Anion exchange resin as well as preparation method and application thereof

Abstract

The invention discloses anion exchange resin as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing alkene tertiary amine, alkene tertiary amine styrene, a cross-linking agent and an initiator to obtain an oil phase; the oil phase and the water phase are mixed for dispersion, heating polymerization and curing, an intermediate is prepared, and the water phase comprises a dispersing agent; and mixing the intermediate with a quaternization reagent, and carrying out quaternization reaction to obtain the anion exchange resin. Compared with the traditional process, the preparation method has the advantages of simple operation steps and milder reaction conditions. The anion exchange resin prepared by the preparation method is high in strength, not easy to break and good in stability, the ion exchange capacity of the anion exchange resin is obviously superior to that of traditional grafted resin, and the anion exchange resin has more excellent adsorption performance. Even under the extreme conditions of strong acidity and the like, the resin can still keep high adsorption capacity and shows good environmental adaptability.

Description

Technical Field

[0001] This application relates to the field of adsorption materials technology, specifically to anion exchange resins, their preparation methods, and applications. Background Technology

[0002] Currently, among various precious metal extraction technologies (such as gold, tungsten, and molybdenum), the adsorption resin method has become a core direction for replacing traditional processes due to its significant convenience and environmental friendliness: Convenience: The resin can be directly mixed with the leachate for adsorption, requiring no complex equipment modifications and adaptable to both batch and continuous production; the adsorption equilibrium time is short (usually 2-6 hours), much faster than the traditional cyanide method (24-72 hours), and subsequent gold recovery and resin regeneration can be achieved through acid washing, alkali washing, or complexing agent elution, making the operation process simple and easy to integrate with existing gold extraction processes. Environmental friendliness: The entire process does not require the use of highly toxic cyanide, avoiding the risk of soil and water pollution at the source; the resin can be reused, reducing solid waste generation, while avoiding the problem of excessive reagent consumption in the traditional zinc powder replacement method, thus reducing the overall environmental treatment cost.

[0003] However, current precious metal adsorption resin technology still has significant shortcomings: First, the resin framework pore structure design is unreasonable, resulting in low mass transfer efficiency of macroporous resins and insufficient stability of mesoporous resins, leading to the entrapment of gold ions (such as [Au(CN)2)). - First, the diffusion resistance of tungstate and molybdate ions is high, resulting in poor treatment of high-viscosity leachates or fine-particle slurries. Second, the functional groups have weak stability and are easily detached in strong acid-base (e.g., pH < 2 or pH > 12) or high-temperature (e.g., > 60℃) leaching systems, shortening the resin's lifespan. Third, it is ineffective in ultra-low concentration gold solutions (containing Au). 3+ The adsorption efficiency of <1ppm is low, making it difficult to meet the needs of deep recycling of industrial wastewater. Summary of the Invention

[0004] Therefore, it is necessary to provide anion exchange resins, their preparation methods, and applications.

[0005] The first aspect of this application provides a method for preparing anion exchange resin, comprising the following steps:

[0006] An oil phase is obtained by mixing olefinic tertiary amines, olefinic tertiary amine styrene, a crosslinking agent, and an initiator;

[0007] The oil phase and the aqueous phase are mixed and dispersed, then heated to polymerize and solidify to prepare an intermediate, wherein the aqueous phase includes a dispersant;

[0008] The intermediate is mixed with a quaternizing agent to carry out a quaternization reaction, thereby obtaining the anion exchange resin.

[0009] In some embodiments, the mass ratio of the tertiary olefin amine, the tertiary olefin amine styrene, the crosslinking agent, and the initiator is 1:(0.2~0.5):(0.05~0.15):(0.01~0.02).

[0010] In some embodiments, the tertiary amines include one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylallylamine, and N,N-diethylallylamine.

[0011] In some embodiments, the olefinic tertiary amine styrene includes one or more of 4-dimethylaminostyrene and 2-dimethylaminostyrene.

[0012] In some embodiments, the crosslinking agent includes one or more of divinylbenzene and ethylene glycol dimethacrylate.

[0013] In some embodiments, the initiator includes one or more of azobisisobutyronitrile and benzoyl peroxide.

[0014] In some embodiments, the aqueous phase satisfies one or more of the following conditions:

[0015] (1) The dispersant includes one or more of polyvinyl alcohol, biogelatin, and hydroxyethyl cellulose;

[0016] (2) The aqueous phase also includes a buffer system and inorganic salts;

[0017] Optionally, the buffer system comprises a mixed solution of sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of sodium dihydrogen phosphate to disodium hydrogen phosphate is (4~6):1, and the pH value of the buffer system is 7.4~7.6;

[0018] Optionally, the inorganic salt includes one or more of sodium chloride, calcium chloride, potassium chloride, and magnesium chloride; further optionally, the mass ratio of the buffer system, the inorganic salt, and the dispersant in the aqueous phase is 1:(0.05~0.25):(0.0075~0.02).

