CN115287458A - Method for recovering valuable metals in lithium-containing power battery waste - Google Patents
Method for recovering valuable metals in lithium-containing power battery waste Download PDFInfo
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- CN115287458A CN115287458A CN202210911744.3A CN202210911744A CN115287458A CN 115287458 A CN115287458 A CN 115287458A CN 202210911744 A CN202210911744 A CN 202210911744A CN 115287458 A CN115287458 A CN 115287458A
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- Prior art keywords
- lithium
- power battery
- containing power
- battery waste
- leaching
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 125
- 239000002699 waste material Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 150000002739 metals Chemical class 0.000 title claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 65
- 239000002893 slag Substances 0.000 claims abstract description 53
- 238000000605 extraction Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 4
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims abstract description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 238000011084 recovery Methods 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000011272 standard treatment 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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recovering valuable metals in lithium-containing power battery waste, which comprises the following steps: adding a reagent and carbon powder into the lithium-containing power battery waste material, and then curing and uniformly mixing to obtain cured lithium-containing power battery waste material; the reagent is one of concentrated sulfuric acid, sodium bisulfate, sodium sulfate, ammonium sulfate and ammonium bisulfate; sequentially roasting, crushing, water leaching, filtering and washing the aged lithium-containing power battery waste to obtain lithium extraction slag; drying the lithium extraction slag to obtain dried lithium extraction slag; putting the dried lithium extraction slag into a reducing furnace, introducing reducing gas into the reducing furnace or adding a reducing agent into the reducing furnace, and reducing the dried lithium extraction slag to obtain reduced lithium extraction slag; adding acid and oxidant into the reduced lithium extraction slag for leaching to obtain leachate and leaching slag; and adding a reducing agent into the leached residues for washing. The method is efficient, safe and environment-friendly.
Description
Technical Field
The invention belongs to the field of metallurgy, and particularly relates to a method for recovering valuable metals in lithium-containing power battery waste.
Background
In the prior art, although the recovery rate of cobalt nickel manganese lithium is high in the one-time whole leaching process of cobalt nickel manganese lithium, nickel is not easy to separate from lithium, so that the content of lithium in the produced nickel salt is high, and the process flow for producing battery-grade lithium carbonate is long; the process for selectively extracting lithium by hydrogen reduction and then extracting cobalt, nickel and manganese has weak adaptability to raw materials, and only can treat battery waste with low aluminum content and fully pyrolyzed organic matters. Therefore, a lithium-containing power battery waste recovery method with strong raw material applicability and high cobalt-nickel-manganese-lithium recovery rate is needed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for efficiently, safely and environmentally recovering valuable metals in lithium-containing power battery waste.
The invention adopts the following technical scheme:
a method of recovering valuable metals from lithium-containing power cell waste, the method comprising the steps of:
(1) Adding a reagent and carbon powder into the lithium-containing power battery waste, and curing and uniformly mixing to obtain cured lithium-containing power battery waste; the reagent is one of concentrated sulfuric acid, sodium bisulfate, sodium sulfate, ammonium sulfate and ammonium bisulfate; the ratio of the molar weight of lithium in the lithium-containing power battery waste to the molar weight of the reagent is 1.1-1.8, and the mass ratio of the lithium-containing power battery waste to the carbon powder is 5-20;
(2) Sequentially roasting, crushing, water leaching, filtering and washing the aged lithium-containing power battery waste to obtain lithium extraction slag;
(3) Drying the lithium extraction slag to obtain dried lithium extraction slag;
(4) Putting the dried lithium extraction slag into a reducing furnace, introducing reducing gas into the reducing furnace or adding a reducing agent into the reducing furnace, and reducing the dried lithium extraction slag to obtain reduced lithium extraction slag; when reducing gas is introduced into the reducing furnace, controlling the pressure in the reducing furnace to be 0.15MPa-0.2MPa; when a reducing agent is added into the reducing furnace, the mass ratio of the reducing agent to the dried lithium extraction slag is 0.2-1;
(5) Adding acid and oxidant into the reduced lithium extraction slag for leaching to obtain leachate and leaching slag;
(6) And adding a reducing agent into the leached residues for washing.
