CN114906863B - Comprehensive recovery method of waste lithium manganate anode material - Google Patents
Comprehensive recovery method of waste lithium manganate anode material Download PDFInfo
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- CN114906863B CN114906863B CN202210606493.8A CN202210606493A CN114906863B CN 114906863 B CN114906863 B CN 114906863B CN 202210606493 A CN202210606493 A CN 202210606493A CN 114906863 B CN114906863 B CN 114906863B
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000011084 recovery Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 239000010405 anode material Substances 0.000 title claims abstract description 32
- 238000002425 crystallisation Methods 0.000 claims abstract description 67
- 230000008025 crystallization Effects 0.000 claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 65
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 63
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 63
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 63
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 63
- 239000000243 solution Substances 0.000 claims abstract description 54
- 238000002386 leaching Methods 0.000 claims abstract description 44
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 34
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 239000012452 mother liquor Substances 0.000 claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000010413 mother solution Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 239000012629 purifying agent Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 239000007774 positive electrode material 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
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 14
- 238000001953 recrystallisation Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009388 chemical precipitation Methods 0.000 abstract description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical group [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- 238000003825 pressing Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 iron and the like Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 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 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 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 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Abstract
The application provides a comprehensive recovery method of a waste lithium manganate battery anode material, which takes the waste lithium manganate anode material as a raw material and comprises the steps of sequentially leaching anode black powder, chemical impurity removal of leaching liquid, crystallization separation of impurity removal liquid, preparation of battery-grade manganese sulfate by recrystallization of crude manganese sulfate, preparation of battery-grade lithium carbonate by crystallization separation mother liquor and the like. According to the application, separation and recovery of lithium and manganese can be realized without adopting a chemical precipitation separation and extraction process, the leaching solution containing manganese and lithium is used for preferentially separating manganese in a crystallization mode by a high-temperature pressurized crystallization separation method and preparing battery-grade manganese sulfate, lithium is still left in a mother solution in a lithium sulfate form, and the crystallization mother solution is further precipitated and recovered to prepare battery-grade lithium carbonate. The process method has the advantages of high recovery rate of valuable metal manganese and lithium, simple process, short flow, low production cost, environmental protection, high added value of products and the like.
Description
Technical Field
The application relates to the technical field of waste anode material recovery, in particular to a comprehensive recovery method of waste lithium manganate anode material.
Background
In recent years, the industry of China electric automobiles is rapidly developed, and the sales of the electric automobiles are increasing. But the average service life of the power battery in the electric automobile is about 10 years, and the electric automobile which enters the market early enters the battery retirement stage at present. According to market research prediction, the scrapped amount of the lithium battery for the vehicle in 2020 reaches 32GWh, and the scrapped battery is converted into about 50 ten thousand tons in mass; by 2030, the scrapped amount of the lithium battery for the vehicle can reach 300GWh, and the scrapped amount of the lithium battery is about 300 ten thousand tons. Lithium batteries are mainly divided into lithium iron phosphate batteries, ternary lithium batteries, lithium titanate batteries, lithium manganate batteries and the like according to different positive electrode materials, and the lithium manganate batteries are more and more valued by virtue of the advantages of good rate performance, easier preparation, lower cost and the like. At present, the metal raw materials such as lithium, manganese and the like for preparing the ternary positive electrode material or the lithium manganate positive electrode material are high in price and large in demand. Therefore, the method for extracting metals such as lithium, manganese and the like from the waste lithium batteries can solve the problem of raw material supply and create great benefits for society.
