CN112981107A - Method for recycling lithium carbonate from waste ternary lithium battery positive electrode material - Google Patents
Method for recycling lithium carbonate from waste ternary lithium battery positive electrode material Download PDFInfo
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- CN112981107A CN112981107A CN202110168762.2A CN202110168762A CN112981107A CN 112981107 A CN112981107 A CN 112981107A CN 202110168762 A CN202110168762 A CN 202110168762A CN 112981107 A CN112981107 A CN 112981107A
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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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- 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
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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
Abstract
The invention discloses a method for recovering lithium carbonate from a waste ternary lithium battery positive electrode material, which relates to the technical field of waste ternary lithium battery positive electrode material recovery and comprises the following preparation steps: crushing and separating, primary leaching with sulfuric acid, and secondary leaching with sulfuric acid: putting the carbon powder slag into water, adding sulfuric acid for reaction and dissolution to obtain a carbon powder slag dissolving solution, removing aluminum and iron from a primary leaching solution, filtering, extracting and precipitating lithium; the prepared sodium carbonate has high recovery rate, low content of impurity elements, safe and environment-friendly process and suitability for industrial production.
Description
Technical Field
The invention relates to the technical field of recycling of anode materials of waste ternary lithium batteries, in particular to a method for recycling lithium carbonate from the anode materials of the waste ternary lithium batteries.
Background
With the continuous development of society, due to the increasing shortage of energy and the increasing awareness of environmental protection, more and more people turn their eyes to the transition to new energy, and therefore, since the lithium ion battery was commercialized in 1991, due to the characteristics of environmental protection, little pollution and excellent electrochemical performance, the electrochemical material is widely applied to the fields of telephones, notebook computers and electric automobiles, the electric automobiles mostly adopt ternary lithium batteries as power sources, so the demand of the ternary lithium batteries is continuously increased along with the rise of the electric automobile industry, however, the service life of the ternary lithium batteries is generally 3-8 years, the waste ternary lithium batteries are also called as non-negligible parts in solid wastes along with the increase of the demand, and a large amount of waste lithium batteries can cause environmental pollution and resource waste if not treated; meanwhile, because lithium resources are scarce in China, the recovery of lithium from the waste ternary lithium battery can relieve the resource pressure and eliminate the hidden danger of pollution. However, the present lithium recovery process of lithium battery usually requires high temperature roasting, for example, a method disclosed in chinese patent document "a method for recovering cobalt and lithium metal from waste lithium cobalt oxide battery", which is disclosed in publication No. CN112095000A, discloses a method for recovering lithium metal from waste lithium cobalt oxide battery, which is characterized in that: the method comprises the following specific steps: (1) performing discharge treatment on the waste lithium cobaltate battery, and obtaining black lithium cobaltate powder after disassembling, crushing, pyrolyzing and screening; (2) mixing the black lithium cobaltate powder obtained in the step (1) with ammonium salt according to a molar ratio of 1: 1.5-4, placing the mixture in a high-temperature ball mill for carrying out enhanced ammonia roasting to convert lithium cobaltate into sulfate, carrying out water leaching to obtain a leaching solution rich in Co2+ and Li +, and recovering ammonia gas generated in the process and recovering and recycling the ammonia gas in the form of ammonium sulfate; (3) and (3) selectively recovering cobalt and lithium components from the leaching solution rich in Co2+ and Li + obtained in the step (2), recovering cobalt by using an organic extractant, recovering lithium in residual liquid by a precipitation method, and recovering lithium in the form of lithium carbonate. However, the high-temperature roasting method not only consumes a large amount of energy, but also easily produces waste gas after burning of a diaphragm, a binder and the like remaining in the lithium battery, easily causes environmental pollution, and has a high waste gas treatment cost.
Disclosure of Invention
The invention provides a method for recovering lithium carbonate from a waste ternary lithium battery positive electrode material, aiming at overcoming the problems that in the prior art, lithium is recovered by a method for roasting waste lithium batteries at a high temperature, energy consumption is high, waste gas is easily generated after residual diaphragms, binders and the like in the lithium batteries are combusted, environment pollution is easily caused, the waste gas treatment cost is high, and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recycling lithium carbonate from a waste ternary lithium battery positive electrode material comprises the following preparation steps:
s1: crushing and separating: crushing the waste ternary lithium battery, and then performing magnetic attraction, grading sieving and cyclone sedimentation to prepare battery powder;
s2: primary leaching of sulfuric acid: placing the battery powder into water and secondary leaching solution to obtain mixed solution, and then adding sulfuric acid to react and dissolve to obtain dissolved solution;
s3: adding a reducing agent into the dissolved solution, and carrying out solid-liquid separation after reaction to obtain carbon powder slag and primary leaching solution;
s4: secondary leaching of sulfuric acid: putting the carbon powder slag into water, adding sulfuric acid to react and dissolve to obtain a carbon powder slag dissolving solution;
s5: adding a reducing agent into the carbon powder slag dissolved solution, and carrying out solid-liquid separation after reaction to obtain secondary carbon powder slag and a secondary leaching solution; s6: removing aluminum and iron from primary leachate: adding a sodium carbonate solution into the primary leaching solution for deironing reaction, and filtering to prepare aluminum-iron slag and deironing aluminum liquid;
s7: and (3) filtering: performing nanofiltration treatment on the iron-removed aluminum liquid by adopting a high-selectivity nanofiltration membrane to prepare filtrate;
s8: and (3) extraction: adding a metal extracting agent into the filtrate, and separating after extraction to obtain a lithium-containing water phase;
s9: and (3) lithium deposition: controlling the pH value of the lithium-containing water phase to be 8-8.5, adding a sodium carbonate solution for precipitation reaction to obtain lithium water, then concentrating the lithium water, controlling the pH value to be 9.5-10.5, adding the sodium carbonate solution for precipitation reaction, filtering, washing and drying the precipitate to prepare the lithium carbonate.
According to the invention, firstly, after the waste ternary lithium battery is crushed, the diaphragm, the aluminum, the copper and the iron can be separated from the battery powder through magnetic attraction, grading sieving and cyclone sedimentation by utilizing the different physical properties of the diaphragm, the aluminum, the copper and the iron and the battery powder, so that the substances such as the diaphragm, the aluminum, the copper and the iron in the battery powder are reduced, the subsequent treatment procedures are favorably reduced, and the content of impurities in a product is reduced; then, mixing the battery powder with water and secondary leachate, adding sulfuric acid to generate corresponding iso-sulfate, and reducing high-valence metal ions by using a reducing agent to facilitate subsequent recovery treatment; after solid-liquid separation is carried out by adopting a filter press, carbon powder slag and primary leachate are prepared, in order to further improve the yield, the carbon powder slag is subjected to secondary leaching, the specific operation is that the carbon powder slag is placed in water and added with sulfuric acid for reaction and dissolution, then a reducing agent is added into a carbon powder slag solution for solid-liquid separation to prepare secondary leachate, and the secondary leachate and the water are mixed to be used as a base solution of the battery powder in the step S2, so that lithium element in the battery powder can be transferred to the primary leachate as much as possible; then, adding a sodium carbonate solution into the primary leachate to enable iron and aluminum to generate corresponding iron and aluminum hydroxide precipitates to remove iron and aluminum, then performing nanofiltration treatment on the iron-removed aluminum liquid by using a high-selectivity nanofiltration membrane, wherein the high-selectivity nanofiltration membrane can effectively intercept high-valence metal ions, so that monovalent lithium ions can be separated from other divalent cations, then further separating residual metal ions such as copper, iron, zinc, calcium, aluminum, chromium, manganese and the like from the filtrate through extraction to obtain a lithium-containing water phase, then controlling the pH of the lithium-containing water phase to be 8-8.5, performing nickel and magnesium precipitation separation by using the sodium carbonate solution, then concentrating the obtained lithium water, adjusting the pH to be 9.5-10.5, performing reaction filtration by using the sodium carbonate solution, washing and drying, and preparing the lithium carbonate. According to the invention, through the steps of crushing separation, primary sulfuric acid leaching, secondary sulfuric acid leaching, aluminum and iron removal of primary leachate, filtering, extraction and lithium precipitation, the prepared sodium carbonate has high recovery rate, low content of impurity elements, safe and environment-friendly process and suitability for industrial production.
