CN110911675A - Method for preparing lithium battery positive electrode material precursor from seabed polymetallic nodule - Google Patents
Method for preparing lithium battery positive electrode material precursor from seabed polymetallic nodule Download PDFInfo
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- CN110911675A CN110911675A CN201811084156.7A CN201811084156A CN110911675A CN 110911675 A CN110911675 A CN 110911675A CN 201811084156 A CN201811084156 A CN 201811084156A CN 110911675 A CN110911675 A CN 110911675A
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- manganese
- cobalt
- nickel
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- 239000002243 precursor Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 title abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 161
- 238000000605 extraction Methods 0.000 claims abstract description 101
- 239000011572 manganese Substances 0.000 claims abstract description 98
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 82
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 75
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 72
- 239000010941 cobalt Substances 0.000 claims abstract description 72
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000002386 leaching Methods 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 139
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 83
- 239000012074 organic phase Substances 0.000 claims description 63
- 229910052742 iron Inorganic materials 0.000 claims description 46
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 238000007127 saponification reaction Methods 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 230000001276 controlling effect Effects 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 238000011084 recovery Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 12
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 11
- -1 rare earth ion Chemical class 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 8
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052683 pyrite Inorganic materials 0.000 claims description 8
- 239000011028 pyrite Substances 0.000 claims description 8
- 229910052598 goethite Inorganic materials 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 229910052935 jarosite Inorganic materials 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000012527 feed solution Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 abstract description 35
- 239000011702 manganese sulphate Substances 0.000 abstract description 35
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 35
- 150000002910 rare earth metals Chemical class 0.000 abstract description 23
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 18
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 18
- 150000002739 metals Chemical class 0.000 abstract description 15
- 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 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 12
- 239000010406 cathode material Substances 0.000 abstract description 6
- 238000009388 chemical precipitation Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 abstract 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract 1
- 229910052727 yttrium Inorganic materials 0.000 abstract 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract 1
- 229940073644 nickel Drugs 0.000 description 68
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000000047 product Substances 0.000 description 22
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 21
- 229940044175 cobalt sulfate Drugs 0.000 description 21
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 21
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 21
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 21
- 229940053662 nickel sulfate Drugs 0.000 description 18
- 239000003350 kerosene Substances 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 8
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 7
- 239000000284 extract Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 201000008827 tuberculosis Diseases 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for extracting valuable metals from seabed polymetallic nodule resources, and particularly discloses a method for preparing a precursor of a ternary positive electrode material, namely copper sulfate, manganese sulfate, yttrium oxide and lithium battery, by using the seabed polymetallic nodule resources as raw materials and adopting a full wet process. The seabed polymetallic nodule resource is subjected to sulfuric acid reduction leaching, copper, rare earth yttrium, nickel, cobalt and manganese in the leaching solution are separated and purified by chemical precipitation and extraction, and a nickel-cobalt-manganese sulfate solution obtained by combined extraction is subjected to chemical precipitation to prepare the lithium battery ternary cathode material precursor. The invention provides a brand new solution for comprehensive utilization of the seabed polymetallic nodule. The process has the advantages of combined extraction of nickel, cobalt and manganese, no need of thorough separation, shortened process flow, simplified operation, pure prepared product and high added value.
Description
The technical field is as follows:
the invention belongs to the field of extraction of valuable marine minerals, and particularly relates to a method for extracting valuable metals from seabed polymetallic nodules, namely a method for seabed co-production of a precursor of a positive electrode material.
Background art:
the seabed polymetallic nodule is rich in iron and manganese, and also contains copper, nickel, cobalt, molybdenum, vanadium, zinc, tungsten, titanium, rare earth, noble metal and other valuable elements. Seabed polymetallic nodule is regarded as an important strategic metal resource which can replace land resources in the 21 st century. Manganese in the multi-metal nodule mainly exists in the form of manganite, and exists in the form of other manganese ores such as manganite and the like; the iron exists mainly in the forms of goethite, ferrihydrite and lepidocrocite, and a small amount of iron exists in the forms of independent minerals such as titaniferous magnetite, ilmenite and the like, wherein copper, cobalt and nickel are mainly adsorbed by manganese ore in the form of dispersed ions to be present in the manganite and the calciumusite. Because copper, cobalt and nickel in the polymetallic nodule do not exist in an independent mineral form, physical mineral separation is difficult to enrich, and smelting treatment is required to be directly carried out.
Since the 20 th century 60 s, the western countries have conducted a great deal of research on the smelting and processing of manganese nodules, and several tens of proposals have been made, and the representatives include smelting-sulfidization-oxygen pressure acid leaching, direct hydrochloric acid leaching, high-pressure sulfuric acid leaching, cuprous ion ammonia leaching and reduction ammonia leaching. The smelting and processing research of multi-metal nodule and cobalt-rich crust in China since 1983 obtains a series of achievements, mainly comprises a smelting-rusting-extraction process, the process realizes the separation of Mn from Cu, Ni and Co in one step through reduction smelting to obtain manganese-rich slag and smelting alloy which is rich in almost all of Cu, Ni and Co, and the manganese-rich slag can be directly used for smelting manganese alloy with a wide market. However, all the processes aim at the extraction of single metal, particularly the nickel and cobalt have similar properties, are difficult to separate, have long flow, are complex in process and have low added value of products.
With the development of new energy automobiles, the demand for ternary lithium ion batteries has increased dramatically, resulting in a high price of ternary cathode materials (NCM) for lithium ion batteries. The ternary positive electrode material of the lithium ion battery is generally prepared by roasting a nickel-cobalt-manganese hydroxide precursor and a lithium salt. Therefore, the preparation of the lithium battery ternary cathode material precursor by using the seabed polymetallic nodule can improve the added value of products, realize the combined extraction of nickel, cobalt and manganese, shorten the process flow and increase the recovery rate of metals.
The invention content is as follows:
the invention provides a method for preparing a lithium battery ternary cathode material precursor by taking seabed polymetallic nodules as a raw material aiming at overcoming the defects of the existing technology for extracting nickel, cobalt and manganese from seabed polymetallic nodules, and aims to shorten the process flow of extracting valuable metals, improve the recovery rate of the metals, and improve the added value of products by producing manganese sulfate, copper sulfate and rare earth oxide as by-products.
Different from the existing ternary waste lithium ion battery material recovery preparation precursor, the waste lithium ion battery is generally recovered class by class, the ratio of Ni to Co to Mn in the ternary battery is usually 5: 2: 3 or 6: 2 or 1: 1 and the like, the proportion is relatively stable, the nickel-cobalt-manganese content in the waste material is high, the impurity metal types are few, the impurity content is low, the impurity removal is easy, only three metals of nickel, cobalt and manganese are required to be recovered to prepare the precursor, and other metals are not required to be considered. The seabed polymetallic nodule is a manganese ore containing various nonferrous metals, has complex composition, high manganese content, low contents of copper, nickel and cobalt, various metal types and more impurities, particularly contains a large amount of iron, the manganese and the iron exist in the form of polymetallic ores, and the copper, the nickel and the cobalt exist in the form of ions adsorbed by the manganese ore and dispersed, so that the extraction and the separation are difficult.
