Method for separating rhenium from rhenium-containing solution by adopting anion exchange resin

Abstract

The method comprises the following steps: (1) putting 1-vinyl imidazole into a flask containing N, N-dimethylformamide and D314 type resin, adding an initiator, carrying out a grafting reaction under the action of the initiator, and obtaining imidazolyl anion exchange resin after the reaction is finished; (2) pre-treating the imidazolyl anion exchange resin, and then adsorbing a rhenium-containing solution to be treated by adopting the pre-treated imidazolyl anion exchange resin; and (3) washing the imidazolyl anion exchange resin subjected to saturated adsorption in the step (2) by using ultrapure water, and then analyzing by using ammonia water to obtain a high-purity rhenium-containing solution. According to the method, the imidazolyl anion exchange resin is synthesized, the imidazolyl anion exchange resin has excellent selective adsorption capacity on rhenate ions, and efficient separation of rhenium and other impurities can be achieved when the imidazolyl anion exchange resin is applied to the rhenium-containing solution.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrometallurgy, and in particular relates to a method for efficiently separating rhenium and impurities from a rhenium-containing solution by using a selective ion exchange resin. Background Art

[0002] The main component of molybdenite is molybdenum sulfide, and it is the mineral with the highest rhenium content. It has abundant reserves worldwide and is an important raw material for refining rhenium and molybdenum. However, rhenium and molybdenum are similar in chemical properties and are difficult to separate. Traditional separation methods such as chemical precipitation and solvent extraction have problems such as poor selectivity, high cost, and complex processes. Therefore, it is necessary to study an efficient and environmentally friendly rhenium separation technology, which is of great significance to improving resource utilization efficiency and promoting the green and sustainable development of the metallurgical industry.

[0003] At present, the purity of crude ammonium rhenate is usually improved by multiple re-dissolution and crystallization in China. This method can obtain ammonium rhenate with a purity of 4N grade, but this method has the disadvantages of complicated process and high cost.

[0004] Patent document with publication number CN109179506A discloses a method for synergistically recovering rhenium and molybdenum from the eluent of molybdenum concentrate roasting. In this method, the eluent is pretreated and then adjusted to a pH of 0.2 to 1.5. Rhenium is first adsorbed using a composite amine-based ethylene-based macroporous weak-base anion exchange resin, and then molybdenum is adsorbed using a tertiary amine-based acrylic acid-based macroporous weak-base anion exchange resin. This method requires the use of a large amount of acid to adjust the pH, generates a large amount of wastewater, and is difficult to treat.

[0005] Patent document with publication number CN118480155A discloses a multi-active group chelated ion exchange resin, a preparation method and an application thereof. The method synthesizes a chelated ion exchange resin with multiple active groups, which can effectively treat wastewater containing metal ions and electronic chemicals containing metal ions. This scheme requires grafting of multiple groups, and the adsorption efficiency is not considerable, and the process is cumbersome. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the shortcomings and defects mentioned in the above background technology and provide a method for separating rhenium from a rhenium-containing solution using an anion exchange resin.

[0007] In order to solve the above technical problems, the technical solution proposed by the present invention is:

[0008] A method for separating rhenium from a rhenium-containing solution using an anion exchange resin comprises the following steps:

[0009] (1) placing 1-vinylimidazole in a flask containing N,N-dimethylformamide and D314 resin, and adding an initiator, and carrying out a grafting reaction under the action of the initiator. After the reaction is completed, an imidazole-based anion exchange resin is obtained;

[0010] (2) pretreating the imidazole-based anion exchange resin, and then using the pretreated imidazole-based anion exchange resin to adsorb the rhenium-containing solution to be treated;

[0011] (3) The imidazole anion exchange resin saturated with adsorption in step (2) is rinsed with ultrapure water, and then analyzed with an ammonia solution to obtain a high-purity rhenium-containing solution.

[0012] In the above method for separating rhenium from a rhenium-containing solution, preferably, in step (1), the initiator is one of ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile and benzoyl peroxide.

