CN113957247A - Method for recovering valuable metals from electrode waste - Google Patents
Method for recovering valuable metals from electrode waste Download PDFInfo
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- CN113957247A CN113957247A CN202010697789.6A CN202010697789A CN113957247A CN 113957247 A CN113957247 A CN 113957247A CN 202010697789 A CN202010697789 A CN 202010697789A CN 113957247 A CN113957247 A CN 113957247A
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- China
- Prior art keywords
- nickel
- cobalt
- lithium
- waste
- tungsten
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- 239000002699 waste material Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 150000002739 metals Chemical class 0.000 title abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 37
- 239000010937 tungsten Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 31
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 29
- 230000001603 reducing effect Effects 0.000 claims description 25
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 23
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- RDKNJNIWWVJMIK-UHFFFAOYSA-N [Ni].[Co].[Mn].[W] Chemical compound [Ni].[Co].[Mn].[W] RDKNJNIWWVJMIK-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 11
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 10
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 10
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 10
- 235000010265 sodium sulphite Nutrition 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- -1 lithium tungstate modified lithium nickel-cobalt oxide Chemical class 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- WPXWANCYVRRWEX-UHFFFAOYSA-L manganese(2+);dinitrite Chemical compound [Mn+2].[O-]N=O.[O-]N=O WPXWANCYVRRWEX-UHFFFAOYSA-L 0.000 claims description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000003916 acid precipitation Methods 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 244000025254 Cannabis sativa Species 0.000 claims 1
- HBEROZPRCVLLBF-UHFFFAOYSA-N [Li].[W].[Co].[Ni] Chemical compound [Li].[W].[Co].[Ni] HBEROZPRCVLLBF-UHFFFAOYSA-N 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 description 21
- 239000012266 salt solution Substances 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 13
- 239000002893 slag Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 150000003657 tungsten Chemical class 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical group [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- MRSPBKIUPJRMPO-UHFFFAOYSA-N [W]=O.[Ni].[Co] Chemical compound [W]=O.[Ni].[Co] MRSPBKIUPJRMPO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- UMBKDMHSHCGADO-UHFFFAOYSA-N [W]=O.[Co].[Ni].[Li] Chemical compound [W]=O.[Co].[Ni].[Li] UMBKDMHSHCGADO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering valuable metals from electrode waste containing nickel, cobalt, tungsten, oxygen and lithium. The method comprises the following steps: mixing the electrode waste with a reducing agent, and carrying out thermal grinding or calcination treatment under the condition of flowing atmosphere to obtain a mixture; soaking the obtained mixture in water, and separating to obtain a lithium-containing solution and primary filter residue; and (3) carrying out alkaline leaching on the obtained primary filter residue, and separating to obtain a tungsten-containing solution and secondary filter residue. The method solves the problem that valuable metals in the waste tungsten-containing waste lithium ion batteries cannot be effectively recovered in the prior art.
Description
Technical Field
The invention relates to the technical field of electrode waste recovery, and relates to a method for recovering valuable metals from electrode waste.
Background
Lithium ion batteries have many excellent properties and are widely used in mobile devices such as mobile phones and notebook computers. However, in order to further improve the conductivity and stability of the lithium ion battery, the lithium ion battery is modified by high-valence metal ions, wherein the reversible capacity, the rate capability and the stability of the lithium ion battery modified by the lithium tungstate and the tungsten oxide are all better improved. According to preliminary statistics, the yield of the lithium ion batteries is increased from 10 hundred million in 2010 to 157 hundred million in 2019, and with the scrapping and stacking of a large number of lithium ion batteries, not only is valuable metals wasted, but also a large amount of land resources are occupied, and environmental pollution is caused under natural conditions for a long time.