[0019] In some embodiments, the dispersion conditions include a temperature of 40°C to 50°C and a time of 1 to 2 hours.

[0020] In some embodiments, the conditions for the heating polymerization include a temperature of 60°C to 75°C and a time of 4 to 16 hours.

[0021] In some embodiments, the curing conditions include a temperature of 80°C to 90°C and a time of 1 hour to 3 hours.

[0022] In some embodiments, the intermediate is further purified; optionally, the purification includes extraction with an organic solvent, the organic solvent including one or more of ethanol, methylal and acetone.

[0023] In some embodiments, the step of mixing the intermediate with the quaternizing agent to carry out the quaternization reaction includes mixing the intermediate with the quaternizing agent in a polar organic solvent to carry out the quaternization reaction, wherein the mass ratio of the intermediate, the polar organic solvent and the quaternizing agent is 1:(2~4):(1.2~1.8).

[0024] In some embodiments, the quaternizing agent includes one or more of haloalkanes and dimethyl sulfate; optionally, the haloalkanes include one or more of iodomethane, chloromethane, chloroethane, bromomethane, bromoethane, bromochloromethane, and 1,2-bromochloroethane.

[0025] In some embodiments, the polar organic solvent includes one or more of acetonitrile, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide.

[0026] In some embodiments, the quaternization reaction is carried out at a temperature of 20°C to 30°C for 5 to 7 hours.

[0027] The second aspect of this application provides an anion exchange resin, which is prepared using the anion exchange resin preparation method described in the first aspect of this application.

[0028] The third aspect of this application provides the use of the anion exchange resin described in the second aspect of this application in the adsorption of noble metals from the liquid phase;

[0029] Optionally, the precious metal includes one or more of gold, tungsten, and molybdenum;

[0030] Optionally, the pH value of the liquid phase is 1 to 2.

[0031] The aforementioned method for preparing anion exchange resins is simpler and uses milder reaction conditions compared to the traditional process of preparing ion exchange resins through chloromethylation followed by amination. The anion exchange resin prepared using this method exhibits high strength, is not easily broken, and has good stability. Furthermore, its ion exchange capacity is significantly superior to that of traditional grafted resins, demonstrating superior adsorption performance. Even under extreme conditions such as strong acidity (pH 1-2), the resin maintains a high adsorption capacity, demonstrating excellent environmental adaptability. Attached Figure Description

[0032] To more clearly illustrate the technical solutions in the embodiments and examples of this application, and to more completely understand this application and its beneficial effects, the accompanying drawings used in the description of the embodiments or examples will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of this application. Those skilled in the art can obtain other drawings based on these drawings without any creative effort.

[0033] Figure 1 The chemical reaction equation for the synthesis in Example 1;

[0034] Figure 2 The image shows the FTIR spectrum of the adsorption resin material prepared in Example 1. Detailed Implementation

[0035] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this application are shown in the drawings. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this application.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0037] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0038] In this application, terms such as "preferred," "better," "more suitable," and "ideal" are merely used to describe implementation methods or embodiments that achieve better results, and should be understood not to limit the scope of protection of this application.

[0039] The terms “having,” “containing,” “comprising,” and “including” as used in this application are synonyms and are inclusive or open-ended, not excluding additional, uncited members or features. Members or features include, for example, materials or components, structures, elements, instruments, etc.; non-limiting examples of members or features include actions, conditions under which actions occur, timing, states, etc.

[0040] In this application, the technical features or solutions described in open-ended language include both closed-ended technical features or solutions consisting of the listed contents and open-ended technical features or solutions that include the listed contents.

[0041] In this application, if the unit of a data range is only followed by the right endpoint, it means that the units of the left and right endpoints are the same.

[0042] In this application, where the method flow involves multiple steps, unless otherwise explicitly stated herein, there is no strict order restriction on the execution of these steps; they can be executed in any order other than those described. Moreover, any step may include multiple sub-steps or multiple stages, which are not necessarily completed at the same time, but can be executed at different times, and their execution order is not necessarily sequential, but can be performed alternately or simultaneously with other steps or parts of the sub-steps or stages of other steps.

[0043] In this application, the exemplary descriptions such as "in some implementations (or embodiments)" and "in one implementation (or embodiment)" may cover, but are not limited to, the following meanings: these solutions can be combined with other solutions in a suitable manner to form new technical solutions.

[0044] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0045] In this application, when numerical intervals (i.e., numerical ranges) are mentioned, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include numerical interval types such as percentage intervals, ratio intervals, and proportion intervals.

[0046] In this application, the terms "room temperature" or "normal temperature" generally refer to 4°C to 35°C, for example, 20°C ± 5°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20°C to 30°C.