The key link of recycling the lithium manganate anode material is to recycle the lithium manganate anode materialAnd then further preparing related lithium salt and manganese salt. The Chinese patent with application number 201710380170.0 adds the lithium manganate positive electrode material obtained by disassembly into organic acid for reduction leaching, then extracts lithium from the leaching solution through phosphoric acid extractant, and adds carbonate into the back extraction solution to prepare lithium carbonate. The method adopts organic acid leaching, has low leaching rate of valuable metals, and has higher treatment difficulty and cost of later-stage wastewater; meanwhile, the extracting agent is used for extracting lithium from the leaching solution containing manganese and lithium, so that the selectivity is poor, the extraction efficiency is low, and the production cost is high. The Chinese patent with the application number of 201811093693.8 utilizes a nanofiltration membrane technology to separate lithium ions in the acidified leaching solution from other cations different from the lithium ions to obtain a lithium-containing solution and a solution containing other cations, and then adopts a reverse osmosis technology to concentrate and enrich the lithium-containing solution and the solution containing other cations respectively; the process has low lithium separation efficiency, needs to consume a large amount of water, and has low lithium enrichment concentration, so that the recovery process is long and the cost is high. The Chinese patent with application number 202110677455.7 puts the pretreated lithium manganate positive electrode material into inorganic acid, and the alpha-MnO is obtained after high-pressure reaction 2 Or beta-MnO 2 Or gamma-MnO 2 Thereby preparing MnO with larger specific surface area and porous structure 2 The product can be further used for battery anode materials and super capacitor electrode materials. Although the method can well realize the recycling of the lithium manganate anode material, the impurity ions are difficult to control in the treatment process, and the performance of the obtained material is not stable enough and is not suitable for wide popularization and use.
In conclusion, the existing recovery process of the waste lithium manganate anode material has the problems of low recovery rate of valuable metals, long process flow, low production efficiency, high recovery treatment cost, low added value of products and the like.
Disclosure of Invention
The application solves the technical problem of providing a comprehensive recovery method of waste lithium manganate anode materials, which can recover battery-grade manganese sulfate and battery-grade lithium carbonate and has high recovery rate.
In view of the above, the application provides a comprehensive recovery method of waste lithium manganate anode materials, which comprises the following steps:
a) Mixing waste lithium manganate anode materials with water to obtain slurry, and carrying out reduction leaching on the slurry to obtain leaching liquid;
b) Adding a impurity removing agent into the leaching solution to remove impurities, and then adding an oxidizing agent to obtain an impurity-removed liquid;
c) Performing high-temperature crystallization on the impurity-removed liquid, and performing centrifugal separation to obtain crude manganese sulfate crystals and lithium-containing crystallization mother liquor;
d) Dissolving the crude manganese sulfate crystal, then carrying out high-temperature crystallization again, and carrying out centrifugal separation to obtain refined manganese sulfate crystal and crystallization mother liquor;
e) Drying the refined manganese sulfate crystal to obtain battery-grade manganese sulfate, adding a purifying agent into the lithium-containing crystallization mother liquor, and reacting to obtain a lithium-containing purified solution;
f) And precipitating lithium from the purified solution containing lithium to obtain a wet lithium carbonate material and a mother solution for precipitating lithium, and washing and drying the wet lithium carbonate material to obtain the battery-grade lithium carbonate.
Preferably, in the step A), the reagent for reducing leaching is sulfuric acid and a reducing agent, the sulfuric acid is 98% concentrated sulfuric acid, the pH value of the system is regulated to be 0.5-3.0, and the reducing agent is one or more selected from hydrogen peroxide, sodium sulfite and sodium thiosulfate.
Preferably, in the step A), the liquid-solid ratio of the water to the waste lithium manganate anode material is 2:1-5:1.
Preferably, in the step B), the impurity removing agent is selected from one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water, and the oxidizing agent is selected from one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite.
Preferably, in the step C), the high-temperature crystallization process specifically includes:
and (3) pumping the impurity-removed liquid into a crystallization reaction kettle for high-temperature crystallization, and centrifugally separating the obtained crystal slurry when the manganese concentration reaches 80-120 g/L to obtain crude manganese sulfate crystals and lithium-containing crystallization mother liquor.
Preferably, in the step C), the temperature of the high-temperature crystallization is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h.
