Polyion gel adsorption material and method for separating and purifying complex gold and copper

Abstract

The present application provides a polyion gel adsorption material and a method for separating and purifying complex gold and copper, belonging to the field of purification and separation of gold- and copper-containing waste liquids, wherein the polyion gel adsorption material includes an imidazole ring structure fragment and an oxygen-heteroaliphatic bridge ring and an aliphatic ether long-chain composite molecular skeleton. The present application provides favorable conditions for the adsorption of gold and copper by introducing an imidazole ring structure fragment into the molecular backbone of the polyion gel adsorption material; by introducing a composite molecular skeleton between the imidazole rings of the molecular backbone of the polyion gel adsorption material, the reduced activity caused by the π-π conjugated stacking of the imidazole structure fragment is avoided, so that the active sites of the imidazole ring structure fragment can be fully exposed, and a specific target metal with a larger volume can be fully adsorbed, and the efficient and selective adsorption of the target metal with a larger volume is achieved under the cooperation of the oxygen-heteroaliphatic bridge ring and the aliphatic ether long-chain composite molecular skeleton and the imidazole ring structure fragment.

Description

Technical Field

[0001] The invention relates to the technical field of purification and separation of waste liquid containing gold and copper, and in particular to a polyion gel adsorption material and a method for separating and purifying complex gold and copper. Background Art

[0002] The recovery of high-value metals such as gold and copper from industrial wastewater typically involves chemical extraction followed by adsorption using ion exchange resins. Due to the low specific surface area and limited adsorption capacity of ion exchange resins, large quantities are required to treat high-concentration metal industrial wastewater, resulting in high treatment costs and poor results. Therefore, ion exchange resins are generally used to treat low-concentration, high-value metal industrial wastewater.

[0003] As a new type of adsorption material, gel adsorption material has the advantages of porous network structure, high capacity and easy mass transfer. It can achieve high adsorption capacity and rapid adsorption at the same time, and has good application prospects in the treatment of high-concentration metal industrial wastewater. In recent years, imidazole-type gel adsorption materials have become a research hotspot in this field, expanding the application of gel adsorption materials in metallurgy, wastewater treatment and other fields. However, the steric hindrance of the molecular fragments between the imidazole rings in the molecular main chain structure of traditional imidazole-type gel adsorption materials is large, and only simple metal ions of a specific size (such as AuCl4 - 、PtCl6 2- 、PdCl4 2- ), for some complex chelated ions or complex chelates with large spatial volume, such as gold-glycine chelated ions, gold-glutamate chelated ions, etc., due to the presence of molecular fragments with large steric hindrance between the imidazole rings in the main chain structure of the molecules of this type of imidazole-type gel adsorption material, it is difficult for the complex chelated ions with large spatial volume to effectively contact the imidazole rings, and thus the adsorption of the complex chelated ions cannot be effectively achieved. Summary of the Invention

[0004] In view of the technical problems existing in the background technology, the present application provides a polyion gel adsorption material and a method for separating and purifying complex gold and copper, aiming to solve the technical problem that traditional imidazole-type gel adsorption materials cannot effectively adsorb complex chelated ions or complex chelates.

[0005] In a first aspect, the embodiments of the present application provide a polyion gel adsorption material, the structural formula of the polyion gel adsorption material is as follows:

[0006] ;

[0007] Wherein, R is one of hydrogen, methyl, ethyl, and propyl.

[0008] In the technical solution of the embodiment of the present application, favorable conditions for the adsorption of gold and copper are provided by introducing imidazole ring structure fragments on the molecular main chain of the polyion gel adsorption material; by introducing an oxygen-heteroaliphatic bridge ring and an aliphatic ether long-chain composite molecular skeleton between the imidazole rings of the molecular main chain of the polyion gel adsorption material, the steric hindrance between different imidazole ring structure fragments is reduced, and at the same time, the positional relationship between the double-para oxygen atoms in the oxygen-heterobridge ring structure and the oxygen atoms in the flexible aliphatic ether long chain is reasonably controlled, thereby avoiding the reduction in activity caused by the π-π conjugated stacking of the imidazole structure fragments, so that the active sites of the imidazole ring structure fragments can be fully exposed, and can fully adsorb specific target metals with larger volumes (i.e., complex chelated ions or complex chelates), thereby achieving efficient chemical adsorption of specific metal ions.

[0009] In some embodiments, the polyion gel adsorption material has an adsorption rate for gold of ≥94%, and an adsorption rate for copper of ≥95%.