[0047] Current precious metal adsorption resin technology still has significant shortcomings: Firstly, the resin framework pore structure design is unreasonable, resulting in low mass transfer efficiency of macroporous resins and insufficient stability of mesoporous resins, leading to the formation of gold complex ions (such as [Au(CN)2)). - First, the diffusion resistance of tungstate ions, molybdate ions, etc., is high, resulting in poor treatment of high-viscosity leachates or fine-particle slurries. Second, the functional groups have weak stability and are easily detached in strong acid-base (pH < 2 or pH > 12) or high-temperature (> 60℃) leaching systems, shortening the resin's service life. Third, it is ineffective in ultra-low concentration gold solutions (containing Au). 3+ The adsorption efficiency of <1ppm is low, making it difficult to meet the needs of deep recycling of industrial wastewater.

[0048] Furthermore, regarding gold extraction adsorption resins, the core materials in current patents are mainly divided into three categories, but all have limitations: Polystyrene-divinylbenzene (PS-DVB) based resin: the most commonly used framework material. Modified by introducing amine or thiourea groups (e.g., CN202310256789.1, CN202211034567.2), although it has high mechanical strength, its pore structure is simple, resulting in insufficient selectivity for Au in cyanide-free leaching systems (e.g., thiosulfate systems), and it is easily affected by Cu. 2+ Fe 3+ Interference. Polyacrylonitrile (PAN)-based resins: often modified by ammonium oxime modification (e.g., CN202310123456.7, CN202110876543.0), affecting [Au(CN)2]. - While exhibiting high adsorption capacity (up to 300-400 mg / g), the resin suffers from poor acid resistance and is prone to skeletal hydrolysis in leachates with pH < 3. Furthermore, its adsorption capacity significantly decreases after regeneration (single regeneration attenuation rate > 10%). Composite resin materials: Some patents attempt resin-nanoparticle composites (e.g., CN202310567890.3, which combines nano-SiO2 with PS-DVB). Although this improves the adsorption rate, the nanoparticles are prone to agglomeration, leading to pore blockage and insufficient long-term stability. Moreover, the preparation cost is high (30%-50% higher than traditional resins), making large-scale application difficult.

[0049] Based on this, the embodiments of this application at least provide anion exchange resins, their preparation methods, and applications.

[0050] In this application, the term "olefinic tertiary amine" refers to an organic compound molecule whose molecular structure simultaneously contains a carbon-carbon double bond and a tertiary amine group (-NR2, where R is an alkyl group).

[0051] In this application, the term "tertiary amine styrene" refers to a compound molecule in which a tertiary amine group is introduced as a substituent onto the benzene ring of styrene.

[0052] In a first aspect of this application, a method for preparing anion exchange resin is provided, comprising the following steps:

[0053] S100: An oil phase is obtained by mixing olefinic tertiary amines, olefinic tertiary amine styrene, crosslinking agents, and initiators;

[0054] S200: An intermediate is prepared by mixing and dispersing an oil phase and an aqueous phase, heating and polymerizing, and then curing. The aqueous phase includes a dispersant.

[0055] S300: The intermediate is mixed with the quaternizing agent to carry out the quaternization reaction, and anion exchange resin is obtained.

[0056] It should be noted that tertiary amines, as the main functional monomers, provide tertiary amine groups, which provide active sites for subsequent quaternization reactions and directly affect the ion exchange adsorption performance of the resin. Tertiary amines, such as styrene, as comonomers, enhance the rigidity and stability of the resin skeleton through their benzene ring structure. Furthermore, their own tertiary amine groups can also participate in the quaternization reaction, helping to increase the density of functional groups on the resin surface. Crosslinking agents are used to construct the three-dimensional network structure of the resin and control its porosity, mechanical strength, and swelling properties. Initiators are used to initiate the free radical polymerization reaction of alkene monomers. Their dosage affects the polymerization rate and molecular weight distribution, thereby affecting the structural uniformity and performance stability of the resin.

[0057] In some embodiments, in step S100, the mass ratio of the tertiary olefin amine, the tertiary olefin amine styrene, the crosslinking agent, and the initiator is 1:(0.2~0.5):(0.05~0.15):(0.01~0.02). Non-limitingly, the mass ratio of the tertiary olefin amine, the tertiary olefin amine styrene, the crosslinking agent, and the initiator can be, but is not limited to, 1:0.2:0.05:0.01, 1:0.3:0.05:0.01, 1:0.4:0.05:0.01, 1:0.5:0.05:0.01, 1:0.2:0.1:0.01, 1:0.3:0.1:0.01, 1:0.4:0.1:0.01, 1:0.5:0.1:0.01, 1:0.2 ...01:0.01, 1:0.2:0.01, 1:0.01:0.01, 1:0.2:0.01, 1:0.01:0.01, 1:0.01:0.01, 1:0.2:0.01, 1:0.01:0.01, 1:0.01:0.01, 1:0.2:0.01, 1:0.01:0.01, 1 15:0.01, 1:0.3:0.15:0.01, 1:0.4:0.15:0.01, 1:0.5:0.15:0.01, 1:0.2:0.05:0.02, 1:0.5:0.05:0.02, 1:0.2:0.1:0.02, 1:0.5:0.1:0.021, 1:0.2:0.15:0.02, 1:0.5:0.15:0.02, or any two of the above ratios or the range thereof.