[0013] In the above method for separating rhenium from a rhenium-containing solution, preferably, in step (1), 40 mL of N,N-dimethylformamide and 4-14 mL of 1-vinylimidazole are used for every 1 g of D314 resin treated; wherein the amount of the initiator added is 0.2%-2.0% of the mass of the vinylimidazole.

[0014] In the above method for separating rhenium from a rhenium-containing solution, preferably, in step (1), the temperature of the grafting reaction is 30-60° C., and the time of the grafting reaction is 5-15 hours.

[0015] In the above method for separating rhenium from a rhenium-containing solution, preferably, in step (2), the pretreatment comprises first washing the imidazole-based anion exchange resin with a sodium chloride solution to remove surface impurities, and then soaking the imidazole-based anion exchange resin in a sulfuric acid solution for transformation; and adjusting the pH value of the solution to be adsorbed to 3-4 using the sulfuric acid solution.

[0016] In the above method for separating rhenium from a rhenium-containing solution, preferably, in step (2), the adsorption includes using a dynamic countercurrent adsorption method to pump the rhenium-containing solution from the lower end into an ion exchange column at a flow rate of 5 to 15 BV / h to contact with an imidazole anion exchange resin and then flow out.

[0017] In the above method for separating rhenium from a rhenium-containing solution, preferably, in step (3), the volume of the ammonia solution used for analysis is 20 to 60 BV (resin volume).

[0018] In the above method for separating rhenium from a rhenium-containing solution, preferably, in step (2), the rhenium-containing solution to be treated contains one or more of the impurities potassium, sulfur, copper, and molybdenum.

[0019] In the above method for separating rhenium from a rhenium-containing solution, preferably, in step (3), the resistivity of ultrapure water is ≥18 MΩ·cm.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The present invention synthesizes an imidazole-based anion exchange resin, which has excellent selective adsorption capacity for rhenate ions. The imidazole-based anion exchange resin can be used in a rhenium-containing solution to achieve efficient separation of rhenium and other impurities.

[0022] (2) In the process of separating rhenium from a rhenium-containing solution using an imidazole-based anion exchange resin, the present invention selects a countercurrent adsorption method, which can increase the contact time between the solution and the imidazole-based anion exchange resin and improve the adsorption efficiency.

[0023] (3) In the process of separating rhenium from a rhenium-containing solution using imidazole-based anion exchange resin, the present invention does not need to use a large amount of toxic and harmful extractants, thereby reducing environmental pollution and meeting the development requirements of green metallurgy.

[0024] (4) The present invention uses a synthetic anion exchange resin with a specific structure and cooperates with the process of the present invention to remove trace impurity ions in a rhenium-containing solution, and the purity of rhenium can be increased from 90% to 99.99%.

[0025] (5) The method for separating rhenium from a rhenium-containing solution of the present invention is simple and has a high recovery rate of rhenium.

[0026] (6) The process flow of the present invention is simple, easy to operate, and easy to realize industrial production; compared with traditional separation methods, the method of the present invention has lower cost and significant economic benefits. DETAILED DESCRIPTION

[0027] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully in combination with preferred embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments.

[0028] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0029] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0030] Embodiment 1:

[0031] A method for separating rhenium from a rhenium-containing solution using an anion exchange resin comprises the following steps:

[0032] (1) Synthesis of imidazole-based anion exchange resin: 8 mL of 1-vinylimidazole (VIM) was placed in a flask containing 40 mL of N,N-dimethylformamide (DMF) and 1 g of D314 resin. At 40° C., 0.4% ammonium persulfate based on the mass of vinylimidazole was added as an initiator. Under the action of the initiator, a grafting reaction occurred for 10 hours to obtain the imidazole-based anion exchange resin D314-VIM.

