Rhenium recovery functional material and preparation method thereof
The rhenium recovery functional material prepared by modifying chlorine balls solves the problem of insufficient desorption capacity of amino functional materials, realizes efficient rhenium recovery and the preparation of high-purity rhenium raw materials, and is suitable for the field of rhenium recovery.
Patent Information
- Application Number
- CN202510846986.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-24
- Publication Date
- 2025-09-23
AI Technical Summary
Existing amino-functional materials have insufficient desorption capacity in the process of recovering ammonium perrhenate, which makes it difficult to effectively recover rhenium resources. In particular, impurity interference is serious in complex solution environments, affecting the purification and purity of rhenium.
Chlorine balls modified with N-ethylthiourea aminating agent were used to prepare rhenium recovery functional materials. Through water bath heating and pH adjustment, a resin material with high adsorption capacity and strong desorption ability was formed. In particular, it showed efficient rhenium recovery effect when desorbed using ammonia water.
It achieves efficient adsorption and high desorption rates, significantly improves the recovery rate of ammonium perrhenate, reduces impurity adsorption, provides high-purity rhenium raw materials, and lays the foundation for the subsequent production of high-purity metallic rhenium.
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Figure CN120683379A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of rhenium recovery, and in particular to a rhenium recovery functional material and a preparation method thereof. Background Art
[0002] In the modern industrial system, the booming aviation engine industry has led to the increasing strategic importance of rhenium metal, which is indispensable in key areas such as high-temperature alloy manufacturing. Waste acid generated during the copper smelting process contains rich rhenium resources, typically with a rhenium concentration ranging from 3-30 mg / L. However, when purifying copper smelting waste acid, conventional water treatment methods cause large amounts of rhenium to enter the arsenic filter cake and neutralization slag, making it difficult to effectively recover rhenium resources. This situation urgently requires new technological breakthroughs.
[0003] Currently, the technologies for recovering metallic rhenium from waste acid wastewater mainly include extraction, ion exchange and precipitation. Among them, the ion exchange method has been put into practical application in industrial production due to its advantages of simple process and low environmental pollution. The core principle of the ion exchange method is to use the perrhenate ReO4 - Ion exchange reaction occurs with the anions on the material column, making ReO4 - Selectively adsorbed on the material column, the ion association complex is subsequently destroyed by a stronger ion exchanger or specific reagent to achieve ReO4 - Among various ion exchange materials, amino-functional synthetic resins have shown considerable potential for rhenium recovery. Studies have shown that amino-functional synthetic resins can undergo specific chemical reactions with rhenium ions, resulting in a strong adsorption capacity for rhenium, thereby achieving the goal of enriching rhenium from complex solution systems.
[0004] However, there are significant differences in the desorption capacity of different amino-functional materials, especially in the process of using ammonia water to recover ammonium perrhenate, where this difference is more prominent. Some materials have poor desorption effects in ammonia water, which seriously limits the recovery efficiency and purity improvement of ammonium perrhenate. For example, when common ion exchange materials are faced with copper smelting waste acid containing various impurities, they will not only be interfered with by impurities such as copper, arsenic, fluorine, and chlorine, which reduces the adsorption performance, but also when using ammonia water for desorption, the desorption rate is low, resulting in a large amount of rhenium unable to be effectively detached from the adsorption material, making it difficult to convert it into ammonium perrhenate, which in turn affects the purification and subsequent application of rhenium. This problem has become a key bottleneck restricting the further development of amino-functional materials in the field of rhenium recovery. Summary of the Invention
[0005] The object of the present invention is to provide a rhenium recovery functional material and a preparation method thereof, so as to solve the problem of insufficient desorption capacity of existing amino-functional materials in the rhenium recovery process, especially when using ammonia water to recover ammonium perrhenate.
[0006] In a first aspect, the present invention provides a method for preparing a rhenium recovery functional material, comprising:
[0007] Step 1: Weigh 10-50g of chlorine balls in a 100ml beaker, then add 10-40g of N,N-dimethylformamide, ensuring that the chlorine balls are completely immersed, and soak for 2-4 hours;
[0008] Step 2: Weigh N-ethylthiourea aminating agent according to a preset ratio of available chlorine content to amine and place it in a constant pressure separatory funnel;
[0009] Step 3: Heat the reaction system in a water bath and add N-ethylthiourea aminating agent dropwise within 2-3 hours. After the addition of the aminating agent is completed, add sodium hydroxide solution dropwise to the reaction flask to adjust the pH value of the reaction system to 5-12, and continue the reaction for 6-14 hours;
[0010] Step 4: After the reaction is completed, the resin is repeatedly washed with deionized water until the washed solution is neutral to remove residual impurities and reaction by-products; and dried under a vacuum environment to obtain a dry rhenium recovery functional material.