[0058] It should be noted that, in the embodiments of this application, the mass ratio range of the aforementioned tertiary amine, tertiary amine styrene, crosslinking agent, and initiator was optimized and determined, which ensures high resin exchange capacity while also taking into account good mechanical strength, pore structure, and mass transfer efficiency. If the proportion of tertiary amine styrene is too low, the resin skeleton will lack rigidity and will easily swell and collapse in a strong acid environment; if the proportion is too high, it may lead to increased phase separation during polymerization, affecting the uniformity of the resin and the distribution of functional groups. If the proportion of crosslinking agent is too low, the resin structure will be loose and the strength insufficient; if it is too high, the pores may be too small and the mass transfer resistance will increase. If the proportion of initiator is too low, the polymerization initiation efficiency will be low, the reaction will be incomplete, and the residual monomer will increase; if the proportion is too high, the initiation rate will be too fast, leading to localized polymerization heat concentration, excessively wide molecular weight distribution, or uneven crosslinking, thereby affecting the performance stability of the resin structure.

[0059] In some embodiments, tertiary amines include, but are not limited to, one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylallylamine, and N,N-diethylallylamine.

[0060] In some embodiments, the tertiary amine styrene includes, but is not limited to, one or more of 4-dimethylaminostyrene and 2-dimethylaminostyrene.

[0061] In some embodiments, the crosslinking agent includes, but is not limited to, one or more of divinylbenzene and ethylene glycol dimethacrylate.

[0062] In some embodiments, the initiator includes, but is not limited to, one or more of azobisisobutyronitrile and benzoyl peroxide.

[0063] In some embodiments, in step S200, the aqueous phase further includes a buffer system and inorganic salts.

[0064] In some embodiments, the dispersant may be a conventional dispersant in the art, including but not limited to one or more of polyvinyl alcohol, biogelatin and hydroxyethyl cellulose.

[0065] In some embodiments, the buffer system comprises a mixed solution of sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of sodium dihydrogen phosphate to disodium hydrogen phosphate is (4~6):1. Further, the mass ratio of sodium dihydrogen phosphate to disodium hydrogen phosphate is 5:1.

[0066] In some implementations, the pH of the buffer system can be 7.4, 7.5, or 7.6.

[0067] In some embodiments, the inorganic salt includes, but is not limited to, one or more of sodium chloride, calcium chloride, potassium chloride, and magnesium chloride.

[0068] In some embodiments, the mass ratio of the buffer system, inorganic salt, and dispersant in the aqueous phase is 1:(0.05~0.25):(0.0075~0.02). Non-limitingly, the mass ratio of the buffer system, inorganic salt, and dispersant in the aqueous phase can be, but is not limited to, 1:0.05:0.0075, 1:0.15:0.0075, 1:0.25:0.0075, 1:0.05:0.01, 1:0.15:0.01, 1:0.25:0.01, 1:0.05:0.02, 1:0.15:0.02, 1:0.25:0.02, or any ratio or range between two of the above.

[0069] In some embodiments, in step S200, the dispersion conditions include: a temperature of 40°C to 50°C and a time of 1 hour to 2 hours. Non-limitingly, the dispersion temperature can be, but is not limited to, 40°C, 45°C, or 50°C; the dispersion time can be, but is not limited to, 1 hour, 1.5 hours, or 2 hours.

[0070] In some embodiments, in step S200, the conditions for heating polymerization include: a temperature of 60°C to 75°C and a time of 4h to 16h. Non-limitingly, the heating polymerization temperature can be 60°C, 65°C, 70°C, or 75°C; and the heating polymerization time can be 4h, 6h, 8h, 10h, 12h, 14h, or 16h.

[0071] In some embodiments, the curing conditions in step S200 include: a temperature of 80°C to 90°C and a time of 1 hour to 3 hours. Non-limitingly, the curing temperature can be 80°C, 85°C, or 90°C; and the curing time can be 1 hour, 2 hours, or 3 hours.

[0072] In some embodiments, step S200 further includes purifying the intermediate; further, the purification step includes extraction with an organic solvent, which includes, but is not limited to, one or more of ethanol, methylal and acetone.