The prior art mainly extracts single metal in seabed polymetallic nodules, but the single metal, particularly manganese, nickel and cobalt, has similar physical and chemical properties, is difficult to completely separate, has multiple extraction and separation stages, usually needs 20-30 stages of countercurrent extraction to completely separate manganese, cobalt and nickel, has complex process and high cost, and is easy to cause environmental burden. In order to overcome the defects, the invention innovatively provides a thought for preparing an NCM ternary material precursor by adopting seabed polymetallic nodules. However, the manganese content in the nodule ore is generally 15-30%, the nickel-cobalt content is low, the Co content is less than 0.5%, the Ni content is less than 1.2%, and the proportion of nickel, cobalt and manganese is far from that of the lithium ion battery ternary precursor; in addition, manganese mainly exists in the forms of manganite, manganosite and the like, valuable metals such as copper, titanium, rare earth and the like also exist in the tuberculosis ore, and the extraction of the valuable metals of the tuberculosis ore needs to recover nickel, cobalt and manganese and also needs to consider the recovery of metals such as copper, rare earth and the like. Because the water content of the seabed polymetallic nodule ore is high, 30-40%, valuable metals cannot be enriched by a mineral separation method, and the energy consumption of mineral drying and pyrometallurgical smelting is too high. The invention innovatively provides an all-wet process route, namely a process for carrying out acid leaching on seabed polymetallic nodules, recovering copper, recovering rare earth, jointly extracting Ni and Co and selectively extracting part of Mn. The process has the advantages of no need of thorough separation of nickel, cobalt and manganese, few extraction stages, short flow and simple operation, and provides a brand new solution for comprehensive recycling of seabed polymetallic nodule resources.
The technical scheme of the invention is as follows:
a method for preparing a lithium battery anode material precursor by using seabed polymetallic nodules comprises the following steps:
step (a): leaching:
crushing, grinding and leaching the seabed polymetallic nodule to obtain the product containing Fe2+、Mn2+、Co2+、Ni2+、Cu2+、Y3+The leachate of (2);
step (b): iron removal:
iron removal treatment is carried out on the leaching solution to obtain the solution containing Mn2+、Co2+、Ni2+、Cu2+、Y3+The iron-removed liquid is obtained;
step (c): and (3) recovering copper:
the liquid after iron removal is subjected to copper removal treatment to obtain Mn enriched2+、Co2+、Ni2+、Y3+The copper-removed solution;
step (d): recovery of rare earth ion Y3+：
Extracting the copper-removed solution to obtain rare earth ion Y3+Enrichment ofTo the organic phase of extraction to obtain Mn-enriched2+、Co2+、Ni2+Removing impurity liquid;
a step (e): combined extraction of nickel, cobalt and manganese:
extracting the impurity-removed liquid obtained in the step (d) by adopting a combined extracting agent to obtain Co2+、Ni2+And part of Mn2+Enriching into an extracted organic phase to obtain Co2+、Ni2+、Mn2+Precursor solution of (2) and Mn-containing2+The raffinate of (a);
the combined extracting agent comprises a first extracting agent and a second extracting agent;
the first extractant is P204 and/or P507; the saponification degree of the first extracting agent is 60% -100%; further preferably 60% -90%; more preferably 70% to 80%.
The second extractant is HBL 110; the saponification degree of the second extractant is 60-70%.
The mass ratio of the first extractant to the second extractant is 3-8: 30-50;
and carrying out coprecipitation on the precursor solution to obtain an NCM precursor.
According to the innovative process route and the innovative step (e), the precursor solution beneficial to synthesis of the NCM material can be obtained by combining the complete extraction of the extracting agents Ni and Co and the selective extraction of Mn, firstly, the preparation of the lithium battery ternary precursor material from the seabed polymetallic nodule is realized, and simultaneously, manganese sulfate, copper sulfate and rare earth oxide are jointly extracted. The process selects a proper extractant system and concentration to realize the synergistic extraction of nickel, cobalt and manganese, meets the proportion range of NCM materials, co-produces a pure manganese sulfate product, does not need to completely separate nickel, cobalt and manganese, has few extraction stages and short flow.
Preferably, in step (a), the leaching process is sulfuric acid reduction leaching.
Preferably, the ground minerals are leached under a system of sulfuric acid and a reducing agent, and the particle size of the minerals is controlled to be below 200 meshes.
Preferably, the reducing agent is SO2Starch and/or pyrite.
In the inventionObtaining a leaching solution by the leaching method, wherein Fe is contained in the leaching solution2+、Mn2+、Co2+、Ni2 +、Cu2+、Y3+And some impurity elements.
The invention innovatively carries out iron removal treatment on the leachate in advance.
Preferably, in the step (b), the step of removing iron comprises:
firstly, regulating the pH value of the leaching solution to 1.5-2.5; then adding hydrogen peroxide, regulating and controlling the pH value of the system to be 3.0-4.0, and precipitating iron in the system to obtain iron-removed liquid. The preferred iron removal method can effectively recover the iron in the leachate, so that the iron forms a mixture of the jarosite and the goethite, and the aim of removing the silicon in the leachate can be fulfilled by adopting the method because the goethite adsorbs the silicon.
Further preferably, the pH value of the leachate is adjusted to 1.8-2.2 by using lime, hydrogen peroxide is added to oxidize iron, then the pH value of the mixed solution is adjusted to 3.0-4.0 by using sodium carbonate, so that iron forms a mixture of the jarosite and goethite, and the iron in the leachate is removed.
Preferably, in the step (c), extraction is adopted to separate Cu in the iron-removed liquid2+。
Preferably, the extractant used for extraction is at least one of lix984 and M5640, and researches show that the Cu in the iron-removed liquid can be selectively extracted with high selectivity by using the preferred extractant2+Extracting to organic phase, effectively removing copper in the liquid after iron removal. And carrying out back extraction, enrichment, evaporation and concentration on the organic phase obtained by extraction to obtain the copper salt.
In the present invention, the copper-removed solution contains Mn2+、Co2+、Ni2+、Y3+And a small amount of Ca2+、Fe3+、Al3+And the like.
Preferably, in step (d), extraction is adopted to remove Y in copper from the solution3+Enriched in the organic phase.
The invention innovatively carries out the treatment of the step (d), not only can effectively extract a small amount of impurities in the rare earth ions, but also can lead the rare earth ions Y to be3+Extracted into the organic phase.
Preferably, in step (d), the extractant used for the extraction is unsaponifiable P204. Researches find that the content of impurities in the impurity removing liquid can be effectively reduced by adopting the preferred extracting agent; in addition, rare earth ion Y can be used3+And (4) enriching and recovering.