[0010] In this embodiment, by rationally setting the structure of the polyion gel adsorption material, the polyion gel adsorption material can undergo qualitative chemical adsorption with the target metal ions, thereby achieving efficient adsorption of gold and copper.

[0011] In some embodiments, the pore size of the polyion gel adsorption material is 50-3000 μm.

[0012] In this embodiment, by reasonably setting the pore size of the polyion gel adsorption material, the solution to be treated can more fully enter the polyion gel adsorption material, thereby enabling the qualitative chemical adsorption reaction to proceed smoothly and fully, thereby achieving efficient adsorption of gold and copper in the solution.

[0013] In some embodiments, the gel fraction of the polyion gel adsorption material is ≥50%.

[0014] In this embodiment, by reasonably controlling the gel fraction, the cross-linking degree of the polyion gel adsorption material is made higher, thereby improving the stability of the polyion gel adsorption material and the adsorption efficiency of gold and copper.

[0015] In a second aspect, an embodiment of the present application provides a method for separating and purifying complex gold and copper using a polyion gel adsorption material, which is carried out using the polyion gel adsorption material provided in the first aspect of the present application, and comprises the following steps: adding the polyion gel adsorption material to a solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate, and utilizing directional chemical adsorption between the gold-glycine chelate ions or copper-glycine chelate or copper-glycine chelate and the polyion gel adsorption material to achieve selective adsorption of gold or copper in the solution; wherein, gold is present in the solution as [Au(Gly)2] - Copper exists in the form of [Cu(Gly)2] -, cis-Cu(Gly)2, trans-Cu(Gly)2, [Cu(NH3)4]²⁺ in one or more forms; the solution containing gold-glycine anions is adjusted to pH ≥ 10; the solution containing copper-glycine chelate ions or copper-glycine chelate is adjusted to pH ≥ 9.

[0016] In the technical solution of the embodiment of the present application, the directional chemical adsorption of target metal ions by the polyion gel adsorption material with a specific structure is used to achieve efficient and selective recovery and purification of gold and copper, and the operation is simple.

[0017] In some embodiments, the solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate comprises mineral hydrometallurgical solution, catalyst waste liquid, metallurgical waste liquid, and electroplating anti-corrosion waste liquid.

[0018] In this embodiment, the types of solutions containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate solutions are diverse, indicating that the polyion gel adsorption material of the present application has universal applicability in the process of efficiently adsorbing gold and copper.

[0019] In some embodiments, the method for preparing the polyion gel adsorption material comprises the following steps:

[0020] S1, dissolving an oxygen heterocyclic dicarboxylic acid in tetrahydrofuran to obtain a solution A; dispersing lithium aluminum hydride in tetrahydrofuran to obtain a suspension B; adding the suspension B dropwise to the solution A in an ice-water bath and a nitrogen atmosphere, reacting for 20-30 hours, filtering, and rotary evaporating the filtrate to obtain an oxygen heterocyclic diol;

[0021] S2, adding the oxygen heterocyclic diol and imidazole salt to an ethanol aqueous solution, adding sodium hydroxide after stirring, heating and refluxing for 100-140 minutes, filtering, and washing the solid with dilute hydrochloric acid 5-7 times to obtain a polymerized monomer;

[0022] S3. Dissolve the polymerizable monomer in ethanol and pour the solution into a polyethylene bag. Degas the bag with N2 and seal the bag. Use an electron accelerator to irradiate the bag with an electron beam to cause the vinyl groups to generate active free radicals for polymerization and cross-linking reactions, thereby inducing polymerization and cross-linking of the reactant molecular chains to obtain the polyion gel adsorption material.

[0023] In this embodiment, the oxygen heterocyclic dicarboxylic acid is first reduced by lithium aluminum hydride to obtain an oxygen heterocyclic diol; then the oxygen heterocyclic diol and an imidazole salt undergo a nucleophilic substitution reaction to form a polymer monomer; finally, the polymer monomer is cross-linked and polymerized by a cross-linking reaction to form a polyion gel adsorption material.

[0024] In some embodiments, in step S1, the structural formula of the oxygen heterocyclic dicarboxylic acid is

[0025] ;

[0026] In step S2, the structural formula of the imidazole salt is

[0027] .

