) After the comprehensive recovery treatment of the dressing and smelting, the purity of the obtained product is as follows: the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent and 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium carbonate obtained by wet lithium extraction is 98.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are 77.6 percent, 99.3 percent, 99.5 percent and 99.2 percent respectively.
Example 7
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) The waste ternary lithium ion battery is treated by chemical discharge, and the discharged battery is subjected to multistage crushing in a nitrogen atmosphere. And carrying out pyrolysis pretreatment on the crushed battery for 2h at 640 ℃ in a nitrogen atmosphere to obtain a pyrolysis product, and discharging generated pyrolysis smoke after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) Washing and grading the pyrolysis product into three size fractions of more than 2mm, 0.15-2 mm and less than 0.15mm and a lithium-rich solution, carrying out magnetic separation on the three size fractions at the magnetic field intensity of 180kA/m to obtain a nickel-cobalt-manganese intermediate product, using magnetic tailings of two size fractions of more than 2mm and 0.15-2 mm as copper-aluminum products, and respectively carrying out recovery rates of 92.89% and 91.22%. The magnetic separation tailings with the grain size of less than 0.15mm are black powder and graphite products, the black powder and the graphite products are mixed with water to form flotation slurry with the concentration of 20 wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to perform graphite flotation, graphite with the carbon grade of 90.33% and the recovery rate of 87.11% is obtained through the graphite flotation, and the flotation tailings are black powder and nickel-cobalt-manganese intermediate products and enter a subsequent reduction roasting process.
(3) And carrying out reduction roasting on the black powder nickel-cobalt-manganese intermediate product for 5 hours at 350 ℃ in a hydrogen reduction atmosphere to obtain reduction roasting slag. Water is used as a leaching agent, hydrogen reduction roasting slag is leached out under the conditions of liquid-solid ratio of 4:1 and 80 ℃ and leaching for 1h, and water leaching slag and lithium-containing leaching liquid are obtained through solid-liquid separation treatment. Mixing the lithium-rich solution and the lithium-containing leaching solution, and introducing CO2Evaporating and crystallizing to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 23.5%.
(4) And (4) leaching the water leaching slag obtained in the step (3) by using sulfuric acid with the concentration of 5mol/L to obtain leaching solution containing nickel, cobalt and manganese. Neutralizing, precipitating and removing iron and aluminum (the pH value is 4.6), removing copper and zinc by using sodium sulfide, and removing magnesium by using sodium fluoride to obtain a purified liquid, wherein the purified liquid is a solution product containing nickel, cobalt and manganese.
(5) After the comprehensive recovery treatment of the dressing and smelting, the purity of the obtained product is as follows: the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent and 90.37 percent, the recovery rate of graphite reaches 88.10 percent, the purity of lithium carbonate obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are 23.5 percent, 99.3 percent, 99.5 percent and 99.2 percent respectively.
Example 8
The battery adopted in the embodiment is a cylindrical 18650 ternary lithium ion battery in a factory in Zhejiang.
(1) The waste ternary lithium ion battery is treated by chemical discharge, and the discharged battery is subjected to multistage crushing in a nitrogen atmosphere. And carrying out pyrolysis pretreatment on the crushed battery for 3h at 610 ℃ in a nitrogen atmosphere to obtain a pyrolysis product, and discharging generated pyrolysis smoke after secondary combustion, surface cooling, high-temperature cloth bag dust collection and tail gas purification treatment.
(2) Washing and grading the pyrolysis product into three size fractions of more than 2mm, 0.15-2 mm and less than 0.15mm and a lithium-rich solution, carrying out magnetic separation on the three size fractions respectively at the magnetic field intensity of 180kA/m to obtain a nickel-cobalt-manganese intermediate product, using magnetic tailings of more than 2mm and 0.15-2 mm as copper-aluminum products, and respectively obtaining the recovery rates of 89.04% and 89.12%. The magnetic separation tailings with the size fraction below 0.15mm are black powder and graphite products, the black powder and the graphite products are mixed with water to form flotation slurry with the concentration of 15 wt%, 1000g/t of sodium sulfide, 200g/t of diesel oil and 40g/t of pine oil are added into the flotation slurry to perform graphite flotation, graphite with the carbon grade of 89.59% and the recovery rate of 88.40% is obtained through the graphite flotation, and the flotation tailings are black powder and nickel-cobalt-manganese intermediate products and enter a subsequent reduction roasting process.