[0033] (2) Preparation of ammonium rhenate solution: 5 g of purchased crude ammonium rhenate with a purity of 90% was placed in a beaker, and 1000 mL of ultrapure water with a resistivity of 18 MΩ·cm was used to stir and dissolve it at 40° C. for 20 min. Then, impurities were removed by filtering through a 45-micron mixed cellulose ester filter membrane to obtain a clear and transparent ammonium rhenate solution. The composition of the crude ammonium rhenate is shown in Table 1 below.

[0034] Table 1 Composition of crude ammonium rhenate (ppm)

[0035] Re(%) Mo K S Cu other 62.49 20.76 64.32 28 8.21 /

[0036] (3) The imidazole anion exchange resin D314-VIM prepared in step (1) was refluxed with ethanol in a Soxhlet exchanger at 65° C. for 10 h, and then vacuum dried. Before adsorption, impurities on the surface of the resin were washed with a 5% sodium chloride solution, and then immersed in a 5% sulfuric acid solution for transformation, and the pH value of the adsorption solution was adjusted to 3 with sulfuric acid solution.

[0037] (4) Use the anion exchange resin D314-VIM pretreated in step (3) to treat the ammonium rhenate solution, measure 20 mL of wet resin and remove ReO4 - Selectively combine with the imidazole functional group in the resin. Specifically, the ammonium rhenate solution is pumped into the ion exchange column from the lower end at a flow rate of 10 BV / h using a dynamic countercurrent adsorption method, and then flows out after contacting with the anion exchange resin D314-VIM.

[0038] (5) After rinsing the saturated adsorbed anion exchange resin in step (4) with ultrapure water having a resistivity of 18 MΩ·cm, the saturated resin is analyzed with an ammonia solution having a volume ratio of pure water to ammonia water of 1:1, wherein the volume of the ammonia solution is 40 BV, to obtain a decontaminated ammonium rhenate solution.

[0039] After the ammonium rhenate solution components obtained after analysis were evaporated and crystallized, the product components were shown in Table 2. The recovery rate of rhenium could reach 99.6%, while the recovery rate of molybdenum was 3.4%, thereby achieving the separation of rhenium from other impurities.

[0040] Table 2 Product composition after crystallization (ppm)

[0041] Re(%) Mo K S Cu other 69.38 0.71 0.28 1.12 0.05 /

[0042] Embodiment 2:

[0043] A method for separating rhenium from a rhenium-containing solution using an anion exchange resin comprises the following steps:

[0044] (1) Synthesis of imidazole-based anion exchange resin: 6 mL of 1-vinylimidazole (VIM) was placed in a flask containing 40 mL of N,N-dimethylformamide (DMF) and 1 g of D314 resin. At 40° C., 0.2% ammonium persulfate based on the mass of vinylimidazole was added as an initiator. Under the action of the initiator, a grafting reaction occurred for 6 hours to obtain the imidazole-based anion exchange resin D314-VIM.

[0045] (2) Preparation of ammonium rhenate solution: 5 g of purchased crude ammonium rhenate with a purity of 90% was placed in a beaker, and 2000 mL of ultrapure water with a resistivity of 18 MΩ·cm was used to stir and dissolve it at 40° C. for 20 min. Then, impurities were removed by filtering through a 45-micron mixed cellulose ester filter membrane to obtain a clear and transparent ammonium rhenate solution. The composition of the crude ammonium rhenate is shown in Table 1.

[0046] (3) The anion exchange resin D314-VIM prepared in step (1) was refluxed with ethanol in a Soxhlet exchanger at 65° C. for 10 h, and then vacuum dried. Before adsorption, impurities on the surface of the resin were washed with a 5% sodium chloride solution, and then immersed in a 5% sulfuric acid solution for transformation, and the pH value of the adsorption solution was adjusted to 3 with sulfuric acid solution.

[0047] (4) using the anion exchange resin D314-VIM pretreated in step (3) to treat the ammonium rhenate solution, and converting the ReO4 - Selectively combine with the imidazole functional group in the resin. Specifically, the ammonium rhenate solution is pumped into the ion exchange column from the lower end at a flow rate of 15 BV / h using a dynamic countercurrent adsorption method, and then flows out after contacting with the anion exchange resin D314-VIM.