Preferably, the high-selectivity nanofiltration membrane in the step S7 is a polysulfone and sulfonated polysulfone composite membrane, and the molecular weight cut-off is 150-2000 Da.
Preferably, the nanofiltration treatment condition in step S7 is performed at 0.5 to 1MPa and 20 to 40 ℃.
Preferably, the precipitation reaction temperature in step S9 is 60-80 ℃; the lithium content after concentration is 8-10 g/L.
Preferably, in step S2, the mixed solution contains the following raw materials in parts by weight: 30-40 parts of battery powder, 10-100 parts of water and 0-60 parts of secondary leaching solution; the pH value is 0.5-1.5 after adding the sulfuric acid.
Preferably, the reducing agent is 25-30wt% of hydrogen peroxide or sodium metabisulfite, and the mass ratio of the reducing agent to the battery powder in the step S3 is 0.2-0.4: 1; the reaction is carried out for 6-10h at the temperature of 60-85 ℃; and controlling the pH value to be 2-2.5 during the solid-liquid separation, wherein the concentration of cobalt, nickel and magnesium in the primary leaching solution is 60-90 g/L.
Preferably, the steps S4 and S5 comprise the following raw materials in parts by weight: 20-30 parts of carbon powder slag, 30-50 parts of water, 10-20 parts of sulfuric acid and 5-10 parts of a reducing agent; in the step S5, the reaction is carried out for 6-10h at 65-95 ℃, and the cobalt content in the secondary carbon powder slag is less than or equal to 0.1 wt%.
Preferably, the concentration of the sodium carbonate solution is 20-25 wt%; in the step S6, the reaction conditions for removing iron and aluminum are as follows: controlling the pH value to be 5-5.4, and reacting at the temperature of 50-80 ℃ and the stirring speed of 200-; the aluminum in the iron-removed aluminum liquid is less than or equal to 0.6g/L, the iron is less than or equal to 0.01g/L, and the content of nickel, cobalt, manganese and copper is 35-60 g/L; the cobalt content in the ferro-aluminum slag is less than or equal to 0.3wt percent, and the nickel content in the ferro-aluminum slag is less than or equal to 0.5wt percent.
Preferably, the pH of the filtrate during the extraction in step S8 is controlled to 3-3.5.
Preferably, the metal extractant comprises the following preparation steps:
(1) placing 2-5 parts of ferric chloride hexahydrate in 120 parts of glycol 100-;
(2) dispersing 3-5 parts of ferroferric oxide particles in 400 parts of 300-piece deionized water, then adding 10-12 parts of fructose and 25-30 parts of urea, stirring and dissolving, reacting at 210 ℃ for 10-12h, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 15-20 parts of isobutyl acrylate and 2-4 parts of diacetone acrylamide into 140-160 parts of N, N-dimethylformamide, then adding 5-8 parts of mesoporous ferroferric oxide particles with cavities and 0.1-0.5 part of azobisisobutyronitrile, stirring for 1-2h for preloading, then reacting for 4-5h at 75-85 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding 1-2 parts of adipic dihydrazide, adjusting the pH to 5-6, reacting for 1-3h, and then performing centrifugal drying to prepare crosslinked polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing the crosslinked polymer loaded mesoporous ferroferric oxide particles in 2-5wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(6) dissolving sodium dodecyl sulfate in 150 parts of 130-one water to prepare a prepolymerization emulsion with the concentration of 9-12mmol/L, then adding 10-15 parts of methyl methacrylate and 0.1-0.5 part of potassium persulfate, carrying out prepolymerization reaction at 60-75 ℃ for 0.5-1h, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(7) dissolving sodium dodecyl sulfate in 200 parts of 180-phase water to prepare a polymerization emulsion with the concentration of 9-12mmol/L, adding 5-8 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 5-10 parts of polymethyl methacrylate prepolymer, 8-15 parts of methyl methacrylate, 2-4 parts of methacrylamide, 1-2 parts of trimethylolpropane trimethacrylate and 0.1-0.5 part of potassium persulfate, carrying out polymerization reaction for 3-4h at the temperature of 60-75 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing and adsorbing for 15-20 hours under a vacuum condition, and filtering to prepare the metal extractant.
The research personnel of the invention found in a large number of experiments and production that floccules are easily generated on an oil-water interface when a P204 liquid-phase extractant is adopted for extracting metal ions, thereby influencing metal extraction, meanwhile, the liquid-phase extractant is also very easy to cause the loss of the extractant, phase separation is difficult, thereby causing the purity of the prepared product to be low and the cost to be high, in order to overcome the defects, the metal extractant prepared by the invention is a solid-phase metal extractant and has a three-layer structure, wherein, a shell layer is a polymer coating layer, a middle layer is mesoporous ferroferric oxide particles, the innermost layer is coated with an organic liquid-phase extractant, when the metal extractant is used, the metal extractant can be put into water containing metal ions, the metal extractant can be filled into a column for extracting the metal ions, and during the metal ion extraction process of the metal extractant, metal ions can be adsorbed to the surface of a polymer layer of the metal extractant, and because the surfaces of the mesoporous ferroferric oxide particles in the intermediate layer are full of holes, the metal ions can be extracted into the metal extractant in a solid phase form through the organic liquid phase extractant coated by the innermost layer, and meanwhile, because the mesoporous ferroferric oxide particles have magnetism, the metal extractant can be recovered through the permanent magnet after extraction is completed, so that the metal extractant is convenient and fast; and the metal extractant which is extracted and adsorbed with the metal ions is placed in a water body, and the back extraction of the metal ions can be realized by adjusting the pH and the temperature, so that the regeneration of the metal extractant is realized. Therefore, the metal extractant prepared by the invention is in a solid phase form, floccules are generated in the using process, the organic liquid phase extractant is not excessively lost, the extraction effect is good, the purity of the extracted product is high, the magnetism is realized, the metal extractant can be conveniently and quickly recovered by a magnet after the adsorption is finished, the metal extractant is placed in water, the back extraction of metal ions is realized by adjusting the pH value and the temperature, and the industrial use is facilitated.
