CN115584393A - Method for selectively recovering lithium from waste lithium batteries and simultaneously preparing cobalt ferrite catalyst - Google Patents
Method for selectively recovering lithium from waste lithium batteries and simultaneously preparing cobalt ferrite catalyst Download PDFInfo
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- CN115584393A CN115584393A CN202211094584.4A CN202211094584A CN115584393A CN 115584393 A CN115584393 A CN 115584393A CN 202211094584 A CN202211094584 A CN 202211094584A CN 115584393 A CN115584393 A CN 115584393A
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- lithium
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- cobalt ferrite
- leaching
- copperas
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 239000010941 cobalt Substances 0.000 title claims abstract description 23
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 35
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 32
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 14
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 7
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 239000012265 solid product Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- -1 iron ions Chemical class 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910052772 Samarium Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 229910003321 CoFe Inorganic materials 0.000 abstract 1
- 238000003763 carbonization Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000002910 solid waste Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 6
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Images
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
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- 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
- 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
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for selectively recovering lithium from a waste lithium battery and preparing a cobalt ferrite catalyst, which comprises the following steps: (1) Discharging, disassembling and classifying the waste lithium cobaltate battery to obtain a positive electrode material, and then performing high-temperature treatment to remove the adhesive; (2) Drying and screening lithium cobaltate positive electrode powder, uniformly mixing the lithium cobaltate positive electrode powder with copperas according to a certain mass ratio, and roasting for a certain time at a certain temperature; (3) Leaching the roasted product obtained in the first step by using deionized water to obtain a lithium sulfate leaching solution and a solution rich in CoFe 2 O 4 Leaching residue of (2); (3) Adding ammonia water into the leachate obtained in the second step to adjust the pH value, and filtering iron impurities; (4) Adding an ammonium carbonate solution into the filtrate obtained in the third step for carbonization, and filtering and drying the precipitate to obtain lithium carbonate; (5) Loading activity to the leaching residue obtained in the third stepAnd modifying the substance to obtain the SCR catalyst. The mixed roasting leaching process of the waste lithium cobaltate batteries and the copperas is adopted, the operation is simple, the production cost is low, the separation is easy, the waste lithium cobaltate batteries and the copperas are recycled, and the method has the characteristics of remarkable economic benefit and environmental friendliness.
Description
Technical Field
The invention belongs to the field of solid waste resource utilization, and mainly relates to a method for selectively recovering lithium and simultaneously preparing a cobalt ferrite catalyst by using waste lithium batteries.
Background
Since the industrial revolution, the burning of fossil mass fuels has promoted the development of global industrialization, but has posed serious energy and environmental problems. The new energy technology can be applied to the environmental problems and the energy shortage of the world, and has attracted extensive attention. As one of the most important new energy carriers, lithium ion batteries have been widely used in mobile electronic devices and electric vehicles due to their high energy density, good cycle performance, and low memory effect. However, the long-term charge and discharge processes of lithium ion batteries result in short cycle life, producing a large amount of spent lithium ion batteries each year. It is estimated that by 2030, the number of global spent lithium ion batteries is expected to reach 193 ten thousand tons and the global lithium ion battery recycling market is expected to reach 2000 yen. The waste lithium cobalt oxide battery is used as the earliest used anode material and accounts for more than 20 percent of the waste lithium batteries in the world. However, waste lithium ion batteries are classified as hazardous waste because toxic materials such as cobalt, nickel and organic solvents will result in heavy metal contamination, spontaneous combustion and explosion hazards. Meanwhile, the waste lithium ion battery is an important secondary resource, and contains more valuable elements than natural resources such as minerals and brine. Therefore, the method for recovering valuable metals from the waste lithium ion batteries can effectively solve the problems of environmental pollution and resource shortage.