Preferably, the high temperature crystallization in step D) is specifically:
adding the crude manganese sulfate crystals into pure water for dissolution, pumping the solution into a crystallization reaction kettle again for high-temperature crystallization, and obtaining refined manganese sulfate crystals and crystallization mother liquor after centrifugal separation when the manganese concentration reaches 80-120 g/L.
Preferably, in the step D), the high-temperature crystallization temperature is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h.
Preferably, in the step E), the purifying agent is one or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water, the concentration of the purifying agent is 5-30%, the pH value of the reaction is 10.0-12.0, and the reaction time is 0.5-1 h.
Preferably, the lithium depositing reagent is sodium carbonate solution with the concentration of 200-300 g/L, the reaction temperature of the lithium depositing is 50-100 ℃ and the time is 1-5 h.
The application provides a comprehensive recovery method of waste lithium manganate anode materials, which takes waste lithium manganate anode materials as recovery objects, and can realize comprehensive recovery of lithium and manganese through the steps of reduction leaching of anode black powder, chemical impurity removal of leaching liquid, crystallization separation of impurity removal liquid, preparation of battery-grade manganese sulfate by recrystallization of crude manganese sulfate, preparation of battery-grade lithium carbonate by crystallization separation mother liquor and the like; the recovery method does not need the traditional extraction process and the chemical precipitation separation process, and the application realizes the separation and recovery of lithium and manganese by utilizing the difference of the solubility of manganese sulfate and lithium sulfate along with the temperature change; the method has the advantages of simple and stable process, high production efficiency, low production cost, zero emission of wastewater and the like, is easy to realize industrial production, has high recovery rate of valuable metal manganese and lithium, and has excellent quality of manganese sulfate and lithium carbonate and extremely high production benefit.
Drawings
Fig. 1 is a schematic flow chart of a comprehensive recovery method of waste lithium manganate anode materials.
Detailed Description
For a further understanding of the present application, preferred embodiments of the application are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the application, and are not limiting of the claims of the application.
In view of the technical problems of recovery treatment of waste lithium manganate anode materials in the prior art, the application provides a comprehensive recovery method of waste lithium manganate anode materials, which comprises the steps of carrying out reduction leaching of the waste lithium manganate anode materials, adding precipitants into leaching solution to remove impurities such as copper, iron, aluminum and the like, carrying out crystallization separation on manganese and lithium under a high temperature condition, carrying out recrystallization on crude manganese sulfate to prepare battery-grade manganese sulfate, and preparing battery-grade lithium carbonate from crystallization separation mother liquor, wherein the flow is shown in a figure 1; through a series of operations, the application can prepare high-quality manganese sulfate and lithium carbonate. Specifically, the embodiment of the application discloses a comprehensive recovery method of waste lithium manganate anode materials, which comprises the following steps:
a) Mixing waste lithium manganate anode materials with water to obtain slurry, and carrying out reduction leaching on the slurry to obtain leaching liquid;
b) Adding a impurity removing agent into the leaching solution to remove impurities, and then adding an oxidizing agent to obtain an impurity-removed liquid;
c) Performing high-temperature crystallization on the impurity-removed liquid, and performing centrifugal separation to obtain crude manganese sulfate crystals and lithium-containing crystallization mother liquor;
d) Dissolving the crude manganese sulfate crystal, then carrying out high-temperature crystallization again, and carrying out centrifugal separation to obtain refined manganese sulfate crystal and crystallization mother liquor;
e) Drying the refined manganese sulfate crystal to obtain battery-grade manganese sulfate, adding a purifying agent into the lithium-containing crystallization mother liquor, and reacting to obtain a lithium-containing purified solution;
f) And precipitating lithium from the purified solution containing lithium to obtain a wet lithium carbonate material and a mother solution for precipitating lithium, and washing and drying the wet lithium carbonate material to obtain the battery-grade lithium carbonate.