[0011] Furthermore, in step 1, the chlorine balls are chloromethylated polystyrene cross-linked microspheres with a mesh size of 40-60.
[0012] Furthermore, in step 2, N-ethylthiourea aminating agent is weighed according to a preset ratio of available chlorine content to amine of 0.5-1:1-6.
[0013] Furthermore, in step three, the water bath heating temperature is controlled at 30-60°C.
[0014] Furthermore, in step 4, drying is performed at 30-60° C. under vacuum for 4-8 hours.
[0015] In a second aspect, the present invention provides a rhenium recovery functional material, which is prepared using the above-mentioned method for preparing the rhenium recovery functional material.
[0016] The present invention has the following beneficial effects: the rhenium recovery functional material not only possesses a high adsorption capacity, enabling efficient enrichment of rhenium from complex copper smelting waste acid, but also possesses a strong desorption capacity. In particular, when using ammonia as a desorbent, it enables efficient recovery of ammonium perrhenate, significantly improving the desorption rate. Furthermore, the rhenium recovery functional material exhibits excellent selectivity, enabling precise adsorption of rhenium in complex solution environments, reducing the adsorption of impurities, and providing high-quality raw materials for the subsequent production of high-purity metallic rhenium. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In order to more clearly illustrate the technical solution of the present invention, the following briefly introduces the drawings required for use in the embodiments. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.
[0018] Figure 1 It is the adsorption diagram of synthetic resin material;
[0019] Figure 2 It is the desorption diagram of synthetic resin material;
[0020] Figure 3 This is a diagram showing the effect of N-ethylthiourea resin material adsorbing rhenium. DETAILED DESCRIPTION
[0021] It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of the present application may be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments. It should be noted that the following detailed descriptions are illustrative and are intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this application belongs.
[0022] Screening and Preparation of Functional Materials for Rhenium Recovery: By comparing the molecular structures and HOMO and LUMO orbital energies of various functional groups, we selected those with lower HOMO energies, such as alkylthioureas, dicyclohexylamine, aminopyridine, and aminotriazole. After in-depth research and screening, we identified a group of potentially advantageous aminating agents, including hexamethyleneimine, methylimidazole, cyclohexylamine, vinylimidazole, dicyclohexylamine, dicyandiamide, and N-ethylthiourea. By comparing the absolute hardness of thioureas from the following groups (A, B, C, D, E, H, G, O, N, and N), we found that only those with the lowest absolute density (E, C, and D) showed the best reaction with perrhenate ions.
[0023] Table 1 HOMO and LOMO orbital energies of different functional groups and their energy level differences with perrhenate
[0024]
[0025]
[0026] Based on these aminating agents, functional materials with rhenium recovery capabilities were synthesized. Taking N-ethylthiourea as an example, the synthesis steps are as follows: Accurately weigh 10-50g of chlorine spheres (chloromethylated polystyrene cross-linked microspheres with a mesh size of 40-60, purchased from a chromatographic adsorption separation material factory) into a 100ml beaker. Then, add 10-40g of N,N-dimethylformamide, ensuring the chlorine spheres are completely submerged. Soak for 2-4 hours to allow the chlorine spheres to fully swell and create favorable conditions for subsequent reactions. Accurately weigh the N-ethylthiourea aminating agent at a ratio of available chlorine content to amine of 0.5-1:1-6 and place it in a constant pressure separatory funnel to precisely control the addition rate. Heat the reaction system in a water bath at 30-60°C. Slowly add the N-ethylthiourea aminating agent dropwise over 2-3 hours to ensure a complete and uniform reaction. After the amination agent is added, sodium hydroxide solution is added to the reaction flask to adjust the pH of the reaction system to approximately 5-12. The reaction is continued for 6-14 hours to promote the functionalization of the material and ensure stable adsorption properties. After the reaction, the resin is repeatedly rinsed with deionized water until the solution is neutral to remove residual impurities and reaction byproducts. The resin is then dried under vacuum at 30-60°C for 4-8 hours to obtain the dried functional material.
[0027] The following describes in detail the effects of rhenium recovery materials prepared using different aminating agent materials in combination with specific examples and comparative examples.
