Method for recovering manganese from ternary battery waste liquid

Abstract

The present invention relates to a method for recovering manganese from ternary battery waste liquid. The method comprises the following steps: subjecting the ternary battery waste liquid to column chromatography treatment and collecting the eluate; subjecting the eluate to ion exchange treatment through a cation exchange resin and enriching the manganese ions in the eluate; wherein the chromatographic column filler used in the column chromatography treatment is a cross-linked aminosilane-modified silica microsphere. Through the reverse adsorption and elution effect of the aminosilane-modified silica microsphere, the impurity ions are adsorbed by the silica gel column and the manganese ions enter the eluate, thereby realizing the separation of manganese ions from impurity ions, and in conjunction with the subsequent cation exchange process, the manganese ions are adsorbed by the cation exchange resin to realize the enrichment of manganese ions. In addition, the method has a simple and easy-to-control process, is easy to operate, has low equipment investment, low reagent cost, mild reaction conditions, is green and environmentally friendly, has controllable quality and is easy to industrialize, has good environmental and economic effects, and has broad application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of battery material recovery, and in particular to a method for recovering manganese from ternary battery waste liquid. Background Art

[0002] The rapid industrial development of lithium batteries has greatly promoted the development of the alloy industry. Currently, lithium-ion batteries are widely used in medical, automotive, aviation and other fields. After the battery is discarded, it is necessary to recycle and reuse the high value-added heavy metal elements such as cobalt and lithium. Ternary power batteries usually refer to the use of lithium nickel cobalt manganese oxide (LiNi x Co y Mn z O2) ternary materials as the positive electrode material of the battery, compared with lithium iron phosphate, lithium nickel oxide, lithium cobalt oxide and lithium manganese oxide batteries, have the advantages of low cost, large discharge capacity, good cycle performance, good thermal stability and relatively stable structure.

[0003] At present, according to the differences in the failure modes of lithium-ion batteries, there are two main technical routes for the recovery and regeneration of ternary cathode materials: one is physical repair and regeneration. For ternary cathode materials that have only lost active lithium elements, lithium sources are directly added to perform in-situ reverse lithium replenishment and repair and regeneration through high-temperature sintering. For cathode materials with severe capacity attenuation and changes in surface crystal structure, hydrothermal treatment and short-term high-temperature sintering and regeneration are performed; the second is metallurgical recovery. Currently, hydrometallurgical processes are widely used, and the main process flow includes pretreatment, leaching and regeneration. In addition to manganese ions, the ternary lithium battery extracted by acid leaching also has the main component nickel ions (Ni 2+ ), cobalt ion (Co 2+ ) and lithium ions, etc., and the materials that have an adsorption effect on manganese ions often also have an adsorption effect on cobalt ions and nickel ions, resulting in large interference, poor adsorption effect, and difficulty in separating manganese ions, not to mention enriching manganese ions or recovering manganese ions for subsequent regeneration of ternary positive electrode materials. Summary of the invention

[0004] Based on this, the present invention provides a method for recovering manganese from ternary battery waste liquid, which can selectively separate and enrich manganese ions, thereby turning waste into treasure.

[0005] The technical solution is as follows:

[0006] A method for recovering manganese from ternary battery waste liquid comprises the following steps:

[0007] Performing column chromatography on the ternary battery waste liquid and collecting the eluate;

[0008] Performing ion exchange treatment on the eluate by using a cation exchange resin to enrich the manganese ions in the eluate;

[0009] The chromatographic column filler used in the column chromatography treatment is cross-linked aminosilane-modified silica microspheres.

[0010] In one embodiment, the aminosilane-modified silica microspheres have a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm.

[0011] In one of the embodiments, the chromatographic column is further subjected to elution and regeneration treatment after column chromatography, and the elution procedures adopted are acid washing, water washing and alkaline treatment, wherein the acid washing solution is a nickel-cobalt-copper ion enriched solution.

[0012] In one embodiment, the column temperature is 20-50°C.

[0013] In one embodiment, the desorbent used in the pickling step is a mixture of one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1% to 15%.

[0014] In one embodiment, in the pickling step, the flow rate of the eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 10 h.

[0015] In one embodiment, the water washing step is to use pure water to wash the packed column, the water flow rate is 0.5BV / h to 5BV / h, and the treatment time is 1h to 10h.

[0016] In one embodiment, the alkaline solution used in the alkaline treatment step is a mixed solution of one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the mass concentration of the alkali in the alkaline solution is 1% to 15%.

[0017] In one of the embodiments, in the alkaline treatment step, the flow rate of the eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 4 h.

[0018] In one of the embodiments, the surface of the aminosilane-modified silica microspheres contains 14% to 35% amino groups by mass percentage.

[0019] In one embodiment, the preparation method of the cross-linked aminosilane-modified silica microspheres is as follows:

[0020] Mixing silica microspheres and an aminosilane coupling agent in a first solvent to prepare aminosilane-modified silica microspheres through a grafting reaction;

[0021] The aminosilane-modified silica microspheres are mixed with a crosslinking agent, and the crosslinked aminosilane-modified silica microspheres are prepared through a crosslinking reaction.

[0022] In one embodiment, before the step of mixing the silica microspheres and the aminosilane coupling agent in the first solvent, the step of mixing the crude silica microspheres with an acid to perform an impurity removal reaction is also included.

[0023] In one of the embodiments, the mass ratio of the crude silica microspheres to the acid is 1:(0.1-0.75).

