Method for preparing hydrometallurgical resin

Abstract

The invention relates to the technical field of preparation of new resin materials, in particular to a method for preparing hydrometallurgical resin. The method comprises the following steps: mixing a polymer monomer, a cross-linking agent, an initiator, a pore-foaming agent and a spherical matrix with a cyano skeleton to obtain an oil-phase matrix; performing polymerization reaction on the dispersing agent and the oil-phase matrix for multiple times to obtain an intermediate; hydroxylamine, an alkaline solution and the intermediate are subjected to amidoximation reaction, and a wet metallurgy chelating resin crude product is obtained; and carrying out alkali treatment on the wet metallurgy chelating resin crude product to obtain the wet metallurgy chelating resin. According to the method, on the basis of multiple polymerization reactions among a polymer monomer, a cross-linking agent, an initiator, a pore-foaming agent and a spherical matrix, a complex and interpenetrating polymer network structure can be formed, and meanwhile, the proportion, reaction conditions and the like of the polymerization reactions are controlled, so that the pore structure distribution of the polymer network structure is more uniform; therefore, the hydrometallurgical chelating resin with high mechanical strength and compressive strength can be obtained.

Description

Technical Field

[0001] This application relates to the technical field of resin new material preparation, and particularly relates to a method for preparing a hydrometallurgy resin. Background Art

[0002] In order to improve the good adsorption effect and service life of the hydrometallurgy resin, it is generally necessary to improve the physical and chemical properties of the resin, and these physical and chemical properties include mechanical strength, chemical stability, abrasion resistance, etc. At present, acrylonitrile-divinylbenzene can be used as a cross-linked skeleton to prepare a macroporous chelating resin with amidoxime groups. By characterizing the structure and morphology of this macroporous chelating resin, it can be found that this macroporous chelating resin can be used for the adsorption of gallium in Bayer solution and has a good adsorption effect on gallium in Bayer solution.

[0003] However, the mechanical strength of the macroporous chelating resin obtained by this preparation method is not high, and the service life of this macroporous chelating resin is not long during the adsorption process of gallium in Bayer solution. Summary of the Invention

[0004] This application provides a method for preparing a hydrometallurgy resin to solve the following technical problem: how to improve the strength of the macroporous chelating resin.

[0005] In a first aspect, this application provides a method for preparing a hydrometallurgy resin, and the method includes:

[0006] Mix a polymer monomer, a cross-linking agent, an initiator, a pore-forming agent, and a spherical matrix with a cyano skeleton to obtain an oil-phase matrix;

[0007] Perform multiple polymerization reactions on a dispersant and the oil-phase matrix so that the polymer monomer, the cross-linking agent, the initiator, the pore-forming agent, and the small sphere matrix pass through and wind around each other to form an interpenetrating polymer network, obtaining an intermediate;

[0008] Perform an amidoximation reaction on hydroxylamine, an alkaline solution, and the intermediate to obtain a crude product of a hydrometallurgy chelating resin;

[0009] Perform alkali treatment on the crude product of the hydrometallurgy chelating resin to obtain a hydrometallurgy chelating resin.

[0010] Optionally, the polymerization reaction includes a first polymerization reaction and a second polymerization reaction; the temperature of the first polymerization reaction is 50°C to 70°C, and the time of the first polymerization reaction is 1h to 4h; the temperature of the second polymerization reaction is 85°C to 98°C, and the time of the second polymerization reaction is 4h to 7h.

[0011] Optionally, the mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = (0.3 - 2.0):(0.3 - 0.8):(0.01 - 0.05):(1 - 5):1.

[0012] Optionally, the polymer monomer includes at least one of the following: styrene, methyl methacrylate, and ethylene glycol dimethacrylate; and / or

[0013] The crosslinking agent includes at least one of the following: divinylbenzene, isoprene, and triallyl isocyanurate; and / or

[0014] The initiator includes at least one of the following: azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and benzoyl peroxide; and / or

[0015] The pore-forming agent includes at least one of the following: liquid paraffin, kerosene, xylene, cyclohexane, and isooctane; and / or

[0016] The spherical matrix includes acrylonitrile and / or vinyl cyanide.

[0017] Optionally, the crosslinking degree of the spherical matrix is 4% - 20%, and the particle size of the spherical matrix is 0.06 mm - 0.30 mm; and / or

[0018] The particle size of the intermediate > 0.315 mm.

[0019] Optionally, the temperature of the amidoximation reaction is 60°C - 90°C, and the time of the amidoximation reaction is 5 h - 24 h.

[0020] Optionally, the step of subjecting hydroxylamine, an alkaline solution, and the intermediate to an amidoximation reaction to obtain a crude wet metallurgy chelating resin includes the steps of:

[0021] Using hydroxylamine, an alkaline solution, and a solvent to swell the intermediate to obtain a swollen intermediate;

[0022] Subjecting the swollen intermediate to an amidoximation reaction to obtain a crude wet metallurgy chelating resin.

[0023] Optionally, the types of the alkaline solution include at least one of the following: sodium carbonate, sodium hydroxide, sodium nitrite, and sodium bisulfite; and / or

[0024] The solvent includes at least one of the following: ethylene glycol, methanol, N,N-dimethylformamide, dimethyl sulfoxide, dichloroethane, n-butanol, and water.

[0025] Optionally, the step of subjecting the crude hydrometallurgical chelating resin to alkali treatment to obtain a hydrometallurgical chelating resin includes the following steps:

[0026] Subject the crude hydrometallurgical chelating resin to alkali treatment to obtain a crude alkaline resin;

[0027] Wash the crude alkaline resin to obtain a crude neutral resin;

[0028] Dry the crude neutral resin to obtain a hydrometallurgical chelating resin.

[0029] Optionally, the temperature of the alkali treatment is 40°C to 50°C, and the time of the alkali treatment is 5h to 24h; and / or

[0030] The temperature of the drying is 40°C to 60°C, and the time of the drying is ≥12h.

[0031] The above technical solution provided by the embodiments of the present application has the following advantages compared with the prior art:

[0032] A method for preparing a hydrometallurgical resin provided by an embodiment of the present application uses a spherical matrix with a cyano skeleton as the skeleton, and performs multiple polymerization reactions of a polymer monomer, a crosslinking agent, an initiator, and a pore-forming agent within the skeleton, so that a complex and interpenetrating polymer network structure is formed between the polymer monomer, the crosslinking agent, the initiator, the pore-forming agent, and the cyano group of the skeleton. These polymer network structures have complex and very strong polymer scaffolds, making the intermediate have high mechanical strength; in addition, there are many and evenly distributed pores between these polymer network structures, and these pores can provide sufficient deformation space for the polymer network structures when bearing external pressure deformation, and can improve the compressive strength of the intermediate to a certain extent. The intermediate with high mechanical strength and compressive strength can form a hydrometallurgical chelating resin with high mechanical strength and compressive strength after amidoximation reaction and alkali treatment. Description of the Drawings

[0033] The drawings here are incorporated into the specification and constitute a part of this specification, showing the embodiments that conform to the present application, and are used together with the specification to explain the principles of the present application.