In the preparation process of the solid-phase metal extractant, firstly, ferroferric oxide particles are prepared, and then the ferroferric oxide particles are converted into mesoporous ferroferric oxide particles with cavities by a hydrothermal method; then, loading a polymer by using a cavity in a mesoporous ferroferric oxide particle with the cavity, stirring and pre-loading isobutyl acrylate, diacetone acrylamide, an initiator azobisisobutyronitrile and the mesoporous ferroferric oxide particle with the cavity in a loading process, then enabling the isobutyl acrylate, the diacetone acrylamide and the azobisisobutyronitrile to enter the cavity, raising the temperature to initiate a reaction and preserving the temperature to prepare the polymer-loaded mesoporous ferroferric oxide particle, wherein a loaded polymer molecular chain has an isobutyl polyacrylate chain segment and polydiacetone acrylamide, the isobutyl polyacrylate chain segment has strong oleophylic property and can help a metal extractant to adsorb an organic liquid phase extractant, and the polydiacetone acrylamide chain segment has an active ketocarbonyl group, by adding adipimide, active ketone carbonyl can perform a crosslinking reaction with active hydrazide groups on the adipimide, so that a linear polymer loaded in a cavity of the mesoporous ferroferric oxide particle is converted into a three-dimensional network structure, the crosslinked polymer loaded mesoporous ferroferric oxide particle is prepared, the linear polymer is converted into the three-dimensional network structure, and the polymer in the cavity of the mesoporous ferroferric oxide particle can be prevented from being removed through mesopores; subsequently, polymer coating is carried out on the crosslinked polymer loaded mesoporous ferroferric oxide particles, as the surfaces of the crosslinked polymer loaded mesoporous ferroferric oxide particles are rich in hydroxyl groups, silane coupling agent modification is carried out on the hydroxyl groups, and the hydroxyl groups are endowed with active groups polymerized with acrylate monomers, the crosslinked polymer loaded mesoporous ferroferric oxide particles are coated by the segmented copolymer, during coating, methyl methacrylate is firstly pre-polymerized to prepare polymethyl methacrylate prepolymer, and research personnel discover that if the crosslinked polymer loaded mesoporous ferroferric oxide particles are completely coated by adopting a monomer form, part of the monomer can enter a cavity through the mesopores, so that the adsorption of a subsequent organic liquid phase extracting agent is influenced, the extraction efficiency is further influenced, and the part of the crosslinked polymer loaded mesoporous ferroferric oxide particles adopts a prepolymer form, so that the probability of the monomer entering the cavity can be reduced; meanwhile, in the invention, methacrylamide and trimethylolpropane trimethacrylate are adopted in the polymer coating, wherein the methacrylamide has active amino, so that the polymer coating can generate strong interaction with metal ions, the extraction rate is increased, and the trimethylolpropane trimethacrylate is used as a cross-linking agent to increase the cross-linking density of the polymer coating and prevent the leakage of an organic liquid phase extracting agent; after the polymer-coated ferroferric oxide particles are prepared, the polymer-coated ferroferric oxide particles are immersed in an organic liquid phase extracting agent, and after standing and adsorption under a vacuum condition, the cavities of the polymer-coated ferroferric oxide particles are filled with the organic liquid phase for extraction, so that the metal extracting agent is successfully prepared.
Therefore, the invention has the following beneficial effects:
(1) according to the invention, through the steps of crushing separation, primary sulfuric acid leaching, secondary sulfuric acid leaching, aluminum and iron removal of primary leachate, filtering, extraction and lithium precipitation, the prepared sodium carbonate has high recovery rate, low content of impurity elements, safe and environment-friendly working procedures and is suitable for industrial production;
(2) the metal extractant prepared by the invention is in a solid phase form, floccules are generated in the using process, the organic liquid phase extractant is not excessively lost, the extraction effect is good, the purity of the extracted product is high, the magnetism is realized, and the metal extractant can be conveniently and quickly recovered by a magnet after the adsorption is finished.
Detailed Description
The invention is further described with reference to specific embodiments.
General example: a method for recycling lithium carbonate from a waste ternary lithium battery positive electrode material comprises the following preparation steps:
s1: crushing and separating: crushing the waste ternary lithium battery, and then performing magnetic attraction, grading sieving and cyclone sedimentation to prepare battery powder;
s2: primary leaching of sulfuric acid: placing 30-40 parts of battery powder into 10-100 parts of water and 0-60 parts of secondary leaching solution to obtain a mixed solution, then adding sulfuric acid to adjust the pH value to 0.5-1.5, and reacting and dissolving to obtain a dissolved solution;
s3: adding a reducing agent into the dissolved solution, keeping the temperature at 60-85 ℃ for reaction for 6-10h, adjusting the pH value to 2-2.5, and then carrying out solid-liquid separation to obtain carbon powder slag and a primary leachate, wherein the concentration of cobalt, nickel and magnesium in the primary leachate is 60-90 g/L; the reducing agent is 25-30wt% of hydrogen peroxide or sodium metabisulfite, and the mass ratio of the reducing agent to the battery powder is 0.2-0.4: 1;
s4: secondary leaching of sulfuric acid: putting 20-30 parts of carbon powder slag into 30-50 parts of water, adding 10-20 parts of sulfuric acid, and reacting and dissolving to obtain a carbon powder slag dissolving solution;
s5: adding 5-10 parts of reducing agent into the carbon powder slag dissolved solution, carrying out heat preservation reaction at 65-95 ℃ for 6-10h, and then carrying out solid-liquid separation to obtain secondary carbon powder slag and secondary leaching solution, wherein the cobalt content in the secondary carbon powder slag is less than or equal to 0.1 wt%;
s6: removing aluminum and iron from primary leachate: controlling the pH value to be 5-5.4, adding 20-25wt% of sodium carbonate solution into the primary leaching solution at the temperature of 50-80 ℃ and the stirring speed of 200-250 r/min for deironing reaction, and filtering to prepare ferro-aluminum slag and deironing aluminum liquid; the aluminum in the iron-removed aluminum liquid is less than or equal to 0.6g/L, the iron is less than or equal to 0.01g/L, and the content of nickel, cobalt, manganese and copper is 35-60 g/L; the cobalt content in the ferro-aluminum slag is less than or equal to 0.3wt percent, and the nickel content in the ferro-aluminum slag is less than or equal to 0.5wt percent;
s7: and (3) filtering: performing nanofiltration treatment on the iron-removed aluminum liquid by adopting a polysulfone and sulfonated polysulfone composite nanofiltration membrane with the molecular weight cutoff of 150-;
s8: and (3) extraction: controlling the pH value of the filtrate to be 3-3.5, adding a metal extractant, and separating after extraction to obtain a lithium-containing water phase;
s9: and (3) lithium deposition: controlling the pH value of a lithium-containing water phase to be 8-8.5, adding 20-25wt% of sodium carbonate solution, precipitating and reacting at 60-80 ℃ to obtain lithium water, then concentrating the lithium water until the lithium content is 8-10g/L, controlling the pH value to be 9.5-10.5, adding the sodium carbonate solution, precipitating and reacting at 60-80 ℃, filtering, washing and drying the precipitate, and preparing to obtain lithium carbonate;
the metal extractant comprises the following preparation steps:
(1) placing 2-5 parts of ferric chloride hexahydrate in 120 parts of glycol 100-;
(2) dispersing 3-5 parts of ferroferric oxide particles in 400 parts of 300-piece deionized water, then adding 10-12 parts of fructose and 25-30 parts of urea, stirring and dissolving, reacting at 210 ℃ for 10-12h, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 15-20 parts of isobutyl acrylate and 2-4 parts of diacetone acrylamide into 140-160 parts of N, N-dimethylformamide, then adding 5-8 parts of mesoporous ferroferric oxide particles with cavities and 0.1-0.5 part of azobisisobutyronitrile, stirring for 1-2h for preloading, then reacting for 4-5h at 75-85 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding 1-2 parts of adipic dihydrazide, adjusting the pH to 5-6, reacting for 1-3h, and then performing centrifugal drying to prepare crosslinked polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing the crosslinked polymer loaded mesoporous ferroferric oxide particles in 2-5wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(6) dissolving sodium dodecyl sulfate in 150 parts of 130-one water to prepare a prepolymerization emulsion with the concentration of 9-12mmol/L, then adding 10-15 parts of methyl methacrylate and 0.1-0.5 part of potassium persulfate, carrying out prepolymerization reaction at 60-75 ℃ for 0.5-1h, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(7) dissolving sodium dodecyl sulfate in 200 parts of 180-phase water to prepare a polymerization emulsion with the concentration of 9-12mmol/L, adding 5-8 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 5-10 parts of polymethyl methacrylate prepolymer, 8-15 parts of methyl methacrylate, 2-4 parts of methacrylamide, 1-2 parts of trimethylolpropane trimethacrylate and 0.1-0.5 part of potassium persulfate, carrying out polymerization reaction for 3-4h at the temperature of 60-75 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing and adsorbing for 15-20 hours under a vacuum condition, and filtering to prepare the metal extractant.