[0048] (5) After rinsing the saturated adsorbed anion exchange resin in step (4) with ultrapure water having a resistivity of 18 MΩ·cm, the resin is analyzed with an ammonia solution having a volume ratio of pure water to ammonia water of 1:2, wherein the volume of the ammonia solution is 20 BV, to obtain a decontaminated ammonium rhenate solution.

[0049] After the ammonium rhenate solution components obtained after analysis were evaporated and crystallized, the product components were shown in Table 3. The recovery rate of rhenium could reach 89.7%, while the recovery rate of molybdenum was 5.2%, thereby achieving the separation of rhenium from other impurities.

[0050] Table 3 Product composition table (ppm)

[0051] Re(%) Mo K S Cu other 67.72 1.08 0.31 1.54 0.06 /

[0052] Embodiment 3:

[0053] A method for separating rhenium from a rhenium-containing solution using an anion exchange resin comprises the following steps:

[0054] (1) Synthesis of imidazole-based anion exchange resin: 4 mL of 1-vinylimidazole (VIM) was placed in a flask containing 40 mL of N,N-dimethylformamide (DMF) and 1 g of D314 resin. At 30° C., 0.6% of ammonium persulfate based on the mass of vinylimidazole was added as an initiator. Under the action of the initiator, a grafting reaction occurred for 6 hours to obtain the imidazole-based anion exchange resin D314-VIM.

[0055] (2) Preparation of ammonium rhenate solution: 5 g of purchased crude ammonium rhenate with a purity of 90% was placed in a beaker, and 2500 mL of ultrapure water with a resistivity of 18 MΩ·cm was used to stir and dissolve it at 40° C. for 20 min. Then, impurities were removed by filtering through a 45-micron mixed cellulose ester filter membrane to obtain a clear and transparent ammonium rhenate solution. The composition of the crude ammonium rhenate is shown in Table 1.

[0056] (3) The anion exchange resin D314-VIM prepared in step (1) was refluxed with ethanol in a Soxhlet exchanger at 65° C. for 10 h, and then vacuum dried. Before adsorption, impurities on the surface of the resin were washed with a 5% sodium chloride solution, and then immersed in a 5% sulfuric acid solution for transformation, and the pH value of the adsorption solution was adjusted to 3 with sulfuric acid solution.

[0057] (4) using the anion exchange resin D314-VIM pretreated in step (3) to treat the ammonium rhenate solution, and converting the ReO4 - Selectively combine with the imidazole functional group in the resin. Specifically, the ammonium rhenate solution is pumped into the ion exchange column from the lower end at a flow rate of 5 BV / h using a dynamic countercurrent adsorption method, and then flows out after contacting with the anion exchange resin D314-VIM.

[0058] (5) After the anion exchange resin saturated with adsorption in step (4) is rinsed with ultrapure water having a resistivity of 18 MΩ·cm, the resin is analyzed with an ammonia solution having a volume ratio of pure water to ammonia water of 1:2, wherein the volume of the ammonia solution is 60 BV, to obtain a decontaminated ammonium rhenate solution.

[0059] After evaporation and crystallization of the analyzed ammonium rhenate solution components, the product components are shown in Table 4. The recovery rate of rhenium can reach 92.5%, while the recovery rate of molybdenum is 6.2%, thereby achieving the separation of rhenium and other impurities.

[0060] Table 4 Product composition table (ppm)

[0061] Re(%) Mo K S Cu other 68.83 1.29 0.35 1.79 0.04 /

[0062] Comparative Example 1:

[0063] The method for separating rhenium from a rhenium-containing solution in this comparative example comprises the following steps:

[0064] (1) Preparation of ammonium rhenate solution: 5 g of purchased crude ammonium rhenate with a purity of 90% was placed in a beaker, and 1000 mL of pure water with a resistivity of 18 MΩ·cm was used to stir and dissolve it at 40° C. for 20 min. Then, impurities were removed by filtering through a 45 μm mixed cellulose ester filter membrane to obtain a clear and transparent ammonium rhenate solution. The composition of the crude ammonium rhenate is shown in Table 1.