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative efforts.

[0035] Figure 1 It is a schematic flow chart of a method for preparing a hydrometallurgical resin provided by an embodiment of the present application;

[0036] Figure 2 This is a schematic diagram of the detailed process for a method provided by an embodiment of the present application for preparing a hydrometallurgy resin. Specific embodiments

[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts shall fall within the scope of protection of the present application.

[0038] The various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be construed as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values within that range; for example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within that range, such as 1, 2, 3, 4, 5, and 6, regardless of the range; in addition, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0039] In this text, terms such as "including" mean "including but not limited to". Relative terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. "And / or" describes the associated relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist simultaneously, or B exists alone; where A and B can be singular or plural. "At least one" means one or more, and "multiple" means two or more; "at least one kind", "at least one of the following items", or similar expressions refer to any combination of these items, including any combination of single items or plural items; for example, "at least one of a, b, or c", or "at least one of a, b, and c" can both mean: a, b, c, a - b (that is, a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively. "Part representation methods" such as weight parts and mass parts represent the proportional relationship between each component. In the proportional relationships involved in this text, the parameters that need to be described by proportion should be understood as the antecedents of the proportion formula in the order of description, and the proportional numbers should be understood as the consequents of the proportion formula. For example, if the mass ratio of substance A, substance B, and substance C is 1:2:3, then substance A, substance B, and substance C should correspond one by one with the proportional numbers in the proportion formula in the order of description, that is, the mass of substance A: the mass of substance B: the mass of substance C = 1:2:3.

[0040] Unless otherwise specifically stated, various raw materials, reagents, instruments, and equipment used in this text can be obtained through market purchases or can be prepared by existing methods.

[0041] It should be noted that for the prior art described in the background art, the inventor found that: during the cyclic adsorption of gallium in the Bayer solution, the macroporous chelating resin with lower mechanical strength decays faster; in addition, in the application of gallium adsorption in the automated fluidized bed of the Bayer process, the continuously flowing Bayer solution will cause the macroporous chelating resin to be subject to greater resistance and friction. At the same time, due to the high alkalinity of the Bayer solution, these macroporous chelating resins with lower mechanical strength are prone to pulverization, thereby reducing the service life of the macroporous chelating resin. Therefore, improving the strength of the macroporous chelating resin is beneficial to extending the service life of the macroporous chelating resin.

[0042] Figure 1 Exemplarily, a schematic flow diagram of a method for preparing a hydrometallurgical resin provided by an embodiment of the present application is shown;

[0043] As Figure 1 shown, an embodiment of the present application provides a method for preparing a hydrometallurgical resin, and the method includes:

[0044] S1. mixing a polymer monomer, a crosslinking agent, an initiator, a porogen and a spherical matrix having a cyano skeleton to obtain an oil phase matrix;

[0045] S2. The dispersant and the oil phase matrix are subjected to multiple polymerization reactions so that the polymer monomer, the crosslinking agent, the initiator, the porogen and the ball matrix are interpenetrated and entangled to form an interpenetrating polymer network to obtain an intermediate;

[0046] S3. subjecting hydroxylamine, alkaline solution and the intermediate to amidoximation reaction to obtain a crude hydrometallurgical chelating resin;

[0047] S4. treating the crude hydrometallurgical chelating resin with alkali to obtain a hydrometallurgical chelating resin.

[0048] It should be noted that the polymerization reaction may be carried out twice or three times.

[0049] It should be noted that the polymer obtained by the polymerization reaction needs to be washed in various ways, such as using acetone, ethanol, hot water and cold water as detergents to wash in sequence, and then the washed polymer is dried in an oven at 60° C. to obtain an intermediate.

[0050] It should be noted that the amidoximation reaction is carried out based on the hydration method to introduce an amidoxime group into the intermediate.

[0051] It should be noted that the spherical matrix can be acrylonitrile sphere undersize material, and its particle size is ≤0.30 mm.

[0052] It should be noted that the dispersant can be gelatin, polypropylene alcohol, or water.

[0053] It should be noted that the hydroxylamine may be hydroxylamine hydrochloride or hydroxylamine sulfate.

[0054] It should be noted that the present embodiment provides a method for preparing a hydrometallurgical resin, which is a process technology with great innovation and practical value in the field of materials science, and its preparation process contains fine chemical principles and rigorous process design. The specific principles are as follows:

[0055] At the initial stage of preparation, a spherical matrix with a cyano skeleton is selected as the basic skeleton for the entire synthesis process. The cyano group (-C≡N) has unique chemical properties, and its highly unsaturated structure endows the spherical matrix with certain chemical activity and stability. This chemical activity enables the cyano group to actively participate in the chemical bonding process with other reactants in subsequent polymerization reactions, laying the foundation for constructing a complex polymer network structure; while the stability ensures that the spherical matrix maintains its basic physical form throughout the preparation process, providing a stable carrier for the reaction. In addition, from a microscopic perspective, the spherical shape of the spherical matrix has a large specific surface area, which is conducive to the uniform dispersion of polymer monomers, cross-linking agents, initiators, and porogens inside the spherical matrix, providing good spatial distribution conditions for subsequent polymerization reactions to ensure that all substances can come into full contact and react.

[0056] Subsequently, polymer monomers, cross-linking agents, initiators, and porogens are introduced into the spherical matrix of the cyano skeleton. Polymer monomers, as the basic units for constructing the polymer network, usually contain unsaturated bonds, such as carbon-carbon double bonds (C=C), etc. These unsaturated bonds can be activated under the action of initiators and undergo chain polymerization reactions, gradually forming long-chain polymer molecules. The cross-linking agent plays a crucial bridging role in the entire system. It contains multiple active groups that can react with polymer monomers. During the polymerization process, cross-linking agent molecules can react with multiple polymer molecular chains, connecting these independent molecular chains through chemical bonds to form a three-dimensional network structure. This cross-linked structure greatly enhances the stability and strength of the polymer network, making the entire polymer network structure more stable.