In the comprehensive recovery method of the waste lithium manganate anode material, the application firstly carries out reduction leaching, namely, the waste lithium manganate anode material is mixed with water to obtain slurry, and then the slurry is subjected to reduction leaching to obtain leaching liquid; in the process, the waste lithium manganate anode material is subjected to reduction leaching of manganese element under the action of a reducing agent. The reducing leaching reagent is sulfuric acid and a reducing agent, wherein the sulfuric acid is 98% concentrated sulfuric acid, the pH value of the system is regulated to 0.5-3.0, and the reducing agent is one or more selected from hydrogen peroxide, sodium sulfite and sodium thiosulfate; in a specific embodiment, the reducing agent is selected from sodium sulfite or sodium thiosulfate, and the pH of the system is adjusted to 0.5-2.0. The liquid-solid ratio of the water to the waste lithium manganate anode material is 2:1-5:1, more specifically, the liquid-solid ratio of the water to the waste lithium manganate anode material is 3:1-4:1. The temperature of the reduction leaching is 50-100 ℃ and the time is 1-5 h; more specifically, the temperature of the reduction leaching is 60-80 ℃ and the time is 2-4 h.
The application further carries out chemical impurity removal, adds an impurity removing agent into the leaching solution to remove impurities such as copper, iron, aluminum and the like in the leaching solution, adds an oxidizing agent, and obtains impurity-removed liquid after stirring and filter pressing; in the process, the impurity removing agent is selected from one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water, and the oxidant completely oxidizes impurity ions such as iron and the like, and is specifically selected from one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite.
According to the application, the obtained solution after impurity removal is subjected to high-temperature crystallization of manganese sulfate in a crystallization reaction kettle, and preferably, when the manganese concentration reaches 80-120 g/L, the crystallization slurry is placed in a centrifuge for centrifugal separation, so as to obtain crude manganese sulfate crystals and lithium-containing crystallization mother liquor; the crude manganese sulfate crystal is used for preparing battery-grade manganese sulfate, and the lithium-containing crystallization mother liquor is used for preparing lithium carbonate; in this process, the solution after impurity removal contains manganese, which is separated in a crystallization manner during high-temperature crystallization. And then adding the crude manganese sulfate crystals into pure water for dissolution, stirring and dissolving, then pouring the obtained product into a crystallization reaction kettle again for high-temperature crystallization of manganese sulfate, and when the manganese concentration reaches 80-120 g/L, putting the crystallization slurry into a centrifuge for centrifugal separation to obtain refined manganese sulfate crystals and recrystallization mother liquor, drying the refined manganese sulfate crystals to obtain a battery-grade manganese sulfate product, and returning the recrystallization mother liquor to the step one for size mixing. In the process, the temperature of the high-temperature crystallization is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h; more specifically, the high-temperature crystallization temperature is 120-180 ℃, the reaction pressure is 0.2-0.4 MPa, and the time is 1.5-2.5 h.
The application then adds purifying agent into the lithium-containing crystallization mother liquor, and the lithium-containing purified liquid is obtained after the reaction. In the process, the purifying agent is selected from one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water, the concentration of the purifying agent is 5-30%, the pH value of the reaction is 10.0-12.0, and the reaction time is 0.5-1 h; more specifically, the concentration of the purifying agent is 10-20%, and the reaction time is 0.6-0.8 h. The above process is used to purify residual manganese and impurity elements.
And finally, precipitating lithium from the purified solution to obtain a lithium carbonate wet material and a lithium precipitation mother solution, and washing and drying the lithium carbonate wet material to obtain the battery-grade lithium carbonate. In the process, the lithium depositing reagent is a sodium carbonate solution with the concentration of 200-300 g/L, the reaction temperature of the lithium depositing is 50-100 ℃ for 1-5 h, specifically, the lithium depositing reagent is a sodium carbonate solution with the concentration of 220-270 g/L, and the reaction temperature of the lithium depositing is 60-80 ℃ for 2-4 h; the washing temperature is 50-100 ℃, the washing times are 1-3 times, and the washing liquid-solid ratio is 1:1-3:1; the drying temperature is 100-200 ℃, and the drying time is 5-10 h.