The method for recovering valuable metals from the lithium-containing power battery waste is characterized in that the mesh number of the carbon powder in the step (1) is 100-325 meshes.
The method for recovering valuable metals from lithium-containing power battery waste is characterized in that in the step (2), the aged lithium-containing power battery waste is placed into a rotary kiln for roasting, the oxygen content in the rotary kiln is controlled to be 4% -6%, and roasting process conditions are as follows: the roasting temperature is 550-600 ℃, and the roasting time is 1-3 h.
According to the method for recovering valuable metals in lithium-containing power battery waste, the process conditions of water immersion in the step (2) are as follows: the water temperature is 80-85 ℃, and the leaching time is 1-2 h; the washing mode is countercurrent washing for 2-3 times.
The method for recovering valuable metals from lithium-containing power battery waste is characterized in that the process conditions for reducing the dried lithium extraction slag in the step (4) are as follows: the reduction temperature is 450-600 ℃, and the reduction time is 2-3 h.
The method for recovering valuable metals from the lithium-containing power battery waste is characterized in that the reducing gas introduced into the reducing furnace in the step (4) is one of hydrogen, ammonia, methane and sulfur dioxide; the reducing agent added into the reducing furnace is one of carbon powder, sodium sulfide, sulfur, fructose, glucose, oxalic acid and edible flour.
The method for recovering valuable metals from the lithium-containing power battery waste is characterized in that the acid in the step (5) is sulfuric acid or hydrochloric acid or nitric acid, and the oxidant is one of potassium peroxide, sodium peroxide, potassium dichromate, sodium dichromate, potassium chlorate, sodium chlorate, hydrogen peroxide, potassium permanganate, sodium permanganate, perchloric acid, potassium hypochlorite, sodium hypochlorite, potassium persulfate and sodium persulfate; the technological conditions for leaching the reduced lithium extraction slag by adding acid and oxidant are as follows: the leaching pH is 1.5-2.0, and the leaching temperature is 70-90 ℃.
According to the method for recovering valuable metals in the lithium-containing power battery waste, the method is characterized in that the reducing agent added into the leaching slag in the step (6) is sodium sulfite or sodium metabisulfite or hydrogen peroxide; the process conditions for adding the reducing agent into the leaching residue for washing are as follows: the pH value of washing is 1.0-1.5, and the washing temperature is 50-80 ℃.
The method for recovering valuable metals from the lithium-containing power battery waste is characterized in that the drying temperature for drying the lithium extraction slag in the step (3) is 80-105 ℃.
The invention has the beneficial technical effects that: the method can lead the recovery rate of lithium in the lithium-containing power battery waste to reach about 95 percent, lead the recovery rate of nickel, cobalt and manganese to reach more than 99 percent, lead the finally obtained leaching slag to meet the standard treatment requirement and lead the leaching liquid to meet the process index requirement of the next working procedure. When the method is used for treating the lithium-containing power battery waste, the valuable metals in the lithium-containing power battery waste can be efficiently recovered, and the treatment process is safe, environment-friendly and harmless.
Detailed Description
The invention relates to a method for recovering valuable metals in lithium-containing power battery waste, which comprises the following steps:
(1) Adding a reagent and carbon powder into the lithium-containing power battery waste material, and then curing and uniformly mixing to obtain cured lithium-containing power battery waste material; the reagent is one of concentrated sulfuric acid, sodium bisulfate, sodium sulfate, ammonium sulfate and ammonium bisulfate; the ratio of the molar weight of lithium in the lithium-containing power battery waste to the molar weight of the reagent is 1.1-1.8, and the mass ratio of the lithium-containing power battery waste to the carbon powder is 5-20; the mesh number of the carbon powder is 100-325 meshes.