At present, the existing recovery direction of waste lithium ion batteries mainly has the following aspects, firstly, reduction acid leaching is adopted, corresponding salt solution is obtained by extraction and back extraction of leachate, and crystal salt such as sulfate, chloride and the like is obtained by flash evaporation of the salt solution; secondly, leaching solution of the leaching solution is subjected to an extraction-back extraction process, and the solution after impurity removal is diluted to a certain concentration and then corresponding precipitate is prepared; thirdly, preparing the metal simple substance by adopting an electrodeposition mode after the leaching solution is extracted and back extracted. Although the method can solve the problem of stockpiling of the waste lithium ion batteries to a certain extent, the related process flow is complex, the production cost is high, and the waste lithium ion batteries are difficult to recover with high value.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a method for recovering valuable metals from electrode scraps. Solves the problem that the method in the prior art can not effectively recover valuable metals in the waste materials of the tungsten-containing waste lithium ion batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of recovering valuable metals from electrode scrap, the method comprising the steps of:
mixing the electrode waste with a reducing agent, and carrying out thermal grinding or calcination treatment under an atmosphere condition to obtain a mixture; soaking the mixture in water, separating to obtain lithium-containing solution and primary filter residue, and
and (3) carrying out alkaline leaching on the primary filter residue, and separating to obtain a tungsten-containing solution and secondary filter residue.
The kind of the electrode waste is not limited in the present invention, and may be, for example, an electrode waste containing nickel, cobalt, tungsten, oxygen and lithium, such as at least one of a lithium nickel cobalt tungstate ternary waste, a tungsten-doped lithium nickel cobalt manganese oxide ternary waste, and a lithium tungstate-coated lithium nickel cobalt manganese oxide.
Preferably, the reducing agent includes at least one of a reducing gas, carbon, and a reducing metal salt.
Preferably, the reducing gas is at least one of hydrogen, carbon monoxide and methane.
Preferably, the carbon is at least one of activated carbon and coke.
Preferably, the cation element in the reducing metal salt comprises at least one of nickel, cobalt and manganese, and the anion comprises S2-At least one of oxalate and nitrite.
Preferably, the reducing metal salt is a manganese salt.
Preferably, the manganese salt is at least one of manganese sulfide, manganese oxalate and manganese nitrite.
Preferably, the molar ratio of the electrode waste to the reducing agent is 2-8: 1.
Preferably, the atmospheric conditions are flowing atmospheric conditions.
Preferably, the gas of the flowing atmosphere is at least one of inert gas, nitrogen gas, hydrogen gas, air and nitrogen-oxygen mixed gas, and the volume percentage of oxygen in the nitrogen-oxygen mixed gas is less than 5%.
Preferably, the rotation speed of the thermal grinding treatment is 200rpm to 1000rpm, and the temperature is 30 ℃ to 100 ℃.
Preferably, the temperature of the calcination treatment is 200-600 ℃, and the time is 10-60 min.
Preferably, the liquid-solid ratio in the water leaching process is 3-10: 1L/kg, and the temperature is 20-50 ℃.
Preferably, the leaching agent used in the alkaline leaching includes at least one of sodium carbonate, sodium bicarbonate and sodium hydroxide.
Preferably, the method further comprises the step of carrying out reduction acid leaching on the secondary filter residue.
Preferably, the leaching agent adopted in the reduction acid leaching comprises acid and a reduction component, the acid comprises at least one of sulfuric acid, hydrochloric acid and phosphoric acid, and the reduction component comprises at least one of hydrogen peroxide, sodium metabisulfite, sodium sulfite, oxalic acid and oxalate.
Preferably, the acid concentration is 1.5mol/L to 2 mol/L.
Preferably, the mass content of the reducing component is 8-15%.
Preferably, the method further comprises the step of adjusting the pH of the tungsten-containing solution to 1-3, and blowing oxygen or air to prepare tungstic acid precipitate.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
mixing the nickel cobalt lithium tungstate waste and manganese salt with reducibility according to the molar ratio of 2-8: 1, and carrying out thermal grinding or calcination treatment under the condition of flowing atmosphere to obtain a mixture; the nickel cobalt lithium tungstate waste material is as follows: lithium nickel cobalt tungstate obtained by modifying lithium nickel cobalt tungstate with tungsten oxide and lithium tungstate and/or lithium nickel cobalt tungsten hydroxide and lithium hydroxide are sintered to prepare lithium nickel cobalt tungstate waste;
soaking the mixture in water, and performing solid-liquid separation to obtain a lithium-containing solution and nickel-cobalt-manganese-tungsten filter residues; heating the nickel-cobalt-manganese-tungsten filter residue for alkaline leaching to obtain a tungstate solution, and filtering to obtain nickel-cobalt-manganese-containing filter residue and the tungstate solution;
carrying out reduction acid leaching on the filter residue containing nickel, cobalt and manganese to obtain a nickel, cobalt and manganese mixed solution; and
adjusting the pH value of the tungstate solution to 1-3, and blowing oxygen or air to obtain tungstic acid precipitate.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other. Without departing from the principles of embodiments of the present invention, several modifications and refinements may be made, and these are considered to be within the scope of the embodiments of the present invention.