Preferably, it will be enriched with rare earth ions Y3+The organic phase is subjected to a first back extraction in 0.5-2.0mol/L acid liquor in advance, and then a second back extraction is performed in 4-6mol/L acid liquor to obtain rare earth ion-enriched Y3+The stripping solution of (1).
In the invention, Ca in the organic phase can be removed through the first back extraction desorption relative to the low-concentration acid liquor2+、Fe3+、Al3+And the like; then desorbing the mixture under the high-concentration acid liquid to obtain the rare earth ion Y enriched by back extraction3+The stripping solution of (1).
The acid of the first stripping is preferably hydrochloric acid. The acid of the second stripping is preferably sulfuric acid. Preferably the acid, and the pH control, unexpectedly increases the purity of the resulting rare earth.
Preferably, a rare earth ion Y enriched with3+Evaporating and calcining the stripping solution to obtain rare earth Y oxide (Y)2O3)。
Preferably, the combined extracting agent is a mixed extracting agent of P204 and HBL110, so that nickel and cobalt are completely extracted.
And (3) combining the P204 and HBL110 extracting agents, completely and synergistically extracting Ni and Co in the impurity-removed solution, selectively extracting part of Mn, and evaporating and crystallizing manganese in the raffinate to obtain a manganese sulfate product. On one hand, the recovery rate of Ni and Co can be improved; in addition, the proportion of manganese-nickel-cobalt in the extraction liquid is close to the range of the ternary anode material of the lithium ion battery, and the precursor can be synthesized by only adding a small amount of sulfate corresponding to the lacking metal in the subsequent synthesis of the precursor. The properties of manganese, nickel and cobalt are similar, and the separation of manganese from cobalt and nickel and cobalt from nickel is difficult to realize by adopting a single extracting agent, particularly for a solution with high manganese concentration and low nickel and cobalt concentration. The traditional method adopts acid leaching, then uses manganese sulfide to precipitate nickel and cobalt, then uses acid to oxidize and leach sulfide precipitation slag, finally uses P204 to extract manganese, P507 to extract nickel and cobalt, and obtains solution of manganese sulfate, nickel sulfate and cobalt sulfate through 20-30 levels of countercurrent extraction, the flow is long, the recovery rate of nickel and cobalt is low, and the cost is high.
In the invention, the combined extraction agent is used to extract Ni and Co and selectively and partially extract Mn, further controls the saponification degree, the component proportion and the pH value of the feed liquid of the components of the combined extraction agent, can further regulate and control the proportion of Ni, Co and Mn in the precursor solution, and realizes the short-flow and high-efficiency recovery of nickel, cobalt and manganese.
Preferably, the saponification degree of P204 is 60-100%; more preferably 70 to 80%, and the manganese portion is extracted.
The saponification degree of HBL110 is 60-70%.
Preferably, the mass ratio of P204 to HBL110 is 3-7: 40-50; more preferably 3-4: 40-50. Under the saponification degree, the preferable proportion range is controlled, Ni and Co in the impurity removing solution can be fully extracted, the recovery rate of the Ni and the Co is ensured, and in addition, the Mn extraction rate is favorably controlled within the range suitable for the preparation requirement of the ternary precursor, so that the extraction ratio of the nickel, the cobalt and the manganese is close to the proportion range of NCM.
Further preferably, the combined extracting agent is subjected to dilution treatment by a diluent before use; in the diluted combined extracting agent, the content of the first extracting agent is 3-8% (by weight).
Preferably, the diluent is sulfonated kerosene.
Preferably, in step (e), the equilibrium pH of the feed solution is 2 to 5; preferably 3-4, and the extraction stages are 5-7, so that the extraction rate meets the requirement. The method is beneficial to regulating and controlling the extraction ratio of Mn, so that the Mn accords with an NCM ternary material and approaches to the application requirement.
Extracting in the step (e), wherein the extracted organic phase is the precursor solution, and the extracted water phase is Mn-containing2+And (3) solution.
Preferably, the proportion of Ni, Co and Mn elements in the precursor solution is controlled, then alkali and ammonia water are added, and the nickel-cobalt-manganese hydroxide precursor is obtained through coprecipitation.
Preferably, in the step (e), the ratio of nickel, cobalt and manganese is regulated to be 5-6: 2-3.
The alkali is preferably an alkali metal hydroxide, and more preferably sodium hydroxide.
Preferably, the total metal concentration in the coprecipitation starting solution is controlled to be 60-100 g/L; the concentration of the ammonia water is preferably 2-3 mol/L; the pH is preferably 10-12.
Preferably, Mn is contained2+Concentrating and crystallizing the raffinate to obtain manganese sulfate.
The invention discloses a method for preparing a lithium ion battery ternary positive electrode material precursor by using a preferable seabed polymetallic nodule, which comprises the following steps:
step (a): leaching:
crushing and grinding the polymetallic nodule, and reducing and leaching by adopting sulfuric acid to obtain a mixed solution of ferrous sulfate, manganese sulfate, cobalt sulfate, nickel sulfate and copper sulfate.
Step (b): removing impurities:
firstly, adjusting the pH value of the solution to 1.5-2.5 by using lime, adding a small amount of hydrogen peroxide to oxidize iron, then adjusting the pH value of the mixed solution to 3.0-4.0 by using sodium carbonate to ensure that iron forms a mixture of jarosite and goethite, adsorbing silicon by the goethite, and removing the iron and the silicon in the leachate.
Step (c): extraction of copper
Copper ions in the solution are removed by using an extractant lix984 or M5640, and copper sulfate is obtained by sulfuric acid back extraction.
Step (d): extraction of rare earth and impurity ions
Carrying out extraction by unsaponifiable P204, deeply removing Ca, Fe and Al in the solution, simultaneously extracting rare earth Y, carrying out back extraction by dilute sulfuric acid to remove Ca, Fe and Al, and carrying out back extraction by high-concentration sulfuric acid to obtain yttrium sulfate solution.
A step (e): extraction of nickel, cobalt and manganese
Extracting nickel cobalt and part of manganese in the solution by adopting the saponified P204+ HBL110, and controlling the saponification degree, the proportion of P204 to HBL110 and the pH value of the feed liquid to ensure that nickel and cobalt completely enter an organic phase and manganese partially enters the organic phase; and back-extracting the organic phase by using sulfuric acid to obtain refined solutions of cobalt sulfate, nickel sulfate and manganese sulfate.
Step (f): crystalline manganese sulfate
Concentrating and crystallizing raffinate after extracting nickel, cobalt and manganese to obtain a manganese sulfate product.
Step (g): preparation of the precursor
According to the proportion of cobalt sulfate, nickel sulfate and manganese sulfate required by the precursor, adding sulfate of the elements lacking in the refined solution, wherein the total metal concentration of the solution is 60-100g/L, adding sodium hydroxide solution and ammonia water, and synthesizing the nickel-cobalt-manganese hydroxide precursor under certain conditions. Adding yttrium sulfate solution in the synthesis process to obtain the yttrium-doped nickel-cobalt-manganese hydroxide precursor.
