Cationic polymer material for adsorbing rhenium under electric field assistance, and preparation method and application thereof

Abstract

The application discloses a cationic polymer material for electric field-assisted adsorption of rhenium and a preparation method and application thereof, and belongs to the technical field of functional polymer adsorbents and electrochemical separation and recovery of rare and dispersed noble metals. The cationic polymer material is cross-linked and constructed through multi-pyridine structural units, and is subjected to methylation and anion exchange treatment, so that a porous polymer structure with high-density cationic sites is formed. Under the action of an applied electric field, the cationic polymer material exists in a suspended and dispersed state in a rhenium-containing solution, the electric field drives directional migration of perrhenate anions, and the perrhenate anions are synergistically adsorbed with the cationic sites in the material through electrostatic attraction and anion exchange, so that efficient enrichment and separation of rhenium are realized. The application avoids the limitation that the adsorption material needs to be fixed on the surface of an electrode, is especially suitable for a low-concentration rhenium-containing solution system, and provides a new technical approach for efficient recovery of rhenium.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer adsorbents and electrochemical separation and recovery of rare and precious metals, specifically relating to a cationic polymer material for electric field-assisted adsorption of rhenium, its preparation method and application. Background Technology

[0002] Rhenium is an important rare and dispersed precious metal with significant applications in aerospace high-temperature structural materials, catalysts, and electronic materials. However, its abundance in nature is extremely low, and it mostly exists in low concentrations in ore leachates or industrial wastewater, making efficient separation and enrichment of rhenium challenging. Adsorption separation methods are widely used in rhenium recovery research due to their mild operating conditions and wide applicability. Among these methods, cationic polymer materials, which can introduce high-density cation sites into their molecular structure and possess excellent electrostatic attraction and anion exchange capabilities for anionic species such as perrhenate, have been used in rhenium adsorption separation research.

[0003] However, in existing technologies, the adsorption process of rhenium by cationic polymer materials is mostly carried out under static or simple stirring conditions. Even if the material can exist in a dispersed state in the solution system, the migration of perrhenate ions in the solution still mainly depends on the concentration gradient, which makes it difficult to fully utilize some effective adsorption sites in the material, thus limiting the adsorption efficiency and adsorption rate. On the other hand, existing electric field-assisted adsorption or electrochemical adsorption methods usually involve fixing or adhering the adsorbent material to the surface of a conductive electrode to capture the target ion under the action of an applied electric field. The adsorption process of this type of method is mainly limited to the electrode surface, and the effective contact area of ​​the material is limited, making it difficult to fully utilize the potential adsorption capacity of the adsorbent material.

[0004] An applied electric field can induce the directional migration of negatively charged perrhenate anions, causing them to accumulate in specific regions under the influence of the electric field. Combining the application of an applied electric field with the adsorption process of dispersed cationic polymer materials, allowing the adsorbent material to exist in a suspended, dispersed form in the solution and synergistically achieve the migration and capture of perrhenate anions under the influence of an electric field, holds promise for improving the migration efficiency and adsorption site utilization of rhenium in solution systems without relying on electrode surface fixation. Therefore, it is necessary to develop an electric field-assisted adsorption method using dispersed cationic polymer materials as the adsorption medium under an applied electric field to achieve efficient separation and enrichment of rhenium in complex solution systems. Summary of the Invention