Example 1: a method for recycling lithium carbonate from a waste ternary lithium battery positive electrode material comprises the following preparation steps:
s1: crushing and separating: crushing the waste ternary lithium battery, and then performing magnetic attraction, grading sieving and cyclone sedimentation to prepare battery powder;
s2: primary leaching of sulfuric acid: placing 36 parts of battery powder into 60 parts of water and 30 parts of secondary leaching solution to obtain a mixed solution, then adding sulfuric acid to adjust the pH value to 1.2, and reacting and dissolving to obtain a dissolved solution;
s3: adding 12 parts of 26 wt% hydrogen peroxide into the dissolved solution, keeping the temperature at 80 ℃ for 7 hours for reaction, adjusting the pH value to 2.2, and then carrying out solid-liquid separation to obtain carbon powder slag and a primary leachate, wherein the concentration of cobalt, nickel and magnesium in the primary leachate is 70 g/L;
s4: secondary leaching of sulfuric acid: putting 25 parts of carbon powder slag into 40 parts of water, adding 17 parts of sulfuric acid, and reacting and dissolving to obtain a carbon powder slag dissolving solution;
s5: adding 8 parts of 26 wt% hydrogen peroxide into the carbon powder slag dissolved solution, carrying out heat preservation reaction at 85 ℃ for 7 hours, and then carrying out solid-liquid separation to obtain secondary carbon powder slag and a secondary leaching solution, wherein the cobalt content in the secondary carbon powder slag is less than or equal to 0.1 wt%;
s6: removing aluminum and iron from primary leachate: controlling the pH value to be 5.3, adding 2 wt% of sodium carbonate solution into primary leaching solution at the temperature of 65 ℃ and the stirring speed of 230 r/min for deironing reaction, and filtering to prepare ferro-aluminum slag and deironing aluminum liquid; the aluminum in the iron-removed aluminum liquid is less than or equal to 0.6g/L, the iron is less than or equal to 0.01g/L, and the content of nickel, cobalt, manganese and copper is 35-60 g/L; the cobalt content in the ferro-aluminum slag is less than or equal to 0.3wt percent, and the nickel content in the ferro-aluminum slag is less than or equal to 0.5wt percent; s7: and (3) filtering: performing nanofiltration treatment on the iron-removed aluminum liquid by adopting a polysulfone and sulfonated polysulfone composite nanofiltration membrane with the molecular weight cutoff of 1000Da at 0.8MPa and 30 ℃ to prepare filtrate;
s8: and (3) extraction: controlling the pH value of the filtrate to be 3.3, adding a metal extracting agent, and separating after extraction to obtain a lithium-containing water phase;
s9: and (3) lithium deposition: controlling the pH value of a lithium-containing water phase to be 8.2, adding 22 wt% of sodium carbonate solution, precipitating and reacting at 70 ℃ to obtain lithium water, then concentrating the lithium water until the lithium content is 9g/L, controlling the pH value to be 10, adding the sodium carbonate solution, precipitating and reacting at 70 ℃, filtering, washing and drying the precipitate, and preparing lithium carbonate;
the metal extractant comprises the following preparation steps:
(1) putting 4 parts of ferric chloride hexahydrate in 110 parts of glycol, stirring for dissolving, then adding 12 parts of sodium acetate and 1.5 parts of polypropylene glycol, stirring, and then calcining at 210 ℃ for 7 hours to prepare ferroferric oxide particles;
(2) dispersing 4 parts of ferroferric oxide particles in 350 parts of deionized water, then adding 11 parts of fructose and 28 parts of urea, stirring and dissolving, reacting for 11 hours at 200 ℃, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 17 parts of isobutyl acrylate and 3 parts of diacetone acrylamide in 150 parts of N, N-dimethylformamide, then adding 7 parts of mesoporous ferroferric oxide particles with cavities and 0.4 part of azobisisobutyronitrile, stirring for 1.5h for preloading, then reacting for 4.5h at 80 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding 1.5 parts of adipic dihydrazide, adjusting the pH to 5.5, reacting for 2 hours, and then performing centrifugal drying to prepare crosslinked polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing the crosslinked polymer loaded mesoporous ferroferric oxide particles in 2.5 wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(6) dissolving sodium dodecyl sulfate in 140 parts of water to prepare 10mmol/L pre-polymerization emulsion, then adding 13 parts of methyl methacrylate and 0.3 part of potassium persulfate, carrying out pre-polymerization reaction at 70 ℃ for 0.8h, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(7) dissolving sodium dodecyl sulfate in 190 parts of water to prepare a polymerization emulsion with the concentration of 10mmol/L, adding 7 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 8 parts of polymethyl methacrylate prepolymer, 13 parts of methyl methacrylate, 3 parts of methacrylamide, 1.5 parts of trimethylolpropane trimethacrylate and 0.3 part of potassium persulfate, carrying out polymerization reaction for 3.5 hours at 70 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing and adsorbing for 17 hours under a vacuum condition, and filtering to prepare the metal extractant.
