CN111254276A - Method for selective extraction of valuable metals from waste lithium-ion battery powder based on phase inversion of reductive sodium roasting - Google Patents
Method for selective extraction of valuable metals from waste lithium-ion battery powder based on phase inversion of reductive sodium roasting Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000002699 waste material Substances 0.000 title claims abstract description 51
- 239000000843 powder Substances 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 150000002739 metals Chemical class 0.000 title claims abstract description 33
- 239000011734 sodium Substances 0.000 title claims abstract description 30
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 29
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 29
- 230000002829 reductive effect Effects 0.000 title claims abstract description 27
- 238000000605 extraction Methods 0.000 title description 8
- 238000002386 leaching Methods 0.000 claims abstract description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 239000002893 slag Substances 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000009466 transformation Effects 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000007832 Na2SO4 Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 22
- 238000011084 recovery Methods 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 abstract description 3
- 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 abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000012535 impurity Substances 0.000 description 9
- 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 description 8
- 239000000047 product Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 229910000905 alloy phase Inorganic materials 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000013550 pizza Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
Images
Classifications
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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- 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
- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
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- 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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Abstract
本发明公开了一种基于还原钠化焙烧物相转化的废锂离子电池粉末选择性提取有价金属方法，包括如下步骤：将废锂离子电池粉末与硫酸钠按照预定摩尔配比混合并球磨预定时间，得到混合料；将混合料置于电炉中在预定温度下进行还原钠化焙烧，所得还原钠化焙烧产物称为焙砂；将焙砂采用纯水浸出，获得含锂浸出液与转化渣；将转化渣采用硫酸浸出提取镍、钴、锰等有价金属。本发明流程简单、生产成本低、有价金属回收率高；本发明通过还原钠化焙烧使锂从电池粉末中脱嵌并形成水溶性硫酸锂，采用纯水浸出即可实现锂的优先选择性提取；同时镍钴锰等有价金属物相转化为易于酸浸的低价氧化物，为后续湿法浸出回收镍钴锰创造有利条件。
The invention discloses a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase transformation of reductive sodium calcined products, comprising the following steps: mixing waste lithium ion battery powder and sodium sulfate according to a predetermined molar ratio, and ball milling a predetermined method. time to obtain a mixture; the mixture is placed in an electric furnace and subjected to reduction and sodium roasting at a predetermined temperature, and the obtained reduced sodium roasting product is called calcine; the calcine is leached with pure water to obtain a lithium-containing leachate and conversion slag; The conversion residue is leached with sulfuric acid to extract valuable metals such as nickel, cobalt and manganese. The invention has the advantages of simple process, low production cost and high recovery rate of valuable metals; in the invention, lithium is deintercalated from battery powder through reductive sodium roasting to form water-soluble lithium sulfate, and the preferential selectivity of lithium can be realized by leaching with pure water. At the same time, valuable metals such as nickel, cobalt, and manganese are converted into low-valent oxides that are easy to acid leaching, creating favorable conditions for subsequent wet leaching and recovery of nickel, cobalt, and manganese.
Description
Technical Field
The invention belongs to the field of secondary resource recycling, and particularly relates to a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting.
Background
The lithium ion battery has the advantages of light weight, large energy density, long cycle life, no memory effect and the like, and is widely applied to the fields of portable electronic equipment, power automobiles and the like. However, the service life of the lithium ion battery is generally 3-6 years, and a large amount of waste lithium ion batteries are generated in the huge lithium ion battery application market, wherein the waste lithium ion batteries contain valuable metals such as lithium, nickel, cobalt, manganese and the like and toxic electrolyte, and improper disposal not only causes environmental pollution, but also causes resource waste. Therefore, the method has multiple meanings of resource recovery and environmental protection for the recovery of valuable metals in the waste lithium ion batteries.
