CN116179858A - Method for homogeneous modified complementary leaching of cobalt-containing waste lithium battery - Google Patents
Method for homogeneous modified complementary leaching of cobalt-containing waste lithium battery Download PDFInfo
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- CN116179858A CN116179858A CN202310216255.0A CN202310216255A CN116179858A CN 116179858 A CN116179858 A CN 116179858A CN 202310216255 A CN202310216255 A CN 202310216255A CN 116179858 A CN116179858 A CN 116179858A
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- cobalt
- leaching
- lithium battery
- waste lithium
- containing waste
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 50
- 239000010941 cobalt Substances 0.000 title claims abstract description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 50
- 238000002386 leaching Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000000295 complement effect Effects 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000000956 alloy Substances 0.000 claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical compound [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 claims description 3
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005188 flotation Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 150000002697 manganese compounds Chemical class 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000010926 waste battery Substances 0.000 claims 2
- 238000002955 isolation Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001698 pyrogenic effect Effects 0.000 abstract description 4
- 230000001603 reducing effect Effects 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical group [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- -1 separator Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002912 waste gas Substances 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
- C22B7/007—Wet processes by acid leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0006—Preliminary treatment without modification of the copper constituent by 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
- C22B21/00—Obtaining aluminium
- C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
-
- 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
- C22B23/043—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
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for carrying out homogeneous modification and complementary leaching on a cobalt-containing waste lithium battery, which comprises the steps of discharging, preparing positive black powder and alloy powder, carrying out complementary leaching, removing copper, iron and aluminum, preparing ternary hydroxide, evaporating ammonia, precipitating lithium and the like. The method comprises the steps of respectively preparing anode black powder and alloy powder from cobalt-containing waste lithium batteries; the oxidizing property of the positive black powder and the reducing property of the alloy powder are utilized, and the acid is directly added for complementary leaching, SO that no reducing agent or oxidant is required to be additionally added, and SO generated by adding sulfite when the positive black powder is subjected to independent acid leaching is avoided 2 The gas hazard also avoids the potential safety hazard of generating a large amount of hydrogen in direct acid leaching after the alloy powder is obtained by the traditional pyrogenic process. The process has high leaching speed, and the leaching rates of valuable elements cobalt, nickel, manganese, copper and lithium are all up to more than 99.5 percent. The process has the advantages of good production safety, economy, environmental protection and easy industrial application.
Description
Technical Field
The invention relates to a recycling method of waste lithium batteries in the metallurgical field, in particular to a method for carrying out homogeneous modification and complementary leaching on waste lithium batteries (lithium cobaltate batteries and ternary lithium batteries) containing cobalt.
Background
The waste lithium batteries are treated and recycled in a plurality of methods, which generally comprise a fire method, a wet method and a bioleaching method. The pyrogenic process is simpler but has high energy consumption and produces a large amount of waste gas. Wet processing primarily leaches metals through mineral or organic acids. Using mineral acids (HCl, H) 2 SO 4 、HNO 3 Etc.) as leaching agent, has high leaching rate and large treatment capacity, but can generate toxic and harmful gas (Cl) 2 、SO 2 、NO 2 ) And the like, the residual acid waste liquid is difficult to treat, and secondary pollution is caused. Organic acid (citric acid, oxalic acid, ascorbic acid, grape acid and the like) is used as a leaching agent, so that the ternary lithium ion power battery has good treatment effect, and the acidity of the acidic waste liquid is low, so that the subsequent treatment and recovery are easy; however, the cost of the organic acid raw material is higher than that of the inorganic acid, and the subsequent nickel-cobalt-manganese separation process is more complex, so that the recovery cost is further increased. The bioleaching method has low cost and environmental protection, but bacteria are difficult to culture, the leaching period is long, and the leaching rate is low, so that the industrial application of the bioleaching method is limited. Accordingly, the prior art is still in need of improvement and development. The optimal combination of various leaching methods can be an ideal treatment method, and a large number of scientific researchers are continuously researching and optimizing.
