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

Abstract

The invention provides a polyion gel adsorption material and a method for separating and purifying complex gold and copper through the polyion gel adsorption material, and belongs to the field of purification and separation of waste liquid containing gold and copper, and the polyion gel adsorption material comprises an imidazole ring structure fragment and an oxa-aliphatic bridge ring and aliphatic ether long-chain composite molecular skeleton. According to the invention, an imidazole ring structure fragment is introduced into a molecular main chain of the polyion gel adsorption material, so that favorable conditions are provided for adsorption of gold and copper; by introducing a composite molecular skeleton between imidazole rings of a molecular main chain of the polyion gel adsorption material, activity reduction caused by pi-pi conjugate accumulation of imidazole structure fragments is avoided, so that active sites of the imidazole ring structure fragments can be fully exposed, and specific target metal with large volume can be fully adsorbed; under the cooperation of the oxa-aliphatic bridged ring, the aliphatic ether long-chain composite molecular skeleton and the imidazole ring structure fragment, the efficient selective adsorption of the target metal with larger volume is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of purification and separation of waste liquid containing gold and copper, and particularly relates to a polyionic gel adsorption material and a method for separating and purifying complex gold and copper by using the same. Background Art

[0002] In the recovery of high-value metals such as gold and copper from industrial waste liquid, chemical extraction is usually adopted first, and then ion exchange resin is used for adsorption. Due to the low specific surface area and limited adsorption capacity of ion exchange resin, a large amount of ion exchange resin is used in the treatment of high-concentration metal industrial wastewater, resulting in high treatment cost and poor treatment effect. Therefore, ion exchange resin is generally used to treat low-concentration high-value metal industrial waste liquid.

[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 amount and fast adsorption at the same time, and has good application prospects in the treatment of high-concentration metal industrial wastewater. In recent years, imidazole-based gel adsorption materials have become a research hotspot in this field, expanding the application of gel adsorption materials in the fields of metallurgy, wastewater treatment, etc. However, in the molecular main chain structure of traditional imidazole-based gel adsorption materials, the steric hindrance of the molecular fragments between imidazole rings is relatively large. Through the space sieving effect, only simple metal ions with specific sizes (such as AuCl4 - , PtCl6 2- , PdCl4 2- ) can be selected. For some complex chelating ions or complex chelates with relatively large spatial volume, such as gold-glycine chelating ion, gold-glutamic acid chelating ion, etc., due to the existence of molecular fragments with relatively large steric hindrance between imidazole rings in the molecular main chain structure of such imidazole-based gel adsorption materials, it is difficult for complex chelating ions with relatively large spatial volume to effectively contact with imidazole rings, and thus the adsorption of complex chelating ions cannot be effectively achieved. Summary of the Invention

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

[0005] In the first aspect, an embodiment of the present application provides a polyionic gel adsorption material, and the structural formula of the polyionic gel adsorption material is as follows: ; wherein, R is one of hydrogen, methyl, ethyl and propyl.

[0006] In the technical solution of the embodiment of the present application, introducing an imidazole ring structure fragment on the molecular main chain of the polyionic gel adsorption material provides favorable conditions for the adsorption of gold and copper; by introducing an oxaaliphatic bridged ring and an aliphatic ether long-chain composite molecular skeleton between the imidazole rings on the molecular main chain of the polyionic gel adsorption material, the steric hindrance between different imidazole ring structure fragments is reduced, and at the same time, the positional relationship between the para-dioxygen atoms in the oxa-bridged ring structure and the oxygen atoms in the flexible aliphatic ether long chain is reasonably controlled, avoiding the reduction of activity caused by the π-π conjugate stacking of the imidazole structure fragments, enabling the active sites of the imidazole ring structure fragments to be fully exposed, and being able to fully adsorb specific target metals with larger volumes (i.e., complex chelating ions or complex chelates), realizing the efficient chemical adsorption of specific metal ions.

[0007] In some embodiments, the adsorption rate of the polyionic gel adsorption material for gold is ≥94%, and the adsorption rate for copper is ≥95%.

[0008] In this embodiment, by reasonably setting the structure of the polyionic gel adsorption material, the polyionic gel adsorption material can undergo qualitative chemical adsorption with target metal ions, realizing the efficient adsorption of gold and copper.