[0028] In this embodiment, by rationally arranging the structure of the oxygen heterocyclic dicarboxylic acid and the structure of the imidazole salt, a polyion gel adsorption material with a specific structure is generated, thereby achieving efficient adsorption of gold and copper.

[0029] In some embodiments, in step S3, the radiation is 60 Co γ-rays, irradiation voltage is 5-20MeV, irradiation dose is 10-300kGy, and dose rate is 1-50kGy / pass.

[0030] In this embodiment, by reasonably setting the irradiation conditions, it is ensured that the polymerization and cross-linking reaction proceeds smoothly and fully, thereby obtaining a high-performance polyion gel adsorption material.

[0031] In some embodiments, step S3 further includes drying the polyion gel adsorption material at 40-60° C. to a constant weight, then soaking it in deionized water to remove the sol, and drying it again at 40-60° C. to a constant weight.

[0032] In this embodiment, water in the gel solution is removed by constant weight; then the sol is removed to purify the polyion gel adsorption material and improve its purity; finally, the polyion gel adsorption material is again constant weighted to remove water to obtain a dry, high-purity polyion gel adsorption material.

[0033] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] To more clearly illustrate the technical solution of this application, the following is a brief introduction to the drawings used in this application. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be derived from these drawings without inventive effort.

[0035] Figure 1 This is a flow chart for preparing the polyion gel adsorption material in the examples of this application;

[0036] Figure 2This is a flow chart for preparing the polyion gel adsorption material in Example 1 of the present application. DETAILED DESCRIPTION

[0037] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0039] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0040] Gel adsorption materials have the advantages of porous network structure, high capacity and easy mass transfer, and have good application prospects in the treatment of high-concentration metal industrial wastewater. In recent years, imidazole-type gel adsorption materials have become a research hotspot in this field, expanding the application of gel adsorption materials in metallurgy, wastewater treatment and other fields. However, the steric hindrance of the molecular fragments between the imidazole rings in the molecular main chain structure of traditional imidazole-type gel adsorption materials is large, and only simple metal ions of specific sizes (such as AuCl4 - 、PtCl6 2- 、PdCl4 2- ), it cannot effectively adsorb some complex chelated ions or complex chelates with large spatial volume.

[0041] In order to solve the technical problem that traditional imidazole-type gel adsorption materials cannot effectively adsorb complex chelated ions or complex chelates, the present application provides a polyion gel adsorption material and a method for separating and purifying complex gold and copper. By introducing imidazole ring structure fragments into the molecular main chain of the polyion gel adsorption material, favorable conditions for the adsorption of gold and copper are provided. By introducing an oxygen-heteroaliphatic bridge ring and an aliphatic ether long chain composite molecular skeleton between the imidazole rings in the molecular main chain of the polyion gel adsorption material, the oxygen-heteroaliphatic bridge ring structure and the aliphatic ether long chain structure regulate the length and spatial arrangement structure of the composite molecular skeleton, reducing the steric hindrance between different imidazole ring structure fragments. At the same time, the positional relationship between the diparatide oxygen atoms in the oxygen-heteroaliphatic bridge ring structure and the oxygen atoms in the flexible aliphatic ether long chain is reasonably controlled, avoiding the reduction in activity caused by π-π conjugated stacking of the imidazole structure fragments, ensuring the spatial multi-dimensional extension of the polyion gel adsorption material, so that the active sites of the imidazole ring structure fragments can be fully exposed, and can fully adsorb large-volume specific target metals (i.e., complex chelated ions or complex chelates), thereby achieving efficient chemical adsorption of specific metal ions.

[0042] In a first aspect, the present invention provides a polyion gel adsorption material, the structural formula of which is as follows:

[0043] ;

[0044] Wherein, R is one of hydrogen, methyl, ethyl, and propyl.