The invention provides a brand new thought for smelting a seabed manganese nodule, and the method comprises the steps of obtaining a manganese sulfate solution, a nickel sulfate solution and a cobalt sulfate solution from a seabed manganese nodule manganese resource through the process route, and then carrying out chemical precipitation to obtain a precursor of the ternary cathode material of the lithium ion battery. In addition, different from the existing seabed manganese nodule smelting method, in the invention, the extraction agent in the step (d) and the saponification degree of the extraction agent are controlled to cooperatively extract nickel, cobalt and Mn in the system, corresponding salts are supplemented to control the proportion of nickel, cobalt and manganese to accord with the proportion of nickel, cobalt and manganese of the ternary battery material, and then the precursor of the ternary positive electrode material of the lithium ion battery is synthesized by adopting a precipitation method.
In the step (a), the sulfuric acid is subjected to reduction leaching, and the reducing agent can be SO2At least one of starch and pyrite; pyrite is preferred.
In the step (e), the HBL110+ P204 extracts nickel, cobalt and manganese, the saponification degree of the HBL110 is controlled to be 60-70%, the saponification degree of the P204 is controlled to be 60-100%, and the balanced pH value of the feed liquid is 2-5. The back extraction solution is 2.0mol/L H25O4。
Preferably, in step (e), the saponification degree of HBL110 is 60% -70%, the saponification degree of P204 is 70% -80%, and the equilibrium pH value of the feed liquid is 3-4.
Preferably, in step (e), the number of extraction stages is 5 to 7.
And (g) preparing the precursor, wherein the ratio of nickel, cobalt and manganese as the precursor is controlled to be 5-6: 2-3, the concentration of ammonia water in the solution is 1.29mol/L, and the pH value is 10.5-12.5.
The recovery rate of manganese is more than 92%, the recovery rate of nickel is more than 96%, the recovery rate of cobalt is more than 95%, and the recovery rate of copper is more than 95%. In the process, the nickel, the cobalt and the manganese do not need to be thoroughly separated, and the ternary cathode material precursor is directly prepared after purification and impurity removal, so that the problems of long flow, low efficiency and the like caused by deep separation of the manganese, the nickel and the cobalt are solved, the production cost is low, and the added value of the product is high.
Principle and advantageous effects of the invention
The method directly prepares the nickel-cobalt-manganese ternary lithium battery anode material precursor, copper sulfate, manganese sulfate and rare earth oxide by using seabed polymetallic nodules as raw materials and adopting a full wet process. In the process, the saponified P204 and the saponified HBL110 are directly used for synergistic extraction, and complete separation is not needed.
Different from the conventional method for extracting valuable metals from multi-metal nodules on the seabed, the valuable metals are extracted from the sea bottom by single metal, particularly, the physical and chemical properties of nickel and cobalt are similar, the thorough separation is difficult, and the extraction separation stages are multiple. In the invention, an innovative combined extraction agent (preferably the saponified P204+ HBL110) is adopted to jointly extract nickel, cobalt and manganese, and cobalt, nickel and manganese in the leachate are synergistically extracted by controlling parameters in the extraction process, so that the cobalt, nickel and manganese are not required to be completely separated, and the proportion of nickel, cobalt and manganese is adjusted by supplementing the lacking elements, so that the nickel, cobalt and manganese meets the requirement of a precursor of a lithium ion battery anode material.
The method has the advantages of short and clean process flow, no side reaction in the preparation process, high metal recovery rate and high added value of products, and is suitable for industrial production, and the comprehensive recovery and utilization of other valuable metals such as copper, rare earth and the like are considered besides the recovery of nickel, cobalt and manganese are considered.
Description of the drawings:
fig. 1 is an XRD pattern of the precursor prepared in example 1.
The specific implementation mode is as follows:
the present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
The main metal components of the seafloor polymetallic nodule are shown in table 1:
TABLE 1
Example 1
(1) Crushing and grinding polymetallic nodules, weighing 100g of nodule ore, adding into 500mL of 3mol/L sulfuric acid solution, adding 10g of pyrite, leaching at 90 ℃ for 5h, and filtering to obtain filtrate (sulfuric acid leaching solution) with the components shown in Table 2.
(2) Adjusting pH of the filtrate to 1.8 with lime, adding a small amount of hydrogen peroxide to oxidize iron, adding 50g/L sodium carbonate to adjust pH to 3.0, heating to 90 deg.C, and adjusting pH to 3.0 with Ti4+、Fe3+And SiO2Precipitate formed and was removed from the mixed solution.
(3) Removing copper ions in the solution by using an extracting agent Lix984, controlling the O/A to be 1: 1, controlling the concentration of Lix984 to be 15%, using sulfonated kerosene as a diluent, and controlling the pH value to be 3.0 to obtain an organic phase enriched with copper and a copper raffinate; and (3) carrying out back extraction on the organic phase by adopting 2.0mol/L sulfuric acid, wherein the ratio of O/A to O/A is 20: 1, so as to obtain a copper sulfate solution, and carrying out enrichment, evaporation and concentration on the copper sulfate solution so as to obtain a copper sulfate pentahydrate crystal, wherein the analytical purity is 99.1%.
(4) Extracting by unsaponifiable 5% P204 (a diluent is sulfonated kerosene), wherein O/A is 1: 1, the balance pH value is 2.5, extracting copper raffinate in the step (3) to obtain an organic phase containing Ca, Fe and rare earth raffinate, back-extracting the organic phase by 2mol/L hydrochloric acid to remove Ca and Fe in the organic phase, then back-extracting by 4mol/L sulfuric acid to obtain a yttrium sulfate solution, and obtaining yttrium oxide by enrichment, evaporative concentration and roasting, wherein the analytical purity is 98.0%.
(5) Extracting rare earth raffinate obtained in step (4) by adopting a P204+ HBL110 combined extracting agent (a diluting agent is sulfonated kerosene) saponified by NaOH, wherein nickel, cobalt and a small part of manganese in an extraction solution have the P204 saponification degree of 70%, the HBL110 saponification degree of 60%, the P204 dosage of 3%, the HBL110 dosage of 40%, the equilibrium pH value of 3.0, and the O/A ratio of 1: 1, and performing 6-grade countercurrent extraction to obtain an organic phase and nickel cobalt manganese raffinate; the extraction rate of nickel is 99.0 percent, the extraction rate of cobalt is 98.5 percent, the concentration of manganese is high, and only 12 percent of manganese enters an organic phase; and back-extracting the organic phase by using sulfuric acid to obtain a nickel-cobalt-manganese refined solution of cobalt sulfate, nickel sulfate and manganese sulfate. The composition of each solution is shown in Table 2.