[0009] In some embodiments, the pore size of the polyionic gel adsorption material is 50 - 3000 μm.

[0010] In this embodiment, by reasonably setting the pore size of the polyionic gel adsorption material, the solution to be treated can enter the polyionic gel adsorption material more fully, and then the qualitative chemical adsorption reaction can proceed smoothly and fully, realizing the efficient adsorption of gold and copper in the solution.

[0011] In some embodiments, the gel fraction of the polyionic gel adsorption material is ≥50%.

[0012] In this embodiment, by reasonably controlling the gel fraction, the crosslinking degree of the polyionic gel adsorption material is relatively high, thereby improving the stability of the polyionic gel adsorption material and the adsorption efficiency for gold and copper.

[0013] In the second aspect, the embodiment of the present application provides a method for separating and purifying complex gold and copper using the polyionic gel adsorption material, which is carried out using the polyionic gel adsorption material provided in the first aspect of the present application, and includes the following steps: adding the polyionic gel adsorption material to a solution containing gold-glycine chelating ions or copper-glycine chelating ions or copper-glycine chelates, and using the directional chemical adsorption of gold-glycine chelating ions or copper-glycine chelating ions or copper-glycine chelates and the polyionic gel adsorption material to realize the selective adsorption of gold or copper in the solution; wherein, gold exists in the solution in the form of [Au(Gly)2] - form, and copper exists in the solution in the form of [Cu(Gly)2] -, cis-Cu(Gly)2, trans-Cu(Gly)2, [Cu(NH3)4]² + exists in one or more of these forms; the pH of the solution containing gold-glycine anions is adjusted to be ≥10; the pH of the solution containing copper-glycine chelate ions or copper-glycine chelates is adjusted to be ≥9.

[0014] In the technical solution of the embodiment of the present application, through the directional chemical adsorption of target metal ions by the polyionic gel adsorption material with a specific structure, the efficient selective recovery and purification of gold and copper are realized, and the operation is simple.

[0015] In some embodiments, the solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelates includes a hydrometallurgy solution of minerals, a catalyst waste liquid, a metallurgy waste liquid, and an electroplating anti-corrosion waste liquid.

[0016] In this embodiment, the types of solutions containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelates are diverse, indicating the universality of the polyionic gel adsorption material of the present application in the process of efficiently adsorbing gold and copper.

[0017] In some embodiments, the preparation method of the polyionic gel adsorption material includes the following steps: S1. Dissolve the oxacyclic dicarboxylic acid in tetrahydrofuran to obtain solution A; disperse lithium aluminum hydride in tetrahydrofuran to obtain suspension B. Under an ice-water bath and a nitrogen atmosphere, drop suspension B into solution A and react for 20 - 30 h, filter, and rotary evaporate the filtrate to obtain the oxacyclic dicarboxylic acid; S2. Add the oxacyclic dicarboxylic acid and the imidazolium salt to an ethanol aqueous solution, stir, then add sodium hydroxide, heat under reflux for 100 - 140 min, filter, and wash the solid with dilute hydrochloric acid 5 - 7 times to obtain the polymerization monomer; S3. Dissolve the polymerization monomer in ethanol, pour the solution into a polyethylene bag, degas with N2 and seal it, and use an electron accelerator for electron beam irradiation to generate reactive free radicals for polymerization cross-linking reaction on the vinyl group, inducing the polymerization cross-linking of the reactant molecular chains to obtain the polyionic gel adsorption material.

[0018] In this embodiment, first, the oxacyclic dicarboxylic acid is reduced by lithium aluminum hydride to obtain oxacyclic diol; then, the oxacyclic diol undergoes a nucleophilic substitution reaction with the imidazolium salt to form a polymerization monomer; finally, the polymerization monomer is cross-linked and polymerized through a cross-linking reaction to form the polyionic gel adsorption material.

[0019] In some embodiments, in step S1, the structural formula of the oxacyclic dicarboxylic acid is ; In step S2, the structural formula of the imidazolium salt is .

[0020] In this embodiment, by reasonably setting the structures of the oxacyclic dicarboxylic acid and the imidazolium salt, a polyionic gel adsorption material with a specific structure is generated, thereby achieving efficient adsorption of gold and copper.