[0057] The main role of the initiator is to initiate and start the polymerization reaction. Common initiators are mostly compounds that can decompose to generate free radicals under certain conditions, such as peroxides. When the initiator is heated or under other excitation conditions, the initiator will decompose to generate highly active free radicals, which can quickly react with polymer monomer molecules, open the unsaturated bonds in the polymer monomer molecules, and initiate the chain polymerization reaction between polymer monomer molecules, thus starting the entire polymerization reaction process.

[0058] The presence of the porogen is to introduce a large number of fine pores into the finally formed polymer network structure. These porogens are usually some substances that can be dissolved in other substances in the reaction system but can be removed by specific methods after the polymerization reaction is completed, such as certain organic solvents or small molecule compounds. During the polymerization reaction, the porogens are uniformly dispersed in the reaction system. After the polymerization reaction is completed, the porogens are removed by methods such as evaporation and extraction, leaving pores with controllable sizes and distributions in the polymer network structure.

[0059] Within the spherical matrix of the cyano skeleton, the polymer monomer, crosslinking agent, initiator, and porogen undergo multiple polymerization reactions. Each polymerization reaction is a complex and orderly process. As the reaction progresses, the polymer molecular chains continuously grow, and the crosslinking agent gradually forms crosslinking points between the molecular chains, causing the polymer network structure to gradually grow and improve. The finally formed polymer network structure is extremely complex and interpenetrating, containing polymer scaffolds with high strength. These scaffolds are composed of intertwined polymer molecular chains and crosslinking points, which endow the intermediate with high mechanical strength, enabling it to maintain the integrity of its structure under normal physical actions and not easily break or deform.

[0060] In addition, there are numerous and evenly distributed pores between these polymer network structures. The existence of these pores is of great significance for improving the performance of the intermediate. When the intermediate is deformed under external pressure, these pores can provide sufficient deformation space for the polymer network structure. The pores allow it to disperse and buffer the pressure through the deformation of its internal structure when being squeezed, thus avoiding the destruction of the material caused by local stress concentration. This property significantly improves the compressive strength of the intermediate to a certain extent, enabling it to adapt to more severe usage environments.

[0061] Finally, the intermediate with high mechanical strength and compressive strength also needs to undergo two key steps: amidoximation reaction and alkali treatment. The amidoximation reaction is a process of introducing amidoxime groups (-C(=NH)NHOH) into the molecular structure of the intermediate. This reaction usually occurs through a specific chemical reaction path, enabling certain groups in the intermediate molecule to react with reagents containing amidoxime structures, thereby successfully introducing amidoxime groups into the polymer network structure. Amidoxime groups have a strong ability to complex metal ions and can form stable complexes with various metal ions. This property endows the material with the chelating performance required for hydrometallurgy and enables it to effectively adsorb and separate metal ions from solutions.

[0062] Alkali treatment is an important step to further optimize the material properties. During the alkali treatment process, the alkaline reagent reacts chemically with the intermediate, which may adjust certain chemical bonds in the polymer network structure or remove some residual impurities and unreacted substances. This process can not only further improve the microscopic structure of the polymer network but also regulate the surface charge distribution and chemical activity of the material, thereby making the material's properties more stable and excellent. After the amidoximation reaction and alkali treatment, a hydrometallurgy chelating resin with high mechanical strength and compressive strength is finally successfully prepared. This hydrometallurgy chelating resin demonstrates great application potential in the field of hydrometallurgy due to its excellent properties and can be efficiently applied to key process steps such as the extraction, separation, and enrichment of metal ions, providing strong technical support for fields such as resource recovery and environmental protection.

[0063] In some alternative embodiments, the polymerization reaction includes a first polymerization reaction and a second polymerization reaction; the temperature of the first polymerization reaction is 50°C to 70°C, and the time of the first polymerization reaction is 1 h to 4 h; the temperature of the second polymerization reaction is 85°C to 98°C, and the time of the second polymerization reaction is 4 h to 7 h.

[0064] In these embodiments, the polymerization reaction may include a first polymerization reaction, and the temperature of the first polymerization reaction may be 50°C to 70°C, and the time of the first polymerization reaction may be 1 h to 4 h, such that a preliminary polymerization reaction occurs between the polymer monomer, the crosslinking agent, the initiator, the pore-forming agent, and the cyano group of the spherical matrix to preliminarily form a complex and interpenetrating polymer network structure; additionally, the polymerization reaction may include a second polymerization reaction, and the temperature of the second polymerization reaction may be 85°C to 98°C, and the time of the second polymerization reaction may be 4 h to 7 h, such that the preliminarily formed complex and interpenetrating polymer network structure further undergoes a polymerization reaction to finally form a polymer network structure with a complex and very high strength, and these polymer network structures endow the intermediate with high mechanical strength and compressive strength, thereby finally forming a hydrometallurgical chelating resin with high mechanical strength and compressive strength.

[0065] The temperature of the first polymerization reaction may be 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, or 70°C.

[0066] The time of the first polymerization reaction may be 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, or 4 h.

[0067] The temperature of the second polymerization reaction may be 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, or 98°C.

[0068] The time of the second polymerization reaction may be 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, or 7 h.

[0069] In some alternative embodiments, the mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = (0.3 to 2.0):(0.3 to 0.8):(0.01 to 0.05):(1 to 5):1.

[0070] In these embodiments, the mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix may satisfy the relational expression: m1:m2:m3:m4:m5 = (0.3 - 2.0):(0.3 - 0.8):(0.01 - 0.05):(1 - 5):1, such that the polymerization reaction has sufficient polymer monomer, crosslinking agent, initiator, pore-forming agent, and spherical matrix. After multiple polymerization reactions, the sufficient polymer monomer, crosslinking agent, initiator, pore-forming agent, and spherical matrix can form a complex and interconnected polymer network structure. These polymer network structures can endow the intermediate with high mechanical strength and compressive strength, thereby enabling the formation of a hydrometallurgical chelating resin with high mechanical strength and compressive strength.

[0071] The value of the mass m1 of the polymer monomer may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, or 2.0.

[0072] The value of the mass m2 of the crosslinking agent may be 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8.

[0073] The value of the mass m3 of the initiator may be 0.01, 0.02, 0.03, 0.04, or 0.05.

[0074] The value of the mass m4 of the pore-forming agent may be 1, 2, 3, 4, or 5.

[0075] In some alternative embodiments, the polymer monomer includes at least one of the following: styrene, methyl methacrylate, and ethylene glycol dimethacrylate; and / or

[0076] The crosslinking agent includes at least one of the following: divinylbenzene, isoprene, and triallyl isocyanurate; and / or

[0077] The initiator includes at least one of the following: azobisisobutyronitrile, azobicyclohexylcarbonitrile, and benzoyl peroxide; and / or

[0078] The pore-forming agent includes at least one of the following: liquid paraffin, kerosene, xylene, cyclohexane, and isooctane; and / or

[0079] The spherical matrix includes acrylonitrile and / or vinyl cyanide.