[0005] The purpose of this invention is to provide a cationic polymer material for electric field-assisted adsorption of rhenium, its preparation method, and its application. This method allows the cationic polymer material to exist in a dispersed state in a rhenium-containing solution system. Under the driving force of an electric field, the electrostatic attraction and anion exchange capabilities of the high-density cation sites in the material are synergistically utilized to promote the directional migration and efficient capture of perrhenate anions in the solution. This improves the utilization rate of effective adsorption sites in the cationic polymer material, achieving efficient separation and enrichment of rhenium in the solution system. This overcomes the shortcomings of existing adsorption methods that rely solely on concentration gradients and electrode surface-adhesive electrochemical adsorption methods in terms of material utilization and adsorption efficiency.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a method for preparing a cationic polymer material for electric field-assisted adsorption of rhenium, comprising the following steps: (1) Tris(pyridin-4-yl)amine and 5,5′-bis(bromomethyl)-2,2′-bipyridine were added to an organic solvent to form a reaction system. After nitrogen purging to remove oxygen, the system was sealed under a nitrogen atmosphere and then heated to carry out a cross-linking polymerization reaction to generate a polymer precursor containing a pyridine structure. After the reaction was completed, the system was cooled to room temperature and polymer materials were obtained by solid-liquid separation, Soxhlet extraction and drying. (2) The polymer material prepared in step (1) is subjected to a post-modification reaction with a methylating agent in a polar solvent to induce methylation of the pyridine group. After the reaction is completed, the mixture is cooled to room temperature, and the solid product is separated by centrifugation. After washing, the solid product is subjected to anion exchange treatment. Finally, the solid product is filtered, washed, and dried to obtain a cationic polymer material with chloride ions as the counter ion.

[0007] Preferably, in step (1), the molar ratio between the tri(pyridin-4-yl)amine and 5,5′-bis(bromomethyl)-2,2′-bipyridine is 1:(1-3); the temperature of the crosslinking polymerization reaction is 80-140 °C and the time is 12-168 h.

[0008] Preferably, in step (1), the organic solvent is one or more of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, and mesitylene; the solvent used for Soxhlet extraction is one or more of tetrahydrofuran, methanol, ethanol, and water, and the extraction time is 12 to 48 h.

[0009] Preferably, in step (2), the mass-to-volume ratio of the polymer material to the methylating agent is 1 g: 4~10 mL; the methylating agent is one or more of iodomethane, methyl trifluoromethanesulfonate, and dimethyl sulfate; the temperature of the post-modification reaction is 40~120 °C and the time is 6~48 h.

[0010] Preferably, in step (2), the polar solvent is acetonitrile, dichloromethane or nitrobenzene; the solution used for the anion exchange treatment is a 0.1-3 mol / L sodium chloride aqueous solution, and the anion exchange treatment time is 4-24 h.

[0011] To achieve the above-mentioned objectives, this invention also provides a cationic polymer material prepared by the above-mentioned preparation method, wherein the cationic polymer material is a porous cationic polymer solid insoluble in water, and the chemical structural formula of the cationic polymer material is shown in Formula I: Formula I.

[0012] To achieve the above-mentioned objectives, the present invention also provides the application of the above-mentioned cationic polymer material as an adsorbent in electric field-assisted adsorption of rhenium.

[0013] Furthermore, the specific application process is as follows: S1. Provide a rhenium-containing solution and introduce the rhenium-containing solution into an electrolytic cell. The electrolytic cell includes a working electrode region and a counter electrode region that are separated from each other. Ion migration between the two regions is achieved through an ion conduction structure. S2. Add cationic polymer material to the rhenium-containing solution in the working electrode area so that the cationic polymer material exists in the solution system in a suspended and dispersed state; S3. Under stirring conditions, a set voltage is applied to the electrolytic cell to establish an electric field, driving rhenium-containing anions to migrate directionally to the working electrode region and adsorb onto the cationic polymer material. Through electrostatic attraction of cation sites and anion exchange, the adsorption and separation of rhenium in the solution are achieved.

[0014] Preferably, in step S1, the rhenium-containing solution is an ore leaching solution, metallurgical waste liquid, or a simulated rhenium-containing solution; the rhenium in the rhenium-containing solution is in the form of perrhenate ReO4. - It exists in the form of an ion exchange membrane, a porous membrane, or a salt bridge.

[0015] Preferably, in step S3, a positive voltage of 0.1 to 5 V is applied to the working electrode to establish an external electric field; the adsorption time is 1 min to 24 h.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention uses cationic polymer materials in a dispersed state in a rhenium-containing solution system, which avoids the problem of limited effective contact area caused by the need for adsorption materials to be fixed or adhered to the electrode surface in the existing electrochemical adsorption technology, so that the adsorption sites in the material can fully participate in the adsorption process of rhenium, and significantly improve the utilization efficiency of the material.