Researchers have conducted extensive research aiming at resource utilization of valuable elements in waste lithium cobaltate batteries. CN106868317A is a method for precipitating Fe by mixing a cobalt acid lithium battery anode material with ferrous sulfate, placing the mixture in a reactor, adding inorganic acid solution into slurry after adding water and mixing the slurry, reacting, adding inorganic base to neutralize residual acid, adjusting the pH value of the slurry and precipitating Fe 3+ And completing liquid-solid separation, wherein solid slag is a mixture of carbon powder and ferric hydroxide, and the leaching solution is a high-concentration cobalt and lithium solution. CN113481368A is a method for reacting waste lithium cobaltate battery powder with a high-concentration first sodium hydroxide solution, performing solid-liquid separation to obtain a first filter residue and a first filtrate, and then performing first filtration on the first filter residue and the first filtrateAnd reacting the filter residue with a low-concentration second sodium hydroxide solution, and then carrying out solid-liquid separation to obtain a second filter residue and a second filtrate, wherein the first filtrate and the second filtrate are jointly used as a first leaching solution containing aluminum, the second filter residue is used as a first leaching residue, the first leaching residue is reacted with phosphoric acid, and the solid-liquid separation is carried out to obtain a second leaching residue and a second leaching solution containing lithium. And reacting the second leaching residue with a mixed solution of sulfuric acid and ascorbic acid, and performing solid-liquid separation to obtain a third leaching residue and a third leaching solution containing cobalt. The consumption of alkali for removing aluminum is reduced by adopting high and low alkali, and lithium cobaltate is prevented from being leached in the process of leaching aluminum, so that higher recovery rate of cobalt and lithium is obtained. In patent CN114317977a, polyvinyl chloride and waste lithium cobaltate are pyrolyzed in a circulating inert gas atmosphere to obtain a co-pyrolysis product containing lithium and cobalt; and then, leaching the co-pyrolysis product by using water, and filtering to obtain a leaching solution and a leaching product, wherein the leaching solution is a lithium salt-containing leaching solution, and the leaching product is a cobalt-containing leaching product. Patent CN113943867a is to put the positive electrode active material into vitamin C and dilute nitric acid to react to obtain a mixed solution, and then filter the mixed solution after reaction to obtain a leaching solution containing valuable metal ions and a residue. However, the above method has problems of expensive reducing agent or acid-base solution and complicated process, and limits the recycling of the waste lithium cobalt oxide battery to a certain extent. Therefore, it is necessary to find cheaper raw materials or simpler operation process to meet the resource utilization of the waste lithium cobalt oxide battery.
The copperas are solid wastes discharged in the process of producing titanium dioxide by a sulfuric acid method. For every ton of titanium dioxide produced, about 3.5 tons of copperas are produced. The titanium dioxide yield in 2021 years in china is about 426 ten thousand tons, of which 91% is produced by sulfuric acid process, producing nearly 1200 ten thousand tons of copperas. At present, the main purpose of copperas is to produce sulfuric acid by thermal decomposition, but the process needs a large amount of energy consumption and has higher production cost than the existing sulfur-based acid production. With the rapid development of the titanium dioxide industry, the problem of resource utilization of copperas needs to be solved urgently.
Based on the above, the invention utilizes the solid waste copperas of titanium dioxide as an auxiliary agent, mixes and roasts the solid waste copperas with the anode material of the waste lithium cobaltate battery, selectively extracts and separates lithium elements of the lithium cobaltate battery into a solution, and the leaching residue is cobalt ferrite, and the lithium carbonate and the iron-based SCR catalyst are respectively prepared. The process adopts the mixed roasting and leaching process of the lithium cobaltate and the copperas, has simple operation, low production cost and easy separation, realizes the recycling of the lithium cobaltate battery and the copperas, simultaneously has little iron leached from the solution and greatly simplifies the purification process. The process combines the characteristics of lithium cobaltate and copperas, so that solid waste is recycled, and the process has the characteristics of remarkable economic benefit and environmental friendliness.
Disclosure of Invention
The invention provides a method for selectively recycling lithium and preparing a cobalt ferrite catalyst from waste lithium batteries, aiming at the problems of resource utilization of the waste lithium cobalt oxide batteries and solid waste treatment of the titanium dioxide industry.
The invention discloses a method for preparing lithium carbonate and SCR catalyst by using waste lithium cobaltate and copperas, which takes the waste lithium cobaltate and the copperas as raw materials and sequentially comprises the following process steps:
1. carrying out pre-treatment processes such as discharging, disassembling, crushing and screening on the waste lithium cobalt oxide battery to obtain a lithium battery positive electrode material lithium cobalt oxide;
2. copperas decomposed positive electrode material lithium cobaltate
Uniformly mixing lithium cobaltate anode powder which is finely ground to less than 2000 mu m with copperas, and controlling the mass ratio of the lithium cobaltate to the copperas to be 1:1-10; roasting the mixture at 800-1000 ℃ for 60-240 min to obtain a solid product;
3. leaching of roasted product
Leaching the solid product obtained in the step 2 by using deionized water at 25-80 ℃, wherein the leaching time is 30-240 min, the liquid-solid mass ratio is 4-20;
3. preparation of SCR catalyst
Adding the filter residue obtained in the step (3) into a salt solution (cerium nitrate, niobium nitrate, ammonium metavanadate and samarium nitrate), stirring in a water bath at 80 ℃ until the mixture is completely evaporated to dryness, and placing the mixture in a forced air drying oven for vacuum drying at 100 ℃ for 12 hours to obtain an SCR catalyst;
4. preparation of lithium carbonate
And (3) adding ammonia water slowly into the filtrate obtained in the step (3), removing impurities, adding a proper amount of ammonium carbonate solution (the molar ratio of lithium sulfate to ammonium carbonate is 1:1-6) with the concentration of 1-5 mol/L into the filtrate, collecting a precipitate product, and drying to obtain a lithium carbonate product.