[0073] In some embodiments, step S300 includes mixing the intermediate with the quaternizing agent in a polar organic solvent to carry out a quaternization reaction, wherein the mass ratio of the intermediate, the polar organic solvent, and the quaternizing agent is 1:(2~4):(1.2~1.8). Non-limitingly, the mass ratio of the intermediate, the polar organic solvent, and the quaternizing agent can be, but is not limited to, 1:2:1.2, 1:3:1.2, 1:4:1.2, 1:2:1.4, 1:3:1.4, 1:4:1.4, 1:2:1.6, 1:3:1.6, 1:4:1.6, 1:2:1.8, 1:3:1.8, 1:4:1.8, or any ratio or range between two of the above.

[0074] It should be noted that maintaining the mass ratio of intermediate, polar organic solvent, and quaternizing agent within the aforementioned range ensures an efficient and uniform quaternization reaction, guaranteeing sufficient swelling of the resin's internal structure and complete conversion of functional groups, while avoiding imbalance in the reaction system. Insufficient polar organic solvent may lead to incomplete swelling, limiting the reaction to the surface; excessive solvent will reduce reactant concentration and slow the reaction rate. Insufficient quaternizing agent will result in incomplete reaction and low functional group density; excessive agent may trigger unnecessary side reactions or generate excess impurities, affecting resin purity and regeneration performance.

[0075] In some embodiments, the quaternizing agent includes one or more of haloalkanes and dimethyl sulfate; further, the haloalkanes include, but are not limited to, one or more of iodomethane, chloromethane, chloroethane, bromomethane, bromoethane, bromochloromethane, and 1,2-bromochloroethane.

[0076] In some embodiments, a polar organic solvent is used as a reaction medium to swell the intermediate, allowing the quaternizing agent to penetrate into the resin and fully contact the tertiary amine groups, thus promoting a uniform reaction. Further, the polar organic solvent includes, but is not limited to, one or more of acetonitrile, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide.

[0077] In some embodiments, the quaternization reaction is carried out at a temperature of 20°C to 30°C for 5 to 7 hours. Non-limitingly, the quaternization reaction temperature can be 20°C, 25°C, or 30°C, and the time can be 5 hours, 6 hours, or 7 hours. It should be noted that controlling the quaternization reaction parameters within the above range can achieve efficient and uniform quaternization, resulting in anion exchange resins with high adsorption capacity, excellent structural stability, and good regeneration performance.

[0078] In a second aspect of this application, an anion exchange resin is provided, which is prepared by the above-described preparation method.

[0079] In a third aspect of this application, the above-described anion exchange resin is provided for the application of adsorbing noble metals from a liquid phase.

[0080] In some implementations, the precious metal includes one or more of gold, tungsten, and molybdenum.

[0081] In some implementations, the pH of the liquid phase is 1 to 2.

[0082] The following are some examples.

[0083] The embodiments of this application will be described in detail below with reference to examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. For experimental methods in the following embodiments where conditions are not specified, reference should be made to the guidelines given in this application, or to experimental manuals or conventional conditions in the art, or to the conditions recommended by the manufacturer, or to experimental methods known in the art.

[0084] In the following examples, the measurement parameters of the raw material components may have slight deviations within the weighing accuracy range unless otherwise specified. Temperature and time parameters are subject to acceptable deviations due to instrument testing accuracy or operational precision.

[0085] Example 1

[0086] A schematic diagram of a chemical reaction route is shown below. Figure 1 As shown, the specific steps are as follows:

[0087] S1, Oil phase: 70g dimethylaminoethyl methacrylate, 35g 4-dimethylaminostyrene, 7g divinylbenzene, 1.0g benzoyl peroxide;

[0088] Aqueous phase: Dissolve 5.0g of sodium dihydrogen phosphate and 1g of disodium hydrogen phosphate in 420 mL of pure water, adjust the pH to 7.5, add 85.2g of sodium chloride and 6.39g of gelatin, mix well and dissolve;

[0089] S2. Pour the aqueous phase from S1 into a four-necked flask. After adjusting the stirrer to the appropriate position, add the oil phase and start stirring to disperse it into uniform oil droplets. After stabilization, increase the temperature according to the following steps: dispersion at 45℃ for 1.5h; polymerization at 65℃ for 12h; and curing at 85℃ for 2h.

[0090] S3. Extract the resin obtained in S2 with ethanol to obtain a relatively pure intermediate.

[0091] S4. The resin obtained in S3 is reacted with dimethyl sulfate at a mass ratio of 1:1.2. At the same time, resin and acetonitrile are added to the reaction system at a mass ratio of 1:4. The reaction is carried out at room temperature for 6 hours to obtain an anion exchange resin with a high exchange capacity.

[0092] The Fourier transform infrared (FTIR) spectrum of the anion exchange resin prepared in Example 1 of this application is as follows: Figure 2 As shown.