Example 2: a method for recycling lithium carbonate from a waste ternary lithium battery positive electrode material comprises the following preparation steps:
s1: crushing and separating: crushing the waste ternary lithium battery, and then performing magnetic attraction, grading sieving and cyclone sedimentation to prepare battery powder;
s2: primary leaching of sulfuric acid: placing 30 parts of battery powder into 10 parts of water and 60 parts of secondary leaching solution to obtain a mixed solution, then adding sulfuric acid to adjust the pH value to 0.5, and reacting and dissolving to obtain a dissolved solution;
s3: adding 6 parts of sodium metabisulfite into the dissolved solution, keeping the temperature at 60 ℃ for reaction for 10 hours, adjusting the pH value to 2, and then carrying out solid-liquid separation to obtain carbon powder slag and primary leachate, wherein the concentration of cobalt, nickel and magnesium in the primary leachate is 60 g/L;
s4: secondary leaching of sulfuric acid: putting 20 parts of carbon powder slag into 30 parts of water, adding 10 parts of sulfuric acid, and reacting and dissolving to obtain a carbon powder slag dissolving solution;
s5: adding 5 parts of sodium pyrosulfite into the carbon powder slag dissolved solution, carrying out heat preservation reaction at 65 ℃ for 10 hours, and then carrying out solid-liquid separation to obtain secondary carbon powder slag and secondary leachate, wherein the cobalt content in the secondary carbon powder slag is less than or equal to 0.1 wt%;
s6: removing aluminum and iron from primary leachate: controlling the pH value to be 5, adding 20 wt% of sodium carbonate solution into primary leaching solution at the stirring speed of 200 r/min at 50 ℃ to perform iron and aluminum removing reaction, and filtering to prepare aluminum iron slag and iron and aluminum removing liquid; the aluminum in the iron-removed aluminum liquid is less than or equal to 0.6g/L, the iron is less than or equal to 0.01g/L, and the content of nickel, cobalt, manganese and copper is 35-60 g/L; the cobalt content in the ferro-aluminum slag is less than or equal to 0.3wt percent, and the nickel content in the ferro-aluminum slag is less than or equal to 0.5wt percent; s7: and (3) filtering: performing nanofiltration treatment on the iron-removed aluminum liquid by adopting a polysulfone and sulfonated polysulfone composite nanofiltration membrane with the molecular weight cutoff of 1000Da at 0.5MPa and 20 ℃ to prepare filtrate;
s8: and (3) extraction: controlling the pH value of the filtrate to be 3, adding a metal extractant, and separating after extraction to obtain a lithium-containing water phase;
s9: and (3) lithium deposition: controlling the pH value of a lithium-containing water phase to be 8, adding 20 wt% of sodium carbonate solution, precipitating and reacting at 60 ℃ to obtain lithium water, then concentrating the lithium water until the lithium content is 8g/L, controlling the pH value to be 9.5, adding the sodium carbonate solution, precipitating and reacting at 60 ℃, filtering, washing and drying precipitates, and preparing lithium carbonate;
the metal extractant comprises the following preparation steps:
(1) placing 2 parts of ferric chloride hexahydrate in 100 parts of glycol, stirring for dissolving, then adding 10 parts of sodium acetate and 1 part of polypropylene glycol, stirring, and then placing at 200 ℃ for calcining for 8 hours to prepare ferroferric oxide particles;
(2) dispersing 3 parts of ferroferric oxide particles into 300 parts of deionized water, then adding 10 parts of fructose and 25 parts of urea, stirring and dissolving, reacting at 190 ℃ for 12 hours, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 15 parts of isobutyl acrylate and 2 parts of diacetone acrylamide in 140 parts of N, N-dimethylformamide, then adding 5 parts of mesoporous ferroferric oxide particles with cavities and 0.1 part of azobisisobutyronitrile, stirring for 1 hour for preloading, then reacting for 5 hours at 75 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding 1 part of adipic dihydrazide, adjusting the pH to 5, reacting for 1 hour, and then centrifugally drying to prepare crosslinked polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing the crosslinked polymer loaded mesoporous ferroferric oxide particles in 2 wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(6) dissolving sodium dodecyl sulfate in 130 parts of water to prepare a prepolymerization emulsion with the concentration of 9mmol/L, then adding 10 parts of methyl methacrylate and 0.1 part of potassium persulfate, carrying out prepolymerization reaction at 60 ℃ for 1h, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(7) dissolving sodium dodecyl sulfate in 180 parts of water to prepare a polymerization emulsion with the concentration of 9mmol/L, adding 5 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 5 parts of polymethyl methacrylate prepolymer, 8 parts of methyl methacrylate, 2 parts of methacrylamide, 1 part of trimethylolpropane trimethacrylate and 0.1 part of potassium persulfate, carrying out polymerization reaction for 4 hours at 60 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing and adsorbing for 15 hours under a vacuum condition, and filtering to prepare the metal extractant.
Example 3: a method for recycling lithium carbonate from a waste ternary lithium battery positive electrode material comprises the following preparation steps:
s1: crushing and separating: crushing the waste ternary lithium battery, and then performing magnetic attraction, grading sieving and cyclone sedimentation to prepare battery powder;
s2: primary leaching of sulfuric acid: putting 40 parts of battery powder into 100 parts of water to obtain a mixed solution, adding sulfuric acid to adjust the pH to 1.5, and then reacting and dissolving to obtain a dissolved solution;
s3: adding 16 parts of 30wt% hydrogen peroxide into the dissolved solution, keeping the temperature at 85 ℃ for reaction for 6 hours, adjusting the pH value to 2.5, and then carrying out solid-liquid separation to obtain carbon powder slag and a primary leachate, wherein the concentration of cobalt, nickel and magnesium in the primary leachate is 90 g/L;
s4: secondary leaching of sulfuric acid: putting 30 parts of carbon powder slag into 50 parts of water, adding 20 parts of sulfuric acid, and reacting and dissolving to obtain a carbon powder slag dissolving solution;
s5: adding 10 parts of reducing agent into the carbon powder slag dissolved solution, carrying out heat preservation reaction at 95 ℃ for 6 hours, and then carrying out solid-liquid separation to obtain secondary carbon powder slag and secondary leaching solution, wherein the cobalt content in the secondary carbon powder slag is less than or equal to 0.1 wt%;
s6: removing aluminum and iron from primary leachate: controlling the pH value to be 5.4, adding 25wt% of sodium carbonate solution into primary leaching solution at the temperature of 80 ℃ and the stirring speed of 250 r/min for deironing reaction, and filtering to prepare ferro-aluminum slag and deironing aluminum liquid; the aluminum in the iron-removed aluminum liquid is less than or equal to 0.6g/L, the iron is less than or equal to 0.01g/L, and the content of nickel, cobalt, manganese and copper is 60 g/L; the cobalt content in the ferro-aluminum slag is less than or equal to 0.3wt percent, and the nickel content in the ferro-aluminum slag is less than or equal to 0.5wt percent;
s7: and (3) filtering: performing nanofiltration treatment on the iron-removed aluminum liquid by adopting a polysulfone and sulfonated polysulfone composite nanofiltration membrane with the molecular weight cutoff of 1000Da at 1MPa and 40 ℃ to prepare filtrate;
s8: and (3) extraction: controlling the pH value of the filtrate to be 3.5, adding a metal extracting agent, and separating after extraction to obtain a lithium-containing water phase;
s9: and (3) lithium deposition: controlling the pH value of a lithium-containing water phase to be 8.5, adding 25wt% of sodium carbonate solution, precipitating and reacting at 80 ℃ to obtain lithium water, then concentrating the lithium water until the lithium content is 10g/L, controlling the pH value to be 10.5, adding the sodium carbonate solution, precipitating and reacting at 80 ℃, filtering, washing and drying the precipitate, and preparing lithium carbonate;
the metal extractant comprises the following preparation steps:
(1) placing 5 parts of ferric chloride hexahydrate in 120 parts of glycol, stirring for dissolving, then adding 13 parts of sodium acetate and 2 parts of polypropylene glycol, stirring, and then placing at 220 ℃ for calcining for 6 hours to prepare ferroferric oxide particles;
(2) dispersing 5 parts of ferroferric oxide particles into 400 parts of deionized water, then adding 12 parts of fructose and 30 parts of urea, stirring and dissolving, reacting for 10 hours at 210 ℃, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 20 parts of isobutyl acrylate and 4 parts of diacetone acrylamide in 160 parts of N, N-dimethylformamide, then adding 8 parts of mesoporous ferroferric oxide particles with cavities and 0.5 part of azobisisobutyronitrile, stirring for 2 hours for preloading, then reacting for 4 hours at 85 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding 2 parts of adipic dihydrazide, adjusting the pH to 6, reacting for 3 hours, and then centrifugally drying to prepare crosslinked polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing the crosslinked polymer loaded mesoporous ferroferric oxide particles in 5wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(6) dissolving sodium dodecyl sulfate in 150 parts of water to prepare a pre-polymerization emulsion with the concentration of 12mmol/L, then adding 15 parts of methyl methacrylate and 0.5 part of potassium persulfate, carrying out pre-polymerization reaction at 75 ℃ for 1 hour, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(7) dissolving sodium dodecyl sulfate in 200 parts of water to prepare a polymerization emulsion with the concentration of 12mmol/L, adding 8 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 10 parts of polymethyl methacrylate prepolymer, 15 parts of methyl methacrylate, 4 parts of methacrylamide, 2 parts of trimethylolpropane trimethacrylate and 0.5 part of potassium persulfate, carrying out polymerization reaction for 3 hours at 75 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing and adsorbing for 20 hours under a vacuum condition, and filtering to prepare the metal extractant.