[0017] (2) In this invention, an external electric field is introduced during the adsorption process. The electric field is used to guide the directional migration of negatively charged species such as perrhenate anions, causing perrhenate anions to accumulate in the cationic polymer material under the drive of the electric field. This forms a synergistic effect with the electrostatic attraction and anion exchange of the high-density cation sites in the material. In particular, for industrial rhenium-containing waste liquids where the rhenium concentration is usually low and it is difficult to achieve effective migration and accumulation by relying solely on the concentration gradient, the external electric field can significantly enhance the migration efficiency of perrhenate anions in the solution system, enabling them to rapidly accumulate in the dispersed cationic polymer material, thereby significantly improving the adsorption rate and adsorption efficiency of rhenium in low-concentration systems.

[0018] (3) The cationic polymer material of the present invention introduces polypyridine units into the backbone through molecular structure design and methylation treatment to construct high-density, uniformly distributed permanent positive charge sites, so that the material exhibits excellent adsorption capacity for perrhenate and can achieve efficient enrichment and separation of rhenium under the assistance of an external electric field.

[0019] (4) The adsorption process of the present invention is carried out by dispersion adsorption, which does not depend on the direct fixation or loading relationship between the adsorbent material and the electrode surface. The adsorption mechanism is mainly based on electric field-induced migration, electrostatic adsorption and anion exchange, which avoids the influence of electrode surface structure on adsorption performance and has good applicability and scalability.

[0020] (5) The method described in this invention is simple to operate and applicable to rhenium-containing solutions of different sources and concentrations. It can still maintain good adsorption effect in complex solution systems, providing a new technical path for the efficient separation and recovery of rhenium and has good application prospects. Attached Figure Description

[0021] Figure 1 A simplified diagram of the reaction apparatus for the application of the cationic polymer prepared in Example 1 in the electric field-assisted adsorption of rhenium; Figure 2 The infrared spectra of TPA, BB2By, TPA-BB2By, and TPA-BB2By in Example 1 are shown below. Figure 3 For Comparative Example 1, TPA-BB2By-Cl affects ReO4 - Isothermal adsorption curves; Figure 4 The effect of TPA-BB2By-Cl on ReO4 under different applied voltage conditions in Example 2 - The graph shows the change in adsorption capacity. Figure 5 The low concentration of ReO4 in Example 3 - Plot of electric field-assisted adsorption kinetics under the given conditions; Figure 6As a comparative example 2, ReO4 under the action of an applied electric field - Migration and enrichment behavior diagram in a two-compartment electrolysis system; Figure 7 Example 4: Electric field-assisted adsorption of ReO4 under coexisting anion conditions. - Selective comparison chart. Detailed Implementation

[0022] To make the objectives, technical solutions, and beneficial effects of this invention clearer, the invention will be further described below in conjunction with specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of protection of this invention. All equivalent substitutions or modifications made based on the technical solutions of this invention should fall within the scope of protection of this invention.

[0023] Unless otherwise specified, all raw materials and reagents used in the following examples are commercially available products with a purity of analytical grade or higher. Example 1

[0024] A method for preparing a cationic polymer material for electric field-assisted adsorption of rhenium includes the following steps: (1) Tris(pyridin-4-yl)amine (TPA) (0.50 g, 1.94 mmol) and 5,5′-bis(bromomethyl)-2,2′-bipyridine (BB2By) (1.02 g, 2.91 mmol) were added to a reaction vessel, and 8 mL of a 1:1 mixture of acetonitrile and mesitylene was added as the reaction solvent to fully disperse the reactants and form a reaction system. The reaction system was then subjected to multiple nitrogen purging treatments to remove oxygen from the system and form an inert atmosphere. The reaction vessel was then sealed under an inert atmosphere. The sealed reaction system was heated in a 100 °C oven for 72 h to allow the polypyridine structural units in the tri(pyridine-4-yl)amine molecule to crosslink with the bromomethyl group, forming a polymer precursor containing a pyridine structure. After the reaction was completed, the mixture was cooled to room temperature, and the solid product was separated by vacuum filtration. The product was washed multiple times with deionized water and then subjected to Soxhlet extraction with tetrahydrofuran for 24 h to remove unreacted monomers and low-molecular-weight impurities. After extraction, the product was dried under vacuum at 60 °C for 12 h to obtain the polymer material TPA-BB2By. The reaction equation is shown in Reaction I.