[0080] In these embodiments, the polymer monomers may include at least one of the following: styrene, methyl methacrylate, and ethylene glycol dimethacrylate, such that the polymer monomers can cover the raw materials of most common synthetic resins, thereby facilitating subsequent multiple polymerization reactions to ultimately obtain an intermediate with high mechanical strength and compressive strength; additionally, the crosslinking agent may include at least one of the following: divinylbenzene, isoprene, and triallyl isocyanurate, such that the crosslinking agent can cover most commonly used crosslinking agents, enabling subsequent multiple polymerization reactions to obtain an intermediate with high mechanical strength and compressive strength; furthermore, the initiator may include at least one of the following: azobisisobutyronitrile, azobicyclohexylcarbonitrile, and benzoyl peroxide, such that the initiator can cover most commonly used initiators to promote the full progress of the polymerization reaction, thereby obtaining an intermediate with high mechanical strength and compressive strength; in addition, the pore-forming agent may include at least one of the following: liquid paraffin, kerosene, xylene, cyclohexane, and isooctane, such that a large number of fine pores are introduced into the polymer network formed by the polymerization reaction to form fine and uniformly distributed pores in the polymer network, and these pores can improve the compressive strength of the intermediate to a certain extent; moreover, the spherical matrix may include acrylonitrile and / or vinyl cyanide, which can endow the spherical matrix with a sufficient amount of cyano groups to enable the full progress of the polymerization reaction to obtain an intermediate with high mechanical strength and compressive strength.

[0081] In some alternative embodiments, the crosslinking degree of the spherical matrix is 4% - 20%, and the particle size of the spherical matrix is 0.06 mm - 0.30 mm; and / or

[0082] The particle size of the intermediate > 0.315 mm.

[0083] In these embodiments, the crosslinking degree of the spherical matrix can be 4% - 20%, and the particle size of the spherical matrix can be 0.06 mm - 0.30 mm, such that the spherical matrix has a sufficient specific surface area and certain pores, and the spherical matrix with sufficient specific surface area and pores can fully undergo polymerization reactions with the polymer monomers, crosslinking agent, initiator, and pore-forming agent to obtain an intermediate with high mechanical strength and compressive strength.

[0084] The crosslinking degree of the spherical matrix can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, or 20%.

[0085] The particle size of the spherical matrix can be 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.10 mm, 0.15 mm, 0.20 mm, 0.25 mm, or 0.30 mm.

[0086] In some alternative embodiments, the temperature of the amidoximation reaction is 60°C to 90°C, and the time of the amidoximation reaction is 5h to 24h.

[0087] In these embodiments, the temperature of the amidoximation reaction can be 60°C to 90°C, and the time of the amidoximation reaction can be 5h to 24h, such that hydroxylamine and the intermediate fully undergo the amidoximation reaction in the environment of the alkaline solution, thereby introducing a large number of amidoxime groups into the intermediate to improve the adsorption capacity of the hydrometallurgical chelating resin.

[0088] The temperature of the amidoximation reaction can be 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, or 90°C.

[0089] The time of the amidoximation reaction can be 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, or 24h.

[0090] Figure 2 Exemplarily, a detailed process schematic diagram of a method for preparing a hydrometallurgical resin provided by an embodiment of the present application is shown;

[0091] In some alternative embodiments, as Figure 2 shown, the step of subjecting hydroxylamine, an alkaline solution, and the intermediate to an amidoximation reaction to obtain a crude hydrometallurgical chelating resin includes the steps of:

[0092] S301. Swelling the intermediate with hydroxylamine, an alkaline solution, and a solvent to obtain a swollen intermediate;

[0093] S302. Subjecting the swollen intermediate to an amidoximation reaction to obtain a crude hydrometallurgical chelating resin.

[0094] In these embodiments, the intermediate is first swollen so that the specific surface area and pore structure of the intermediate can reach an appropriate level, facilitating the subsequent amidoximation reaction of the swollen intermediate and hydroxylamine in the alkaline environment of the alkaline solution to introduce a large number of amidoxime groups into the intermediate, thereby improving the adsorption capacity of the hydrometallurgical chelating resin.

[0095] In some alternative embodiments, the types of the alkaline solution include at least one of the following: sodium carbonate, sodium hydroxide, sodium nitrite, and sodium bisulfite; and / or

[0096] The solvent includes at least one of the following: ethylene glycol, methanol, N,N-dimethylformamide, dimethyl sulfoxide, dichloroethane, n-butanol, and water.

[0097] In these embodiments, the types of the alkaline solution may include at least one of the following: sodium carbonate, sodium hydroxide, sodium nitrite, and sodium bisulfite, so that the swelling intermediate and hydroxylamine can fully carry out the amidoximation reaction to introduce a large number of amidoxime groups into the intermediate, thereby improving the adsorption capacity of the hydrometallurgical chelating resin; in addition, the solvent may include at least one of the following: ethylene glycol, methanol, N,N-dimethylformamide, dimethyl sulfoxide, dichloroethane, n-butanol, and water. The solvent can effectively promote the swelling and shaping of the intermediate, thereby facilitating the subsequent amidoximation reaction of the swelling intermediate and hydroxylamine in the alkaline environment of the alkaline solution to introduce a large number of amidoxime groups into the intermediate, and further improving the adsorption capacity of the hydrometallurgical chelating resin.

[0098] In some alternative embodiments, the step of subjecting the crude hydrometallurgical chelating resin to an alkali treatment to obtain a hydrometallurgical chelating resin includes the steps of:

[0099] S401. Subjecting the crude hydrometallurgical chelating resin to an alkali treatment to obtain a crude alkaline resin;

[0100] S402. Washing the crude alkaline resin to obtain a crude neutral resin;

[0101] S403. Drying the crude neutral resin to obtain a hydrometallurgical chelating resin.

[0102] In these embodiments, first subject the crude hydrometallurgical chelating resin to an alkali treatment. Through the alkali treatment, impurities in the crude hydrometallurgical chelating resin can be removed to ensure the smoothness of the polymer network structure of the crude hydrometallurgical chelating resin, so as to finally obtain a hydrometallurgical chelating resin with good mechanical strength and compressive strength; in addition, the alkaline substances introduced by the alkaline treatment can be removed through washing, and the moisture introduced in the washing stage can be removed by drying, so as to finally obtain a relatively pure hydrometallurgical chelating resin product.

[0103] In some alternative embodiments, the temperature of the alkali treatment is 40°C to 50°C, and the time of the alkali treatment is 5 h to 24 h; and / or

[0104] the temperature of the drying is 40°C to 60°C, and the time of the drying is ≥12 h.