[0024] In one embodiment, the acid includes one or more of hydrochloric acid, sulfuric acid and nitric acid.

[0025] In one embodiment, the temperature of the impurity removal reaction is 30° C. to 60° C., and the time is 4 h to 8 h.

[0026] In one embodiment, the aminosilane coupling agent includes one or more of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 1-propyl-1-(triethoxysilyl)methyl urea, γ-aminopropylmethyldiethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyl-dimethoxysilane.

[0027] In one embodiment, the first solvent includes one or more of methanol, ethanol, dichloromethane, isopropanol and 1,2-dichloroethane.

[0028] In one of the embodiments, the mass ratio of the silica microspheres to the aminosilane coupling agent is 1:(0.05-0.3).

[0029] In one embodiment, the grafting reaction temperature is 40° C. to 80° C., and the time is 8 h to 16 h.

[0030] In one of the embodiments, the mixing mass ratio of the aminosilane-modified silica microspheres to the crosslinking agent is 1:(0.05-0.3).

[0031] In one embodiment, the crosslinking agent includes one or more of epichlorohydrin, tetraethyl silicate and tetrabutyl titanate.

[0032] In one embodiment, the cross-linking reaction temperature is 40° C. to 80° C., and the time is 8 h to 16 h.

[0033] In one embodiment, after the step of preparing the cross-linked aminosilane-modified silica microspheres through a cross-linking reaction, the method further includes a step of purifying the product of the cross-linking reaction.

[0034] In one embodiment, the purification process comprises the following steps:

[0035] The cross-linking reaction product is subjected to alcohol washing treatment and water washing treatment.

[0036] In one embodiment, the cation exchange resin includes one or more of sulfonic acid resin, iminodiacetic acid resin, phosphoric acid resin and aminophosphoric acid resin.

[0037] In one embodiment, the particle size of the cation exchange resin is 0.1 mm to 0.5 mm, and the pore size is 10 mm to 1000 nm.

[0038] In one embodiment, after the ion exchange treatment step, the method further includes a step of desorbing and regenerating the cation exchange resin enriched with manganese ions.

[0039] In one embodiment, the elution procedure used for desorption regeneration is acid washing, water washing and alkaline treatment, wherein the acid washing solution is the manganese ion-enriched solution obtained after the ion exchange treatment.

[0040] In one embodiment, during the desorption and regeneration step of the cation exchange resin, the column temperature is 20-50°C.

[0041] In one embodiment, in the desorption regeneration step of the cation exchange resin, the desorbent used for pickling is a mixture of one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1% to 15%.

[0042] In one embodiment, in the desorption regeneration step of the cation exchange resin, the flow rate of the acid washing eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 10 h.

[0043] In one embodiment, in the desorption regeneration step of the cation exchange resin, the water washing is to use pure water to rinse the packed column, the water flow rate is 0.5BV / h to 5BV / h, and the treatment time is 1h to 10h.

[0044] In one embodiment, in the desorption regeneration step of the cation exchange resin, the alkaline solution used for the alkaline treatment includes a mixed solution of one or more of sodium hydroxide, potassium hydroxide and barium hydroxide, and the mass concentration of the alkali in the alkaline solution is 1% to 15%.

[0045] In one embodiment, in the desorption regeneration step of the cation exchange resin, the flow rate of the alkali-treated eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 4 h.

[0046] The present invention has at least the following beneficial effects:

[0047] The method for recovering manganese from ternary battery waste liquid provided by the present invention comprises the steps of subjecting the ternary battery waste liquid to column chromatography, collecting eluate, and subjecting the eluate to ion exchange treatment by means of a cation exchange resin to enrich the manganese ions in the eluate. The chromatographic column filler used in the column chromatography treatment is a cross-linked aminosilane-modified silica microsphere, the amino functional group of which can selectively adsorb impurity ions (cobalt ions, nickel ions and copper ions) by means of the chelation effect of its N-coordinating atom, but does not adsorb or adsorbs a small amount of manganese ions. Through the reverse adsorption and elution effect of the microsphere, the impurity ions are adsorbed by the silica gel column and the manganese ions enter the eluate, thereby realizing the separation of manganese ions from impurity ions. In conjunction with the subsequent cation exchange process, the manganese ions are adsorbed by the cation exchange resin, thereby realizing the enrichment of manganese ions.

[0048] In addition, the method for recovering manganese from ternary battery waste liquid provided by the present invention has simple and easy controllable process, simple operation, low equipment investment, low reagent cost, mild reaction conditions, green and environmentally friendly, controllable quality and easy industrialization, good environmental and economic effects, wide applicability, and can be used to recover manganese from industrially produced ternary battery recovery liquid. The cross-linked aminosilane-modified silica microspheres have a stable structure, the column bed is stable and not easy to collapse during use, and the microspheres can be recycled and reused, and have broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 is an infrared spectrum of the cross-linked aminosilane-modified silica microspheres prepared in Example 1;

[0050] Figure 2 This is an adsorption experiment diagram of the cross-linked aminosilane-modified silica microspheres prepared in Example 1 for enriching copper, cobalt and nickel by adsorption, and of the macroporous cation exchange resin for enriching manganese by adsorption;

[0051] Figure 3 It is a schematic diagram of the device for recovering manganese from ternary battery waste liquid in Examples 1 to 4. DETAILED DESCRIPTION

[0052] The present invention will be further described in detail below in conjunction with specific embodiments and accompanying drawings. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0053] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0054] Where “including,” “having,” and “comprising” are used herein, it is intended to cover a non-exclusive inclusion, and another component may also be added unless explicit limiting terms such as “only,” “consisting of,” etc. are used.