(6) Concentrating and crystallizing raffinate (nickel cobalt manganese raffinate) after extracting nickel, cobalt and manganese to obtain a manganese sulfate monohydrate product. The detection proves that the purity of the product is more than 99%.
(7) According to the requirement of a precursor Ni0.5Co0.2Mn0.3(OH)2 on the proportion of cobalt sulfate, nickel sulfate and manganese sulfate, adding sulfate which is a deficient element in the refined solution, controlling the total metal concentration of the solution to be 60-70g/L, adding sodium hydroxide solution and ammonia water to ensure that the pH value is 10.9 and the concentration of the ammonia water is 2.1mol/L, synthesizing a nickel-cobalt-manganese hydroxide precursor Ni-manganese hydroxide at 70 DEG C0.5Co0.2Mn0.3(OH)2. The XRD pattern is shown in FIG. 1, and it can be seen from FIG. 1 that the precursor with high purity of crystal phase is obtained.
TABLE 2 concentrations of various solutions of metal ions
Example 2
(1) Crushing and grinding polymetallic nodule, weighing 100g of nodule ore, adding into 500mL of 3mol/L sulfuric acid solution, and introducing SO2Leaching at 90 deg.C for 5 hr, and filtering to obtain filtrate (sulfuric acid leaching solution) with components shown in Table 3.
(2) Adjusting pH of the filtrate to 2.2 with lime, adding a small amount of hydrogen peroxide to oxidize iron, adding 50g/L sodium carbonate to adjust pH to 3.0, heating to 90 deg.C, and adjusting pH to 3.0 with Ti4+、Fe3+And SiO2Precipitate formed and was removed from the mixed solution.
(3) Removing copper ions in the solution by using an extracting agent M5640, controlling the O/A ratio to be 1: 1, controlling the concentration in the M5640 to be 15%, using sulfonated kerosene as a diluent, and controlling the pH value to be 3.0 to obtain an organic phase enriched with copper and a copper raffinate; and (3) carrying out back extraction on the organic phase by adopting 2.0mol/L sulfuric acid, wherein the ratio of O/A to O/A is 20: 1, so as to obtain a copper sulfate solution, and carrying out enrichment, evaporation and concentration on the copper sulfate solution so as to obtain a copper sulfate pentahydrate crystal with the purity of 99.2%.
(4) Extracting by unsaponifiable 5% P204 (a diluent is sulfonated kerosene), wherein O/A is 1: 1, the balance pH value is 2.5, extracting the copper raffinate in the step (3) to obtain an organic phase containing Ca and Fe and rare earth raffinate, back-extracting the organic phase by using 2mol/L hydrochloric acid to remove the Ca and Fe in the organic phase, then back-extracting by using 4mol/L sulfuric acid to obtain a yttrium sulfate solution, and enriching, evaporating, concentrating and roasting to obtain yttrium oxide with the purity of 98.0%.
(5) Extracting rare earth raffinate obtained in step (4) by adopting a P204+ HBL110 combined extracting agent (a diluting agent is sulfonated kerosene) saponified by NaOH, wherein nickel, cobalt and a small part of manganese in an extraction solution have a P204 saponification degree of 80%, a HBL110 saponification degree of 70%, a P204 dosage of 4%, a HBL110 dosage of 50%, an equilibrium pH value of 4.0, an O/A (oxygen/oxygen) ratio of 1: 1 and 7-level countercurrent extraction to obtain an organic phase and nickel-cobalt-manganese raffinate; the extraction rate of nickel is 99.5 percent, the extraction rate of cobalt is 99 percent, the concentration of manganese is high, and only 15 percent of manganese enters an organic phase; and back-extracting the organic phase by using sulfuric acid to obtain refined solutions of cobalt sulfate, nickel sulfate and manganese sulfate. The composition of each solution is shown in Table 3.
(6) Concentrating and crystallizing raffinate (nickel cobalt manganese raffinate) after extracting nickel, cobalt and manganese to obtain a manganese sulfate monohydrate product. The detection proves that the purity of the product is more than 99.2 percent.
(7) According to the preparation of precursors of cobalt sulfate, nickel sulfate and manganese sulfate, adding sulfate which is lack of elements in the refined solution, wherein the total metal concentration of the solution is 60-70g/L, the pH value of the solution is 12, the concentration of ammonia water is 3.0M, and synthesizing the nickel-cobalt-manganese hydroxide precursor at 70 ℃.
TABLE 3 concentration of various solution Metal ions
Example 3
(1) Crushing and grinding polymetallic nodules, weighing 100g of nodule ore, adding into 500mL of 3mol/L sulfuric acid solution, adding 50g of starch, leaching for 5h at 90 ℃, and then filtering; the composition of the filtrate (sulfuric acid leach solution) is shown in Table 4.
(2) Adjusting pH of the filtrate to 2.5 with lime, adding a small amount of hydrogen peroxide to oxidize iron, adding 50g/L sodium carbonate to adjust pH to 3.0, heating to 90 deg.C, and adjusting pH to 3.0 with Ti4+、Fe3+And SiO2Precipitate formed and was removed from the mixed solution.
(3) Removing copper ions in the solution by using an extracting agent Lix984, controlling the O/A to be 1: 1, controlling the concentration of Lix984 to be 15%, using sulfonated kerosene as a diluent, and controlling the pH value to be 3.0 to obtain an organic phase enriched with copper and a copper raffinate; and (3) carrying out back extraction on the organic phase by adopting 2.0mol/L sulfuric acid, wherein the ratio of O/A to O/A is 20: 1, so as to obtain a copper sulfate solution, and carrying out enrichment, evaporation and concentration on the copper sulfate solution so as to obtain a copper sulfate pentahydrate crystal with the purity of 98.9%.
(4) Extracting by unsaponifiable 5% P204 (a diluent is sulfonated kerosene), wherein O/A is 1: 1, the balance pH value is 2.5, extracting the copper raffinate in the step (3) to obtain an organic phase containing Ca, Fe and rare earth in the solution and rare earth raffinate, back-extracting the organic phase by 2mol/L hydrochloric acid to remove Ca and Fe in the organic phase, back-extracting by 4mol/L sulfuric acid to obtain a yttrium sulfate solution, and enriching, evaporating, concentrating and roasting to obtain yttrium oxide with the purity of 98.0%.
(5) Extracting rare earth raffinate obtained in step (4) by adopting a P507 and HBL110 combined extracting agent (a diluting agent is sulfonated kerosene) saponified by NaOH, wherein nickel, cobalt and a small part of manganese in an extraction solution have a P507 saponification degree of 90%, an HBL110 saponification degree of 70%, a P507 dosage of 7%, an HBL110 dosage of 40%, an equilibrium pH value of 4.0, and O/A (1: 1), and performing 6-grade countercurrent extraction to obtain an organic phase and nickel-cobalt-manganese raffinate; the extraction rate of nickel is 98 percent, the extraction rate of cobalt is 97 percent, the concentration of manganese is high, and only 16 percent of manganese enters an organic phase; and back-extracting the organic phase by using sulfuric acid to obtain a nickel-cobalt-manganese refined solution of cobalt sulfate, nickel sulfate and manganese sulfate. The composition of each solution is shown in Table 4.