The embodiment of the invention provides a method for recovering valuable metals from electrode waste containing nickel, cobalt, tungsten, oxygen and lithium, and aims to solve the problem that the valuable metals in the waste lithium ion battery waste containing tungsten cannot be effectively recovered by the method in the prior art.
The embodiment of the invention provides a method for recovering valuable metals from electrode waste containing nickel, cobalt, tungsten, oxygen and lithium, which comprises the following steps:
mixing the electrode waste with a reducing agent, and carrying out thermal grinding or calcination treatment under an atmosphere condition to obtain a mixture;
soaking the obtained mixture in water, separating to obtain lithium-containing solution and primary filter residue, and
and (3) carrying out alkaline leaching on the primary filter residue, and separating to obtain a tungsten-containing solution and secondary filter residue.
According to the method provided by the embodiment of the invention, the electrode waste is mixed with the reducing agent, and is subjected to thermal grinding or calcination treatment under the atmosphere condition, so that the metallic bond between tungsten and lithium is broken, and the bond between part of tungsten and oxygen is broken. The elements in the mixture obtained except lithium are present in the form of oxides, simple substances or hydroxides, while the lithium element is present in the form of lithium oxide. Through the step of soaking the mixture in water, lithium is transferred into the solution, a lithium-containing solution and primary filter residue are obtained through separation, the primary filter residue contains tungsten, and if the electrode waste contains metal elements such as nickel, cobalt and the like, the elements are remained in the primary filter residue.
According to the method provided by the embodiment of the invention, the reducing agent is utilized to carry out hot grinding or calcination treatment under the atmosphere condition, so that tungsten and lithium are separated, and if other common metal elements (such as nickel, cobalt and the like) of the electrode waste are contained, the separation of tungsten, lithium and other elements can be realized, and a tungsten product, a lithium product and other metal element products are obtained.
In the embodiment of the invention, the thermal grinding mode is preferably adopted to realize the key breaking effect, because the thermal grinding can effectively act on the materials in all directions, the particle size is effectively reduced, the contact between the reducing agent and the waste is facilitated, and the subsequent element separation effect is improved.
In the embodiment of the present invention, the step of mixing the electrode scrap with the reducing agent and the step of the thermal grinding or calcination treatment under the flowing atmosphere may be performed in two steps or may be performed in one step. For example, the hot milling or calcination can be carried out in the presence of hydrogen, i.e., in one step.
In an embodiment of the present invention, the nickel, cobalt, tungsten, oxygen and lithium containing electrode scrap includes: at least one of the ternary waste of nickel cobalt lithium tungstate, the ternary waste of tungsten-doped nickel cobalt lithium manganate, and lithium tungstate coated nickel cobalt lithium manganate.
In an embodiment of the present invention, the reducing agent includes at least one of a reducing gas, carbon, and a reducing metal salt. The reducing gas is at least one of hydrogen, carbon monoxide and methane, and the carbon is at least one of activated carbon and coke. Preferably, a reducing metal salt is used as the reducing agent.
In an embodiment of the present invention, the cation element in the reducing metal salt includes at least one of nickel, cobalt, and manganese, and the anion includes S2-At least one of oxalate and nitrite.
When reducing metal salt is used as a reducing agent, cations in the metal salt are transferred into primary filter residue after water leaching, preferably, main metal elements in the electrode waste are nickel, cobalt, tungsten and lithium, or the main metal elements in the electrode waste are nickel, cobalt, aluminum, tungsten and lithium, the metal elements in the electrode waste generally exist in the form of lithium nickelate, lithium cobaltate, lithium aluminate, lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate, the electrode waste is treated according to the method disclosed by the invention, and the obtained filter residue is converted into filtrate which can be directly used for preparing the electrode material, so that the application prospect is good. It should be noted that the cation is generally not selected as a doping element of the inactive component (e.g., iron, copper, etc.), because these elements can act as impurities, for example, the presence of iron can easily cause self-discharge of the prepared battery material, resulting in short circuit.