In the application, the waste lithium manganate positive electrode material is at least one of positive electrode powder produced by a battery disassembling factory and positive electrode leftover materials produced by the positive electrode factory.
In order to further understand the application, the method for comprehensively recycling the waste lithium manganate anode material provided by the application is described in detail below by combining the examples, and the protection scope of the application is not limited by the examples below.
Example 1
100kg of waste lithium manganate anode materials (Li: 3.2 percent; mn:60 percent) purchased in a battery disassembling factory, water and recrystallization mother liquor are prepared into slurry according to a liquid-solid ratio of 2:1, 98 percent sulfuric acid is added into the slurry to adjust the pH value of a system to be 0.5, then 76.1kg of sodium sulfite is added according to 1.1 times of the required theoretical amount, the reaction temperature is controlled to be 85 ℃, and after stirring leaching for 2 hours, 400L of leaching liquid and 15kg of acid leaching slag are obtained by filter pressing; adding 5kg of sodium carbonate into the leaching solution to remove impurities, adjusting the pH value of the system to 5.0, adding 1.1kg of hydrogen peroxide, stirring and reacting for 1h, and then performing filter pressing; filtering and pressing to obtain impurity-removed liquid;
pumping the impurity-removed solution into a high-temperature crystallization kettle, keeping the crystallization temperature at 120 ℃, preserving the temperature for 1.5 hours, and performing centrifugal separation to obtain crude manganese sulfate crystals, and pumping the crude manganese sulfate crystals into a new impurity-removed solution again for concentration; after the manganese concentration reaches 120g/L, carrying out high-temperature crystallization on the concentrated solution again, mixing the crude manganese sulfate crystal with 280L of water for dissolution, pouring the mixed solution into a high-temperature crystallization kettle again after the crude manganese sulfate crystal is completely dissolved for high-temperature recrystallization, carrying out centrifugal separation after the crystallization temperature is 120 ℃, preserving heat for 1.5h, and drying the refined manganese sulfate crystal to obtain 180.7kg battery-grade manganese sulfate product No. 1. The recovery rate of manganese reaches 98 percent, and the main content of manganese sulfate is 99.3 percent.
Example 2
This example was further optimized based on example 1, specifically:
adding 6kg of 30% sodium hydroxide solution into the obtained lithium-containing crystallization mother liquor, adjusting the pH value of the system to 11.0, keeping the temperature at 50 ℃, stirring for 1h, and performing filter pressing to obtain a lithium-containing purified solution; pumping purified solution into a reaction kettle, adding 93.2L of 260g/L sodium carbonate solution with the required theoretical amount being 1.1 times, keeping the temperature at 80 ℃, stirring and reacting for 1h, and performing centrifugal separation to obtain 18.42kg of lithium carbonate wet material; washing twice at 90 ℃ according to the liquid-solid ratio of 1:1, and drying the centrifugally separated material in a baking oven at 120 ℃ for 5 hours to finally obtain 16.13kg of battery grade lithium carbonate. The recovery rate of lithium reaches 95.2%, and the main content of lithium carbonate is 99.6%.