[0055] The words "preferably", "more preferably", "preferably", "better", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the statement of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention. That is, in the present invention, "preferably", "more preferably", "preferably", "better", etc. are only used to describe implementation methods or examples with better effects, but do not constitute a limitation on the scope of protection of the present invention.

[0056] In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0057] In the present invention, "at least one" means more than one, such as one, two and more than two. "Multiple" or "several" means at least two, such as two, three, etc., and "multilayer" means at least two layers, such as two layers, three layers, etc., unless otherwise clearly and specifically defined. In the description of the present invention, "several" means at least one, such as one, two, etc., unless otherwise clearly and specifically defined.

[0058] When a numerical range is disclosed herein, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0059] If not otherwise specified, all steps of the present invention may be performed sequentially or randomly. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0060] In the present invention, "above" or "below" includes the number itself. For example, "below 1" includes 1.

[0061] The temperature parameters in the present invention, if not specifically limited, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the precision range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0062] Unless mentioned to the contrary, terms in the singular may include plural forms and should not be construed as being one in number.

[0063] The raw materials, reagents and materials used in the following specific embodiments are all commercially available products unless otherwise specified.

[0064] At present, according to the differences in the failure modes of lithium-ion batteries, there are two main technical routes for the recovery and regeneration of ternary cathode materials: one is physical repair and regeneration. For ternary cathode materials that have only lost active lithium elements, lithium sources are directly added to perform in-situ reverse lithium replenishment and repair and regeneration through high-temperature sintering. For cathode materials with severe capacity attenuation and changes in surface crystal structure, hydrothermal treatment and short-term high-temperature sintering and regeneration are performed; the second is metallurgical recovery. At present, hydrometallurgical processes are widely used. The main process flow includes pretreatment, leaching, regeneration and other processes. In addition to manganese, the ternary lithium battery leached by acid also has the main component nickel ions (Ni 2+ ): Cobalt ion (Co 2+ ) and lithium ions, how to effectively separate these valuable ions has always been a problem for technicians in the industry.

[0065] There are few reports on manganese adsorbents on the market. The main reason is that manganese ions have a positive divalent charge and their electronic configuration is a half-filled structure [Ar]3d 5 The five unpaired 3d electrons in the manganese ion's electronic configuration give it a high electron density, which may lead to an electron repulsion effect when forming covalent bonds with other ligands. This electron repulsion can increase the energy barrier of the coordination reaction, making it more difficult for manganese ions to coordinate and adsorb. However, materials that have an adsorption effect on manganese ions often also have an adsorption effect on cobalt ions and nickel ions, resulting in large interference and poor selective adsorption.

[0066] The technical solution is as follows:

[0067] A method for recovering manganese from ternary battery waste liquid comprises the following steps:

[0068] Performing column chromatography on the ternary battery waste liquid and collecting the eluate;

[0069] Performing ion exchange treatment on the eluate by using a cation exchange resin to enrich the manganese ions in the eluate;

[0070] The chromatographic column filler used in the column chromatography treatment is cross-linked aminosilane-modified silica microspheres.

[0071] The method for recovering manganese from ternary battery waste liquid of the present invention is described in detail below in a step-by-step manner.

[0072] S100: performing column chromatography on the ternary battery waste liquid and collecting the eluate, wherein the chromatographic column filler used in the column chromatography treatment is cross-linked aminosilane-modified silica microspheres.

[0073] In one of the embodiments, the surface of the aminosilane-modified silica microspheres contains 14% to 35% amino groups by mass percentage.

[0074] In one embodiment, the aminosilane-modified silica microspheres have a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm.

[0075] In one embodiment, the preparation method of the cross-linked aminosilane-modified silica microspheres is as follows:

[0076] Mixing silica microspheres and an aminosilane coupling agent in a first solvent to prepare aminosilane-modified silica microspheres (Formula I) through a grafting reaction;

[0077] The aminosilane-modified silica microspheres are mixed with a crosslinking agent to prepare the crosslinked aminosilane-modified silica microspheres through a crosslinking reaction, the chemical formula of which is (SiO2) n (SiC3O3NH8) m , n is (0.1~10), m is (0.1~10);

[0078]

[0079] In one embodiment, before the step of mixing the silica microspheres and the aminosilane coupling agent in the first solvent, the step of mixing the crude silica microspheres with an acid to perform an impurity removal reaction is also included. The crude silica microspheres are mixed with the acid to wash away excess impurities on the surface of the microspheres.

[0080] It can be understood that in the present invention, the crude silica microspheres can be sourced from or can be commercially available, and there is no special requirement for this. In a specific example, the crude silica microspheres are purchased from Qingdao Xinchanglai Silica Gel Co., Ltd.

[0081] In one embodiment, the mass ratio of the crude silica microspheres to the acid is 1:(0.1-0.75), including but not limited to 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7 or 1:0.75.

[0082] In one embodiment, the acid includes one or more of hydrochloric acid, sulfuric acid and nitric acid. It is understandable that when used, the concentrated acid is diluted to a dilute acid aqueous solution before use, and the mass concentration of the acid in the dilute acid aqueous solution is 5% to 15%.

[0083] In one embodiment, the temperature of the impurity removal reaction is 30°C to 60°C, including but not limited to 30°C, 40°C, 50°C or 60°C.