[0028] Comparative Example 1: A1 (hexamethyleneimine modified)
[0029] Weigh 20g of chlorine balls and 32g of hexamethyleneimine and carry out resin treatment for 2h; weigh the aminating agent according to the ratio of effective chlorine content: amine = 1:3, place the resin into the assembled experimental device, and place the aminating agent into a constant pressure separatory funnel; keep the water heated at 40°C and control the aminating agent to be added dropwise within 2h; after the aminating agent is added dropwise, add sodium hydroxide solution into the reaction flask to control the pH to about 10, and react for 14h; after the reaction is completed, take out the resin and place it into a sand core funnel, and wash the resin with deionized water until it is neutral; dry the washed neutral resin under vacuum at 40°C for 6h.
[0030] Comparative Example 2: A2 (cyclohexylamine modified)
[0031] The experiment involved weighing 20 g of chlorine balls and 28 g of cyclohexylamine for resin modification for 2 h; weighing an aminating agent at a ratio of 1:3 between effective chlorine content and amine, placing the resin into the assembled experimental apparatus, and placing the aminating agent into a constant-pressure separatory funnel; keeping the water heated at 40°C, the aminating agent was added dropwise within 2 h; after the aminating agent was added dropwise, sodium hydroxide solution was added dropwise to the reaction flask to control the pH to approximately 10, and the reaction was allowed to proceed for 14 h; after the reaction was complete, the resin was removed and placed into a sand core funnel, and the resin was washed with deionized water until neutral; the washed neutral resin was dried under vacuum at 40°C for 6 h.
[0032] Comparative Example 3: A3 (1-vinylazole imidazole modified)
[0033] The laboratory weighed 20 g of chlorine balls and 26 g of 1-vinylimidazole for 2 hours; the aminating agent was weighed according to the ratio of effective chlorine content: amine = 1:3, the resin was placed in the assembled experimental device, and the aminating agent was placed in a constant pressure separatory funnel; the water area was kept heated at 40°C, and the aminating agent was added dropwise within 2 hours; after the aminating agent was added dropwise, sodium hydroxide solution was added to the reaction flask to control the pH to about 10, and the reaction was carried out for 14 hours; after the reaction was completed, the resin was taken out and placed in a sand core funnel, and the resin was washed with deionized water until it was neutral; the washed neutral resin was dried under vacuum at 40°C for 6 hours.
[0034] Comparative Example 4: A4 (dicyandiamide modified)
[0035] The laboratory weighed 20 g of chlorine balls and 20 g of dicyandiamide for modification for 2 hours; weighed the aminating agent according to the ratio of effective chlorine content: amine = 1:3, placed the resin into the assembled experimental device, and placed the aminating agent into a constant pressure separatory funnel; kept the water heated at 40°C, and controlled the aminating agent to be added dropwise within 2 hours; after the aminating agent was added dropwise, sodium hydroxide solution was added dropwise to the reaction flask to control the pH to about 10, and the reaction was carried out for 14 hours; after the reaction was completed, the resin was taken out and placed in a sand core funnel, and the resin was washed with deionized water until it was neutral; the washed neutral resin was dried under vacuum at 40°C for 6 hours.
[0036] Comparative Example 5: A5 (dicyclohexylamine modified)
[0037] Weigh 50g of dicyclohexylamine (pH=8-9) and 20g of chlorine balls and modify for 2h; weigh the aminating agent according to the ratio of effective chlorine content: amine=1:3, place the resin into the assembled experimental device, and place the aminating agent into a constant pressure separatory funnel; keep the water heated at 40°C, and control the aminating agent to be added dropwise within 2h; after the aminating agent is added dropwise, add sodium hydroxide solution into the reaction flask to control the pH to about 10, and react for 14h; after the reaction is complete, remove the resin and place it into a sand core funnel, and wash the resin with deionized water until it is neutral; dry the washed neutral resin under vacuum at 40°C for 6h.
[0038] Example: A6 (N-ethylthiourea modified)
[0039] Weigh 20g of chlorine balls. Dissolve 10g of N-ethylthiourea in 50mL of N,N-dimethylformamide. Weigh the aminating agent in a ratio of 1:3 between available chlorine content and amine. Place the resin into the assembled experimental apparatus and the aminating agent into a constant-pressure separatory funnel. Maintain a 40°C temperature and ensure the aminating agent is added dropwise within 2 hours. During the addition of liquid caustic soda, the solution turns brownish-black. Thioureas react with the caustic soda to produce ammonia and carbon dioxide, so avoid adding too much liquid caustic soda; 5mL of 10% liquid caustic soda is sufficient. After the reaction is complete, remove the resin and place it into a sand-core funnel. Rinse the resin with deionized water until neutral. Dry the neutralized resin under vacuum at 40°C for 6 hours.