[0045] In the technical solution of the embodiment of the present application, on the one hand, π-π conjugation is achieved by introducing imidazole ring structure fragments on the molecular main chain of the polyion gel adsorption material, thereby ensuring the activity of the imidazole ring and providing favorable conditions for the adsorption of gold and copper; on the other hand, an oxygen-heteroaliphatic bridge ring and an aliphatic ether long chain composite molecular skeleton are introduced between the imidazole rings of the molecular main chain of the polyion gel adsorption material. First, the rigid oxygen-heteroaliphatic bridge ring structure fragments and the flexible aliphatic ether long chain cooperate with each other, which not only ensures the overall stability of the polyion gel adsorption material, but also gives it flexibility; secondly, the length and spatial arrangement structure of the composite molecular skeleton are regulated by the oxygen-heteroaliphatic bridge ring structure and the aliphatic ether long chain structure, thereby reducing the size of the imidazole rings. The steric hindrance between the structural fragments ensures the spatial gain effect of the main chain of the molecular structure; at the same time, the positional relationship between the double-para oxygen atoms in the oxygen-bridged ring structure and the oxygen atoms in the flexible fatty ether long chain is reasonably controlled. The repulsive effect of the lone pair electrons of the oxygen atom avoids the planar stacking of the imidazole structural fragments, realizes the change of the π-π conjugated stacking density, and thus avoids the reduction in activity caused by the π-π conjugated stacking of the imidazole structural fragments, ensuring the spatial multi-dimensional extension of the polyion gel adsorption material, so that the active sites of the imidazole ring structural fragments can be fully exposed, and can fully adsorb larger specific target metals (i.e., complex chelated ions or complex chelates), thereby realizing efficient chemical adsorption of specific metal ions.

[0046] Compared to setting a ring structure with large steric hindrance between imidazole ring structure fragments, the steric hindrance of the composite molecular skeleton of the present application is relatively small, which is more conducive to the efficient adsorption of target metals with larger volumes. Compared to setting an axially rotatable chain structure fragment between imidazole ring structure fragments, the composite molecular skeleton of the present application can better improve the axial displacement of the π-π conjugation of the imidazole ring structure fragment on the molecular main chain, further ensuring that the molecular structure has spatial multi-dimensional ductility, forming a specific structure of π-π conjugated arrangement in the molecular structure of the polyion gel adsorption material, and ultimately achieving efficient and selective adsorption of target metals with larger volumes under the cooperation of the oxygen-heteroaliphatic bridge ring and the aliphatic ether long-chain composite molecular skeleton and the imidazole ring structure fragment.

[0047] Furthermore, in some embodiments, the polyion gel adsorption material has an adsorption rate of ≥94% for gold and ≥95% for copper.

[0048] In the technical solution of the embodiment of the present application, by rationally setting the structure of the polyion gel adsorption material, the polyion gel adsorption material can undergo qualitative chemical adsorption with the target metal ions, thereby achieving efficient adsorption of gold and copper, thereby achieving purification and separation of gold and copper in the solution system.

[0049] Furthermore, in some embodiments, the pore size of the polyion gel adsorption material is 50-3000 μm.

[0050] In the technical solution of the embodiment of the present application, by reasonably setting the pore size of the polyion gel adsorption material, the solution to be treated can more fully enter the polyion gel adsorption material, thereby enabling the qualitative chemical adsorption reaction to proceed smoothly and fully, thereby achieving efficient adsorption of gold and copper in the solution.

[0051] Furthermore, in some embodiments, the gel fraction of the polyion gel adsorption material is ≥50%.

[0052] In the technical solution of the embodiment of the present application, by controlling the gel fraction of the polyion gel adsorption material to above 50%, the degree of cross-linking of the polyion gel adsorption material is higher, that is, the molecular structure is more stable and more orderly, thereby improving the stability of the polyion gel adsorption material and the adsorption efficiency of gold and copper.

[0053] In a second aspect, an embodiment of the present application provides a method for separating and purifying complex gold and copper using a polyion gel adsorption material, which is carried out using the polyion gel adsorption material provided in the first aspect of the present application, and comprises the following steps: adding the polyion gel adsorption material to a solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate, and utilizing directional chemical adsorption between the gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate and the polyion gel adsorption material to achieve selective adsorption of gold (referring to gold-glycine chelate ions) or copper (referring to copper-glycine chelate ions or copper-glycine chelate) in the solution; wherein gold is present in the solution as [Au(Gly)2] - Copper exists in the form of [Cu(Gly)2] - , cis-Cu(Gly)2, trans-Cu(Gly)2, [Cu(NH3)4]²⁺ in one or more forms; containing a solution of gold-glycine anions and adjusting the pH to ≥ 10; containing a solution of copper-glycine chelate ions or copper-glycine chelate and adjusting the pH to ≥ 9. Specifically, [Au(Gly)2] - Refers to the gold-glycine chelate anion, [Cu(Gly)2] - Refers to copper-glycine chelate anion, cis-Cu(Gly)2 refers to trans-Cu(Gly)2 and trans-Cu(Gly)2 refers to cis-Cu(Gly)2, and [Cu(NH3)4]²⁺ refers to copper ammonium ion.