At present, the recovery of valuable metals in waste lithium ion batteries at home and abroad is mainly divided into a fire-wet combined process and a full-wet process. The combined fire-wet process is to remove the adhesive in the waste lithium ion battery by high-temperature smeltingOrganic matters such as a caking agent, a diaphragm, electrolyte and the like, and simultaneously, metals such as nickel, cobalt, manganese, copper, aluminum, iron, lithium and the like enter an alloy phase and a slag phase respectively, and then the recovery of valuable metals in the alloy phase and the slag phase is realized by adopting a wet process. For example, the American company in Belgium directly puts untreated waste lithium ion batteries into an pizza furnace for high-temperature smelting, most of lithium is discharged along with smoke dust, a small part of lithium and aluminum are fixed by slag phase, and metal elements such as copper, iron, manganese, cobalt, nickel and the like enter alloy phase and then are sent into a wet refining system to recover copper nickel cobalt. The investment of fixed assets such as high-temperature smelting equipment and the like in the fire-wet combined process is large, only the recovery of metals such as copper, nickel, cobalt and the like in an alloy phase is concerned, lithium is dispersed in smoke dust and slag, the recovery difficulty is large, and the yield is low. The full wet process mostly adopts a technical route of firstly recovering nickel, cobalt and manganese and then extracting lithium, and mainly comprises the working procedures of pretreatment, leaching, impurity removal, extraction, concentration crystallization or neutralization precipitation and the like. The method comprises the steps of dissolving metals such as lithium, nickel, cobalt, manganese, copper, iron, aluminum and the like into leachate together through reduction leaching, purifying and removing impurities such as copper, iron, aluminum and the like, separating and enriching nickel, cobalt and manganese through solvent extraction, and preparing nickel-cobalt-manganese sulfate or a ternary precursor through concentration crystallization or coprecipitation. The whole wet process has long process flow and multiple working procedures, and lithium is dispersed in intermediate products such as purified slag, raffinate, concentrated mother liquor and the like in each unit process in a disordered way, so that the recovery rate of the lithium is very low; meanwhile, hydrogen peroxide, sodium sulfite and SO are required to be added in the leaching process2The reagent is used as a reducing agent to improve the leaching rate of cobalt and manganese, and the reducing agent has high reagent consumption and high production cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium salt roasting, which is characterized in that the waste lithium ion battery powder and sodium sulfate are mixed, reduced sodium salt roasting treatment is carried out through innovation, then pure water leaching is carried out, preferential selective extraction of lithium is realized, meanwhile, a nickel-cobalt-manganese valuable metal phase is converted from a high-valence oxide into a low-valence oxide easy to acid leach under a reducing atmosphere, and favorable conditions are created for recovering nickel, cobalt and manganese through subsequent wet leaching.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting substances comprises the following steps:
(1) mixing waste lithium ion battery powder and sodium sulfate according to a preset molar ratio, and performing ball milling for a preset time to obtain a mixture;
(2) placing the mixture obtained in the step (1) in an electric furnace to perform reduced sodium roasting at a preset temperature, wherein the obtained reduced sodium roasting product is called calcine;
(3) leaching the calcine in the step (2) by using pure water to obtain a lithium-containing leaching solution and conversion slag;
(4) and (4) leaching the conversion slag obtained in the step (3) by using sulfuric acid to extract valuable metals such as nickel, cobalt, manganese and the like.
Further, the waste lithium ion battery powder in the step (1) is black powder produced by crushing and sorting waste lithium ion batteries, and the contained positive electrode material is one or a mixture of lithium manganate, lithium cobaltate and a ternary material.
Further, in the step (1), sodium sulfate is anhydrous sodium sulfate produced by a lithium salt preparation and ternary precursor synthesis system in a lithium battery material enterprise.
Further, the molar ratio in the step (1) is the molar ratio of lithium to sodium sulfate in the waste lithium ion battery powder (n)Li:nNa2SO4) The ratio of the raw materials to the mixed powder is 1:0.5-2, and the mixing and ball milling time is 0.5-3 h.
Further, the reaction temperature of the reduction sodium roasting in the step (2) is 500-850 ℃, and the reaction time is 1-4 h.
Further, the reaction time of pure water leaching in the step (3) is 0.5-4h, the reaction temperature is 30-98 ℃, and the liquid-solid ratio is 3-10: 1.
Further, the acid concentration of sulfuric acid leaching of the conversion slag in the step (4) is 0.5-4mol/L, the reaction time is 0.5-3h, the reaction temperature is 30-98 ℃, and the liquid-solid ratio is 4-20: 1.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the technical route of 'firstly recovering nickel, cobalt and manganese and then extracting lithium' of the existing full-wet process is changed, lithium in waste lithium ion battery powder is de-intercalated from crystal lattices and converted into water-soluble lithium sulfate through reduction sodium roasting, efficient and preferential extraction of lithium can be realized, elements such as nickel, cobalt, manganese, iron, aluminum and the like are hardly leached, the impurity content of leachate is below 1mg/L, and the purification and impurity removal burden of a lithium salt preparation system is greatly reduced.
