阅读说明：本技术 一种废三元锂电池正极材料回收用金属萃取剂的制备方法及其应用 (Preparation method and application of metal extractant for recycling waste ternary lithium battery positive electrode material ) 是由 高月春 于 2021-02-07 设计创作，主要内容包括：本发明公开了一种废三元锂电池正极材料回收用金属萃取剂的制备方法及其应用,涉及萃取剂制备技术领域,包括以下制备步骤：(1)具有空腔的介孔四氧化三铁颗粒制备；(2)交联聚合物负载介孔四氧化三铁颗粒制备；(3)硅烷改性四氧化三铁颗粒制备；(4)聚甲基丙烯酸甲酯预聚物制备；(5)聚合物包覆四氧化三铁颗粒制备；(6)废三元锂电池正极材料回收用金属萃取剂制备；本发明制备得到的金属萃取剂为固相形态,在使用过程中不会产生絮状物,同时也不会过多损耗有机液相金属萃取剂,同时具有磁性,在吸附完成之后可以通过磁体方便快捷的对金属萃取剂进行回收,置于水中,通过pH和温度的调节实现金属离子的反萃取,利于工业化使用。(The invention discloses a preparation method and application of a metal extractant for recycling a waste ternary lithium battery positive electrode material, relating to the technical field of extractant preparation and comprising the following preparation steps: (1) preparing mesoporous ferroferric oxide particles with cavities; (2) preparing crosslinked polymer loaded mesoporous ferroferric oxide particles; (3) preparing silane modified ferroferric oxide particles; (4) preparing a polymethyl methacrylate prepolymer; (5) preparing polymer-coated ferroferric oxide particles; (6) preparing a metal extractant for recycling the anode material of the waste ternary lithium battery; the metal extractant prepared by the invention is in a solid phase form, floccules cannot be generated in the using process, the organic liquid phase metal extractant cannot be excessively lost, and the metal extractant has magnetism, can be conveniently and quickly recovered by a magnet after adsorption is finished, is placed in water, realizes back extraction of metal ions by regulating pH and temperature, and is beneficial to industrial use.)

1. A preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material is characterized by comprising the following preparation steps:

(1) putting ferric chloride hexahydrate into glycol, stirring and dissolving, then adding sodium acetate and polypropylene glycol, stirring, and calcining to prepare ferroferric oxide particles;

(2) dispersing ferroferric oxide particles in deionized water, then adding fructose and urea, stirring and dissolving, carrying out heat preservation reaction, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;

(3) putting isobutyl acrylate and diacetone acrylamide into N, N-dimethylformamide, adding mesoporous ferroferric oxide particles with cavities and azobisisobutyronitrile, stirring for preloading, then carrying out heat preservation reaction, and carrying out centrifugal drying to prepare polymer-loaded mesoporous ferroferric oxide particles;

(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding adipic dihydrazide, performing crosslinking reaction, 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 a silane coupling agent solution to prepare silane modified ferroferric oxide particles;

(6) dissolving sodium dodecyl sulfate in water to prepare a pre-polymerization emulsion, then adding methyl methacrylate and potassium persulfate, carrying out pre-polymerization reaction, and demulsifying to prepare a polymethyl methacrylate prepolymer;

(7) dissolving sodium dodecyl sulfate in water to prepare a polymerization emulsion, adding silane modified ferroferric oxide particles, uniformly mixing, adding a polymethyl methacrylate prepolymer, methyl methacrylate, methacrylamide, trimethylolpropane trimethacrylate and potassium persulfate, performing polymerization reaction, demulsifying, washing and drying precipitates, and preparing polymer-coated ferroferric oxide particles;

(8) and (3) placing the polymer-coated ferroferric oxide particles into an extracting agent, standing under a vacuum condition, and filtering to prepare the metal extracting agent for recycling the waste ternary lithium battery anode material.

2. The method for preparing the metal extractant for recycling the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the proportion of the raw materials in parts in the step (1) is as follows: 2-5 parts of ferric chloride hexahydrate, 100-120 parts of glycol, 10-13 parts of sodium acetate and 1-2 parts of polypropylene glycol; the calcination is carried out for 6-8h at the temperature of 200-220 ℃.

3. The method for preparing the metal extractant for recycling the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the proportion of the raw materials in the step (2) is as follows: 3-5 parts of ferroferric oxide particles, 300-400 parts of deionized water, 10-12 parts of fructose and 25-30 parts of urea; the reaction is carried out at the temperature of 190-210 ℃ for 10-12 h.