Disclosure of Invention
In view of the drawbacks and deficiencies of the prior art, the present invention is directed to a method for homogeneous modified complementary leaching of spent lithium batteries containing cobalt.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method of homogeneity-modified complementary leaching of waste lithium batteries containing cobalt, the method comprising the steps of:
s1, discharging: the cobalt-containing waste lithium battery is put into the battery containing NaCl and/or Na 2 SO 4 In the discharge cell of the sodium salt solution, discharging for 24-48 hours, draining, and feeding the drained water into the discharge cell for recycling;
s2, preparing positive electrode black powder and alloy powder: dividing the discharged cobalt-containing waste lithium battery into two parts according to the size, wherein the large-size cobalt-containing waste lithium battery is used for preparing positive black powder, and the small-size cobalt-containing waste lithium battery is used for preparing alloy powder;
s3, complementary leaching: mixing the obtained anode black powder and alloy powder according to an electron gain-loss balance principle, mixing the materials according to the weight ratio of 1:1-3:1, and leaching in dilute acid;
s4, copper, iron and aluminum removal: after leaching, ammonium bicarbonate or ammonia water is added to adjust the pH value to 2.5-3, ammonia sulfide is added to precipitate Cu, solid-liquid separation is carried out, and copper sulfide slag is recovered; adding ammonium bicarbonate or ammonia water into the filtrate to raise the pH to 5-6, precipitating Fe and Al, and carrying out solid-liquid separation to obtain impurity-removed filtrate and iron-aluminum slag;
s5, preparing a ternary hydroxide: the filtrate containing Mn, co, ni, li obtained in the step S4 is supplemented with one or two of Mn salt, co salt and Ni salt in proper amount according to the requirement; adding NaOH solution and ammonia water for coprecipitation in an inert atmosphere at the temperature of 45-55 ℃, and obtaining nickel cobalt manganese ternary hydroxide and coprecipitation solution after solid-liquid separation;
s6, ammonia distillation: heating and distilling ammonia from the coprecipitated liquid obtained in the step S5 by utilizing steam to obtain ammonia distilled liquid and ammonia gas;
s7, lithium precipitation: and (3) adding a carbonate solution into the ammonia distillation liquid obtained in the step (S6) to precipitate lithium, thereby obtaining lithium carbonate.
It should be noted that, the step S2 further includes:
s2.1, preparing positive electrode black powder: disassembling the drained large-size cobalt-containing waste lithium battery, removing the battery shell, performing low-temperature pyrolysis at 500-700 ℃, preserving heat for 1-2 h, and removing substances without recycling value; removing graphite powder and scrap iron by using the differences of powder density, magnetism and granularity after physical crushing through flotation, magnetic separation and screening, and separating to obtain copper scraps, aluminum scraps and positive black powder with higher purity;
s2.2, preparing alloy powder: putting the drained small-size cobalt-containing waste lithium battery into a high-temperature furnace for roasting, under the conditions of isolating air, protective atmosphere or negative pressure, keeping the roasting temperature at 1000-1200 ℃, preserving heat for 1-4 hours, modifying nickel, cobalt and manganese compounds by utilizing graphite contained in the cobalt-containing waste lithium battery, reducing the compounds into alloy, and crushing the alloy into alloy powder below 10 meshes by adopting a physical crushing mode;
the ammonia gas obtained in step S5 may be absorbed by water to obtain ammonia water, and the ammonia water obtained may be reused in step S4.
The waste lithium battery containing cobalt is a lithium cobalt oxide battery or a ternary lithium battery.
The large-size cobalt-containing waste lithium battery is a power lithium battery, and the small-size cobalt-containing waste lithium battery is a 3C lithium battery.
In the step S3, the dilute acid is dilute sulfuric acid.
The leaching in the step S3 has the technological parameters of pH 1.5-2.0, temperature 60-90 ℃ and stirring speed 50-200 r/min for 2-5 h;
the temperature is 70-80 ℃, the time is 3-4 hours, and the stirring speed is 60-120 r/min.