[0084] In one embodiment, the impurity removal reaction time is 4 h to 8 h, including but not limited to 4 h, 5 h, 6 h, 7 h or 8 h.

[0085] In one embodiment, the aminosilane coupling agent includes one or more of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 1-propyl-1-(triethoxysilyl)methyl urea, γ-aminopropylmethyldiethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyl-dimethoxysilane.

[0086] In one embodiment, the first solvent includes one or more of methanol, ethanol, dichloromethane, isopropanol and 1,2-dichloroethane.

[0087] In one embodiment, the mass ratio of the silica microspheres to the aminosilane coupling agent is 1:(0.05-0.3), including but not limited to 1:0.05, 1:0.1, 1:0.2 or 1:0.3.

[0088] In one embodiment, the temperature of the grafting reaction is 40°C to 80°C, including but not limited to 40°C, 50°C, 60°C, 70°C or 80°C.

[0089] In one embodiment, the grafting reaction time is 8 h to 16 h, including but not limited to 8 h, 10 h, 12 h, 14 h or 16 h.

[0090] In one embodiment, the silica microspheres after impurity removal are swollen in a first solvent for 0.5 h to 4 h, and then an aminosilane coupling agent is added and the temperature is raised to carry out a grafting reaction.

[0091] In one embodiment, the mixing mass ratio of the aminosilane-modified silica microspheres to the crosslinking agent is 1:(0.05-0.3), including but not limited to 1:0.05, 1:0.1, 1:0.2 or 1:0.3.

[0092] In one embodiment, the crosslinking agent includes one or more of epichlorohydrin, tetraethyl silicate and tetrabutyl titanate.

[0093] In one embodiment, the temperature of the cross-linking reaction is 40°C to 80°C, including but not limited to 40°C, 50°C, 60°C, 70°C or 80°C.

[0094] In one embodiment, the cross-linking reaction time is 8 h to 16 h, including but not limited to 8 h, 10 h, 12 h, 14 h or 16 h.

[0095] In one embodiment, after the step of preparing the cross-linked aminosilane-modified silica microspheres through a cross-linking reaction, the method further includes a step of purifying the product of the cross-linking reaction.

[0096] In one embodiment, the purification process comprises the following steps:

[0097] The cross-linking reaction product is subjected to alcohol washing treatment and water washing treatment.

[0098] The organic matter remaining on the surface of the material after the synthesis is removed by alcohol washing, and the alcohol on the surface of the material is removed by water washing.

[0099] In one embodiment, the alcohol used in the alcohol washing treatment is a mixture of one or more of methanol, ethanol and isopropanol.

[0100] In one embodiment, after the column chromatography step, the chromatographic column (or packed column) is also subjected to elution and regeneration treatment. Further, the elution procedure adopted is acid washing, water washing and alkaline treatment, wherein the acid washing solution is a nickel-cobalt-copper ion enriched solution.

[0101] In one embodiment, the column temperature is 20-50°C.

[0102] In one embodiment, the desorbent used in the pickling step is a mixture of one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1% to 15%.

[0103] In one embodiment, in the pickling step, the flow rate of the eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 10 h.

[0104] In one embodiment, the water washing step is to use pure water to wash the packed column, the water flow rate is 0.5BV / h to 5BV / h, and the treatment time is 1h to 10h.

[0105] In one embodiment, the alkaline solution used in the alkaline treatment step is a mixed solution of one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the mass concentration of the alkali in the alkaline solution is 1% to 15%.

[0106] In one of the embodiments, in the alkaline treatment step, the flow rate of the eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 4 h.

[0107] S200: performing ion exchange treatment on the eluate by using a cation exchange resin to enrich the manganese ions in the eluate.

[0108] In one embodiment, the cation exchange resin comprises one or more of sulfonic acid resin, iminodiacetic acid resin, phosphoric acid resin and aminophosphoric acid resin. Further, the matrix of the ion exchange resin is polystyrene.

[0109] In one embodiment, the particle size of the cation exchange resin is 0.1 mm to 0.5 mm, and the pore size is 10 mm to 1000 nm.

[0110] S300: Post-processing.

[0111] In one embodiment, after the ion exchange treatment step, a step of desorbing the cation exchange resin enriched with manganese ions is further included.

[0112] In one embodiment, the elution procedure used for the macroporous cation exchange resin column is acid washing, water washing and alkali treatment, wherein the acid washing solution is a manganese ion-enriched solution obtained after ion exchange treatment;

[0113] In one embodiment, during the desorption and regeneration step of the cation exchange resin, the column temperature is 20 to 50°C;

[0114] In one embodiment, in the desorption regeneration step of the cation exchange resin, the desorbent used in the pickling is a mixture of one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, with a mass concentration of 1% to 15%. It can be understood that the acid is prepared into a dilute acid aqueous solution for use, and the mass concentration of the acid in the dilute acid aqueous solution is 1% to 15%.

[0115] In one embodiment, in the desorption regeneration step of the cation exchange resin, the flow rate of the acid washing eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 10 h.

[0116] In one embodiment, in the desorption regeneration step of the cation exchange resin, the water washing is to use pure water to rinse the packed column, the water flow rate is 0.5BV / h to 5BV / h, and the treatment time is 1h to 10h.

[0117] In one embodiment, in the desorption regeneration step of the cation exchange resin, the alkaline solution used in the alkaline treatment includes a mixed solution of one or more of sodium hydroxide, potassium hydroxide and barium hydroxide, and the mass concentration of the alkali in the alkaline solution is 1% to 15%. It can be understood that the alkali is prepared into a dilute alkali aqueous solution for use, and the mass concentration of the alkali in the dilute alkali aqueous solution is 1% to 15%.