[0105] In these embodiments, the temperature of the alkali treatment can be 40°C to 50°C, and the time of the alkali treatment can be 5 h to 24 h, such that the alkali treatment of the crude hydrometallurgical chelating resin is carried out sufficiently, so that impurities in the crude hydrometallurgical chelating resin can be effectively removed, ensuring the smoothness of the polymer network structure of the crude hydrometallurgical chelating resin, and thus a hydrometallurgical chelating resin with good mechanical strength and compressive strength can be finally obtained; in addition, the drying temperature can be 40°C to 60°C, and the drying time can be ≥12 h, so that the moisture introduced in the washing stage can be fully removed from the neutral resin crude product to obtain a pure hydrometallurgical chelating resin product.

[0106] The temperature of the alkali treatment can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C.

[0107] The time of the alkali treatment can be 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h or 24 h.

[0108] The drying temperature can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C.

[0109] The present application will be further elaborated below in conjunction with specific embodiments. For the experimental methods without specific conditions noted in the following embodiments, they are generally determined according to national standards / industry standards; if there are no corresponding national standards / industry standards, they are carried out according to general international standards, conventional conditions or conditions recommended by the manufacturer.

[0110] Example 1

[0111] As Figure 2 shown, a method for preparing a hydrometallurgical resin includes:

[0112] S1. Mixing a polymer monomer, a crosslinking agent, an initiator, a pore-forming agent and a spherical matrix with a cyano skeleton to obtain an oil-phase matrix; specific steps: Mixing the polymer monomer, the crosslinking agent, the initiator, the pore-forming agent and the spherical matrix with a cyano skeleton in a beaker to obtain an oil-phase matrix;

[0113] S2. Performing multiple polymerization reactions on a dispersant and the oil-phase matrix, so that the polymer monomer, the crosslinking agent, the initiator, the pore-forming agent and the small spherical matrix form an interpenetrating polymer network through interpenetrating winding to obtain an intermediate; specific steps:

[0114] A dispersant is added to a three-necked flask at 40° C. and mixed. After the dispersant is dissolved, an oil phase matrix is ​​added. The stirring speed in the three-necked flask is adjusted to 180 r / min to 500 r / min. Then, the temperature is increased to perform two first polymerization reactions and one second polymerization reaction. After all polymerization reactions are completed, the polymerization product is transferred to a sand core funnel. Then, the polymerization product in the sand core funnel is washed with anhydrous ethanol and hot water in sequence to remove the unreacted porogen. After the porogen is removed, the polymerization product is subsequently filtered and vacuum dried for a total of 24 hours to obtain an intermediate.

[0115] S301. The intermediate is swelled by using hydroxylamine sulfate, an alkaline solution and a solvent to obtain a swollen intermediate; the specific steps are: adding hydroxylamine sulfate in a volume ratio of 1:2 to the intermediate and an aqueous solution of ethylene glycol with a mass concentration of 40% in a volume ratio of 1:6 to the intermediate in a three-necked flask, and then adding sodium hydroxide in a volume ratio of 1:2 to the intermediate to form a mixed solution in the three-necked flask, and then adding the intermediate to the mixed solution, and stirring and swelling at 50°C for 60 minutes to obtain a swollen intermediate;

[0116] S302. The swollen intermediate is subjected to an amidoximation reaction to obtain a crude hydrometallurgical chelating resin;

[0117] S401. The crude hydrometallurgical chelate resin is treated with alkali to obtain a crude alkaline resin; specifically, the crude hydrometallurgical chelate resin is transferred to a sand core funnel to filter and separate a mixed solution of the crude hydrometallurgical chelate resin, and then the crude hydrometallurgical chelate resin is added to an aqueous sodium carbonate solution for alkali treatment;

[0118] S402. Washing the crude alkaline resin with hot water and cold water in sequence until it becomes neutral to obtain a crude neutral resin;

[0119] S403. Drying the crude neutral resin to obtain a hydrometallurgical chelating resin comprises the following steps: filtering the crude neutral resin to obtain a solid phase; vacuum drying the solid phase obtained by filtration to obtain a vacuum dried product; screening the vacuum dried product using a 0.4 mm to 1.0 mm mesh screen, taking the sieve under the screen to obtain a hydrometallurgical chelating resin.

[0120] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50°C, and the time of the first first polymerization reaction is 1 hour; the temperature of the second first polymerization reaction is 60°C, and the time of the second first polymerization reaction is 2 hours; the temperature of the second polymerization reaction is 95°C, and the time of the second polymerization reaction is 6 hours.

[0121] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.9 parts:0.5 parts:0.01 parts:3 parts:1 part.

[0122] The polymer monomer is styrene;

[0123] The crosslinking agent is divinylbenzene;

[0124] The initiator is benzoyl peroxide;

[0125] The pore-forming agent includes a mixture formed by mixing liquid paraffin and xylene in a mass ratio of 2:1;

[0126] The spherical matrix is acrylonitrile.

[0127] The dispersant is 0.1 part of gelatin and 6 parts of water.

[0128] The crosslinking degree of the spherical matrix is 4% - 20%, and the particle size of the spherical matrix is 0.06 mm - 0.30 mm;

[0129] The particle size of the intermediate > 0.315 mm.

[0130] The temperature of the amidoximation reaction is 90 °C, and the time of the amidoximation reaction is 12 h.

[0131] The type of the alkaline solution is sodium hydroxide, and the alkaline solution is added in a volume ratio of 1:2 to the intermediate;

[0132] The solvent is a mixed solution of ethylene glycol and water, the mass ratio of ethylene glycol and water is 40:100, and the solvent is added in a volume ratio of 1:6 to the intermediate.

[0133] The temperature of the alkali treatment is 50 °C, and the time of the alkali treatment is 12 h;

[0134] The temperature of the drying is 40 °C - 60 °C, and the time of the drying is 12 h.

[0135] Example 2

[0136] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0137] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C, and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 65 °C, and the time of the second first polymerization reaction is 3 h; the temperature of the second polymerization reaction is 90 °C, and the time of the second polymerization reaction is 6 h.

[0138] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.5 parts: 0.3 parts: 0.05 parts: 1 part: 1 part.

[0139] The polymer monomer is methyl methacrylate;

[0140] The crosslinking agent is isoprene;

[0141] The initiator is azobis(cyclohexanecarbonitrile);

[0142] The pore-forming agent is a mixture formed by mixing liquid paraffin and cyclohexane in a mass ratio of 1:1;

[0143] The spherical matrix is acrylonitrile.