4. The method for preparing the metal extractant for recycling the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the proportion of the raw materials in the step (3) is as follows: 15-20 parts of isobutyl acrylate, 2-4 parts of diacetone acrylamide, 140 parts of N, N-dimethylformamide, 5-8 parts of mesoporous ferroferric oxide particles with cavities and 0.1-0.5 part of azobisisobutyronitrile; the pre-loading stirring time is 1-2h, and the reaction is carried out at the temperature of 75-85 ℃ for 4-5 h.

5. The method for preparing the metal extractant for recycling the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the crosslinking reaction in the step (4) is performed for 1-3h after the pH is adjusted to 5-6.

6. The method for preparing the metal extractant for recycling the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the silane coupling agent solution in the step (5) is 2-5wt% of methacryloxypropyltriethoxysilane ethanol aqueous solution.

7. The method for preparing the metal extractant for recycling the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the concentration of the emulsifier in the pre-polymerization emulsion in the step (6) is 9-12 mmol/L; the mixture ratio of the parts of the raw materials is as follows: 130-150 parts of water, 10-15 parts of methyl methacrylate and 0.1-0.5 part of potassium persulfate, wherein the prepolymerization reaction is carried out for 0.5-1h at the temperature of 60-75 ℃.

8. The method for preparing the metal extractant for recycling the anode material of the waste ternary lithium battery as claimed in claim 1, wherein the concentration of the polymeric emulsion emulsifier in the step (7) is 9-12 mmol/L; the mixture ratio of the parts of the raw materials is as follows: 180-200 parts of water, 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; the polymerization reaction is carried out for 3-4h at the temperature of 60-75 ℃.

9. The method for preparing the metal extractant for recycling the positive electrode material of the waste ternary lithium battery as claimed in claim 1, wherein the extractant in the step (8) comprises one or a mixture of P204 and P507, and the standing time is 15-20 h.

10. The use of the metal extractant prepared by the method according to any one of claims 1 to 9 in the recovery of metals from the anode material of a waste ternary lithium battery.

Technical Field

The invention relates to the technical field of extraction agent preparation, in particular to a preparation method and application of a metal extraction agent for recycling a waste ternary lithium battery positive electrode material.

Background

The lithium battery has excellent performances such as high energy density, high voltage, good cycle performance, small self-discharge, high charge-discharge efficiency and the like, so that the lithium battery initially replaces the traditional nickel-hydrogen nickel-cadmium battery at present and is widely used as energy storage equipment. However, the lithium battery has the problem that solid waste of the lithium battery becomes one of the wastes growing fastest in the world due to the excessively high consumption of the lithium battery, a series of problems such as resource waste and environmental pollution are caused, the theoretical scrappage of the lithium battery in China in 2018 reaches 24.1 ten thousand tons, and how to properly treat the waste lithium battery is expected to become a big problem to be faced by human beings. At present, there are reports related to recovery of metals from a waste ternary lithium battery positive electrode material, for example, a method for comprehensively recovering valuable metals from a ternary lithium battery positive electrode material based on magnesium salt cycle disclosed in chinese patent literature, which is published under the publication number CN111334664A, and discloses a method for comprehensively recovering valuable metals from a ternary lithium battery positive electrode material based on magnesium salt cycle. Although the method realizes the recovery of valuable metals, the P204 and P507 liquid phase extractants are directly adopted to extract metal ions in the method, and during the actual use process, floccules are easily generated on an oil-water interface in the liquid phase extraction to influence the metal extraction, and meanwhile, the liquid phase extractants are also easily caused to lose the extractants, phase separation is difficult, and the cost is easily increased.

Disclosure of Invention

The invention provides a preparation method of a metal extractant for recycling a waste ternary lithium battery anode material and application thereof, aiming at overcoming the problems that floccules are easily generated on an oil-water interface in the existing liquid phase extraction to influence metal extraction, and meanwhile, a liquid phase extractant is also easily lost to cause the loss of the extractant, the phase separation is difficult, the cost is easily increased and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material comprises the following preparation steps:

(1) putting ferric chloride hexahydrate into glycol, stirring and dissolving, then adding sodium acetate and polypropylene glycol, stirring, and calcining to prepare ferroferric oxide particles;

(2) dispersing ferroferric oxide particles in deionized water, then adding fructose and urea, stirring and dissolving, carrying out heat preservation reaction, separating, washing and drying to prepare mesoporous ferroferric oxide particles with cavities;