(2) Sequentially roasting, crushing, water leaching, filtering and washing the aged lithium-containing power battery waste to obtain lithium extraction slag; placing the aged lithium-containing power battery waste into a rotary kiln for roasting, wherein the oxygen content in the rotary kiln is controlled to be 4-6%, and the roasting process conditions are as follows: the roasting temperature is 550-600 ℃, and the roasting time is 1-3 h. The crushing mode is ball milling. The process conditions of water leaching are as follows: the water temperature is 80-85 ℃, and the leaching time is 1-2 h; the washing mode is countercurrent washing for 2-3 times. Adding water during water leaching, controlling the temperature at 80-85 deg.C, leaching for 1-2h, filtering, and washing the leaching residue with counter current for 2-3 times.
(3) Putting the lithium extraction slag into an oven for drying to obtain dried lithium extraction slag; the drying temperature for drying the lithium extraction slag is 80-105 ℃.
(4) Putting the dried lithium extraction slag into a reduction furnace with good tightness, introducing reducing gas into the reduction furnace or adding a reducing agent into the reduction furnace, and reducing the dried lithium extraction slag to obtain reduced lithium extraction slag; when reducing gas is introduced into the reducing furnace, controlling the pressure in the reducing furnace to be 0.15-0.2 MPa, and controlling the micro-positive pressure in the reducing furnace; when a reducing agent is added into the reducing furnace, the mass ratio of the reducing agent to the dried lithium extraction slag is 0.2-1; the technological conditions for reducing the dried lithium extraction slag are as follows: the reduction temperature is 450-600 ℃, and the reduction time is 2-3 h. The reducing gas introduced into the reduction furnace is one of hydrogen, ammonia, methane and sulfur dioxide; the reducing agent added into the reducing furnace is one of carbon powder, sodium sulfide, sulfur, fructose, glucose, oxalic acid and edible flour.
(5) Adding acid and oxidant into the reduced lithium extraction slag for leaching to obtain leachate and leaching slag; the acid is sulfuric acid or hydrochloric acid or nitric acid, and the oxidant is one of potassium peroxide, sodium peroxide, potassium dichromate, sodium dichromate, potassium chlorate, sodium chlorate, hydrogen peroxide, potassium permanganate, sodium permanganate, perchloric acid, potassium hypochlorite, sodium hypochlorite, potassium persulfate and sodium persulfate; the technological conditions for leaching the reduced lithium extraction slag by adding acid and oxidant are as follows: the leaching pH is 1.5-2.0, and the leaching temperature is 70-90 ℃. Valuable metals of nickel, cobalt and manganese contained in the reduced lithium extraction slag are dissolved into the leaching solution by acid.
(6) And adding a reducing agent into the leaching residue for washing. Adding a reducing agent into the leaching residue, wherein the reducing agent is sodium sulfite or sodium pyrosulfite or hydrogen peroxide; the process conditions for adding the reducing agent into the leaching residue for washing are as follows: the pH value of washing is 1.0-1.5, and the washing temperature is 50-80 ℃.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail with reference to the embodiments.
Example 1
And (3) adding 30mL of concentrated sulfuric acid into 100g of cracked lithium-containing power battery waste for curing for 30 minutes, continuously adding 20g of 200-mesh carbon powder, and uniformly stirring to obtain the cured lithium-containing power battery waste. And placing the obtained aged lithium-containing power battery waste into a rotary kiln to be roasted for 2 hours at the temperature of 600 ℃. And then grinding the sample, and leaching with water to recover lithium to obtain water leaching residue. And drying the water leaching residues, flattening the water leaching residues, putting the water leaching residues into an atmosphere furnace, vacuumizing the atmosphere furnace, introducing hydrogen, and roasting the water leaching residues at 500 ℃ for 2 hours in the atmosphere of the hydrogen to obtain a reduced material. Leaching the reduced materials step by step. In example 1, the recovery rate of lithium in the lithium-containing power battery waste material is 95.46%, and the recovery rate of nickel, cobalt and manganese is more than 98%.