[0021] In some embodiments, in step S3, the radiation uses 60 Co γ-rays, the irradiation voltage is 5 - 20 MeV, the irradiation dose is 10 - 300 kGy, and the dose rate is 1 - 50 kGy / pass.

[0022] In this embodiment, by reasonably setting the irradiation conditions, the polymerization cross-linking reaction is ensured to proceed smoothly and fully, and a high-performance polyionic gel adsorption material is obtained.

[0023] In some embodiments, in step S3, it further includes drying the polyionic gel adsorption material at 40 - 60 °C to constant weight, then soaking it in deionized water to remove the sol, and drying it again at 40 - 60 °C to constant weight.

[0024] In this embodiment, the moisture in the gel solution is removed by constant weight; then the sol is removed to purify the polyionic gel adsorption material and improve its purity; finally, the polyionic gel adsorption material is weighed to constant weight again to remove moisture, and a dry and high-purity polyionic gel adsorption material is obtained.

[0025] The above description is only an overview of the technical solution of the present application. In order to be able to understand the technical means of the present application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features and advantages of the present application more obvious and understandable, the specific embodiments of the present application are specifically given below. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solution of the present application, the drawings used in the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0027] Figure 1 is the preparation flow chart of the polyionic gel adsorption material in the embodiment of the present application; Figure 2 is the preparation flow chart of the polyionic gel adsorption material in Embodiment 1 of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0028] The embodiments of the technical solution of the present application will be described in detail below with reference to the accompanying drawings. The following embodiments are only used to illustrate the technical solution of the present application more clearly, so they are only examples and cannot be used to limit the protection scope of the present application.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field 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 drawings are intended to cover non-exclusive inclusion.

[0030] Referring to "embodiments" herein means that specific features, structures, or characteristics described in connection with the embodiments can be included in at least one embodiment of this application. The phrase appears in various places in the specification and does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art will explicitly and implicitly understand that the embodiments described herein can be combined with other embodiments.

[0031] The gel adsorption material itself has the advantages of a porous network structure, high capacity, and easy mass transfer, and has good application prospects in the treatment of high-concentration metal industrial wastewater. In recent years, imidazole-based gel adsorption materials have become a research hotspot in this field, expanding the application of gel adsorption materials in fields such as metallurgy and wastewater treatment. However, the steric hindrance of the molecular fragments between imidazole rings in the molecular backbone structure of traditional imidazole-based gel adsorption materials is relatively large, and only simple metal ions of specific sizes (such as AuCl4 - 、PtCl6 2- 、PdCl4 2- ) can be selected, and it is impossible to effectively adsorb some complex chelating ions or complex chelates with larger spatial volumes.

[0032] In order to solve the technical problem that traditional imidazole-based gel adsorption materials cannot effectively adsorb complex chelating 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 an imidazole ring structural fragment on the molecular main chain of the polyion gel adsorption material, favorable conditions are provided for the adsorption of gold and copper. By introducing an oxaaliphatic bridged ring and an aliphatic ether long-chain composite molecular skeleton between the imidazole rings on the molecular main chain of the polyion gel adsorption material, the oxa-bridged ring structure and the aliphatic ether long-chain structure regulate the length and spatial arrangement structure of the composite molecular skeleton, reduce the steric hindrance between different imidazole ring structural fragments, and at the same time reasonably control the positional relationship between the para-dioxygen atoms in the oxa-bridged ring structure and the oxygen atoms in the flexible aliphatic ether long-chain, avoiding the decrease in activity caused by the π-π conjugate stacking of the imidazole structural fragments, ensuring the multi-dimensional extension of the space of the polyion gel adsorption material, enabling the active sites of the imidazole ring structural fragments to be fully exposed, and being able to fully adsorb specific target metals with larger volumes (i.e., complex chelating ions or complex chelates), realizing the efficient chemical adsorption of specific metal ions.

[0033] In the first aspect, an embodiment of the present application provides a polyion gel adsorption material, and the structural formula of the polyion gel adsorption material is as follows: ; Wherein, R is one of hydrogen, methyl, ethyl, and propyl.