The method utilizes ferrous iron in copperas and SO generated by thermal decomposition 2 The lithium cobaltate positive electrode material continues to be reduced and sulfated, converting lithium and cobalt to the corresponding sulfates. The thermal stability of cobalt sulfate is inferior to that of lithium sulfate, and the cobalt sulfate can be decomposed into oxides at a temperature of more than 800 ℃, so that the selective extraction of lithium is realized, and cobalt oxide is further combined with iron oxide generated by the decomposition of copperas to generate cobalt ferrite.
8LiCoO 2 +12FeSO 4 ·7H 2 O+O 2 (g)＝6Fe 2 O 3 +4Li 2 SO 4 +84H 2 O(g)+8CoSO 4 (1)
8CoSO 4 +8Fe 2 O 3 ＝8CoFe 2 O 4 +8SO 2 (g)+4O 2 (g) (2)
Compared with the prior art, the invention has the following advantages: (1) The process adopts industrial solid wastes as raw materials, thereby realizing the resource utilization of wastes; (2) the reaction conditions of the process are mild; (3) The process uses the solid waste copperas, has wide sources, reduces the environmental pollution and saves the production cost; (4) The method has the advantages of simple process, convenient operation, low production cost and industrial application prospect.
Drawings
FIG. 1 is a process flow diagram of the present invention
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
The elemental composition (mass%) of the positive electrode material after pretreatment of the used lithium batteries in each of the following examples was 54.38% by weight of CO, 6.76% by weight of Li, 0.1% by weight of Al, 0.05% by weight of Ni, and the XRD analysis result showed that the main phase in the positive electrode powder was lithium cobaltate.
Example one
(1) Discharging, disassembling and classifying the waste lithium cobaltate battery to obtain a positive electrode material, and then performing high-temperature treatment to remove the adhesive;
(2) Uniformly mixing lithium cobaltate positive electrode powder which is finely ground to be less than 200 mu m with copperas, wherein the mass ratio of the lithium cobaltate to the copperas is 1:1; roasting the mixture at 800 ℃ for 60min to obtain a solid product;
(3) Magnetically stirring the solid product obtained in the step 2 with deionized water at 25 ℃, leaching for 180min, wherein the liquid-solid mass ratio is 4:1, and performing solid-liquid separation to obtain a leaching solution containing lithium sulfate and filter residue;
(4) Adding the filter residue obtained in the step 3 into a cerous nitrate solution, stirring in a water bath at 80 ℃ until the filter residue is completely evaporated to dryness, and placing the filter residue in an air-blast drying oven for vacuum drying at 100 ℃ for 12 hours to obtain an SCR catalyst;
(5) And (4) adding ammonia water slowly into the filtrate obtained in the step (3), filtering to remove aluminum and iron ions, adding a proper amount of ammonium carbonate solution (the molar ratio of manganese sulfate to ammonium carbonate is 1:1) with the concentration of 5mol/L into the filtrate, collecting a precipitate product, and drying to obtain a lithium carbonate product.
Example two
(1) Discharging, disassembling and classifying the waste lithium cobaltate battery to obtain a positive electrode material, and then performing high-temperature treatment to remove the adhesive;
(2) Uniformly mixing lithium cobaltate positive electrode powder which is finely ground to be less than 200 mu m with copperas, wherein the mass ratio of the lithium cobaltate to the copperas is 1:4; roasting the mixture at 900 ℃ for 120min to obtain a solid product;
(3) Magnetically stirring the solid product obtained in the step 2 with deionized water at 55 ℃, leaching for 60min, wherein the mass ratio of liquid to solid is 8:1, and performing solid-liquid separation to obtain leachate containing lithium sulfate and filter residue;
(4) Adding the filter residue obtained in the step 3 into a niobium nitrate solution, stirring in a water bath at 80 ℃ until the filter residue is completely evaporated to dryness, and placing the filter residue in an air-blast drying oven for vacuum drying at 100 ℃ for 12 hours to obtain an SCR catalyst;
(5) And (3) adding ammonia water slowly into the filtrate obtained in the step (3), filtering to remove aluminum and iron ions, adding a proper amount of ammonium carbonate solution (the molar ratio of manganese sulfate to ammonium carbonate is 1:2) with the concentration of 6mol/L into the filtrate, collecting a precipitate product, and drying to obtain a lithium carbonate product.