Example 2
And (3) adding 35mL of concentrated sulfuric acid into 100g of cracked lithium-containing power battery waste for curing for 30 minutes, continuously adding 5g of 200-mesh carbon powder, and uniformly stirring to obtain the cured lithium-containing power battery waste. The obtained aged lithium-containing power battery waste is put into a rotary kiln to be roasted for 2 hours at 550 ℃. And grinding the sample, and leaching with water to recover lithium to obtain water leaching residue. Drying the water leaching slag, flattening the water leaching slag, putting the water leaching slag into an atmosphere furnace, vacuumizing the atmosphere furnace, introducing sulfur dioxide, and roasting the water leaching slag at 450 ℃ for 2 hours in an atmosphere with the sulfur dioxide to obtain a reduced material. Leaching the reduced materials step by step. In example 2, the recovery rate of lithium in lithium-containing power battery waste is 94.57%, and the recovery rate of nickel, cobalt and manganese reaches more than 98%.
Example 3
And (3) taking 100g of cracked lithium-containing power battery waste, adding 28mL of concentrated sulfuric acid, curing for 30 minutes, continuously adding 5g of 200-mesh carbon powder, and uniformly stirring to obtain the cured lithium-containing power battery waste. And (3) placing the aged lithium-containing power battery waste into a muffle furnace to be roasted for 2 hours at the temperature of 600 ℃. And grinding the sample, and leaching with water to recover lithium to obtain water leaching residue. And drying the water leaching residues, adding 20g of glucose, grinding uniformly to obtain a mixture, flattening the mixture, putting the mixture into an atmosphere furnace, vacuumizing the atmosphere furnace, introducing hydrogen, and roasting at 550 ℃ for 2 hours in the atmosphere with the hydrogen to obtain a reduced material. Leaching the reduced materials step by step. In example 3, the recovery rate of lithium in lithium-containing power battery waste is 96.01%, and the recovery rate of nickel, cobalt and manganese reaches more than 98%.
Example 4
And (3) adding 25mL of concentrated sulfuric acid into 100g of cracked lithium-containing power battery waste for curing for 30 minutes, continuously adding 20g of 200-mesh carbon powder, and uniformly stirring to obtain the cured lithium-containing power battery waste. And (3) putting the obtained aged lithium-containing power battery waste into a muffle furnace, and roasting for 2 hours at 600 ℃. And grinding the sample, and leaching with water to recover lithium to obtain water leaching residue. Drying the water-soaked slag, adding 20g of edible flour, grinding uniformly to obtain a mixture, flattening the mixture, putting the mixture into an atmosphere furnace, vacuumizing the atmosphere furnace firstly, then introducing carbon monoxide, and roasting for 2 hours at 600 ℃ in the atmosphere with the carbon monoxide to obtain a reduced material. Leaching the reduced materials step by step. In example 4, the recovery rate of lithium in the lithium-containing power battery waste material is 96.01%, and the recovery rate of nickel, cobalt and manganese is more than 98%.
Example 5
Taking 100g of the lithium-containing waste ternary material, adding 25mL of concentrated sulfuric acid, curing for 30 minutes, continuously adding 20g of 200-mesh carbon powder, and uniformly stirring to obtain a cured material. The cured material was calcined in a muffle furnace at 600 ℃ for 2 hours. And crushing and grinding the materials, and leaching in water to recover lithium to obtain water leaching residue. And (3) drying the water leaching slag, adding 30g of sulfur, flattening the material, putting the material into an atmosphere furnace, vacuumizing the atmosphere furnace, introducing nitrogen, and roasting at 1200 ℃ for 2 hours in the atmosphere with nitrogen to obtain the reduced material. Leaching the reduced materials step by step. In example 5, the recovery rate of lithium in the lithium-containing waste ternary material is 96.01 percent, and the recovery rate of nickel, cobalt and manganese reaches more than 98 percent.