[0065] (2) Before adsorption, soak the D314 resin in 5% sodium chloride solution for 5 hours to wash away impurities on the resin surface, then soak it in 5% sulfuric acid solution to transform it. Place 20 mL of the pre-treated anion exchange resin D314 in the ion exchange column and pump ammonium rhenate solution into it from the bottom at a rate of 10 BV / h. The ReO4 - and MoO4 2- With the amine functional groups in the resin SO4 2- Displacement and binding to the resin surface.

[0066] (3) After the anion exchange resin saturated with adsorption in step (2) was rinsed with ultrapure water having a resistivity of 18 MΩ·cm, the resin was analyzed with an ammonia solution having a volume ratio of pure water to ammonia of 1:1, and the volume of the ammonia solution used was 40 BV, to obtain a decontaminated ammonium rhenate solution.

[0067] The components of the ammonium rhenate solution after analysis were evaporated and crystallized. The product components are shown in Table 5. The recovery rate of rhenium can reach 83.1%, while the recovery rate of molybdenum is 18.9%.

[0068] Table 5 Product composition table (ppm)

[0069] Re(%) Mo K S Cu other 65.27 3.92 6.28 3.64 0.35 /

Claims

1. A method for separating rhenium from a rhenium-containing solution using an anion exchange resin, characterized in that: The following steps are involved: (1) placing 1-vinylimidazole in a flask containing N,N-dimethylformamide and D314 resin, and adding an initiator, and carrying out a grafting reaction under the action of the initiator. After the reaction is completed, an imidazole-based anion exchange resin is obtained; (2) pretreating the imidazole-based anion exchange resin, and then using the pretreated imidazole-based anion exchange resin to adsorb the rhenium-containing solution to be treated; (3) The imidazole anion exchange resin saturated with adsorption in step (2) is rinsed with ultrapure water, and then analyzed with an ammonia solution to obtain a high-purity rhenium-containing solution.

2. The method for separating rhenium from a rhenium-containing solution according to claim 1, characterized in that: In step (1), the initiator is one of ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile and benzoyl peroxide.

3. The method for separating rhenium from a rhenium-containing solution according to claim 1, characterized in that: In step (1), 40 mL of N,N-dimethylformamide and 4-14 mL of 1-vinylimidazole are used for each 1 g of D314 resin treated; wherein the amount of the initiator added accounts for 0.2%-2.0% of the mass of the vinylimidazole.

4. The method for separating rhenium from a rhenium-containing solution according to claim 1, characterized in that: In step (1), the temperature of the grafting reaction is 30-60° C., and the time of the grafting reaction is 5-15 hours.

5. The method for separating rhenium from a rhenium-containing solution according to claim 1, characterized in that: In step (2), the pretreatment includes first washing the imidazole anion exchange resin with a sodium chloride solution to remove surface impurities, and then soaking it in a sulfuric acid solution for transformation.

6. The method for separating rhenium from a rhenium-containing solution according to claim 1, characterized in that: In step (2), the adsorption includes using a dynamic countercurrent adsorption method to pump the rhenium-containing solution to be treated from the lower end into the ion exchange column at a flow rate of 5 to 15 BV / h, contacting with the imidazole-based anion exchange resin, and then flowing out.

7. The method for separating rhenium from a rhenium-containing solution according to claim 1, characterized in that: In step (3), the volume of the ammonia solution used for analysis is 20 to 60 BV.

8. The method for separating rhenium from a rhenium-containing solution according to claim 1, characterized in that: In step (2), the rhenium-containing solution to be treated contains one or more of the impurities potassium, sulfur, copper and molybdenum.

9. The method for separating rhenium from a rhenium-containing solution according to claim 1, characterized in that: In step (3), the resistivity of the ultrapure water is ≥18 MΩ·cm.