Taking the example that the metal elements in the electrode waste are nickel, cobalt, aluminum, tungsten and lithium, for the electrode waste, if manganese salt with reducibility is used as a reducing agent, filter residue is converted into filtrate, and if the filtrate is not subjected to impurity removal, the electrode waste is directly used for preparing the electrode material, and is the quaternary material NCMA.
In the embodiment of the present invention, the reducing metal salt is preferably a manganese salt, and more preferably at least one of manganese sulfide, manganese oxalate, and manganese nitrite. The method is described by taking manganese salt with reducibility as an example for treating the nickel-cobalt-lithium tungstate ternary waste, the manganese salt with reducibility is adopted to extract mixed elements of lithium, tungsten and nickel-cobalt-manganese from the waste, the lithium and tungsten are continuously treated subsequently, the purpose of recycling can be achieved, the nickel-cobalt-manganese element in the filter residue can be used for preparing a ternary precursor, for example, sulfuric acid is adopted to carry out reduction acid leaching to obtain nickel-cobalt-manganese mixed sulfate, the purpose of preparing the ternary precursor at low cost can be achieved, or the method can be used for preparing other compounds.
In an embodiment of the present invention, the molar ratio of the electrode scrap to the reducing agent is 2 to 8:1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 6.5:1, 7:1, or 8: 1.
In an embodiment of the invention, the atmospheric conditions are flowing atmospheric conditions; the flowing atmosphere can carry away the product, reduce the concentration of the product and promote the reaction to proceed toward a low concentration direction.
In the embodiment of the invention, the atmosphere gas is at least one of inert gas, nitrogen, hydrogen, air and a nitrogen-oxygen mixture, and the volume percentage of oxygen in the nitrogen-oxygen mixture is less than 5%.
In an embodiment of the present invention, the rotation speed of the thermal polishing treatment is 200rpm to 1000rpm, for example, 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 750rpm, 850rpm, 950rpm, or the like; the temperature is 30 ℃ to 100 ℃, for example, 30 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
In the embodiment of the present invention, the temperature of the calcination treatment is 200 to 600 ℃, for example, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 550 ℃, or 600 ℃; the time is 10 min-60 min, such as 10min, 20min, 30min, 45min, 50min or 60 min.
In the embodiment of the invention, the liquid-solid ratio in the water leaching process is 3L/kg to 10:1L/kg, such as 3: 1L/kg, 4.5:1L/kg, 5:1L/kg, 7:1L/kg, 8:1L/kg or 10: 1L/kg; the temperature is 20 ℃ to 50 ℃, for example 20 ℃, 25 ℃, 30 ℃, 40 ℃ or 50 ℃ and the like.
In an embodiment of the present invention, the leaching agent used in the alkaline leaching includes at least one of sodium carbonate, sodium bicarbonate, and sodium hydroxide.
In a preferred embodiment of the present invention, the method further comprises the step of performing reduction acid leaching on the secondary filter residue. The electrode waste containing nickel, cobalt, tungsten, oxygen and lithium generally also contains nickel element, and may also contain active elements such as cobalt or manganese, and these elements can be present in the secondary filter residue, and the example is given by taking nickel, cobalt and manganese in the secondary filter residue as an example.
In the embodiment of the invention, an impregnation system adopted by the reduction acid leaching comprises acid and a reduction component, wherein the acid comprises at least one of sulfuric acid, hydrochloric acid and phosphoric acid, and the reduction component comprises at least one of hydrogen peroxide, sodium metabisulfite, sodium sulfite, oxalic acid and oxalate.
In an embodiment of the present invention, the acid concentration is 1.5mol/L to 2mol/L, for example, 1.5mol/L, 1.7mol/L, 1.8mol/L, or 2 mol/L.
In an embodiment of the present invention, the mass content of the reducing component is 8% to 15%, for example, 8%, 9%, 10%, 11%, 12%, 12.5%, 13%, 14%, 15%, or the like.
In still another preferred embodiment of the present invention, the method further comprises the step of adjusting the pH of the tungsten-containing solution to 1 to 3(pH, e.g., 1, 1.5, 2, or 3, etc.), and bubbling oxygen or air to prepare tungstic acid precipitate. Tungsten-containing solutions (e.g., sodium tungstate solutions) are highly prone to tungstic acid precipitation at pH below 3, while oxygen or air is bubbled to promote oxidation of lower tungsten salts to higher tungstates, which in turn are more prone to tungstic acid precipitation at pH below 3.