(2) Graphite in waste lithium ion battery powder is used as a reducing agent, indissolvable high-valence nickel, cobalt and manganese compounds in the battery powder are converted into low-valence oxides easy to dissolve in acid in the sodium salt roasting process, favorable conditions are created for recovering nickel, cobalt and manganese through subsequent wet leaching, and leaching rate of valuable metals such as nickel, cobalt, manganese and the like in the conversion slag is more than 99% through sulfuric acid leaching without adding the reducing agent.
(3) The lithium battery material enterprise lithium salt preparation and the synergistic comprehensive utilization of the byproduct sodium sulfate produced by the ternary precursor synthesis system are realized, and the production cost is low.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The method for selectively extracting valuable metals from the waste lithium ion battery powder based on phase transformation of the reduced sodium roasting substance is further described below with reference to specific embodiments.
Example 1
As shown in fig. 1, this example provides a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase transformation of reduced sodium roasting substance, which includes the following steps:
(1) the waste ternary battery powder is used as a raw material, and mainly comprises the following components: li4.5wt%, Ni20.0wt%, Co7.6wt%, Mn11.7wt%, Cu0.09wt%, Fe0.03wt%, Al0.3wt%, and C28.5wt%. Waste ternary battery powder and sodium sulfate are mixed according to a molar ratio nLi:nNa2SO4Mixing and ball milling for 1.5h in a ratio of 1:1 to obtain a mixture.
(2) And (2) placing the mixture obtained in the step (1) in an electric furnace, and reducing and sodium-treating for roasting for 1.5 hours at 750 ℃ to obtain roasted sand.
(3) And (3) leaching the calcine obtained in the step (2) by pure water, reacting for 2 hours at 80 ℃ according to the liquid-solid ratio of 8:1 to obtain a lithium-containing leaching solution and conversion slag, wherein the lithium-containing leaching solution can be used for preparing lithium salt products such as lithium carbonate or lithium hydroxide.
(4) Reacting the conversion slag for 1h according to the liquid-solid ratio of 5:1, the temperature of 60 ℃ and the sulfuric acid concentration of 2mol/L, filtering to obtain leachate containing nickel, cobalt and manganese, and preparing the battery-grade nickel-cobalt-manganese sulfate through the working procedures of extraction, purification and the like.
Detecting the content of each element in the obtained leachate, and calculating that the leaching rate of Li in the calcine water leaching procedure reaches 92.53 percent, the leaching rates of Ni, Co and Mn are all lower than 0.5 percent, and the contents of other impurity ions are all lower than 1 mg/L; in the acid leaching process of the conversion slag, the leaching rates of Ni, Co and Mn are respectively 99.81%, 99.51% and 99.56%.
Example 2
The embodiment provides a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting, which comprises the following steps:
(1) the waste ternary and lithium cobaltate mixed battery powder is used as a raw material, and the main components of the waste ternary and lithium cobaltate mixed battery powder are controlled to be Li6.57wt%, Ni5.93wt%, Co42.37wt%, Mn3.79wt%, Cu0.93wt%, Fe0.08wt%, Al0.38wt% and C24.59wt%. Waste lithium battery powder and sodium sulfate are mixed according to a molar ratio nLi:nNa2SO4Mixing and ball milling for 1.5h at the ratio of 1:1.2 to obtain a mixture.
(2) And (2) placing the mixture obtained in the step (1) in an electric furnace, and reducing and sodium-treating for roasting for 3 hours at 700 ℃ to obtain roasted sand.
(3) And (3) leaching the calcine obtained in the step (2) by pure water, reacting for 3 hours at 40 ℃ according to the liquid-solid ratio of 5:1 to obtain a lithium-containing leaching solution and conversion slag, wherein the lithium-containing leaching solution can be used for preparing lithium salt products such as lithium carbonate or lithium hydroxide.
(4) Reacting the conversion slag for 2 hours according to the liquid-solid ratio of 10:1, the temperature of 60 ℃ and the sulfuric acid concentration of 3mol/L, filtering to obtain leachate containing nickel, cobalt and manganese, and preparing the battery-grade nickel-cobalt-manganese sulfate through the working procedures of extraction, purification and the like.