(6) Concentrating and crystallizing raffinate (nickel cobalt manganese raffinate) after extracting nickel, cobalt and manganese to obtain a manganese sulfate monohydrate product, wherein the purity of the product is 98.5%.
(7) According to the preparation of precursors of cobalt sulfate, nickel sulfate and manganese sulfate, adding sulfate of elements lacking in refined solution, the total metal concentration of the solution is 90-100g/L, the pH value of sodium hydroxide solution and ammonia water is 12, the concentration of the ammonia water is 3.0M, and synthesizing a precursor Ni of nickel-cobalt-manganese hydroxide at 70 DEG C0.5Co0.2Mn0.3(OH)2。
TABLE 4 concentration of various solution Metal ions
Example 4
The same parameters and conditions as in example 1 were used, except that in the case of sulfuric acid reduction leaching, the reducing agent was H2O2，H2O2The concentration is 1.5mol/L, the concentration of each ion in each solution is shown in Table 5, the purity of the obtained yttrium oxide is 98.0 percent, and the purity of the manganese sulfate product is 99 percent.
TABLE 5 concentration of Metal ions in the leachate
Example 5
The same parameters and conditions as those in example 1 were adopted, except that when nickel and cobalt were extracted jointly, the saponification degree of P204 was 70%, the saponification degree of HBL110 was 60%, the amount of P204 was 3%, the amount of HBL110 was 30%, the equilibrium pH was 3.0, O/a was 1: 1, 6-stage countercurrent extraction, the extraction rate of nickel was 92.0%, the extraction rate of cobalt was 80%, the concentration of manganese was high, and only 11% of manganese entered the organic phase; the organic phase was back-extracted with sulfuric acid to obtain refined solutions of cobalt sulfate, nickel sulfate and manganese sulfate, the concentration of each ion in each solution being shown in table 6. The purity of the obtained yttrium oxide is 98.5 percent, and the purity of the manganese sulfate product is 96.7 percent.
TABLE 6 concentrations of various solutions of metal ions
Example 6
The same parameters and conditions as in example 1 were used, except that when nickel and cobalt were extracted jointly, the degree of saponification of P204 was 70%, the degree of saponification of HBL110 was 60%, the amount of P204 was 3%, the amount of HBL110 was 40%, the equilibrium pH was 2.2, O/a was 1: 1, the extraction rate of nickel was 93.0%, the extraction rate of cobalt was 92%, the concentration of manganese was high, and only 10% of manganese entered the organic phase; the organic phase was back-extracted with sulfuric acid to obtain refined solutions of cobalt sulfate, nickel sulfate and manganese sulfate, the concentration of each ion in each solution being shown in table 6. The purity of the obtained yttrium oxide is 98.0 percent, and the purity of the manganese sulfate product is 97.3 percent.
TABLE 6 concentrations of various solutions of metal ions
Comparative example 1
In the step (5), it is discussed that a combined extracting agent is not adopted, and only saponified P204 is adopted, and the concrete steps are as follows:
(1) crushing and grinding polymetallic nodules, weighing 100g of nodule ore, adding into 500mL of 3mol/L sulfuric acid solution, adding 10g of pyrite, leaching at 90 ℃ for 5h, and filtering, wherein the components of filtrate (sulfuric acid leaching solution) are shown in Table 2.
(2) Adjusting pH of the filtrate to 1.8 with lime, adding a small amount of hydrogen peroxide to oxidize iron, adding 50g/L sodium carbonate to adjust pH to 3.0, heating to 90 deg.C, and adjusting pH to 3.0 with Ti4+、Fe3+And SiO2Precipitate formed and was removed from the mixed solution.
(3) Removing copper ions in the solution by using an extracting agent Lix984, controlling the O/A to be 1: 1, controlling the concentration of Lix984 to be 15%, using sulfonated kerosene as a diluent, and controlling the pH value to be 3.0 to obtain an organic phase enriched with copper and a copper raffinate; and (3) carrying out back extraction on the organic phase by adopting 2.0mol/L sulfuric acid, wherein the ratio of O/A to O/A is 20: 1, carrying out back extraction to obtain a copper sulfate solution, enriching the copper sulfate solution, evaporating and concentrating to obtain a copper sulfate pentahydrate crystal, and analyzing the purity to be 99.1%.
(4) Extracting by unsaponifiable 5% P204 (a diluent is sulfonated kerosene), wherein O/A is 1: 1, the balance pH value is 2.5, extracting the copper raffinate in the step (3) to obtain an organic phase containing Ca, Fe and rare earth and a rare earth raffinate, back-extracting the organic phase by 2mol/L hydrochloric acid to remove Ca and Fe in the organic phase, then back-extracting by 4mol/L sulfuric acid to obtain a yttrium sulfate solution, and obtaining yttrium oxide by enrichment, evaporative concentration and roasting, wherein the analytical purity is 98.0%.
(5) Adopting NaOH saponified P204 to extract rare earth raffinate obtained in the step (4), wherein nickel, cobalt and a small part of manganese in an extraction solution have a P204 saponification degree of 70%, the P204 dosage is 15% (a diluent is sulfonated kerosene), the equilibrium pH value is 3.0, the O/A ratio is 1: 1, 6-grade countercurrent extraction is carried out, the extraction rate of nickel is 60.0%, the extraction rate of cobalt is 73%, the manganese concentration is high, and only 23% of manganese enters an organic phase; and back-extracting the organic phase by using sulfuric acid to obtain refined solutions of cobalt sulfate, nickel sulfate and manganese sulfate. The composition of each solution is shown in Table 7.
(6) Concentrating and crystallizing raffinate after extracting nickel, cobalt and manganese to obtain a manganese sulfate monohydrate product, wherein nickel sulfate and cobalt sulfate are mixed in manganese sulfate, and the purity of the manganese sulfate is 95.7%.
(7) According to the precursor Ni0.5Co0.2Mn0.3(OH)2The proportion of cobalt sulfate, nickel sulfate and manganese sulfate is required, sulfate which is lack of elements in refined solution is supplemented, the total metal concentration of the solution is controlled to be 60-70g/L, sodium hydroxide solution and ammonia water are added, the pH value is 10.9, the concentration of the ammonia water is 2.1mol/L, and a nickel-cobalt-manganese hydroxide precursor Ni is synthesized at 70 DEG C0.5Co0.2Mn0.3(OH)2。
TABLE 7 concentrations of various solutions of metal ions
Comparative example 2
In the step (5), it is discussed that only saponified HBL110 is used without using a joint extractant, and specifically:
(1) crushing and grinding polymetallic nodules, weighing 100g of nodule ore, adding into 500mL of 3mol/L sulfuric acid solution, adding 10g of pyrite, leaching for 5h at 90 ℃, and then filtering, wherein the components of filtrate are shown in Table 2.