(3) putting isobutyl acrylate and diacetone acrylamide into N, N-dimethylformamide, adding mesoporous ferroferric oxide particles with cavities and azobisisobutyronitrile, stirring for preloading, then carrying out heat preservation reaction, and carrying out centrifugal drying to prepare polymer-loaded mesoporous ferroferric oxide particles;

(4) dispersing the prepared polymer-loaded mesoporous ferroferric oxide particles into deionized water, adding adipic dihydrazide, performing crosslinking reaction, 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 a silane coupling agent solution to prepare silane modified ferroferric oxide particles;

(6) dissolving sodium dodecyl sulfate in water to prepare a pre-polymerization emulsion, then adding methyl methacrylate and potassium persulfate, carrying out pre-polymerization reaction, and demulsifying to prepare a polymethyl methacrylate prepolymer;

(7) dissolving sodium dodecyl sulfate in water to prepare a polymerization emulsion, adding silane modified ferroferric oxide particles, uniformly mixing, adding a polymethyl methacrylate prepolymer, methyl methacrylate, methacrylamide, trimethylolpropane trimethacrylate and potassium persulfate, performing polymerization reaction, demulsifying, washing and drying precipitates, and preparing polymer-coated ferroferric oxide particles;

(8) and (3) placing the polymer-coated ferroferric oxide particles into an extracting agent, standing under a vacuum condition, and filtering to prepare the metal extracting agent.

The prepared solid-phase metal extractant has a three-layer structure, wherein the shell layer is a polymer coating layer, the middle layer is mesoporous ferroferric oxide particles, and 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, or the metal extractant can be filled into a column for metal ion extraction, in the process of metal ion extraction of the metal extractant, the metal ions can be adsorbed to the surface of the polymer layer of the metal extractant, because the surface of the mesoporous ferroferric oxide particles of the middle layer is full of holes, the metal ions can be extracted into the solid-phase metal extractant by the organic liquid-phase extractant coated by the innermost layer, and meanwhile, because the mesoporous ferroferric oxide particles have magnetism, after extraction is completed, the recovery of the metal extractant can be carried out through the permanent magnet, so that the method 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, and the metal extractant has magnetism, can be conveniently and quickly recovered by a magnet after adsorption is finished, is placed in water, realizes back extraction of metal ions by regulating pH and temperature, and is beneficial to industrial use.

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 extraction agent, and the polymer-coated ferroferric oxide particles are kept stand under a vacuum condition, so that the cavities of the polymer-coated ferroferric oxide particles are filled with the organic liquid phase extraction agent for extraction, and the metal extraction agent for recycling the waste ternary lithium battery anode material is successfully prepared.

Preferably, the mixture ratio of the parts of the raw materials in the step (1) is as follows: 2-5 parts of ferric chloride hexahydrate, 100-120 parts of glycol, 10-13 parts of sodium acetate and 1-2 parts of polypropylene glycol; the calcination is carried out for 6-8h at the temperature of 200-220 ℃.

Preferably, the mixture ratio of the parts of the raw materials in the step (2) is as follows: 3-5 parts of ferroferric oxide particles, 300-400 parts of deionized water, 10-12 parts of fructose and 25-30 parts of urea; the reaction is carried out at the temperature of 190-210 ℃ for 10-12 h.

Preferably, the mixture ratio of the parts of the raw materials in the step (3) is as follows: 15-20 parts of isobutyl acrylate, 2-4 parts of diacetone acrylamide, 140 parts of N, N-dimethylformamide, 5-8 parts of mesoporous ferroferric oxide particles with cavities and 0.1-0.5 part of azobisisobutyronitrile; the pre-loading stirring time is 1-2h, and the reaction is carried out at the temperature of 75-85 ℃ for 4-5 h.

Preferably, the crosslinking reaction in step (4) is carried out for 1 to 3 hours after the pH is adjusted to 5 to 6.

Preferably, the silane coupling agent solution in step (5) is a 2-5wt% methacryloxypropyltriethoxysilane ethanol aqueous solution.

Preferably, the concentration of the emulsifier in the pre-polymerization emulsion in the step (6) is 9-12 mmol/L; the mixture ratio of the parts of the raw materials is as follows: 130-150 parts of water, 10-15 parts of methyl methacrylate and 0.1-0.5 part of potassium persulfate, wherein the prepolymerization reaction is carried out for 0.5-1h at the temperature of 60-75 ℃.