[0025] Reaction Formula I (2) Add 50 mg of the polymer material TPA-BB2By obtained in step (1) to a dry 25 mL round-bottom flask, add 8.0 mL of anhydrous acetonitrile, and disperse it thoroughly. Slowly add 0.4 mL of methyl trifluoromethanesulfonate under nitrogen protection, heat the reaction system to 90 °C and reflux and stir for 24 h to induce methylation of the pyridine groups in the polymer backbone. After the reaction is completed, cool to room temperature, separate the solid product by centrifugation, and wash with acetonitrile (3 × 10 mL) and anhydrous diethyl ether in sequence to remove unreacted methylating agents and soluble impurities. Add the obtained solid to 30 mL of 1 mol / L sodium chloride aqueous solution and stir at room temperature for 12 h to achieve anion exchange. After the treatment is completed, separate the solid product by filtration, wash with deionized water until the filtrate does not contain obvious chloride ions, and dry under vacuum at 60 °C for 12 h to obtain the final reddish-brown cationic polymer material TPA-BB2By-Cl. The reaction equation is shown in reaction formula II below.

[0026] Reaction formula II Figure 2 These are the infrared spectra of TPA, BB2By, TPA-BB2By, and TPA-BB2By-Cl. Compared to BB2By, TPA-BB2By and TPA-BB2By-Cl show higher infrared spectra at approximately 610 cm⁻¹. -1 The characteristic absorption peak of CH2-Br disappears at approximately 1160 cm⁻¹, while at approximately 1160 cm⁻¹... -1 CN appeared at the location + The characteristic absorption peak indicates that the methylation reaction has successfully occurred, proving the successful synthesis of the target compound.

[0027] Comparative Example 1 Weigh 5 mg of TPA-BB2By-Cl prepared in Example 1 and add it to 10 mL of ReO4 with a concentration of 20–1400 ppm. - In the solution, the mixture was stirred overnight until adsorption equilibrium was reached. The solid was then separated using a 0.22 μm microporous membrane, and the ReO4 content in the filtrate was detected by ultraviolet spectrophotometry. - Concentration, to obtain the cationic polymer TPA-BB2By-Cl on ReO4 - Calculate the maximum saturated adsorption capacity and plot the isothermal adsorption fitting curve.

[0028] The results are as follows Figure 3 As shown, TPA-BB2By-Cl affects ReO4 - The adsorption capacity varies with the equilibrium concentration C eThe adsorption rate increases rapidly and then gradually plateaus, exhibiting typical saturated adsorption behavior. Isothermal model fitting of the experimental data revealed that the Langmuir model fits the experimental points better than the Freundlich model, indicating that this material exhibits good adsorption properties for ReO4. - The adsorption is mainly a monolayer ion exchange process with relatively uniform sites. The maximum saturated adsorption capacity q obtained by Langmuir fitting is... max Approximately 1605 mg / g, with a fitting correlation coefficient R. 2 The value of 0.972 indicates that the material has high capacity and good fitting reliability. Example 2

[0029] like Figure 1 As shown, take 10 mL containing 1000 ppm ReO4 - The solution was placed in a two-chamber electrolytic cell, which could be divided into a working electrode region and a counter electrode region. Conductive glass was used as the conductive electrode. 5 mg of TPA-BB2By-Cl prepared in Example 1 was added to the rhenium-containing solution corresponding to the working electrode region, allowing it to exist in a suspended dispersion state in the solution. Under stirring conditions, external voltages of 0 V, 1 V, 1.5 V, 2 V, and 2.5 V were applied to the electrolytic cell, respectively, making the working electrode the positive electrode. After 24 h of adsorption, the solution was filtered through a 0.22 μm microporous membrane. The concentration of rhenium in the solution before and after adsorption was determined by inductively coupled plasma mass spectrometry, and the adsorption capacity was calculated.