[0093] Example 2

[0094] S1, Oil phase: 70g N,N-diethylaminoacrylate, 35g 4-dimethylaminostyrene, 7g divinylbenzene, 1.0g benzoyl peroxide;

[0095] Aqueous phase: Dissolve 5.0g of sodium dihydrogen phosphate and 1g of disodium hydrogen phosphate in 420 mL of pure water, adjust the pH to 7.5, add 85.2g of sodium chloride and 6.39g of gelatin, mix well and dissolve;

[0096] S2. Pour the aqueous phase from S1 into a four-necked flask. After adjusting the stirrer to the appropriate position, add the oil phase and start stirring to disperse it into uniform oil droplets. After stabilization, increase the temperature according to the following steps: dispersion at 45℃ for 1.5h; polymerization at 65℃ for 12h; and curing at 85℃ for 2h.

[0097] S3. Extract the resin obtained in S2 with ethanol to obtain a relatively pure intermediate.

[0098] S4. The resin obtained in S3 is reacted with dimethyl sulfate at a mass ratio of 1:1.2. At the same time, resin and acetonitrile are added to the reaction system at a mass ratio of 1:4. The reaction is carried out at room temperature for 6 hours to obtain an anion exchange resin with a high exchange capacity.

[0099] Example 3

[0100] S1, Oil phase: N,N-diethylallylamine 70g, 4-dimethylaminostyrene 35g, divinylbenzene 7g, benzoyl peroxide 1.0g;

[0101] Aqueous phase: Dissolve 5.0g of sodium dihydrogen phosphate and 1g of disodium hydrogen phosphate in 420 mL of pure water, adjust the pH to 7.5, add 85.2g of sodium chloride and 6.39g of gelatin, mix well and dissolve;

[0102] S2. Pour the aqueous phase from S1 into a four-necked flask. After adjusting the stirrer to the appropriate position, add the oil phase and start stirring to disperse it into uniform oil droplets. After stabilization, increase the temperature according to the following steps: dispersion at 45℃ for 1.5h; polymerization at 65℃ for 12h; and curing at 85℃ for 2h.

[0103] S3. Extract the resin obtained in S2 with ethanol to obtain a relatively pure intermediate.

[0104] S4. The resin obtained in S3 is reacted with dimethyl sulfate at a mass ratio of 1:1.2. At the same time, resin and acetonitrile are added to the reaction system at a mass ratio of 1:4. The reaction is carried out at room temperature for 6 hours to obtain an anion exchange resin with a high exchange capacity.

[0105] Example 4

[0106] S1, Oil phase: 70g dimethylaminoethyl methacrylate, 35g 2-dimethylaminostyrene, 7g divinylbenzene, 1.0g benzoyl peroxide;

[0107] Aqueous phase: Dissolve 5.0g of sodium dihydrogen phosphate and 1g of disodium hydrogen phosphate in 420 mL of pure water, adjust the pH to 7.5, add 85.2g of sodium chloride and 6.39g of gelatin, mix well and dissolve;

[0108] S2. Pour the aqueous phase from S1 into a four-necked flask. After adjusting the stirrer to the appropriate position, add the oil phase and start stirring to disperse it into uniform oil droplets. After stabilization, increase the temperature according to the following steps: dispersion at 45℃ for 1.5h; polymerization at 65℃ for 12h; and curing at 85℃ for 2h.

[0109] S3. Extract the resin obtained in S2 with ethanol to obtain a relatively pure intermediate.

[0110] S4. The resin obtained in S3 is reacted with dimethyl sulfate at a mass ratio of 1:1.2. At the same time, resin and acetonitrile are added to the reaction system at a mass ratio of 1:4. The reaction is carried out at room temperature for 6 hours to obtain an anion exchange resin with a high exchange capacity.

[0111] Example 5

[0112] S1, Oil phase: N,N-diethylallylamine 70g, 2-dimethylaminostyrene 35g, divinylbenzene 7g, benzoyl peroxide 1.0g;

[0113] Aqueous phase: Dissolve 5.0g of sodium dihydrogen phosphate and 1g of disodium hydrogen phosphate in 420 mL of pure water, adjust the pH to 7.5, add 85.2g of sodium chloride and 6.39g of gelatin, mix well and dissolve;

[0114] S2. Pour the aqueous phase from S1 into a four-necked flask. After adjusting the stirrer to the appropriate position, add the oil phase and start stirring to disperse it into uniform oil droplets. After stabilization, increase the temperature according to the following steps: dispersion at 45℃ for 1.5h; polymerization at 65℃ for 12h; and curing at 85℃ for 2h.

[0115] S3. Extract the resin obtained in S2 with ethanol to obtain a relatively pure intermediate.

[0116] S4. The resin obtained in S3 is reacted with dimethyl sulfate at a mass ratio of 1:1.2. At the same time, resin and acetonitrile are added to the reaction system at a mass ratio of 1:4. The reaction is carried out at room temperature for 6 hours to obtain an anion exchange resin with a high exchange capacity.