[0034] In the technical solution of the embodiment of the present application, on the one hand, π-π conjugation is achieved by introducing an imidazole ring structural fragment on the molecular main chain of the polyion gel adsorption material to ensure the activity of the imidazole ring and provide favorable conditions for the adsorption of gold and copper. On the other hand, an oxaaliphatic bridged ring and an aliphatic ether long-chain composite molecular skeleton are introduced between the imidazole rings on the molecular main chain of the polyion gel adsorption material. First, the rigid oxa-bridged ring structural fragment and the flexible aliphatic ether long-chain cooperate with each other, ensuring both the overall stability and flexibility of the polyion gel adsorption material. Secondly, the length and spatial arrangement structure of the composite molecular skeleton are regulated by the oxa-bridged ring structure and the aliphatic ether long-chain structure, reducing the steric hindrance between different imidazole ring structural fragments and ensuring the spatial gain effect of the molecular structure main chain. At the same time, the positional relationship between the para-dioxygen atoms in the oxa-bridged ring structure and the oxygen atoms in the flexible aliphatic ether long-chain is reasonably controlled, and the repulsive effect of the lone pair electrons of the oxygen atoms avoids the planar stacking of the imidazole structural fragments, realizing the change in the π-π conjugate stacking density, thereby avoiding the decrease in activity caused by the π-π conjugate stacking of the imidazole structural fragments, ensuring the multi-dimensional extension of the space of the polyion gel adsorption material, enabling the active sites of the imidazole ring structural fragments to be fully exposed, and being able to fully adsorb specific target metals with larger volumes (i.e., complex chelating ions or complex chelates), realizing the efficient chemical adsorption of specific metal ions.

[0035] Compared with setting a cyclic structure with a relatively large steric hindrance between imidazole ring structural fragments, the steric hindrance of the composite molecular backbone of the present application is relatively small, which is more conducive to the efficient adsorption of a target metal with a relatively large volume. Compared with setting a chain-like structural fragment that can rotate axially between imidazole ring structural fragments, the composite molecular backbone of the present application can better improve the axial displacement of π-π conjugation of the imidazole ring structural fragment on the molecular main chain, further ensuring that the molecular structure has spatial multi-dimensional ductility, forming a π-π conjugate arrangement with a specific structure in the molecular structure of the polyion gel adsorption material, and finally realizing the efficient selective adsorption of a target metal with a relatively large volume under the cooperation of the oxa-aliphatic bridged ring and the aliphatic ether long-chain composite molecular backbone and the imidazole ring structural fragment.

[0036] Further, in some embodiments, the gold adsorption rate of the polyion gel adsorption material is ≥94%, and the copper adsorption rate is ≥95%.

[0037] In the technical solution of the embodiment of the present application, by reasonably setting the structure of the polyion gel adsorption material, the polyion gel adsorption material can undergo qualitative chemical adsorption with the target metal ions, realizing the efficient adsorption of gold and copper, and thus realizing the purification and separation of gold and copper in the solution system.

[0038] Further, in some embodiments, the pore size of the polyion gel adsorption material is 50 - 3000 μm.

[0039] 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 enter the polyion gel adsorption material more fully, and then the qualitative chemical adsorption reaction can proceed smoothly and fully, realizing the efficient adsorption of gold and copper in the solution.

[0040] Further, in some embodiments, the gel fraction of the polyion gel adsorption material is ≥50%.

[0041] In the technical solution of the embodiment of the present application, by controlling the gel fraction of the polyion gel adsorption material above 50%, the crosslinking degree of the polyion gel adsorption material is relatively high, that is, the molecular structure is more stable and neater, thereby improving the stability of the polyion gel adsorption material and the adsorption efficiency of gold and copper.

[0042] Second aspect, an embodiment of the present application provides a method for separating and purifying complex gold and copper using a polyionic gel adsorbent material, which is carried out using the polyionic gel adsorbent material provided in the first aspect of the present application, and includes the following steps: adding the polyionic gel adsorbent material to a solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelates, and utilizing the directional chemical adsorption of the gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelates with the polyionic gel adsorbent material to achieve selective adsorption of gold (referring to gold-glycine chelate ions) or copper (referring to copper-glycine chelate ions or copper-glycine chelates) in the solution; where gold exists in the solution in the form of [Au(Gly)2] - form, and copper exists in the solution in one or several forms of [Cu(Gly)2] - , cis-Cu(Gly)2, trans-Cu(Gly)2, [Cu(NH3)4]² + ; adjusting the pH of the solution containing gold-glycine anions to ≥10; adjusting the pH of the solution containing copper-glycine chelate ions or copper-glycine chelates to ≥9. Specifically, [Au(Gly)2] - refers to the gold-glycine chelate anion, [Cu(Gly)2] - refers to the copper-glycine chelate anion, cis-Cu(Gly)2 refers to the trans-copper-glycine chelate, and trans-Cu(Gly)2 refers to the cis-copper-glycine chelate, [Cu(NH3)4]² + refers to the copper ammonia ion.