[0118] In one embodiment, in the desorption regeneration step of the cation exchange resin, the flow rate of the alkaline-treated eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 4 h.

[0119] In order to make the purpose, technical solution and advantages of the present invention more clear, the present invention is further described in detail below in combination with specific implementation methods and with reference to the accompanying drawings. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention.

[0120] It is understandable that the elemental composition of ternary battery waste liquid may be slightly different, but the method for recovering manganese from ternary battery waste liquid provided by the present invention is applicable to various ternary battery waste liquids. For the convenience of describing the present invention, the element content analysis of the ternary battery waste liquid used in the following embodiments and comparative examples is shown in Table 1 below.

[0121] Table 1

[0122]

[0123] In addition to the above elements, the remainder is basically carbon and oxygen.

[0124] Example 1

[0125] This embodiment provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0126] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0127] (b) Grafting reaction: The pretreated silica microspheres were swollen in methanol for 2 h, and γ-aminopropyltriethoxysilane KH550 was added at a mass ratio of silica microspheres to γ-aminopropyltriethoxysilane of 1:0.2, and the temperature was raised to 60 °C and the reaction was refluxed for 12 h;

[0128] (c) Cross-linking reaction: the aminosilane-modified silica microspheres prepared in step (b) were mixed with tetraethyl silicate in a mass ratio of 1:0.1 and stirred evenly, and the mixture was heated to 60° C. and reacted for 4 h to improve the stability of the modified microspheres;

[0129] (d) Purification: The modified microspheres obtained in step (c) are washed with ethanol and water to obtain a reaction product, which is a cross-linked aminosilane-modified silica microsphere with a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm. Fourier transform infrared analysis is performed on the microspheres. The results are as follows: Figure 1 As shown by Figure 1 It can be seen that 3500cm -1 and 1590cm -1 The absorption peak at represents the successful synthesis of a composite material with amino functional groups on the surface.

[0130] (e) using a method of connecting a silica gel material filled column and a macroporous cationic ion exchange resin filled column in series to distribute and separate nickel, cobalt, copper and manganese ions to achieve the purpose of recovering manganese ions, such as Figure 2 As shown in the figure, the silica gel column can clearly observe the phenomenon of nickel, cobalt and copper stratification, indicating that nickel, cobalt and copper are adsorbed on the silica gel material. Figure 2 The iminodiacetic acid resin shown in the figure adsorbs manganese ions, wherein the desorption and regeneration method of the silica gel column is to use 5% HCl solution to treat at a flow rate of 2BV / h for 2h, then use pure water to treat at a flow rate of 5BV / h for 1h, and then use 15% sodium carbonate solution for regeneration, and treat at a flow rate of 2BV / h for 1h. The whole column temperature is 45°C, and the acid wash solution is the nickel-cobalt-copper enriched solution. The desorption and regeneration method of the macroporous cation exchange resin is to use 15% HCl solution to treat at a flow rate of 2BV / h for 2h, then use pure water to treat at a flow rate of 5BV / h for 1h, and then use 5% sodium hydroxide solution for regeneration, and treat at a flow rate of 2BV / h for 1h. The whole column temperature is 45°C, and the acid wash solution is the manganese enriched solution. The specific process flow is as follows: Figure 3 shown.

[0131] After testing, the results of each metal ion in the eluent are shown in Table 2 below;

[0132] The manganese ions in the eluent were adsorbed by iminodiacetic acid type polystyrene resin (particle size of 0.1 mm to 0.5 mm, pore size of 10 nm to 1000 nm) to enrich manganese. After testing, the manganese ions contained in the eluent flowing out through the ion exchange resin are shown in Table 3 below.

[0133] Example 2

[0134] This embodiment provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0135] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0136] (b) Grafting reaction: The pretreated silica microspheres were swollen in methanol for 2 h, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane was added at a mass ratio of 1:0.2 of silica microspheres to N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and the temperature was raised to 60 °C and the reaction was refluxed for 12 h;

[0137] (c) Cross-linking reaction: the aminosilane-modified silica microspheres prepared in step (b) were mixed with tetraethyl silicate in a mass ratio of 1:0.1 and stirred evenly, and the mixture was heated to 60° C. and reacted for 4 h to improve the stability of the modified microspheres;

[0138] (d) Purification: washing the modified microspheres obtained in step (c) with ethanol and water to obtain a reaction product, which is a cross-linked aminosilane-modified silica microsphere having a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm;

[0139] (e) using the silica gel material prepared in step d to separate nickel, cobalt, copper and manganese from the ternary battery waste liquid by a filling column method, the process parameters are the same as those in Example 1, collecting the eluate, and testing the results of the metal ions in the eluate are shown in Table 2 below;

[0140] The manganese ions in the eluent were adsorbed by iminodiacetic acid type polystyrene resin (particle size of 0.1 mm to 0.5 mm, pore size of 10 nm to 1000 nm) to enrich manganese. After testing, the manganese ions contained in the eluent flowing out through the ion exchange resin are shown in Table 3 below.