Example 3
300kg of waste lithium manganate anode scraps (Li: 3.5 percent; mn:61 percent) produced by an anode factory, water and recrystallization mother liquor are prepared into slurry according to a liquid-solid ratio of 3:1, 98 percent sulfuric acid is added into the slurry to adjust the pH value of a system to be 1.5, 132kg of hydrogen peroxide is added according to 1.8 times of the required theoretical amount, the reaction temperature is controlled to be 50 ℃, and the mixture is stirred and leached for 5 hours and then is subjected to pressure filtration to obtain 1200L of leaching liquid and 10kg of acid leaching slag; adding 13.8kg of sodium hydroxide into the leaching solution to remove impurities, adjusting the pH value of the system to 4.5, adding 1.6kg of sodium chlorate, stirring and reacting for 1h, and performing filter pressing to obtain impurity-removed liquid;
pumping the impurity-removed solution into a high-temperature crystallization kettle, keeping the crystallization temperature at 160 ℃, preserving the temperature for 3 hours, and performing centrifugal separation to obtain crude manganese sulfate crystals, and pumping the crude manganese sulfate crystals into a new impurity-removed solution again for concentration; after the manganese concentration reaches 100g/L, carrying out high-temperature crystallization on the concentrated solution again, mixing the crude manganese sulfate crystal with 1830L of water for dissolution, pouring the solution into a high-temperature crystallization kettle again after the dissolution is completed for high-temperature recrystallization, carrying out centrifugal separation after the crystallization temperature is 160 ℃, preserving heat for 2.5h, and drying the refined manganese sulfate crystal to obtain 557.84kg battery-grade manganese sulfate product No. 2. The recovery rate of manganese reaches 98.3 percent, and the main content of manganese sulfate is 99.1 percent.
Example 4
This example was further optimized based on example 3, specifically:
adding 10kg of 10% lithium hydroxide solution into the obtained lithium-containing crystallization mother liquor, regulating the pH value of the system to 10, keeping the temperature to 30 ℃, stirring for 0.5h, and performing filter pressing to obtain a lithium-containing purified solution; pumping purified solution into a reaction kettle, adding 270g/L sodium carbonate solution 382.8L which is 1.3 times of the required theoretical amount, keeping the temperature at 95 ℃, stirring and reacting for 5 hours, and performing centrifugal separation to obtain 61.66kg of lithium carbonate wet material; adding pure water according to a liquid-solid ratio of 3:1, washing for three times at 90 ℃, and drying the centrifugally separated material in a 200 ℃ oven for 8 hours to finally obtain 53.39kg of battery grade lithium carbonate. The recovery rate of lithium reaches 96.3%, and the main content of lithium carbonate is 99.6%.
Example 5
500kg of waste lithium manganate anode material (Li: 3.0 percent; mn:58.8 percent) purchased in a battery disassembling factory, water and recrystallization mother liquor are prepared into slurry according to a liquid-solid ratio of 5:1, 98 percent sulfuric acid is added into the slurry to adjust the pH value of the system to 2.0, then 60.45kg of sodium thiosulfate is added according to 1.5 times of the required theoretical amount, the reaction temperature is controlled to be 60 ℃, and after stirring leaching for 3 hours, 3200L leaching liquid and 70kg acid leaching slag are obtained by filter pressing; adding 10kg of ammonia water into the leaching solution to remove impurities, adjusting the pH value of the system to 5.0, adding 2.5kg of sodium hypochlorite, stirring to react for 0.5h, and performing filter pressing to obtain the impurity-removed solution.
Pumping the impurity-removed solution into a high-temperature crystallization kettle, keeping the crystallization temperature at 180 ℃, preserving the temperature for 2 hours, and performing centrifugal separation to obtain crude manganese sulfate crystals, and pumping the crude manganese sulfate crystals into a new impurity-removed solution again for concentration; after the manganese concentration reaches 110g/L, carrying out high-temperature crystallization on the concentrated solution again, mixing the crude manganese sulfate crystals with 9126.3L of water for dissolution, pouring the mixed solution into a high-temperature crystallization kettle again after the crude manganese sulfate crystals are completely dissolved for high-temperature recrystallization, carrying out centrifugal separation after the crystallization temperature is 180 ℃, preserving heat for 2 hours, and drying the refined manganese sulfate crystals to obtain 887.24kg of battery-grade manganese sulfate product No. 1. The recovery rate of manganese reaches 98.2 percent, and the main content of manganese sulfate is 99.2 percent.