[0054] In the technical solution of the embodiment of the present application, the directional chemical adsorption of the target metal ions is achieved through the polyion gel adsorption material with a specific structure, avoiding the interference of other impurity metals, achieving efficient adsorption of gold and copper in the glycine-containing solution system, and realizing efficient selective recovery and purification of gold and copper with simple operation.

[0055] Furthermore, in some embodiments, the solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate includes mineral hydrometallurgical solution, catalyst waste liquid, metallurgical waste liquid, and electroplating anti-corrosion waste liquid.

[0056] In the technical solution of the embodiment of the present application, the solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate solution can be a variety of mineral hydrometallurgical solutions, catalyst waste liquids, metallurgical waste liquids, electroplating anti-corrosion waste liquids, etc., indicating that the polyion gel adsorption material of the present application has universal applicability in the process of efficient adsorption of gold and copper.

[0057] Furthermore, if Figure 1 As shown, in some embodiments, the preparation method of the polyion gel adsorption material includes the following steps:

[0058] S1, dissolving an oxygen heterocyclic dicarboxylic acid in tetrahydrofuran to obtain solution A; dispersing lithium aluminum hydride in tetrahydrofuran to obtain suspension B, adding suspension B dropwise to solution A in an ice-water bath and nitrogen atmosphere, reacting for 20-30 hours, filtering, and rotary evaporating the filtrate to obtain an oxygen heterocyclic diol;

[0059] S2, adding the oxygen heterocyclic diol and the imidazole salt to an ethanol aqueous solution, stirring, adding sodium hydroxide, heating and refluxing for 100-140 minutes, filtering, and washing the solid with dilute hydrochloric acid 5-7 times to obtain a polymerized monomer;

[0060] S3. Dissolve the polymerization monomer in ethanol and pour the solution into a polyethylene bag. Degas with N2 and seal it. Use an electron accelerator to irradiate the bag with an electron beam to make the vinyl group produce active free radicals for polymerization and cross-linking reactions, thereby inducing polymerization and cross-linking of the reactant molecular chains to obtain a polyion gel adsorption material.

[0061] In the technical solution of the embodiment of the present application, the oxygen-heterocyclic dicarboxylic acid is first reduced by lithium aluminum hydride to reduce the carboxyl group to a hydroxyl group to obtain an oxygen-heterocyclic diol; then the oxygen-heterocyclic diol is reacted with an imidazole salt to undergo a nucleophilic substitution reaction to form a polymer monomer containing an imidazole ring structure, an oxygen-heteroaliphatic bridge ring and an aliphatic ether long-chain composite molecular skeleton; finally, the polymer monomer is cross-linked and polymerized through a cross-linking reaction to form a polyion gel adsorption material.

[0062] Furthermore, in some embodiments, in step S1, the structural formula of the oxygen heterocyclic dicarboxylic acid is

[0063] ;

[0064] In step S2, the structural formula of the imidazole salt is

[0065] .

[0066] In the technical solution of the embodiment of the present application, by rationally setting the structure of the oxygen heterocyclic dicarboxylic acid and the structure of the imidazole salt, a polyion gel adsorption material with a specific structure is generated, thereby achieving efficient adsorption of gold and copper.

[0067] Furthermore, in some embodiments, in step S3, the radiation is applied 60 Co γ-rays, irradiation voltage is 5-20MeV, irradiation dose is 10-300kGy, and dose rate is 1-50kGy / pass.

[0068] In the technical solution of the embodiment of the present application, by reasonably setting the radiation source, irradiation voltage, irradiation dose and dose rate of the irradiation, the polymerization and cross-linking reaction in step S3 is ensured to proceed smoothly and fully, so that the gel fraction of the polyion gel adsorption material reaches the preset standard, thereby obtaining a high-performance polyion gel adsorption material.

[0069] Furthermore, in some embodiments, step S3 further includes drying the polyion gel adsorption material at 40-60° C. to a constant weight, then soaking it in deionized water to remove the sol, and drying it again at 40-60° C. to a constant weight.

[0070] In the technical solution of the embodiment of the present application, the polyion gel adsorption material is subjected to constant weight at 40-60°C to remove moisture from the gel solution; the polyion gel adsorption material is then soaked in deionized water to remove the sol, thereby purifying the polyion gel adsorption material and improving its purity; the polyion gel adsorption material is then subjected to constant weight again to remove moisture to obtain a dry, high-purity polyion gel adsorption material.