[0141] Example 3

[0142] This embodiment provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0143] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0144] (b) Grafting reaction: The pretreated silica microspheres were swollen in methanol for 2 h, and γ-aminopropylmethyldiethoxysilane was added at a mass ratio of 1:0.2 between silica microspheres and γ-aminopropylmethyldiethoxysilane, and the temperature was raised to 60 °C and the reaction was refluxed for 12 h;

[0145] (c) Cross-linking reaction: the aminosilane-modified silica microspheres prepared in step (b) were mixed with tetraethyl silicate in a mass ratio of 1:0.1 and stirred evenly, and the mixture was heated to 60° C. and reacted for 4 h to improve the stability of the modified microspheres;

[0146] (d) Purification: washing the modified microspheres obtained in step (c) with ethanol and water to obtain a reaction product, which is a cross-linked aminosilane-modified silica microsphere with a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm;

[0147] (e) using the silica gel material prepared in step d to separate nickel, cobalt, copper and manganese from the ternary battery waste liquid by a filling column method, the process parameters are the same as those in Example 1, collecting the eluate, and testing the results of the metal ions in the eluate are shown in Table 2 below;

[0148] The manganese ions in the eluent were adsorbed by iminodiacetic acid type polystyrene resin (particle size of 0.1 mm to 0.5 mm, pore size of 10 nm to 1000 nm) to enrich manganese. After testing, the manganese ions contained in the eluent flowing out through the ion exchange resin are shown in Table 3 below.

[0149] Example 4

[0150] This embodiment provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0151] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0152] (b) Grafting reaction: The pretreated silica microspheres were swollen in methanol for 2 h, and γ-aminopropyltriethoxysilane was added at a mass ratio of 1:0.3 of silica microspheres to γ-aminopropyltriethoxysilane, and the temperature was raised to 60 °C and the reaction was refluxed for 12 h;

[0153] (c) Cross-linking reaction: the aminosilane-modified silica microspheres prepared in step (b) were mixed with tetraethyl silicate in a mass ratio of 1:0.1 and stirred evenly, and the mixture was heated to 60° C. and reacted for 4 h to improve the stability of the modified microspheres;

[0154] (d) Purification: washing the modified microspheres obtained in step (c) with ethanol and water to obtain a reaction product, which is a cross-linked aminosilane-modified silica microsphere having a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm;

[0155] (e) using the silica gel material prepared in step d to separate nickel, cobalt, copper and manganese from the ternary battery waste liquid by a filling column method, the process parameters are the same as those in Example 1, collecting the eluate, and testing the results of the metal ions in the eluate are shown in Table 2 below;

[0156] The manganese ions in the eluent were adsorbed by iminodiacetic acid type polystyrene resin (particle size of 0.1 mm to 0.5 mm, pore size of 10 nm to 1000 nm) to enrich manganese. After testing, the manganese ions contained in the eluent flowing out through the ion exchange resin are shown in Table 3 below.

[0157] Example 5

[0158] This embodiment provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0159] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0160] (b) Grafting reaction: The pretreated silica microspheres were swollen in methanol for 2 h, and γ-aminopropyltriethoxysilane was added at a mass ratio of 1:0.2 of silica microspheres to γ-aminopropyltriethoxysilane, and the temperature was raised to 60 °C and the reaction was refluxed for 12 h;

[0161] (c) Cross-linking reaction: The aminosilane-modified silica microspheres prepared in step (b) were mixed with tetraethyl silicate in a mass ratio of 1:0.2 and stirred evenly, and the mixture was heated to 60° C. and reacted for 4 h to improve the stability of the modified microspheres;

[0162] (d) Purification: washing the modified microspheres obtained in step (c) with ethanol and water to obtain a reaction product, which is a cross-linked aminosilane-modified silica microsphere having a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm;

[0163] (e) using the silica gel material prepared in step d to separate nickel, cobalt, copper and manganese from the ternary battery waste liquid by a filling column method, the process parameters are the same as those in Example 1, collecting the eluate, and testing the results of the metal ions in the eluate are shown in Table 2 below;

[0164] The manganese ions in the eluent were adsorbed by iminodiacetic acid type polystyrene resin (particle size of 0.1 mm to 0.5 mm, pore size of 10 nm to 1000 nm) to enrich manganese. After testing, the manganese ions contained in the eluent flowing out through the ion exchange resin are shown in Table 3 below.

[0165] Example 6

[0166] This embodiment provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0167] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0168] (b) Grafting reaction: The pretreated silica microspheres were swollen in methanol for 2 h, and γ-aminopropyltriethoxysilane was added at a mass ratio of 1:0.2 of silica microspheres to γ-aminopropyltriethoxysilane, and the temperature was raised to 40 °C and the reaction was refluxed for 12 h;

[0169] (c) Cross-linking reaction: the aminosilane-modified silica microspheres prepared in step (b) were mixed with tetraethyl silicate in a mass ratio of 1:0.1 and stirred evenly, and the mixture was heated to 40° C. and reacted for 4 h to improve the stability of the modified microspheres;

[0170] (d) Purification: washing the modified microspheres obtained in step (c) with ethanol and water to obtain a reaction product, which is a cross-linked aminosilane-modified silica microsphere having a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm;

[0171] (e) using the silica gel material prepared in step d to separate nickel, cobalt, copper and manganese from the ternary battery waste liquid by a filling column method, the process parameters are the same as those in Example 1, collecting the eluate, and testing the results of the metal ions in the eluate are shown in Table 2 below;

[0172] The manganese ions in the eluent were adsorbed by iminodiacetic acid type polystyrene resin (particle size of 0.1 mm to 0.5 mm, pore size of 10 nm to 1000 nm) to enrich manganese. After testing, the manganese ions contained in the eluent flowing out through the ion exchange resin are shown in Table 3 below.