[0117] Comparative Example 1

[0118] A comparison was made using commercially available D201*7 resin, which was purchased from a foreign company.

[0119] Comparative Example 2

[0120] The remaining steps are the same as in Example 1, except that 4-dimethylaminostyrene is not added.

[0121] Comparative Example 3

[0122] The remaining steps are the same as in Example 1, except that dimethylaminoethyl methacrylate is not added.

[0123] The gold extraction performance of the products obtained in Examples 1-5 was tested, as follows:

[0124] (1) Take 10g of the adsorbent material synthesized in Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, wherein the gold-containing acid leaching solution (pH 1.5) is the raw solution of the mining project, which contains: Au 0.67 ppm, Ag 0.55 ppm, Cu 2680 ppm, Fe 726.5 ppm, Pb 23 ppm, Zn 1380 ppm, pH 1.5;

[0125] (2) The resin from step (1) was packed into a glass chromatography column to treat 800 BV of wastewater at a flow rate of 10 BV / h. The gold content in the water was determined by ICP, and the results are shown in Table 1.

[0126] Table 1. Adsorption effect test of gold extraction adsorption materials

[0127]

[0128] Breakthrough volume refers to the maximum volume of water that can be processed while maintaining the adsorbed effluent at a level below the detection limit.

[0129] As can be clearly seen from Table 1 above, the gold extraction adsorption material synthesized in the embodiments of this application has excellent adsorption performance. Compared with the comparative example, the adsorption material of the embodiments of this application has certain advantages, with more complete adsorption of gold and a larger water penetration.

[0130] The resin was desorbed and regenerated using a 15% H2SO4 solution as the regenerator. After regeneration and re-adsorption, the process was repeated three times. The average regeneration rate of the material is shown in Table 2.

[0131] Table 2 Comparison of Regeneration Rates of Gold Extraction Adsorption Materials

[0132]

[0133] Table 2 above clearly shows that the gold extraction resin has a high regeneration rate, which indicates that the polymerized gold extraction resin has better regeneration ability than the grafted resin purchased on the market.

[0134] The tungsten extraction performance of the products obtained in Examples 1-5 was tested, as follows:

[0135] (1) Take 10g of the adsorbent material synthesized in Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, wherein the tungstic acid leaching solution (pH 1.8) is the raw solution of the mining project, which contains: W 314ppm, Fe 158300ppm, Mn 8700ppm, Ca 580ppm, Mg 325ppm, Al 178ppm, Si 296ppm, pH 1.8;

[0136] (2) The resin from step (1) was packed into a glass chromatography column to treat 50 BV of wastewater at a flow rate of 2 BV / h. The gold content in the water was determined by ICP, and the results are shown in Table 3.

[0137] Table 3 Adsorption effect test of tungsten-containing adsorbent materials

[0138]

[0139] As can be clearly seen from Table 3 above, the tungsten adsorption material synthesized in the embodiments of this application has excellent adsorption performance. Compared with the comparative example, the adsorption material of the embodiments of this application has certain advantages, with more complete adsorption of tungsten and greater water penetration.

[0140] The resin was desorbed and regenerated using a 15% H2SO4 solution as the regenerator. After regeneration and re-adsorption, the process was repeated three times. The average regeneration rate of the material is shown in Table 4.

[0141] Table 4 Comparison of Regeneration Rates of Tungsten Extraction Adsorption Materials

[0142]

[0143] Table 4 above clearly shows that the tungsten extraction resin has a high regeneration rate, which indicates that the polymerized tungsten extraction resin has better regeneration ability than the grafted resin purchased on the market.

[0144] The molybdenum extraction performance of the products obtained in Examples 1-5 was tested, as follows:

[0145] (1) Take 10 mL of the adsorbent material synthesized in Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, wherein the molybdenum acid leaching solution (pH 2) is the original solution of the mining project, which contains: Mo 4267 ppm, Cu 3250 ppm, Pb 426 ppm, Al 1300 ppm, Ca 346 ppm, Mg 284 ppm, Zn 180 ppm, pH 2;

[0146] (2) The resin from step (1) was packed into a glass chromatography column to treat 20 BV of wastewater at a flow rate of 1 BV / h. The gold content in the water was determined by ICP, and the results are shown in Table 5.

[0147] Table 5. Adsorption effect test of molybdenum extraction adsorption material

[0148]

[0149] As can be clearly seen from Table 5 above, the molybdenum adsorption material synthesized in the embodiments of this application has excellent adsorption performance. Compared with the comparative example, the adsorption material of the embodiments of this application has certain advantages, with more complete adsorption of molybdenum and a larger water permeation.

[0150] The resin was desorbed and regenerated using a 15% H2SO4 solution as the regenerator. After regeneration and re-adsorption, the process was repeated three times. The average regeneration rate of the material is shown in Table 6.