The waste nickel cobalt lithium tungstate powder used in embodiments 1 to 7 of the present invention is: the mixture of the nickel cobalt tungsten oxide obtained by modifying the lithium nickel cobalt oxide with the tungsten oxide or the lithium tungstate and the mixture of one or two of the nickel cobalt tungsten oxide and the lithium nickel cobalt tungsten oxide waste prepared by sintering the nickel cobalt tungsten hydroxide and the lithium hydroxide have any mixing proportion.
Example 1:
(1) mixing waste nickel cobalt lithium tungstate powder and manganese sulfide according to a molar ratio of 6:1 to obtain a mixture, putting the mixture into a sintering furnace, introducing nitrogen for sintering, calcining at 500 ℃ for 2 hours, and cooling along with the furnace.
(2) And (3) soaking the cooled waste in water according to the liquid-solid ratio of 3:1 at the water soaking temperature of 20 ℃, and filtering to obtain a lithium-containing solution and nickel-cobalt-manganese-tungsten filter residues.
(3) Leaching the nickel-cobalt-manganese-tungsten filter residue by using a 12mol/L sodium hydroxide solution at the temperature of 80 ℃ to obtain a tungsten-containing salt solution and nickel-cobalt-manganese slag.
Oxygen is introduced into the solution containing tungsten salt at a rate of 100ml/min, and the solution is adjusted to 1-3 with sulfuric acid until no yellow precipitate is formed.
Carrying out reduction acid leaching on the nickel-cobalt-manganese slag and the filter residue in the step (2) by adopting a sulfuric acid and hydrogen peroxide system according to a liquid-solid ratio of 10:1, wherein in the sulfuric acid and hydrogen peroxide system, the concentration of sulfuric acid is 2.0mol/L, and H is2O2The mass content of the nickel-cobalt-manganese mixed sulfate is 8 percent, and the mixed salt solution can be used for preparing ternary precursors, sulfates and other compounds.
Example 2:
(1) mixing waste nickel cobalt lithium tungstate powder and manganese sulfide according to a molar ratio of 3:1 to obtain a mixture, putting the mixture into a sintering furnace, introducing air for sintering, calcining at 600 ℃ for 2 hours, and cooling along with the furnace.
(2) And (3) soaking the cooled waste in water according to the liquid-solid ratio of 5:1 at the water soaking temperature of 50 ℃, and filtering to obtain a lithium-containing solution and nickel-cobalt-manganese-tungsten filter residues.
(3) Leaching the nickel-cobalt-manganese-tungsten filter residue by using 0.5mol/L sodium carbonate solution at the temperature of 100 ℃ to obtain a tungsten-containing salt solution and nickel-cobalt-manganese slag.
Oxygen is introduced into the solution containing tungsten salt at a rate of 100ml/min, and the solution is adjusted to 1-3 with sulfuric acid until no yellow precipitate is formed.
And (3) carrying out reduction acid leaching on the nickel-cobalt-manganese slag and the filter residue in the step (2) by adopting a sulfuric acid and sodium metabisulfite system according to a liquid-solid ratio of 10:1, wherein in the sulfuric acid and sodium metabisulfite system, the concentration of sulfuric acid is 1.5mol/L, and the mass content of sodium metabisulfite is 15%, so as to obtain a nickel-cobalt-manganese mixed sulfate, and the mixed salt solution can be used for preparing a ternary precursor, sulfate and other compounds.
Example 3:
(1) weighing waste nickel cobalt tungsten acid lithium powder and manganese oxalate according to a molar ratio of 2:1, putting the mixture into a grinder, introducing air, grinding at 800rpm, calcining at 90 ℃ for 2 hours, and cooling along with a furnace.
(2) And (3) soaking the cooled waste in water according to the liquid-solid ratio of 6:1 at the water soaking temperature of 35 ℃, and filtering to obtain a lithium-containing solution and nickel-cobalt-manganese-tungsten filter residues.
(3) Leaching the nickel-cobalt-manganese-tungsten filter residue by using 0.5mol/L sodium carbonate solution at the temperature of 100 ℃ to obtain a tungsten-containing salt solution and nickel-cobalt-manganese slag.