[0071] Some specific examples are listed below. It should be noted that the examples described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in this area or the product specifications are used. Reagents or instruments used without manufacturer's indication are all commercially available conventional products.

[0072] Example 1

[0073] A method for preparing a polyion gel adsorption material, such as Figure 2 As shown, the following steps are included:

[0074] S1. Add 0.1 mol of an oxygen-heterocyclic dicarboxylic acid (a) to 500 mL of anhydrous tetrahydrofuran solution and stir until the oxygen-heterocyclic dicarboxylic acid (a) is completely dissolved to obtain solution A. Next, add 2 g of lithium aluminum hydride to 100 mL of anhydrous tetrahydrofuran solution and stir for 10 minutes to prepare suspension B. Add suspension B dropwise to solution A in an ice-water bath and react under nitrogen for 24 hours in an ice-water bath. Filter, collect the filtrate, and remove the solvent by rotary evaporation to obtain oxygen-heterocyclic diol (b) in a yield of 87%-89%.

[0075] S2. Mix 0.1 mol of the heterocyclic diol (b) and 0.4 mol of the imidazole salt (c) and add them to 500 mL of a water-ethanol solution (water:ethanol volume ratio of 4:1). Stir for 10 minutes. Add 5 g of sodium hydroxide and heat under reflux with stirring for 120 minutes. Collect the solid by filtration and wash it 5-7 times with 100 mL of 0.1 mol / L dilute hydrochloric acid. Collect the white solid after acid washing to obtain the polymerized monomer (d) in a yield of 58%-61%.

[0076] S3. Add the polymer monomer (d) prepared in S2 to ethanol, dissolve it by ultrasonication, pour the solution into a polyethylene bag, degas with N2, and seal it. Use an electron accelerator to irradiate the vinyl group with electron beams to generate active free radicals that can be used for polymerization and cross-linking reactions, inducing polymerization and cross-linking of the reactant molecular chains to form a polyionic liquid gel core. Specifically, the irradiation is carried out by 60 Coγ-rays were irradiated at a voltage of 10 MeV, a dose of 80 kGy, and a dose rate of 10 kGy / pass. Subsequently, the polyion gel adsorbent material was dried at 50°C to a constant weight, then immersed in deionized water to remove the sol, and dried again at 50°C to a constant weight, yielding the final polyion gel adsorbent material (e).

[0077] Example 2

[0078] The polyion gel adsorption material prepared in Example 1 was subjected to an experiment on the adsorption of gold in a gold-glycine chelate ion solution system under different pH conditions. The specific operation steps are as follows:

[0079] Weigh 100 mg of the polyion gel adsorption material prepared in Example 1 and add 1 L of 0.5 mg / L [Au(Gly)2] - Static adsorption tests were conducted in a 25°C water bath shaker. After 24 hours of adsorption, the supernatant was collected and the gold concentration in the solution was measured by ICP-OES. The adsorption rate of the polyion gel adsorbent was calculated. The results are shown in Table 1.

[0080] Table 1 Adsorption properties of gold in different pH systems

[0081]

[0082] As shown in Table 1, when pH≥10, the polyion gel adsorption material prepared in Example 1 has a strong affinity for the adsorption of [Au(Gly)2] - Gold in solution (referring to [Au(Gly)2] -) has an adsorption rate of ≥94%, which can achieve efficient adsorption of gold. When pH ≤ 9, the polyion gel adsorption material cannot achieve the adsorption of gold containing [Au(Gly)2] - The adsorption of gold in the solution is mainly due to the fact that when pH ≤ 9, [Au(Gly)2] - The stability of chelated anions is poor, [Au(Gly)2] - Decomposition, at this time gold is Au + When pH is ≥ 10, glycine exists in the form of anions and chelates with gold ions to form [Au(Gly)2] - , thereby achieving efficient adsorption of gold.

[0083] Example 3

[0084] The polyion gel adsorption material prepared in Example 1 was subjected to an experiment on the adsorption of copper in a copper-glycine chelate ion solution system under different pH conditions. The specific operation steps are as follows:

[0085] Weigh 5 g of the polyion gel adsorption material prepared in Example 1 and add 0.5 L of 1 g / L [Cu(Gly)2] - Static adsorption tests were conducted in solutions of 1,000 mol / L (100 mol / L) and 1,000 mol / L (100 mol / L) with sodium hydroxide to adjust the pH of the solutions to 9, 10, 11, 12, 13, and 14, respectively. The adsorption tests were conducted in a 25°C water bath shaker. After 24 hours of adsorption, the clear solution was collected and the gold concentration in the solution was measured by ICP-OES. The adsorption rate of the polyion gel adsorbent was then calculated. The results are shown in Table 2.