Comparative example 1: the difference from example 1 is that a conventional P204 extractant is used in S8.
Comparative example 2: the difference from example 1 is that the metal extractant comprises the following preparation steps:
(1) putting 4 parts of ferric chloride hexahydrate in 110 parts of glycol, stirring for dissolving, then adding 12 parts of sodium acetate and 1.5 parts of polypropylene glycol, stirring, and then calcining at 210 ℃ for 7 hours to prepare ferroferric oxide particles;
(2) dispersing 4 parts of ferroferric oxide particles in 350 parts of deionized water, then adding 11 parts of fructose and 28 parts of urea, stirring and dissolving, reacting for 11 hours at 200 ℃, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) dispersing mesoporous ferroferric oxide particles with cavities in 2.5 wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(4) dissolving sodium dodecyl sulfate in 140 parts of water to prepare 10mmol/L pre-polymerization emulsion, then adding 13 parts of methyl methacrylate and 0.3 part of potassium persulfate, carrying out pre-polymerization reaction at 70 ℃ for 0.8h, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(5) dissolving sodium dodecyl sulfate in 190 parts of water to prepare a polymerization emulsion with the concentration of 10mmol/L, adding 7 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 8 parts of polymethyl methacrylate prepolymer, 13 parts of methyl methacrylate, 3 parts of methacrylamide, 1.5 parts of trimethylolpropane trimethacrylate and 0.3 part of potassium persulfate, carrying out polymerization reaction for 3.5 hours at 70 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(6) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing for 17 hours under a vacuum condition, and filtering to prepare the metal extractant.
Comparative example 3: the difference from example 1 is that the metal extractant comprises the following preparation steps:
(1) putting 4 parts of ferric chloride hexahydrate in 110 parts of glycol, stirring for dissolving, then adding 12 parts of sodium acetate and 1.5 parts of polypropylene glycol, stirring, and then calcining at 210 ℃ for 7 hours to prepare ferroferric oxide particles;
(2) dispersing 4 parts of ferroferric oxide particles in 350 parts of deionized water, then adding 11 parts of fructose and 28 parts of urea, stirring and dissolving, reacting for 11 hours at 200 ℃, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 17 parts of isobutyl acrylate in 150 parts of N, N-dimethylformamide, then adding 7 parts of mesoporous ferroferric oxide particles with cavities and 0.4 part of azobisisobutyronitrile, stirring for 1.5 hours for preloading, then reacting for 4.5 hours at 80 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing polymer-loaded mesoporous ferroferric oxide particles into 2.5 wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane-modified ferroferric oxide particles;
(6) dissolving sodium dodecyl sulfate in 140 parts of water to prepare 10mmol/L pre-polymerization emulsion, then adding 13 parts of methyl methacrylate and 0.3 part of potassium persulfate, carrying out pre-polymerization reaction at 70 ℃ for 0.8h, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(7) dissolving sodium dodecyl sulfate in 190 parts of water to prepare a polymerization emulsion with the concentration of 10mmol/L, adding 7 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 8 parts of polymethyl methacrylate prepolymer, 13 parts of methyl methacrylate, 3 parts of methacrylamide, 1.5 parts of trimethylolpropane trimethacrylate and 0.3 part of potassium persulfate, carrying out polymerization reaction for 3.5 hours at 70 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing for 17 hours under a vacuum condition, and filtering to prepare the metal extractant.
Comparative example 4: the difference from example 1 is that the metal extractant comprises the following preparation steps:
(1) putting 4 parts of ferric chloride hexahydrate in 110 parts of glycol, stirring for dissolving, then adding 12 parts of sodium acetate and 1.5 parts of polypropylene glycol, stirring, and then calcining at 210 ℃ for 7 hours to prepare ferroferric oxide particles;
(2) dispersing 4 parts of ferroferric oxide particles in 350 parts of deionized water, then adding 11 parts of fructose and 28 parts of urea, stirring and dissolving, reacting for 11 hours at 200 ℃, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 17 parts of isobutyl acrylate and 3 parts of diacetone acrylamide in 150 parts of N, N-dimethylformamide, then adding 7 parts of mesoporous ferroferric oxide particles with cavities and 0.4 part of azobisisobutyronitrile, stirring for 1.5h for preloading, then reacting for 4.5h at 80 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding 1.5 parts of adipic dihydrazide, adjusting the pH to 5.5, reacting for 2 hours, and then performing centrifugal drying to prepare crosslinked polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing the crosslinked polymer loaded mesoporous ferroferric oxide particles in 2.5 wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(7) dissolving sodium dodecyl sulfate in 190 parts of water to prepare a polymerization emulsion with the concentration of 10mmol/L, adding 7 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 21 parts of methyl methacrylate, 3 parts of methacrylamide, 1.5 parts of trimethylolpropane trimethacrylate and 0.3 part of potassium persulfate, carrying out polymerization reaction for 3.5 hours at 70 ℃, demulsifying, washing and drying precipitates, and preparing to obtain polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing for 17 hours under a vacuum condition, and filtering to prepare the metal extractant.
Comparative example 5: the difference from example 1 is that the prepolymerization time for preparing the polymethyl methacrylate prepolymer is 0.2h when the metal extractant is prepared.