The impurity removal filtrate obtained in the step S4 has the content of Fe, al and Cu less than 1mg/L.
The invention has the beneficial effects that:
1. the alloy powder in the 0 valence state mainly reacts with the positive electrode black powder (mainly metal oxide) in the high valence state by adopting low acid leaching, only a small amount of alloy powder reacts with acid, the hydrogen generation amount is small, and the potential safety hazard that a large amount of hydrogen is generated when acid is added to leach the alloy powder after the alloy powder is obtained when waste lithium batteries are recovered by a pyrogenic process is avoided.
2. The alloy powder and the positive black powder are respectively used as the reducing agent and the oxidizing agent in the self-leaching process, so that the oxidizing agent and the reducing agent are not required to be added, auxiliary materials are saved, and the leaching cost is reduced.
3. Only sulfuric acid is added in the self-leaching process, SO that SO generated by adding a reducing agent in the leaching process of wet-process recovered waste lithium batteries is avoided 2 And the harm of the gas.
4. The leaching rate of nickel, cobalt, manganese, copper and lithium exceeds 99%, the purity of copper scraps and aluminum scraps obtained in the step (b) is higher, the copper scraps and aluminum scraps can be directly sold, and the recovery rate is more than 92%.
Detailed Description
The present invention will be further described below, and it should be noted that, while the present embodiment provides a detailed implementation manner and a specific operation process on the premise of the present technical solution, the protection scope of the present invention is not limited to the present embodiment.
Example 1
The invention relates to a method for leaching cobalt-containing waste lithium batteries in a homogeneous modified complementary manner, which comprises the following steps:
s1, discharging: the cobalt-containing waste lithium battery is put into the battery containing NaCl and/or Na 2 SO 4 In the discharge cell of the sodium salt solution, discharging for 24-48 hours, draining, and feeding the drained water into the discharge cell for recycling;
s2, preparing positive electrode black powder and alloy powder: dividing the discharged cobalt-containing waste lithium battery into two parts according to the size, wherein the large-size cobalt-containing waste lithium battery is used for preparing positive black powder, and the small-size cobalt-containing waste lithium battery is used for preparing alloy powder;
s3, complementary leaching: mixing the obtained anode black powder and alloy powder according to an electron gain-loss balance principle, mixing the materials according to the weight ratio of 1:1-3:1, and leaching in dilute acid;
s4, copper, iron and aluminum removal: after leaching, ammonium bicarbonate or ammonia water is added to adjust the pH value to 2.5-3, ammonia sulfide is added to precipitate Cu, solid-liquid separation is carried out, and copper sulfide slag is recovered; adding ammonium bicarbonate or ammonia water into the filtrate to raise the pH to 5-6, precipitating Fe and Al, and carrying out solid-liquid separation to obtain impurity-removed filtrate and iron-aluminum slag;
s5, preparing a ternary hydroxide: the filtrate containing Mn, co, ni, li obtained in the step S4 is supplemented with one or two of Mn salt, co salt and Ni salt in proper amount according to the requirement; adding NaOH solution and ammonia water for coprecipitation in an inert atmosphere at the temperature of 45-55 ℃, and obtaining nickel cobalt manganese ternary hydroxide and coprecipitation solution after solid-liquid separation;
s6, ammonia distillation: heating and distilling ammonia from the coprecipitated liquid obtained in the step S5 by utilizing steam to obtain ammonia distilled liquid and ammonia gas;
s7, lithium precipitation: and (3) adding a carbonate solution into the ammonia distillation liquid obtained in the step (S6) to precipitate lithium, thereby obtaining lithium carbonate.