[0043] In the technical solution of the embodiment of the present application, through the directional chemical adsorption of the target metal ions by the polyionic gel adsorbent material with a specific structure, the interference of other impurity metals is avoided, and the efficient adsorption of gold and copper in the glycine solution system is achieved, realizing the efficient selective recovery and purification of gold and copper, with simple operation.

[0044] Further, in some embodiments, the solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelates includes a hydrometallurgy solution of minerals, a catalyst waste liquid, a metallurgy waste liquid, and an electroplating anti-corrosion waste liquid.

[0045] 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 chelates can be various, such as a hydrometallurgy solution of minerals, a catalyst waste liquid, a metallurgy waste liquid, and an electroplating anti-corrosion waste liquid, indicating the universality of the polyionic gel adsorbent material of the present application in the process of efficiently adsorbing gold and copper.

[0046] Further, as Figure 1 shown, in some embodiments, the preparation method of the polyionic gel adsorbent material includes the following steps: S1. Dissolve the oxacyclic dicarboxylic acid in tetrahydrofuran to obtain solution A; disperse lithium aluminum hydride in tetrahydrofuran to obtain suspension B. Under an ice-water bath and a nitrogen atmosphere, drop suspension B into solution A and react for 20 - 30 h. Filter and rotary evaporate the filtrate to obtain oxacyclic diol; S2. Add the oxacyclic diol and imidazolium salt to an ethanol aqueous solution, stir and then add sodium hydroxide, heat under reflux for 100 - 140 min, filter, and wash the solid with dilute hydrochloric acid 5 - 7 times to obtain the polymerization monomer; S3. Dissolve the polymerization monomer in ethanol, pour the solution into a polyethylene bag, degas with N2 and seal it, and use an electron accelerator for electron beam radiation to generate active free radicals for polymerization cross-linking reaction in the vinyl group, inducing the polymerization cross-linking of the reactant molecular chains to obtain the polyion gel adsorption material.

[0047] In the technical solution of the embodiment of the present application, first, the oxacyclic dicarboxylic acid is reduced by lithium aluminum hydride to reduce the carboxyl group to a hydroxyl group to obtain oxacyclic diol; then, the oxacyclic diol and the imidazolium salt undergo a nucleophilic substitution reaction to form a polymerization monomer containing an imidazole ring structure, an oxaaliphatic bridged ring, and an aliphatic ether long-chain composite molecular skeleton; finally, the polymerization monomer is cross-linked and polymerized through a cross-linking reaction to form the polyion gel adsorption material.

[0048] Further, in some embodiments, in step S1, the structural formula of the oxacyclic dicarboxylic acid is ; In step S2, the structural formula of the imidazolium salt is .

[0049] In the technical solution of the embodiment of the present application, by reasonably setting the structures of the oxacyclic dicarboxylic acid and the imidazolium salt, a polyion gel adsorption material with a specific structure is generated, thereby realizing the efficient adsorption of gold and copper.

[0050] Further, in some embodiments, in step S3, the radiation uses 60 Co γ-rays, the irradiation voltage is 5 - 20 MeV, the irradiation dose is 10 - 300 kGy, and the dose rate is 1 - 50 kGy / pass.

[0051] 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, it is ensured that the polymerization cross-linking reaction in step S3 proceeds smoothly and sufficiently, and further, the gel fraction of the polyion gel adsorption material reaches the preset standard, obtaining a high-performance polyion gel adsorption material.

[0052] Further, in some embodiments, in step S3, it further includes drying the polyionic gel adsorbent material at 40 - 60 °C until constant weight, then soaking it in deionized water to remove the sol, and drying it again at 40 - 60 °C until constant weight.