Preferably, the concentration of the emulsifier in the polymerization emulsion in the step (7) is 9-12 mmol/L; the mixture ratio of the parts of the raw materials is as follows: 180-200 parts of water, 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; the polymerization reaction is carried out for 3-4h at the temperature of 60-75 ℃.

According to the invention, the prepolymerization time of methyl methacrylate is controlled to be 0.5-1h, and the polymerization time is controlled to be 3-4h, so that the coating effect of crosslinked polymer loaded mesoporous ferroferric oxide particles is better, the prepolymerization time is too short, the probability of a monomer entering a cavity is higher, the prepolymerization time is long, the subsequent coating efficiency is influenced, and the loss of an inner-layer organic liquid phase extracting agent is easily caused; therefore, too long or too short a prepolymerization time will affect the subsequent extraction.

Preferably, the extractant in the step (8) comprises one or a mixture of two of P204 and P507, and the standing time is 15-20 h.

The application of the metal extractant in the metal recovery of the anode material of the waste ternary lithium battery.

Therefore, the invention has the following beneficial effects: the metal extractant prepared by the invention is in a solid phase form, floccules cannot be generated in the using process, the organic liquid phase metal extractant cannot be excessively lost, and the metal extractant has magnetism, can be conveniently and quickly recovered by a magnet after adsorption is finished, is placed in water, realizes back extraction of metal ions by regulating pH and temperature, and is beneficial to industrial use.

Detailed Description

The invention is further described with reference to specific embodiments.

General example: a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material 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) placing the polymer-coated ferroferric oxide particles into an extracting agent, standing for 15-20h under a vacuum condition, and filtering to prepare a metal extracting agent for recycling the waste ternary lithium battery anode material; the extractant comprises one or a mixture of P204 and P507;

the application of the metal extractant in the metal recovery of the anode material of the waste ternary lithium battery.

Example 1: a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material 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 for 17 hours under a vacuum condition, and filtering to prepare the metal extractant for recycling the waste ternary lithium battery anode material.

Example 2: a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material 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 for 15 hours under a vacuum condition, and filtering to prepare the metal extractant for recycling the waste ternary lithium battery anode material.

Example 3: a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material 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 for 20 hours under a vacuum condition, and filtering to prepare the metal extractant for recycling the waste ternary lithium battery anode material.

Comparative example 1: a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material 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 for recycling the waste ternary lithium battery anode material.

Comparative example 2: a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material 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 for recycling the waste ternary lithium battery anode material.

Comparative example 3: a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material 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 for recycling the waste ternary lithium battery anode material.

Comparative example 4: the difference from example 1 is that the prepolymerization time in step (6) for preparing the polymethyl methacrylate prepolymer was 0.2 h.

Comparative example 5: the difference from example 1 is that the prepolymerization time in step (6) for preparing the polymethyl methacrylate prepolymer was 1.5 hours.

Comparative example 6: a preparation method of a metal extractant for recycling a waste ternary lithium battery positive electrode material 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 for recycling the waste ternary lithium battery anode material.

The metal extractants prepared in the examples and the comparative examples are subjected to extraction rate tests under the following test conditions: preparing a manganese sulfate aqueous solution with the concentration of 200ppm, controlling the pH value of the aqueous phase to be 3-3.5, placing 1g of the metal extractant prepared in the examples and the comparative examples in 40ml of the manganese sulfate aqueous solution, stirring and extracting, measuring the concentration of manganese ions in the extracted aqueous phase by adopting ICP-OES, and calculating to obtain the extraction rate, wherein the extraction rate results are shown in the following table.

Item	Extraction ratio (%)
		Example 1	99.14
Example 2	99.07
		Example 3	99.26
Comparative example 1	84.51
		Comparative example 2	93.69
Comparative example 3	78.34
		Comparative example 4	82.54
Comparative example 5	83.76
		Comparative example 6	84.31

From the data, the metal extractant prepared in the embodiment of the invention has a high extraction rate for metal ions, and the difference between the comparative example 1 and the embodiment 1 is that polymer loading is not carried out in a cavity of a mesoporous ferroferric oxide particle, so that the P204 extractant is not adsorbed sufficiently or is lost subsequently, and the extraction rate is influenced; the difference between the comparative example 2 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 extraction rate is influenced; in comparative examples 3 to 5, the extraction results were poor when methyl methacrylate was not prepolymerized or the prepolymerization time exceeded the defined range; comparative example 6 differs from example 1 in that the polymer coating does not use methacrylamide, reducing the interaction between the polymer coating and the metal ions, which affects the extraction.

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.