[0173] Comparative Example 1

[0174] This comparative example provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0175] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0176] (b) Grafting reaction: The pretreated silica microspheres were swollen in ethylenediamine for 4 h, mixed in a mass ratio of silica microspheres to ethylenediamine of 1:0.2, and heated to 110 °C for 12 h under reflux.

[0177] (c) Cross-linking reaction: the ethylenediamine-modified silica microspheres prepared in step (b) were mixed with tetraethyl silicate in a mass ratio of 1:0.1 and stirred evenly, and the mixture was heated to 60° C. and reacted for 4 h to improve the stability of the modified microspheres;

[0178] (d) purification: washing the microspheres obtained in step (c) with ethanol and water to obtain a silica gel reaction product;

[0179] (e) using the silica gel material prepared in step d to separate nickel, cobalt, copper and manganese from the ternary battery waste liquid by a filling column method, the specific process parameters are the same as those in Example 1, collecting the eluate, and testing the results of the metal ions in the eluate are shown in Table 2 below;

[0180] Aminocarboxylic acid type polystyrene resin (particle size of 0.1 mm to 0.5 mm, pore size of 10 nm to 1000 nm) was used to adsorb manganese ions in the eluate to enrich manganese. After testing, the manganese ions contained in the eluate flowing out through the ion exchange resin are shown in Table 3 below.

[0181] Comparative Example 2

[0182] This comparative example provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0183] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0184] (b) purification: washing the silica microspheres obtained in step (a) with water to obtain a product;

[0185] The remaining steps are the same as in Example 1.

[0186] Comparative Example 3

[0187] This comparative example provides a method for recovering manganese from ternary battery waste liquid, which is as follows:

[0188] (a) Pretreatment of silica microspheres: Purchased silica microspheres were mixed with 15 wt % hydrochloric acid solution, heated to 70 ° C, and refluxed for 12 h to wash away excess impurities on the surface of the microspheres;

[0189] (b) Grafting reaction: The pretreated silica microspheres were swollen in methanol for 2 h, and γ-aminopropyltriethoxysilane KH550 was added at a mass ratio of silica microspheres to γ-aminopropyltriethoxysilane of 1:0.2, and the temperature was raised to 60 °C and the reaction was refluxed for 12 h;

[0190] (c) Purification: The modified microspheres obtained in step (b) are washed with ethanol and water to obtain a reaction product. The remaining steps are the same as those in Example 1.

[0191] Comparative Example 4

[0192] The carboxylate cationic silica gel is a purchased product. In this comparative example, 5 columns filled with carboxylate cationic silica gel material (10 mL each, about 8.1 g) were connected end to end in series. The other process parameters were the same as those in Example 1.

[0193] The performance tests of the products obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were carried out as follows:

[0194] (1) Take 10 mL of the amino silica gel adsorption material synthesized in Examples 1 to 6 (named products A to F, respectively), and the materials obtained in Comparative Examples 1 to 4 are respectively named products G to J, and load them into columns. Add 100 mL of ternary battery waste liquid containing 200 ppm of cobalt, nickel, copper and manganese, respectively, to conduct an adsorption experiment, wherein product J is 5 columns connected in series;

[0195] (2) The effluent from step (1) was passed through a 0.45 μm membrane to determine the contents of cobalt, nickel, copper and manganese ions. The results are shown in Table 2.

[0196] Table 2 Adsorption effect of different silica gel adsorption materials on cobalt, nickel, copper and manganese

[0197] Sample name <![CDATA[Co 2+ (ppm)]]> <![CDATA[Ni + (ppm)]]> <![CDATA[Cu 2+ (ppm)]]> <![CDATA[Mn 2+ (ppm)]]> Raw water 200 200 200 200 Product A 0 0 0 163 Product B 0 0 0 146 Product C 0 0 0 133 Product D 0 0 0 131 Product E 23.4 31.9 13.6 186 Product F 9.33 7.62 0.560 183 Product G 3.30 4.10 2.90 13.2 Product H 178 184 169 194 Product I 4.76 5.12 0.780 177 Product J 0 0 0 0

[0198] It can be seen from Table 2 above that, compared with Comparative Examples 1 to 4, the amino silica gel adsorption materials synthesized in Examples 1 to 6 of the present invention have better performance in adsorbing nickel, cobalt and copper ions, among which the measured effect of the sample described in Example 1 is better.

[0199] The effluents obtained after adsorption on the silica gel columns of Examples 1 to 6 and Comparative Examples 1 to 4 were collected respectively, and the manganese ions in the effluents were enriched using a cation exchange resin, iminodiacetic acid type polystyrene resin, which is sold on the market, as follows:

[0200] Table 3 Results of manganese ions contained in the eluate from the ion exchange resin

[0201] Sample name <![CDATA[Mn 2+ (ppm)]]> Product A 0 Product B 0 Product C 0 Product D 0 Product E 0 Product F 0 Product G 0 Product H 0 Product I 0 Product J 0

[0202] As can be seen from Table 3 above, the manganese ions in the effluent of the silica gel column are completely adsorbed by the cation exchange resin, indicating that this method is effective in enriching manganese ions.