Example 6
This example was further optimized based on example 5, specifically:
adding 65kg of 20% potassium hydroxide solution into the obtained lithium-containing crystallization mother liquor, regulating the pH value of the system to 12, stirring for 1h at normal temperature, and then performing filter pressing to obtain a lithium-containing purified solution; pumping purified solution into a reaction kettle, adding 608.4L of 280g/L sodium carbonate solution with the required theoretical amount being 1.5 times, keeping the temperature at 100 ℃, stirring and reacting for 3 hours, and performing centrifugal separation to obtain 88.1kg of lithium carbonate wet material; washing once at 95 ℃ according to the liquid-solid ratio of 2:1, and drying the centrifugally separated material in a 160 ℃ oven for 6 hours to finally obtain 75.3kg of battery grade lithium carbonate. The recovery rate of lithium reaches 94.7%, and the main content of lithium carbonate is 99.7%.
The technical indexes of the manganese sulfate prepared in the above examples 1, 3 and 5 are shown in table 1, and the technical indexes of the lithium carbonate products in the examples 2, 4 and 6 are shown in table 2:
table 1 technical indices of battery grade manganese sulfate prepared in examples 1, 3, 5
Table 2 technical indices of battery grade lithium carbonate prepared in examples 2, 4, 6
According to Table 1, the manganese sulfate recovered by the method provided by the example has high content and low impurity content, and according to Table 2, the lithium carbonate recovered by the method provided by the example has high content and low impurity content, so that the recovery method provided by the application can obtain battery-grade manganese sulfate and lithium carbonate.
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (3)
1. A comprehensive recovery method of waste lithium manganate anode materials comprises the following steps:
a) Mixing waste lithium manganate anode materials with water to obtain slurry, and carrying out reduction leaching on the slurry to obtain leaching liquid;
b) Adding a impurity removing agent into the leaching solution to remove impurities, and then adding an oxidizing agent to obtain an impurity-removed liquid; the impurity removing agent is selected from one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water, and the oxidant is selected from one or more of hydrogen peroxide, sodium chlorate and sodium hypochlorite;
c) Performing high-temperature crystallization on the impurity-removed liquid, and performing centrifugal separation to obtain crude manganese sulfate crystals and lithium-containing crystallization mother liquor;
d) Adding the crude manganese sulfate crystals into pure water for dissolution, pumping the crude manganese sulfate crystals into a crystallization reaction kettle again for high-temperature crystallization, and obtaining refined manganese sulfate crystals and crystallization mother liquor after centrifugal separation when the manganese concentration reaches 80-120 g/L; the high-temperature crystallization temperature is 100-200 ℃, the reaction pressure is 0.1-0.5 MPa, and the time is 1-3 h;
e) Drying the refined manganese sulfate crystal to obtain battery-grade manganese sulfate, adding a purifying agent into the lithium-containing crystallization mother liquor, and reacting to obtain a lithium-containing purified solution; in the step E), the purifying agent is selected from one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia water, the concentration of the purifying agent is 5-30%, the pH value of the reaction is 10.0-12.0, and the reaction time is 0.5-1 h;
f) Precipitating lithium from the purified solution to obtain a lithium carbonate wet material and a lithium precipitation mother solution, and washing and drying the lithium carbonate wet material to obtain battery-grade lithium carbonate; the lithium depositing reagent is sodium carbonate solution with the concentration of 200-300 g/L, the reaction temperature of the lithium depositing is 50-100 ℃ and the time is 1-5 h.
2. The comprehensive recovery method according to claim 1, wherein in the step a), the reagent for the reduction leaching is sulfuric acid and a reducing agent, the sulfuric acid is 98% concentrated sulfuric acid, the pH of the system is adjusted to 0.5-3.0, and the reducing agent is one or more selected from hydrogen peroxide, sodium sulfite and sodium thiosulfate.
3. The comprehensive recovery method according to claim 1, wherein in the step a), the liquid-solid ratio of the water to the waste lithium manganate positive electrode material is 2:1-5:1.
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