EXAMPLE III
(1) Discharging, disassembling and classifying the waste lithium cobaltate battery to obtain a positive electrode material, and then performing high-temperature treatment to remove the adhesive;
(2) Uniformly mixing lithium cobaltate positive electrode powder which is finely ground to be less than 200 mu m with copperas, wherein the mass ratio of the lithium cobaltate to the copperas is 1:1; roasting the mixture at 1000 ℃ for 120min to obtain a solid product;
(3) Magnetically stirring the solid product obtained in the step 2 with deionized water at 70 ℃, leaching for 240min, wherein the liquid-solid mass ratio is 10, and performing solid-liquid separation to obtain leachate containing lithium sulfate and filter residue;
(4) Adding the filter residue obtained in the step 3 into a vanadium nitrate solution, stirring in a water bath at 80 ℃ until the filter residue is completely evaporated to dryness, and placing the filter residue in an air-blast drying oven for vacuum drying at 100 ℃ for 12 hours to obtain an SCR catalyst;
(5) And (3) adding ammonia water slowly into the filtrate obtained in the step (3), filtering to remove aluminum and iron ions, adding a proper amount of ammonium carbonate solution (the molar ratio of manganese sulfate to ammonium carbonate is 1:4) with the concentration of 4mol/L into the filtrate, collecting a precipitate product, and drying to obtain a lithium carbonate product.
Example four
(1) Discharging, disassembling and classifying the waste lithium cobaltate battery to obtain a positive electrode material, and then performing high-temperature treatment to remove the adhesive;
(2) Uniformly mixing the lithium cobaltate which is finely ground to be a positive electrode material with the particle size of less than 200 mu m with the copperas, wherein the mass ratio of the lithium cobaltate to the copperas is 1:1; roasting the mixture at 1000 ℃ for 240min to obtain a solid product;
(3) Magnetically stirring the solid product obtained in the step 2 with deionized water at 80 ℃, leaching for 240min, wherein the liquid-solid mass ratio is 20;
(4) Adding the filter residue obtained in the step 3 into a cerous nitrate solution, stirring in a water bath at 80 ℃ until the filter residue is completely evaporated to dryness, and placing the filter residue in an air-blast drying oven for vacuum drying at 100 ℃ for 12 hours to obtain an SCR catalyst;
(5) And (3) adding ammonia water slowly into the filtrate obtained in the step (3), filtering to remove aluminum and iron ions, adding a proper amount of ammonium carbonate solution (the molar ratio of manganese sulfate to ammonium carbonate is 1:6) with the concentration of 1mol/L into the filtrate, collecting a precipitate product, and drying to obtain a lithium carbonate product.
Claims (6)
1. A method for selectively recovering lithium from waste lithium batteries and simultaneously preparing a cobalt ferrite catalyst is characterized by comprising the following steps:
step 1: discharging, disassembling and classifying the waste lithium cobaltate battery to obtain a positive electrode material, and then performing high-temperature treatment to remove the adhesive;
step 2: uniformly mixing lithium cobaltate positive electrode powder which is finely ground to be less than 200 mu m with copperas according to a certain mass ratio, and roasting for a certain time at 800-1000 ℃ to obtain a solid product;
and step 3: magnetically stirring the solid product obtained in the step 2 with deionized water at a certain temperature for a certain time, and performing suction filtration on the leachate to realize solid-liquid separation to obtain leachate containing lithium sulfate and filter residue containing cobalt ferrite;
and 4, step 4: modifying the cobalt ferrite filter residue obtained in the step 3 by adopting an impregnation method to load an active component to obtain an SCR catalyst;
and 5: and 3, adjusting the pH value of the leachate obtained in the step 3 by using ammonia water, filtering iron ions, adding ammonium carbonate into the filtrate, collecting a precipitate product and drying to obtain a lithium carbonate product.
2. The method for selectively recycling lithium and simultaneously preparing a cobalt ferrite catalyst by using waste lithium batteries as claimed in claim 1, wherein the mass ratio of the lithium cobaltate to the copperas in the step 2 is 1:1-10.
3. The method for selectively recovering lithium and simultaneously preparing a cobalt ferrite catalyst by using waste lithium batteries as claimed in claim 1, wherein the calcination time in step 2 is 60-240 min.
4. The method for selectively recovering lithium and simultaneously preparing the cobalt ferrite catalyst by using the waste lithium batteries as claimed in claim 1, wherein the solid product in the step 3 has a water leaching temperature of 25-80 ℃, a leaching time of 30-250 min and a liquid-solid mass ratio of 2-20.
5. The method for selectively recovering lithium and simultaneously preparing a cobalt ferrite catalyst by using the waste lithium batteries as claimed in claim 1, wherein the active components in the step 4 comprise one or more of Ce, nb, V and Sm.
6. The method for selectively recovering lithium from waste lithium batteries and simultaneously preparing a cobalt ferrite catalyst according to claim 1, wherein the pH value of the solution obtained in the step 5 after adding ammonia water is 4-8, the solution temperature is 25-100 ℃, the concentration of ammonium carbonate is 1-5 mol/L, the molar ratio of lithium cobaltate to ammonium carbonate is 1:1-6, and the reaction time is 30-180 min.
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