(3) And carrying out reduction roasting on the black powder nickel-cobalt-manganese intermediate product for 2h at 480 ℃ in a hydrogen reduction atmosphere to obtain reduction roasting slag. Water is used as a leaching agent, hydrogen reduction roasting slag is leached out under the conditions of liquid-solid ratio of 4.5:1 and 80 ℃ and leaching for 1h, and water leaching slag and lithium-containing leaching liquid are obtained through solid-liquid separation treatment. Mixing the lithium-rich solution and the lithium-containing leaching solution, and introducing CO2Evaporating and crystallizing to obtain a lithium carbonate product, wherein the comprehensive recovery rate of lithium is 99.1%.
(4) Reducing and smelting the water leaching slag, the flux quartz sand, the limestone and the reducing agent coal at 1200 ℃ for 5 hours to obtain nickel-cobalt alloy and smelting slag, wherein the smelting slag belongs to harmless slag after high-temperature curing treatment and can be directly buried. And (3) discharging the smoke generated by reduction smelting after secondary combustion, a waste heat boiler, surface cooling, high-temperature cloth bag dust collection and tail gas purification and absorption.
(5) After the comprehensive recovery treatment of the dressing and smelting, the purity of the obtained product is as follows: the recovery rate of copper and aluminum in the copper and aluminum product can reach 92.47 percent and 90.37 percent, the recovery rate of graphite can reach 88.10 percent, the purity of lithium hydroxide obtained by wet lithium extraction is 99.8 percent, and the recovery rates of lithium, nickel, cobalt and manganese are respectively 99.1 percent, 99.3 percent, 99.5 percent and 99.2 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. A dressing and smelting combined comprehensive recovery method of waste lithium ion batteries is characterized by comprising the following steps:
s1, carrying out pyrogenic pretreatment on the waste lithium ion battery to obtain a pretreatment product;
s2, carrying out ore washing and grading treatment on the pretreatment product to obtain coarse fraction particles, medium and fine fraction particles, fine fraction particles and a first part of lithium-containing solution, wherein the particle size of the coarse fraction particles is larger than that of the medium and fine fraction particles, and the particle size of the medium and fine fraction particles is larger than that of the fine fraction particles;
s3, respectively carrying out magnetic separation on the coarse-fraction particles, the medium-fine-fraction particles and the fine-fraction particles to obtain magnetic separation concentrate serving as a nickel-cobalt-manganese intermediate product, wherein magnetic separation tailings of the coarse-fraction particles and the medium-fine-fraction particles serve as a copper-aluminum product, and the magnetic separation tailings of the fine-fraction particles are graphite and black powder products; sequentially carrying out size mixing and graphite flotation on the graphite and black powder products to obtain graphite products and black powder;
s4, carrying out reduction roasting on the nickel-cobalt-manganese intermediate product and the black powder to obtain roasted slag; carrying out water leaching on the roasting slag to extract lithium, so as to obtain a second part of lithium-containing solution and water leaching slag;
s5, combining the first part of the lithium-containing solution and the second part of the lithium-containing solution to obtain a combined solution; preparing a lithium product by adopting the combined solution;
s6, carrying out acid leaching and impurity removal on the water leaching residue to obtain a solution product containing nickel, cobalt and manganese.
2. The recycling method according to claim 1, wherein in the step S1, the pyrogenic pretreatment process includes:
disassembling and crushing the waste lithium ion battery to obtain a crushed material; preferably, the particle size of the crushed material is below 50 mm;
carrying out low-temperature pyrolysis on the crushed material under the conditions of protective atmosphere and temperature of 400-700 ℃ to obtain the pretreatment product; preferably, the temperature of the low-temperature pyrolysis is 600-650 ℃, and more preferably 610-640 ℃; preferably, the low-temperature pyrolysis time is 0.5-6 h;
preferably, before the step of disassembling and crushing the waste lithium ion battery, the step S1 further includes a step of discharging the waste lithium ion battery.