(2) Adjusting pH of the filtrate to 1.8 with lime, adding a small amount of hydrogen peroxide to oxidize iron, adding 50g/L sodium carbonate to adjust pH to 3.0, heating to 90 deg.C, and adjusting pH to 3.0 with Ti4+、Fe3+And SiO2Precipitate formed and was removed from the mixed solution.
(3) The copper ions in the solution are removed by using an extractant Lix984, the O/A concentration is controlled to be 1: 1, the concentration of the Lix984 is controlled to be 15%, sulfonated kerosene is used as a diluent, the pH value is 3.0, 2.0mol/L sulfuric acid is used for back-extracting an organic phase, the organic phase is compared with the O/A ratio of 20: 1, a copper sulfate solution is obtained by back-extraction, the copper sulfate solution is enriched, evaporated and concentrated to obtain copper sulfate pentahydrate crystals, and the analytical purity is 99.1%.
(4) Extracting by unsaponifiable 5% P204 (a diluent is sulfonated kerosene), wherein O/A is 1: 1, the balance pH value is 2.5, Ca, Fe and rare earth in the solution enter an organic phase, performing back extraction by using 2mol/L hydrochloric acid to remove Ca and Fe in the organic phase, performing back extraction by using 4mol/L sulfuric acid to obtain a yttrium sulfate solution, and performing enrichment, evaporative concentration and roasting to obtain yttrium oxide with the analytical purity of 98.0%.
(5) Extracting nickel, cobalt and a small part of manganese in a solution by adopting HBL110 (a diluent is sulfonated kerosene) saponified by NaOH, wherein the saponification degree of the HBL110 is 60%, the dosage of the HBL110 is 50%, the equilibrium pH value is 3.0, the O/A ratio is 1: 1, 6-grade countercurrent extraction is carried out, the extraction rate of nickel is 87.1%, the extraction rate of cobalt is 68.5%, the concentration of manganese is high, and only 2% of manganese enters an organic phase; and back-extracting the organic phase by using sulfuric acid to obtain refined solutions of cobalt sulfate, nickel sulfate and manganese sulfate. The composition of each solution is shown in Table 8.
(6) Concentrating and crystallizing raffinate after extracting nickel, cobalt and manganese to obtain a manganese sulfate monohydrate product, wherein the manganese sulfate contains a large amount of nickel sulfate and cobalt sulfate, and the purity of the manganese sulfate is 95%.
(7) According to the precursor Ni0.5Co0.2Mn0.3(OH)2The proportion of cobalt sulfate, nickel sulfate and manganese sulfate is required, sulfate which is lack of elements in refined solution is supplemented, the total metal concentration of the solution is controlled to be 60-70g/L, sodium hydroxide solution and ammonia water are added, the pH value is 10.9, the concentration of the ammonia water is 2.1mol/L, and a nickel-cobalt-manganese hydroxide precursor Ni is synthesized at 70 DEG C0.5Co0.2Mn0.3(OH)2。
TABLE 8 various solution Metal ion concentrations
Example 7
Discussing the extraction of rare earth by P204, the two steps of back extraction are sulfuric acid, which specifically comprises the following steps:
(1) crushing and grinding polymetallic nodules, weighing 100g of nodule ore, adding into 500mL of 3mol/L sulfuric acid solution, adding 10g of pyrite, leaching for 5h at 90 ℃, and then filtering, wherein the components of filtrate are shown in Table 2.
(2) Adjusting pH of the filtrate to 1.8 with lime, adding a small amount of hydrogen peroxide to oxidize iron, adding 50g/L sodium carbonate to adjust pH to 3.0, heating to 90 deg.C, and adjusting pH to 3.0 with Ti4+、Fe3+And SiO2Precipitate formed and was removed from the mixed solution.
(3) The copper ions in the solution are removed by using an extractant Lix984, the O/A concentration is controlled to be 1: 1, the concentration of the Lix984 is controlled to be 15%, sulfonated kerosene is used as a diluent, the pH value is 3.0, 2.0mol/L sulfuric acid is used for back-extracting an organic phase, the organic phase is compared with the O/A ratio of 20: 1, a copper sulfate solution is obtained by back-extraction, the copper sulfate solution is enriched, evaporated and concentrated to obtain copper sulfate pentahydrate crystals, and the analytical purity is 99.1%.
(4) Extracting by unsaponifiable 5% P204, wherein O/A is 1: 1, the balance pH value is 2.5, Ca, Fe and rare earth in the solution enter an organic phase, performing back extraction by adopting 2mol/L sulfuric acid to remove Ca and Fe in the organic phase, performing back extraction by adopting 4mol/L sulfuric acid to obtain an yttrium sulfate solution, and performing enrichment, evaporative concentration and roasting to obtain yttrium oxide, wherein the analytical purity is 96.0%.
(5) Adopting P204 and HBL110 which are saponified by NaOH to jointly extract nickel, cobalt and a small part of manganese in the solution, wherein the saponification degree of P204 is 70 percent, the saponification degree of HBL110 is 60 percent, the dosage of P204 is 3 percent, the dosage of HBL110 is 40 percent, the equilibrium pH value is 3.0, O/A is 1: 1, 6-grade countercurrent extraction is carried out, the extraction rate of nickel is 99.0 percent, the extraction rate of cobalt is 98.5 percent, the concentration of manganese is high, and only 12 percent of manganese enters an organic phase; and back-extracting the organic phase by using sulfuric acid to obtain refined solutions of cobalt sulfate, nickel sulfate and manganese sulfate. The composition of each solution is shown in Table 9.
(6) Concentrating and crystallizing raffinate after extracting nickel, cobalt and manganese to obtain a manganese sulfate monohydrate product. The detection proves that the purity of the product is more than 99%.
(7) According to the precursor Ni0.5Co0.2Mn0.3(OH)2The proportion of cobalt sulfate, nickel sulfate and manganese sulfate is required, sulfate which is lack of elements in refined solution is supplemented, the total metal concentration of the solution is controlled to be 60-70g/L, sodium hydroxide solution and ammonia water are added, the pH value is 10.9, the concentration of the ammonia water is 1.8mol/L, and a precursor Ni of nickel-cobalt-manganese hydroxide is synthesized at 65 DEG C0.5Co0.2Mn0.3(OH)2。
TABLE 9 concentrations of various solution Metal ions
In conclusion, by the technical route of the invention, the control of the process parameters is further controlled, and the NCM precursor with high crystal phase purity can be successfully prepared.