[0144] The dispersant is 0.2 parts of a mixture formed by mixing gelatin and polyvinyl alcohol in a mass ratio of 3:1 and 4 parts of water.

[0145] The hydroxylamine used is a mixed hydroxylamine formed by mixing hydroxylamine hydrochloride and hydroxylamine sulfate in a volume ratio of 1:3. The hydroxylamine is added in a ratio of 1:4 by volume to the intermediate. The temperature of the swelling treatment is 40 °C, and the time of the swelling treatment is 60 min.

[0146] The temperature of the amidoximation reaction is 80 °C, and the time of the amidoximation reaction is 10 h.

[0147] The type of the alkaline solution is sodium carbonate, and the alkaline solution is added in a ratio of 1:1.5 by volume to the intermediate;

[0148] The solvent is water, and the solvent is added in a ratio of 1:20 by volume to the intermediate.

[0149] The temperature of the alkali treatment is 40 °C, and the time of the alkali treatment is 18 h.

[0150] Example 3

[0151] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0152] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C, and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 62 °C, and the time of the second first polymerization reaction is 2.5 h; the temperature of the second polymerization reaction is 96 °C, and the time of the second polymerization reaction is 12 h.

[0153] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 1.5 parts: 0.5 parts: 0.02 parts: 4 parts: 1 part.

[0154] The polymer monomer is a mixture formed by mixing methyl methacrylate and styrene in a mass ratio of 1:1;

[0155] The crosslinking agent is triallyl isocyanurate;

[0156] The initiator is azobis(cyclohexanecarbonitrile);

[0157] The pore-forming agent is a mixture formed by mixing cyclohexane and xylene in a mass ratio of 1:2;

[0158] The spherical matrix is acrylonitrile.

[0159] The dispersant is 0.1 part of a mixture formed by mixing gelatin and polyvinyl alcohol in a mass ratio of 1:1 and 5 parts of water.

[0160] Hydroxylamine uses a mixed hydroxylamine formed by mixing hydroxylamine hydrochloride and hydroxylamine sulfate in a volume ratio of 1:1. Hydroxylamine is added in a ratio of 1:2 by volume to the intermediate. The temperature of the swelling treatment is 40 °C, and the time of the swelling treatment is 60 min.

[0161] The temperature of the amidoximation reaction is 70 °C, and the time of the amidoximation reaction is 24 h.

[0162] The type of the alkaline solution is sodium carbonate, and the alkaline solution is added in a ratio of 1:2 by volume to the intermediate;

[0163] The solvent is water, and the solvent is added in a ratio of 1:8 by volume to the intermediate.

[0164] The temperature of the alkali treatment is 45 °C, and the time of the alkali treatment is 10 h.

[0165] Example 4

[0166] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0167] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C, and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 60 °C, and the time of the second first polymerization reaction is 2 h; the temperature of the second polymerization reaction is 95 °C, and the time of the second polymerization reaction is 6 h.

[0168] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.9 parts:0.5 parts:0.01 parts:3 parts:1 part.

[0169] The polymer monomer is methyl acrylate;

[0170] The crosslinking agent is divinylbenzene;

[0171] The initiator is benzoyl peroxide;

[0172] The pore-forming agent is a mixture formed by mixing isooctane and liquid paraffin in a mass ratio of 4:1;

[0173] The spherical matrix is acrylonitrile.

[0174] The dispersant is 0.1 part of gelatin and 6 parts of water.

[0175] Hydroxylamine uses hydroxylamine sulfate. Hydroxylamine is added in a volume ratio of 1:2 to the intermediate.

[0176] The temperature of the amidoximation reaction is 90 °C, and the time of the amidoximation reaction is 12 h.

[0177] The type of the alkaline solution is sodium hydroxide, and the alkaline solution is added in a volume ratio of 1:2 to the intermediate;

[0178] The solvent is a mixture formed by mixing dichloroethane, N,N-dimethylformamide and water in a mass ratio of 2 parts:3 parts:5 parts, and the solvent is added in a volume ratio of 1:10 to the intermediate.

[0179] The temperature of the alkali treatment is 50 °C, and the time of the alkali treatment is 12 h.

[0180] Example 5

[0181] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0182] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C, and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 60 °C, and the time of the second first polymerization reaction is 2 h; the temperature of the second polymerization reaction is 95 °C, and the time of the second polymerization reaction is 6 h.

[0183] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.9 parts:0.5 parts:0.01 parts:3 parts:1 part.

[0184] The polymer monomer is styrene;

[0185] The crosslinking agent is divinylbenzene;

[0186] The initiator is benzoyl peroxide;

[0187] The pore-forming agent is a mixture formed by mixing xylene and liquid paraffin in a mass ratio of 2:1;

[0188] The spherical matrix is acrylonitrile.

[0189] The dispersant is 0.1 part of gelatin and 6 parts of water.

[0190] Hydroxylamine used is hydroxylamine sulfate. Hydroxylamine is added in a volume ratio of 1:2 to the intermediate.

[0191] The temperature of the amidoximation reaction is 90 °C, and the time of the amidoximation reaction is 12 h.

[0192] The type of the alkaline solution is sodium hydroxide, and the alkaline solution is added in a volume ratio of 1:2 to the intermediate;

[0193] The solvent is a mixture formed by mixing dichloroethane and water in a mass ratio of 40:100, and the solvent is added in a volume ratio of 1:6 to the intermediate.

[0194] The temperature of the alkali treatment is 50 °C, and the time of the alkali treatment is 12 h.

[0195] Example 6

[0196] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0197] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C, and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 60 °C, and the time of the second first polymerization reaction is 2 h; the temperature of the second polymerization reaction is 95 °C, and the time of the second polymerization reaction is 6 h.

[0198] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.9 part:0.5 part:0.01 part:3 parts:1 part.

[0199] The polymer monomer is styrene;

[0200] The crosslinking agent is triallyl isocyanurate;

[0201] The initiator is benzoyl peroxide;

[0202] The pore-forming agent is a mixture formed by mixing xylene and liquid paraffin in a mass ratio of 3:1;

[0203] The spherical matrix is acrylonitrile.

[0204] The dispersant is 0.1 part of gelatin and 6 parts of water.

[0205] Hydroxylamine used is hydroxylamine sulfate. Hydroxylamine is added in a volume ratio of 1:2 to the intermediate.

[0206] The temperature of the amidoximation reaction is 90 °C, and the time of the amidoximation reaction is 12 h.

[0207] The type of the alkaline solution is sodium hydroxide, and the alkaline solution is added in a volume ratio of 1:2 to the intermediate;

[0208] The solvent is a mixture formed by mixing dichloroethane and water in a mass ratio of 40:100, and the solvent is added in a volume ratio of 1:6 to the intermediate.