3. The recycling method according to claim 1 or 2, wherein in the step S2, the particle size of the coarse fraction particles is larger than 2mm, the particle size of the fine fraction particles is smaller than 0.2mm, and the particle size of the medium fine fraction particles is between the particle sizes of the coarse fraction particles and the fine fraction particles;
preferably, in step S3, the magnetic separation magnetic field strength of the coarse fraction particles, the medium-fine fraction particles and the fine fraction particles is 40 to 280kA/m respectively.
4. The recycling method according to claim 3, wherein the step of subjecting the graphite and black powder products to size mixing and graphite flotation in sequence comprises:
mixing the graphite and black powder product into flotation pulp with the concentration of 5-35 wt% by using water;
and adding a regulator, a graphite collector and a foaming agent into the flotation pulp to perform graphite flotation so as to obtain the graphite product and the black powder.
5. The recovery method according to any one of claims 1 to 4, wherein in the step S4, the reducing agent used in the reduction roasting process is the graphite product obtained in the step S3, or the reduction roasting process is performed under a reducing atmosphere;
preferably, the reducing atmosphere consists of a reducing gas and an optional inert gas, the reducing gas is one or more of hydrogen, ammonia, methane and sulfur dioxide, and the inert gas is nitrogen and/or argon;
preferably, the temperature in the reduction roasting process is 400-700 ℃, and the reaction time is 0.5-6 h.
6. The recovery method according to any one of claims 1 to 4, wherein in the step S5, lithium in the combined solution is evaporated and crystallized in the form of lithium hydroxide, or carbon dioxide is introduced into the combined solution or soluble carbonate is added to precipitate lithium in the form of lithium carbonate, so as to obtain the lithium product;
preferably, the step S5 further includes a step of removing impurity ions in the combined solution using chemical precipitation or ion exchange resin before the step of preparing the lithium product using the combined solution.
7. The recovery method according to any one of claims 1 to 4, wherein in step S6, the water leachate is subjected to acid leaching to obtain a pickle liquor;
the impurity removing step comprises the following steps:
adjusting the pH value of the pickle liquor to be more than 4.2, and removing iron impurities and aluminum impurities to obtain an iron and aluminum removing solution;
adding fluoride into the solution for removing the iron and the aluminum, and removing magnesium impurities to obtain a magnesium-removed solution; preferably, the fluoride is sodium fluoride;
adding sulfide salt and/or hydrogen sulfide into the magnesium removal solution to remove copper impurities and zinc impurities to obtain a solution product containing nickel, cobalt and manganese; preferably, the sulfide salt is sodium sulfide; or, the impurity removing step comprises:
extracting the pickle liquor by using an extracting agent to obtain the solution product containing nickel, cobalt and manganese; preferably, the extractant is a P204 extractant.
8. The recovery method according to any one of claims 1 to 5, wherein the step S6 further includes a step of subjecting the water-leached slag to reduction smelting, before the step of subjecting the water-leached slag to acid leaching; preferably, the water leaching residue is reduced and smelted for 0.5-5 hours at the temperature of 1200-1600 ℃ to obtain a nickel-cobalt-manganese alloy, and then the nickel-cobalt-manganese alloy is subjected to acid leaching and impurity removal in sequence to obtain the solution product containing nickel, cobalt and manganese.
9. The recycling method according to claim 8, wherein a first flue gas is obtained in the pyrogenic pretreatment step and a second flue gas is obtained in the reduction smelting step, and the recycling method further comprises the steps of secondary combustion, surface cooling, dust removal and tail gas purification of the first flue gas and the second flue gas in sequence.
10. The recycling method according to claim 1, wherein the waste lithium ion battery is one or more of a waste lithium cobalt oxide battery, a lithium manganate battery, a nickel-manganese binary composite lithium ion battery, a nickel-cobalt binary composite lithium ion battery, a cobalt-manganese binary composite lithium ion battery, a nickel-cobalt-manganese ternary composite lithium ion battery, and a nickel-cobalt-aluminum ternary composite lithium ion battery.