Detecting the content of each element in the obtained leachate, and calculating that the leaching rate of Li in the calcine water leaching process reaches 93.06 percent, the leaching rates of Ni, Co and Mn are all lower than 0.5 percent, and the contents of other impurity ions are all lower than 0.8 mg/L; the leaching rates of Ni, Co and Mn in the acid leaching process of the conversion slag are respectively 99.45%, 99.75% and 99.67%.
Example 3
The embodiment provides a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting, which comprises the following steps:
(1) the waste ternary and lithium manganate mixed battery powder is used as a raw material, and the main components of the waste ternary and lithium manganate mixed battery powder are controlled to be Li6.25wt%, Ni5.23wt%, Co1.32wt%, Mn48.67wt%, Cu0.61wt%, Fe 0%, Al0.26wt% and C17.89wt%. Waste lithium battery powder and sodium sulfate are mixed according to a molar ratio nLi:nNa2SO4Mixing and ball milling for 2h in a ratio of 1:1 to obtain a mixture.
(2) And (2) placing the mixture obtained in the step (1) in an electric furnace, and reducing and sodium-treating for roasting for 4 hours at 700 ℃ to obtain roasted sand.
(3) And (3) leaching the calcine obtained in the step (2) by pure water, reacting for 3 hours at 80 ℃ according to the liquid-solid ratio of 6:1 to obtain a lithium-containing leaching solution and conversion slag, wherein the lithium-containing leaching solution can be used for preparing lithium salt products such as lithium carbonate or lithium hydroxide.
(4) Reacting the conversion slag for 2 hours according to the liquid-solid ratio of 6:1, the temperature of 70 ℃ and the sulfuric acid concentration of 2mol/L, filtering to obtain leachate containing nickel, cobalt and manganese, and preparing the battery-grade nickel-cobalt-manganese sulfate through the working procedures of extraction, purification and the like.
Detecting the content of each element in the obtained leachate, and calculating that the leaching rate of Li in the roasting water leaching process reaches 93.43%, the leaching rates of Ni, Co and Mn are all lower than 0.4%, and the contents of other impurity ions are all lower than 0.9 mg/L; the leaching rates of Ni, Co and Mn in the acid leaching process of the conversion slag are respectively 99.79%, 99.61% and 99.89%.
Example 4
The embodiment provides a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting, which comprises the following steps:
(1) waste lithium cobalt oxide battery powder is used as a raw material, and the main components of the waste lithium cobalt oxide battery powder are Li5.9wt% and Co32.7 wt%, Cu0.2wt%, Fe0.01wt%, Al0.66wt%, and C38.4wt%. Waste lithium battery powder and sodium sulfate are mixed according to a molar ratio nLi:nNa2SO4Mixing and ball milling for 1.5h at the ratio of 1:0.9 to obtain a mixture.
(2) And (3) placing the mixture obtained in the step (1) in an electric furnace, and carrying out reduction sodium salt roasting for 1h at 850 ℃ to obtain roasted sand.
(3) And (3) carrying out water leaching on the calcine obtained in the step (2), reacting for 1.5h at 60 ℃ according to the liquid-solid ratio of 7:1 to obtain a lithium-containing leaching solution and conversion slag, wherein the lithium-containing leaching solution can be used for preparing lithium salt products such as lithium carbonate or lithium hydroxide.
(4) Reacting the conversion slag for 2 hours according to the liquid-solid ratio of 8:1, the temperature of 75 ℃ and the sulfuric acid concentration of 2mol/L, and filtering to obtain a leaching solution containing cobalt.
Detecting the content of each element in the obtained leachate, and calculating that the Li leaching rate in the roasting water leaching process reaches 94.57%, the Co leaching rate is lower than 0.5%, and the content of other impurity ions is less than 0.8 mg/L; the Co leaching rate in the acid leaching process of the conversion slag is 99.78 percent.
Example 5
The embodiment provides a method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting, which comprises the following steps:
(1) the waste lithium cobaltate and lithium manganate mixed battery powder is used as a raw material, and the main components of the mixed battery powder are controlled to be Li6.87wt%, Co35.05wt%, Mn31.62wt%, Cu0.92wt%, Fe0.23wt% and Al0.32wt%. Waste lithium battery powder and sodium sulfate are mixed according to a molar ratio (Li: Na)2SO4) Mixing and ball milling for 1h at a ratio of 1:1.1 to obtain a mixture.