[0151] Table 6 Comparison of regeneration rates of molybdenum extraction adsorption materials

[0152]

[0153] Table 6 above clearly shows that the resin regeneration rate is high, which indicates that the polymerized adsorption resin has better regeneration ability than the grafted resin purchased on the market.

[0154] The strength of the adsorbent materials of Examples 1-5 and Comparative Examples 1-3 was tested, and the results are shown in Table 7:

[0155] Table 7 Comparison of Adsorption Material Strength

[0156]

[0157] As can be seen from Table 7 above, the resin in the embodiments of this application has higher particle strength, which means that it can withstand higher inlet water pressure in the adsorption tower, making it easier to process more acid leaching solution, increase production capacity, and has industrial significance.

[0158] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0159] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. A method for preparing anion exchange resin, characterized in that, Includes the following steps: An oil phase is obtained by mixing olefinic tertiary amines, olefinic tertiary amine styrene, a crosslinking agent, and an initiator; The oil phase and the aqueous phase are mixed and dispersed, then heated to polymerize and solidify to prepare an intermediate, wherein the aqueous phase includes a dispersant; The intermediate is mixed with a quaternizing agent to carry out a quaternization reaction, thereby obtaining the anion exchange resin.

2. The method for preparing the anion exchange resin according to claim 1, characterized in that, The mass ratio of the tertiary alkene amine, the tertiary alkene amine styrene, the crosslinking agent, and the initiator is 1:(0.2~0.5):(0.05~0.15):(0.01~0.02).

3. The method for preparing the anion exchange resin as described in claim 2, characterized in that, The tertiary amines include one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylallylamine, and N,N-diethylallylamine.

4. The method for preparing the anion exchange resin according to claim 2, characterized in that, The tertiary amine styrene of the olefins includes one or more of 4-dimethylaminostyrene and 2-dimethylaminostyrene.

5. The method for preparing the anion exchange resin according to any one of claims 1 to 4, characterized in that, One or more of the following conditions must be met: (1) The crosslinking agent includes one or more of divinylbenzene and ethylene glycol dimethacrylate; (2) The initiator includes one or more of azobisisobutyronitrile and benzoyl peroxide.

6. The method for preparing the anion exchange resin according to claim 1, characterized in that, The aqueous phase satisfies one or more of the following conditions: (1) The dispersant includes one or more of polyvinyl alcohol, biogelatin, and hydroxyethyl cellulose; (2) The aqueous phase also includes a buffer system and inorganic salts; Optionally, the buffer system comprises a mixed solution of sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of sodium dihydrogen phosphate to disodium hydrogen phosphate is (4~6):1, and the pH value of the buffer system is 7.4~7.6; Optionally, the inorganic salt includes one or more of sodium chloride, calcium chloride, potassium chloride, and magnesium chloride; further optionally, the mass ratio of the buffer system, the inorganic salt, and the dispersant in the aqueous phase is 1:(0.05~0.25):(0.0075~0.02).

7. The method for preparing the resin according to claim 1, characterized in that, One or more of the following conditions must be met: (1) The dispersion conditions include: temperature of 40℃~50℃ and time of 1h~2h; (2) The conditions for the heating polymerization include: a temperature of 60℃~75℃ and a time of 4h~16h; (3) The curing conditions include: a temperature of 80℃~90℃ and a time of 1h~3h; (4) It also includes purifying the intermediate; optionally, the purification includes extraction with an organic solvent, the organic solvent including one or more of ethanol, methylal and acetone.

8. The method for preparing the resin according to claim 1, characterized in that, The step of mixing the intermediate with the quaternizing agent to carry out the quaternization reaction includes mixing the intermediate with the quaternizing agent in a polar organic solvent to carry out the quaternization reaction, wherein the mass ratio of the intermediate, the polar organic solvent and the quaternizing agent is 1:(2~4):(1.2~1.8). Optionally, one or more of the following conditions must be met: (1) The quaternizing agent includes one or more of haloalkanes and dimethyl sulfate; optionally, the haloalkanes include one or more of iodomethane, chloromethane, chloroethane, bromomethane, bromoethane, bromochloromethane and 1,2-bromochloroethane; (2) The polar organic solvent includes one or more of acetonitrile, dimethyl sulfoxide, dimethylformamide and dimethylacetamide; (3) The temperature for carrying out the quaternization reaction is 20℃~30℃ and the time is 5h~7h.

9. An anion exchange resin, characterized in that, It is prepared by the method for preparing anion exchange resin as described in any one of claims 1 to 8.

10. The application of the anion exchange resin as described in claim 9 in the adsorption of noble metals from the liquid phase; Optionally, the precious metal includes one or more of gold, tungsten, and molybdenum; Optionally, the pH value of the liquid phase is 1 to 2.

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