11. The utility model provides a recovery unit is synthesized in selection of old and useless lithium ion battery jointly which characterized in that, recovery unit includes:
the device comprises a pyrogenic pretreatment unit (10) and a pretreatment unit, wherein the pyrogenic pretreatment unit (10) is provided with a waste lithium ion battery inlet and a pretreatment product outlet, and the pyrogenic pretreatment unit (10) is used for carrying out pyrogenic pretreatment on the waste lithium ion battery to obtain a pretreatment product;
an ore washing and classifying unit (20) which is provided with a pretreatment product inlet and a first water inlet, wherein the pretreatment product inlet is connected with the pretreatment product inlet, the ore washing and classifying unit (20) is used for carrying out ore washing and classifying treatment on the pretreatment product to obtain coarse-fraction particles, medium-fine-fraction particles, fine-fraction particles and a first part of lithium-containing solution, the particle size of the coarse-fraction particles is larger than that of the medium-fine-fraction particles, and the particle size of the medium-fine-fraction particles is larger than that of the fine-fraction particles;
the magnetic separation unit (30) is connected with an outlet of the ore washing classification unit (20), and the magnetic separation unit (30) is used for respectively carrying out magnetic separation on the coarse-fraction particles, the medium-fine-fraction particles and the fine-fraction particles to obtain a nickel-cobalt-manganese intermediate product, coarse-fraction particle magnetic separation tailings, medium-fine-fraction particle magnetic separation tailings and fine-fraction particle magnetic separation tailings, wherein the coarse-fraction particle magnetic separation tailings and the medium-fine-fraction particle magnetic separation tailings are used as copper and aluminum products, and the fine-fraction particle magnetic separation tailings are graphite and black powder products;
the graphite recovery unit (40) is connected with an outlet of the magnetic separation unit (30), the graphite recovery unit (40) comprises a size mixing unit (41) and a flotation unit (42) which are sequentially connected, the size mixing unit (41) is used for mixing the graphite and the black powder products, and the flotation unit (42) is used for carrying out graphite flotation to obtain graphite products and black powder;
the reducing roasting unit (50) is respectively connected with an outlet of the magnetic separation unit (30) and an outlet of the flotation unit (42), and the reducing roasting unit (50) is used for reducing and roasting the nickel-cobalt-manganese intermediate product and the black powder to obtain roasted slag;
the water leaching unit (60) is provided with a roasting slag inlet and a second water inlet, the roasting slag inlet is connected with an outlet of the reduction roasting unit (50), and the water leaching unit (60) is used for performing water leaching lithium extraction on the roasting slag to obtain a second part of lithium-containing solution and water leaching slag;
a lithium recovery unit (70) having an inlet connected to the outlet of the water leaching unit (60) and the outlet of the ore washing classification unit (20), respectively, the lithium recovery unit (70) being configured to prepare a lithium product using a combined solution of the first portion of lithium-containing solution and the second portion of lithium-containing solution;
the acid leaching unit (80) is provided with a water leaching residue inlet, an acid inlet and an acid leaching solution outlet, the water leaching residue inlet is connected with the outlet of the water leaching unit (60), and the acid leaching unit (80) is used for performing acid leaching on the water leaching residue to obtain acid leaching solution;
and the impurity removal unit (90) is connected with the pickle liquor outlet, and the impurity removal unit (90) is used for removing impurities from the pickle liquor to obtain a solution product containing nickel, cobalt and manganese.
12. A recovery device according to claim 11, characterized in that said pyrometallurgical pretreatment unit (10) comprises:
a disassembly crushing unit (11) which is provided with the waste lithium ion battery inlet and a crushed material outlet;
a low temperature pyrolysis unit (12) having a crushed material inlet, an inert gas inlet, and the pretreated product outlet, the crushed material inlet being connected to the crushed material outlet.