(2) And (2) placing the mixture obtained in the step (1) in an electric furnace, and reducing and sodium-treating for roasting for 2 hours at 750 ℃ to obtain roasted sand.
(3) And (3) soaking the roasted product obtained in the step (2) in water, reacting for 2 hours at 85 ℃ according to the liquid-solid ratio of 5:1 to obtain a lithium-containing leaching solution and conversion slag, wherein the lithium-containing leaching solution can be used for preparing lithium salt products such as lithium carbonate or lithium hydroxide.
(4) Reacting the conversion slag for 2 hours according to the liquid-solid ratio of 5:1, the temperature of 80 ℃ and the sulfuric acid concentration of 3mol/L, and filtering to obtain a leaching solution containing cobalt and manganese.
Detecting the content of each element in the obtained leachate, and calculating that the leaching rate of Li in the roasting water leaching process reaches 93.85 percent, the leaching rates of Co and Mn are lower than 0.5 percent, and the contents of other impurity ions are less than 0.9 mg/L; the leaching rates of Co and Mn in the acid leaching process of the conversion slag are respectively 99.85 percent and 99.81 percent.
The method can synergistically utilize the anhydrous sodium sulphate produced by the lithium salt preparation and ternary precursor synthesis system of the lithium battery material enterprise, and has the advantages of simple process, low production cost, high recovery rate of valuable metals and the like. Lithium is extracted from battery powder and forms water-soluble lithium sulfate by reducing sodium roasting, and preferential selective extraction of lithium can be realized by adopting pure water leaching; meanwhile, valuable metal phases such as nickel, cobalt, manganese and the like are converted from high-valence oxides into low-valence oxides easy to be subjected to acid leaching in a reducing atmosphere, and favorable conditions are created for recovering nickel, cobalt and manganese through subsequent wet leaching.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting substance is characterized by comprising the following steps:
(1) mixing waste lithium ion battery powder and sodium sulfate according to a preset molar ratio, and performing ball milling for a preset time to obtain a mixture;
(2) placing the mixture obtained in the step (1) in an electric furnace to perform reduced sodium roasting at a preset temperature, wherein the obtained reduced sodium roasting product is called calcine;
(3) leaching the calcine in the step (2) by using pure water to obtain a lithium-containing leaching solution and conversion slag;
(4) and (4) leaching the conversion slag obtained in the step (3) by using sulfuric acid to extract valuable metals such as nickel, cobalt and manganese.
2. The method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting substance as claimed in claim 1, wherein the waste lithium ion battery powder in the step (1) is black powder produced by crushing and sorting waste lithium ion batteries, and the positive electrode material of the black powder is one or more of lithium manganate, lithium cobaltate and ternary mixtures.
3. The method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting agent as claimed in claim 1, wherein the sodium sulfate in the step (1) is anhydrous sodium sulfate produced by lithium salt preparation and ternary precursor synthesis system of lithium battery material enterprise.
4. The method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting material as claimed in claim 1, wherein the molar ratio in the step (1) is the molar ratio of lithium to sodium sulfate in the waste lithium ion battery powder (n)Li:nNa2SO4) The ratio of the raw materials to the mixed powder is 1:0.5-2, and the mixing and ball milling time is 0.5-3 h.
5. The method for selectively extracting valuable metals from waste lithium ion battery powder based on phase transformation of reduced sodium roasting material as claimed in claim 1, wherein the reaction temperature of the reduced sodium roasting material in the step (2) is 500-850 ℃, and the reaction time is 1-4 h.
6. The method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting substance according to claim 1, wherein the reaction time of pure water leaching in the step (3) is 0.5-4h, the reaction temperature is 30-98 ℃, and the liquid-solid ratio is 3-10: 1.
7. The method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of reduced sodium roasting substance as claimed in claim 1, wherein the acid concentration of sulfuric acid leaching of the conversion residue in the step (4) is 0.5-4mol/L, the reaction time is 0.5-3h, the reaction temperature is 30-98 ℃, and the liquid-solid ratio is 4-20: 1.
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