[0203] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0204] The above-described embodiments only express several implementation methods of the present invention, which are convenient for understanding the technical solutions of the present invention in detail, but they cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by ordinary technicians in this field through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the protection scope of the claims attached to the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. A method for recovering manganese from ternary battery waste liquid, characterized in that: The steps include: Performing column chromatography on the ternary battery waste liquid and collecting the eluate; Performing ion exchange treatment on the eluate by using a cation exchange resin to enrich the manganese ions in the eluate; The chromatographic column filler used in the column chromatography treatment is cross-linked aminosilane-modified silica microspheres, and the preparation method of the cross-linked aminosilane-modified silica microspheres is as follows: Mixing silica microspheres and an aminosilane coupling agent in a first solvent to prepare aminosilane-modified silica microspheres through a grafting reaction; The aminosilane-modified silica microspheres are mixed with a crosslinking agent to prepare the crosslinked aminosilane-modified silica microspheres through a crosslinking reaction; The aminosilane coupling agent includes one or more of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 1-propyl-1-(triethoxysilyl)methylurea, γ-aminopropylmethyldiethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyl-dimethoxysilane; The crosslinking agent includes one or more of epichlorohydrin, tetraethyl silicate and tetrabutyl titanate.

2. The method for recovering manganese from ternary battery waste liquid according to claim 1, characterized in that: The grafting reaction satisfies at least one of the following (1) to (3): (1) The mass ratio of the silica microspheres to the aminosilane coupling agent is 1:(0.05-0.3); (2) The grafting reaction temperature is 40°C to 80°C and the time is 8h to 16h; (3) The first solvent includes one or more of methanol, ethanol, dichloromethane, isopropanol and 1,2-dichloroethane.

3. The method for recovering manganese from ternary battery waste liquid according to claim 1, characterized in that: The cross-linking reaction satisfies at least one of the following (1) to (2): (1) The mixing mass ratio of the aminosilane-modified silica microspheres to the crosslinking agent is 1:(0.05-0.3); (2) The temperature of the cross-linking reaction is 40°C to 80°C, and the time is 8h to 16h.

4. The method for recovering manganese from ternary battery waste liquid according to claim 1, characterized in that: Before the step of mixing the silica microspheres and the aminosilane coupling agent in the first solvent, the method further includes mixing the crude silica microspheres with an acid to perform an impurity removal reaction.

5. The method for recovering manganese from ternary battery waste liquid according to claim 4, characterized in that: The impurity removal reaction satisfies at least one of the following (1) to (3): (1) The mass ratio of the crude silica microspheres to the acid is 1:(0.1-0.75); (2) The acid includes one or more of hydrochloric acid, sulfuric acid and nitric acid; (3) The temperature of the impurity removal reaction is 30℃~60℃, and the time is 4h~8h.

6. The method for recovering manganese from ternary battery waste liquid according to claim 1, characterized in that: After the step of preparing the cross-linked aminosilane-modified silica microspheres through a cross-linking reaction, the method further includes a step of purifying the product of the cross-linking reaction.

7. The method for recovering manganese from ternary battery waste liquid according to claim 6, characterized in that: The purification process includes the following steps: The cross-linking reaction product is subjected to alcohol washing treatment and water washing treatment.

8. The method for recovering manganese from ternary battery waste liquid according to any one of claims 1 to 7, characterized in that: After column chromatography, the chromatographic column is subjected to elution and regeneration treatment, satisfying at least one of the following (1) to (7): (1) The elution procedure adopted for elution regeneration is pickling, wherein the pickling solution is a nickel-cobalt-copper ion enriched solution; (2) Column temperature is 20-50°C; (3) the desorbent used in the pickling step is a mixture of one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1% to 15%; (4) The flow rate of the eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 10 h; (5) The water washing step is to use pure water to wash the packed column, the water flow rate is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 10 h; (6) the alkaline solution used in the alkaline treatment step is a mixed solution of one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the mass concentration of the alkali in the alkaline solution is 1% to 15%; (7) In the alkali treatment step, the flow rate of the eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 4 h.

9. The method for recovering manganese from ternary battery waste liquid according to any one of claims 1 to 7, characterized in that: Satisfy at least one of the following (1) to (3): (1) The aminosilane-modified silica microspheres have a particle size of 0.1 mm to 0.8 mm and a pore size of 10 nm to 1000 nm; (2) the cation exchange resin comprises one or more of a sulfonic acid resin, an iminodiacetic acid resin, a phosphoric acid resin and an aminophosphoric acid resin; (3) The particle size of the cation exchange resin is 0.1 mm to 0.5 mm, and the pore size is 10 nm to 1000 nm.

10. The method for recovering manganese from ternary battery waste liquid according to any one of claims 1 to 7, characterized in that: After the ion exchange treatment step, the method further includes a step of desorbing and regenerating the cation exchange resin enriched with manganese ions, wherein the step satisfies at least one of the following (1) to (7): (1) The elution procedure adopted for desorption regeneration is acid washing, water washing and alkali treatment, wherein the acid washing solution is the manganese ion-enriched solution obtained after the ion exchange treatment; (2) Column temperature is 20-50°C; (3) the desorbent used in the pickling step is a mixture of one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1% to 15%; (4) In the pickling step, the flow rate of the eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 10 h; (5) The water washing step is to use pure water to wash the packed column, the water flow rate is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 10 h; (6) the alkaline solution used in the alkaline treatment step comprises a mixed solution of one or more of sodium hydroxide, potassium hydroxide and barium hydroxide, and the mass concentration of the alkali in the alkaline solution is 1% to 15%; (7) In the alkali treatment step, the flow rate of the eluent is 0.5 BV / h to 5 BV / h, and the treatment time is 1 h to 4 h.

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