[0030] Depend on Figure 4 It can be seen that the adsorption capacity increases significantly with the increase of the applied voltage. When the voltage increases from 0 V to 1.5 V, the adsorption capacity increases from 1508.4 mg / g to 1658.96 mg / g, an increase of about 150 mg / g, indicating that the applied electric field can effectively promote the adsorption of ReO4. - The migration and enrichment of adsorption sites can improve the utilization rate of effective adsorption sites in materials.

[0031] When the voltage was increased to 2.0 V, the adsorption capacity basically reached equilibrium, indicating that the electric field-driven effect tended to saturate within this voltage range. However, when the voltage was increased to 2.5 V, charred black deposits appeared on the conductive glass surface, and the adsorption capacity decreased slightly (1602.9 mg / g). This is speculated to be related to the enhanced electrochemical side reactions at the electrode interface at high potentials, redox processes on the electrode surface, or local deposition of organic components. This phenomenon may lead to changes in local mass transfer conditions or uneven distribution of the effective electric field, thereby causing a certain degree of decrease in adsorption capacity. Example 3

[0032] like Figure 1 As shown, take 10 mL containing 20 ppm ReO4 -The solution was placed in a two-chamber electrolytic cell, which could be divided into a working electrode region and a counter electrode region. Conductive glass was used as the conductive electrode. 5 mg of TPA-BB2By-Cl prepared in Example 1 was added to the rhenium-containing solution corresponding to the working electrode region, allowing it to exist in a suspended dispersion state in the solution. Under stirring conditions, 0 V and 1.5 V external voltages were applied to the electrolytic cell, and samples were taken at time intervals of 30 s, 1 min, 2 min, 3 min, 5 min, 10 min, 15 min, 20 min, and 30 min. After filtration through a 0.22 μm microporous membrane, the ReO4 content in the solution was measured by inductively coupled plasma mass spectrometry. - Concentration, to obtain the cationic polymer material TPA-BB2By-Cl for lower concentrations of ReO4 - Adsorption kinetics.

[0033] Depend on Figure 5 It can be seen that at a low concentration of 20 ppm ReO4 - Under the specified conditions, TPA-BB2By-Cl exhibited significantly enhanced adsorption kinetics under an applied electric field. Without applied voltage (0 V), the adsorption reaction primarily relied on concentration gradient-driven adsorption and electrostatic adsorption and anion exchange of the material itself. The removal rate was 63.6% within 1 min, reaching 90.6% after 5 min, and tending towards adsorption equilibrium at approximately 30 min, with a final removal rate of 98.7%. In contrast, under an applied electric field of 1.5 V, ReO4... - Driven by an electric field, the material undergoes directional migration and accumulates in the working electrode region, significantly increasing its contact probability with the dispersed cationic polymer material. The adsorption reaction achieves a removal rate of 77.4% within 1 minute, 87.9% within 2 minutes, over 96.8% within 5 minutes, and over 99% within 20 minutes, eventually stabilizing at 99.7%.

[0034] The above results indicate that an applied electric field can significantly accelerate the reaction of ReO4 in a low-concentration system. - The migration and enrichment rates are increased, shortening the adsorption equilibrium time by approximately 30%–50% and simultaneously improving adsorption efficiency under low concentration conditions. This phenomenon further demonstrates that the electric field-assisted adsorption method described in this invention has a significant synergistic enhancement effect in low-concentration rhenium-containing systems. Especially under low concentration conditions, the electric field-driven migration effect is more significant than that relying solely on the concentration gradient diffusion mechanism, thereby effectively improving the utilization rate of adsorption sites in cationic polymer materials.

[0035] Comparative Example 2 Take 10 mL of ReO4 containing different concentrations -The solution (1~2000ppm) was placed in a two-chamber electrolytic cell that could be divided into a working electrode region and a counter electrode region. Conductive glass was used as the conductive electrode. No cationic polymer material was added in this experiment; it was only used to verify the effect of the applied electric field on ReO4. - The migration and enrichment of ReO4 were investigated. An external voltage of 1.5 V was applied to the electrolytic cell, and samples were taken after 1 h. The samples were filtered through a 0.22 μm microporous membrane, and the ReO4 concentration in the solution was measured by inductively coupled plasma mass spectrometry. - Concentration, thus calculating ReO4 under the influence of an electric field. - The migration rate and enrichment rate between the two regions.