Air is introduced into the solution containing tungsten salt at a rate of 200ml/min, and the solution is adjusted to 1-3 by nitric acid until no yellow precipitate is formed in the reaction.
And (3) carrying out reduction acid leaching on the nickel-cobalt-manganese slag and the filter residue in the step (2) by adopting a sulfuric acid and sodium metabisulfite system according to a liquid-solid ratio of 10:1, wherein in the sulfuric acid and sodium metabisulfite system, the concentration of sulfuric acid is 1.5mol/L, the mass content of the sodium metabisulfite is 15%, so as to obtain a nickel-cobalt-manganese mixed sulfate, and the mixed salt solution can be used for preparing a ternary precursor, sulfate and other compounds.
Example 4:
the procedure and conditions were the same as in example 1 except that the calcination temperature in step (1) was adjusted to 300 ℃.
Example 5:
the method and conditions were the same as in example 2 except that the calcination atmosphere in step (1) was changed to nitrogen.
Example 6:
(1) calcining waste nickel cobalt lithium tungstate powder at the hydrogen flow rate of 1000ml/min at the temperature of 400 ℃ for 1.5h, and cooling along with the furnace.
(2) And (3) soaking the cooled waste in water according to the liquid-solid ratio of 8:1 at the water soaking temperature of 25 ℃, and filtering to obtain a lithium-containing solution and nickel-cobalt-tungsten filter residues.
(3) And leaching the nickel-cobalt-tungsten filter residue by using sodium carbonate at the temperature of 90 ℃ to obtain a tungsten-containing salt solution and nickel-cobalt residue.
Air was introduced into the tungsten salt solution at 160ml/min while adjusting the solution to 2 with nitric acid until no yellow precipitate was formed.
And (3) carrying out reduction acid leaching on the nickel-cobalt slag and the filter residue in the step (2) by adopting a sulfuric acid and sodium sulfite system according to a liquid-solid ratio of 10:1, wherein in the sulfuric acid and sodium sulfite system, the concentration of sulfuric acid is 1.5mol/L, the mass content of sodium sulfite is 15%, so as to obtain nickel-cobalt mixed sulfate, and the mixed salt solution can be used for preparing a ternary precursor, sulfate and other compounds.
Example 7:
(1) mixing waste nickel cobalt lithium tungstate powder and activated carbon according to a molar ratio of 2:1 to obtain a mixture, carrying out hot grinding on the mixture at a rotation speed of 500rpm and a temperature of 85 ℃ for 3 hours, and cooling.
(2) And (3) soaking the cooled waste in water according to the liquid-solid ratio of 10:1 at the water soaking temperature of 30 ℃, and filtering to obtain a lithium-containing solution and nickel-cobalt-tungsten filter residues.
(3) And leaching the nickel-cobalt-tungsten filter residue by using sodium carbonate at the temperature of 110 ℃ to obtain a tungsten-containing salt solution and nickel-cobalt residue.
Air was introduced into the tungsten salt solution at 210ml/min while adjusting the solution to 2.5 with nitric acid until no yellow precipitate was formed.
And (3) carrying out reduction acid leaching on the nickel-cobalt slag and the filter residue in the step (2) by adopting a sulfuric acid and sodium sulfite system according to a liquid-solid ratio of 10:1, wherein in the sulfuric acid and sodium sulfite system, the concentration of sulfuric acid is 1.5mol/L, the mass content of sodium sulfite is 15%, so as to obtain nickel-cobalt mixed sulfate, and the mixed salt solution can be used for preparing a ternary precursor, sulfate and other compounds.
Example 8:
(1) mixing lithium tungstate: mixing waste powder prepared by doping nickel cobalt lithium manganate with the molar ratio of 8:92 with manganese oxalate with the molar ratio of 1.5:1 to obtain a mixture, carrying out hot grinding on the mixture at the rotation speed of 950rpm and the temperature of 90 ℃ for 3 hours, and cooling.
(2) And (3) soaking the cooled waste in water according to the liquid-solid ratio of 10:1 at the water soaking temperature of 30 ℃, and filtering to obtain a lithium-containing solution and nickel-cobalt-manganese-tungsten filter residues.
(3) Leaching the nickel-cobalt-manganese-tungsten filter residue by using a 12mol/L sodium hydroxide solution at the temperature of 110 ℃ to obtain a tungsten-containing salt solution and nickel-cobalt-manganese slag.