Claims (10)
1. A method for preparing a lithium battery anode material precursor from a seabed polymetallic nodule is characterized by comprising the following steps:
step (a): leaching:
crushing, grinding and leaching the seabed polymetallic nodule to obtain the product containing Fe2+、Mn2+、Co2+、Ni2+、Cu2+、Y3+The leachate of (2);
step (b): iron removal:
iron removal treatment is carried out on the leaching solution to obtain the solution containing Mn2+、Co2+、Ni2+、Cu2+、Y3+The iron-removed liquid is obtained;
step (c): and (3) recovering copper:
the liquid after iron removal is subjected to copper removal treatment to obtain Mn enriched2+、Co2+、Ni2+、Y3+The copper-removed solution;
step (d): recovery of rare earth ion Y3+：
Extracting the copper-removed solution to obtain Y3+Enriching into an extracted organic phase to obtain Mn-enriched2+、Co2+、Ni2+Removing impurity liquid;
a step (e): combined extraction of nickel, cobalt and manganese:
extracting the impurity-removed liquid obtained in the step (d) by adopting a combined extracting agent to obtain Co2+、Ni2+And part of Mn2+Enriching into an extracted organic phase to obtain Co2+、Ni2+、Mn2+Precursor solution of (2) and Mn-containing2+The raffinate of (a);
the combined extracting agent comprises a first extracting agent and a second extracting agent;
the first extractant is P204 and/or P507; the saponification degree of the first extracting agent is 60% -100%;
the second extractant is HBL 110; the saponification degree of the second extracting agent is 60-70%;
the mass ratio of the first extracting agent to the second extracting agent is 3-8: 30-50;
and carrying out coprecipitation on the precursor solution to obtain an NCM precursor.
2. The method of claim 1, wherein in step (a), the leaching process is sulfuric acid reduction leaching:
preferably, the ground minerals are leached under a system of sulfuric acid and a reducing agent;
preferably, the reducing agent is SO2Starch and/or pyrite.
3. The method of claim 1, wherein in step (b), the step of removing iron comprises:
firstly, regulating the pH value of the leaching solution to be 1.5-2.5; then adding hydrogen peroxide, regulating and controlling the pH value of the system to be 3.0-4.0, and precipitating iron in the system to obtain iron-removed liquid;
preferably, the pH value of the leachate is adjusted to 1.8-2.2 by lime, hydrogen peroxide is added to oxidize iron, then the pH value of the mixed solution is adjusted to 3.0-4.0 by sodium carbonate, so that iron forms a mixture of the jarosite and goethite, and the iron in the leachate is removed.
4. The method of claim 1, wherein in step (c), extraction is used to separate the Cu from the iron-depleted solution2 +；
Preferably, the extractant used for the extraction is at least one of lix984 and M5640.
5. The method of claim 1, wherein in step (d), the rare earth ions in the copper-removed solution are enriched in Y by extraction3+Collecting into an organic phase;
preferably, the extractant used for the extraction is unsaponifiable P204;
preferably, will be enriched with Y3+The organic phase is subjected to a first back extraction in 0.5-2.0mol/L acid liquor in advance, and then a second back extraction is performed in 4-6mol/L acid liquor to obtain the Y-enriched product3+The stripping solution of (4);
preferably, the acid of the first stripping is hydrochloric acid; the acid of the second back extraction is preferably sulfuric acid;
enriched with Y3+Evaporating and calcining the stripping solution to obtain yttrium oxide.
6. The method of claim 1,
the combined extracting agent is a mixed extracting agent of P204 and HBL 110;
wherein the saponification degree of P204 is 60-100%; the saponification degree of the HBL110 is 60-70%; it is further preferable that the degree of saponification of P204 is 70 to 80%;
the mass ratio of the P204 to the HBL110 is 3-7: 40-50; further preferably 3-4: 40-50.
7. The method of claim 1, wherein the combined extraction agent is diluted with a diluent before use; in the diluted combined extracting agent, the content of the first extracting agent is 3-8% (by weight).
8. The method of claim 1, wherein in step (e), the feed solution has an equilibrium pH of 2 to 5; preferably 3 to 4.
9. The method of claim 1, wherein the element ratios of Ni, Co and Mn in the precursor solution are controlled, and then alkali and ammonia water are added to obtain a nickel-cobalt-manganese hydroxide precursor through coprecipitation;
preferably, the total metal concentration in the coprecipitation starting solution is controlled to be 60 to 100 g/L; the concentration of the ammonia water is preferably 2-3 mol/L; the pH is preferably 10-12.
10. An NCM precursor prepared by the method of any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111304439A (en) * | 2020-03-31 | 2020-06-19 | 北京矿冶科技集团有限公司 | Method for recovering valuable metals from submarine manganese ore resources |
| CN113718116A (en) * | 2021-08-30 | 2021-11-30 | 安徽南都华铂新材料科技有限公司 | Method for extracting nickel, cobalt and manganese from acidic lithium-rich solution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775966A (en) * | 2005-12-15 | 2006-05-24 | 北京矿冶研究总院 | Deep sea polymetallic nodule autocatalytic reduction ammonia leaching method |
| CN106191477A (en) * | 2016-08-24 | 2016-12-07 | 北京矿冶研究总院 | Method for separating and recovering rare earth from seabed cobalt-manganese multi-metal oxidized ore |
| CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
| CN106904667A (en) * | 2017-04-01 | 2017-06-30 | 贵州大龙汇成新材料有限公司 | The method that purification nickel cobalt is reclaimed from manganese-containing waste |
| CN107591584A (en) * | 2017-09-21 | 2018-01-16 | 合肥国轩高科动力能源有限公司 | Recycling method of waste lithium ion battery anode powder |
| CN108456779A (en) * | 2017-02-18 | 2018-08-28 | 唐翔 | Electroplating sludge, leather-making mud, metal solid waste produce metal and metallic compound technique |
-
2018
- 2018-09-15 CN CN201811084156.7A patent/CN110911675B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775966A (en) * | 2005-12-15 | 2006-05-24 | 北京矿冶研究总院 | Deep sea polymetallic nodule autocatalytic reduction ammonia leaching method |
| CN106191477A (en) * | 2016-08-24 | 2016-12-07 | 北京矿冶研究总院 | Method for separating and recovering rare earth from seabed cobalt-manganese multi-metal oxidized ore |
| CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
| CN108456779A (en) * | 2017-02-18 | 2018-08-28 | 唐翔 | Electroplating sludge, leather-making mud, metal solid waste produce metal and metallic compound technique |
| CN106904667A (en) * | 2017-04-01 | 2017-06-30 | 贵州大龙汇成新材料有限公司 | The method that purification nickel cobalt is reclaimed from manganese-containing waste |
| CN107591584A (en) * | 2017-09-21 | 2018-01-16 | 合肥国轩高科动力能源有限公司 | Recycling method of waste lithium ion battery anode powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111304439A (en) * | 2020-03-31 | 2020-06-19 | 北京矿冶科技集团有限公司 | Method for recovering valuable metals from submarine manganese ore resources |
| CN113718116A (en) * | 2021-08-30 | 2021-11-30 | 安徽南都华铂新材料科技有限公司 | Method for extracting nickel, cobalt and manganese from acidic lithium-rich solution |
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