[0040] Table 2 Comparison of adsorption rate of different aminating agent materials and desorption rate of 10% ammonia water
[0041] Material Adsorption rate% 10% ammonia desorption rate% A1 99.91 2.56 A2 99.84 5.32 A3 99.99 8.18 A4 99.95 5.65 A5 99.55 11.1 A6 99.51 60.83
[0042] Adsorption and desorption performance test and analysis: Prepare a simulated liquid with a Re concentration of approximately 200 mg / L and a sulfuric acid acidity of approximately 2%, add it at a volume ratio of 1:20 between the activated resin and the simulated liquid, and perform static adsorption for 16 hours; filter out the adsorbed resin and use 10% ammonia water to perform static desorption for 2 hours at a volume ratio of 1:10 between the adsorbed resin and the desorption liquid. The activation method is as follows: first use a 5% sodium hydroxide solution, then soak in 4BV of water for two hours, then wash with deionized water until neutral, and then soak in 5% sulfuric acid for two hours. Comprehensive adsorption and desorption performance tests were conducted on the different materials screened out, and the specific data are as follows:
[0043] Table 3 Adsorption and desorption performance test data
[0044] Material Adsorption rate% 10% ammonia desorption rate% Saturated adsorption capacity (g / l) A1 99.91 2.56 3.996 A2 99.84 5.32 3.994 A3 99.99 8.18 4.000 A4 99.95 5.65 3.998 A5 99.55 11.1 3.982 A6 99.51 60.83 3.980
[0045] The data clearly demonstrates that the resin synthesized with N-ethylthiourea exhibits excellent adsorption performance, achieving adsorption rates of 98.30% to 99.68% for a rhenium simulant solution with a concentration of approximately 200 mg / L, with an average of 99.51%. More importantly, when desorbed using 10% ammonia, the desorption rate reached a staggering 60.83%, significantly outperforming other comparative materials. In the actual process of recovering rhenium from copper smelting waste acid, this high desorption rate means that when ammonia is used as the desorbent, the adsorbed rhenium on the material is largely converted into ammonium perrhenate and removed from the material. Compared to other materials with lower desorption rates, N-ethylthiourea allows more rhenium to enter the desorption solution, significantly increasing the amount of ammonium perrhenate recovered. Furthermore, this high desorption rate reduces rhenium residue on the material and the risk of impurities contaminating the ammonium perrhenate, greatly facilitating subsequent purification of the ammonium perrhenate and effectively ensuring the quality of the raw materials used to produce high-purity metallic rhenium.
[0046] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.
Claims
1. A method for preparing a rhenium recovery functional material, characterized in that: include: Step 1: Weigh 10-50g of chlorine balls in a 100ml beaker, then add 10-40g of N,N-dimethylformamide, ensuring that the chlorine balls are completely immersed, and soak for 2-4 hours; Step 2: Weigh N-ethylthiourea aminating agent according to a preset ratio of available chlorine content to amine and place it in a constant pressure separatory funnel; Step 3: Heat the reaction system in a water bath and add N-ethylthiourea aminating agent dropwise within 2-3 hours. After the addition of the aminating agent is completed, add sodium hydroxide solution dropwise to the reaction flask to adjust the pH value of the reaction system to 5-12, and continue the reaction for 6-14 hours; Step 4: After the reaction is completed, the resin is repeatedly washed with deionized water until the washed solution is neutral to remove residual impurities and reaction by-products; and dried under a vacuum environment to obtain a dry rhenium recovery functional material.
2. The method for preparing a rhenium recovery functional material according to claim 1, wherein: In step 1, the chlorine balls are chloromethylated polystyrene cross-linked microspheres with a mesh size of 40-60.
3. The method for preparing a rhenium recovery functional material according to claim 1, wherein: In step 2, N-ethylthiourea aminating agent is weighed according to a preset ratio of available chlorine content to amine of 0.5-1:1-6.
4. The method for preparing a rhenium recovery functional material according to claim 1, wherein: In step 3, the water bath heating temperature is controlled at 30-60°C.
5. The method for preparing a rhenium recovery functional material according to claim 1, wherein: In step 4, the product is dried at 30-60°C under vacuum for 4-8 hours.
6. A rhenium recovery functional material, characterized in that: The rhenium recovery functional material is prepared by the preparation method of any one of claims 1 to 5.