[0209] The temperature of the alkali treatment is 50 °C, and the time of the alkali treatment is 12 h.

[0210] Example 7

[0211] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0212] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C, and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 60 °C, and the time of the second first polymerization reaction is 2 h; the temperature of the second polymerization reaction is 95 °C, and the time of the second polymerization reaction is 6 h.

[0213] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.9 part:0.5 part:0.01 part:3 parts:1 part.

[0214] The polymer monomer is styrene;

[0215] The crosslinking agent is divinylbenzene;

[0216] The initiator is a mixture formed by mixing benzoyl peroxide and azobisisobutyronitrile in a mass ratio of 1:1;

[0217] The pore-forming agent is a mixture formed by mixing xylene and liquid paraffin in a mass ratio of 1:2;

[0218] The spherical matrix is acrylonitrile.

[0219] The dispersant is 0.1 part of gelatin and 6 parts of water.

[0220] Hydroxylamine used is hydroxylamine sulfate. Hydroxylamine is added in a ratio of 1:2 by volume to the intermediate.

[0221] The temperature of the amidoximation reaction is 90 °C and the time of the amidoximation reaction is 12 h.

[0222] The type of the alkaline solution is sodium hydroxide. The alkaline solution is added in a ratio of 1:2 by volume to the intermediate;

[0223] The solvent is a mixture formed by mixing dichloroethane and water in a mass ratio of 40:100. The solvent is added in a ratio of 1:6 by volume to the intermediate.

[0224] The temperature of the alkali treatment is 50 °C and the time of the alkali treatment is 12 h.

[0225] Example 8

[0226] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0227] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 60 °C and the time of the second first polymerization reaction is 2 h; the temperature of the second polymerization reaction is 95 °C and the time of the second polymerization reaction is 6 h.

[0228] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.9 part:0.5 part:0.01 part:3 parts:1 part.

[0229] The polymer monomer is styrene;

[0230] The crosslinking agent is a mixture formed by mixing divinylbenzene and triallyl isocyanurate in a mass ratio of 3:1;

[0231] The initiator is benzoyl peroxide;

[0232] The pore-forming agent is a mixture formed by mixing xylene and liquid paraffin in a mass ratio of 1:2;

[0233] The spherical matrix is acrylonitrile.

[0234] The dispersant is 0.1 part of gelatin and 6 parts of water.

[0235] Hydroxylamine used is hydroxylamine sulfate. Hydroxylamine is added in a ratio of 1:2 by volume to the intermediate.

[0236] The temperature of the amidoximation reaction is 90 °C, and the time of the amidoximation reaction is 12 h.

[0237] The type of the alkaline solution is sodium hydroxide, and the alkaline solution is added in a volume ratio of 1:2 to the intermediate.

[0238] The solvent is a mixture formed by mixing dichloroethane and water in a mass ratio of 40:100, and the solvent is added in a volume ratio of 1:6 to the intermediate.

[0239] The temperature of the alkali treatment is 50 °C, and the time of the alkali treatment is 12 h.

[0240] Example 9

[0241] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0242] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C, and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 60 °C, and the time of the second first polymerization reaction is 2 h; the temperature of the second polymerization reaction is 95 °C, and the time of the second polymerization reaction is 6 h.

[0243] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.9 parts:0.5 parts:0.01 parts:3 parts:1 part.

[0244] The polymer monomer is styrene;

[0245] The crosslinking agent is divinylbenzene;

[0246] The initiator is benzoyl peroxide;

[0247] The pore-forming agent is a mixture formed by mixing xylene and liquid paraffin in a mass ratio of 2:1;

[0248] The spherical matrix is acrylonitrile.

[0249] The dispersant is 0.1 part of gelatin and 6 parts of water.

[0250] Hydroxylamine sulfate is used as the hydroxylamine. The hydroxylamine is added in a volume ratio of 1:2 to the intermediate.

[0251] The temperature of the amidoximation reaction is 90 °C, and the time of the amidoximation reaction is 24 h.

[0252] The type of the alkaline solution is sodium hydroxide, and the alkaline solution is added in a volume ratio of 1:2 to the intermediate.

[0253] The solvent is a mixture formed by mixing dichloroethane and water in a mass ratio of 40:100, and the solvent is added in a volume ratio of 1:6 to the intermediate.

[0254] The temperature of the alkali treatment is 50 °C, and the time of the alkali treatment is 12 h.

[0255] Example 10

[0256] On the basis of the content disclosed in Example 1, the following further modifications are made:

[0257] The polymerization reaction includes two first polymerization reactions and one second polymerization reaction; the temperature of the first first polymerization reaction is 50 °C, and the time of the first first polymerization reaction is 1 h; the temperature of the second first polymerization reaction is 60 °C, and the time of the second first polymerization reaction is 2 h; the temperature of the second polymerization reaction is 95 °C, and the time of the second polymerization reaction is 6 h.

[0258] The mass m1 of the polymer monomer, the mass m2 of the crosslinking agent, the mass m3 of the initiator, the mass m4 of the pore-forming agent, and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5 = 0.9 parts:0.5 parts:0.01 parts:3 parts:1 part.

[0259] The polymer monomer is styrene;

[0260] The crosslinking agent is benzoyl peroxide;

[0261] The initiator is benzoyl peroxide;

[0262] The pore-forming agent is a mixture formed by mixing xylene and liquid paraffin in a mass ratio of 4:1;

[0263] The spherical matrix is acrylonitrile.

[0264] The dispersant is 0.1 part of gelatin and 6 parts of water.

[0265] Hydroxylamine uses hydroxylamine sulfate. Hydroxylamine is added in a volume ratio of 1:2 to the intermediate.

[0266] The temperature of the amidoximation reaction is 90 °C, and the time of the amidoximation reaction is 12 h.

[0267] The type of the alkaline solution is sodium hydroxide, and the alkaline solution is added in a volume ratio of 1:2 to the intermediate;

[0268] The solvent is a mixture formed by mixing dichloroethane and water in a mass ratio of 40:100, and the solvent is added in a volume ratio of 1:6 to the intermediate.

[0269] The temperature of the alkali treatment is 50 °C, and the time of the alkali treatment is 12 h.

[0270] Comparative Example 1

[0271] On the basis of the content disclosed in Example 1, the following further modifications were made:

[0272] The amidoximation reaction was directly carried out without using the intermediate.

[0273] Comparative Example 2

[0274] On the basis of the content disclosed in Example 1, the following further modifications were made:

[0275] The pore-forming agent was not added.

[0276] Comparative Example 3

[0277] On the basis of the content disclosed in Example 1, the following further modifications were made:

[0278] The dispersant was not added.