Claims (9)
1. A method of recovering valuable metals from lithium-containing power cell waste, the method comprising the steps of:
(1) Adding a reagent and carbon powder into the lithium-containing power battery waste, and curing and uniformly mixing to obtain cured lithium-containing power battery waste; the reagent is one of concentrated sulfuric acid, sodium bisulfate, sodium sulfate, ammonium sulfate and ammonium bisulfate; the ratio of the molar weight of lithium in the lithium-containing power battery waste to the molar weight of the reagent is 1: 1.1-1.8, and the mass ratio of the lithium-containing power battery waste to the carbon powder is 5-20;
(2) Sequentially roasting, crushing, water leaching, filtering and washing the aged lithium-containing power battery waste to obtain lithium extraction slag;
(3) Drying the lithium extraction slag to obtain dried lithium extraction slag;
(4) Putting the dried lithium extraction slag into a reduction furnace, introducing reducing gas into the reduction furnace or adding a reducing agent into the reduction furnace, and reducing the dried lithium extraction slag to obtain reduced lithium extraction slag; when reducing gas is introduced into the reducing furnace, controlling the pressure in the reducing furnace to be 0.15MPa-0.2MPa; when a reducing agent is added into the reducing furnace, the mass ratio of the reducing agent to the dried lithium extraction slag is 0.2-1;
(5) Adding acid and oxidant into the reduced lithium extraction slag for leaching to obtain leachate and leaching slag;
(6) And adding a reducing agent into the leached residues for washing.
2. The method for recovering valuable metals from lithium-containing power battery wastes according to claim 1, wherein the mesh number of the carbon powder in the step (1) is 100-325 meshes.
3. The method for recovering valuable metals from lithium-containing power battery waste as claimed in claim 1, wherein in the step (2), the aged lithium-containing power battery waste is placed into a rotary kiln for roasting, the oxygen content in the rotary kiln is controlled to be 4% -6%, and the roasting process conditions are as follows: the roasting temperature is 550-600 ℃, and the roasting time is 1-3 h.
4. The method for recovering valuable metals from lithium-containing power battery waste materials according to claim 1, wherein the water leaching in the step (2) is carried out under the following process conditions: the water temperature is 80-85 ℃, and the leaching time is 1-2 h; the washing mode is countercurrent washing for 2-3 times.
5. The method for recovering valuable metals from lithium-containing power battery waste material according to claim 1, wherein the process conditions for reducing the dried lithium extraction slag in the step (4) are as follows: the reduction temperature is 450-600 ℃, and the reduction time is 2-3 h.
6. The method for recovering valuable metals from lithium-containing power battery waste materials as claimed in claim 5, wherein the reducing gas introduced into the reducing furnace in the step (4) is one of hydrogen, ammonia, methane and sulfur dioxide; the reducing agent added into the reducing furnace is one of carbon powder, sodium sulfide, sulfur, fructose, glucose, oxalic acid and edible flour.
7. The method for recycling valuable metals from lithium-containing power battery waste material according to claim 1, wherein the acid in step (5) is sulfuric acid or hydrochloric acid or nitric acid, and the oxidizing agent is one of potassium peroxide, sodium peroxide, potassium dichromate, sodium dichromate, potassium chlorate, sodium chlorate, hydrogen peroxide, potassium permanganate, sodium permanganate, perchloric acid, potassium hypochlorite, sodium hypochlorite, potassium persulfate and sodium persulfate; the technological conditions for leaching the reduced lithium extraction slag by adding acid and oxidant are as follows: the leaching pH is 1.5-2.0, and the leaching temperature is 70-90 ℃.
8. The method for recovering valuable metals from lithium-containing power battery wastes according to claim 1, characterized in that the reducing agent added to the leaching residue in the step (6) is sodium sulfite or sodium metabisulfite or hydrogen peroxide; the process conditions for adding the reducing agent into the leaching residue for washing are as follows: the pH value of washing is 1.0-1.5, and the washing temperature is 50-80 ℃.
9. The method for recycling valuable metals in lithium-containing power battery waste material according to claim 1, wherein the drying temperature for drying the lithium extraction slag in the step (3) is 80-105 ℃.
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