[0053] In the technical solution of the embodiment of the present application, by drying the polyionic gel adsorbent material at 40 - 60 °C until constant weight, the moisture in the gel solution is removed; then the polyionic gel adsorbent material is soaked in deionized water to remove the sol, realizing the purification of the polyionic gel adsorbent material and improving its purity; then the polyionic gel adsorbent material is dried until constant weight again to remove the moisture, obtaining a dry and high-purity polyionic gel adsorbent material.

[0054] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as a limitation to the present application. For those not specified in the embodiments regarding specific technologies or conditions, they shall be carried out according to the technologies or conditions described in the literature in this field or according to the product specifications. For reagents or instruments not indicated by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0055] Example 1 A preparation method of a polyionic gel adsorbent material, as Figure 2 shown, includes the following steps: S1. Add 0.1 mol of oxacyclic dicarboxylic acid (a) to 500 mL of anhydrous tetrahydrofuran solution, stir until oxacyclic dicarboxylic acid (a) is completely dissolved to obtain solution A; then add 2 g of lithium aluminum hydride to 100 mL of anhydrous tetrahydrofuran solution, stir for 10 min to prepare suspension B. Under the condition of an ice-water bath, add suspension B dropwise to solution A, and under the condition of an ice-water bath, react for 24 h under nitrogen protection. Filter, collect the filtrate, and rotary evaporate the filtrate to remove the solvent to obtain oxacyclic diol (b), with a yield of 87% - 89%.

[0056] S2. Mix 0.1 mol of oxacyclic diol (b) with 0.4 mol of imidazolium salt (c), add them to 500 mL of a water-ethanol solution (the volume ratio of water to ethanol is 4:1), stir for 10 min, add 5 g of sodium hydroxide, heat under reflux and stir for 120 min, filter to collect the solid, and wash it 5 - 7 times with 100 mL of dilute hydrochloric acid with a concentration of 0.1 mol / L. Collect the white solid after pickling to obtain the polymerization monomer (d), with a yield of 58% - 61%.

[0057] S3. Add the polymer monomer (d) prepared in S2 into ethanol. After ultrasonic dissolution, pour the solution into a polyethylene bag, degas it with N2 and then seal it. Use an electron accelerator for electron beam radiation to generate active free radicals in the vinyl group that can be used for polymerization cross-linking reactions, induce the polymerization cross-linking of the reactant molecular chains, and form a polyionic liquid gel core. Specifically, the radiation uses 60 Coγ-rays, the irradiation voltage is 10 MeV, the irradiation dose is 80 kGy, and the dose rate is 10 kGy / pass. Subsequently, dry the polyionic gel adsorbent material at 50 °C until constant weight, then soak it in deionized water to remove the sol part, and dry it again at 50 °C until constant weight to obtain the final polyionic gel adsorbent material (e).

[0058] Example 2 Carry out an experiment on the adsorption effect of gold in the gold-glycine chelate ion solution system with the polyionic gel adsorbent material prepared in Example 1 under different pH environments. The specific operation steps are as follows: Weigh 100 mg of the polyionic gel adsorbent material prepared in Example 1 and put it into 1 L of a solution containing [Au(Gly)2] with a concentration of 0.5 mg / L at room temperature. - Adjust the pH of the solution to 9, 10, 11, 12, 13, and 14 respectively with sodium hydroxide for static adsorption tests. The above adsorption tests are carried out in a water bath oscillator at 25 °C. After adsorption for 24 h, take the supernatant and detect the concentration of gold in the solution by ICP-OES, so as to calculate the adsorption rate of the polyionic gel adsorbent material. The results are shown in Table 1.

[0059] Table 1 Adsorption performance of gold in different pH systems As can be seen from Table 1, when pH ≥ 10, the polyionic gel adsorbent material prepared in Example 1 has an adsorption rate of ≥ 94% for gold (referring to [Au(Gly)2] - ) in the solution containing [Au(Gly)2] - ), and can achieve efficient adsorption of gold. When pH ≤ 9, the polyionic gel adsorbent material cannot achieve the adsorption of gold in the solution containing [Au(Gly)2] - . This is mainly because when pH ≤ 9, the stability of the chelating anion of [Au(Gly)2] - is poor, and [Au(Gly)2] - decomposes. At this time, gold exists in the form of Au + , and the polyionic gel adsorbent material cannot achieve the adsorption of gold; while when pH ≥ 10, glycine exists in the form of an anion and chelates with gold ions to form [Au(Gly)2] - , thus achieving efficient adsorption of gold.