[0279] Comparative Example 4

[0280] On the basis of the content disclosed in Example 1, the following further modifications were made:

[0281] The initiator was not added.

[0282] Comparative Example 5

[0283] On the basis of the content disclosed in Example 1, the following further modifications were made:

[0284] The amidoximation reaction was not carried out.

[0285] Comparative Example 6

[0286] On the basis of the content disclosed in Example 1, the following further modifications were made:

[0287] The initiator was added to 10% of the total weight of the oil-phase matrix.

[0288] Related experiments and effect data:

[0289] The performance of the hydrometallurgical chelating resin obtained in each example and comparative example was measured, and the results are shown in Table 1. Among them, the measurement standard of the roundness rate after grinding refers to GB / T 12598-2023, and the roundness rate after grinding refers to the proportion of resin particles that still remain intact spherical after mechanical wear; the measurement standard of the particle size qualification rate refers to GB / T 5758-2023, indicating the particle size distribution state of resin particles; the measurement standards of the adsorption rate and desorption rate refer to GB / T 8144-2008, indicating the adsorption capacity and desorption capacity of the resin.

[0290] Table 1 Performance results of hydrometallurgical chelating resins in each example and comparative example

[0291]

[0292] As can be seen from Table 1, a method for preparing a hydrometallurgical resin provided by an embodiment of the present application is based on multiple polymerization reactions among polymer monomers, crosslinking agents, initiators, pore-forming agents, and spherical substrates, which can form a complex and interpenetrating polymer network structure. At the same time, by controlling the proportion of the polymerization reaction and reaction conditions, etc., the pore structure distribution of these polymer network structures can be made more uniform, so that a hydrometallurgical chelating resin with high mechanical strength and compressive strength can be obtained, and the roundness rate of the resin after grinding can reach more than 85%. In addition, adding an excessive amount of initiator will cause the resin to rupture during the polymerization process, affecting the properties such as the mechanical strength and compressive strength of the resin, resulting in the roundness rate of the resin after grinding being below 50%.

[0293] In summary, a method for preparing a hydrometallurgical resin provided by an embodiment of the present application, the hydrometallurgical chelating resin prepared by this method has higher strength and a longer service life compared with traditional chelating resins.

[0294] In addition, a method for preparing a hydrometallurgical resin provided by an embodiment of the present application, the hydrometallurgical chelating resin prepared by this method has a relatively large number of uniformly dispersed pore structures, which can improve the adsorption rate and desorption rate of the hydrometallurgical chelating resin, so as to ultimately improve the product yield of the hydrometallurgical chelating resin in the actual application stage.

[0295] The above are only specific embodiments of the present application, enabling those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be obvious to those skilled in the art. The general principles defined in the present application can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown in the present application, but will conform to the widest scope consistent with the principles and novel features claimed in the present application.

Claims

1. A method for preparing a hydrometallurgical resin, the method comprising: The polymer monomer, the cross-linking agent, the initiator, the porogen and the spherical matrix with a cyano skeleton are mixed to obtain an oil phase matrix; The dispersant and the oil phase matrix are subjected to multiple polymerization reactions, so that the polymer monomer, the cross-linking agent, the initiator, the porogen and the ball matrix are interpenetrated and entangled to form an interpenetrating polymer network, thereby obtaining an intermediate; The hydroxylamine, the alkaline solution and the intermediate are subjected to amidoximation reaction to obtain a crude hydrometallurgical chelating resin; The crude hydrometallurgical chelate resin is subjected to alkali treatment to obtain the hydrometallurgical chelate resin.

2. The method according to claim 1, wherein the polymerization reaction comprises a first polymerization reaction and a second polymerization reaction; the temperature of the first polymerization reaction is 50°C to 70°C, and the time of the first polymerization reaction is 1h to 4h; the temperature of the second polymerization reaction is 85°C to 98°C, and the time of the second polymerization reaction is 4h to 7h.

3. According to the method according to claim 1, the mass m1 of the polymer monomer, the mass m2 of the cross-linking agent, the mass m3 of the initiator, the mass m4 of the porogen and the mass m5 of the spherical matrix satisfy the relationship: m1:m2:m3:m4:m5=(0.3~2.0):(0.3~0.8):(0.01~0.05):(1~5):

1.

4. The method according to claim 1 or 3, wherein the polymer monomer comprises at least one of the following: styrene, methyl methacrylate and ethylene glycol dimethacrylate; and / or The cross-linking agent comprises at least one of: divinylbenzene, isoprene and triallyl isocyanurate; and / or The initiator comprises at least one of: azobisisobutyronitrile, azobiscyclohexylcarbonitrile and benzoyl peroxide; and / or The porogen comprises at least one of liquid paraffin, kerosene, xylene, cyclohexane and isooctane; and / or The spherical matrix includes acrylonitrile and / or vinyl nitrile.

5. The method according to claim 1, wherein the crosslinking degree of the spherical matrix is ​​4% to 20%, and the particle size of the spherical matrix is ​​0.06 mm to 0.30 mm; and / or The particle size of the intermediate is greater than 0.315 mm.

6. The method according to claim 1, wherein the temperature of the amidoximation reaction is 60°C to 90°C, and the time of the amidoximation reaction is 5h to 24h.

7. The method according to claim 1, wherein the hydroxylamine, alkaline solution and the intermediate are subjected to amidoximation reaction to obtain a crude hydrometallurgical chelating resin, comprising the steps of: The intermediate is subjected to swelling treatment using hydroxylamine, an alkaline solution and a solvent to obtain a swollen intermediate; The swelling intermediate is subjected to amidoximation reaction to obtain a crude hydrometallurgical chelating resin.

8. The method according to claim 7, wherein the alkaline solution comprises at least one of the following: sodium carbonate, sodium hydroxide, sodium nitrite and sodium bisulfite; and / or The solvent includes at least one of ethylene glycol, methanol, N,N-dimethylformamide, dimethyl sulfoxide, ethylene dichloride, n-butanol and water.

9. The method according to claim 1, wherein the crude hydrometallurgical chelate resin is subjected to alkali treatment to obtain the hydrometallurgical chelate resin, comprising the steps of: The hydrometallurgical chelate resin crude product is subjected to alkali treatment to obtain a basic resin crude product; Washing the crude alkaline resin to obtain a crude neutral resin; The crude neutral resin is dried to obtain a hydrometallurgical chelating resin.

10. The method according to claim 9, wherein the temperature of the alkali treatment is 40°C to 50°C, and the time of the alkali treatment is 5h to 24h; and / or The drying temperature is 40° C. to 60° C., and the drying time is ≥12 h.

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