[0036] Depend on Figure 6 It can be seen that, without the addition of cationic polymer materials, applying an external electric field of 1.5 V for 1 hour in a two-chamber electrolytic cell is sufficient to induce ReO4 to undergo electrolysis. - Significant directional migration and enrichment occur in the working electrode region. When the initial concentration is 1–1000 ppm, ReO4… - The enrichment rate in the working electrode region reached over 99%; even at a higher concentration of 2000 ppm, the enrichment rate remained at 97.43%. These results indicate that an applied electric field can effectively drive negatively charged ReO4 over a wide concentration range. - Rapid directional migration occurs, resulting in a highly enriched state in the working electrode region.

[0037] The experimental results fully demonstrate that an applied electric field can significantly enhance the concentration of ReO4 in the solution. - The migration efficiency and regional concentration capability of the dispersed cationic polymer material in the working electrode region are crucial for the subsequent dispersion of ReO4. - The capture provides a high-concentration contact environment, thereby improving the utilization rate of adsorption sites and the overall adsorption efficiency. Especially in low-concentration systems, the electric field-driven migration effect can effectively compensate for the mass transfer limitations caused by relying solely on concentration gradient diffusion, providing key technical support for achieving efficient separation and enrichment in low-concentration rhenium-containing systems. Example 4

[0038] like Figure 1 As shown, take 10 mL containing 20 ppm ReO4 - The solution was placed in a two-chamber electrolytic cell that could be divided into a working electrode region and a counter electrode region. Conductive glass was used as the conductive electrode, and equimolar amounts of interfering anions, including Cl, were added to the system. - CO3 2- NO3 - SO4 2- and PO4 3-5 mg of TPA-BB2By-Cl prepared in Example 1 was added to the rhenium-containing solution corresponding to the working electrode region, allowing it to exist in a suspended dispersion state in the solution. Under stirring conditions, 0 V and 1.5 V external voltages were applied to the electrolytic cell, respectively. After reacting for 12 h, the solution was filtered through a 0.22 μm microporous membrane, and the ReO4 content in the solution was measured by inductively coupled plasma mass spectrometry. - Concentration, to obtain the cationic polymer TPA-BB2By-Cl on ReO4 - The adsorption selectivity. (By...) Figure 7 It can be seen that at 20 ppm ReO4 - Under these conditions, even if equimolar Cl exists - SO4 2- NO3 - CO3 2- and PO4 3- Even when faced with common interfering anions, the TPA-BB2By-Cl described in this invention still exhibits excellent selective adsorption performance. Under conditions without an applied electric field (0 V), ReO4... - The removal rates remained between 97.96% and 99.12%, indicating that the material itself possesses strong anion exchange capacity and selective recognition ability.

[0039] When an external electric field of 1.5 V is applied, the ReO4 in each interference system... - The removal rate was further improved to 99.04%–99.56%, with all values ​​approaching or exceeding 99%. This result indicates that the applied electric field not only does not weaken the material's selectivity in complex anionic systems, but can actually promote the removal of ReO4+. - The directional migration and regional enrichment of the molecules allow them to preferentially contact and adsorb onto dispersed cationic polymer materials, thus maintaining a high separation efficiency even under conditions of interference from coexisting ions.

[0040] The above experimental results further demonstrate that the electric field-assisted adsorption method described in this invention has good anti-interference ability and selective enhancement effect in complex solution systems, and can achieve adsorption of ReO4 under various common anion coexistence conditions. - The stable and efficient enrichment provides reliable technical support for the selective separation of rhenium-containing waste liquid in actual industrial systems.