[0060] Example 3 The polyionic gel adsorbent prepared in Example 1 was used to conduct an experiment on the adsorption of copper in a copper-glycine chelate ion solution system under different pH environments. The specific operation steps are as follows: Weigh 5 g of the polyionic gel adsorbent prepared in Example 1 and put it into 0.5 L of a solution with a concentration of 1 g / L containing - [Cu(Gly)2] at room temperature. Adjust the pH of the solution to 9, 10, 11, 12, 13, and 14 respectively with sodium hydroxide for static adsorption experiments. The above adsorption experiments were carried out in a water bath oscillator at 25 °C. After adsorption for 24 h, take the supernatant and detect the concentration of gold in the solution by ICP-OES, so as to calculate the adsorption rate of the polyionic gel adsorbent. The results are shown in Table 2.

[0061] Table 2 Adsorption performance of copper in different pH systems As can be seen from Table 2, when pH ≥ 9, the polyionic gel adsorbent prepared in Example 1 has an adsorption rate of copper (referring to - [Cu(Gly)2] in the solution - ) ≥ 95% in the solution containing [[Cu(Gly)2]], and can achieve efficient adsorption of gold.

[0062] Example 4 The polyionic gel adsorbent prepared in Example 1 was used to conduct an experiment on the adsorption of copper in a mixed solution system of copper-glycine chelate ion-ammonia water under different pH environments. At this time, copper in the solution exists in two forms: copper-glycine chelate ion and copper ammonia ion. The specific operation steps are as follows: Weigh 5 g of the polyionic gel adsorbent prepared in Example 1 and put it into a mixed solution of 0.3 L of a solution with a concentration of 1 g / L containing - [Cu(Gly)2] and 0.2 L of a copper ammonia solution with a concentration of 0.2 g / L at room temperature. Adjust the pH of the solution to 9, 10, 11, 12, 13, and 14 respectively with sodium hydroxide for static adsorption experiments. The above adsorption experiments were carried out in a water bath oscillator at 25 °C. After adsorption for 24 h, take the supernatant and detect the concentration of gold in the solution by ICP-OES, so as to calculate the adsorption rate of the polyionic gel adsorbent. The results are shown in Table 3.

[0063] Table 3 Adsorption performance of mixed copper in different pH systems As can be seen from Table 3, when pH ≥ 9, the polyionic gel adsorbent prepared in Example 1 has an adsorption rate of copper (referring to -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 polyionic gel adsorbent on copper.

[0064] Example 5 Perform a saturation adsorption experiment on the polyionic gel adsorbent prepared in Example 1 for adsorbing copper ions. The specific operation steps are as follows: Take 1 g of the polyionic gel adsorbent prepared in Example 1 and add it to 500 mL of a series of [Cu(Gly)2] - solutions with different gradient concentrations (10 mg / L - 2 g / L). Carry out the experiment in a water bath oscillator at 25 °C. After 48 h of adsorption, take the supernatant, and use ICP-OES to detect the concentration of copper in the solution, so as to calculate the adsorption capacity (Qe) of the polyionic liquid gel adsorbent.

[0065] The results show that the saturation adsorption capacity of the polyionic gel adsorbent prepared in Example 1 for copper in the [Cu(Gly)2] - solution system is 1200 mg / g.

[0066] Example 6 Perform a kinetic adsorption experiment on the polyionic gel adsorbent prepared in Example 1. The specific operation steps are as follows: Take 10 mg of the polyionic gel adsorbent prepared in Example 1 and add it to 10 mL of a solution with a concentration of 100 ppm of [Au(Gly)2] - or [Cu(Gly)2] - solution. Take samples at 1 - 60 min during the reaction respectively, take the supernatant, and use ICP-OES to detect the concentration of gold or copper in the solution to calculate the gel adsorption capacity (Qe).

[0067] The results show that the kinetic adsorption of gold and copper by the polyionic gel adsorbent prepared in Example 1 reaches equilibrium within 5 min.