Further, the step S2 of the present invention further includes:
s2.1, preparing positive electrode black powder: disassembling the drained large-size cobalt-containing waste lithium battery, removing the battery shell, performing low-temperature pyrolysis at 500-700 ℃, preserving heat for 1-2 h, and removing substances without recycling value; removing graphite powder and scrap iron by using the differences of powder density, magnetism and granularity after physical crushing through flotation, magnetic separation and screening, and separating to obtain copper scraps, aluminum scraps and positive black powder with higher purity;
s2.2, preparing alloy powder: putting the drained small-size cobalt-containing waste lithium battery into a high-temperature furnace for roasting, under the conditions of isolating air, protective atmosphere or negative pressure, keeping the roasting temperature at 1000-1200 ℃, preserving heat for 1-4 hours, modifying nickel, cobalt and manganese compounds by utilizing graphite contained in the cobalt-containing waste lithium battery, reducing the compounds into alloy, and crushing the alloy into alloy powder below 10 meshes by adopting a physical crushing mode;
it is noted that in the implementation step of the present invention, the alloy powder preparation process in step S2.2 can decompose and volatilize substances without recycling value, such as binder, separator, electrolyte, etc., in the battery cell, and also generate a reaction of reducing metal compounds by carbon, 2meo+c=me+co 2 Either ∈, or meo+c=me+co +..
On the other hand, in step S3, the reducibility of the alloy and the positive electrode black are mainly utilizedThe oxidability of the powder, which reacts directly under acidic conditions to form soluble low valence metal ions, e.g. Co 2+ 、Ni 2+ 、Mn 2+ 、Cu 2+ Etc. Because part of the battery shell is made of iron material, the complementary leaching system contains a small amount of iron element, and the iron is prepared by Fe under the acidic condition 2+ 、Fe 3+ The state exists in the solution, and the solid-solid oxidation-reduction reaction between the positive black powder and the alloy powder is accelerated by the transfer medium serving as electrons, so that the leaching rate is improved
Further, the ammonia gas obtained in the step S5 can be absorbed by water to obtain ammonia water, and the obtained ammonia water is reused in the step S4.
Further, the waste lithium battery containing cobalt is a lithium cobalt oxide battery or a ternary lithium battery.
Furthermore, the large-size cobalt-containing waste lithium battery is a power lithium battery, and the small-size cobalt-containing waste lithium battery is a 3C lithium battery.
Further, in the step S3 of the present invention, the dilute acid is dilute sulfuric acid.
Further, the leaching in the step S3 has the technological parameters of pH 1.5-2.0, temperature 60-90 ℃ and time 1-4 h, and stirring speed 50-200 r/min;
further, the temperature is 70-80 ℃, the time is 3-4 hours, and the stirring speed is 60-120 r/min.
Furthermore, the impurity removal filtrate obtained in the step S4 has the content of Fe, al and Cu less than 1mg/L.
Examples 2 to 5:
the process flow is the same as in example 1, the process parameters are adjusted, and the process parameters and implementation effects of examples 1 to 5 are shown in the following table.
As can be seen from the process parameters and results of examples 1 to 5, the technology of the invention obtains the waste lithium batteries containing cobalt respectively with oxidability and oxidation by different methodsThe two materials with reducibility are mixed and then added with acid for complementary leaching, SO that the addition of a reducing agent and an oxidant and the generation of SO are avoided 2 、NO x The harm of gas saves the leaching cost and greatly reduces the generation of H in the pyrogenic recovery process 2 Has the advantages of high recovery rate of valuable metals.