[0086] Table 2 Adsorption performance of copper in different pH systems

[0087]

[0088] As shown in Table 2, when pH ≥ 9, the polyion gel adsorption material prepared in Example 1 has a strong affinity for the adsorption of [Cu(Gly)2] - Copper in solution (referring to [Cu(Gly)2] - ) has an adsorption rate of ≥95%, which can achieve efficient adsorption of gold.

[0089] Example 4

[0090] The polyion gel adsorption material prepared in Example 1 was subjected to an experiment to investigate the effect of copper adsorption in a copper-glycine chelate ion-ammonia mixed solution system under different pH conditions. The copper in the solution existed in the form of copper-glycine chelate ions and copper ammonia ions. The specific steps were as follows:

[0091] Weigh 5 g of the polyion gel adsorbent prepared in Example 1 and add 0.3 L of 1 g / L [Cu(Gly)2] - Static adsorption tests were conducted on a mixture of a 0.2L solution of 0.5% GOLD and 0.2L of a 0.2g / L copper ammonia solution. The pH of the solution was adjusted to 9, 10, 11, 12, 13, and 14 using sodium hydroxide. The adsorption tests were conducted in a 25°C water bath shaker. After 24 hours of adsorption, the clear solution was collected and the gold concentration in the solution was determined by ICP-OES. The adsorption rate of the polyion gel adsorbent was calculated, and the results are shown in Table 3.

[0092] Table 3 Adsorption performance of mixed copper in different pH systems

[0093]

[0094] As shown in Table 3, when pH≥9, the polyion gel adsorption material prepared in Example 1 has no significant effect on the adsorption of [Cu(Gly)2] - The adsorption rate of copper in the mixed solution of ammonia and copper is ≥97%, and the adsorption effect is good, indicating that the presence of ammonia water does not affect the adsorption effect of the polyion gel adsorption material on copper.

[0095] Example 5

[0096] The polyion gel adsorption material prepared in Example 1 was subjected to a saturated adsorption experiment for copper ions. The specific operation steps were as follows: 1 g of the polyion gel adsorption material prepared in Example 1 was added to 500 mL of a series of different gradient concentrations of [Cu(Gly)2] - The adsorption was carried out in a water bath oscillator at 25°C in a solution (10 mg / L-2 g / L). After 48 hours of adsorption, the clear solution was taken and the copper concentration in the solution was detected by ICP-OES to calculate the adsorption capacity (Qe) of the polyionic liquid gel adsorbent.

[0097] The results showed that the polyion gel adsorption material prepared in Example 1 had a strong affinity for [Cu(Gly)2] - The saturated adsorption capacity of copper in the solution system is 1200 mg / g.

[0098] Example 6

[0099] The polyion gel adsorption material prepared in Example 1 was subjected to a kinetic adsorption experiment. The specific operation steps were as follows: 10 mg of the polyion gel adsorption material prepared in Example 1 was added to 10 mL of 100 ppm [Au(Gly)2] - or [Cu(Gly)2] - The solution was reacted within 1-60 min, and the clear solution was taken out. The concentration of gold or copper in the solution was detected by ICP-OES to calculate the gel adsorption amount (Qe).

[0100] The results showed that the kinetic adsorption of gold and copper by the polyion gel adsorption material prepared in Example 1 reached equilibrium within 5 minutes.

[0101] Example 7

[0102] The polyion gel adsorption material prepared in Example 1 was subjected to the adsorption and separation experiments of gold and copper in various coexisting chelated metal anion solutions. The specific operation steps were as follows: a series of mixed glycine anion solutions containing gold or copper with iron, zinc, and cobalt at different concentration ratios were prepared. Specifically, gold was adsorbed in the solution as [Au(Gly)2] - Copper exists in the form of [Cu(Gly)2] - Iron in solution is [Fe(Gly)4] - Zinc in solution is [Zn(Gly)3] - Cobalt is present in solution as [Co(Gly)4] - 50 mg of the polyion gel adsorption material prepared in Example 1 was added to 50 mL of a solution (pH = 10). After 24 h of adsorption, the clear solution was collected and the concentration of each metal ion in the solution was detected by ICP-OES to calculate the gel adsorption rate. The results are shown in Table 4. In Table 4, "-" represents a value below the detection limit of ICP-OES.