13. The recycling apparatus according to claim 12, characterized in that the pyrometallurgical pretreatment unit (10) further comprises a discharge unit (13), the discharge unit (13) being located upstream of the dismantling and crushing unit (11) and connected to the spent lithium ion battery inlet, the discharge unit (13) being adapted to discharge the spent lithium ion battery.
14. The recycling apparatus according to any one of claims 11 to 13, wherein the graphite recycling unit (40) further comprises:
a conditioning agent supply unit (43) connected to the flotation unit (42) for supplying conditioning agent thereto;
a graphite collector supply unit (44) connected to the flotation unit (42) for supplying a graphite collector thereto;
a frother supply unit (45) connected to the flotation unit (42) for supplying frother thereto.
15. The recycling apparatus according to claim 12 or 13,
the reduction roasting unit (50) is also provided with a first reducing agent inlet which is connected with an outlet of the flotation unit (42) and is used for taking the graphite product obtained in the graphite flotation process as a reducing agent in the reduction roasting process; or,
the reduction roasting unit (50) further has a reducing gas inlet, and the recovery apparatus further includes a reducing gas supply unit connected to the reducing gas inlet.
16. A recycling apparatus according to claim 15, characterized in that the recycling apparatus further comprises an inert gas supply unit (100), the inert gas supply unit (100) being connected to the reducing gas inlet and the inert gas inlet of the low temperature pyrolysis unit (12), respectively.
17. The recovery device according to any one of claims 11 to 13, wherein the lithium recovery unit (70) comprises:
an impurity removing agent supply unit (71) for supplying an impurity removing agent;
an impurity removal and purification unit (72), an inlet of which is respectively connected with an outlet of the water leaching unit (60), an outlet of the ore washing and classifying unit (20) and the impurity removing agent supply unit (71), wherein the impurity removal and purification unit (72) is used for carrying out impurity removal reaction on the combined solution of the first part of lithium-containing solution and the second part of lithium-containing solution to obtain an impurity-removed lithium solution;
and the lithium product preparation unit (73) is connected with the outlet of the impurity removal and purification unit (72), and the lithium product preparation unit (73) is used for carrying out evaporation crystallization on the impurity removal lithium solution or depositing lithium carbonate to obtain the lithium product.
18. The recycling apparatus according to any one of claims 11 to 13,
the impurity removal unit (90) includes:
the pH adjusting unit (91) is connected with the pickle liquor outlet, and the pH adjusting unit (91) is used for adjusting the pH value of the pickle liquor to be more than 4.2 so as to obtain an aluminum-removed solution;
the magnesium removing unit (92) is provided with a fluoride inlet and an deironing solution inlet, the deironing solution inlet is connected with the outlet of the pH adjusting unit (91), and the magnesium removing unit (92) is used for removing magnesium impurities in the deironing solution to obtain a magnesium removing solution;
the copper and zinc removing unit (93) is provided with a magnesium removing solution inlet and a sulfide inlet, the magnesium removing solution inlet is connected with an outlet of the magnesium removing unit (92), the sulfide inlet is used for introducing sulfide salt and/or hydrogen sulfide, and the copper and zinc removing unit (93) is used for removing copper impurities and zinc impurities in the magnesium removing solution to obtain a solution product containing nickel, cobalt and manganese;
or the impurity removal unit (90) is an extraction impurity removal unit.
19. The recycling apparatus according to claim 18, further comprising a reduction smelting unit (110),
the reduction smelting unit (110) is arranged on a flow path connecting the water leaching slag inlet and the water leaching unit (60), the reduction smelting unit (110) is also provided with a flux inlet, the reduction smelting unit (110) is used for reduction smelting on the water leaching slag to obtain a nickel-cobalt-manganese alloy, and the acid leaching unit (80) is used for acid leaching on the nickel-cobalt-manganese alloy to obtain the acid leaching solution.
20. The recycling apparatus according to claim 19, wherein the pyrometallurgical pretreatment unit (10) further has a first flue gas outlet, the reduction smelting unit (110) further has a second flue gas outlet, the recycling apparatus further comprising a flue gas treatment unit (120), the flue gas treatment unit (120) being connected to the first flue gas outlet and the second flue gas outlet, respectively.
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