[0068] Example 7 Perform experiments on the adsorption and separation of gold and copper respectively from a solution of multiple coexisting chelated metal anions using the polyionic gel adsorbent prepared in Example 1. The specific operation steps are as follows: Prepare a series of mixed glycine anion solutions containing different concentration ratios of gold or copper and iron, zinc, and cobalt. Specifically, gold exists in the solution in the form of [Au(Gly)2] - form, copper exists in the solution in the form of [Cu(Gly)2] - , iron exists in the solution in the form of [Fe(Gly)4] - , zinc exists in the solution in the form of [Zn(Gly)3] - , and cobalt exists in the solution in the form of [Co(Gly)4] -。50 mg of the polyion gel adsorbent material prepared in Example 1 was added to 50 mL of a solution (pH = 10). After 24 h of adsorption, the supernatant was taken, 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, where "--" in Table 4 represents below the detection limit of ICP-OES.

[0069] Table 4 Adsorption results of polyion gel adsorbent material for various metal ions in the blended solution As can be seen from Table 4, the polyion gel adsorbent material has an excellent selective adsorption effect on gold or copper in the glycine solution system, and does not adsorb the remaining coexisting metal ions.

[0070] It should be noted that this application is not limited to the above embodiments. The above embodiments are only examples, and embodiments having the same composition and the same effect as the technical idea within the technical scope of this application are included in the technical scope of this application. In addition, within the scope of not departing from the gist of this application, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways constructed by combining some constituent elements in the embodiments are also included in the scope of this application.

Claims

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

2. The polyionic gel adsorption material according to claim 1, characterized in that, The gold adsorption rate of the polyionic gel adsorbent material is ≥94%, and the copper adsorption rate is ≥95%.

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

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

5. A method for separating and purifying complex gold and copper by using the polyionic gel adsorption material, characterized in that, Using the polyionic gel adsorbent material described in any one of claims 1 to 4, it includes the following steps: adding the polyionic gel adsorbent material to a solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate, and using the directional chemical adsorption of gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate with the polyionic gel adsorbent material to achieve selective adsorption of gold or copper in the solution; Among them, gold exists in the solution in the form of [Au(Gly)2] - and copper exists in the solution in the form of [Cu(Gly)2] - , cis-Cu(Gly)2, trans-Cu(Gly)2, [Cu(NH3)4]² + or one or more of the above forms; The pH of the solution containing gold-glycine anions is adjusted to ≥10; the pH of the solution containing copper-glycine chelate ions or copper-glycine chelate is adjusted to ≥9.

6. The method for separating and purifying complex gold and copper by using the polyionic gel adsorption material according to claim 5, characterized in that, The solution containing gold-glycine chelate ions or copper-glycine chelate ions or copper-glycine chelate includes hydrometallurgy solution of minerals, catalyst waste liquid, metallurgical waste liquid, and electroplating anti-corrosion waste liquid.

7. The method for separating and purifying complex gold and copper by using the polyionic gel adsorption material according to claim 5, characterized in that, The preparation method of the polyionic gel adsorbent material includes the following steps: S1. Dissolve the oxacyclic dicarboxylic acid in tetrahydrofuran to obtain solution A; disperse lithium aluminum hydride in tetrahydrofuran to obtain suspension B. Under an ice-water bath and nitrogen atmosphere, drop suspension B into solution A and react for 20 - 30 h, filter, and rotary evaporate the filtrate to obtain oxacyclic dicarboxylic acid; S2. Add the oxacyclic dicarboxylic acid and imidazolium salt to an ethanol-water solution, stir and then add sodium hydroxide, heat under reflux for 100 - 140 min, filter, and wash the solid with dilute hydrochloric acid 5 - 7 times to obtain the polymerization monomer; S3. Dissolve the polymerization monomer in ethanol, pour the solution into a polyethylene bag, degas with N2 and seal, and use an electron accelerator for electron beam radiation to generate active free radicals for polymerization cross-linking reaction of vinyl groups, inducing the polymerization cross-linking of the reactant molecular chains to obtain the polyionic gel adsorbent material.

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

10. The method for separating and purifying complex gold and copper by using the polyionic gel adsorption material according to claim 7, characterized in that, In step S3, it also includes drying the polyionic gel adsorbent material at 40 - 60 °C to constant weight, then soaking it in deionized water to remove the sol, and drying it again at 40 - 60 °C to constant weight.

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