Various other corresponding changes and modifications will occur to those skilled in the art from the foregoing description and the accompanying drawings, and all such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (9)
1. A method for the homogeneity-modified complementary leaching of waste lithium batteries containing cobalt, the method comprising the steps of:
s1, discharging: the cobalt-containing waste lithium battery is put into the battery containing NaCl and/or Na 2 SO 4 In the discharge cell of the sodium salt solution, discharging for 24-48 hours, draining, and feeding the drained water into the discharge cell for recycling;
s2, preparing positive electrode black powder and alloy powder: dividing the discharged cobalt-containing waste lithium battery into two parts according to the size, wherein the large-size cobalt-containing waste lithium battery is used for preparing positive black powder, and the small-size cobalt-containing waste lithium battery is used for preparing alloy powder;
s3, complementary leaching: mixing the obtained anode black powder and alloy powder according to an electron gain-loss balance principle, mixing the materials according to the weight ratio of 1:1-3:1, and leaching in dilute acid;
s4, copper, iron and aluminum removal: after leaching, ammonium bicarbonate or ammonia water is added to adjust the pH value to 2.5-3, ammonia sulfide is added to precipitate Cu, solid-liquid separation is carried out, and copper sulfide slag is recovered; adding ammonium bicarbonate or ammonia water into the filtrate to raise the pH to 5-6, precipitating Fe and Al, and carrying out solid-liquid separation to obtain impurity-removed filtrate and iron-aluminum slag;
s5, preparing a ternary hydroxide: the filtrate containing Mn, co, ni, li obtained in the step S4 is supplemented with one or two of Mn salt, co salt and Ni salt in proper amount according to the requirement; adding NaOH solution and ammonia water for coprecipitation in an inert atmosphere at the temperature of 45-55 ℃, and obtaining nickel cobalt manganese ternary hydroxide and coprecipitation solution after solid-liquid separation;
s6, ammonia distillation: heating and distilling ammonia from the coprecipitated liquid obtained in the step S5 by utilizing steam to obtain ammonia distilled liquid and ammonia gas;
s7, lithium precipitation: and (3) adding a carbonate solution into the ammonia distillation liquid obtained in the step (S6) to precipitate lithium, thereby obtaining lithium carbonate.
2. The method of homogeneous modified complementary leaching of lithium waste batteries containing cobalt according to claim 1, wherein said step S2 further comprises:
s2.1, preparing positive electrode black powder: disassembling the drained large-size cobalt-containing waste lithium battery, removing the battery shell, performing low-temperature pyrolysis at 500-700 ℃, preserving heat for 1-2 h, and removing substances without recycling value; removing graphite powder and scrap iron by using the differences of powder density, magnetism and granularity after physical crushing through flotation, magnetic separation and screening, and separating to obtain copper scraps, aluminum scraps and positive black powder with higher purity;
s2.2, preparing alloy powder: putting the drained small-size cobalt-containing waste lithium battery into a high-temperature furnace for roasting, under the conditions of air isolation, protective atmosphere or negative pressure, the roasting temperature is 1000-1200 ℃, the heat preservation is carried out for 1-4 hours, the nickel, cobalt and manganese compounds are modified by utilizing graphite contained in the cobalt-containing waste lithium battery, the compounds are reduced into alloy, and the alloy is crushed into alloy powder below 10 meshes by adopting a physical crushing mode.
3. The method for the homogeneous modified complementary leaching of waste lithium batteries containing cobalt according to claim 1, wherein the ammonia gas obtained in the step S5 can be absorbed by water to obtain ammonia water, and the ammonia water obtained is recycled in the step S4.
4. The method for the homogeneous modified complementary leaching of a waste lithium battery containing cobalt according to claim 1, wherein the waste lithium battery containing cobalt is a lithium cobaltate battery or a ternary lithium battery.
5. The method of claim 1, wherein the large size waste lithium battery is a power lithium battery and the small size waste lithium battery is a 3C lithium battery.
6. The method for homogeneous modified complementary leaching of lithium waste batteries containing cobalt according to claim 1, wherein the dilute acid in step S3 is dilute sulfuric acid.
7. The method for the homogeneous modified complementary leaching of the cobalt-containing waste lithium battery according to claim 1, wherein the leaching in the step S3 is characterized in that the technological parameters are that the pH is 1.5-2.0, the temperature is 60-90 ℃, the time is 2-5 h, and the stirring speed is 50 r/min-200 r/min;
8. the method for the homogeneous modified complementary leaching of the cobalt-containing waste lithium battery according to claim 7, wherein the temperature is 70-80 ℃, the time is 3-4 hours, and the stirring speed is 60-120 r/min.
9. The method for the homogeneous modified complementary leaching of the cobalt-containing waste lithium battery as claimed in claim 1, wherein the impurity removal filtrate obtained in the step S4 has the contents of Fe, al and Cu of less than 1mg/L.
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