Comparative example 6: the difference from example 1 is that the prepolymerization time for preparing the polymethyl methacrylate prepolymer is 1.5h when the metal extractant is prepared.
Comparative example 7: the difference from example 1 is that the metal extractant comprises the following preparation steps:
(1) putting 4 parts of ferric chloride hexahydrate in 110 parts of glycol, stirring for dissolving, then adding 12 parts of sodium acetate and 1.5 parts of polypropylene glycol, stirring, and then calcining at 210 ℃ for 7 hours to prepare ferroferric oxide particles;
(2) dispersing 4 parts of ferroferric oxide particles in 350 parts of deionized water, then adding 11 parts of fructose and 28 parts of urea, stirring and dissolving, reacting for 11 hours at 200 ℃, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 17 parts of isobutyl acrylate and 3 parts of diacetone acrylamide in 150 parts of N, N-dimethylformamide, then adding 7 parts of mesoporous ferroferric oxide particles with cavities and 0.4 part of azobisisobutyronitrile, stirring for 1.5h for preloading, then reacting for 4.5h at 80 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding 1.5 parts of adipic dihydrazide, adjusting the pH to 5.5, reacting for 2 hours, and then performing centrifugal drying to prepare crosslinked polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing the crosslinked polymer loaded mesoporous ferroferric oxide particles in 2.5 wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(6) dissolving sodium dodecyl sulfate in 140 parts of water to prepare 10mmol/L pre-polymerization emulsion, then adding 13 parts of methyl methacrylate and 0.3 part of potassium persulfate, carrying out pre-polymerization reaction at 70 ℃ for 0.8h, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(7) dissolving sodium dodecyl sulfate in 190 parts of water to prepare a polymerization emulsion with the concentration of 10mmol/L, adding 7 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 8 parts of polymethyl methacrylate prepolymer, 16 parts of methyl methacrylate, 1.5 parts of trimethylolpropane trimethacrylate and 0.3 part of potassium persulfate, carrying out polymerization reaction for 3.5 hours at 70 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing for 17 hours under a vacuum condition, and filtering to prepare the metal extractant.
The lithium carbonate prepared in the example is detected according to the GB/T11075-2003 standard.
| Item | Lithium carbonate | Na2O | Fe2O3 | CaO | SO2 4 - | Cl- | H2O | Hydrochloric acid insoluble substance |
| Standard of merit | ≥98.5％ | ≤0.25 | ≤0.015 | ≤0.1 | ≤0.5 | ≤0.020 | ≤0.8 | ≤0.050 |
| Example 1 | 98.7 | 0.18 | 0.004 | 0.05 | 0.42 | 0.007 | 0.2 | 0.024 |
| Example 2 | 98.7 | 0.19 | 0.006 | 0.04 | 0.37 | 0.012 | 0.1 | 0.021 |
| Example 3 | 98.8 | 0.19 | 0.006 | 0.03 | 0.32 | 0.010 | 0.2 | 0.025 |
According to the data, the lithium carbonate prepared by the invention has high purity and meets the standard.
The lithium recovery rates of the examples and comparative examples were measured and the results are shown in the following table.
| Item | Lithium recovery (%) |
| Example 1 | 88.7 |
| Example 2 | 88.4 |
| Example 3 | 88.3 |
| Comparative example 1 | 81.2 |
| Comparative example 2 | 69.3 |
| Comparative example 3 | 64.6 |
| Comparative example 4 | 68.4 |
| Comparative example 5 | 69.8 |
| Comparative example 6 | 71.2 |
| Comparative example 7 | 70.9 |
According to the data, the lithium recovery rate is higher in the embodiment of the invention, the conventional liquid-phase P204 extractant is adopted in the comparative example 1, and the metal extractant prepared by the invention is not adopted, so that the lithium recovery rate is relatively lower; the difference between the comparative example 2 and the example 1 is that polymer loading is not carried out in a cavity of the mesoporous ferroferric oxide particle, so that the extraction agent is insufficiently adsorbed or is subsequently lost, the extraction rate is influenced, and the lithium recovery rate is reduced; the difference between the comparative example 3 and the example 1 is that the polymer loaded in the cavity is not crosslinked, so that the polymer is removed in the preparation process, the load is insufficient, and the lithium recovery rate is influenced; in comparative examples 4 to 6, the prepolymerization of methyl methacrylate was not carried out or the prepolymerization time exceeded the defined range, and the lithium recovery rate was reduced; comparative example 7 differs from example 1 in that methacrylamide was not used for the polymer coating, reducing the interaction between the polymer coating and the metal ions, affecting the recovery of lithium.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for recycling lithium carbonate from a waste ternary lithium battery positive electrode material is characterized by comprising the following preparation steps:
s1: crushing and separating: crushing the waste ternary lithium battery, and then performing magnetic attraction, grading sieving and cyclone sedimentation to prepare battery powder;
s2: primary leaching of sulfuric acid: placing the battery powder into water and secondary leaching solution to obtain mixed solution, and then adding sulfuric acid to react and dissolve to obtain dissolved solution;
s3: adding a reducing agent into the dissolved solution, and carrying out solid-liquid separation after reaction to obtain carbon powder slag and primary leaching solution;
s4: secondary leaching of sulfuric acid: putting the carbon powder slag into water, adding sulfuric acid to react and dissolve to obtain a carbon powder slag dissolving solution;
s5: adding a reducing agent into the carbon powder slag dissolved solution, and carrying out solid-liquid separation after reaction to obtain secondary carbon powder slag and a secondary leaching solution;
s6: removing aluminum and iron from primary leachate: adding a sodium carbonate solution into the primary leaching solution for deironing reaction, and filtering to prepare aluminum-iron slag and deironing aluminum liquid;
s7: and (3) filtering: performing nanofiltration treatment on the iron-removed aluminum liquid by adopting a high-selectivity nanofiltration membrane to prepare filtrate;
s8: and (3) extraction: adding a metal extracting agent into the filtrate, and separating after extraction to obtain a lithium-containing water phase;
s9: and (3) lithium deposition: controlling the pH value of the lithium-containing water phase to be 8-8.5, adding a sodium carbonate solution for precipitation reaction to obtain lithium water, then concentrating the lithium water, controlling the pH value to be 9.5-10.5, adding the sodium carbonate solution for precipitation reaction, filtering, washing and drying the precipitate to prepare the lithium carbonate.
2. The method for recycling lithium carbonate from the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the high-selectivity nanofiltration membrane in step S7 is a polysulfone and sulfonated polysulfone composite membrane, and the molecular weight cut-off is 150-2000 Da.
3. The method for recycling lithium carbonate from the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the nanofiltration treatment condition in the step S7 is performed at 20-40 ℃ under 0.5-1 MPa.
4. The method for recycling lithium carbonate from the positive electrode material of the waste ternary lithium battery as claimed in claim 1, wherein the precipitation reaction temperature in step S9 is 60-80 ℃; the lithium content after concentration is 8-10 g/L.
5. The method for recycling lithium carbonate from the positive electrode material of the waste ternary lithium battery as claimed in claim 1, wherein the mixed solution in the step S2 comprises the following raw materials in parts by weight: 30-40 parts of battery powder, 10-100 parts of water and 0-60 parts of secondary leaching solution; the pH value is 0.5-1.5 after adding the sulfuric acid.