Air was introduced into the tungsten salt solution at 210ml/min while adjusting the solution to 2.5 with sulfuric acid until no yellow precipitate was formed.
The nickel-cobalt-manganese slag is subjected to reduction acid leaching by adopting a system of sulfuric acid and hydrogen peroxide according to a liquid-solid ratio of 8:1, wherein in the system of sulfuric acid and hydrogen peroxide, the concentration of sulfuric acid is 2.0mol/L, and H is2O2The mass content of the nickel-cobalt-manganese mixed sulfate is 8 percent, and the mixed salt solution can be used for preparing ternary precursors, sulfates and other compounds.
Example 9:
(1) mixing waste powder prepared by doping nickel cobalt lithium manganate and tungsten oxide with the molar ratio of 90:10 with manganese nitrite according to the molar ratio of 6:1 to obtain a mixture, carrying out hot grinding on the mixture at the rotation speed of 900rpm and the temperature of 95 ℃ for 3 hours, and cooling.
(2) And (3) soaking the cooled waste in water according to the liquid-solid ratio of 10:1 at the water soaking temperature of 30 ℃, and filtering to obtain a lithium-containing solution and nickel-cobalt-manganese-tungsten filter residues.
(3) Leaching the nickel-cobalt-manganese-tungsten filter residue by using a 12mol/L sodium hydroxide solution at the temperature of 110 ℃ to obtain a tungsten-containing salt solution and nickel-cobalt-manganese slag.
Air was introduced into the tungsten salt solution at 210ml/min while adjusting the solution to 2.5 with sulfuric acid until no yellow precipitate was formed.
The nickel-cobalt-manganese slag is subjected to reduction acid leaching by adopting a system of sulfuric acid and hydrogen peroxide according to a liquid-solid ratio of 7:1, wherein in the system of sulfuric acid and hydrogen peroxide, the concentration of sulfuric acid is 2.0mol/L, and H is2O2The mass content of the nickel-cobalt-manganese mixed sulfate is 8 percent, and the mixed salt solution can be used for preparing ternary precursors, sulfates and other compounds.
Example 10:
the preparation method and conditions were the same as in example 1 except that manganese sulfide was replaced with manganese oxalate.
Comparative example 1:
the procedure and conditions were the same as in example 1 except that manganese sulfide was not added.
Comparative example 2:
the method and conditions were the same as in example 1 except that the air atmosphere in example 2 was replaced with an oxygen atmosphere.
TABLE 1
Note: the Li leaching rate is the leaching rate in the water leaching process, and the subsequent acid leaching rate is not included. The leaching rate of W is the alkaline leaching rate, and the leaching rates of Ni and Co are the leaching rates in the reduction acid leaching process.
As can be seen from the above table, the leaching rates of Ni and Co are mainly affected by the acid concentration and the types and amounts of three reducing agents, i.e., hydrogen peroxide, sodium metabisulfite and sodium sulfite, and then the reaction degree of the waste nickel-cobalt lithium tungstate with additives, i.e., manganese sulfide, manganese nitrite, hydrogen gas, activated carbon, and the like. The leaching rate of tungsten is mainly influenced by factors such as temperature, concentration of a leaching agent, reduction degree and the like.
The main reason why the leaching rate of lithium in example 1 is higher than that in example 10 is that the dosage of the waste nickel cobalt lithium tungstate and the manganese sulfide reaches the corresponding molar ratio, the valence of the sulfur element is increased from-2 to +6 when the manganese sulfide exerts the reduction effect, and the dosage of the reducing agent is sufficient; when manganese oxalate exerts its reducing action, carbon element is increased from +3 to +4, and the amount of the reducing agent is insufficient in the molar ratio in example 1, and manganese oxalate is easily decomposed.
In contrast, comparative example 1, which lacks a reducing agent, makes it difficult to reduce the lithium nickel cobalt tungstate, and thus the leaching of lithium is difficult.
In comparative example 2, oxygen was used to oxidize part of the sulfur in manganese sulfide to form sulfur dioxide or manganese sulfate, and part of the sulfur had not reacted with lithium nickel cobalt tungstate. So that the reaction of the lithium nickel cobalt tungstate is insufficient, and the leaching rate of elements is relatively low.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
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