Claims

1. A method for preparing a cationic polymer material for electric field-assisted adsorption of rhenium, characterized in that, Includes the following steps: (1) Tris(pyridin-4-yl)amine and 5,5′-bis(bromomethyl)-2,2′-bipyridine were added to an organic solvent to form a reaction system. After nitrogen purging to remove oxygen, the system was sealed under a nitrogen atmosphere and then heated to carry out a cross-linking polymerization reaction to generate a polymer precursor containing a pyridine structure. After the reaction was completed, the system was cooled to room temperature and polymer materials were obtained by solid-liquid separation, Soxhlet extraction and drying. (2) The polymer material prepared in step (1) is subjected to a post-modification reaction with a methylating agent in a polar solvent to induce methylation of the pyridine group. After the reaction is completed, the mixture is cooled to room temperature, and the solid product is separated by centrifugation. After washing, the solid product is subjected to anion exchange treatment. Finally, the solid product is filtered, washed, and dried to obtain a cationic polymer material with chloride ions as the counter ion.

2. The method for preparing a cationic polymer material according to claim 1, characterized in that, In step (1), the molar ratio between tris(pyridin-4-yl)amine and 5,5′-bis(bromomethyl)-2,2′-bipyridine is 1:(1-3); the temperature of the crosslinking polymerization reaction is 80-140 °C and the time is 12-168 h.

3. The method for preparing a cationic polymer material for electric field-assisted adsorption of rhenium according to claim 1 or 2, characterized in that, In step (1), the organic solvent is one or more of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, and mesitylene; the solvent used for Soxhlet extraction is one or more of tetrahydrofuran, methanol, ethanol, and water, and the extraction time is 12 to 48 h.

4. A method for preparing a cationic polymer material for electric field-assisted adsorption of rhenium according to claim 1 or 2, characterized in that, In step (2), the mass-to-volume ratio of the polymer material to the methylating agent is 1 g: 4~10 mL; the methylating agent is one or more of iodomethane, methyl trifluoromethanesulfonate, and dimethyl sulfate; the temperature of the post-modification reaction is 40~120 ℃ and the time is 6~48 h.

5. A method for preparing a cationic polymer material for electric field-assisted adsorption of rhenium according to claim 1 or 2, characterized in that, In step (2), the polar solvent is acetonitrile, dichloromethane or nitrobenzene; the solution used for the anion exchange treatment is a 0.1-3 mol / L sodium chloride aqueous solution, and the anion exchange treatment time is 4-24 h.

6. A cationic polymer material prepared by the preparation method according to any one of claims 1-5, wherein the cationic polymer material is a porous cationic polymer solid insoluble in water, and the chemical structural formula of the cationic polymer material is shown in Formula I: Formula I.

7. The application of the cationic polymer material prepared by the preparation method according to any one of claims 1-5 or the cationic polymer material according to claim 6 as an adsorbent in electric field-assisted adsorption of rhenium.

8. The application according to claim 7, characterized in that, The specific application process is as follows: S1. Provide a rhenium-containing solution and introduce the rhenium-containing solution into an electrolytic cell. The electrolytic cell includes a working electrode region and a counter electrode region that are separated from each other. Ion migration between the two regions is achieved through an ion conduction structure. S2. Add cationic polymer material to the rhenium-containing solution in the working electrode area so that the cationic polymer material exists in the solution system in a suspended and dispersed state; S3. Under stirring conditions, a set voltage is applied to the electrolytic cell to establish an electric field, driving rhenium-containing anions to migrate directionally to the working electrode region and adsorb onto the cationic polymer material. Through electrostatic attraction of cation sites and anion exchange, the adsorption and separation of rhenium in the solution are achieved.

9. The application according to claim 8, characterized in that, In step S1, the rhenium-containing solution is an ore leaching solution, metallurgical waste liquid, or a simulated rhenium-containing solution; the rhenium in the rhenium-containing solution is in the form of perrhenate ReO4. - It exists in the form of an ion exchange membrane, a porous membrane, or a salt bridge.

10. The application according to claim 8, characterized in that, In step S3, a positive voltage of 0.1 to 5 V is applied to the working electrode to establish an external electric field; the adsorption time is 1 min to 24 h.

Images