6. The method for recycling the lithium carbonate from the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the reducing agent is 25-30wt% of hydrogen peroxide or sodium metabisulfite, and the mass ratio of the reducing agent to the battery powder in the step S3 is 0.2-0.4: 1; the reaction is carried out for 6-10h at the temperature of 60-85 ℃; and controlling the pH value to be 2-2.5 during the solid-liquid separation, wherein the concentration of cobalt, nickel and magnesium in the primary leaching solution is 60-90 g/L.
7. The method for recycling lithium carbonate from the positive electrode material of the waste ternary lithium battery as claimed in claim 1, wherein the steps S4 and S5 are as follows in parts by weight: 20-30 parts of carbon powder slag, 30-50 parts of water, 10-20 parts of sulfuric acid and 5-10 parts of a reducing agent; in the step S5, the reaction is carried out for 6-10h at 65-95 ℃, and the cobalt content in the secondary carbon powder slag is less than or equal to 0.1 wt%.
8. The method for recycling lithium carbonate from the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the concentration of the sodium carbonate solution is 20-25 wt%; in the step S6, the reaction conditions for removing iron and aluminum are as follows: controlling the pH value to be 5-5.4, and reacting at the temperature of 50-80 ℃ and the stirring speed of 200-; the aluminum in the iron-removed aluminum liquid is less than or equal to 0.6g/L, the iron is less than or equal to 0.01g/L, and the content of nickel, cobalt, manganese and copper is 35-60 g/L; the cobalt content in the ferro-aluminum slag is less than or equal to 0.3wt percent, and the nickel content in the ferro-aluminum slag is less than or equal to 0.5wt percent.
9. The method for recycling lithium carbonate from the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the pH of the filtrate during the extraction in the step S8 is controlled to be 3-3.5.
10. The method for recycling lithium carbonate from the positive electrode material of the waste ternary lithium battery as claimed in claim 1, wherein the metal extractant comprises the following preparation steps:
(1) placing 2-5 parts of ferric chloride hexahydrate in 120 parts of glycol 100-;
(2) dispersing 3-5 parts of ferroferric oxide particles in 400 parts of 300-piece deionized water, then adding 10-12 parts of fructose and 25-30 parts of urea, stirring and dissolving, reacting at 210 ℃ for 10-12h, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;
(3) placing 15-20 parts of isobutyl acrylate and 2-4 parts of diacetone acrylamide into 140-160 parts of N, N-dimethylformamide, then adding 5-8 parts of mesoporous ferroferric oxide particles with cavities and 0.1-0.5 part of azobisisobutyronitrile, stirring for 1-2h for preloading, then reacting for 4-5h at 75-85 ℃, and centrifugally drying to prepare polymer-loaded mesoporous ferroferric oxide particles;
(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding 1-2 parts of adipic dihydrazide, adjusting the pH to 5-6, reacting for 1-3h, and then performing centrifugal drying to prepare crosslinked polymer-loaded mesoporous ferroferric oxide particles;
(5) dispersing the crosslinked polymer loaded mesoporous ferroferric oxide particles in 2-5wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution to prepare silane modified ferroferric oxide particles;
(6) dissolving sodium dodecyl sulfate in 150 parts of 130-one water to prepare a prepolymerization emulsion with the concentration of 9-12mmol/L, then adding 10-15 parts of methyl methacrylate and 0.1-0.5 part of potassium persulfate, carrying out prepolymerization reaction at 60-75 ℃ for 0.5-1h, and demulsifying to prepare a polymethyl methacrylate prepolymer;
(7) dissolving sodium dodecyl sulfate in 200 parts of 180-phase water to prepare a polymerization emulsion with the concentration of 9-12mmol/L, adding 5-8 parts of silane modified ferroferric oxide particles, uniformly mixing, adding 5-10 parts of polymethyl methacrylate prepolymer, 8-15 parts of methyl methacrylate, 2-4 parts of methacrylamide, 1-2 parts of trimethylolpropane trimethacrylate and 0.1-0.5 part of potassium persulfate, carrying out polymerization reaction for 3-4h at the temperature of 60-75 ℃, demulsifying, washing and drying precipitates, and preparing polymer coated ferroferric oxide particles;
(8) and (3) placing the polymer-coated ferroferric oxide particles into a P204 extractant, standing and adsorbing for 15-20 hours under a vacuum condition, and filtering to prepare the metal extractant.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2067126C1 (en) * | 1993-07-01 | 1996-09-27 | Институт химии твердого тела и переработки минерального сырья СО РАН | Method of lithium extraction from lithium- and aluminium-containing waste |
| CN102163760A (en) * | 2011-03-17 | 2011-08-24 | 江西格林美资源循环有限公司 | Method for separating and recovering lithium and cobalt from positive electrode material of lithium battery |
| CN105762433A (en) * | 2016-05-16 | 2016-07-13 | 兰州理工大学 | Method for collaboratively treating acid-production tail gas and waste nickel cobalt lithium manganate and recovering metal |
| WO2017181766A1 (en) * | 2016-04-20 | 2017-10-26 | 天齐锂业股份有限公司 | Method for extracting lithium using slag from thermal recycling of lithium battery |
| CN109411842A (en) * | 2018-09-18 | 2019-03-01 | 余姚市鑫和电池材料有限公司 | A kind of environment-friendly preparation method of ternary precursor |
| CN111206148A (en) * | 2020-03-16 | 2020-05-29 | 宁波容百新能源科技股份有限公司 | Method for recycling and preparing ternary cathode material by using waste ternary lithium battery |
| CA3144716A1 (en) * | 2019-07-26 | 2021-02-04 | Wolfgang Rohde | Process for the recovery of lithium and other metals from waste lithium ion batteries |
-
2021
- 2021-02-07 CN CN202110168762.2A patent/CN112981107B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2067126C1 (en) * | 1993-07-01 | 1996-09-27 | Институт химии твердого тела и переработки минерального сырья СО РАН | Method of lithium extraction from lithium- and aluminium-containing waste |
| CN102163760A (en) * | 2011-03-17 | 2011-08-24 | 江西格林美资源循环有限公司 | Method for separating and recovering lithium and cobalt from positive electrode material of lithium battery |
| WO2017181766A1 (en) * | 2016-04-20 | 2017-10-26 | 天齐锂业股份有限公司 | Method for extracting lithium using slag from thermal recycling of lithium battery |
| CN105762433A (en) * | 2016-05-16 | 2016-07-13 | 兰州理工大学 | Method for collaboratively treating acid-production tail gas and waste nickel cobalt lithium manganate and recovering metal |
| CN109411842A (en) * | 2018-09-18 | 2019-03-01 | 余姚市鑫和电池材料有限公司 | A kind of environment-friendly preparation method of ternary precursor |
| CA3144716A1 (en) * | 2019-07-26 | 2021-02-04 | Wolfgang Rohde | Process for the recovery of lithium and other metals from waste lithium ion batteries |
| CN111206148A (en) * | 2020-03-16 | 2020-05-29 | 宁波容百新能源科技股份有限公司 | Method for recycling and preparing ternary cathode material by using waste ternary lithium battery |
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