[0103] Table 4 Adsorption results of polyion gel adsorption materials on various metal ions in the blend solution

[0104]

[0105] As shown in Table 4, the polyion gel adsorption material has an excellent selective adsorption effect on gold or copper in the glycine solution system, but does not adsorb other coexisting metal ions.

[0106] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same structure and effect as the technical concept within the scope of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the present application, any other embodiments that can be conceived by those skilled in the art and that combine some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A polyion gel adsorption material, characterized in that: The structural formula of the polyion gel adsorption material is as follows: ； Wherein, R is one of hydrogen, methyl, ethyl, and propyl.

2. The polyion gel adsorption material according to claim 1, characterized in that The polyion gel adsorption material has an adsorption rate of ≥94% for gold and ≥95% for copper.

3. The polyion gel adsorption material according to claim 1, characterized in that The pore size of the polyion gel adsorption material is 50-3000 μm.

4. The polyion gel adsorption material according to claim 1, characterized in that The gel fraction of the polyion gel adsorption material is ≥50%.

5. A method for separating and purifying complex gold and copper using a polyion gel adsorption material, characterized in that: The method is carried out using the polyion gel adsorption material according to any one of claims 1 to 4, comprising the following steps: adding the polyion gel adsorption material to a solution containing gold-glycine chelate ions or copper-glycine chelate, and utilizing directional chemical adsorption between the gold-glycine chelate ions or copper-glycine chelate and the polyion gel adsorption material to achieve selective adsorption of gold or copper in the solution; Among them, gold is present in the solution as [Au(Gly)2] - Copper exists in the form of [Cu(Gly)2] - , cis-Cu(Gly)2, trans-Cu(Gly)2 or several other forms; The pH of the solution containing gold-glycine anions is adjusted to ≥10; the pH of the solution containing copper-glycine chelates is adjusted to ≥9.

6. The method for separating and purifying complex gold and copper using a polyion gel adsorption material according to claim 5, characterized in that: The solution containing the gold-glycine chelate ion or the copper-glycine chelate includes mineral hydrometallurgical solution, catalyst waste liquid, metallurgical waste liquid, and electroplating anti-corrosion waste liquid.

7. The method for separating and purifying complex gold and copper using a polyion gel adsorption material according to claim 5, characterized in that: The preparation method of the polyion gel adsorption material comprises the following steps: S1, dissolving an oxygen heterocyclic dicarboxylic acid in tetrahydrofuran to obtain a solution A; dispersing lithium aluminum hydride in tetrahydrofuran to obtain a suspension B; adding the suspension B dropwise to the solution A in an ice-water bath and a nitrogen atmosphere, reacting for 20-30 hours, filtering, and rotary evaporating the filtrate to obtain an oxygen heterocyclic diol; S2, adding the oxygen heterocyclic diol and imidazole salt to an ethanol aqueous solution, adding sodium hydroxide after stirring, heating and refluxing for 100-140 minutes, filtering, and washing the solid with dilute hydrochloric acid 5-7 times to obtain a polymerized monomer; S3. Dissolve the polymerizable monomer in ethanol and pour the solution into a polyethylene bag. Degas the bag with N2 and seal the bag. Use an electron accelerator to irradiate the bag with an electron beam to cause the vinyl groups to generate active free radicals for polymerization and cross-linking reactions, thereby inducing polymerization and cross-linking of the reactant molecular chains to obtain the polyion gel adsorption material.

8. The method for separating and purifying complex gold and copper using a polyion gel adsorption material according to claim 7, characterized in that: In step S1, the structural formula of the oxygen heterocyclic dicarboxylic acid is ； In step S2, the structural formula of the imidazole salt is 。 9. The method for separating and purifying complex gold and copper using a polyion gel adsorption material according to claim 7, characterized in that: In step S3, the radiation is 60 Co γ-rays, irradiation voltage is 5-20MeV, irradiation dose is 10-300kGy, and dose rate is 1-50kGy / pass.

10. The method for separating and purifying complex gold and copper using a polyion gel adsorption material according to claim 7, characterized in that: Step S3 further includes drying the polyion gel adsorption material at 40-60° C. to a constant weight, then soaking it in deionized water to remove the sol, and drying it again at 40-60° C. to a constant weight.

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